JPH05301997A - Adhesive resin composition - Google Patents

Abstract

PURPOSE:To provide the subject adhesive resin composition suitable for laminating a polyolefin-based resin film to a gas barrier film, a light-screening material or another functional material and capable of firmly bonding at a low cost. CONSTITUTION:This invented adhesive resin composition is composed of (a) an ethylene-based copolymer resin containing (meth)acrylamide derivative-derived units in an amount of 0.1 to 50wt.% and (b) a thermoplastic resin containing an unsaturated carboxylic acid (anhydride). The ratio of the (meth)acrylamide derivative-derived units contained in the above-mentioned composition is 0.05 to 40wt.%.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to an adhesive resin composition. More specifically, the units derived from an acrylamide derivative and / or a methacrylamide derivative (hereinafter, these are referred to as acrylamide derivatives, etc.) are 0.
The adhesive resin composition blended in a proportion of 05 to 40% by weight is used in food packaging materials, industrial packaging materials, automobile industry and the like.

In particular, the present invention relates to a resin composition which imparts high lamination adhesive strength between a thermoplastic resin such as polyester, polyamide, polyvinylidene chloride or a saponified product of ethylene-vinyl acetate copolymer and a polyolefin resin.

[0003]

2. Description of the Related Art In the field of packaging materials for food and industrial materials and automobile materials, it has been impossible for a single thermoplastic resin to satisfy all the required properties at the same time. In the field, in order to meet this demand, efforts have been made to combine various thermoplastic resins and alloy them.

Although there is a lamination of materials in one direction according to the purpose, it is not always in a situation where the lamination can be performed as intended.

[0005] The main reason for this is that the stacks intended for stacking usually have conflicting properties, and the adhesion between the materials becomes insufficient.

For this reason, various adhesive resins have been proposed so far, but they are not always able to meet the demand for higher sophistication.

For example, polyolefin resins are widely used because of their low cost, mechanical strength, hygiene and moldability. However, since the polyolefin resin has a poor gas barrier property, when it is used as a food container for mayonnaise, soy sauce, etc., long-term storage of such food is impossible. Further, the oil resistance is insufficient, and when used as a gasoline container, there are drawbacks such as a large amount of gasoline being lost and the container being swollen and deformed.

Various proposals have been made in the past in order to improve these drawbacks of the polyolefin resin, but they are subject to restrictions such as complicated manufacturing process, high cost and limited application design. Have not obtained satisfactory results.

One of the solutions is a polyester (hereinafter PE) having a property of compensating for the above-mentioned drawbacks of the polyolefin resin.
Abbreviated as T. ), Polyamide (hereinafter abbreviated as PA), saponified ethylene-vinyl acetate copolymer (hereinafter abbreviated as EVOH), laminated with aluminum foil, glass, or a gas barrier of olefin resin such as metal or inorganic material. Although a means for vapor-depositing a material is used, originally, it was difficult to obtain a laminate or a vapor-deposited layer having a high adhesive strength due to a poor affinity of the polyolefin resin with the above-mentioned resin or the like due to its chemical structure.

As a countermeasure, there is a proposal to provide an adhesive layer between layers. As the adhesive layer, a method of applying a dry lamination adhesive such as a polyurethane-based, polyacrylic-based, or polyester-based adhesive and laminating it, and an unsaturated carboxylic acid or an anhydride as an adhesive resin for lamination is graft-modified or co-deposited. Polymerized polyolefin resin (eg US Pat. No. 3,483,276; US Pat. No. 4,026,976)
No. 3,953,655, JP-A-51-9878.
No. 4, JP-B-44-15423, JP-B-49-482
No. 2, JP-B-52-39636, JP-B-52-326
No. 54, JP-A No. 50-77485, and many other known documents. ), Polyolefin resin and EV
A method of coextrusion molding with different extruders together with OH, PET, and PA has been proposed.

Further, there is a proposal to use an acrylamide derivative or the like as an adhesive resin between layers of a laminate of a polyolefin resin and EVOH, and has a general formula CH ₂ = CR ¹ CON.
A compound represented by R ² R ³ (wherein R ¹ , R ² and R ³ are H
Alternatively, it represents a lower alkyl group. ) Is used to graft the resin to an olefin resin (JP-A-60-165).
242), a method in which the grafted resin is mixed with a carboxy-modified olefin (co) polymer and used (JP-A-60-187550), and JP-A-60-1848.
No. 39 discloses a method in which an olefin (co) polymer is mixed with the grafted resin and used.

