JP2000086841A - Adherent resin composition and laminated product formed therefrom - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide adherent resin compositions for obtaining laminated products improved in gas barrier properties (oxygen, carbon dioxide and the like), mechanical strength, resistance to contents (flavoring, preservation of a fragrance), designing (surface gloss, transparency), and the like. SOLUTION: Adherent resin compositions comprise (a) 1-85 wt.% modified etylene type polymer modified with 0.01-10 wt.% unsaturated carboxylic acid or a derivative thereof which has a melt flow rate(MFR) of 0.05-50 g/10 min and a density of 0.880-0.950 g/cm3, (b) 1-59 wt.% tackifier, and (c) 5-80 wt.% hydrogenated block copolymer obtained by hydrogenating a block copolymer of a vinyl aromatic compound and a conjugated diene compound, with the proviso that the sum of the C4 contents in components (a) and (c) of the composition is not less than 8.0 wt.% and, at the same time, the ratio of the sum of the C4 contents in components (a) and (c) to the weight of component (b) is not more than 5.0.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to gas barrier properties (oxygen, carbon dioxide, etc.), mechanical strength, and content resistance (flavor properties, preservation, etc.) widely required in various fields of industries such as food packaging materials. Fragrance), design (surface gloss, transparency)
The present invention relates to an adhesive resin composition capable of forming a laminate having improved properties and a laminate formed therefrom.

[0002]

2. Description of the Related Art Polyolefin resins such as polypropylene and polyethylene are widely used in various fields.
However, the polyolefin-based resin is excellent in moldability, mechanical strength, and chemical resistance, but is inferior in gas barrier property and content resistance, and has a design property (surface gloss, transparency, etc.) depending on the molding method and resin type. ). As a method of improving this defect, lamination with a polyester resin (polyethylene terephthalate, polycarbonate, etc.) has been proposed. Further, lamination of a polyolefin-based resin with a saponified ethylene / vinyl acetate copolymer (hereinafter simply referred to as “EVOH”) and a polyamide-based resin having excellent gas barrier properties has been widely proposed. As an adhesive resin, there is a polyolefin composition in which a polar group is modified. However, in laminating a polyester resin and a polyolefin resin or an EVOH or polyamide resin, the interlayer adhesive force is extremely weak and cannot be put to practical use as a laminated material.

[0003] In order to solve the above-mentioned drawback, as a method of improving the above-mentioned disadvantage, a laminate of an olefin resin and an alicyclic or aromatic polymer as a tackifier is bonded to a laminate of a polyolefin resin and a polyester resin. (JP-A-50-116536), a method of using a composition of an ethylene / vinyl acetate copolymer (hereinafter, simply abbreviated as “EVA”) and a tackifier as an adhesive. JP-A-53-147733, JP-A-54-1
No. 0384), a method of using a composition of EVA, a modified polyolefin and an aliphatic petroleum resin as a tackifier as an adhesive (JP-A-53-127546),
A method in which a composition of a modified low-crystalline ethylene / α-olefin random copolymer and an adhesion-imparting agent is used as an adhesive (Japanese Patent Application Laid-Open No. 61-241144), a low-crystalline (low-density) ethylene / α-olefin A method using a composition of an olefin random copolymer, a tackifier, and polyethylene as an adhesive (Japanese Patent Application Laid-Open No. 61-162538), hot-melt bonding comprising a mixture of a styrene-based thermoplastic rubber, low-molecular-weight polypropylene, and process oil Material composition (JP-A-1-144483), SBS, SEBS
Hot-melt type pressure-sensitive adhesive composition comprising a polyolefin, an alicyclic pressure-sensitive adhesive and a cyclic olefin random copolymer (JP-A-3-22
No. 3381) has been proposed. However,
In any case, the adhesive strength and durability of the laminate are insufficient as an adhesive using any of the above-mentioned techniques, and the present situation is that the practical problems have not been solved.

[0004]

SUMMARY OF THE INVENTION The present invention provides an adhesive resin composition and a laminate having excellent adhesive strength and durable adhesive strength between the polyester resin and the laminate in the laminate with the polyester resin. The purpose is to do so.

[0005]

According to the present invention, as a result of various investigations to obtain a thermoplastic resin having excellent adhesiveness, particularly adhesiveness with a polyester resin, extrusion moldability, hue, and uniform thickness of a film, it has been found that the present invention is not satisfactory. Adhesion is a composition comprising a block copolymer of a modified ethylene polymer modified with a saturated carboxylic acid or a derivative thereof and a tackifier, and a block copolymer of a vinyl aromatic compound and a conjugated diene compound hydrogenated. The present inventors have found that an adhesive resin composition, and furthermore, an adhesive resin composition comprising the above composition and an ethylene / butene copolymer have the above characteristics, and have completed the present invention.

That is, the adhesive resin composition of the present invention comprises:
A composition comprising the following components (a) to (c), wherein C ₄ contained in components (a) and (c) in the composition:
The total amount of the content is 8.0% by weight or more, and the ratio of the total amount of the C ₄ content contained in the components (a) and (c) to the weight of the component (b) is 5.0 or less. It is characterized by being. Component (a): Modified with an unsaturated carboxylic acid or a derivative thereof, the content of the unsaturated carboxylic acid or a derivative thereof is 0.01 to 10% by weight, and the melt flow rate is 0.1% by weight. Modified ethylene polymer having a density of 0.5 to 50 g / 10 min and a density of 0.880 to 0.950 g / cm ^{3 1} to 85% by weight Component (b): Tackifier 1 to 59% by weight Component (c): A hydrogenated block copolymer obtained by hydrogenating a block copolymer of a vinyl aromatic compound and a conjugated diene compound 5 to 80% by weight

A laminate according to another aspect of the present invention is a laminate obtained by laminating a polyester resin layer (B layer) and an adhesive resin layer (A layer). A) is formed from an adhesive resin composition comprising the following components (a) to (c), and the content of C ₄ contained in components (a) and (c) in the composition: And the ratio of the total amount of the C ₄ content contained in the components (a) and (c) to the weight of the component (b) is 5.0 or less. It is characterized by being. Component (a): Modified with an unsaturated carboxylic acid or a derivative thereof, the content of the unsaturated carboxylic acid or a derivative thereof is 0.01 to 10% by weight, and the melt flow rate is 0.1% by weight. Modified ethylene polymer having a density of 0.5 to 50 g / 10 min and a density of 0.880 to 0.950 g / cm ^{3 1} to 85% by weight Component (b): Tackifier 1 to 59% by weight Component (c): A hydrogenated block copolymer obtained by hydrogenating a block copolymer of a vinyl aromatic compound and a conjugated diene compound 5 to 80% by weight

[0008]

BEST MODE FOR CARRYING OUT THE INVENTION The adhesive resin composition of the present invention and a laminate formed therefrom will be specifically described below. [I] Adhesive resin composition (1) Constituents The adhesive resin composition of the present invention includes a modified ethylene polymer of component (a), a tackifier of component (b), and a block of component (c). It is a resin composition comprising a copolymer, and further a resin composition obtained by blending the ethylene / butene copolymer of the component (d) with these components (a) to (c).

