Title of invention: Adhesive resin composition and laminate
Technical field
[0001]
　The present invention relates to an adhesive resin composition and a laminate. Specifically, the present invention comprises an adhesive resin composition having high adhesiveness to a gas barrier resin, and a layer containing the adhesive resin composition, which has a high barrier property. Regarding the body.
Background technology
[0002]
　Polyethylene is widely used as packaging and containers for various foods and chemicals because it has excellent transparency, flexibility, hygiene, processability, etc., and is inexpensive.
　Since polyethylene has high gas permeability, it cannot be used alone as a packaging or container. For this reason, polyethylene is often used as a packaging or container after laminating another material having a high gas barrier property, for example, a gas barrier resin such as polyamide or an ethylene / vinyl alcohol copolymer. Further, since polyethylene is a non-polar material and has almost no adhesive strength, various improvements have been made in laminating polyethylene with a gas barrier resin.
[0003]
　For example, in Patent Document 1, a layer of a polyethylene resin composition containing an ethylene-based polymer and a modified ethylene-based polymer and a layer of a saponified product of an ethylene-vinyl acetate copolymer, a polyamide, a polyester, or the like are laminated. The laminate is disclosed. Patent Document 1 describes that the resin composition has excellent adhesiveness to other resins, and the adhesiveness is not deteriorated by heat, water, salt water, or the like.
[0004]
　On the other hand, with the increasing demand for reduction of food loss in recent years, the trend toward higher barriers for food packaging materials is progressing, and higher barrier properties are required for gas barrier resins such as ethylene / vinyl alcohol copolymers. In order to meet this demand, in recent years, there has been an increasing tendency to lower the ethylene of gas barrier resins to enhance the gas barrier.
[0005]
　However, ethylene / vinyl alcohol copolymers, which are gas barrier resins, become rigid and brittle when the ethylene content is lowered. Therefore, an additive (styrene elastomer, etc.) is added to the ethylene / vinyl alcohol copolymer, etc. for softening. Measures have been taken (Patent Documents 2 and 3). However, in that case, since the additive hinders the adhesion to polyethylene, there are increasing cases where the adhesive force between polyethylene and the gas barrier resin is insufficient with the conventional adhesive resin.
Prior art literature
Patent documents
[0006]
Patent Document 1: Japanese Patent Application
Laid-Open No. 59-066351 Patent Document 2: Japanese Patent Application Laid-Open No. 2010-254966
Patent Document 3: Japanese Patent Application Laid-Open No. 2011-202147
Outline of the invention
Problems to be solved by the invention
[0007]
　An object of the present invention is to provide an adhesive resin having excellent adhesive strength with a gas barrier resin such as an ethylene / vinyl alcohol copolymer.
Means to solve problems
[0008]
　The present invention that achieves the above object is the following [1] to [9].
[0009]
[1] Adhesion containing an ethylene polymer (A) containing an ethylene polymer graft-modified with an unsaturated carboxylic acid or a derivative thereof, and satisfying the following requirements (1) to (4). Sex resin composition.
(1) The melt flow rate (MFR) measured based on ASTM D 1238 at a temperature of 190 ° C. and a load of 2160 g is 0.1 to 3 g / 10 minutes.
(2) The density is 910 to 930 kg / m 3 .
(3) In the crystallization elution fractional chromatography measurement, the ratio of the eluted components at 50 ° C. or lower is 20% by mass or more.
(4) In the crystallization elution fractional chromatography measurement, the ratio of the eluted components at 90 ° C. or higher is 25% by mass or more.
[2] The ethylene-based polymer (A) is 20 to 40% by mass of the following ethylene-based polymer (A1) and 60 to 80% by mass of the ethylene-based polymer (A2) [however, the ethylene-based polymer (A) The total of A1) and the ethylene-based polymer (A2) is 100% by mass], and at least one of the ethylene-based polymer (A1) and the ethylene-based polymer (A2) is an unsaturated carboxylic acid. The adhesive resin composition according to [1], which comprises an ethylene-based polymer graft-modified with a derivative thereof.
(A1) An ethylene polymer having a density of 930 to 965 kg / m 3 and a melt flow rate (MFR) of 0.1 to 10 g / 10 min at a temperature of 190 ° C. and a load of 2160 g as measured based on ASTM D 1238. ..
