WO2001068785A1

WO2001068785A1 - Adhesive, process for producing layered product with the adhesive, and layered product

Info

Publication number: WO2001068785A1
Application number: PCT/JP2001/001926
Authority: WO
Inventors: Toru Fujiki; Toshiki Mori; Hironobu Iyama; Shigeki Naitoh
Original assignee: Sumitomo Chemical Company, Limited
Priority date: 2000-03-13
Filing date: 2001-03-12
Publication date: 2001-09-20
Also published as: AU2001241107A1

Abstract

A resin composition characterized by being obtained by blending two modified block copolymers which are obtained by graft-polymerizing maleic anhydride with a hydrogenated styrene/conjugated diene/styrene block copolymer and differ in MFR in such a degree that the ratio of the MFR of one of the modified block copolymers to that of the other is from 3 to 2,000; an adhesive comprising the resin composition as the active ingredient; a method of heat curing characterized by heat-curing the adhesive under such conditions that C represented by the following general equation (I) C= (AxB)/1000 is in the range of 2.5 to 12; and a layered product characterized by being obtained by bonding adherends by the heat-curing method [wherein A represents temperature (°C) for heat curing and B represents heating time (min) for heat curing].

Description

Description Adhesive, manufacturing method of laminate using the adhesive, and laminate

The present invention relates to an adhesive, a method for producing a laminate using the adhesive, and the laminate.

Specifically, a modified block copolymer obtained by graft-polymerizing water-free maleic acid to a hydrogenated product of a styrene-conjugated-gen-styrene-based block copolymer, and / or water of a styrene-conjugated-gen-styrene-based block copolymer The present invention relates to a resin composition containing an additive, an adhesive containing the resin composition as an active ingredient, a method for producing a laminate using the adhesive, and a laminate obtained using the adhesive. Background art

Laminates made of a resin such as olefin resin such as polypropylene and a polar group-containing resin such as urethane-based resin and acryl-based resin with a design property are laminated or coated to form a housing for home appliances, Used in automotive exterior products, etc.Uses a modified block copolymer obtained by graft-polymerizing maleic anhydride to a hydrogenated product of styrene, conjugated gen, and styrene-based block copolymer as an adhesive for both base materials. It is known to

For example, Japanese Patent Publication No. 4-45532 discloses a modified block copolymer obtained by graft-polymerizing maleic anhydride to a hydrogenated product of a styrene 'conjugated gen' styrene block copolymer and a solvent. Adhesives have been proposed. However, when a laminate was trial-produced using this adhesive, when a film of a polar group-containing resin or the like was laminated, streaks were formed on the surface of the film, and the appearance properties were impaired

The problem arises.

Japanese Patent Application Laid-Open No. 9-314767 discloses that one type of modified block copolymer (melt flow) is used as an adhesive between a substrate such as an olefin resin and a substrate of a polar group-containing resin. Rate (hereinafter referred to as MFR) = 102 g It is shown.

However, since the adhesive strength of these adhesives is not sufficient, there has been a demand for an adhesive which can further strongly bond a base material of a polar group-containing resin or a base material such as an olefin resin.

Similarly, in the case of bonding a base material of a polar group-containing resin to a base material such as an olefin resin, or bonding a base material such as an olefin resin to a metal such as aluminum, a method for improving the adhesiveness. An adhesive containing a modified block copolymer obtained by graft-polymerizing maleic anhydride to a hydrogenated product of styrene, conjugated gen, and styrene-based block copolymer, an organic peroxide and a solvent is used as a material of 130 tx 1 A method of thermosetting under the condition of 0 minutes has also been proposed (Japanese Patent Publication No. 63-65116).

However, the inventors of the present invention have studied that, using polar resins such as olefin resin and acryl resin as the adherend, and laminating them via the above-mentioned adhesive, 130 V 10 minutes When the laminate obtained by thermosetting under the above conditions is immersed in gasoline, the polar resin is peeled off, and the problem that the solvent resistance of the laminate obtained by bonding by this method is extremely low is apparent. It has become. Disclosure of the invention

The present inventors have intensively studied a modified block copolymer obtained by graft-polymerizing maleic anhydride to a hydrogenated product of a styrene-conjugated gen-styrene block copolymer in order to solve such a problem. As a result, as a modified block copolymer obtained by graft-polymerizing maleic anhydride to a hydrogenated product of a styrene-conjugated-gen-styrene-based block copolymer, the viscosity in a 20% by weight toluene solution was 10 to 10%. By using a specific modified block copolymer of 200 mPa · s, even when laminating a polar group-containing resin film, etc., there is no streak on the film surface and excellent It has been found that a laminate having appearance properties can be obtained.

The present inventors have also conducted intensive studies on a resin composition comprising a modified block copolymer obtained by graft-polymerizing maleic anhydride to a hydrogenated product of a styrene-conjugated gen-styrene block copolymer. Two types of the modified block copolymers having different flow rates (hereinafter referred to as MFRs) are mixed at a specific MFR ratio. By squeezing, it was found that the obtained resin composition had high adhesiveness. In order to find a bonding method that provides a laminate having excellent solvent resistance, the present inventors have further developed a modified block obtained by graft-polymerizing maleic anhydride to a hydrogenated product of a styrene-conjugated-gen-styrene block copolymer. As a result of intensive studies on adhesives containing copolymers, organic peroxides and solvents, the thermosetting method under specific conditions has shown that a laminate made of a polyolefin-based resin and a polar resin has significantly improved solvent resistance. Found to give.

The present inventors further carried out graft polymerization of maleic anhydride onto a hydrogenated product of styrene · conjugated gen, styrene-based block copolymer and / or a hydrogenated product of styrene · conjugated gen · styrene-based block copolymer. It has been found that a modified block copolymer and a resin composition containing a styrene resin have excellent adhesiveness. The present invention has been completed based on these findings.

That is, the present invention provides an adhesive comprising a solvent and a modified block copolymer obtained by graft-polymerizing maleic anhydride to a hydrogenated product of a styrene-conjugated gen-styrene block copolymer, and a solvent. The present invention provides a practically excellent adhesive (hereinafter referred to as "adhesive M"), characterized in that the viscosity in a 20% by weight toluene solution is 10 to 200 mPa's. .

The present invention also relates to a modified block copolymer obtained by graft-polymerizing maleic anhydride to a hydrogenated styrene-conjugated-gen-styrene block copolymer, wherein the two types of modified block copolymers having different MFRs are provided. Are mixed at an MFR ratio of 3 to 200, and an adhesive containing the resin composition as an active ingredient (hereinafter referred to as a resin composition N). And a laminate (hereinafter, referred to as a laminate N) obtained by laminating a base material via the adhesive N.

The present invention further provides an adhesive containing a modified block copolymer obtained by graft-polymerizing maleic anhydride to a hydrogenated styrene-conjugated-gen-styrene-based block copolymer, an organic peroxide and a solvent (hereinafter referred to as “adhesive”). , An adhesive O.) is a thermosetting method characterized in that C represented by the following general formula (1) is thermoset under the conditions of 2.5 to 12; It is characterized by attaching a kimono (Hereinafter referred to as a laminate O).

C = (A X B) / 1 0 0 0 (1)

(In the formula, A represents the heating temperature (° C) during thermosetting, and B represents the heating time (minutes) during thermosetting.)

The present invention further provides a resin composition characterized by containing the following resin (I) and resin (II) (hereinafter referred to as “resin composition P”), and the resin composition P as an active ingredient. It provides an adhesive (hereinafter referred to as adhesive P).

(I): Modification obtained by graft polymerization of maleic anhydride onto a hydrogenated product of styrene · conjugated gen · styrene block copolymer and / or a hydrogenated product of styrene · conjugated gen · styrene block copolymer. Block copolymer

(II): Styrene resin

Hereinafter, unless otherwise specified, a modified block copolymer is a modified block copolymer obtained by graft polymerizing maleic anhydride to a hydrogenated product of styrene, conjugated gen, and styrene block copolymer. Refers to union.

