Technical field
[0001]
The present invention relates to a laminated body for composing the like bags.
BACKGROUND
[0002]
Conventionally, cooked or semi-cooked liquid, the contents of the viscous or liquid and solid are mixed, which was filled sealed bag constructed from a plastic laminate has been around for many markets. In the bag, non-sealing portion laminated bodies is not bonded constitute a housing portion which the contents are accommodated. The seal portion laminated bodies are joining, to seal the housing portion. Content is, for example, a semi-cooked food to be cooked curry, stew, cooked food such as soup or by heating.
[0003]
　Laminate constituting the pouch includes a plastic film as the substrate. Patent Document 1, the polyethylene terephthalate as the material of the base material of the laminate, proposes the use of polypropylene or nylon. The substrate contributes to improving the strength of the laminate.
CITATION
Patent Document
[0004]
Patent Document 1: JP 2014-94767 JP
Summary of the Invention
Problems that the Invention is to Solve
[0005]
　Nylon is known as a material having a high strength. However, nylon has the property of easily absorbing moisture. Therefore, when using a nylon substrate, it and the nylon is impaired appearance of being colored bag with contents, the laminate strength of the laminate may be decreased.
[0006]
　The present invention aims at providing such a problem effectively resolved can laminate.
Means for Solving the Problems
[0007]
　The present invention is a laminate, a substrate containing 51 wt% or more of polybutylene terephthalate, wherein at least one of linear low density polyethylene or polypropylene, and the sealant layer constituting the inner surface of the laminate It comprises a laminate.
[0008]
　In the laminate according to the present invention, the substrate comprising polybutylene terephthalate may have a multilayer structure comprising more than 10 layers. Or, it said substrate comprising a polybutylene terephthalate, may comprise a single layer structure having a 1.10 dl / g or more and 1.35dl / g or less of IV values.
[0009]
　In the laminate according to the present invention, the sealant layer may comprise 90 wt% or more polypropylene.
[0010]
　In the laminate according to the present invention, the sealant layer may comprise a linear low density polyethylene having a 100 ° C. melting point above.
[0011]
　Laminate according to the present invention is provided on the outer surface side of the sealant layer further comprises an adhesive layer comprising a cured product of a polyol and an aliphatic isocyanate compound, the aliphatic isocyanate compound to the hydroxyl groups of the polyol the molar ratio of the isocyanate groups, may be 3.5 or more.
[0012]
　Laminate according to the present invention,
　the substrate / adhesive layer / sealant layer,
　substrate / printed layer / adhesive layer / sealant layer,
　substrate / transparent deposition layer / transparent gas barrier coating film / printed layer / adhesive layer / sealant layer, or a
　substrate / transparent deposition layer / transparent gas barrier coating film / adhesive layer / sealant layer, may a comprise in this order. In this case, piercing strength of the laminate may be more than 11N.
[0013]
　Laminate according to the present invention,
　the substrate / transparent deposition layer / transparent gas barrier coating film / printed layer / adhesive layer / sealant layer, or a
　substrate / transparent deposition layer / transparent gas barrier coating film / adhesive layer / sealant layer , hints in this order,
　the transparent deposition layer comprises aluminum oxide, the interface between the transparent evaporated layer and the substrate, covalent attachment of aluminum and carbon atoms may be formed.
[0014]
　In the laminate according to the present invention, impact strength of the laminate may be 800kJ / m or more.
[0015]
　Laminate according to the present invention,
　the substrate / first adhesive layer / metal foil / second adhesive layer / sealant layer, or a
　substrate / printed layer / first adhesive layer / metal foil / second adhesive layer / wherein the sealant layer, in this order,
　the second adhesive layer may comprise a cured product of a polyol and an aliphatic isocyanate compound. In this case, piercing strength of the laminate may be more than 13N.
[0016]
　Laminate according to the present invention, the first substrate, the second substrate and the sealant layer comprises at least in this order, the second substrate is 51 mass% or more of polyethylene terephthalate or 51 wt% or more polybutylene terephthalate wherein, when the second substrate comprises polyethylene terephthalate or 51 wt%, the first substrate may contain 51 mass% or more of polybutylene terephthalate. In this case, piercing strength of the laminate may be more than 13N.
[0017]
　Laminate according to the present invention, a transparent evaporated layer provided on said first substrate or said second substrate between said second substrate and said first substrate, provided on the transparent vapor deposition layer and a transparent gas barrier coating film may further contain a.
[0018]
　In the laminate according to the present invention, the transparent deposition layer comprises aluminum oxide, the interface between the transparent evaporated layer and the first substrate or the second substrate, covalent attachment of aluminum and carbon atoms is formed it may be.
[0019]
　In the laminate according to the present invention, the laminate, further includes a light-shielding printed layer and the first substrate located between the second substrate, the total light transmittance of the laminate was 20% or less it may be.
[0020]
　In the laminate according to the present invention, the first substrate comprises a polybutylene terephthalate, the second substrate may also include a polyethylene terephthalate.
[0021]
　In the laminate according to the present invention, the first substrate comprises polyethylene terephthalate, the second substrate may also comprise polybutylene terephthalate.
Effect of the invention
[0022]
　According to the present invention can have a penetration resistance and heat resistance to the laminate.
BRIEF DESCRIPTION OF THE DRAWINGS
[0023]
FIG. 1 is a front view showing the bag in the first embodiment of the present invention.
Is a cross-sectional view showing an example of a layer configuration of FIG. 2 laminate constituting the bag.
It is a cross-sectional view illustrating an example of FIG. 3 layer structure of the first film of the laminate.
It is a sectional view showing another example of FIG. 4 layer structure of the laminate constituting the bag.
5 is a sectional view showing an example of the layer structure of the laminate in the second embodiment.
6 is a sectional view showing an example of the layer structure of the laminate in the third embodiment.
7 is a sectional view showing another example of the layer structure of the multilayer body in the third embodiment.
8 is a sectional view showing another example of the layer structure of the multilayer body in the third embodiment.
9 is a sectional view showing an example of the layer structure of the laminate according to the fourth embodiment.
FIG. 10 is a sectional view showing another example of the layer structure of the multilayer body in the fourth embodiment.
11 is a diagram showing an example of a method of measuring the lamination strength.
It is a diagram illustrating an example of FIG. 12 measuring method of lamination strength.
13 is a graph showing changes in tensile stress to the distance between the pair of jaws pulling the first film and the sealant film to measure the lamination strength.
It is a plan view showing a test piece for evaluating FIG. 14 tear.
It is a plan view showing a test piece for evaluating FIG. 15 impact strength.
It is a cross-sectional view of the test piece shown in FIG. 16 FIG. 15.
17 is a diagram showing an example of a method for measuring the impact strength.
18 is a diagram showing an example of a method for measuring the puncture strength.
19 is a graph showing evaluation results of Examples A1 ~ A5 and Comparative Examples A1 ~ A3.
Is a graph showing evaluation results of FIG. 20 Examples B1 ~ B3 and Comparative Examples B1 ~ B3.
21 is a graph showing evaluation results of Examples C1 ~ C6 and Comparative Examples C1, C2.
22 is a graph showing evaluation results of Examples D1 ~ D4 and Comparative Examples D1, D2.
DESCRIPTION OF THE INVENTION
[0024]
　 First embodiment of
　with reference to FIGS. 1 to 4, a description will be given of a first embodiment of the present invention. In the accompanying drawings to the present specification, for convenience of easy understanding and illustration, the scale and aspect of the dimensional ratio and the like, are exaggerated appropriately changed from those of the real.
[0025]
　Also, as used herein, identifies the shape and geometric conditions and the degree thereof, such as "parallel", the "orthogonal", terms and the length of such "identity" and angle values ​​or the like, exact meaning without being bound, and interpreting including range that can expect a similar function.
[0026]
　Figure 1 is a front view of a bag 10 according to this embodiment. Bag 10 includes a receptacle 17 for accommodating the contents. In FIG. 1, the bag 10 in a state where contents are not accommodated are shown. Bag 10 according to this embodiment is configured so that can be subjected to retort processing. The following describes the structure of the bag 10.
[0027]
　 Bag
　in this embodiment, the bag 10 is self-standing constructed bag of the gusset type. Bag 10 includes a top 11, bottom 12 and side 13, having a substantially rectangular outline in a front view. Note that "top", the name, such as "lower" and "side", and "upper", terms such as "below", bags state the bag 10 by the gusset portion to the lower is standing on its own as a reference only 10 or those which relative position and orientation of the components. Etc. during transportation and during use orientation of the bag 10 are not limited by name or term in this specification.
[0028]
　As shown in FIG. 1, the bag 10, the surface film 14, the back surface film 15 constituting the rear surface constituting the surface and comprises a bottom film 16 constituting the lower 12. Bottom film 16 is in a state of being folded at the folded portion 16f, it is disposed between the surface film 14 and the back film 15.
[0029]
　Incidentally, the above-mentioned "surface film", the term "back film" and "lower film", only those partitioning the film according to the positional relationship, provides a method of film in the production of bags 10, It is not limited by the above terms. For example, the bag 10 may be surface film 14 and the back film 15 and bottom film 16 is manufactured by using one sheet of film which is continuously provided, the surface film 14 and bottom film 16 of one which is continuously provided film and may be manufactured using a total of two films of one backside film 15, one surface film 14 and one backside film 15 one the total of three films in the bottom film 16 it may be fabricated using.
[0030]
　Surface film 14, the back surface film 15 and bottom film 16, inner faces are joined by a seal portion. Front view odor bag 10, such as Figure 1, hatching is applied to the seal portion.
[0031]
　As shown in FIG. 1, the sealing portion has an outer edge seal portion extending along the outer edge of the bag 10. Outer sealing portion, a lower seal portion 12a extending in the lower 12, and includes a pair of side seal portion 13a extending along the pair of side portions 13. Incidentally, in the bag 10 of the previous state (contents are not filled) that the contents are filled, as shown in FIG. 1, top 11 of the bag 10 is in the opening 11b. After receiving the contents of the bag 10, by joining the inner surface of the inner surface and the back film 15 of the surface film 14 in the upper 11, the bag 10 is sealed upper seal portion is formed.
[0032]
　Upper seal portion for side sealing portion 13a and below are sealed portion formed by joining the inner surface of the inner surface and the back film 15 of the surface film 14. On the other hand, the lower sealing part 12a, the seal portion constituted by joining the inner surface of the surface film 14 and the inner surface of the lower film 16, and, by joining the inner surfaces of the lower film 16 of the back film 15 including configured seal.
[0033]
　By joining opposing film together as long as it is possible to seal the bag 10, there is no possibility that a method for forming a seal portion is particularly limited. For example, heating the inner surface of the film is melted by the like, by welding inner faces, i.e. the heat seal may form a seal portion. Or, by adhering the inner surfaces of the film which faces with an adhesive, it may form a seal portion.
[0034]
　 Peelable means
　the surface film 14 and the back surface film 15 may be easily openable means 25 is provided for opening the bag 10 by tearing the surface film 14 and the back surface film 15. For example, as shown in FIG. 1, the easy-open means 25, formed in the side seal portion 13a of the bag 10 may include a notch 26 serving as a starting point for tearing. Also, the portion serving as the route of tearing the bag 10, as easy-open means 25, the half-cut line formed by a laser processing or a cutter may be provided.
[0035]
　Further, although not shown, the easy-open means 25 may include a surface film 14 and the cut and scar group sealing portion is formed in the region formed of the backside film 15. Scar group, for example, may include a plurality of through-holes formed so as to penetrate the surface film 14 and / or back surface film 15. Or, scar group may include a surface film 14 and / or the back film 15 so as not to penetrate the surface film 14 and / or a plurality of holes formed on the outer surface of the back film 15.
[0036]
　 Layer structure of surface film and back film
　will now be described layer structure of surface film 14 and the back surface film 15. Figure 2 is a sectional view showing a laminated body 30 constituting the surface film 14 and the back surface film 15.
[0037]
　As shown in FIG. 2, the laminate 30 includes a first film 40, a sealant film 70 laminated on the first film 40 through an adhesive layer 45. The first film 40 is located on the outer surface 30y side, the sealant film 70 is positioned on the inner surface 30x side opposite the outer surface 30y. Inner surface 30x is a surface facing the accommodating portion 17 side in the bag 10 constructed by the laminated body 30, the outer surface 30y is a surface located opposite the inner surface 30x.
[0038]
　The first film 40 comprises at least a substrate 41. The first film 40 may further include a print layer 42 provided on the inner surface 30x side of the substrate 41. Also, sealant film 70 comprises a sealant layer 71. Therefore, the laminated body 30 according to this embodiment, in order to the inner surface from the outer surface side
　　substrate / printed layer / adhesive layer / sealant layer
comprises a, and say. It should be noted that, "/" represents the boundary of the layer and the layer.
[0039]
　Hereinafter, the first film 40, respectively will be described in detail sealant film 70 and adhesive layer 45.
[0040]
　(First film)
　first film 40 comprises at least a substrate 41 constituting the outer surface 30y of the stack 30. As shown in FIG. 2, the first film 40 may further comprise a printed layer 42 provided on the inner surface 30x side of the substrate 41.
[0041]
　[Substrate]
　substrate 41, polybutylene terephthalate (hereinafter, also referred to as PBT) as the main component including. For example, substrate 41 comprises 51 wt% or more PBT. Hereinafter, the substrate 41 will be described benefits of including PBT.
[0042]
　PBT has excellent dimensional stability, thus is excellent in printability. Thus, polyethylene terephthalate (hereinafter, referred to as PET) as in the case of, it can be provided a printed layer 42 on the substrate 41 including the PBT.
[0043]
　Also, PBT has excellent heat resistance. Therefore, it is possible to prevent the strength of the substrate 41 or substrate 41 is deformed or reduced when performing a boiling treatment or retort treatment to the bag 10. The retort processing, after sealing the bag 10 is filled with contents into the bag 10, a process utilizing steam or heated hot water to heat the bag 10 in a pressurized state. Temperature of the retort processing is, for example, 120 ° C. or higher. The boil treatment, after sealing the bag 10 is filled with contents into the bag 10, a process of hot water bags 10 at atmospheric pressure. Temperature of boiling treatment is, for example, 90 ° C. or higher and 100 ° C. or less.
[0044]
　Also, PBT has a high strength. Therefore, as in the case where the laminated body constituting the bag 10 comprises a nylon, it can have a penetration resistance to the bag 10.
[0045]
　Also, PBT has a characteristic that it is difficult to absorb water as compared to nylon. Therefore, even when placing the substrate 41 including the PBT to the outer surface 30y of the stack 30, the substrate 41 is a laminate strength of the laminate 30 absorbs moisture to prevent the lowered can.
[0046]
　Hereinafter, a detailed description of the construction of the substrate 41 including the PBT. In this embodiment, the configuration of the substrate 41 including the PBT, may employ any of the first configuration or the second configuration below.
[0047]
　[First configuration of the base material]
　The content of PBT in the substrate 41 according to the first configuration is preferably at least 51 wt%, more preferably at least 60 wt%, more than 70 mass%, in particular 75 preferably more mass%, most preferably at least 80 wt%. The content of PBT by more than 51% by weight, can have excellent impact strength and pinhole resistance in the first film 40.
[0048]
　PBT is used as a main component, a dicarboxylic acid component is preferably terephthalic acid is 90 mol%, more preferably at least 95 mol%, more preferably at least 98 mol%, and most preferably 100 is the mole percent. Preferably 1,4-butanediol as a glycol component is not less than 90 mol%, more is preferably 95 mol% or more, more preferably 97 mol% or more, and most preferably, at the time of polymerization of 1,4 except by-products produced by the ether linkage of butanediol is not included.
[0049]
　Substrate 41 may include a polyester resin other than PBT. Thus, for example, a film-like substrate 41 can be adjusted mechanical properties of film formability and substrate 41 of case of biaxial stretching.
　The polyester resin other than PBT, PET, polyethylene naphthalate (PEN), polybutylene naphthalate (PBN), other polyester resins such as polypropylene terephthalate (PPT), isophthalic acid, orthophthalic acid, naphthalene dicarboxylic acid, biphenyl dicarboxylic acid , cyclohexane dicarboxylic acid, adipic acid, azelaic acid, and PBT resin dicarboxylic acid is copolymerized, such as sebacic acid, ethylene glycol, 1,3-propylene glycol, 1,2-propylene glycol, neopentyl glycol, 1,5 - pentanediol, 1,6-hexanediol, diethylene glycol, cyclohexanediol, polyethylene glycol, polytetramethylene glycol, diol and polycarbonate diol Min can be mentioned copolymerized PBT resin.
[0050]
　The addition amount of the polyester resin other than the above PBT is preferably 49 wt% or less, more preferably 40% by mass. If the amount of the polyester resin other than PBT exceeds 49 mass%, mechanical properties of the PBT is impaired, impact strength and pinhole resistance, it is considered that drawing formability becomes insufficient.
[0051]
　Substrate 41, as an additive, flexible polyether component, polycarbonate component may include a polyester and polyamide elastomer obtained by copolymerizing at least one of the polyester components. This makes it possible to improve pinhole resistance at the time of bending. The addition amount of the additive is, for example, 20% by mass. When the amount of the additive exceeds 20 wt%, and that the effect of the additive is saturated, transparency of the substrate 41 can occur and be lowered.
[0052]
　An example of a method of making a film-like base material 41 according to the first configuration will be described. Here, a method for producing a film-like base material 41 by casting. More specifically, a method for casting and multi-layered resin of the same composition at the time of casting.
[0053]
　For PBT is fast crystallization rate, crystallization proceeds even at the time of casting. In this case, when cast as a single layer without multilayered, because there is no barrier, such as to be able to suppress the growth of crystals, crystal will grow to a larger size, resulting unstretched raw film the yield stress increases of. Therefore, it becomes easy to break unstretched raw an in biaxial orientation. Moreover, the yield stress of the obtained biaxially oriented film becomes high, it is considered that the moldability of the biaxially stretched film becomes insufficient.
　In contrast, if multi-layered same resin during casting, it is possible to reduce the stretching stress of the undrawn sheet. Therefore, it is possible to stably biaxially oriented, also, the yield stress of the obtained biaxially stretched film becomes low. Thus, it is possible to obtain a highly flexible and breaking strength film.
[0054]
　Figure 3 is a cross-sectional view showing an example of the layer structure of the first film. If the substrate 41 by casting the resin multilayered is produced, as shown in FIG. 3, the substrate 41 of the first film 40 is made of a multilayer structure including a plurality of layers 41a. Each of the plurality of layers 41a includes a PBT as a main component. For example, each of the plurality of layers 41a preferably comprises 51 mass% or more PBT, more preferably 60 mass% or more of PBT. In the plurality of layers 41a, n + 1 th layer 41a is stacked directly on the n-th layer 41a. That is, between a plurality of layers 41a, the adhesive layer and the adhesive layer is not interposed.
