JP2886114B2 - Composite molded article and method for producing the same - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a non-olefin resin,
For example, a layer made of polycarbonate, acrylic resin, styrene resin, polyvinyl chloride, and modified polyphenylene ether resin, and a styrene-based thermoplastic elastomer (hereinafter referred to as a styrene-based thermoplastic elastomer having no stickiness in the molded product and having good mold release property during molding) , Which may be simply abbreviated as "styrene-based TPE") and a method for producing the same.

[0002]

2. Description of the Related Art Conventionally, since a non-olefin resin layer and a styrene-based thermoplastic elastomer (styrene-based TPE) are inferior in heat-fusibility, when a composite molded article of both is produced, a composite portion of the two is required. To provide irregularities, partially cover the core material with a surface material, make a hole in the core material, turn the surface material to the back side and physically join, or apply an adhesive to the joint part What serves as a component, for example, a primer or the like is applied to form a composite. Therefore, the obtained composite molded body has problems such as inferior bonding strength, complicated structure, and an increase in the number of steps. As an attempt to solve such a problem, Japanese Patent Laid-Open Publication No.
0, JP-A-1-139240, JP-A-2-139
No. 147306, JP-A-6-65467, styrene / ethylene / butylene / styrene copolymer (hereinafter may be simply abbreviated as "SEBS") or styrene / ethylene / propylene / styrene. There is known a method of adding a polyester-based thermoplastic elastomer, a polyamide-based thermoplastic elastomer, or a polyurethane-based thermoplastic elastomer to a polymer (hereinafter sometimes simply referred to as “SEPS”).

[0003]

However, such an SE
When only a polyester-based thermoplastic elastomer, a polyamide-based thermoplastic elastomer, or a polyurethane-based thermoplastic elastomer was added to BS or SEPS, the flexibility and moldability were poor, and the appearance of the obtained molded article was poor. In addition, in the case of adding a polyester-based thermoplastic elastomer, a polyamide-based thermoplastic elastomer, or a polyurethane-based thermoplastic elastomer to SEBS or SEPS, there is a sticky feeling on the surface of the molded product, and the releasability during molding is poor. There are problems such as dust easily adhering to the molded product and poor heat-fusibility with the non-olefin resin. For this reason, the shape of the product is restricted, and it is necessary to apply the coating immediately after molding on parts that require coating.

[0004]

[Means for Solving the Problems]

[Summary of the Invention] The present inventors have conducted intensive studies in order to solve the above-mentioned problems, and as a result, by using a specific styrene-based thermoplastic elastomer (styrene-based TPE), a non-olefin-based resin has been Completed the present invention by finding that a composite molded body with good adhesion, excellent flexibility and moldability, good appearance of the resulting molded body, and no stickiness on the molded product surface can be obtained. It is.

That is, the composite molded article of the present invention comprises at least one resin layer selected from the group consisting of polycarbonate, acrylic resin, styrene resin, polyvinyl chloride and modified polyphenylene ether and a styrene thermoplastic elastomer layer. The composite molded article is characterized in that the styrene-based thermoplastic elastomer layer comprises a base material containing the following components A to C. Component A: a hydrogenated styrene / conjugated diene block copolymer in which the conjugated diene is a mixture of isoprene and butadiene 30 to 90% by weight Component B: paraffinic oil 70 to 10% by weight Component C: Polyester At least one thermoplastic elastomer selected from the group consisting of a thermoplastic thermoplastic elastomer, a polyamide thermoplastic elastomer, and a polyurethane thermoplastic elastomer; 10 to 200 parts by weight based on 100 parts by weight of the total amount of the components A and B

A method for producing a composite molded article according to another aspect of the present invention comprises molding at least one resin selected from the group consisting of polycarbonate, acrylic resin, styrene resin, polyvinyl chloride, and modified polyphenylene ether. Then, in a method for producing a composite molded body using an insert injection molding method, a two-color injection molding method or a core back injection molding method for injection molding a styrene-based thermoplastic elastomer, the styrene-based thermoplastic elastomer comprises the following components: It is characterized by comprising a base material containing A to C. Component A: a hydrogenated styrene / conjugated diene block copolymer in which the conjugated diene is a mixture of isoprene and butadiene 30 to 90% by weight Component B: paraffinic oil 70 to 10% by weight Component C: Polyester At least one thermoplastic elastomer selected from the group consisting of a thermoplastic thermoplastic elastomer, a polyamide thermoplastic elastomer, and a polyurethane thermoplastic elastomer; 10 to 200 parts by weight based on 100 parts by weight of the total amount of the components A and B

DETAILED DESCRIPTION OF THE INVENTION [I] Layer Configuration of Composite Molded Article (1) Styrene-based thermoplastic elastomer layer (A) Styrene-based thermoplastic elastomer The styrene-based thermoplastic elastomer layer of the composite molded article of the present invention The physical properties of the styrene-based thermoplastic elastomer (styrene-based TPE) used are determined according to JIS-K6301.
It has an IS-A hardness of 98 or less, preferably 5 to 95, particularly preferably 10 to 90, and JIS-K6
Compression set (70 ° C., 22 hours) conforming to 301 is 8
0% or less, preferably 0 to 75%, particularly preferably 0 to 75%
70% is preferred. Such styrenic TPE
Are hydrogenated styrene / conjugated diene block copolymers, that is, hydrogenated styrene / isoprene / butadiene / styrene block copolymers whose conjugated diene is a mixture of isoprene and butadiene (hereinafter simply referred to as “water”). The composition may be abbreviated as "Additional S-BI-S".) As a basic component (the following component A), and further blended a paraffinic oil of a component B and a specific thermoplastic elastomer of a component C described below. Things.

