JP6913501B2 - Laminate - Google Patents

Description

The present invention relates to an adhesive resin having excellent adhesive strength even under low-speed peeling conditions and a laminate having excellent interlayer adhesive strength under low-speed peeling conditions.

A graft-modified ethylene / α-olefin random copolymer composition grafted with an unsaturated carboxylic acid or a derivative thereof is applied to a polar resin that is difficult to bond with polyolefin, such as polyester such as polyethylene terephthalate and polycarbonate. It is already known to be used as (see Patent Document 1 and Patent Document 2). However, the conventional adhesive has a large dependence on the peeling speed of the adhesive force, and there is a problem that the adhesive force is greatly reduced when peeled at a low speed. Further, the above problem is not limited to the type of adherend, and even in a laminate of a layer made of polyamide or an ethylene / vinyl alcohol copolymer and an adhesive layer, the adhesive strength is greatly reduced when peeled at a low speed. Problems arise. When opening the lid of the packaging material, infants will not peel it off at a high speed, but will inevitably peel off at a low speed, so with conventional packaging materials, infants can easily open the seal. As a result, it has become a problem with medicines and food packaging materials.

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

An object of the present invention is to provide an adhesive having excellent adhesive strength even under low-speed peeling conditions, and a laminate having excellent interlayer adhesive strength under low-speed peeling conditions.

The adhesive resin (B) of the present invention that solves the above problems satisfies the following requirement (1):
Requirement (1) A layer (I) containing at least one selected from at least polyester (A1) and / or gas barrier resin (A2) and a layer containing the adhesive resin (B) in direct contact with the layer (I). In the laminated body containing (II), the interlayer adhesive force between the layer (I) and the layer (II) satisfies the following formula (1).
S1 ≧ S2 × 0.5 ・ ・ ・ Equation (1)
(In the formula (1), the adhesive force when the peeling speed is 5 mm / min is S1, and the adhesive force when the peeling speed is 300 mm / min is S2.)

The adhesive resin (B), under 23 ° C. atmosphere, it is preferable loss modulus at 1Hz is not more than 2.8 × 10 ⁶ MPa.
The adhesive resin (B) is preferably a modified polyolefin modified with an unsaturated carboxylic acid or a derivative thereof, and the modified polyolefin is preferably a modified polyethylene or a modified ethylene / α-olefin copolymer.

The laminate of the present invention that solves the above problems has a layer (I-1) made of polyester (A1) and a layer (II) containing the adhesive resin (B) that is in direct contact with the layer (I-1). ) And.
The laminate has a layer (I) containing polyester (A1) and / or a gas barrier resin (A2) or a polyolefin resin (C) on a surface of the layer (II) that is not in contact with the layer (I-1). It is preferable that the containing layer (III) is in contact with each other.

In the laminate, the gas barrier resin (A2) is preferably at least one selected from the group consisting of an ethylene / vinyl alcohol copolymer and a polyamide resin.

The adhesive material of the present invention has excellent adhesive strength even under low-speed peeling conditions. The laminate of the present invention is excellent in interlayer adhesion under low-speed peeling conditions.

Hereinafter, the present invention will be described in more detail.
The adhesive resin (B) of the present invention satisfies the following requirement (1):
Requirement (1) A layer (I) containing at least one selected from at least polyester (A1) and / or gas barrier resin (A2) and a layer containing the adhesive resin (B) in direct contact with the layer (I). In the laminated body containing (II), the interlayer adhesive force between the layer (I) and the layer (II) satisfies the following formula (1).
S1 ≧ S2 × 0.5 ・ ・ ・ Equation (1)
(In the formula (1), the adhesive force when the peeling speed is 5 mm / min is S1, and the adhesive force when the peeling speed is 300 mm / min is S2.)
The laminate of the present invention includes a layer (I-1) made of polyester (A1) and a layer (II) containing the adhesive resin (B) that is in direct contact with the layer (I-1).

