JP7069801B2 - Adhesive and laminate made of this - Google Patents

Description

The present invention relates to (i) a copolymer of ethylene and a vinyl ester and / or an acrylic acid ester, which has a vinyl ester and / or acrylic acid ester content of 5 mol% or more more than that of the thermoplastic resin (A) and (A). It relates to B), and a hydrolyzate of a resin composition containing a polymer grafted with (A) and (B), and an adhesive containing (ii) a fatty acid metal salt (C). Further, the present invention relates to a laminate containing at least one layer made of these adhesives.

Packaging materials made of thermoplastic resins for foods, beverages, pharmaceuticals, etc. are ethylene / vinyl alcohol-based copolymers with excellent gas barrier properties, fragrance retention, solvent resistance, etc. for the purpose of preventing deterioration of the contents (hereinafter referred to as , EVOH) is used for various purposes. However, EVOH is hydrophilic and its gas barrier property is deteriorated due to moisture absorption. Therefore, it is generally known that EVOH is used as an intermediate layer of a laminate with a polyolefin having excellent water resistance such as polyethylene or polypropylene. ing.

Since EVOH has many hydroxyl groups in the molecule, its affinity with thermoplastic resins having no polar group such as polyethylene and polypropylene is extremely low, and they generally do not adhere to each other. Therefore, a graft-modified ethylene resin composition (for example, Patent Documents 1 and 2) grafted with an unsaturated carboxylic acid or a derivative thereof for EVOH which is difficult to adhere to a polyolefin and an ethylene / vinyl acetate copolymer hydrolyzate (for example). , Patent Document 3) is already known to be used as an adhesive.

The graft-modified ethylene-based resin composition grafted with the former unsaturated carboxylic acid or a derivative thereof has excellent adhesiveness, but is highly reactive with EVOH, so that it can be repeatedly kneaded in an extruder or die. As the viscosity of the resin staying in the resin increases, it is colored and gelled, and as a result, a large number of fish eyes and gel-like substances are mixed in the product, which causes a problem that the commercial value is lowered.

On the other hand, the latter ethylene-vinyl acetate copolymer hydrolyzate does not cause coloring or gelation due to repeated kneading, and by adding an adhesive resin to the ethylene-vinyl acetate copolymer hydrolyzate, it has adhesiveness to EVOH. However, the effect was small, and it often peeled off when subjected to a small impact or friction during transportation or use, and sufficient adhesive strength could not be obtained.

Against this background, there has been a demand for an adhesive having excellent adhesiveness and reusable repeatedly.

Japanese Unexamined Patent Publication No. 61-270155 Japanese Unexamined Patent Publication No. 62-158043 Japanese Unexamined Patent Publication No. 7-108655

The present invention has been made in view of the above circumstances, and an object of the present invention is to provide an adhesive having excellent adhesiveness to polyethylene and EVOH and having a small amount of foreign substances such as fish eyes, and a laminate made of the same. Is to be.

The above problem is solved by providing an adhesive containing the following (i) and (ii), in which (i) the content of vinyl ester and / or acrylic acid ester is higher than that of the thermoplastic resin (A) and (A). Hydrolyzate (ii) of a resin composition containing a copolymer (B) of ethylene and a vinyl ester and / or an acrylic acid ester in an amount of 5 mol% or more, and a modified product in which (A) is grafted by (B). Ester metal salt (C)
The present invention will be described in detail below.

The thermoplastic resin (A) of the present invention (hereinafter, may be abbreviated as (A) or component (A)) is a copolymer of α-olefin having 2 to 12 carbon atoms such as ethylene, propylene and 1-butene, or a homopolymer. Ethylene and vinyl ester and / or acrylic having a vinyl ester content and / or acrylic acid ester content of 5 mol% or more less than these copolymers, a copolymer (B) of ethylene and vinyl ester and / or acrylic acid ester. Examples thereof include copolymers with acid esters, polystyrenes, styrene-based polymers, polyvinyl chlorides, polyesters, polyamides and the like.