(A2) Density is 858-929 kg / m 3 is an ethylene polymer having a melt flow rate (MFR) of 0.1 to 10 g / 10 min at a temperature of 190 ° C. and a load of 2160 g as measured based on ASTM D 1238.
[3] A layer (I) containing an ethylene-based polymer, an adhesive layer (II) containing the adhesive resin composition according to [1] or [2], and a layer containing an ethylene / vinyl alcohol copolymer ( It is characterized in that a layer (IV) containing III) and / or a polyamide resin is laminated, and the layer (II) is in direct contact with at least one of the layer (III) and the layer (IV). Laminated body.
[4] The ethylene-vinyl alcohol copolymer is a polymer obtained by saponifying an ethylene-vinyl acetate copolymer having a structural unit content of 20 to 30 mol% derived from ethylene, according to [3]. The laminate described.
[5] The laminate according to claim 3, wherein the layer (III) further contains 10 to 40% by mass of a styrene-based elastomer.
[6] Any of [3] to [5], wherein the above-mentioned polyamide resin contains at least one of nylon 6, nylon 66, nylon 610, nylon 12, nylon 11, MXD nylon, amorphous nylon, and copolymerized nylon. The laminate described in.
[7] A film containing the laminate according to any one of [3] to [6].
[8] A bag obtained from the film according to [7].
[9] A packaging container containing the laminate according to any one of [3] to [6].
Effect of the invention
[0010]
　The adhesive resin composition of the present invention has excellent adhesive strength to gas barrier resins such as ethylene / vinyl alcohol copolymers. Therefore, in the laminate containing the adhesive layer containing the adhesive resin composition and the gas barrier resin layer in direct contact with the adhesive layer, an additive is added to the gas barrier resin layer for softening. Even in such a case, since the two layers are firmly adhered to each other, peeling is unlikely to occur between the two layers. Therefore, the laminate can be effectively used as packaging, containers, and the like having high barrier properties.
Mode for carrying out the invention
[0011]

　The adhesive resin composition of the present invention contains an ethylene polymer (A) containing an ethylene polymer graft-modified with an unsaturated carboxylic acid or a derivative thereof.
[0012]
　As a preferred embodiment of the ethylene-based polymer (A), the ethylene-based polymer (A) contains the following ethylene-based polymer (A1) and the ethylene-based polymer (A2), and the ethylene-based polymer (A) is contained. At least one of A1) and (A2) contains an ethylene-based polymer graft-modified with an unsaturated carboxylic acid or a derivative thereof.
(A1) An ethylene polymer having a density of 930 to 965 kg / m 3 and a melt flow rate (MFR) of 0.1 to 10 g / 10 min at a temperature of 190 ° C. and a load of 2160 g as measured based on ASTM D 1238. ..
(A2) An ethylene polymer having a density of 858 to 929 kg / m 3 and a melt flow rate (MFR) of 0.1 to 10 g / 10 min at a temperature of 190 ° C. and a load of 2160 g as measured based on ASTM D 1238. ..
[0013]
　The ethylene polymer (A1) has a density of 930 to 965 kg / m 3 , preferably 940 to 965 kg / m 3 .
By using the ethylene polymer (A1) having a density in this range, it is easy to obtain an adhesive resin composition having excellent adhesiveness.
[0014]
　The ethylene polymer (A1) has a melt flow rate (MFR) of 0.1 to 10 g / 10 min, preferably 0.2 to 8 g / 10 at 190 ° C. and a load of 2160 g, as measured based on ASTM D 1238. Minutes. The polymer having an MFR of less than 0.1 g / 10 minutes may make it difficult to extrude the obtained adhesive resin composition, and the pressure may increase to exceed the limit pressure of the molding machine. On the other hand, in the case of a polymer having an MFR of more than 10 g / 10 minutes, when the obtained adhesive resin composition is molded, the uniformity of the thickness of the molded product tends to be poor, and the molecular weight becomes too low, resulting in a laminate. There is a risk that the impact strength of the plastic will decrease.