(A) Modified Ethylene Polymer [Component (a)] As the modified ethylene polymer of the component (a) used in the adhesive resin composition of the present invention, an ethylene polymer may be an unsaturated carboxylic acid. Or, it is modified by graft copolymerization with a derivative thereof, or this modified ethylene-based polymer is diluted with an unmodified ethylene-based polymer. Suitable ethylene polymers used for ethylene polymer modification include a melt flow rate (MFR) of 0.05 to 50 g / 10 minutes,
Preferably 0.08 to 45 g / 10 min, density 0.88
0 to 0.950 g / cm ³ , preferably 0.88 to 0.
940 g / cm ³ ethylene homopolymer or ethylene / α-olefin copolymer, ethylene / vinyl ester copolymer which is a copolymer of ethylene and α-olefin, vinyl ester, unsaturated carboxylic acid ester, etc. Coalescing,
Ethylene copolymers such as ethylene / unsaturated carboxylic acid ester copolymers can be mentioned. The above ethylene
The α-olefin constituting the α-olefin copolymer is usually an α-olefin not containing a cyclic molecule having 3 to 20 carbon atoms, for example, propylene, 11-butene (C ₄ comonomer), 11-hexene, 1-methyl-11-pentene, 1-octene, 1-decene, 1-tetradecene, 1
One octadecene or the like, each of which is a single or a mixture of two or more. Examples of the ethylene / vinyl ester copolymer include an ethylene / vinyl acetate copolymer. Examples of the ethylene / unsaturated carboxylic acid ester copolymer include an ethylene / acrylic acid ester copolymer and an ethylene / methacrylic acid ester copolymer. Further, these ethylene polymers may be used as a mixture of two or more kinds.

[0010] Specific examples of the ethylene polymer include:
For example, low density polyethylene (usually referred to as "LDPE"), high density polyethylene (usually "HDPE")
It is called. ), Medium density polyethylene (usually "MDP
E ". ), Linear low-density polyethylene (commonly referred to as “LLDPE”), ultra-low-density polyethylene (commonly referred to as “VLDPE”), low-crystalline ethylene-butene-1 random copolymer ( Usually, "EB
M ". ), Ethylene-propylene copolymer,
Examples thereof include an ethylene / vinyl acetate copolymer (usually referred to as “EVA”) and an ethylene / ethyl acrylate copolymer.

Unsaturated carboxylic acids or derivatives thereof The unsaturated carboxylic acids or derivatives thereof used for modification include acrylic acid, maleic acid, fumaric acid, tetrahydrophthalic acid, itaconic acid, citraconic acid, crotonic acid,
Unsaturated carboxylic acids such as isocrotonic acid and nadic acid R (endosis-bicyclo [2,2,1] hept-5-ene-2,3-dicarboxylic acid) or derivatives thereof, for example, acid halides, amides, imides, anhydrides Products, esters and the like. Specific examples include maleenyl chloride, maleimide, maleic anhydride, citraconic anhydride, monomethyl maleate, dimethyl maleate, glycidyl maleate, and the like. Among these, unsaturated dicarboxylic acids or acid anhydrides thereof are preferable, and maleic acid, nadic acid R or acid anhydrides thereof are particularly preferable.

In order to produce the modified ethylene polymer (a), various conventionally known methods can be employed. For example, a method in which an ethylene polymer and an unsaturated carboxylic acid or a derivative thereof, a radical generator are mixed in advance, and the mixture is melted by an extruder and graft-copolymerized, or the ethylene polymer is dissolved in a solvent to form a radical generator. Examples thereof include a method of adding an unsaturated carboxylic acid or a derivative thereof to carry out graft copolymerization. In any case, it is preferable to carry out the reaction in the presence of a radical generator in order to graft copolymerize the unsaturated carboxylic acid or its derivative efficiently. The grafting reaction is usually performed at a temperature of 60 to 350C. The amount of the radical generator used is usually in the range of 0.001 to 1 part by weight based on 100 parts by weight of the ethylene polymer.

Examples of the radical generator include organic peroxides and organic peresters, for example, benzoyl peroxide, dichlorobenzoyl peroxide, dicumyl peroxide, di-tert-butyl peroxide, 2,5-dimethyl-2,5-di (peroxybenzoate). Hexin-3,1,4-bis (t-butylperoxyisopropyl) benzene, lauroyl peroxide, t-butylperacetate, 2,5-1-dimethyl-2,5-1- (t-butylperoxy) hexyne-3,2,5-dimethyl −
2,5-di (t-butylperoxy) hexane, t-butyl perbenzoate, t-butyl perphenyl acetate, t-butyl perisobutyrate, t-butyl persec sec-octoate, t-butyl perpivalate, cumyl Examples include perpivalate and t-butyl perdiethyl acetate, and other azo compounds such as azobisisobutyronitrile and dimethylazoisobutyrate. Among these, dicumyl peroxide, di-tert-butyl peroxide, 2,5-dimethyl-2,5
Dialkyl peroxide such as 1,2- (t-butylperoxy) hexyne-3,2,5-dimeter-2,5-di (t-butylperoxy) hexane, 1,4-bis (t-butylperoxyisopropyl) benzene is used. Is preferred.

Modified ethylene polymer The modified ethylene polymer of the component (a) has an unsaturated carboxylic acid or derivative thereof content of 0.01 to 10% by weight, preferably 0.03 to 8% by weight. belongs to. If the content of the unsaturated carboxylic acid or its derivative is less than the above range, the adhesiveness is not improved, while if it exceeds the above range, the dispersibility is reduced due to crosslinking, and the appearance of the molded article is poor, Adhesion decreases. The modified ethylene polymer of the component (a) has a melt flow rate (MFR) of 0.05 to 50 g / 10 min, preferably 0.08 to 45 g / min.
g / 10 minutes, density 0.880-0.950 g / c
m ³ , preferably 0.880 to 0.940 g / cm ³ . If the density of the modified ethylene polymer of the component (a) is too lower than the above range, the workability during molding processing will be significantly deteriorated. On the other hand, if it is higher than the upper range, the adhesive strength is low, and it is not practical. If the melt flow rate is outside the above range, the melt viscosity is too high or too low, so that the moldability is poor and the adhesive strength is poor. The melt flow rate (MFR) in the present invention is defined by JIS
Based on K7210, temperature 190 ° C, load 2.16k
g means a value measured under the conditions of 10 minutes.

Incorporation of Unmodified Ethylene Polymer When this modified ethylene polymer is diluted with an unmodified ethylene polymer of the same type or a different type as the unmodified ethylene polymer, an unsaturated carboxylic acid or After dilution, the content of the derivative must be within the above range for the unsaturated carboxylic acid or its derivative.

(B) Tackifier [Component (b)] The tackifier of component (b) used in the adhesive resin composition of the present invention is an amorphous resin which is solid at ordinary temperature, It is preferable to use a resin, a rosin-based resin, a terpene-based resin, or a hydrogenated product thereof, and these can be appropriately selected from commercially available products.

[0017] As the petroleum resin petroleum resin, for example, aliphatic petroleum resins, aromatic petroleum resins, or their copolymers, and these hydrogenated products etc. There, specifically, a commercially available Toho High Resin (Toho Chemical Co., Ltd.), Picopale (Rika Hercules Co., Ltd.), Alcon P and M (Arakawa Chemical Industries, Ltd.), Admarb (Idemitsu Petrochemical Co., Ltd.), Super Star Tack (Reichhold Co., Ltd.) )), Escolets (Tonex Co., Ltd.), Toho Petroresin (Tozen Petroleum Resins Co., Ltd.), Heylets (Mitsui Petrochemicals Co., Ltd.), Quinton (Zeon Corporation), and the like.

Rosin-based resin As the rosin-based resin, natural rosin, polymerized rosin and derivatives thereof, for example, pentaerythroester rosin,
Glycerin ester rosin and hydrogenated products thereof, and specifically, commercially available gum rosin, wood rosin,
Examples thereof include ester gum A, percene A, percene C (Arakawa Chemical Industries, Ltd.), pentalin A, ventalin C, and Foral 105 (Rika Hercules).

Terpene-based resins Terpene-based resins include polyterpene-based resins, terpene-phenol-based resins and hydrogenated products thereof. Specifically, commercially available picolite S and A (Rika Hercules), YS resin, Clearon (Yasuhara Yushi Co., Ltd.) and the like can be mentioned.