[0055]
　The cause of the characteristics of the PBT film is improved by the multi-layer is estimated as follows. When laminating the resin, the composition of the resin in the case of the same there is an interface layer, the crystallization is accelerated by the interface. On the other hand, the growth of large crystals that exceeds the thickness of the layer is suppressed. Therefore, it is considered that the size of the crystals (spherulites) decreases.
[0056]
　As a specific method for reducing the size of the spherulites by multilayered, the general multi-layered device (multi-layer feed block, a static mixer, such as multi-layer multi-manifold) can be used. For example, it is possible to use a method in which laminating a thermoplastic resin fed from different flow paths using two or more units of extruder feed block and a static mixer, such as a multilayer by using a multi-manifold die. In the case of multi-layered resin of the same composition, using only a single extruder, it is also possible to introduce the above-mentioned multilayered device in the melt line from an extruder to the die.
[0057]
　Substrate 41 is at least 10 layers or more, preferably 60 or more layers, more preferably 250 layers or more, more preferably a multilayer structure including the 1000 or more layers 41a. By increasing the number of layers, it is possible to reduce the size of spherulites in the PBT of the unstretched raw state, subsequent biaxial stretching can be carried out stably. Further, it is possible to reduce the yield stress of PBT state of biaxially oriented film. Preferably, the diameter of spherulites in the PBT of the unstretched raw is 500nm or less.
[0058]
　Of making the unstretched raw film biaxially stretched to biaxially oriented films of PBT, longitudinal stretching direction (hereinafter, MD) stretching temperature in (hereinafter, referred to as MD stretching temperature) is preferably 40 ° C. or higher There, more preferably 45 ° C. or higher. The MD stretching temperature by the 40 ° C. or higher, it is possible to prevent the breakage of the film occurs. Further, MD stretching temperature is preferably not 100 ° C. or less, more preferably 95 ° C. or less. By the MD stretching temperature to 100 ° C. or less, it is possible to suppress the phenomenon does not occur orientation of the biaxially oriented film.
[0059]
　Stretch ratio in the MD (hereinafter, referred to as MD stretching ratio) is preferably 2.5 times or more. Thus, to align the biaxially oriented film, it is possible to achieve good mechanical properties and uniform thickness. MD stretching ratio is, for example, 5 times or less.
[0060]
　Transverse stretching direction (hereinafter, referred to as TD) stretching temperature in (hereinafter, referred to as TD stretching temperature) is preferably 40 ° C. or higher. The TD stretching temperature by the 40 ° C. or higher, it is possible to prevent the breakage of the film occurs. Further, TD stretching temperature is preferably 100 ° C. or less. By the TD stretching temperature to 100 ° C. or less, it is possible to suppress the phenomenon does not occur orientation of the biaxially oriented film.
[0061]
　Stretching ratio in TD (hereinafter, also referred to as a TD stretching ratio) is preferably 2.5 times or more. Thus, to align the biaxially oriented film, it is possible to achieve good mechanical properties and uniform thickness. MD stretching ratio is, for example, 5 times or less.
[0062]
　TD relaxation ratio is preferably at least 0.5%. Thus, it is possible to prevent the breakage at the time of heat-setting the biaxially oriented film of PBT results. Further, TD relax ratio is preferably 10% or less. Thus, it is possible to suppress the like slack thickness unevenness occurs in the biaxially oriented film of PBT.
[0063]
　The thickness of the layer 41a of the substrate 41 shown in FIG. 3, is preferably 3nm or more, and more preferably 10nm or more. The thickness of the layer 41a is preferably not 200nm or less, more preferably 100nm or less.
　The thickness of the substrate 41 is preferably 9μm or more, more preferably 12μm or more. The thickness of the substrate 41 is preferably not 25μm or less, more preferably 20μm or less. By setting the thickness of the substrate 41 than 9 .mu.m, substrate 41 will have sufficient strength. Further, by setting the thickness of the base material 41 to 25μm or less, it exhibits a superior formability substrate 41. Therefore, it is possible to carry out the process for manufacturing the processed bag 10 a laminate 30 comprising a substrate 41 efficiently.
[0064]
　Second configuration of the substrate]
　substrate 41 according to the second configuration, a single layer film comprising a polyester butylene terephthalate as the main repeating unit. For example, substrate 41 1,4-butanediol as a glycol component, or its ester-forming derivative of terephthalic acid as the dibasic acid component, or as a main component an ester-forming derivative, they fused including are homo- or copolymer type polyester, obtained Te. The content of PBT in the substrate 41 according to the second configuration, preferably at least 51 wt%, more preferably at least 60 wt%, more preferably at least 70 wt%, more preferably at least 80 wt%, and most preferably is at least 90 mass%. Further, the substrate 41 according to the second configuration, it is preferably composed of only the polybutylene terephthalate and the additive.
[0065]
　In order to impart mechanical strength to the substrate 41, of PBT, melting point 200 ° C. or higher and 250 ° C. or less, IV value (intrinsic viscosity) of 1.10 dl / g or more and 1.35dl / g or less of those It is preferred. Furthermore, melting point of 215 ° C. or higher and 225 ° C. or less, IV value or less are particularly preferred 1.15 dl / g or more and 1.30 dl / g. These IV values, may be filled by the overall material constituting the substrate 41. IV value, JIS K 7367-5: may be calculated based on 2000.
[0066]
　Substrate 41 according to the second configuration, a polyester resin other than PBT, such as PET may be contained in an amount below 30 wt%. Due to the substrate 41 comprises PET in addition to PBT, it can be suppressed PBT crystallization, thereby improving the stretchability of the PBT film. The PET to be blended in the PBT of the base material 41, a polyester containing ethylene terephthalate as the main repeating unit. For example, ethylene glycol as the glycol component, can be preferably used homotypic mainly containing terephthalic acid as the dibasic acid component. In order to impart good mechanical strength properties, of the PET, melting point 240 ° C. or higher and 265 ° C. or less, IV value is preferably from less 0.55 dl / g or more and 0.90 dl / g. Furthermore, melting point of 245 ° C. or higher and 260 ° C. or less, IV value or less are particularly preferred 0.60 dl / g or more and 0.80 dl / g.
　By the amount of PET below 30 wt%, it is possible to prevent the rigidity of the unstretched raw and stretching the film becomes too high. Thus, the stretched film becomes brittle, pressure resistance of the stretched film, impact strength, etc. puncture strength can be suppressed to decrease. Further, it is possible to prevent the stretching upset when stretching the unstretched raw film is produced.
[0067]
　Substrate 41, if necessary, a lubricant, an antiblocking agent, inorganic fillers, antioxidants, ultraviolet absorbers, antistatic agents, flame retardants, plasticizers, colorants, crystallization inhibitors, crystallization promoter additives may include equal. Further, the polyester resin pellets used as the raw material of the substrate 41, to avoid viscosity reduction due to hydrolysis during heat-melting, water content 0.05 wt% or less before heat-melted, preferably not more than 0.01 wt% preferred for use is in terms of a sufficient preliminary drying was carried out so as to.
[0068]
　An example of a method of making a film-like base material 41 according to the second configuration will be described.
[0069]
　To stably produce a film of the base material 41 of the structure described above, to suppress the growth of crystals in the state of the unstretched raw sheet becomes important. Specifically, when forming by cooling the extruded PBT-based melt is cooled at a higher rate in the crystallization temperature region of the polymer, i.e. raw cooling rate is an important factor. Raw cooling rate, for example, 200 ° C. / sec or more, preferably 250 ° C. / sec or higher, particularly preferably 350 ° C. / sec or more. High cooling rate unstretched raw which is formed in, because it maintains a low crystalline state, thus improving the bubble stability during stretching. Furthermore, since it is possible even film formation at a high speed, thereby improving productivity of the film. If the cooling rate is less than 200 ° C. / sec, stretchability increases the crystallinity of the unstretched raw obtained may deteriorate. Also, in extreme cases, stretching bubble burst is also contemplated that stretching does not continue.
[0070]
　Unstretched raw film comprising PBT as a main component, the ambient temperature 25 ° C. or less, preferably while maintaining the 20 ° C. or less, it is preferably transported to the space for performing the biaxial stretching. Accordingly, even when the retention time is long, it is possible to maintain the unstretched raw sheet of a crystalline immediately after the film formation.
[0071]
　Biaxial stretching method to obtain a stretched film by stretching the unstretched raw film is not particularly limited. For example, the tubular method or tenter method, vertical and horizontal directions may be simultaneously stretched, or the longitudinal and transverse directions may be sequential stretching. Among them, tubular method may circumferential balance of physical properties to obtain a satisfactory stretched film is particularly preferably employed.
[0072]
　In tubular method, unstretched raw guided in stretching space, after being inserted between a pair of low-speed nip rolls, heated at a stretching heater while pressed air into. After stretching completion, the stretched film, air is blown by the cooling shoulder air ring. Draw ratio, the strength properties of the stretched stability and stretched film, transparency, and in consideration of the thickness uniformity, MD, and TD is preferably at most and 4.5 times 2.7 times or more, respectively. By the stretching ratio more than 2.7 times, it is possible to secure a sufficient tensile modulus and impact strength of the stretched film. Further, by setting the draw ratio to 4.5 times or less, the strain of excessive molecular chains is suppressed from occurring by stretching, it is possible to suppress the breakage or puncture occurs during stretching, stabilize the stretched film it can be made to.
[0073]
　The stretching temperature is preferably 40 ° C. or higher and 80 ° C. or less, particularly preferably and 65 ° C. 45 ° C. inclusive. Unstretched raw manufactured in high above cooling rate has a low crystallinity, even when the stretching temperature is a relatively low temperature, it can be stretched stably unstretched raw. Further, by the stretching temperature to 80 ° C. or less, and suppress the sway of the stretched bubble, it is possible to obtain a good stretched film of thickness accuracy. Further, by the stretching temperature to 40 ° C. or higher, to suppress the excessive stretch orientation crystallization by cold drawing occurs, it is possible to prevent the whitening and the like of the film.
[0074]
　Substrate 41 manufactured as described above, for example, it is constituted by a single layer comprising a polyester butylene terephthalate as the main repeating unit. According to the manufacturing method described above, since the formation of the unstretched raw sheet at a high cooling rate even when unstretched raw film is constituted by a single layer, it is possible to maintain a low crystalline state, Therefore, it is possible to stretch the stable unstretched raw.
[0075]
　[Print Layer]
　Printing layer 42 is a layer printed on the substrate 41 in order to grant or aesthetics or indicate product information on the bag 10. Printing layer 42 expresses characters, numbers, symbols, graphics, pictures and the like. The material constituting the printing layer 42, it is possible to use ink and ink for flexographic printing for gravure printing.
[0076]
　Ink constituting the printing layer 42 comprises a binder and a pigment. Binders, for example, similarly to the adhesive layer 45 to be described later, and the like polyurethane. Polyurethane is a cured product and a polyol as a main agent, and an isocyanate compound as a curing agent is produced by reacting. For details of the polyol and the isocyanate compound, described in the paragraph of the adhesive layer 45.
[0077]
　Pigment printing layer 42 is a powder colored, present in the binder at a predetermined distribution density. Not the color exhibited by the pigment is particularly limited, it is possible to use red, blue, green, white, various pigments, such as black. For example, the average particle size of the pigment may also be 0.1μm or more and 1μm or less, and may be 1μm or less than 0.5 [mu] m. Incidentally, the white pigment generally has a large size as compared with the pigment of other colors. For example, the average particle size of the white pigment is 0.5μm or more and 1μm or less. The average particle size of the pigment can be measured by dynamic light scattering method.
[0078]
　Printed layer 42 may be formed of a single layer or may include a plurality of layers. For example, the printing layer 42 has a first layer containing a pigment exhibiting a first color, a second layer comprising a pigment exhibiting a second color different from the first color, may contain . One layer of the thickness of the printed layer 42 is, for example, 0.5μm or more and 3μm or less.
[0079]
　[Gas barrier layer]
　FIG. 4 is a sectional view showing another example of the layer structure of the laminate 30. As shown in FIG. 4, the first film 40 of the laminate 30 is located on the inner surface 30x side of the substrate 41 may further include a transparent gas barrier layer 35 having transparency. In this case, the print layer 42 is located on the inner surface 30x of the transparent gas barrier layer 35. Figure 4 laminate 30 in the example shown, the sequentially to the inner surface from the outer surface side
　　substrate / transparent gas barrier layer / print layer / adhesive layer / sealant layer
comprises a, and say.
[0080]
　The following describes a transparent gas barrier layer 35. Transparent gas barrier layer 35 is formed on the surface of the inner surface 30x side of the substrate 41, including at least a transparent vapor deposition layer 36 made of an inorganic material having transparency. The transparent gas barrier layer 35 is formed on the surface of the inner surface 30x of the transparent evaporated layer 36 may further include a transparent gas barrier coating film 37 having transparency. In this case, the laminated body 30, in order to the inner surface from the outer surface side
　　substrate / transparent deposition layer / transparent gas barrier coating film / printed layer / adhesive layer / sealant layer
comprises a, and say.
[0081]
　Transparent evaporated layer 36 functions as a layer having gas barrier properties of the function of blocking the transmission, such as oxygen gas and water vapor. The transparent evaporated layer 36 may be provided two or more layers. If a transparent evaporated layer 36 two or more layers, each of which may be the same composition or a different composition. Transparent As a method for forming the vapor deposition layer 36, for example, vacuum deposition, sputtering, and ion plating - physical vapor deposition of plating method (Physical Vapor Deposition method, PVD method), or plasma enhanced chemical vapor deposition, thermal chemical vapor deposition, and photochemical vapor phase chemical vapor deposition growth method (chemical vapor deposition method, CVD method) and the like. Specifically, it is possible to use a roller-type deposition film forming apparatus to form a deposited layer on the deposition roller.
[0082]
　Transparent evaporated layer 36 is aluminum oxide (aluminum oxide), such as silicon oxide, is formed of an inorganic material having transparency. The transparent evaporated layer 36, it is preferable to use a non-crystalline thin film of aluminum oxide. Specifically, the transparent deposition layer 36 has the formula AlO X (wherein, X represents. A number in the range of 0.5 to 1.5) is non-crystalline thin film of aluminum oxide which is represented by . Transparent evaporated layer 36 may use a non-crystalline thin film of aluminum oxide which the value of X along the depth direction toward the inner surface of the membrane surface is reduced. Non-crystalline thin film of aluminum oxide, (wherein, X represents. A number in the range of 0.5 to 1.5) Formula AlOX is represented by, along the depth direction toward the inner surface of the thin film surface it is preferable that the value of X is increasing Te. As the value of X in the above formula, basically, it is possible to use the X = 0.5 or more of, when less than X = 1.0, coloring violently, and transparent since the inferior sex, it is preferable to use the X = 1.0 or more. Further, those of X = 1.5, since it is intended a state in which Al is completely oxidized, the upper limit can be used as up to X = 1.5. Incidentally, if the value of X in the above formula is zero, a complete inorganic simple substance (pure substance), not transparent.
[0083]
　Incidentally, reduction ratio of the value of X, for example, X-ray photoelectron spectrometer (Xray Photoelectron Spectroscopy: XPS), secondary ion mass spectrometer (Secondary Ion Mass Spectroscopy: SIMS) using a surface analyzer such as the depth direction using the method of and analyze such as ion etching, it can be confirmed from performing the elemental analysis of the transparent evaporated layer 36.
[0084]
　Transparent evaporated layer 36 may be a layer comprising a mixture of inorganic compounds containing covalent bonds of aluminum atoms and carbon atoms. In this case, the transparent deposition layer 36, X-ray photoelectron spectrometer: Share of aluminum atoms and carbon atoms (Measurement conditions X-ray source AlK, X-ray output 120 W) using a peak as measured by ion etching in the depth direction It shows the presence of binding, also has transparency and oxygen, may have a gas barrier property that prevents the permeation of water vapor or the like.
[0085]
　The interface between the transparent evaporated layer 36 and the substrate 41 may be formed a covalent bond of the metal and carbon atoms. For example, when the transparent evaporated layer 36 comprises aluminum oxide, the interface between the substrate 41 and the transparent evaporated layer 36, it can be assumed that covalent attachment of the aluminum atoms and carbon atoms are formed. Covalent bond, measured by X-ray photoelectron spectroscopy (hereinafter abbreviated as "XPS measurement") it can be detected by.
[0086]
　Further, in the transparent evaporated layer 36, the abundance ratio of the covalent bond of the aluminum atoms and carbon atoms, the total bond containing a carbon atom that is observed when measuring the interface between the transparent evaporated layer 36 and the substrate 41 by XPS measurement it is preferably in the range and below 30% 0.3% or more of the. Thus, enhanced adhesion between the transparent evaporated layer 36 and the substrate 41, excellent transparency, those good performance balanced is obtained as a gas barrier property of the deposited film.
[0087]
　When the presence ratio of the covalent bond of the aluminum atoms and carbon atoms is less than 0.3%, the improvement of adhesion of the transparent evaporated layer 36 is insufficient, it is difficult to maintain the barrier property stably.
[0088]
　Further, the transparent deposition layer 36 mainly containing aluminum oxide, AL (aluminum) / O (oxygen) ratio, from the interface between the substrate 41 and the transparent evaporated layer 36, opposite the transparent deposition the substrate 41 in towards the surface of the layer 36 within a range of up to 3 nm, it is preferably 1.0 or less.
　From the interface between the transparent evaporated layer 36 and the substrate 41, the extent towards the surface of the opposite side of the transparent evaporated layer 36 and the substrate 41, the ratio of AL / O exceeds 1.0, the base material 41 adhesion becomes insufficient between the transparent evaporated layer 36, and increasing the proportion of aluminum, the transparency of the transparent evaporated layer 36 is lowered.
[0089]
　The thickness of the transparent evaporated layer 36 is, for example, 30Å or more and 150Å or less. If it is less than 30 Å, even when used in combination with transparent gas barrier coating film 37 in some cases the gas barrier property becomes insufficient. On the other hand, when it exceeds 150 Å, it may not be possible to maintain the gas barrier performance of the laminate 30. The reason is not clear, the thickness of the transparent evaporated layer 36 is decreased flexibility of the laminate 30 exceeds 150 Å, the laminate 30 to no crack in a part of the transparent evaporated layer 36 when used in the bag 10 gas barrier property pinholes occur is thought to be reduced. The thickness of the transparent evaporated layer 36 is preferably 40 Å or more and 130Å or less, more preferably 50Å or more and 120Å or less. The thickness of the transparent evaporated layer 36 is, for example, fluorescent X-ray analyzer (trade name: RIX2000 type, manufactured by Rigaku Corporation) using, can be measured by fundamental parameter method. As the means for changing the thickness of the transparent evaporated layer 36, a method of changing the deposition rate of the transparent evaporated layer 36 can be performed by a method of changing the rate of evaporation.
