JP2000086840A - 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, mechanical strength, resistance to contents, designing, and the like. SOLUTION: Adherent resin compositions comprise (a) a modified ethylene type polymer modified with 0.01-10 wt.% unsaturated carboxylic acid or a derivative thereof which has an MFR of 0.05-50 g/10 min and a density of 0.880-0.950 g/cm3, (b) a tackifier, and (c) a hydrogenated product of a block copolymer having a vinyl aromatic compound polymer block and a conjugated diene compound polymer block, and meet the formula: Tg1-Tg2>=5 deg (wherein Tg1 is a Tg of the conjugated diene compound polymer block in component (c) by the DSC measurement of the resin composition comprising components (a), (b), and (c); and Tg2 is a Tg of the conjugated diene compound polymer block in the block copolymer by the DSC measurement of component (c) alone, provided that Tg2 <=-45 deg.C).

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 for obtaining a laminate having improved properties and a laminate using the same.

[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), a hot melt comprising a mixture of a styrene thermoplastic rubber, a low molecular weight polypropylene and a process oil Adhesive 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]

SUMMARY OF THE INVENTION The present invention has been studied in order to obtain a thermoplastic resin having excellent adhesiveness, in particular, adhesiveness with a polyester resin, extrusion moldability, hue, and uniform film thickness. A composition comprising a modified ethylene polymer (a) modified with a carboxylic acid or a derivative thereof, a tackifier (b), a block copolymer or a hydrogenated product thereof (c), and a block copolymer (c A) The conjugated diene component has a glass transition temperature (Tg ₂ ) of -45 ° C. or lower, and the composition ((a) + (b) + (c)) has a glass transition temperature (Tg ₁ ) of 5 ° C. measured by DSC. The composition characterized by the above-mentioned increase, and further, the composition ((a) + (b) +
(C)) The glass transition temperature (Tg ₄ ) by DSC measurement
Is a composition to which an ethylene / α-olefin copolymer (d) having a glass transition temperature (Tg ₃ ) of -45 ° C. or less is added.
Found that the composition having a temperature rise of 5 ° C. or more by DSC measurement had the above characteristics, and 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 the composition satisfies the following formula (I). 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 product of at least one polymer block of a polymer of a vinyl aromatic compound and a block copolymer having at least one polymer block of a polymer of a conjugated diene compound 5 to 80% by weight I): Tg ₁ −Tg ₂ ≧ 5 deg (Tg ₁ : Conjugation of component (c) in block copolymer by DSC measurement of resin composition comprising component (a), component (b) and component (c) Glass transition temperature of polymer block derived from diene compound, Tg ₂ : DSC of block copolymer of component (c) alone
By measurement, the glass transition temperature of the polymer block derived from the conjugated diene compound in the block copolymer, provided that Tg ₂ ≦
(-45 ° C, DSC measurement temperature: -70 to 100 ° C)

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 layer) is formed from an adhesive resin composition comprising the following components (a) to (c), and the composition satisfies the following formula (I). Is what you do. 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 product of at least one polymer block of a polymer of a vinyl aromatic compound and a block copolymer having at least one polymer block of a polymer of a conjugated diene compound 5 to 80% by weight I): Tg ₁ −Tg ₂ ≧ 5 deg (Tg ₁ : Conjugation of component (c) in block copolymer by DSC measurement of resin composition comprising component (a), component (b) and component (c) Glass transition temperature of polymer block derived from diene compound, Tg ₂ : DSC of block copolymer of component (c) alone
By measurement, the glass transition temperature of the polymer block derived from the conjugated diene compound in the block copolymer, provided that Tg ₂ ≦
(-45 ° C, DSC measurement temperature: -70 to 100 ° C)

[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 constituents of the adhesive resin composition of the present invention include a modified ethylene polymer of the component (a), a tackifier of the component (b), and a component ( c) a block copolymer or a hydrogenated product thereof,
The ethylene / α-olefin copolymer of the component (d) used as needed is used. (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, the ethylene polymer is an unsaturated carboxylic acid or a derivative thereof. Or a modified ethylene polymer diluted with an unmodified ethylene polymer.

