JP2007177215A - Styrene-based resin composition and process for producing the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a styrene-based resin composition which can easily have excellent mechanical characteristics, fluidity, plating property and flame-retardancy and can be highly useful as a general molding material. <P>SOLUTION: A styrene-based resin composition comprises (A) a styrene-based resin, (B) a thermoplastic resin which is not a styrene resin, (c1) a modified styrene-based polymer, and (c2) a polycarbonate-based graft polymer, wherein the styrene-based resin composition preferably has either a continuous structure consisting of both phases with a structure period of 0.001-1 μm or a dispersion structure with an inter-particle distance of 0.001-1 μm. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to a structural material that makes use of excellent mechanical properties and a styrene resin composition that can be usefully used as a functional material making use of excellent regularity. The present invention also relates to a method for producing a styrenic resin composition whose structure can be controlled from nanometer order to micron order.

  Styrenic resins are used in a wide range of fields such as electrical and electronic equipment, automobiles, machine parts, general merchandise, and various other applications due to their excellent mechanical properties, molding processability, and appearance. However, since styrene resin is inferior in impact resistance and heat resistance, a flexible component such as rubber is added to improve impact resistance, and a resin having a high glass transition temperature or a crystalline resin is used in order to improve heat resistance. Various techniques such as addition have been proposed.

  Among them, as a method for improving the toughness and heat resistance of the styrene resin, many methods for blending other thermoplastic resins have been tried. In particular, many polycarbonate resins have been reported as representative thermoplastic resins blended with styrene resins. However, since the polymer blend of the styrene resin and the polycarbonate resin has poor compatibility, there has been a problem that the mechanical properties, molding processability, and appearance, which are features of the styrene resin, are deteriorated.

  Therefore, as a technique for solving these problems, a method of adding an epoxy-modified / acid-modified diene block copolymer as a compatibilizer to a polycarbonate resin and a polystyrene resin (Patent Document 1), syndiotactic polystyrene A block or graft copolymer composed of two or more of an aromatic vinyl monomer, a carbonate monomer, and an acrylic monomer as a compatibilizing agent to a polymer resin and an aromatic polycarbonate resin (Patent Literature) 2) One or more of polycarbonate-based resin, polyester-based resin, polyamide-based resin, polyarylene sulfide-based resin, styrene-based resin, and multi-phase structure consisting of polycarbonate-based resin segment and epoxy group-containing vinyl-based polymer segment Method of adding a graft copolymer having a patent (patent text) 3) is disclosed. However, when the resin composition obtained by the invention described in the publication is manufactured by a general method such as injection molding or blow molding after melt kneading or melt blending with an extruder or the like, the compatibility with the styrenic resin is improved. Is not sufficient, does not form a regular structural period, and is not sufficiently effective in improving toughness.

  Furthermore, it is a polymer alloy composed of two or more components phase-separated by spinodal decomposition, and has a two-phase continuous structure with a periodic structure of 0.01 to 1 μm, or a dispersed structure with a distance between particles of 0.01 to 1 μm. A method (Patent Document 4) is disclosed. However, the polymer alloy described in the publication is obtained by melt-kneading and then obtaining the structure by special press molding, and if this is simply molded by a general molding method such as injection molding, However, the structure period was too large to obtain excellent physical properties, and the above phase structure could not be obtained stably.

Further, it consists of a polycarbonate resin and acrylonitrile-butadiene-styrene resin (hereinafter referred to as ABS resin), and has a weight average molecular weight of 100,000 or more of acetone-soluble components in ABS, and contains a vinyl cyanide monomer in the acetone-soluble components. The resin composition for plating which makes a rate 15 to 32 weight% (patent document 5) is disclosed. However, the publication does not describe any improvement in mechanical properties and the like by the compatibilizing agent, and further does not describe that an excellent plating property can be expressed by forming a regular structural period. Not even suggested.
Japanese Patent Laid-Open No. 11-080528 (second page) Japanese Patent Laying-Open No. 2004-210916 (Section 2-3) JP-A-11-080287 (2nd page) JP 2003-286414 A (page 2, pages 15-17) Japanese Patent Laid-Open No. 10-046019 (second page)

  The present invention solves the above problems, has excellent mechanical properties, fluidity, plating properties, is easy to impart flame retardancy, and a molded product having the above excellent performance can be stably obtained, An object of the present invention is to provide a highly practical styrenic resin composition as a general molding material.

  As a result of intensive studies to solve the above problems, the present inventors have found that (A) a styrene resin, (B) a thermoplastic resin other than a styrene resin, (c1) a modified styrene polymer, and (c2) a polycarbonate system. It has been found that the above-mentioned problems can be solved by including a graft polymer, and the present invention has been completed.

That is, the present invention
(1) (A) styrene resin, (B) thermoplastic resin other than styrene resin, (c1) modified styrene polymer and (c2) polycarbonate graft polymer, styrene resin composition,
(2) A thermoplastic resin other than (A) styrene resin and (B) styrene resin has a biphasic continuous structure with a structural period of 0.001 to 1 μm, or a dispersed structure with a distance between particles of 0.001 to 1 μm. (1) The styrenic resin composition according to the description,
(3) A thermoplastic resin other than (A) styrenic resin and (B) styrenic resin has a biphasic continuous structure with a structural period of 0.01 to 0.5 μm, or a distance between particles of 0.01 to 0.5 μm. The styrenic resin composition according to (2) having a dispersion structure;
(4) (c1) The modified styrene polymer includes a vinyl monomer unit containing at least one functional group selected from a carboxyl group, a hydroxyl group, an epoxy group, an amino group, and an oxazoline group (1 ) Styrenic resin composition according to
(5) (c2) The styrene resin composition according to (1), wherein the polycarbonate graft polymer includes a polycarbonate resin segment and a vinyl polymer segment,
(6) (A) The styrene resin composition according to (1), wherein the styrene resin includes a styrene monomer unit substituted with an alkyl group having 1 to 4 carbon atoms,
(7) The styrene resin composition according to (1), wherein the thermoplastic resin other than (B) the styrene resin is (b) a polycarbonate resin,
(8) The above (b) polycarbonate resin comprises (b1) 2,2′-bis (4-hydroxyphenyl) propane and (b2) 2,2′-bis (4-hydroxy-3,5-dimethylphenyl) propane. 2,2′-bis (4-hydroxy-3,5-diethylphenyl) propane, at least one bifunctional selected from 2,2′-bis (4-hydroxy-3,5-dipropylphenyl) propane The styrene resin composition according to (7), which comprises an aromatic copolymer polycarbonate obtained by copolymerizing a phenol compound;
(9) (A) Styrenic resin in the presence of (r) 5 to 80% by weight of rubbery polymer, (a1) 5 to 90% by weight of styrenic monomer units, (a2) vinyl cyanide It is obtained by graft polymerization of 1 to 50% by weight of monomer units and 20 to 95% by weight of a monomer mixture consisting of 0 to 80% by weight of (a3) other vinyl monomer units copolymerizable therewith. (A-1) 5 to 100 parts by weight of graft (co) polymer, (a1) 5 to 90% by weight of styrene monomer units, (a2) 1 to 50% by weight of vinyl cyanide monomer units, And (a3) a vinyl (co) polymer 0 to 95 obtained by polymerizing a monomer mixture composed of 0 to 80% by weight of other vinyl monomer units copolymerizable with these (a3). The styrene resin composition according to (1), which is a rubber-modified styrene resin comprising And (a1) a total of 100 wt% respectively of ~ (a3)),
(10) (A) styrene resin, (B) thermoplastic resin other than styrene resin, (c1) modified styrene polymer and (c2) polycarbonate graft polymer are melt-kneaded (1) to (9) A method for producing the styrene-based resin composition according to any one of
(11) The component (A), the component (B), the component (c1), and the component (c2) are compatible with each other under shear during the melt kneading, and phase separation is performed under non-shear after discharge. (10) The method for producing the styrene-based resin composition according to
(12) A molded article comprising the styrenic resin composition according to any one of (1) to (9),
(13) The molded product according to (12), which is subjected to painting or plating treatment,
It is.

  By controlling the dispersion structure of the resin composition according to the present invention, the molded product has excellent mechanical properties, fluidity, plating properties, and easily imparts flame retardancy, and has the above-described excellent performance. Can be stably obtained, and a styrenic resin composition having high practicality as a general molding material can be obtained.

