JPH10279774A - Resin composition for adhesion, laminate and drawn film - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a resin composition for adhesion, excellent in bond strength to various resins after drawing and in extrusion molding suitability for film, sheet or blow, a laminate using the composition and a drawn film of the laminate. SOLUTION: This resin composition for adhesion comprises (a) 50-99 wt.% of a modified hydrogenated block copolymer which is obtained by hydrogenating a block copolymer of a vinyl aromatic compound and a conjugated diene compound to give a hydrogenated block copolymer and modifying the hydrogenated block copolymer with an unsaturated carboxylic acid or its derivative and has 0.01-20 wt.% content of the unsaturated carboxylic acid or-its derivative and (b) 1-50 wt.% of a tackifier. The composition is laid various resins to give a laminate, which is drawn to give a drawn film.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to gas barrier properties (oxygen, carbon dioxide, etc.), contents resistance (flavor properties, fragrance retention properties), and design properties (widely required in various fields such as food packaging materials). The present invention relates to an adhesive resin composition for obtaining a laminate having improved surface glossiness, transparency), mechanical strength, shrinkage, and the like, a laminate, and a stretched film obtained by stretching the laminate.

[0002]

2. Description of the Related Art PO resins such as polypropylene, polyethylene, ethylene-vinyl acetate copolymer and the like are widely used in various fields, but PO resins are characterized by moldability, mechanical strength, chemical resistance and heat sealing. It has excellent properties, but is inferior in gas barrier properties and fragrance retention properties, and has drawbacks such as poor design properties (surface gloss and transparency) depending on the molding technique and resin type.

As a method of improving this defect, lamination with an EVOH or PA-based resin having excellent gas barrier properties, and lamination with a PES-based resin for improving the content resistance and design properties have been proposed. However, since PO resins do not have polarity,
Even when directly laminated with EVOH, PA-based resin and PES-based resin, the interlayer adhesion after lamination is extremely low and is not practical.

Therefore, a method of laminating using various adhesives has been proposed. For example, PO resin and EVOH or PA
With respect to adhesion to polar resins such as a series resin, a polyolefin-based adhesive resin modified with an unsaturated carboxylic acid or the like has been proposed. Further, a laminate other than the PO resin and the EVOH and PA resins, that is, the PO resin and the PES resin, PC
-Based resin, laminate with acrylic resin or PS-based resin,
And for a laminate of PS resin and EVOH, PA resin, PES resin, etc., using a composition of an olefin polymer and an alicyclic or aromatic polymer as a tackifier as an adhesive. (Japanese Patent Laid-Open No. 50-116)
No. 536), a method of laminating using a composition of an ethylene-vinyl acetate copolymer (hereinafter referred to as EVA) and a tackifier as an adhesive (JP-A-53-147733, JP-A-54-10384). And a method of laminating using a composition of EVA, a modified polyolefin, and an aliphatic petroleum resin as a tackifier as an adhesive (Japanese Unexamined Patent Publication No.
No. 3-127546), modified low crystalline ethylene-α
-A method of laminating using a composition of an olefin random copolymer and a tackifier as an adhesive (JP-A-61-241)
144), low crystalline (low density) ethylene-α-
A method of laminating a composition of an olefin random copolymer, a tackifier and a modified polyethylene as an adhesive (Japanese Patent Application Laid-Open No. 61-62539), a styrene-based thermoplastic elastomer, a pressure-sensitive adhesive, a low-molecular-weight polypropylene and a process oil And lamination using a hot-melt adhesive composition (JP-A-1-144483) comprising a mixture of a styrene-based thermoplastic elastomer, an alicyclic-based pressure-sensitive adhesive, and a cycloolefin random copolymer. Melt type pressure-sensitive adhesive composition
No. 223381) has been proposed.

[0005] In recent years, in order to further improve the performance of various packaging materials, attempts have been made to stretch co-extruded products, improve strength and gas barrier properties, and further apply them to the field of shrink wrapping.
Stretched laminated film and method for producing the same
No. 46487), a heat-shrinkable multilayer film and a package thereof (JP-A-57-205147, 58-86).
No. 44), a heat-shrinkable multilayer film and a method for producing the same (JP-A-59-152853), and a biaxially stretched molded product of a thermoplastic polyester composition (JP-A-60-7632).
No. 5), a method for producing a biaxially stretched laminate (Japanese Unexamined Patent Publication No.
No. 82324), a heat-shrinkable packaging film (Japanese Unexamined Patent Publication No.
-94753), maleic anhydride-modified polyethylene, maleic anhydride-modified polypropylene, maleic anhydride-modified ethylene-vinyl acetate copolymer, maleic anhydride-modified ethylene-1-butene copolymer and styrene-modified It has been proposed to apply a hydrogenated product of a crystalline ethylene-propylene copolymer or a maleic anhydride-modified styrene-butadiene copolymer.

[0006]

However, the co-extruded laminate using any of the methods, when cooled and solidified, reheated and stretch-formed at least 1.5 times in both the longitudinal and transverse directions, has an extremely high adhesive strength. Decreased and did not reach the practical range. In addition, even at a normal temperature, even at a practical range, there are many problems in application such as poor moldability and low adhesive strength in a high temperature state such as hot fill. In light of this situation,
The present invention has excellent adhesive strength after stretching with EVOH, PA-based resin, PO-based resin, PS-based resin, PES-based resin, acrylic-based resin, PC-based resin, etc., and extrusion molding of films, sheets, blows, etc. An object of the present invention is to provide an adhesive resin composition excellent in suitability, a laminate using the same, and a stretched film of the laminate.

[0007]

Means for Solving the Problems The inventors of the present invention have solved the above problems and made intensive studies for the purpose of improving workability, adhesiveness and thermal stability. As a result, the following means have shown a dramatic improvement in performance. And arrived at the present invention.

That is, the present invention provides a hydrogenated block copolymer obtained by hydrogenating a block copolymer of a vinyl aromatic compound and a conjugated diene compound, wherein the hydrogenated block copolymer is modified with an unsaturated carboxylic acid or a derivative thereof. Adhesion comprising 50 to 99% by weight of a modified hydrogenated block copolymer (a) having a carboxylic acid or derivative content of 0.01 to 20% by weight and 1 to 50% by weight of a tackifier (b) It provides a resin composition for use.

[0009] The present invention also relates to a modified hydrogenated block copolymer (a) and a tackifier (b) in a total of 100 parts by weight, a melt flow rate of 0.05 to 50 g / 10 minutes,
And an adhesive resin composition comprising 10 to 1000 parts by weight of an ethylene polymer (c) having a density of 0.850 to 0.950 g / cm ³ .

