TWI694003B - Thermoplastic resin composition, adhesive coating and laminate using the same - Google Patents

Abstract

The present invention provides a thermoplastic resin composition or an adhesive coating that can adhere to a metal or metal compound such as a cyclic polyolefin polymer and aluminum foil or an ethylene-vinyl alcohol copolymer with sufficient strength. The thermoplastic resin composition contains (A) 100 parts by mass of thermoplastic resin; (B) one or more than 0.05 to 5 parts by mass selected from the group consisting of unsaturated carboxylic acids and derivatives of unsaturated carboxylic acids; and (C) 0.01 to 3 parts by mass of organic peroxide, the above component (A) is made of the following: (a1) cyclic polyolefin polymer 10 to 90% by mass; and (a2) made of aromatic vinyl compound as 90 to 10% by mass of the hydride of the block copolymer composed of the main polymer block and the random copolymer block of the conjugated diene compound and aromatic vinyl compound (however, the above component (a1) and The total of the above components (a2) is 100% by mass).

Description

Thermoplastic resin composition, adhesive coating and laminate using the same

The present invention relates to thermoplastic resin compositions and adhesive coatings. More specifically, it is composed of a cyclic polyolefin-based polymer, a polymer block mainly composed of an aromatic vinyl compound, and a random copolymer block of an aromatic compound and a conjugated diene compound. A thermoplastic resin composition and adhesive coating of a hydride of a block copolymer, and a laminate using the thermoplastic resin composition or adhesive coating.

In the past, laminates of cyclic polyolefin polymers and ethylene-vinyl alcohol copolymers have been used as packaging films or containers due to their excellent strength, transparency, gas barrier properties, and chemical resistance. In addition, since the laminate of a cyclic polyolefin polymer and a metal or metal compound such as aluminum foil has very high gas barrier properties and is excellent in strength and chemical resistance, it is used as extremely resistant to oxygen or moisture Packaging film or container of the contents.

However, as described above, the laminate has a problem of lack of adhesion between metals or metal compounds such as cyclic olefin polymers and ethylene-vinyl alcohol copolymers or aluminum foil. Therefore, it is proposed to interpose a polyolefin-based polymer or its acid-modified product as the following component (for example, Patent Documents 1 and 2). However, the adhesion strength of these technologies is insufficient, and it is desired to further improve the adhesion strength.

[Prior Technical Literature] [Patent Literature]

Patent Document 1: Japanese Patent Laid-Open No. 11-070624

Patent Document 2: Japanese Patent Laid-Open No. 2003-191380

An object of the present invention is to provide a thermoplastic resin composition and an adhesive coating capable of sufficiently bonding a cyclic polyolefin polymer and an ethylene-vinyl alcohol copolymer.

In addition, another object of the present invention is to provide a thermoplastic resin composition and an adhesive coating capable of sufficiently bonding a metal or metal compound such as a cyclic polyolefin polymer and aluminum foil.

In addition, another object of the present invention is to provide a laminate using the above thermoplastic resin composition or adhesive paint.

Furthermore, another object of the present invention is to provide a press-through pack product using the above laminate and a method for manufacturing the same.

As a result of active research, the present inventors have found that a specific thermoplastic resin composition or adhesive coating can achieve the above-mentioned problems.

That is, the present invention is a thermoplastic resin composition comprising (A) 100 parts by mass of a thermoplastic resin; (B) one or more species selected from the group consisting of unsaturated carboxylic acids and derivatives of unsaturated carboxylic acids 0.05~ 5 parts by mass; and (C) 0.01 to 3 parts by mass of organic peroxide, the above component (A) is composed of the following component (a1) and component (a2): (a1) cyclic polyolefin polymer 10 ~90% by mass; and (a2) a block copolymer composed of a polymer block mainly composed of an aromatic vinyl compound and a random copolymer block of a conjugated diene compound and an aromatic vinyl compound 90 to 10% by mass of hydride (however, the total of the above component (a1) and the above component (a2) is 100% by mass).

The second invention is the thermoplastic resin composition of the first invention, wherein the aforementioned component (a1) is a copolymer of a cyclic olefin and an α-olefin having 2 to 8 carbon atoms.

The third invention is a method for producing a thermoplastic resin composition, which is a composition obtained by melt-kneading the following components (A) to (C), (A) 100 parts by mass of a thermoplastic resin; (B) self-unsaturated 0.05 to 5 parts by mass or more selected from the group consisting of carboxylic acid and unsaturated carboxylic acid derivatives; and (C) 0.01 to 3 parts by mass of organic peroxide. The above component (A) is composed of the following components (a1) and (a2): (a1) cyclic polyolefin polymer 10 to 90% by mass; And (a2) a hydride of a block copolymer composed of a polymer block mainly composed of an aromatic vinyl compound and a random copolymer block of a conjugated diene compound and an aromatic vinyl compound 90~ 10% by mass (however, the total of the aforementioned component (a1) and the aforementioned component (a2) is 100% by mass).

The fourth invention is the method of the third invention, wherein the aforementioned component (a1) is a copolymer of a cyclic olefin and an α-olefin having 2 to 8 carbon atoms.

The fifth invention is an adhesive coating comprising (A) 100 parts by mass of a thermoplastic resin; (B) one or more than 0.05 to 5 parts by mass selected from the group consisting of unsaturated carboxylic acids and derivatives of unsaturated carboxylic acids ; (C) 0.01-3 parts by mass of organic peroxide; and (D) solvent; the above component (A) is composed of the following components (a1) and (a2): (a1) cyclic polyolefin polymerization 10 to 90% by mass; and (a2) a block composed of a polymer block mainly composed of an aromatic vinyl compound and a random copolymer block of a conjugated diene compound and an aromatic vinyl compound The hydride of the copolymer is 90 to 10% by mass (however, the total of the aforementioned component (a1) and the aforementioned component (a2) is 100% by mass).

The sixth invention is the adhesive paint of the fifth invention, in which the front The component (a1) is a copolymer of a cyclic olefin and an α-olefin having 2 to 8 carbon atoms.

The seventh invention is a method for manufacturing an adhesive paint, which comprises the steps (1) and (A) of melting and kneading a composition composed of the following components (A) to (C) to produce a thermoplastic resin composition 100 parts by mass of thermoplastic resin; (B) one or more species selected from the group consisting of unsaturated carboxylic acids and derivatives of unsaturated carboxylic acids 0.05 to 5 parts by mass; and (C) 0.01 to 3 parts by mass of organic peroxides The above component (A) is composed of the following component (a1) and component (a2): (a1) cyclic polyolefin polymer 10 to 90% by mass; and (a2) is based on an aromatic vinyl compound as 90 to 10% by mass of the hydride of the block copolymer composed of the main polymer block and the random copolymer block of the conjugated diene compound and aromatic vinyl compound (however, the above component (a1) and The total of the components (a2) is 100% by mass); and the step (2) of dissolving the thermoplastic resin composition obtained in the step (1) in the solvent (D).