[0015]
　Ethylene polymer (A2) has a density of ~ 929Kg 858 / m 3 is preferably 865 ~ 925 kg / m 3 is. By using the ethylene polymer (A2) having a density in this range, it is easy to obtain an adhesive resin composition having excellent adhesiveness.
[0016]
　The ethylene polymer (A2) has a melt flow rate (MFR) of 0.1 to 10 g / 10 minutes, preferably 0.5 to 7 g / 10 at 190 ° C. and a load of 2160 g, as measured based on ASTM D 1238. Minutes. The polymer having an MFR of less than 0.1 g / 10 minutes may make it difficult to extrude the obtained adhesive resin composition, and the pressure may increase to exceed the limit pressure of the molding machine. On the other hand, in the case of a polymer having an MFR of more than 10 g / 10 minutes, when the obtained adhesive resin composition is molded, the uniformity of the thickness of the molded product tends to be poor, and the molecular weight becomes too low, resulting in a laminate. There is a risk that the impact strength of the plastic will decrease.
[0017]
　At least one of the ethylene-based polymers (A1) and (A2) contains an ethylene-based polymer graft-modified with an unsaturated carboxylic acid or a derivative thereof. That is, the ethylene-based polymer (A1) contains the modified ethylene-based polymer, the ethylene-based polymer (A2) does not contain the modified ethylene-based polymer, and the ethylene-based polymer (A1) contains the modified ethylene-based polymer. Examples thereof include a mode in which the ethylene-based polymer (A2) contains a modified ethylene-based polymer, and a mode in which both the ethylene-based polymer (A1) and the ethylene-based polymer (A2) contain a modified ethylene-based polymer.
[0018]
　When the ethylene-based polymer (A1) or (A2) contains a modified ethylene-based polymer, the graft amount of the unsaturated carboxylic acid or its derivative in each of the ethylene-based polymers (A1) and (A2) is usually 0. It is in the range of .01 to 10% by mass, preferably 0.02 to 5% by mass. If the amount of graft is less than 0.01% by mass, the adhesive strength may not be sufficient, and if it is more than 10% by mass, a cross-linking reaction is likely to occur, and the quality of the obtained modified ethylene polymer is difficult to stabilize.
[0019]
　Examples of the unsaturated carboxylic acid or a derivative thereof include acrylic acid, maleic acid, fumaric acid, tetrahydrophthalic acid, itaconic acid, citraconic acid, crotonic acid, isocrotonic acid, and nagic acid (endosis-bicyclo [2.2.1]. ] Unsaturated carboxylic acids such as hepto-5-ene-dicarboxylic acid); or derivatives thereof, such as acid halides, amidimides, anhydrides, esters and the like. Specific examples of such derivatives include maleyl chloride, maleimide, maleic anhydride, citraconic anhydride, monomethyl maleate, dimethyl maleate, glycidyl maleate and the like. Among these, unsaturated dicarboxylic acids and their acid anhydrides are preferable, and maleic acid, nadic acid and their acid anhydrides are particularly preferable.
[0020]
　The modified ethylene polymer can be produced by various known methods. For example, an ethylene polymer is dissolved in an organic solvent, and then an unsaturated carboxylic acid or a derivative thereof and, if necessary, a radical initiator such as an organic peroxide are added to the obtained solution, and the temperature is usually 60 to 350 ° C. The reaction is preferably carried out at a temperature of 80 to 190 ° C. for 0.5 to 15 hours, preferably 1 to 10 hours, or using an extruder or the like, in a solvent-free manner, with an ethylene polymer and an unsaturated carboxylic peroxide. A method may be adopted in which an acid or a derivative thereof and, if necessary, a radical initiator such as an organic peroxide are added and the reaction is usually carried out at a temperature equal to or higher than the melting point of the ethylene polymer, preferably 120 to 350 ° C. for 0.5 to 10 minutes. ..