For example, high-pressure method low-density polyethylene, high-density polyethylene, medium-density polyethylene, ethylene / 1-butene copolymer, ethylene / 1-hexene copolymer, ethylene / 1-octene copolymer, ethylene / 4-methyl- 1-Penten copolymer, ethylene / vinyl acetate copolymer, ethylene / acrylic acid ester copolymer, ethylene / methacrylic acid ester copolymer and other ethylene-based polymers, polypropylene, propylene / ethylene copolymer, propylene / Examples thereof include 1-butene copolymer, poly1-butene, poly1-hexene, poly4-methyl-1-pentene, etc., and the thermoplastic resin (A) may be used alone or in combination of two or more. It is also good. Among them, high-pressure low-density polyethylene, high-density polyethylene, ethylene / 1-butene copolymer, ethylene / 1-hexene copolymer, and polypropylene are preferable from the viewpoint of adhesion to a thermoplastic resin layer such as polyethylene and cost. , These compositions are most preferable because they are also excellent in moldability.

The method for producing low-density polyethylene by the high-pressure method can exemplify high-pressure radical polymerization, and such a resin can be conveniently selected from commercially available products, and is commercially available from, for example, Tosoh Corporation under the trade name of Petrosen. ing. The method for producing high-density polyethylene, ethylene / 1-butene copolymer and ethylene / 1-hexene copolymer is not particularly limited, but high / medium using a Ziegler-Natta catalyst, a Phillips catalyst, or a metallocene catalyst is used. -A low-pressure ion polymerization method or the like can be exemplified, and such a resin can be conveniently selected from commercially available products. For example, it is commercially available from Tosoh Corporation under the trade names of Niporon Hard, Niporon-L, and Niporon-Z.

The method for producing polypropylene is not particularly limited, but for example, a catalyst typically formed from a solid titanium catalyst component and an organic metal compound catalyst component, or a catalyst formed from both of these components and an electron donor. Alternatively, it can be obtained by polymerizing propylene in the presence of a single-site catalyst typified by a metallocene catalyst, or by copolymerizing propylene with one or more other α-olefins. Such a resin can be conveniently selected from commercially available products. For example, it is commercially available from Japan Polypropylene Corporation under the trade names of Novatec and Wintech.

The copolymer (B) of ethylene and vinyl ester and / or acrylic acid ester of the present invention (hereinafter, may be abbreviated as (B) or component (B)) is more vinyl ester and / or than (A). The acrylic ester content is 5 mol% or more.
Examples of the vinyl ester and / or acrylic acid ester of the copolymer (B) of ethylene and vinyl ester and / or acrylic acid ester include vinyl acetate, vinyl formate, vinyl propionate, vinyl valerate, vinyl butyrate, and vinyl isobutyrate. , An aliphatic vinyl ester such as vinyl pivalate, vinyl caprate, vinyl laurate, vinyl stearate, aromatic vinyl ester such as vinyl benzoate, methyl acrylate, ethyl acrylate, butyl acrylate and the like. Of these, an ethylene-vinyl acetate copolymer is preferable from the viewpoint of cost. Further, from the viewpoint of adhesiveness to EVOH, the vinyl ester and / or acrylic acid ester content is preferably 10 to 80 mol%.

The method for producing the ethylene / vinyl acetate copolymer is not particularly limited as long as the ethylene / vinyl acetate copolymer can be produced, but is known for high pressure method radical polymerization, solution polymerization, latex polymerization and the like. Methods are mentioned, and such resins can be conveniently selected from commercially available products, and are commercially available under the trade name of Ultrasen from Toso Co., Ltd. and under the trade name of Revaplen from Rankses Co., Ltd.

The modified product obtained by grafting the thermoplastic resin (A) constituting the adhesive in the present invention with ethylene and vinyl ester and / or acrylic acid ester (B) has a composition containing the component (A) and the component (B). It is produced by graft modification.

Further, as a constituent component of the adhesive in the present invention, a compatibilizer (D) (hereinafter, may be abbreviated as (D) or component (D)) of the component (A) and the component (B) may be contained. ..

Examples of the component (D) include a copolymer of ethylene and a vinyl ester and / or an acrylic acid ester, and the vinyl ester content and / or the acrylic acid ester of the component (D) is higher than that of the component (A). A copolymer of ethylene and a vinyl ester and / or an acrylic acid ester having a lower vinyl ester and / or acrylic acid ester content than the component (B) is preferable. Examples of the vinyl ester and / or acrylic acid ester include fats such as vinyl acetate, vinyl formate, vinyl propionate, vinyl valerate, vinyl butyrate, vinyl isobutyrate, vinyl pivalate, vinyl capricate, vinyl laurate, and vinyl stearate. Examples thereof include group vinyl esters, aromatic vinyl esters such as vinyl benzoate, methyl acrylate, ethyl acrylate, butyl acrylate, and the like.