However, even by these methods, delamination of the laminate was often observed. Further, the production of the graft-modified product has an economical problem because it requires a modification step other than the polymerization of the base resin.

[0013]

DISCLOSURE OF THE INVENTION The present invention is an inexpensive method for laminating a polyolefin resin and a gas barrier material, a light shielding material or other functional material in the fields of packaging materials for foods and industrial materials and automobile materials. Moreover, it is an object of the present invention to develop an adhesive resin composition that can be firmly bonded.

[0014]

[Means for Solving the Problems] In order to solve the above-mentioned problems, the inventors of the present invention have conducted extensive studies and as a result, as a result, ethylene-based polymers containing 0.1 to 50% by weight of units derived from acrylamide derivatives and / or methacrylamide derivatives. A copolymer resin and a thermoplastic resin containing an unsaturated carboxylic acid or an anhydride group thereof, and an acrylamide derivative and / or
Alternatively, an adhesive resin composition, an acrylamide derivative, and / or an adhesive resin composition blended so that a unit derived from a methacrylamide derivative is 0.05 to 40% by weight with respect to the entire composition.
Alternatively, the unit derived from the methacrylamide derivative is 0.
1 to 50% by weight of an ethylene copolymer resin, an unsaturated carboxylic acid or a thermoplastic resin containing an anhydride group thereof and other thermoplastic resins, and derived from an acrylamide derivative unit and / or a methacrylamide derivative Ethylene containing 0.1 to 50% by weight of a unit derived from an adhesive resin composition and an acrylamide derivative and / or a methacrylamide derivative, which are blended in a proportion of 0.05 to 40% by weight based on the total amount of -Based copolymer resin, thermoplastic resin containing unsaturated carboxylic acid or its anhydride group, other thermoplastic resin and rubber substance, and the unit derived from acrylamide derivative unit and / or methacrylamide derivative Adhesive resin group compounded in a proportion of 0.05 to 40% by weight Could strongly adhere to the hard-to-bond of the polyolefin resin and other functional resin or metal foil such as a laminate by developing things.

The ethylene-based copolymer resin (hereinafter referred to as resin A) comprising ethylene and an acrylamide derivative of the present invention is described in Polymer Papers, Vol. 35, No.
12, pp. 795 (1978) and US Patent 3629.
209, Japanese Patent Publication No. 43-21655, Japanese Patent Publication 44-1
No. 9537, Japanese Patent Publication No. 43-23766, Japanese Patent Publication No. 43-
It can be obtained by a usual method described in JP-A No. 9063 and JP-A No. 63-304010.

Examples of the acrylamide derivative of the resin A of the present invention include N-alkylacrylamide, N, N-dialkylacrylamide, N-alkylmethacrylamide and N, N-alkylmethacrylamide.

Specifically, N-methylacrylamide,
N-ethylacrylamide, Nn-propylacrylamide, N-isopropylacrylamide, Nn-butylacrylamide, N-isobutylacrylamide,
Nt-butyl acrylamide, N, N-dimethyl acrylamide, N, N-diethyl acrylamide, N-ethyl methacrylamide, Nn-propyl methacrylamide, Nt-butyl methacrylamide, N, N-dimethyl methacrylamide , N, N-ditylmethacrylamide and the like and mixtures thereof may be used.

Of these, N-ethyl acrylamide, N-isopropyl acrylamide and Nt are preferred.
-Butylacrylamide, N, N-dimethylacrylamide, N, N-diethylacrylamide, Nn-propylmethacrylamide, Nt-butylmethacrylamide, etc. may be used.

The content of the units derived from the acrylamide derivative in the resin A is 0.1 to 50% by weight, preferably 1 to 45% by weight. If it is less than 0.1% by weight, the adhesive strength is poor, which is not preferable. On the other hand, if it exceeds 50% by weight, the copolymer resin gradually loses flexibility and becomes brittle, which is not preferable in some cases.

The resin A may contain a polymerizable third component monomer in addition to ethylene and the above acrylamide derivative.