The styrene-conjugated-gen-styrene-based block copolymer used in the present invention or the styrene-conjugated-gen-styrene-based block copolymer used in the production of the modified block copolymer used in the present invention are: It is a copolymer containing at least one, preferably at least two, polymer blocks mainly composed of styrene units and one or more polymer blocks mainly composed of conjugated gen units.

In the case of the styrene-conjugated-gen-styrene-based block copolymer (I) that constitutes the resin composition P, the polymer block mainly composed of styrene units usually contains a styrene unit and a conjugated gen unit. The styrene unit in the polymer block is preferably at least about 60 mol%, more preferably at least 80 mol%. The polymer block mainly composed of a conjugated gen unit usually contains a styrene unit and a conjugated gen unit, and the conjugated gen unit in the polymer block is preferably about 60 mol% or more, more preferably 8% or more. 0 mol% or more.

Examples of the monomer that will be the styrene unit of the styrene / conjugated / styrene-based block copolymer include styrene, α-methylstyrene, vinyltoluene, p-tert-butylstyrene, and among others, styrene Is preferred. Examples of the monomer which is a conjugated diene unit include 1,3-butadiene, isoprene, 1,3-pentene diene, and 2,3-dimethyl-1,3-butadiene. , 3-butadiene and isoprene are preferred.

The molar ratio of the styrene unit to the conjugated unit in the styrene / conjugated / styrene-based block copolymer as a monomer is usually about 通常 ΒΖΘ ΒΖΘ ΟΖΙ 、, preferably about 8/92 to 34-66. is there.

The hydrogenated product of styrene-conjugated gen-styrene block copolymer is obtained by hydrogenating the unsaturated bond in the main chain olefin bond of the styrene-conjugated gen-styrene block copolymer. It is. It is preferable that the hydrogenated product is generally hydrogenated with about 80% or more of main chain olefin bonds. If the degree of hydrogenation does not reach 80%, the adhesion to an adherend such as an olefin resin and the thermal stability tend to decrease, which is not preferable.

Examples of the method for producing a hydrogenated product of styrene, conjugated gen, and styrene-based block copolymer include, for example, JP-B-36-19286, JP-B-40-23798, JP-B-49_36957, and The block copolymers obtained by the methods described in JP-B-48-2423, JP-B-48-4106 and the like can be obtained by combining JP-B-42-8704, JP-A-59-133203 and JP-A-59-133203. A method of hydrogenating by the method described in 0-79005 and the like can be mentioned.

Examples of hydrogenated styrene, conjugated gen, and styrene block copolymers include, for example, “Septon 8007”, “Septon 2007”, “Septon 1001”,

"Septon 1050", "Septon 2002", "Septon 2005", "Septon 2006", "Septon 2007", "Septon 2043", "Septon 2063", "Septon 4033", "Septon 4055", "Septon 4077" , "Septon 8004", "Septon 8006", "Septon 8007", "Hybler 5127", "Hybler 5125", "Hybler 7125" (all made by Kuraray Co., Ltd.), "Toughtec HI 042", " Tuftec HI 052, Tuftec H 1075, Tuftec HI031, Tuftec H1041, Tuftec H1043, Tuftec H1 141 "," ToughTech H 1062 "," ToughTech H 1065 ",

"Tuff-Tech H 1051", "Tuff-Tech HI 053" (from Asahi Kasei Corporation), "Clayton G1650", "Clayton G1652", "Clayton G1657X", "Clayton G1726X", Commercial products such as “Clayton G170 IX” (all manufactured by Shell Chemical Co., Ltd.) may be used.

The modified block copolymer obtained by graft polymerizing maleic anhydride to the hydrogenated styrene-conjugated-styrene-based block copolymer thus obtained is the modified block copolymer used in the present invention.

The grafting amount of maleic anhydride in the modified block copolymer is usually about 0.1 to 5 parts by weight, preferably 0.1 to 5 parts by weight, per 100 parts by weight of the hydrogenated product of the block copolymer. It is about 3 parts by weight. When the grafting amount of maleic anhydride is less than 0.1 part by weight, the adhesion to an adherend such as a polar group-containing resin tends to decrease, which is not preferable. This is not preferable because the brittleness of the steel tends to increase to cause cohesive separation.

Examples of the method for producing the modified block copolymer of the present invention include the methods described in JP-B-62-79211, JP-B-3-12087, and JP-B-63-44784. Specifically, a hydrogenated product of the block copolymer, maleic anhydride and a radical initiator are dry-blended, then put into an extruder, mixed while being heated and melted, and unreacted maleic anhydride is heated and depressurized. A method obtained by distilling off is exemplified.

Examples of the modified block copolymer include “Tuftec M1913 (MFR = 5)”, “Tuftec M1943 (MFR = 8)”, “Tuftec M1953 (MFR = 0.9)”, and “Tuftec M1962 (MFR-102)” ( A commercially available product such as Asahi Kasei Kogyo Co., Ltd.) may be used. Here, the MFR in the present invention is a value obtained by measuring at 230 ° C. under a load of 2160 g according to JISK-7210. It is.

The viscosity of a 20% by weight toluene solution of the modified block copolymer constituting the adhesive M is 10 to 200 OmPa · s (B-type viscometer, 25 ° C.).

If the above viscosity does not reach 1 OmPa's, workability when applying adhesive When the viscosity exceeds 200 OmPa · s, it is not preferable because the appearance properties tend to be impaired, such as streaking on the surface of the obtained adhesive.

As a solvent for the adhesive M, an organic solvent or the like that dissolves the modified block copolymer is usually used, and among them, aromatic hydrocarbon solvents are preferable, and toluene and xylene are particularly preferable. Further, as the adhesive M, a modified block copolymer dispersed in water or the like may be used.

The content of the modified block copolymer contained in the adhesive M is usually about 5 to 40% by weight, preferably 10 to 30% by weight.

The adhesive M in the present invention may be, if necessary, a transition metal compound such as titanium oxide (rutile type) or zinc oxide, a pigment such as carbon black, a thixotropic agent, a thickener, a defoaming agent, and a surface conditioner. Coating additives such as anti-settling agents, antioxidants, weathering agents, heat stabilizers, light stabilizers, pigment dispersants, and antistatic agents may be added.

By laminating the polar group-containing resin (a) and the olefin resin (b) via the adhesive thus obtained, a laminate having excellent appearance properties can be obtained.

(Hereinafter, this laminate is referred to as a laminate M.)

The resin composition N of the present invention, which is obtained by mixing two types of modified block copolymers having different MFRs at an MFR ratio of 3 to 2,000, is a modified block having a higher MFR than the other. The copolymer (III) and the other modified block copolymer (IV) having a low MFR are obtained by mixing two kinds of MFRs in a specific ratio.

The MFR ratio of the modified block copolymer (II I) having a high MFR and the modified block copolymer (IV) having a low MFR in the resin composition N of the present invention (MFR of [(III)] / [( MFR]) of IV) is 3 to 2,000, and the above ratio is preferably about 5 to 1,000, and particularly preferably about 10 to 500.

As the modified block copolymer (III) having a high MFR, for example, a modified block copolymer having an MFR of about 30 to 200 (gZlO content) is mentioned, and among them, the MFR is 40 to 150 (gZlO content). Degree of modified block copolymer It is suitable. Further, as the modified block copolymer (IV) having a low MFR, for example, a modified block copolymer having an MFR of about 0.1 to 20 (g / 10 minutes) is exemplified. A modified block copolymer having a viscosity of about 5 to 10 (g / 10 minutes) is preferable.

Examples of the method for producing the resin composition N of the present invention include a method of dissolving or dispersing two types of modified block copolymers in a solvent and mixing the resulting solutions, and a method of producing two types of modified block copolymers. Simultaneously dissolving or dispersing in a solvent, dry blending two types of modified block copolymers, melting and mixing two types of modified block copolymers, and roll mixing two types of modified block copolymers And other methods.

The resin composition N can be used for, for example, an adhesive N.

The adhesive N may be, for example, a solution obtained by dissolving or dispersing the resin composition N in a solvent, a sheet or film obtained by hot pressing, extrusion molding, injection molding, or the like of the resin composition N. Having.