[0009] Suitable ethylene-based polymer used in the ethylene polymer modification, the melt flow rate (MFR) 0.05~50g / 10 min, density 0.
880-0.950 g / cm ³ ethylene homopolymer,
Or, ethylene / α-olefin copolymer, ethylene / vinyl ester copolymer, ethylene / unsaturated, which is a copolymer of ethylene and α-olefin, vinyl ester such as vinyl acetate, unsaturated carboxylic acid ester, etc. Ethylene copolymers such as carboxylate copolymers can be mentioned. The α-olefin constituting the ethylene / α-olefin copolymer usually has 3 to 2 carbon atoms.
Α-olefins not containing 0 cyclic molecules, for example, propylene, 1-butene, 1-hexene, 4-methyl-11-pentene, 1-octene, 1-decene, 1-tetradecene, 1-octadecene, etc. Alone or 2
It consists of a mixture of more than one species. 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. Specific examples of the ethylene-based polymer include, for example, low-density polyethylene (usually, “LDPE”
It is called. ), High density polyethylene (usually "HDP
E ". ), Medium density polyethylene (usually "M
DPE ". ), 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 ( Normal,
Called "EBM". ), Ethylene-propylene copolymer, ethylene-vinyl acetate copolymer (usually "EV
A ". ), Ethylene-ethyl acrylate copolymer and the like.

The unsaturated carboxylic acid or derivative thereof used for modifying the unsaturated carboxylic acid or derivative thereof includes 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 (endo-cis-bicyclo [2,2,1] hept-5-ene-2,31-dicarboxylic acid) or derivatives thereof, for example, acid halides, amides, imides , Anhydrides, esters and the like. Specific examples include maleenyl chloride, maleimide, maleic anhydride, citraconic anhydride, monometer 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), conventionally known various 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-2,5-1-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-butyl peroxy) hexane, t-butyl perbenzoate, t-butyl perphenyl acetate, t-butyl perisobutyrate, t-butyl persec sec-octoate, t-butyl perpivalate, cumyl Perpivalate and t one-butylperoxide diethyl acetate, other azo compounds, for example, can be mentioned azobisisobutyronitrile, dimethyl azoisobutyrate, and the like. Among these, dicumyl peroxide, di-tert-butyl peroxide, 2,5-dimethyl-2,5
Use of dialkyl peroxides such as 1,2- (t-butylperoxy) hexyne-3,2,5-dimethyl-2,5-di (t-butylperoxy) hexane and 1,4-bis (t-butylperoxydiisopropyl) benzene 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 or 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.

Examples of 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.), Archon P and M (Arakawa Chemical Industries, Ltd.),
Admarve (Idemitsu Petrochemical Co., Ltd.), Super Star Tack (Reichhold Co., Ltd.), Escolets (Tonex Corporation), Heylets (Mitsui Chemicals Co., Ltd.),
Quinton (Zeon Corporation), Tackirole (Sumitomo Chemical Co., Ltd.) and the like can be mentioned.

Rosin-based resins As rosin-based resins, natural rosin, polymerized rosin and derivatives thereof, for example, pentaerythroester rosin,
Glycerin ester rosin and hydrogenated products thereof; specifically, commercially available products such as gum rosin, wood rosin, ester gum A, percene A, percene C (Arakawa Chemical Industry Co., Ltd.), pentalin A, ventalin C, and Foral 105 (Rika Hercules Co., Ltd.) and the like.

Terpene-based resins Terpene-based resins include polyterpene-based resins, terpene-phenol-based resins and hydrogenated products thereof. Specifically, picolite S and A (Rika Hercules Co., Ltd.) and YS resin are commercially available. And Clearon (Yasuhara Chemical Co., Ltd.).

[0019] can be selectively used depending on the application of these tackifiers in product properties present invention, 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, when 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, prevention of yellow coloring), an aliphatic petroleum resin, an aromatic petroleum resin, or
It is preferable to use those copolymers, and it is particularly preferable to use their hydrogenated products. The hydrogenation rate is 80%
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 is a vinyl aromatic compound of at least one polymer. It is a block copolymer having a block or a hydrogenated block copolymer obtained by hydrogenating the block copolymer. Especially, it is preferable to use a hydrogenated block copolymer. A block copolymer is a polymer block in which block A is a vinyl aromatic compound, block B
Is a polymer block composed of a conjugated diene compound, a general formula, AB, ABA, BAB-
A, ABABA, a block copolymer represented by BABAB, etc., as a vinyl aromatic compound constituting the polymer block portion A, for example, One of styrene, α-methylstyrene, vinyltoluene, etc.
At least one species is selected, and among these, styrene is preferably used.