[0010] The present invention further provides the above-mentioned adhesive resin composition in which a hydrogenated block copolymer is obtained by hydrogenating at least 50% of olefinic double bonds in a polymer block comprising a conjugated diene compound. Is what you do.

Furthermore, the present invention relates to a method for producing an ethylene content of 15
It is made of a saponified ethylene-vinyl acetate copolymer having a saponification degree of 90% or more, a polyamide resin, a polyolefin resin, a styrene resin, a polyester resin, an acrylic resin and a polycarbonate resin having a saponification degree of 90% or more. An object of the present invention is to provide a laminate comprising a layer (A layer) of at least one thermoplastic resin selected from the group and a layer (B layer) made of the above-mentioned adhesive resin composition.

The present invention also provides a stretched film obtained by subjecting the laminate to a stretching treatment at least 1.5 times in area ratio in at least one axial direction.

Still another object of the present invention is to provide a stretched film obtained by subjecting the laminate to a stretching treatment in an area ratio of 1.5 times or more in a biaxial direction.

[0014]

BEST MODE FOR CARRYING OUT THE INVENTION

(1) Modified hydrogenated block copolymer (a) The modified hydrogenated block copolymer (a) used in the present invention is:
A hydrogenated block copolymer obtained by hydrogenating a block copolymer of a vinyl aromatic compound and a conjugated diene compound is modified with an unsaturated carboxylic acid or a derivative thereof, or the modified product is an unmodified hydrogenated block. It is diluted with a copolymer and has a content of the unsaturated carboxylic acid or its derivative of 0.01 to 20% by weight. More preferably, the content of the unsaturated carboxylic acid or its derivative is from 0.05 to 1
It is 5% by weight, particularly preferably 0.1 to 7% by weight.
When the block A is a vinyl aromatic compound and the block B is a conjugated diene compound, the block copolymer is represented by the general formulas AB, ABAA, BABA, AB- A-
In the block copolymer represented by B-A or the like, as the compound mainly containing a vinyl aromatic compound constituting the polymer block portion A, for example, styrene, α-methylstyrene,
One or more kinds are selected from vinyltoluene and the like, and among them, styrene is preferable.

As the conjugated diene compound constituting the polymer block portion B, for example, one or more of butadiene, isoprene, 1,3 pentadiene and the like are selected, and among them, butadiene, isoprene and a combination thereof are preferable. The content of the polymer block mainly composed of a vinyl aromatic compound serving as the A block is preferably 10%.
-80% by weight, more preferably 10-70% by weight. If the content of the present polymer block is too small or too large, sufficient adhesive strength cannot be obtained.
The hydrogenation rate of the polymer block containing a conjugated diene compound as a main component is generally 50% or more, preferably 80% or more.
The content is more preferably 90% or more, particularly preferably 95% or more, and the higher the value, the more the thermal stability is improved.

The number average molecular weight of the hydrogenated block copolymer is as follows:
Preferably it is about 10,000 to 400,000, more preferably 20,000 to 300,000. If the molecular weight is too large or too small, the adhesive strength tends to decrease, and if the number average molecular weight is too large, the processability of the present composition tends to decrease. Further, even if the number average molecular weight of the hydrogenated block copolymer is 400,000 or less, when the number average molecular weight is higher, it is selected from process oil, liquid polybutadiene, and an olefin wax having a number average molecular weight of 6,000 or less. By adding about 1 to 40% by weight of the obtained fluidity improver to the hydrogenated block copolymer, it is possible to suppress a decrease in adhesive strength and workability, which is an effective means. The hydrogenated block copolymer of the present invention preferably contains a block copolymer having an ABA structure. Specifically, commercially available products include "Tuftec" as a hydrogenated styrene-butadiene-based block copolymer. Examples include H type (Asahi Kasei Corporation), “Clayton” G1600 type (manufactured by Shell Chemical), and “Septon” 2000 type (manufactured by Kuraray Co., Ltd.) as a hydrogenated styrene-isoprene block copolymer. Further, a hydrogenated styrene-isoprene-based block copolymer having an AB structure, "Septon" 1000 type (manufactured by Kuraray Co., Ltd.), "Clayton" G1700 type (manufactured by Shell Chemical Co., Ltd.) and the like can be mentioned.

Further, two or more kinds of the above hydrogenated block copolymers can be used as a mixture. Next, the modified hydrogenated block copolymer (a) in the present invention is obtained by graft-polymerizing an unsaturated carboxylic acid or a derivative thereof to the hydrogenated block copolymer.

To produce a modified product by graft polymerization,
Conventionally known various methods can be adopted. For example, a method in which the above-described hydrogenated block copolymer, a graft monomer, and a radical generator are mixed in advance and melted by an extruder to perform graft copolymerization, or a method in which the hydrogenated block copolymer is dissolved in a solvent to form a radical There is a method in which a generator and a graft monomer are added to carry out graft copolymerization. The grafting reaction temperature is usually preferably from 80 to 300 ° C. The general amount of the radical generator is usually 0.001 to 100 parts by weight of the hydrogenated block copolymer.
A range of 8 parts by weight is preferred. Organic peroxides are generally used as radical generators, such as 2,5-dimethylhexane-2,5-dihydroperoxide and 2,5-dimethylhexane.
Dimethyl-2,5-di (t-butylperoxy) -3-
Hexin, di-t-butyl peroxide, t-butylcumyl peroxide, 2,5-dimethyl-2,5-di (t
-Butylperoxy) hexane, dicumyl peroxide, t-butylperoxybenzoate, t-butylperoxyacetate, t-butylperoxyisopropyl carbonate, benzoyl peroxide, m-toluoyl peroxide and the like are preferred.

Examples of the unsaturated carboxylic acids or derivatives thereof include unsaturated carboxylic acids such as acrylic acid, maleic acid, fumaric acid, itaconic acid and citraconic acid, and derivatives thereof, for example, anhydrides, amides and esters.
One or two or more of them are used. Of these, unsaturated dicarboxylic acids or anhydrides thereof are preferred, and maleic acid or anhydrides thereof are particularly preferred. The amount of the graft (measurement method; infrared spectrophotometer) is preferably 0.1%.
01 to 20% by weight. If the amount of the graft is too small, the adhesiveness is poor. If the amount is too large, partial cross-linking occurs during graft copolymerization, resulting in poor moldability. .
The unreacted graft monomer may remain in the modified hydrogenated block copolymer (a) depending on the modification technique, but it can be obtained from the viewpoints of adhesiveness, hygiene when used as an adhesive for food containers, and the like. It is preferable not to leave only Therefore, it is preferable to carry out various post-treatments such as extraction with a poor solvent such as acetone and post-treatment such as deaeration of unreacted graft monomer by heating and drying.