The eighth invention is the method of the seventh invention, wherein the aforementioned component (a1) is a copolymer of a cyclic olefin and an α-olefin having 2 to 8 carbon atoms.

The ninth invention is a laminate formed by sequentially laminating the following layers: a layer made of a cyclic polyolefin polymer; A layer made of the thermoplastic resin composition of the first or second invention, or a layer made of the adhesive paint of the fifth or sixth invention; and a layer made of a resin having a polar group.

The tenth invention is a laminate formed by sequentially laminating the following layers: a layer made of a cyclic polyolefin polymer; a layer made of the thermoplastic resin composition of the first or second invention; A layer composed of a resin having a polar group; a layer composed of the thermoplastic resin composition of the first or second invention; and a layer composed of a cyclic polyolefin polymer.

The eleventh invention is the laminate of the ninth or tenth invention, wherein the resin having the aforementioned polar group is an ethylene-vinyl alcohol copolymer.

The twelfth invention is a laminate formed by sequentially laminating the following layers: a layer made of a cyclic polyolefin polymer; a layer made of the thermoplastic resin composition of the first or second invention, Or a layer made of the adhesive paint of the fifth or sixth invention; and a layer made of metal or metal compound.

The thirteenth invention is a laminate formed by sequentially laminating the following layers: a layer composed of a cyclic polyolefin polymer; a layer composed of the thermoplastic resin composition of the first or second invention, Or a layer made of the adhesive paint of the fifth or sixth invention; a layer made of metal or metal compound; A layer made of the thermoplastic resin composition of the first or second invention, or a layer made of the adhesive coating of the fifth or sixth invention; and a layer made of a cyclic polyolefin polymer.

The fourteenth invention is the laminate of the twelfth or thirteenth invention, wherein the aforementioned layer made of metal or metal compound is a layer made of aluminum foil.

The fifteenth invention is a method for manufacturing a laminate, comprising the following steps: the step of producing an adhesive coating using the method of the seventh or eighth invention; and using the adhesive coating obtained in the foregoing steps to make the cyclic polyolefin system The step (3) of bonding the polymer film to the foil made of metal or metal compound.

The 16th invention is a press through package product comprising the laminate of any of the 9th to 14th inventions.

The 17th invention is a method for manufacturing a blister package product, which includes the following steps: a step for producing a laminate using the method of the 15th invention; and a step (4) for producing a blister package product using the laminate obtained in the foregoing steps.

The thermoplastic resin composition of the present invention can adhere to a metal or metal compound such as a resin having a polar group such as a cyclic polyolefin polymer and an ethylene-vinyl alcohol copolymer or an aluminum foil with sufficient strength. And impact resistance and It is excellent in transparency and does not impair the characteristics possessed by cyclic polyolefin-based polymers and the characteristics of metals or metal compounds such as resins with polar groups such as ethylene-vinyl alcohol copolymers or aluminum foil. Therefore, by interposing the thermoplastic resin composition of the present invention as an adjunct component between them, a laminate of both can be obtained with high productivity by a method such as co-extrusion. Furthermore, the thermoplastic resin composition of the present invention is also excellent in productivity as a composition.

In addition, the adhesive coating of the present invention can sufficiently bond a metal or metal compound such as a resin having a polar group such as a cyclic polyolefin polymer and an ethylene-vinyl alcohol copolymer, aluminum foil, or the like. It does not impair the characteristics possessed by the cyclic polyolefin polymer and the characteristics possessed by metals or metal compounds such as resins with polar groups such as ethylene-vinyl alcohol copolymers or aluminum foil. Therefore, by bonding the two using the adhesive coating of the present invention, a laminate of the two can be obtained with high productivity. Moreover, the resulting laminate can be preferably used as a blister package product. Furthermore, the adhesive paint of the present invention has good coatability and excellent productivity as a paint. Furthermore, according to the method for manufacturing an adhesive coating of the present invention, an excellent adhesive coating, a laminate using the coating, and a blister packaging product using the laminate can be obtained.

The thermoplastic resin composition of the present invention contains (A) 100 parts by mass of thermoplastic resin; (B) one or more than 0.05 to 5 parts by mass selected from the group consisting of unsaturated carboxylic acids and derivatives of unsaturated carboxylic acids; and ( C) 0.01 to 3 parts by mass of organic peroxides. The following is about the thermoplastic constituting the present invention Each component of the resin composition will be described.

<Thermoplastic resin composition> (A) Thermoplastic resin:

The above component (A) is composed of (a1) cyclic polyolefin polymer 10 to 90% by mass; and (a2) is composed of a polymer block mainly composed of an aromatic vinyl compound, a conjugated diene compound and an aromatic The hydride of the block copolymer composed of the random copolymer block of the vinyl group compound is composed of 90 to 10% by mass. It is preferably composed of 40 to 80% by mass of the above component (a1) and 60 to 20% by mass of the above component (a2). Here, the sum of the aforementioned component (a1) and the aforementioned component (a2) is 100% by mass

By making the said component (a1) 10 mass% or more, preferably 40 mass% or more (the said component (a2) 90 mass% or less, preferably 60 mass% or less), transparency and adhesiveness are good . By making the said component (a1) 90 mass% or less, preferably 80 mass% or less (the said component (a2) 10 mass% or more, preferably 20 mass% or more), impact resistance is made favorable.

(a1) Cyclic polyolefin polymer:

The above component (a1) is mainly composed of structural units derived from cyclic olefins (polymerizable compounds having a cyclic structure formed of carbon atoms and having an ethylenic carbon-carbon double bond in the ring) (usually 50 mass % Or more, preferably 70% by mass or more, and more preferably 90% by mass or more) of the polymer.

Examples of the cyclic olefins include cyclobutene, cyclopentene, cyclopentadiene, norbornene (bicyclo[2.2.1]hept-2-ene), cyclopentadiene (tricyclo[4.3.0.1 ^2,5 ]dec-3,7-diene), tetracyclododecene (tetracyclo[4.4.0.1 ^2,5 .1 ^7,10 ]dec-3-ene) and derivatives of these.

The cyclic olefin-based polymer can be produced by a conventional polymerization method using one or more of the cyclic polyolefins. In this case, one or more other monomers copolymerizable with the cyclic olefin can be used.

Examples of the other monomers include ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 3-methyl-1-butene, 2-methyl-1-pentene, 3-ethyl 1-pentene, 4-methyl-1-pentene, 4-methyl-1-hexene, 4,4-dimethyl-1-hexene, 4,4-dimethyl-1- Pentene, 4-ethyl-1-hexene, 3-ethyl-1-hexene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-decene Alpha-olefins such as hexadecene, 1-octadecene and 1-eicosene; 1,4-hexadiene, 4-methyl-1,4-hexadiene, 5-methyl-1 , 4-hexadiene, 1,7-octadiene and other non-conjugated diene.

As the above component (a1), from the viewpoint of adhesiveness, cyclic olefins and α-olefins having 2 to 8 carbon atoms (for example, ethylene, propylene, 1-butene, 1-pentene, 1-hexene and 1-octene) copolymer. More preferably, it is a copolymer selected from the group consisting of norbornene and its derivatives and one or more kinds of α-olefins having 2 to 8 carbon atoms.

