JPH0872204A - Composite molding and production thereof - Google Patents

Abstract

PURPOSE: To obtain a composite molding good in thermal fusion properties, excellent in flexibility or moldability and having a surface free from a sticking feeling from a specific resin layer and a styrenic thermoplastic elastomer layer composed of a base material containing a specific component. CONSTITUTION: The layered constitution of a composite molding consists of a resin layer composed of at least one kind of a resin selected from a group consisting of polycarbonate, an acrylic resin, a styrenic resin, polyvinyl chloride and modified polyphenylene ether and a styrenic thermoplastic elastomer layer. The styrenic thermoplastic elastomer layer consists of 30-90wt.% of a component A being a hydrogenated styrene/conjugated diene block copolymer characterized by that conjugated diene is a mixture of isoprene and butadiene, 70-10wt.% of a component B being a paraffinic oil and a component C being at least one kind of a thermoplastic elastomer selected from a group consisting of polyester, polyamide and polyurethane type thermoplastic elastomers and the component C is 100-200 pts.wt. per 100 pts.wt. of the sum total amt. of the components A, B.

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, modified polyphenylene ether resin, and a styrene thermoplastic elastomer that does not have a sticky feeling in the molded product and has good releasability during molding (hereinafter , Which may be simply abbreviated as "styrene-based TPE") and a method for producing the same.

[0002]

2. Description of the Related Art Conventionally, a non-olefin resin layer and a styrene thermoplastic elastomer (styrene TPE) are inferior in heat fusion property. Unevenness, partially covering the core material with the surface layer material, making a hole in the core material, and turning the surface layer material to the back side to physically join it, or to the joint part with an adhesive What has a role, for example, a primer is applied to form a composite. Therefore, the obtained composite molded article has problems such as poor bonding strength, complicated structure, and increased number of steps. As an attempt to solve such a problem, Japanese Patent Laid-Open No. 13924/1989
No. 0, JP-A-1-139240, JP-A-2-
Styrene / ethylene / butylene / styrene copolymer (hereinafter sometimes simply abbreviated as "SEBS") or styrene / ethylene / propylene / styrene described in JP-A-147306 and JP-A-6-65467. 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 abbreviated as “SEPS”).

[0003]

[Problems to be Solved by the Invention] However, such SE
When only the polyester-based thermoplastic elastomer, polyamide-based thermoplastic elastomer, or polyurethane-based thermoplastic elastomer was added to BS or SEPS, the flexibility and moldability were poor, and the appearance of the resulting molded article was also poor. Further, in the case of SEBS or SEPS to which a polyester thermoplastic elastomer, a polyamide thermoplastic elastomer, or a polyurethane thermoplastic elastomer is added, there is a problem that the surface of the molded product is sticky and the releasability at the time of molding is poor. There are problems that dust is easily attached to the molded product and that the heat fusion property with the above-mentioned non-olefin resin is poor. For this reason, the shape of the product is restricted, and it is necessary to apply coating immediately after molding to parts that require painting.

[0004]

[Means for Solving the Problems]

[Summary of the Invention] The present inventors have conducted extensive studies to solve the above-mentioned problems, and as a result, by using a specific styrene-based thermoplastic elastomer (styrene-based TPE), a non-olefin resin and a heat-meltable resin The present invention has been completed by finding that a composite molded article having good adherence, excellent flexibility and moldability, and a good appearance of the resulting molded article and having no sticky feeling on the surface of the molded article can be obtained. 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. In the composite molded article described above, the styrene-based thermoplastic elastomer layer is composed of a base material containing the following components A to C. Component A: Hydrogenated product of styrene / conjugated diene block copolymer, the conjugated diene of which is a mixture of isoprene and butadiene 30 to 90% by weight Component B: Paraffin oil 70 to 10% by weight Component C: Polyester At least one thermoplastic elastomer selected from the group consisting of thermoplastic thermoplastic elastomer, thermoplastic polyamide elastomer, and thermoplastic polyurethane elastomer 10 to 200 parts by weight per 100 parts by weight of the total amount of the above components A and B