[Polyester (A1)]
The polyester in the present invention refers to aromatic dicarboxylic acids such as terephthalic acid, isophthalic acid, diphenyl ether-4,4-dicarboxylic acid, naphthalin-1,4- or 2,6-dicarboxylic acid, oxalic acid, and succinic acid. Acid components of aliphatic dicarboxylic acids such as adipic acid, sebacic acid, and undecadicarboxylic acid, dicarboxylic acids such as alicyclic dicarboxylic acid such as hexahydroterephthalic acid, and ethylene glycol, propylene glycol, 1,4-butanediol, It is obtained from an alicyclic glycol such as neopentyl glycol, an alicyclic glycol such as cyclohexanedimethanol, and a glycol component such as an aromatic dihydroxy compound such as bisphenol A, and is obtained from polyethylene terephthalate (PET) and copolymer PET. , Polybutylene terephthalate (PBT), polyethylene naphthalate (PEN), polycyclohexine terephthalate (PCT) and the like. Of these, polyethylene terephthalate (PET) is particularly preferable as the polyester (A1), and usually 80 mol% or more of the dicarboxylic acid component is terephthalic acid and 80 mol% or more of the glycol component is ethylene glycol. It is a plastic polyester resin. Further, the polyester (A1) may be a copolymer PET or a mixture of PET and another polyester.

[Gas barrier resin (A2)]
Examples of the gas barrier resin include ethylene-vinyl acetate copolymer saponified product (EVOH) and polyamide-based resin.

As a saponified ethylene / vinyl acetate copolymer, that is, an ethylene / vinyl alcohol copolymer, the content of structural units derived from ethylene is 15 to 60 mol%, preferably 25 to 50 mol% of ethylene / vinyl acetate copolymer weight. A mixture saponified so that the degree of saponification is 50% or more, preferably 90% or more is preferably used. When the content of the structural unit derived from ethylene is less than 15 mol%, it tends to be easily thermally decomposed, difficult to melt-mold, poor in stretchability, and easily absorbs water and swells, resulting in poor water resistance. On the other hand, when the ethylene content exceeds 60 mol%, the gas permeability tends to be inferior. Further, if the saponification degree is less than 50%, the gas permeability tends to be inferior.

Polyamide-based resins include hexamethylenediamine, decamethylenediamine, dodecamethylenediamine, 2,2,4- or 2,4,4-trimethylhexamethylenediamine, 1,3- or 1,4-bis (aminomethyl) cyclohexane. , Bis (p-aminocyclohexylmethane), m- or p-xylylenediamine and other aliphatic, alicyclic, aromatic and other diamines and adipic acid, suberic acid, sebacic acid, cyclohexanedicarboxylic acid, terephthalic acid, isophthalic acid. Polyamides obtained by polycondensation with aliphatic, alicyclic, aromatic and other dicarboxylic acids such as acids, polyamides obtained by condensation of aminocarboxylic acids such as ε-aminocaproic acid and 11-aminoundecane, ε-caprolactam, Examples thereof include polyamides obtained from lactams such as ω-laurolactam and mixtures of copolymerized polyamides composed of these components. Specific examples thereof include nylon 6, nylon 66, nylon 610, nylon 9, nylon 11, nylon 12, nylon 6/66, nylon 66/610, and nylon 6/11. Further, examples of the polyamide-based resin that can be used for the laminate include a mixture of EVOH and one or more kinds of polyamide-based resin, polyester-based resin, polycarbonate, plate-like filler, and the like.

[Adhesive resin (B)]
The type of adhesive resin (B) is not particularly limited as long as it satisfies the above requirement (1). One of the preferred embodiments of the adhesive resin (B) is a modified polyolefin obtained by modifying a polyolefin with an unsaturated carboxylic acid or a derivative thereof. The density of the modified polyolefin is preferably 0.8 to 1.2 g / cm ³ .

Further, the adhesive resin (B) may contain an unmodified polyolefin, an ethylene / polar monomer copolymer, or the like in addition to the modified polyolefin.
The lower the density of the adhesive resin, the lower the loss elasticity. Therefore, the density of the adhesive resin is 0.8 to 0.9 g / cm ^{3 when the components other than the modified polyolefin are composed only of polyolefin. Preferably, 0.8 to 1.2 g / cm 3} is preferable when an ethylene / polar monomer copolymer is contained in addition to the polyolefin. Under 23 ° C. atmosphere With such a density range, the loss modulus at 1Hz is less 2.8 × 10 ⁶ MPa.