The glass transition temperature of the above component (a1) is preferably 70 to 160°C, more preferably 75 to 140°C. By setting the glass transition temperature to 70° C. or higher, the heat resistance is improved. With a temperature of 160°C or lower, the productivity as a composition is good.

In this specification, the glass transition temperature is based on JIS K7121-1987, using a Diamond DSC type differential scanning calorimeter from Perkin Elmer Co., Ltd., held at 350°C for 5 minutes, cooled to 30°C at 10°C/min, at 30°C Hold for 3 minutes, and calculate the mid-point glass transition temperature calculated from the curve of the final temperature rise process measured at the temperature rise of 10°C/min to 350°C.

The melt flow rate (hereinafter abbreviated as "MFR") measured at 260°C and 21.18N according to JIS K7210-1999 for the above component (a1) is preferably 0.1 to 50 g/10 minutes, more preferably 1 to 20 g/10 minutes. By setting the MFR within the above range, the moldability is improved.

From the viewpoint of transparency, the light transmittance (ASTM D1003, 2 mm thick) of the above component (a1) is preferably 85% or more, and more preferably 90% or more. The higher the light transmittance, the better.

Examples of the commercially available products of the above component (a1) include "TOPAS 8007 (trade name)", "TOPAS 6013 (trade name)", "TOPAS 6015 (trade name)" of POLYPLASTIC Co., Ltd., and Mitsui Chemicals Co., Ltd. The company's "APEL APL6013T (trade name)", "APEL APL6015T (trade name)", Japan's ZEON Corporation's "ZEONOR 1020R (trade name)", "ZEONOR 1060R (trade name)", etc.

As the above component (a1), one or more of these can be used.

(a2) Randomly composed of a polymer block mainly composed of an aromatic vinyl compound, a conjugated diene compound and an aromatic vinyl compound Hydrides of block copolymers made of copolymer blocks: the above component (a2) is composed of at least one, preferably at least two or more polymer blocks mainly composed of aromatic vinyl compounds, and at least 1 Hydrides of block copolymers formed by random copolymer blocks of conjugated diene compounds and aromatic vinyl compounds. It can be exemplified by a hydride of a block copolymer having a structure such as P-Q, P-Q-P, P-Q-P-Q, and P-Q-P-Q-P.

The "polymer block mainly composed of an aromatic vinyl compound" as used herein means that the content of structural units derived from the aromatic vinyl compound in the polymer block is usually 90% by mass or more, preferably 95 Mass% or more.

The random copolymer block of the conjugated diene compound and the aromatic vinyl compound is preferably composed of a structural unit derived from the conjugated diene compound of 10 to 97% by mass and a structural unit derived from the aromatic vinyl compound of 90 to 3% by mass. It is more preferably composed of 70 to 95% by mass of structural units derived from conjugated diene compounds and 30 to 5% by mass of structural units derived from aromatic vinyl compounds. Here, the sum of the structural unit content derived from the conjugated diene compound and the structural unit content derived from the aromatic vinyl compound is 100% by mass.

The composition distribution of the polymer block mainly composed of an aromatic vinyl compound is not particularly limited. The composition distribution of the random copolymer block of the conjugated diene compound and the aromatic vinyl compound is not particularly limited.

The above aromatic vinyl compound is a polymerizable carbon- Polymerizable monomer with carbon double bond and aromatic ring. Examples of the aromatic vinyl compound include styrene, tert-butylstyrene, α-methylstyrene, p-methylstyrene, divinylbenzene, 1,1-diphenylstyrene, N , N-diethyl-p-aminoethylstyrene, vinyl toluene and p-third butylstyrene, etc. Among these, styrene is preferred. One or more of these aromatic vinyl compounds can be used.

The above-mentioned conjugated diene is a polymerizable monomer having a structure in which one carbon-carbon single bond bonds two carbon-carbon double bonds. Examples of conjugated dienes include 1,3-butadiene, isobutadiene (2-methyl-1,3-butadiene), and 2,3-dimethyl-1,3-butadiene. Ene and chloroprene (2-chloro-1,3-butadiene), etc. Among these, from the viewpoint of impact resistance, 1,3-butadiene is preferred. As the conjugated diene, one or more of these can be used.

The hydrogenation rate of the above component (a2) (the ratio of the number of carbon-carbon double bonds in the block copolymer before hydrogenation to the number of carbon-carbon single bonds due to hydrogenation), from the viewpoint of heat resistance, It is preferably 50 mol% or more, more preferably 80 mol% or more, and even more preferably 98 mol% or more.

The content of the structural unit derived from the aromatic vinyl compound of the component (a2) is preferably 5 to 75% by mass, more preferably 20 to 70% by mass. Within this range, a composition that balances transparency and impact resistance is obtained.

The molecular weight of the above component (a2) is not particularly limited. From the viewpoint of forming processability, it is preferable that the melt flow rate measured at 230°C and 21.18N in accordance with JIS K 7210-1999 be 0.1 to 30 g/10 minutes.

Examples of commercially available products as the above component (a2) are, for example, "SOES1605 (brand name)", "SOES1606 (brand name)", "SOES1611 (brand name)", and "SOEL609 (brand name)" of Asahi Kasei Chemical Co., Ltd. Trade name)" etc.

As the above component (a2), one or more of these can be used.

(B) unsaturated carboxylic acid, derivatives of unsaturated carboxylic acid:

The above component (B) is one or more selected from the group consisting of unsaturated carboxylic acids and derivatives of unsaturated carboxylic acids. The above-mentioned component (B) is graft-polymerized with the above-mentioned component (A) to exert a resin having polar groups such as ethylene vinyl alcohol copolymer (EVOH), nylon and polyester, or aluminum with the thermoplastic resin composition of the present invention. , Copper, silver, gold and tin and other metals, aluminum, tin, zinc, indium, germanium, antimony and cerium and other metals of more than one type of oxide, nitride, fluoride and sulfide metal compounds (inorganic Metal compound).

Examples of the unsaturated carboxylic acid include maleic acid, itaconic acid, fumaric acid, acrylic acid, and methacrylic acid. Examples of the derivatives of unsaturated carboxylic acids include maleic acid monoesters, maleic acid diesters, maleic anhydride, itaconic acid monoesters, itaconic acid diesters, itaconic anhydride, fumaric acid monoesters, rich Maleic diester, fumaric anhydride, alkyl acrylate such as methyl acrylate, and methacrylate such as methyl methacrylate. As the above-mentioned component (B), one kind or a mixture of two or more kinds can be used.

As the above component (B), based on the above component (A) From the viewpoint of reactivity or adhesion of the composition, maleic anhydride is preferred.

The compounding amount of the said component (B) is 0.05-5 mass parts with respect to 100 mass parts of said component (A). From the viewpoint of improving the adhesiveness of the thermoplastic resin of the present invention, it is 0.05 parts by mass or more, preferably 0.1 parts by mass or more. And based on the modification (at the time of graft polymerization), the component (B) is prevented from remaining unreacted in the composition, and the appearance of the color change (yellowing) or gelation of the article made of the composition is not good. From a viewpoint, it is 5 parts by mass or less, and more preferably 3 parts by mass or less.