The method for producing a composite molded article, which is another invention 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 article using an insert injection molding method, a two-color injection molding method, or a core-back injection molding method in which a styrene-based thermoplastic elastomer is injection-molded, the styrene-based thermoplastic elastomer has the following components. It is characterized by comprising a base material containing A to component C. Component A: Hydrogenated product of styrene / conjugated diene block copolymer, the conjugated diene of which is a mixture of isoprene and butadiene 30 to 90% by weight Component B: Paraffin oil 70 to 10% by weight Component C: Polyester At least one thermoplastic elastomer selected from the group consisting of thermoplastic thermoplastic elastomer, thermoplastic polyamide elastomer, and thermoplastic polyurethane elastomer 10 to 200 parts by weight per 100 parts by weight of the total amount of the above components A and B

[Detailed Description of the Invention] [I] Layer Structure of Composite Molded Product (1) Styrene-based thermoplastic elastomer layer (A) Styrene-based thermoplastic elastomer For the styrene-based thermoplastic elastomer layer of the composite molded product of the present invention The physical properties of the styrene-based thermoplastic elastomer (styrene-based TPE) used are J-K6301 according to JIS-K6301.
IS-A hardness of 98 or less, preferably 5 to 95, particularly preferably 10 to 90, and JIS-K6
Compression set according to 301 (70 ℃, 22 hours) is 8
0% or less, preferably 0 to 75%, particularly preferably 0 to
70% is preferable. Such styrene-based TPE
Is a hydrogenated product of a styrene / conjugated diene block copolymer, that is, a hydrogenated product of a styrene / isoprene / butadiene / styrene block copolymer whose conjugated diene is a mixture of isoprene and butadiene. Abbreviated as "Additional S-BI-S") as a basic component (the following component A), and further contains a paraffin oil of component B and a specific thermoplastic elastomer of component C described below. It is a thing.

<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 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. When the content of isoprene is too low, the flexibility is deteriorated, which is not preferable. On the other hand, if the content of isoprene is too high, the heat fusion property is deteriorated, 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,
Preferably 60,000 to 400,000, particularly preferably 70,000 to 300,000, styrene content 5 to 50% by weight, preferably 8 to 45% by weight, particularly preferably 10 to 40% by weight, 1, 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% 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 becomes sticky. There is a problem that the property becomes poor.

Here, the "weight average molecular weight" is a polystyrene equivalent weight average molecular weight measured by gel permeation chromatography (GPC) under the following conditions. (Conditions) Equipment: 150C ALC / GPC (MILL
Column: AD80M / S (manufactured by Showa Denko KK) Three: Solvent: o-dichlorobenzene Temperature: 140 ° C. Flow rate: 1 ml / min Injection amount: 200 μl Concentration: 2 mg / ml (antioxidants 2, 6 -0.2% by weight of di-t-butyl-p-phenol was added, and the concentration was detected with an infrared spectrophotometer MIRAN 1A manufactured by FOXBORO at a wavelength of 3.42 μm.) Weight of the hydrogenated S-BI-S Average molecular weight is 500,000
If it exceeds 0, the moldability is poor, and
Those less than 0 are inferior in rubber elasticity and mechanical strength. If the styrene content is less than 5% by weight, the mechanical strength is poor, and if the styrene content exceeds 50% by weight, the flexibility is poor. Furthermore, if the hydrogenation rate is less than 95%, the weather resistance and heat resistance will be poor. These hydrogenated S
As a method of manufacturing -BI-S, for example, Japanese Patent Laid-Open No. 3-1
It is synthesized by the method described in Japanese Patent No. 88114.

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

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

Polyester Thermoplastic Elastomer The above-mentioned 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).

The aromatic polyester block (a) means an aromatic dicarboxylic acid or its alkyl ester and 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 thereof include polyethylene terephthalate oligomer, polypropylene terephthalate oligomer, polybutylene terephthalate oligomer (polytetramethylene terephthalate oligomer), and polypentamethylene terephthalate oligomer.

As the above-mentioned aromatic dicarboxylic acid, it is possible to use a raw material of polyester, particularly one known as a raw material of polyester elastomer. Specifically, terephthalic acid, isophthalic acid, phthalic acid, 2,6-
Examples thereof include naphthalenedicarboxylic acid. Among these, terephthalic acid and 2,6-naphthalenedicarboxylic acid are preferably used, and those containing terephthalic acid as a main component are particularly preferably used. These can be used in combination of two or more. Examples of the alkyl ester of aromatic dicarboxylic acid include dimethyl esters such as dimethyl terephthalate, dimethyl isophthalate, dimethyl phthalate, and 2,6-dimethyl naphthalate. Of these, dimethyl terephthalate and 2,6-dimethyl naphthalate are preferably used, and dimethyl terephthalate is particularly preferably used. These can be used in combination of two or more.

