JPS6235909B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a laminate comprising a thermoplastic polyester resin layer, a polyolefin resin composition layer, and optionally a polyolefin resin layer, and relates to a laminate in which each layer is firmly adhered. Thermoplastic polyester resins such as polyethylene terephthalate and polybutylene terephthalate have excellent rigidity, gas barrier properties, transparency, oil resistance, and gloss, and their physical properties are significantly improved, especially in the stretched state, and they are also tough. For this reason, food and pharmaceutical containers,
Its use in fields such as packaging materials is expanding. However, polyester resins have drawbacks such as poor heat sealability, low water resistance, and low acid/alkali resistance. On the other hand, polyolefin resins have excellent heat-sealing properties, and also have good water resistance, moisture resistance, and acid/alkali resistance. Therefore, a laminate made of both materials has excellent gas barrier properties, water resistance, chemical resistance, heat sealability, mechanical strength, and heat resistance. However, it is inherently difficult to bond polyester and polyolefin, and an adhesive needs to be interposed between the two materials. Dry lamination and pressure lamination are currently the main methods used to laminate polyester and polyolefin.
As the adhesive, organic metal primers such as organic titanates and organic aluminum compounds, and isocyanate adhesives are used. However, these adhesives have no other function than adhesion;
In addition, there are problems with the toxicity of adhesives, occupational health problems due to the use of organic solvents, and other problems. Therefore, if there is a material that can firmly bond polyester and polyolefin together under heat without using such adhesives or organic solvents, and has good processability,
A laminate can be easily formed by coextrusion molding, extrusion lamination, or other methods. However, because it is difficult to bond polyolefin and polyester together, there have been few proposals for such materials or laminates, and there is only one proposal, JP-A No. 52-32078. However, although this proposal involves co-extrusion of modified polyolefin and polybutylene terephthalate, the polyester is limited to polybutylene terephthalate in a molten state, and the resulting laminate has low adhesive strength. However, the present inventors have completed the present invention as a result of intensive research into a laminate in which a thermoplastic polyester resin and a polyolefin resin are firmly adhered without the intervention of an adhesive. That is, the present invention comprises a thermoplastic polyester resin layer (A), 5 to 70 parts by weight of a thermoplastic polyurethane elastomer having a softening temperature of 105°C or higher, and a carboxylic acid group, carboxylic acid base, or carboxylic acid anhydride 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 chemical groups, amide groups, hydroxyl groups, and epoxy groups, or a copolymer mainly composed of olefins containing the above functional groups. The present invention relates to a laminate formed by laminating at least two resin composition layers (B) in contact with each other, or a laminate formed by further laminating a polyolefin resin layer (C) on this laminate. In the present invention, the thermoplastic polyester resin constituting the resin layer (A) includes, for example, terephthalic acid,
Isophthalic acid, 1,5-naphthalene dicarboxylic acid, 2,6-naphthalene dicarboxylic acid, 4,4'-
Aromatic dicarboxylic acids or esters thereof such as diphenyl dicarboxylic acid and bis(4-carboxydiphenyl) sulfone, and ethylene glycol, propylene glycol, tetramethylene glycol, pentamethylene glycol, 2,2-dimethyltrimethylene glycol, hexamethylene Polyesters produced from diols such as glycol, decamethylene glycol, P-xylylene glycol, and cyclohexanedimethanol, or copolyesters using two or more of these dicarboxylic acids or two or more diols, or P-
(β-hydroxyethoxy)benzoic acid, polyesters derived from oxyacids such as P-oxybenzoic acid and their esters, polylactones such as polypivalolactone, 1,2-bis(4,