The conjugated diene compound constituting the polymer block portion B has a glass transition temperature of -45 ° C. or less. For example, butadiene, isoprene, 1,1,
One or more types are selected from among 31-pentadiene and the like. Of these, butadiene, isoprene and combinations thereof are preferred. The content of the polymer block composed of the vinyl aromatic compound serving as the block A is generally from 10 to 80.
%, 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 degree of hydrogenation 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. If the number average molecular weight is too high or too 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. is there. According to DSC measurement, the glass transition temperature (Tg ₂ ) of the conjugated diene compound component of the block copolymer is preferably −45 ° C. or lower, more preferably −48 ° C. or lower, and −50 ° C.
The following are particularly preferred. The block copolymer (component (c)) has two glass transition temperatures (Tg). One is derived from a vinyl aromatic compound and has a value of 65 to 65.
It exists near 120 ° C and the other is derived from the conjugated diene moiety and exists below -45 ° C. In the present invention, (Tg ₂ ) means a glass transition temperature (Tg) derived from a conjugated diene moiety. Further, even if the number average molecular weight of the block copolymer of component (c) does not exceed the above range,
If it is moderately high, a fluidity improver selected from process oil, liquid polybutadiene, and an olefin wax having a number average molecular weight of 6,000 or less is added to the component (c).
By adding 1 to 40 parts by weight with respect to 100 parts by weight of the block copolymer, it is possible to suppress a decrease in adhesive strength and workability. Such a method is an effective means for improving fluidity.

Among the above block copolymers, AB-
A block copolymer having an A structure and a BABAB structure is preferable. Specifically, as a styrene-butadiene-based hydrogenated block copolymer, a commercially available “ToughTech” H type (Asahi Kasei Corporation) Co., Ltd.), "Clayton" G1600 type (Shell Chemical)
As an isoprene-based hydrogenated block copolymer, commercially available “Septon” 2000 type (manufactured by Kuraray Co., Ltd.)
Examples of the styrene-butadiene-based block copolymer and the styrene-isoprene-based block copolymer include commercially available “Califlex” TR type (manufactured by Shell Chemical), Vectol (manufactured by Dexico), and the like. Examples of the styrene-isoprene-based hydrogenated block copolymer having an AB structure include commercially available “Septon” 1000 type (manufactured by Kuraray Co., Ltd.) and “Clayton” G1700 type (manufactured by Shell Chemical). it can. Further, two or more kinds of the above block copolymers can be used as a mixture.

(D) Ethylene / α-olefin copolymer [Component (d)] The ethylene / α-olefin copolymer of component (d) used in the adhesive resin composition of the present invention includes:
Melt flow rate (MFR) is 0.01 to 55 g / 1
0 min, preferably 0.05-50 g / 10 min, density 0.
850 to 0.900 g / cm ³ , preferably 0.855
~ 0.910 g / cm ³ , glass transition temperature -45 ° C
The following are preferred, and those having a temperature of −48 ° C. or less are more preferred, and those having a temperature of −50 ° C. or less are particularly preferred. The α-olefin constituting the ethylene / α-olefin copolymer usually has 3 to 20 carbon atoms.
Α-olefins containing no cyclic molecules of, for example, propylene, 1-butene, 1-hexene, 4-methyl-11-pentene, 1-octene, 1-decene, 1-tetradecene, 1-octadecene, etc. Or 2
It consists of a mixture of more than one species. Further, two or more ethylene / α-olefin copolymers can be used in combination. It is preferable to use an ethylene / butene copolymer using 11-butene as the α-olefin.
Specific examples of the ethylene / α-olefin copolymer include, for example, ultra-low density polyethylene (usually “VLDP”).
E), low-crystalline ethylene-butene-1 random copolymer (usually referred to as “EBM”), ethylene-propylene copolymer, ethylene-vinyl acetate copolymer (usually referred to as “EVA”). ), Ethylene-ethyl acrylate copolymer and the like.

The α-olefin content in the ethylene / α-olefin copolymer of the component (d) is generally 5 to 50% by weight, preferably 10 to 40% by weight. 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. In the present invention, the melt flow rate (MFR) is
Based on JIS K7210, temperature 190 ° C, load 2.
It means the value measured under the conditions of 16 kg and 10 minutes.

