JPH0152180B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention provides a laminate consisting of a nitrile resin layer and a polyolefin resin composition layer, and a laminate including this laminate and a polyolefin resin layer, a vinyl chloride resin or vinylidene chloride resin layer, a thermoplastic polyester resin layer, etc. The invention relates to a laminate in which each layer is firmly adhered, and particularly to a laminate useful as a film or container for food packaging. Nitrile resin has good rigidity, heat resistance, transparency, and gas permeation resistance, so it is used in foods,
It has desirable properties for packaging films and containers for pharmaceuticals, etc. However, nitrile resins have drawbacks such as relatively high moisture permeability and poor heat sealability, and therefore it has been proposed that they be put to practical use as a laminate with polyolefin. Although coextrusion methods and extrusion lamination methods are useful for obtaining such laminates, good laminates cannot be obtained because polyolefins and nitrile resins have poor affinity. Therefore, in the case of the extrusion lamination method, various anchor coating treatments are applied, and in the case of the coextrusion method, the adhesiveness is improved by modifying the polyolefin resin. However, the anchor coating treatment has many problems due to the use of organic solvents, and modification of polyolefin resins has not yet sufficiently improved adhesion.
For example, in JP-A-49-28683, there is an example of a combination of nitrile resin and modified polyolefin.
It is necessary to use a specific nitrile resin, and the adhesive strength between the two is not sufficient. Also, JP-A-54
-11978 has an example in which a conjugated diene styrene block copolymer is used as an intermediate layer to melt and bond a nitrile resin and a polyolefin, but the heat resistance and oil resistance as an adhesive layer are insufficient, and the adhesive strength is also insufficient. It's not something. Moreover, if useful resin layers such as other types of polyolefin layers, vinyl chloride resin or vinylidene chloride resin layers, and polyamide resin layers can be laminated on both laminated components, the barrier properties, mechanical strength, heat resistance, etc. will be significantly improved. Although excellent laminates can be expected, a strong adhesive resin capable of simultaneously bonding such resin layers has not yet been invented. As a result of intensive research into such strong adhesive resins, the present inventors have arrived at the laminate of the present invention. That is, the present invention comprises 1 a high nitrile copolymer resin layer (A) containing 50% by weight or more of polyacrylonitrile or unsaturated nitrile, 5 to 70 parts by weight of a thermoplastic polyurethane elastomer, and a carboxylic acid in the main chain or side chain. Modified polyolefin containing one or more functional groups selected from the group consisting of carboxylic acid salts, carboxylic acid anhydrides, amide groups, hydroxyl groups, and epoxy groups, or copolymers mainly composed of olefins containing the above functional groups95- The resin composition layer (B) consisting of 30 parts by weight consists of at least two layers laminated in the order of (B)/(A), or the resin composition layer (B) consists of at least two layers laminated in the order of (B)/(A)/(B). Laminated product 2 consisting of at least three laminated layers The same resin composition layer as the resin layer (A) described in item 1 above
A laminate consisting of at least two layers in which (B) is in contact with each other and at least three layers in which a resin layer selected from the following resin layers is in contact with layer (B) 50% by weight of polyacrylonitrile or unsaturated nitrile High nitrile copolymer resin layer containing the above (A) Polyolefin resin layer (C) Polyamide resin layer (D) Vinylidene chloride resin layer (E) Polyester resin layer (F) Ethylene-vinyl alcohol copolymer resin layer
(G) 3 The above item 1 or 2, wherein the high nitrile copolymer resin layer (A) is an unstretched or stretched film formed by a wet method of an acrylonitrile polymer containing 65 to 98% by weight of acrylonitrile. Laminate 4 Laminate 5 according to item 1 or 2 above, wherein the high nitrile copolymer resin (A) layer is a thermoplastic high nitrile copolymer resin containing 50 to 85% by weight of unsaturated nitrile. Resin composition Laminate 6 according to item 1 or 2 above, wherein the modified polyolefin in the product (B) is a modified polyolefin grafted with an unsaturated carboxylic acid or an unsaturated carboxylic acid hydrate.Modification in the resin composition layer (B) Polyolefin is
The laminate according to item 1 or 2 above, which is an ionomer resin made of an ethylene-unsaturated carboxylic acid copolymer or a partial metal salt of an ethylene-unsaturated carboxylic acid copolymer. In the present invention, the resin constituting the resin layer (A) is polyacrylonitrile or unsaturated nitrile.
