JP2009137159A - Composite resin molding - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a composite resin molding excellent in adhesion between a thermoplastic and a polystyrene resin. <P>SOLUTION: The composite resin molding is composed of a substrate and a surface member formed of a thermoplastic resin (IV) on at least a surface part of the substrate, the substrate is formed by a resin composition (III) comprising 90-10 mass parts of a polystyrene resin (I) and 10-90 mass parts of a copolymer (II) of vinyl cyanide-aromatic vinyl compounds, and the content of the acetone soluble vinyl cyanide unit is 1-15 mass% in the copolymer (II) of vinyl cyanide-aromatic vinyl compounds. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to a composite resin molded article in which a surface layer material is formed on a base material and used for a building material member or the like.

As a material of composite building materials that are joined by co-extrusion or injection molding of multiple materials, or bonded to multiple molded products, conventional vinyl chloride resin or composites filled with filler in vinyl chloride resin The material has been mainly used. In recent years, however, vinyl chloride resins that can generate hydrogen chloride during combustion have been avoided due to the influence of consumers' environmental awareness.
Against this background, alternative materials for vinyl chloride resin have been studied, and styrene-based materials such as acrylonitrile-butadiene-styrene resin (hereinafter referred to as “ABS resin”) and polystyrene resins whose extrusion molding conditions are relatively similar to vinyl chloride. Thermoplastic resins are listed as an alternative material.

So far, composite building materials have been molded using the same kind of resin or a resin that can be adhered. However, in recent years, there has been an increasing need for composite resin molded products combining various resins by taking advantage of the characteristics of each resin. As an example, Patent Document 1 discloses a composite resin molded article of acrylate-styrene-acrylonitrile resin (hereinafter referred to as “ASA resin”) and polystyrene resin.
In such composite resin molded products, thermoplastic resins such as ASA resin and ABS resin are highly functional materials having excellent processability and appearance, and excellent in weather resistance and chemical resistance. It is relatively often used as a surface layer material (design surface).
On the other hand, polystyrene resins and the like have excellent processability and appearance, but have the drawback of poor weather resistance and chemical resistance. Therefore, it is often used for a base material (non-design surface) depending on applications. In addition, polystyrene resin is frequently used for a base material (non-design surface) in terms of cost advantage (thermoplastic resin), good foam moldability, and recycling of waste polystyrene resin.
For this reason, a composite with enhanced functionality as a composite material by using a highly functional material for the surface material (design surface) and a general material such as polystyrene resin for the base material (non-design surface) The demand for resin molded products is expected to continue to expand.
Japanese Patent Laid-Open No. 2005-212474

  However, both thermoplastic resins such as ASA resin and ABS resin and polystyrene resin have poor adhesion to each other, and there is a problem that peeling is likely to occur in a composite resin molded product. There is a method to increase the adhesion by mixing ABS resin or the like with polystyrene resin, but these two resins are incompatible, and when mixed, the dispersion of the thermoplastic resin becomes non-uniform and the adhesion strength varies. is there.

  The present invention has been made in view of the above circumstances, and is a composite resin molded article having excellent adhesion between a surface layer material containing a thermoplastic resin such as ABS resin and a base material containing a polystyrene-based resin, and excellent in appearance. The purpose is to provide.

The present invention includes the following aspects.
[1] A composite resin molded article having a base material and a surface layer material made of a thermoplastic resin (IV) formed on at least a part of the surface of the base material, wherein the base material is a polystyrene resin (I) The vinyl cyanide compound-aromatic vinyl formed from a resin composition (III) containing 90-10 parts by mass and 10-90 parts by mass of a vinyl cyanide compound-aromatic vinyl compound polymer (II) A composite resin molded article in which the content of vinyl cyanide compound units in the acetone-soluble component of the compound polymer (II) is 1 to 15% by mass.
[2] The composite resin molded article according to [1], wherein the vinyl cyanide compound-aromatic vinyl compound polymer (II) includes an acrylonitrile unit and / or a methacrylonitrile unit.
[3] The composite resin molded article according to [1] or [2], wherein the vinyl cyanide compound-aromatic vinyl compound polymer (II) further includes a styrene unit and / or an α-methylstyrene unit.
[4] The composite resin molded article according to any one of [1] to [3], wherein the polystyrene resin (I) includes a polystyrene polymer and / or a high impact polystyrene resin.
[5] The composite resin molded product according to [4], wherein the polystyrene resin (I) is a recycled product.
[6] The thermoplastic resin (IV) is at least one selected from the group consisting of acrylonitrile-butadiene-styrene resin, acrylate-styrene-acrylonitrile resin, acrylonitrile-ethylenepropylenediene-styrene resin. The composite resin molded product according to any one of [1] to [5].
[7] The composite resin molded article according to any one of [1] to [6], which is formed by injection molding or extrusion molding.

  According to the present invention, such a composite resin molded article has excellent adhesion between a surface layer material containing a thermoplastic resin such as ABS resin and a base material containing a polystyrene resin, and also has an excellent appearance. In addition to being suitable for various parts such as exterior and interior, it can also be used for some decorations and can be used for a wide range of purposes.

Hereinafter, the present invention will be described in detail.
The composite resin molded article of the present invention has a base material and a surface layer material made of a thermoplastic resin (IV) formed on at least a part of the surface of the base material.

〔Base material〕
The base material is formed from a resin composition (III) containing 90 to 10 parts by mass of a polystyrene resin (I) and 10 to 90 parts by mass of a vinyl cyanide compound-aromatic vinyl compound polymer (II). It is a thing.

<Polystyrene resin (I)>
Known polystyrene resins (I) can be used in the present invention.
The polystyrene resin (I) is preferably a polystyrene polymer and / or a high impact polystyrene resin. In addition, waste polystyrene resin, waste high-impact polystyrene resin, and the like that are recycled products can be used, and can include one or more selected from the group consisting of these.

Here, polystyrene polymers include styrene, methyl styrene, ethyl styrene, isopropyl styrene, dimethyl styrene, paramethyl styrene, chlorostyrene, bromostyrene, vinyl toluene, vinyl xylene homopolymer or copolymer, and styrene- Those containing one or more selected from the group of maleic anhydride copolymers, styrene-acrylic acid copolymers, and styrene-methacrylic acid copolymers are preferred.
The high impact polystyrene resin is obtained by copolymerizing at least one of butadiene rubber, ethylene-propylene rubber, and styrene-butadiene rubber with the above polystyrene polymer.

Waste polystyrene resin and waste high-impact polystyrene resin are resin scraps (including lumps), pellets and surplus products that do not become products generated at the beginning or end of the production process of the above-mentioned polystyrene polymer and high-impact polystyrene resin. It is a recycled product made of waste such as.
Wastes that become waste polystyrene resin and waste high-impact polystyrene resin include resin waste (including lumps) and nonconforming molded products that are generated in various molding processes to mold molded products made of polystyrene polymer and high-impact polystyrene resin. Unnecessary resins and resin molded products such as surplus molded products and surplus pellets are also included.
Furthermore, the resin part of products such as products that have finished their role in the market and unsold goods can be cited, for example, used for food containers, stationery, foamed polystyrene, optical discs, magneto-optical discs, cassette tapes, etc., and miscellaneous goods. The high impact polystyrene resin used in the polystyrene polymer, home appliances, information equipment, machine parts and the like.

  In addition to the polystyrene polymer and / or high-impact polystyrene resin and its recycled products, the polystyrene resin (I) includes polyphenylene as long as the original mechanical properties are not impaired in order to impart properties such as heat resistance. Other resins such as ether may be included.