Polyolefin The polyolefin is a polymer containing an aliphatic α-olefin having 2 to 20 carbon atoms, a cyclic olefin, and a non-conjugated diene as main components, preferably an α-olefin having 2 to 10 carbon atoms, and more preferably. Examples thereof include polymers containing 2 to 8 α-olefins as main components. These olefins may be used alone or in combination of two or more. When the polyolefin is a copolymer, the content of the olefin serving as a comonomer is usually 50 mol% or less, preferably 40 mol% or less, and more preferably 30 mol% or less. Examples of the polyolefin include homopolymers or copolymers of ethylene, propylene, 1-butene, 4-methyl-1-pentene, 3-methyl-1-butene, 1-hexene, 1-octene, tetracyclododecene, and norbornene. The coalescence is preferable, and polyethylene and the polyethylene / α-olefin copolymer are more preferable. Further, these polyolefins can be used in both an isotactic structure and a syndiotactic structure, and there is no particular limitation on the stereoregularity.

The density of the polyolefin used for graft modification is usually 0.8 to 1.2 g / cm ³ , preferably 0.8 to 1.1 g / cm ³ , and more preferably 0.8 to 1.0 g / cm ³ . .. The melt flow rate (MFR) according to ASTM D1238 at 190 ° C. and a load of 2.16 kg is usually 0.01 to 500 g / 10 minutes, preferably 0.05 to 200 g / 10 minutes, and more preferably 0.1 to 100 g. / 10 minutes. If the density and MFR of the polyolefin used for graft modification are within this range, the density and MFR of the graft copolymer after modification will be about the same, so that handling is easy.

The above-mentioned polyolefin can be produced by any conventionally known method, and can be polymerized by using, for example, a titanium-based catalyst, a vanadium-based catalyst, a metallocene catalyst, or the like. Further, the polyolefin used for graft modification may be in either a resin form or an elastomer form, and both an isotactic structure and a syndiotactic structure can be used, and there is no particular limitation on the stereoregularity. It is also possible to use a commercially available resin as it is.

Unsaturated carboxylic acids or derivatives thereof As unsaturated carboxylic acids or derivatives thereof used for graft modification of polyolefins, unsaturated compounds having one or more carboxylic acid groups, unsaturated compounds having one or more anhydrous carboxylic acid groups and derivatives thereof are used. Examples of the unsaturated group contained in the unsaturated compound include a vinyl group, a vinylene group, and an unsaturated cyclic hydrocarbon group. Specific compounds include acrylic acid, methacrylic acid, maleic acid, fumaric acid, tetrahydrophthalic acid, itaconic acid, citraconic acid, crotonic acid, isocrotonic acid, norbornenedicarboxylic acid, and bicyclo [2,2,1] hept-2. Unsaturated carboxylic acids such as -ene-5,6-dicarboxylic acid, or acid anhydrides thereof or derivatives thereof (eg, acid halides, amides, imides, esters, etc.) can be mentioned. Specific examples of the compounds include malenyl chloride, malenylimide, maleic anhydride, itaconic anhydride, citraconic anhydride, tetrahydrophthalic anhydride, and bicyclo [2,2,1] hept-2-ene-5,6-dicarboxylic acid. Acid anhydride, dimethyl maleate, monomethyl maleate, diethyl maleate, diethyl fumarate, dimethyl itaconic acid, diethyl citraconic acid, dimethyl tetrahydrophthalate, bicyclo [2,2,1] hept-2-ene-5,6 -Dimethyl dicarboxylic acid, hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, glycidyl (meth) acrylate, aminoethyl methacrylate, aminopropyl methacrylate and the like can be mentioned. Further, the unsaturated carboxylic acid or a derivative thereof may be used alone or in combination of two or more. Among these, maleic anhydride, (meth) acrylic acid, itaconic anhydride, citraconic anhydride, phthalic anhydride, bicyclo [2,2,1] hept-2-ene-5,6-dicarboxylic acid anhydride , Hydroxyethyl (meth) acrylate, glycidyl methacrylate, aminopropyl methacrylate are preferred. Furthermore, dicarboxylic acid anhydrides such as maleic anhydride, itaconic anhydride, citraconic anhydride, tetrahydrophthalic anhydride, and bicyclo [2,2,1] hept-2-ene-5,6-dicarboxylic acid anhydride are particularly preferred. preferable. As a method for introducing an unsaturated carboxylic acid or a derivative thereof into a polyolefin, a well-known method can be adopted. For example, a method for graft-copolymerizing an unsaturated carboxylic acid or a derivative thereof on a polyolefin main chain or an olefin And a method of radical copolymerizing an unsaturated carboxylic acid or a derivative thereof can be exemplified.