Polyether esters produced from aromatic ether dicarboxylic acids such as 4'-dicarboxyphenoxy)ethane and the aforementioned diols; polyether esters produced from aliphatic dicarboxylic acids such as adipic acid and sebacic acid and the aforementioned diols; Possible examples include polyesters and copolyesters made by combining the above dicarboxylic acids, oxyacids, and diols. Particularly useful polyesters include polyethylene terephthalate and polybutylene terephthalate, but are not limited to these. However, rigid polyesters with melting points of 150° C. or higher are generally desirable for packaging applications. It is also possible to use the above resins in combination, and of course it is possible to mix various additives such as heat stabilizers, plasticizers, lubricants, fillers and others. In the present invention, the resin composition constituting the resin layer (B) includes 5 to 70 parts by weight of a thermoplastic polyurethane elastomer, a carboxylic acid group, a carboxylic acid base, a carboxylic acid anhydride group, an amide group, a hydroxyl group in the main chain or side chain,
It is a resin composition comprising 95 to 30 parts by weight of a modified polyolefin containing one or more functional groups selected from the group consisting of epoxy groups or a copolymer mainly composed of an olefin containing the above-mentioned functional groups. The thermoplastic polyurethane elastomer used in the present invention includes polyether diols such as polyoxytetramethylene glycol and polyethylene ether glycol, polyethylene adipate, poly(1,4-butylene adipate), and poly(1,6-hexane). adipate), polyester diols such as polytetramethylene sebacate, polycaprolactane, polyhexamethylene carbonate, or mixtures thereof, ethylene glycol, 1,4-butylene glycol, 1,6-hexane Glycols such as methylene glycol, bishydroxyethoxybenzene, diamines such as ethylenediamine, 1,4-butylenediamine, cyclohexanediamine, tolylenediamine, hydrazine, monoalkylhydrazine, N・N'-diaminopiperazine, etc. Difunctional low molecular weight compound components of hydrazines, carbodihydrazides, dihydrazides such as adipic acid dihydrazide, water or mixtures thereof, diphenylmethane diisocyanate, dicyclohexylmethane diisocyanate, isophorone diisocyanate, tolylene diisocyanate, xylylene diisocyanate diisocyanate components such as isocyanate, 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 in a molar ratio of [NCO]/[AH]≒/. This is a reacted linear polymer. In the present invention, approximately 0.5<
[NCO]/[AH]≦1, preferably approximately 0.95<
Completely thermoplastic type synthesized with [NCO]/[AH]≦1 and incomplete thermoplastic type synthesized with approximately 1<[NCO]/[AH]<1.2, preferably approximately 1<[NCO]/[AH]<1.1 Both plastic types 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. In addition, thermoplastic polyurethane elastomers include heat stabilizers, plasticizers, lubricants, hydrolysis resistance improvers, yellowing improvers,
Additives such as fillers, dyes and pigments may be blended. The softening temperature in the present invention is determined according to the Vikat softening temperature measurement method at a load of 10 kg/ ^cm2 and a needle cross-sectional area of 1 ^mm2 .
It is defined as the temperature when the needle penetrates the specimen by a depth of mm. In the present invention, a modified polyolefin or a copolymer mainly composed of an olefin is selected from the group consisting of a carboxylic acid group, a carboxylic acid base, a carboxylic acid anhydride group, an amide group, a hydroxyl group, and an epoxy group in its main chain or side chain. For example, the following types of functional groups are possible. One is a modified polyolefin in which an unsaturated carboxylic acid or its derivative, or other functional vinyl monomer is grafted onto the polyolefin.
In this case, the polyolefins include high-density polyethylene, medium-density polyethylene, low-density polyethylene, polypropylene, polybutene, poly4-methylpentene-1, a copolymer of ethylene and α-olefin, a copolymer of propylene and α-olefin, etc. class, ethylene-propylene rubber,
Ethylene-propylene-diene ternary copolymer rubber,
Butyl rubber, butadiene rubber, polyolefin thermoplastic elastomers made of low-crystalline ethylene-propylene copolymers or low-crystalline ethylene-butene copolymers, polyolefin-based thermoplastic elastomers mainly made of blends of polypropylene and ethylene-propylene rubber It includes polyolefin-based elastomers such as 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 acrylamide and methacrylic acid amide;
Epoxies such as glycidyl acrylate and glycidyl methacrylate, hydroxy compounds such as 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, and polyethylene glycol monoacrylate, metals such as sodium acrylate, sodium methacrylate, and zinc acrylate. Examples include salts, 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 10 mol%, more preferably 0.01 to 5.0 mol%.