<Vinyl cyanide compound-aromatic vinyl compound polymer (II)>
The vinyl cyanide compound-aromatic vinyl compound polymer (II) is a copolymer of a vinyl cyanide compound and an aromatic vinyl compound monomer copolymerizable therewith. In addition, content of the vinyl cyanide compound unit in acetone soluble part of this copolymer is 1-15 mass%.

(Vinyl cyanide compound)
Specific examples of the vinyl cyanide compound forming the vinyl cyanide compound-aromatic vinyl compound polymer (II) include acrylonitrile, methacrylonitrile, etc., and these may be used alone. Two or more kinds may be used in combination. Of these, acrylonitrile is preferred.

(Aromatic vinyl compound)
Specific examples of the aromatic vinyl compound forming the vinyl cyanide compound-aromatic vinyl compound polymer (II) include styrene and α-methylstyrene, and these may be used alone. Two or more types may be used in combination, but styrene is particularly preferable.

The content ratio of the vinyl cyanide compound unit and the aromatic vinyl compound unit in the vinyl cyanide compound-aromatic vinyl compound polymer (II) (vinyl cyanide compound unit / aromatic vinyl compound unit) is preferably 1 to 15 mass% / 99-85 mass%, More preferably, it is 2-10 mass% / 98-90 mass%, Most preferably, it is 3-7 mass% / 97-93 mass%.
When the content of the vinyl cyanide compound unit exceeds 15% by mass (the aromatic vinyl compound unit is less than 85%), the polystyrene resin (I) and the vinyl cyanide compound-aromatic vinyl compound polymer (II) This is not preferable because not only the compatibility of the polystyrene resin is lowered and the mechanical properties inherent to the polystyrene resin are lowered, but also the moldability inherent in the polystyrene resin is impaired. On the other hand, if the content of the vinyl cyanide compound unit is less than 1% by mass <the aromatic vinyl compound unit exceeds 99% by mass), sufficient adhesion strength with the thermoplastic resin (IV) cannot be obtained.

(Other copolymerizable compounds)
If necessary, the vinyl cyanide compound-aromatic vinyl compound polymer (II) is a compound copolymerizable with an aromatic vinyl compound unit, a vinyl cyanide compound unit, such as a rubbery polymer unit and other vinyls. It can contain compound units.

The rubbery polymer unit and other vinyl compound units to be contained are preferably 50% by mass or less, particularly preferably 45% by mass or less, in the vinyl cyanide compound-aromatic vinyl compound polymer (II). it can. In this case, it is preferable that the content ratio of the vinyl cyanide compound unit and the aromatic vinyl compound unit in the vinyl cyanide compound-aromatic vinyl compound polymer (II) maintains the above-described content ratio.
When the content of the rubbery polymer unit and other vinyl compound units is 50% by mass or less, the original mechanical properties of the polystyrene resin are not lowered, the original processability of the polystyrene resin is not impaired, and the surface layer material This is preferable because the adhesion can be obtained.

  Rubber polymers include conjugated diene copolymers of polybutadiene, butadiene, and vinyl monomers copolymerizable with butadiene; acrylate esters (co) polymers; acrylate esters and copolymers thereof. Acrylic ester copolymer with possible vinyl monomer; ethylene-propylene-nonconjugated diene copolymer or butene (preferably propylene) -nonconjugated diene copolymer; polyorganosiloxane (co) A polymer etc. are mentioned.

Here, polybutadiene is a generic term for those having structures such as cis and trans.
Examples of the conjugated diene copolymer of polybutadiene and a vinyl monomer copolymerizable therewith include styrene-butadiene rubber and nitrile rubber.
Examples of the acrylic acid ester (co) polymer acrylic acid ester include methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, isobutyl acrylate, pentyl acrylate, isoamyl acrylate, n-hexyl acrylate, 2-methylpentyl acrylate, and 2-ethylhexyl. Examples thereof include acrylate and n-octyl acrylate.
Examples of the diene contained in the ethylene-propylene-nonconjugated diene copolymer or the butene-nonconjugated diene copolymer include dicyclopentadiene, 1,4-hexadiene, 1,4-heptadiene, 1,5-cycloocta Diene, 6-methyl-1,5-heptadiene, 11-ethyl-1,11-tridecadiene, 5-methylene-2-norbornene and the like can be mentioned.
Examples of the polyorganosiloxane-based (co) polymer include silicone rubber, and other examples include a polybutadiene hydrogenated product, a copolymer comprising at least one styrene polymer block and at least one butadiene polymer block. And hydrogenated products.

As the rubbery polymer, one of these can be used alone, or two or more of them can be used as a blend or a composite rubber. Furthermore, the structure of the rubbery polymer may take a core-shell structure. For example, a rubbery polymer having polybutadiene as the core and shelled with an acrylate ester may be used.
The average particle diameter of the rubbery polymer used in the vinyl cyanide compound-aromatic vinyl compound polymer (II) according to the present invention is preferably 0.08 to 2 μm, preferably 0.12 to 0.5 μm. Particularly preferred. If the average particle size of the rubbery polymer is 0.08 μm or more, the mechanical properties of the polystyrene resin (I) will not be deteriorated. If it is 2 μm or less, the original surface appearance of the molded product will be affected. This is because there is not.

Other vinyl compounds include acrylics such as methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, amyl acrylate, hexyl acrylate, octyl acrylate, 2-ethylhexyl acrylate, cyclohexyl acrylate, dodecyl acrylate, octadecyl acrylate, phenyl acrylate, and benzyl acrylate. Acid ester; methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, amyl methacrylate, hexyl methacrylate, octyl methacrylate, 2-ethylhexyl methacrylate, cyclohexyl methacrylate, dodecyl methacrylate, octadecyl methacrylate, phenyl methacrylate, benzyl methacrylate Methacrylic acid esters such as maleic anhydride; unsaturated acid anhydrides such as maleic anhydride, itaconic anhydride and citraconic anhydride; unsaturated acids such as acrylic acid and methacrylic acid; maleimide, N-methylmaleimide, N-butylmaleimide, N -(P-methylphenyl) maleimide, N-phenylmaleimide, N-cyclohexylmaleimide and other α- or β-unsaturated dicarboxylic acid imide compounds (also referred to as maleimide monomers); glycidyl methacrylate, allyl glycidyl ether, etc. Epoxy compounds; unsaturated carboxylic acid amides such as acrylamide and methacrylamide; amino group-containing unsaturated compounds such as acrylic amine, aminomethyl methacrylate, aminoethyl methacrylate, aminopropyl methacrylate, and aminostyrene; 3-hydroxy-1- Lopen, 4-hydroxy-1-butene, cis-4-hydroxy-2-butene, trans-4-hydroxy-2-butene, 3-hydroxy-2-methyl-1-propene, 2-hydroxyethyl acrylate, 2- Examples thereof include hydroxyl group-containing unsaturated compounds such as hydroxyethyl methacrylate; oxazoline group-containing unsaturated compounds such as vinyl oxazoline.
One of these other vinyl monomers may be used alone, or two or more thereof may be used in combination.

(Polymerization method)
The vinyl cyanide compound-aromatic vinyl compound polymer (II) is a known polymerization method for the above-mentioned vinyl cyanide compound, aromatic vinyl compound and other compounds copolymerizable with these vinyl compounds. It can be obtained by emulsion polymerization, suspension polymerization, solution polymerization, bulk polymerization, or a polymerization method combining these.

