Technical field
[0001]
The present invention comprises a substrate layer, an adhesive layer, a barrier layer, the oxygen barrier property of a laminate having a sealant layer, the base layer, deposited layer, the barrier coat layer, an adhesive layer, a barrier layer, and a sealant layer oxygen barrier property of a laminate having, and relates to the oxygen barrier properties of the packaging material consisting of a laminate thereof, an adhesive layer having excellent oxygen-barrier property to the adhesive layer in contact with the barrier layer and the barrier layer made of the deposited layer used, excellent oxygen barrier property (permeability of oxygen is reduced) relates a packaging material.
BACKGROUND
[0002]
Generally, packaging materials having oxygen barrier properties, at least, the base layer, a barrier layer, an adhesive layer, and a multilayer body having a sealant layer, as a barrier layer for improving the oxygen barrier property, metal foil, metal or evaporation film of metal oxide is used.
The metal foil as the barrier layer can achieve high oxygen barrier property, thicker films than are deposited film, as a result, packaging materials using metal foil becomes thicker, the bending resistance it is known that inferior.
In contrast, it is possible to reduce the thickness by using the deposited film of a metal or a metal oxide is excellent in bending resistance, or since the deposited film surface having unevenness, sufficient oxygen barrier property that was not a problem that can not be achieved.
[0003]
　Furthermore, Patent Document 1, as an oxygen barrier material, with an active hydrogen-containing compound (A) and the organic polyisocyanate compound (B) thermosetting gas containing resin cured product obtained by reacting (oxygen) barrier polyurethane resin there, to the resin cured product, backbone structure derived from meta-xylene diisocyanate are contained 20% by mass or more, and among the (a) and (B), the proportion of trifunctional or more compounds, (a) a thermosetting oxygen barrier polyurethane resin gas used (oxygen) barrier composite film (base film layer and the thermosetting gas barrier properties, characterized in that the total amount of 7 mass% or more with respect to the (B) and a layer containing a polyurethane resin) has been described.
[0004]
　Furthermore, Patent Document 2, on at least one side of a polymer film substrate, silicon oxide, or a thin film layer surface of the coating film having transparency forming a thin layer of aluminum oxide, a heat sealable resin film silicon oxide inorganic or barrier laminate, characterized in that adhered by dry lamination via a barrier adhesive containing one or more groups of particles and polyester polyol and an isocyanate compound selected from the materials aluminum oxide body, and packaging materials using the same have been described.
[0005]
　However, in Patent Document 1, the composition since it must use a highly polar solvent, poor workability. For example in the case of using a highly soluble solvents such as acetone, since the boiling point is likely to take in low and ambient air of water, adjusting the viscosity by the reaction of water with isocyanate there is a problem easily increased.
[0006]
　Further, in Patent Document 2 (Japanese Patent No. 3829526), ​​since the particle size of the inorganic compound contained in the adhesive is spherical or amorphous inorganic compound nano-order, the oxygen barrier property of the adhesive itself , there is a problem that not high oxygen barrier property particularly when given load bending.
CITATION
Patent Document
[0007]
Patent Document 1: Patent No. 4054972 Patent specification
Patent Document 2: Patent No. 3829526
Summary of the Invention
Problems that the Invention is to Solve
[0008]
The present invention is to solve the above problems, is excellent in oxygen barrier property, and to provide a packaging material comprising a laminate and the laminate was excellent in bending resistance.
Means for Solving the Problems
[0009]
The present inventors, as a result of various studies, at least, the base layer, an adhesive layer, a barrier layer, and the packaging material a laminate and the laminate having a sealant layer or the substrate layer, deposition layer, a barrier coat layer, an adhesive layer, a packaging material comprising a laminate and the laminate having a barrier layer, and a sealant layer, the barrier layer comprises deposition layer, by adhesive layer has an oxygen barrier property, It found that to achieve the above purpose.
[0010]
The present invention is characterized in the following points.
1. Base layer, an adhesive layer, a barrier layer, a laminate having at least a sealant layer, a laminate wherein the adhesive layer is characterized by having an oxygen barrier property.
2. The laminate according to the above 1 to between the base layer and the adhesive layer, and the deposition layer, characterized in that it has a barrier coat layer.
3. The laminate according to the 2 characterized by having a print layer between the barrier coat layer and the adhesive layer.
4. Packaging material for the substrate layer, an adhesive layer, a barrier layer, composed of a multilayer structure having at least a sealant layer, wherein the adhesive layer has an oxygen barrier property.
5. Between the base layer and the adhesive layer, the packaging material according to the 4, characterized in that a laminate having a vapor deposition layer, a barrier coat layer.
6. Packaging material according to the 5, characterized in that a laminate having a print layer between the barrier coat layer and the adhesive layer.
7. Packaging material, wherein said deposition layer, aluminum deposition film, the above 5 or 6, characterized in that it consists of any of alumina deposited film, silica-deposited film.
8. Packaging material according to the 4-7, wherein the barrier layer is a vapor-deposited aluminum film.
9. Packaging material according to the 4-8, wherein the thickness of the barrier layer is 1 ~ 100 nm.
10. Packaging material according to the 4-9, wherein the coating amount of the adhesive of the adhesive layer is 2.0 .mu.m ~ 4.0 .mu.m.
11. Wherein the laminate, 23 ° C., the oxygen permeability under 90% RH environment, 0.05 ~ 1.00 cc / m 2 packaging material according to the 4-10, which is a · day · atm.