(2) Pressure-sensitive adhesive (b) The pressure-sensitive adhesive (b) used in the present invention is an amorphous resin which is solid at ordinary temperature, among which a petroleum resin, a rosin resin, a terpene resin or a hydrogenated resin thereof. Are preferred, and can be appropriately selected from commercially available products. Examples of the petroleum resin include an aliphatic petroleum resin, an aromatic petroleum resin, a copolymer thereof, and a hydrogenated product thereof. Specifically, as a commercially available product, Toho High Resin (Toho Petroleum Resin) Co., Ltd.), Pico Pale (Pico), Alcon P
And M (Arakawa Chemical Industry Co., Ltd.), Admarp (Idemitsu Petrochemical Industry Co., Ltd.), Super Star Tack (Rayhill Hold Co., Ltd.), Escolets (Esso Chemical Co., Ltd.), Toho Petroresin (Tonen Petroleum Resin) Co., Ltd.), Heylets (Mitsui Petrochemical Co., Ltd.), Quinton (Nihon Zeon Co., Ltd.) and the like. Examples of the rosin-based resin include natural rosin, polymerized rosin and derivatives thereof, such as pentaerythroester rosin, glycerin ester rosin and hydrogenated products thereof, and specifically, commercially available products such as gum rosin, wood rosin, ester gum A, Persen A, Pensen C (Arakawa Chemical Industries, Ltd.), Pentaline A, Pentaline C, Foral 1
05 (Rika Hercules Co., Ltd.). Examples of the terpene-based resin include polyterpene-based resin, terpene-phenol-based resin and hydrogenated products thereof. Specifically, picolite S and A (Pico), YS resin, clearon (Yasuhara Yushi Co., Ltd.) are commercially available. ).

In the present invention, these tackifiers can be properly used depending on the intended use. Among these tackifiers, the softening point (ring and ball method) is preferably 70 to 15.
A temperature of 0 ° C, particularly preferably 90 to 150 ° C, is used. If the softening point is too low, the adhesive strength will be low, and at the same time, it will be difficult to melt-knead with the hydrogenated block copolymer or ethylene polymer. In addition, the hue of the adhesive resin composition of the present invention is as natural as possible (white or colorless and transparent, preventing yellow coloring).
In order to approach the above, an aliphatic petroleum resin, an aromatic petroleum resin, or a copolymer thereof is preferable, and a hydrogenated product thereof is particularly preferable. The degree of hydrogenation is preferably 80% or more, more preferably 90% or more.

(3) Ethylene polymer (c) The ethylene polymer (c) optionally used in the present invention is a melt flow rate of 0.05 to 50 g / 1.
It is an ethylene homopolymer or an ethylene-α-olefin copolymer having a density of 0.850 to 0.950 g / cm ³ for 0 minutes. The α-olefin constituting the ethylene-α-olefin copolymer is usually an α-olefin containing no cyclic molecule having 3 to 20 carbon atoms, for example, propylene, 1-butene, 1-hexene, 4-methyl-1-pentene , 1-octene, 1-decene, 1-tetradecene, 1-octadecene and the like, each of which may be used alone or as a mixture of two or more. Further, a vinyl ester (eg, vinyl acetate), an unsaturated carboxylic acid or an ester thereof (eg, acrylic acid, methacrylic acid, methyl acrylate, methyl methacrylate, ethyl acrylate) may be used. Further, two or more ethylene polymers (c) may be used in combination.

As a specific example, low density polyethylene (L
DPE), high density polyethylene (HDPE), medium density polyethylene (MDPE), linear low density polyethylene (LLDPE), very low density polyethylene (VLDP)
E), low crystalline ethylene-butene-1 random copolymer (EBM), ethylene-propylene copolymer, ethylene-vinyl acetate copolymer, ethylene-acrylic acid copolymer, ethylene-acrylate copolymer Etc.,
Among them, LDPE and VLDPE are preferable. In addition, the melt flow rate (MFR) here is JIS K
7210, temperature 190 ° C, load 2.16kg, 1
It means the value measured under the condition of 0 minutes.

(4) Composition ratio of composition The composition ratio of each of the above components is 50 to 99% by weight, preferably 50 to 98% by weight, particularly preferably 50 to 95% by weight of the modified hydrogenated block copolymer (a). % And the tackifier (b) is 1 to 50% by weight, preferably 2 to 50% by weight, particularly preferably 5 to 50% by weight, and the total of the component (a) and the component (b) is 100%. 10 to 1000 parts by weight, preferably 13 to 950 parts by weight, particularly preferably 15 to 9 parts by weight of ethylene polymer (c) based on parts by weight
00 parts by weight. (I) When the amount of the tackifier (b) is less than 1% by weight, the adhesiveness to each adherend decreases, which is not preferable.
If it exceeds, the fluidity becomes too high and the moldability tends to deteriorate, which is not preferred. (Ii) The moldability and handling can be significantly improved by adding 10 parts by weight or more of the ethylene-based polymer (c),
If it is added in excess of 1000 parts by weight, the adhesive strength tends to decrease extremely, which is not preferable.

(5) Method for Producing the Composition The adhesive resin composition of the present invention is mixed using various known methods, for example, using a tumbler blender, a V blender, a ribbon blender, a Henschel mixer, and the like. It can be prepared by a technique of melt-kneading with an extruder, a twin-screw extruder, a Banbury mixer, a kneader or the like, and granulating or pulverizing. The composition contains, in addition to the components described above, a heat stabilizer, a weather stabilizer, an antiblocking agent, a slip agent, an antistatic agent, a flame retardant, a catalyst residue neutralizer, a pigment, a dye, an inorganic and / or organic compound. A commonly used additive such as a filler can be blended within a range that does not impair the purpose of the present invention. Since the resin composition of the present invention has excellent adhesive strength with various thermoplastic resins described below, it can be used as a laminate with the thermoplastic resin and a stretched film obtained by stretching the laminate.