(C) Organic peroxides:

The component (C) of the present invention is an organic peroxide and functions to catalyze the graft polymerization reaction of the component (A) and the component (B).

Examples of organic peroxides include, for example, dicumyl peroxide, di-third butyl peroxide, 2,5-dimethyl-2,5-di(third butylperoxy)hexane, 2,5-Dimethyl-2,5-bis(t-butylperoxy)hexene-3, 1,3-bis(t-butylperoxyisopropyl)benzene, 1,1-bis (Third butylperoxy)-3,3,5-trimethylcyclohexane, n-butyl-4,4-bis(third butylperoxy) valerate, benzoyl peroxide Compounds, p-chlorobenzoyl peroxide, 2,4-dichlorobenzoyl peroxide, tert-butyl peroxybenzoate, tert-butyl peroxyisopropyl carbonate, diethyl Acetate peroxide, laurel peroxide and tert-butylcumyl peroxide, etc. As the above-mentioned component (C), one kind or a mixture of two or more kinds can be used.

As the above component (C), from the viewpoint of the manufacturability or adhesiveness of the composition, it is preferably 2,5-dimethyl-2,5-bis(third butylperoxy Group) hexane and 2,5-dimethyl-2,5-di(third butylperoxy)hexene-3.

The blending amount of the component (C) is 0.001 to 3 parts by mass with respect to 100 parts by mass of the component (A). From the viewpoint of improving the adhesiveness of the thermoplastic resin composition of the present invention and preventing gelation during film formation, it is 0.001 part by mass or more, preferably 0.03 parts by mass or more. And from the viewpoint of suppressing a change in color tone (yellowing) or a decrease in melt viscosity during modification, it is 3 parts by mass or less, preferably 2 parts by mass or less.

Examples of commercially available products as the above component (C) are, for example, "PERHEXA 25B (trade name)" and "PERHEXANE 25B (trade name)" of Nippon Oil & Fats Corporation.

The thermoplastic resin composition of the present invention may further contain components other than the above-mentioned components (A) to (C) as desired, for example, thermoplastic resins other than the above-mentioned component (A); pigments, Additives for inorganic fillers, organic fillers, resin fillers; lubricants, antioxidants, weathering stabilizers, thermal stabilizers, mold release agents, antistatic agents, and surfactants; etc.

<Manufacturing method of thermoplastic resin composition>

The thermoplastic resin composition of the present invention can be obtained by any method without particular limitation. For example, it can be obtained by melt-kneading the above-mentioned components (A) to (C) and any components used as needed using any melt-kneading machine.

The above-mentioned thermoplastic resin composition is preferably composed of the above-mentioned components (A) to (C) and any components used as required, using any melt The melt-kneading machine is preferably obtained by melting and kneading at a temperature equal to or higher than 1 minute half-life temperature of the above component (C) for 1 minute or more, and more preferably obtained by melting and kneading at a temperature above 1 minute half-life temperature of the above component (C) for 2 minutes or more.

The above-mentioned melt-kneading machine is not particularly limited, and examples thereof include a single-screw extruder, a twin-screw extruder, a Banbury kneader, various kneaders, and a device in which two or more of these are combined.

The melt flow rate of the thermoplastic resin composition measured under the conditions of 230° C. and 21.18 N according to JIS K7210: 1999 is preferably 0.5 g/10 min or more from the viewpoint of good manufacturability in the subsequent melt-kneading step. Moreover, from the viewpoint of moldability when forming a laminate using a thermoplastic resin composition or adhesion of the composition, it is preferably 15 g/10 min or less.

<adhesive coating>

The adhesive coating of the present invention includes, in addition to the above (A) 100 parts by mass of the thermoplastic resin; (B) one or more than 0.05 to 5 parts by mass selected from the group consisting of unsaturated carboxylic acids and derivatives of unsaturated carboxylic acids; And (C) 0.01 to 3 parts by mass of organic peroxide, (D) solvent is also included.

As the (A) thermoplastic resin constituting the adhesive coating of the present invention, the same ones as the (A) thermoplastic resin described above can be used. In addition, as the hydride of (a1) cyclic polyolefin polymer and (a2) block copolymer as (A) thermoplastic resin, by making component (a1) 10 mass% or more, preferably 40 mass % Or more (the above component (a2) is 90% by mass or less, preferably 60% by mass or less), and the adhesion, coating properties and Transparency is good. By making the above-mentioned component (a1) 90% by mass or less, preferably 80% by mass or less (the above-mentioned component (a2) is 10% by mass or more, preferably 20% by mass or more), the above step (1) is made The productivity (the productivity of the thermoplastic resin composition including the above (A) to (C)) is good. Moreover, by using the component (a1) of the glass transition temperature as mentioned above, the productivity of the adhesive paint is improved. Furthermore, by using the component (a1) having MFR as described above, the productivity of the adhesive coating is improved. Furthermore, by using the component (a1) having the light transmittance as described above, the adhesive coating of the present invention can be preferably used in applications requiring transparency. Hereinafter, the description of the above-mentioned component (A), component (B), component (C), and optional components will be omitted, and the component (D) will be described.

(D) Solvent:

The component (D) of the present invention is a solvent. As said component (D), if it is the solvent which can melt|dissolve the thermoplastic resin composition obtained by melt-kneading the said component (A)-(C), it is preferable that the composition containing the said component (A)-(C), Any solvent is not particularly limited.

Examples of the component (D) include toluene, xylene, methyl isobutyl ketone, cyclohexane, tetrahydrofuran, and chloroform. Among these, from the viewpoint of solubility and storage stability, toluene is preferred. As the above component (D), one or more of these can be used.

The compounding amount of the above component (D) depends on the thickness of the coating film to be formed by using the adhesive coating of the present invention, but the normal coating is used In the case of an apparatus, 100 parts by mass of the above-mentioned component (A) is usually 100 to 2000 parts by mass, preferably 300 to 1800 parts by mass, and more preferably 500 to 1500 parts by mass.

<Manufacturing method of adhesive paint>

The adhesive coating of the present invention is not particularly limited, and can be obtained by any method. For example, the adhesive coating of the present invention can be obtained by a manufacturing method including the following steps: the step (1) of producing the thermoplastic resin composition by melt-kneading the above components (A) to (C) using any melt-kneading machine; and The step (2) of dissolving the thermoplastic resin composition obtained in the step (1) in the solvent (D). As the melt-kneading machine, the same as described above can be used.

In the production step of the thermoplastic resin composition in the above step (1), it is preferably melt-kneaded at a temperature above 1 minute half-life temperature of the above component (C) for 1 minute or more, more preferably above 1 minute half-life temperature of the above component (C) The above temperature is melted and kneaded for more than 2 minutes.