12. Wherein the laminate, after giving the load of three bent Gelbo flex tester, of the laminate, 23 ° C., the oxygen permeability under 90% RH environment, from before applying a load of the bent increment value is 0.7 ~ 4.0 cc / m 2 packaging material according to the 4-11, which is a · day · atm.
Effect of the invention
[0011]
Packaging material comprising a laminate and the laminate of the present invention includes a base layer, an adhesive layer, a barrier layer, and the laminate having at least a sealant layer, or base layer, deposited layer, the barrier coat layer, an adhesive layer, a barrier layer, and composed of a multilayer structure having at least a sealant layer, in combination with the adhesive layer having a barrier layer and the oxygen barrier property is vapor-deposited film, the concave portion of the irregularities occurring in the deposition layer surface, the oxygen barrier property by being filled with an adhesive having, as a uniform surface direction of the barrier, while maintaining flexibility by reducing the thickness of the barrier layer, it can exhibit a high oxygen barrier property which not been achieved conventionally .
BRIEF DESCRIPTION OF THE DRAWINGS
[0012]
FIG. 1 is a schematic sectional view showing an example of the layer structure of the packaging material of the present invention.
FIG. 2 is a schematic sectional view showing another example for the layer structure of the packaging material of the present invention.
3 is a schematic sectional view showing an example yet another for the layer structure of the packaging material of the present invention.
DESCRIPTION OF THE INVENTION
[0013]
For packaging material comprising an oxygen barrier laminate and the laminate of the present invention will be described in detail below with reference to the drawings.
　1 to 3 are schematic cross-sectional view showing an example of the layer structure of the multilayer body forming the packaging material of the present invention.
[0014]
The laminate of the present invention, as shown in FIG. 1, is for a base layer, an adhesive layer, a barrier layer, and a sealant layer, the laminate was formed by constituting a basic structure.
Other aspects of the laminate of the present invention, as shown in FIG. 2, between the substrate layer and the adhesive layer, and the deposition layer may be formed by laminating a barrier coat layer.
Yet another embodiment of the laminate of the present invention, as shown in FIG. 3, between the barrier coating layer and the adhesive layer may be a laminated structure of the printing layer.
The above example is one example of a packaging material of the present invention, the present invention is not limited thereto.
[0015]
Next, the material of the laminate for use in an oxygen barrier packaging material according to the present invention, its manufacturing method will be described.
　Resins names used in the present invention is the use of what is customary in the industry.
[0016]
[Substrate Layer]
The substrate layer constituting the laminate of the present invention, excellent chemical or physical strength to withstand the conditions of forming a deposited film of an inorganic oxide vapor deposition film thereof and the like inorganic oxides may be of use metallic properties can be satisfactorily maintained without impairing the organic material such as an inorganic material or a resin such as metal oxides such as a film or sheet.
[0017]
　In the laminate of the present invention, the base material layer, a single layer film or is multilayered film is used, it can be used is not particularly limited, any film for use in various packaging materials. From these, according to the use conditions of the presence or absence of heat treatment after the type and filling of the contents to be packaged, selected and used freely those suitable.
[0018]
　Specific examples of the film which is preferably used as the substrate layer is paper, aluminum foil, cellophane, polyamide resin film, polyester resin film, an olefin resin film, the acid-modified polyolefin resin film, polystyrene resin film, a polyurethane system resin film, acetal resin film, they were uniaxially or biaxially oriented film, K-coated film, for example, low density polyethylene, medium density polyethylene, high density polyethylene, linear low density polyethylene, polypropylene, polybutene, polyvinyl alcohol, ethylene - vinyl acetate copolymer, ionomer, ethylene - (meth) acrylic acid copolymer, ethylene - (meth) acrylic acid ester copolymer, ethylene - propylene copolymer, methylpentene, Poriakuriro Tolyl, acrylonitrile - styrene copolymers, acrylonitrile - butadiene - styrene copolymer, polycarbonate, polyvinyl chloride (PVC), polyvinylidene chloride (PVDC), polyvinylidene fluoride (PVDF), ethylene - tetrafluoroethylene copolymer ( ETFE), polytetrafluoroethylene (PTFE), polyethylene terephthalate (PET), polybutylene terephthalate, a resin film made of polyethylene naphthalate, K coated oriented polypropylene film, K-coated stretched nylon film, laminating these two or more films the composite film and the like that.
[0019]
　Among them, polyethylene terephthalate, uniaxially or biaxially stretched polyester film, nylon 6, nylon 66, MXD6 (poly-m-xylylene adipamide) uniaxially or biaxially stretched polyamide film of polyamide, such as polyethylene naphthalate, and, biaxial it can be suitably used a stretched polypropylene film OPP or the like.
[0020]
(Thickness of the substrate layer)
thickness of the substrate layer, but may be selected arbitrarily, in view of moldability and transparency, it can be used by selecting from a range of 1μm to 300μm position, preferably it is in the range of 1 ~ 100μm. If the thickness is less than this, the strength is insufficient, and when the thickness is larger than this, rigidity becomes too high, processing may be difficult.