Among them, it is preferable to use an ethylene-vinyl acetate copolymer because it is excellent in economy, and one kind alone or two or more kinds may be used in combination. In particular, by using two or more kinds of compatibilizers (D) in combination, the dispersibility of the component (A) and the component (B) is improved, and the adhesiveness of the present invention to polyethylene and EVOH is improved. ..

When a copolymer of ethylene and vinyl ester is used as the compatibilizer (D), the vinyl ester content differs between the compatibilizer (D) and the component (A) or the component (B) by 1. A copolymer of ethylene and vinyl ester having an amount of about 40% by weight is preferable, and a copolymer of ethylene and vinyl ester having a vinyl ester content difference of 1 to 30% by weight is more preferable, and a vinyl ester content difference is most preferable. Is a polymer of ethylene and vinyl ester in an amount of 1 to 20% by weight.

When a copolymer of two or more kinds of ethylene and vinyl ester is used as the compatibilizer (D), the difference in vinyl ester content is preferably 1 to 20% by weight, more preferably 1 to 15%. By weight%, most preferably 1 to 10% by weight.

The method for producing a copolymer of ethylene and vinyl ester of the compatibilizer (D) in the present invention is not limited, but known production methods such as high-pressure radical polymerization, solution polymerization and latex polymerization can be mentioned. The resin can be conveniently selected from commercially available products, and is commercially available as an ethylene / vinyl acetate copolymer under the trade name of Ultrasen from Toso Co., Ltd. and the trade name of Revaprene from Lanxess Co., Ltd.

The method for graft-modifying the thermoplastic resin (A), ethylene, vinyl ester and / or the acrylic acid ester (B) is not particularly limited as long as it can be graft-modified, and is appropriately selected in consideration of reactivity and the like. A method of graft-copolymerizing ethylene and vinyl acetate to (A), a method of graft-copolymerizing ethylene alone or ethylene and α-olefin to (B), prepolymerizing (A) and (B), and using these as a cross-linking agent. A method of graft modification by (E) can be mentioned, but from the viewpoint of productivity, it is preferable to add the cross-linking agent (E) to the composition containing the above components (A) and (B).

When the thermoplastic resin (A) is polyethylene or polyproprene, it is most preferable to use an organic oxide as the cross-linking agent (E).

The organic peroxide of the cross-linking agent (E) is not particularly limited as long as it is an organic peroxide, and for example, dicumyl peroxide, dit-butyl peroxide, 2,5-dimethyl-2,5-di (t-). Butylperoxy) hexane, 1,1-di (t-butylperoxy) cyclohexane, 2,5-dimethyl-2,5-di (t-butylperoxy) hexin-3,1,3-bis (t-butylperoxyisopropyl) ) Benzene, 1,1-bis (t-butylperoxy) -3,3,5-trimethylcyclohexane, 1,3-di- (t-butylperoxy) -diisopropylbenzene, n-butyl-4,4-bis ( t-butylperoxy) valerate, benzoyl peroxide, p-chlorobenzoyl peroxide, 2,4-dichlorobenzoyl peroxide, t-butylperoxybenzoate, t-butylperoxyisopropyl carbonate, diacetylperoxide, lauroyl peroxide, t-butylcumyl peroxide, etc. Can be mentioned. These can be used alone or in combination of two or more.

Of these, 2,5-dimethyl-2,5-di (t-butylperoxy) hexane and 1,1-di (t-butylperoxy) cyclohexane are preferably used from the viewpoint of reactivity. Further, a cross-linking aid such as triallyl isocyanurate or divinylbenzene may be used together with the cross-linking agent (E), if necessary.