It is a high nitrile copolymer resin containing at least % by weight. Among these, copolymer resins or homopolymers containing 85% by weight or more of unsaturated nitriles such as acrylonitrile and methacrylonitrile are usually difficult to mold by heating and melting, and are molded into fibers or films by wet methods. For example, it can be made into a film by the method disclosed in Japanese Patent Publication No. 54-15069, which was invented by the present applicant. Such a film can be laminated with the resin composition layer (B) by extrusion lamination, heat fusion, etc. Copolymer resins containing less than 85% by weight of unsaturated nitrile can usually be molded by heating and melting. General-purpose molding methods for plastic resins can be applied, and the resin composition layer
It can also be laminated with (B) by a molding method such as coextrusion blowing or coextrusion film. The unsaturated nitrile content is desirably 50% by weight or more in order to obtain good gas barrier properties. Monomers that can be copolymerized with unsaturated nitriles include acrylic esters, vinyl esters, vinyl halides, vinyl aromatic compounds, unsaturated carboxylic acids, dienes, etc. Random copolymers and graft copolymers , block copolymers, alternating copolymers, etc., or mixtures of these various copolymers. In the present invention, the resin composition constituting the resin composition layer (B) is a thermoplastic polyurethane elastomer 5
~70 parts by weight and a carboxylic acid group in the main chain or side chain,
Modified polyolefin containing one or more functional groups selected from the group consisting of carboxylic acid bases, carboxylic acid anhydride groups, amide groups, hydroxyl groups, and epoxy groups, or copolymers mainly composed of olefins containing the above functional groups 95 It is a resin composition consisting of ~30 parts by weight. The thermoplastic polyurethane elastomer used in the resin composition layer (B) used in the present invention includes polyether diols such as polyoxytetramethylene glycol and polyethylene ether glycol, polyethylene adipate, and poly(1,4- butylene adipate), poly(1,6-hexane adipate), polyester diols such as polytetramethylene sebacate, polycaprolactone, polyhexamethylene carbonate, or mixtures thereof, ethylene glycol, 1,4 -butylene glycol, 1,
Glycols such as 6-hexamethylene glycol, bishydroxyethoxybenzene, diamines such as ethylenediamine, 1,4-butylenediamine, cyclohexanediamine, tolylenediamine, hydrazine, monoalkylhydrazine, N,N'-diaminopiperazine hydrazines such as carbodihydrazide, dihydrazides such as adipic acid dihydrazide, difunctional low molecular weight compound components of water or mixtures thereof, diphenylmethane diisocyanate, dicyclohexylmethane diisocyanate, isophorone diisocyanate, tolylene diisocyanate ,
and a diisocyanate component such as xylylene diisocyanate, isopropylidene bis(4-phenyl isocyanate), tetramethylene diisocyanate, hexamethylene diisocyanate or mixtures thereof. Thermoplastic polyurethane elastomers are made by combining the active hydrogen groups [AH] contained in the bifunctional polyol component and the bifunctional low molecular weight compound component and the [NCO] groups contained in the diisocyanate component at a molar ratio of [NCO]/[AH]≒1. This is a reacted linear polymer. In the present invention,
A fully thermoplastic type synthesized with approximately 0.5<[NCO]/[AH]≦1, preferably approximately 0.95<[NCO]/[AH]≦, and 1<[NCO]/[AH]
<1.2 Preferably approximately 1<[NCO]/[AH]<
Both the incomplete thermoplastic type synthesized in 1.1 can be used. The former has a completely linear structure at the end of the hydroxyl group or amino group, and the latter has a partially linear structure with crosslinking points. Such thermoplastic polyurethane elastomers can be produced by various known methods such as bulk polymerization or solution polymerization.
