JP7018176B2 - Resin composition and laminate made of the resin composition - Google Patents

Description

The present invention relates to a resin composition containing an adhesive and a laminate containing a layer composed of the resin composition.

Packaging materials made of thermoplastic resins for foods, beverages, pharmaceuticals, etc. are ethylene / vinyl alcohol copolymers (hereinafter referred to as "e." (Sometimes abbreviated as EVOH) is used for various purposes. However, it is known that EVOH is generally used as an intermediate layer of a laminate with a polyolefin having excellent water resistance such as polyethylene or polypropylene because EVOH is hydrophilic and the gas barrier property is lowered due to moisture absorption. There is.

Since EVOH has many hydroxyl groups in the molecule, its affinity with polyolefins 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, see 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, or an ethylene / vinyl acetate copolymer hydrolyzate. (For example, see Patent Document 3) is already known to be used as an adhesive between the polyolefin layer and the EVOH layer.

The graft-modified ethylene-based resin composition grafted with the former unsaturated carboxylic acid or a derivative thereof has excellent adhesiveness, but since it is highly reactive with EVOH, it is repeatedly kneaded or added to EVOH. As the viscosity of the resin accumulated in the extruder or die increases, the resin 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 even when repeatedly kneaded or added to EVOH, and an adhesive resin is added to the ethylene-vinyl acetate copolymer hydrolyzate. As a result, the adhesiveness to EVOH is improved, but the effect is small, and it often peels off when subjected to a small impact or friction during transportation or use, and sufficient adhesive strength cannot be obtained.

Against this background, there has been a demand for an adhesive that has excellent adhesiveness and can be repeatedly reused even when added to EVOH.

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 a resin composition having excellent adhesiveness to polyolefins such as polyethylene and polypropropylene, and a laminate made of the same. Is.

The present invention relates to a resin composition comprising an adhesive satisfying the following requirements (1) and (2) and a polyvinyl alcohol and / or an ethylene / vinyl alcohol copolymer satisfying the following requirements (3). be.

(1) A copolymer (B) of ethylene and vinyl ester and / or acrylic acid ester having a vinyl ester and / or acrylic acid ester content of 5 mol% or more higher than that of the thermoplastic resin (A) and (A), and Hydrolyzate of melt-kneaded product containing the modified product (C) grafted with (A) and (B) (2) Vinyl alcohol content is 0.5-40 mol%, vinyl ester and / or acrylic acid ester content is 30 mol. % Or less (3) Ethylene content is 55 mol% or less The present invention will be described in detail below.

The thermoplastic resin (A) constituting the adhesive in the present invention includes homopolymers of α-olefins having 2 to 12 carbon atoms such as ethylene, propylene and 1-butene, copolymers thereof, ethylene and vinyl esters, and the like. / Or a copolymer of ethylene with a vinyl ester and / or an acrylic acid ester, which has a vinyl ester content and / or an acrylic acid ester content of 5 mol% or more less than that of the copolymer (B) with an acrylic acid ester. ..

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. May be good. Among them, from the viewpoint of adhesion to polyolefin and cost, high pressure method low density polyethylene, ethylene / vinyl acetate copolymer, high density polyethylene, ethylene / 1-butene copolymer, ethylene / 1-hexene copolymer, polypropylene Is preferable, and 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 the ethylene-vinyl acetate copolymer is not particularly limited as long as the ethylene-vinyl acetate copolymer can be produced, but known high-pressure radical polymerization methods and ionic polymerization methods can be exemplified. can. As an ethylene-vinyl acetate copolymer produced by a high-pressure radical polymerization method, it is commercially available from Tosoh Corporation under the trade name of Ultrasen.

The copolymer (B) of ethylene and vinyl ester and / or acrylic acid ester constituting the adhesive in the present invention has a vinyl ester and / or acrylic acid ester content of 5 mol% or more as compared with the thermoplastic resin (A). There are many.