As the solvent used in the adhesive N having a solution shape, an organic solvent or the like that dissolves the resin composition is usually used, and among them, an aromatic hydrocarbon solvent is preferable, and toluene and xylene are particularly preferable. It is. Further, the resin composition may be dispersed in a solvent such as water.

The content of the solvent contained in the adhesive N is usually about 60 to 95% by weight, preferably 70 to 90% by weight.

In the resin composition of the adhesive N in the form of a solution, the weight ratio of the modified block copolymer (III) having a high MFR to the modified block copolymer (IV) having a low MFR is usually represented by [ (Weight of (III)) / [weight of (IV)] = about 955 to 4565.

Further, in the resin composition N used for the adhesive N having a sheet or film shape, the weight of the modified block copolymer (III) having a high MFR and the modified block copolymer (IV) having a low MFR The ratio is usually [weight of (III)] / [weight of (IV)] = 45Z65 to 5/95. If the weight ratio of (III) and (IV) is out of the above range, the adhesiveness tends to decrease, which is not preferable. The adhesive N of the present invention includes, for example, a olefin resin such as a hydrogenated product of styrene, conjugated gen, and styrene block copolymer, a polyester resin, and a polyamide resin, as long as the adhesiveness is not impaired. A thermoplastic resin or the like may be mixed.

The adhesive N of the present invention may include a transition metal compound such as titanium oxide (rutile type) and zinc oxide, a pigment such as carbon black, a thixotropic agent, a thickener, a defoaming agent, and a surface, if necessary. Coating additives such as conditioners, antisettling agents, antioxidants, weathering agents, heat stabilizers, light stabilizers, pigment dispersants, and antistatic agents may be added.

By laminating substrates such as the polar group-containing resin (a) and the olefin resin (b) via the adhesive N thus obtained, a laminate of the present invention having excellent adhesiveness can be obtained. That is, as the laminate of the present invention, a laminate N such as (a) a Z adhesive layer (a), (a) an adhesive layer (b), (b) an adhesive layer Z (b) is exemplified. .

The polar group-containing resin used in the production of the laminate M or the laminate N is a resin containing a polar group such as a hydroxyl group, an ester group, an amide group, an ether group, a nitrile group, a carbonyl group, and a carboxyl group. Yes, specifically, hydroxyl group-containing resins such as polyvinyl alcohol and saponified ethylene-vinyl acetate copolymer; saturated polyester resins such as polyethylene terephthalate, polybutylene terephthalate and polyethylene naphthalate; polyamides — Polyamide resins such as 6, polyamide-6,6 and polyamide-6,10; urethane resins; melamine resins; polycarbonate resins; polyphenylene ether resins; (meth) acrylic acid, (meth) acrylic acid Acrylic ester, (meth) acrylamide, (meth) acrylo nitrile Examples of the base resin (a) include a composition comprising the above resin and a (meth) acrylic acid / methyl (meth) acrylate copolymer. And a copolymer of a monomer containing a polar group.

The shape of the substrate (a) is not particularly limited, and examples thereof include shapes of paints, films, sheets and the like.

Paints are usually acrylic resin, melamine resin and urethane resin For example, a polar group-containing resin such as a urethane-based resin is preferable. An acrylic resin or the like is usually used as the film and sheet. Examples of the olefin resin (b) include homopolyolefins such as polyethylene and homopolypropylene, block polypropylene such as ethylene-propylene block copolymer, ethylene-propylene copolymer, ethylene-butene copolymer, propylene- Olefin copolymers such as butene copolymer, ethylene propylene butene copolymer, styrene block copolymer, styrene block copolymer, styrene block copolymer, styrene block copolymer such as SBR, etc. And hydrogenated products of the aforementioned homopolyolefins and copolymers.

Further, as the base material (b), a composition comprising two or more types of the olefin resin may be used.

The base material (b) contains additives that are added to the olefin resin as required, for example, inorganic fillers such as talc, silica, myriki, clay, and glass fiber, pigments, antioxidants, and processing stability. Agents, weathering agents, heat stabilizers, light stabilizers, nucleating agents, lubricants, release agents, flame retardants, antistatic agents and the like.

As a method for producing the laminate M or the laminate N of the present invention, for example, a laminate composed of (a) a Z adhesive layer / (b) is as follows: In the case of the adhesive M or the adhesive N having a solution shape, The adhesive is spray-coated by air spray, air atomization electrostatic, electrostatic atomization electrostatic coating, etc., or by a coating method such as bar coater, doctor blade, wire coater, etc. for (a) and Z or (b). A method in which an adhesive is applied to the surface, and then the solvent is dried by standing drying at room temperature, heating and drying, and (a) and (b) are laminated via the obtained adhesive layer. Can be

When the adhesive N has a sheet or film shape, a sheet or film adhesive is prepared, and then (a) and (b) are laminated via the adhesive to form a heat sealer. Usually, a method of thermocompression bonding at about 100 to 220 ° C. using a press machine, an extruder or the like can be used. The obtained laminate may be further subjected to pressing, pressing, heating, and the like.

In the case of adhesive M or adhesive N in the form of a solution, after drying the adhesive The thickness of the adhesive layer is usually about l to 20 / m, preferably about 5 to 15 mm.If the thickness of the adhesive layer does not reach 1 m, the adhesive strength is When the thickness is more than 20 / m, cohesive separation tends to occur, which is not preferable.

When the adhesive N has a sheet or film shape, its thickness is usually 10 to 100 mm. When the thickness of the adhesive layer does not reach 100 m or is larger than 100 m, the adhesiveness tends to decrease, which is not preferable.

Since a laminate M obtained by laminating an olefin resin such as polypropylene and a polar group-containing resin such as a decorative film or a paint via the adhesive M of the present invention has excellent appearance properties, It can be used for packaging materials, building materials, housing for home appliances, pampers, door moldings, door mirrors, polypropylene resin laminates for automobile exteriors such as door undercovers, etc.

Since a laminate N obtained by laminating an olefin resin such as polypropylene and a polar group-containing resin such as a decorative film or a paint via the adhesive N of the present invention has excellent adhesive properties, Materials, building materials, household electrical appliance housings, bumpers, door moldings, door mirrors, door under covers, and other automotive exterior polypropylene resin laminates.