(6) Thermoplastic Resin Layer (Layer A) In the present invention, the thermoplastic resin layer (Layer A) laminated with the layer (B layer) composed of the adhesive resin composition is ethylene-based.
Thermoplastic resins such as a saponified vinyl acetate copolymer, a polyamide resin, a polyolefin resin, a styrene resin, a polyester resin, an acrylic resin, and a polycarbonate resin are used. As the thermoplastic resin,
Specifically, a saponified ethylene-vinyl acetate copolymer (EVOH) having an ethylene content of 15 to 65 mol% and a saponification degree of 90% or more; polyethylene terephthalate (P
ET), copolymerized PET, polybutylene terephthalate,
Polyester resins (PES resins) such as polyethylene naphthalate and polycyclohexylene terephthalate;
Polyamide-based resins (PA-based resins) such as 6-nylon, 6,6-nylon, 6-6,6-nylon, 12-nylon, xylylene group-containing polyamide resin; polypropylene-based resin, polyethylene-based resin, ethylene-vinyl acetate Polyolefin resins (PO resins) such as copolymers, ethylene-acrylic acid copolymers, ethylene-acrylate copolymers, and 4-methyl-1-pentene resin; general-purpose polystyrene, impact-resistant polystyrene, and styrene A styrene resin (PS resin) such as a methacrylic acid copolymer;
An acrylic resin such as polyacrylonitrile, polymethyl methacrylate, acrylonitrile-methyl acrylate-butadiene copolymer; and a polycarbonate resin (PC resin); and a mixture of the resin and a filler such as a plate-like filler. One or more materials are included.

The saponified ethylene-vinyl acetate copolymer used for the thermoplastic resin layer (layer A) preferably has an ethylene content of 15 to 65 mol%, more preferably 2 to 65 mol%.
5 to 50 mol% of ethylene-vinyl acetate copolymer having a saponification degree of preferably 50% or more, more preferably 9%
What is saponified so as to be 0% or more is used. If the ethylene content is too low, the composition is liable to be thermally decomposed, is difficult to melt-mold, is poor in stretchability, easily absorbs water and swells, and has poor water resistance. On the other hand, if the ethylene content is too large, the gas permeability resistance tends to decrease. When the saponification degree is too low, the gas permeability resistance tends to decrease.

As the polyamide resin used for the thermoplastic resin layer (layer A), hexamethylene diamine, decamethylene diamine, dodecamethylene diamine, 2,2,4-
Or an aliphatic such as 2,4,4-trimethylhexamethylenediamine, 1,3- or 1,4-bis (aminomethyl) cyclohexane, bis (p-aminocyclohexylmethane), m- or p-xylylenediamine, Obtained by polycondensation of alicyclic and aromatic diamines with adipic acid, suberic acid, sebacic acid, cyclohexanedicarboxylic acid, terephthalic acid, isophthalic acid and other aliphatic, alicyclic and aromatic dicarboxylic acids. Polyamide, ε-aminocaproic acid, polyamide obtained by condensation of aminocarboxylic acids such as 11-aminoundecanecarboxylic acid, ε-caprolactam, polyamide obtained from lactams such as ω-laurolactam or copolymerized polyamide comprising these components Mixtures and the like are exemplified. Specifically, nylon 6, nylon 66, nylon 610, nylon 9, nylon 11, nylon 1
2, nylon 6/66, nylon 66/610, nylon 6/11 and the like. Among these, the melting point,
Nylon 6 and nylon 66 which are excellent in rigidity and the like are preferable. Although the molecular weight is not particularly limited, polyamide having a relative viscosity ηr (measured in 98% sulfuric acid of JIS K6810) of 0.5 or more is usually used.
The above are preferred.

The polyolefin-based resin used for the thermoplastic resin layer (layer A) is a polyolefin having 2 to 4 carbon atoms such as ethylene, propylene, 1-butene, etc., alone or as a main component. Is a polymer. Specific examples of these polyolefin-based resins include polyethylene, polypropylene, and poly-1-butene. However, these are not limited to homopolymers, and other carbon-containing resins having a carbon number of 2 to 2 can be used as long as the olefin is the main component. 20 α
-Olefin or vinyl acetate, vinyl chloride, acrylic acid, methacrylic acid, copolymers with vinyl compounds such as styrene, and unsaturated carboxylic acids such as maleic anhydride, maleic acid, acrylic acid or the like. A graft copolymer modified with a derivative may be used. Further, these polyolefins may be a mixture.

Specific examples of the polyethylene include high-pressure low-density polyethylene (LDPE), ethylene-propylene copolymer, ethylene-1-butene copolymer, ethylene-4-methyl-1-pentene polymer and ethylene. -1-hexene copolymer, high-density polyethylene (H
DPE), ethylene-vinyl acetate copolymer, ethylene-
An acrylic acid copolymer, an ethylene-acrylic acid ester copolymer, and the like can be given. Among these, LDPE,
Ethylene-α-olefin random copolymer, ethylene-vinyl acetate copolymer and the like are preferable because they are excellent in transparency and low-temperature heat sealability, and particularly have a density of 0.910 to 0.910.
Those having 0.960 g / cm ³ and a melting point in the range of 100 to 135 ° C. are preferred. In addition, the melt flow rate of polyethylene is not particularly limited, but is usually 0.01 to 30 g / 10 min.
/ 10 minutes is preferable.

Specific examples of the polypropylene include, for example, polypropylene (propylene homopolymer), propylene-ethylene random copolymer, propylene-ethylene-1-butene random copolymer and propylene-propylene.
Propylene random copolymer such as 1-butene random copolymer (propylene content is usually 90 mol% or more,
Preferably 95% mol or more), and a propylene-ethylene block copolymer (ethylene content is usually 5 to 30 mol%). Among these are homopolymers,
A random copolymer is preferable because of its excellent transparency, and a random copolymer having a melting point of 130 to 140 ° C. is particularly preferable because of its excellent heat sealability. The propylene melt flow rate is not particularly limited, but is usually 0.5 to 30 g / 10 min, and more preferably 0.5 to 30 g / min from the viewpoint of moldability.
Those having a range of 10 g / 10 minutes are preferred.

Specific examples of the poly-1-butene include:
Examples thereof include 1-butene homopolymer, 1-butene-ethylene copolymer, 1-butene-propylene copolymer, and 1-butene-4-methyl-1-pentene copolymer. The melt flow rate of poly-1-butene is not particularly limited, but is usually 0.01 to 100 g from the viewpoint of moldability.
/ 10 min, more preferably 0.03 to 30 g / 10 min.