(2) Compounding ratio The adhesive composition of the present invention comprises the modified ethylene polymer of the component (a): 1 to 85% by weight, preferably 5 to 80% by weight,
Component (b) tackifier: 1 to 59% by weight, preferably 3 to 50% by weight, Component (c) block copolymer: 5 to 5% by weight
80% by weight, preferably 7-80% 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, the D of the block copolymer of the component (c)
When the glass transition temperature (Tg ₂ ) by SC measurement is higher than −45 ° C., the adhesive strength to the adherend tends to decrease, and the above composition (a), component (b) and component (c) The difference (Tg ₁ −Tg ₂ ) from the glass transition temperature (Tg ₁ ) of the resin composition composed of
If it is less than the above range, the decrease due to the change over time in the adhesive strength tends to be large. Further, 1 to 40 parts by weight of the ethylene / α-olefin copolymer of the component (d) is added to 100 parts by weight of the composition comprising the components (a), (b) and (c).
The composition containing 0 parts by weight of the composition is easy to mold and handle by adding 1 part by weight or more of the ethylene / α-olefin copolymer of the component (d), and adheres when it exceeds 400 parts by weight. Power tends to decrease.

The ethylene / α-olefin copolymer of the component (d) was measured for its glass transition temperature (Tg
_{If 4} ) is higher than -45 ° C, the adhesive strength with the adherend decreases. The difference (Tg ₃ −Tg ₄ ) from the glass transition temperature (Tg ₃ ) of the resin composition comprising the above composition (a), component (b), component (c) and component (d) measured by DSC was 5%.
If it is less than deg, the decrease in the adhesive force due to the change over time will be large. Note that this Tg ₃ is determined by comparing the components (c) and (d)
Are compatible with each other, the glass transition temperature T derived from the conjugated diene compound in the block copolymer of the component (c) in the composition
and g _1, the glass transition temperature Tg ₃ from ethylene · alpha-olefin copolymer component glass transition temperature and component of the polymer block derived from a conjugated diene compound in the block copolymer of (c) (d) is Show the same peak (T
g ₁ = Tg ₃ ). Further, in addition to the above-described components, a heat-resistant stabilizer, a weather-resistant stabilizer, an antistatic agent, a pigment, a dye, a rust inhibitor, and the like may be added to the composition, if necessary.

(3) Method for Producing Adhesive Resin Composition In order 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 / α-olefin copolymer of component (d) by various known methods,
For example, a method of mixing with a Henschel mixer, a V-blender, a ribbon blender, a tumbler blender, or the like, or after mixing, melt-kneading with a single-screw extruder, a twin-screw extruder, a kneader, a Hanbury mixer, or the like, and then granulating or pulverizing. A method may be adopted.

(4) Physical Properties of Adhesive Resin Composition The physical properties of the adhesive resin composition of the present invention obtained by the method described above are those of the resin composition comprising component (a), component (b) and component (c). In this case, it is important to satisfy the following expression (I). Formula (I): Tg ₁ −Tg ₂ ≧ 5 deg, preferably Tg ₁ −Tg ₂ ≧ 6 to 35 deg, (Tg ₁ : DSC of resin composition comprising component (a), component (b) and component (c) The glass transition temperature of the polymer block derived from the conjugated diene compound in the block copolymer of the component (c) by measurement, Tg ₂ : DSC of the block copolymer alone of the component (c)
By measurement, the glass transition temperature of the polymer block derived from the conjugated diene compound in the block copolymer, provided that Tg ₂ ≦
(-45 ° C, DSC measurement temperature: -70 to 100 ° C)

In the case of the resin composition comprising the components (a), (b), (c) and (d), it is preferable that the resin composition satisfies the following formula (II). Formula (II): Tg ₃ −Tg ₄ ≧ 5 deg, preferably Tg ₃ −Tg ₄ ≧ 6 to 35 deg, (Tg ₃ : Consists of component (a), component (b), component (c) and component (d) The glass transition temperature of the polymer block derived from the conjugated diene compound in the block copolymer of component (c) and the glass transition temperature of the ethylene / α-olefin copolymer of component (d), as determined by DSC of the resin composition. , Tg ₄ : glass transition temperature of the ethylene / α-olefin copolymer alone of component (d) as measured by DSC;
g ₄ ≦ −45 ° C., DSC measurement temperature: −70 to 100 ° C.)

[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, polyolefin resin, saponified ethylene / vinyl acetate copolymer (EVOH), polyamide resin A resin selected from a resin, a polycarbonate, a polystyrene resin, and an acrylic resin is used.