A mole % range is desirable. If the functional group contained in the polyolefin has a strong interaction with the thermoplastic polyurethane elastomer, even a small amount can be effective. However, below the above range, the remarkable effects of the present invention cannot be obtained.
Moreover, if the amount exceeds 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, there is a modified product in which the above-mentioned unsaturated carboxylic acid or its derivative or other functional vinyl monomer is grafted onto a saponified product of an ethylene-vinyl ester copolymer. In this case, the ethylene-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%. This range forms compositions with thermoplastic polyurethane elastomers that have good molding 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 combination with each other. the thermoplastic polyurethane elastomer;
The blending ratio of the modified polyolefin or copolymer mainly composed of olefin is 5 to 70%.
parts by weight and the latter ranges from 95 to 30 parts by weight. In particular, when such a resin composition is used as an adhesive resin layer (B) between a thermoplastic polyester resin layer (A) and a polyolefin resin layer (C), The blending ratio of the thermoplastic polyurethane 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 A dispersion state in which the polyurethane elastomer is a "sea" (continuous phase) and the modified polyolefin or copolymer mainly composed of olefin is "islands" (discontinuous phase) is desirable. Conversely, a resin layer that has adhesiveness to modified polyolefin or a copolymer mainly composed of olefin, but has low adhesiveness to thermoplastic polyurethane elastomer.
For surface (C), the modified polyolefin or olefin-based copolymer in the resin composition is the "sea" (continuous phase), and the thermoplastic polyurethane elastomer is the "island" (discontinuous phase). Dispersion is preferred. Therefore, the resin composition layer (B) is the same as the resin layer (A).
and the resin layer (C), and in order to obtain the best adhesion to both layers, it is desirable that both components in the resin composition have a structure in which both are "sea" (continuous phase). It turns out. That is, in the laminate of the present invention, when the resin composition layer (B) acts as an intermediate adhesive layer between the thermoplastic polyester resin layer (A) and the polyolefin resin layer (C), The dispersion structure of the thermoplastic polyurethane elastomer and the modified polyolefin or copolymer mainly composed of olefin is such that the "sea-island" dispersion state is reversed, and the "sea-island" dispersion state is destroyed. Preferably an area where 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. It is preferable to select 80 to 40 parts by weight of the modified polyolefin or the copolymer mainly composed of olefin, in order to obtain optimum adhesiveness, as well as from the viewpoint of moldability and economical efficiency. On the other hand, in order to simultaneously melt and bond the resin layer (A) made of thermoplastic polyester resin and the polyolefin resin layer (C), even if the dispersion structure in the resin composition layer (B) is Even if the above-mentioned modified polyolefin or olefin-based copolymer exhibits a dispersion structure of "islands", if the minor axis of the discontinuous phase particles forming the "islands" is finely dispersed and is 100μ or less, The same effect as in the area where the "sea-island" dispersion state is destroyed can be obtained. In particular, the smaller the minor axis of the discontinuous phase particles, the more desirable it is.
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 bonding 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, heat stabilizers, ultraviolet absorbers, lubricants, antistatic agents, fillers, flame retardants, tackifiers,
Various additives such as dyes and pigments can also be added. The polyolefin resin constituting the polyolefin resin layer (C) according to the present invention includes a resin composition layer (B).
The above-mentioned modified polyolefins in the resin composition constituting the olefin, the above-mentioned polyolefins that can be used as raw materials for the modified polyolefin, and copolymers mainly composed of the above-mentioned olefins are included. In particular, the polyolefin resin layer (C) is a resin composition layer.