[0021]
　The non-modified ethylene-based polymer contained in the ethylene-based polymer (A1) and the ethylene-based polymer (A2), which is not a modified ethylene-based polymer, and the ethylene-based polymer before modification in the modified ethylene-based polymer are It is a homopolymer of ethylene or a copolymer of ethylene and α-olefin. Examples of the α-olefin include α-olefins having 3 or more carbon atoms, preferably 3 to 10 carbon atoms, and specifically, propylene, 1-butene, 1-pentene, 1-hexene, 1-octene, and the like. Examples thereof include 1-decene, 4-methyl-1-pentene and a combination of two or more thereof. The copolymerization amount of the α-olefin is not particularly limited as long as the obtained density is within the above range, but is usually 10 mol% or less. The density of the ethylene-based polymer before modification is not particularly limited as long as the density of the obtained modified ethylene-based polymer is within the above range.
[0022]
　The ethylene-based polymer before modification can be produced by a known method, for example, a high-pressure method or a low-pressure method using a Ziegler-type Ti-based catalyst, a Co-based catalyst, a metallocene-based catalyst, or the like.
[0023]
　The content ratio of the ethylene polymer (A1) and the ethylene polymer (A2) in the ethylene polymer (A) is 100% by weight of the total of the ethylene polymer (A1) and the ethylene polymer (A2). % Is preferably 20 to 40% by mass of the ethylene-based polymer (A1) and 60 to 80% by mass of the ethylene-based polymer (A2), and 23 to 37% by mass of the ethylene-based polymer (A1) and an ethylene-based weight. The coalescence (A2) is more preferably 63 to 77% by mass. When the content ratio of the ethylene-based polymer (A1) and the ethylene-based polymer (A2) is within the above range, the adhesive strength of the adhesive resin composition is more strongly expressed.
[0024]
　The ethylene-based polymer (A1) and the ethylene-based polymer (A2) may each contain one type of ethylene-based polymer alone, or may contain two or more types of ethylene-based polymers.
　When the ethylene-based polymer (A1) contains two or more kinds of ethylene-based polymers, the two or more kinds of ethylene-based polymers have the requirements of density and melt flow rate described for the above-mentioned ethylene-based polymer (A1), respectively. Meet.
　Even when the ethylene-based polymer (A2) contains two or more kinds of ethylene-based polymers, the two or more kinds of ethylene-based polymers have the same density and melt flow rate as those of the above-mentioned ethylene-based polymer (A2), respectively. Meet the requirements.
[0025]
　The adhesive resin composition of the present invention satisfies the following requirements (1) to (4).
(1) The melt flow rate (MFR) measured based on ASTM D 1238 at a temperature of 190 ° C. and a load of 2160 g is 0.1 to 3 g / 10 minutes, preferably 0.5 to 2 g / 10 minutes. When the melt flow rate is within the above range, an adhesive resin composition having good moldability can be obtained.
(2) density of 910 ~ 930 kg / m 3 is preferably 913 ~ 927 kg / m 3 is, more preferably 914 ~ 925 kg / m 3 is, more preferably 915 ~ 920 kg / m 3 is. When the adhesive resin composition having a density of less than 910 kg / m 3 is used, for example, in a container or the like, the mechanical strength may decrease, and the interlayer adhesive force at a high temperature of 80 ° C. or higher tends to decrease. .. When an adhesive resin composition having a density exceeding 930 kg / m 3 is used for a laminate with, for example, an ethylene / vinyl alcohol copolymer, the interlayer adhesive strength tends to be unstable, and the low-temperature drop impact strength of the laminate is high. Tends to decline.
(3) In the crystallization elution fractional chromatography (CEF) measurement, the ratio of the eluted components at 50 ° C. or lower is 20% by mass or more, preferably 23% by mass or more. The ratio of the eluted components at 50 ° C. or lower is preferably 45% by mass or less, and more preferably 40% by mass or less.
(4) In the crystallization elution fractional chromatography (CEF) measurement, the ratio of the eluted components at 90 ° C. or higher is 25% by mass or more, preferably 28% by mass or more. The ratio of the eluted components at 90 ° C. or higher is preferably 45% by mass or less, and more preferably 40% by mass or less.
[0026]
　By satisfying the above requirements (3) and (4) for the crystallization elution fractional chromatography measurement, the adhesive strength of the adhesive resin composition is more strongly exhibited. Those skilled in the art can appropriately adjust the ratio of the above-mentioned eluted components in the crystallization elution fractional chromatography measurement.