  The resin composition of the present invention will be specifically described below.

  As the (A) styrene resin used in the present invention, a resin obtained by polymerizing at least one styrene monomer can be used. Specific examples include polystyrene, styrene-acrylonitrile copolymers, rubber-modified styrene resins, and polymer blends of rubber-modified styrene resins and polyphenylene oxide (modified polyphenylene oxide resins).

  As the rubber-modified styrene resin, a monomer obtained by adding a styrene monomer such as styrene and α-methylstyrene and a vinyl monomer copolymerizable therewith if necessary in the presence of a rubber-like polymer. The mixture is obtained by polymerization or copolymerization (hereinafter sometimes referred to as “(co) polymerization”) by a method such as bulk polymerization, bulk suspension polymerization, solution polymerization, precipitation polymerization or emulsion polymerization. A (co) polymer containing a styrene monomer has a structure grafted to a rubber polymer, and a (co) polymer containing a styrene monomer is not grafted to a rubber polymer. A structure can be used.

  Specific examples of such a rubber-modified styrene resin include, for example, impact-resistant polystyrene, ABS resin, AAS resin (acrylonitrile-acrylic rubber-styrene copolymer), MBS resin (methyl methacrylate-butadiene rubber-styrene copolymer). Polymer) and AES resin (acrylonitrile-ethylenepropylene rubber-styrene copolymer).

  Specifically, 95 to 20% by weight of a monomer mixture composed of a styrene monomer and another copolymerizable vinyl monomer is graft-polymerized with respect to 5 to 80% by weight of the rubbery polymer. 5 to 100 parts by weight of the obtained graft (co) polymer, a styrene monomer (copolymer) obtained by polymerizing a monomer mixture comprising a styrene monomer and other copolymerizable vinyl monomers. A polymer consisting of 0 to 95 parts by weight of polymer is preferred.

  As the rubbery polymer, those having a glass transition temperature of 0 ° C. or less are preferable. Specifically, polybutadiene, styrene-butadiene copolymer, acrylonitrile-butadiene copolymer, and styrene-butadiene block copolymer. , Diene rubber such as butyl acrylate-butadiene copolymer, acrylic rubber such as polybutyl acrylate, polyisoprene, ethylene-olefin copolymer, ethylene-unsaturated carboxylic acid ester copolymer, ethylene-fatty acid vinyl Examples thereof include a copolymer and an ethylene-propylene-diene terpolymer. Of these, the use of polybutadiene or butadiene copolymer is preferred.

  As a specific example of the styrenic monomer, styrene is preferably used, but substituted with an alkyl group having 1 to 4 carbon atoms from the viewpoint of improving compatibility by reducing the free volume under shear during melt-kneading. One or more styrenic monomers can be preferably contained. Examples of the styrene monomer substituted with an alkyl group having 1 to 4 carbon atoms include α-methyl styrene, p-methyl styrene, m-methyl styrene, o-methyl styrene, p-ethyl styrene, m-ethyl styrene. , O-ethyl styrene, t-butyl styrene and the like, and α-methyl styrene, o-methyl styrene and t-butyl styrene are particularly preferably used.

  For monomers other than styrene monomers, vinyl cyanide monomers are used to improve impact resistance, chemical resistance, and plating properties, and to improve toughness and color tone. In this case, (meth) acrylic acid ester monomers are preferably used.

  Specific examples of the vinyl cyanide monomer include acrylonitrile, methacrylonitrile, ethacrylonitrile and the like, and acrylonitrile is particularly preferably used.

  Specific examples of the (meth) acrylic acid ester monomer include methyl, ethyl, propyl, n-butyl, isobutyl ester and the like of acrylic acid and methacrylic acid, and methyl methacrylate is particularly preferably used.

  If necessary, other vinyl monomers such as vinyl toluene, aromatic vinyl monomers other than styrene monomers, maleimides such as maleimide, N-methylmaleimide, and N-phenylmaleimide A monomer etc. can also be used.

  From the viewpoint of impact resistance of the resin composition, the monomer or monomer mixture used in the graft (co) polymer is preferably 5 to 90% by weight, more preferably Is 10 to 80% by weight. In the case of mixing a vinyl cyanide monomer, it is preferably 1 to 50% by weight, particularly preferably 40% by weight or less, from the viewpoint of moldability of the resin composition. In particular, when plating adhesion is required, the catalyst adsorption capacity in the catalyst process during the plating process can be improved by setting the content in the range of 25 to 40% by weight, more preferably 35 to 40% by weight. Therefore, it is preferably used. Moreover, when mixing a (meth) acrylic acid ester-type monomer, it is preferable that it is 80 weight% or less from a viewpoint of toughness and impact resistance, and especially 75 weight% or less is used preferably. The total amount of aromatic vinyl monomer, vinyl cyanide monomer and (meth) acrylic acid ester monomer in the monomer or monomer mixture is 95 to 20% by weight. Is more preferable, and 90 to 30% by weight is more preferable.

  From the viewpoint of impact resistance of the resin composition, the blending ratio of the rubbery polymer and the monomer mixture in obtaining the graft (co) polymer is 100% by weight of the total graft (co) polymer. The quality polymer is preferably 5% by weight or more, more preferably 10% by weight or more. Further, from the viewpoint of the impact resistance of the resin composition and the appearance of the molded product, it is preferably 80% by weight or less, more preferably 70% by weight or less. The blending ratio of the monomer or monomer mixture is preferably 95% by weight or less, more preferably 90% by weight or less, or preferably 20% by weight or more, more preferably 30% by weight. That's it.

  The graft (co) polymer can be obtained by a known polymerization method. For example, it can be obtained by a method of emulsion polymerization by continuously supplying a mixture of a monomer and a chain transfer agent and a solution of a radical generator dissolved in an emulsifier to a polymerization vessel in the presence of a rubbery polymer latex. .

The graft (co) polymer contained an ungrafted (co) polymer in addition to the graft (co) polymer having a structure in which a monomer or a monomer mixture was grafted to a rubbery polymer. Is. The graft ratio of the graft (co) polymer is not particularly limited, but is 20 to 80%, particularly 25 to 50% in order to obtain a resin composition having a good balance between impact resistance and gloss. It is preferable. Here, the graft ratio is a value calculated by the following equation.
Graft rate (%) = [<Amount of vinyl copolymer graft-polymerized to rubbery polymer> / <Rubber content of graft copolymer>] × 100

  The properties of the ungrafted (co) polymer are not particularly limited, but the intrinsic viscosity [η] (measured at 30 ° C.) of methyl ethyl ketone solubles is 0.25 to 1.00 dl / g, particularly 0.25 to A range of 0.80 dl / g is a preferable condition for obtaining a resin composition having excellent impact resistance.

  The styrene (co) polymer is a copolymer having a styrene monomer as an essential component. Examples of the styrene monomer include styrene, α-methylstyrene, p-methylstyrene, t-butylstyrene, and o-ethylstyrene, and styrene is particularly preferably used. These can use 1 type (s) or 2 or more types.

  As a specific example of the styrenic monomer, styrene is preferably used, but substituted with an alkyl group having 1 to 4 carbon atoms from the viewpoint of improving compatibility by reducing the free volume under shear during melt-kneading. One or more styrenic monomers can be preferably contained. Examples of the styrene monomer substituted with an alkyl group having 1 to 4 carbon atoms include α-methyl styrene, p-methyl styrene, m-methyl styrene, o-methyl styrene, p-ethyl styrene, m-ethyl styrene. , O-ethyl styrene, t-butyl styrene and the like, and α-methyl styrene, o-methyl styrene and t-butyl styrene are particularly preferably used.

  As monomers other than aromatic vinyl monomers, vinyl cyanide monomers are used for the purpose of further improving impact resistance and chemical resistance, and for the purpose of improving toughness and color tone. In this case, a (meth) acrylic acid ester monomer is preferably used.

  Specific examples of the vinyl cyanide monomer include acrylonitrile, methacrylonitrile, ethacrylonitrile and the like, and acrylonitrile is particularly preferably used. Specific examples of the (meth) acrylic acid ester monomer include methyl, ethyl, propyl, n-butyl, and isobutyl esterified products of acrylic acid and methacrylic acid. In particular, methyl methacrylate is preferably used. .

  In addition, other vinyl monomers copolymerizable with these used as necessary include vinyl toluene and other aromatic vinyl monomers other than styrene monomers, maleimide, N-methylmaleimide And maleimide monomers such as N-phenylmaleimide.