The styrene-based resin used for the thermoplastic resin layer (layer A) is mainly composed of styrene such as styrene homopolymer, styrene and a copolymer such as acrylonitrile and methyl (meth) acrylate, or a rubber modified product thereof. Specifically, polystyrene, impact-resistant polystyrene (rubber-containing polystyrene), and AS resin (SA
A thermoplastic resin called N), ABS, SMA (styrene-maleic anhydride polymer) or the like is used.
Polystyrene usually has a melt flow rate of 0.1 to 5
0 g / 10 min, preferably 1 to 20 g / 10 min. If the MFR is outside the above range, the moldability tends to decrease.

The polyester resin used for the thermoplastic resin layer (layer A) includes terephthalic acid, isophthalic acid, diphenyl ether-4,4-dicarboxylic acid, naphthalene-
Aromatic dicarboxylic acids such as 1,4- or 2,6-dicarboxylic acid, oxalic acid, succinic acid, adipic acid, sebacic acid, aliphatic dicarboxylic acids such as undecadicarboxylic acid,
An acid component of a dicarboxylic acid such as an alicyclic dicarboxylic acid such as hexahydroterephthalic acid and an alicyclic glycol such as ethylene glycol, propylene glycol, 1,4-butanediol, neopentyl glycol, and an oil such as cyclohexanedimethanol. It is composed of a glycol component such as an aromatic dihydroxy compound such as a cyclic glycol and bisphenol A, and includes polyethylene terephthalate (PET), copolymer PET, polybutylene terephthalate, polyethylene naphthalate, and polycyclohexine terephthalate. . Particularly preferred among these is polyethylene terephthalate (PET), a thermoplastic polyester resin in which at least 80 mol% of the dicarboxylic acid component is terephthalic acid and at least 80 mol% of the glycol component is ethylene glycol. Furthermore, copolymer PET or a mixture of PET and another polyester may be used.

The acrylic resin used in the thermoplastic resin layer (layer A) includes polymethyl acrylate, polyethyl acrylate, polybutyl acrylate, and polyacrylic acid-2-
Examples include ethylhexyl, polymethyl methacrylate, polyacrylonitrile, polymethacrylonitrile, methyl methacrylate-acrylonitrile copolymer, and methyl methacrylate-α-methylstyrene copolymer. Further, a styrene-acrylonitrile copolymer, a styrene-acrylonitrile-butadiene copolymer, a styrene-methyl methacrylate copolymer, or the like may be used.
Among them, polyacrylonitrile and styrene-acrylonitrile-butadiene copolymer are preferred. These acrylic resins can be appropriately selected from commercially available products, and various plasticizers, stabilizers, inorganic fillers, additives such as antistatic agents and pigments, as long as the effects of the present invention are not impaired. May be blended.

The polycarbonate resins used for the thermoplastic resin layer (layer A) are various polycarbonates obtained by reacting a dihydroxy compound with phosgene or diphenyl carbonate by a known method. As dihydroxy compounds, hydroquinone, resorcinol,
4,4'-dihydroxydiphenylmethane, 4,4'-
Dihydroxydiphenylethane, 4,4'-dihydroxydiphenyl-n-butane, 4,4'-dihydroxydiphenylheptane, 4,4'-dihydroxydiphenylmethane, 4,4'-dihydroxydiphenyl-2,2-
Propane (bisphenol A), 4,4'-dihydroxy-3,3'-dimethyldiphenyl-2,2-propane, 4,4'-dihydroxy-3,3'-diphenyldiphenyl-2,2-propane, 4, 4′-dihydroxydichlorodiphenyl-2,2-propane, 4,4′-dihydroxydiphenyl-1,1-cyclopentane, 4,
4'-dihydroxydiphenyl-1,1-cyclohexane, 4,4'-dihydroxy-diphenylmethylphenylmethane, 4,4'-dihydroxydiphenylethylphenylmethane, 4,4'-dihydroxydiphenyl-
2,2,2-trichloro-1,1-ethane, 2,2′-
Dihydroxydiphenyl, 2,6-dihydroxynaphthalene, 4,4′-dihydroxydiphenyl ether,
4,4'-dihydroxy-3,3'-dichlorodiphenyl ether, 4,4'-dihydroxy-2,5-diethoxyphenyl ether and the like are used. 4,
Polycarbonate using 4'-dihydroxy-diphenyl-2,2-propane (bisphenol A) is preferred because of its excellent mechanical performance and transparency.

(7) Method for Producing Laminate As a method for producing the laminate of the present invention, conventionally known various methods can be employed. For example, an inflation film, a T-die film, a sheet, a pipe, and a melted individual resin, which are melted by an extruder, are supplied to a multilayer die by a co-extrusion method in which the individual resins are laminated in the die, and the same individual resin is melted. A co-extrusion of a non-stretched test tube parison or the like is performed by co-injection molding in which a time lag is provided in a mold and injected.

(8) Production of Stretched Film As a method for producing the stretched film of the present invention, various conventionally known methods can be employed. For example,
After cooling and solidifying the unstretched (multi-layer) laminate obtained from the above (7), each molded product is reheated to a stretching temperature of 60 to 160 ° C. in-line or out-line, and a tenter, a plug, compressed air and the like are removed. For example, there is a method in which stretching is performed at least 1.5 times in an area ratio in a uniaxial direction or a biaxial direction to obtain a molded product such as a film, a cup, or a bottle, which is uniaxially or biaxially stretched. For inflation film, inflation simultaneous biaxial stretching method, for T-die film, tenter simultaneous biaxial stretching method, sequential biaxial stretching method using roll and tenter, etc., for cup, only by compressed air etc. in the mold Compressed air molding, SPP using both plug and compressed air
In the case of bottles such as F-molding, a test tube with a bottomed parison is formed by a pipe stretching method in which a laminated pipe is vertically stretched and then horizontally stretched with compressed air or the like in a mold, and injection molding is performed. A bottomed parison stretching method or the like in which a rod is stretched in a longitudinal direction in a mold and then stretched in a transverse direction by compressed air or the like is generally used. The stretched film can be formed into two or more layers by interposing the adhesive resin composition of the present invention as desired.

Further, the stretched film of the present invention is optionally reheated after stretching, that is, heat-set to improve heat resistance (shrinkage slightly decreases).
be able to.