Further, TPU may contain additives such as a heat stabilizer, a plasticizer, a lubricant, a hydrolysis resistance improver, a yellowing improver, and a filler. The modified polyolefin or the copolymer mainly composed of olefin used in the resin composition layer (B) used in the present invention means that the main chain or side chain thereof contains a carboxylic acid group, a carboxylic acid base, or a carboxylic acid anhydride. base,
Contains one or more functional groups selected from the group consisting of an amide group, a hydroxyl group, and an epoxy group,
For example, the following types are possible: One is a modified polyolefin in which a saturated carboxylic acid or its derivative, and other possible vinyl monomers are grafted onto the polyolefin. In this case, the polyolefins include high density polyethylene, medium density polyethylene, low density polyethylene, polypropylene,
Polybutene, poly4-methylpentene-1, copolymer of ethylene and alpha olefin, propylene and alpha
Polyolefins such as olefin copolymers, ethylene-propylene rubber, ethylene-propylene-diene ternary copolymer rubber, butyl rubber, butadiene rubber, low-crystalline ethylene-propylene copolymers or low-crystalline ethylene-butene copolymers Polyolefin thermoplastic elastomers consisting of
It includes polyolefin elastomers such as polyolefin thermoplastic elastomers mainly composed of blends of polypropylene and ethylene-propylene rubber, ethylene-vinyl ester copolymers, ethylene-acrylic ester copolymers, etc., and also includes blends of various polyolefins. . On the other hand, the unsaturated carboxylic acids or derivatives thereof and other functional vinyl monomers referred to in the present invention include, for example, carboxylic acids such as acrylic acid, methacrylic acid, maleic acid, fumaric acid, itaconic acid, and sorbic acid, maleic anhydride, Acid anhydrides such as itaconic anhydride, amides such as acrylic acid amide and methacrylic acid amide, epoxies such as glycidyl acrylate and glycidyl methacrylate, 2-hydroxyethyl acrylate, 2-methacrylic acid
-Hydroxy compounds such as hydroxyethyl and polyethylene glycol monoacrylate, metal salts such as sodium acrylate, sodium methacrylate, and zinc acrylate, etc., and they can be used in combination. Among them, acrylic acid, maleic acid, and maleic anhydride give preferable results. In addition, when using the above-mentioned monomer, it is also possible to use it simultaneously with other kinds of monomers such as styrene, vinyl acetate, acrylic ester, etc. to carry out co-graft copolymerization. The amount of unsaturated carboxylic acid or its derivative or other functional vinyl monomer contained in the graft-modified polyolefin is preferably 0.005 to 5 mol%, more preferably 0.01 to 1.0%.
A range of mol % is desirable, and even if the amount is small, it can be effective if the functional group contained in the polyolefin has a strong interaction with the thermoplastic polyurethane elastomer. However, if the amount is less than the above range, the remarkable effects of the present invention cannot be obtained, and if the amount is more than the above range, the moldability, thermal stability, etc. of the composition will deteriorate, which is not preferable. In addition, unsaturated carboxylic acid or its derivative,
Various methods can be employed to prepare polyolefins graft-modified with other functional vinyl monomers. One method is to simultaneously mix polyolefins, unsaturated carboxylic acids or derivatives thereof, and other functional vinyl monomers with a radical generator to homogenize the melt. There is a method of adding an unsaturated carboxylic acid or its derivative, other functional vinyl monomer, and a radical generator to suspended polyolefin. On the other hand,
It is also possible to carry out the above reaction in the presence of the thermoplastic polyurethane elastomer referred to in the present invention. Another type of modified polyolefin referred to in the present invention is a saponified product of an ethylene-vinyl ester copolymer,
Alternatively, it is possible to use a modified product obtained by grafting the above-mentioned unsaturated carboxylic acid or its derivative or other functional vinyl monomer onto a saponified product of an ethylene-vinyl ester copolymer. In this case, ethylene-
The vinyl ester copolymer is preferably a copolymer mainly composed of ethylene, and the ethylene content is preferably 50 mol% or more. Further, the degree of saponification is preferably in the range of 10 to 100%. Those in this range include thermoplastic polyurethane elastomer,