<Component A: Hydrogenated product of styrene / conjugated diene block copolymer (hydrogenated S-BI-S)> Hydrogenated product of styrene / conjugated diene block copolymer which is a basic component of the styrene-based TPE As (hydrogenated S-BI-S), the conjugated diene is composed of a mixture of isoprene and butadiene, and the mixing weight ratio (isoprene / butadiene) is 99/1 to 1/99, preferably 90/10.
30/70, particularly preferably 80/20 to 40/60. If the content of isoprene is too low, the flexibility becomes poor, which is not preferable. On the other hand, if the content of isoprene is too high, the heat-fusibility becomes poor, which is not preferable. Hydrogenated product of the styrene / isoprene / butadiene / styrene block copolymer (hydrogenated S-BI-S)
Has a weight average molecular weight of 50,000 to 500,000,
It is preferably 60,000 to 400,000, particularly preferably 70,000 to 300,000, and has a styrene content of 5 to 50% by weight, preferably 8 to 45% by weight, particularly preferably 10 to 40% by weight, The content of 2-microstructure is less than 20%, preferably 0 to 17%, particularly preferably 1 to 15%, and the hydrogenation rate is 95% or more, preferably 97%.
It is important to use ~ 100% of the block copolymer. The content of the 1,2-microstructure is determined by the ratio of the catalyst species and butadiene during the production of the block copolymer, and the content is measured by NMR. If the content is larger than the above numerical range, the stickiness is increased. The problem that the property becomes worse arises.

Here, "weight average molecular weight" is a weight average molecular weight in terms of polystyrene measured by gel permeation chromatography (GPC) under the following conditions. (Conditions) Equipment: 150C ALC / GPC (manufactured by MILLIPORE) Column: AD80M / S (manufactured by Showa Denko KK) 3 solvents: o-dichlorobenzene Temperature: 140 ° C Flow rate: 1 ml / min Injection amount : 200 μl Concentration: 2 mg / ml (addition of 0.2% by weight of an antioxidant 2,6-di-t-butyl-4-methylphenol. The concentration was detected by an infrared spectrophotometer MIRAN 1A manufactured by FOXBORO. The weight average molecular weight of the hydrogenated S-BI-S was 500,00.
If it exceeds 0, the moldability is inferior, and 50,000
Those having a value of less than 0 are inferior in rubber elasticity and mechanical strength. Those having a styrene content of less than 5% by weight are inferior in mechanical strength, while those having a styrene content of more than 50% by weight are inferior in flexibility. Further, those having a hydrogenation rate of less than 95% are inferior in weather resistance and heat resistance. These hydrogenated S
For example, Japanese Patent Application Laid-Open No.
It is synthesized by the method described in JP-A-88114.

<Component B: Paraffinic Oil> The paraffinic oil used in the styrene-based thermoplastic elastomer layer of the composite molded article of the present invention has a kinematic viscosity at 40 ° C. of 2
0-800 centistokes (cst), preferably 5
0 to 600 cst, fluidity of 0 to -40 ° C, preferably 0 to -30 ° C, and flash point (COC) of 200 to 40
Oils at 0 ° C, preferably 250-350 ° C, are suitably used. The oil is generally a mixture of an aromatic ring, a naphthene ring and a paraffin ring,
Those having a paraffin chain carbon number of 50% by weight or more of the total carbon are called paraffinic oils, those having a naphthene ring carbon number of 30 to 45% by weight are called naphthenic oils, and those having an aromatic carbon number of 30. Those with more than% by weight are called aromatic oils and are classified. When oils other than paraffinic oils are used in the present invention among these various oils, the weather resistance is poor.

<Component C: Specific Thermoplastic Elastomer> The specific thermoplastic elastomer used for the styrene-based TPE of the composite molded article of the present invention includes polyester-based thermoplastic elastomer, polyamide-based thermoplastic elastomer, and polyurethane-based thermoplastic elastomer. At least one selected from the group of plastic elastomers is used.

Polyester Thermoplastic Elastomer The polyester thermoplastic elastomer is a block copolymer comprising an aromatic polyester block (a) and a non-aromatic polyester block (b). An aromatic polyester block (a) and a polyether Block copolymer composed of block (c) A block copolymer composed of the aromatic polyester block (a), the block (b) and the block (c), and the like.

The aromatic polyester block (a) is obtained by subjecting an aromatic dicarboxylic acid or an alkyl ester thereof to an aliphatic and / or alicyclic diol having 2 to 12 carbon atoms by an esterification reaction or a transesterification reaction. The resulting polyester oligomer. Specific examples include polyethylene terephthalate oligomer, polypropylene terephthalate oligomer, polybutylene terephthalate oligomer (polytetramethylene terephthalate oligomer), and polypentamethylene terephthalate oligomer.

