JP2000167990A - Composite molded object - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a plastic composite molded object wherein a primary layer comprising a thermoplastic elastomer and a secondary layer comprising hard plastic are thermally fused strongly. SOLUTION: A plastic composite molded object is formed by fusing a primary layer comprising a thermoplastic elastomer based on an epoxidized diene block copolymer obtained by epoxidizing a vinyl aromatic-diene block copolymer consisting of a block comprising a vinyl aromatic compd. and a block comprising a conjugated diene compd. or a partial hydrogenated system thereof and a secondary layer comprising hard plastic with bending modulus of 1,000 kg/cm2 or more in JIS-K7203.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a plastic composite molded article composed of a layer composed of a thermoplastic elastomer mainly composed of an epoxidized diene-based block copolymer which maintains flexibility and a layer composed of a hard plastic.
This molded body can be obtained by injection molding, extrusion molding, blow molding, etc., and a turntable for a CD-ROM driver,
It is used for side moldings of automobile doors, grips and handles for electric products, spacers, packing, airbag covers, push buttons on personal computer keyboards, noise reduction gears, and sports shoe soles.

[0002]

2. Description of the Related Art Hitherto, multi-layer molding of a hard plastic and a thermoplastic elastomer has been performed. By this multi-layer molding, in addition to utilizing the function of the elastomer such as the feel of the elastomer as a skin material and the difficulty of sliding, the elastomer can be integrally molded as a sealing material and a packing material, and a molded article excellent in waterproofness can be obtained. .

[0003] Since hard plastics and thermoplastic elastomers are dissimilar materials, a method of using an adhesive or a method of fitting has conventionally been used for their integration. However, when an adhesive is used, it is often difficult to obtain sufficient adhesive strength because the properties of both layers are often greatly different. Also,
Since an organic solvent is used in most cases, the working environment is deteriorated, and in some cases, dissolution, swelling, cracks and the like of the member to be bonded are caused by the solvent, which is not preferable. Also, when using the fitting method, since both members are not completely adhered, peeling of the members,
Desorption occurs. Further, a mold for molding each member is complicated and expensive, and furthermore, the fitting operation is complicated. Therefore, in recent years, integration by heat fusion has been proposed.

For example, in Japanese Patent Publication No. 4-2412, (a) at least two polymer blocks A mainly composed of a vinyl aromatic compound and at least one polymer block B mainly composed of a conjugated diene compound are disclosed. A multi-layer injection-molded article comprising a hydrogenated block copolymer elastomer obtained by hydrogenating a block copolymer consisting of: and (a) a resin selected from a polyolefin resin, a polystyrene resin, and an ABS resin has been proposed. I have. The hydrogenated block copolymer elastomer used here does not have a functional group that enhances the adhesiveness, and has a limited heat-fusing property.

Further, Japanese Patent Application Laid-Open No.
JP-A-139241, JP-A-3-100045, JP-A-6-65467 and JP-A-6-107898, a thermoplastic resin obtained by combining a thermoplastic elastomer such as a styrene-based thermoplastic elastomer having no functional group with another thermoplastic elastomer. A method for producing a composite molded article of an elastic composition and a hard resin selected from polycarbonate, nylon 11, nylon 12, ABS resin, and PMMA resin has been proposed. There is no functional group that enhances the adhesiveness, and the heat fusibility is not sufficient.

Further, a method for obtaining a composite molded article comprising a polypropylene member and a thermoplastic elastomer member is disclosed in Japanese Patent Laid-Open Publication No. Hei.
139232 proposes. In this method, a styrene-ethylene butylene-styrene block copolymer (SEB) is used as a thermoplastic elastomer.
S) is used, and the adhesive strength with the polypropylene member is sufficient. However, the styrene-ethylenebutylene-styrene block copolymer has insufficient bonding strength with polar resins such as polycarbonate, and the method described in the above publication is limited in its application.