Forms a composition with good moldability and physical properties. On the other hand, a modified product obtained by grafting the above-mentioned unsaturated carboxylic acid, a derivative thereof, or other functional vinyl monomer onto the saponified product of the above-mentioned ethylene-vinyl ester copolymer can also be used in the present invention. The type, amount, and modification method of monomers are the same as those for the modified polyolefin described above. As copolymers mainly composed of olefins that can be used in the present invention, copolymers of α-olefins and unsaturated carboxylic acids or derivatives thereof, and other functional vinyl monomers are possible. Also possible are so-called ionomer resins consisting of partial metal salts of copolymers of. For example, it consists of partial metal salts of ethylene-acrylic acid copolymer, ethylene-methacrylic acid copolymer, ethylene-acrylic acid-methacrylic acid ester copolymer, and ethylene-acrylic acid-methacrylic acid ester copolymer. There are ionomer resins, ionomer resins made of partial metal salts of ethylene-acrylic acid copolymers, and the like. The above-mentioned various modified polyolefins and copolymers mainly composed of olefins can be used in mixtures with each other, or they can be used in mixtures with unmodified polyolefins to the extent that the concentration of the functional groups does not become too low. can. the thermoplastic polyurethane elastomer;
The blending ratio of the modified polyolefin or the copolymer mainly composed of olefin is in the range of 5 to 70 parts by weight for the former and 95 to 30 parts by weight for the latter. especially,
When such a resin composition is used as an adhesive resin layer (B) between a nitrile resin layer (A) and a polyolefin resin layer (C), the thermoplastic polyurethane in the resin composition layer The blending ratio of the elastomer and the above-mentioned modified polyolefin or olefin-based copolymer is preferably within the inverted phase region of the "sea-island" dispersed structure of both. In other words, for the resin layer (A) side which has adhesiveness to thermoplastic polyurethane elastomer but has low adhesiveness to modified polyolefin or copolymer mainly composed of olefin, the thermoplastic in the resin composition Polyurethane elastomer is the “sea” (continuous phase)
A dispersed state in which the modified polyolefin or the copolymer mainly composed of olefin forms "islands" (discontinuous phase) is desirable. Conversely, for the resin layer (C) side, which has adhesive properties to modified polyolefins or copolymers mainly composed of olefins, but has low adhesive properties to thermoplastic polyurethane elastomers, A desirable dispersion state is that the polyolefin or copolymer mainly composed of olefin is the "sea" (continuous phase) and the thermoplastic polyurethane elastomer is "island" (discontinuous phase). Therefore, the resin composition layer (B) is the same as the resin layer (B) and the resin layer (C).
In order to obtain the highest adhesion for both layers, it is desirable that both components in the resin composition have a structure in which both components form a "sea" (continuous phase). That is, in the laminate of the present invention, when the resin composition layer (B) acts as an intermediate adhesive layer between the resin layer (A) and the resin layer (C), the thermoplastic polyurethane elastomer in the resin composition and , a region where the "sea-island" dispersion state of the modified polyolefin or the olefin-based copolymer is reversed and the "sea-island" dispersion state is destroyed. The optimal blending ratio of both components to achieve such a dispersed state varies depending on their melt viscosity, chemical affinity, manufacturing method or molding method, etc., but the thermoplastic polyurethane elastomer is 10 to 60% by weight. It is preferable to select 90 to 40 parts by weight of the modified polyolefin or the copolymer mainly composed of olefin, in order to obtain optimum adhesion, as well as from the viewpoint of moldability and economy. On the other hand, the resin layer (A) made of nitrile resin
In order to simultaneously melt and bond to the polyolefin resin layer (C), even if the dispersion structure in the resin composition layer (B) shows a clear "sea-island" dispersion structure, it is necessary to ”, the minor axis of the discontinuous phase particle is
If the fine dispersion is 100 μm or less, the same effect as in the region where the “sea-island” dispersion state of the above-mentioned modified polyolefin or olefin-based copolymer is destroyed can be obtained. In particular, it is desirable that the minor axis of the discontinuous phase particles is as small as possible, and more preferably