  In the present invention, a styrene copolymer obtained by copolymerizing a maleimide monomer, that is, a maleimide group-modified styrene copolymer is used by being contained in a polystyrene resin. Can be improved, and the flame retardancy can also be specifically improved, so that it can be preferably used.

  From the viewpoint of impact resistance of the resin composition, the proportion of the styrene monomer that is a constituent component of the styrene (co) polymer is preferably 5 to 90% by weight, more preferably 10%. It is in the range of ˜80% by weight. In the case of mixing a vinyl cyanide monomer, the content is preferably 1 to 50% by weight, more preferably 40% by weight or less from the viewpoint of impact resistance and fluidity. In particular, when plating adhesion is required, the catalyst adsorption capacity in the catalyst process during the plating process can be improved by setting the content in the range of 25 to 40% by weight, more preferably 35 to 40% by weight. Therefore, it is preferably used. Moreover, when mixing a (meth) acrylic-ester monomer, 80 weight% or less is preferable from a viewpoint of toughness and impact resistance, More preferably, it is the range of 75 weight% or less. Furthermore, when other vinyl monomers copolymerizable with these are mixed, the content is preferably 60% by weight or less, and particularly preferably 50% by weight or less.

  Although there is no restriction | limiting in the characteristic of a styrene-type (co) polymer, The intrinsic viscosity [(eta)] measured at 30 degreeC using the methyl ethyl ketone solvent is 0.25-5.00 dl / g, Especially 0.35-3 The range of 0.001 dl / g is preferable because a resin composition having excellent impact resistance and molding processability can be obtained.

  There are no particular restrictions on the method for producing the styrene (co) polymer, and usual methods such as bulk polymerization, suspension polymerization, emulsion polymerization, solution polymerization, bulk-suspension polymerization, and solution-bulk polymerization are used. Can be used.

  The thermoplastic resin other than the (B) styrene resin of the present invention is a thermoplastic resin capable of forming a phase structure defined in the present invention with the styrene resin. For example, polyester, polyamide, polyphenylene oxide, polysulfone, Fluoropolyethylene, polyetherimide, polyamideimide, polyimide, polycarbonate, polyethersulfone, polyetherketone, polythioetherketone, polyetheretherketone, epoxy resin, phenolic resin, polyethylene, polypropylene, polyphenylene sulfide, polyamide elastomer, polyester elastomer , Polyalkylene oxide, resins such as olefin copolymers containing a carboxyl group, and the like. Carbonate, among them impact, the most effective is to contain polycarbonate resin for improving heat resistance.

  The polycarbonate resin can be selected from aromatic homopolycarbonate and aromatic copolycarbonate. Examples of the production method include a phosgene method in which phosgene is blown into a bifunctional phenol compound in the presence of caustic alkali and a solvent, or a transesterification method in which a bifunctional phenol compound and diethyl carbonate are transesterified in the presence of a catalyst. Can do. The aromatic polycarbonate preferably has a viscosity average molecular weight in the range of 10,000 to 100,000. Here, the above bifunctional phenolic compounds are 2,2′-bis (4-hydroxyphenyl) propane, 2,2′-bis (4-hydroxy-3,5-dimethylphenyl) propane, bis (4-hydroxy). Phenyl) methane, 1,1′-bis (4-hydroxyphenyl) ethane, 2,2′-bis (4-hydroxyphenyl) butane, 2,2′-bis (4-hydroxy-3,5-diphenyl) butane 2,2′-bis (4-hydroxy-3,5-dipropylphenyl) propane, 1,1′-bis (4-hydroxyphenyl) cyclohexane, 1-phenyl-1,1′-bis (4-hydroxy) Phenyl) ethane and the like, but from the viewpoint of improving compatibility by reducing the free volume under shear during melt-kneading, 2,2′-bis (4-hydroxy-3,5-dimethylpheny ) Propane, 2,2'-bis (4-hydroxy-3,5-diethyl-phenyl) propane, 2,2'-bis (include 4-hydroxy-3,5-dipropyl phenyl) propane is preferable. In the present invention, the bifunctional phenol compound may be used alone or in combination.

  (A) In alloying a styrene resin and a polycarbonate resin, the difference in melt viscosity between the two is reduced, (a2) the content of vinyl cyanide is reduced, and the copolymer polycarbonate is used in combination with the above bifunctional phenol compound. Thus, the phase structure of the resin composition can be controlled. Furthermore, it becomes possible to know the structural control range easily by preparing a phase diagram with respect to the resin composition and temperature described later.

  When (A) styrenic resin and polycarbonate resin are alloyed, (b) polycarbonate resin is preferably used in the range of 20 to 70% by weight, more preferably in the range of 25 to 60% by weight, particularly 30. If it is in the range of ˜50% by weight, a two-phase continuous structure can be obtained relatively easily, and further, mechanical properties, fluidity and plating properties can be obtained, and flame retardancy can be easily imparted. Conventionally, if the polycarbonate resin is not a rich component, the impact strength was low, but according to the present invention, the polycarbonate resin can be increased in impact by 30% by weight. , Chemical resistance, and plating properties can be dramatically improved.

  Examples of the polyester resin include those obtained by condensing an aromatic dicarboxylic acid or an ester thereof or an ester-forming derivative and a diol by a known method. Examples of the polyester resin include aromatic polyesters, wholly aromatic polyesters, and liquid crystal polyesters. Can be used. Here, examples of the aromatic dicarboxylic acid include naphthalene dicarboxylic acid such as naphthalene-2,6-dicarboxylic acid, terephthalic acid, isophthalic acid, p-hydroxybenzoic acid, and the like. Can be used in the manufacture of Examples of the diol include polymethylene glycol having 2 to 6 carbon atoms such as ethylene glycol, 1,4-butanediol, 1,6-hexanediol, or 1,4-cyclohexanediol, bisphenol A, and the like. Examples include ester-forming derivatives.

  Preferable specific examples of the polyester resin include polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polybisphenol A isophthalate and the like. The polyester resin preferably has an intrinsic viscosity at 25 ° C. ([η] 25 ° C., o-chlorophenol, unit dl / g) in an o-chlorophenol solvent of 0.4 to 2, more preferably 0. .6 to 1.5.

  (A) In alloying a styrene-based resin and a polyester resin, the compatible region is expanded by lowering the molecular weight of both, and a desired phase structure can be easily obtained.

  As the polyamide resin, those usually produced by condensation of diamine and dicarboxylic acid, those produced by ring-opening polymerization of lactam, and the like can be used. Preferable examples of these polyamide resins include nylon 6,6, nylon 6,9, nylon 6,10, nylon 6,12, nylon 6, nylon 12, nylon 11, nylon 4,6 and the like. Nylon 6 / 6,6, nylon 6 / 6,10, nylon 6/12, nylon 6 / 6,12, nylon 6 / 6,6 / 6,10, nylon 6 / 6,6 / 12, etc. Polymerized polyamides can also be used. Furthermore, semi-aromatic polyamides and polyesteramides obtained from nylon 6/6, T (T: terephthalic acid component), terephthalic acid, isophthalic acid and aromatic dicarboxylic acid and metaxylylenediamine, or alicyclic diamine Etc. can also be used. The polyamide resin preferably has a relative viscosity [ηrel] measured in a 90% formic acid solvent at a concentration of 1 g / 100 cc and a temperature of 25 ° C. of 1.0 to 4.0, more preferably 1.5 to 3.5. belongs to. The above polyamide resins can be used singly or in combination of two or more.

  (A) In alloying a styrene resin and a polyamide resin, the compatibility region is increased by increasing the vinyl cyanide content in the styrene resin to approximate both SP (solubility parameter) values. The desired phase structure can be easily obtained.

  Although there is no restriction | limiting in particular about the composition of the resin component which comprises the styrene resin composition in this invention, With respect to a total of 100 weight% of (A) styrene resin and (B) thermoplastic resins other than a styrene resin. Usually, (A) a styrene resin is preferably used in a range of 10 to 95% by weight, more preferably in a range of 15 to 85% by weight, and particularly in a range of 20 to 80% by weight. Since it is relatively easy to obtain, it is preferably used.

  In the styrene resin composition of the present invention, it is important to use (c1) a modified styrene polymer and (c2) a polycarbonate graft polymer in combination.