The content of the vinyl cyanide compound unit in the acetone-soluble component of the vinyl cyanide compound-aromatic vinyl compound polymer (II) formed as described above is 1 to 15% by mass, It is preferable in it being 10 mass%, Most preferably, it is 3-7 mass%.
When the content of the vinyl cyanide compound unit in the acetone-soluble component is less than 1% by mass, sufficient adhesion with the thermoplastic resin (IV) cannot be obtained. When the content exceeds 15% by mass, the compatibility between the polystyrene resin (I) and the vinyl cyanide compound-aromatic vinyl compound polymer (II) is lowered, and the original mechanical properties of the polystyrene resin are lowered. In addition, the original moldability of the polystyrene resin is impaired, which is not preferable.

The content of vinyl cyanide compound unit in the acetone-soluble component is measured by the following method.
First, 1 g of vinyl cyanide compound-aromatic vinyl compound polymer (II) is put into 80 ml of acetone and left overnight, and the soluble component is eluted by applying an ultrasonic cleaner for 30 minutes. Thereafter, centrifugation is performed at 30,000 rpm for 1 hour using a centrifuge to separate a soluble component and an insoluble component. Further, after concentrating the soluble component in acetone with an evaporator, 150 ml of methanol is added to precipitate the soluble component again.
Although there is no restriction | limiting in particular as an analytical instrument which measures content of the vinyl cyanide compound unit in the obtained soluble part, Pyrolysis gas chromatography can be used. In some cases, it is also possible to analyze by combining a plurality of analytical instruments.

  The mass average molecular weight of the acetone-soluble component of the vinyl cyanide compound-aromatic vinyl compound polymer (II) is preferably 75,000 to 250,000, and preferably 100,000 to 200,000. And more preferred. If the mass average molecular weight of the acetone-soluble component is 75,000 or more, sufficient adhesion to the thermoplastic resin (IV) can be obtained, and the impact peel resistance tends to be excellent, and if it is 250,000 or less, the resin. The extrusion moldability of the composition (III) is improved.

The mass average molecular weight in the acetone-soluble component of the vinyl cyanide compound-aromatic vinyl compound polymer (II) is measured by the following method.
In the method for measuring the content of vinyl cyanide compound units in the acetone-soluble matter, the resulting precipitate was separated from methanol, dried, dissolved in tetrahydrofuran, and gel permeation chromatography (GPC). Measured by molecular weight in terms of standard polystyrene.

<Resin composition (III)>
The blending ratio of the polystyrene resin (I) and the vinyl cyanide compound-aromatic vinyl compound polymer (II) in the resin composition (III) forming the base material is 10 to 90 mass% of the polystyrene resin (I). Parts, 10 to 90 parts by mass of vinyl cyanide compound-aromatic vinyl compound polymer (II). Preferably they are 10-80 mass parts of polystyrene-type resin (I), and 20-90 mass parts of vinyl cyanide compound-aromatic vinyl compound type polymers (II). Particularly preferred are 20 to 70 parts by mass of polystyrene resin (I) and 30 to 80 parts by mass of vinyl cyanide compound-aromatic vinyl compound polymer (II).
When the polystyrene resin (I) is less than 10 parts by mass and the vinyl cyanide compound-aromatic vinyl compound polymer (II) exceeds 90 parts by mass, the moldability of the resin composition (III) is impaired. On the other hand, when the polystyrene resin (I) exceeds 90 parts by mass and the vinyl cyanide compound-aromatic vinyl compound polymer (II) is less than 10 parts by mass, sufficient with the thermoplastic resin (IV). Good adhesion cannot be obtained.

In addition, the resin composition (III) includes polystyrene resin (I), vinyl cyanide compound-aromatic vinyl compound system, so as not to affect the adhesion between the base material and the surface layer material (thermoplastic resin (IV)). In addition to the polymer (II), other resins (including waste materials thereof) can be blended.
Examples of other resins include ABS resin, ASA resin, rubber-reinforced styrene resin such as acrylonitrile-ethylene propylene diene-styrene resin (hereinafter referred to as “AES resin”), and acrylonitrile-styrene resin (hereinafter referred to as “AS”). Resin ”), polycarbonate resin, polybutylene terephthalate resin, polyethylene terephthalate resin, polyacetal resin, nylon resin, methyl methacrylate resin (hereinafter referred to as“ PMMA resin ”), polypropylene resin, polyvinyl chloride resin, polyphenylene ether resin, Polylactic acid resin, polysulfone, polyetherketone, polyethersulfone, polyethersulfone, fluororesin, silicone resin, polyethylene, polyester elastomer, polycaprolactone, aromatic poly Ester elastomer, polyamide elastomer, acrylonitrile - styrene - graft polyethylene, acrylonitrile - styrene - such as polyethylene waxes such graft polypropylene. These may be used alone or in a blend of two or more. Furthermore, you may mix | blend the said resin modified | denatured with the compatibilizing agent, the functional group, etc.

  Furthermore, the resin composition (III) includes various known additives in addition to the above resins, for example, paraffin wax, lubricants such as fatty acid esters, hindered phenols, antioxidants such as phosphate esters and phosphites, Weathering improvers such as triazine compounds, colorants such as pigments and dyes, flame retardants, antistatic agents, wood flour and the like may be included.

There is no restriction | limiting in particular in the method for manufacturing the said resin composition (III), A normal method can be used satisfactorily.
For example, by blending a predetermined amount of polystyrene-based resin (I), vinyl cyanide compound-aromatic vinyl compound-based polymer (II), and various additive components used as desired, kneading with a kneader It may be prepared. Examples of the kneader include an extruder, a Banbury mixer, and a kneader. Furthermore, as extruders, screw extruders such as single-screw extruders and multi-screw extruders, elastic extruders, hydrodynamic extruders, ram-type continuous extruders, roll-type extruders, non-screws such as gear-type extruders Among these, a screw extruder, particularly a twin screw extruder is preferable.
There is no particular limitation on the method for molding the resin composition (III) thus produced as a base material, and ordinary methods can be used. For example, injection molding, extrusion molding, cast molding, compression molding, transfer molding and the like can be mentioned.

[Surface material]
<Thermoplastic resin (IV)>
Examples of the thermoplastic resin (IV) used in the present invention include rubber-reinforced styrene resins such as ABS resin, ASA resin, AES resin, AS resin, polycarbonate resin, polybutylene terephthalate resin, polyethylene terephthalate resin, polyacetal resin. , Nylon resin, PMMA resin, polypropylene resin, polyvinyl chloride resin, polyphenylene ether resin, polylactic acid resin, polysulfone, polyether ketone, polyether sulfone, polyether sulfone, fluororesin, silicone resin, polyethylene, polyester elastomer, polycaprolactone , Aromatic polyester elastomer, polyamide-based elastomer, acrylonitrile-styrene-graft polyethylene, acrylonitrile-styrene-graft poly Polyethylene waxes such as propylene and the like. Moreover, what blended these 2 or more types may be sufficient, and resin modified | denatured by the compatibilizing agent, the functional group, etc. is mentioned further.

  Among them, from the viewpoint of design, the appearance and impact-resistant peeling are excellent. ABS resin, ASA resin, AES resin and other rubber-reinforced styrene resins, AS resin, polycarbonate resin, polybutylene terephthalate resin, polyethylene terephthalate resin, polyacetal resin, Nylon resin, PMMA resin, polylactic acid resin, and resins obtained by blending two or more of these are particularly preferable. Moreover, it can be made to mix | blend using the recycled product of these resin.