<Graft polymerization method>
When the modified polyolefin used in the present invention is obtained by graft copolymerization, an unsaturated carboxylic acid or a derivative thereof, and if necessary, another ethylenically unsaturated monomer or the like is radically added to the polyolefin as the main chain of the graft. Graft copolymerization in the presence of initiator.

The method of grafting the unsaturated carboxylic acid or its derivative on the polyolefin main chain is not particularly limited, and conventionally known graft polymerization methods such as a solution method and a melt-kneading method can be adopted.

<Radical copolymerization>
The modified polyolefin in the present invention can also be obtained by radical copolymerizing an olefin with an unsaturated carboxylic acid or a derivative thereof. As the olefin, the same olefin as the olefin used for forming the polyolefin serving as the graft main chain can be adopted, and the unsaturated carboxylic acid or its derivative is also as described above.
The method for copolymerizing an olefin with an unsaturated carboxylic acid or a derivative thereof is not particularly limited, and a conventionally known radical copolymerization method can be adopted.

(Modified polyolefin)
The content of the unsaturated carboxylic acid or its derivative in the modified polyolefin used in the present invention is usually 0.01 to 10% by weight, preferably 0.05 to 3.0% by weight, more preferably 0.1. ~ 2.0% by weight. If the content of the unsaturated carboxylic acid or its derivative exceeds the above range, it becomes uneconomical, while if the content of the unsaturated carboxylic acid or its derivative in the modified polyolefin is less than the above range, the adhesive strength is said to be small. There is a tendency.

The modified polyolefin used in the present invention has a melt flow rate (MFR) of 2.16 kg under a load of ASTM D1238 at 190 ° C., usually 0.01 to 500 g / 10 min, preferably 0.05 to 100 g / 10 min. .. Within the above range, the moldability is good and the adhesive strength is also excellent. In the method of measuring the adhesive strength by performing a peeling test by sandwiching an adhesive layer having a thickness of 100 microns with a base material by hot press molding, the adhesive strength tends to be higher as the molecular chain is longer with a low MFR. In a film formed by cast molding, the opposite tendency tends to occur in the case of an adhesive layer having a thickness of 30 to 50 microns. In the method of performing a cast molding film peeling test and measuring the adhesive strength, the higher the MFR and the shorter the molecular chain, the higher the adhesive strength tends to be. It is considered that the higher the MFR and the shorter the molecular chain, the better the flowability at the interface.

The density of the modified polyolefin is usually 0.8 to 1.2 g / cm ³ , preferably 0.80 to 1.1 g / cm ³ , and more preferably 0.8 to 1.0 g / cm ³ .
Among the modified polyolefins that satisfy the above conditions, maleic anhydride graft copolymers of crystalline polyolefins such as polyethylene, polypropylene, polybutene 1, poly-4-methylpentene-1, and copolymers of these with α-olefins. Is preferable, and a maleic anhydride-grafted copolymer of polyethylene or a maleic anhydride-grafted copolymer of a polyethylene / α-olefin copolymer is more preferable.

The adhesive resin (B) of the present invention may be composed of only the above-mentioned modified polyolefin, and may contain an unmodified polyolefin, an ethylene / polar monomer copolymer, or the like in addition to the above-mentioned modified polyolefin. Examples of the polar monomer of the ethylene / polar monomer copolymer include unsaturated carboxylic acids, salts thereof, esters thereof, amides thereof, vinyl esters, carbon monoxide and the like. Specifically, unsaturated carboxylic acids such as acrylic acid, methacrylic acid, fumaric acid, itaconic acid, monomethyl maleate, monoethyl maleate, maleic anhydride, and itaconic anhydride; these unsaturated carboxylic acids are lithium, sodium, and potassium. Salts of monovalent metals such as; salts of polyvalent metals such as magnesium, calcium and zinc of these unsaturated carboxylic acids; methyl acrylate, ethyl acrylate, isopropyl acrylate, isobutyl acrylate, n butyl acrylate, acrylic acid Unsaturated carboxylic acid esters such as isooctyl, methyl methacrylate, ethyl methacrylate, isobutyl methacrylate, dimethyl maleate; vinyl esters such as vinyl acetate and vinyl propionate; carbon monoxide; one or more such as sulfur dioxide It can be exemplified.