As the aliphatic and / or alicyclic diol having 2 to 12 carbon atoms, those known as a raw material of polyester, particularly a raw material of polyester elastomer can be used. Specifically, ethylene glycol, propylene glycol, trimethylene glycol, 1,4-
Butanediol, 1,4-cyclohexanediol,
1,4-cyclohexane dimethanol etc. can be mentioned. Among these, it is preferable to use 1,4-butanediol and ethylene glycol, and it is particularly preferable to use one containing 1,4-butanediol as a main component. These can be used in combination of two or more. In addition to the above, trifunctional diols, other diols and other dicarboxylic acids and their esters may be copolymerized in a small amount, and further, aliphatic or alicyclic dicarboxylic acids such as adipic acid. Alternatively, its alkyl ester or the like may be used as a copolymerization 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 monoolcarboxylic acid, and specific examples of the former include 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. A polyester oligomer having a structure obtained by condensing one or more kinds of dicarboxylic acids and one or more kinds of diols such as ethylene glycol, propylene glycol, tetramethylene glycol and pentamethylene glycol can be mentioned. Specific examples of the latter include polycaprolactone-based polyester oligomers synthesized from ε-caprolactone, ω-oxycaproic acid and the like.

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

As a method for producing the polyester elastomer, the blocks of the oligomer comprising the components may be separately synthesized first, and then the blocks of the oligomer may be further ester-bonded to each other. As a method, for example, a method of polymerizing the block (b) first and then further mixing with the component monomer of the block (a) and condensing may be adopted. As such a polyester-based elastomer, a commercially available polymer "Perprene P" is used.
Or "Perprene S" (trade name of Toyobo Co., Ltd.),
"Hytrel" (trade name of Toray DuPont Co., Ltd.),
"Low Mod" (product name of Nippon GE Plastics Co., Ltd.), "Nichigo Polyester" (product name of Nippon Synthetic Chemical Industry Co., Ltd.), "Teijin Polyester Elastomer"
(Teijin Co., Ltd. product name) and the like.

Polyamide-Based Thermoplastic Elastomer The polyamide-based thermoplastic elastomer comprises polyamide (nylon 6,66,11,12, etc.) 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.) Represented by the chemical formula represented by the above general formula [I] used in the present invention. The polyether block amide described above is a substance known per se as disclosed in US Pat. No. 3,044,978 and the like. This is, for example, (a) salt of diamine and dicarboxylic acid, lactam, or aminodicarboxylic acid (PA constituent), (b)
Polyoxyalkylene glycol (PG such as polyoxyethylene glycol, polyoxypropylene glycol)
It is prepared by polycondensing the constituent components) and (c) dicarboxylic acid. These are "Pebax"
(Toray Co., Ltd. product name) “Daiamide-PAE” (Daicel Hüls Co., Ltd. product name), “UBE polyamide elastomer”, (Ube Industries Co., Ltd. product name) “Novamit PAE” (Mitsubishi Chemical Co., Ltd.) Product name), "Grelax A" (product name manufactured by Dainippon Ink and Chemicals, Inc.), "Grillon ELX, ELY" (product name manufactured by EMS Japan Co., Ltd.) 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 composed of diisocyanate and a long-chain polyol. As the long-chain polyol, a polyether type one having a molecular weight of 500 to 10,000 such as polyalkylene glycol, or a polyester type one such as polyalkylene adipate, polycaprolactone or polycarbonate is used.
This type of polyurethane thermoplastic elastomer is a compound having a structure represented by the following general formula [II]. General formula [II]

[0023]

(A in the formula represents a hard segment composed of a diisocyanate and a short chain glycol, B represents a soft segment composed of a diisocyanate and a long chain polyol, and Y represents a urethane-bonded diisocyanate connecting the A segment and the B segment. It represents the residue of a compound.) Incidentally, as this type of diisocyanate compound, phenylene diisocyanate, tolylene diisocyanate,
Known and conventional ones such as xylene diisocyanate, 4,4′-diphenylmethane diisocyanate, and hexamethylene diisocyanate are used. Commercially available products of the thermoplastic polyurethane elastomer include "Mistran" (trade name of Takeda Birdish Urethane Co., Ltd.), "miractran" (trade name of Nippon Miractolan Co., Ltd.),
Examples include "Resamine P" (trade name, manufactured by Dainichiseika Co., Ltd.), "U-FINE P" (trade name, manufactured by Asahi Glass Co., Ltd.), and the like.