As the aromatic dicarboxylic acid, those which are known as raw materials for polyesters, especially polyester elastomers can be used. Specifically, terephthalic acid, isophthalic acid, phthalic acid, 2,6-
Naphthalenedicarboxylic acid and the like can be mentioned. Among these, terephthalic acid and 2,6-naphthalenedicarboxylic acid are preferably used, and those containing terephthalic acid as a main component are particularly preferable. These may be used in combination of two or more. Examples of the alkyl ester of the aromatic dicarboxylic acid include dimethyl esters such as dimethyl terephthalate, dimethyl isophthalate, dimethyl phthalate, and 2,6-dimethyl naphthalate. Among these, dimethyl terephthalate and 2,6-dimethylnaphthalate are preferably used, and dimethyl terephthalate is particularly preferably used. These may be used in combination of two or more.

As the above-mentioned aliphatic and / or alicyclic diol having 2 to 12 carbon atoms, those known as raw materials for polyesters, in particular, raw materials for polyester elastomers can be used. Specifically, ethylene glycol, propylene glycol, trimethylene glycol, 1,4-
Butanediol, 1,4-cyclohexanediol,
1,4-cyclohexanedimethanol and the like can be mentioned. Among these, 1,4-butanediol and ethylene glycol are preferably used, and those containing 1,4-butanediol as a main component are particularly preferable. These may be used in combination of two or more. Further, in addition to the above, trifunctional diols, other diols and other dicarboxylic acids and esters thereof may be copolymerized in a small amount, and further, aliphatic or alicyclic dicarboxylic acids such as adipic acid. Or an alkyl ester thereof may be used as a copolymer component.

The non-aromatic polyester block (b)
Is a polyester oligomer obtained by condensing an aliphatic or alicyclic dicarboxylic acid with an aliphatic diol, a polyester oligomer synthesized from an aliphatic lactone or an aliphatic monool carboxylic acid, and as the specific examples of the former, Is an alicyclic dicarboxylic acid such as 1,4-cyclohexanedicarboxylic acid, 1,2-cyclohexanedicarboxylic acid, dicyclohexyl-4,4′-dicarboxylic acid or an aliphatic such as succinic acid, oxalic acid, adipic acid, sebacic acid, etc. Examples include polyester oligomers having a structure obtained by condensing one or more of dicarboxylic acids with one or more of diols such as ethylene glycol, propylene glycol, tetramethylene glycol, and pentamethylene glycol. Specific examples of the latter include a polycaprolactone-based polyester oligomer synthesized from ε-caprolactone, ω-oxycaproic acid, and the like.

As the polyether block (c), for example, a poly (alkylene oxide) glycol or the like having an average molecular weight of 400 to 6,000, preferably 500
To 4,000, particularly preferably 600 to 3,000. Specific poly (alkylene oxide) glycols include polyethylene glycol, poly (1,2,1,3-propylene oxide) glycol, poly (tetramethylene oxide) glycol, poly (hexamethylene oxide) glycol, ethylene oxide and propylene oxide Or a random copolymer or a block or random copolymer of ethylene oxide and tetrahydrofuran. The content of the non-aromatic polyester block (b) and the polyether block (c) is desirably 5 to 95% by weight, and particularly desirably 20 to 80% by weight in the resulting block copolymer. . When the content is less than 5% by weight, characteristics as a copolymer cannot be obtained. When the content is more than 95% by weight, it is difficult to obtain a polymer by condensation polymerization.

The polyester elastomer may be produced by first synthesizing the oligomer blocks composed of the components separately and then forming an ester bond between the oligomer blocks. As a method, for example, a method in which the block (b) is polymerized first, and further mixed with the component monomer of the block (a) and condensed, may be used. As such a polyester-based elastomer, commercially available polymer "Perprene P"
Or "Perprene S" (trade name, manufactured by Toyobo Co., Ltd.)
"Hytrel" (trade name, manufactured by Dupont Toray),
"Low Mod" (trade name, manufactured by Nippon GE Plastics Co., Ltd.), "Nichigo Polyester" (trade name, manufactured by Nippon Synthetic Chemical Industry Co., Ltd.), "Teijin Polyester Elastomer"
(Trade name of Teijin Limited) and the like.

Polyamide Thermoplastic Elastomer The above-mentioned polyamide thermoplastic elastomer has polyamide (nylon 6, 66, 11, 12 or the like) as a hard segment and polyether or polyester as a soft segment. For example, polyether block amide is a compound having a structure represented by the following general formula [I]. General formula [I]

[0020]

Embedded image

(PA in the formula represents a block of polyamide which is a hard segment, and PG represents a block of polyether which is a soft segment.) In the present invention, it is represented by the chemical formula represented by the above general formula [I]. The polyether block amide is a substance known per se, as disclosed in U.S. Pat. No. 3,044,978. These include, for example, (a) salts of diamine and dicarboxylic acid, lactams, or aminodicarboxylic acid (PA component), (b)
Polyoxyalkylene glycols such as polyoxyethylene glycol and polyoxypropylene glycol (PG
And (c) polycondensation of dicarboxylic acid. These are "Pebaks"
(Trade name, manufactured by Toray Industries, Inc.) “Daiamide-PAE” (trade name, manufactured by Daicel Huls), “UBE polyamide elastomer”, (trade name, manufactured by Ube Industries, Ltd.) “Novamit PAE” (Mitsubishi Chemical Corporation) Commercially available under the trade name of "Greak A" (trade name of Dainippon Ink and Chemicals, Inc.), "Grillon ELX, ELY" (trade name of Ms Japan KK) and the like.