It is desirable that the thickness be 50μ or less, more preferably 20μ or less, still more preferably 10μ or less. If the minor axis of the discontinuous phase particles exceeds 100μ, the adhesive strength by thermal bonding will be particularly low, and both the physical properties and moldability will decrease. The concentration range of both components for achieving such a dispersed state can be selected within the above range, although the optimal blending ratio varies depending on the melt viscosity of both components, chemical affinity, manufacturing method or molding method, etc. Melt-kneading is the simplest method for producing such a resin composition. It can be produced by melt-kneading a mixture mixed at a predetermined blending ratio using a device such as a single-screw extruder, a multi-screw extruder, a Banbury mixer, a kneader, or a mixing roll. Points to be noted are that the degree of kneading affects the dispersion state and physical properties of the resin composition, and that the thermoplastic polyurethane elastomer has low thermal stability. It is desirable to sufficiently increase the degree of kneading within a range that does not impair the thermal stability of the thermoplastic polyurethane elastomer. In addition to the above-mentioned composition, other kinds of synthetic elastomers can be additionally added to such a resin composition. In addition, molding scraps of the laminate,
Various additives such as heat stabilizers, ultraviolet absorbers, lubricants, antistatic agents, fillers, flame retardants, tackifiers, dyes and pigments can also be added to the extent that they do not significantly reduce adhesiveness. The polyolefin resin constituting layer (C) in the present invention includes the above-mentioned modified polyolefins in the resin composition constituting layer (B), the above-mentioned polyolefins that can be raw materials for the modified polyolefin, and the above-mentioned polyolefins that can be used as raw materials for the modified polyolefin. Includes copolymers based on olefins. In particular, for layer (C), it is desirable to use the same type of polyolefin as the modified polyolefin constituting layer (B) from the viewpoint of adhesiveness and moldability. The polyamide resin constituting the layer (D) in the present invention is a thermoplastic polymer having an amide bond,
For example, nylon 6, nylon 66, nylon 10,
These polyamides, such as nylon 11, nylon 12, nylon 610, polymethaxylylene adipamide, polymethaxylylene sebacamide, etc., may be in an unstretched state or in a uniaxially or biaxially stretched state. It may be hot. The vinyl chloride resin or vinylidene chloride resin constituting the layer (E) in the present invention is mainly a polymer or copolymer of vinyl chloride or vinylidene chloride. As a comonomer for the copolymer,
Vinyl acetate, acrylic esters, acrylonitrile, olefins, maleic acid derivatives, etc. are possible. Particularly preferred as the vinylidene chloride resin is a copolymer containing 70 to 90% by weight of vinylidene chloride and 10 to 30% by weight of vinyl chloride as main components. In addition, modified resins such as post-chlorinated vinyl chloride resin, blended resins with ABS resin, MBS resin, chlorinated polyethylene, etc., and vinyl chloride graft copolymer resins with ethylene vinyl acetate copolymer or polyfin as the backbone polymer are also available. It is. It is also possible to use a mixture of the above-mentioned resins, and it goes without saying that various additives such as stabilizers, plasticizers, lubricants, fillers and the like can be used in combination. The thermoplastic polyester resin constituting layer (F) in the present invention is a thermoplastic polymer having an ester bond, such as polyethylene terephthalate, polybutylene terephthalate, polyethylene terephthalate/isophthalate copolymer, polyethylene terephthalate/ Refers to adipate copolymers, etc. In the present invention, the ethylene-vinyl alcohol copolymer resin constituting the resin layer (G) is produced by saponifying an ethylene-vinyl acetate copolymer, has an ethylene content of 15 to 50 mol%, and a saponification degree of 90.
% or more is desirable. Outside the above range, the balance between gas permeation resistance, moldability, and physical properties is not sufficient for practical use. The above-mentioned ethylene-vinyl alcohol copolymer resin may include polyolefins, modified polyolefins, copolymers mainly composed of olefins, and resin compositions (B) as long as they do not significantly reduce gas permeation resistance. resin composition,
It is possible to add other blend polymers, and it is also possible to blend heat stabilizers, plasticizers, lubricants, and other various additives. The laminate of the present invention has (A) (B) both layers, or (A), (B),
(C), (D), (E), (F), It is obtained by joining each layer, but the joining method is known, such as coextrusion molding, extrusion lamination, multilayer injection molding, and various heat welding methods. Any method can be adopted, such as the law. In particular, it is preferable to melt-extrude each component using separate extruders and join each layer inside a circular die or T-shaped die to obtain a multilayer film, multilayer sheet, multilayer blow molded product, etc. in a desired shape. On the other hand, the resin composition layer (B) alone or in combination with the resin layer (A) is melt-extruded to produce unstretched or stretched polyester resin, polyolefin resin, vinyl chloride resin, or vinylidene chloride resin. A laminate can also be obtained by extrusion lamination onto a resin and a base film or sheet such as the resin layer (A). Molding is possible as long as the molding temperature is higher than the softening temperature and lower than the decomposition temperature of each component, but a range of 150 to 230°C is usually desirable. In particular, in the case of coextrusion molding, it is desirable from the viewpoint of adhesiveness and moldability that the melt viscosities of the components constituting each layer are not extremely different. The structure of the laminate of the present invention includes not only a two-layer structure consisting of a resin layer (A) and a resin composition layer (B), but also