Further, it is also possible to add known process stabilizers, heat-resistant stabilizers, heat-resistant aging agents, pressure-sensitive adhesives and the like to the adhesive resin (B) of the present invention as long as the object of the present invention is not impaired. Examples of the pressure-sensitive adhesive include rosin derivatives, terpene resins, petroleum resins, and hydrogenated products thereof. Among these, hydrogenated terpene resins and hydrogenated petroleum resins are preferable.

Elastic modulus of loss The adhesive resin (B) preferably has an elastic modulus of loss at 1 Hz of 2.8 × 10 ⁶ MPa or less, more preferably 2.0 × 10 ⁶ MPa or less, in an atmosphere of 23 ° C. is less than 1.5 × 10 ⁶ MPa. The lower limit of the loss modulus is usually 0.3 × 10 ⁶ MPa. When the loss modulus of the adhesive resin (B) is less than 2.8 × 10 ⁶ MPa, the requirement (1) easily is satisfied, small peel rate dependence of adhesive strength, high even during low-speed peeling layer Adhesive strength is shown.

[Layer (I)]
The layer (I) contains at least one selected from polyester (A1) and / or gas barrier resin (A2). That is, the layer (I) contains one or both of the polyester (A1) and the gas barrier resin (A2). The layer (I) may also contain components other than the polyester (A1) and the gas barrier resin (A2) as long as the above requirement (1) is satisfied.

[Layer (II)]
The layer (II) contains the adhesive resin (B). The layer (II) may also contain components other than the adhesive resin (B) as long as the above requirement (1) is satisfied.

[Equation (1)]
In a laminated body formed by directly contacting the layer (I) and the layer (II), the interlayer adhesive force between the layer (I) and the layer (II) satisfies the following formula (1).
S1 ≧ S2 × 0.5 ・ ・ ・ Equation (1)
In the formula (1), the adhesive force when the peeling speed is 5 mm / min is S1, and the adhesive force when the peeling speed is 300 mm / min is S2.

When the formula (1) is satisfied, the peeling speed dependence of the adhesive force is small, and a high interlayer adhesive force is exhibited even at low speed peeling.
The adhesive forces S1 and S2 can be measured using a tensile tester at 23 ° C. (room temperature) with crosshead speeds of 5 mm / min and 300 mm / min, respectively.

[Laminate]
The laminate of the present invention includes a layer (I-1) made of polyester (A1) and a layer (II) containing the adhesive resin (B) that is in direct contact with the layer (I-1). The layer (I-1) is a layer in which the components contained in the layer (I) are limited to the polyester (A1).
The laminate can have various modes as long as the above conditions are satisfied. For example, the polyester (A1) and / or the gas barrier resin (A2) is formed on a surface of the layer (II) that is not in contact with the layer (I-1). ) Is in contact with any of the layer (I) containing the polyolefin resin (C) and the layer (III) containing the polyolefin resin (C). The layer (I) is as described above.

Polyolefin (C)
The polyolefin (C) contained in the layer (III) has 2 carbon atoms such as ethylene, propylene, 1-butene, 1-hexene, 3-methyl-1-butene, 4-methyl-1-pentene, and 1-octene. ~ 12, preferably about 2 to 8 α-olefin homopolymers, or two or more types of the above α-olefin copolymers, or the above α-olefins and vinyl esters, unsaturated organic acids or derivatives thereof, etc. And the copolymer with. These copolymers may be in any bonding mode such as random, block or graft, and may be in the form of resin or elastomer. Two or more kinds of these polyolefin-based polymers can be mixed and used. Specific examples of the polyolefin (C) include high-density polyethylene, medium-density polyethylene, low-density polyethylene, linear low-density polyethylene, polypropylene, poly1-butene, poly1-hexene, and poly (3-methyl-1-butene). ), Poly (4-methyl-1-pentene), poly1-heptene, poly1-octene, ethylene / propylene copolymer (random, block), ethylene / 1-butene copolymer, ethylene / 1-hexene Polymers, ethylene / 1-octene copolymers, ethylene / propylene / 1-butene random copolymers, ethylene / vinyl acetate copolymers, ethylene / methyl acrylate copolymers, ethylene / ethyl acrylate copolymers, Ethylene / methyl methacrylate copolymer, ethylene / acrylic acid copolymer, ethylene / methacrylate copolymer, ethylene / acrylic acid / methyl acrylate copolymer, ethylene / methacrylate / methyl methacrylate copolymer, etc. It can be mentioned as a typical one.
The layer (III) may also contain components other than the polyolefin (C) as long as the above requirement (1) is satisfied.