[0021]
(Surface treatment)
The base material layer (film or sheet of the substrate), in order to improve the adhesion between the adhesive layer or (inorganic oxide deposited layer), (evaporation of an inorganic oxide) laminating before or if necessary the adhesive layer side surface of the substrate layer (base film or sheet), a corona discharge treatment, ozone treatment, low-temperature plasma treatment using oxygen gas or nitrogen gas or the like, physical, such as a glow discharge treatment Do processing, chemical treatment such as oxidation treatment is treated with such chemicals, the adhesive layer, a primer coating agent layer, an undercoat layer, or treatment for forming a deposition anchor coating agent layer or the like, other pretreatment may be subjected to, after the surface treatment of the substrate film provided with the (vapor deposited layer of an inorganic oxide), further, a configuration in which the gas barrier coating film (barrier coat layer) was formed on the deposition layer of inorganic oxide It may be.
[0022]
(Molding of the film)
The film or sheet of a base layer resin, for example, using the above one resin or more, extrusion method, a cast molding method, T-die method, a cutting method, an inflation method or the like the film of methods have been conventionally used, or can be produced by multi-layer co-extrusion casting Act using two or more resins.
　Furthermore, the strength of the film, dimensional stability, in view of heat resistance, for example, a tenter method or can be stretched to biaxially uniaxial not using the tubular method or the like.
[0023]
(Additives)
film of resin as the base material layer, if necessary, the workability of the film, heat resistance, weather resistance, mechanical properties, dimensional stability, oxidation resistance, slip properties, releasability, flame retardant, anti-fungal, electrical properties, improved strength, etc., in the reforming purposes, lubricants, crosslinking agents, antioxidants, ultraviolet absorbers, light stabilizers, fillers, reinforcing agents, antistatic agents, pigments plastic compounding agents or additives and the like can be added etc., as the amount added, can be according to the purpose without affecting the gas barrier property or the like, it is optionally added.
[0024]
[Adhesive layer]
　The adhesive layer of the present invention, it is necessary that an adhesive layer having an oxygen barrier property.
　The adhesive resin composition for forming an adhesive layer having an oxygen barrier property, for example, a resin having two or more hydroxyl groups in a molecule as a functional group (A), an isocyanate group in a molecule as a functional group isocyanate compound having two or more (B), and a resin containing a specific phosphoric acid-reactive compound (C), the main skeleton, a polyester, polyester polyurethane, polyether, or by containing a polyether polyurethane to have a feature, the adhesive resin composition has a feature can be mentioned that further contains a plate-like inorganic compounds.
[0025]
(Resin having two or more hydroxyl groups in one molecule as a functional group (A))
　, where the main skeleton contains a polyester resin having two or more hydroxyl groups in a molecule as a functional group (A) is the polycarboxylic acid component having, as the aliphatic polycarboxylic acid, succinic acid, adipic acid, azelaic acid, sebacic acid, dodecane dicarboxylic acid, 1,4-cyclohexanedicarboxylic acid and the like, aromatic polycarboxylic acids the, orthophthalic acid, terephthalic acid, isophthalic acid, pyromellitic acid, trimellitic acid, 1,4-naphthalenedicarboxylic acid, 2,5-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, naphthalic acid, biphenyl dicarboxylic acid , 1,2-bis (phenoxy) ethane -p, p'-dicarboxylic acid and anhydrides or esters of these dicarboxylic acids Forming derivatives; p-hydroxybenzoic acid, it can be used in p-(2-hydroxyethoxy) benzoic acid and alone or in mixture of two or more polybasic acids such as ester-forming derivatives of these dihydroxy carboxylic acid it can.
[0026]
　As the polyhydric alcohol component, specifically, examples of the aliphatic diol include ethylene glycol, propylene glycol, butylene glycol, neopentyl glycol, cyclohexanedimethanol, 1,5-pentanediol, 3-methyl-1, 5-pentanediol, 1,6-hexanediol, methyl pentanediol, dimethyl butanediol, butyl ethyl propanediol, diethylene glycol, triethylene glycol, tetraethylene glycol, dipropylene glycol, tripropylene glycol, aromatic polyhydric phenol, hydroquinone, resorcinol, catechol, naphthalene diol, biphenol, bisphenol a, His phenol F, and tetramethyl biphenol, these, ethylene-oxa De extension product, there can be mentioned hydrogenated alicyclic.
　Polycondensation reaction of polyhydric alcohols and polycarboxylic acids can be carried out by known conventional methods.
[0027]
(Isocyanate compound having two or more isocyanate groups in one molecule as a functional group (B))
as the isocyanate compound having two or more isocyanate groups in one molecule as a functional group (B), a diisocyanate compound, polyisocyanate compound Ya epoxy compounds, known compounds capable of reacting with the hydroxyl group of the resin (a) can be used. Among them, it is possible from the viewpoint of adhesiveness and retort resistance, the polyisocyanate compound is preferably used.
Aromatic polyisocyanate compounds, aliphatic diisocyanates, there are 3 or more valences polyisocyanate compounds, low molecular compounds, may be any polymeric compound.
[0028]
　For example, tetramethylene diisocyanate, hexamethylene diisocyanate, toluene diisocyanate, trimer of diphenylmethane diisocyanate, hydrogenated diphenylmethane diisocyanate, xylylene diisocyanate, hydrogenated xylylene diisocyanate, isophorone diisocyanate or these isocyanate compounds, and excess of isocyanate compounds the amount and, for example, ethylene glycol, propylene glycol, meta-xylylene alcohol, 1,3-bis hydroxy ethyl benzene, 1,4-bis-hydroxy ethyl benzene, trimethylolpropane, glycerol, pentaerythritol, erythritol, sorbitol, ethylenediamine, monoethanolamine, diethanolamine, Torietano Amines, low molecular weight active hydrogen compound and alkylene oxide adducts thereof, such as m-xylylenediamine, various polyester resins, polyether polyols include adducts obtained by reacting with such polymer active hydrogen compound polyamides .