Sanderch structures such as (B)/(A)/(B) and (A)/(B)/(A) are also possible. Also, by adding a resin layer (C), (C)/(B)/(A), (C)/
A multilayer structure such as (B)/(A)/(B) or (C)/(B)/(A)/(B)/(C) can also be used. Furthermore, by adding a resin layer (D), (D)/(B)/(A) or (C)/(B)/(A)/(B)/(D)/(C)/(B )／(D)／(B)／(
A multilayer structure can also be formed by laminating layers in the order of A). Furthermore, by adding a resin layer (E), (E)/(B)/(A),
(A)／(B)／(E)／(B), (E)／(B)／(B)／(B)／(E), (C)／
(B)/
(A)／(B)／(E)、(C)／(B)／(E)／(B)／(A)、(C)／(B)／
(A)/
It is also possible to have a multilayer structure in which layers are stacked in the order of (B)/(E)/(B)/(C). Furthermore, by adding a resin layer (F), (F)/(B)/(A),
(F)／(B)／(A)／(B), (F)／(B)／(A)／(B)／(F), (C)／
(B)/
It is also possible to have a multilayer structure in which layers are stacked in the order of (A)/(B)/(F) and (C)/(B)/(F)/(B)/(A). Furthermore, by adding a resin layer (G), (G)/(B)/(A),
(A)／(B)／(G)／(B)、(A)／(B)／(G)／(B)／(C)、(G)／
(B)/
It is also possible to have a multilayer structure in which layers are laminated in the order of (A)/(B)/(C). The laminate of the present invention can also be used by being laminated with aluminum foil, OPP, polystyrene sheet, foamed polystyrene sheet, paper, or other laminate base material as a laminate base material by a method such as dry lamination. The thickness structure of each layer of the laminate can be arbitrarily selected to meet requirements for quality, economy, etc. Also,
The shape of the laminate can be a film, a sheet, a pipe or other irregularly extruded product, a hollow molded product, or various other molded products. The laminate of the present invention has extremely good adhesion between resin layers, and has sufficient adhesion even under particularly severe conditions. Moreover, the nitrile resin layer (A) and the resin composition layer (B)
In addition to the two laminated components, polyolefin resin layers, vinyl chloride resin layers, vinyl chloride resins or vinylidene chloride resins, thermoplastic polyester resin layers, etc. are laminated in various combinations, resulting in high gas permeability. resistance, stiffness, mechanical strength,
It has water vapor permeation resistance, heat resistance, heat sealability, water resistance, oil resistance, and chemical resistance. For this reason, it is suitable for packaging films and containers for foods, medicines, cosmetics, etc., and can also be made into a laminate with excellent heat resistance so that it can be boiled and sterilized at high temperatures. Examples Aspects of the present invention will be illustrated below, but these are intended to explain the present invention in more detail and are not intended to limit the present invention. In addition, parts and % in Examples and Reference Examples indicate parts by weight and % by weight, respectively. Example 1 Maleic anhydride and medium density polyethylene were melt-kneaded in the presence of a radical generator to give an MI of 1.0 and a density of
0.933, maleic anhydride graft modified medium density polyethylene with a maleic anhydride content of 0.1% was obtained. This modified medium density polyethylene and thermoplastic polyurethane elastomer (manufactured by Nippon Polyurethane Co., Ltd., trade name: Paraprene P22S) were melt mixed and extruded using an extruder (extruder temperature 190°C) at the compounding ratio shown in Table 1. Resin composition pellets (B) were obtained. This resin composition pellet (B) is melted in an extruder,
A two-layer blown film molding die was fed. Meanwhile, in another extruder, 75 parts of acrylonitrile,
A copolymer (A) consisting of 25 parts of methyl acrylate was melted and supplied to the die to form a two-layer film having a layer (B) of 50 μm and a layer (A) of 30 μm. Width 10 from this film
A sample with a length of 10 cm and a length of 10 cm was cut, and one end of the sample was forcibly peeled off to measure the peel strength. (180° peeling, 200
mm/min chuck speed), the results are shown in Table 1. Reference Example 1 The resin composition of Example 1 was the same as Example 1 except that unmodified medium density polyethylene with an MI of 1.0 and a density of 0.933 was used instead of the maleic anhydride graft modified medium density polyethylene used in the production. Various resin compositions were produced in the same manner as above. Using this resin composition, a laminate was produced in the same manner as in Example 1, and its peel strength was measured. The results are shown in Table 1.