The preferable compounding ratio of the adhesive (i) in the present invention is that the thermoplastic resin (A) is 5 to 95 parts by weight and ethylene and vinyl ester and / or acrylic acid ester (B) from the viewpoint of improving the adhesiveness to both. ) Contains 5 to 95 parts by weight (the total of (1) and (2) is 100 parts by weight), more preferably 15 to 85 parts by weight of the thermoplastic resin (A), ethylene and vinyl ester, and /. Alternatively, the acrylic acid ester (B) is 15 to 85 parts by weight (the total of (A) and (B) is 100 parts by weight), most preferably the thermoplastic resin (A) is 20 to 80 parts by weight, ethylene and vinyl ester, and the like. / Or the acrylic acid ester (B) contains 20 to 80 parts by weight (the total of (A) and (B) is 100 parts by weight).

When the adhesive (i) in the present invention contains the compatibilizer (D), the blending amount of the compatibilizer (D) is (A) and (B) from the viewpoint of improving the adhesiveness to polyethylene and EVOH. The total amount of the binder (D) is 1 to 50 parts by weight, more preferably 5 to 45 parts by weight, and most preferably 10 to 40 parts by weight with respect to 100 parts by weight.

When the cross-linking agent (E) is contained in the adhesive (i) in the present invention, the total amount of the thermoplastic resin (A) and the copolymer (B) of ethylene and vinyl ester and / or acrylic acid ester is 100 parts by weight. The blending amount of the cross-linking agent (E) with respect to the above is preferably in the range of 0.005 to 1 part by weight from the viewpoint of improving the adhesiveness to EVOH and the moldability.

The fatty acid metal salt (C) of the present invention (hereinafter, may be abbreviated as (C) or component (C)) is a saturated or unsaturated fatty acid having 6 to 30 carbon atoms such as lithium, sodium, potassium and barium. Examples thereof include alkali metal salts, group 2 metal salts such as magnesium and calcium, and metal salts such as transition metal salts such as zinc, copper, cobalt, nickel, manganese and iron. Of these, metal salts of magnesium, calcium and zinc, which are fatty acids selected from stearic acid, oleic acid and lauric acid, are preferable from the viewpoint of cost and reduction of the number of fish eyes.
These fatty acid metal salts (C) can be appropriately selected from commercially available products, and may be used alone or in combination of two or more.

Further, the blending amount of the fatty acid metal salt (C) contains 0.005 to 1 part by weight of the fatty acid metal salt (C) with respect to 100 parts by weight of the above (i) from the viewpoint of reducing the number of fish eyes of the adhesive. It is more preferably 0.01 to 0.8 parts by weight, and most preferably 0.02 to 0.5 parts by weight. If it is less than 0.005, the number of fish eyes increases and the appearance deteriorates, and if it exceeds 1 part by weight, the molding stability deteriorates.

The adhesive of the present invention can be produced by kneading the components (A) to (E) and hydrolyzing them. The method of melt-kneading the components (A) to (E) is not particularly limited as long as it is a melt-kneading device capable of uniformly dispersing each component, and can be produced by a commonly used resin mixing device. Examples thereof include melt kneading devices such as single-screw extruders, multi-screw extruders, Banbury mixers, pressurized kneaders, and rotary rolls. Among them, a twin-screw extruder having a high degree of kneading and capable of continuous operation is preferable because the dispersed state can be made fine and uniform. The melting temperature is preferably about 260 ° C. from the melting point of the thermoplastic resin (A).

Specific examples of the adhesive manufacturing process of the present invention are as follows.

The dry blend of the components (A) to (E) is charged into the hopper of the extruder. At least a part of the thermoplastic resin (A), the copolymer (B) of ethylene and vinyl ester and / or acrylic acid ester, and the cross-linking agent (E) may be added from a side feeder or the like. Further, two or more extruders may be used to sequentially melt and knead in stages. A Henschel mixer, a V blender, a ribbon blender, a tumbler, or the like may be used for mixing the components (A) to (E).

In addition to the above-mentioned components, the adhesive of the present invention is usually used as a thermoplastic resin such as a cross-linking aid, an antioxidant, a lubricant, a neutralizing agent, an anti-blocking agent, a surfactant, and a slip agent. It may be added with the additives used or a thermoplastic resin such as other polyolefins.

Further, the adhesive of the present invention preferably contains a thermoplastic resin (A) or a resin containing a copolymer (B) of ethylene and a vinyl ester and / or an acrylic acid ester. At this time, it is preferable that the dispersed particle size of the resin containing the thermoplastic resin (A) or the copolymer (B) of ethylene and vinyl ester and / or acrylic acid ester is 0.01 to 50 μm.