[0029]
Glass transition temperature of cured coating film of the resin (A) isocyanate compound and (B) is preferably in the range of -30 ℃ ~ 80 ℃. More preferably from 0 ℃ ~ 70 ℃. More preferably 25 ℃ ~ 70 ℃. If the glass transition temperature is higher than 80 ° C., by the lower flexibility of the cured coating in the vicinity of room temperature, the adhesive strength may be reduced by the adhesion to the substrate is poor. If on the other hand lower than -30 ° C., there is sufficient possibility and the oxygen barrier properties does not come out, the risk of adhesion decreases due to an insufficient cohesive strength by vigorous molecular motion of the cured coating film at about room temperature.
[0030]
(Phosphoric acid-reactive compound (C))
specific phosphorus acid-reactive compound (C) has the effect of improving the laminate strength for the inorganic base material of the present invention, it can be used conventionally known.
More specifically, phosphoric acid, pyrophosphoric acid, triphosphate, methyl acid phosphate, ethyl acid phosphate, butyl acid phosphate, dibutyl phosphate, 2-ethylhexyl acid phosphate, bis (2-ethylhexyl) phosphate, isododecyl acid phosphate, butoxy ethyl acid phosphate include oleyl acid phosphate, tetracosyl acid phosphate, 2-hydroxyethyl methacrylate acid phosphate, a polyoxyethylene alkyl ether phosphoric acid and the like.
[0031]
(Plate-like inorganic compound (D))
The adhesive resin composition, characterized in that it contains a plate-like inorganic compounds.
　Plate-like inorganic compound used has the effect of improving the laminate strength and oxygen barrier properties obtained by curing the adhesive resin composition adhesive.
Examples of such plate-like inorganic compounds, for example, kaolinite - serpentine group clay minerals (halloysite, kaolinite, Ende light, dickite, nacrite and the like, antigorite, chrysotile, etc.), pyrophyllite - Talc Group (Pairofi light, talc, may be mentioned Kerorai etc.) and the like.
[0032]
　Such a resin having two or more hydroxyl groups in a molecule as a functional group (A), an isocyanate compound having two or more isocyanate groups in one molecule as a functional group (B), and a specific phosphoric acid-reactive compound ( specific examples of the adhesive layer having an oxygen barrier property using an adhesive resin composition containing C) is commercially available from DIC Corporation, Series oxygen barrier adhesive Pasurimu (PASLIM) is used can, a main skeleton polyester, curing agent PASLIM vM001 / VM102CP such a compound is having two or more isocyanate groups is preferably used.
[0033]
[Barrier layer]
In the laminate of the present invention, the barrier layer provided between the sealant layer (heat sealing layer) an adhesive layer, a barrier film having a gas barrier property to prevent permeation such as oxygen gas and water vapor, deposited film made of an inorganic substance or inorganic oxides.
The deposited film made of an inorganic substance or an inorganic oxide, specifically, an aluminum deposited film, an alumina deposited film, the barrier film can be mentioned consisting of silica-deposited film, in particular, aluminum evaporation film.
[0034]
As the barrier layer, when providing a vapor deposition film is directly on the sealant layer can be provided without using the adhesive layer such as an adhesive.
If necessary, it is also possible to impart a light-shielding property to block transmission of such visible light and ultraviolet light. It may also have a barrier layer two or more layers. If having a barrier layer two or more layers, each of which may be the same composition or a different composition.
[0035]
　Usually, as the thickness of the deposited film, for example, a 10 ~ 2000 Å position, preferably it is desirable to form selected arbitrarily within a range of 10 ~ 1000 Å position. When specifically described, in the case of an aluminum deposited film, the film thickness is preferably 10 ~ 600 Å position, more preferably 10 ~ 400 Å position. In the case of vapor-deposited film of silicon oxide or aluminum oxide, the thickness is preferably 10 ~ 500 Å position, more preferably 10 ~ 300 Å.
[0036]
Deposited film, using a conventionally known inorganic or inorganic oxide, can be formed by a conventionally known method, the composition and forming method is not particularly limited. As a method for forming deposited film, for example, vacuum deposition, sputtering, and ion plating method physical vapor deposition method such as (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.
[0037]
　In the present invention, a deposited film composed of a barrier layer, provided on the adhesive layer side surface of the sealant layer.
　Also, at that time, as required to the sealant layer surface, corona discharge treatment, ozone treatment, low-temperature plasma treatment using oxygen gas or nitrogen gas or the like, physical procedures such as when a glow discharge treatment, and the like chemicals it may be subjected to chemical treatment such as oxidation treatment is treated with.
[0038]
[Sealant layer (heat sealing layer)
sealant layer constituting the laminate of the present invention is also intended to packaging material comprising a laminate and the laminate of the present invention provide heat sealability. Further, bending resistance in the laminate of the present invention is intended to impart a function such as impact resistance. In particular, by bending resistance is imparted, it is desirable that it is possible to suppress a decrease in gas barrier properties after bending.
Therefore in the present invention, it may optionally be used a material satisfying the conditions as described above.
[0039]
In the present invention, a heat sealable resin layer is desirable as a sealant layer. Heat sealable resin layer may be any of those capable of being fused to each other and melted by heat.