A modified block copolymer obtained by graft polymerization of maleic anhydride to a hydrogenated product of styrene, conjugated gen, and styrene block copolymer, an adhesive O containing an organic peroxide and a solvent are heated under specific conditions. In the case of the thermosetting method characterized by curing, the organic peroxide contained in the adhesive O includes, for example, methyl ethyl ketone peroxide, black hexanone peroxide, methyl black hexanone peroxide, methyl oxalate. Ketone peroxides such as acetoacetate peroxide and acetylacetone peroxide, 1,1-bis (t-hexylperoxy) _3,3,5-trimethylcyclohexane, 1,1-bis (t_ Hexylpropoxy) cyclohexane, 1,1-bis (t-butylperoxy) -1,3,3,5-trimethylcyclyl Hexane, 1,1-bis (t-butylperoxy) -12-methylcyclohexane, 1,1-bis (t-butylperoxy) cyclohexane, 1,1-bis (t-butylperoxy) cyclododecane, 2, 2-bis ( t-butylperoxy) butane, n-butyl-4,4-bis (t-butylperoxy) valerate, 2,2-bis (4,4-di-t-butylperoxycyclohexyl) propane , P-menthane hydride peroxide, diisopropylbenzene hydride peroxide, 1,1,3,3-tetramethylbutyl hydroperoxide, cumene hydride peroxide, t-hexyl hydroperoxide, t — Hydroperoxides such as butyl hydroperoxide, 1, 1 ′ —bis (t-butylperoxy) diisopropylpropylbenzene, dicumyl peroxide, 2,5-dimethyl—2,5-bis (t-butylperoxide) Hexane) Hexane, t-Butylcumyl peroxide, Di-t-butyl peroxide, 2, 5 Dialkyl peroxides such as dimethyl-2,5-bis (t-butylhydroxy) hexine-3, isobutyl peroxide, 3,5,5-trimethylhexanoyl peroxide, octyl nonyl peroxide, lauroyl Peroxides, stearoyl peroxide, succinic acid peroxide, benzoyl peroxide, m-toluoyl peroxide, and other diacyl peroxides, etc., n-propyl peroxy dicarbonate, diisopropyl par Oxydicarbonate, bis (4-t-butylcyclohexyl) veroxydicarbonate, di-2-ethoxyhexylperoxydicarbonate, di-2-ethylhexylperoxydicarbonate, Di-3-methoxybutylba one-year-old xydicarbonate, di-sec— Chilva 1-year-old xydicarbonate, di (3-methyl-3-methoxybutyl) peroxydicarbonate, and other baroxydicarbonates, 1,1'-bis (neodecanylbaroxy) diisopropylbenzene, cumylpara Xineodecanoate, 1,1,3,3-tetramethylbutylperoxynedecanoate, 1-cyclohexyl-1- 1-methylethylperoxyneocanoate, t-to Kisiloxyne neodecanoate, t-butyl peroxy neodecanoate, t_hexyl peroxypivalate, t-butyl butoxyvivalate, 1,1,3,3-tetramethyl butyral 2-ethoxyethylhexanoate, 2,5-dimethyl-2,5_bis (2-ethylhexanoylperoxy) hexane, 1-cyclohexyl-1-methylethyl Okishi Kishirupaokishi one 2 one 2-to Echiru Kisanoe Ichiboku, to t one 1-ethylhexanoate, t-butylhexanoate 2-ethylhexanoate, t-butylperoxyisobutyrate, t-hexylperoxyisopropyl monocarbonate, t-butylbutyloxymaleic acid, t-butylperoxy 1,3,5,5-Trimethylhexanoate, t-butylperoxylaurate, 2,5-dimethyl-2,5-bis (m-toluoyloxy) hexane, t-butylperoxyisopropyl Monocarbonate, t-butylperoxy-2-ethylhexyl monocarbonate, t-hexyloxybenzoate, 2,5-dimethyl-2,5-bis (benzoylperoxy) hexane, t-Butyl baroxia acetate, t-butyl benzoate m-toluoyl benzoate, t-butyl propyl peroxybenzoate, bis Peroxyesters such as t-butylperoxy) isophthalate, t-butylperoxyaryl monocarbonate, t-butyltrimethylsilyl peroxide, 3,3 ', 4,4'-tetra (t-butylperoxy) Oxycarbonyl) benzophenone and the like.

Among them, an organic peroxide having a one-hour half-life temperature of about 80 to 160 is preferable. Specific examples are oxyperoxide, lauroylperoxide, stearoyl peroxide, 1,1,3,3_tetramethylbutylperoxy-12-ethylhexanoate, succinic peroxide, 2,5- Dimethyl 2,5-bis (2-ethylhexanoylperoxy) hexane, 1 _ cyclohexyl 1-methylethylbenzoyl 2-ethylhexanoate, t-hexylpropoxy-1-ethylhexanoe Tert-butylperoxy-1-ethylhexanoate, m-toluoyl peroxide, benzoylperoxide, tert-butylperoxyisobutyrate, 1,1-bis (t-hexylpa) —3,3,5-trimethylcyclohexane, 1,1-bis (t-hexylsiloxy) cyclohexane, 1,1, _bis (t —Butylperoxy) 3,3,5-trimethylcyclohexane, 1,1-bis (t-butylvinyloxy) cyclohexane, 2,2_bis (4,4-di-t-butylperoxycyclohexyl) Syl) propane, 1,1-bis (t-butylvinyl) cyclododecane, t-hexyloxyisopropylmonocarbonate, t-butylperoxymaleic acid, t-butylvinyloxy_3,5, 5-trimethylhexanoate, t- Butylperoxylaurate, 2,5-dimethyl-2,5_bis (m-toluoylpropyloxy) hexane, t-butylvinyloxyisopropyl monocarbonate, t-butylperoxy-2-ethylhexyl monocarbonate, t-hexyl par Oxybenzoate, 2,5_dimethyl-2,5_bis (benzoylperoxy) hexane, t_butylperoxyacetate, 2,2_bis (t_butylperoxy) butane, t_butylperoxy Xybenzoate, n-butyl-4,4-bis (t-butylvinyloxy) valerate, bis (t-butylvinyloxy) isophthalate, dicumyl peroxide, 2,5-dimethyl-1,2,5-bis (t —Butylba—Hexane, α, α'_bis (t-butylperoxy) diisopropylpropyl, t-butylcum Pas one peroxide, di _ t _ Buchirubao Kisaido, p- menthane eight Ido port peroxide, 2, 5-dimethyl-2, 5-bis to (t-Buchirupaokishi) Relaxin - 3, and the like.

As the organic peroxide, two or more kinds of organic peroxides may be used. Further, the content of the organic peroxide in the adhesive O of the present invention is usually about 0.05 to 0.1 mol based on 1 kg of the modified block copolymer. When the content of the organic peroxide per 1 kg of the modified block copolymer is less than 0.05 mol, the solvent resistance of the obtained laminate 0 tends to decrease, and when it exceeds 0.1 mol. However, the intermolecular crosslinking reaction of the modified block copolymer tends to proceed excessively, and the adhesiveness between the adhesive layer and the adherend tends to decrease.

As the organic peroxide, a crosslinking accelerator such as a compound having a redox effect or a crosslinking aid such as a compound having a reducing property such as an amine compound may be contained. As the solvent used for the adhesive O, an organic solvent or the like that dissolves the modified block copolymer is usually used, and among them, aromatic hydrocarbon solvents are preferable, and toluene and xylene are particularly preferable. Further, water or the like may be used as a solvent, and the modified block copolymer may be dispersed in water.

The content of the solvent in the adhesive 〇 is usually about 150 to 200 parts by weight, preferably 200 to 100 parts by weight, based on 100 parts by weight of the modified block copolymer. It is moderate.

Adhesive 〇 is a mixture of modified block copolymer, organic peroxide and solvent Things.

Adhesives〇 include transition metal compounds such as titanium oxide (rutile type) and zinc oxide, pigments such as carbon black, etc. as necessary; thixotropic agents, thickeners, defoamers, surface conditioners

It may contain paint additives such as anti-settling agents, antioxidants, weathering agents, heat stabilizers, light stabilizers, pigment dispersants, and antistatic agents.

The adhesive 〇 thus obtained is represented by the following general formula (1)

C = (AXB) / 1000 (1)

(In the formula, A represents the heating temperature () during thermosetting, and B represents the heating time (minutes) during thermosetting.)

Is thermally cured under the conditions of 2.5 to 12, thereby obtaining a laminate から composed of a polyolefin-based resin and a polar resin and having extremely excellent solvent resistance. Among them, C is preferably 3 to 12, and particularly preferably C is 5 to 11.

When C is less than 2.5, the obtained laminate (2) has a tendency to decrease in solvent resistance, and is unfavorable. When C exceeds 12, the adhesive strength tends to decrease.

Here, the heating temperature (A) is a heating temperature for the laminate 、, such as an oven temperature in an oven, a press temperature in a hot press, etc., and is usually about 60 to 250 t: about, preferably about 80 to 200 t. It is.

The heating time (B) is the heating time for the laminate 〇 such as the residence time in an oven and the press time in a hot press, and is usually about 10 to 180 minutes, preferably about 15 to 160 minutes. Yes, particularly preferably about 30 to 140 minutes.

The laminate O of the present invention is obtained by bonding an adherend using an adhesive により by a thermosetting method under the above conditions.

Since the laminate of the present invention is excellent in solvent resistance, it is used for a building material, a housing for home electric appliances, a bumper, a door molding, a door mirror, a door under cover, a polypropylene resin laminate for an automobile exterior, and the like. I can do it.