  (C1) The modified styrene polymer is a styrene polymer containing a vinyl monomer unit containing at least one functional group selected from a carboxyl group, a hydroxyl group, an epoxy group, an amino group, and an oxazoline group. (Hereinafter abbreviated as (c1) modified styrenic polymer) can be used, and (c1) modified styrenic polymer includes (c2) polycarbonate resin segment contained in polycarbonate graft polymer described below. There is nothing.

  This (c1) modified styrene polymer has a structure obtained by polymerizing or copolymerizing one or two or more vinyl monomers including a styrene monomer, and has a carboxyl group in the molecule. , A polymer containing at least one functional group selected from a hydroxyl group, an epoxy group, an amino group, and an oxazoline group. The content of the compound containing these functional groups is not limited, but is particularly preferably in the range of 0.01 to 20% by weight per 100 parts by weight of the modified styrenic polymer.

  (C1) The method for introducing a carboxyl group into the modified styrenic polymer is not particularly limited, and examples thereof include acrylic acid, methacrylic acid, maleic acid, maleic acid monoethyl ester, maleic anhydride, phthalic acid, and itaconic acid. A method of copolymerizing a vinyl monomer having a carboxyl group or an anhydrous carboxyl group with a predetermined vinyl monomer, γ, γ′-azobis (γ-cyanovaleric acid), α, α′-azobis (α-cyanoethyl) ) -Polymerization initiators and / or thioglycolic acid, [alpha] -mercaptopropionic acid, [beta] -mercaptopropionic acid, [alpha] -mercapto-isobutyric acid and 2,3 or Using a polymerization degree regulator having a carboxyl group such as 4-mercaptobenzoic acid, a predetermined vinyl monomer And (meth) acrylic acid ester monomers such as methyl methacrylate and methyl acrylate and a predetermined vinyl monomer, and if necessary, a vinyl cyanide monomer For example, a method of saponifying the copolymer with an alkali can be used.

  The method for introducing the hydroxyl group is not particularly limited. For example, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 3-hydroxypropyl acrylate, 3-hydroxypropyl methacrylate, 2,3, acrylic acid 4,5,6-pentahydroxyhexyl, 2,3,4,5,6-pentahydroxyhexyl methacrylate, 2,3,4,5-tetrahydroxypentyl acrylate, 2,3,4,5-methacrylic acid Tetrahydroxypentyl, 3-hydroxy-1-propene, 4-hydroxy-1-butene, cis-4-hydroxy-2-butene, trans-4-hydroxy-2-butene, 3-hydroxy-2-methyl-1- Propene, cis-5-hydroxy-2-pentene, trans-5-hydroxy-2-pente , 4,4-dihydroxy-2-butene a vinyl monomer having a hydroxyl group such as, a method of copolymerizing with a predetermined vinyl monomer can be used.

  The method for introducing the epoxy group is not particularly limited. For example, epoxies such as glycidyl acrylate, glycidyl methacrylate, glycidyl ethacrylate, glycidyl itaconate, allyl glycidyl ether, styrene-p-glycidyl ether and p-glycidyl styrene For example, a method of copolymerizing a vinyl monomer having a group with a predetermined vinyl monomer can be used.

  Among them, the epoxy-modified styrene polymer introduced with an epoxy group by copolymerizing glycidyl methacrylate improves the impact strength of the resin composition of the present invention when used in a polystyrene resin, and Since it is easy to impart flame retardancy, it can be preferably used.

  The method for introducing the amino group is not particularly limited. For example, acrylamide, methacrylamide, N-methylacrylamide, butoxymethylacrylamide, N-propylmethacrylamide, aminoethyl acrylate, propylaminoethyl acrylate, dimethyl methacrylate. Amino groups such as aminoethyl, ethylaminopropyl methacrylate, phenylaminoethyl methacrylate, cyclohexylaminoethyl methacrylate, N-vinyldiethylamine, N-acetylvinylamine, allylamine, methallylamine, N-methylallylamine, p-aminostyrene And a method of copolymerizing a vinyl monomer having a derivative thereof and a predetermined vinyl monomer.

  The method for introducing the oxazoline group is not particularly limited. For example, a vinyl-based monomer having an oxazoline group such as 2-isopropenyl-oxazoline, 2-vinyl-oxazoline, 2-acryloyl-oxazoline, and 2-styryl-oxazoline. For example, a method of copolymerizing the body with a predetermined vinyl monomer can be used.

  (C1) The properties of the modified styrene polymer are not limited, but the intrinsic viscosity [η] measured at 30 ° C. using a methyl ethyl ketone solvent is 0.25 to 5.00 dl / g, particularly 0.35. Those in the range of 3.00 dl / g are preferable because a resin composition having excellent impact resistance and molding processability can be obtained.

  (C1) The production method of the modified styrenic polymer is not particularly limited, and usual methods such as bulk polymerization method, suspension polymerization method, emulsion polymerization method, solution polymerization method, bulk-suspension polymerization method and solution-bulk polymerization method are used. The method can be used.

  Further, the (c2) polycarbonate graft polymer used in the present invention is preferably composed of a polycarbonate resin segment and a vinyl polymer segment, the polycarbonate resin segment forms a continuous phase, and the vinyl polymer segment is a dispersed phase. A graft polymer having a multilayer structure (hereinafter abbreviated as (c2) polycarbonate-based graft polymer) is preferred.

  As the polycarbonate resin forming the polycarbonate resin segment in the (c2) polycarbonate graft polymer, all the polycarbonate resins exemplified as the thermoplastic resin other than the (B) styrene resin can be used.

  The vinyl polymer forming the vinyl polymer segment in the polycarbonate graft polymer (c2) is the vinyl monomer exemplified in the (A) styrene resin and (c1) the modified styrene polymer. All bodies can be used.

  (C2) A polycarbonate graft polymer is produced by adding a vinyl monomer, a radical copolymerizable organic peroxide and a radical polymerization initiator to an aqueous suspension of a polycarbonate resin to decompose the radical polymerization initiator. Is heated under conditions that do not substantially cause impregnation of the vinyl monomer, radical copolymerizable organic peroxide and radical polymerization initiator into the polycarbonate resin, and then the temperature of the aqueous suspension is increased. (C2) polycarbonate grafting by melting and mixing a grafting precursor produced by copolymerizing a vinyl monomer and a radical copolymerizable organic peroxide in a polycarbonate resin at 100 to 350 ° C. A polymer can be obtained.

  As such (c2) polycarbonate-based graft polymer, for example, a PC-g-SAN (polycarbonate-graft-styrene / acrylonitrile copolymer) obtained by graft polymerization of a monomer mixture composed of styrene and acrylonitrile on a polycarbonate resin. PC-g-PS obtained by graft polymerization of a styrene monomer onto a polycarbonate resin (for example, “MODIPER CL130D” manufactured by NOF Corporation) PC-g-mSAN (polycarbonate-graft-modified styrene / acrylonitrile) obtained by graft polymerization of a monomer mixture comprising styrene, acrylonitrile and functional group-modified vinyl onto a polycarbonate resin Polymer, can be mentioned, for example, Nippon Oil & Fats Co., Ltd. "Modiper CL440G").

  (C1) Modified styrene-based polymer and (c2) polycarbonate-based graft polymer are used in combination to reduce the free energy at the interface between the phase-decomposed phases. Control of the distance between dispersed particles can be facilitated, and the mechanical properties and the like of the resin composition can be improved.

  The addition amount of the (c1) modified styrene polymer and (c2) the polycarbonate graft polymer is preferably in the range of 0.2 to 40 parts by weight with respect to 100 parts by weight as the total of the component (A) and the component (B). . More preferably, it is the range of 0.5-35 weight part, As a particularly preferable range, it is a case where it exists in the range of 1-30 weight part. By using 0.2 parts by weight or more of the addition amount, the effect as a compatibilizer can be exhibited, and the structural period and the interparticle distance can be controlled. Moreover, it is preferable for the addition amount to be 40 parts by weight or less because the fluidity and residence stability of the resin composition can be maintained.

  The addition ratio of (c1) modified styrene polymer and (c2) polycarbonate graft polymer is used in the range of (c1) :( c2) = 99: 1 to 1:99 (weight ratio). Preferably it is the range of 99: 1-10: 90 (weight ratio), and it is a case where it exists in the range of 99: 1-20: 80 (weight ratio) as an especially preferable range. By setting it as these ranges, since the outstanding effect as a compatibilizing agent can be acquired and control of a structure period and the distance between particles becomes possible, it is preferable.