[0040]

The present invention will be described below in more detail with reference to examples. (1) The production of the laminate was performed by the following method A or B. Method A: Two- and three-layer coextrusion water-cooled blown film forming method The layer structure was various adherends / adhesives / various adherends from the inner layer to the outer layer. The thickness of each layer is 100 μm
And The die width of the extruder is 4 from the inner layer to the outer layer.
0 mmφ / 35 mmφ / 40 mmφ. The molding conditions for each adherend are shown below. Coextrusion temperature Polyester resin = 275 ° C Polyamide resin = 250 ° C Saponified ethylene-vinyl acetate copolymer = 230 ° C Acrylic resin = 220 ° C Styrene resin = 220 ° C Polycarbonate resin = 275 ° C Polyolefin resin = 230 ° C The molding speed was set at 5 m / min. Method B: Three-type, five-layer coextrusion sheet molding method The layer structure is composed of various adherends / adhesives / gas barrier resin / adhesives / various adherends from the inner layer to the outer layer, each having a thickness of 220 μm. / 40μm / 50μm / 40μm /
It was 220 μm. Extruder die width is 65mmφ / 45m
mφ / 45 mmφ / 45 mmφ / 65 mmφ. The molding conditions for each adherend are shown below. Co-extrusion temperature Polyester resin = 235 ° C Polyamide resin = 250 ° C Saponified ethylene-vinyl acetate copolymer = 230 ° C Acrylic resin = 220 ° C Styrene resin = 220 ° C Polycarbonate resin = 275 ° C Polyolefin resin = 200 ° C The molding speed was set at 5 m / min.

(2) The laminate was stretched by the following method. Tenter method Standard type biaxial stretching machine: T. M. Long stretch ratio: 7.2 × 7.2 times Stretching speed: 7.6 to 3000 cm / min Heating method: hot air circulation (room temperature to 350 ° C.) Stretching head drive: hydraulic cylinder Stretchable sample thickness: 0.08 ２2 mm Stretch ratio: 3.3 × 3.3 times

The evaluation items of Examples and Comparative Examples were evaluated by the following methods. (3) The adhesive strength (kg / 10 mm) of the laminate is determined according to JIS
It measured on condition of the following according to K-6854. Peeling width: 10 mm Peeling state: T-peel peeling Peeling speed: 50 mm / min Temperature: 23 ° C and 60 ° C

(4) Boil treatment The laminate of the present invention prepared by the method A and the method B was 3.3 ×
This was performed using a film obtained by stretching by a factor of 3.3.
Put the stretched film in a PE bag and seal with heat seal.
The sample was treated in hot water at 0 ° C. for 30 minutes, taken out of the hot water, and cooled in water at 23 ° C. (about 30 minutes) to obtain a sample.

Example 1 Maleic anhydride graft-modified styrene-butadiene copolymer hydrogenated product (graft ratio: 2)
5% by weight, MFR-200 ° C., 5 kg: 22 g / 10 min, styrene ratio: 30% by weight, hydrogenation rate: 98%) 90% by weight,
And tackifier (alicyclic petroleum resin, number average molecular weight:
860, specific gravity: 0.999, softening point 140 ° C.) The mixture was previously mixed at a blending ratio of 10% by weight in a 50-liter V-type blender for 5 minutes, and a twin-screw extruder PCM30 (D = 30 mm)
φ, L / D = 32, manufactured by Ikegai Iron Works Co., Ltd.
80 ° C, screw rotation speed 180 rpm, extrusion amount 1
The mixture was melt-kneaded at 1 kg / hour, extruded into a string, cooled, and cut to obtain pellets.

Example 2 Maleic anhydride graft-modified styrene-butadiene copolymer hydrogenated product (graft ratio: 2)
MFR-200 ° C. 5 kg: 22 g / 10 min, styrene weight ratio: 30%, hydrogenation rate: 98%) 20% by weight,
Tackifier (alicyclic petroleum resin, number average molecular weight: 71
0, specific gravity: 0.998, softening point 115 ° C) 30% by weight, and hydrogenated styrene-butadiene copolymer (styrene ratio: 30% by weight, MFR-200 ° C 5kg: 3.5g /
10 minutes) The mixture was previously mixed at a blending ratio of 50% by weight with a 50-liter V-blender for 5 minutes, and a twin-screw extruder PCM30 was used.
(D = 30mmφ, L / D = 32, manufactured by Ikegai Iron Works Co., Ltd.)
At a temperature of 180 ° C. and a screw rotation speed of 180 rpm
m, melt-kneaded at an extrusion rate of 11 kg / hour, extruded into a string, cooled, and cut to obtain pellets.

Example 3 Maleic anhydride graft-modified styrene-butadiene copolymer hydrogenated product (graft ratio: 2)
5% by weight, MFR-200 ° C., 5 kg: 22 g / 10 min, styrene ratio: 30% by weight, hydrogenation rate: 98%) 30% by weight,
Tackifier (alicyclic petroleum resin, number average molecular weight: 71
0, specific gravity: 0.998, softening point 115 ° C.) 20% by weight and ethylene-butene copolymer (density: 0.900 g /
cm ³ , melting point: 88 ° C., MFR-190 ° C. 2.16 k
g: 5 g / 10 min) 50% by weight in advance and 50
The mixture was mixed in a liter V-type blender for 5 minutes, and using a twin-screw extruder PCM30 (D = 30 mmφ, L / D = 32, manufactured by Ikegai Iron Works Co., Ltd.) at a temperature of 180 ° C. and a screw rotation speed of 1
The mixture was melt-kneaded at 80 rpm at an extrusion rate of 11 kg / hour, extruded into a string, cooled, and cut to obtain pellets.

Example 4 Maleic anhydride graft-modified styrene-butadiene copolymer hydrogenated product (graft ratio: 2)
5% by weight, MFR-200 ° C., 5 kg: 22 g / 10 min, styrene weight ratio: 30%, hydrogenation rate: 98%) 10% by weight,
Tackifier (alicyclic petroleum resin, number average molecular weight: 86
0, specific gravity: 0.999, softening point 140 ° C) 20% by weight,
Styrene-butadiene copolymer hydrogenated product (styrene ratio: 2
0% by weight, MFR-200 ° C 5 kg: 0.3 g / 10
35% by weight of ethylene-butene copolymer (density: 0.88 g / cm ³ , melting point: 72)
° C, MFR-190 ° C 2.16 kg: 4 g / 10 min) 3
The mixture was previously mixed at a blending ratio of 5% by weight in a 50-liter V-blender for 5 minutes, and a twin-screw extruder PCM30 (D = 30) was used.
mmφ, L / D = 32, manufactured by Ikegai Iron Works Co., Ltd.), melt-kneaded at a temperature of 180 ° C., a screw rotation speed of 180 rpm, and an extrusion amount of 11 kg / hour, extruded into a string, cooled, cut, and obtained pellets. Was.