Polyurethane-based thermoplastic elastomer Examples of the above-mentioned polyurethane-based thermoplastic elastomer include diisocyanate and short-chain glycol having a molecular weight of about 50 to 500 (for example, ethylene glycol, propylene glycol, 1,4-butanediol, bisphenol A, etc.). And a soft segment comprising a diisocyanate and a long-chain polyol. As the long-chain polyol, a polyether-based polyol such as polyalkylene glycol having a molecular weight of 500 to 10,000, or a polyester-based polyol such as polyalkylene adipate, polycaprolactone, polycarbonate or the like is used.
This type of polyurethane-based thermoplastic elastomer is a compound having a structure represented by the following general formula [II]. General formula [II]

[0023]

(Wherein A represents a hard segment comprising a diisocyanate and a short-chain glycol, B represents a soft segment comprising a diisocyanate and a long-chain polyol, and Y represents a urethane-bonded diisocyanate connecting the A segment and the B segment. The residue of the compound is used.) As this type of diisocyanate compound, known and commonly used compounds such as phenylene diisocyanate, tolylene diisocyanate, xylene diisocyanate, 4,4'-diphenylmethane diisocyanate, and hexamethylene diisocyanate are used. Commercially available polyurethane thermoplastic elastomers include “Elastolane” (trade name, manufactured by Takeda Bird Urethane Co., Ltd.), “Milactran” (trade name, manufactured by Nippon Milactran Co., Ltd.), and “Resamine P” (Dainichi Seika Kogyo Co., Ltd.) (Trade name, manufactured by Asahi Glass Co., Ltd.) and the like.

(B) Additional compounding material In addition to the above components A, B and C, the styrene-based thermoplastic elastomer (styrene-based TPE) layer of the composite molded article of the present invention may further contain optional components according to various purposes. Can be blended. Specifically, antioxidants, heat stabilizers, light stabilizers, ultraviolet absorbers, neutralizers, lubricants, anti-fog agents, anti-blocking agents, slip agents, crosslinking agents, crosslinking assistants, coloring agents, flame retardants And various additives such as a dispersant and an antistatic agent. Among these, it is particularly important to add an antioxidant, and phenol-based,
At least one of various antioxidants such as phosphite-based and thioether-based can be used. Further, additional compounding materials such as various thermoplastic resins, various elastomers, and various plasticizers can be compounded within a range that does not significantly impair the effects of the present invention. In particular, the components D to E described below are particularly preferable among the additional compounding components.

<Component D: Propylene-based resin> The styrene-based thermoplastic elastomer of the present invention (styrene-based TP)
E) The propylene resin used as an additional component in the layer includes a melt flow rate (JIS-K67).
58, 230 ° C, 2.16 kg load) 0.01 to 10
0 g / 10 min, preferably 0.05 to 80 g / 10 min,
Particularly preferred is a propylene-based resin having a content of 0.1 to 60 g / 10 min and an ethylene content of 0 to 15% by weight, preferably 0 to 13% by weight, particularly preferably 0 to 10% by weight. Here, the ethylene content is a value measured by an infrared spectrum analysis method or the like. The propylene-based resin has a crystallinity of at least 35% by X-ray diffraction, preferably 40 to 80%. As the propylene-based resin, a propylene homopolymer, a copolymer resin containing propylene as a main component, and specifically, propylene / ethylene random copolymer, propylene / ethylene block copolymer, and the like can be given. . When the melt flow rate is less than the above range, the injection moldability is deteriorated, and the appearance of the obtained injection molded article, particularly the occurrence of flow marks, tends to be remarkable. If the melt flow rate exceeds the above range, the material strength tends to decrease. The amount of such a propylene-based resin is determined based on the hydrogenated product of the styrene / isoprene / butadiene / styrene block copolymer (hydrogenated SB
It is preferable to add 0 to 150 parts by weight, preferably 1 to 120 parts by weight, particularly preferably 3 to 100 parts by weight, based on 100 parts by weight of the total of IS) and the paraffinic oil of the component B. It is. By blending the propylene-based resin, in addition to the purpose of adjusting the hardness, there is an effect that pelletization is easy and an effect that the heat resistance of the molded article is increased.

<Component E: Inorganic Filler> The inorganic filler used as an additional component in the styrene-based thermoplastic elastomer (styrene-based TPE) layer of the present invention includes talc, calcium carbonate, mica, glass fiber,
Glass balloon, carbon fiber, etc., having a specific surface area of 37,
000cm ² / g or more, preferably 40,000 cm ²
/ G or more and a length of substantially 15 μm or less, preferably 1 μm or less.
Talc having an average particle diameter of 0.8 to 3.0 μm, preferably 0.8 to 2.5 μm, and an average aspect ratio of 5 or more, preferably 6 or more, and a specific surface area of 50,000 or less.
0 cm ² / g or less, preferably 40,000 cm ² / g
Calcium carbonate having an average particle diameter of 5 μm or less, preferably 4 μm or less is suitable. Such an inorganic filler is a hydrogenated product of a styrene / isoprene / butadiene / styrene block copolymer (hydrogenated S-
0 to 200 parts by weight, preferably 5 to 150 parts by weight, particularly preferably 10 to 100 parts by weight, based on 100 parts by weight of the total amount of BI-S) and the paraffinic oil of the component B. It is suitable. By blending the inorganic filler, there is an object of adjusting hardness, density and gloss of a molded article. Each of these components D to E may be used alone or
A plurality of types may be mixed and used.