Further, in Japanese Patent Application Laid-Open No. 8-59954, (A) a polymer block A mainly composed of at least one vinyl aromatic compound and a polymer block B mainly composed of at least one conjugated diene compound are disclosed. Hydrogenated block copolymer obtained by hydrogenating a block copolymer comprising: and / or a modified hydrogenated hydrogenated copolymer obtained by bonding a molecular unit containing a carboxylic acid group or a derivative group thereof to the hydrogenated block copolymer. Elastomer, (a) a thermoplastic elastomer comprising a polystyrene resin and / or a polyphenylene polymer, and (c) an ethylene-unsaturated carboxylic acid ester copolymer are laminated to a resin mainly composed of (a). Compositions have been proposed. The modified hydrogenated block copolymer used here has been modified with a carboxylic acid group or a derivative group thereof, and the heat-fusing property has been improved by the functional group. There is a demand for a heat-fusible resin that can be fused to a wider range of resins.

[0008]

An object of the present invention is to provide a plastic composite molded article in which a primary layer made of a thermoplastic elastomer and a secondary layer made of a hard plastic are strongly heat-sealed.

[0009]

Means for Solving the Problems From the above viewpoints, the present inventors have searched and studied an epoxidized block copolymer compound having an epoxy as a functional group. The combination of a layer made of a thermoplastic elastomer and a layer made of a hard plastic having a flexural modulus of not less than 1,000 kg / cm2 according to JIS-K7203 can provide a multilayer molded body utilizing excellent heat-fusibility. Found and arrived at the present invention.

[0010] The plastic composite molded article of the present invention uses heat fusion without using an adhesive or mating for composite integration of a primary layer mainly composed of a thermoplastic elastomer and a secondary layer composed of a hard plastic. It is characterized in that it is used and has sufficient strength.

[0011]

BEST MODE FOR CARRYING OUT THE INVENTION A plastic composite molded article of the present invention comprises a vinyl aromatic-diene block copolymer composed of a block composed of a vinyl aromatic compound and a block composed of a conjugated diene compound, or a partially hydrogenated product thereof. It is molded from a primary layer made of a thermoplastic elastomer mainly composed of an epoxidized diene-based block copolymer and a secondary layer made of a hard plastic.

In forming the primary layer made of the thermoplastic elastomer in the present invention, an epoxidized diene-based block copolymer may be used alone, but an amino group, a carboxylic anhydride group, a phenolic hydroxyl group, The epoxidized block copolymer is contained by containing 0.01 to 30 parts by weight of a polyfunctional compound containing at least two functional groups which react with an epoxy group selected from a carboxyl group and a hydroxyl group in a molecule. Due to the reaction with the epoxy group in the heat-fusible composition thus obtained, the heat-fusibility is further enhanced, and a stronger composite molded body can be obtained.
At least two functional groups of the multifunctional compound may be the same or different. The molecular weight of the polyfunctional compound is not particularly limited, and typically includes a polymer compound having a weight average molecular weight of about 1,000,000 to 2,000,000.

Hereinafter, the polyfunctional compound will be described.