  In the present invention, by adding (c1) a modified styrene polymer and (c2) a polycarbonate graft polymer, the styrene resin composition has a biphasic continuous structure having a structural period of 0.001 to 1 μm, or a distance between particles. It can have a dispersion structure of 0.001 to 1 μm and exhibits excellent mechanical properties, fluidity, and plating properties.

  In order to obtain a resin composition having such a structural period, (A) a styrene resin, (B) a thermoplastic resin other than the styrene resin, (c1) a modified styrene polymer, and (c2) a polycarbonate graft. It is preferable that the polymer is once phase-dissolved to form a structure by spinodal decomposition described later. Furthermore, in order to realize this structure formation, (A) a styrene-based resin and (B) a thermoplastic resin other than the styrene-based resin, a later-described partial compatibility system, or a system in which shear field-dependent phase dissolution / phase decomposition is performed. In addition, a reaction-induced phase decomposition system is preferable.

  In general, polymer alloys composed of two-component resins are compatible with these compositions in a practical system where the glass transition temperature is higher than the thermal decomposition temperature or lower, and vice versa. There are incompatible systems that dissolve, and partially compatible systems that are compatible in one region and phase separated in another region. In this partially compatible system, phase separation is performed by spinodal decomposition depending on the conditions of the phase separated state. And phase separation by nucleation and growth.

  Furthermore, in the case of a polymer alloy composed of three or more components, a system in which all three or more components are compatible, a system in which all three or more components are incompatible, a compatible phase having two or more components, and the rest There is a system in which one or more phases are incompatible, two components are partially compatible, and the remaining components are distributed in a partially compatible system composed of these two components. The polymer alloy composed of 3 or more components preferred in the present invention is a system in which 2 components are partially compatible and the remaining components are distributed to the partially compatible system composed of 2 components. In this case, the structure of the polymer alloy is 2 Since it can be replaced by a partially compatible structure composed of components, the following description will be made on behalf of a polymer alloy composed of a two-component resin.

  Phase separation by spinodal decomposition refers to phase separation that occurs in an unstable state inside the spinodal curve in phase diagrams for different two-component resin compositions and temperatures, and phase separation by nucleation and growth refers to the phase separation. In the figure, it refers to phase separation that occurs in the metastable state inside the binodal curve and outside the spinodal curve.

  The spinodal curve refers to the difference (ΔGmix) between the free energy when compatibilized and the sum of the free energies in two phases that are not compatible (ΔGmix) when two different resins are mixed with respect to the composition and temperature. φ) is a curve in which the partial differential twice (∂2ΔGmix / ∂φ2) is 0, and inside the spinodal curve is an unstable state of ∂2ΔGmix / ∂φ2 <0, and outside is ∂ 2ΔGmix / ∂φ2> 0.

  The binodal curve is a boundary curve between the region where the system is compatible and the region where the system is separated with respect to the composition and temperature.

  Here, the case of being compatible in the present invention is a state in which they are uniformly mixed at the molecular level. Specifically, both phases having different two-component resins as main components are 0.001 μm or more. The case where the phase structure is not formed is indicated, and the case where the phase is incompatible is the case where the phase is not in a compatible state, that is, the phases mainly composed of two different resin components are 0.001 μm or more. It refers to the state of forming a phase structure. Whether or not they are compatible is determined by various methods such as an electron microscope, a differential scanning calorimeter (DSC), as described in Polymer Alloys and Blends, Leszek A Utracki, hanser Publishers, Munich Viema New York, P64. can do.

  According to detailed theory, in spinodal decomposition, once the temperature of a mixed system that has been uniformly mixed at the temperature of the compatible region is rapidly increased to the temperature of the unstable region, the system will rapidly phase-separate toward the coexisting composition. To start. At that time, the concentration is monochromatized at a constant wavelength, and a two-phase continuous structure is formed in which both separated phases are continuously intertwined regularly with a structure period (Λm). After the formation of the two-phase continuous structure, the process in which only the concentration difference between the two phases increases while keeping the structure period constant is called the initial process of spinodal decomposition.

Furthermore, the structural period (Λm) in the initial process of the above-mentioned spinodal decomposition has a thermodynamic relationship as shown in the following equation.
Λm to [│Ts-T│ / Ts] ^-1/2 (where Ts is the temperature on the spinodal curve)

  In spinodal decomposition, after going through such an initial process, it goes through a medium-term process in which an increase in wavelength and an increase in concentration difference occur simultaneously, and a later process in which an increase in wavelength occurs in a self-similar manner after the concentration difference reaches the coexisting composition. In order to obtain the structure defined in the present invention, the desired structural period before the final separation into the macroscopic two phases has been reached. What is necessary is just to fix a structure in a step.

  In addition, in the process of increasing the wavelength from the mid-stage process to the late-stage process, depending on the influence of the composition and the interfacial tension, the continuity of one phase may be interrupted and the above-described biphasic continuous structure may be changed to a dispersed structure. In this case, the structure may be fixed when the desired interparticle distance is reached.

  The two-phase continuous structure referred to in the present invention refers to a structure in which both components of the resin to be mixed each form a continuous phase and are entangled three-dimensionally. A schematic diagram of this two-phase continuous structure is described, for example, in “Polymer Alloy Fundamentals and Applications (Second Edition) (Chapter 10.1)” (edited by the Society of Polymer Science: Tokyo Kagaku Dojin).

  The dispersion structure referred to in the present invention refers to a so-called sea-island structure in which particles mainly composed of the other resin component are interspersed in a matrix mainly composed of the other resin component. .

  The styrenic resin composition of the present invention can obtain a structure whose structure is controlled to a biphasic continuous structure having a structural period of 0.001 to 1 μm or a dispersed structure having a distance between particles of 0.001 to 1 μm. . In order to obtain more excellent mechanical properties, it is preferable to control to a two-phase continuous structure with a structural period of 0.01 to 0.5 μm or a dispersed structure with a distance between particles of 0.01 to 0.5 μm. Furthermore, it is more preferable to control to a two-phase continuous structure with a structural period of 0.01 to 0.4 μm, or a dispersed structure with a distance between particles of 0.01 to 0.4 μm, and extremely excellent characteristics. In order to obtain it, it is most preferable to control to a two-phase continuous structure having a structural period of 0.01 to 0.3 μm or a dispersed structure having a distance between particles of 0.01 to 0.3 μm. A structure having excellent mechanical properties, fluidity, plating properties, and flame retardancy, which are the effects of the present invention, can be effectively obtained by controlling the range of the structural period and the range of the interparticle distance.

  On the other hand, in the nucleation and growth, which is the phase separation in the metastable region described above, a dispersed structure that is a sea-island structure is formed from the initial stage, and it grows. It is difficult to form a biphasic continuous structure in the range of 0.001 to 1 μm or a dispersed structure in the range of a distance between particles of 0.001 to 1 μm.

Moreover, in order to confirm the biphasic continuous structure by these spinodal decompositions or a disperse structure, it is important to confirm a regular periodic structure. For example, in addition to confirming that a two-phase continuous structure is formed by observation with an optical microscope or a transmission electron microscope, the scattering maximum in a scattering measurement performed using a light scattering device or a small-angle X-ray scattering device Confirmation of appearing is necessary. Note that the light scattering device and the small-angle X-ray scattering device have different optimum measurement regions, so that they are appropriately selected according to the size of the structure period. The existence of the scattering maximum in this scattering measurement is a proof that there is a regular phase separation structure with a certain period. The period Λm corresponds to the structure period in the case of the biphasic continuous structure, and the interparticle distance in the case of the dispersion structure. Correspond. The value can be calculated by the following equation using the wavelength λ of the scattered light in the scatterer and the scattering angle θm that gives the scattering maximum.
Λm = (λ / 2) / sin (θm / 2)

  In order to realize the spinodal decomposition, it is necessary to make the styrenic resin and the thermoplastic resin other than the styrenic resin compatible with each other, and then make the unstable state inside the spinodal curve.

  First, as a method of realizing a compatible state with a resin composed of two or more components, after dissolving in a common solvent, spray drying, freeze drying, coagulation in a non-solvent substance, film formation by solvent evaporation, etc. from this solution is used. Examples thereof include a solvent casting method and a melt-kneading method in which a partially compatible system is melt-kneaded under compatible conditions. Among these, compatibilization by melt kneading, which is a dry process that does not use a solvent, is preferably used in practice.