Examples of the monomer of the third component include ester compounds, acid compounds, ether compounds, hydrocarbon compounds and the like. Specifically, as the ester compound, vinyl acetate, methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate,
Hexyl acrylate, octyl acrylate, lauryl acrylate, benzyl acrylate, N, N-dimethylaminoethyl acrylate, methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, hexyl methacrylate, octyl methacrylate, Lauryl methacrylate, N, N-dimethylaminoethyl methacrylate, methyl fumarate, ethyl fumarate, propyl fumarate, butyl fumarate, dimethyl fumarate, diethyl fumarate, dipropyl fumarate, dibutyl fumarate, methyl maleate, Examples thereof include ethyl maleate, propyl maleate, butyl maleate, dimethyl maleate, diethyl maleate, dipropyl maleate and dibutyl maleate.

Examples of the acid compound include acrylic acid, methacrylic acid, maleic acid, fumaric acid and the like.

Examples of the ether compound include methyl vinyl ether, ethyl vinyl ether, propyl vinyl ether, butyl vinyl ether, octadecyl vinyl ether, phenyl vinyl ether and the like.

Examples of the hydrocarbon compound include styrene, norbornene, butadiene, acrylonitrile, methacrylonitrile, acrolein, crotonaldehyde, trimethoxyvinylsilane, vinyl chloride and vinylidene chloride.

One type or two or more types of monomers for the third component can be selected according to the intended use. The content of the unit derived from the monomer of the third component in the polymer is at most 40% by weight. If the content exceeds 40% by weight, the original characteristics of the ethylene copolymer resin will be impaired.

The above-mentioned third component monomer that can be used in the present invention is basically preferably one that does not undergo any reaction other than the copolymerization reaction with the acrylamide derivative of the present invention, but the amount used should be determined in consideration of stoichiometry. If carried out, a monomer capable of reacting with the acrylamide derivative or the like can also be used.

Particularly, for applications requiring transparency,
In order to reduce the crystallinity of the ethylene copolymer resin, it is preferable to contain at least 3% by weight of the monomer of the third component. More preferably at least 5% by weight, particularly preferably at least 10% by weight are used.

When used in a field requiring oil resistance in industrial material applications, it is preferable to select and copolymerize a third component monomer having high polarity. In particular,
Specific examples of preferable monomers include acrylonitrile, acrylic acid, and acrylic acid ester.

In addition, in the field of food packaging, which is used, hygiene, low odor and low taste are strongly required. The odor caused by the monomer of the third component usually depends on the amount remaining in the copolymer and cannot be unconditionally limited, but is preferably at most 10% by weight. Particularly preferably, the amount of said monomer is at most 3% by weight. Especially for a laminate for which strict odorlessness and tastelessness are required, there is no or very little third component comonomer having a strong odor, and it is desirable that the amount of the comonomer is at most 1% by weight. ..

The ratio of the resin A containing 0.1 to 50% by weight of a unit derived from an acrylamide derivative is such that the ratio of the above-mentioned component units to the entire resin composition according to the present invention is
It should be blended in a proportion of 0.05 to 40% by weight, preferably 1 to 35% by weight, particularly preferably 3 to 30% by weight.

If it is less than 0.05% by weight, a strong adhesive strength cannot be obtained, which is not preferable. On the other hand, when the content is 40% by weight or more, the water absorbency becomes strong, which may hinder the extrusion molding.

The melt flow rate (190 ° C.) of the resin A of the present invention is preferably less than 300 g / 10 minutes, but in order to improve the miscibility with the resin C described later, a part of the resin C is used. It may be blended in advance and used, but in that case, there is basically no problem even if MI exceeds 300 g / 10 minutes.

Specific examples of the resin C used for this purpose include high-pressure low-density polyethylene, vinyl acetate obtained by the high-pressure method, ethyl (meth) acrylate, glycidyl (meth) acrylate, and (meth) acrylic acid. And copolymers of ethylene with comonomers, linear low-density polyethylene, high- and medium-density polyethylene, polypropylene, and block or random copolymers of propylene and ethylene or α-olefin.