(B) Additional compounding material In the styrene-based thermoplastic elastomer (styrene-based TPE) layer of the composite molded article of the present invention, in addition to the above-mentioned components A, B and C, it is optional according to various purposes. The compounding ingredients of can be compounded. Specifically, antioxidants, heat stabilizers, light stabilizers, ultraviolet absorbers, neutralizing agents, lubricants, antifogging agents, antiblocking agents, slip agents, crosslinkers, crosslinkers, colorants, flame retardants. Various additives such as a dispersant and an antistatic agent can be added. Among these, it is important to add an antioxidant, especially phenolic,
At least one of various antioxidants such as phosphite-based and thioether-based antioxidants can be used. Further, additional compounding materials such as various thermoplastic resins, various elastomers, various plasticizers, etc. 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 above-mentioned additional compounding components.

<Component D: Propylene-based resin> The above-mentioned styrene-based thermoplastic elastomer of the present invention (styrene-based TP
Examples of the propylene-based resin used as an additional component in the E) layer include melt flow rate (JIS-K67).
58, 230 ° C, 2.16 kg load) is 0.01 to 10
0 g / 10 minutes, preferably 0.05 to 80 g / 10 minutes,
Particularly preferred is a propylene resin having an ethylene content of 0.1 to 60 g / 10 minutes and an ethylene content of 0 to 15% by weight, preferably 0 to 13% by weight, and particularly preferably 0 to 10% by weight. The ethylene content here is a value measured by an infrared spectrum analysis method or the like. The crystallinity of the propylene resin by X-ray diffractometry is 35% or more, preferably 40 to 80%. The propylene-based resin is a propylene homopolymer, a copolymer resin containing propylene as a main component, and specific examples thereof include a propylene / ethylene random copolymer and a propylene / ethylene block copolymer. . If a melt flow rate lower than the above range is used, the injection moldability tends to deteriorate, and the appearance of the obtained injection molded article, particularly the generation of flow marks, tends to be remarkable. If a melt flow rate exceeding the above range is used, the material strength tends to decrease. The blending amount of such a propylene-based resin is such that the hydrogenated product of the styrene / isoprene / butadiene / styrene block copolymer (hydrogenated SB
I-S) and the total amount of the paraffinic oil of the component B are 100 parts by weight, preferably 0 to 150 parts by weight, preferably 1 to 120 parts by weight, particularly preferably 3 to 100 parts by weight. Is. By blending the propylene-based resin, in addition to the purpose of adjusting the hardness, it has the effect of being easily pelletized and the effect of increasing the heat resistance of the molded product.

<Component E: Inorganic filler> As the inorganic filler used as an additional component in the styrene thermoplastic elastomer (styrene TPE) layer of the present invention, talc, calcium carbonate, mica, glass fiber,
Glass balloon, carbon fiber, etc., with a specific surface area of 37,
000 cm ² / g or more, preferably 40,000 cm ²
/ G or more, the length is substantially 15 μm or less, preferably 1
0 μm or less, average particle size 0.8 to 3.0 μm, preferably 0.8 to 2.5 μm, and average aspect ratio 5 or more, preferably 6 or more talc, specific surface area 50000.
0 cm ² / g or less, preferably 40,000 cm ² / g
Calcium carbonate having the following average particle size of 5 μm or less, preferably 4 μm or less is suitable. Such an inorganic filler is a hydrogenated product of the styrene / isoprene / butadiene / styrene block copolymer (hydrogenated S-
BI-S) and the paraffinic oil of the component B are combined in an amount of 0 to 200 parts by weight, preferably 5 to 150 parts by weight, and particularly preferably 10 to 100 parts by weight. It is suitable. By blending the inorganic filler, the purpose is to adjust hardness, density and gloss of a molded product. These components D to E may be used alone,
A plurality of types can be mixed and used.