Specific examples of the compound containing two or more amino groups in one molecule are shown below. For example, aliphatic diamines such as 1,6-hexamethylenediamine, trimethylhexamethylenediamine, 1,4-diaminobutane, 1,3-diaminopropane, ethylenediamine, polyetherdiamine; hexamethylenediaminecarbamate;
Aliphatic diamine carbamates such as ethylenediamine carbamate; diethylenetriamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, ethylaminoethylamine, methylaminopropylamine, 2-hydroxyethylaminopropylamine, aminoethylethanolamine, 1,3 Aliphatic polyamines such as -bis (3-aminopropoxy) -2,2-dimethylpropane, 1,3,6-trisaminomethylhexane, iminobispropylamine, methyliminobispropylamine and bis (hexamethylene) triamine An alicyclic poly such as mensendiamine, N-aminoethylpiperazine, 1,3-diaminocyclohexane, isophoronediamine, bis (4-amino-3-methylcyclohexyl) methane; Amines; aliphatic polyamines having an aromatic ring such as m-xylylenediamine, tetrachloro-p-xylylenediamine; m-phenylenediamine, diaminodiphenyl ether, 4,4′-methylenedianiline, diaminodiphenylsulfone, benzidine; 4,4'-bis (o-toluidine), 4,4'-thiodianiline, o-phenylenediamine, dianisidine, methylenebis (o-chloroaniline), 2,4-toluenediamine, bis (3,4-diaminophenyl) Sulfone, diaminoditolyl sulfone, 4-chloro-o-
Phenylenediamine, 4-methoxy-6-methyl-m-
Aromatic amines such as phenylenediamine and m-aminobenzylamine; 1,3-bis (γ-aminopropyl)-
Examples thereof include polyamines containing silicon such as 1,1,3,3-tetramethyldicycloxane. An amine-modified silicone oil; a butadiene-acrylonitrile copolymer whose terminal functional group is an amine; N, N, N ′,
N'-tetramethylhexamethylenediamine, N, N,
Tertiary amine compounds such as N ', N ", N"-pentamethyldiethylenetriamine; ethylene units such as a copolymer of ethylene and N, N-dimethylaminoethyl methacrylate and α, β-unsaturated carboxylic acid N, N Ethylene copolymer comprising -dialkylaminoalkyl ester units; from ethylene units such as copolymers of ethylene and N, N-dimethylaminopropylacrylamide and N, N-dialkylaminoalkyl α, β-unsaturated carboxylic acid amide units Ethylene copolymers; dihydrazide compounds such as succinic dihydrazide, adipic dihydrazide, isophthalic dihydrazide, eicosane diacid dihydrazide; diaminomaleonitrile; and solamin.

Examples of the polyfunctional compound having two or more carboxylic acid anhydride groups in one molecule include an ethylene copolymer comprising ethylene units and maleic anhydride units, and a copolymer of isobutylene and maleic anhydride. And copolymers of styrene and maleic anhydride. These copolymers further contain α, β-unsaturated carboxylic acid alkyl esters or carboxylic acid vinyl esters as copolymer components. You may. For example, acrylic acid such as methyl acrylate, ethyl acrylate, butyl acrylate, methyl methacrylate, ethyl methacrylate, butyl methacrylate, etc., alkyl esters of methacrylic acid, vinyl acetate, vinyl propionate and the like are contained as copolymer components. It may be. Further, trimellitic anhydride, pyromellitic anhydride, ethylene glycol bis (anhydrotrimellitate) and the like can be mentioned.

Examples of the polyfunctional compound having two or more phenolic hydroxyl groups in one molecule include catechol, resorcin, hydroquinone, novolak phenol resin, bisphenol A, and a phenolic hydroxyl group urethane prepolymer at both ends. be able to.

Examples of the polyfunctional compound having two or more hydroxyl groups in one molecule include saponified ethylene-vinyl acetate copolymer, poly (oxytetramethylene) glycol, poly (oxypropylene) Glycol, poly (ethylene adipate) glycol, polyethylene glycol, polyvinyl alcohol and the like.

Examples of the polyfunctional compound having two or more carboxyl groups in one molecule include oxalic acid, succinic acid, adipic acid, azelaic acid, sebacic acid, dodecanedicarboxylic acid, carballylic acid, cyclohexanedicarboxylic acid, Cyclopentanedicarboxylic acid, ethylene-acrylic acid copolymer, ethylene-methacrylic acid copolymer, ethylene-acrylic acid-acrylic acid methyl ester copolymer, ethylene-acrylic acid-ethyl acrylate copolymer, ethylene-acrylic Acid-butyl acrylate copolymer, ethylene-acrylic acid-vinyl acetate copolymer, ethylene-methacrylic acid-methyl methacrylate copolymer, ethylene-methacrylic acid-
Methacrylic acid ethyl ester copolymer, ethylene-methacrylic acid-butyl methacrylate copolymer, ethylene-methacrylic acid-vinyl acetate copolymer and other aliphatic polycarboxylic acids, terephthalic acid, isophthalic acid, orthophthalic acid, Examples include aromatic polycarboxylic acids such as naphthalenedicarboxylic acid, biphenyldicarboxylic acid, trimesic acid, and trimellitic acid, and aliphatic polycarboxylic acids are particularly preferably used.