[0090]
　When forming the inner surface 30x side surface transparent deposition layer on 36 of the substrate 41, in advance to corona discharge treatment on the surface of the inner surface 30x side of the substrate 41, the frame processing, be previously subjected to pre-treatment such as plasma treatment good. In particular, the interface between the transparent evaporated layer 36 and the substrate 41, in the case of forming a covalent bond of the metal and carbon atoms is subjected to a pretreatment to the surface of the substrate 41 to be formed a transparent vapor deposition layer 36 it is preferable. If the pretreatment is a plasma treatment, the pre-processing device, in the following reduced pressure environment 0.1Pa above 100 Pa, and supplies the plasma to the surface of the substrate 41. Plasma, using inert gas alone or oxygen such as argon, nitrogen, carbon dioxide gas and a gas mixture thereof with one or more gases as a plasma source gas, the potential difference due to the high frequency voltage, etc., the plasma source gas in the excited state by, it can be generated.
[0091]
　The pretreatment can be confined plasma in the vicinity of the surface of the substrate 41. This makes it possible to shape of the surface of the substrate 41, by changing the chemical bonding state or a functional group, alters the chemical properties of the surface of the substrate 41. Thus, it is possible to improve the adhesion between the substrate 41 and the transparent evaporated layer 36.
[0092]
　Transparent gas barrier coating film 37 is a layer that functions as an inhibiting layer transmission, such as oxygen gas and water vapor. Transparent gas barrier coating film 37 has the general formula R 1 n M (OR 2 ) m (In the formula, R 1 , R 2 represents an organic group having 1 to 8 carbon atoms, M represents a metal atom , n is an integer of 0 or more, m represents an integer of 1 or more, n + m is at least one or more alkoxides represented by represents) the valence of M, polyvinyl described above Arco. - Le resin and / or an ethylene-vinylalcohol - containing and alcohol copolymer, further, a sol-gel method the catalyst, acid, water, and, in the presence of an organic solvent, a transparent gas barrier composition polycondensation by the sol-gel method can get.
[0093]
　The general formula R 1 n M (OR 2 ) m as alkoxide represented by the partial hydrolyzate of the alkoxide, can be used at least one kind of condensates of the alkoxide hydrolysis. As the partial hydrolyzate of the alkoxide, it is not necessary for all alkoxyl groups are hydrolyzed, which more than one is hydrolyzed, and may be a mixture thereof. The condensation products of an alkoxide hydrolysis, more than dimer partially hydrolyzed alkoxide is specifically use a 2-6 mers.
[0094]
　The general formula R 1 n M (OR 2 ) m in alkoxide represented by the examples of the metal atom represented by M, it is possible to use silicon, zirconium, titanium, aluminum, and other the like. Preferred metals include, for example, silicon, titanium and the like. Further, in the present invention, the manner of using alkoxides, can also be used alone or as a mixture of alkoxides of two or more different metal atoms in the same solution.
[0095]
　Further, the above-mentioned general formula R 1 n M (OR 2 ) m in alkoxide represented by, R 1 Specific examples of the organic groups represented by, for example, a methyl group, an ethyl group, n- propyl group, i - propyl, n- butyl group, i- butyl group, sec- butyl group, t- butyl group, n- hexyl, n- octyl group, and an alkyl group and other. Further, the above-mentioned general formula R 1 n M (OR 2 ) m in alkoxide represented by, R 2 Specific examples of the organic groups represented by, for example, a methyl group, an ethyl group, n- propyl group, i - propyl, n- butyl group, sec- butyl group, and the like other. Incidentally, the alkyl groups in the same molecule may the be the same or different.
[0096]
　In preparing the above-mentioned transparent gas barrier composition, for example, a silane coupling agent may be added. Examples of the silane coupling agent may be a known organic reactive group-containing organoalkoxysilane. In particular, it organoalkoxysilane having an epoxy group is preferably used, specifically, for example, .gamma.-glycidoxypropyltrimethoxysilane, .gamma.-glycidoxypropylmethyldiethoxysilane or,, beta-(3, , 4-epoxycyclohexyl) ethyltrimethoxysilane can be used. Silane coupling agents as described above may be mixed and used one or two or more.
[0097]
　(Second film)
　sealant film 70 includes at least a sealant layer 71 which constitutes the inner surface 30x of the laminate 30. The material constituting the sealant layer 71, may be used alone or two or more resins selected low density polyethylene, polyethylene such as linear low density polyethylene, polypropylene. The sealant layer 71 may be a single layer or may be a multilayer. Further, the sealant layer 71 is preferably made of a film of unoriented. Note that "undrawn" is a concept including a film that is at all not only films that have not been stretched slightly stretched due to the tension applied during film formation.
[0098]
　As mentioned above, the bag 10 constructed from the laminate 30, sterilization treatment such as boiling treatment or retort treatment is performed at a high temperature. Thus, the sealant layer 71 are those having heat resistance to withstand the processing at these elevated temperatures are used.
[0099]
　The melting point of the material constituting the sealant layer 71 is preferably 0.99 ° C. or higher, more preferably 160 ° C. or higher. By increasing the melting point of the sealant layer 71, it is possible to carry out the retort processing of the bag 10 at a high temperature, this makes it possible to shorten the time required for the retort processing. The melting point of the material constituting the sealant layer 71 is lower than the melting point of the resin constituting the base material 41.
[0100]
　When considering in terms of retort processing, as the material constituting the sealant layer 71, it is possible to use a material mainly containing propylene. Here, "the main component" propylene and the material, the content of propylene means a material is 90 mass% or more. The material composed mainly of propylene include propylene-ethylene block copolymer, propylene-ethylene random copolymer, and the like a mixture of polypropylene, or polypropylene and a polyethylene, such as homopolypropylene can. Here, the "propylene-ethylene block copolymer" is meant a material having a structural formula shown in the following formula (I). In addition, "propylene-ethylene random copolymer" is meant a material having a structural formula shown in the following formula (II). Further, the "homopolypropylene" means a material having a structural formula shown in the following formula (III).
[0101]
[Formula 1]

[0102]
[Formula 2]

[0103]
[Formula 3]

[0104]
　As material composed mainly of propylene, when using a mixture of polypropylene and polyethylene, the material may have a sea-island structure. Here, the "sea-island structure", within the region where the polypropylene is continuous, refers to a structure in which polyethylene is discontinuously dispersed.
[0105]
　When considering in terms of boiling treatment, examples of the material constituting the sealant layer 71, polyethylene, polypropylene, or a combination thereof can be mentioned. The polyethylene, medium density polyethylene, and the like linear low density polyethylene or a combination thereof. For example, it is also possible to use materials listed as the material constituting the sealant layer in view of the retort process described above. The material constituting the sealant layer, for example 100 ° C. or higher, more preferably 105 ° C. or higher, more preferably has a melting point of at least 110 ° C.. When using polyethylene as the material constituting the sealant layer, 100 ° C. or higher melting points, for example, the density of the polyethylene is 0.920 g / cm 3 may be realized when at least. Specific examples of the sealant film for constituting the sealant layer having a 100 ° C. melting point above, Mitsui Chemicals Tohcello made TUX-HC, manufactured by Toyobo Co. L6101, mention may be made of Idemitsu Unitech made LS700C like. Specific examples of the sealant film for constituting the sealant layer having a 105 ° C. melting point above, mention may be made of Tamapoly made NB-1 and the like. Specific examples of the sealant film for constituting the sealant layer having a 110 ° C. or more melting point, Idemitsu Unitech made LS760C, mention may be made of Mitsui Chemicals Tohcello made TUX-HZ like.
[0106]
　Preferably, sealant layer 71 comprises propylene-ethylene block copolymer. For example, sealant film 70 including the sealant layer 71 is a non-stretched film composed mainly of propylene-ethylene block copolymer. The use of propylene-ethylene block copolymer, it is possible to improve the impact resistance of the sealant film 70, which makes it possible to prevent the bag 10 will be breakage by drop impact. Further, it is possible to enhance the resistance to piercing of the laminate 30.
[0107]
　Further, the sealant layer 71 may further comprise a thermoplastic elastomer. By using a thermoplastic elastomer, it is possible to further improve the impact resistance and penetration resistance of the sealant film 70.
[0108]
　Thermoplastic elastomers are, for example, hydrogenated styrene-based thermoplastic elastomer. Hydrogenated styrenic thermoplastic elastomers has a structure consisting of polymer block B mainly comprising at least one vinyl aromatic compound as a main component polymer block A and at least one hydrogenated conjugated diene compound . The thermoplastic elastomer may be an ethylene · alpha-olefin elastomer. Ethylene · alpha-olefin elastomer is a copolymer elastomer of the low crystalline or amorphous, random copolymer of alpha-olefin is 50 to 90% by weight of ethylene and copolymerized monomer as a main component is there.
[0109]
　The content of the propylene-ethylene block copolymer in sealant layer 71 is, for example 80 wt% or more, preferably 90 mass% or more.
[0110]
　As a method for producing a propylene-ethylene block copolymer, a method of polymerizing propylene and ethylene as a raw material using a catalyst. As the catalyst, or the like can be used Ziegler-Natta type or metallocene catalysts.
[0111]
　The thickness of the sealant layer 71 is preferably 30μm or more, more preferably 40μm or more. The thickness of the sealant layer 71 is preferably not 100μm or less, more preferably 80μm or less.
[0112]
　(Adhesive layer)
　The adhesive layer 45 comprises an adhesive for bonding the first film 40 and sealant film 70. Adhesive constituting the adhesive layer 45 is produced from the first composition and the adhesive composition prepared by mixing the second composition comprising a curing agent and a solvent containing a main agent and a solvent. Specifically, the adhesive comprises a cured product main agent and the solvent in the adhesive composition is produced by the reaction.
[0113]
　Examples of adhesives include a two-component reactive adhesive of a two liquid reaction type adhesive or an ester of ether. The two-component reactive adhesive of ether, and the like polyether polyurethane. Polyether polyurethanes, polyether polyol as the main agent, and an isocyanate compound as a curing agent is a cured product produced by reacting. The two-component reactive adhesive of the ester, for example, and the like polyester polyurethane or polyester. Polyester polyurethane is a cured product and a polyester polyol as a main agent, and an isocyanate compound as a curing agent is produced by reacting.
[0114]
　Examples of the isocyanate compound reacts with a polyol such as polyether polyol or polyester polyol to produce a cured product, aromatic isocyanate compounds and aliphatic isocyanate compound is present. Among aromatic isocyanate compound, in a high temperature environment, such as when heat sterilization (retort treatment), eluting component which can not be used in food applications. Incidentally, the adhesive layer 45, as shown in FIGS. 2 and 4, in contact with the sealant film 70 constituting the inner surface 30x of the laminate 30. Therefore, if the adhesive layer 45 comprises an aromatic isocyanate compound, components eluted from an aromatic isocyanate compound, which may be attached to the contents of the bag 10 constructed by the laminated body 30.
[0115]
　In consideration of such problems, as the adhesive constituting the adhesive layer 45, it is used a polyol as the main agent, a cured product with aliphatic isocyanate compound as a curing agent is produced by reacting. Thus, due to the adhesive layer 45, components that can not be used in food applications can be prevented from adhering to the contents. Examples of the aliphatic isocyanates include hexamethylene diisocyanate (HDI), and the like isophorone diisocyanate (IPDI).
[0116]
　On the other hand, as shown in examples described later, the case of using an aliphatic isocyanate compound as a curing agent, lamination strength between the first film 40 and sealant film 70, as compared with the case of using an aromatic isocyanate compound lower.
[0117]
　In particular, in this embodiment, the first film 40, the printed layer 42 is provided in the sealant film 70 side of the substrate 41. The binder contained in the ink constituting the printing layer 42, like the adhesive layer 45 comprises a polyol as a main agent, a cured product and an isocyanate compound as a curing agent is produced by reacting, for example, a polyurethane including. Examples of the isocyanate compound, to prevent the components that can not be used in food applications are eluted similarly used aliphatic isocyanate compound and the adhesive layer 45. Further, the ink constituting the printing layer 42 may include a pigment in addition to the polyurethane. Pigment acts to inhibit adhesion between the adhesive and / or printed layer 42 and the adhesive layer 45 between the substrate 41 and the print layer 42. Also, the first film 40 after forming the first film 40 comprising a substrate 41 and a printed layer 42 in winding into a roll, in order to prevent the front surface and rear surface of the first film 40 overlapping to close contact is the binder of the printing layer 42, it is required a small percentage of the curing agent to the base resin. Therefore, the first film 40 includes a printed layer 42 acts to reduce the lamination strength between the first film 40 and sealant film 70. If the pigment is a white, large size of the pigment is, Therefore, the degree of adhesion by the cured product is inhibited by the pigment becomes larger, the degree of reduction of the lamination strength is greater.
[0118]
　In consideration of such problems, in the present embodiment, the main component constituting the adhesive layer 45 (a polyol) and the curing agent (aliphatic isocyanate compound), to be larger than the conventional ratio of curing agent to base resin Suggest. For example, the weight ratio of the first composition comprising a main agent and a solvent, and a second composition comprising a curing agent and a solvent is conventionally about 0.1. In contrast, in the present embodiment, for the first composition comprising a main agent and a solvent, the weight ratio of the second composition comprising a curing agent and a solvent, greater than 0.1, for example 0.15 or higher to, specifically to 0.15 or 0.2. By increasing the curing agent to base resin, and promotes the reaction of the main agent and the curing agent, it is possible to enhance the adhesion of the adhesive layer 45 to the first film 40 and sealant film 70. Thus, it is possible to enhance the lamination strength between the first film 40 and sealant film 70. Thus, for example, to enhance the tear resistance of the laminate 30, or can enhance the impact resistance of the laminate 30.
[0119]
　For example, the molar ratio of curing agent to hydroxyl groups of the base resin (polyol) (aliphatic isocyanate compounds) is conventionally is about 3. In this embodiment it, the molar ratio of the isocyanate groups of the aliphatic isocyanate compound to the hydroxyl groups of the polyol is preferably 3.5 or more, and more preferably 4 or more, 4.5 or more There further preferred. More preferably, the molar ratio of the isocyanate groups of the aliphatic isocyanate compound to the hydroxyl groups of the polyol is greater than 5.
[0120]
　On the other hand, aliphatic isocyanate compounds are expensive, increasing the amount of aliphatic isocyanate compounds are not preferred in view of production cost. Also, the larger the molar ratio of the isocyanate groups of the aliphatic isocyanate compound to the hydroxyl groups of the polyol, the temperature becomes higher required to cure the adhesive composition, or the time is prolonged. Considering these points, the molar ratio of the aliphatic isocyanate groups to hydroxy groups is preferably 7 or less, more preferably 6 or less.
[0121]
　Incidentally, in the binder of the printing layer 42, the molar ratio of the isocyanate groups of the aliphatic isocyanate for hydroxy groups of the polyol, in the adhesive layer 45 is smaller than the molar ratio of isocyanate groups of the aliphatic isocyanate for hydroxy groups of the polyol Become. Even in such a case, as described above, by the molar ratio of the isocyanate groups of an aliphatic isocyanate compound to the hydroxyl groups of the polyol in the adhesive layer 45 to 3.5 or more, in the adhesive layer 45 it is considered possible to move the aliphatic isocyanate compound into the printing layer 42. Thus, it is possible to further improve the lamination strength between the first film 40 and sealant film 70.
[0122]
　The adhesive layer 45, the adhesive composition is applied to the first film 40 or the sealant film 70, then the adhesive composition is dried and, a main agent and the solvent in the adhesive composition is reacted bonded composition is formed by curing. In this embodiment, the adhesive composition after drying, the weight per unit area, for example, 2 g / m 2 or more and 5 g / m 2 is preferably not more than, 3 g / m 2 or more and 4g / m 2 less. The thickness of the adhesive layer 45 is preferably set to 2μm or more and 5μm or less, and more preferably to 3μm or more and 4μm or less.
[0123]
　 Layer structure of the bottom film
　will be described layer structure of the lower film 16.
[0124]
　As long as having an inner surface and an inner surface and joinable inner surface of the back surface film 15 of the surface film 14, the layer structure of the lower film 16 is arbitrary. For example, like the surface film 14 and the back surface film 15 may be a multilayer body 30 described above as the lower film 16. Or, the inner surface is formed by the sealant layer and the film having a structure different from that of the laminate 30 may be used as the lower film 16.
[0125]
　 Manufacturing method of the first film
　Next, an example of a manufacturing method of the first film 40.
[0126]
　First, a resin material containing a PBT as a main component. Subsequently, by extruding the resin material in the melt extrusion method such as casting method or tubular method, to prepare a film-like substrate 41. Subsequently, by depositing an inorganic material such as aluminum oxide into a film-like substrate 41 may be formed a transparent vapor deposition layer 36. Subsequently, by applying a transparent gas barrier composition onto the transparent deposition layer 36 may be formed a transparent gas barrier coating film 37. Thereafter, a print layer 42 on the substrate 41 or on transparent gas barrier coating film 37. In this way, the substrate 41, the first film 40 and a printing layer 42 or a substrate 41, a transparent gas barrier layer 35 comprising a transparent vapor deposition layer 36 and the transparent gas barrier coating film 37, printed layer 42 it is possible to obtain the first film 40 with and.
[0127]
　 Method for producing a laminate
　Next, an example of a method for producing a laminate 30.
[0128]
　First, to prepare a first composition comprising a main agent and a solvent, the mixture to an adhesive composition and a second composition comprising a curing agent and a solvent. Then, applying an adhesive composition to the first film 40 or the sealant film 70. For example, it applied onto the print layer 42 of the first film 40. Subsequently, the dried applied adhesive composition to volatilize the solvent. Then, laminating a first film 40 and sealant film 70 via the adhesive composition after drying. Subsequently, the laminate is aged over 24 hours under example 20 ° C. or higher environment. Thus, by curing the adhesive composition to obtain an adhesive comprising a cured product of a polyol and an aliphatic isocyanate compound. In this way, it is possible to obtain a laminate 30 comprising a first film 40 and sealant film 70.
[0129]
　 Method for manufacturing a bag
　to prepare the surface film 14 and the back surface film 15 consisting of the laminate 30 described above. Between the surface film 14 and the back film 15, insert the bottom film 16 in the state folded. Subsequently, the inner surfaces of each film was heat sealed, the lower seal portion 12a, to form a seal portion, such as side seal portion 13a. Further, by cutting the film are joined together by heat sealing to the appropriate shape to obtain a bag 10 shown in FIG. Subsequently, the contents 18 is filled into the bag 10 through the opening 11b of the upper 11. Contents 18, for example, is a cooked food, including curry, stew, soup or the like, and moisture. Thereafter, an upper seal portion upper 11 by heat sealing. In this way, it is possible to obtain a bag 10 the contents 18 are sealed is housed.