Further, the thermoplastic resin (IV) is preferably obtained as follows.
The thermoplastic resin (IV) is a group consisting of an aromatic vinyl compound, a vinyl cyanide compound, and other vinyl monomers copolymerizable with these vinyl compounds in the presence or absence of a rubbery polymer. A resin obtained by (co) polymerizing at least one monomer component selected from
A resin obtained by blending a copolymer obtained in the presence of the rubber polymer and a (co) polymer obtained in the absence of the rubber polymer is also a preferred thermoplastic resin ( IV).
Further, a mixture of a plurality of different (co) polymers such as the composition and the particle size of the rubbery polymer may be used.
Here, the copolymer obtained in the presence of the rubbery polymer is referred to as “graft copolymer (A)”, and the (co) polymer obtained in the absence of the rubbery polymer is referred to as “(copolymer). ) Polymer (B) "and the production method is shown below.

(Graft copolymer (A))
The rubbery polymer used in the graft copolymer (A) includes a conjugated diene copolymer of polybutadiene, butadiene and a vinyl monomer copolymerizable with these dienes; acrylate (co) polymer Acrylate ester copolymer of acrylic acid ester and vinyl monomer copolymerizable therewith; ethylene-propylene-nonconjugated diene copolymer, or butene (preferably propylene) -nonconjugated diene Copolymer; polyorganosiloxane-based (co) polymers and the like.

Here, polybutadiene is a generic term for those having structures such as cis and trans.
Examples of the conjugated diene copolymer of polybutadiene and a vinyl monomer copolymerizable therewith include styrene-butadiene rubber and nitrile rubber.
Examples of the acrylic acid ester (co) polymer acrylic acid ester include methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, isobutyl acrylate, pentyl acrylate, isoamyl acrylate, n-hexyl acrylate, 2-methylpentyl acrylate, and 2-ethylhexyl. Examples thereof include acrylate and n-octyl acrylate.
Examples of the diene contained in the ethylene-propylene-nonconjugated diene copolymer or the butene-nonconjugated diene copolymer include dicyclopentadiene, 1,4-hexadiene, 1,4-heptadiene, 1,5-cycloocta Examples include diene, 6-methyl-1,5-heptadiene, 11-ethyl-1,11-tridecadiene, 5-ethylidene-2-norbornene, and the like.
Examples of the polyorganosiloxane-based (co) polymer include silicone rubber, and other examples include a polybutadiene hydrogenated product, a copolymer comprising at least one styrene polymer block and at least one butadiene polymer block. And hydrogenated products, silicone rubber and the like.

As the rubbery polymer, one of the above can be used alone, or two or more blends or composite rubber can be used. Furthermore, the structure of the rubbery polymer may take a core-shell structure. For example, a rubbery polymer having polybutadiene as the core and acrylic acid ester as the shell can be used.
The average particle diameter of the rubber polymer is preferably 0.08 to 2 μm, and particularly preferably 0.12 to 0.5 μm. If the average particle size is 0.08 μm or more, the impact resistance is excellent, and if it is 2 μm or less, the surface appearance (designability) of the molded product is excellent.

  The content of the rubbery polymer in the graft copolymer (A) is preferably 5 to 70% by mass, more preferably 10 to 60% by mass, and still more preferably 15 to 50% by mass. If the content of the rubbery polymer is 5% by mass or more, impact resistance tends to be obtained, and if it is 70% by mass or less, the extrusion moldability tends to be good.

Among the vinyl monomers used in the graft copolymer (A), aromatic vinyl compounds include styrene, t-butylstyrene, α-methylstyrene, p-methylstyrene, divinylbenzene, 1,1-diphenyl. Styrene, N, N-diethyl-p-aminoethylstyrene, N, N-diethyl-p-aminomethylstyrene, vinylpyridine, vinylxylene, monochlorostyrene, dichlorostyrene, monobromostyrene, dibromostyrene, tribromostyrene, fluoro Examples thereof include styrene and vinyl naphthalene, and styrene and α-methylstyrene are particularly preferable.
Among the vinyl monomers used in the graft copolymer (A), examples of the vinyl cyanide compound include acrylonitrile and methacrylonitrile, with acrylonitrile being particularly preferred.

Further, other vinyl monomers copolymerizable with these vinyl compounds include methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, amyl acrylate, hexyl acrylate, octyl acrylate, 2-ethylhexyl acrylate, cyclohexyl acrylate, Acrylic esters such as dodecyl acrylate, octadecyl acrylate, phenyl acrylate, benzyl acrylate; methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, amyl methacrylate, hexyl methacrylate, octyl methacrylate, 2-ethylhexyl methacrylate, cyclohexyl methacrylate, dodecyl methacrylate, octadecyl Methacrylate, Methacrylic acid esters such as phenyl methacrylate and benzyl methacrylate; unsaturated acid anhydrides such as maleic anhydride, itaconic anhydride and citraconic anhydride; unsaturated acids such as acrylic acid and methacrylic acid; maleimide, N-methylmaleimide, N- Imide compounds of α- or β-unsaturated dicarboxylic acids such as butylmaleimide, N- (p-methylphenyl) maleimide, N-phenylmaleimide, N-cyclohexylmaleimide (also called maleimide monomers); glycidyl methacrylate, allyl Epoxy compounds such as glycidyl ether; unsaturated carboxylic acid amides such as acrylamide and methacrylamide; amines such as acrylic amine, aminomethyl methacrylate, aminoethyl methacrylate, aminopropyl methacrylate, and aminostyrene Group-containing unsaturated compounds; 3-hydroxy-1-propene, 4-hydroxy-1-butene, cis-4-hydroxy-2-butene, trans-4-hydroxy-2-butene, 3-hydroxy-2-methyl- And hydroxyl group-containing unsaturated compounds such as 1-propene, 2-hydroxyethyl acrylate, and 2-hydroxyethyl methacrylate; oxazoline group-containing unsaturated compounds such as vinyl oxazoline;
The above aromatic vinyl compounds, vinyl cyanide compounds and other vinyl monomers copolymerizable with these vinyl compounds may be used alone or in combination of two or more. .
As the combination of the vinyl monomers used in the graft copolymer (A), styrene, styrene and acrylonitrile, α-methylstyrene and acrylonitrile, methyl methacrylate, or styrene and methyl methacrylate are particularly preferable.

In addition, the content of the vinyl monomer unit in the graft copolymer (A) is preferably 95 to 30% by mass, more preferably 90 to 40% by mass, still more preferably 85 to 50% by mass, particularly Preferably it is 85-75 mass%. If the vinyl monomer content is 95% by mass or less, impact resistance tends to be obtained, and if it is 30% by mass or more, extrusion moldability tends to be good.
Furthermore, the graft copolymer (A) is preferably obtained by a known polymerization method such as emulsion polymerization, suspension polymerization, solution polymerization, bulk polymerization, or a polymerization method combining these.

((Co) polymer (B))
Examples of the aromatic vinyl compound, vinyl cyanide compound, and other vinyl monomers copolymerizable with these vinyl compounds that form the (co) polymer (B) are exemplified in the graft copolymer (A). These monomers can be used alone or in combination of two or more.
Examples of combinations of vinyl monomers used in the (co) polymer (B) include styrene, styrene and acrylonitrile, α-methylstyrene and acrylonitrile, methyl methacrylate, styrene and methyl methacrylate, or methyl methacrylate and methyl acrylate. Is preferred.
Furthermore. The (co) polymer (B) is preferably obtained by a known polymerization method exemplified for the graft copolymer (A).