It is desirable to use the same type of polyolefin as the modified polyolefin constituting (B) from the viewpoint of adhesiveness and moldability. The laminate of the present invention can be obtained by joining both layers (A) and (B) or each layer (A), (B), and (C). For joining,
At least the resin composition layer (B) needs to be adhered to (A) in a molten state. Thermoplastic polyester resin layer (A)
may be in a molten state at the time of adhesion, may be in a cooled and solidified state, or may be in a uniaxially or biaxially stretched state. It is desirable that the polyolefin resin layer (C) be in a molten state when bonded, similar to the layer (B). Therefore, any known method such as coextrusion molding, extrusion lamination, extrusion coating, multilayer injection molding, various fusion bonding methods, etc. can be employed as the joining method. In particular, for polyester resins with relatively low melting points, such as polybutylene terephthalate, each component is melt-extruded using separate extruders and the layers are joined inside a circular die or T-shaped die to form the desired shape. Preferred is a method of obtaining a multilayer film, a multilayer sheet, a multilayer blow molded product, or the like. In this case, it is also possible to perform post-processing such as biaxial stretching subsequent to or after molding. In addition, when a polyethylene terephthalate biaxially stretched film has a high melting point and you want to take advantage of the excellent properties achieved by biaxially stretching, a method of extrusion lamination of the resin composition layer (B) onto the biaxially stretched film is preferable. . In this case, the polyolefin resin layer (C) is laminated on the resin composition layer (B) in a molten state by a method such as coextrusion molding or sequential extrusion molding, and the resin composition layer (B) is made of polyester biaxially stretched. Multilayer extrusion lamination with adhesive onto the film is also possible. 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
(B)／(A)／(B)、(A)／(B)／(A)′／(B)／(A)、(B)／(A)
/
Sanderch structures such as (B)/(A)'/(B) are also possible. (Here, A' indicates a polyester resin different from A.) Also, by adding a resin layer (C), (C)/(B)/
(A), (C)/(B)/(A)/(B), (C)/(B)/(A)/(B)/(C),
(C)/
A multilayer structure such as (B)/(A)/(B)/(A)'/(B)/(C) can also be used. In this case, by taking advantage of the features of the resin layer (C), a laminate with excellent mechanical strength, heat sealability, water resistance, chemical resistance, heat resistance, etc. can be obtained. Furthermore, combinations using other resins that have good adhesion to the resin composition layer (B), such as polyamide/(B)/(A), polyamide/(B)/(A)/(B)/( C), polyester/(B)/(A), vinyl chloride resin or vinylidene chloride resin/(B)/(A), vinyl chloride resin or vinylidene chloride resin/(B)/(A)/( B)／(C)
It can also be made into a laminate such as. Furthermore, using the laminate of the present invention as a laminate base material, aluminum foil, polyethylene terephthalate biaxially stretched film, nylon 66 biaxially stretched film, OPP, polystyrene sheet, paper, and other laminate base materials, and methods such as dry lamination can be used. It can also be used by laminating it. The thickness structure of each layer of the laminate can be arbitrarily selected to meet requirements such as quality and economy. Further, the shape of the laminate may be a film, a sheet, a pipe or other irregularly extruded product, a hollow molded product, or various other molded product shapes. The laminate of the present invention not only has extremely good adhesion between resin layers, excellent gas permeation prevention properties, and is easy to heat seal, but also has excellent resistance to water, oil, and chemicals. Due to its high rigidity, toughness, and good transparency, it is suitable for food packaging,
Ideal for packaging precision industrial products. In particular, when a polyolefin with a relatively high melting point, such as crystalline polypropylene or high/medium density polyethylene, is used as the base polymer for the resin composition layer (B), it has a high heat resistance that allows boiling and high temperature sterilization. It can also be made into a laminate with excellent properties. 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 high-density polyethylene were melt-kneaded in the presence of a radical generator to obtain a mixture with MI8.0 and density.
0.953, maleic anhydride graft-modified high-density polyethylene with a maleic anhydride content of 0.1% was obtained. This modified high-density polyethylene and thermoplastic polyurethane elastomer (manufactured by Nippon Polyurethane Co., Ltd., trade name: Paraprene P22S) were melt-mixed and extruded at 190°C using an extruder at the compounding ratio shown in Table 1 to form various resin compositions. Got pellets. This resin composition was supplied at a cylinder temperature of 210°C, and high-density polyethylene with a density of 0.945 and MI8 was supplied at a cylinder temperature of 230°C to a T-shaped multi-manifold multilayer die with a die temperature of approximately 220°C, and the molten laminated film was extruded. . The thickness of this laminated film was 15 μm for the resin composition layer (B) and 45 μm for the high density polyethylene layer (C). The resin composition layer (B) side of this molten film has a thickness of 50 mm without being subjected to anchor coating treatment.