[0020] can be selectively used depending on the application in the present invention the product of these tackifiers, among these tackifiers, softening point (ring and ball method), preferably 70 to 170 ° C., particularly preferably 90 to It is preferable to use one at 150 ° C. When the softening point is less than the above range, the adhesive strength tends to decrease, and at the same time, the melt kneading with the hydrogenated block copolymer or the ethylene-based polymer tends to be difficult. On the other hand, if the softening point exceeds the above range, the adhesive strength tends to decrease. In order to make the hue of the resin composition as close as possible to a natural color (white or colorless and transparent, preventing yellow coloring), an aliphatic petroleum resin, an aromatic petroleum resin, or a copolymer thereof is used. It is preferable to use it, and it is particularly preferable to use its hydrogenated product. Its hydrogenation rate is 8
0% or more, more preferably 90% or more.

(C) Block Copolymer [Component (c)] The block copolymer of the component (c) used in the adhesive resin composition of the present invention may be a block copolymer of a vinyl aromatic compound and a conjugated diene compound. It is a block copolymer obtained by hydrogenating a copolymer. What is a block copolymer?
When the block A is a polymer block composed of a vinyl aromatic compound, and the block B is a polymer block composed of a conjugated diene compound, a general formula, AB, ABA,
BABA, ABABA, BABA
-B or the like, and as the vinyl aromatic compound constituting the polymer block portion A, for example, one or more kinds are selected from styrene, α-methylstyrene, vinyltoluene, and the like. Of these, it is preferable to use styrene.

[0022] As the conjugated diene compound constituting the polymer block portion B, for example, butadiene (C ₄ comonomer), isoprene, may be mentioned 1,3 one pentadiene, using butadiene Among these Is preferred. Further, the conjugated diene compound may be a copolymer with ethylene. In such a case,
The content of a conjugated diene compound such as butene is 10 to 60% by weight, preferably 13 to 58% by weight, more preferably 15% by weight.
It is desirably about 55% by weight. If the content of the conjugated diene compound is out of the above range, adhesiveness and durable adhesiveness tend to decrease. The content of the polymer block composed of a vinyl aromatic compound as the block A is generally 10 to 80% by weight, preferably 10 to 70% by weight. If the content of the polymer block is smaller or larger than the above range, the adhesive strength is undesirably reduced.

The hydrogenation rate of the polymer block comprising the conjugated diene compound is generally 50% or more, preferably 80%.
Or more, more preferably 90% or more, particularly preferably 95% or more.
% Or more, and it is particularly preferable that the hydrogenation rate be high because the thermal stability is improved. The number average molecular weight of the hydrogenated product of the block copolymer of component (c) is from 10,000 to 400,000.
It is preferably 0, particularly preferably 20,000 to 300,000. Regardless of whether the number average molecular weight is high or low, the adhesive strength tends to decrease, and a block copolymer having a number average molecular weight exceeding the above range tends to decrease the processability of the resin composition. Further, if the number average molecular weight of the block copolymer of component (c) does not exceed the above range, if it is moderately high, process oil, liquid polybutadiene, and an olefin wax having a number average molecular weight of 6,000 or less are used. The fluidity improver selected from the above is used in an amount of 1 to 4 with respect to 100 parts by weight of the block copolymer of the component (c).
By adding 0 parts by weight, it is possible to suppress a decrease in adhesive strength and workability. Such a method is an effective means for improving fluidity.

A block copolymer having an ABA structure is preferred. Specifically, a commercially available styrene-butadiene-based hydrogenated block copolymer, "TUFTEC"
H type (made by Asahi Kasei Corporation), "Clayton" G160
0 type (manufactured by Shell Chemical), “Septon” 8000 type (manufactured by Kuraray Co., Ltd.) and the like. Furthermore,
The block copolymer may be used as a mixture of two or more kinds.

(D) Ethylene / butene copolymer [Component (d)] The ethylene / butene copolymer of the component (d) used in the adhesive resin composition of the present invention has a melt flow rate (MFR). Generally 0.01 to 55 g / 10
Min, preferably 0.05 to 50 g / 10 min, particularly preferably 0.08 to 45 g / 10 min and a density of 0.850 to 10 g / min.
0.900 g / cm ³ , preferably 0.853 to 0.8
95 g / cm ³ , particularly preferably 0.853 to 0.89
0 g / cm ^{3 of} an ethylene / butene copolymer. Butene _{(C 4} comonomer) content of the ethylene-butene copolymer component (d), generally 5 to 50% by weight, preferably 10 to 45 wt%. These may be used in combination of two or more. When the density is less than the above range, the workability during the molding process is remarkably deteriorated. On the other hand, if the melt flow rate (MFR) is outside the above range, the melt viscosity is too high or too low, so that the moldability is poor and the adhesive strength tends to decrease, which is not preferable.

(2) Compounding ratio The adhesive composition of the present invention contains 1 to 85% by weight, preferably 3 to 80% by weight of the modified ethylene polymer of the component (a).
1 to 59% by weight, preferably 3 to 50% by weight of the tackifier of the component (b), and 5 to 5% by weight of the block copolymer of the component (c).
The content is 80% by weight, preferably 5 to 75% by weight, and the total amount is 100% by weight. When the amount of the modified ethylene-based polymer of the component (a) is less than the above range, the adhesive strength to the adherend decreases. On the other hand, if it exceeds the above range, the dispersibility is lowered due to crosslinking, and the appearance of the molded product becomes poor. If the compounding amount of the tackifier of the component (b) is less than the above range or exceeds the above range, the adhesive strength to the adherend decreases. If the amount of the component (c) block copolymer is less than the above range, the adhesive strength to the adherend is reduced. On the other hand, if it exceeds the above range, the appearance of the molded article will be inferior.

Further, a composition obtained by adding 1 to 400 parts by weight of the ethylene / butene copolymer of the component (d) to 100 parts by weight of the composition comprising the above components (a) to (c). When 1 part by weight or more of the ethylene / butene copolymer of the component (d) is added, moldability and handling become easy, and when it exceeds 400 parts by weight, adhesive strength tends to decrease. _{C 4} content in the composition (total amount of the _{C 4} content of the derived from the components _{(C 4} content and components derived from a) (c)) is 8.0 wt% or more, preferably 8.0 to 40 .0
%, The adhesiveness to the adherend and the durable adhesiveness decrease. Further, the total amount of the C ₄ content contained in the components (a) and (c) in the composition and the component (b)
Is 5.0 or less, preferably 5.0 to 0.0
When it exceeds 5, the adhesiveness to the adherend and the durable adhesiveness tend to decrease, and the moldability decreases. When the component (d) is blended, the C ₄ content in the composition (the total of the C ₄ content derived from the components (a) and (c) and the C ₄ content derived from the component (d)) is used. Amount) is 8.
It is preferably at least 0% by weight, more preferably 8.0 to 40.0% by weight. Furthermore, the ratio of the total amount of the C ₄ content contained in (a), (c) and (d) in the composition to the weight of the component (b) is 5.0 or less, preferably 5.0. ~
It is preferably 0.05. The “C ₄ content” means the content of α-olefin units having four carbon atoms, such as butene, butadiene, and isoprene. Further, in this composition, if necessary, in addition to the above components, a heat stabilizer, a weather stabilizer, an antistatic agent, a pigment,
You may mix | blend a dye, a rust inhibitor, etc.

(3) Method for Producing Adhesive Resin Composition To obtain this adhesive resin composition, the modified ethylene polymer of the component (a), the tackifier of the component (b), and the component (c) ), And the ethylene / butene copolymer of the component (d) are further mixed by various known methods, for example, a Henschel mixer, a V-blender, a ribbon blender, a tumbler blender, or the like, or After mixing, a method of melt-kneading with a single-screw extruder, a twin-screw extruder, a kneader, a Banbury mixer, or the like, and then granulating or pulverizing may be employed.