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 isobutyric acid. Examples include aliphatic vinyl esters such as vinyl, vinyl pivalate, vinyl capricate, vinyl laurate, vinyl stearate, aromatic vinyl esters such as vinyl benzoate, methyl acrylate, ethyl acrylate, butyl acrylate and the like. Be done. Of these, an ethylene-vinyl acetate copolymer is preferable from the viewpoint of cost. Further, from the viewpoint of compatibility with polyvinyl alcohol and / or EVOH, the vinyl ester and / or acrylic acid ester content of the copolymer (B) of ethylene and vinyl ester and / or acrylic acid ester is 10 to 35 mol%. Is preferable.

A suitable compounding ratio of the thermoplastic resin (A) constituting the adhesive in the present invention and the copolymer (B) of ethylene and vinyl ester and / or acrylic acid ester is the adhesiveness with polyolefins such as polyethylene and polypropylene. From the viewpoint of improvement, the thermoplastic resin (A) is 5 to 95 parts by weight and the polyethylene and vinyl ester and / or the acrylic acid ester (B) is 5 to 95 parts by weight (the total of (A) and (B) is 100 parts by weight. Parts), more preferably 15 to 85 parts by weight of the thermoplastic resin (A) and 15 to 85 parts by weight of polyethylene and vinyl ester and / or acrylic acid ester (B) ((A) and (B). ) Is 100 parts by weight), most preferably 20 to 80 parts by weight of the thermoplastic resin (A) and 20 to 80 parts by weight of polyethylene and vinyl ester and / or acrylic acid ester (B) ((A) and (). The total of B) includes 100 parts by weight).

Further, as a constituent component of the adhesive in the present invention, a copolymer (B) (B) of a thermoplastic resin (A) (hereinafter, may be abbreviated as a component (A)) and ethylene and a vinyl ester and / or an acrylic acid ester. Hereinafter, it may contain a compatibilizer (D) (hereinafter, may be abbreviated as component (D)) of the component (B). 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 compatibilizer (D) is higher than that of the component (A). A polymer of ethylene and vinyl ester and / or acrylic acid ester, which is high and has 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.

Further, 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.

From the viewpoint of improving the adhesiveness to polyethylene and EVOH, the total amount of the compatibilizer (D) is 100 parts by weight, while the amount of the compatibilizer (D) is 1 to 50 weight by weight. It contains parts, more preferably 5 to 45 parts by weight, and most preferably 10 to 40 parts by weight.

As the method for graft-modifying the modified product (C) to which the thermoplastic resin (A) constituting the adhesive, ethylene, vinyl ester and / or acrylic acid ester (B) are grafted in the present invention, any graft-modifying method can be used. The method is not particularly limited, and is appropriately selected in consideration of reactivity and the like. (A) is a method of graft-copolymerizing ethylene and vinyl acetate, (B) is a method of graft-copolymerizing ethylene alone and ethylene and α-olefin. , (A) and (B) are prepolymerized and graft-modified with a cross-linking agent (E). From the viewpoint of productivity, the cross-linking agent (E) is added to the components (A) and (B). The method of graft modification is preferable. When the thermoplastic resin (A) is polyethylene or polypropylene, it is most preferable to use an organic peroxide 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, 1,1-di (t-butylperoxy) cyclohexane and the like are preferable 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 blending amount of the cross-linking agent (E) with respect to a total of 100 parts by weight of the thermoplastic resin (A) and the copolymer (B) of ethylene and vinyl ester and / or acrylic acid ester ranges from 0.005 to 1 part by weight. It is preferable from the viewpoint of improving adhesion to polyolefins such as polyethylene and polypropylene and moldability.

The modified product (C) grafted with the thermoplastic resin (A) and the copolymer (B) of ethylene and vinyl ester and / or acrylic acid ester is the component (A), (B), (E). When a graft body is produced using the above, a method of melt-kneading them is preferable from the viewpoint of economic efficiency.

The method of melt-kneading 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. For example, a melt kneader such as a single-screw extruder, a multi-screw extruder, a Banbury mixer, a pressurized kneader, a rotary roll, and a lab plast mill can be mentioned. 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 finely and uniformly. The melting temperature is preferably about 260 ° C. from the melting point of the thermoplastic resin (A).

Copolymer (B) of ethylene and vinyl ester and / or acrylic acid ester having a vinyl ester and / or acrylic acid ester content of 5 mol% or more more than the thermoplastic resins (A) and (A), and (A). Specific examples of the manufacturing process of the melt-kneaded product containing the modified product (C) grafted with and (B) are as follows.