[0027]
　The adhesive resin composition of the present invention can be prepared by using various known methods, for example, ethylene-based polymer (A1) and ethylene-based polymer (A2) in the above ratio range by a Henschel mixer, a tumbler blender, a V-blender or the like. It can be prepared by a method of dry blending, a method of dry blending and then melt-kneading with a single-screw extruder, a multi-screw extruder, a Banbury mixer or the like, a method of stirring and mixing in the presence of a solvent, and the like.
[0028]
The adhesive resin composition of the present invention contains commonly used antioxidants, weather stabilizers, antistatic agents, antifogging agents, antiblocking agents, lubricants, nucleating agents, pigments, etc., as long as the object of the present invention is not impaired. Additives or other polymers, rubber, etc. can be contained as required.
[0029]

　The laminate of the present invention includes a layer (I) containing an ethylene polymer, an adhesive layer (II) containing the adhesive resin composition, and a layer (III) containing an ethylene / vinyl alcohol copolymer. ) And / or a layer (IV) containing a polyamide resin is laminated, and the layer (II) is in direct contact with at least one of the layer (III) and the layer (IV).
[0030]
　In the laminate of the present invention, a regrind layer (V) can be further present between the layer (I) containing the ethylene polymer and the adhesive layer (II). The regrind layer (V) is a burr portion (unnecessary portion) generated when molding a laminate, a recovered product (scrap) of the laminate, a defective product generated during molding, etc., if necessary. This layer is made by melting and kneading the pulverized product with an extruder or the like (grind). The regrind layer (V) does not have to consist only of the recovered product, and the regrind layer (V) can be blended with, for example, the ethylene polymer used in the layer (I) to improve mechanical properties. ..
[0031]
　Additives known per se such as fillers, stabilizers, lubricants, antistatic agents, flame retardants, foaming agents, etc. are blended into each of the above layers constituting the laminate of the present invention as long as the object of the present invention is not impaired. be able to.
[0032]
　The ethylene-based polymer contained in the layer (I) is a homopolymer of ethylene or a random copolymer of ethylene and α-olefin. The copolymerization amount of the α-olefin is not particularly limited as long as the density of the ethylene-based polymer is within the following range, but is usually preferably 10 mol% or less, and more preferably 5 mol% or less. preferable. The α-olefin is preferably an α-olefin having 3 to 10 carbon atoms, and specifically, for example, propylene, 1-butene, 1-hexene, 4-methyl-1-pentene, 1-octene, 1-decene and the like. Can be mentioned.
[0033]
　The melt flow rate (MFR) of the ethylene-based polymer [ASTM D 1238 (temperature: 190 ° C., load: 2160 g load)] is preferably 0.01 to 5.0 g / 10 minutes, more preferably 0.05. The range is ~ 4 g / 10 minutes. The density of the ethylene polymer is preferably in the range of 940 to 980 kg / m 3 , more preferably 950 to 970 kg / m 3 . When an ethylene polymer having an MFR larger than the above range is used, the impact strength in the case of a laminated body may not be sufficient. On the other hand, ethylene-based polymers having an MFR smaller than the above range tend to be difficult to be extruded. When an ethylene polymer having a density lower than the above range is used, the permeability of the obtained laminate may be inferior.
[0034]
　The layer (III) and the layer (IV) are gas barrier resin layers.
　The ethylene-vinyl alcohol copolymer (hereinafter, also referred to as EVOH) contained in the layer (III) preferably has an ethylene-vinyl acetate copolymer weight of 20 to 30 mol%, preferably 22 to 29 mol%. Obtained by converting coalescence into Ken. The degree of saponification is not particularly limited, but is, for example, 90 to 100%, preferably 95 to 100%. A saponified product having an ethylene content of less than 20 mol% has a melting point and a decomposition temperature close to each other, and may be difficult to disperse finely in an ethylene polymer. Further, if the ethylene content becomes too large, the barrier property may be lowered and the object of the present invention may not be met.
[0035]
　The EVOH contained in the layer (III) may be a polymer further containing 10 to 40% by mass of a styrene-based elastomer. By containing the styrene-based elastomer in the layer (III), it is possible to impart flexibility of the film while maintaining excellent gas barrier properties.