[II] Laminate (1) Layer Structure (A) Polyester Resin Layer (B Layer) As the polyester resin used for the polyester resin layer (B layer), terephthalic acid, isophthalic acid, diphenyl ether-4, 4-dicarboxylic acid, naphthalene-1,
Aromatic dicarboxylic acids such as aromatic dicarboxylic acids such as 4-1 or 2,6-dicarboxylic acid, oxalic acid, succinic acid, adipic acid, sebacic acid, undecadicarboxylic acid, and alicyclic dicarboxylic acids such as hexahydroterephthalic acid Acid components of dicarboxylic acids such as ethylene glycol, propylene glycol, 1,4-butanediol, aliphatic glycols such as neopentyl glycol, alicyclic glycols such as cyclohexanedimethanol, aromatic dihydroxy compounds such as bisphenol A, etc. And polyethylene glycol terephthalate (PET), copolymer PET, polybutylene terephthalate (PBT),
Examples include polyethylene naphthalate (PEN) and polycyclohexyne terephthalate (PCT). Among these, polyethylene terephthalate (PET) is particularly preferred, and is 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. is there. Furthermore, copolymer PET or a mixture of PET and another polyester may be used.

(B) Thermoplastic resin layer (C layer) As the thermoplastic resin layer (C layer) in the laminate of the present invention, a polyolefin resin, a saponified ethylene / vinyl acetate copolymer (EVOH), a polyamide resin A resin selected from a resin, a polycarbonate, a polystyrene resin, and an acrylic resin is used. Polyolefin resin As the polyolefin resin used for the thermoplastic resin layer (C layer), ethylene, propylene and 11-butene, which are α-olefins having 2 to 4 carbon atoms, are used alone or as a main component to polymerize or copolymerize. It is a crystalline polymer or copolymer obtained by polymerization. Specific examples of these polyolefin-based resins include polyethylene-based resins, polypropylene-based resins, and poly-butene-based resins. Further, these are not limited to homopolymers,
As long as the olefin is the main component, other carbon number 2
20 α-olefins or vinyl acetate, vinyl chloride,
It also includes a copolymer with a vinyl compound such as acrylic acid, methacrylic acid, and styrene. Further, a graft copolymer which is graft-modified with an unsaturated carboxylic acid such as maleic anhydride, maleic acid, acrylic acid, or a derivative thereof may be used. Further, these polyolefin resins may be a mixture of two or more kinds.

Specific examples of the polyethylene resin include, for example, high-pressure low-density polyethylene (LDPE),
Ethylene / propylene copolymer, ethylene / 1-butene copolymer, ethylene / 4-methyl-11-pentene polymer, ethylene-11-hexene copolymer, high density polyethylene (HDPE), ethylene / vinyl acetate copolymer And a copolymer of ethylene and acrylic acid, and a copolymer of ethylene and acrylic ester. 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, the density is 0.910 to 0.960 g. / Cm ³ and melting point 100 ~
Those having a temperature range of 135 ° C. are preferred. The melt flow rate of the polyethylene resin is not particularly limited,
From the viewpoint of moldability, a range of usually 0.01 to 30 g / 10 min, and more preferably 0.03 to 28 g / 10 min is preferable.

Specific examples of the polypropylene resin include, for example, polypropylene (propylene homopolymer), propylene / ethylene random copolymer, propylene / ethylene / 1-butene random copolymer, and
Propylene random copolymers such as propylene-11-butene random copolymer (propylene content is usually 90
Mol% or more, preferably 95 mol% or more), or a propylene / ethylene block copolymer (ethylene content is usually 5 to 30 mol%). Of these, homopolymers and random copolymers are preferred because of their excellent transparency. In particular, a random copolymer having a melting point of 130 to 140 ° C. is preferable because of excellent heat sealing properties. The melt flow rate of the propylene-based resin is not particularly limited, but is usually 0.5 to 30 from the viewpoint of moldability.
g / 10 minutes, more preferably in the range of 0.5 to 10 g / 10 minutes.

Specific examples of the poly-1-butene-based resin include, for example, a homopolymer of 11-butene, a copolymer of butene-ethylene and ethylene, a copolymer of butene-propylene and a copolymer of 1-butene and 4-methyl-1 One pentene copolymer is exemplified. The melt flow rate (MFR) of the poly (1-butene) resin is not particularly limited, but is usually 0.01 to 100 g / 10 min, and further preferably 0.03 to 30 from the viewpoint of moldability.
It is preferably in the range of g / 10 minutes.

Saponified ethylene / vinyl acetate copolymer The saponified ethylene / vinyl acetate copolymer (EVOH) used in the thermoplastic resin layer (C layer) has an ethylene content of 15 to 60 mol%, preferably 25 mol%. A saponified ethylene-vinyl acetate copolymer having a saponification degree of 50% or more, preferably 90% or more is used. When the ethylene content is less than the above range,
It tends to be thermally decomposed, is difficult to melt-mold, is poor in stretchability, and tends to swell by absorbing water, and tends to have poor water resistance. on the other hand,
If the ethylene content exceeds the above range, the gas permeation resistance tends to decrease. When the degree of saponification of the ethylene / vinyl acetate copolymer is less than the above range, the gas permeability tends to decrease.

[0035] The polyamide resin used in the polyamide resin thermoplastic resin layer (C layer), hexamethylene diamine, decamethylene diamine, dodecamethylene diamine, 2,2,4- one or 2,
Aliphatic or alicyclic such as 4,4-trimethylhexamethylenediamine, 1,3- or 1,4-bis (aminomethyl) cyclohexane, bis (p-aminocyclohexylmethane), m- or p-xylylenediamine Polyamide resin obtained by polycondensation of an aromatic diamine and adipic acid, suberic acid, sebacic acid, cyclohexanedicarboxylic acid, terephthalic acid, aliphatic such as isophthalic acid, alicyclic, aromatic dicarboxylic acid and the like, Polyamide resins obtained by condensation of aminocarboxylic acids such as ε-aminocaproic acid and 11-aminoundecanecarboxylic acid, polyamide resins obtained from lactams such as ε-caprolactam and ω-laurolactam, or copolymers composed of these components Examples thereof include a mixture of polyamide resins. Specifically, nylon 6, nylon 66, nylon 610, nylon 9, nylon 11, nylon 12, nylon 6/66, nylon 66/610, nylon 6 /
11 and the like. Among these, it is preferable to use nylon 6 and nylon 66 which are excellent in melting point, rigidity and the like. The molecular weight is not particularly limited, but usually,
A polyamide resin having a relative viscosity ηr (measured in 98% sulfuric acid of JIS K6810) of 0.5 or more is used. Among them, a polyamide resin of 2.0 or more is preferable.

Polycarbonate resin Examples of the polycarbonate resin used for the thermoplastic resin layer (C layer) include various polycarbonates obtained by reacting a dihydroxy compound with phosgene or diphenyl carbonate by a known method. Examples of the dihydroxy compound include hydroquinone, resorcinol, 4,4 ′
-Dihydroxydiphenyl-methane, 4,4'-dihydroxydiphenyl-ethane, 4,4'-dihydroxydiphenyl-n-butane, 4,4'-dihydroxydiphenyl-heptane, 4,4'-dihydroxy- Diphenyl-methane, 4,4'-dihydroxydiphenyl-2,2-propane (bisphenol A), 4,4 '
-Dihydroxy-3,3'-dimethyldiphenyl-2,21-propane, 4,4'-dihydroxy-3,3 '
-Diphenyl-2,2-propane, 4,4'-dihydroxydichlorodiphenyl-2,2-propane, 4,
4'-dihydroxydiphenyl-1,1-cyclopentane, 4,4'-dihydroxydiphenyl-1,1-cyclohexane, 4,4'-dihydroxydiphenyl-methyl-phenyl-methane, 4,4'-dihydro Xydiphenyl-ethyl-phenyl-methane, 4,4'-
Dihydroxydiphenyl-2,2,2-trichloro-1,111ethane, 2,2′-dihydroxydiphenyl,
2,6-dihydroxynaphthalene, 4,4'-dihydroxydiphenyl ether, 4,4'-dihydroxy-3,3'-dichlorodiphenyl ether and 4,4'-
Dihydroxy-2,5-diethoxyphenyl ether and the like are used. Among them, 4,4'-dihydroxydiphenyl-2,2-propane (bisphenol A)
Is preferred because it is excellent in mechanical performance and transparency.