[0130]
　(This embodiment of the effect of Embodiment)
　According to this embodiment, the laminate 30 constituting the surface film 14 and the back surface film 15, by comprising a substrate 41 consisting mainly of PBT, the following effects be able to.
　First, PBT has excellent printability. Therefore, as in the case of polyethylene terephthalate, it can be provided a printed layer 42 on the substrate 41 including the PBT.
　Also, PBT has excellent heat resistance. Therefore, it is possible to prevent the strength of the substrate 41 or substrate 41 is deformed or reduced when performing a boiling treatment or retort treatment to the bag 10.
　Also, PBT has a high strength. Therefore, as in the case where the laminated body constituting the bag 10 comprises a nylon, it can have a penetration resistance to the bag 10. Penetration resistance of the laminated body constituting the bag 10 is preferably at least 11N, more preferably at least 13N, more preferably at least 15N, and particularly preferably at least 17N. The piercing strength measuring method is described in Example A1 described below.
　Also, PBT has a characteristic that it is difficult to absorb water as compared to nylon. Therefore, even when placing the substrate 41 including the PBT to the outer surface 30y of the stack 30, the substrate 41 is a laminate strength of the laminate 30 absorbs moisture to prevent the lowered can.
[0131]
　Further, in this embodiment, the adhesive layer 45 for joining the first film 40 and sealant film 70 includes a number of curing agent as compared with the prior art. For example, the adhesive layer 45, the molar ratio of the isocyanate groups of the aliphatic isocyanate compound to the hydroxyl groups of the polyol is 3.5 or more. Therefore, even in the case of using the aliphatic isocyanate compound as a curing agent, it is possible to accelerate the reaction of the main agent and curing agent, enhances the adhesion of the adhesive layer 45 to the first film 40 and sealant film 70 . Thus, it is possible to enhance the lamination strength between the first film 40 and sealant film 70. Further, since the use of aliphatic isocyanate compound as a curing agent, it is possible to prevent the components that can not be used in food applications are eluted.
[0132]
　Further, according to this embodiment, by increasing the lamination strength between the first film 40 and sealant film 70, it is possible to improve the tear resistance of the bag 10. The following describes tear.
[0133]
　Sealant film 70 including the sealant layer 71, the first film 40 small tensile modulus as compared to that comprising a substrate 41, tends to stretch for this. Incidentally, if the laminate strength between the first film 40 and sealant film 70 is low, sealant film 70 when the consumer tears the bag 10 may be peeled from the first film 40. In this case, force the consumer is added to the bag 10, since mainly acts as a force to extend the sealant film 70 peeled from the first film 40, it becomes difficult to tear the bag 10.
[0134]
　In the present embodiment here, by increasing the lamination strength between the first film 40 and sealant film 70, that the sealant film 70 is peeled from the first film 40 when the consumer tears the bag 10 it can be suppressed. Therefore, the force the consumer is added to the bag 10 can laminate 30 in which the first film 40 and sealant film 70 is joined to act as linearly tearing, unsealing the bag 10 smoothly. Therefore, the laminated body 30 constituting the bag 10, even if it consists of two films of the first film 40 and sealant film 70, it is possible to realize an excellent tear resistance.
[0135]
　Of the laminate 30, the laminate strength in 15mm width is preferably at least 5N, more preferably 6N or more. Method of measuring the lamination strength is described in Example A1 described below.
[0136]
　Further, in this embodiment, the substrate 41 of the first film 40 includes a PBT as a main component. PBT, as described above, has a heat resistance and penetration resistance. Therefore, the substrate 41 can be used as a layer constituting the outer surface 30y of the stack 30. Therefore, according to this embodiment, by using the first film 40 and the laminate 30 of sealant film 70 and is stacked two-layer structure, tear resistance, heat resistance, and penetration resistance is the bag 10 to be determined it can be configured. By the laminate 30 to the two-layer structure, compared to the case of a three-layer structure, the cost required for the laminate 30 and the bag 10, to reduce such steps. Incidentally, in the laminate 30 of two-layer structure composed of substrate 41 and the sealant layer 71, the ratio of thickness a layer having a certain hardness, such as substrate 41 is occupied for the entire laminate 30, 3 lower than in the case of a laminate of a layer structure (first substrate / second substrate / sealant layer). Thus, for tear resistance, as well as that the laminate strength, also in terms of the ratio of the layer having a certain hardness, towards the two-layer structure is disadvantageous as compared with the three-layer structure. In contrast, according to this embodiment, as described above, the adhesive layer 45, by increasing the molar ratio of the isocyanate groups of the aliphatic isocyanate compound to the hydroxyl groups of the polyol, a two-layer structure and it is possible to realize the excellent tear resistance even. For example, in the case of two-layer structure, the thickness ratio of the sealant layer 71 to the substrate 41 is 2.5 to 10.0.
[0137]
　Further, in the present embodiment, the sealant layer 71 of the sealant film 70 comprises a propylene-ethylene block copolymer. Therefore, it is possible to improve the impact resistance of the laminate 30 comprises the sealant film 70 and sealant film 70. Therefore, even when constituting a bag 10 with a two-layer structure laminate 30 (the laminate 30 comprising only one substrate), it prevents the bag 10 to breakage by an impact such as falling be able to.
[0138]
　Impact strength of the laminate 30 is preferably at 800kJ / m or more, more preferably 900kJ / m or more, further preferably 1000 kJ / m or more, particularly preferably 1100kJ / m or more . Method of measuring the impact strength are described in Example A1 described below.
[0139]
　Note that it is possible to make various modifications to the embodiments described above. Hereinafter, with reference to the drawings as needed, a modified example will be described. The following drawings used in the description and the following description, the parts that may be configured similarly to the embodiment described above will be referred to with the same reference numerals as those used for corresponding parts in the embodiment described above, and overlapping description will be omitted. Also, when the effects obtained in the embodiment described above it is clear that also obtained in the modification, it may be omitted from the description.
[0140]
　(Modification of the layer structure)
　In the present embodiment described above, the first film 40 of the laminate 30 constituting the bag 10, an example having a printed layer 42 in addition to the substrate 41. However, it is not limited thereto, the first film 40 may not have a printing layer 42. Therefore, as a layer structure of the multilayer body 30, it is also possible sequence as follows in order to inner surface from the outer surface side.
　　Substrate / adhesive layer / sealant layer
　　substrate / transparent gas barrier layer / adhesive layer / sealant layer
[0141]
　(Modification of the molar ratio of isocyanate groups to hydroxyl groups)
　in the embodiment described above, the polyol and aliphatic isocyanate compound constituting the adhesive layer 45, the isocyanate groups of the aliphatic isocyanate compound to the hydroxyl groups of the polyol molar ratio of an example of 3.5 or more. However, as examples support to be described later, to a molar ratio of isocyanate groups to hydroxyl groups of 3.5 or more, the prerequisite in order to impact strength of the laminate 30 than 800kJ / m Absent. For example, as shown in the examples below, by using a sealant layer 71 comprising a propylene-ethylene block copolymer, the molar ratio of isocyanate groups to hydroxy groups even when less than 3.5, the laminate it can enhance the impact strength of 30 or more 800kJ / m.
[0142]
　(Modification of the sealant layer)
　In the present embodiment described above, the sealant layer 71 of the laminate 30 is an example including a propylene-ethylene block copolymer. However, as examples support to be described later, the use of propylene-ethylene block copolymer as the material of the sealant layer 71 is not an essential condition of the laminate strength of the laminate 30 in terms of more than 5N.
[0143]
　 Second Embodiment
　The following describes a second embodiment of the present invention. In this embodiment, the metal foil 47 is an example will be described which is present between the substrate 41 and the sealant layer 71 of the laminate 30. In this embodiment, the shape and the same parts of the first embodiment and detailed the same reference numerals description is omitted. Also, when the effects obtained in the first embodiment it is apparent that also obtained in the present embodiment, it may be omitted from the description.
[0144]
　It will be described first problem which the present embodiment is to solve. The laminate for constituting the bag suppresses characteristic that a sharp member having a sharp tip would tear the bag even when in contact with the bag, so-called penetration resistance is required. Conventionally, for example, in the laminate described in JP-A-2012-223992, the polyamide resins such as nylon contained in the deposited film, penetration resistance is ensured. Meanwhile, nylon, easy to absorb moisture, and poor heat resistance. In the laminated body according to Patent Document 1, a polyester resin present on the outer surface side of the nylon, is thought to contribute to heat resistance of the laminate.
[0145]
　Incidentally, the size of the resin material is to absorb moisture such as water vapor in the atmosphere, that is, be changed by moisture absorption. The degree of moisture absorption depends resin material. For example, the dimensions of the polyamide resin, as compared with the size of the polyester resin is easy to change by moisture absorption. Therefore, when using a coextruded oriented film of a polyester resin and a polyamide resin as disclosed in JP 2012-223992, based on the difference in hygroscopicity, relatively large changes size of the polyamide resin, as a result, which may warp occurs in the coextruded oriented film. In this case, or in transporting the coextruded oriented film, when coextruded oriented film and other film and laminating step of laminating, required additional equipment and steps for or to eliminate or suppress warpage now, the manufacturing cost of the laminate is increased. This embodiment aims to provide such problems effectively solved can laminate.
[0146]
　Next, it will be described laminate 30 according to this embodiment. Figure 5 is a sectional view showing an example of the layer structure of the laminate 30 in the present embodiment. As shown in FIG. 5, the laminate 30 includes at least a first film 40, the metal foil 47 and the sealant film 70 in this order. Metal foil 47 is joined to the first film 40 through the first adhesive layer 46, also it is bonded to the sealant film 70 via a second adhesive layer 48.
[0147]
　As in the first embodiment described above, the first film 40 includes a substrate 41, sealant film 70 comprises a sealant layer 71. The first film 40 may further include a print layer 42 provided on the inner surface 30x side of the substrate 41. Therefore, the laminated body 30 according to this embodiment, in order from the outer surface to the inner surface side
　　substrate / first adhesive layer / metal foil / second adhesive layer / sealant layer, or
　　substrate / printed layer / first adhesive layer / metal foil / second adhesive layer / sealant layer,
and a, and it can be said. It should be noted that, "/" represents the boundary of the layer and the layer.
[0148]
　Hereinafter, the first film 40, the first adhesive layer 46, the metal foil 47, respectively will be described in detail for the second adhesive layer 48 and sealant film 70.
[0149]
　(First film)
　substrate 41 of the first film 40, as in the first embodiment described above, including polybutylene terephthalate as a main component. For example, first substrate 51 includes 51 mass% or more PBT. The structure of the first substrate 51 including the PBT, may employ any of the first configuration or the second configuration described with respect to the substrate 41 in the first embodiment described above.
[0150]
　(First adhesive layer)
　first adhesive layer 46 includes a first adhesive for bonding the first film 50 and the metal foil 47. Examples of the first adhesive, as in the case of the adhesive layer 45 in the first embodiment described above, and the like ether of a two-liquid reactive adhesive, an ester of a two-liquid reaction type adhesive be able to.
[0151]
　Preferably, the first adhesive agent constituting the first adhesive layer 46, using a polyol as a main agent, a cured product and an aromatic isocyanate compound as a curing agent is produced by reacting. By using an aromatic isocyanate compound as a curing agent, it is possible to further enhance the lamination strength between the first film 40 and the metal foil 47. As the polyol, it is possible to use a polyether polyol or polyester polyol, it is preferable to use a polyester polyol.
[0152]
　The molar ratio of the isocyanate groups of the first adhesive constituting the first adhesive layer 46, an aromatic isocyanate compound to the hydroxyl groups of the polyol is in the range for example of 1 to 5.
[0153]
　(Metal foil)
　metal foil 47 in order to enhance a barrier property against water vapor and oxygen, is provided between the first film 40 and sealant film 70. Metallic material constituting the metal foil 47, for example, aluminum or the like. The thickness of the metal foil 47 is, for example, 5μm or more and 15μm or less.
[0154]
　(Second adhesive layer)
　The second adhesive layer 48 includes a second adhesive for bonding the metal foil 47 and the sealant film 70. Examples of the second adhesive, mention may be made of two-component reactive adhesive of ether. The two-component reactive adhesive of the ether, as in the first adhesive, and the like polyurethane. Polyurethane is a cured product and a polyol as a main agent, and an isocyanate compound as a curing agent is produced by reacting. As the polyol, it is possible to use a polyether polyol or polyester polyol, it is preferable to use a polyester polyol.
[0155]
　Examples of the isocyanate compound, as described above, the aromatic isocyanate compound and an aliphatic isocyanate compound is present. Among aromatic isocyanate compound, in a high temperature environment such as heat sterilization, the components can not be used in food applications are eluted. Meanwhile, second adhesive layer 48, as shown in FIG. 5, located on the inner surface 30x side of the metal foil 47. Therefore, when the second adhesive layer 48 comprises an aromatic isocyanate compound, component eluted from an aromatic isocyanate compound, which may be attached to the contents of the bag 10 constructed by the laminated body 30.
[0156]
　In consideration of such problems, as a second adhesive constituting the second adhesive layer 48, and a polyol as a main agent, a cured product with aliphatic isocyanate compound as a curing agent is produced by reacting It proposes to use. Thus, it is possible to prevent the components that can not be used in food applications due to the second adhesive layer 48 adheres to the contents.
[0157]
　In the second adhesive constituting the second adhesive layer 48, the molar ratio of the isocyanate groups of the aliphatic isocyanate compound to the hydroxyl groups of polyether polyols, for example in the range of 1-5.
[0158]
　(Sealant film)
　sealant film 70 includes at least a sealant layer 71 which constitutes the inner surface 30x of the laminate 30. The material constituting the sealant layer 71, as in the first embodiment described above, low density polyethylene, such as linear low density polyethylene polyethylene, one or more selected from polypropylene resin can be used.
[0159]
　 Method for producing a laminate
　Next, an example of a method for producing a laminate 30.
[0160]
　First, a first film 40 and the metal foil 47 described above. Subsequently, by a dry lamination method, a first film 40 and the metal foil 47 is laminated via a first adhesive layer 46. Then, by a dry lamination method, a laminate comprising a first film 40 and the metal foil 47, and a sealant film 70 is laminated via the second adhesive layer 48. This makes it possible to obtain a laminate 30 comprising a first film 40, the metal foil 47 and the sealant film 70.
[0161]
　Or, first, a metal foil 47 and the sealant film 70 are layered with a second adhesive layer 48, then, the first film 40, the first adhesive layer and a laminate comprising a metal foil 47 and sealant film 70 by stacking through 46, it may be produced a laminate 30.
[0162]
　According to this embodiment, the substrate 41 of the first film 40 comprises a PBT as a main component. In the base material 41 according to the first configuration, for the composition of the layers 41a are identical, it is possible to suppress the warpage occurs in the first film 40 comprising a substrate 41. The first film comprising the base material 41 according to the second configuration, since the composition is the same, for example, for the substrate 41 is a film of composed monolayer only PBT and additives, the base material 41 it is possible to suppress the warpage occurs in 40. Thus, it is possible to efficiently produce a laminated body 30.
[0163]
　The following describes the effect of the laminate 30 according to this embodiment is achieved.
[0164]
　In this embodiment, the laminate 30 constituting the surface film 14 and the back surface film 15 of the bag 10, by comprising a substrate 41 mainly composed of PBT, can be obtained the following effects.
　First, PBT has excellent printability. Therefore, as in the case of polyethylene terephthalate, it can be provided a printed layer 42 on the substrate 41 including the PBT.
　Also, PBT has excellent heat resistance. Therefore, it is possible to prevent the strength of the substrate 41 or substrate 41 is deformed or reduced when performing a boiling treatment or retort treatment to the bag 10.
　Also, PBT has a high strength. Therefore, it is possible to laminate constituting the bag 10 is similar to the case of including nylon, increasing the piercing strength of the laminate 30 and the bag 10. Piercing strength of the laminate 30 is preferably at least 13N, more preferably at least 15N, more preferably not less than 17N.
　Also, PBT has a characteristic that it is difficult to absorb water as compared to nylon. Therefore, even when placing the substrate 41 including the PBT to the outer surface 30y of the stack 30, the substrate 41 is a laminate strength of the laminate 30 absorbs moisture to prevent the lowered can.
[0165]
　Further, according to this embodiment, the laminate 30 constituting the surface film 14 and the back surface film 15 of the bag 10 includes a metal foil 47. Therefore, it is possible to prevent the external moisture or oxygen bag 10 is transmitted to the interior of the bag 10, it is possible to prevent the contents is degraded.
[0166]
　Further, according to this embodiment, the sealant layer 71 of the laminate 30 constituting the surface film 14 and the back surface film 15 of the bag 10 comprises a propylene-ethylene block copolymer. Therefore, it is possible to improve the impact resistance and penetration resistance of the bag 10.
[0167]
　 The third embodiment
　will be described a third embodiment of the present invention. In the first embodiment described above, the plastic film constituting the substrate of the laminate is an example there is only one. In this embodiment, the plastic film constituting the substrate of the laminate will be described an example in which there are two. In this embodiment, the shape and the same parts of the first embodiment and detailed the same reference numerals description is omitted. Also, when the effects obtained in the first embodiment it is apparent that also obtained in the present embodiment, it may be omitted from the description.
[0168]
　It will be described first problem which the present embodiment is to solve. Conventionally, in order to increase the strength of the laminate, such as a penetration resistance, it is possible to construct a laminate with two plastic films are known. For example, conventional laminate comprises a PET film, nylon film and the sealant film. Nylon, while having a high strength, because it has a property of easily absorbing moisture, nylon film is disposed between the PET film and the sealant film. However, in this case, since the nylon tends to be colored by the contents of the bag, there is the appearance of the bag is impaired. This embodiment aims to provide such problems effectively solved can laminate.
[0169]
　Next, it will be described laminate 30 according to this embodiment. Figure 6 is a sectional view showing an example of the layer structure of the laminate 30 in the third embodiment. As shown in FIG. 6, the laminate 30 includes at least a first film 50, the second film 60 and sealant film 70 in this order. The first film 50 is located on the outer surface 30y side, the sealant film 70 is positioned on the inner surface 30x side opposite the outer surface 30y.