[0034] As the polyolefin resin thermoplastic resin layer polyolefin resin used in the (C layer), ethylene is α one olefin having 2 to 4 carbon atoms, propylene, 1 one butene, alone or mainly of these It is a crystalline polymer or copolymer obtained by polymerization or copolymerization. Specific examples of these polyolefin-based resins include a polyethylene-based resin, a polypropylene resin, and a poly-butene resin.
In addition, these are not limited to homopolymers, and as long as they are mainly composed of olefins, other α-α having 2 to 20 carbon atoms can be used.
It also includes monoolefins or copolymers with vinyl compounds such as vinyl acetate, vinyl chloride, 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 method low density polyethylene (LDPE),
Ethylene-propylene copolymer, ethylene-11-butene copolymer, ethylene-4-methyl-11-pentene polymer, ethylene-11-hexene copolymer, high-density polyethylene (HDPE), ethylene-vinyl acetate copolymer And an ethylene / acrylic acid copolymer and an ethylene / acrylic acid ester copolymer. 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, it is usually preferably from 0.01 to 30 g / 10 min, more preferably from 0.03 to 28 g / 10 min.

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, and more preferably 0.5 to 28 g / 10 minutes.

Specific examples of the poly-butene 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.

Polyamide Resin The polyamide resin used for the thermoplastic resin layer (C layer) includes hexamethylene diamine, decamethylene diamine, dodecamethylene diamine, 2,2,4-1 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-diethoxydiphenyl 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 with acrylonitrile, methyl methacrylate, or the like, or a modified rubber 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 for 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.

[0045]

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 50μm / 20μm / 50μ
m. The extruder is 40 mm from the inner layer to the outer layer.
φ / 30 mmφ / 40 mmφ. The molding conditions for each adherend are shown below. Coextrusion temperature Polyester resin: 235 ° C Polyolefin resin: 220 ° C Ethylene / vinyl acetate saponified product: 230 ° C Polyamide resin: 250 ° C Polycarbonate: 250 ° C Polystyrene resin: 220 ° C Acrylic resin: 200 ° C Molding speed: 15 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 Mitsubishi Rayon Co., Ltd. Diamondite PA500D (density: 1.34 g / cm)
³ , intrinsic viscosity: 0.76 dl / g)], polyolefin resin : "Novatech 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” S 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: 0.90 g / c)
m ³ , melt flow rate; 1.9 g / 10 min)] Saponified ethylene / vinyl acetate copolymer : [EVAL EP-F101 manufactured by Kuraray Co., Ltd. (density: 1.19 g / c)
c, melt index: 1.3, ethylene content: 32
mo1%)] Polyamide resin : [Novatec 1020CA2 manufactured by Mitsubishi Chemical Corporation (melting point: 224 ° C.)] Polycarbonate resin : [Iupilon E-2000 manufactured by Mitsubishi Gas Chemical Co., Ltd. (density: 1.2 g / cm ³⁾ )] Polystyrene resin : [Denka Styrol HI-E-4 manufactured by Denki Kagaku Kogyo KK (density: 1.04 g / cm)
³ , melt index: 3.5)] acrylic resin : [Mitsui Toatsu Chemicals Co., Ltd. “Barex” 2090 (density: 1.15 g / cm ³ , melt index: 3 g / 10 minutes)] A seed three-layer film was obtained.

(2) Glass transition temperature measurement conditions The glass transition temperature was measured by DSC (manufactured by Seiko Instruments Inc.). Temperature: -100 to 180 ° C Rate: 20 ° C / min