Polystyrene resin Examples of the polystyrene resin used for the thermoplastic resin layer (C layer) include a homopolymer of styrene, a copolymer of styrene and acrylonitrile, methyl methacrylate, or the like, or a rubber modified product thereof. Is a resin mainly composed of styrene. Specifically, polystyrene resin, impact-resistant polystyrene resin (polystyrene resin containing rubber), styrene
A thermoplastic resin called an acrylonitrile resin (AS resin), an acrylonitrile-styrene-butadiene copolymer resin (ABS resin), or the like is used. Polystyrene usually has a melt flow rate (MFR) of 0.1
-50 g / 10 min, preferably 1-20 g / 10 min. If the MFR is outside the above range, the moldability tends to decrease.

Acrylic Resin The acrylic resin used for the thermoplastic resin layer (layer C) includes polymethyl acrylate, polyethyl acrylate, polybutyl acrylate, poly (ethyl hexyl acrylate), poly (methyl methacrylate), Polyacrylonitrile,
Examples include polymethacrylonitrile, methyl methacrylate / acrylonitrile copolymer, methyl methacrylate / α-methylstyrene copolymer, and the like. 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 and used from commercial products,
Further, within the range not impairing the effects of the present invention, various plasticizers,
It may be a mixture of additives such as a stabilizer, an inorganic filler, an antistatic agent and a pigment.

(2) Production of laminate (A) Molding method The method of producing a laminate with a polyester resin layer using the adhesive resin composition of the present invention includes coextrusion molding,
Known methods such as press molding and extrusion lamination molding can be applied. Among these molding methods, it is preferable to use a co-extrusion molding method from the viewpoint of interlayer adhesion. The co-extrusion 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. Known dies can be used for any of the dies used for the inflation method.

(3) Multilayer Laminate The multilayer laminate generally comprises an adhesive resin composition and an intermediate layer (A
As the layer), a polyester resin layer (layer B) and another thermoplastic resin layer (layer C), specifically, a polyolefin resin, a saponified ethylene / vinyl acetate copolymer (EV)
OH), a polyamide-based resin, a polycarbonate-based resin, or a polystyrene-based resin. As a method of manufacturing such a laminate,
For example, an adhesive resin composition (A layer), a polyester resin layer (B layer) and a thermoplastic resin, for example, a polyolefin resin, a saponified ethylene / vinyl acetate copolymer (EVO)
H), polyamide-based resin, polycarbonate-based resin or polystyrene-based resin (C layer) are each melted by a separate extruder, and then supplied to a three-layer die, and co-extrusion molding is performed using the adhesive resin composition as an intermediate layer. Or a polyester resin layer (B layer) and a heat-sensitive resin layer (C
Layer), for example, an adhesive resin composition layer (A) between a polyolefin resin, a saponified ethylene / vinyl acetate copolymer (EVOH), a polyamide resin, a polycarbonate resin, a polystyrene resin, or an acrylic resin layer. layer)
And a sand laminating method for extruding the same.

[0041]

The present invention will be described in more detail with reference to the following examples and comparative examples, but the present invention is not limited to these examples unless it exceeds the gist thereof. (1) Production of laminate The production of the laminate was carried out by the following molding method. The three-layer, three-layer coextrusion die molding method has a layer structure of polyester layer (B layer) / adhesive resin composition layer (A layer) / thermoplastic resin layer (C layer) from the inner layer to the outer layer. The thickness is 100 μm / 50 μm / 10
It was set to 0 μm. The extruder moves 50 from the inner layer to the outer layer.
mmφ / 40 mmφ / 40 mmφ. The molding conditions for each adherend are shown below. Coextrusion temperature Polyester resin: 255 ° C Polyolefin resin: 230 ° C Ethylene vinyl acetate saponified product: 245 ° C Polyamide resin: 235 ° C Polycarbonate: 280 ° C Polystyrene resin: 220 ° C Acrylic resin: 210 ° C Molding speed: 5 m / Min

The following materials were used as adherends. Polyester resin : [Eastman Kodak PE
TG 6763 (density: 1.27 g / cm ³ , intrinsic viscosity: 0.75 dl / g), or Diamondite PA500D manufactured by Mitsubishi Rayon Co., Ltd. (specific gravity: 1.34, intrinsic viscosity: 0.76 dl / g) )], Polyolefin-based resin : [Novatec HD HY340 manufactured by Nippon Polychem Co., Ltd. (density: 0.953 g / c)
m ³ , melt flow rate: 1.5 g / 10 min), or “Novatech LLD” U manufactured by Nippon Polychem Co., Ltd.
F240 (density: 0.920 g / cm ³ , melt flow rate: 2 g / 10 min), “Novatech PP” FY6H manufactured by Nippon Polychem Co., Ltd. (density: 0.91 g / c)
m ³ , melt flow rate: 2.3 g / 10 min)] Ethylene vinyl acetate saponified product : [EVAL EP-F101 manufactured by Kuraray Co., Ltd. (density: 1.19 g / cm ³ , melt index: 1.3 g / 10) Min, ethylene content: 3
Polyamide-based resin : Novatec 1020CA2 (melting point: 224 ° C., manufactured by Mitsubishi Chemical Corporation) Polycarbonate-based resin : Iupilon E-2000 (density: 1.2 g / cm ³ manufactured by Mitsubishi Gas Chemical Co., Ltd.) )] Polystyrene resin : [Denka Styrol HI-E-4 (density: 1.04, melt index: 3.5 g / 10 min.) Manufactured by Denki Kagaku Kogyo KK] Acrylic resin : [Mitsui Tomasa Chemical Co., Ltd. "Barex" 2090 (density: 1.15 g / cm ³ , melt index: 3 g / 10 min)].

(2) Evaluation Method Evaluation Method of Adhesive Strength of Alcohol Resistance The above molded film was cut into strips, immersed in a sample bottle filled with a solution of ethyl alcohol: distilled water = 1: 1, and heated at 50 ° C. The adhesive strength after storage for 1 to 7 days in the incubator adjusted to the following, "measurement of the adhesive strength of the laminate" shown below
It was measured according to. Measurement of adhesive strength of laminate The adhesive strength (kg / 10 mm) of the laminate was measured according to JIS K-6.
Polyester resin (B
Layer) or a thermoplastic resin layer (C layer). Peeling width: 10 mm Peeling state: T-peel peeling Peeling speed: 50 mm / min Temperature: 23 ° C

(3) Examples and Comparative Examples Example 1 Production of Adhesive Resin Composition Maleic anhydride-modified linear polyethylene (maleic anhydride content: 1% by weight, MFR: 1 g / 10 minutes, density: 0.1%).
923 g / cm ³ , melting point: 125 ° C.): 10% by weight, ethylene / butene copolymer (C ₄ content: 16% by weight, M
FR: 4 g / 10 min, density: 0.890 g / cm ³ , melting point: 86 ° C.): 50% by weight, tackifier (β-pinene-terpene resin, softening temperature:
112 ° C., number average molecular weight: 820): 20% by weight, styrene / butadiene copolymer (styrene content: 30% by weight, C ₄ content: 24.5% by weight (block polymer: 3)
5% by weight), hydrogenation rate: 98%, MFR: 3.5 g / 10
Min): 5% by a 50-liter V-blender in advance with a blending ratio of 20% by weight.
After mixing for 2 minutes, the twin screw extruder PCM30 (30 mm
φ, L / D = 32, manufactured by Ikegai Iron Works Co., Ltd.
70 ° C, screw rotation speed 100rpm, extrusion rate 12k
g, melt-kneaded, extruded into a string, cooled, and cut to obtain an adhesive resin composition used for the adhesive resin composition layer. The adhesive strength of the laminate was measured in accordance with "Method for evaluating alcohol-resistant adhesive strength" and "measurement of adhesive strength of laminate" of this adhesive resin composition. Table 1 shows the results.