The thermoplastic resin composition of the step (1) above is based on JIS K7210-1999, and the melt flow rate measured under the conditions of 230°C and 21.18N is not particularly limited, but from the viewpoint of the productivity of the adhesive coating, it is preferably 0.5g/10min~15g/10min.

In the step (2), the method for dissolving the thermoplastic resin composition in the step (1) in the solvent in the (D) is not particularly limited, but any mixing mixer is preferably used at a temperature of normal temperature to 50°C , Obtained by mixing for 15 minutes or more.

When the above step (1) or/and the above step (2) is further performed, components other than the above components (A) to (D) may be further contained as desired, for example, the above component (A ) Thermoplastic resins other than; pigments, inorganic fillers, organic fillers, resin fillers; additives such as lubricants, antioxidants, weathering stabilizers, heat stabilizers, mold release agents, antistatic agents and surfactants; Wait.

The thermoplastic resin composition and the adhesive paint of the present invention introduce polar groups such as carboxyl groups into the cyclic polyolefin-based non-polar material, and show good adhesion to various materials. Examples of non-polar materials exhibiting good adhesiveness include polyethylene, polypropylene, poly 1-butene, poly 4-methyl-1-pentene, and cyclic polyolefin. Examples of polar materials include resins with polar groups such as ethylene vinyl alcohol copolymer (EVOH), nylon, polyurethane and polyester; and metals such as iron, aluminum, copper, silver, gold and tin; Metal compounds (inorganic metal compounds) such as one or more oxides, nitrides, fluorides, and sulfides of metals such as aluminum, tin, zinc, indium, germanium, antimony, and cerium; etc. It is particularly surprising that any of the polyolefin and the ethylene-vinyl alcohol copolymer having a large number of hydroxyl groups shows good adhesion. Therefore, the thermoplastic resin composition and adhesive paint of the present invention can be preferably used as an adhesive material.

<Laminate>

As a preferable article using the thermoplastic resin composition or adhesive coating of the present invention, a laminate having at least one layer made of the thermoplastic resin composition or adhesive coating of the present invention can be exemplified.

The thickness of the layer made of the thermoplastic resin composition or adhesive paint of the present invention is not particularly limited, but from the viewpoint of adhesiveness, it is usually 0.5 μm or more, preferably 1 μm or more, and more preferably 2 μm or more. And from the viewpoint of economy, it is usually 100 μm or less, more preferably 50 μm or less, and still more preferably 30 μm or less.

The overall thickness of the laminate is not particularly limited, but from the viewpoint of the manufacturability, mechanical strength, and sheet handling properties of the laminate, it is usually 10 to 1000 μm, more preferably 20 to 500 μm.

<The first embodiment of the laminate>

Preferred embodiments of the laminate of the present invention include, for example, a layer formed of a cyclic polyolefin polymer, a layer formed of the thermoplastic resin composition of the present invention or an adhesive coating, and a resin having a polar group A laminate formed by sequentially laminating the formed layers; or a layer formed of a cyclic polyolefin polymer, a layer formed of the thermoplastic resin composition of the present invention or an adhesive coating, and a resin having a polar group The formed layer, the layer formed of the thermoplastic resin composition of the present invention or the adhesive coating, and the layer formed of the cyclic polyolefin polymer are sequentially laminated.

In the laminate of the above embodiment, it is preferable that the layers are directly laminated.

The layer composed of a resin having a polar group in the laminate is preferably a layer composed of an ethylene-vinyl alcohol copolymer.

The method for producing the laminate of the above embodiment using the thermoplastic resin composition of the present invention is not particularly limited, and any equipment can be used. It can be manufactured by any method, for example, the constituent materials of each layer are melted by each extruder, and the method of co-extrusion by a T-die nozzle by the multiple manifold method or the stacked plate method or the feed head method; obtained by any method After at least one resin film, an extrusion lamination method in which other resin layers are melt-extruded on the film; and a method in which each layer of resin film is obtained by an arbitrary method and then integrated by thermal lamination, etc.

The laminate of the above embodiment using the thermoplastic resin composition of the present invention can be preferably used as a laminate having high strength, high transparency, high gas barrier properties, chemical resistance, etc., for example, as food or medical equipment, etc. Packaging film or storage container.

The method for manufacturing the laminate of the above embodiment using the adhesive coating of the present invention is not particularly limited, and it can be manufactured by any method using any device, for example, in a film made of a cyclic polyolefin polymer or by having A method of coating the adhesive coating of the present invention on one of the films formed by the polar-based resin, and then laminating another film thereon; and coating the adhesive coating of the present invention on any film substrate to form a coating film And transfer the obtained coating film to one of the film made of cyclic polyolefin polymer or the film made of resin with polar group, and then laminate another film on it; etc.

The method for forming a coating film using an adhesive paint is not particularly limited, and a conventional thin-film coating method can be used. Specifically, methods such as roll coating, gravure coating, reverse roll coating, roll brush, spray coating, knife coating, and die coating are exemplified.

The above embodiment of the adhesive coating of the present invention is used The laminate can be preferably used as a laminate having high strength, high transparency, high gas barrier property, chemical resistance, etc., for example, as a packaging film or storage container for food, medical equipment, etc., especially as a laminate Blister packaging (PTP packaging) products.

<The second embodiment of the laminate>

Other preferred embodiments of the laminate of the present invention can be exemplified by, for example, a layer made of a cyclic polyolefin polymer, a layer made of the thermoplastic resin composition of the present invention or an adhesive coating, and a metal or metal compound The layer formed by laminating the layers in sequence; or the layer formed by the cyclic polyolefin polymer, the layer formed by the thermoplastic resin composition of the present invention or the adhesive coating, and the layer formed by the metal or metal compound The layered layer, the layer formed of the thermoplastic resin composition of the present invention or the adhesive coating, and the layer formed of the cyclic polyolefin polymer are sequentially laminated.

In the laminate of the above embodiment, it is preferable that the layers are directly laminated.

In the above laminate, the layer made of metal or metal compound is preferably a layer made of aluminum foil.

The method for manufacturing the laminate of the above embodiment using the thermoplastic resin composition of the present invention is not particularly limited, and any device can be used, and any method can be used. For example, a foil made of metal or metal compound can be used. The laminate of the layer made of the cyclic polyolefin-based polymer and the layer made of the thermoplastic resin composition of the present invention, on the above foil, the layer made of the thermoplastic resin composition of the present invention becomes the above An extrusion lamination method of melt extrusion by foil side; after obtaining a laminate having a layer composed of a cyclic polyolefin polymer and a layer composed of the thermoplastic resin composition of the present invention by any method, make the above A method of thermally laminating a foil and a layer made of the thermoplastic resin composition of the present invention to the foil side.

As the above method, for example, a laminate having a layer formed of a cyclic polyolefin polymer and a layer formed of the thermoplastic resin composition of the present invention, having a metal or a metal compound on at least one surface On the layer of the layered body made of metal or metal compound, the extruded layer melt-extruded in such a way that the layer made of the thermoplastic resin composition of the present invention becomes the above-mentioned layer side made of metal or metal compound Combined method; After obtaining a laminate having a layer formed of a cyclic polyolefin polymer and a layer formed of the thermoplastic resin composition of the present invention by any method, at least one surface has a layer formed of a metal or a metal compound The layered body of the layer and the method of thermally laminating the layer formed of the thermoplastic resin composition of the present invention to the layer side formed of the metal or metal compound described above.