(3) 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

(4) Examples and Comparative Examples Example 1 Production of Adhesive Resin Composition Maleic anhydride-modified ethylene / butene copolymer (maleic anhydride content: 1% by weight, MFR: 0.5 g / 10 minutes,
Density: 0.920 g / cm ³ , melting point: 121 ° C.) 5% by weight, tackifier (aromatic hydrogenated petroleum resin, softening temperature: 1)
25 ° C., number average molecular weight: 750, density: 0.999 g /
cm ³ ) 15% by weight, styrene / butadiene copolymer (styrene content: 20% by weight, hydrogenation rate: 98%, MF
R: 0.1 g / 10 min, Tg ₂ : -59 ° C.) 80% by weight
The mixture was previously mixed in a 50-liter V-type blender at a mixing ratio of 1 minute for 1 minute, and then the twin-screw extruder TEX40 (40 m
mφ, L / D = 45, manufactured by Nippon Steel Works, Ltd., temperature 180 ° C., screw rotation speed 80 rpm, extrusion rate 10
The mixture was melt-kneaded in kg, 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 Tackifier (aromatic hydrogenated petroleum resin, softening temperature: 115
° C, number average molecular weight: 710, density: 0.998 g / cm
³ ) 20% by weight, styrene / butadiene copolymer (styrene content: 40% by weight, hydrogenation rate: 97%, MFR: 0.1%)
3 g / 10 min, Tg ₂ : -55 ° C.) The mixture was previously mixed at a blending ratio of 60% by weight in a V-type blender having a content of 50 liters for 1 minute, and a twin-screw extruder TEX40 (40 mmφ, L / D) was used.
= 45, manufactured by Nippon Steel Works Co., Ltd.), melt-kneaded at a temperature of 170 ° C, a screw rotation speed of 80 rpm, and an extrusion rate of 10 kg, extruded into a string, cooled, cut and dried.
Thereafter, 50% by weight of the above composition, maleic anhydride-modified linear polyethylene (maleic anhydride content: 0.95% by weight, MFR: 0.5 g / 10 min, density: 0.921 g /
cm ³ , melting point: 122 ° C.) 10% by weight, low density polyethylene (MFR: 14 g / 10 min, density: 0.918 g /
cm ³ , melting point: 107 ° C.) The mixture was preliminarily mixed at a blending ratio of 40% by weight in a 50-liter V-blender for 5 minutes, and again a twin-screw extruder TEX40 (40 mmφ, L / D: 45 manufactured by Nippon Steel Works, Ltd.) ), The mixture was melt-kneaded at a temperature of 180 ° C., a screw rotation speed of 80 rpm, and an extrusion rate of 10 kg, extruded in a string shape, 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 Maleic anhydride-modified linear polyethylene (maleic anhydride content: 1% by weight, MFR: 1 g / 10 min, density: 0.1%)
921 g / cm ³ , melting point: 121 ° C.) 40% by weight, ethylene / butene copolymer (density: 0.860 g / cm ³ ,
MFR: 3 g / 10 min, melting point: 23 ° C., Tg ₄ : −59
℃) 30% by weight, tackifier (aromatic hydrogenated petroleum resin,
Softening temperature: 125 ° C., number average molecular weight: 750, specific gravity:
0.999) 20% by weight, styrene-butadiene copolymer (styrene content: 29% by weight, hydrogenation rate: 98%, MF
R: 10 g / 10 min, Tg ₂ : -57 ° C.) 10% by weight,
In a V-type blender having a content of 50 liters for 5 minutes in advance, and a twin screw extruder PCM45 (45 mm
φ, L / D = 26, manufactured by Ikegai Iron Works Co., Ltd.)
80 ° C, screw rotation speed 150rpm, extrusion rate 10k
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 Maleic anhydride-modified ethylene / butadiene copolymer (maleic anhydride content: 0.75% by weight, MFR: 1 g / 1)
0 min, density: 0.880 g / cm ³ , melting point: 72 ° C.)
10% by weight, ethylene / propylene copolymer (density:
0.865 g / cm ³ , MFR; 0.3 g / 10 min, melting point: 15 ° C.) 10% by weight, tackifier (aromatic hydrogenated petroleum resin, softening temperature: 140 ° C., number average molecular weight: 860)
Density: 0.999 g / cm ³ ) 40% by weight, styrene
Butadiene copolymer (styrene content: 40 wt%, hydrogenation ratio: 97%, MFR: 0.7 g / 10 min, Tg _2: -5
5 ° C.) 20% by weight, low density polyethylene (MFR; 14)
g / 10 minutes, density: 0.919 g / cm ³ , melting point: 10
6 ° C.) The mixture was previously mixed at a blending ratio of 20% by weight for 5 minutes in a V-type blender having a content of 50 liters, and then the twin-screw extruder P
CM45 (45mmφ, L / D = 26, Ikekai Iron Works Co., Ltd.)
170 ° C, screw rotation speed 110r
pm, melt-kneaded at an extrusion rate of 10 kg, extruded in a string shape,
After cooling, cutting was performed 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 Tackifier (aromatic hydrogenated petroleum resin, softening temperature: 125
° C, number average molecular weight: 750, specific gravity: 0.999) 70% by weight, styrene-butadiene copolymer (styrene content:
20% by weight, hydrogenation rate: 98%, MFR: 0.3 g / 10
Min, Tg ₂ : -60 ° C) 20% by weight, ethylene / butene copolymer (density: 0.860 g / cm ³ , MFR: 3 g)
/ 10 min, melting point: 23 ° C., Tg ₄ : −59 ° C.) The mixture was previously mixed at a blending ratio of 10% by weight in a 50-liter V-blender for 1 minute, and then a twin-screw extruder TEX40 (40 mm) was used.
φ, L / D = 45, manufactured by Nippon Steel Works Co., Ltd.), fed from a hopper at an extrusion rate of 5 kg, and melt-kneaded at a temperature of 150 ° C. and a screw rotation speed of 100 rpm.
% By weight, maleic anhydride-modified linear polyethylene (maleic anhydride content: 1% by weight, MFR: 1 g / 10 min,
Density: 0.919 g / cm ³ , melting point: 121 ° C) 30% by weight, ethylene-butadiene copolymer (MFR: 5 g /
(10 minutes, density: 0.900 g / cm ³ , melting point: 88 ° C.)
V content of 50 liters in advance with a mixing ratio of 10% by weight
What was mixed for 5 minutes in a mold blender was fed through a feed port on the way to a twin screw extruder TEX40 (40 mmφ, L / D: 4).
5, manufactured by Japan Steel Works, Ltd.)
The mixture was melt-kneaded at a temperature of 180 ° C., a screw rotation speed of 100 rpm, and a total extrusion amount of 10 kg, extruded in a string shape, cooled, and cut to obtain an adhesive resin composition used for the adhesive resin composition layer. "Evaluation method of alcohol-resistant adhesive strength" and "measurement of adhesive strength of laminate" of this adhesive resin composition
According to the above, the adhesive strength of the laminate was measured. Table 1 shows the results.
Shown in