<Other Additional Components> As other additional compounding components, thermoplastic resins other than those described above can be mentioned. As the thermoplastic resin, ethylene resins, olefin resins such as polybutene-1 resin,
Polystyrene, acrylonitrile-styrene copolymer,
Styrene resins such as acrylonitrile-butadiene-styrene copolymer, polyphenylene ether resins, polyamide resins such as nylon 6, nylon 66, polyester resins such as polyethylene terephthalate and polybutylene terephthalate, polyoxymethylene homopolymer, polyoxy A polyoxymethylene resin such as a methylene copolymer, a polymethyl methacrylate resin, or the like can be used. Examples of the ethylene resin include a polyethylene resin, an ethylene / α-olefin copolymer, an ethylene / vinyl acetate copolymer, an ethylene / (meth) acrylic acid copolymer, and an ethylene / (meth) acrylate copolymer. Can be mentioned. As the polyethylene resin, a crystal measured by an X-ray diffraction method, which is a low-density polyethylene resin obtained by a high-pressure method or a copolymer of ethylene and an α-olefin obtained by a medium-low pressure method, produced by a conventional method. Low-density and medium-density polyethylene resins having a degree of conversion of 30 to 95%, preferably 35 to 80%, and a density of 0.940 g / cm ³ or less, preferably 0.910 to 0.930 g / cm ^3. Can be.
Examples of the straight-chain α-olefin as the comonomer include butene-1, pentene-1, hexene-1, 4-methylpentene-1, octene-1, and the like. good. Only one type of thermoplastic resin may be used, or a mixture of a plurality of types may be used.

Further, as other additional compounding components,
Various elastomers other than the components A and C can be mentioned. The elastomer has a crystallinity of 30.
% Or less of an amorphous or low-crystalline polymer
Propylene binary copolymer rubber (EPM), ethylene
Propylene / non-conjugated diene terpolymer rubber (EPD
M), ethylene / butene-1 copolymer rubber (EB
M) or an ethylene-based elastomer such as ethylene-propylene-butene-1 terpolymer rubber. One type of elastomer may be used, or a mixture of a plurality of types may be used. In addition, styrene TP
In order to further increase the compatibilization of the component A and the component C blended in E and further increase the bonding strength with the non-olefin resin, as a compatibilizer, for example, maleated polypropylene such as maleated polypropylene or maleated polyethylene is used. A hydrogenated product of a maleated styrene / conjugated diene block copolymer such as polyolefin or maleated SEBS, maleated SEPS, or maleated hydrogenated S-BI-S can also be blended.

(C) Compounding ratio The compounding ratio of each component constituting the styrene-based TPE of the composite molded article of the present invention is such that the component A is 30 to 90% by weight, preferably the total amount of the components A and B. 35-85% by weight,
Particularly preferably, it is 40 to 80% by weight. Styrene TPE obtained when the blending ratio of the component A is less than the above range
If the rubber elasticity and the heat resistance are inferior, and those exceeding the above range, the flexibility and moldability deteriorate. In the total amount of the components A and B, the content of the component B is 70 to 10% by weight, preferably 65 to 15% by weight, and particularly preferably 60 to 20% by weight. When the proportion of the component B exceeds the above range, the rubber elasticity and heat resistance of the styrene-based TPE are inferior, and when the proportion is less than the above range, the flexibility and moldability deteriorate. Component C is added in an amount of 1 part by weight based on 100 parts by weight of the total of components A and B.
0 to 200 parts by weight, preferably 15 to 185 parts by weight, particularly preferably 20 to 150 parts by weight. If the compounding ratio of the component C is less than the above range, the moldability deteriorates,
Those exceeding the above range are inferior in flexibility and compression set. When another elastomer such as a vinyl chloride thermoplastic elastomer is used as the component C, the compatibility is poor and the appearance is poor.

(2) Resin Layer The resin used for the resin layer of the other layer in the composite molded article of the present invention (hereinafter, may be simply referred to as “resin layer”) is physically as follows. The flexural modulus according to JIS-K7203 is 15,000 kg / cm ² or more, preferably 18,000 to 150,000 kg / cm ² , and the load deflection temperature (18.5) according to JIS-K7207.
kg / cm ² ) is 50 ° C. or higher, preferably 90 to 300 ° C.
It is a non-olefin resin having a temperature of ° C. Among non-olefin-based resins exhibiting such physical properties, from the viewpoint of heat fusion with styrene-based TPE, polycarbonate, acrylic resin,
At least one resin selected from the group consisting of styrene resins, polyvinyl chloride, and modified polyphenylene ether is selected. Further, among these resins, it is preferable to use polycarbonate and an acrylic resin, and it is particularly preferable to use polycarbonate.

The polycarbonate is produced by reacting an aromatic hydroxy compound or a small amount thereof with a phosgene. Further, it can also be produced by subjecting an aromatic dihydroxy compound or a small amount of a polyhydroxy compound to a transesterification reaction with a carbonic acid diester. If necessary, a compound having a trifunctional or higher function as a branching agent and a molecular weight modifier are supplied to the reaction. This aromatic polycarbonate resin is a thermoplastic aromatic polycarbonate resin which may be branched or unbranched.