Example 2 Preparation of Adhesive Resin Composition Maleic anhydride-modified ethylene / butene copolymer (maleic anhydride content: 0.7% by weight, MFR: 1 g / 10 minutes,
Density: 0.880 g / cm ^3, melting point: 72 ° C., _{C 4} content: 20 wt%): 30 wt%, low density polyethylene (MFR; 14g / 10 min, density:
0.919 g / cm ³ , melting point: 106 ° C.): 10% by weight, tackifier (aromatic hydrogenated petroleum resin, softening temperature: 125)
° C, number average molecular weight: 750, density: 0.999 g / cm
^3): 10 wt%, a styrene-butadiene copolymer (styrene content: 20 wt%, _{C 4} content: 30.4 wt% (block polymer:
38% by weight), hydrogenation rate: 97%, MFR: 0.3 g / 1
0 min): 50% by weight in advance using a 50-liter V-blender at a blending ratio of 5% by weight.
After mixing for 2 minutes, the twin screw extruder PCM30 (30 mm
φ, L / D: 32, manufactured by Ikegai Iron Works Co., Ltd.), temperature 1
70 ° C, screw rotation speed 100rPm, extrusion rate 12k
g, melt-blended, extruded into a string, cooled, and cut to obtain an adhesive resin composition used for the adhesive resin composition layer. The adhesive strength of the laminate was measured in accordance with "Method for evaluating alcohol-resistant adhesive strength" and "measurement of adhesive strength of laminate" of this adhesive resin composition. Table 1 shows the results.

Example 3 Preparation of Adhesive Resin Composition Maleic anhydride-modified linear polyethylene (maleic anhydride content: 0.8% by weight, MFR: 0.5 g / 10 min, density: 0.923 g / cm ³⁾ , Melting point: 125 ° C.): 10% by weight, low density polyethylene (MFR: 2 g / 10 min, density:
0.919 g / cm ³ , melting point: 106 ° C.): 40% by weight, tackifier (aromatic hydrogenated petroleum resin, softening temperature: 115)
° C, number average molecular weight: 700, density: 0.997 g / cm
^3): 20 wt%, a styrene-butadiene copolymer (styrene content: 20 wt%, _{C 4} content: 34.4 wt% (block polymer:
43% by weight), hydrogenation rate: 98%, MFR: 0.1 g / 1
0 min): 5% with a 50 liter V-blender in advance at a blending ratio of 30% by weight.
After mixing for 2 minutes, the twin screw extruder PCM30 (30 mm
φ, L / D = 32, manufactured by Ikegai Iron Works Co., Ltd.
70 ° C, screw rotation speed 100rpm, extrusion rate 12k
g, melt-kneaded, extruded into a string, cooled, and cut to obtain an adhesive resin composition used for the adhesive resin composition layer. The adhesive strength of the laminate was measured in accordance with "Method for evaluating alcohol-resistant adhesive strength" and "measurement of adhesive strength of laminate" of this adhesive resin composition. Table 1 shows the results.

Example 4 Production of Adhesive Resin Composition Maleic anhydride-modified ethylene / butene polymer (maleic anhydride content: 0.15% by weight, MFR: 4.5 g / 10
Min, density: 0.880 g / cm ³ , melting point: 72 ° C., C ₄
Content: 20% by weight): 85% by weight Tackifier (aromatic hydrogenated petroleum resin, softening temperature: 115
° C, number average molecular weight: 700, density: 0.997 g / cm
^3): 5 wt%, a styrene-butadiene copolymer (styrene content: 40 wt%, _{C 4} content: 21 wt% (block polymer: 35
% By weight), hydrogenation ratio: 98%, MFR: 0.7 g / 10
Min): 5% in advance with a 50-liter V-blender at a blending ratio of 10% by weight.
After mixing for 2 minutes, the twin screw extruder PCM30 (30 mm
φ, L / D = 32, manufactured by Ikegai Iron Works Co., Ltd.
70 ° C, screw rotation speed 100rpm, extrusion rate 12k
g, melt-kneaded, extruded into a string, cooled, and cut to obtain an adhesive resin composition used for the adhesive resin composition layer. The adhesive strength of the laminate was measured in accordance with "Method for evaluating alcohol-resistant adhesive strength" and "measurement of adhesive strength of laminate" of this adhesive resin composition. Table 1 shows the results.

Example 5 Preparation of Adhesive Resin Composition Maleic anhydride-modified linear polyethylene (maleic anhydride content: 0.7% by weight, MFR: 0.6 g / 10 minutes, density: 0.923 g / cm ³⁾ , Melting point: 125 ° C) 5% by weight, linear polyethylene (MFR: 2 g / 10 min, density:
0.920 g / cm ³ , melting point: 124 ° C.) 5% by weight, excess tackifier (aromatic hydrogenated petroleum resin, softening temperature: 140)
° C, number average molecular weight: 860, density: 0.999 g / cm
³⁾ 40 wt%, a styrene-butadiene copolymer (styrene content: 29 wt%, _{C 4} content: 27 wt% (block polymer: 38
% By weight), hydrogenation rate: 98%, MFR: 10 g / 10
Min): 50% by weight in advance with a 50 liter V-blender at a blending ratio of 50% by weight.
After mixing for 2 minutes, the twin screw extruder PCM30 (30 mm
φ, L / D = 32, manufactured by Ikegai Iron Works Co., Ltd.
70 ° C, screw rotation speed 100rpm, extrusion rate 12k
g, melt-kneaded, extruded into a string, cooled, and cut to obtain an adhesive resin composition used for the adhesive resin composition layer. The adhesive strength of the laminate was measured in accordance with "Method for evaluating alcohol-resistant adhesive strength" and "measurement of adhesive strength of laminate" of this adhesive resin composition. Table 1 shows the results.

Example 6 Preparation of Adhesive Resin Composition Maleic anhydride-modified linear polyethylene (maleic anhydride content: 1% by weight, MFR: 1 g / 10 min, density: 0.1%)
923 g / cm ³ , melting point: 125 ° C.): 20% by weight, low density polyethylene (MFR: 14 g / 10 min, density:
0.919 g / cm ³ , melting point: 106 ° C.): 20% by weight, tackifier (aromatic hydrogenated petroleum resin, softening temperature 115)
° C, number average molecular weight: 700, density: 0.997 g / cm
^3): 15 wt%, a styrene-butadiene copolymer (styrene content: 20 wt%, _{C 4} content: 32 wt% (block polymer: 40
% By weight), hydrogenation rate: 98%, MFR: 0.1 g / 10
Min): 10 wt%, ethylene-butene copolymer _{(C 4} content: 20 wt%, M
FR: 3.6 g / 10 min. Density: 0.880 g / c
m ³ , melting point: 72 ° C.): 35% by weight in advance with a 50-liter V-blender.
After mixing for 2 minutes, the twin screw extruder PCM30 (30 mm
φ, L / D = 32, manufactured by Ikegai Iron Works Co., Ltd.
70 ° C, screw rotation speed 100rpm, extrusion rate 12k
g, melt-kneaded, extruded into a string, cooled, and cut to obtain an adhesive resin composition used for the adhesive resin composition layer. The adhesive strength of the laminate was measured in accordance with "Method for evaluating alcohol-resistant adhesive strength" and "measurement of adhesive strength of laminate" of this adhesive resin composition. Table 1 shows the results.