Specifically, low density polyethylene, medium density polyethylene, high density polyethylene, linear (linear) low density polyethylene, polypropylene, ethylene - vinyl acetate copolymer, ionomer resin, ethylene - (meth) acrylate copolymer polymer, ethylene - (meth) acrylic acid copolymer, ethylene - propylene copolymer, methylpentene polymer, acrylic acid a polyolefin resin such as polyethylene or polypropylene, methacrylic acid, maleic anhydride, and other fumaric acid- modified polyolefin resin with a saturated carboxylic acid, ethylene - (meth) acrylic acid ester - terpolymer resin of an unsaturated carboxylic acid, cyclic polyolefin resin, a cyclic olefin copolymer, polyethylene terephthalate (PET), polyacrylonitrile (PAN) , Of one or resin comprising more resins other such a film or sheet or other coating film or the like can be used for.
The above-mentioned resin layer may be blended as needed, known bending resistance-improving agent, an inorganic or organic additives.
[0040]
The film or sheet forming the layer of the resin, can be used but any of the stretched film or sheet or the like was stretched unstretched film or sheet, or uniaxially or biaxially.
　Stretched film was stretched in two axial directions is, for example, 50 to longitudinally stretched 2 to 4 times by ~ 100 ° C. of roll stretching machine, it brought further transversely stretched 3-5 times by a tenter stretching machine of the atmosphere 90 ~ 0.99 ° C., the same tenter can be obtained by heat treatment at 100 ~ 240 ° C. in an atmosphere. In addition, the stretched film, simultaneous biaxial stretching, may be a sequential biaxial stretching.
[0041]
(Sealant layer of film thickness)
The thickness of the sealant layer comprising a film or sheet of the resin is capable of arbitrarily selected, from the viewpoint of strength as a packaging material, used to select from a range of 5 ~ 500 [mu] m-position it can be, preferably in the range of 10 ~ 250 [mu] m. Thinner than this without sufficient lamination strength can be obtained even if heat-sealing, penetration resistance, etc. do not function as wrapping material is抵下. In addition, when thicker than this, the film becomes hard workability is deteriorated with the cost is increased.
[0042]
[Deposited layer]
In the laminate of the packaging material according to the present invention, in order to improve the gas barrier properties against oxygen gas and water vapor, etc., may be on the side in contact with the adhesive layer of the base layer providing a deposition layer. The vapor deposition layer, as in the above-mentioned barrier layer, but deposited film made of an inorganic substance or an inorganic oxide can be used, preferably, the aluminum deposition film as a metal deposition film, and as a metal oxide deposited film, an alumina deposited film , silica-deposited film. Further, it is possible for the method of forming the deposited film is formed by a known method similar to the method for forming the barrier layer.
[0043]
　 In the present invention, when forming a deposition layer on the base material layer surface, in order to improve the adhesion between the deposited layer, the base layer surface, corona discharge treatment, ozone treatment, oxygen gas or nitrogen gas, etc. low-temperature plasma treatment using, physical procedures such as when the glow discharge treatment is preferably subjected to chemical treatment such as oxidation treatment is treated with such chemicals.
[0044]
[Barrier coat layer]
In the present invention, on the deposited layer provided on the base layer described above, in order to improve the gas barrier properties such as oxygen gas and water vapor, it is possible to further provide a barrier coat layer.
　In the present invention, the barrier coating film forming the barrier coat layer, an alkoxide and a water-soluble polymer, a sol-gel method the catalyst, acid, in the presence of water and an organic solvent, obtained by polycondensation by the sol-gel method a film made of alkoxide hydrolyzate or gas barrier composition, such as hydrolysis-condensation product of an alkoxide. The barrier composition may optionally, be further contains a silane coupling agent.
[0045]
　The alkoxides can be used in the barrier composition of 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 preferably at least one kind of an alkoxide represented by the representative.) the valency of M it can be used. Here, as the metal atom M, silicon, zirconium, titanium, aluminum and other can be used. Further, R 1 and 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, an alkyl group such as i- butyl it can be mentioned. In the same molecule, even these alkyl groups the same or may be different. Such alkoxides such as tetramethoxysilane Si (OCH 3 ) 4 , tetraethoxysilane Si (OC 2 H 5 ) 4 , tetrapropoxysilane Si (OC 3 H 7 ) 4 , tetrabutoxysilane Si (OC 4 H 9 ) 4 , and the like.
[0046]
　As the water-soluble polymer can be used in the barrier composition can be preferably used one or both of polyvinyl alcohol resin or ethylene-vinyl alcohol copolymer. These resins may be used commercially available ones, for example, as ethylene-vinyl alcohol copolymer, manufactured by Kuraray Co., EVAL EP-F101 (ethylene content: 32 mol%), manufactured by The Nippon Synthetic Chemical Industry Co., Ltd., Soarnol D2908 (ethylene content: 29 mol%) and the like can be used. Also, as polyvinyl alcohol, RS-110 is a RS polymer manufactured by Kuraray Co., Ltd. (saponification degree = 99%, degree of polymerization = 1,000), manufactured by the same company Kuraray Poval LM-20SO (saponification degree = 40%, degree of polymerization = 2,000), the Nippon Synthetic Chemical Industry GOSENOL NM-14 (saponification degree = 99% Co., Ltd., can be used the degree of polymerization = 1,400), and the like.
[0047]
　As the sol-gel method the catalyst is substantially insoluble in water, soluble tertiary amine is used and an organic solvent. Specifically, for example, N, N-dimethylbenzylamine, tripropylamine, tributylamine, may be used tripentylamine like. In particular, N, N-dimethyl base Njiruamin are preferred, alkoxysilane and silane coupling agent per 100 parts by weight per, for example, from 0.01 to 1.0 part by weight, in particular using about 0.03 parts by weight it is preferable to.