[0170]
　The first film 50 comprises at least a first substrate 51. The second film 60 includes at least a second substrate 61. Sealant film 70 includes at least a sealant layer 71. Also, the first film 50 and second film 60 are joined by a first adhesive layer 55 and the second film 60 and sealant film 70 are joined by a second adhesive layer 65. Therefore, the laminated body 30 according to this embodiment, in order from the outer surface to the inner surface
　　the first substrate / first adhesive layer / second base / second adhesive layer / sealant layer
can be said and a, and . It should be noted that, "/" represents the boundary of the layer and the layer. Although not illustrated, the printing layer between the first substrate 51 and second substrate 61 may be provided on the first substrate 51 or second substrate 61.
[0171]
　Hereinafter, the first film 50, the first adhesive layer 55, the second film 60, respectively will be described in detail for the second adhesive layer 65 and sealant film 70.
[0172]
　(First film)
　first substrate 51 of the first film 50 includes a first substrate 51 which constitutes the outer surface 30y of the stack 30. First substrate 51, similarly to the substrate 41 in the first embodiment described above, including polybutylene terephthalate as a main component. For example, first substrate 51 includes 51 mass% or more PBT. The structure of the first substrate 51 including the PBT, may employ any of the first configuration or the second configuration described with respect to the substrate 41 in the first embodiment described above.
[0173]
　(First adhesive layer)
　first adhesive layer 55 includes a first adhesive for bonding the first film 50 and second film 60. Examples of the first adhesive, as in the case of the adhesive layer 45 in the first embodiment described above, and the like ether of a two-liquid reactive adhesive, an ester of a two-liquid reaction type adhesive be able to.
[0174]
　(Second film)
　second film 60 comprises at least a second substrate 61. The second substrate 61 includes a PET as a main component. For example, the second substrate 61 includes 51 mass% or more PET. By the second substrate 61 including PET, second substrate 61 may have a heat resistance. For example, the second substrate 61 as compared with the case including nylon, the melting point of the second substrate 61 is increased, also the hygroscopicity of the second substrate 61 becomes lower. Thus, when heating the bag 10, it is possible to prevent the hole in the second substrate 61 due like superheated water will open. Further, the heat resistance of PET is higher than the heat resistance of the PBT. Therefore, according to this embodiment, it is possible to second substrate 61 is also compared with the case made of PBT, increase the heat resistance of the laminate 30. Thus, for example, it is possible to prevent the stack 30 is reduced the performance of the laminate 30 damaged when the temperature of the contents of the bag 10 is heated in a microwave oven is increased.
[0175]
　The thickness of the second substrate 61 is preferably 9μm or more, more preferably 12μm or more. The thickness of the second substrate 61 is preferably not 25μm or less, more preferably 20μm or less. By setting the thickness of the second substrate 61 than 9 .mu.m, the second substrate 61 will have sufficient strength. Further, by setting the thickness of the second substrate 61 to 25μm or less is as shown second substrate 61 excellent moldability. Therefore, it is possible to efficiently implement the step of producing the bag 10 by processing the laminated body 30.
[0176]
　(Second adhesive layer)
　The second adhesive layer 65 includes a second adhesive for bonding the second film 60 and sealant film 70. Examples of the second adhesive, mention may be made of two-component reactive adhesive of ether. The two-component reactive adhesive of the ether, as in the first adhesive, and the like polyurethane. Polyurethane is a cured product and a polyol as a main agent, and an isocyanate compound as a curing agent is produced by reacting. As the polyol, it is possible to use a polyether polyol or polyester polyol, it is preferable to use a polyester polyol.
[0177]
　Examples of the isocyanate compound, as described above, the aromatic isocyanate compound and an aliphatic isocyanate compound is present. Among aromatic isocyanate compound, in a high temperature environment such as heat sterilization, the components can not be used in food applications are eluted. Meanwhile, second adhesive layer 65, as shown in FIG. 6, in contact with the sealant film 70. Therefore, when the second adhesive layer 65 comprises an aromatic isocyanate compound, component eluted from an aromatic isocyanate compound, which may be attached to the contents of the bag 10 constructed by the laminated body 30.
[0178]
　In consideration of such problems, as a second adhesive constituting the second adhesive layer 65, and a polyol as a main agent, a cured product with aliphatic isocyanate compound as a curing agent is produced by reacting It proposes to use. Thus, it is possible to prevent the components that can not be used in food applications due to the second adhesive layer 65 adheres to the contents.
[0179]
　Incidentally, the second film 60 is a case where no barrier properties such as gas barrier property, and if the first adhesive layer 55 described above containing the aromatic isocyanate compound was eluted from an aromatic isocyanate compound also contemplated that the components may adhere to the contents. In this case, as in the case of the second adhesive layer 65, a first adhesive constituting the first adhesive layer 55, that a polyol as the main agent, and the aliphatic isocyanate compound as a curing agent to react it is preferable to use a cured product produced by.
[0180]
　(Sealant film)
　sealant film 70 includes at least a sealant layer 71 which constitutes the inner surface 30x of the laminate 30. The material constituting the sealant layer 71, as in the first embodiment described above, low density polyethylene, such as linear low density polyethylene polyethylene, one or more selected from polypropylene resin can be used.
[0181]
　 Method for producing a laminate
　Next, an example of a method for producing a laminate 30.
[0182]
　First, a first film 50 and second film 60, above. Subsequently, by a dry lamination method, a first film 50 and second film 60 is laminated via a first adhesive layer 55. Then, by a dry lamination method, a laminate comprising a first film 50 and second film 60, and a sealant film 70 is laminated via the second adhesive layer 65. This makes it possible to obtain a laminate 30 comprising a first film 50, second film 60 and sealant film 70.
[0183]
　Or, first and second films 60 and sealant film 70 are layered with a second adhesive layer 65, then, the first film 50, and a laminate comprising a second film 60 and sealant film 70 first adhesive by laminated through the adhesive layer 55 may be produced a laminate 30.
[0184]
　The following describes the effect of the laminate 30 according to this embodiment is achieved.
[0185]
　In this embodiment, the laminate 30 constituting the surface film 14 and the back surface film 15 of the bag 10, by including a first substrate 51 mainly composed of PBT, can be obtained the following effects.
　First, PBT has excellent heat resistance. Therefore, it is possible to suppress the intensity of the or the first substrate 51 is deformed first substrate 51 is lowered when carrying out the bag 10 such as retort treatment or boil treatment.
　Also, PBT has a high strength. Therefore, it is possible to laminate constituting the bag 10 is similar to the case of including nylon, increasing the piercing strength of the laminate 30 and the bag 10. Piercing strength of the laminate 30 is preferably at least 13N, more preferably at least 15N, more preferably not less than 17N.
　Also, PBT has a characteristic that it is difficult to absorb water as compared to nylon. Therefore, even when placing the first substrate 51 including the PBT to the outer surface 30y of the stack 30, the first substrate 51 is a laminate strength of the laminate 30 absorbs moisture decreases it is possible to suppress.
[0186]
　Further, in the present embodiment, the laminated body 30 by including a second substrate 61 composed mainly of PET, second substrate 61 as compared with the case of nylon, the second substrate 61 it is possible to suppress that would be colored by the contents. Thus, it is possible to suppress the appearance of the bag 10 may be impaired. Further, it is possible to second substrate 61 as compared with the case of nylon, foamed due to moisture second substrate 61 has absorbed occurs, to suppress the appearance of the bag 10 is deteriorated. In this respect, it is possible to suppress the appearance of the bag 10 may be impaired.
[0187]
　If, when the second substrate 61 comprises a nylon, a nylon, a raw material for nylon, such as caprolactam leaching standards have been established by the Ministry of Health and Welfare Notification No. 370 "instruments and containers and packaging" is eluted, there is a risk of contaminating the contents. In contrast, according to this embodiment, the second substrate 61 by forming with PET, it is possible to reduce the possibility of such caprolactam is eluted.
[0188]
　Further, the laminate 30 constituting the surface film 14 and the back surface film 15 of the bag 10, by including a second substrate 61 composed mainly of PET, as compared with the case where the second substrate 61 is made of PBT, it is possible to improve the heat resistance of the laminate 30. Thus, for example, is possible to prevent the surface film 14 and the back surface film 15 is reduced the performance of the surface film 14 and the back surface film 15 damaged when the temperature of the contents by heating the bag 10 becomes higher it can.
[0189]
　Note that it is possible to make various modifications to the embodiments described above. Hereinafter, with reference to the drawings as needed, a modified example will be described. The following drawings used in the description and the following description, the parts that may be configured similarly to the embodiment described above will be referred to with the same reference numerals as those used for corresponding parts in the embodiment described above, and overlapping description will be omitted. Also, when the effects obtained in the embodiment described above it is clear that also obtained in the modification, it may be omitted from the description.
[0190]
　(Modification of the layer structure)
　In the present embodiment described above, the first substrate 51 comprises 51 wt% or more of PBT, the laminate 30 by the second substrate 61 containing 51 wt% or more PET an example of increasing the penetration resistance and heat resistance. However, it is not limited thereto, the first substrate 51 comprises 51 wt% or more of PET, penetration resistance and heat the laminate 30 by the second substrate 61 containing 51 wt% or more PBT it may be enhanced sex. The PBT of the second substrate 61, it is possible to use a PBT of the PBT or second configuration according to the first configuration described in the first embodiment described above.
[0191]
　The second substrate 61 comprises 51 wt% or more of PBT, the first substrate 51 comprises 51 wt% or more of PET, the dimensional stability of the laminate 30, which contributes to the improvement of printability.
[0192]
　Further, both the first substrate 51 and second substrate 61 may contain 51 mass% or more PBT. Even PBT in this case, it is possible to use a PBT of the PBT or second configuration according to the first configuration described above.
[0193]
　Table 1 shows the example of combination of materials for the first substrate 51 and second substrate 61. In Table 1, reference to "PBT" is meant to include 51 mass% or more of PBT in the resin constituting the film of the first substrate 51 or second substrate 61. In Table 1, reference to "PET" is meant to include 51 mass% or more of PET in the resin constituting the film of the first substrate 51 or second substrate 61.
[table 1]

[0194]
　Incidentally, if the first substrate 51 comprises PET, if possible choose containing PBT is, from the viewpoint of heat sealability, it is preferable that the first substrate 51 comprises PET. PET has a relatively higher melting point than PBT. Therefore, first substrate 51 may include a PET, heat resistance of the outer surface 30y of the stack 30 is further improved. Therefore, when forming a seal portion of the bag 10 by heat sealing, it is possible to perform the heat-sealing higher at elevated temperature.
[0195]
　Further, at a position between the first substrate 51 and second substrate 61, the first substrate 51 and / or the second substrate 61, transparent evaporated layer 36 is provided made of an inorganic material having transparency it may be. Transparent evaporated layer 36, as shown in FIG. 7, may be provided on the surface of the inner surface 30x side of the first substrate 51, as shown in FIG. 8, the surface of the outer surface 30y side of the second substrate 61 it may be provided to. Further, on the transparent vapor deposition layer 36, transparent gas barrier coating film 37 may be provided with transparency. Specific structure of the transparent evaporated layer 36 and transparent gas barrier coating film 37 are the same as those of the first embodiment described above.
[0196]
　A transparent vapor deposition layer 36 at the interface between the first substrate 51 or second substrate 61 may be formed a covalent bond of the metal and carbon atoms. For example, a transparent case deposited layer 36 comprises aluminum oxide, the interface between the first substrate 51 or second substrate 61 and the transparent evaporated layer 36, covalent attachment of aluminum and carbon atoms may be formed . The covalent binding can be detected by the XPS measurement.
[0197]
　Further, in the transparent evaporated layer 36 is observed when the abundance ratio of the covalent bond of the aluminum atoms and carbon atoms were measured interface between the transparent evaporated layer 36 by XPS measurement to the first substrate 51 or second substrate 61 it is preferably in the range and below 30% 0.3% or more of the total bonds including carbon atoms. Thus, enhanced adhesion between the transparent evaporated layer 36 and the first substrate 51 or second substrate 61, excellent transparency, those good performance balanced is obtained as a gas barrier property of the deposited film.
[0198]
　When the presence ratio of the covalent bond of the aluminum atoms and carbon atoms is less than 0.3%, the improvement of adhesion of the transparent evaporated layer 36 is insufficient, it is difficult to maintain the barrier property stably.
[0199]
　Further, the transparent deposition layer 36 mainly containing aluminum oxide, AL (aluminum) / O (oxygen) ratio, from the interface between the first substrate 51 or second substrate 61 and the transparent evaporated layer 36, a first within the scope of the base member 51 or the second substrate 61 to 3nm toward the surface of the opposite side of the transparent evaporated layer 36 is preferably 1.0 or less.
　From the interface between the transparent evaporated layer 36 and the first substrate 51 or second substrate 61, the first substrate 51 or second substrate 61 within the range toward the surface on the opposite side of the transparent evaporated layer 36, AL the / O ratio exceeds 1.0, adhesion becomes insufficient between the first substrate 51 or second substrate 61 and the transparent evaporated layer 36, and increasing the proportion of aluminum, transparent evaporated layer 36 transparency is reduced.
[0200]
　When forming a transparent vapor deposition layer 36 on the first substrate 51 or second substrate 61, in advance to corona discharge treatment on the surface of the first substrate 51 or second substrate 61, the frame processing, the pre-treatment such as plasma treatment it may have been subjected. In particular, a transparent evaporated layer 36 at the interface between the first substrate 51 or second substrate 61, in the case of forming a covalent bond of the metal and carbon atoms is first base to be formed a transparent vapor deposition layer 36 it is preferable to perform pre-processing on the timber 51 or the surface of the second substrate 61. If the pretreatment is a plasma treatment, the pre-processing device, in the following reduced pressure environment 0.1Pa above 100 Pa, the surface supplies a plasma relative to the first substrate 51 or second substrate 61. Plasma, using inert gas alone or oxygen such as argon, nitrogen, carbon dioxide gas and a gas mixture thereof with one or more gases as a plasma source gas, the potential difference due to the high frequency voltage, etc., the plasma source gas in the excited state by, it can be generated.
[0201]
　The pretreatment can be confined plasma in the vicinity of the surface of the first substrate 51 or second substrate 61. Thus, the shape and the surface of the first substrate 51 or second substrate 61, chemical bonding state or a functional group is varied, and the chemical properties of the surface of the first substrate 51 or second substrate 61 it is possible to change. Thus, it is possible to improve the adhesion between the first substrate 51 or second substrate 61 and the transparent evaporated layer 36.
[0202]
　 The fourth embodiment
　The following describes the fourth embodiment of the present invention. In the present embodiment, as described in the third embodiment, the laminated body 30 comprising two plastic film, printed layer having a light-shielding property (hereinafter, referred to as a light-shielding printed layer) further for example having describing . In this embodiment, detailed description are denoted by the same reference numerals in the form of the same parts of the third embodiment will be omitted. Also, when the effects obtained in the third embodiment it is apparent that also obtained in the present embodiment, it may be omitted from the description.
[0203]
　It will be described first problem which the present embodiment is to solve. The laminate constituting the bag, in order to save the contents while preventing deterioration of the contents, there is that high light-shielding property is required. To solve these problems, for example, Patent Document 1 described above proposes the provision of the light blocking printed layer having a light shielding property to the substrate comprising a resin such as polyethylene terephthalate.
[0204]
　In Patent Document 1, the light-shielding printed layer is obtained by printing thick enough ink containing a pigment and a binder to a substrate. On the other hand, a pigment, a binder, from the ink component such as the residual solvent, human feel uncomfortable odor (hereinafter, also referred to as off-flavor) is generated, which may odor adheres to the contents transmitted through the sealant layer . Such an odor, becomes particularly problematic when the contents of the food. This embodiment aims to provide such problems effectively solved can laminate.
[0205]
　Next, it will be described laminate 30 according to this embodiment. Figure 9 is a sectional view showing an example of the layer structure of the laminate 30 in the fourth embodiment. Further, FIG. 10 is a sectional view showing another example of the layer structure of the multilayer body 30 in the fourth embodiment. Laminate 30 is, as in the third embodiment, at least a first film 50, the second film 60 and sealant film 70 in this order.
[0206]
　The first film 50, as shown in FIG. 9, includes a first substrate 51, and the light-shielding printed layer 52 provided on the surface of the second film 60 side of the surface of the first substrate 51, at least. The first film 50, as shown in FIG. 10 may further include a picture-printed layer 53 positioned between the first substrate 51 and the light-shielding printed layer 52. The second film 60 includes at least a second substrate 61. Sealant film 70 includes at least a sealant layer 71. Also, the first film 50 and second film 60 are joined by a first adhesive layer 55 and the second film 60 and sealant film 70 are joined by a second adhesive layer 65. Therefore, the laminated body 30 according to this embodiment, the outer surface in order to inner surface side from the side
　　first substrate / light-shielding printed layer / first adhesive layer / second base / second adhesive layer / sealant layer,
　or,
　　first base / picture-printed layer / light-shielding printed layer / first adhesive layer / second base / second adhesive layer / sealant layer
comprises a, and say. It should be noted that, "/" represents the boundary of the layer and the layer.
[0207]
　Next, a description will be given shielding printed layer 52 and the picture-printed layer 53. The first substrate 51, the first adhesive layer 55, second substrate 61, the structure of the second adhesive layer 65 and sealant layer 71 is the same as in the third embodiment, description omitted.
[0208]
　[Shielding printed layer]
　shielding printed layer 52 is a layer stack 30 is configured to have a light shielding property. Shielding printed layer 52 has an ink containing a pigment and a binder. The thickness of the light-shielding printed layer 52 is, for example, 2μm or more, preferably 3μm or more, more preferably 4μm or more. The thickness of the light-shielding printed layer 52 is preferably 10μm or less, more preferably 6μm or less. Total light transmittance of the laminate 30 including the light-shielding printed layer 52 is less than or equal to at least 20%, preferably 15% or less, more preferably 10% or less. If the total light transmittance is 20% or less, it is possible to cut off visible light and ultraviolet light consisting of external light in the wavelength range of 800nm from 300nm incident on the bag 10 under normal use conditions effectively, the bag can contents accommodated in 10 to effectively suppress the deterioration by the external light.
[0209]
　The total light transmittance, relative to the total amount of incident light of the light incident on the test specimen made of a laminate 30 comprising a light-blocking printed layer 52, refers to the percentage of total transmitted light quantity passing through the laminate 30. Since the test piece usually having a light diffusing property, the total light transmittance is the sum of diffusion transmittance and parallel transmittance. The total light transmittance is measured according to the optical characteristic test method JIS-K7361-1 to use an integrating sphere defined by JIS.