The resin (Π) constituting the resin composition P is, for example, a homopolymer of styrene units, It is a styrene resin such as a copolymer of a styrene unit, an α, i3-unsaturated carboxylic acid unit, an acrylonitrile unit, and the like. Here, examples of the monomer of α,] 3-unsaturated carboxylic acid unit include (meth) acrylic acid esters such as (meth) acrylic acid and (meth) methyl acrylate, maleic acid, and maleic anhydride. And so on.

Specific examples of the resin (π) include polystyrene, acrylonitrile-styrene copolymer, styrene-α-methylstyrene copolymer, styrene-maleic anhydride copolymer, styrene- (meth) acrylic acid copolymer, and styrene. · Methyl (meth) acrylate copolymer and the like. Among them, polystyrene and styrene / maleic anhydride copolymer are preferred.

The styrene unit content in the styrene resin (II) is usually about 50% by weight or more.

The resin composition の of the present invention is a resin composition containing the resin (I) and the resin (Π). The content of the resin (Π) in the resin composition 通常 is usually about 1 to 30 parts by weight based on 100 parts by weight of the resin (I). If the resin (I) is out of the above range, the adhesiveness tends to decrease, which is not preferable.

In particular, when the resin (I) is a hydrogenated product of a block copolymer, it is preferably about 5 to 20 parts by weight based on 100 parts by weight of the resin (I). When I) is a modified block copolymer, it is preferably about 5 to 25 parts by weight based on 100 parts by weight of the resin (I).

As a method for producing the resin composition Ρ, for example, a method of dissolving or dispersing the resin (I) and the resin (II) in a solvent and then mixing the obtained solution or dispersion, the method of resin (I) and the method of resin A method of dissolving or dispersing (II) in a solvent, a method of dry-blending resin (I) and resin (II), a method of melt-mixing resin (I) and resin (II), a method of melting and mixing resin (I) and resin ( )), And the like.

The resin composition 得 thus obtained is, for example, an active ingredient such as an adhesive or a molding material, and is particularly suitable as an active ingredient of the adhesive. The adhesive has a shape such as a sheet or film obtained by, for example, a solution obtained by dissolving or dispersing a resin composition in a solvent, hot pressing, extrusion molding, injection molding, or the like. As the solvent used for the adhesive P, an organic solvent or the like that dissolves the resin composition of the present invention is usually used, and among them, an aromatic hydrocarbon solvent is preferable, and particularly, toluene and xylene are preferable. . Further, water or the like may be used as a solvent, and the resin composition may be dispersed in water.

The content of the solvent in the adhesive P is usually about 150 to 2000 parts by weight, preferably about 200 to 100 parts by weight, based on 100 parts by weight of the resin composition. is there. Adhesive P may include, if necessary, transition metal compounds such as titanium oxide (rutile type) and zinc oxide; pigments such as carbon black; thixotropic agents, thickeners, defoamers, surface conditioners, anti-settling agents It may contain additives for paints, such as agents, antioxidants, weathering agents, heat stabilizers, light stabilizers, pigment dispersants, and antistatic agents.

The laminated body of the present invention can be obtained by laminating and bonding the adherends via the adhesive P thus obtained.

The adherend laminated via the adhesive O or the adhesive P is, for example, an olefin resin, a hydrogenated product obtained by hydrogenating the olefin bond of the main chain of the olefin resin, a cell-based polymer material, Materials that can be bonded to adhesives, such as metals and polar group-containing resins. Further, two or more different types of adherends may be used as a mixture. The adherend may be a liquid such as a solution. In this case, the liquid adherend is applied on the adhesive and cured.

Specifically, examples of the olefin-based resin include homopolyolefins such as polyethylene and homopolypropylene, block polypropylene such as ethylene-propylene block copolymer, ethylene-propylene copolymer, ethylene-butene copolymer, and the like. Olefin-based copolymers such as propylene-butene copolymer, ethylene-propylene-butene copolymer, styrene-butadiene-styrene block copolymer, styrene-isoprene-styrene block copolymer, styrene-based copolymer such as SBR Polymers. Examples of the metal include aluminum, iron, and copper, and examples of the cellulosic polymer material include paper and wood.

The polar group-containing resin may be a melamine resin, an acrylic / urethane resin, a urethane resin, a (meth) acrylic resin, when laminated via an adhesive O. Examples include styrene / acrylonitrile copolymer, polycarbonate resin, phenol resin, alkyd resin, and epoxy resin.

When laminated via the adhesive P, it is a resin containing polar groups such as a hydroxyl group, an ester group, an amide group, an ether group, a nitrile group, a carbonyl group, and a carboxyl group. Hydroxyl-containing resins such as alcohols and saponified ethylene-vinyl acetate copolymers; saturated polyester resins such as polyethylene terephthalate, polybutylene terephthalate and polyethylene naphthalate; polyamide-6, polyamide-6,6 and polyamide- Polyamide resins such as 6, 10; urethane resins; melamine resins; polycarbonate resins; polyphenylene ether resins; (meth) acrylic acid, (meth) acrylic acid esters, (meth) acrylamide, ( Meta) Vinyl-based compounds such as acrylonitrile as monomers And an acryl resin.

In addition, a copolymer of a monomer containing a polar group, such as a composition comprising the above resin or a methyl (meth) acrylate (meth) acrylate copolymer, may also be used. Among the adherends laminated via the adhesive O or the adhesive P, among others, an olefin resin, a hydrogenated product obtained by hydrogenating the olefin bond of the main chain of the olefin resin, and a polar group-containing resin are preferable. is there.

The adherends laminated via the adhesive O or the adhesive P include, for example, inorganic fillers such as talc, silica, myriki, clay, and glass fiber, antioxidants, heat stabilizers, and weathering agents. , Heat stabilizers, light stabilizers, nucleating agents, lubricants, release agents, flame retardants, antistatic agents, etc .; inorganic pigments such as titanium oxide (rutile type), zinc oxide, carbon black, and organic pigments Pigments such as water; aromatic hydrocarbons such as water, toluene and xylene; aliphatic hydrocarbons such as hexane; esters such as ethyl acetate and butyl acetate; methylethyl ketone; methyl isobutyl ketone; Solvents such as ketones, alcohols such as methanol, isopropyl alcohol, ethylene glycol and propylene glycol.

Examples of the shape of the adherend laminated via the adhesive O or the adhesive P include, for example, a solution containing a pigment, a solvent, etc. in a polar group-containing resin, a film such as a decorative film, a sheet, etc. Shape. Among them, polar group-containing resin, pigment, solvent The adherend in the form of a solution containing, for example, is preferable because it can be handled as a coating material.Also, a sheet or film such as an olefin resin and a hydrogenated product obtained by hydrogenating the olefin bond of the main chain of the resin may be used. It is suitable.

As the paint, two or more kinds of polar group-containing resins may be used as a mixture, and furthermore, the same or different kinds of paints may be applied a plurality of times.

The laminate is usually a laminate obtained by laminating at least one or more types of adherends and thermosetting. The specific lamination order of the laminates 〇 or P is as follows: olefin resin Z adhesive Z olefin -Based resin, Orefin-based resin Adhesive Hydrogenated product obtained by hydrogenating the main-chain Orefin bond of the Norefin-based resin, Hydrogenated product obtained by hydrogenating the main-chain Orefin-bond of Orefin-based resin and / or Orefin-based resin Z Adhesive Z Metals, olefinic resins and / or hydrogenated hydrogenated olefin bonds in the main chain of olefinic resins Z adhesives Non-polar group-containing resins, metal adhesives Z-polar group-containing resins, polar group-containing resins Adhesives Examples of the resin include a polar group-containing resin, and particularly, an olefin resin and / or a hydrogenated product obtained by hydrogenating the olefin bond of the main chain of the olefin resin Adhesive Z A resin containing a polar group is preferable It is.

The thickness of the adhesive layer after heat curing in the laminates 〇 and P is usually about 1 to 20 m, preferably 5 to 15 m. When the thickness of the adhesive layer does not reach 1 zm, the adhesiveness tends to decrease, and when the thickness is more than 20 m, the adhesiveness tends to decrease, which is not preferable.