  For compatibilization by melt kneading, an ordinary extruder is used, but a twin screw extruder is preferably used. Further, depending on the combination of resins, there are cases where compatibilization can be achieved in the plasticizing process of the injection molding machine. The temperature for compatibilization needs to be a condition in which the partially compatible resin is compatible.

  Next, when the resin composition made into a compatible state by the above melt kneading is in an unstable state inside the spinodal curve, the temperature for making the unstable state when the spinodal decomposition is performed, and other conditions vary depending on the combination of the resins. Although it cannot be generally stated, it can be set by performing a simple preliminary experiment based on the phase diagram.

  As a method of immobilizing the structure product by spinodal decomposition, one or both components of the phase-separated phase can be fixed in a short period of time by rapid cooling or the like, or if one is a component that is thermosetting, the phase of the thermosetting component May be fixed by utilizing the fact that they cannot move freely due to reaction, and when the other is a crystalline resin, it may be fixed by utilizing the fact that the crystalline resin phase cannot be freely moved by crystallization.

  In the present invention, in order to phase-separate (A) the styrenic resin and (B) the thermoplastic resin other than the styrenic resin by spinodal decomposition to obtain the styrenic resin composition of the present invention, as described above, the styrenic resin It is preferable to combine a resin and a resin that is a partially compatible system, a shear field-dependent phase dissolution / phase decomposition system, or a reaction-induced phase decomposition system.

  In general, partial compatible systems are known to have a low-temperature compatible phase diagram that is easy to be compatible on the low temperature side in the same composition, and a high temperature compatible phase diagram that is easy to be compatible on the high temperature side. It has been. The lowest temperature between the compatible and incompatible branching temperatures in this low-temperature compatible phase diagram is called the lower critical solution temperature (LCST for short). The highest temperature among the incompatible branching temperatures is called the upper critical solution temperature (UCST).

  In the case of a low-temperature compatible phase diagram, a resin of two or more components that have become compatible using a partially compatible system can be brought to a temperature higher than the LCST and a temperature inside the spinodal curve. In the case of the figure, spinodal decomposition can be performed by setting the temperature below UCST and the temperature inside the spinodal curve.

  In addition to spinodal decomposition by this partially compatible system, spinodal decomposition is also induced by melt kneading in non-compatible systems, for example, once compatible under shearing during melt kneading, etc., and then in an unstable state again under non-shearing. Phase separation by spinodal decomposition is also possible by so-called shear field-dependent phase dissolution / phase decomposition in which phase decomposition occurs, and in this case as well, in the same manner as in the case of a partially miscible system, decomposition proceeds in a spinodal decomposition mode and both phases are ordered. Has a continuous structure. Furthermore, this shear field-dependent phase dissolution / phase decomposition is the same as the method based on the temperature change of the partially miscible system in which the spinodal curve does not change because the spinodal curve changes due to the shear field and the unstable region expands. The substantial degree of supercooling (| Ts−T |) also increases in the temperature change range, and as a result, it is easy to reduce the structural period in the initial process of spinodal decomposition in the above relational expression, so that it is preferably used. It is done. In order to achieve compatibilization by shearing during such melt kneading, a normal extruder is used, but a twin screw extruder is preferably used. Further, depending on the combination of resins, there are cases where compatibilization can be achieved in the plasticizing process of the injection molding machine. In this case, the temperature for compatibilization, the heat treatment temperature for forming the initial process, the heat treatment temperature for developing the structure from the initial process, and other conditions differ depending on the combination of the resins, and cannot be generally stated. The conditions can be set by performing a simple preliminary experiment based on the phase diagram under the shear conditions. Also, as a method of reliably realizing the compatibilization in the plasticizing process of the injection molding machine, it is melt-kneaded with a twin-screw extruder in advance and compatibilized, and after discharging, it is rapidly cooled in ice water and the structure is fixed in a compatibilized state. A preferred example is a method of injection molding using a paste.

  In addition, the addition of the third component, which is a copolymer such as a block copolymer, a graft copolymer, or a random copolymer, that further includes a component constituting the polymer alloy to the styrene resin composition constituting the present invention is performed between the phase-decomposed phases. In order to reduce the free energy of the interface, it is preferably used in order to easily control the structural period in the biphasic continuous structure and the distance between dispersed particles in the dispersed structure. In this case, the third component such as the copolymer is usually distributed to each phase of the polymer alloy composed of the two-component resin except the copolymer, and thus can be handled in the same manner as the polymer alloy composed of the two-component resin.

  Therefore, in order to stably obtain the above-mentioned specific phase separation structure under practical molding process conditions, the components (A), (B), (c1) and (c2) are melt kneaded. Although obtained, it is preferable to perform melt-kneading at a resin pressure of 2.0 MPa or more.

  The resin pressure in the production method of the present invention is a value measured with a resin pressure gauge attached to the melt-kneading apparatus, and the gauge pressure is taken as the resin pressure.

  The resin pressure at the time of the melt kneading does not need to be consistently 2.0 MPa or more, and it is sufficient that there is at least one region where the resin pressure is 2.0 MPa or more, and melt kneading is performed using an extruder. In this case, it is preferable that the resin pressure is 2.0 MPa or more at a location where the resin pressure is usually highest, for example, at a location where the resin stays by reverse full flight or kneading block.

  The resin pressure at the time of melt kneading is not particularly limited as long as the mechanical performance allows as long as the pressure is 2.0 MPa or more, but it is preferably used in the range of 2.0 to 10.0 MPa, and more preferably 2.0 to 7.0 MPa. In particular, a range of 2.0 to 5.0 MPa is preferably used because a two-phase continuous structure can be obtained more stably and the deterioration of the resin is small.

  The method for adjusting the resin pressure at the time of melt kneading is not particularly limited. For example, (b) improvement of the resin viscosity by lowering the melt kneading temperature, (b) selection of a polymer having a molecular weight that achieves the desired resin pressure. (C) Resin retention by changing screw arrangements such as reverse full flight and kneading block introduction, (d) Improving the feed rate of raw materials, and increasing the polymer filling rate in the barrel by introducing mesh into the die part. (F) Improvement of resin viscosity by mixing arbitrary additives, (g) Supercritical state such as introduction of carbon dioxide gas, and the like.

  The styrenic resin composition of the present invention has a specific phase structure such as the above-described two-phase continuous structure having a structural period of 0.001 to 1 μm or a dispersed structure having a distance between particles of 0.001 to 1 μm by practical molding. It can be stably obtained, and the mechanical properties, flowability, plating properties, and flame retardancy (limits measured according to JIS K7021) without impairing the excellent mechanical properties, moldability and appearance of the styrene resin. An effect of facilitating the provision of an oxygen index (LOI) is exhibited.

  Furthermore, in the styrene resin composition of this invention, a flame retardance can be easily provided by adding a flame retardant. The flame retardant used in the present invention is not particularly limited, and is a so-called general flame retardant. In addition to phosphorus compounds and halogen organic compounds, nitrogen-containing organic compounds such as melamine, inorganics such as magnesium hydroxide and aluminum hydroxide Compounds, polyorganosiloxane compounds, arsenic oxide, antimony oxide, bismuth oxide, metal oxides such as iron oxide, zinc oxide, tin oxide, silica, etc. are used, preferably phosphorous compounds or halogen organics Although it is a combined use of a compound and a halogen organic compound and antimony oxide, a phosphorus compound is particularly preferable.

  The phosphorus compound is not particularly limited as long as it is an organic or inorganic compound containing phosphorus, and examples thereof include ammonium polyphosphate, polyphosphazene, phosphate, phosphonate, phosphinate, and phosphine oxide. Among these, polyphosphazenes and phosphates are preferable, and aromatic phosphates can be particularly preferably used.

  The content of the phosphorus compound is generally in the range of 0.1 to 30 parts by weight with respect to 100 parts by weight as the total of the components (A) and (B). The range is preferably 0.5 to 25 parts by weight, and particularly preferably 1 to 20 parts by weight. If it is less than 0.1 part by weight, the necessary flame retardant effect is not exhibited, and if it exceeds 30 parts by weight, the mechanical strength and heat resistance of the resin are greatly reduced, which is not preferable.