"Other thermoplastic resin" used in the present invention
(Hereinafter, referred to as resin C) is a polyolefin resin (for example, polyethylene, polypropylene, polyisoprene, polybutene, poly-3-methylbutene-).
1, poly-4-methylpentene-1, polybutadiene, polystyrene, and copolymers of the constitutional units of the resin, for example, ethylene-propylene copolymer, butene-1, 4,
-Linear low-density polyethylene using methyl pentene-1, hexene-1, octene-1, etc. as comonomer, block copolymer of propylene-ethylene, styrene-butadiene copolymer, or mixture of these resins, graft weight Polymers, crosslinked products, block copolymers, etc.), ethylene-vinyl acetate copolymers and partially saponified products thereof, halogen-containing polymers (for example, polyvinylidene chloride, polyvinyl chloride, polyvinyl fluoride, polyvinylidene fluoride, Polychloroprene, chlorinated rubber, etc.), polymers of unsaturated carboxylic acids and their derivatives (for example, polymethylmethacrylate, polyalkyl acrylates, polyacrylonitrile, and copolymerization of the constituent monomers of the polymer with other monomers) Combined, for example, acrylonitrile styrene copolymer, ABS resin Ethylene - alkyl acrylate copolymers, ethylene - glycidyl methacrylate copolymer, ethylene - methacrylic acid copolymer and ionically crosslinked, etc.), polyacetal, polycarbonate, polyester (By way of example, polyethylene terephthalate,
Examples thereof include polybutylene terephthalate), nylon, polyphenylene oxide, polysulfone, and the like.

The thermoplastic resin containing an unsaturated carboxylic acid or an anhydride thereof used in the present invention includes the resin C including a dicarboxylic acid such as (anhydrous) maleic acid or an anhydride thereof, and a (meth) acrylic acid or the like. It is obtained by copolymerizing a monocarboxylic acid or the like in the polymer molecular chain, or by graft modification (hereinafter referred to as resin B). The resin A or the resin B does not achieve the object of the present invention even if the resin C is added, but the present inventors can achieve the object by the combination of the resin A and the resin B or the combination of the resin A, the resin B and the resin C. I found it.

Further, in the present invention, it was found that a rubber substance may be blended with the adhesive resin composition and used. The following may be mentioned as the rubber substance. For example, styrene-butadiene rubber, acrylonitrile-butadiene rubber, butyl rubber, chloroprene rubber, silicone rubber, acrylic rubber, urethane rubber,
Polybutadiene rubber, ethylene-propylene rubber, ethylene-propylene diene-polymer, polyisobutylene rubber, polybutene-1 rubber and the like are used. Further, ethylene and, for example, butene-1,4-methylpentene-
1, a low crystalline polyethylene (ULD) having a lower density than ordinary low density polyethylene as an application of the manufacturing technology of linear low density polyethylene (sometimes called LLD) as a copolymer with an α-olefin such as octene Or sometimes referred to as VLDPE) can also be used as the rubber component. Among these, especially in the field of food packaging, ethylene and propylene, butene-1,
A copolymer rubber containing one or more α-olefins such as 4-methylpentene-1 is excellent in hygiene.

From the viewpoint of compatibility with the resin A of the present invention, hygiene, price, etc., ethylene and .alpha.- of butene-1 or more carbon atoms.
Copolymer rubber materials with olefins are especially preferred. Also,
In the field of industrial packaging materials, the ethylene-α-olefin-dienter-polymers are excellent. Furthermore, these ethylene-
The α-olefin copolymer rubber material has especially a molecular weight of 200.
The very low molecular weight component of less than 0 is preferably 0.2% by weight or less.

The content of these rubber substances in the adhesive resin composition of the present invention is 3 to 50% by weight. This compounding amount is determined by the effect of improving the adhesive strength between the two resins of the laminate, practical physical properties, moldability, etc. When the compounding amount of the rubber substance exceeds 50% by weight, the moldability and flexibility of the adhesive layer are improved. ,
Properties such as heat resistance are lost. Further, if the amount of rubber is less than 3% by weight, the effect of improving the adhesive performance between the laminates is not clear. The rubber content in the adhesive resin composition is preferably 5 to 40% by weight, particularly preferably 10 to 30% by weight.

The polymer of ethylene and the acrylamide derivative and / or the methacrylamide derivative may be a block, a solution,
It is produced by a process such as suspension or emulsion, but the most common is bulk copolymerization method, which is
It is produced by radical polymerization in the temperature range of 100 to 300 ° C. under a pressure of 3000 atm. The preferable pressure and temperature ranges are 1000 to 2500 atm, and the average temperature in the reactor is 150 to 270 ° C. If the pressure is less than 700 atm, the molecular weight of the polymer cannot be sufficiently increased, resulting in deterioration of moldability and physical properties. Pressures over 3000 atm are essentially meaningless and only increase manufacturing costs. When the temperature is 100 ° C. or lower, the reaction is not stable and the conversion rate to the polymer is lowered, which is economically problematic. Three
If the temperature exceeds 00 ° C, the molecular weight of the polymer cannot be increased, and there is a risk of a runaway reaction.