As a polyfunctional compound, different functional groups such as one or more carboxyl groups and one or more functional groups selected from an amino group, a carboxylic anhydride group, a phenolic hydroxyl group and a hydroxyl group in one molecule are used. It also includes those having a plurality. For example, specific examples thereof include 4-aminobutyric acid, 6-aminohexanoic acid, 12-aminododecanoic acid,
4-hydroxybutyric acid, 6-hydroxyhexanoic acid, 12
-Hydroxydodecanoic acid, 5-hydroxybarbituric acid, 5-aminobarbituric acid, 5-hydroxyiminobarbituric acid, tris (dimethylaminomethyl) phenol and the like. Examples of the polyfunctional compound having one or more phenolic hydroxyl groups and amino groups in one molecule include o-aminophenol and m-aminophenol. It should be noted that the above-mentioned polyfunctional compounds may be used in combination.

In the present invention, the blending ratio of the polyfunctional compound must be adjusted depending on the reactivity with the epoxy group, but is preferably 0.01 to 30% by weight, and more preferably 0.1 to 20% by weight. Is particularly preferred.
If the blending ratio of the polyfunctional compound exceeds 30% by weight, an excessive amount of epoxy reaction occurs and a gel is formed, which is not preferable.

The above-mentioned diembroic rock copolymer used in the present invention is a block copolymer comprising a polymer block mainly composed of a vinyl aromatic compound and a polymer block mainly composed of a conjugated diene compound. Wherein the copolymerization ratio (on a molar basis) of the vinyl aromatic compound and the conjugated diene compound is from 5/95 to 70/30, particularly from 10/90 to
A copolymerization ratio of 60/40 is preferred. The number average molecular weight of the block copolymer used in the present invention is 5,000 to 60.
0000, preferably 10,000 to 500,000
And the molecular weight distribution [the ratio (Mw / Mn) of the weight average molecular weight (w) to the number average molecular weight (Mn)] is 10 or less. The molecular structure of the block polymer may be linear, branched, radial, or any combination thereof. For example, XYX, YXYX,
It is a vinyl aromatic compound (X) block-conjugated diene compound (Y) block copolymer having a structure such as (XY-) 4Si or XYXYX. Further, the unsaturated bond of the conjugated diene compound of the diene-based block copolymer is
It may be partially hydrogenated.

Examples of the vinyl aromatic compound constituting the diene block polymer include styrene, α-methylstyrene, vinyltoluene, p-tertiary butylstyrene,
One or more of divinylbenzene, p-methylstyrene, 1,1-diphenylstyrene and the like can be selected, and styrene is particularly preferred. As the conjugated diene compound, for example, butadiene, isoprene, 1,
One of 3-pentadiene, 2,3-dimethyl-1,3-butadiene, piperylene, 3-butyl-1,3-octadiene, phenyl-1,3-butadiene, and the like;
Alternatively, two or more are selected, and among them, butadiene, isoprene and a combination thereof are preferable.

As a method for producing the diene-based block copolymer used in the present invention, any production method having the above-mentioned structure can be adopted. For example, Japanese Patent Publication No. 40-23798, Japanese Patent Publication No. 47-3252, Japanese Patent Publication No. 48-2423, Japanese Patent Application No. 49-105970, Japanese Patent Application No. 50-27094, Japanese Patent Publication No. 46-32415,
JP-A-59-166518, JP-B-49-36957.
No., JP-B-43-17979, JP-B-46-3241
No. 5, JP-B-56-28925, etc., a vinyl aromatic compound-conjugated diene compound block copolymer can be synthesized in an inert solvent using a lithium catalyst or the like. Furthermore, Japanese Patent Publication No. 42-87
No. 04, JP-B-43-6636, or JP-A-59-133203, by which hydrogenation is carried out in an inert solvent in the presence of a hydrogenation catalyst to provide a portion to be used in the present invention. A hydrogenated block copolymer can be synthesized.