The adhesive in the present invention is not particularly limited in the method for hydrolyzing the resin composition, but from the viewpoint of productivity, it is preferable to directly hydrolyze the pellets or powders of the resin composition in an alkali. Further, the adhesive of the present invention preferably has a saponification degree of 10% by weight or more of the vinyl ester and / or acrylic acid ester component. If it is 10% by weight or more, the adhesiveness to EVOH is sufficient.

Further, under the condition that the complex elastic modulus G * ((storage elastic modulus G'2 ⁺ loss elastic modulus ^{G''2) 1/2 )} obtained by the dynamic viscoelasticity measurement of the hydrolyzate in the present invention is 500 Pa. The loss angle δ (arctan (G'' / G')), which is the phase angle of strain and stress or deflection and load, is 80 degrees or less, which is the viewpoint of improving the adhesiveness with polyolefins such as polyethylene and polypropylene, and EVOH. Is preferable.

Further, the adhesive of the present invention can be used in any form such as pellets and powder.

Further, the adhesive of the present invention may be used as a laminate composed of a layer made of the adhesive and at least one layer made of another material.

The laminate of the present invention preferably has a layer made of the adhesive, at least one polyolefin such as polyethylene or polypropylene, polyester such as polylactic acid or polybutylene terephthalate, polyamide such as nylon, or an EVOH layer. Further, it may have a laminated structure having a combination of two or more sets thereof or a combination of various thermoplastic resin layers. In particular, from the viewpoint of cost and moldability, those having polyethylene or polypropylene and EVOH are preferable.

The laminate of the present invention can be molded using a normal molding device, and examples of the molding method include extrusion molding, blow molding, sheet molding, injection molding, compression molding, calendar molding, and vacuum molding. Any method such as sheet shape, film shape, pipe shape, block shape and other arbitrary shapes can be mentioned, and by adopting a laminated structure with other materials, the laminated body has gas barrier properties. , Mechanical properties, oil resistance, weather resistance, and other properties of other materials can be imparted.

The laminate of the present invention can be used for packaging materials and containers made of thermoplastic resins such as foods, beverages and pharmaceuticals that require these properties.

Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited to these Examples.
[Saponification degree]
Each adhesive obtained from the production example was measured according to JIS K7192 (1999). The degree of saponification was calculated assuming that only the copolymer (B) of ethylene and vinyl ester and / or acrylic acid ester was saponified.
[Adhesive strength to each adherend]
The adhesiveness with each adherend (LDPE and EVOH) was investigated using each adhesive obtained from the examples. The procedure for evaluating the adhesive strength is as follows. Each resin composition was press-molded using a 50-ton automatic press machine manufactured by Shinto Kogyo Co., Ltd. to prepare a press-molded product having a thickness of 0.1 mm. Subsequently, using a hot tack tester manufactured by Tester Sangyo Co., Ltd., the adhesive and the adherend are heat-sealed by heating up and down at a sealing temperature of 200 ° C., a sealing pressure of 0.1 MPa, and a sealing time of 2.5 seconds, and then tensioned. Using a testing machine (TENCYRON RTE-1210 manufactured by ORIENTEC), the adhesive strength (N / 15 mm width) at 180 degree peeling was measured at a sample width of 15 mm and a tensile speed of 300 mm / min. The measurement was repeated 3-5 times for the same sample. The LDPE and EVOH used for the evaluation were as shown below.
(1) LDPE: Melt mass flow rate 7 g / 10 minutes, low density polyethylene with a density of 922 kg / m3 ⁽ manufactured by Tosoh Corporation, trade name Petrosen 204)
(2) EVOH: Ethylene vinyl alcohol copolymer having a melt mass flow rate of 1.7 g / 10 minutes and an ethylene content of 44 mol% (Kuraray Co., Ltd., trade name EVAL E171B)
[Number of fish eyes]
A single-layer film was prepared using each of the adhesives obtained from the examples. The single-layer film was produced at a set temperature of 200 ° C. using a single-layer cast film molding machine (manufactured by Sumitomo Modern Co., Ltd.). The obtained single-layer film was cut into 10 cm × 10 cm, and the presence or absence of fish eyes of 0.5 mm or more in the film was observed. If there were 50 or more gels (foreign substances) of 0.5 mm or more, it was rated as "more", and if it was less than 20, it was rated as "less".