As a method for producing the laminate 0 or P of the present invention, for example, a method for producing a laminate in which a sheet-like adherend Z solution liquid adhesive Z solution adherend (paint) is sequentially laminated and adhered In the following, the adhesive is applied to a sheet-like material by spraying methods such as air spray, air atomization electrostatic, electrostatic atomization electrostatic coating, etc., Barco overnight, doctor blade, wireco overnight, etc. Apply to the surface of the body, then apply paint. Then, when using adhesive 0, thermosetting under the condition that C in general formula (1) becomes 2.5 to 12; When P is used, a method of bonding by heating at about 80 to 250 may be used. Further, a method of manufacturing a laminated body P composed of a sheet-like adherend Z sheet-like adhesive Z and a sheet-like adherend using the adhesive P will be described. Heat sealer, press machine, extrusion molding machine, etc. Usually, a method of crimping at 110 to 220 is exemplified. Further, the obtained laminate O or P may be further subjected to pressing, pressing, heating, or the like.

Since the resin composition P of the present invention has high adhesiveness to an olefin resin, a hydrogenated hydrogenated main chain olefin bond of the olefin resin, a polar group-containing resin, and the like, the resin composition P can be used for building materials, It can be used as an adhesive for polypropylene-based resin laminates for automobile exteriors such as home appliance housings, bumpers, door moldings, door mirrors, and door undercovers.

The solution of the resin composition P is also suitable as a paint. Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited thereto. Examples 1 to 5 and Comparative Examples 1 and 2

(1) Preparation of adhesive M:

Styrene-butadiene-styrene block copolymer hydrogenated products 1-4 of the following maleic anhydride graft copolymerized or styrene-butadiene-styrene block copolymer hydrogenated products 5, and toluene in a four-necked flask The mixture was stirred and dissolved for 1 hour while keeping the temperature at 80 to obtain an adhesive in the form of a toluene solution containing 20% by weight of the modified block copolymer.

1: "ToughTech Ml 962" manufactured by Asahi Kasei Corporation, styrene content =

30 weight ^ MFR measured in accordance with JISK 7210 (230: 2160g) = 102g / 10min, acid value = 5mg CH30Na / g (Grat amount of maleic anhydride is based on 100 parts by weight of copolymer 0.9 parts by weight)

2: Measured according to JISK 7210 (230Τ, 2160g), “ToughTech Ml 913” manufactured by Asahi Kasei Kogyo Co., Ltd., styrene content = 30 weight

MFR = 5 g / 10 min, acid value = 1 OmgCH30Na / g (the grafting amount of maleic anhydride is 1.8 parts by weight per 100 parts by weight of copolymer)

3: "ToughTech Ml 953" manufactured by Asahi Kasei Corporation, styrene content =

40 weight ^ Measured in accordance with JIS K7210 (230 :, 2160g) MFR = 0.9 g / 10 min, acid value = 10 mg CH30Na / g (the graft amount of maleic anhydride is 1.8 parts by weight with respect to 100 parts by weight of the copolymer) 4: "Asahi Kasei Kogyo Co., Ltd." Tuftec Ml 943 ", styrene content =

20 weight, MFR measured in accordance with JIS K7210 (230: 2160g) = 8g / 10min, acid value = 1 OmgCH30Na / g (The grafting amount of maleic anhydride is based on 100 parts by weight of the copolymer. 1.8 parts by weight)

5: "Clayton G 1652" manufactured by Shell Chemical Co., Ltd., styrene content =

29% by weight, measured according to JIS K 7210 (230 :, 2160g)

MFR = 2.7g / 10min

(2) Viscosity: The above adhesive was measured under the conditions of 25 using a B-type viscometer.

(3) Example of production of laminate M: The adhesive obtained in (1) was applied to the following corona-treated surface of the olefin resin using “Aprike Ichiichi” manufactured by Toyo Seiki Seisakusho Co., Ltd. 50 m was applied and dried in an oven at 80 for 20 minutes to obtain a laminate of the adhesive layer / olefin resin.

Next, on the adhesive layer side of the laminate, the polar group-containing resin shown in Table 1 was heat-sealed at a heat seal bar temperature of 1 using “Hyster-Lites Yuichi TP-701_B” manufactured by Tester Sangyo Co., Ltd. 60: A laminate comprising a polar group-containing resin Z adhesive layer and a olefin-based resin was obtained by thermocompression bonding at a pressure of 0.294 MPa for 3 seconds.

[0024]

(4) Appearance properties: The adhesive layer obtained in (3) The surface state of the adhesive layer of the laminate of the olefin-based resin was visually observed.

〇: No streaks were observed. X: Generation of muscle is observed.

(5) Peel strength: A test piece having a length of 100 and a width of 1 Omm was cut out from a laminate composed of a olefin resin containing a polar group-containing resin adhesive layer obtained in (3). Using AGS-20 kNG, the peel strength was measured at 180 ° peeling at a peeling speed of 100 t / min. Polar group-containing resin

A-1: Toseiguchi Co., Ltd. “Vinylon film LH # 17R (biaxially stretched PVA , Film thickness = 17 m

A-2: "Sumipex HT0 IX" manufactured by Sumitomo Chemical Co., Ltd., JIS

MFR measured according to K7210 (230t, 3800 g) = 2.Og / 10min, film thickness = 120m

B-1: "San Tokus II P film (one-sided corona-treated expanded polypropylene film)" manufactured by Tokuyama Co., Ltd., film thickness = 50 m

(Modified block copolymer)

The modified block copolymer used is shown below.

"Tuftec Ml 962" manufactured by Asahi Kasei Kogyo Co., Ltd. (MFR = 102g / 10min., A modified block copolymer 1)

"Tuftec M 1953" manufactured by Asahi Kasei Kogyo Co., Ltd. (MFR = 0.9 g / 10 min., A modified block copolymer 2) Production example 1 of adhesive N (in the case of adhesive in the form of a solution)

Asahi Kasei Kogyo Co., Ltd. “Tuftec Ml 962” (MFR = 102 g / 10 min, modified block copolymer 1), Asahi Kasei Kogyo Co., Ltd. “Tuftec M 1953” (MFR = 0.9 g / 10 And the modified block copolymer 2.) and toluene in parts by weight shown in Table 2 in a four-necked flask, and stirred and dissolved for 1 hour while keeping the temperature at 80 to obtain modified block copolymers 1 and 2. An adhesive N in an 80% by weight toluene solution containing a resin composition comprising as an active ingredient was obtained. Production example 2 of adhesive (in the case of adhesive having sheet shape)

After preheating Labo Plastomill (R-100, manufactured by Toyo Seiki Co., Ltd.) to 23, the modified block copolymer was added according to the parts by weight shown in Table 2, and then kneaded at 60 rpm for 5 minutes. A resin composition was obtained. Next, the resin composition was preheated for 5 minutes in a heat press machine set at 230, followed by pressing at 29.4 Mpa (300 kg / cm ² ) for 3 minutes, followed by cooling press for 2 minutes. A sheet-like adhesive N having a thickness of 50 m was obtained. Examples 6 to 9, Comparative Examples 3 and 4)

The adhesive obtained in Production Example 1 of adhesive N was applied to an olefin resin ((B-1), “San Tokus OP film (one-sided corona-treated stretched polypropylene film)” manufactured by Tokuyama Co., Ltd.), film thickness = 5 Of the adhesive layer Z (B-1) is applied to the surface of the adhesive layer Z (B-1) by applying 75 m using “Doc Yuichi Blade” manufactured by Toyo Seiki Seisakusho Co., Ltd., and drying in an oven at 80 for 20 minutes. A laminate was obtained.