As described above, the thermoplastic resin (IV) may be composed of only one of the graft copolymer (A) or the (co) polymer (B), or may be a resin obtained by blending them.
The thermoplastic resin (IV) does not necessarily need to contain a rubbery polymer for use as a surface layer material, but preferably contains a rubbery polymer in terms of impact resistance and extrusion moldability.
The content of the rubbery polymer in the thermoplastic resin (IV) is preferably 5 to 70% by mass, more preferably 10 to 60% by mass, further preferably 15 to 50% by mass, and particularly preferably 15 to 25% by mass. %.
If the content of the rubbery polymer is 5% by mass or more, impact resistance tends to be obtained, and if it is 70% by mass or less, the extrusion moldability tends to be good.

The thermoplastic resin (IV) preferably has a vinyl cyanide compound component content in the acetone-soluble content of 20 to 50% by mass and a mass average molecular weight of 100,000 to 300,000, The graft copolymer (A) is preferably in this range.
If the content of the vinyl cyanide compound component in the acetone-soluble component of the thermoplastic resin (IV) is 20% by mass or more, chemical resistance tends to be obtained, and if it is 50% by mass or less, moldability. , Heat stability and adhesion to the substrate (resin composition (III)) tend to be obtained. Further, if the mass average molecular weight of the acetone-soluble component is 100,000 or more, impact resistance and impact peelability tend to be obtained, and if it is 300,000 or less, extrusion moldability tends to be obtained. It is in.
In addition, the vinyl cyanide compound and mass average molecular weight in acetone soluble part can be computed from each analysis value of the graft copolymer (A) and (co) polymer (B) which comprise.

Furthermore, adhesion between the base material made of the resin composition (III) containing the polystyrene resin (I) and the vinyl cyanide compound-aromatic vinyl compound polymer (II) and the surface layer material made of the thermoplastic resin (IV) Various additives can be blended in the thermoplastic resin (IV) to the extent that it does not affect the properties.
In this case, various additives include known antioxidants, light stabilizers, ultraviolet absorbers, lubricants, plasticizers, stabilizers, mold release agents, antistatic agents, colorants (pigments, dyes, etc.), carbon fibers. , Fillers such as glass fiber, wollastonite, calcium carbonate, silica, flame retardant, brominated flame retardant, flame retardant auxiliary such as antimony trioxide, phosphorus flame retardant, anti-drip agent such as fluororesin, antibacterial agent 1 type or 2 types or more, such as an antifungal agent, a silicone oil, a coupling agent, and wood flour.

[Composite resin molded product]
In order to obtain the composite resin molded article of the present invention, the surface layer material formed from the thermoplastic resin (IV) contains a polystyrene resin (I) and a vinyl cyanide compound-aromatic vinyl compound polymer (II). What is necessary is just to provide to the surface of the base material formed from the resin composition (III) to do. In order to produce a composite resin molded product, for example, a method in which the surface layer material produced in advance is pressure-bonded to the surface of the substrate by heat; the resin composition (III) is molded in advance inside or outside the die Two-color molding in which a base material is placed in a mold and a thermoplastic resin (IV) is injection-molded in accordance with a conventional method to form a surface layer material (however, a surface layer material made of thermoplastic resin (IV) It may be molded in advance.); Extrusion method by co-extrusion of the resin composition (III) and the thermoplastic resin (IV); laminate extrusion, multilayer extrusion, blow molding or the like.
Of these, extrusion molding by co-extrusion and two-color molding are particularly preferred because of the high degree of freedom in the shape of the molded product.

Co-extrusion molding uses thermoplastic resin (IV), polystyrene resin (I), vinyl cyanide compound-aromatic vinyl compound using various extrusion methods such as extrusion, sheet extrusion, and profile extrusion. In this method, the resin composition (III) containing the base polymer (II) is extruded separately, and the extrudates are brought into close contact with each other and molded.
Coextrusion molding can be generally performed using a known apparatus. Although there is no restriction | limiting in particular in the shaping | molding apparatus to be used, The apparatus provided with an extruder, die | dye, sizing die, a cooling tank, a take-up machine, and a winder or a cutting machine can be used. In addition to this, an apparatus generally used in extrusion molding can be provided.
A base material composed of a resin composition (III) containing a polystyrene resin (I) and a vinyl cyanide compound-aromatic vinyl compound polymer (II) is molded in advance, and a thermoplastic resin ( It is also possible to adhere IV) while extruding. The reverse is also possible.

There is no restriction | limiting in particular as foaming, the presence or absence of a hollow as a shaping | molding form of a base material. Moreover, there is no restriction | limiting in particular about the presence or absence of reinforcing materials, such as steel materials.
In the case of foaming the base material, it is preferable to form a foam by adding a spreading agent as necessary in addition to adding a foaming agent when forming the resin composition (III).
In the foam molding, the extruder used is not particularly limited, but a single or twin screw extruder generally used in extrusion molding can be used. The screw diameter (D) of the extruder is preferably 10 mm or more, and the screw screw length / screw diameter (L / D) is preferably 16 or more. The screw design is not particularly limited, but a screw design generally used in extrusion molding can be used, and a full flight type is preferable.
When molding a foamed molded product with an extruder, it is important that the molded product is molded under appropriate conditions. The molding conditions vary depending on the performance of the extruder and the shape of the molded product. A range of conditions for molding the thermoplastic resin can be used, and the resin temperature is preferably 140 to 220 ° C, particularly 150 to 200 ° C.
Further, the type of foaming agent that can be used when foaming the resin composition (III) is not particularly limited, but one kind selected from azo compounds, nitroso compounds, hydrazine derivatives, and bicarbonates. Or it is preferable to use 2 or more types in combination. Moreover, as a spreading agent when mixing a foaming agent, a dietary oil, a liquid paraffin, a fatty acid, etc. can be used.

  Moreover, when molding thermoplastic resin (IV), by adding a pattern material such as colored pellets made of a thermoplastic resin containing a colorant, a grain pattern or a stone pattern is imparted to the surface layer material. Is also possible.

In the composite resin molded article of the present invention, a base material comprising a resin composition (III) containing a polystyrene resin (I) and a vinyl cyanide compound-aromatic vinyl compound polymer (II) is a thermoplastic resin ( Since it has very good adhesiveness with the surface layer material consisting of IV), it can be used for decorations for exteriors, interior members or parts thereof.
Specific examples of applications include building materials, sill, duck, frame, bathroom door frame, bathroom bay frame, window frame, furniture, bathroom, flooring, baseboard, fence, wood deck, fence, outer wall, roofing material, Housing and housing related parts such as wall materials. Sanitary-related parts include toilet seats, tank covers, costume cases, kitchen parts, washstand-related parts, bathroom-related parts, and the like.
Other composite resin molded products can be shaped from sheets, pipes, squares, tubes, etc. from various shapes. Various cases such as personal computer cases, parabolic antennas, VTR parts, TV parts, liquid crystals TV parts, speaker parts, audio equipment, facsimile parts, copier parts, personal computers, printers, displays, cathode ray tube displays, notebook computers, mobile phones, PHS (registered trademark), DVD drives, PD drives, flexible disk drives, and other housings, It can be used for a wide range of applications depending on the purpose, such as case members for switches, lighting parts, exterior members for vehicles such as bumpers and fenders.