[0210]
　Shielding printed layer 52 has an achromatic color layer comprising, for example of the achromatic inks. The achromatic color among the colors of the three-dimensional of lightness and saturation, is that the color is described only by the lightness. Examples of achromatic, mention may be made of white, gray, black. The thickness of the achromatic layer is, for example, 1μm or more and 3μm or less. Achromatic layer is preferably a single color layer of spread over the entire surface of the first substrate 51 in the same plane. In the following description, the printed layer area ratio of the halftone dots having an area of ​​100%, also referred to as a solid layer. For example, the area ratio of the white halftone dots to a print layer having a region that is 100%, referred to as white solid layer. Similarly, the printing layer area ratio of the black halftone dots having an area of ​​100%, referred to as black solid layer. White solid layer is formed by solid printing of a white ink containing a white pigment to the first substrate 51. Further, black solid layer is formed by solid printing a black ink containing a black pigment in the first substrate 51. Shielding printed layer 52 may include a plurality of achromatic layers stacked. Hereinafter, a description will be given of a specific layer constitution of the light-shielding printed layer 52.
[0211]
　Shielding printed layer 52, for example, it may consist of solid black layer. Incidentally, if the picture-printed layer 53 on the outer surface 30y side of the light-shielding printed layer 52 is laminated, when viewing the bag 10 from the outer surface 30y side of the laminate, the light-shielding printed layer 52 is observed as the background of the picture-printed layer 53 . Therefore, if the light-shielding printed layer 52 is made of only the black solid layer, it is difficult to visually recognize the picture-printed layer 53. Thus, if the laminate 30 comprises a picture-printed layer 53, light-shielding printed layer 52 in addition to the solid black layer, as described below, is located on the outer surface 30y side of the solid black layer, other than black free preferably further comprising a color layer.
[0212]
　Shielding printed layer 52 may comprise a solid white layer and achromatic layer laminated in this order to the inner surface 30x side from the first substrate 51 side. Achromatic layer may be a white solid layer, or may be a solid black layer. Further, achromatic layer may be a gray solid layer formed by solid printing gray ink to the first substrate 51. Gray ink, for example, obtained by mixing a black ink containing a white ink and a black pigment comprises a white pigment. Gray ink, the mixing ratio of the white ink is preferably higher than the mixing ratio of the black ink. By achromatic layer laminated on the inner surface 30x side of the solid white layer and ash solid layer, as compared with the case of laminating a solid black layer on the inner surface 30x side of the white solid layer, the color of achromatic layer pattern it is possible to suppress the influence on the hue of the printed layer 53.
　Incidentally, there is no possibility that the number of achromatic layer is limited to two layers. For example, the light-shielding printed layer 52 may include three or four layers or more achromatic layers stacked. For example, the light-shielding printed layer 52, a white solid layer laminated in this order to the inner surface 30x side from the first substrate 51 side, may include a solid white layer and ash solid layer.
[0213]
　The light-shielding printed layer 52 may consist of solid white layer. Blackout printing layer 52 is a case which does not include a black solid layer and ash solid layer described above, by increasing the thickness of the solid white layer can have a sufficient light-shielding property to the light-shielding printed layer 52.
[0214]
　The light-shielding printed layer 52 may have a chromatic color layer containing a chromatic color ink. The chromatic hue means color or colors contain all three-dimensional color of lightness and saturation. In other words, the chromatic color, which is a color other than the achromatic color. The thickness of the chromatic color layer is, for example, 0.3μm or more and 2μm or less. Chromatic color layer is preferably a single color layer of spread over the entire surface of the first substrate 51 in the same plane. Shielding printed layer 52 may include a plurality of chromatic color layers stacked.
[0215]
　Shielding printed layer 52 may include both an achromatic layer and chromatic color layer. For example, the light-shielding printed layer 52 has one or more non-color layer, one or a plurality of chromatic color layer located on the inner surface 30x side of the achromatic layer. The light-shielding printed layer 52 may have one or more chromatic layer, one or a plurality of achromatic layer located on the inner surface 30x side of the chromatic color layer. For example, the light-shielding printed layer 52 may comprise a solid white layer and chromatic layer laminated in this order to the inner surface 30x side from the first substrate 51 side.
[0216]
　[Picture-printed layer]
　picture-printed layer 53 is a layer provided by printing to grant or aesthetics or indicate product information on the bag 10. Picture-printed layer 53, to represent letters, numbers, symbols, graphics, pictures and the like. In picture-printed layer 53, a layer of a plurality of colors are spread in the same plane. The material constituting the picture-printed layer 53, it is possible to use ink and ink for flexographic printing for gravure printing. Specific examples of the inks for gravure printing, can be mentioned Finato made of DIC Graphics Corporation.
[0217]
　The following describes the effect of the laminate 30 according to this embodiment is achieved.
[0218]
　In this embodiment, the laminate 30 constituting the surface film 14 and the back surface film 15 of the bag 10, by including a first substrate 51 mainly composed of PBT, can be obtained the following effects.
　First, PBT has excellent printability. Therefore, it is possible as in the case of polyethylene terephthalate, providing the light-shielding printed layer 52 and picture-printed layer 53 on the first substrate 51 including the PBT.
　Also, PBT has excellent heat resistance. Therefore, it is possible to suppress the intensity of the or the first substrate 51 is deformed first substrate 51 is lowered when carrying out the bag 10 such as retort treatment or boil treatment.
　Also, PBT has a high strength. Therefore, it is possible to laminate constituting the bag 10 is similar to the case of including nylon, increasing the piercing strength of the laminate 30 and the bag 10. Piercing strength of the laminate 30 is preferably at least 13N, more preferably at least 15N, more preferably not less than 17N.
　Also, PBT has a characteristic that it is difficult to absorb water as compared to nylon. Therefore, even when placing the first substrate 51 including the PBT to the outer surface 30y of the stack 30, the first substrate 51 is a laminate strength of the laminate 30 absorbs moisture decreases it is possible to suppress.
[0219]
　Further, in this embodiment, laminate 30 comprises a first substrate 51 of the light-shielding printed layer 52 located between the second substrate 61. Therefore, it is possible to prevent the external light from being irradiated on the contents are transmitted through the laminate 30, thereby, it is possible to prevent the contents are degraded by external light.
[0220]
　Further, in the present embodiment, the laminated body 30 by including a second substrate 61 composed mainly of PET or PBT, as compared with the case where the second substrate 61 is made of nylon, the light-shielding printed layer 52 in it is possible to suppress the generated odor adheres to the contents transmitted through the second film 60 and sealant film 70. Further, it is possible to second substrate 61 as compared with a case made of PBT, increase the heat resistance of the laminate 30. Thus, for example, it is possible to prevent the surface film 14 and the back surface film 15 is reduced the performance of the surface film 14 and the back surface film 15 damaged upon heating the bag 10.
[0221]
　Note that it is possible to make various modifications to the embodiments described above. Hereinafter, with reference to the drawings as needed, a modified example will be described. The following drawings used in the description and the following description, the parts that may be configured similarly to the embodiment described above will be referred to with the same reference numerals as those used for corresponding parts in the embodiment described above, and overlapping description will be omitted. Also, when the effects obtained in the embodiment described above it is clear that also obtained in the modification, it may be omitted from the description.
[0222]
　According to the present embodiment, the laminated body 30 comprising a light-shielding printed layer 52, as in the third embodiment, and a transparent evaporated layer 36, transparent gas barrier coating film located on the transparent vapor deposition layer 36 37 it may further comprise a.
　Transparent evaporated layer 36 may be provided on a surface of the inner surface 30x side of the first substrate 51. In this case, the laminated body 30, the outer surface in order to inner surface side from the side
　　first substrate / transparent deposition layer / transparent gas barrier coating film / light-shielding printed layer / first adhesive layer / second base / second adhesive layer / sealant layer
has a, and it can be said.
　The transparent evaporated layer 36 may be provided on a surface of the outer surface 30y side of the second substrate 61. In this case, the laminate 30 includes, in order from the outer surface side to the inner side
　　first substrate / first adhesive layer / light-shielding printed layer / transparent gas barrier coating film / transparent deposition layer / second base / second adhesive layer / sealant layer
has a, and it can be said.
[0223]
　(Modification of the bag)
　in each of the embodiments described above, but the bag 10 is an example of a bag of the gusset type, will not be specific configuration of the bag 10 is particularly limited. For example, the bag 10 of which is, or may be a so-called pillow bag made by a laminate of one sheet to form a back lined sealing unit so that the tubular. Further, the bag 10 may be a four-side sealed bag and a three-way seal bag.
Example
[0224]
　Next, it will be more specifically described by the present invention embodiment, the present invention unless departing from the gist of the present invention is not limited to the following examples.
[0225]
　Examples A1 ~ A5 and Comparative Examples A1 ~ A3 described below, has been described in the first embodiment, an example relates to a case plastic film constituting the substrate of the laminate is only one. Further, Examples B1 ~ B3 and Comparative Examples B1 ~ B3, described in the second embodiment, the laminate is an example of the case of providing a metal foil positioned between the substrate and the sealant layer. In Examples C1 ~ C6 and Comparative Examples C1, C2 is described in the third embodiment, an example relates to a case plastic film constituting the substrate of the laminate are present two. In Examples D1 ~ D4 and Comparative Examples D1, D2 is described in the fourth embodiment, the plastic film is present two constituting the substrate of the laminate, the laminate further comprises a light-shielding printed layer it is an example relates to a case. First, a description will be given of an embodiment A1 ~ A4 and Comparative Examples A1, A2.
[0226]
　(Example A1)
　Preparation of laminate]
　described in the first construction described above, comprises a plurality of layers 41a, made with casting was prepared a film-like base material 41. The content of PBT in each layer 41a is 80%, the number of layers of the layer 41a is 1024, the thickness of the substrate 41 was 15 [mu] m. Subsequently, to form a printed layer 42 by gravure printing on the film-like substrate 41. The ink for forming the printed layer 42, using the Dainichi Seika made of white ink ceramic FB. Thus, to produce a first film 40 having a substrate 41 and a printed layer 42. The thickness of the printed layer 42 was 1 [mu] m.
[0227]
　Next, to produce a first composition comprising a main agent and a solvent, the mixture to an adhesive composition and a second composition comprising a curing agent and a solvent. As the first composition comprising a main agent and a solvent, using RU-40 manufactured by Rock Paint Corporation. RU-40 comprises a polyester polyol. The curing agent and a second composition comprising a solvent, using H-4 manufactured by locking Paint Corporation. H-4 comprises an aliphatic isocyanate compound. The weight ratio of the second composition to the first composition was 0.15. Further, in the adhesive composition, the molar ratio of the isocyanate groups of the aliphatic isocyanate compound to the hydroxyl groups of the polyol was 4.5.
[0228]
　Then, applying the adhesive composition onto the print layer 42 of the first film 40. Subsequently, the adhesive composition coated on the first film 40 is dried to evaporate the solvent. Then, by laminating a first film 40 and sealant film 70 via the adhesive composition after drying. Subsequently, the laminate was heated for 96 hours under 40 ° C. environment. Thus, by curing the adhesive composition to give an adhesive layer 45 comprising a cured product of a polyol and an aliphatic isocyanate compound. The thickness of the adhesive layer 45 was 3 [mu] m.
[0229]
　It was then prepared sealant film 70 including the sealant layer 71. The sealant layer 71, using an unstretched polypropylene film ZK93FM of Toray Film Corporation. The thickness of the sealant layer 71 was 70 [mu] m.
[0230]
　[Evaluation of laminate strength]
　was then measured lamination strength between the first film 40 and sealant film 70 of the laminate 30. As a measuring instrument, using a Tensilon universal testing machine RTC-1310 manufactured by A & D. Specifically, first, cut the laminate 30, as shown in FIG. 11, was prepared first film 40 and the rectangular test pieces 80 and sealant film 70 is 15mm peeling in long-side direction. The width of the test piece 80 (the length of the short side) was set to 15 mm. Thereafter, as shown in FIG. 12, respectively already moiety that is peeled out of the first film 40 and sealant film 70, and gripped by the jaws 81 and jaws 82 of the instrument. Further, each of the jaws 81 and 82, opposite to each other in the first film 40 and sealant film 70 and is still a direction orthogonal to the surface direction of a portion which is stacked, pulled at 50 mm / min, stable It was measured the average value of the tensile stress in the area (see Figure 13). At the start of tensioning, the spacing S between jaws 81 and 82 and 30 mm, on leaving the tension, spacing S between jaws 81 and 82 was 60 mm. Figure 13 is a graph showing changes in tensile stress to the spacing S between jaws 81 and 82. As shown in FIG. 13, the change of the tensile stress to spacing S, via the first region and enters the second region smaller rate of change than the first region (stable area).
[0231]
　The five test pieces 80 to measure the average value of the tensile in the stable region stresses, and the average was taken as the laminate strength of the laminate 30. During measurement of the environment, temperature 23 ° C., and a relative humidity of 50%. Result, the laminate strength in 15mm width was 6.7 N.
[0232]
　[Tearability Evaluation]
　an elongate laminate 30, as shown in FIG. 14, cut so that the width W1 is 15 mm, made the length W2 is a 100 mm, to prepare a test piece 90. Width W1 of the test piece 90 is parallel to the direction of the height S1 of the bag 10 shown in FIG. The length W2 of the test piece 90 is parallel to the flow direction at the time of forming the substrate 41, also parallel to the direction of the width S2 of the bag 10 shown in FIG. Subsequently, as shown in FIG. 14, to form a notch 28 at the center in the direction of the width W1 of the test piece 90. Then, starting from the notch 28, tore manually specimen 90 in the direction of the length W2. Results without sealant film 70 of the laminate 30 extends in the middle, I was able to tear the specimen 90 in the direction of the length W2.
[0233]
　[Impact resistance evaluation]
　Next, overlapping the two laminates 30 and heated for 1 second at 190 ° C., and heat sealed to the inner surface 30x between the laminate 30. Next, a laminate 30 of two sheets which are heat sealed cut in 15mm width, to prepare a test piece 100. Figure 15 is a plan view showing a test piece 100, FIG. 16 is a cross-sectional view of a test strip 90 of Figure 15. Specimens 90 is the length W4 is 50mm in width W3 is 15 mm, the sealing portion 101 to extend from one end to the length W5 of 10mm is formed, to extend from the other end to a length of 40mm in which the sealing portion is not formed. Subsequently, as shown in FIG. 17, opposite to each other in a direction perpendicular to portions which are not sealed portion and the other of the laminated body 30 which is not sealed in one of the stacked body 30 with respect to the surface direction of the sealing portion 101 so that, i.e. after the so that the T-shape, the ends of each jig end and the portion other unsealed the laminate 30 of the portions which are not sealed to the one of the stack 30 102 , it was fixed at 103. The distance T between the jig 102 and 103 in a direction orthogonal to the plane direction of the seal portion 101 was 40 mm. Subsequently, impact when for one jig 102, banging the surface of one of the first film 40 side of the laminated body 30 with a hammer 104, in which the one of the laminate 30 and the other of the laminate 30 are separated the strength was measured. As a measuring instrument, it was evaluated using the Toyo Seiki Seisakusho of digital impact tester Corporation. As a hammer for applying an impact to the test piece 100 used was a 2J. Result, the impact strength was 1056kJ / m.
[0234]
　Subsequently, a piercing strength of the laminate 30 was measured according to JIS Z1707 7.4. As a measuring instrument, using a Tensilon universal testing machine RTC-1310 manufactured by A & D. Specifically, as shown in FIG. 18, on specimens of the laminate 30 in a state of being fixed, from the outer surface 30y side, diameter 1.0 mm, semicircular needle tip shape radius 0.5 mm 110 the piercing at a speed of 50 mm / min (50mm per minute) was measured the maximum stress until the needle 110 penetrates the laminate 30. About 5 or more specimens, to measure the maximum value of the stress, and the average was taken as the piercing strength of the laminate 30. During measurement of the environment, temperature 23 ° C., and a relative humidity of 50%. A result, piercing strength was 15N.
[0235]
　[Drop Evaluation of Strength]
　Subsequently, overlapping two of the stacked body 30 was heated for 1 second at 190 ° C., with heat sealing inner surfaces 30x between the laminate 30, filled with water 200g as content , to produce a four-side seal bag 10. Height S1 of the bag 10 is set to 180 mm, a width S2 are set to 130 mm.
[0236]
　After storage overnight in an environment of the bag 10 in a state where water is accommodated 3 ° C., the bag 10 of surface film 14 and the back surface film 15 is held so as to horizontally and dropped from a height of 120 cm, bag 10 is examined whether or not to breakage. But it was dropped five times repeating the bag 10, breakage was observed.
[0237]
　(Example A2)
　of making the adhesive composition, the weight ratio of the second composition to the first composition except that the 0.2, in the same manner as in Example A1, the laminate 30 It was produced. In the adhesive composition, the molar ratio of the isocyanate groups of the aliphatic isocyanate compound to the hydroxyl groups of the polyol was 6.
[0238]
　In the same manner as in Example A1, it was evaluated laminate strength of the laminate 30. Result, the laminate strength in 15mm width was 7.1 N. In the same manner as in Example A1, it was evaluated tear of the laminate 30. Results without sealant film 70 of the laminate 30 extends in the middle, I was able to tear the specimen 90 in the direction of the length W2. In the same manner as in Example A1, 2 sheets of the inner surface 30x between the laminate 30 was evaluated the impact resistance of the heat-sealed laminate. Result, the impact strength of the layered product was 1137kJ / m. In the same manner as in Example A1, it was measured piercing strength of the laminate 30. A result, piercing strength was 15N. In the same manner as in Example A1, it was evaluated drop strength of the bag 10 constructed using a stack 30. But it was dropped five times repeating the bag 10, breakage was observed.
[0239]
　(Example A3)
　The content of PBT in each layer 41a, except for using the substrate 41 is 70%, in the same manner as in Example A1, was prepared a laminate 30. In the same manner as in Example A1, it was evaluated laminate strength of the laminate 30. Result, the laminate strength in 15mm width was 6.5 N. In the same manner as in Example A1, it was evaluated tear of the laminate 30. Results without sealant film 70 of the laminate 30 extends in the middle, I was able to tear the specimen 90 in the direction of the length W2. In the same manner as in Example A1, 2 sheets of the inner surface 30x between the laminate 30 was evaluated the impact resistance of the heat-sealed laminate. Result, the impact strength of the layered product was 912kJ / m. In the same manner as in Example A1, it was measured piercing strength of the laminate 30. A result, piercing strength was 13N. In the same manner as in Example A1, it was evaluated drop strength of the bag 10 constructed using a stack 30. But it was dropped five times repeating the bag 10, breakage was observed.
[0240]
　(Comparative Example A1)
　of making the adhesive composition, except that the weight ratio of the second composition to the first composition and 0.1, in the same manner as in Example A1, the laminate 30 It was produced. In the adhesive composition, the molar ratio of the isocyanate groups of the aliphatic isocyanate compound to the hydroxyl groups of the polyol was 3.