Manufacture of Laminated Body The laminated body of the present invention can be manufactured by a known method such as coextrusion molding, press molding, and extrusion laminating molding. Among these, it is preferable to use the coextrusion molding method in terms of interlayer adhesion. The coextrusion molding method includes a T-die method using a flat die and an inflation method using a circular die. The flat die may be either a single manifold type using a black box or a multi-manifold type. A known die can also be used as the die used in the inflation method.

The laminate is preferably a layer (I) containing at least one selected from polyester (A1) and / or gas barrier resin (A2) with the layer (II) containing the adhesive resin (B) as an intermediate layer. 3 consists of a layer (I-1) containing a polyester (A1) and a layer (I) containing a polyester (A1) and / or a gas barrier resin (A2), or a layer (III) containing a polyolefin resin (C). It is generally used in the form of a laminated body of layers or more.

As a method for producing such a laminate, for example, the resin composition as a raw material for each layer is melted by a separate extruder, supplied to a die having a three-layer structure, and coextruded with the layer (II) as an intermediate layer. In addition to the molding method, the resin compositions used as the raw materials for the layers (I) and (II) are melted by separate extruders and then supplied to a die having a two-layer structure to prepare a stretched film (preliminary). Stretched polyethylene terephthalate: O-PET, stretched nylon: O-NY, stretched polypropylene: O-PP, stretched ethylene / vinyl acetate copolymer saponified product: O-EVOH), metal foil (Al, Cu), resin sheet (polyolefin) , Polyester, etc.), or a method of co-extruding and laminating so that the layer of the composition comes into contact with the polyester resin, or the polyester resin and the polyolefin resin or the gas barrier resin layer are molded in advance, and the polyester resin layer and the polyolefin resin or the gas barrier resin are formed. Examples thereof include a sand laminating method in which the composition is melt-extruded between the layers.

Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples, but the present invention is not limited to these Examples as long as the gist of the present invention is not exceeded.

(Various measurement methods)
In this example and the like, the measurement was carried out according to the following method.
[Melt Flow Rate (MFR)]
The melt flow rate was measured according to ASTM D1238 at 190 ° C. under a load of 2.16 kg.
[density]
The density was measured according to JIS K7112.
[Resilience loss]
The elastic modulus loss was measured under nitrogen using RSA-III manufactured by TA-Instruments. Here, the loss elastic modulus is a term constituting the complex elastic modulus representing the relationship between the stress and the strain when a viscoelastic body is subjected to a sinusoidal vibration strain, and is a tension according to RSA-III manufactured by TA-Instruments. It is a value measured by viscoelasticity measurement at a temperature rise temperature of 2 ° C./min, a frequency of 1 Hz, and a strain of 0.1.

(Resin used for layer (II))
The polyolefins used in Examples and Comparative Examples are shown below. Unless otherwise specified, all of them were prepared by polymerizing according to a conventional method.
PE-1: Polyethylene
(Melt flow rate 2.0 g / 10 minutes, density 0.92 g / cm ³ )
EBR-1: Ethylene / 1-butene copolymer
(Melt flow rate 2.0 g / 10 minutes, density 0.87 g / cm ³ )
Modified EBR-1: Maleic anhydride-modified ethylene / 1-butene copolymer
(Melt flow rate 2.0 g / 10 minutes, density 0.89 g / cm ³ ,
Maleic anhydride graft amount 0.2 wt%)

(Example 1)
<Manufacturing of adhesive resin>
25% by weight of ethylene / 1-butene copolymer (EBR-1) having a melt flow rate of 2.0 g / 10 minutes and a density of 0.87 g / cm ^{3, and a melt flow rate of 2.0 g / 10 minutes.} Using a twin-screw kneader (manufactured by Japan Steel Works, TEX-30), 75% by weight of a maleic anhydride-modified ethylene / 1-butene copolymer (modified EBR-1) having a density of 0.89 g / cm ^{3 was used.} It was melt-kneaded at 230 ° C. to obtain an adhesive resin. The melt flow rate of the obtained adhesive resin was 2.0 g / 10 minutes, and the density was 0.89 g / cm ³ . The 23 ° C., the loss modulus at 1Hz was 1.1 × 10 ⁶ MPa.