Hereinafter, the present invention will be specifically described by way of examples, but the present invention is not limited thereto. Unless otherwise specified, “parts” in the examples below represent parts by mass, and “%” represents mass%.
Each physical property was evaluated by the following method.

(Content of vinyl cyanide compound in acetone-soluble matter)
1 g of vinyl cyanide compound-aromatic vinyl compound polymer (II) was put in 80 ml of acetone and allowed to stand overnight, and the soluble component was eluted by applying an ultrasonic cleaner for 30 minutes. Thereafter, centrifugation was performed at 30,000 rpm for 1 hour using a centrifuge to separate a soluble component and an insoluble component. Further, after concentrating the soluble component in acetone with an evaporator, 150 ml of methanol was added to precipitate the soluble component again.
The precipitate was dried with a vacuum dryer, and the content of vinyl cyanide compound units in the acetone-soluble component was measured by pyrolysis gas chromatography (manufactured by Shimadzu Corporation).

(Mass average molecular weight)
The precipitate when measuring the content of the vinyl cyanide compound unit in the acetone-soluble component is separated from methanol. Thereafter, the dried product was dissolved in tetrahydrofuran and measured by the molecular weight in terms of standard polystyrene using gel permeation chromatography.

(Average particle diameter of rubbery polymer)
Nikkiso Co., Ltd. product: Microtrac Model: 9230UPA was used, and the dynamic light scattering method was used.

<Styrene resin (I)>
Styrene resin (I-1): “G210B” (polystyrene polymer) manufactured by Toyo Styrene Co., Ltd.

<Production of vinyl cyanide compound-aromatic vinyl compound polymer (II)>
Synthesis Example 1: Vinyl cyanide compound-aromatic vinyl compound polymer (II-1)
In a nitrogen-substituted reactor, 120 parts of water, 0.002 part of sodium alkylbenzene sulfonate, 0.5 part of polyvinyl alcohol, 0.3 part of azoisobutyronitrile, 0.5 part of terrestrial decyl mercaptan, and 5 parts of acrylonitrile , And a monomer mixture consisting of 95 parts of styrene, the temperature was raised from 60 ° C. over 5 hours to 120 ° C. while adding a part of styrene sequentially. Furthermore, after reacting at 120 ° C. for 4 hours, the obtained polymer was taken out to obtain a vinyl cyanide compound-aromatic vinyl compound polymer (II-1).
The content of vinyl cyanide compound unit in the acetone-soluble component of the obtained vinyl cyanide compound-aromatic vinyl compound polymer (II-1) was 5.4% by mass, and acetone was acceptable in the copolymer. The mass average molecular weight of the solute was 178,000.

Synthesis Example 2: Vinyl cyanide compound-aromatic vinyl compound polymer (II-2)
(Combination)
40 parts of polybutadiene latex (as solids)
Acrylonitrile 5 parts Styrene 55 parts Disproportionated potassium rosinate 1 part Potassium hydroxide 0.03 parts Tertiary decyl mercaptan 0.3 parts Cumene hydroperoxide 0.3 parts Ferrous sulfate 0.007 parts Sodium pyrophosphate 0. 1 part Crystal glucose 0.3 part Distilled water 190 parts Distilled water, disproportionated potassium rosinate, potassium hydroxide and polybutadiene latex (average particle size 0.28 μm, solid content concentration 34% by mass) are charged into an autoclave at 60 ° C. Heated to. Next, ferrous sulfate, sodium pyrophosphate and crystalline glucose were added, and styrene, acrylonitrile, tertiary decyl mercaptan and cumene hydroperoxide were continuously added over 2 hours while maintaining the temperature at 60 ° C. Warmed for 1 hour to complete the reaction. An antioxidant is added to the copolymer latex obtained by such a reaction, then coagulated with sulfuric acid, thoroughly washed with water, and dried to give a vinyl cyanide compound-aromatic vinyl compound polymer (II-2). Obtained.
The content of vinyl cyanide compound unit in the acetone-soluble component of the obtained vinyl cyanide compound-aromatic vinyl compound polymer (II-2) was 6.2% by mass, and acetone in the copolymer was acceptable. The mass average molecular weight of the solute was 137,000, and the content of the rubbery polymer in the copolymer was 41.1% by mass.

Synthesis Example 3: Vinyl cyanide compound-aromatic vinyl compound polymer (II-3)
The polymer was taken out in the same manner as in Synthesis Example 1 except that 1 part of acrylonitrile and 99 parts of styrene were used, except that the same monomer mixture as in Synthesis Example 1 was used. Vinyl cyanide compound-aromatic vinyl compound A system polymer (II-3) was obtained.
The content of the vinyl cyanide compound unit in the acetone-soluble component in the obtained vinyl cyanide compound-aromatic vinyl compound polymer (II-3) was 1.1% by mass, and acetone was acceptable in the copolymer. The mass average molecular weight of the solute was 169,000.

Synthesis Example 4: Vinyl cyanide compound-aromatic vinyl compound polymer (II-4)
A vinyl cyanide compound-aromatic vinyl compound polymer (II-4) was obtained in the same manner as in Synthesis Example 2, except that 10 parts of acrylonitrile and 50 parts of styrene were synthesized in Synthesis Example 2.
The content of vinyl cyanide compound unit in the acetone-soluble component in the obtained vinyl cyanide compound-aromatic vinyl compound polymer (II-4) was 14.6% by mass, and acetone in the copolymer was acceptable. The mass average molecular weight of the solute was 163,000, and the content of the rubbery polymer in the copolymer was 40.6% by mass.

Synthesis Example 5: Vinyl cyanide compound-aromatic vinyl compound polymer (II-5)
The polymer was taken out in the same manner as in Synthesis Example 1 except that 25 parts of acrylonitrile and 75 parts of styrene were used, except that the same monomer mixture as in Synthesis Example 1 was used. Vinyl cyanide compound-aromatic vinyl compound A system polymer (II-5) was obtained.
The content of vinyl cyanide compound unit in the acetone-soluble component of the obtained vinyl cyanide compound-aromatic vinyl compound polymer (II-5) was 23.6% by mass, and acetone in the copolymer was acceptable. The mass average molecular weight of the solute was 164,000.

Synthesis Example 6: Vinyl cyanide compound-aromatic vinyl compound polymer (II-6)
A vinyl cyanide compound-aromatic vinyl compound polymer (II-6) was obtained in the same manner as in Synthesis Example 2, except that 14 parts of acrylonitrile and 46 parts of styrene were synthesized.
The content of vinyl cyanide compound unit in the acetone-soluble component of the obtained vinyl cyanide compound-aromatic vinyl compound polymer (II-6) was 21.8% by mass, and acetone was acceptable in the copolymer. The mass average molecular weight of the solute was 167,000, and the content of the rubbery polymer in the copolymer was 40.8% by mass.