<Other Additional Components> As other additional compounding components, thermoplastic resins other than those mentioned above can be mentioned. As the thermoplastic resin, an ethylene resin, an olefin resin such as polybutene-1 resin,
Polystyrene, acrylonitrile-styrene copolymer,
Styrene resin such as acrylonitrile / butadiene / styrene copolymer, polyphenylene ether resin, polyamide resin such as nylon 6, nylon 66, polyester resin such as polyethylene terephthalate and polybutylene terephthalate, polyoxymethylene homopolymer, polyoxy A polyoxymethylene-based resin such as a methylene copolymer, a polymethylmethacrylate-based resin, or the like can be used. Examples of the ethylene-based resin include polyethylene resin, ethylene / α-olefin copolymer, ethylene / vinyl acetate copolymer, ethylene / (meth) acrylic acid copolymer, ethylene / (meth) acrylic acid ester copolymer and the like. Can be mentioned. The polyethylene resin is a low density polyethylene resin produced by a high pressure method or a copolymer of ethylene and α-olefin obtained by a medium and low pressure method, which is a crystal produced by an ordinary method and measured by an X-ray diffraction method. The low- and medium-density polyethylene resin having a degree of chemical 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. You can
Examples of the linear α-olefin that is the comonomer include butene-1, pentene-1, hexene-1, 4-methylpentene-1, octene-1, and the like. These may be used in combination of two or more. good. The thermoplastic resin used may be only one kind or a mixture of plural kinds.

As other additional compounding ingredients,
Various elastomers other than the component A and the component C can be mentioned. The elastomer has a crystallinity of 30.
% Or less of the amorphous or low crystalline polymer ethylene.
Propylene binary copolymer rubber (EPM), ethylene
Propylene / non-conjugated diene terpolymer rubber (EPD
M), ethylene / butene-1 binary copolymer rubber (EB
M) and ethylene-based elastomers such as ethylene / propylene / butene-1 terpolymer rubber can be used. The elastomer used may be one kind or a mixture of plural kinds. In addition, styrene-based TP
For the purpose of further increasing the compatibilization of the components A and C to be mixed with E or further enhancing the bonding strength with the non-olefin resin, as a compatibilizing agent, for example, maleation of maleated polypropylene, maleated polyethylene, etc. It is also possible to blend a polyolefin, a maleated SEBS, a maleated SEPS, a hydrogenated product of a maleated styrene / conjugated diene block copolymer such as maleated hydrogenated S-BI-S.

(C) Mixing ratio The mixing ratio of each component constituting the styrenic TPE of the composite molded article of the present invention is 30 to 90% by weight, preferably 30 to 90% by weight, of the total amount of the components A and B. 35-85% by weight,
It is particularly preferably 40 to 80% by weight. Styrene-based TPE obtained when the mixing ratio of the component A is less than the above range
Inferior in rubber elasticity and heat resistance, and those exceeding the above range deteriorate in flexibility and moldability. Further, in the total amount of the component A and the component B, the component B is 70 to 10% by weight, preferably 65 to 15% by weight, and particularly preferably 60 to 20% by weight. If the blending ratio of the component B exceeds the above range, the rubber elasticity and heat resistance of the styrene-based TPE are poor, and if it is less than the above range, the flexibility and molding processability deteriorate. Further, the component C is 1 with respect to 100 parts by weight of the total amount of the components A and B.
The amount is 0 to 200 parts by weight, preferably 15 to 185 parts by weight, and particularly preferably 20 to 150 parts by weight. If the mixing ratio of the component C is less than the above range, the moldability is deteriorated,
Those exceeding the above range are inferior in flexibility and compression set. Further, when another elastomer such as a thermoplastic vinyl chloride elastomer is used as the component C, the compatibility is poor and the appearance is poor.

(2) Resin Layer The resin used for the other resin layer (hereinafter sometimes simply referred to as “resin layer”) in the composite molded article of the present invention has the following physical properties. 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 deflection temperature under load (18.5) according to JIS-K7207.
kg / cm ² ) is 50 ° C. or higher, preferably 90 to 300
It is a non-olefin resin whose temperature is ° C. Among the non-olefin resins having such physical properties, from the viewpoint of heat fusion with styrene-based TPE, polycarbonate, acrylic resin,
At least one resin selected from the group of styrene resins, polyvinyl chloride, and modified polyphenylene ether is selected. Further, among these resins, polycarbonate and acrylic resin are preferably used, and polycarbonate is particularly preferably used.