[0036]
　Specific examples of the styrene-based elastomer include styrene-butadiene-styrene block copolymer (SBS), styrene-isoprene-styrene block copolymer (SIS), SBS hydrogenated block copolymer (SEBS), and SIS. Hydrogenated block copolymer (SEPS), block copolymer obtained by hydrogenating the vinyl bond portion of the butadiene block of SBS (SBBS), styrene-isobutylene-styrene triblock copolymer (SIBS), styrene-ethylene-butylene- Crystalline polyolefin block copolymer (SEBC) and the like can be mentioned. Of these, SEBS, which is excellent in thermal stability and weather resistance, is preferably used. In SEBS, the polybutadiene block is a copolymer block of ethylene and butylene by hydrogenation.
[0037]
　Examples of the polyamide contained in the layer (IV) include nylon 6, nylon 66, nylon 610, nylon 12, nylon 11, MXD nylon, amorphous nylon, and copolymerized nylon.
[0038]
　The layer structure of the laminate of the present invention is, for example, a layer (I) containing an ethylene polymer (hereinafter abbreviated as “PE layer (I)”) / an adhesive layer (II) containing an adhesive resin composition. (Hereinafter abbreviated as "adhesive layer (II)") / layer containing an ethylene / vinyl alcohol copolymer (hereinafter abbreviated as "EVOH layer") (III), and PE layer (I) / adhesive layer (hereinafter abbreviated as "adhesive layer (II)"). II) / A three-layer structure of a layer containing a polyamide resin (hereinafter, abbreviated as “NY layer”) (IV) can be mentioned.
[0039]
　Other than that,
　PE layer (I) / regrind layer (V) / adhesive layer (II) / EVOH layer (III), PE layer (I) / regrind layer (V) / adhesive layer (II) / NY layer (IV), PE layer (I) / adhesive layer (II) / EVOH layer (III) / adhesive layer (II), PE layer (I) / adhesive layer (II) / NY layer (IV) / adhesive layer (II) ) 4 layer structure;
　PE layer (I) / regrind layer (V) / adhesive layer (II) / EVOH layer (III) / adhesive layer (II), PE layer (I) / regrind layer (V) / Adhesive layer (II) / NY layer (IV) / Adhesive layer (II), PE layer (I) / Adhesive layer (II) / EVOH layer (III) / Adhesive layer (II) / PE layer (I), PE layer (I) / Adhesive layer (II) / NY layer (IV) / Adhesive layer (II) / PE layer (I) 5-layer structure;
　PE layer (I) / Regrind layer (V) / Adhesive layer (II) / EVOH layer (III) / adhesive layer (II) / PE layer (I), PE layer (I) / regrind layer (V) / adhesive layer (II) / NY layer (IV) / adhesive layer (II) / 6-layer structure of
　PE layer (I) ; PE layer (I) / regrind layer (V) / adhesive layer (II) / EVOH layer (III) / adhesive layer (II) / regrind layer (V) / PE layer 7 layers (I), PE layer (I) / regrind layer (V) / adhesive layer (II) / NY layer (IV) / adhesive layer (II) / regrind layer (V) / PE layer (I) A layered structure such as a structure can be taken.
[0040]
　The laminate of the present invention can be produced by a known molding method such as coextrusion film molding, sheet molding, coating, blowing, or extrusion laminating.
　The laminate of the present invention has excellent gas barrier properties, and exhibits excellent interlayer adhesive strength, durability, and heat-resistant adhesiveness. Since the laminate of the present invention has such characteristics, it can be used for various purposes. For example, a film containing the laminate can be produced from the laminate of the present invention, and a bag can be obtained from the film. In addition, a packaging container containing the laminate can be produced from the laminate of the present invention.
Example
[0041]
　Next, the present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples as long as the gist of the present invention is not exceeded.
　The physical properties of Examples and Comparative Examples were measured by the following measurement methods.
(1) Melt flow rate (MFR) (g / 10 minutes) The
　melt flow rate was measured at a temperature of 190 ° C. and a load of 2160 g in accordance with ASTM D 1238.
(2) Density (kg / m 3 ) The
　density was measured according to ASTM D 1505.