In the production, the usual low-density polyethylene production equipment and techniques can be basically used. As a reactor type, an autoclave with a stirrer or a tubular type can be used, and if necessary, a plurality of reactors can be connected in series or in parallel to carry out multistage polymerization. Further, in the case of an autoclave type reactor, by dividing the inside of the reactor into a plurality of zones, it is possible to provide a temperature distribution and perform more strict temperature control.

In the polymerization, ethylene, the acrylamide derivative according to the present invention and the other monomer of the third component, if necessary, are compressed and injected into the reactor, and the radical initiator injected separately is used for polymerization.

As the radical initiator, a compound generating a free radical, mainly an organic peroxide is used.

It is also possible to use various chain transfer agents as molecular weight regulators in the polymerization.

The copolymer obtained by the polymerization as described above is discharged from the reactor together with the unreacted monomer, and is passed through the high-pressure separator, the intermediate-pressure separator and the low-pressure separator to form the polymer. After separating the monomer or the low molecular weight polymer, the monomer is pelletized through an extruder, and the unreacted monomer is recycled after removing the low molecular weight polymer with a filter. At the time of pelletizing, various additives as described later may be added.

The resin composition of the present invention is particularly excellent in the adhesive strength between the polyolefin resin and EVOH, PA, PET or metal. The latter material is not particularly limited, but particularly preferable characteristics when used as a laminate will be described.

EVOH has an ethylene content of 15 to
A composition having a composition of 60 mol% and a saponification degree of 90% or more of a vinyl acetate component is used. When the ethylene content is less than 15 mol%, melt moldability is deteriorated, and when the saponification degree of a vinyl acetate component is less than 90%. However, the gas barrier property is deteriorated.

EVOH having an ethylene content of 25 to 50 mol% and a saponification degree of 96% or more is preferable. In addition to ethylene and vinyl acetate (or saponified vinyl alcohol), acrylic acid, methacrylic acid, crotonic acid,
A small amount of unsaturated acid such as maleic acid or its alkyl ester, α-olefin such as propylene, butene, α-decene or α-octadecene may be contained as a comonomer.

PA is a linear polymer having an acid amide bond obtained by (1) condensation of diamine and dicarboxylic acid, (2) condensation of amino acid, and (3) ring opening of lactam. , 6-nylon, 6-nylon, 11-nylon, 12-nylon, copolymer nylon and the like.

PET is obtained by condensation of a saturated dibasic acid and glycols, and examples thereof include polyethylene terephthalate obtained from ethylene glycol and terephthalic acid, as well as phthalic acid, isophthalic acid, sebacic acid, adipic acid and azelaic acid. Polyethylene terephthalate copolymers containing saturated dibasic acids such as glutaric acid, succinic acid, and oxalic acid as other copolymer components, and 1,4-cyclohexanediol, diethylene glycol, propylene glycol, etc. as other diol components. Other polyethylene terephthalate-based copolymers used as other copolymer components, or a mixture thereof or the like.

Examples of the metal include iron, aluminum, copper, stainless steel and the like. It also includes a substance obtained by vapor-depositing a metal on the surface of a resin. The shape of the metal is a plate, a foil,
Examples include rods, tubes, wires and powder. Fine paper,
Examples include kraft paper, paperboard, glassine paper, and Japanese paper. Examples of the cloth include woven cloth and non-woven cloth.

The method for melt-laminating the adhesive resin composition of the present invention and the polyolefin resin is in-die laminating method, outside-die laminating method, and in some cases, the formed adhesive film is melted between the laminating substrates by a heat roll. A method such as a heat laminating method for pressure bonding or thermocompression bonding using a press or the like can be used. In addition, the composition of the present invention can use well-known additives and compounding agents, if necessary.

Examples of additives and compounding agents include antioxidants (heat stabilizers), ultraviolet absorbers (light stabilizers), antistatic agents, antifogging agents, flame retardants, lubricants (slip agents, antiblocking agents). Agents), inorganic and organic fillers, reinforcing materials, colorants (dyes, pigments), foaming agents, cross-linking agents, fragrances and the like.

In adding these additives, they may be added at the time of pelletizing in a polymerization line, but as in the conventional practice, the pellets and additives may be mixed in a Banbury mixer, rolls, various extruders or the like. It is common to use and knead. Depending on the case, it is also possible to dry-blend the pellets and the additive without melt-mixing them and then directly form them in a molding machine.

Hereinafter, description will be made according to examples. The present invention is not limited to these examples and can take any form as long as it is in line with its purpose.