The epoxidized diene-based copolymer used in the present invention can be obtained by epoxidizing the diene-based block copolymer.

The epoxidized diene-based block copolymer in the present invention can be obtained by reacting the above-mentioned block copolymer with an epoxidizing agent such as a hydroperoxide or a peracid in an inert solvent. Examples of peracids include formic acid, peracetic acid, and perbenzoic acid.

In the case of hydroperoxides, a catalytic effect is obtained by using a mixture of tungstic acid and caustic soda with hydrogen peroxide, an organic acid with hydrogen peroxide, or molybdenum hexacarbonyl with tertiary butyl hydroperoxide. be able to.

There is no strict limit on the amount of epoxidizing agent,
The optimal amount in each case will depend on variables such as the particular epoxidizing agent used, the degree of epoxidation desired, the particular block copolymer used, and the like.

The obtained epoxidized diene copolymer is isolated by an appropriate method, for example, a method of precipitating with a poor solvent, a method of throwing the polymer into hot water with stirring and distilling off the solvent, or a method of directly removing the solvent. It can be performed by a desolvation method or the like.

The epoxy equivalent of the obtained epoxidized (hydrogenated) diene-based block copolymer is preferably from 320 to 8
000.

The epoxidized diene-based block copolymer can be formed into an arbitrary shape by a known molding method such as, for example, extrusion molding, injection molding, blow molding or the like to form a layer made of a thermoplastic elastomer. .

The hard plastic used for the secondary layer composed of the hard plastic layer of the plastic composite molded article of the present invention has a flexural modulus of 1,000 according to JIS-K7203.
0 kg / cm 2 or more. If the flexural modulus of the hard plastic is less than 1,000 kg / cm 2, the mechanical strength of the obtained plastic composite molded article will be inferior, which is not preferable.

Examples of such hard plastics include low-density polyethylene, high-density polyethylene, linear polyethylene, linear low-density polyethylene, polypropylene, ethylene-propylene random copolymer, ethylene-propylene block copolymer, and attack. Tick polypropylene, ethylene-vinyl acetate copolymer, ethylene-acrylic acid copolymer, ethylene-methacrylate copolymer, ethylene-unsaturated carboxylic acid copolymer metal ion crosslinked resin, ethylene-vinyl chloride copolymer, ethylene −
Propylene-diene copolymer, ethylene-vinyl alcohol copolymer, saponified ethylene-vinyl acetate copolymer,
Chlorosulfonated polyethylene, ethylene-vinyl chloride-1,2-chloroethylene copolymer, chlorinated polypropylene, vinyl chloride- (ethylene-vinyl acetate copolymer)
Graft copolymer, ethylene-maleic anhydride copolymer, ethylene-glycidyl methacrylate copolymer, ethylene-dimethylaminoethyl methacrylate copolymer, polymethylpentene, polybutene-1, amorphous polyolefin, polymer of cyclic olefin , Propylene and 1
Polyolefin resins such as copolymers with α-olefins such as butene; polystyrene, high-impact polystyrene, syndiotactic polystyrene;
Styrene resins such as ABS, ACS, AES, AS, SAN, MS; polyester resins such as polyethylene terephthalate and polybutylene terephthalate; nylon
6, nylon-6,6, nylon-12, nylon-
6, 12 and the like; polyamide resins; polycarbonate resins; polyacetal resins; polyphenylene ether resins and the like. These may be used alone or in combination of two or more.

Such a hard plastic can be formed into an arbitrary shape by a known molding method such as extrusion molding, injection molding, blow molding or the like to form a hard plastic layer.

In order to form a composite layer of a primary layer made of a thermoplastic elastomer mainly composed of the epoxidized diene block copolymer composition of the present invention and a secondary layer made of a hard plastic, an injection molding machine or an extrusion molding machine is used. And a blow molding machine or a molding machine combining these. Methods for performing composite molding of different materials using an injection molding machine include a method using a double (also called two-color) molding machine and a method using insert molding.