[0048]
　As the acid used in the barrier compositions, for example, sulfuric, hydrochloric, mineral acids such as nitric acid, and acetic, organic acids tartaric such like, may use other. The amount of acid, relative to the total molar amount of the alkoxysilane partial alkoxides and silane coupling agents (e.g., silicate moiety), preferably from 0.001 to 0.05 mol, more preferably 0.01 to 0 .03 is the mole.
　As the organic solvent, there can be used methyl alcohol, ethyl alcohol, n- propyl alcohol, isopropyl alcohol, n- butanol.
[0049]
　The silane coupling agent may be a known organic reactive group-containing organoalkoxysilane, in particular, organoalkoxysilane having an epoxy group is preferred, for example, .gamma.-glycidoxypropyltrimethoxysilane, γ- glycidoxypropylmethyldiethoxysilane or can be used beta-(3,4-epoxycyclohexyl) ethyltrimethoxysilane and the like. Silane coupling agents as described above may be used in admixture of two or more to one without. In the present invention, the amount of the silane coupling agent as described above can be used within the range of about 1 to 20 parts by weight per 100 parts by weight The above alkoxide.
[0050]
　The content of the water-soluble polymer barrier composition is preferably in the range of 5 to 500 parts by weight per 100 parts by weight of the total amount of the alkoxide. In the above, if it exceeds 500 parts by weight, the brittleness of the barrier coat layer formed becomes large, undesirable since it lowers also the weather resistance and the like.
[0051]
Barrier coat layer using the barrier coat layer forming coating solution, usually used, roll coating such as gravure roll coater, spray coating, spin coating, dipping, brushing, bar code, known means such as applicator by is formed by applying one or more times.
[0052]
　A specific example of a method for forming a barrier coat layer is described below.
　First, prepare an alkoxide, polyvinyl alcohol resin and / or an ethylene-vinyl alcohol copolymer, a sol-gel method the catalyst, water, organic solvents, and, by mixing the silane coupling agent, optionally a gas barrier coating solution to. Gradually polycondensation with the gas barrier coating liquid progresses.
　Then, on the deposited layer (film), by a conventional method, by coating the above-mentioned gas barrier coating solution in the usual way, and dried. Dried, the alkoxide and vinyl alcohol polymers (and a silane coupling agent) polycondensation is further progress of the layers of the composite polymer is formed. Preferably, it is also possible to repeat the above operation, stacking a plurality of composite polymer layer.
　Finally, the coating liquid laminate was coated with 20 ~ 250 ° C., preferably at temperatures of 50 - 220 ° C., it is heated for 1 second to 10 minutes. Thus, it is possible to form the barrier coat layer on the deposited layer.
[0053]
　Barrier coat layer may be a composite polymer layer overlaid with one or more layers. The thickness of the barrier coat layer after drying is in the range of 0.01 ~ 100 [mu] m, preferably 0.01 ~ 50 [mu] m. The thickness after drying can be suppressed and 100μm smaller, the occurrence of cracks.
[0054]
Print layer]
packaging material comprising a laminate of the present invention, if necessary, as shown in FIG. 3, for example, between the barrier coating layer and the adhesive layer, characters, figures, symbols, other desired pattern can be a provided a printing layer formed on any at ordinary printing scheme.
　Packaging material comprising a laminate and the laminate of the present invention, the barrier layer surface provided with a barrier layer on one side of the above-mentioned base layer surface and the sealant layer, deposited layer on one side of the substrate layer, a barrier coat layer the provided was a barrier coat layer side of the substrate layer and the barrier layer surface having a barrier layer on one side of the sealant layer, furthermore, on one side of the printing surface and the sealant layer of the base layer having a printed layer as required and a barrier layer surface provided with the barrier layer may each be prepared by laminating with an adhesive layer described above.
　The present invention will be specifically described by way of examples.
Example
[0055]
[Example 1]
Transparent deposited PET 12 / oxygen barrier adhesive / VM-CPP25
　as substrate layer, using polyethylene terephthalate (PET) film having a thickness of 12 [mu] m, further attached it to delivery roll of a plasma chemical vapor deposition apparatus and, then, under the following conditions, the corona-treated surface of the polyester resin, thereby forming a deposited film of silicon oxide having a thickness of 200 Å.
[0056]
　
　deposition surface: corona-treated surface
　of introduced gas: hexamethyldisiloxane: oxygen gas: helium 1.0: 3.0: 3.0 (unit: S1M)
　Vacuum chamber - vacuum in; 2 ~ 6 × 10 -6 mBar
　deposition chamber - the degree of vacuum: 2 ~ 5 × 10 -3 mBar
　cooling-electrode drum supply power: 10 kW
　line speed: 100 m / min
[0057]
　Then, immediately after forming the deposited film of silicon oxide film thickness 200 Å (20 nm) above, the vapor deposited film surface of the silicon oxide, using a glow discharge plasma generating apparatus, power 9 kW, oxygen gas: argon gas = 7.0: 2.5 (unit: S1M) using a mixed gas consisting of a mixed gas pressure of 6 × 10 -3 subjected to oxygen / argon mixed gas plasma treatment at Torr, the surface tension of the vapor deposited film surface of silicon oxide was to form a plasma treated surface with improved 54 dyne / cm or more.