[0241]
　In the same manner as in Example A1, it was evaluated laminate strength of the laminate 30. Result, the laminate strength in 15mm width was 4.2 N. In the same manner as in Example A1, it was evaluated tear of the laminate 30. Result, will extend sealant film 70 of the laminate 30 on the way, thus, could not tear the specimen 90 in the direction of the length W2. In the same manner as in Example A1, 2 sheets of the inner surface 30x between the laminate 30 was evaluated the impact resistance of the heat-sealed laminate. Result, the impact strength of the layered product was 758kJ / m. In the same manner as in Example A1, it was measured piercing strength of the laminate 30. A result, piercing strength was 15N. In the same manner as in Example A1, it was evaluated drop strength of the bag 10 constructed using a stack 30. A result, the bag 10 is breakage in the fall of the fourth.
[0242]
　(Example A4)
　was produced a laminate 30 comprising a substrate 41 / layer 45 / sealant layer 71 in this order from the outer surface side to the inner side. As the substrate 41, as in Example A1, it comprises a plurality of layers 41a, made with casting, using a film-like base material 41. Things as the adhesive composition for constituting the adhesive layer 45, which as in Example A1, constituted by a second composition comprising a first composition and H-4 containing RU-40 It was used. The weight ratio of the second composition to the first composition was the case as with 0.10 in Comparative Example A1. In the adhesive composition, the molar ratio of the isocyanate groups of the aliphatic isocyanate compound to the hydroxyl groups of the polyol was 3. The sealant layer 71, using an unstretched polypropylene film ZK500 of Toray Film Corporation. ZK500 comprises propylene-ethylene block copolymer and elastomer described above. The thickness of the sealant layer 71 was 70 [mu] m.
　Laminate 30 of Example A4 deletes the print layer 42 from the laminate 30 of Comparative Example A1, and, it can be said is obtained by replacing the sealant layer 71 on the ZK500.
[0243]
　In the same manner as in Example A1, 2 sheets of the inner surface 30x between the laminate 30 is heat sealed to prepare a test piece 100 was measured impact strength. Result, the impact strength was 946kJ / m. In the same manner as in Example A1, it was measured piercing strength of the laminate 30. A result, piercing strength was 15N. In the same manner as in Example A1, it was evaluated drop strength of the bag 10 constructed using a stack 30. But it was dropped five times repeating the bag 10, breakage was observed.
[0244]
　(Example A5)
　as the base material 41 comprises a PBT, except for using a film-like substrate 41 manufactured by the tubular method, in the same manner as in Example A4, to prepare a laminate 30 . Substrate 41 is a film of composed monolayer only PBT and additives, the thickness of the substrate 41 was 15 [mu] m.
[0245]
　In the same manner as in Example A1, 2 sheets of the inner surface 30x between the laminate 30 is heat sealed to prepare a test piece 100 was measured impact strength. Result, the impact strength was 838kJ / m. In the same manner as in Example A1, it was measured piercing strength of the laminate 30. A result, piercing strength was 15N. In the same manner as in Example A1, it was evaluated drop strength of the bag 10 constructed using a stack 30. But it was dropped five times repeating the bag 10, breakage was observed.
[0246]
　(Comparative Example A2)
　as a sealant layer 71, except for using an unstretched polypropylene film ZK93FM made Toray Advanced Film Co., Ltd., in the same manner as in Example A4, to prepare a laminate 30. The thickness of the sealant layer 71 was 70 [mu] m.
[0247]
　In the same manner as in Example A1, 2 sheets of the inner surface 30x between the laminate 30 is heat sealed to prepare a test piece 100 was measured impact strength. Result, the impact strength was 502kJ / m. In the same manner as in Example A1, it was evaluated drop strength of the bag 10 constructed using a stack 30. A result, the bag 10 is breakage in the fall of the fourth.
[0248]
　(Comparative Example A3)
　except for using Toyobo PET film as a substrate 41 E5100 (thickness 12 [mu] m), in the same manner as in Comparative Example A2, was produced a laminate 30. In the same manner as in Example A1, it was evaluated laminate strength of the laminate 30. Result, the laminate strength in 15mm width was 3.8 N. In the same manner as in Example A1, it was evaluated tear of the laminate 30. Result, will extend sealant film 70 of the laminate 30 on the way, thus, could not tear the specimen 90 in the direction of the length W2. In the same manner as in Example A1, 2 sheets of the inner surface 30x between the laminate 30 was evaluated the impact resistance of the heat-sealed laminate. Result, the impact strength of the layered product was 537kJ / m. In the same manner as in Example A1, it was measured piercing strength of the laminate 30. A result, piercing strength was 10N. In the same manner as in Example A1, it was evaluated drop strength of the bag 10 constructed using a stack 30. A result, the bag 10 is breakage in the fall of the fourth.
[0249]
　The layer structure and evaluation results of the laminate 30 of the embodiment A1 ~ A5 and Comparative Examples A1 ~ A3, are summarized in Figure 19. As it can be seen from a comparison of Comparative Example A1, A2 Example A1 ~ A5, by constructing the bag 10 by using the laminated body 30 having an impact strength of at least 800kJ / m, so as not to breakage in five drops the drop strength was able to have in the bag 10.
[0250]
　As can be seen from the comparison between Comparative Example A1, A2 of Example A4, A5, in enhancing the impact strength of the laminated body 30, and it sealant layer 71 comprises a propylene-ethylene block copolymer, it includes an elastomeric it can be said that is preferable. As can be seen from the comparison between Comparative Example A1, A3 to example A1, A2, A3, for increasing the impact strength of the laminated body 30, in the adhesive composition, aliphatic isocyanate compound to the hydroxyl groups of the polyol molar ratio of isocyanate groups to have high be preferred for.
[0251]
　Example A1, A2, A3 and As can be seen from a comparison of Comparative Example A1, A3, even in the case of using the aliphatic isocyanate compound as a curing agent, to increase the component ratio of the curing agent in the adhesive layer 45 Accordingly, it was possible to increase the laminate strength of the laminate 30. Thus, it was possible to have a good tear resistance to the laminate 30. Moreover, it was possible to increase the impact strength of the laminate 30. Regarding tearability, in the embodiment A1, A2, A3, we have been able to tear smoothly over the entire region in the direction of the test piece 90 of the length W2, and the evaluation result is "good". On the other hand, in Comparative Example A1, A3 is would extend sealant film 70 of the laminate 30 in the middle, Therefore, because it could not be torn smoothly over the entire region in the direction of the length W2 of the test piece 90, evaluation the results were as "bad" and.
[0252]
　Further, as shown in Comparative Example A3, if the substrate 41 is made of a PET film, piercing strength of the laminate 30 is equal to or less than 10 N. On the other hand, as shown in Examples A1 ~ A5, if the substrate 41 is made of a film containing as a main component PBT, the piercing strength of the laminate 30 can be at least 11N, more particularly more than 13N We were able to.
[0253]
　Next, explained in the second embodiment, the laminate of Example B1, B2 and Comparative Examples B1, B2 will be described about the case of providing a metal foil positioned between the substrate and the sealant layer.
[0254]
　(Example B1)
　in the same manner as in Example A1, described in the first construction described above, comprises a plurality of layers, and providing a first substrate 51 of the prepared film-form by casting method. The content of PBT in each layer is 80%, the number of layers of the layer is 1024, the thickness of the first substrate 51 was 15 [mu] m. It was also prepared sealant film 70 including the sealant layer 71. The sealant layer 71, using an unstretched polypropylene film ZK99S of Toray Film Corporation. The thickness of the sealant layer 71 was 70 [mu] m. The metal foil 47 was prepared aluminum foil having a thickness of 7 [mu] m.
[0255]
　It was evaluated warpage in the first film 40 consisting of the substrate 41. Specifically, first, by cutting a first film 40, to prepare a square test piece of side 10 cm. Subsequently, each of the four corners of the square-shaped specimen to measure the height of the warp. Result, the maximum value of the warp of the height at four corners was 0 mm. Incidentally, in suppressing warpage and the broken like it occurs in the end portion in the width direction of the first film 40 when conveyed along the first film 40 in the longitudinal direction, high warp in the four corners of the test specimen it is preferably not more than the maximum value of 5 mm, and more preferably less than 3mm.
[0256]
　Next, a first film 40 and the metal foil 47 via the first adhesive layer 46 by performing a first laminating step of laminating by a dry lamination method. More specifically, first, after applying the adhesive containing a solvent to the first film 40, and the solvent was volatilized by drying the adhesive to form a first adhesive layer 46 in an uncured state. The adhesive was used Toyo Morton Co., Ltd. TM-556S as the main agent, the CAT-56 manufactured by Toyo-Morton Ltd. as a hardening agent. TM-556S includes a polyester polyol. CAT-56 contains an aromatic isocyanate compound. The molar ratio of the isocyanate groups of aromatic isocyanate compound to the hydroxyl groups of the polyol was 3. Subsequently, the first film 40 and the metal foil 47 to the first adhesive layer 46 was formed was conveyed to the Ramiroru for laminating both. Thereafter, the metal foil 47 is bonded to the first film 40 with Ramiroru to prepare a laminate of the first film 40 and the metal foil 47. Subsequently, the laminate was heated for 96 hours under 40 ° C. environment. Thus, to cure the adhesive, to obtain a first adhesive layer 46 comprising a cured product of a polyol and an aromatic isocyanate compound. The thickness of the first adhesive layer 46 was 3 [mu] m.
[0257]
　When transporting the first film 40 in the first laminating step, the warp or bending the end portion of the first film 40 was not observed. Therefore, the task of adjusting the tension applied to the first film 40 in order to eliminate warping or bending, etc. was not required.
[0258]
　Subsequently, after applying the adhesive containing the solvent to the metal foil 47, and the solvent was volatilized by drying the adhesive to form a second adhesive layer 48 in an uncured state. Adhesives, locking Paint Co., Ltd. of RU-40 as a main component was used H-4 manufactured by Rock Paint Co., Ltd. as a hardening agent. RU-40 comprises a polyester polyol. H-4 comprises an aliphatic isocyanate compound. The molar ratio of the isocyanate groups of the aliphatic isocyanate compound to the hydroxyl groups of the polyol was 3. Thereafter, the laminate and the sealant film 70 of the first film 40 and the metal foil 47 via the second adhesive layer 48 to perform the second lamination step of laminating by a dry lamination method. In this manner, the first film 40 in order from the outer surface 30y side to the inner surface 30x side, to produce a laminate 30 comprising a metal foil 47 and the sealant film 70. Subsequently, the laminated body 30 was heated for 96 hours under 40 ° C. environment. Thus, to cure the adhesive, to obtain a second adhesive layer 48 comprising a cured product of a polyol and an aliphatic isocyanate compound. The thickness of the second adhesive layer 48 was 3 [mu] m. Layer structure of the multilayer body 30 is expressed as follows.
　PBT (multilayer) / first adhesive layer / aluminum foil / second adhesive layer / polypropylene
[0259]
　Subsequently, in the same manner as in Example A1, it was measured piercing strength of the laminate 30. A result, piercing strength was 19N.
[0260]
　(Example B2)
　as the base material 41 comprises a PBT, except for using a film-like substrate 41 manufactured by the tubular method, in the same manner as in Example B1, was prepared a laminate 30 . Substrate 41 is a film of composed monolayer only PBT and additives, the thickness of the substrate 41 was 15 [mu] m. In the same manner as in Example B1, was evaluated warpage in the first film 40. Result, the maximum value of the warp of the height was 0 mm. Also, when conveying the first film 40, the warp or bending the end portion of the first film 40 was not observed.
[0261]
Layer structure of the multilayer body 30 is expressed as follows.
　PBT (single layer) / first adhesive layer / aluminum foil / second adhesive layer / polypropylene
was then measured piercing strength of the laminate 30. A result, piercing strength was 18N.
[0262]
　(Example B3)
　except that the content of PBT in each layer 41a is used a substrate 41 is 55%, in the same manner as in Example B1, evaluate the warpage of the first film 40 made of a substrate 41 did. Result, the maximum value of the warp of the height was 0 mm. Further, by using the substrate 41 content of PBT is 55%, to prepare a laminate 30 as in Example B1. When transporting the first film 40 consisting of the substrate 41 in the step of preparing a laminated body 30, the warp or bending the end portion of the first film 40 was not observed. Further, the piercing strength of the laminate 30 was 13N.
[0263]
　(Comparative Example B1)
　as the base material 41, except for using the thickness 15μm Heputakkusu HBN (manufactured by Gunze Ltd.), in the same manner as in Example B1, was prepared a laminate 30. Heputakkusu HBN is press 2 layer co films prepared by coextruding a PET and nylon. In the same manner as in Example B1, was evaluated warpage in the first film 40. Result, the degree of warpage will be rounded four corners of too large specimens, it was not possible to measure the height of the warp. Also, when conveying the first film 40, the fold on the end portion in the width direction of the first film 40 has occurred, to adjust the tension applied to the first film 40 in order to eliminate the break.
[0264]
　Layer structure of the multilayer body 30 is expressed as follows.
　Heputakkusu HBN / first adhesive layer / aluminum foil / second adhesive layer / polypropylene
was then measured piercing strength of the laminate 30. A result, piercing strength was 12N.
[0265]
　(Comparative Example B2)
　as a substrate, were prepared nylon film of a PET film and the thickness 15μm of thickness 12 [mu] m. In the same manner as in Example B1, it was evaluated warping in the PET film. Result, the maximum value of the warp of the height was 0 mm.
[0266]
　Subsequently, after applying the adhesive containing a solvent on a PET film, and the solvent evaporated by drying the adhesive to form a first adhesive layer in an uncured state. The adhesive was used Toyo Morton Co., Ltd. TM-556S as the main agent, the CAT-56 manufactured by Toyo-Morton Ltd. as a hardening agent. The molar ratio of the isocyanate groups of aromatic isocyanate compound to the hydroxyl groups of the polyol was 3. When transporting PET film, warp or bending was observed on the end of PET film. Subsequently, by crimping nylon film PET film to produce a laminate of the PET film and nylon film. Subsequently, the laminate was heated for 96 hours under 40 ° C. environment. Thus, to cure the adhesive, to obtain a first adhesive layer comprising a cured product of a polyol and an aromatic isocyanate compound. The thickness of the first adhesive layer was 3 [mu] m.
[0267]
　Subsequently, an adhesive is applied containing a solvent to a nylon film, and evaporating the solvent by drying the adhesive to form a second adhesive layer in an uncured state. The adhesive was used Toyo Morton Co., Ltd. TM-556S as the main agent, the CAT-56 manufactured by Toyo-Morton Ltd. as a hardening agent. The molar ratio of the isocyanate groups of aromatic isocyanate compound to the hydroxyl groups of the polyol was 3. Then, a nylon film is crimped aluminum foil having a thickness of 7 [mu] m, to prepare a laminate of PET film and a nylon film and aluminum foil. Subsequently, the laminate was heated for 96 hours under 40 ° C. environment. Thus, to cure the adhesive, to obtain a second adhesive layer comprising a cured product of a polyol and an aromatic isocyanate compound. The thickness of the second adhesive layer was 3 [mu] m.
[0268]
　Subsequently, after applying the adhesive containing the solvent to the aluminum foil and the solvent evaporated by drying the adhesive to form a third adhesive layer in an uncured state. Adhesives, locking Paint Co., Ltd. of RU-40 as a main component was used H-4 manufactured by Rock Paint Co., Ltd. as a hardening agent. The molar ratio of the isocyanate groups of the aliphatic isocyanate compound to the hydroxyl groups of the polyol was 3. Subsequently, the polypropylene film is crimped to the aluminum foil to prepare a laminate. The polypropylene film was used as a non-oriented polypropylene film ZK99S manufactured by Toray Advanced Film Co., Ltd.. Subsequently, the laminate was heated for 96 hours under 40 ° C. environment. Thus, to cure the adhesive, to obtain a third adhesive layer comprising a cured product of a polyol and an aliphatic isocyanate compound. The thickness of the third adhesive layer was 3 [mu] m.
[0269]
Layer structure of the laminate may be expressed as follows.
　PET / first adhesive layer / nylon / second adhesive layer / aluminum foil / third adhesive layer / polypropylene
was then measured piercing strength of the laminate. A result, piercing strength was 19N.
[0270]
　(Comparative Example B3)
　as the substrate 41, except for using a PET film having a thickness of 12 [mu] m (manufactured by Toyobo Co. E5100), in the same manner as in Example B1, evaluate the warpage of the first film 40 made of a substrate 41 did. Result, the maximum value of the warp of the height was 0 mm.
[0271]
　Further, by using a substrate 41 made of PET film to produce a laminate 30 as in Example B1. When transporting the first film 40 consisting of the substrate 41 in the step of preparing a laminated body 30, the warp or bending the end portion of the first film 40 was not observed.
[0272]
　Layer structure of the laminate may be expressed as follows.
　PET / first adhesive layer / aluminum foil / second adhesive layer / polypropylene
was then measured piercing strength of the laminate. A result, piercing strength was 11N.
[0273]
　The layer structure and evaluation results of the laminates of Examples B1 ~ B3 and Comparative Examples B1 ~ B3, are summarized in Figure 20. In Figure 20, the column of "layer structure" is a component of the laminate, excluding the adhesive layer, are described from the top of a layer of the outer surface side. Further, with respect to the column of "lamination process", in Examples B1 ~ B3 and Comparative Example B2, B3, since warp or bending the end of the film was observed, and the evaluation result is "good". On the other hand, in Comparative Example B1 is folded on the end portion of the film was observed, so the work was necessary to adjust the tension at the time of laminating the first film 40 and the metal foil 47, and the evaluation results are "bad" did.
[0274]
　As it can be seen from FIG. 20, according to Examples B1 ~ B3, by constituting the substrate 41 of the first film 40 by using the PBT, it was possible to suppress the warpage occurs in the first film 40 . Therefore, it was possible to efficiently produce a laminated body 30. Moreover, it was possible to realize the above piercing strength 13N.
[0275]
　Next, explained in the third embodiment, the plastic film constituting the substrate of the laminate Examples C1 ~ C6 and Comparative Examples for the case where there are two C1, C2 will be described.
[0276]
　(Example C1)
　in the same manner as in Example A1, described in the first construction described above, comprises a plurality of layers, and providing a first substrate 51 of the prepared film-form by casting method. The content of PBT in each layer is 80%, the number of layers of the layer is 1024, the thickness of the first substrate 51 was 15 [mu] m. It was also prepared second film 60 film-like, including a second substrate 61. The second substrate 61, was used containing 100 wt% of PET. The thickness of the second substrate 61 was 12 [mu] m. It was also prepared sealant film 70 including the sealant layer 71. The sealant layer 71, using an unstretched polypropylene film ZK207 of Toray Film Corporation. The thickness of the sealant layer 71 was 60 [mu] m.