Next, on the adhesive layer side of the laminate, a polar group-containing resin ((A-1): a biaxially stretched PVA film “Vinylon film LH # 17R”, film thickness = 17 / m) manufactured by Toseguchi Co., Ltd. Using “Heat Seal Tester TP-701-B” manufactured by Tester Sangyo Co., Ltd., heat bonding is performed for 3 seconds at a heat seal bar temperature of 120 and a pressure of 0.294MPa for (A-1) Z adhesive layer Z ( B-1) was obtained. Examples 10 and 11, Comparative Examples 5 and 6

On a Teflon sheet, a polar group-containing resin ((A-3): PET film “Lumirror M351” manufactured by Toray Industries, Ltd., film thickness = 5 μμπι), and a sheet-like sheet obtained in Production Example 2 of the adhesive Adhesive, polar group-containing resin ((Α-4): Sumitomo Chemical Co., Ltd. Mesacrylic resin “Sumipex ΗΤ01Χ”, film thickness = 30 Ομπι) and Teflon sheet are laminated sequentially from the bottom, Using “Heat Shields Yuichi TP-701_Β” manufactured by Co., Ltd., heat-press at a temperature of 180 ℃ and a pressure of 0.294 MPa (3 kg / cm ² ) for 3 seconds from above. (A-3) A laminate comprising the Z adhesive layer Z (A-4) was obtained. Example 12, Comparative Examples 7 and 8

Polar group-containing resin (A-4) is replaced by olefin resin (B-2), Sumitomo Chemical

(A-2) Adhesive layer Z, except that the polypropylene film “Noblen AY564” (film thickness = 2) was changed.

A laminate comprising (B-2) was obtained.

(Measurement method of peeling strength): The obtained laminate was cut into test pieces of length 100 and width 10 and the peeling rate was 180 at a peeling rate of 10 Omm / min using “Autograph AGS_20 kNG” manufactured by Shimadzu Corporation. ° Peel strength at the time of peeling was measured. The results are shown in Table 2.

Table—2

(1)

(2)

Examples 13 to 15: Comparative Examples 9 to 11

(1) Preparation of Adhesive 〇: Take the modified block copolymer “Tuftec Ml 9 13” and toluene in a flask in the weight ratio shown in Table 3, and stir for 1 hour while keeping the temperature at 80 ° C. To obtain a toluene solution containing 20% by weight of the modified block copolymer. A liquid was obtained. Organic peroxides 1 and 2 were added to the obtained toluene solution at the weights shown in Table 3 and dissolved at room temperature to obtain an adhesive. The organic peroxides 1 and 2 are as follows.

1: 1, 1 _bis (t-Butyloxy) -3,3,5-trimethylcyclohexane ("Perhexa 3M" manufactured by NOF Corporation)

2: Benzoyl peroxide ("Nipper BW" manufactured by NOF Corporation)

(2) Example of manufacturing a laminate: The adhesive obtained in (1) on the surface of the olefin resin “Noblen AY564 (injection molded sheet, sheet thickness = 2 mm, manufactured by Sumitomo Chemical Co., Ltd.)” Is applied using a “Doctor Blade” manufactured by Toyo Seiki Seisakusho Co., Ltd., and then an acrylic resin is applied to the surface of the obtained adhesive layer with an intermediate paint for repairing automobiles (Holtzker Paint “Toyo Seiki”). Evening 164 Silver I, manufactured by Holz) was spray applied. Next, a laminate was obtained by thermosetting under the conditions described in Table 3. The thickness of the adhesive layer of the obtained laminate was 15 µm, and the thickness of the paint was 3 µm.

(3) Solvent resistance test: Each of the laminates obtained in the previous section was cut into a shape of 70 mm x 4 Omm, immersed in commercial regular gasoline at 20 mm for 10 minutes, and the peeling state of the paint on the laminate was visually observed. Observations were made, and the results were categorized as follows and the results are shown in Table 3.

刼: The paint did not peel off.

: Paint peeled off. Table-3

Preparation example of resin composition Ρ

Set the small batch type kneader ("Laboplast Mill R-100", manufactured by Toyo Seiki Seisaku-sho, Ltd.) to a barrel temperature of 230 kPa, and rotate the rotor to 60 i "pm. And resin (II) were charged in parts by weight shown in Table 4 and mixed for 5 minutes. Resin (I) and resin (II) shown in Table 4 were hydrogenated or modified block weight of the following block copolymer. Coalescing was used.

I-1: Hydrogenated product of styrene · butadiene · styrene block copolymer

“Septon 800 7” manufactured by Kuraray Co., Ltd.

1-2: hydrogenated styrene · isoprene · styrene block copolymer

"Septon 2000" Kuraray Co., Ltd.

1-3: Modified block copolymer "Tuftec Ml 9 13" made by graft polymerization of maleic anhydride to hydrogenated styrene / butadiene / styrene block copolymer Asahi Kasei Kogyo Co., Ltd. 1-4: Styrene, butadiene, styrene block copolymer "Clearylene 530 L" manufactured by Denki Kagaku Kogyo Co., Ltd.

Ku resin (II)>

II-1: Polystyrene

"Polystyrene G490X" Nippon Polystyrene Co., Ltd.

II-1: Styrene / maleic anhydride copolymer

“Dy lark D232” manufactured by ARCO Chemical Co., Ltd. Acid value = 255 mg CH ₃₀ Na / g (the grafting amount of maleic anhydride is 7.0 parts by weight with respect to 100 parts by weight of styrene).

Spread Toray Co., Ltd. PET film `` Lumirror M351 '', film thickness = 5μμπι) on the Teflon sheet, place the resin composition obtained in the previous section on it, and glue it with a press set at 230mm. Hot pressing was performed so that the agent layer became 5 μμπι.

Next, on the surface of the adhesive layer, a polar group-containing resin sheet ((Α-4): Methacrylic resin (“SUMIPEX ΗΤ0 IX” manufactured by Sumitomo Chemical Co., Ltd., JISK 7210 (230 MF R = 2. Og / 10 min) measured according to 3800 g), and film thickness = 30 Ομπι). Then, apply “Heat Seal Tester TP-701_Β” manufactured by Tester Sangyo Co., Ltd. A laminate comprising a PET film Z adhesive layer Z polar group-containing resin sheet (A-4) was obtained by thermocompression bonding at a compression temperature of 180 ° C and a pressure of 0.294 MPa for 3 seconds.

The obtained laminate was cut into test pieces 100 length in length and 1 Omm in width, and peeled at 180 ° peeling rate at a peeling rate of 10 Omm / min using “Autograph AGS-20 kNG” manufactured by Shimadzu Corporation. When the strength was measured, it was 14.5N / 10IM. Examples 17-35, Comparative Examples 12 and 13)

Except that the resin composition of the adhesive, the adherend, and the compression temperature are set to the conditions shown in Table 4, the same procedure as in Example 16 was carried out to obtain a PET film Z adhesive layer. A laminated body was obtained.

The following resin sheet was used as the adherend.

A-4: Mei-acrylic resin

"Sumipex HT0 IX" manufactured by Sumitomo Chemical Co., Ltd.

MFR = 2. Og / 10min (230 刼, 3800g according to JISK 7210)

A-1: Biaxially stretched PVA film manufactured by Toseguchi Co., Ltd.

"VINYLON FILM LH # 17R", Film thickness = 17μΐη A-5: Olefin resin

"Noblen AY 564" manufactured by Sumitomo Chemical Co., Ltd.

MFR = 15g / 10min (230 刼, 2160g according to JISK 7210) was obtained by injection molding using a 5.5οζ injection molding machine at a cylinder set temperature of 230 刼 and a mold temperature of 50 刼 10. Ommxl 50 Flat plate having a thickness of 2 mm Table 4 shows the peel strengths of the laminates obtained in Example 16 35, Comparative Example 12 and Comparative Example 13. The peel strength was measured in the same manner as in Example 16.

In each case, the PET film did not peel between the adhesive layers, but did peel between the adhesive layer Z-polar group-containing resin sheet or the adhesive layer or the olefin resin film.