[0058]
　Further, as a sealant layer, unstretched polypropylene (CPP) film having a thickness of 25μm using (2703, Toray Advanced Film Co., Ltd.), corona treatment on one side of the CPP film, then, aluminum evaporation on the corona-treated surface (film thickness 40 nm) to form a barrier layer, to prepare an aluminum deposited CPP film (sealant layer with a barrier layer).
[0059]
　Then, a barrier coat layer surface of the transparent deposited PET film having a barrier coat layer and a barrier layer surface of the aluminum-deposited CPP film having a barrier layer, the adhesive having an oxygen barrier property (PASLIM VM001 / VM102CP, DIC (Ltd.) was dry laminated through Ltd.). The coating amount of the adhesive used in this case, the thickness of the adhesive layer is 3 g / m as dry coating 2 was an amount that the. After the lamination, and aged for 3 days at 40 ° C., to obtain a laminate of Example 1.
[0060]
Example 2
Transparent deposited PET 12 / oxygen barrier adhesive / VM-PEF25
　as substrate layer, using polyethylene terephthalate (PET) film having a thickness of 12 [mu] m, one side of the PET film corona treated, then the corona-treated surface silica deposition in (thickness 40 nm), forming a barrier coat layer, silica-deposited transparent PET film (base layer having a barrier coat layer) was formed.
　Further, as a sealant layer of polyethylene having a thickness of 25 [mu] m (PE) film using (ML-TUX-F, Mitsui Chemicals Tohcello Co.), corona treatment on one side of the PE film, then, aluminum evaporation on the corona-treated surface (film thickness 40 nm) to form a barrier layer, to prepare aluminum-deposited PE film (sealant layer with a barrier layer).
　Then, a barrier coat layer surface of the transparent deposited PET film having a barrier coat layer and a barrier layer surface of the aluminum-deposited PE film with a barrier layer, the adhesive having an oxygen barrier property (PASLIM VM001 / VM102CP, DIC (Ltd.) was dry laminated through Ltd.). The coating amount of the adhesive used in this case, the thickness of the adhesive layer is 3 g / m as dry coating 2 was an amount that the. After the lamination, and aged for 3 days at 40 ° C., to obtain a laminate of Example 2.
[0061]
[Example 3]
Transparent PET 12 / oxygen barrier adhesive / VM-CPP25
　in Example 1, as a substrate layer, using the biaxially stretched PET (Toyobo T-4102), i.e., without the vapor-deposited layer and the barrier coat layer except for using the base layer to obtain a laminate of example 1 in the same manner as in example 3.
[0062]
[Example 4]
transparent deposited PET 12 / printed layer / oxygen barrier adhesive / VM-CPP25
　in Example 1, on the barrier coat layer, further non having a printing layer made of a urethane-based inks as in Example 1 to obtain a laminate of example 4 in.
[0063]
[Comparative Example 1]
Transparent deposited PET 12 / adhesive / VM-CPP25
　as substrate layer, using polyethylene terephthalate (PET) film having a thickness of 12 [mu] m, corona treatment on one side of the PET film, and then, silica deposited on the corona-treated surface (film thickness 40 nm) to form a barrier coat layer, silica-deposited transparent PET film (base layer having a barrier coat layer) was formed.
　Further, as a sealant layer, unstretched polypropylene having a thickness of 25 [mu] m (CPP) film using a (2703, Toray Advanced Film Co., Ltd.), one side of the CPP film was corona treated to produce a one-sided corona treated CPP film.
　Then, a barrier coat layer surface of the transparent deposited PET film with a barrier coating layer, and a corona-treated surface of the one side corona treated CPP film, two-component curing type urethane adhesive (RU-40 / H-4 , Rock Paint ( It was dry lamination via a Co., Ltd.)). The coating amount of the adhesive used in this case, the thickness of the adhesive layer is 3 g / m as dry coating 2 was an amount that the. After the lamination, and 3 days aged at 40 ° C., to obtain a laminate of Comparative Example 1.
[0064]
[Comparative Example 2]
transparent deposited PET 12 / adhesive / VM-PEF25
　as substrate layer, using polyethylene terephthalate (PET) film having a thickness of 12 [mu] m, corona treatment on one side of the PET film, and then, silica deposited on the corona-treated surface (film thickness 40 nm) to form a barrier coat layer, silica-deposited transparent PET film (base layer having a barrier coat layer) was formed.
　Further, produced as a sealant layer of polyethylene having a thickness of 25 [mu] m (PE) film using (ML-TUX-F, Mitsui Chemicals Tohcello Co.), one side of the PE film was corona treated, one side corona treated PE film did.
　Then, a barrier coat layer surface of the transparent deposited PET film with a barrier coating layer, and a corona-treated surface of the one side corona treated PE film, two-component curing type urethane adhesive (RU-40 / H-4 , Rock Paint ( It was dry lamination via a Co., Ltd.)). The coating amount of the adhesive used in this case, the thickness of the adhesive layer is 3 g / m as dry coating 2 was an amount that the. After the lamination, and 3 days aged at 40 ° C., to obtain a laminate of Comparative Example 2.