[0055]

Although the adhesion mechanism of the adhesive resin composition of the present invention could not be elucidated, it was unsaturated with an ethylene copolymer resin containing 0.1 to 50% by weight of a unit derived from an acrylamide derivative or the like. A thermoplastic resin containing a carboxylic acid or an anhydride group thereof, and a composition in which another thermoplastic resin or a rubber substance is further blended, and 0.05 to 40% by weight of the acrylamide derivative unit relative to the whole.
The above-mentioned problems can be solved by blending such that the ratio becomes. Thus, the adhesive resin composition of the present invention is a copolymer of ethylene and an acrylamide derivative or the like which have been conventionally used, or a thermoplastic resin containing an unsaturated carboxylic acid or an anhydride group thereof, respectively. The adhesive strength is improved by using both of them together rather than by using them, and it is considered that these two components interact with each other. Hereinafter, the present invention will be described more specifically with reference to examples.

[0056]

【Example】

<< Preparation of Ethylene Copolymer Resin >> The ethylene copolymer resin used in the present invention had a volume of 4 liters and was produced using an autoclave type reactor divided into two zones. Polymerization is carried out at a temperature of 190 to 210 ° C. and a pressure of 1100 to 1
It was carried out using tertiary butyl peroxypivalate as an initiator under the condition of 300 atm. N, N dimethyl acrylamide and acrylamide were used as acrylamide derivative components, and other monomers and / or solvents were injected upstream of the second stage compressor and fed with ethylene into the first zone of the reactor. The purified copolymer was separated from unreacted monomers by a high pressure separator and a low pressure separator, and pelletized using an extruder to obtain a product. The following were used as the produced copolymers.

The polymer composition was determined by infrared spectroscopy and ¹³ CNMR.
Was used to determine. (A) Ethylene-N, N dimethylacrylamide copolymer (N, N dimethylacrylamide content = 19.2% by weight) (MFR3.5) (b) Ethylene-N, N dimethylacrylamide copolymer (N, N Dimethylacrylamide content = 37% by weight)
(MFR 3.7) (c) Ethylene-acrylamide copolymer (acrylamide content = 11.4% by weight) (MFR
4.6) (d) Ethylene-methylmethacrylate-N, N dimethylacrylamide copolymer (methylmethacrylate content 6.2% by weight, N, N
Dimethylacrylamide content = 9.1% by weight) (MF
R5.1) (e) Ethylene-N, N-dimethylacrylamide-maleic anhydride copolymer (MFR 7.4, ethylene content 87.9% by weight, N, N-dimethylacrylamide content 8.2% by weight, Maleic anhydride content 3.9% by weight)

<< Preparation of Ethylene-Unsaturated Dicarboxylic Acid Anhydride Copolymer >> It was produced using an autoclave type reactor divided into two zones with a volume of 4 liters. Polymerization was carried out under the conditions of a temperature of 190 to 230 ° C. and a pressure of 1800 to 1950 atm using tert-butyl peroxypivalate as an initiator. Unsaturated dicarboxylic acid anhydride or unsaturated dicarboxylic acid anhydride and other monomers and / or solvents were injected upstream of the second stage compressor and fed with ethylene into the first zone of the reactor. The purified copolymer was separated from unreacted monomers by a high pressure separator and a low pressure separator, and pelletized using an extruder to obtain a product. The following were used as the produced copolymers.

The polymer composition was determined by infrared spectroscopy and ¹³ CNMR.
Was used to determine. (F) Ethylene-methyl methacrylate-maleic anhydride copolymer (MFR 8.3, ethylene content 89.6
% By weight, methyl methacrylate content 7.6% by weight,
Maleic anhydride content 2.8% by weight) (g) Ethylene-ethyl acrylate-maleic anhydride copolymer (MFR 6.8, ethylene content 90.0% by weight, ethyl acrylate content 6.5%, maleic anhydride Acid content 3.5%) (h) Ethylene-itaconic anhydride copolymer (MFR8.
2, ethylene content 95.1% by weight, itaconic anhydride content 4.9% by weight) (i) ethylene-maleic anhydride copolymer (MFR8.
4, ethylene content 95.4% by weight, maleic anhydride content 4.6% by weight)

<< Preparation of Modified Polyolefin Resin >> (j) As modified polypropylene, a graft-modified ethylene / propylene random copolymer having an ethylene content of 4.5% by weight with maleic anhydride was used.
The graft modification was carried out using a twin-screw extruder, and washing with acetone after modification was performed to completely remove unreacted materials and the like. The MFR of modified polypropylene is (JIS K-7210,
230 ° C., 2.16 Kg) was 55 g / 10 minutes, and the content of units derived from maleic anhydride in the modified polypropylene was 0.9% by weight.