The dry blend of the components (A), (B) and (E) is charged into the hopper of the extruder. At least a part of the component (A), the component (B) and the component (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), (B), and (E).

In addition to the above-mentioned components, the adhesive in 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.

The method for hydrolyzing the melt-kneaded product containing the components (A), (B), (C) and (E) constituting the adhesive in the present invention is not particularly limited, but the resin composition is described from the viewpoint of productivity. It is preferred to hydrolyze the pellets or powders of the material directly in 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 mol% or more, the compatibility with EVOH is sufficient.

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

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

Further, the strain 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 adhesive in the present invention is 500 Pa. It is preferable that the loss angle δ (arctan (G'' / G')), which is the phase angle between stress or deflection and load, is 80 degrees or less from the viewpoint of improving the adhesiveness of polyolefins such as polyethylene and polypropylene.

The vinyl alcohol content and vinyl ester and / or acrylic acid ester content of the adhesive in the present invention are the vinyl alcohol content from the viewpoint of compatibility with polyvinyl alcohol and / or EVOH and improvement of adhesion with polyolefins such as polyethylene and polypropylene. The content of 0.5 to 40 mol% and vinyl ester and / or acrylic acid ester is 30 mol% or less, preferably the content of vinyl alcohol is 0.5 to 35 mol% and the content of vinyl ester and / or acrylic acid ester is 28 mol% or less. Most preferably, the vinyl alcohol content is 1 to 35 mol% and the vinyl ester and / or acrylic acid ester content is 26 mol% or less.

The polyvinyl alcohol and / or EVOH in the present invention is a polymer mainly composed of vinyl alcohol units or a copolymer composed of ethylene units and vinyl alcohol units. The polyvinyl alcohol and / or EVOH used in the present invention is not particularly limited, and examples thereof include known ones used in molding applications. However, the content of the ethylene unit of polyvinyl alcohol and / or EVOH is preferably 55 mol% or less, preferably 10 to 55 mol%, from the viewpoint of high barrier property against gas, organic liquid, etc. and good molding processability. More preferred.

The method for producing polyvinyl alcohol and / or EVOH is not particularly limited, and for example, a polymer of fatty acid vinyl ester or a copolymer of ethylene and fatty acid vinyl ester can be produced according to a known method. Then, polyvinyl alcohol and / or EVOH can be produced by hydrolyzing this, and such a resin can be conveniently selected from commercially available products, for example, Poval, Eval, Japan from Kuraray Co., Ltd. It is commercially available from Synthetic Chemistry Co., Ltd. under the trade names of Gosenol and Soanol.

Further, EVOH may have other constituent units in a small amount in addition to the ethylene unit and the vinyl alcohol unit.

The melt flow mass rate of polyvinyl alcohol and / or EVOH (temperature 190 ° C., load 2.16 kg) is preferably 0.1 to 100 g / 10 minutes, preferably 0.5 to 50 g / 10 minutes from the viewpoint of molding processability. It is more preferably 10 minutes, and most preferably 1 to 20 g / 10 minutes.

The preferable blending ratio of the adhesive constituting the resin composition of the present invention with polyvinyl alcohol and / or EVOH is that the adhesive is 10 to 90 parts by weight, polyvinyl, from the viewpoint of improving the adhesiveness with a polyolefin such as polyethylene or polypropylene. The alcohol and / or EVOH contains 10 to 90 parts by weight (the total of these is 100 parts by weight), more preferably 15 to 85 parts by weight of the adhesive, and 15 to 85 parts by weight of polyvinyl alcohol and / or EVOH. (The total of these is 100 parts by weight), most preferably 20 to 80 parts by weight of the adhesive and 20 to 80 parts by weight of polyvinyl alcohol and / or EVOH (the total of these is 100 parts by weight).

The method of melt-kneading the adhesive and polyvinyl alcohol and / or EVOH 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. For example, a melt kneader such as a single-screw extruder, a multi-screw extruder, a Banbury mixer, a pressurized kneader, a rotary roll, and a lab plast mill can be mentioned. The melting temperature is preferably from the melting point of EVOH to about 260 ° C.