Specific examples of the aromatic dihydroxy compound include 2,2-bis (4-hydroxyphenyl) propane (hereinafter sometimes simply referred to as “bisphenol A”), tetramethylbisphenol A, tetrabromobisphenol A, Bis (4-hydroxyphenyl)-
p-isopropylbenzene, hydroquinone, resorcinol, 4,4'-dihydroxyphenyl, bis (4-
(Hydroxyphenyl) methane, bis (4-hydroxyphenyl) ether, bis (4-hydroxyphenyl) sulfone, bis (4-hydroxyphenyl) sulfoxide, bis (4-hydroxyphenyl) sulfide, bis (4-hydroxyphenyl) ketone, 1,1-bis (4
-Hydroxyphenyl) ethane, 1,1-bis (4-hydroxyphenyl) cyclohexane and the like. Among these, it is particularly preferable to use bisphenol A.

In order to obtain a branched aromatic polycarbonate resin, phloroglucin, 4,6-dimethyl-
2,4,6-tri (4-hydroxyphenyl) heptene-2,4,6-dimethyl-2,4,6-tri (4-hydroxyphenyl) heptane, 2,6-dimethyl-2,
4,6-tri (4-hydroxyphenyl) heptene-
3,2,6-dimethyl-2,4,6-tri (4-hydroxyphenyl) heptane, 1,3,5-tri (4-hydroxyphenyl) benzene, 1,1,1-tri (4-hydroxyphenyl) ) Polyhydroxy compounds exemplified by ethane and the like, and 3,3-bis (4-hydroxyaryl) oxindole [= isatin (bisphenol A)], 5-chloroisatin, 5,7-dichloroisatin, 5-bromoisatin And the like can be obtained by substituting a part of the dihydroxy compound, for example, 0.1 to 2 mol% with a polyhydroxy compound. Furthermore, monovalent aromatic hydroxy compounds suitable for controlling the molecular weight are m-
And p-methylphenol, m- and p-propylphenol, p-bromophenol, p-tertiary-butylphenol, and p-long-chain alkyl-substituted phenol.

A preferred aromatic polycarbonate resin is a bis (4-hydroxyphenyl) alkane-based compound, particularly preferably a polycarbonate containing bisphenol A as a main raw material. A polycarbonate copolymer obtained by using two or more aromatic dihydroxy compounds in combination,
Suitable examples thereof include a branched polycarbonate resin obtained by using a small amount of a trivalent phenol compound (JP-A-63-30524, JP-A-56-55).
No. 328, No. 55-414, No. 60-250
No. 49, Japanese Patent Publication No. 3-49930). The aromatic polycarbonate resin may be used as a mixture of two or more kinds. The molecular weight of a preferred polycarbonate resin is in the range of 10,000 to 150,000 in terms of polystyrene equivalent weight average molecular weight measured by GPC, from the balance of heat resistance, mechanical strength, moldability, and the like.
Above all, the range of 15,000 to 100,000 is preferable, and the range of 35,000 to 80,000 is particularly preferable. Examples of commercially available products include "Europillon" manufactured by Mitsubishi Engineering-Plastics Co., Ltd. and "NOVAREX" manufactured by Mitsubishi Engineering-Plastics Co., Ltd.

The acrylic resin is a resin obtained by polymerizing and copolymerizing acrylic acid and its derivatives. Specific examples include polymers and copolymers of acrylic acid, acrylic acid ester, acrylamide, acrylonitrile, methacrylic acid, methacrylic acid ester, and the like. Among these, polymers such as methacrylates such as methyl methacrylate and ethyl methacrylate are preferable, and the use of a polymer of methyl methacrylate (polymethyl methacrylate resin) is particularly preferable. As a commercially available product, "Acripet" manufactured by Mitsubishi Rayon Co., Ltd.
And the like.

The styrene resins include polystyrene which is a homopolymer of styrene (a commercially available product such as "Dialex" manufactured by Mitsubishi Chemical Corporation) and an impact-resistant polystyrene resin (a commercially available product such as Mitsubishi Chemical Corporation) ) Made of "Dialex"), ABS resin (acrylonitrile butadiene styrene resin) (commercially available products such as "Taflex" manufactured by Mitsubishi Chemical Corporation), and AS resin (acrylonitrile styrene resin) (commercially available) Examples of the product include "SUNLEX" manufactured by Mitsubishi Chemical Corporation). The ABS resin contains 10 to 30% by weight of acrylonitrile produced by emulsion polymerization, mass / suspension polymerization, or mass polymerization, butadiene 5
It has a composition of about 45% by weight and 50 to 85% by weight of styrene, and includes a composition using α-methylstyrene instead of styrene.

The above polyvinyl chloride is a compound resin containing a polymer obtained by polymerization of vinyl chloride as a basic component, and is preferably a hard vinyl chloride compound resin. Examples of commercially available products include "Vinika Compound" manufactured by Mitsubishi Chemical MKV Corporation.

The above-mentioned modified polyphenylene ether is a polymer alloy of polyphenylene ether which is an amorphous high heat resistant resin and a crystalline high heat resistant resin. Examples of the crystalline high heat resistant resin include polyamide resin and polybutylene terephthalate. Polyester resin, propylene resin,
Examples include impact-resistant polystyrene. Examples of commercially available products include "UPIACE" manufactured by Mitsubishi Engineering-Plastics Co., Ltd. and "REMALLOY" manufactured by Mitsubishi Chemical Corporation. Polyphenylene ether alone, which is not alloyed with a crystalline high heat-resistant resin, is not practical because it has a too high melting point and is limited to molding at a high temperature, and has poor flowability and poor moldability.