[Table] Example 2 A single layer film having a thickness of 80 μm was formed from the resin composition obtained in Example 1-2 using a single layer inflation film forming machine. This film was layered with a wet process film (thickness 40μ) of acrylonitrile copolymer containing 94% acrylonitrile and 6% methyl acrylate, and heated at 200°C.
A laminated film was obtained by thermocompression bonding at a pressure of 50 kg/cm ² for 5 minutes. The interlayer adhesion force was measured in the same manner as in Example 1, but the adherend broke at 100 g/cm or more. Example 3 A resin kneading product was produced by melt-kneading 60 parts of an ionomer resin (manufactured by DuPont, trade name: Surlyn 1650) and 40 parts of a thermoplastic polyurethane elastomer (manufactured by Kasei Upjion, trade name: Peresene 2102-80A). A film with a thickness of 80μ was obtained. This film and a 40 μm thick film made of a copolymer of 75 parts acrylonitrile and 25 parts styrene were bonded under heat and pressure in the same manner as in Example 2, and the interlayer adhesion was measured, and the adhesion was so strong that it could not be peeled off. Example 4 60 parts of maleic anhydride graft-modified polypropylene with MFI3, density 0.90, maleic anhydride content 0.2%, and thermoplastic polyurethane elastomer (manufactured by Otomo Bayer Urethane, trade name: Desmopan 585)
A resin composition consisting of 40 parts was produced in the same manner as in Example 1 to obtain a film with a thickness of 80 μm. This film and an 80μ thick film of high nitrile resin (manufactured by Sohio Co., Ltd., trade name: Barex 210) were bonded under heat and pressure in the same manner as in Example 2, and the interlayer adhesion was measured, and the adhesion was so strong that it could not be peeled off. Ta. Example 5 Thickness of the resin composition obtained in Example 1-2: 80μ
Single layer film (B) and Barex 210 thickness 80μ
Film (A) and films (C) to (G) below were stacked in contact with layer (B) and bonded under heat in the same manner as in Example 2. (However, (E) was bonded by thermocompression at 180°C.) Each of the obtained laminated films had excellent barrier properties, heat resistance, and oil resistance, and the interlayer adhesion strength was either non-peelable or non-peelable to the adherend. It was so good that it caused destruction. (C) High-density polyethylene film (MI1, density
0.953) Thickness 40μ (D) Nylon 6 (manufactured by Toray Industries, product name: Amilan)
CM1021) Film thickness: 40μ (E) Vinylidene chloride resin film (manufactured by Asahi Dow Co., Ltd., trade name: Saran) Thickness: 10μ (F) Biaxially stretched PET film (manufactured by Toray Industries, product name:
Lumirror) thickness 50μ (G) Ethylene-vinyl alcohol copolymer film (manufactured by Kuraray, product name: EVAL E) thickness
25μ.

Claims (1)

[Scope of Claims] 1. A high nitrile copolymer resin layer (A) containing 50% by weight or more of polyacrylonitrile or unsaturated nitrile, 5 to 70 parts by weight of a thermoplastic polyurethane elastomer, and a carboxylic acid in the main chain or side chain. , a modified polyolefin containing one or more functional groups selected from the group consisting of a carboxylate, a carboxylic acid anhydride, an amide group, a hydroxyl group, and an epoxy group, or a copolymer mainly composed of an olefin containing the above functional groups 95 The resin composition (B) consists of ~30 parts by weight,
A laminate consisting of at least two layers laminated in the order (B)/(A), or a laminate consisting of at least three layers laminated in the order (B)/(A)/(B). 2 High nitrile copolymer resin layer (A) containing 50% by weight or more of polyacrylonitrile or unsaturated nitrile, 5 to 70 parts by weight of thermoplastic polyurethane elastomer, and carboxylic acid, carboxylate, or carbon in the main chain or side chain. 95 to 30 parts by weight of a modified polyolefin containing one or more functional groups selected from the group consisting of acid anhydrides, amide groups, hydroxyl groups, and epoxy groups, or a copolymer mainly composed of olefins containing the above functional groups. A laminate comprising at least two resin composition layers (B) in contact with each other, and at least three resin layers selected from the following resin layers in contact with the layer (B). High nitrile copolymer resin layer containing 50% by weight or more of polyacrylonitrile or unsaturated nitrile (A) Polyolefin resin layer (C) Polyamide resin layer (D) Vinylidene chloride resin layer (E) Polyester resin layer (F) Ethylene-vinyl alcohol copolymer resin layer (G)