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

Further, the resin composition of the present invention may be used as a laminate in which a layer made of the resin composition is laminated on a layer containing polyolefin.

The polyolefin is not particularly limited, and is not particularly limited, for example, high-pressure method low-density polyethylene, high-density polyethylene, medium-density polyethylene, ethylene / 1-butene copolymer, ethylene / 1-hexene copolymer, ethylene / 1. -Octen copolymer, ethylene / 4-methyl-1-pentene 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 / 1-butene copolymer, poly1-butene, poly1-hexene, poly4-methyl-1-pentene and the like.

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.

The resin composition of the present invention has excellent adhesiveness to thermoplastic resins such as polyethylene and polypropylene and can be used as a laminate, and the obtained laminate has a barrier property against gas, organic liquid and the like. It will be expensive.

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 on the assumption that only the copolymer (B) of ethylene and vinyl ester and / or acrylic acid ester was saponified.
[Adhesive strength]
The adhesiveness with LDPE was investigated using each resin composition obtained from the examples. The procedure for evaluating the adhesive strength is as follows. About 4 g of each pellet was press-molded using a 50-ton automatic press machine manufactured by Shinto Kogyo Co., Ltd. The size of the molded product was 150 mm × 150 mm × 0.1 mm. Subsequently, using a hot tack tester manufactured by Tester Sangyo Co., Ltd., the adhesive and the adherend were 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 1 second. (TENSILON RTE-1210 manufactured by ORIENTEC) was used to measure the adhesive strength (N / 15 mm width) at 180 degree peeling at a sample width of 15 mm and a tensile speed of 300 mm / min. The LDPE used for the evaluation was 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)
[Manufacturing example]
Production Example of Adhesive 1 As adhesive 1, high-pressure low-density polyethylene with melt mass flow rate 45 g / 10 minutes and density 924 kg / m ³ (manufactured by Toso Co., Ltd., trade name Petrosen 209, hereinafter referred to as (A-1)). 70 parts by weight, as a copolymer (B) of ethylene and vinyl ester and / or acrylic acid ester, melt mass flow rate 70 g / 10 minutes, density 968 kg / m ³ , vinyl acetate content 42% by weight (19 mol%). 30 parts by weight of an ethylene-vinyl acetate copolymer (manufactured by Toso Co., Ltd., trade name Ultrasen 760, hereinafter referred to as (B)), and an organic peroxide (manufactured by Nichiyu Co., Ltd., trade name Perhexa C). It was dry-blended at a ratio of 0.1 part by weight and melt-kneaded with a twin-screw extruder at a molten resin temperature of 190 ° C. to obtain a pellet-shaped sample. Subsequently, this sample was hydrolyzed at 60 ° C. in a 1 wt% sodium hydroxide methanol solution to form a saponification of the present adhesive (a copolymer (B) of ethylene and a vinyl ester and / or an acrylic acid ester). The degree of conversion was 50% by weight).

Production Example of Adhesive 2 The adhesive 2 is manufactured by the same method as the adhesive 1 except that (A-1) is 70 parts by weight and (B) is 30 parts by weight, and the present adhesive (ethylene and vinyl ester) is used. And / or the degree of saponification of the copolymer (B) with the acrylic acid ester was 50% by weight).

Production Example of Adhesive 3 As the adhesive 3, an ethylene-vinyl acetate copolymer having a melt mass flow rate of 14 g / 10 minutes, a density of 924 kg / m ³ , and a vinyl acetate content of 15% by weight (5.4 mol%) (Tosoh Co., Ltd.) Manufactured by the same method as Adhesive 1 except that 70 parts by weight of Ultrasen 625 (hereinafter referred to as (A-2)) and 30 parts by weight of (B) are used. And / or the degree of saponification of the copolymer (B) with the acrylic acid ester was 50% by weight).

Production Example of Adhesive 4 The adhesive 4 is manufactured by the same method as the adhesive 1 except that (B) is 100 parts by weight, and the present adhesive (coweight of ethylene and vinyl ester and / or acrylic acid ester) is used. The degree of saponification of the coalescence (B) was 50% by weight).

Example of Production of Adhesive 5 The adhesive 5 was produced in the same manner as the adhesive 1 except that (A-1) was made up to 100 parts by weight to obtain the present adhesive.