These resins to be used may be, if necessary,
Rubber component, talc, calcium carbonate, mica, filler such as glass fiber, plasticizer such as paraffin oil, antioxidant, heat stabilizer, light stabilizer, ultraviolet absorber, neutralizer, lubricant, lubricant, antifogging Agents, anti-blocking agents, slip agents, dispersants, coloring agents, antibacterial agents, fluorescent whitening agents, and other various additives.

[II] Production of Composite Molded Product The method for producing such a composite molded product includes a T-die laminate molding method, a co-extrusion molding method, a blow molding method, an insert injection molding method, a two-color injection molding method, and a core molding method. Back injection molding method,
Various molding methods such as a sandwich injection molding method and an injection press molding method can be used. Of the above molding methods, the insert injection molding method is a method in which a core material (resin for a resin layer) is injection-molded in advance, and a shaped molded product is inserted into a mold. Is a molding method for injection molding a surface layer material (styrene-based TPE) in the gaps between
In addition, the two-color injection molding method means that after a core material (resin for a resin layer) is injection-molded by using two or more injection molding machines, the mold is rotated or moved to thereby form the mold. The cavity is exchanged, a gap is formed between the molded product and the mold, and a molding method of injection molding a surface layer material (styrene-based TPE) there. After injection molding the core material (resin for the resin layer) using a molding machine and one mold, the cavity volume of the mold is increased,
In the space between the molded product and the mold, a surface layer material (styrene-based TP
E) is a molding method for injection molding. The molding of the core material may be performed by using a normal injection molding method, or may be performed by gas injection molding.

The injection molding conditions for the core material are generally 10
Molding temperature of 0 to 300 ° C, preferably 150 to 280 ° C, 50 to 1,000 kg / cm ² , preferably 100
It is molded at an injection pressure of ~800kg / cm ^2. Furthermore,
The average thickness of the core material layer in this injection molded body is 0.6 to
It is important that the thickness is 6 mm. If the thickness exceeds the above range, sink marks occur in the core material layer, resulting in poor smoothness of the molded product surface. In some cases, required mechanical properties such as rigidity and strength, heat resistance, and durability may not be satisfied. Further, it is important that the average thickness of the surface layer is 1 to 5 mm. Those exceeding the above range are inferior in soft feeling, and those below the above range have poor adhesion between the core material and the surface layer. .
The injection molding conditions for the surface material layer are generally 150
-300 ° C., preferably 200-290 ° C., particularly preferably 220-280 ° C., molding temperature of 50-1,000 k
g / cm ^2, it is molded preferably injection pressure of 100~800kg / cm ^2. In addition, runners and spools consisting only of the surface material are used as the surface material, and only the core material is used, or runners consisting of the core material and the surface material, spools and the like, and defective molded products are recycled and used as the core material. You can also.

[III] Applications The composite molded article comprising the styrene-based thermoplastic elastomer layer and the resin layer thus obtained can be used as various industrial parts. Specifically, instrument panel, center panel, center console box, door trim, pillar, assist grip, steering wheel, car interior parts such as airbag cover, car exterior parts such as mall, vacuum cleaner bumper, remote control switch,
Home appliances parts such as various key tops of OA equipment, underwater products such as underwater glasses and underwater camera covers, various cover parts, industrial parts with various packings for the purpose of sealing, waterproofing, soundproofing, vibrationproofing, etc., It can be used for automotive functional parts such as rack & pinion boots, suspension boots, constant velocity joint boots, etc., electric and electronic parts such as curled cord wire coverings, belts, hoses, tubes, sound deadening gears, sporting goods and the like.

[0044]

The present invention will be described more specifically with reference to the following experimental examples. [I] Evaluation method Various evaluations in these examples and comparative examples were performed by the following test methods. However, the measurement samples of (1) to (3) were measured using an in-line screw type injection molding machine (small injection molding machine manufactured by Toshiba Machine Co., Ltd .: IS90B) at an injection pressure of 500 kg / cm ² , an injection temperature of 210 ° C.
120mm x 80mm x 2 molded at a mold temperature of 40 ° C
mm sheets were obtained by transverse punching. Also, (4)
The measurement samples of (5) to (5) were molded using a two-color injection molding machine (KS-2C-680, manufactured by Takahashi Seiki Kogyo Co., Ltd.).
The evaluation was performed on a composite injection molded article of 00 mm × 300 mm × 4 mm (both the core material layer and the surface material layer had a thickness of 2 mm). The composite injection molded article of (4) was molded at 220 ° C., and (5)
The composite injection-molded product of the above was evaluated at 220 ° C. and 240 ° C. (1) JIS-A hardness [-]: JIS-K-630
(2) Compression set (cs): JIS-K-630
Condition: 70 ° C. × 22 hours (3) Stickiness The presence or absence of stickiness on the surface of the injection-molded test piece is confirmed by touch. The case where there was no stickiness was evaluated as ○, and the case where there was stickiness was evaluated as ×. (4) Moldability If there is no short shot in the composite injection molded article,
And when there was no remarkable appearance defect (flow mark, delamination), the moldability was evaluated as good. (5) Thermal fusibility (peel strength) Width 25 mm, length 1 punched from the composite injection molded article
Using a strip test piece of a composite injection molded article of 00 mm, a tensile test was performed on the skin material layer and the core material layer in a 180 ° direction at a pulling speed of 200 mm / min, and peeling of the fusion interface between the skin material layer and the core material layer was performed. The strength (kg / 25 mm) was measured.