As a laminate having a layer made of the above-mentioned metal or metal compound on at least one surface, for example, an arbitrary film-like substrate and a foil made of a metal or metal compound can be dry-laminated and thermally laminated. Laminates laminated by the same method; metal or metal compound laminates are vapor-deposited on any film-like substrate by any method; any thermoplastic resin is melt-extruded on a foil made of metal or metal compounds Laminates; and laminates that use arbitrary coating agents to form coating films on foils made of metals or metal compounds, etc.

The laminate of the above-mentioned embodiment using the thermoplastic resin composition of the present invention can be preferably used as a laminate having a very high gas barrier property, for example, as a food or medical device, a pharmaceutical product, etc. resistant to oxygen or moisture Packaging films or containers for sexually weak contents.

The method of manufacturing the laminate of the above-mentioned embodiment using the adhesive coating of the present invention is not particularly limited, and can be manufactured by any method using any apparatus. As the above method, for example, a method of coating the adhesive coating of the present invention on a film made of a cyclic polyolefin-based polymer and then laminating a foil made of a metal or a metal compound thereon; on any film base The adhesive coating of the present invention is coated on the material to form a coating film, and the resulting coating film is transferred to a film made of a cyclic polyolefin polymer, and then a foil made of a metal or metal compound is laminated thereon Method; coating the adhesive coating of the present invention on a film made of a cyclic polyolefin-based polymer, and then on it, making at least one surface have a laminate of a layer made of metal or metal compound, so that The above-mentioned layer made of metal or metal compound becomes a method of laminating the layer formed by the adhesive coating of the present invention; and applying the adhesive coating of the present invention to an arbitrary film substrate to form a coating film, The resulting coating film is transferred onto a film made of a cyclic polyolefin-based polymer, and on it, at least one surface is provided with a laminate of a layer made of a metal or a metal compound, so that The layer formed by the metal compound is a method of laminating the layer formed by the adhesive paint of the present invention. As a method of forming a coating film using an adhesive paint, the above method is exemplified.

The laminate of the above embodiment using the adhesive coating of the present invention can be preferably used as a laminate having a very high gas barrier property, for example For example, it is better used as packaging film or storage container for the contents with weak resistance to oxygen or moisture, such as food, medical instruments and pharmaceuticals. In particular, it can be preferably used in individually packaged blister packs (PTP packs) of medicine tablets, capsules and the like.

[Example]

The present invention is described below by examples, but the present invention is not limited to this.

<Measurement method> (A1) Adequacy: (A1-1) For cyclic polyolefin copolymer (for COC):

Using a 40mm single-shaft extruder, the thermoplastic resin composition obtained below and a 25mm single-shaft extruder were used to convert the cyclic polyolefin-based copolymer (POLYPLASTIC Co., Ltd. "TOPAS 8007F-04 (trade name)") It is extruded from a two-color forming die at a die temperature of 240°C, and the entire cross-sectional shape when cut in the machine direction perpendicular to the machine direction is rectangular, and is a rectangular thermoplastic resin composition with the same shape but a thickness of 1 mm. On the layer, there is a two-color molded product of a layer of a rectangular cyclic polyolefin copolymer of the same shape but with a thickness of 0.1 mm. From the vicinity of the center of the width direction of the two-color molded product obtained above, a sample was cut out with a width of 15 mm, taking JIS Z0237: 2009 No. 10.4 as a reference, the layer of the thermoplastic resin composition was regarded as a test plate, and the cyclic polyolefin The layer of copolymer is regarded as an adhesive tape, and the ring-shaped polymer is measured at the test speed of 300 mm/min. The adhesion of the layer of the olefin copolymer to the layer of the thermoplastic resin composition is 180 degrees peeling. In addition, when the adhesiveness is very high and the starting point of peeling cannot be made, the table is described as ">>".

(A1-2) For ethylene-vinyl alcohol copolymer (for EVOH):

Using a 40 mm single-shaft extruder, the thermoplastic resin composition obtained below and a 25 mm single-shaft extruder were used to convert an ethylene-vinyl alcohol copolymer ("EVAL L-171B (trade name)" of KURARAY Co., Ltd.) from The two-color forming die is extruded at a die temperature of 200°C, and the entire cross-sectional shape when the machine direction is cut perpendicular to the machine direction is rectangular, and is a rectangular thermoplastic resin composition of the same shape but a thickness of 1 mm. On the layer, there are two-color molded products of the same shape but a rectangular ethylene-vinyl alcohol copolymer layer with a thickness of 0.1 mm. From the vicinity of the center of the width direction of the two-color molded product obtained above, a sample was cut out with a width of 15 mm, and the layer of the thermoplastic resin composition was regarded as a test plate with reference to JIS Z0237: 2009 No. 10.4, and ethylene-vinyl alcohol was copolymerized The layer of the material is regarded as an adhesive tape, and the adhesion of the layer of ethylene-vinyl alcohol copolymer to the layer of the thermoplastic resin composition at 180 degrees is measured at a test speed of 300 mm/min.

(A1-3) For metals or metal compounds (for aluminum foil):

On a 25 μm thick aluminum foil (untreated aluminum foil of UACL Co., Ltd.), the thermoplastic resin composition obtained below was extruded at a die temperature of 200° C. with a thickness of 1 mm using a 40 mm uniaxial extruder to perform layering Together. From the vicinity of the center in the width direction of the laminate obtained above, a sample was cut out with a width of 15 mm, taking JIS Z0237: 2009 No. 10.4 as a reference, the layer of the thermoplastic resin composition was regarded as a test plate, and the layer of metal foil was regarded as Adhesive tape was used to measure the adhesion of the metal foil layer to the thermoplastic resin composition layer at 180 degrees at a test speed of 300 mm/min.

(A2) Impact resistance (Izod impact strength)

Using an injection molding machine with a clamping pressure of 125 tons, a 1/4 inch thick injection sheet formed under the conditions of a cylinder temperature of 260 to 280 ℃ and a mold temperature of 30 ℃ is used as a test piece, and the Ehrlich impact strength is measured according to ASTM D256 (with concave mouth). In addition, the test piece was not cracked and described as NB.

(A3) Transparency (turbidity):

According to JIS K7136:2000, using "NDH-300A (trade name)" of Nippon Denshoku Industries Co., Ltd., the injection molding machine with a clamping pressure of 125 tons was used to measure the conditions of cylinder temperature 260~280℃ and mold temperature 30℃ The turbidity value of the formed 2mm thick injection sheet.

(A4) Particle productivity:

The pellets obtained by the strand cutting method of the thermoplastic resin composition (P) were visually observed and evaluated according to the following criteria.

○: The particle shape is good.

×: At least any of the following occurs.

Particle adhesion.

The particle shape is inconsistent.