Example 1
As component (A), an ethylene / vinyl acetate copolymer having a melt mass flow rate of 14/10 minutes, a density of 935 kg / m ³ , and a vinyl acetate content of 15% by weight (manufactured by Toso Co., Ltd., trade name Ultrasen 625, hereinafter, component ( A-1)) is 70 parts by weight, the component (B) is a melt mass flow rate of 70 g / 10 minutes, a density of 968 kg / m ³ , and an ethylene / vinyl acetate copolymer (Tosoh) with a vinyl acetate content of 42% by weight. Made by Co., Ltd., trade name Ultrasen 760, hereinafter may be abbreviated as component (B-1)) in 30 parts by weight, zinc stearate as component (C) (Tannan Chemical Industry Co., Ltd., trade name zinc) Stearate N (hereinafter, may be abbreviated as component (C-1)) is 1000 ppm, and organic peroxide (manufactured by Nichiyu Co., Ltd., trade name Perhexa 25B) is 0.02 part by weight as component (D). It was dry-blended at a ratio and melt-kneaded with a twin-screw extruder to obtain a pellet-shaped resin composition. Subsequently, the present resin composition was hydrolyzed at 60 ° C. in 1 part by weight of sodium hydroxide methanol solution, and the adhesive 1 (copolymer (B) of ethylene and vinyl ester and / or acrylic acid ester) was subjected to hydrolysis treatment. The degree of saponification was 50% by weight). When the adhesiveness to LDPE and EVOH and the number of fish eyes were evaluated using the adhesive 1, it was as shown in Table 2.

Example 2
Manufactured in the same manner as Adhesive 1 except that calcium stearate (Tannan Chemical Industry Co., Ltd., trade name calcium stearate, hereinafter may be abbreviated as component (C-2)) is used as component (C). Adhesive 2 (the degree of saponification of the copolymer (B) of ethylene and vinyl ester and / or acrylic acid ester was 50% by weight) was obtained. When the adhesiveness to LDPE and EVOH and the number of fish eyes were evaluated using the adhesive 2, they were as shown in Table 2.

Example 3
30 parts by weight of an ethylene-vinyl acetate copolymer (manufactured by Rankses Co., Ltd., trade name: Revaprene 800) having a melt mass flow rate of 5/10 minutes as a component (B) and a vinyl acetate content of 80% by weight, and the following as a component (D) The degree of saponification of the adhesive 3 (the copolymer (B) of ethylene and vinyl ester and / or acrylic acid ester) is 50% by weight, which is produced by the same method as that of the adhesive 1 except that 20 parts by weight of the component of the above is used. ) Was obtained. When the adhesiveness to LDPE and EVOH and the number of fish eyes were evaluated using the adhesive 3, they were as shown in Table 2.
[Component of component (D)]
A dry blend of 4 parts by weight of the following 5 types of ethylene-vinyl acetate copolymers-Ethylene-vinyl acetate copolymer with melt mass flow rate of 20 g / 10 minutes, density of 940 kg / m ³ , and vinyl acetate content of 20% by weight ( Tosoh Co., Ltd., trade name Ultrasen 633)
-Ethylene-vinyl acetate copolymer with melt mass flow rate 18 g / 10 minutes, density 949 kg / m ³ , vinyl acetate content 28% by weight (manufactured by Tosoh Corporation, trade name Ultrasen 710)
-Ethylene-vinyl acetate copolymer with melt mass flow rate 30 g / 10 minutes, density 954 kg / m ³ , vinyl acetate content 32% by weight (manufactured by Tosoh Corporation, trade name Ultrasen 750)
-Ethylene-vinyl acetate copolymer with melt mass flow rate 70 g / 10 minutes, density 968 kg / m ³ , vinyl acetate content 42% by weight (manufactured by Tosoh Corporation, trade name Ultrasen 760)
-Ethylene-vinyl acetate copolymer with melt mass flux rate of 5 g / 10 minutes and vinyl acetate content of 50% by weight (manufactured by LANXESS Co., Ltd., trade name: Revaplen 500)
Example 4
It is manufactured by the same method as the adhesive 1 except that the component (C-2) is 500 ppm, and the degree of saponification of the adhesive 4 (copolymer (B) of ethylene and vinyl ester and / or acrylic acid ester is 50). Weight%) was obtained. When the adhesiveness to LDPE and EVOH and the number of fish eyes were evaluated using the adhesive 4, they were as shown in Table 2.