Comparative Example 1 Maleic anhydride-modified linear polyethylene (maleic anhydride content: 0.95% by weight, MFR: 0.5 g / 10 minutes,
Density: 0.921 g / cm ³ , melting point: 122 ° C.) 10% by weight, low density polyethylene (density: 0.919 g / cm)
³ , MFR: 14 g / 10 min, melting point: 106 ° C.) 45% by weight, tackifier (aromatic hydrogenated petroleum resin, softening temperature:
125 ° C, number average molecular weight: 750, specific gravity: 0.999)
15% by weight, styrene / butadiene copolymer (styrene content: 29% by weight, hydrogenation rate: 98%, MFR: 10 g /
10 minutes, Tg ₂ : -57 ° C.) The mixture was previously mixed at a blending ratio of 30% by weight in a V-type blender having a content of 50 liters for 5 minutes, and then a twin screw extruder PCM30 (30 mmφ, L / D) was used.
= 32, manufactured by Ikegai Iron Works Co., Ltd.), melt-blended at a temperature of 200 ° C., a screw rotation speed of 100 rpm, and an extrusion rate of 12 kg, extruded into a string, cut after cooling, and used for the adhesive resin composition layer. A resin composition was obtained. 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: 0.75% by weight, MFR: 1 g / 10 minutes, density: 0.880 g / cm ³ , melting point: 72 ° C.) 5% by weight ,
Ethylene-butene copolymer (density: 0.860 g / cm
³ , MFR: 3 g / 10 min, melting point: 23 ° C., Tg ₄ : −
10% by weight of low-density polyethylene (density: 0.
919 g / cm ³ , MFR: 2 g / 10 min, melting point: 10
6 ° C.) 15% by weight, tackifier (aromatic hydrogenated petroleum resin, softening temperature: 140 ° C., number average molecular weight: 860, specific gravity: 0.999) 40% by weight, styrene / butadiene copolymer (styrene content) : 29% by weight, hydrogenation rate: 98%,
(MFR: 10 g / 10 min, Tg ₂ : -57 ° C.) The mixture was previously mixed at a blending ratio of 30% by weight in a V-type blender having an internal volume of 50 liters for 1 minute, and then a twin-screw extruder PCM30 (3
0mmφ, L / D = 32, manufactured by Ikegai Iron Works Co., Ltd.)
The mixture was melt-blended at a temperature of 200 ° C., a screw rotation speed of 100 rpm, and an extrusion rate of 12 kg, extruded in a string shape, 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.

[0056]

[Table 1]

[0057]

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. are improved. Can be used widely.