Example of Production of Adhesive 6 The adhesive 6 is produced in the same manner as the adhesive 1 except that the graft is not hydrolyzed, and the present adhesive (ethylene and vinyl ester and / or acrylic acid ester) is copolymerized. The degree of saponification of the polymer (B) was 0% by weight).

Production Example of Adhesive 7 As the adhesive 7, an ethylene / vinyl acetate copolymer (rankces) containing 75 parts by weight of (A-2), a melt mass flow rate of 5 g / 10 minutes as a component (B), and a vinyl acetate content of 80% by weight. Made by Co., Ltd., trade name Revaprene 800, hereinafter may be abbreviated as component (B-2)) in 25 parts by weight, melt mass flow rate as component (D) 70 g / 10 minutes, density 968 kg / m ³ , vinyl acetate content. Same as Adhesive 1 except that 42% by weight of ethylene / vinyl acetate copolymer (manufactured by Toso Co., Ltd., trade name Ultrasen 760, hereinafter abbreviated as component (D-1)) is 20 parts by weight. The present adhesive (the degree of saponification of the copolymer (B) of ethylene and vinyl ester and / or acrylic acid ester is 50% by weight) was obtained.

Example of Production of Adhesive 8 The adhesive 8 is manufactured by the same method as the adhesive 7 except that the following component (D-2) is used, and the present adhesive (ethylene and vinyl ester and / or acrylic acid ester) is copolymerized. The degree of saponification of the polymer (B) was 50% by weight).

[Component of component (D-2)]
The following 7 types of ethylene-vinyl acetate copolymers are dry-blended by 3 parts by weight.-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 (manufactured by Tosoh Corporation, trade name Ultrasen 760) with melt mass flow rate 70 g / 10 minutes, density 968 kg / m ³ , vinyl acetate content 42% by weight,
-Ethylene-vinyl acetate copolymer with melt mass flow rate of 5 g / 10 minutes and vinyl acetate content of 50% by weight (manufactured by LANXESS Co., Ltd., trade name: Revaprene 500)
-Ethylene-vinyl acetate copolymer with melt mass flow rate of 5 g / 10 minutes and vinyl acetate content of 60% by weight (manufactured by LANXESS Co., Ltd., trade name: Revaprene 600)
-Ethylene-vinyl acetate copolymer with melt mass flow rate of 5 g / 10 minutes and vinyl acetate content of 70% by weight (manufactured by LANXESS Co., Ltd., trade name: Revaprene 700)
Example of Production of Adhesive 9 The adhesive 9 is produced in the same manner as the adhesive 7 except that (D-2) is 40 parts by weight, and the present adhesive (ethylene and vinyl ester and / or acrylic acid ester) is used. The degree of saponification of the copolymer (B) was 50% by weight).

Example 1
25 parts by weight of Adhesive 1, 5.4 g / 10 min of melt mass flow rate, and 25 ethylene / vinyl alcohol copolymers (manufactured by Kuraray Co., Ltd., trade name E-105B, hereinafter referred to as EVOH1) having an ethylene content of 44 mol%. After dry-blending by weight, the dry blend was put into a laboplast mill set at 200 ° C., and kneading was started. After 3 minutes from the start of kneading, kneading was completed, and then the kneaded product was cooled to room temperature to obtain a resin composition. When the adhesiveness to LDPE was evaluated using the obtained resin composition, it was as shown in Table 2.

Example 2
It was manufactured by the same method as in Example 1 except that the adhesive 1 was 50 parts by weight and the EVOH 1 was 50 parts by weight, and the adhesiveness to LDPE was evaluated using the obtained resin composition. Table 2 shows. It was as shown.

Example 3
It was produced by the same method as in Example 1 except that the adhesive 1 was 30 parts by weight and the EVOH 1 was 70 parts by weight, and the adhesiveness to LDPE was evaluated using the obtained resin composition. Table 2 shows. It was as shown.

Example 4
50 parts by weight of Adhesive 1, 1.7 g / 10 min of melt mass flow rate, and 50 ethylene / vinyl alcohol copolymers (manufactured by Kuraray Co., Ltd., trade name F-171B, hereinafter referred to as EVOH2) having an ethylene content of 32 mol%. It was produced by the same method as in Example 1 except that it was made by weight, and the adhesiveness to LDPE was evaluated using the obtained resin composition. As a result, it was as shown in Table 2.