Example 7 Preparation of Adhesive Resin Composition Maleic anhydride-modified ethylene / butene copolymer (maleic anhydride content: 0.7% by weight, MFR: 1 g / 10 minutes,
Density: 0.880 g / cm ^3, melting point: 72 ° C., _{C 4} content: 20 wt%): 15% by weight, low density polyethylene (MFR: 2 g / 10 min, density 0.
919 g / cm ³ , melting point: 106 ° C.): 40% by weight, tackifier (aromatic hydrogenated petroleum resin, softening temperature: 140)
° C, number average molecular weight: 860, density: 0.999 g / cm
^3): 20 wt%, a styrene-butadiene copolymer (styrene content: 20 wt%, _{C 4} content: 30.4 wt% (block polymer:
38% by weight), hydrogenation rate: 97%, MFR: 0.3 g / 1
0 minutes): 20 wt%, ethylene-butadiene copolymer _{(C 4} content: 33 wt%, MFR: 0.5 g / 10 min, density: 0.861 g /
cm ³ , melting point: 23 ° C.): 5% by weight in advance with a 50 liter V-blender.
After mixing for 2 minutes, the twin screw extruder PCM30 (30 mm
φ, L / D = 32, manufactured by Ikegai Iron Works Co., Ltd.
70 ° C, screw rotation speed 100rpm, extrusion rate 12k
g, melt-kneaded, extruded into a string, cooled, and cut to obtain an adhesive resin composition used for the adhesive resin composition layer. The adhesive strength of the laminate was measured in accordance with "Method for evaluating alcohol-resistant adhesive strength" and "measurement of adhesive strength of laminate" of this adhesive resin composition. Table 1 shows the results.

Example 8 Preparation of Adhesive Resin Composition Maleic anhydride-modified linear polyethylene (maleic anhydride content: 1% by weight, MFR: 0.3 g / 10 min, density:
0.923 g / cm ³ , melting point: 125 ° C.): 5% by weight, low density polyethylene (MFR: 14 g / 10 min, density:
0.919 g / cm ³ , melting point 106 ° C.): 40% by weight, tackifier (aromatic hydrogenated petroleum resin, softening temperature: 115)
° C, number average molecular weight: 700, density: 0.997 g / cm
^3): 15 wt%, a styrene-butadiene copolymer (styrene content: 20 wt%, _{C 4} content: 32 wt% (block polymer: 40
% By weight), hydrogenation rate: 98%, MFR: 0.1 g / 10
Min): 30 wt%, ethylene-butene copolymer _{(C 4} content: 33 wt%, M
FR: 1.3 g / 10 min, density: 0.862 g / cm ³ ,
(Melting point: 23 ° C.): 5 wt.
After mixing for 2 minutes, the twin screw extruder PCM30 (30 mm
φ, L / D: 32, manufactured by Ikegai Iron Works Co., Ltd.), temperature 1
70 ° C, screw rotation speed 100rpm, extrusion rate 12k
g, melt-kneaded, extruded into a string, cooled, and cut to obtain an adhesive resin composition used for the adhesive resin composition layer. The adhesive strength of the laminate was measured in accordance with "Method for evaluating alcohol-resistant adhesive strength" and "measurement of adhesive strength of laminate" of this adhesive resin composition. Table 1 shows the results.

Example 9 Production of Adhesive Resin Composition Maleic anhydride-modified ethylene / butene copolymer (maleic anhydride content: 0.65% by weight, MFR: 4.5 g / 1)
0 min, density: 0.880 g / cm ³ , melting point: 72 ° C., C
₄ content: 20% by weight): 10% by weight, low-density polyethylene (MFR: 14 g / 10 minutes, density:
0.919 g / cm ³ , melting point: 106 ° C.): 45% by weight, tackifier (aromatic hydrogenated petroleum resin, softening temperature: 140)
° C, number average molecular weight: 860, density: 0.999 g / cm
^3): 10 wt%, a styrene-butadiene copolymer (styrene content: 30 wt%, _{C 4} content: 24.5 wt% (block polymer:
35% by weight), hydrogenation rate: 97%, MFR: 0.1 g / 1
0 minutes): 20 wt%, ethylene-butadiene copolymer _{(C 4} content: 33 wt%, MFR: 3.6 g / 10 min, density: 0.862 g /
cm ³ , melting point: 20 ° C.): 15% by weight in a 50 liter V-blender beforehand.
After mixing for 2 minutes, the twin screw extruder PCM30 (30 mm
φ, L / D = 32, manufactured by Ikegai Iron Works Co., Ltd.
70 ° C, screw rotation speed 100rpm, extrusion rate 12k
g, melt-kneaded, extruded into a string, cooled, and cut to obtain an adhesive resin composition used for the adhesive resin composition layer. The adhesive strength of the laminate was measured in accordance with "Method for evaluating alcohol-resistant adhesive strength" and "measurement of adhesive strength of laminate" of this adhesive resin composition. Table 1 shows the results.

Example 10 Preparation of Adhesive Resin Composition Maleic anhydride-modified linear polyethylene (maleic anhydride content: 1% by weight, MFR: 1 g / 10 minutes, density: 0.1%)
923 g / cm ³ , melting point: 125 ° C.): 30% by weight, low density polyethylene (MFR: 14 g / 10 min, density:
0.919 g / cm ³ , melting point: 106 ° C.): 15% by weight, tackifier (aromatic hydrogenated petroleum resin, softening temperature: 140)
° C, number average molecular weight: 860, density: 0.999 g / cm
^3): 25 wt%, a styrene-butadiene copolymer (styrene content: 20 wt%, _{C 4} content: 28 wt% (block polymer: 35
%), Hydrogenation rate: 97%, MFR: 0.1 g / 10
Min): 30% by weight in advance with a 50 liter V-blender in 5
After mixing for 2 minutes, the twin screw extruder PCM30 (30 mm
φ, L / D = 32, manufactured by Ikegai Iron Works Co., Ltd.
70 ° C, screw rotation speed 100rpm, extrusion rate 12k
g, melt-kneaded, extruded into a string, cooled, and cut to obtain an adhesive resin composition used for the adhesive resin composition layer. The adhesive strength of the laminate was measured in accordance with "Method for evaluating alcohol-resistant adhesive strength" and "measurement of adhesive strength of laminate" of this adhesive resin composition. Table 1 shows the results.

Example 11 Preparation of Adhesive Resin Composition Maleic anhydride-modified linear polyethylene (maleic anhydride content: 1% by weight, MFR: 1 g / 10 min, density: 0.1%).
923 g / cm ³ , melting point: 125 ° C.): 10% by weight, tackifier (aromatic hydrogenated petroleum resin, softening temperature: 140)
° C, number average molecular weight: 860, density: 0.999 g / cm
^3): 45 wt%, a styrene-butadiene copolymer (styrene content: 29 wt%, _{C 4} content: 24.85 wt% (block polymer: 35 wt%), the hydrogenation rate 97%, MFR: 0 .1g /
10 minutes): 5% with a blending ratio of 45% by weight in advance using a 50-liter V-blender.
After mixing for 2 minutes, the twin screw extruder PCM30 (30 mm
φ, L / D: 32, manufactured by Ikenin Tekko Co., Ltd.), temperature 1
70 ° C, screw rotation speed 100rpm, extrusion rate 12k
g, melt-kneaded, extruded into a string, cooled, and cut to obtain an adhesive resin composition used for the adhesive resin composition layer. The adhesive strength of the laminate was measured in accordance with "Method for evaluating alcohol-resistant adhesive strength" and "measurement of adhesive strength of laminate" of this adhesive resin composition. Table 1 shows the results.

Comparative Example 1 Maleic anhydride-modified linear polyethylene (maleic anhydride content: 1% by weight, MFR: 0.5 g / 10 min, density:
0.923 g / cm ³ , melting point: 125 ° C.): 5% by weight, low density polyethylene (MFR: 14 g / 10 min, density:
0.919 g / cm ³ , melting point: 106 ° C.): 70% by weight, tackifier (aromatic hydrogenated petroleum resin, softening temperature 125)
° C, number average molecular weight: 750, density: 0.998 g / cm
^3): 5 wt%, a styrene-butadiene copolymer (styrene content: 20 wt%, _{C 4} content: 33.6 wt% (block polymer:
42% by weight), hydrogenation rate: 98%, MFR: 0.1 g / 1
0 minutes): 10 wt%, ethylene-butene copolymer _{(C 4} content: 20 wt%, M
FR: 1.3 g / 10 minutes, density: 0.886 g / c
m ³ , melting point: 72 ° C.): 10% by weight in a 50 liter V-blender beforehand.
After mixing for 2 minutes, the twin screw extruder PCM30 (30 mm
φ, L / D = 32, manufactured by Ikegai Iron Works Co., Ltd.
70 ° C, screw rotation speed 100rpm, extrusion rate 12k
g, melt-kneaded, extruded into a string, cooled, and cut to obtain an adhesive resin composition used for the adhesive resin composition layer. The adhesive strength of the laminate was measured in accordance with "Method for evaluating alcohol-resistant adhesive strength" and "measurement of adhesive strength of laminate" of this adhesive resin composition. Table 1 shows the results.