A laminate film was produced by pressure-bonding and laminating a μ polyethylene terephthalate biaxially stretched film (trademark: Lumirror, manufactured by Toray Industries, Inc.) by a conventional method. Cut the obtained laminate into a piece with a width of 25 mm and a length of 15 cm.
One end of the film was forcibly peeled off, and the peel strength was measured.
(180° peeling, 200 mm/min chuck speed) The results are shown in Table 1. Reference Example 1 Except for using unmodified high-density polyethylene with an MI of 1.0 and a density of 0.953 in place of the maleic anhydride graft-modified high-density polyethylene used in producing the resin composition (B) in Example 1. Various resin compositions were produced in the same manner as in Example 1. Using this resin composition, various laminates were manufactured in the same manner as in Example 1, and their peel strengths were measured. The results are shown in Table 1.

【table】

[Table] Example 2 60 parts of the maleic anhydride graft modified polyethylene used in producing the resin composition (B) in Example 1 and 40 parts of the various thermoplastic polyurethane elastomers listed in Table 2 were used as an example. Various resin compositions were produced by melt-kneading in the same manner as in 1. Using this resin composition, various laminates were produced in the same manner as in Example 1, and their peel strengths were measured. The second result is
Shown in the table. Reference Example 2-1 In Example 2, except that a styrene-butadiene thermoplastic elastomer (manufactured by Asahi Kasei Corporation, trade name: Tuffrene A) was used instead of the thermoplastic polyurethane elastomer.
A laminate was produced and evaluated in the same manner as in Example 2.
The results are shown in Table 2. Reference Example 2-2 Example 2 except that a polyolefin thermoplastic elastomer (manufactured by Mitsui Petrochemical Industries, Ltd., trade name: Tafmer P0680) was used instead of the thermoplastic polyurethane elastomer. A laminate was produced and evaluated in the same manner as in Example 2. The results are shown in Table 2.

[Table] Example 3 Instead of the maleic anhydride graft modified polyethylene used in Example 1, 60 parts of various modified polyolefins or ethylene-based copolymers listed in Table 3 and 60 parts of the ethylene-based copolymer used in Example 1 were added. 40 parts of a thermoplastic polyurethane elastomer was melt-kneaded in the same manner as in Example 1 to produce various resin compositions. These resin compositions were used as the (B) layer and various polyolefin resins listed in Table 3 were used as the (C) layer, and a laminated film melted in the same manner as in Example 1 was extruded to obtain the same polyethylene terephthalate film as in Example 1. Layer (A) was laminated by pressure bonding. The peel strength of the obtained laminate was measured. The results are shown in Table 3.

[Table] Reference Example 3 The (B) layer consisted of the various modified polyolefins listed in Table 3 used in Example 3 or the ethylene-based copolymer alone, and the various polyolefin resins listed in Table 4 ( C) A laminate was produced in the same manner as in Example 3, except that it was used as layer, and its peel strength was measured. The results are shown in Table 4.

【table】

Claims (1)

[Claims] 1. The polyester resin layer (A) has a softening temperature of 105
Thermoplastic polyurethane elastomer 5~
70 parts by weight and a modified polyolefin containing one or more functional groups selected from the group consisting of carboxylic acid groups, carboxylic acid bases, carboxylic acid anhydride groups, amide groups, hydroxyl groups, and epoxy groups in the main chain or side chain, or the above. A resin composition layer (B) consisting of 95 to 30 parts by weight of a copolymer mainly composed of olefin containing a functional group.
A laminate consisting of at least two layers that are in contact with each other. 2 Polyester resin layer (A) and softening temperature of 105
Thermoplastic polyurethane elastomer 5~
70 parts by weight, and carboxylic acid group, carboxylic acid base, carboxylic acid anhydride group, amide group, in the main chain or side chain,
A resin composition layer comprising 95 to 30 parts by weight of a modified polyolefin containing one or more functional groups selected from the group consisting of a hydroxyl group and an epoxy group, or a copolymer mainly composed of an olefin containing the above functional groups.
A laminate in which a polyolefin resin layer (C) is further laminated in contact with the layer (B) of the laminate in which (B) is in contact with each other.