Example 5
It was produced by the same method as in Example 1 except that the adhesive 2 was 50 parts by weight and the EVOH 1 was 50 parts by weight, and the adhesiveness to LDPE was evaluated using the obtained resin composition. Table 2 shows. It was as shown.

Example 6
It was produced by the same method as in Example 1 except that the adhesive 3 was 50 parts by weight and the EVOH 1 was 50 parts by weight, and the adhesiveness to LDPE was evaluated using the obtained resin composition. Table 2 shows. It was as shown.

Example 7
It was produced by the same method as in Example 1 except that the adhesive 7 was 40 parts by weight and the EVOH 1 was 60 parts by weight, and the adhesiveness to LDPE was evaluated using the obtained resin composition. Table 2 shows. It was as shown.

Example 8
It was manufactured by the same method as in Example 1 except that the adhesive 8 was 40 parts by weight and the EVOH 1 was 60 parts by weight, and the adhesiveness to LDPE was evaluated using the obtained resin composition. Table 2 shows. It was as shown.

Example 9
It was produced by the same method as in Example 1 except that the adhesive 9 was 40 parts by weight and the EVOH 1 was 60 parts by weight, and the adhesiveness to LDPE was evaluated using the obtained resin composition. Table 2 shows. It was as shown.

Comparative Example 1
It was produced by the same method as in Example 1 except that EVOH1 was used as the resin composition, and the adhesiveness to LDPE was evaluated using the obtained resin composition. As a result, it was as shown in Table 3.

Comparative Example 2
The adhesive 4 was produced in the same manner as in Example 1 except that the adhesive 4 was 50 parts by weight and the EVOH 1 was 50 parts by weight, and the obtained resin composition was used to evaluate the adhesiveness to LDPE. The results are shown in Table 3. It was a street.

Comparative Example 3
It was manufactured by the same method as in Example 1 except that the adhesive 5 was 50 parts by weight and the EVOH 1 was 50 parts by weight, and the adhesiveness to LDPE was evaluated using the obtained resin composition. Table 3 shows. It was as shown.

Comparative Example 4
It was produced by the same method as in Example 1 except that the adhesive 6 was 50 parts by weight and the EVOH 1 was 50 parts by weight, and the adhesiveness to LDPE was evaluated using the obtained resin composition. Table 3 shows. It was as shown.

Claims (8)

A resin composition comprising an adhesive satisfying the following requirements (1) and (2) and a polyvinyl alcohol and / or an ethylene / vinyl alcohol copolymer satisfying the following requirements (3).
(1) Contains at least one homopolymer of α-olefin having 2 to 12 carbon atoms or a copolymer thereof, a copolymer of ethylene and vinyl ester, or a copolymer of ethylene and acrylic acid ester. Copolymer (B) of ethylene and vinyl ester and / or acrylic acid ester having a vinyl ester and / or acrylic acid ester content of 5 mol% or more more than the thermoplastic resins (A) and (A), and (A). Hydrolyzate of melt-kneaded product containing the polymer (C) grafted with (B) (2) Vinyl alcohol content is 0.5-40 mol%, vinyl ester and / or acrylic acid ester content is 30 mol% or less ( 3) Ethylene content is 55 mol% or less The resin composition according to claim 1, wherein the adhesive contains a compatibilizer (D). The invention according to claim 1 or 2 , wherein the adhesive is 10 to 90 parts by weight, and the polyvinyl alcohol and / or the ethylene / vinyl alcohol copolymer is 10 to 90 parts by weight (the total of these is 100 parts by weight). Resin composition. A laminated body, wherein the layer made of the resin composition according to any one of claims 1 to 3 is laminated with a layer containing polyolefin. A laminated body characterized in that a layer containing a polyolefin is laminated on both sides of a layer made of the resin composition according to any one of claims 1 to 3 . A blow-molded product comprising the laminate according to claim 4 or 5. A sheet molded product made of the laminate according to claim 4 or 5. A film molded product made of the laminate according to claim 4 or 5.