(3) Ratio of eluted components at 50 ° C or lower (%) and ratio of eluted components at 90 ° C or higher (%) The ratio of eluted components at
　50 ° C or lower and the ratio of eluted components at 90 ° C or higher are crystals. It was measured by chemical elution fractional chromatography (CEF), and was determined from the ratio of the peak area of ​​the component eluted at 50 ° C or lower and the peak area of ​​the component eluted at 90 ° C or higher to the total peak area.
(4) Adhesive strength (N / 15 mm)
　The initial adhesive strength of the laminate is a layer containing the adhesive layer (II) on the inner layer side and the ethylene / vinyl alcohol copolymer by cutting out a sample with a width of 15 mm from the side surface side of the laminate. The adhesive strength with (III) was measured in a constant temperature bath at 23 ° C. The measurement method of the peeling test was the T-peeling method, and the peeling speed was 300 mm / min. This measurement was performed 5 times, and the average of the obtained values ​​was taken as the adhesive strength of the laminate.
(5) Melting point (° C)
　The melting point was measured by DSC. Specifically, about 5-10 mg of a sample is packed in a special aluminum pan, the temperature is raised from 30 ° C. to 200 ° C. at 500 ° C./min, the temperature is maintained at 200 ° C. for 10 minutes, and then the temperature from 200 ° C. to 30 ° C. is 10 ° C. The melting point was determined from the endothermic curve when the temperature was lowered at / min, held at 30 ° C. for another 1 minute, and then raised at 10 ° C./min.
[0042]
　The ethylene-based polymers used in Examples and Comparative Examples are PE-0, PE-1, PE-2, PE-3, PE-4, and PE-5 (hereinafter, polyethylene-based polymers (PE-0), respectively). ~ (Also referred to as PE-5)) is shown in Table 1. All of these ethylene-based polymers were prepared by polymerizing according to a conventional method. Further, in Table 1, the amount of MAH means the amount of graft of maleic anhydride used as an unsaturated carboxylic acid or a derivative thereof, and the content of comonomer is derived from comonomer in all structural units constituting the ethylene polymer. It means the molar ratio of structural units.
[0043]
[table 1]

[0044]
[Example 1]
　Ethylene-based polymer (A1), 9% by mass of ethylene-based polymer (PE-0), 26% by mass of ethylene-based polymer (PE-5), and ethylene-based polymer (A2). An adhesive resin composition (1) is obtained by melt-mixing a mixture containing 35% by mass of an ethylene-based polymer (PE-2) and 30% by mass of an ethylene-based polymer (PE-3) with a uniaxial extruder. Got The obtained adhesive resin composition (1) had a density of 0.919 g / cm 3 and an MFR of 0.8 g / 10 min at 190 ° C. and a 2.16 kg load according to ASTM D1238.
[0045]
　Using the adhesive resin composition (1), a laminate (film) consisting of five layers was produced by coextrusion molding under the following molding conditions. The interlayer adhesive strength (peeling strength) between the EVOH layer (III) of the obtained five-layer film and the adhesive layer (II) composed of the adhesive resin composition (1) was measured by the above method. The results are shown in Table 2.
[0046]
　
　Layer structure:
　LLDPE layer (I) / adhesive layer (II) / EVOH layer (III) / adhesive layer (II) / LLDPE layer (I)
　layer thickness: LLDPE layer (I) 350 μm
　　　　　　adhesion Layer (II) 20 μm
　　　　　　EVOH layer (III) 20 μm
　T-die molding machine: LLDPE layer (I) Die diameter 40 mmφ extruder, set temperature 220 ° C
　　　　　　adhesive layer (II) Die diameter 40 mmφ extruder, set temperature 220 ° C
　　　　　　EVOH layer ( III) Die diameter 30 mmφ extruder, set temperature 220 ° C.
　Molding speed: 1.5 m / min As the
　LLDPE layer (I), the following layer made of LLDPE was used.
　As the EVOH layer (III), the following layer made of EVOH1 or EVOH2 was used to produce a laminated body containing the EVOH layer (III) made of EVOH1 and a laminated body containing the EVOH layer (III) made of EVOH2.