(K) The modified polyethylene used was a low density polyethylene melt-grafted with maleic anhydride. Graft modification was carried out using a twin-screw extruder. MFR of modified polyethylene (JIS K-676
0, 190 ° C., 2.16 Kg) was 5 g / 10 minutes, the density was 0.915, and the content of units derived from maleic anhydride in the modified polyethylene was 0.5% by weight.

The following substances were used as the rubber substance. (L) Ethylene-propylene copolymer rubber (ethylene content 70% by weight) (m) Ethylene-butene-1 copolymer rubber (ethylene content 72% by weight)

Example 1 The resins and rubbers used are abbreviated in (a) to (m) above. (K) 18% by weight, 190 ° C. MFR = 4.0 (g / 1
0 minutes) Unmodified low density polyethylene 60 with a density of 0.920
After dry blending wt%, (l) 12 wt% and (b) 10 wt% using a tumbler, 40φ, L
A composition was prepared by extruding in a strand form at 190 ° C. with an extruder of / D28, cooling with water, pelletizing, and melt-mixing. The adhesive resin composition thus obtained, EVOH having an ethylene content of 29 mol% (Soarnol DT manufactured by Nippon Synthetic Chemical Industry Co., Ltd.) and MFR at 190 ° C. were 3.0 (g / g).
Low density polyethylene (LDPE) which is 10 minutes) is used in a coextrusion molding machine with a die temperature of 220 ° C.
A flat film having a layered structure was used. The molding machine used and the conditions are as follows. Extruder 40φ 2 units, 4
It has a feed block of 3 types and 3 layers consisting of 5 φ 1 unit,
The die width is 300 mm, and the thickness of each layer is LDPE / resin composition of the present invention / EVOH = 30 μm / 20 μm / 2
It was set to 0 μm. The take-up speed was 30 m / min. The adhesive strength of the film thus obtained was measured as follows. The adhesive strength was measured by cutting the laminated sample in a width of 1.5 cm in the take-up direction to prepare a test piece, conditioning it at 23 ° C. and 50% humidity for 24 hours, and then performing a 180 ° peel test at a speed of 300 mm / min. Was done.

(Examples 2 to 15 and Comparative Examples 1 to 5) The compositions shown in Table 1 were produced in the same manner as in Example 1 except that the combination and mixing ratio of the resins were changed. The evaluation method was the same as in Example 1. These results are shown in Table 1 together with the results of Example 1. In the table, modified polyethylene (k) is modified PE, unmodified low-density polyethylene is unmodified LDPE, ethylene-based copolymer (a) to
(E) is represented by EDAA, and ethylene-unsaturated dicarboxylic acid anhydride copolymers (f) to (i) are represented by abbreviations of EAN.

Examples 16 to 21 and Comparative Examples 6 to 8 (k) of Example 1 and modified polypropylene instead of unmodified low-density polyethylene and unmodified polypropylene were used, and the ethylene content was 4.5% by weight. Using the ethylene-propylene random copolymer resin of, a resin composition was obtained in the same manner as in Example 1 below. Further, regarding the flat film of 3 types and 3 layers, ethylene content = 3.5% by weight, 23
A laminate with EVOH was obtained using an ethylene-propylene random copolymer resin at 0 ° C MFR = 8.2 (g / 10 minutes). Hereinafter, the molding conditions and the evaluation method were the same as in Example 1. The results are shown in Table-2.
In Comparative Example 8, the phenomenon of easy peeling from the ethylene-propylene random copolymer resin layer was observed. The abbreviations in the table show the modified polypropylene (j) as modified PP, the unmodified polypropylene as unmodified PP, and other resins as shown in Table-1.
The same abbreviations are used.

(Examples 22 to 23, Comparative Examples 9 to 11) Using the resin compositions of Examples 1 and 16, Comparative Example 1, Comparative Example 3 and Comparative Example 6, the specific gravity was 1. 1
The same procedure as in Example 1 was performed using Nylon 6 of No. 4 (1022B manufactured by Ube Industries, Ltd.). These results are shown in Table-3.
It was shown to. Regarding the layer structure of the three-kind three-layer flat film, Example 11 and Comparative Example 22 are ethylene-propylene random copolymer / adhesive resin composition of the present invention / nylon and others are LDPE / adhesive resin of the present invention. Composition/
I used nylon.