The above-mentioned polycarbonate is produced by reacting an aromatic hydroxy compound or a small amount of polyhydroxy compound with phosgene. It can also be produced by transesterifying an aromatic dihydroxy compound or a small amount of a polyhydroxy compound with a carbonic acid diester. If necessary, a trifunctional or higher functional compound of a branching agent and a molecular weight modifier are provided for 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 can be mentioned. Among these, it is particularly preferable to use bisphenol A.

Further, 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 Etc. can be obtained by substituting a part of the dihydroxy compound, for example, 0.1 to 2 mol% with a polyhydroxy compound. Further, a monovalent aromatic hydroxy compound suitable for controlling the molecular weight is 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 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,
A branched polycarbonate resin obtained by using a small amount of a trivalent phenolic compound may also be mentioned as a suitable example (JP-A-63-30524, JP-A-56-55).
No. 328, Japanese Patent Publication No. 55-414, Japanese Patent Publication No. 60-250
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 the 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, molding processability, and the like.
Among them, 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 "Europylon" manufactured by Mitsubishi Engineering Plastics Co., Ltd., "Novarex" manufactured by Mitsubishi Engineering Plastics Co., Ltd., and the like.

The above acrylic resin is a resin obtained by polymerizing and copolymerizing acrylic acid and its derivative. Specific examples thereof 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 methacrylic acid esters such as methyl methacrylate and ethyl methacrylate are preferable, and it is particularly preferable to use a polymer of methyl methacrylate (polymethylmethacrylate resin). As a commercial product, "Acrypet" manufactured by Mitsubishi Rayon Co., Ltd.
Etc. can be mentioned.

The above-mentioned styrene-based resins are polystyrene, which is a homopolymer of styrene (commercially available as "DIAREX" manufactured by Mitsubishi Chemical Co., Ltd.), and impact-resistant polystyrene resin (commercially available as Mitsubishi Chemical (Co., Ltd.). ) "Alexilex"), ABS resin (acrylonitrile / butadiene / styrene resin) (commercially available as "Taflex" manufactured by Mitsubishi Chemical Corporation), AS resin (acrylonitrile / styrene resin) (commercially available) Examples of the product include "Sunlex" manufactured by Mitsubishi Chemical Co., Ltd.) and the like. The ABS resin comprises 10 to 30% by weight of acrylonitrile produced by an emulsion polymerization method, a mass suspension polymerization method and a mass polymerization method, and butadiene 5
.About.45% by weight and 50 to 85% by weight of styrene, and those in which .alpha.-methylstyrene is used instead of styrene are also included.

The above polyvinyl chloride is a compound resin containing a polymer obtained by polymerization of vinyl chloride as a basic component, and preferably a hard vinyl chloride compound resin. Examples of commercially available products include "Binica compound" manufactured by Mitsubishi Kagaku MKV Co., Ltd. and the like.

The 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,
Impact-resistant polystyrene etc. can be mentioned. Examples of commercially available products include "Yupiace" manufactured by Mitsubishi Engineering-Plastics Co., Ltd. and "Remalloy" manufactured by Mitsubishi Chemical Co., Ltd. Polyphenylene ether alone, which is not alloyed with the crystalline highly heat-resistant resin, is not practical because it has a high melting point and thus is limited to molding at high temperature and has poor flowability and poor moldability.

These resins used are, 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 Various additives such as an agent, an anti-blocking agent, a slip agent, a dispersant, a colorant, an antibacterial agent, and an optical brightener can be added.