Commercially available resin: Vinyl cyanide compound-aromatic vinyl compound polymer (II-7)
“Modiper MS10B” manufactured by Nippon Oil & Fats Co., Ltd.
(Styrene-methyl methacrylate block copolymer, styrene / methyl methacrylate = 90/10 (mass ratio), content of vinyl cyanide compound in acetone-soluble content is 0% by mass)

<Thermoplastic resin (IV)>
(Production of graft copolymer (A))
Synthesis Example 7: Graft copolymer (A-1)
(Combination)
50 parts of polybutadiene latex (as solids)
Styrene 35 parts Acrylonitrile 15 parts Disproportionated potassium rosinate 1 part Potassium hydroxide 0.03 parts Tertiary decyl mercaptan 0.22 parts Cumene hydroperoxide 0.30 parts Ferrous sulfate 0.007 parts Sodium pyrophosphate 0. 12 parts Crystalline glucose 0.30 parts Distilled water 190 parts Distilled water, disproportionated potassium rosinate, potassium hydroxide and polybutadiene latex (average particle size 0.29 μm, solid content concentration 34% by mass) are charged into an autoclave at 60 ° C. After heating, ferrous sulfate, sodium pyrophosphate and crystalline glucose were added, and styrene, acrylonitrile, tertiary decyl mercaptan and cumene hydroperoxide were added over 2 hours while maintaining the temperature at 60 ° C. as in Synthesis Example 2. Add continuously, then heat up to 70 ° C The reaction was completed for 1 hour. An antioxidant was added to the graft copolymer latex obtained by such a reaction, then coagulated with sulfuric acid, sufficiently washed with water, and dried to obtain a graft copolymer (A-1).
The content of the vinyl cyanide compound unit in the acetone-soluble component in the obtained graft copolymer (A-1) is 28.2% by mass, and the mass-average molecular weight of the acetone-soluble component in the copolymer is The content of the rubber-like polymer in the copolymer was 130.8, and was 50.8% by mass.

Synthesis Example 8: Graft copolymer (A-2)
Synthesis Example 7 except that 60 parts of a composite rubber latex (average particle size 0.34 μm, as solid content) composed of 20 parts of polybutadiene latex and 80 parts of n-butyl acrylate was used instead of the polybutadiene latex of Synthesis Example 7. In the same manner as above, a dry powder of the graft copolymer (A-2) was obtained.
The content of the vinyl cyanide compound unit in the acetone-soluble component in the obtained graft copolymer (A-2) is 27.2% by mass, and the mass-average molecular weight of the acetone-soluble component in the copolymer is 142. The content of the rubber polymer in the copolymer was 48.2% by mass.

Synthesis Example 9: Graft copolymer (A-3)
Except that 50 parts of ethylene-propylene-5-ethylidene-2-norbornene latex (average particle size 0.41 μm, solid content) was used instead of the polybutadiene latex of Synthesis Example 7, it was the same as that of Synthesis Example 7. A dry powder of the graft copolymer (A-3) was obtained.
The content of the vinyl cyanide compound unit in the acetone-soluble component in the obtained graft copolymer (A-3) is 27.8% by mass, and the mass-average molecular weight of the acetone-soluble component in the copolymer is 144. The content of the rubbery polymer in the copolymer was 49.7% by mass.

(Production of (co) polymer (B))
Synthesis Example 10: Copolymer (B-1)
In a nitrogen-substituted reactor, 120 parts of water, 0.002 part of sodium alkylbenzene sulfonate, 0.5 part of polyvinyl alcohol, 0.3 part of azoisobutyl nitrile, 0.5 part of tertiary decyl mercaptan, 30 parts of acrylonitrile, and A monomer mixture composed of 70 parts of styrene was used and heated at a starting temperature of 60 ° C. for 5 hours and then reached 120 ° C. while sequentially adding a part of styrene. Furthermore, after reacting at 120 ° C. for 4 hours, the polymer was taken out to obtain a copolymer (B-1).
The content of the vinyl cyanide compound unit in the acetone soluble component in the obtained copolymer (B-1) is 30.3% by mass, and the mass average molecular weight of the acetone soluble component in the copolymer is 167, 000.

Synthesis Example 11 Production of Copolymer (B-2) The same procedure as in Synthesis Example 10 except that the monomer mixture of acrylonitrile and styrene was changed to a monomer mixture consisting of 98 parts of methyl methacrylate and 2 parts of methyl acrylate. Polymerization was performed to obtain a copolymer (B-2).
The content of the vinyl cyanide compound unit in the acetone-soluble component in the obtained copolymer (B-2) is 0% by mass, and the mass-average molecular weight of the acetone-soluble component in the copolymer is 134,000. there were.

Commercial product: Polycarbonate resin (hereinafter referred to as “PC resin”)
"Iupilon S3000" manufactured by Mitsubishi Engineering Plastics Co., Ltd.

<Thermoplastic resin (IV)>
(A-1), (A-2), (A-3), (B-1), (B-2), and (PC resin) obtained in Synthesis Examples 7 to 11 were added in the following amounts. After adjusting, 1 part of calcium stearate as a lubricant was blended and kneaded by a twin screw extruder to obtain pellets of thermoplastic resins (IV-1) to (IV-6).

Thermoplastic resin (IV-1): ABS resin (A-1) / (B-1) = 30 parts / 70 parts The content of the rubbery polymer in the thermoplastic resin (IV-1) is 15% by mass, The content of vinyl cyanide compound in the acetone-soluble component is 29.67% by mass.

Thermoplastic resin (IV-2): ASA resin (A-2) / (B-1) = 30 parts / 70 parts The content of the rubbery polymer in the thermoplastic resin (IV-2) is 15% by mass, The vinyl cyanide compound component in the acetone-soluble component is 29.37% by mass.

Thermoplastic resin (IV-3): ABS / PMMA resin (A-1) / (B-1) / (B-2) = 30 parts / 20 parts / 50 parts Rubber in thermoplastic resin (IV-3) The content of the polymer is 15% by mass, and the content of the vinyl cyanide compound in the acetone-soluble component is 14.52% by mass.

Thermoplastic resin (IV-4): ASA / PMMA resin (A-1) / (B-2) = 40 parts / 70 parts The content of the rubber-like polymer in the thermoplastic resin (IV-4) is 20 masses. %, The content of the vinyl cyanide compound in the acetone-soluble component is 10.88% by mass.

Thermoplastic resin (IV-5): AES resin (A-3) / (B-1) = 40 parts / 60 parts The content of the rubbery polymer in the thermoplastic resin (IV-5) is 20% by mass, The vinyl cyanide compound component in the acetone-soluble component is 29.3% by mass.

Thermoplastic resin (IV-4): ABS / PC resin (A-1) / (PC resin) = 50 parts / 50 parts The content of the rubbery polymer in the thermoplastic resin (IV-6) is 25.4. The vinyl cyanide compound component in the mass% acetone-soluble component is 28.2 mass%.

[Examples 1-12, Comparative Examples 1-9]
A resin composition (III) containing a polystyrene resin (I) and a vinyl cyanide compound-aromatic vinyl compound polymer (II) was blended in the proportions of the components shown in Table 1.
Furthermore, as a lubricant, 1.0 part of “ethylene bissteric acid amide” manufactured by Kao Corporation and 0.2 part of “calcium stearate” manufactured by Nippon Oil & Fats Co., Ltd. were added and mixed together. A pellet of the resin composition (III) was prepared by melt mixing at 200 to 240 ° C. (“TEX-30α” manufactured by Nippon Steel) and pelletizing.

Using a pellet-shaped thermoplastic resin (IV) as the material for forming the surface layer material, and 100 parts of the pellet-shaped resin composition (III) obtained above as the material for forming the base material, a spreading agent ( A mixture of 0.1 part of liquid paraffin and 0.5 part of a foaming agent (sodium bicarbonate) was used. The resin composition (III) had a foaming ratio of about 2 times and a surface layer material thickness of 2 mm, and was subjected to coextrusion molding to obtain a composite resin molded product.
For co-extrusion molding, a 40 mm extruder manufactured by Chuo Kikai Co., Ltd. and a 25 mm moving extruder manufactured by Ikegai Co., Ltd. were equipped with an adapter and a multilayer profile die, and a sizing equipment, a take-up machine, and a cutting circular saw were installed. Coextrusion was performed at a resin temperature of 170 to 200 ° C. using a coextrusion apparatus.
About the obtained composite resin molded product, the composite resin molded product appearance, adhesion, impact peel resistance, and heat cycle resistance were evaluated by the following methods, and the results are shown in Tables 1 and 2.