　EVOH1: Ethylene vinyl alcohol copolymer (ethylene content 27 mol%, SEBS 25% by mass, MFR 1.3 g / 10 minutes)
EVOH2: Ethylene vinyl alcohol polymer (ethylene content 44 mol%, MFR 1.7 g) / 10 minutes)
　LLDPE: Linear low density polyethylene (Prime polymer Ethylene2021L)　
[0047]
[Example 2, Comparative Examples 1 to 4] For
　Example 2 and Comparative Examples 1 to 4, the adhesive resin composition was prepared in the same manner as in Example 1 except that the formulation was changed as shown in Table 2. Prepared. A laminate was produced in the same manner as in Example 1 using the obtained adhesive resin composition, and the adhesive strength thereof was measured. The results are shown in Table 2.
[0048]
[Table 2]

[0049]
　As shown in Table 2, in the CEF measurement, the laminates obtained in Examples 1 to 3 having an elution amount of 90 ° C. or higher of 25% or more and an elution amount of 50 ° C. or lower of 20% or more , Showed good adhesive strength with respect to EVOH1. On the other hand, in the CEF measurement, Comparative Examples 1 to 5 in which the elution amount at 90 ° C. or higher was less than 25% or the elution amount at 50 ° C. or lower was less than 20% had low adhesive strength to EVOH1.
The scope of the claims
[Claim 1]
　An adhesive resin composition containing an ethylene polymer (A) containing an ethylene polymer graft-modified with an unsaturated carboxylic acid or a derivative thereof, and satisfying the following requirements (1) to (4). Stuff.
(1) The melt flow rate (MFR) measured based on ASTM D 1238 at a temperature of 190 ° C. and a load of 2160 g is 0.1 to 3 g / 10 minutes.
(2) The density is 910 to 930 kg / m 3 .
(3) In the crystallization elution fractional chromatography measurement, the ratio of the eluted components at 50 ° C. or lower is 20% by mass or more.
(4) In the crystallization elution fractional chromatography measurement, the ratio of the eluted components at 90 ° C. or higher is 25% by mass or more.
[Claim 2]
　The ethylene-based polymer (A) is 20 to 40% by mass of the following ethylene-based polymer (A1) and 60 to 80% by mass of the ethylene-based polymer (A2) [however, the ethylene-based polymer (A1) and The total with the ethylene-based polymer (A2) is 100% by mass], and at least one of the ethylene-based polymer (A1) and the ethylene-based polymer (A2) is an unsaturated carboxylic acid or a derivative thereof. The adhesive resin composition according to claim 1, further comprising an ethylene-based polymer graft-modified with.
(A1) An ethylene polymer having a density of 930 to 965 kg / m 3 and a melt flow rate (MFR) of 0.1 to 10 g / 10 min at a temperature of 190 ° C. and a load of 2160 g as measured based on ASTM D 1238. ..
(A2) An ethylene polymer having a density of 858 to 929 kg / m 3 and a melt flow rate (MFR) of 0.1 to 10 g / 10 min at a temperature of 190 ° C. and a load of 2160 g as measured based on ASTM D 1238. ..
[Claim 3]
　A layer (I) containing an ethylene-based polymer, an adhesive layer (II) containing the adhesive resin composition according to claim 1 or 2, a layer (III) containing an ethylene / vinyl alcohol copolymer, and / or A laminate characterized in that a layer (IV) containing a polyamide resin is laminated, and the layer (II) is in direct contact with at least one of the layer (III) and the layer (IV).
[Claim 4]
　The laminate according to claim 3, wherein the ethylene-vinyl alcohol copolymer is a polymer obtained by saponifying an ethylene-vinyl acetate copolymer having a structural unit content of 20 to 30 mol% derived from ethylene. body.
[Claim 5]
The laminate according to claim 3, wherein the ethylene / vinyl alcohol copolymer is a polymer further containing 10 to 40% by mass of a styrene-based elastomer.
[Claim 6]
　The laminate according to any one of claims 3 to 5, wherein the polyamide resin contains at least one of nylon 6, nylon 66, nylon 610, nylon 12, nylon 11, MXD nylon, amorphous nylon, and copolymerized nylon. ..
[Claim 7]
　A film containing the laminate according to any one of claims 3 to 6.
[Claim 8]
　A bag obtained from the film according to claim 7.
[Claim 9]
　A packaging container containing the laminate according to any one of claims 3 to 6.