Comparative Example 2 Maleic anhydride-modified linear polyethylene (maleic anhydride content: 1% by weight, MFR: 0.3 g / 10 min, density:
0.923 g / cm ³ , melting point: 125 ° C.): 5% by weight, tackifier (aromatic hydrogenated petroleum resin, softening temperature: 140)
° C, number average molecular weight: 860, density: 0.999 g / cm
^3): 65 wt%, a styrene-butadiene copolymer (styrene content: 20 wt%, _{C 4} content: 33.6 wt% (block polymer:
42% by weight), hydrogenation rate: 98%, MFR: 0.1 g / 1
0 minutes): 20 wt%, ethylene-butene copolymer _{(C 4} content: 33 wt%, M
FR: 0.5 g / 10 min, density: 0.861 g / c
m ³ , melting point: 20 ° C.): 5 wt.
After mixing for 2 minutes, the twin screw extruder PCM30 (30 mm
φ, L / D = 32, manufactured by Ikegai Iron Works Co., Ltd.
70 ° C, screw rotation speed 100rpm, extrusion rate 12k
g, melt-kneaded, extruded into a string, cooled, and cut to obtain an adhesive resin composition used for the adhesive resin composition layer. The adhesive strength of the laminate was measured in accordance with "Method for evaluating alcohol-resistant adhesive strength" and "measurement of adhesive strength of laminate" of this adhesive resin composition. Table 1 shows the results.

Comparative Example 3 Maleic anhydride-modified linear polyethylene (maleic anhydride content: 1% by weight, MFR: 0.5 g / 10 min, density:
0.923 g / cm ³ , melting point: 125 ° C.): 20% by weight, low density polyethylene (MFR: 14 g / 10 min, density:
0.919 g / cm ³ , melting point: 106 ° C.): 20% by weight, tackifier (aromatic hydrogenated petroleum resin, softening temperature: 125)
° C, number average molecular weight: 750, density: 0.998 g / cm
^3): 30 wt%, a styrene-butadiene copolymer (styrene content: 30 wt%, _{C 4} content: 24.5 wt% (block polymer:
35% by weight), hydrogenation rate: 98%, MFR: 3.5 g / 1
0 min): 5% with a 50 liter V-blender in advance at a blending ratio of 30% by weight.
After mixing for 2 minutes, the twin screw extruder PCM30 (30 mm
φ, L / D = 32, manufactured by Ikegai Iron Works Co., Ltd.
70 ° C, screw rotation speed 100rpm, extrusion rate 12k
g, melt-kneaded, extruded into a string, cooled, and cut to obtain an adhesive resin composition used for the adhesive resin composition layer. The adhesive strength of the laminate was measured in accordance with "Method for evaluating alcohol-resistant adhesive strength" and "measurement of adhesive strength of laminate" of this adhesive resin composition. Table 1 shows the results.

[0058]

[Table 1]

[0059]

[Table 2]

[0060]

Since the adhesive resin composition of the present invention has excellent adhesive strength and durable adhesive strength particularly with a polyester resin layer, it has a gas barrier property (oxygen, carbonic acid). Gas, etc.), mechanical strength, content resistance (flavor, fragrance retention), design (surface gloss, transparency), etc. as resin laminates in various fields of industries such as food packaging materials. Can be used widely.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) C08L 57/02 C08L 57/02 93/04 93/04 F term (Reference) 4F100 AK03C AK04A AK11A AK12C AK25C AK28A AK41B AK45C AK46C AK65A AK69C AK73A AL02A AL05A AL07A BA02 BA03 BA06 BA10B BA10C BA16 CA16A CB00 JA06A JA13A JD16 JK01 JL11A JN01 JN21 YY00A 4J002 AF02Y BA01Y BB05X BB20W BB21W BN21W BN21W

Claims (7)

[Claims] 1. A composition comprising the following components (a) to (c), wherein the total amount of C ₄ contained in components (a) and (c) in the composition is 8.0. % By weight and the ratio of the total amount of C ₄ contained in the components (a) and (c) to the weight of the component (b) is 5.0 or less. Resin composition. Component (a): Modified with an unsaturated carboxylic acid or a derivative thereof, the content of the unsaturated carboxylic acid or a derivative thereof is 0.01 to 10% by weight, and the melt flow rate is 0.1% by weight. Modified ethylene polymer having a density of 0.5 to 50 g / 10 min and a density of 0.880 to 0.950 g / cm ^{3 1} to 85% by weight Component (b): Tackifier 1 to 59% by weight Component (c): A hydrogenated block copolymer obtained by hydrogenating a block copolymer of a vinyl aromatic compound and a conjugated diene compound 5 to 80% by weight 2. The adhesive resin composition according to claim 1, wherein the following component (d) is blended with the components (a) to (c). Component (d): Melt flow rate is 0.05 to 50 g.
/ 10 minutes, an ethylene / butene copolymer having a density of 0.850 to 0.900 g / cm ³ , 1 to 40 parts by weight based on 100 parts by weight of the components (a) to (c)
0 parts by weight 3. A derived from components of the adhesive resin composition (a) and C ₄ content and components derived from (c) (d) C
₄ content is not less than 8.0% by weight, and the total amount of C ₄ content contained in components (a), (c) and (d) and the weight of component (b) The ratio is less than or equal to 5.0,
The adhesive resin composition according to claim 2. 4. In a laminate comprising a polyester resin layer (layer B) and an adhesive resin layer (layer A), the adhesive resin layer (layer A) comprises the following components (a) to (c). ), Wherein the total amount of C ₄ content contained in components (a) and (c) in the composition is 8.0% by weight or more, and A ratio of the total amount of C ₄ contained in the components (a) and (c) to the weight of the component (b) of 5.0 or less. Component (a): Modified with an unsaturated carboxylic acid or a derivative thereof, the content of the unsaturated carboxylic acid or a derivative thereof is 0.01 to 10% by weight, and the melt flow rate is 0.1% by weight. Modified ethylene polymer having a density of 0.5 to 50 g / 10 min and a density of 0.880 to 0.950 g / cm ^{3 1} to 85% by weight Component (b): Tackifier 1 to 59% by weight Component (c): A hydrogenated block copolymer obtained by hydrogenating a block copolymer of a vinyl aromatic compound and a conjugated diene compound 5 to 80% by weight 5. The laminate according to claim 4, wherein the adhesive resin layer (A layer) is formed from an adhesive resin composition comprising the following component (d). Component (d): Melt flow rate is 0.05 to 50 g.
/ 10 minutes, an ethylene / butene copolymer having a density of 0.850 to 0.900 g / cm ³ , 1 to 40 parts by weight based on 100 parts by weight of the components (a) to (c)
0 parts by weight 6. derived from components of the adhesive resin composition (a) and C ₄ content and components derived from (c) (d) C
₄ content is not less than 8.0% by weight, and the total amount of C ₄ content contained in components (a), (c) and (d) and the weight of component (b) The ratio is less than or equal to 5.0,
The laminate according to claim 5. 7. A polyolefin resin, a saponified ethylene / vinyl acetate copolymer, or a polyamide, on the surface of the adhesive resin layer (A layer) opposite to the surface on which the polyester resin layer (B layer) is laminated. The laminate according to any one of claims 4 to 6, wherein at least one type of thermoplastic resin layer (C layer) selected from a series resin, a polycarbonate resin, a polystyrene resin, and an acrylic resin is laminated.