[II] Manufacture of Composite Molded Product As a method of manufacturing such a composite molded product, a T-die laminate molding method, a coextrusion molding method, a blow molding method, an insert injection molding method, a two-color injection molding method, a core Back injection molding method,
Various molding methods such as a sandwich injection molding method and an injection press molding method can be used. Among the above-mentioned molding methods, the insert injection molding method means that a core material (resin for resin layer) is injection-molded in advance and a shaped molded article is inserted into a mold, and then the molded article and the mold are Is a molding method in which a surface layer material (styrene-based TPE) is injection-molded in the space between
The two-color injection molding method is a method in which two or more injection molding machines are used to injection-mold a core material (resin for resin layer) and then the mold is rotated or moved to The cavity is exchanged, a void is created between the molded product and the mold, and the surface layer material (styrene-based TPE) is injection-molded there. Also, the core-back injection molding method is one injection Using a molding machine and one mold, after injection molding a core material (resin for resin layer), expand the cavity volume of the mold,
A surface layer material (styrene-based TP is provided in the space between the molded product and the mold.
E) is a molding method of injection molding. Further, the core material may be molded by using an ordinary injection molding method or may be molded 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 ~ 800 kg / cm ² . Furthermore,
The average thickness of the core layer in this injection-molded product is 0.6 to
It is important that the thickness is 6 mm. If the thickness exceeds the above range, the core material layer will be sinked and the surface of the molded article will be inferior in smoothness. If the thickness is less than the above range, it will be used, for example, for automobile interior parts. In some cases, mechanical properties such as rigidity and strength, heat resistance, and durability required in some cases cannot be satisfied. Further, it is important that the average thickness of the surface material layer is 1 to 5 mm. If the thickness exceeds the above range, the soft feeling is poor, and if it is less than the above range, the adhesion between the core material and the surface material deteriorates. .
The injection molding condition for the surface material layer is generally 150.
-300 ° C, preferably 200-290 ° C, particularly preferably 220-280 ° C molding temperature, 50-1,000k
It is molded at an injection pressure of g / cm ² , preferably 100 to 800 kg / cm ² . Also, runners, spools, etc. consisting only of surface layer materials are used as surface layer materials, and core materials only, or runners, spools, etc. composed of core material and surface layer materials, defective molded products, etc. are recycled as core materials. You can also

[III] Application The composite molded article composed of the styrene thermoplastic elastomer layer and the resin layer thus obtained can be used as various industrial parts. Specifically, instrument panels, center panels, center console boxes, door trims, pillars, assist grips, steering wheels, automobile interior parts such as airbag covers, automobile exterior parts such as malls, vacuum cleaner bumpers, remote control switches,
Home appliance parts such as various key tops of OA equipment, underwater products such as underwater glasses, underwater camera covers, various cover parts, industrial parts with various packings for the purpose of sealing, waterproofing, soundproofing, vibration proofing, etc. It can be used for automobile functional parts such as rack and pinion boots, suspension boots, constant velocity joint boots, curl cord electric wire coatings, electric and electronic parts such as belts, hoses, tubes, and sound deadening gears, sports equipment and the like.

[0044]

EXAMPLES The present invention will be described in more detail with reference to the following experimental examples. [I] Evaluation Method Various evaluations in these Examples and Comparative Examples were carried out by the following test methods. However, the measurement samples of (1) to (3) were measured with an inline screw type injection molding machine (small injection molding machine: IS90B manufactured by Toshiba Machine Co., Ltd.) at an injection pressure of 500 kg / cm ² , an injection temperature of 210 ° C.
120 mm x 80 mm x 2 molded at a mold temperature of 40 ° C
mm sheets were obtained by lateral 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.) 3
The composite injection molded product of 00 mm × 300 mm × 4 mm (both the core material layer and the surface material layer had a thickness of 2 mm) was evaluated. The composite injection molded body of (4) was molded at 220 ° C.
The composite injection-molded article of 1 was evaluated at 220 ° C. and 240 ° C. (1) JIS-A hardness [-]: JIS-K-630
1 (2) Compression set (cs): JIS-K-630
1) Conditions: 70 ° C x 22 hours (3) Stickiness Check the presence or absence of stickiness on the surface of the injection-molded test piece by touch. The case where there was no stickiness was marked with ◯, and the case where there was stickiness was marked with x. (4) Molding processability When there is no short shot in the composite injection molded body,
In addition, the molding processability was evaluated as good when there were no significant defects in appearance (flow marks, delamination). (5) Thermal fusion bondability (peel strength) Width 25 mm, length 1 punched from the composite injection-molded article
Using a strip test piece of a 00 mm composite injection-molded article, a skin material layer and a core material layer were subjected to a tensile test in a 180 degree direction at a tensile speed of 200 mm / min, and peeling at the fusion interface of the skin material layer / core material layer The strength (kg / 25 mm) was measured.