Table 1 4

Adhesive Compression peeling Resin (I) Resin (II) Temperature strength Kouichi 1 Kouichi 2 Kouichi 3 刼 4 刼 1 1 刼 _1 body (刼) (N / 10mm) Example 16 100 5.3 Α-Α 1丄 o onU

Example 17 100 11.1 Α-4 1 ΟΛ Λ A 丄

Example 18 100 11.1 Α— 4 1 on Λ A 丄 Example 19 100 11.1 A-4 oj 1 A 1 Example 20 100 5.3 1 Λ

丄 1 Top Q.1 丄 Example 21 100 11.1 A— 1 1

丄 on 17 1 Example 22 100 17.6 A-1 1 OA I ICD.DC Example 23 100 5.3 Α— 1 丄 1 丄 7 ί, 1 丄 Example 24 100 11.1 Δ-1 1 n I C Q

丄 U

Example 25 100 17.6 Α 1 1 1 C Λ

1ZUn

丄 0 笔 Example 26 100 5.3 ϋ 1 on

丄 4.b Example 27 100 11.1 r O 1 ΟΛ

丄丄 y Example 28 100 11.1 1 on

丄 3.1 Example 29 100 11.1 Α— 5 1 丄 on

Example 30 100 5.3 r 1 ΟΛ I C O

丄 8U 丄 t) Example 31 100 11.1 A-- 51 o QA 1 A Example 32 100 17.6 A- 5 180 13.1 Example 33 100 5.3 A- 5 180 15.4 Example 34 100 11.1 A-5 180 14.3 Example 35 100 17.6 A- 5 180 13.0 Comparative Example 12 100 5.3 A-1 120 × 0.1 Comparative Example 13 100 A-5 180 × 0.1

Claims

The scope of the claims

1. An adhesive consisting of a solvent and a modified block copolymer obtained by graft-polymerizing maleic anhydride onto a hydrogenated product of styrene 'conjugated gen-styrene block copolymer and 20% by weight of the copolymer An adhesive having a viscosity in a toluene solution of 10 to 2000 mPa-s.

2. A modified block copolymer obtained by graft polymerization of maleic anhydride to a hydrogenated product of styrene, conjugated gen, and styrene-based block copolymer, and two types of the modified block copolymer having different melt flow rates. A resin composition characterized by being mixed at an MFR ratio of 3 to 2,000.

3. The resin composition according to claim 1, wherein the two kinds of modified block copolymers having different melt flow rates have the following melt flow rates (III) and (IV), respectively.

(III) 30-200 (g / 10min)

(IV) 0.1 ~: L 0 (gZl 0 min)

4. An adhesive comprising the resin composition according to claim 2 as an active ingredient.

5. The adhesive according to claim 4, wherein the adhesive contains a solvent.

6. The weight ratio of the modified block copolymer having a higher melt flow rate than the other to the modified block copolymer having the lower melt flow rate is 95%.

The adhesive according to claim 5, wherein the adhesive ratio is 5 to 45/65.

7. The adhesive according to claim 4, which is in the form of a sheet or a film.

8. The weight ratio of the modified block copolymer having a higher melt flow rate than the other to the modified block copolymer having the lower melt flow rate is 45 6

The adhesive according to claim 7, wherein the adhesive is 5 to 5Z95.

9. A resin composition comprising the following resin (I) and resin (II).

(I): hydrogenated styrene, conjugated gen, styrene-based block copolymer, and Z or styrene, conjugated gen, styrene-based block copolymer Block copolymer obtained by graft polymerization of maleic anhydride to hydrogenated product

(II): Styrene resin

10. The resin composition according to claim 9, wherein the content of the resin (II) is 1 to 30 parts by weight based on 100 parts by weight of the resin (I).

11. The resin composition according to claim 10, wherein the styrene-based resin (II) is polystyrene and / or a styrene-α, β-monounsaturated carboxylic acid copolymer.

12. An adhesive comprising the resin composition according to any one of claims 9 to 11 as an active ingredient.

13. The method according to claim 12, wherein the adhesive is a solution containing a solvent.

14. The adhesive according to claim 12, wherein the shape of the adhesive is a shape of a sheet or a film.

15. The grafted amount of maleic anhydride in the modified block copolymer obtained by graft-polymerizing maleic anhydride to the hydrogenated product of styrene, conjugated gen, and styrene-based block copolymer is based on 100 parts by weight of the hydrogenated product. The adhesive according to any one of claims 1, 4 to 8, and 12 to 14, wherein the adhesive is 0.1 to 5 parts by weight.

16. The hydrogenated product of a styrene / conjugated / styrene / styrene block copolymer is a hydrogenated product obtained by hydrogenating at least 80% of the main chain olefin bond of the copolymer. The adhesive according to any one of 1, 4 to 8, and 12 to 14.

17. The adhesive according to any one of claims 1 and 4 to 8, wherein the adhesive contains at least one kind of pigment selected from titanium oxide, zinc oxide, and carbon black.

18. The adhesive according to any one of claims 1, 4 to 6, 12 and 13, wherein the solvent is at least one selected from toluene, xylene and water.

19. Maleic anhydride in modified block copolymer obtained by graft polymerization of maleic anhydride to hydrogenated styrene, conjugated gen, styrene block copolymer 3. The resin composition according to claim 2, wherein the graft amount is 0.1 to 5 parts by weight based on 100 parts by weight of the hydrogenated product.

20. The hydrogenated product of styrene / conjugated / styrene / styrene block copolymer is a hydrogenated product obtained by hydrogenating at least 80% of the main chain olefin bond of the copolymer. 3. The resin composition according to 2.

21. An adhesive containing a modified block copolymer obtained by graft-polymerizing maleic anhydride to a hydrogenated product of styrene, conjugated gen, and styrene-based block copolymer, an organic peroxide, and a solvent is represented by the following general formula: A thermosetting method, wherein C represented by (1) is thermoset under conditions of 2.5 to 12.

C = (AxB) Zl 000 (1)

(In the formula, A represents the heating temperature (刼) during thermosetting, and B represents the heating time (minutes) during thermosetting.)

22. The grafted amount of maleic anhydride in the modified block copolymer is 0.1 to 5 parts by weight with respect to 100 parts by weight of the hydrogenated styrene • conjugated · styrene-based block copolymer. 22. The thermosetting method according to claim 21, wherein

23. The hydrogenated product of styrene / conjugated / styrene / styrene block copolymer is a hydrogenated product obtained by hydrogenating at least 80% of the main chain olefin bond of the copolymer. 23. The thermosetting method according to 21 or 22.

24. The thermosetting method according to any one of claims 21 to 23, wherein the content of the organic peroxide per 1 kg of the modified block copolymer is 0.005 mol to 0.1 mol.

25. The thermosetting method according to any one of claims 21 to 24, wherein the content of the solvent in the adhesive is 150 to 2000 parts by weight based on 100 parts by weight of the modified block copolymer.

26. The thermosetting method according to any one of claims 21 to 25, wherein the solvent is at least one selected from toluene, xylene and water.

27. A laminate having the following (a) and (b) laminated via an adhesive layer, wherein the adhesive layer is obtained from the adhesive according to any one of claims 1 and 4 to 8. A laminated body characterized in that it is a layer formed. (a) Polar group-containing resin.

(b) olefin resin.

28. (a) is at least one selected from a polyester resin, a polyamide resin, a polycarbonate resin, an acrylic resin, a melamine resin, a styrene-acrylonitrile copolymer resin, a polyvinyl alcohol resin and a urethane resin. 28. The laminate according to claim 27, which is a polar group-containing resin.

29. The laminate according to claim 27 or 28, wherein (a) is a polar group-containing resin having at least one form selected from paints, films and sheets.

30. The laminate according to claim 27, wherein (b) is polypropylene.

31. A laminate, wherein an adherend is adhered by the thermosetting method according to any one of claims 21 to 26.

32. The adherend is characterized in that it is at least one selected from metals, cellulosic polymer materials, olefinic resins, hydrogenated hydrogenated olefinic bonds of the olefinic resin, and polar resins. 32. The laminate according to claim 31, wherein

33. A laminate comprising the adhesive according to any one of claims 12 to 14 and an adherend.

34. The adherend is at least one adherend selected from a metal, a cellulosic polymer material, an olefin resin, a hydrogenated hydrogenated olefin bond of the olefin resin, and a polar group-containing resin. 34. The laminate according to claim 33, wherein:

35. The laminate according to claim 33, wherein the shape of the adherend is at least one type selected from paints, films, and sheets.