(Composite resin molded product appearance)
The appearance of the composite resin molded product was visually determined. A composite resin molded product that has a sufficient appearance, ○ that does not cause molding defects such as foaming failure or surging, and that does not cause shaping failure, △ that the appearance is somewhat inferior but that can be used as a secondary product, and appearance The case where there was a defect (appearance unsatisfactory as a product due to sink marks, die lines, transfer unevenness, etc.), molding defects such as foaming defects, and shaping defects was rated as x.

(Adhesion)
A 2 cm square cut is made in the surface layer material (thermoplastic resin (IV)) of the composite resin molded article, and the surface layer material and the base material (polystyrene resin (I) and vinyl cyanide compound-aromatic vinyl compound polymer ( The determination was made based on the difference in the degree of adhesion at the interface with the resin composition (III)) containing II).
Judgment criteria are: x peeled after molding (not in close contact), or x easily peeled with nail at the interface, x not peeled with a cutter knife blade put on the interface, and no peeling The thing and the thing which adhered so that the blade of a cutter knife could not be put into an object and an interface were set as (circle). In addition, in the case of x, the adhesion strength was not sufficient and was rejected, and in the case of Δ or more, the adhesion strength was practically sufficient and was accepted.

(Shock resistance)
The composite resin molded product was cut with an electric circular saw perpendicular to the extrusion direction, and the adhesion between the surface layer material and the equipment at the time of cutting was evaluated according to the following criteria. The case where the surface material of the cut surface was peeled and the chipping of the substrate did not occur was evaluated as ◯, the case where either peeling or chipping occurred was Δ, and the case where both peeling and chipping occurred was rated as x.

(Heat cycle resistance)
After the composite resin molded article was subjected to a heat cycle test under the following conditions, the surface layer material and the base material were observed for blistering, deformation, and peeling, and evaluated according to the following criteria.
Condition-1: Using a constant temperature bath with a humidity of 40%, −30 ° C. × 1 hour → 23 ° C. × 30 minutes → 70 ° C.
× 1 hour → 23 ° C × 30 minutes as one cycle, 10 cycles Condition-2: Use a constant temperature bath of 80% humidity, -30 ° C × 1 hour → 23 ° C × 30 minutes → 70 ° C
× 1 hour → 23 ° C × 30 minutes as one cycle, 10 cycles ○: No blistering, deformation, or peeling occurred, and the surface layer material and the substrate showed practically sufficient adhesion.
Δ: Slightly any of blistering, deformation and peeling occurs, and the surface layer material and the substrate may not be able to exhibit sufficient adhesion depending on the use environment.
X: Any of blistering, deformation, and peeling occurs vigorously, and the adhesion between the surface material and the substrate is not practical.

  The composite resin molded products of Examples 1 to 10 that satisfy the requirements of claim 1 of the present invention from Table 1 are excellent in adhesion between the surface layer material and the base material, impact peel resistance, and heat cycle resistance. Further, the composite resin molded product has a good appearance and is excellent without molding defects.

From Table 2, the content of the vinyl cyanide compound unit in the acetone-soluble component in the vinyl cyanide compound-aromatic vinyl compound polymer (II) of Comparative Examples 1 to 4 not satisfying the requirements of claim 1 The composite resin molded product has low adhesion between the surface layer material and the substrate, impact peel resistance, and heat cycle resistance, and is very low in practicality. In addition, surging occurred, stable molding could not be performed, and there was a shaping failure, and the appearance was uneven.
The composite resin molded articles of Comparative Examples 5 and 6 in which the blending ratio of the polystyrene resin (I) and the vinyl cyanide compound-aromatic vinyl compound polymer (II) does not satisfy the requirements of claim 1 are the appearance of the molded article. Although the adhesiveness is good, the impact peel resistance and heat cycle resistance are inferior, so the product quality and practicality are lacking. Moreover, about Comparative Examples 5 and 6, generation | occurrence | production of peeling was seen by the heat cycle resistance test, and it turns out that there exists an environmental influence.
Content of vinyl cyanide compound unit in acetone-soluble component in vinyl cyanide compound-aromatic vinyl compound polymer (II) and polystyrene resin (I) and vinyl cyanide compound-aromatic vinyl compound system Comparative Example 7 in which the blending ratio of the polymer (II) does not satisfy the requirements of claim 1 has low adhesion between the surface layer material and the base material, impact peel resistance, and heat cycle resistance, and the practicality is very low. . Further, surging occurred and slight transfer unevenness was observed.
In Comparative Example 8, the base material is formed only from the polystyrene-based resin (I), and the appearance such as foaming is excellent, but the adhesion between the surface layer material and the base material, impact peel resistance, and heat cycle resistance are low. The practicality is very low.
Comparative Example 9 in which the content of vinyl cyanide compound unit in the acetone-soluble component in the vinyl cyanide compound-aromatic vinyl compound polymer (II) does not satisfy the requirements of claim 1 is good in appearance of the molded product However, the adhesion between the surface layer material and the substrate, impact peel resistance, and heat cycle resistance are also low, and the practicality is very low. Probably because the polystyrene resin (I) of the base material and the vinyl cyanide compound-aromatic vinyl compound polymer (II) are mixed well, it looks excellent in appearance such as foaming, but the surface layer material and the base material It can be seen that since there is no adhesion to the material, impact peel resistance and heat cycle resistance are low and practicality is low.
From the above Examples and Comparative Examples, the composite resin molded product of the present invention has excellent adhesion between the thermoplastic resin (IV) forming the surface layer material and the resin composition (III) forming the substrate. I understand that.

Claims (7)

A composite resin molded article having a base material and a surface layer material made of a thermoplastic resin (IV) formed on at least a part of the surface of the base material,
The base material is formed from a resin composition (III) containing 90 to 10 parts by mass of a polystyrene resin (I) and 10 to 90 parts by mass of a vinyl cyanide compound-aromatic vinyl compound polymer (II). And
A composite resin molded article in which the content of vinyl cyanide compound units in the acetone-soluble component of the vinyl cyanide compound-aromatic vinyl compound polymer (II) is 1 to 15% by mass.   The composite resin molded article according to claim 1, wherein the vinyl cyanide compound-aromatic vinyl compound polymer (II) contains an acrylonitrile unit and / or a methacrylonitrile unit.   The composite resin molded article according to claim 1 or 2, wherein the vinyl cyanide compound-aromatic vinyl compound polymer (II) contains a styrene unit and / or an α-methylstyrene unit.   The composite resin molded article according to any one of claims 1 to 3, wherein the polystyrene-based resin (I) contains a polystyrene polymer and / or a high-impact polystyrene resin.   The composite resin molded article according to claim 4, wherein the polystyrene resin (I) is a recycled product.   The thermoplastic resin (IV) is at least one selected from the group consisting of an acrylonitrile-butadiene-styrene resin, an acrylate-styrene-acrylonitrile resin, and an acrylonitrile-ethylenepropylene diene-styrene resin. Any one of the composite resin molded products.   The composite resin molded article according to claim 1, which is formed by injection molding or extrusion molding.