In the method using a double molding machine, a mold for the secondary layer (hard plastic) and a mold for the primary layer (thermoplastic elastomer) are arranged, and resins of different materials are alternately injected from two heating cylinders. I do. There are a core rotation type and a core back type in the double molding die. In the core rotation method, only the movable side of the secondary layer side mold is inverted by 180 °,
The secondary layer molded product that was molded first is moved to the cavity of the primary layer side mold to be injected next, and after clamping the mold, a space for filling the primary layer is formed, and the primary layer is filled in this part. To obtain a composite molded body. On the other hand, in the core back method, a slide core is incorporated in a mold, and the core is advanced first to inject the secondary layer, and then the core is retracted to inject the primary layer into the formed cavity, Heat fusion is performed to obtain a composite molded body. A system combining these systems has also been developed. Further, a method of simultaneously obtaining a composite molded body from two cylinders is being developed. The composite molded article of the present invention can be produced by a method using a double molding machine regardless of the method.

In the method by insert molding, the secondary layer is first molded, inserted into a mold on the primary layer side, the primary layer is injected, and the primary layer and the secondary layer are thermally fused. A composite molded article can be obtained. This method is characterized in that the cost of the mold can be reduced, but since the surface of the secondary layer is solidified, there is little molecular entanglement with the primary layer, and the heat fusion property is low. Even in this method, a composite molded body having high heat-fusibility is required. However, according to the present invention, a composite molded body having excellent heat-fusibility can be obtained by this insert molding method.

As a method for performing composite molding of different materials using an extruder, a known multilayer extruder is used. Further, as a method of performing composite molding of different materials using a blow molding machine, there are a multilayer extrusion blow molding method of forming a parison by co-extrusion and a multilayer injection blow molding method of forming a parison by co-injection. In these cases, the method using a known multilayer extrusion blow molding machine can be used for the multilayer molded article of the present invention regardless of the method.

[0038]

The present invention will be described in more detail with reference to the following examples.

(Preparation of Epoxidized Diene Block Copolymer) Preparation Example 1 A polystyrene-polybutadiene-polystyrene block copolymer a [styrene / butadiene] was placed in a jacketed reactor equipped with a stirrer, a reflux condenser, and a thermometer. (Weight ratio = 40/60) 300 g and ethyl acetate 1500 g were charged and dissolved. Then, 165 g of a 30 wt% solution of peracetic acid in ethyl acetate was continuously dropped, and an epoxidation reaction was carried out at 40 ° C. for 3 hours with stirring. The reaction solution was returned to room temperature, taken out of the reactor, and a large amount of methanol was added to precipitate a polymer. The polymer was separated by filtration, washed with water, and dried to obtain an epoxy-modified polymer. The obtained epoxidized diene block copolymer is referred to as epoxidized diene block copolymer A-1 (epoxy equivalent of the copolymer is 490).

Preparation Example 2 A polystyrene-polyisoprene-polystyrene block copolymer [styrene / butadiene weight ratio = 20/80] was placed in a jacketed reactor equipped with a stirrer and a thermometer.
300 g and cyclohexane 3000 g were charged and dissolved,
A temperature of 60 ° C. and di-P-tolylbis (1-
40 ml of a cyclopentadienyl) titanium / cyclohexane solution (concentration 1 mmol / l);
n-butyllithium solution (concentration 5 mmol / l)
8 ml and a mixture obtained by mixing at 0 ° C. under a hydrogen pressure of 2.0 kg / cm 2 and adding a hydrogen partial pressure of 2.5 kg / cm 2.
For 60 minutes. The solvent was removed from the obtained partially hydrogenated polymer solution by drying under reduced pressure (the hydrogenation ratio of the entire butadiene portion was 80%). 300 g of this partially hydrogenated polymer and 1500 g of cyclohexane were charged and dissolved. Then, 200 g of a 30% by weight solution of peracetic acid in ethyl acetate was dropped continuously.
The epoxidation reaction was performed at 40 ° C. for 3 hours with stirring. The reaction solution was returned to room temperature, taken out of the reactor, and a large amount of methanol was added to precipitate a polymer. The polymer was separated by filtration, washed with water, and dried to obtain an epoxy-modified polymer. The obtained epoxidized diene-based block copolymer is referred to as polymer A-2 (epoxy equivalent of the copolymer is 460).