[0277]
　Then, the first film 50 through the first adhesive layer 55 and the second film 60 is laminated by a dry lamination method. The first adhesive layer 55, two-liquid type polyurethane adhesive manufactured by Rock Paint Co., Ltd. (main agent: RU-40, curing agent: H-4) was used. RU-40 comprises a polyester polyol. H-4 comprises an aliphatic isocyanate compound. The thickness of the first adhesive layer 55 was 3 [mu] m.
[0278]
　Then, the laminate and the sealant film 70 of the first film 50 and second film 60, laminated by a dry lamination method through the second adhesive layer 65, to obtain a laminate 30. The second adhesive layer 65, similarly to the first adhesive layer 55, two-liquid type polyurethane adhesive manufactured by Rock Paint Co., Ltd. (main agent: RU-40, curing agent: H-4) was used. The thickness of the second adhesive layer 65 was 3 [mu] m.
[0279]
　Subsequently, in the same manner as in Example A1, it was measured piercing strength of the laminate 30. A result, piercing strength was 17N.
[0280]
　Then, to evaluate the coloring resistance of the laminate 30. Specifically, to seal the inner surface 30x between the two laminates 30, to prepare a bag commercial curry is accommodated as contents. Subsequently, after performing retort processing in a bag, and the bag was opened, the laminate 30 constituting the bag was visually evaluated whether or not it is colored. Each dimension of the two laminates 30, longitudinal 100 mm, was next to 100 mm. The shape of the bag, was a four-side sealed bag. Retorting the bag for 30 minutes at 121 ° C., it was carried out by hot water type. Result, coloration was observed.
[0281]
　(Example C2)
　as the first substrate 51 of the first film 50 has been described in the second configuration described above, comprises 100 wt% of PBT, melting point of PBT is 224 ° C., IV value 1.26dl / g , and the except for using a single-layer film produced by the tubular method, in the same manner as in example C1, it was prepared a laminate 30. The first substrate 51 is a film of composed monolayer only PBT and additives, the thickness of the first substrate 51 was 15 [mu] m.
[0282]
　Subsequently, in the same manner as in Example A1, it was measured piercing strength of the laminate 30. A result, piercing strength was 17N. In the same manner as in Example C1, to evaluate coloring resistance of the laminate 30. Result, coloration was observed.
[0283]
　(Example C3)
　content of PBT in the respective layers except for using the first substrate 51 is 55%, in the same manner as in Example C1, was prepared a laminate 30. In the same manner as in Example A1, it was measured piercing strength of the laminate 30. A result, piercing strength was 13N. In the same manner as in Example C1, to evaluate coloring resistance of the laminate 30. Result, coloration was observed.
[0284]
　(Example C4)
　using the PBT used for the first substrate 51 of Example C1 as the second substrate 61, for the use of PET constituting the second substrate 61 of Example C1 as the first base material 51 Otherwise, in the same manner as in example C1, it was prepared a laminate 30.
[0285]
　Subsequently, in the same manner as in Example A1, it was measured piercing strength of the laminate 30. A result, piercing strength was 16N. In the same manner as in Example C1, to evaluate coloring resistance of the laminate 30. Result, coloration was observed.
[0286]
　(Example C5)
　with PBT used for the first substrate 51 of Example C2 as the second substrate 61, for the use of PET constituting the second substrate 61 of Example C2 as the first base material 51 Otherwise, in the same manner as in example C1, it was prepared a laminate 30.
[0287]
　Subsequently, in the same manner as in Example A1, it was measured piercing strength of the laminate 30. A result, piercing strength was 16N. In the same manner as in Example C1, to evaluate coloring resistance of the laminate 30. Result, coloration was observed.
[0288]
　(Example C6)
　content of PBT in the respective layers except for using the second substrate 61 is 55%, in the same manner as in Example C4, to prepare a laminate 30. In the same manner as in Example A1, it was measured piercing strength of the laminate 30. A result, piercing strength was 13N. In the same manner as in Example C1, to evaluate coloring resistance of the laminate 30. Result, coloration was observed.
[0289]
　(Comparative Example C1)
　as the first substrate 51 of the first film 50, except for using a substrate comprising a 100% by weight of PET, in the same manner as in Example C1, was prepared a laminate 30. The thickness of the first substrate 51 was 12 [mu] m.
[0290]
　Subsequently, in the same manner as in Example C1, it was measured piercing strength of the laminate 30. A result, piercing strength was 11N. In the same manner as in Example C1, to evaluate coloring resistance of the laminate 30. Result, coloration was observed.
[0291]
　(Comparative Example C2)
　as the second substrate 61 of the second film 60, except for using a nylon film having a thickness of 15 [mu] m (Kohjin Holdings Ltd. Boniru W), in the same manner as in Comparative Example C1, laminated the body 30 was prepared.
[0292]
　Subsequently, in the same manner as in Example A1, it was measured piercing strength of the laminate 30. A result, piercing strength was 17N. In the same manner as in Example C1, to evaluate coloring resistance of the laminate 30. Result, coloration was observed.
[0293]
　The layer structure and evaluation results of the laminates of Examples C1 ~ C6 and Comparative Examples C1, C2, are summarized in Figure 21. In Figure 21, the column of "layer structure" is a component of the laminate, excluding the adhesive layer, are described from the top of a layer of the outer surface side. As can be seen from a comparison of Comparative Example C1 and Examples C1 ~ C6, by the first substrate 51 or second substrate 61 including PBT, both the first substrate 51 and second substrate 61 is PET high piercing strength as compared with the case including, specifically could be realized more piercing strength 13N. As can be seen from a comparison of Comparative Example C2 and Examples C1 ~ C6, materials other than nylon as second base material 61, in particular by using a PBT or PET, a second substrate 61 includes a nylon as compared to the case, it was possible to achieve good coloring resistance.
[0294]
　Next, explained in the fourth embodiment, the plastic film constituting the substrate of the laminate are present two embodiments relate to the case where the laminate further comprises a light shielding printed layer Examples D1 ~ D4 and Comparative Examples D1, D2 will be described.
[0295]
　(Example D1)
　in the same manner as in Example A1, described in the first construction described above, comprises a plurality of layers, and providing a first substrate 51 of the prepared film-form by casting method. The content of PBT in each layer is 80%, the number of layers of the layer is 1024, the thickness of the first substrate 51 was 15 [mu] m. Subsequently, on the first substrate 51 a film-like, to form a picture-printed layer 53 using Finato made of DIC Graphics Corporation. Subsequently, to form a light-shielding printed layer 52 on the picture-printed layer 53. Shielding printed layer 52 includes a white solid layer and ash solid layer laminated in this order on the picture-printed layer 53.
[0296]
　White solid layer was formed by twice solid printing white ink on a substrate by gravure printing. The first layer of white solid layer, white ink was formed by solid printing (Toyo Ink Co., Ltd., product name "Fine Star 681AT") on the picture-printed layer 53. The second layer of the white solid layer, white ink was formed by solid printing to (Toyo Ink Co., Ltd., product name "NKFS R69K") a first layer of white solid layer. The thickness of the first layer of solid white layer is 1 [mu] m, the thickness of the second layer of solid white layer was 1.5 [mu] m. The formation of solid white layer was used plate depth 28 .mu.m, the plate cylinder is the line number 175 of the plate cylinder.
　Ash solid layer is white ink (Toyo Ink Co., Ltd., product name "R631AT") black ink gray ink was blended at a ratio of (Toyo Ink Co., Ltd., product name "N800LPGT Sumi") and a 6: 4, It was formed by solid printing once solid white layer. The formation of ash solid layer using a plate depth 22 .mu.m, the plate cylinder is the line number 175 of the plate cylinder. The thickness of the ash solid layer was 1.5 [mu] m.
[0297]
　It was also prepared second film 60 film-like, including a second substrate 61. The second substrate 61, was used containing 100 wt% of PET. The thickness of the second substrate 61 was 12 [mu] m. It was also prepared sealant film 70 including the sealant layer 71. The sealant layer 71, using an unstretched polypropylene film ZK207 of Toray Film Corporation. The thickness of the sealant layer 71 was 60 [mu] m.
[0298]
　Then, the first film 50 through the first adhesive layer 55 and the second film 60 is laminated by a dry lamination method. The first adhesive layer 55, two-liquid type polyurethane adhesive manufactured by Rock Paint Co., Ltd. (main agent: RU-40, curing agent: H-4) was used. RU-40 comprises a polyester polyol. H-4 comprises an aliphatic isocyanate compound. The thickness of the first adhesive layer 55 was 3 [mu] m.
[0299]
　Then, the laminate and the sealant film 70 of the first film 50 and second film 60, laminated by a dry lamination method through the second adhesive layer 65, to obtain a laminate 30. The second adhesive layer 65, similarly to the first adhesive layer 55, two-liquid type polyurethane adhesive manufactured by Rock Paint Co., Ltd. (main agent: RU-40, curing agent: H-4) was used. The thickness of the second adhesive layer 65 was 3 [mu] m.
[0300]
　Subsequently, in the same manner as in Example A1, it was measured piercing strength of the laminate 30. A result, piercing strength was 17N.
[0301]
　Then, to evaluate the shielding of the laminate 30. Specifically, in the case where light is incident from the outer surface 30y of the stack 30, it was measured for total light transmittance of the laminate 30. As a measuring instrument, using a haze meter HM-0.99 the total light transmittance measuring apparatus manufactured by Murakami Color Research Laboratory Co.. Result, the total light transmittance was 9%.
[0302]
　Then, to evaluate the off-flavor barrier properties of the laminate 30. Specifically, sealing the two inner surfaces 30x between the laminate 30 bags were formed, after heating the bag and the bag was opened, it was evaluated whether feel odor. Each dimension of the two laminates 30, longitudinal 100 mm, was next to 100 mm. The shape of the bag, was a four-side sealed bag. Heating the bag was performed for one minute by using an oven controlled at 40 ° C.. A result, did not feel off-flavors.
[0303]
　(Example D2)
　as a first substrate 51 of the first film 50 has been described in the second configuration described above, comprises 100 wt% of PBT, melting point of PBT is 224 ° C., IV value 1.26dl / g , and the except for using a single-layer film produced by the tubular method, in the same manner as in example D1, to prepare a laminate 30. The first substrate 51 is a film of composed monolayer only PBT and additives, the thickness of the first substrate 51 was 15 [mu] m.
[0304]
　Subsequently, in the same manner as in Example A1, it was measured piercing strength of the laminate 30. A result, piercing strength was 17N. In the same manner as in Example D1, it was measured for total light transmittance of the laminate 30. Result, the total light transmittance was 9%. In the same manner as in Example D1, was evaluated odor barrier properties of the laminate 30. A result, did not feel off-flavors.
[0305]
　(Example D3)
　with PBT used for the first substrate 51 of Example D1 as the second substrate 61, for the use of PET constituting the second substrate 61 of Example D1 as the first base material 51 Otherwise, in the same manner as in example D1, to prepare a laminate 30.
[0306]
　Subsequently, in the same manner as in Example A1, it was measured piercing strength of the laminate 30. A result, piercing strength was 17N. In the same manner as in Example D1, it was measured for total light transmittance of the laminate 30. Result, the total light transmittance was 9%. In the same manner as in Example D1, was evaluated odor barrier properties of the laminate 30. A result, did not feel off-flavors.
[0307]
　(Example D4)
　using the PBT used for the first substrate 51 of Example D2 as the second substrate 61, for the use of PET constituting the second substrate 61 of Example D2 as the first base material 51 Otherwise, in the same manner as in example D1, to prepare a laminate 30.
[0308]
　Subsequently, in the same manner as in Example A1, it was measured piercing strength of the laminate 30. A result, piercing strength was 17N. In the same manner as in Example D1, it was measured for total light transmittance of the laminate 30. Result, the total light transmittance was 9%. In the same manner as in Example D1, was evaluated odor barrier properties of the laminate 30. A result, did not feel off-flavors.
[0309]
　(Comparative Example D1)
　as a first substrate 51 of the first film 50, except for using a substrate comprising a 100% by weight of PET, in the same manner as in Example D1, to prepare a laminate 30. The thickness of the first substrate 51 was 12 [mu] m.
[0310]
　Subsequently, in the same manner as in Example A1, it was measured piercing strength of the laminate 30. A result, piercing strength was 12N. In the same manner as in Example D1, it was measured for total light transmittance of the laminate 30. Result, the total light transmittance was 10%. In the same manner as in Example D1, was evaluated odor barrier properties of the laminate 30. A result, did not feel off-flavors.
[0311]
　(Comparative Example D2)
　as the second substrate 61 of the second film 60, except for using a nylon film having a thickness of 15 [mu] m (Kohjin Holdings Ltd. Boniru W), in the same manner as in Comparative Example D1, laminated the body 30 was prepared.
[0312]
　Subsequently, in the same manner as in Example A1, it was measured piercing strength of the laminate 30. A result, piercing strength was 17N. In the same manner as in Example D1, it was measured for total light transmittance of the laminate 30. Result, the total light transmittance was 10%. In the same manner as in Example D1, was evaluated odor barrier properties of the laminate 30. A result, I felt off-flavors.
[0313]
　The layer structure and evaluation results of the laminates of Examples D1 ~ D4 and Comparative Examples D1, D2, are summarized in Figure 22. In Figure 22, the column of "layer structure" is a component of the laminate, excluding the adhesive layer, are described from the top of a layer of the outer surface side. As can be seen from a comparison of Comparative Example D1 Example D1 ~ D4, by the first substrate 51 or second substrate 61 including PBT, both the first substrate 51 and second substrate 61 is PET as compared with the case including, we were able to achieve a high piercing strength. As can be seen from a comparison of Comparative Example D2 Example D1 ~ D4, materials other than nylon as second base material 61, in particular by using a PBT or PET, a second substrate 61 includes a nylon as compared to the case, it was possible to achieve good light shielding property and odor barrier properties.
DESCRIPTION OF SYMBOLS
[0314]
10 bags
11 top
12 bottom
12a bottom seal portion
13 side
13a side seal portion
14 surface film
15 backside film
16 bottom film
17 housing portion
18 contents
25 easily openable means
26 Notch
30 laminate
35 transparent gas barrier layer
36 transparent deposition layer
37 transparent gas barrier coating film
40 first film
41 substrate
41a layer
42 printed layer
45 adhesive layer
46 first adhesive layer
47 metal foil
48 second adhesive layer
50 first film
51 first substrate
52 shielding printing layer
55 first adhesive layer
60 the second film
61 and the second substrate
65 second adhesive layer
70 sealant film
71 sealant layer

The scope of the claims
[Requested item 1]
　A laminate,
　a substrate containing 51 wt% or more of polybutylene terephthalate,
　comprising including at least one of linear low density polyethylene or polypropylene, and the sealant layer constituting the inner surface of the laminate, and laminate.
[Requested item 2]
　Said substrate comprising a polybutylene terephthalate having a multilayer structure comprising more than 10 layers, the laminate of claim 1.
[Requested item 3]
　Said substrate comprising a polybutylene terephthalate, a single layer structure having a 1.10 dl / g or more and 1.35dl / g or less of IV values, laminate according to claim 1.
[Requested item 4]
　The sealant layer comprises 90 wt% or more of polypropylene, the laminated body according to any one of claims 1 to 3.
[Requested item 5]
　The sealant layer comprises a linear low density polyethylene having a 100 ° C. melting point above, the laminated body according to any one of claims 1 to 4.
[Requested item 6]
　Wherein provided on the outer surface side of the sealant layer further comprises an adhesive layer comprising a cured product of a polyol and an aliphatic isocyanate compound,
　the molar ratio of the isocyanate groups of the aliphatic isocyanate compound to the hydroxyl groups of the polyol, it is 3.5 or more, the laminated body according to any one of claims 1 to 5.
[Requested item 7]
　The laminate
　substrate / adhesive layer / sealant layer,
　substrate / printed layer / adhesive layer / sealant layer,
　substrate / transparent deposition layer / transparent gas barrier coating film / printed layer / adhesive layer / sealant layer , or
　comprising a substrate / transparent deposition layer / transparent gas barrier coating film / adhesive layer / sealant layer, in this order, the laminate according to any one of claims 1 to 6.
[Requested item 8]
　The laminate
　substrate / transparent deposition layer / transparent gas barrier coating film / printed layer / adhesive layer / sealant layer, or a
　substrate / transparent deposition layer / transparent gas barrier coating film / adhesive layer / sealant layer, the comprising in this order,
　the transparent deposition layer comprises aluminum oxide,
　the interface between the transparent evaporated layer and the substrate, covalent attachment of aluminum and carbon atoms is formed, stacked according to claim 7 body.
[Requested item 9]
　The impact strength of the laminate is 800kJ / m or more, the laminated body according to claim 7 or 8.
[Requested item 10]
　The piercing strength of the laminate is not less than 11N, the laminated body according to any one of claims 7 to 9.
[Requested item 11]
　The laminate
　base material / first adhesive layer / metal foil / second adhesive layer / sealant layer, or a
　substrate / printed layer / first adhesive layer / metal foil / second adhesive layer / sealant layer , hints in this order,
　the second adhesive layer comprises a cured product of a polyol and an aliphatic isocyanate compound, laminate according to any one of claims 1 to 6.
[Requested item 12]
　The laminate first substrate includes at least a second substrate and the sealant layer in this order,
　the second substrate comprises polyethylene terephthalate or 51 wt% or more of polybutylene terephthalate or 51 wt%,
　when the second substrate comprises polyethylene terephthalate or 51 wt%, the first substrate comprises a 51% by mass or more of polybutylene terephthalate, the laminated body according to any one of claims 1 to 6 .
[Requested item 13]
　The laminate, the a first substrate and the second substrate and the transparent vapor-deposited layer provided on the first substrate or the second substrate between the transparent provided on the transparent vapor deposition layer further comprising a gas barrier coating film, a laminate of claim 12.
[Requested item 14]
　The transparent deposition layer comprises aluminum oxide,
　the interface between the transparent evaporated layer and the first substrate or the second substrate, covalent attachment of aluminum and carbon atoms is formed, in claim 13 laminate according.
[Requested item 15]
　The laminate, the further comprises a light shielding printed layer and the first substrate located between the second substrate,
　the total light transmittance of the laminate is 20% or less, of claims 12 to 14 laminate according to any one.
[Requested item 16]
　Wherein the first substrate comprises a polybutylene terephthalate,
　the second substrate comprises a polyethylene terephthalate, the laminated body according to any one of claims 12 to 15.
[Requested item 17]
　Wherein the first substrate comprises polyethylene terephthalate,
　the second substrate comprises a polybutylene terephthalate, the laminated body according to any one of claims 12 to 15.
[Requested item 18]
　The piercing strength of the laminate is not less than 13N, the laminated body according to any one of claims 11 to 17.