<Manufacturing of 3-layer laminate>
A layer having the structure shown below was coextruded under the following conditions to form a three-layer film.
[Inner layer]
As polyethylene terephthalate (hereinafter referred to as PET), J125 (trade name) manufactured by Mitsui Chemicals, Inc. was extruded at 275 ° C. using a screw having a diameter of 40 mm and L / D 28.

[Outer and middle layers]
Commercially available polyethylene (2021L, MFR 2 manufactured by Prime Polymer Co., Ltd.) was extruded as an outer layer, and the adhesive of the present invention was extruded as an intermediate layer at 220 ° C. using a screw of 50 mm and L / D 28.

[Laminate molding conditions]
The resin extruded for the outer layer, the inner layer, and the intermediate layer was laminated in the feed block in the order of the inner layer (layer (I)), the intermediate layer (layer (II)), and the outer layer (layer (III)). The die temperature was 275 ° C., and each resin laminate co-extruded into a film having a thickness of about 200 μm was taken up at a speed of 5 m / min while being cooled by a chill roll. The thickness of each layer was set to outer layer (polyethylene) / intermediate layer (adhesive) / inner layer (PET) = 80/40/80 μm.
The interlayer adhesive strength of the molded laminate was measured by the following measuring method. The results are shown in Table 1.

[Measurement of interlayer adhesion of laminated body]
The laminate produced above is cut into 15 mm widths, and the interface between the PET layer and the adhesive layer is made of the laminate at 23 ° C (room temperature) using a tensile tester (IM-20ST type manufactured by Intesco Co., Ltd.). Interfacial adhesive strength was measured. The crosshead speed (peeling speed) was set to 300 mm / min and 5 mm / min. The interlayer adhesive force at a crosshead speed of 5 mm / min was defined as S1, and the interlayer adhesive force at a crosshead speed of 300 mm / min was defined as S2.

(Examples 2 to 3)
An adhesive resin was produced in the same manner as in Example 1 according to the formulation shown in Table 1, and a laminate was produced.
Table 1 shows the results of the physical characteristics of the obtained adhesive resin and the interlayer adhesive strength of the molded laminate.

(Comparative Examples 1-2)
An adhesive resin was produced in the same manner as in Example 1 according to the formulation shown in Table 1, and a laminate was produced.
Table 1 shows the results of the physical characteristics of the obtained adhesive resin and the interlayer adhesive strength of the molded laminate.

Claims (4)

A layer (I-1) made of polyester (A1) and
In direct contact with the layer (I-1), satisfies the following requirements (1), under 23 ° C. atmosphere, the loss modulus at 1Hz is not more than 2.8 × 10 ⁶ MPa, modified with an unsaturated carboxylic acid or a derivative thereof look including a layer containing an adhesive resin (B) (II) comprising been modified polyolefin,
A laminate in which a layer (I) containing a polyester (A1) and / or a gas barrier resin (A2) is in contact with a surface of the layer (II) that is not in contact with the layer (I-1) .
Requirement (1) A layer (I) containing at least one selected from at least polyester (A1) and / or gas barrier resin (A2) and a layer containing the adhesive resin (B) in direct contact with the layer (I). In the laminated body containing (II), the interlayer adhesive force between the layer (I) and the layer (II) satisfies the following formula (1).
S1 ≧ S2 × 0.5 ・ ・ ・ Equation (1)
(In the formula (1), the adhesive force at 23 ° C. and a peeling speed of 5 mm / min is S1, and the adhesive force at a peeling speed of 300 mm / min is S2.) The laminate according to claim 1, wherein the modified polyolefin is a modified polyethylene or a modified ethylene / α-olefin copolymer. The laminate according to claim 1 or 2, wherein the adhesive resin (B) contains the modified polyolefin, polyethylene, and an ethylene / 1-butene copolymer. The laminate according to any one of claims 1 to 3, wherein the gas barrier resin (A2) is at least one selected from the group consisting of an ethylene / vinyl alcohol copolymer and a polyamide resin.