Example 5 Maleic anhydride graft-modified styrene-butadiene copolymer hydrogenated product (graft ratio: 2)
MFR-200 ° C. 5 kg: 22 g / 10 min, styrene ratio: 30 wt%, hydrogenation rate: 98%) 5 wt%, tackifier (alicyclic petroleum resin, number average molecular weight: 700,
Specific gravity: 0.995, softening point 100 ° C) 20% by weight, styrene-butadiene copolymer hydrogenated product (styrene ratio: 13% by weight, MFR-200 ° C 5 kg: 8 g / 10 minutes, hydrogenation rate: 98%) 30% by weight and low density polyethylene (density: 0.918 g / cm ³ , melting point: 106 ° C., MFR-
190 ° C. 2.16 kg: 14 g / 10 min) The mixture was previously mixed at a blending ratio of 45% by weight in a 50-liter V-blender for 5 minutes, and a twin-screw extruder PCM30 (D = 30 mmφ, L
/ D = 32, manufactured by Ikegai Iron Works Co., Ltd.) at a temperature of 180
° C, screw rotation speed 180rpm, extrusion amount 11k
The mixture was melt-kneaded at a rate of g / hour, extruded into a string, cooled, and cut to obtain pellets.

Example 6 Maleic anhydride graft-modified styrene-butadiene copolymer hydrogenated product (graft ratio: 2)
MFR-200 ° C. 5 kg: 22 g / 10 min, styrene ratio: 30 wt%, hydrogenation rate: 98%) 5 wt%, tackifier (alicyclic petroleum resin, number average molecular weight: 700,
Specific gravity: 0.995, softening point 100 ° C) 30% by weight, hydrogenated styrene-butadiene copolymer (styrene ratio: 40% by weight, MFR-200 ° C 5kg: 0.7g / 10min, hydrogenation rate: 98 %) And low-density polyethylene (density: 0.918 g / cm ³ , melting point: 106 ° C., MF
R-190 ° C. 2.16 kg: 14 g / 10 min.) The mixture was previously mixed at a blending ratio of 35% by weight in a 50-liter V-blender for 5 minutes, and a twin screw extruder PCM30 (D = 30 mm)
φ, L / D = 32, manufactured by Ikegai Iron Works Co., Ltd.
80 ° C, screw rotation speed 180 rpm, extrusion amount 1
The mixture was melt-kneaded at 1 kg / hour, extruded into a string, cooled, and cut to obtain pellets.

Example 7 Maleic anhydride graft-modified styrene-butadiene copolymer hydrogenated product (graft ratio: 2)
5% by weight, MFR-200 ° C., 5 kg: 22 g / 10 min, styrene ratio: 30% by weight, hydrogenation rate: 98%) 20% by weight,
10% by weight of a tackifier (β-pinene-terpene resin, number average molecular weight: 820, softening point 112 ° C.), styrene-
Propylene copolymer hydrogenated product (styrene ratio: 30% by weight,
MFR-200 ° C. 5 kg: 4 g / 10 min, hydrogenation rate: 98
%) And linear low-density polyethylene (density: 0.918 g / cm ³ , melting point: 106 ° C., MFR-
190 ° C. 2.16 kg: 14 g / 10 min) The mixture was previously mixed at a blending ratio of 40% by weight in a 50-liter V-blender for 5 minutes, and a twin-screw extruder PCM30 (D = 30 mmφ, L
/ D = 32, manufactured by Ikegai Iron Works Co., Ltd.) at a temperature of 180
° C, screw rotation speed 180rpm, extrusion amount 11k
The mixture was melt-kneaded at a rate of g / hour, extruded into a string, cooled, and cut to obtain pellets.

Comparative Example 1 Maleic anhydride graft-modified styrene-butadiene copolymer hydrogenated product (graft ratio: 2)
5% by weight, MFR-200 ° C., 5 kg: 22 g / 10 min, styrene ratio: 30% by weight, hydrogenation rate: 98%) 10% by weight,
Styrene-butadiene copolymer hydrogenated product (styrene ratio 20
Weight%, MFR-200 ° C 5kg: 0.3g / 10min)
30% by weight and an ethylene-butene copolymer (density:
0.900 g / cm ³ , melting point: 88 ° C., MFR-190
2.16 kg: 5 g / 10 min.) The mixture was previously mixed in a mixing ratio of 70% by weight in a 50-liter V-blender for 5 minutes, and a twin-screw extruder PCM30 (D = 30 mmφ, L / D =
32, manufactured by Ikegai Iron Works Co., Ltd.), melt-kneaded at a temperature of 180 ° C., a screw rotation speed of 180 rpm, and an extrusion amount of 11 kg / hour, extruded in a string form, cooled, and cut.
A pellet was obtained.

Comparative Example 2 Maleic anhydride graft-modified styrene-butadiene copolymer hydrogenated product (graft ratio: 2)
% By weight, density: 0.91 g / cm ³ , styrene ratio: 30
40% by weight and a tackifier (alicyclic petroleum resin, number average molecular weight: 860, specific gravity:
0.999, softening point 140 ° C) and mixed in advance in a blending ratio of 60% by weight in a 50-liter V-blender for 5 minutes,
Twin screw extruder PCM30 (D = 30 mmφ, L / D = 3
2, Ikegai Iron Works Co., Ltd.) was used to melt and knead at a temperature of 180 ° C., a screw rotation speed of 180 rpm, and an extrusion rate of 11 kg / hour, but the stickiness was too bad to be formed into pellets. Molding evaluation was not possible.

Comparative Example 3 Hydrogenated styrene-butadiene copolymer (styrene ratio: 30% by weight, MFR-200 ° C.)
5 kg: 10 g / 10 min, hydrogenation ratio: 98%) 30% by weight, tackifier (alicyclic petroleum resin, number average molecular weight: 7)
10, specific gravity: 0.998) 20% by weight and low-density polyethylene (density: 0.919 g / cm ³ , melting point: 109)
° C, MFR-190 ° C 2.16 kg: 14 g / 10 min)
The mixture was previously mixed at a blending ratio of 50% by weight in a 50-liter V-blender for 5 minutes, and a twin-screw extruder PCM30 (D = 3)
0mmφ, L / D = 32, manufactured by Ikegai Iron Works Co., Ltd.)
The mixture was melt-kneaded at a temperature of 180 ° C., a screw rotation speed of 180 rpm, and an extrusion amount of 11 kg / Hr, extruded into a string, cooled, and cut to obtain pellets.