The ingredients seeped out on the granules.

(B1) Adequacy: (B1-1) For cyclic polyolefin copolymer (for COC):

單軸擠出機與T模嘴之裝置，使用環狀聚烯烴系共聚物(POLYPLASTIC股份有限公司之「TOPAS 8007F-04(商品名)」)，以模嘴出口樹脂溫度240℃之條件製膜厚100μm之薄膜。自上述所得之薄膜，切出2片於薄膜之機械方向150mm、寬度方向15mm之大小之短條片，於距一短條片之機械方向前端之100mm內，使用塗敷器以乾燥後之厚為10μm之方式塗佈接著性塗料，以1200W之乾燥器乾燥1分鐘後，與另一短條片以彼此不伸出之方式重疊，以溫度180℃、壓力50kg/cm²之條件加壓2分鐘，使兩者接著，獲得試驗片。使用上述所得之試驗片，以試驗速度50mm/分之條件，測定T字剝離之接著力。數據之處理係參考JIS Z0237：2009之10.4.1進行。亦即，忽略測定開始後最初之25mm長度之測定值，將隨後之50mm之長度之接著力予以平均，作為T字剝離之接著力。又，接著力非常高、上述環狀烯烴系共聚物薄膜變形．材料斷裂時，於表中記載為「>>」。 Use with 40mm

The device of uniaxial extruder and T-die is made of cyclic polyolefin copolymer ("TOPAS 8007F-04 (trade name)" of POLYPLASTIC Co., Ltd.), and the film is produced under the condition that the resin temperature at the die outlet is 240℃ 100μm thick film. From the film obtained above, cut out two short strips with a size of 150 mm in the machine direction of the film and a width of 15 mm in the width direction, within 100 mm from the front end of a short strip in the machine direction, using an applicator to dry the thickness Subsequently embodiment of a coating 10μm coating to 1200W dryer to dry for 1 minute, and the other short strip so as not to overlap with one another extending at a temperature of 180 ℃, pressure of 50kg / cm 2 pressure condition of ² After two minutes, the two are followed to obtain a test piece. Using the test piece obtained above, the T-shaped peeling adhesive force was measured under the condition of a test speed of 50 mm/min. The data processing is performed with reference to 10.4.1 of JIS Z0237:2009. That is, ignoring the measured value of the first 25 mm length after the start of the measurement, and then averaging the adhesive force of the subsequent 50 mm length as the adhesive force of T-shaped peeling. In addition, the adhesion is very high, and the cyclic olefin copolymer film is deformed. When the material breaks, it is described as ">>" in the table.

(B1-2) For metal or metal oxide (for aluminum foil):

In addition to replacing the above-mentioned cyclic olefin polymer film, use thick Except for 25 μm aluminum foil (untreated aluminum foil of UACJ Co., Ltd.), the same procedure as (B1-1) above was performed.

(B1-3) For resins with polar groups (for EVOH):

單軸擠出機與T模嘴之裝置，使用乙烯-乙烯醇共聚物(KURARAY股份有限公司之「EVAL L-171B(商品名)」)，以模嘴出口樹脂溫度200℃之條件製膜厚100μm之薄膜。除了使用上述所得之薄膜替代上述環狀烯烴系共聚物薄膜以外，與上述(B1-1)同樣進行。 Use with 40mm

The device of uniaxial extruder and T-die nozzle uses ethylene-vinyl alcohol copolymer ("EVAL L-171B (trade name)" of KURARAY Co., Ltd.), and the film thickness is made under the condition that the resin temperature at the die outlet is 200°C. 100μm film. Except for using the film obtained above instead of the cyclic olefin copolymer film, the same procedure as in (B1-1) above was carried out.

(B2) Coating property:

The wet coating film when the adhesive coating was applied to the cyclic olefin copolymer film so as to have a wet thickness of 100 μm using an applicator was visually observed and evaluated according to the following criteria.

○: A uniform wet-thick coating film can be obtained.

×: A uniform wet-thick coating film cannot be obtained.

<raw materials used> Ingredient (a1):

(a1-1) POLYPLASTIC Co., Ltd. cyclic olefin copolymer "TOPAS 8007F-04 (trade name)", glass transition temperature 79℃, MFR (260℃, 2.16kg) 32g/10 minutes, light transmittance 91% .

(a1-2) POLYPLASTIC Co., Ltd.'s cyclic olefin copolymer "TOPAS 6013F-04 (trade name)", glass transition temperature 139℃, MFR (260℃, 2.16kg) 14g/10min, light transmittance 91% .

(a1-3) Mitsui Chemicals Co., Ltd.'s cyclic olefin copolymer "APEL 6013T (trade name)", glass transition temperature 125℃, MFR (260℃, 2.16kg) 14g/10 minutes, light transmittance 90%.

(a1-4) ZEONOR 1020R (trade name), a cyclic olefin polymer of Japan Zeon Co., Ltd., glass transition temperature 102°C, MFR (280°C, 21.18N) 20g/10min, light transmittance 92%.

Ingredient (a2):

(a2-1): Asahi Kasei Chemical Co., Ltd. copolymerizes a block composed of a polymer block mainly composed of styrene and a random copolymer block composed of 1,3-butadiene and styrene The hydrogenated compound "SOES1606 (trade name)" is completely hydrogenated and contains 52% by mass of structural units derived from styrene.

(a2-2): Asahi Kasei Chemical Co., Ltd. copolymerized by a polymer block mainly composed of styrene and a block composed of a random copolymer block composed of 1,3-butadiene and styrene The hydride of the compound "SOES1605 (trade name)" is completely hydrogenated, and the content of structural units derived from styrene is 67% by mass.

(a2-3): Asahi Kasei Chemical Co., Ltd. consists of a polymer block mainly composed of styrene and a random combination of 1,3-butadiene and styrene The hydride "S.O.E.S1611 (trade name)" of the block copolymer formed by the polymer block is partially hydrogenated, and the content of the structural unit derived from styrene is 57% by mass.

Reference ingredient (a2’):

(a2'-1) JSR Co., Ltd.'s hydrogenated random copolymer of 1,3-butadiene and styrene "DYNARON 1320P (trade name)", hydrogenation rate 99 mole %, derived from The content of the structural unit of styrene is 10% by mass.

(a2'-2) KURARAY Co., Ltd.'s styrene-ethylene-propylene-styrene block copolymer "CEPTON 2063 (trade name)", with a hydrogenation rate of 90 mol%, derived from the content of structural units of styrene 30% by mass.

Ingredient (B):

(B-1) Maleic anhydride of Japan Catalyst Co., Ltd.

Ingredient (C):

(C-1) 2,5-Dimethyl-2,5-di-(third butylperoxy) hexane "PERHEXA 25B (brand name)" of Nippon Oil & Fats Co., Ltd., 1 minute half-life temperature 180 ℃.