──────────────────────────────────────────────────の 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 AK03B AK04G AK12B AK25B AK41A AK42A AK45B AK46B AK62G AK69B AK70G AK73G AL02G AL05G AL07G BA02 BA10A BA10B BA15 CA16G GB16 GB23 JA04G JA06G JA13G JD02 JK01 JK06 JN01 YY00G 4J002 AF02X BA00X BA01X BB05W BB06W BB07W BB07W BB07W BB07W BB07W BB07W BB07W BB07W

Claims (7)

[Claims] 1. An adhesive resin composition comprising a composition comprising the following components (a) to (c), wherein the composition satisfies the following formula (I). 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 product of at least one polymer block of a polymer of a vinyl aromatic compound and a block copolymer having at least one polymer block of a polymer of a conjugated diene compound 5 to 80% by weight I): Tg ₁ −Tg ₂ ≧ 5 deg (Tg ₁ : Conjugation of component (c) in block copolymer by DSC measurement of resin composition comprising component (a), component (b) and component (c) Glass transition temperature of polymer block derived from diene compound, Tg ₂ : DSC of block copolymer of component (c) alone
By measurement, the glass transition temperature of the polymer block derived from the conjugated diene compound in the block copolymer, provided that Tg ₂ ≦
(-45 ° C, DSC measurement temperature: -70 to 100 ° C) 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 / α-olefin copolymer having a density of 0.850 to 0.900 g / cm ³ , 1 to 40 with respect to 100 parts by weight of component (a) to component (c)
0 parts by weight 3. The adhesive resin composition according to claim 2, which satisfies the following formula (II). Formula (II): Tg ₃ −Tg ₄ ≧ 5 deg (Tg ₃ : of component (c) by DSC measurement of a resin composition comprising component (a), component (b), component (c) and component (d) The glass transition temperature of the polymer block derived from the conjugated diene compound in the block copolymer, the glass transition temperature derived from the ethylene / α-olefin copolymer of the component (d), Tg ₄ : the ethylene / component of the component (d) Glass transition temperature of a polymer block derived from a conjugated diene compound in a block copolymer by DSC measurement of an α-olefin copolymer alone, provided that Tg ₄ ≦ −45 ° C., DSC measurement temperature: −70
~ 100 ° C) 4. A laminate comprising a polyester resin layer (layer B) and an adhesive resin layer (layer A), wherein the adhesive resin layer (layer A) comprises the following components (a) to (a): A laminate formed from the adhesive resin composition comprising (c), wherein the composition satisfies the following formula (I). 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 product of at least one polymer block of a polymer of a vinyl aromatic compound and a block copolymer having at least one polymer block of a polymer of a conjugated diene compound 5 to 80% by weight I): Tg ₁ −Tg ₂ ≧ 5 deg (Tg ₁ : Conjugation of component (c) in block copolymer by DSC measurement of resin composition comprising component (a), component (b) and component (c) Glass transition temperature of polymer block derived from diene compound, Tg ₂ : DSC of block copolymer of component (c) alone
By measurement, the glass transition temperature of the polymer block derived from the conjugated diene compound in the block copolymer, provided that Tg ₂ ≦
(-45 ° C, DSC measurement temperature: -70 to 100 ° C) 5. The adhesive resin layer (A layer) comprises the following component (a):
The laminate according to claim 3, wherein the laminate is formed from an adhesive resin composition obtained by blending the following component (d) with the component (c). Component (d): Melt flow rate is 0.05 to 50 g.
/ 10 minutes, an ethylene / α-olefin copolymer having a density of 0.850 to 0.900 g / cm ³ , 1 to 40 with respect to 100 parts by weight of component (a) to component (c)
0 parts by weight 6. The adhesive resin composition according to claim 5, which satisfies the following formula (II). Formula (II): Tg ₃ −Tg ₄ ≧ 5 deg (Tg ₃ : of component (c) by DSC measurement of a resin composition comprising component (a), component (b), component (c) and component (d) The glass transition temperature of the polymer block derived from the conjugated diene compound in the block copolymer, the glass transition temperature derived from the ethylene / α-olefin copolymer of the component (d), and Tg ₄ : the ethylene / polymer of the component (d) Glass transition temperature by DSC measurement of α-olefin copolymer alone,
g ₄ ≦ −45 ° C., DSC measurement temperature: −70 to 100 ° C.) 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 claim 4, 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.