[0065]
[Comparative Example 3]
Transparent deposited PET 12 / micronized and silicon oxide, the adhesive / VM-PEF25 comprising aluminum oxide
　in Example 1, an adhesive having an oxygen barrier property (PASLIM VM001 / VM102CP, manufactured by DIC (Ltd.)) the terephthalic acid and ethylene glycol, the acetate solution 90 parts by weight of the polycondensation by a number average molecular weight of 25,000 of the polyester polyol obtained (40% solids) of 1,6-hexanediol, respectively than 10 nm, the 15nm by a wet crusher microparticulated silicon oxide, a mixture of aluminum oxide particles added 10 wt% of the polyester polyol resin, then 1 mole of trimethylolpropane and a urethane adduct acetate solution obtained by reacting 3 moles of tolylene diisocyanate (solid content 75 %) were mixed 10 parts by weight, further Except for using a urethane-based barrier adhesives obtained by adding 117 parts by weight of ethyl acetate in the same manner as in Example 1 to obtain a laminated body of Comparative Example 3.
[0066]
[Comparative Example 4]
transparent deposited PET 12 / oxygen barrier adhesive / PE / VM-CPP25
　in Example 1, the barrier coating layer surface of the transparent deposited PET film with a barrier coating layer, so that the thickness after drying of 3μm adhesive having an oxygen barrier property is coated (PASLIM vM001 / VM102CP, DIC (Ltd.)) was melt-extruded polyethylene so that further thickness 15μm on the coating surface, melt extrusion surface of the polyethylene and the barrier layer except laminated with the barrier layer surface of the aluminum-deposited CPP film having a can, to obtain a laminate of Comparative example 4 in the same manner as in example 1.
[0067]
[Laminate strength]
Each laminate obtained in Examples 1-4 and Comparative Examples 1-4, respectively cut a strip to the width of the specimen of 15 mm, Tensilon tensile tester (KK Orientech manufactured RTC-1310A ) using, under 25 ° C. atmosphere, the T-peel method (pulling rate 50 mm / min), to measure the maximum load when peeling the substrate layer and the sealant layer, and the laminate strength (N / 15 mm). The results shown in Table 1 below.
[0068]
[Table 1]

[0069]
　Was then measured and the first to fourth embodiments, the oxygen barrier property of the resulting laminate in Comparative Examples 1 to 4 and the water vapor barrier properties. The measurement of the oxygen barrier property, USA, using a MOCON Co. OXTRAN2 / 20, 23 ℃, oxygen permeability under the conditions of 90% RH (cc / m 2 a · day · atm), the water vapor barrier property for the measurement, USA, using a MOCON Co. PERMATRAN3 / 31, 40 ℃, water vapor permeability under conditions of 90% RH (g / m 2 a · day · atm) was measured. The results are shown in Table 2.
[0070]
[Table 2]

[0071]
　Furthermore, the examples 1-4, each laminate obtained in Comparative Examples 1-4 was cut into A4 size, after giving the load of three bent Gelbo flex tester, each in the same manner as described above oxygen barrier property of the laminate (23 ° C., the oxygen permeability under conditions of 90% RH (cc / m 2 · day · atm) and water vapor barrier properties (40 ° C., the water vapor transmission rate under the conditions of RH 90% (g / m 2 was measured · day · atm) and. Table 3 shows the results.
[0072]
[table 3]

[0073]
　By using an adhesive having an oxygen barrier property, comparable laminate strength was observed as compared to when using conventional two-component curable urethane adhesive. Further, it was confirmed that an oxygen barrier property, oxygen barrier property superior barrier performance, especially when given load bending the laminate film of a laminate film structure using a deposition film as a barrier layer.

The scope of the claims
[Requested item 1]
　Base layer, an adhesive layer, a barrier layer, a laminate having at least a sealant layer, a laminate wherein the adhesive layer is characterized by having an oxygen barrier property.
[Requested item 2]
　The laminate according to claim 1, between the base layer and the adhesive layer, and having a deposited layer, a barrier coat layer.
[Requested item 3]
　Laminate according to claim 2, characterized in that it comprises a print layer between the barrier coat layer and the adhesive layer.
[Requested item 4]
　Packaging material for the substrate layer, an adhesive layer, a barrier layer, composed of a multilayer structure having at least a sealant layer, wherein the adhesive layer has an oxygen barrier property.
[Requested item 5]
　Between the base layer and the adhesive layer, the packaging material according to claim 4, characterized in that a laminate having a vapor deposition layer, a barrier coat layer.
[Requested item 6]
　Packaging material according to claim 5, characterized in that a laminate having a print layer between the barrier coat layer and the adhesive layer.
[Requested item 7]
　The deposition layer, the packaging material according to claim 5 or 6, wherein the aluminum deposited film, an alumina deposited film, that consists of one of silica-deposited film.
[Requested item 8]
　Packaging material according to any one of claims 4-7, wherein the barrier layer, characterized in that an aluminum deposited film.
[Requested item 9]
　Packaging material according to any one of claims 4-8, wherein the thickness of the barrier layer is 1 ~ 100 nm.
[Requested item 10]
　Packaging material according to any one of claims 4-9, wherein the coating amount of the adhesive of the adhesive layer is 2.0 .mu.m ~ 4.0 .mu.m.
[Requested item 11]
　Wherein the laminate, 23 ° C., the oxygen permeability under 90% RH environment, 0.05 ~ 1.00 cc / m 2 any of claims 4 to 10, which is a · day · atm packaging material according to.
[Requested item 12]
　Wherein the laminate, after giving the load of three bent Gelbo flex tester, of the laminate, 23 ° C., the oxygen permeability under 90% RH environment, from before applying a load of the bent increment value is 0.7 ~ 4.0 cc / m 2 packaging material according to any one of claims 4 to 11, which is a · day · atm.