[II] Raw Materials (1) Styrene thermoplastic elastomer (Styrene T
PE) layer [surface material]

[0046]

[Table 1]

[0047]

[Table 2]

[0048]

[Table 3]

[0049]

[Table 4]

[0050]

[Table 5]

(2) Resin layer [core material] PC (polycarbonate resin): "NOVAREX 7027A" manufactured by Mitsubishi Engineering-Plastics Corporation ABS (acrylonitrile butadiene styrene resin): "TAFLEX TFX" manufactured by Mitsubishi Chemical Corporation −41
0 ”PMMA (polymethyl methacrylate resin):“ Acrypet IR H-70 ”manufactured by Mitsubishi Rayon Co., Ltd. PS (polystyrene resin):“ Dialex HT-88 ”manufactured by Mitsubishi Chemical Corporation PVC (polyvinyl chloride resin) ): "Vinika Compound E-320" manufactured by Mitsubishi Chemical MKV. Co., Ltd. Modified PPE (polyphenylene ether resin): "UPIACE AH60" manufactured by Mitsubishi Gas Chemical Co., Ltd.

[III] Experimental Examples Examples 1 to 21 and Comparative Examples 1 to 21 Compounded in the composition (parts by weight) shown in Tables 6 to 11, and further added to 100 parts by weight of the total amount of the composition. , 0.2 parts by weight of a phenolic antioxidant (trade name “Irganox 1010” manufactured by Ciba-Geigy) and a compression ratio L /
D = 33, 23 with a twin screw extruder with a cylinder diameter of 45 mm
The mixture was melt-kneaded at a setting of 0 ° C. to obtain TPE composition pellets.
The pellet was injection molded as described above to form a sheet, which was subjected to the above evaluation. Tables 6 to 11 show these evaluation results.

[0053]

[Table 6]

[0054]

[Table 7]

[0055]

[Table 8]

[0056]

[Table 9]

[0057]

[Table 10]

[0058]

[Table 11]

[0059]

As described above, the composite molded article of the present invention has excellent heat-fusibility between the resin layer and the styrene-based thermoplastic elastomer layer, and has good releasability during molding because the molded article has no stickiness. Therefore, there is an advantage that dust does not easily adhere to the molded product, a free product shape can be molded, and there is no need to apply a coating immediately after molding. In particular, when at least one resin selected from a polycarbonate and an acrylic resin is selected for the resin layer, and when a styrene-based TPE containing a polyester-based thermoplastic elastomer layer is selected for the styrene-based TPE layer, heat-fusing properties are selected. Great effect.

Claims (5)

(57) [Claims] A composite molded article comprising at least one resin layer selected from the group consisting of polycarbonate, acrylic resin, styrene resin, polyvinyl chloride, and modified polyphenylene ether, and a styrene thermoplastic elastomer layer. A composite molded article, wherein the styrene-based thermoplastic elastomer layer comprises a base material containing the following components A to C. Component A: a hydrogenated styrene / conjugated diene block copolymer in which the conjugated diene is a mixture of isoprene and butadiene 30 to 90% by weight Component B: paraffinic oil 70 to 10% by weight Component C: Polyester At least one thermoplastic elastomer selected from the group consisting of a thermoplastic thermoplastic elastomer, a polyamide thermoplastic elastomer, and a polyurethane thermoplastic elastomer; 10 to 200 parts by weight based on 100 parts by weight of the total amount of the components A and B 2. The resin layer is at least one resin selected from polycarbonate and acrylic resin, and
The composite molded article according to claim 1, wherein the component C constituting the styrene-based thermoplastic elastomer is a polyester-based thermoplastic elastomer. 3. The composite molded article according to claim 1, wherein the mixed weight ratio of isoprene and butadiene of the conjugated diene in component A (isoprene / butadiene) is 90/10 to 30/70. 4. A hydrogenated product of a styrene / conjugated diene block copolymer as component A, wherein the hydrogenated product of a styrene / isoprene / butadiene / styrene block copolymer having a 1,2-microstructure content of less than 20%. The composite molded article according to claim 1, which is a product. 5. Forming at least one resin layer selected from the group consisting of polycarbonate, acrylic resin, styrene resin, polyvinyl chloride and modified polyphenylene ether, and then injection molding a styrene thermoplastic elastomer layer. In a method for producing a composite molded article using an insert injection molding method, a two-color injection molding method or a core back injection molding method, the styrene-based thermoplastic elastomer may be composed of a base material containing the following components A to C. A method for producing a composite molded article, which is a feature. Component A: a hydrogenated styrene / conjugated diene block copolymer in which the conjugated diene is a mixture of isoprene and butadiene 30 to 90% by weight Component B: paraffinic oil 70 to 10% by weight Component C: Polyester At least one thermoplastic elastomer selected from the group consisting of a thermoplastic thermoplastic elastomer, a polyamide thermoplastic elastomer, and a polyurethane thermoplastic elastomer; 10 to 200 parts by weight based on 100 parts by weight of the total amount of the components A and B