(Examples 24 to 27) Using the resin composition of Example 1, a 50 mmφ extruder and a laminating machine with a die width of 400 mm were used, and the thickness was 20 for various substrates.
μm, cooling roll temperature 25 ° C., take-up speed 120 m /
Coating was carried out under the conditions of a resin temperature of 260 ° C. for minutes. These results are shown in Table 4 together with the results of Comparative Examples 12-14.

Comparative Examples 12 to 13 Using the resin composition of Comparative Example 1, the same procedure as in Example 24 was performed.

Comparative Examples 14 to 15 Using the resin composition of Comparative Example 3, the same procedure as in Example 24 was performed.

Comparative Examples 16 to 17 Using the resin composition of Comparative Example 4, the same procedure as in Example 24 was performed.

[0071]

[Table 1]

[0072]

[Table 2]

[0073]

[Table 3]

[0074]

[Table 4] (Note) Abbreviation of base material in the table Al: Aluminum OPP: Biaxially oriented polypropylene PET: Polyethylene terephthalate ONY: Biaxially oriented nylon

[0075]

As is apparent from the above examples, the adhesive resin composition according to the present invention can significantly improve the adhesive performance. By using the adhesive resin composition, it is possible to produce a multi-layer laminate having improved adhesive performance as compared with the conventional multi-layer laminate. Since this multi-layer laminate has good adhesive strength, it can be used in a wide range of applications such as food containers, medical containers, laminated steel plates and structural materials.

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[Procedure amendment]

[Submission date] June 15, 1992

[Procedure Amendment 1]

[Document name to be amended] Statement

[Name of item to be corrected] 0066

[Correction method] Change

[Correction content]

(Examples 22 to 23, Comparative Examples 9 to 11) Using the resin compositions of Examples 1 and 16, Comparative Example 3, Comparative Example 4 and Comparative Example 6, the specific gravity was 1. 1
The same procedure as in Example 1 was performed using Nylon 6 of No. 4 (1022B manufactured by Ube Industries, Ltd.). These results are shown in Table-3.
It was shown to. Regarding the layer structure of the three-kind three-layer flat film, Example 23 and Comparative Example 11 are ethylene-propylene random copolymer / adhesive resin composition of the present invention / nylon and others are LDPE / adhesive resin of the present invention. Composition/
I used nylon.

[Procedure Amendment 2]

[Document name to be amended] Statement

[Correction target item name] 0071

[Correction method] Change

[Correction content]

[0071]

[Table 1]

[Procedure 3]

[Document name to be amended] Statement

[Correction target item name] 0073

[Correction method] Change

[Correction content]

[0073]

[Table 3]

Claims (5)

[Claims] 1. From an ethylene copolymer resin containing 0.1 to 50% by weight of a unit derived from an acrylamide derivative and / or a methacrylamide derivative and a thermoplastic resin containing an unsaturated carboxylic acid or an anhydride group thereof. And the unit derived from the acrylamide derivative and / or the methacrylamide derivative is 0.0 with respect to the entire composition.
An adhesive resin composition blended in a proportion of 5 to 40% by weight. 2. An ethylene copolymer resin containing 0.1 to 50% by weight of a unit derived from an acrylamide derivative and / or a methacrylamide derivative, a thermoplastic resin containing an unsaturated carboxylic acid or an anhydride group thereof, and An adhesive resin composition comprising other thermoplastic resin and blended so that the ratio of the acrylamide derivative unit and / or the unit derived from the methacrylamide derivative is 0.05 to 40% by weight based on the whole. 3. Another thermoplastic resin in the composition is 50
The adhesive resin composition according to claim 2, wherein the adhesive resin composition is contained in an amount of not more than wt%. 4. An ethylene copolymer resin containing 0.1 to 50% by weight of a unit derived from an acrylamide derivative and / or a methacrylamide derivative, a thermoplastic resin containing an unsaturated carboxylic acid or an anhydride group thereof, An adhesive resin composition comprising another thermoplastic resin and a rubber substance, and blended so that the ratio of the acrylamide derivative unit and / or the unit derived from the methacrylamide derivative is 0.05 to 40% by weight based on the whole. 5. The adhesive resin composition according to claim 4, wherein the rubber substance is contained in the composition in an amount of 3 to 50% by weight.