Example 5
The degree of saponification of the copolymer (B) of the adhesive 5 (ethylene and vinyl ester and / or acrylic acid ester) is 50, which is produced by the same method as that of the adhesive 1 except that the component (C-2) is 2000 ppm. Weight%) was obtained. When the adhesiveness to LDPE and EVOH and the number of fish eyes were evaluated using the adhesive 5, they were as shown in Table 2.

Comparative Example 1
It is manufactured by the same method as the adhesive 1 except that the component (A-1) is 0 parts by weight and the component (B-1) is 100 parts by weight, and the adhesive 6 (ethylene and vinyl ester and / or acrylic acid ester) is used. The degree of saponification of the copolymer (B) of (B) was 50% by weight). When the adhesiveness to LDPE and EVOH and the number of fish eyes were evaluated using the adhesive 6, the adhesiveness to LDPE was low as shown in Table 3.

Comparative Example 2
It is manufactured by the same method as the adhesive 1 except that the component (A-1) is 100 parts by weight and the component (B-1) is 0 parts by weight, and the adhesive 7 (ethylene and vinyl ester and / or acrylic acid ester) is used. The degree of saponification of the copolymer (B) of (B) was 0% by weight). When the adhesiveness to LDPE and EVOH and the number of fish eyes were evaluated using the adhesive 7, the adhesiveness to EVOH was low as shown in Table 3.

Comparative Example 3
It is manufactured by the same method as the adhesive 1 except that the component (C-1) is not used, and the degree of saponification of the adhesive 8 (copolymer (B) of ethylene and vinyl ester and / or acrylic acid ester is high. 50% by weight) was obtained. When the adhesiveness to LDPE and EVOH and the number of fish eyes were evaluated using the adhesive 8, the number of fish eyes was large as shown in Table 3.

Comparative Example 4
Adhesive 9 produced in the same manner as Adhesive 1 except that it was not hydrolyzed (the degree of saponification of the copolymer (B) of ethylene and vinyl ester and / or acrylic acid ester is 50% by weight). Got When the adhesiveness to LDPE and EVOH and the number of fish eyes were evaluated using the adhesive 9, the adhesiveness to EVOH was low as shown in Table 3.

Claims (9)

An adhesive containing the following (i) and (ii).
(I) Thermoplastic resin containing at least one homopolymer of α-olefin having 2 to 12 carbon atoms or a copolymer thereof (A), vinyl ester and / or acrylic acid ester content more than (A) Hydrolyzate (ii) of a resin composition containing a copolymer (B) of ethylene and a vinyl ester and / or an acrylic acid ester in an amount of 5 mol% or more, and a modified product obtained by grafting (A) and (B). ) Fatty metal salt (C) The thermoplastic resin (A) has a vinyl ester content and / or an acrylic acid ester content of 5 mol% or more less than that of the copolymer (B) of ethylene and vinyl ester and / or acrylic acid ester. The adhesive according to claim 1, which contains at least one copolymer with an acrylic acid ester. The invention according to claim 1 or 2 , wherein the copolymer (B) of ethylene and a vinyl ester and / or an acrylic acid ester has a vinyl ester content and / or an acrylic acid ester content of 5 to 35 mol%. glue. The adhesive according to any one of claims 1 to 3 , wherein the amount of the fatty acid metal salt (C) is 0.005 to 1 part by weight with respect to 100 parts by weight of (i). The adhesive according to any one of claims 1 to 4 , wherein the compatibilizer (D) is contained in the (i). A laminate including a layer made of the adhesive according to claims 1 to 5 and at least one layer made of a material other than the adhesive. The laminate according to claim 6 , wherein at least one layer made of a material other than the adhesive is a layer containing an ethylene / vinyl alcohol copolymer. The laminate according to claim 6 , wherein at least one layer made of a material other than the adhesive is a layer containing polyethylene. A laminate in which a layer containing an ethylene / vinyl alcohol copolymer, a layer made of the adhesive according to any one of claims 1 to 5 , and a layer containing polyethylene are sequentially laminated.