  Examples of the halogen-based organic compound include hexachloropentadiene, hexabromodiphenyl, octabromodiphenyl oxide, tribromophenoxymethane, decabromodiphenyl, decabromodiphenyl oxide, octabromodiphenyl oxide, tetrabromobisphenol A, tetrabromophthalimide, Examples include sabromobutene, trichlorotetrabromophenyl-triphosphate, hexabromocyclododecane, and compounds obtained by modifying these with various substituents.

  The content of the halogen-based organic compound is generally used in the range of 0.1 to 30 parts by weight with respect to 100 parts by weight as a total of the components (A) and (B). The range is preferably 0.5 to 25 parts by weight, and particularly preferably 1 to 20 parts by weight. If the amount is less than 0.1 parts by weight, the necessary flame retardant effect is not exhibited. If the amount exceeds 30 parts by weight, the mechanical strength of the resin is greatly reduced, which is not preferable.

  In the resin composition of the present invention, it is effective to use a dripping inhibitor in combination with the flame retardant in order to enhance the flame retardancy. Examples of the anti-drip agent include perfluoroalkane polymers such as polytetrafluoroethylene, silicon rubber, and graft polymers obtained by graft polymerization of these with vinyl compounds, high molecular weight vinyls such as high molecular weight acrylonitrile-styrene, and high molecular weight PMMA. Examples of the copolymer include glass fibers, carbon fibers, and the like. In particular, polytetrafluoroethylene obtained by acrylic modification is preferably used.

  In general, the content of the anti-dripping agent is preferably used in the range of 0.01 to 5 parts by weight with respect to 100 parts by weight of the total of the components (A) and (B). A particularly preferred range is in the range of 0.05 to 3 parts by weight. If it is less than 0.01 part by weight, the dripping prevention effect at the time of combustion is insufficient, and high flame retardancy cannot be obtained, and if it exceeds 5 parts by weight, the mechanical strength such as fluidity and rigidity is lowered, which is not preferable. .

  Furthermore, in the present invention, a filler may be used as necessary in order to improve strength, dimensional stability, and the like. The filler may be fibrous or non-fibrous, or a combination of fibrous filler and non-fibrous filler may be used. Examples of the filler include glass fiber, glass milled fiber, carbon fiber, potassium titanate whisker, zinc oxide whisker, aluminum borate whisker, aramid fiber, alumina fiber, silicon carbide fiber, ceramic fiber, asbestos fiber, stone-kow fiber, metal Fibrous fillers such as fibers, wollastonite, zeolite, sericite, kaolin, mica, clay, pyrophyllite, bentonite, asbestos, talc, alumina silicate and other silicates, alumina, silicon oxide, magnesium oxide, zirconium oxide, Metal compounds such as titanium oxide and iron oxide, carbonates such as calcium carbonate, magnesium carbonate and dolomite, sulfates such as calcium sulfate and barium sulfate, hydroxides such as magnesium hydroxide, calcium hydroxide and aluminum hydroxide, Rasubizu, ceramic beads, non-fibrous fillers such as boron nitride and silicon carbide and the like, which may be hollow, it is also possible to further combination of these fillers 2 or more. In addition, these fibrous and / or non-fibrous fillers are pretreated with a coupling agent such as an isocyanate compound, an organic silane compound, an organic titanate compound, an organic borane compound, an epoxy compound, It is preferable in terms of obtaining superior mechanical strength.

  In order to improve strength, dimensional stability, etc., when such a filler is used, the blending amount thereof is not particularly limited, but is usually 0.1 to 100 parts by weight in total of the component (A) and the component (B). 200 parts by weight is blended.

  As long as the effects of the present invention are not impaired, the styrene-based resin composition of the present invention includes plasticizers such as polyalkylene oxide oligomer compounds, thioether compounds, ester compounds, and organic phosphorus compounds, talc, kaolin, and organic phosphorus compounds. , Nucleating agents such as polyether ether ketone, polyolefin compounds, silicone compounds, long chain aliphatic ester compounds, long chain aliphatic amide compounds, mold release agents, anticorrosives, anti-coloring agents, antioxidants Ordinary additives such as lubricants, heat stabilizers, lubricants such as lithium stearate and aluminum stearate, UV inhibitors, colorants, and foaming agents can be added.

  These additives can be blended at any stage for producing the styrenic resin composition of the present invention. For example, a method of simultaneously adding at least two components of a resin, or two components in advance. There are a method of adding the resin after melt kneading, and a method of adding the resin to one resin first and then melt-kneading and then blending the remaining resin.

  The molding method of the styrene resin composition obtained from the present invention can be any method, and the molding shape can be any shape. Examples of the molding method include injection molding, extrusion molding, inflation molding, blow molding and the like. Among them, injection molding is preferable because heat treatment and structural fixation can be simultaneously performed in the mold after injection. If it is and / or sheet extrusion molding, heat treatment is preferably performed when the film and / or sheet is stretched, and the structure can be fixed during natural cooling before subsequent winding. Of course, it is possible to heat-treat the molded product separately to form a structure.

  The styrenic resin composition in the present invention can be usefully used as a structural material by taking advantage of excellent impact resistance, heat resistance, fluidity, plating property, and flame retardancy, for example, electric / electronic parts, automobiles, etc. It can be suitably used for housings such as parts, machine mechanism parts, OA equipment, and home appliances, parts thereof, and miscellaneous goods.

  The molded body of the styrene resin composition of the present invention includes, for example, various gears, various cases, sensors, LED lamps, connectors, sockets, resistors, relay cases, switches, coil bobbins, capacitors, variable capacitor cases, optical pickups, and oscillators. Terminal boards, transformers, plugs, printed wiring boards, tuners, speakers, microphones, headphones, small motors, magnetic head bases, power modules, housings, semiconductors, liquid crystals, FDD carriages, FDD chassis, motor brush holders, parabolic antennas Electric / electronic parts represented by computer-related parts; generators, motors, transformers, current transformers, voltage regulators, rectifiers, inverters, relays, power contacts, switches, circuit breakers, knife switches, etc. Polar rod, electrical parts key Vignette, VTR parts, TV parts, irons, hair dryers, rice cooker parts, microwave oven parts, acoustic parts, audio / laser discs / compact discs, audio equipment parts such as DVDs, lighting parts, refrigerator parts, air conditioner parts, typewriters Houses represented by parts, word processor parts, office electrical product parts, office computer related parts, telephone related parts, mobile phone related parts, facsimile related parts, copying machine related parts, cleaning jigs, oilless bearings, stern bearings Various bearings such as underwater bearings, motor-related parts such as motor parts, lighters and typewriters, optical equipment such as microscopes, binoculars, cameras and watches, precision machine-related parts; alternator terminals, alternator connectors IC regulation Potentiometer base for light deer, air intake nozzle snorkel, intake manifold, air flow meter, air pump, fuel pump, engine coolant joint, thermostat housing, carburetor main body, carburetor spacer, engine mount, ignition hobbin, ignition case , Clutch bobbin, sensor housing, idle speed control valve, vacuum switching valve, ECU housing, vacuum pump case, inhibitor switch, rotation sensor, acceleration sensor, distributor cap, coil base, actuator case for ABS, top and bottom of radiator tank , Cooling fan, fan shroud, en Gin cover, cylinder head cover, oil cap, oil pan, oil filter, fuel cap, fuel strainer, distributor cap, vapor canister housing, air cleaner housing, timing belt cover, brake booster parts, various cases, fuel related / exhaust system Various tubes such as intake systems, various tanks, various hoses such as fuel / exhaust systems / intake systems, various clips, various valves such as exhaust gas valves, various pipes, exhaust gas sensors, cooling water sensors, oil temperature sensors, brake pads Wear sensor, brake pad wear sensor, throttle position sensor, crankshaft position sensor, thermostat base for air conditioner, air conditioner panel switch board, heating hot air Low control valve, brush holder for radiator motor, water pump impeller, turbine vane, wiper motor related parts, step motor rotor, brake piston, solenoid bobbin, engine oil filter, ignition device case, torque control lever, starter switch, starter relay, Safety belt parts, register blades, washer levers, window regulator handles, knobs for window regulator handles, passing light levers, distributors, sun visor brackets, various motor housings, roof rails, fenders, garnishes, bumpers, door mirror stays, horn terminals, Window washer nozzle, spoiler, hood louver Wheel cover, wheel cap, radiator grille, grill apron cover frame, lamp reflector, lamp socket, lamp housing, lamp bezel, door handle and other automotive exterior materials, center console, instrument panel, instrument panel core, instrument panel pad, glove box, Automotive parts such as handle columns, armrests, lever parking, front pillar trims, door trims, pillar trims, console boxes, and other automotive interior materials, wire harness connectors, SMJ connectors, PCB connectors, door grommets connectors, and connectors for fuses; , Printer, display, CRT display, fax, copy, word processor, laptop, mobile phone , PHS, DVD drive, PD drive, flexible disk drive and other storage device housings, chassis, relays, switches, case members, transformer members, coil bobbins and other electrical and electronic equipment parts, machine parts, and other various uses .