Comparative Example 4 30% by weight of a tackifier (alicyclic petroleum resin, number average molecular weight: 860, specific gravity: 0.999) and an ethylene-butene copolymer (density: 0.90)
0 g / cm ³ , melting point: 88 ° C., MFR-190 ° C. 2.1
6 kg: 5 g / 10 min) 70 wt% of the mixing ratio was previously mixed in a 50-liter V-blender for 5 minutes, and a twin screw extruder PCM30 (D = 30 mmφ, L / D = 32, manufactured by Ikegai Iron Works Co., Ltd.) ), Melt-kneaded at a temperature of 180 ° C, a screw rotation speed of 180 rpm, and an extrusion amount of 11 kg / hour, extruded in a string shape, cooled, and then cut to obtain pellets.

Using the pellets obtained in the above Examples 1 to 7 and Comparative Examples 1 to 4, by a bonding method of Method A, as a material to be adhered, a polyester resin diamondite PA500 (specific gravity: 1.34, intrinsic viscosity) : 0.76 dl / g, manufactured by Mitsubishi Rayon Co., Ltd., saponified ethylene-vinyl acetate copolymer EVAL EP-F101 (density: 1.19 g / c)
m ³ , melt index: 1.3, ethylene copolymer content: 32 mol% (manufactured by Kuraray Co., Ltd.), polyamide resin
Novatec 1020CA2 (melting point: 224 ° C, manufactured by Mitsubishi Chemical Corporation), styrene resin Denkastyrol HI-
E-4 (specific gravity: 1.04, melt index: 3.
5, Denki Kagaku Kogyo Co., Ltd.), polyolefin resin
Novatec HD HY340 (Density 0.953g / cm
³ , melt flow rate: 1.5 g / 10 min, manufactured by Nippon Polychem Co., Ltd.), Novatec PP FY6H (density of 0.
90 g / cm ³ , melt flow rate: 1.9 g / 10
Minute, manufactured by Nippon Polychem Co., Ltd.), acrylic resin Barex 2090 (specific gravity: 1.15, melt index:
3 g / 10 min, Mitsui Toatsu Chemical Co., Ltd.) and polycarbonate Iupilone E-2000 (specific gravity: 1.2, Mitsubishi Gas Chemical Co., Ltd.) were obtained. 23 ° C as raw adhesive strength, 6 as heat resistant adhesive strength
Measure the adhesive strength in an atmosphere of 0 ° C, and measure the
The adhesive strength when stretched 3.3 × 3.3 times in the machine direction and the transverse direction under the atmosphere, and further, the boiling (90 ° C., 30
Min) The adhesive strength in a 23 ° C. atmosphere after the treatment was measured.
Table 1 shows the results. In Table 1, PS, PC, PAN,
23 ° C. in the column of PP and HDPE is data of the raw adhesive force.

(Examples 8 to 10) Using the pellets obtained in the above Examples 4 to 6, and using a bonding method of Method B, a polyolefin resin LE425 (density: 0.92
3 g / cm ³ , MFR: 2, manufactured by Mitsubishi Chemical Corporation)
Polyester resin PET- as gas barrier resin
G 6763 (specific gravity: 1.27, intrinsic viscosity: 0.75d
l / g, manufactured by Eastman Kodak), polyamide resin Novatec 1020CA2 (melting point: 224 ° C., manufactured by Mitsubishi Chemical Corporation), saponified ethylene-vinyl acetate copolymer EVAL EP-E151B (density: 1.14 g / cm)
³ , melt index: 5.5, ethylene copolymer content: 44 mol%, manufactured by Kuraray Co., Ltd.), to obtain each of the three kinds of five-layer films.
The adhesive strength in a 60 ° C. atmosphere was measured as a heat-resistant adhesive strength at 60 ° C., and the adhesive strength when stretched 3.3 × 3.3 times in the machine direction and the horizontal direction in a 90 ° C. atmosphere with a tenter, and ,
The adhesive strength in a 23 ° C. atmosphere after boil (90 ° C., 30 minutes) treatment was measured. Table 2 shows the results.

[0057]

[Table 1]

[0058]

[Table 2]

[0059]

The adhesive resin composition of the present invention has excellent adhesiveness to various materials after stretching over a wide range from a normal temperature to a high temperature state. Food, pharmaceutical and other film packaging materials with excellent moisture resistance, transparency and strength, thermoformed cups, blow bottles, injection bottles, as well as nonwoven fabrics and films for lamination with metal in the textile and industrial fields Can be suitably used.

Claims (6)

[Claims] 1. A hydrogenated block copolymer obtained by hydrogenating a block copolymer of a vinyl aromatic compound and a conjugated diene compound is modified with an unsaturated carboxylic acid or a derivative thereof,
And the content of the unsaturated carboxylic acid or its derivative is 0.
50 to 99% by weight of the modified hydrogenated block copolymer (a), which is 0.01 to 20% by weight, and tackifiers (b) 1 to 5
An adhesive resin composition containing 0% by weight. 2. A melt flow rate of 0.05 to 50 g / 10 minutes and a density of 0.1 to 100 parts by weight of the total of the modified hydrogenated block copolymer (a) and the tackifier (b).
2. The adhesive resin composition according to claim 1, comprising 10 to 1000 parts by weight of an ethylene polymer (c) having a weight of 850 to 0.950 g / cm ³ . 3. The adhesive resin composition according to claim 1, wherein in the hydrogenated block copolymer, 50% or more of the olefinic double bond in the polymer block comprising the conjugated diene compound is hydrogenated. Stuff. 4. A saponified ethylene-vinyl acetate copolymer having an ethylene content of 15 to 65 mol% and a saponification degree of 90% or more, a polyamide resin, a polyolefin resin, a styrene resin, a polyester resin, Layer (A layer) of at least one or more thermoplastic resins selected from the group consisting of acrylic resins and polycarbonate resins
And a layer (layer B) comprising the adhesive resin composition according to any one of claims 1 to 3. 5. A stretched film obtained by subjecting the laminate according to claim 4 to stretch treatment in at least a uniaxial direction at an area ratio of 1.5 times or more. 6. A stretched film obtained by subjecting the laminate according to claim 4 to stretch treatment in an area ratio of 1.5 times or more in a biaxial direction.