Preparation Example 3 A polystyrene-polyisoprene-polystyrene block copolymer [styrene / butadiene weight ratio = 30/70] was placed in a jacketed reactor equipped with a stirrer and a thermometer.
300 g and cyclohexane 2500 g are charged and dissolved,
Add nickel catalyst as hydrogenation catalyst, hydrogen partial pressure 15Kg
The reaction was carried out at 150 ° C./cm 2 for 3 hours. The solvent was removed from the obtained partially hydrogenated polymer solution by drying under reduced pressure (85% hydrogenation ratio of the whole butadiene portion). 300 g of this partially hydrogenated polymer and 1500 g of cyclohexane were charged and dissolved. Then, a 30% by weight solution of peracetic acid in ethyl acetate 1
50 g was continuously dropped, and an epoxidation reaction was performed at 40 ° C. for 3 hours with stirring. The reaction solution was returned to room temperature, taken out of the reactor, and a large amount of methanol was added to precipitate a polymer. The polymer was separated by filtration, washed with water, and dried to obtain an epoxy-modified polymer. The obtained epoxidized diene-based block copolymer is referred to as a polymer A-3 (epoxy equivalent of the copolymer is 750).

Examples 1 to 5 and Comparative Examples 1 and 2 Using a PS / E injection molding machine (manufactured by Nissei Plastic Industries Co., Ltd.), Table 1
Heat-melt the hard plastic shown in the above, length 60mm,
A secondary layer having a width of 25 mm and a thickness of 2 mm was formed. Then
Each of the thermoplastic elastomers having the compositions shown in Table 1 was heated and melted, and injected into the same mold as used to mold the hard plastic. The size was 60 mm in length, 25 mm in width,
A 2 mm thick primary layer was formed. After cooling, open the mold,
A plastic composite molded article in which the primary layer and the secondary layer were integrally fused was obtained. The interface between the secondary layer made of hard plastic and the primary layer made of the thermoplastic elastomer composition was evaluated for the plastic composite molded article thus obtained. Table 1 shows the results.

The hard plastics and thermoplastic elastomers corresponding to the abbreviations shown in Table 1 are as follows.

PC (polycarbonate): Teijin Limited
-Panlite L1225-PBT (polybutylene terephthalate): Polyplastics Co., Ltd., Duranex 400FP-GPPS (impact polystyrene): Daicel Chemical Industries, Ltd., Daicel Styrol R81-PP (polypropylene): Noblen D501 manufactured by Sumitomo Chemical Co., Ltd. B-1: Polyethylene oxide diamine, manufactured by Kawaken Fine Chemical Co., Ltd., PEO amine 6000 B-2: Ethylene-maleic anhydride-ethyl acrylate copolymer, Sumitomo Chemical Co., Ltd. Bondine AX Co., Ltd.
8000

[Table 1]

[0045]

According to the present invention, there is provided a primary elastomer comprising a thermoplastic elastomer mainly composed of an epoxidized diene block copolymer obtained by epoxidizing a vinyl aromatic-diene block copolymer or a partially hydrogenated product thereof. Layer and JIS-K
By subjecting a secondary layer made of a hard plastic having a flexural modulus of not less than 1,000 kg / cm @ 2 according to 7203 to thermal fusion, a composite molded article having excellent fusion strength can be obtained.

Claims (1)

[Claims] An epoxidized diene-based block copolymer obtained by epoxidizing a vinyl aromatic-diene-based block copolymer comprising a block comprising a vinyl aromatic compound and a block comprising a conjugated diene compound or a partially hydrogenated product thereof. A primary layer composed of a thermoplastic elastomer whose main component is coalescing,
Flexural modulus according to JIS-K7203 is 1,000kg
/ Plastic composite molded product obtained by fusing a secondary layer made of a hard plastic of not less than / cm2.