<Example A1~A13 and Example A1S~A8S>

Using a twin-screw extruder rotating in the same direction, combine any of the following tables 1 to 3 The mixture (parts by mass) as shown is fed in once, melt-kneaded at a resin temperature of 190°C at the outlet of the extruder, and pelletized by the strand cutting method to obtain pellets of the thermoplastic resin composition (P). About the obtained thermoplastic resin composition (P), the above-mentioned evaluations (A1) to (A4) were performed. The evaluation results are shown in Tables 1-3.

<Example B1~B13 and Example B1S~B8S>

Using a twin-screw extruder rotating in the same direction, feed the mixture (parts by mass) as shown in any of the following Tables 4 to 6 at once, and melt-knead at a resin temperature of 190°C at the outlet of the extruder. Pelletizing by strand cutting method to obtain pellets of thermoplastic resin composition. 100 parts by mass of the obtained thermoplastic resin composition was dissolved in 1000 parts by mass of toluene to obtain an adhesive paint having a solid content concentration of 9% by mass. With respect to the obtained adhesive paint, the above-mentioned evaluations (B1) to (B2) were performed. The evaluation results are shown in Tables 1-3.

As understood from the evaluation results of Tables 1 to 6, the thermoplastic resin composition and the adhesive paint of the present invention are excellent in impact resistance, adhesiveness, transparency, and coatability. And the productivity as a composition is also excellent, and the resulting particles have a good shape.

Claims (17)

A thermoplastic resin composition comprising (A) 100 parts by mass of a thermoplastic resin; (B) at least 0.05 to 5 parts by mass selected from the group consisting of unsaturated carboxylic acids and derivatives of unsaturated carboxylic acids; and (C ) 0.01 to 3 parts by mass of organic peroxide, the above component (A) is composed of the following components (a1) and (a2): (a1) cyclic polyolefin polymer 10 to 90% by mass; and ( a2) Hydride of block copolymer composed of polymer block mainly composed of aromatic vinyl compound and random copolymer block of conjugated diene compound and aromatic vinyl compound 90 to 10 mass %, but the total of the aforementioned component (a1) and the aforementioned component (a2) is 100% by mass. The thermoplastic resin composition according to claim 1, wherein the aforementioned component (a1) is a copolymer of a cyclic olefin and an α-olefin having 2 to 8 carbon atoms. A method for manufacturing a thermoplastic resin composition, which is a composition composed of the following components (A) to (C) by melt-kneading, (A) 100 parts by mass of a thermoplastic resin; (B) self-unsaturated carboxylic acid and One or more than 0.05 to 5 parts by mass selected from the group of derivatives of saturated carboxylic acids; and (C) 0.01 to 3 parts by mass of organic peroxides, the above component (A) is composed of the following components (a1) and components ( a2) Formed: (a1) cyclic polyolefin polymer 10 to 90% by mass; and (a2) Hydrides of block copolymers composed of polymer blocks mainly composed of aromatic vinyl compounds and random copolymer blocks of conjugated diene compounds and aromatic vinyl compounds 90 to 10 Mass%, but the total of the above-mentioned component (a1) and the above-mentioned component (a2) is 100% by mass. The method according to claim 3, wherein the aforementioned component (a1) is a copolymer of a cyclic olefin and an α-olefin having 2 to 8 carbon atoms. An adhesive coating comprising (A) 100 parts by mass of a thermoplastic resin; (B) more than 0.05 to 5 parts by mass selected from the group consisting of unsaturated carboxylic acids and derivatives of unsaturated carboxylic acids; (C) organic Peroxide 0.01 to 3 parts by mass; and (D) solvent; the above component (A) is composed of the following component (a1) and component (a2): (a1) cyclic polyolefin polymer 10 to 90 mass %; and (a2) Hydrides of block copolymers composed of polymer blocks mainly composed of aromatic vinyl compounds and random copolymer blocks of conjugated diene compounds and aromatic vinyl compounds 90 to 10% by mass, but the total of the aforementioned component (a1) and the aforementioned component (a2) is 100% by mass. The adhesive paint according to claim 5, wherein the aforementioned component (a1) is a copolymer of a cyclic olefin and an α-olefin having 2 to 8 carbon atoms. A method for manufacturing an adhesive paint, comprising: a step (1) of melting and kneading a composition composed of the following components (A) to (C) to produce a thermoplastic resin composition, (A) 100 parts by mass of thermoplastic resin; (B) one or more than 0.05 to 5 parts by mass selected from the group consisting of unsaturated carboxylic acids and derivatives of unsaturated carboxylic acids; and (C) organic peroxides 0.01 to 3 Parts by mass, the above component (A) is composed of the following components (a1) and (a2): (a1) cyclic polyolefin polymer 10 to 90% by mass; and (a2) is composed of aromatic vinyl The compound is mainly composed of a polymer block and a random copolymer block of a conjugated diene compound and an aromatic vinyl compound. The hydride of the block copolymer is 90 to 10% by mass. However, the above component (a1 ) And the above component (a2) total 100% by mass; and the step (2) of dissolving the thermoplastic resin composition obtained in the step (1) in the solvent (D). The method according to claim 7, wherein the aforementioned component (a1) is a copolymer of a cyclic olefin and an α-olefin having 2 to 8 carbon atoms. A laminate formed by sequentially laminating the following layers: a layer made of a cyclic polyolefin polymer; a layer made of a thermoplastic resin composition as in claim 1 or 2, or as required Item 5 or 6 The layer formed by the adhesive coating; and the layer formed by the resin having a polar group. A laminate formed by sequentially laminating the following layers: a layer composed of a cyclic polyolefin polymer; a layer composed of a thermoplastic resin composition as described in claim 1 or 2; consisting of a polar group A layer of resin; A layer made of a thermoplastic resin composition as claimed in claim 1 or 2; and a layer made of a cyclic polyolefin polymer. The laminate according to claim 9 or 10, wherein the resin having the aforementioned polar group is an ethylene-vinyl alcohol copolymer. A laminate formed by sequentially laminating the following layers: a layer made of a cyclic polyolefin polymer; a layer made of a thermoplastic resin composition as in claim 1 or 2, or as required Item 5 or 6 The layer formed by the adhesive coating; and the layer formed by metal or metal compound. A laminate formed by sequentially laminating the following layers: a layer made of a cyclic polyolefin polymer; a layer made of a thermoplastic resin composition as in claim 1 or 2, or as required Item 5 or 6 Adhesive coating layer; Metal or metal compound layer; Thermoplastic resin composition as in claim 1 or 2, or Adhesive as in claim 5 or 6 The layer formed by the property paint; and the layer formed by the cyclic polyolefin polymer. A laminate according to claim 12 or 13, wherein the aforementioned layer made of metal or metal compound is a layer made of aluminum foil. A method for manufacturing a laminate, comprising the following steps: a step of producing an adhesive coating using the method of claim 7 or 8; and using the adhesive coating obtained in the foregoing steps to make the cyclic polyolefin-based polymer film and Steps for bonding foil made of metal or metal compound (3). A press through package product comprising the laminate according to any one of claims 9 to 14. A method for manufacturing a blister package product, comprising the following steps: a step of producing a laminate using the method of claim 15; and a step (4) of using the laminate obtained in the previous step to produce a blister package product.