[II] Raw materials (1) Styrene-based thermoplastic elastomer (styrene-based T
PE) layer [surface layer material]

[0046]

[Table 1]

[0047]

[Table 2]

[0048]

[Table 3]

[0049]

[Table 4]

[0050]

[Table 5]

(2) Resin layer [core material] PC (polycarbonate resin): Mitsubishi Engineering Plastics "Novarex 7027A" ABS (acrylonitrile butadiene styrene resin): Mitsubishi Chemical "Toughlex TFX" -41
0 "PMMA (polymethylmethacrylate resin): Mitsubishi Rayon Co., Ltd." Acrypet IR H-70 "PS (polystyrene resin): Mitsubishi Chemical Co., Ltd." Dialex HT-88 "PVC (polyvinyl chloride resin) ): Mitsubishi Chemical MKV Co., Ltd. "Vinica Compound E-320" Modified PPE (polyphenylene ether resin): Mitsubishi Gas Chemical Co., Ltd. "Yupiace AH60"

[III] Experimental Examples Examples 1 to 21 and Comparative Examples 1 to 21 Compounds (parts by weight) shown in Tables 6 to 11 were added. , 0.2 parts by weight of a phenolic antioxidant (trade name “Irganox 1010” manufactured by Ciba-Geigy Co., Ltd.) was added, and the compression ratio L /
D = 33, 23 with a twin-screw extruder with a cylinder diameter of 45 mm
Melt-kneading was performed at a setting of 0 ° C. to obtain TPE composition pellets.
The pellets were injection-molded as described above to obtain a sheet, which was subjected to the above evaluation. The evaluation results are shown in Tables 6-11.

[0053]

[Table 6]

[0054]

[Table 7]

[0055]

[Table 8]

[0056]

[Table 9]

[0057]

[Table 10]

[0058]

[Table 11]

[0059]

EFFECT OF THE INVENTION The composite molded article of the present invention is excellent in heat fusion between the resin layer and the styrene-based thermoplastic elastomer layer, and the molded article has no sticky feeling, and therefore has good releasability during molding. Thus, there are advantages that the molded product is less likely to have dust, a free product shape can be molded, and there is no need to apply coating immediately after molding. In particular, when at least one resin selected from polycarbonate and acrylic resin is selected for the resin layer and styrene TPE containing a polyester thermoplastic elastomer layer is selected for the styrene TPE layer, heat fusion property Great effect.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification code Office reference number FI Technical indication location B32B 27/30 A 9349-4F 101 9349-4F 27/36 102 9349-4F C08L 53/02 LLZ 67 / 00 LNZ 75/04 NGF 77/00 LQR 91/00 LSJ // B29K 25:00 B29L 9:00

Claims (4)

[Claims] 1. A composite molded article comprising a styrene thermoplastic elastomer layer and at least one resin layer selected from the group consisting of polycarbonate, acrylic resin, styrene resin, polyvinyl chloride, and modified polyphenylene ether. A composite molded article, characterized in that the styrene-based thermoplastic elastomer layer comprises a base material containing the following components A to C. Component A: Hydrogenated product of styrene / conjugated diene block copolymer, the conjugated diene of which is a mixture of isoprene and butadiene 30 to 90% by weight Component B: Paraffin oil 70 to 10% by weight Component C: Polyester At least one thermoplastic elastomer selected from the group consisting of thermoplastic thermoplastic elastomer, thermoplastic polyamide elastomer, and thermoplastic polyurethane elastomer 10 to 200 parts by weight per 100 parts by weight of the total amount of the above components A and B 2. The resin layer is at least one resin selected from polycarbonate and acrylic resins, 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 or 2, wherein the mixed weight ratio of isoprene and butadiene of conjugated diene in component A (isoprene / butadiene) is 90/10 to 30/70. 4. A resin layer of at least one selected from the group consisting of polycarbonate, acrylic resin, styrene resin, polyvinyl chloride and modified polyphenylene ether is molded, and then a styrene thermoplastic elastomer layer is injection molded. In the method for producing a composite molded article using the insert injection molding method, the two-color injection molding method or the core back injection molding method, the styrene-based thermoplastic elastomer is composed of a base material containing the following components A to C. A method for producing a composite molded article, which is characterized. Component A: Hydrogenated product of styrene / conjugated diene block copolymer, the conjugated diene of which is a mixture of isoprene and butadiene 30 to 90% by weight Component B: Paraffin oil 70 to 10% by weight Component C: Polyester At least one thermoplastic elastomer selected from the group consisting of thermoplastic thermoplastic elastomer, thermoplastic polyamide elastomer, and thermoplastic polyurethane elastomer 10 to 200 parts by weight per 100 parts by weight of the total amount of the above components A and B