  Furthermore, various molded articles made of the styrenic resin composition of the present invention are suitable for coating or plating treatment and exhibit excellent coating adhesion and plating characteristics.

  The coating adhesion can be evaluated from the peeled state of the coating by applying a coating, drying and leaving it, and then performing a cross-cut test with a cellophane tape based on JIS standards.

  Examples of the paint used in the present invention include acrylic paints and urethane paints. Acrylic paints are paints mainly comprising a copolymer resin with acrylic acid and its esters, methacrylic acid and its esters, or other vinyl compounds. The urethane-based paint is a paint having a urethane bond in the resin skeleton or generating a urethane bond in the process of forming a coating film.

  The plating characteristics refer to the initial plating adhesion strength and the presence or absence of plating swelling after the heat cycle. The performance such as plating adhesion strength is caused by the size, depth, number of holes generated by the etching process, the strength of the substrate constituting the periphery of the holes, and the like. The plating component enters the inside of the hole and prevents peeling of the plated portion forming the surface layer portion by an anchor effect that takes root to the substrate. However, if the base material around the anchor is brittle, the base material is peeled off. Therefore, the base material has sufficient mechanical strength, has sufficient solvent resistance to prevent embrittlement by the etching solution, and exhibits a good plating characteristic by having a stable phase structure. Can do.

  The plating method does not require a special plating process, and a plating process method for ABS resin widely used as a resin plating is sufficient. Typical plating processes include (1) pretreatment, (2 ) Roughening treatment (etching) (3) Sensitivity imparting (catalytic) or catalyst treatment, (4) Activation treatment (activation) or acceleration treatment, (5) Electroless plating and (6) Electricity It is performed by sequentially performing each step of plating. Above all, the surface roughening treatment (2) is an important step that affects the adhesion of the metal plating film applied in the subsequent plating step, and various means are used depending on the type of plastic, for example, ABS resin. Then, the chemical etching method by immersing a molded article in a chromic acid-sulfuric acid mixed liquid has been established.

  In the styrene resin composition of the present invention, (A) a styrene resin and (B) a thermoplastic resin other than the styrene resin is a two-phase continuous structure having a structural period of 0.001 to 1 μm, or an interparticle distance of 0.001. By having a unique phase structure of ~ 1 μm dispersion structure, it is possible to uniformly control the coating film adhesion and the size, depth, number, etc. of the holes generated by the etching process, thus providing good plating characteristics. It has been found that it can be obtained.

  In order to describe the present invention more specifically, examples and comparative examples will be described below, but the present invention is not limited to these examples. In the examples, parts and% indicate parts by weight and% by weight, respectively.

[Reference Example 1] (A) Styrenic resin <A-1> Graft (co) polymer A method for preparing a graft copolymer is shown below. The graft ratio was determined by the following method. Acetone was added to a predetermined amount (m) of the graft copolymer and refluxed for 4 hours. This solution was centrifuged at 8000 rpm (centrifugal force 10,000 G (about 100 × 10 3 m / s 2)) for 30 minutes, and the insoluble matter was filtered off. This insoluble matter was dried under reduced pressure at 70 ° C. for 5 hours, and the weight (n) was measured.
Graft ratio = [(n) − (m) × L] / [(m) × L] × 100
Here, L means the rubber content of the graft copolymer.

  The filtrate of the acetone solution was concentrated with a rotary evaporator to obtain a precipitate (acetone soluble matter). This soluble matter was dried under reduced pressure at 70 ° C. for 5 hours, adjusted to 0.4 g / 100 ml (methyl ethyl ketone, 30 ° C.), and the intrinsic viscosity was measured using an Ubbelohde viscometer. Moreover, about the content rate of each monomer unit in the obtained graft copolymer, the film-form sample of about 30 micrometers was created by press molding, and it measured from the peak intensity ratio obtained by FT-IR analysis.

<A-1-1>
In the presence of 50 parts of polybutadiene latex (average rubber particle size 0.3 μm) (in terms of solid content), 50 parts of a monomer mixture composed of 70% styrene and 30% acrylonitrile was added to carry out emulsion polymerization. The obtained graft copolymer was solidified with sulfuric acid, washed and dried to obtain a powder.

  The graft ratio of the obtained graft copolymer was 42%, the intrinsic viscosity of methyl ethyl ketone soluble matter was 0.37 dl / g, the content of each monomer unit was 50% by weight of butadiene units, 35% by weight of styrene units, The acrylonitrile unit was 15% by weight.

<A-1-2>
In the presence of 50 parts of polybutadiene latex (average rubber particle diameter 0.2 μm) (in terms of solid content), 50 parts of a monomer mixture consisting of 70% methyl methacrylate, 25% styrene, and 5% acrylonitrile was added to carry out emulsion polymerization. The obtained graft copolymer was solidified with sulfuric acid, washed and dried to obtain a powder.

  The graft copolymer thus obtained had a graft ratio of 45%, an intrinsic viscosity of methyl ethyl ketone soluble matter of 0.30 dl / g, a content of each monomer unit of 50% by weight of butadiene units, and 35% by weight of methyl methacrylate units. %, Styrene unit 12% by weight, and acrylonitrile unit 3% by weight.

<A-2> Preparation of vinyl copolymer A method for preparing a vinyl copolymer is shown below. The obtained polymer was dried under reduced pressure at 70 ° C. for 5 hours, then prepared to 0.4 g / 100 ml (methyl ethyl ketone, 30 ° C.), and the intrinsic viscosity was measured using an Ubbelohde viscometer. Moreover, about the content rate of each monomer unit in the obtained vinyl-type copolymer, about 30 micrometers film-form sample was created by press molding, and it measured from the peak intensity ratio obtained from FT-IR analysis.

<A-2-1>
A styrene-acrylonitrile copolymer “Toyolac” 1050B (manufactured by Toray Industries, Inc.) was used. The intrinsic viscosity of the soluble part of methyl ethyl ketone was 0.39 dl / g, and the content of each monomer unit was 76% by weight of styrene units and 24% by weight of acrylonitrile units.

<A-2-2>
A monomer mixture consisting of 70% styrene and 30% acrylonitrile was suspension-polymerized to prepare a vinyl copolymer. The vinyl copolymer obtained had an intrinsic viscosity of 0.53 dl / g of the methyl ethyl ketone-soluble component, and the content of each monomer unit was 70% by weight of styrene units and 30% by weight of acrylonitrile units.

<A-2-3>
A monomer mixture consisting of 70% styrene and 30% acrylonitrile was suspension-polymerized to prepare a vinyl copolymer. The vinyl copolymer obtained had an intrinsic viscosity of 0.98 dl / g of methyl ethyl ketone-soluble component, and the content of each monomer unit was 70% by weight of styrene units and 30% by weight of acrylonitrile units.

<A-2-4>
A monomer mixture composed of 40% styrene, 30% acrylonitrile, and 30% α-methylstyrene was subjected to suspension polymerization to prepare a vinyl copolymer. The vinyl copolymer obtained has an intrinsic viscosity of 0.52 dl / g of methyl ethyl ketone-soluble matter, and the content of each monomer unit is 40% by weight of styrene units, 30% by weight of acrylonitrile units, and α-methylstyrene units. It was 30% by weight.

<A2-5>
A monomer mixture composed of 65% styrene and 35% acrylonitrile was suspension-polymerized to prepare a vinyl copolymer. The vinyl copolymer obtained had an intrinsic viscosity of 0.54 dl / g of the methyl ethyl ketone-soluble component, and the content of each monomer unit was 65% by weight of styrene units and 35% by weight of acrylonitrile units.

[Reference Example 2] (B) Thermoplastic resin other than styrene resin <B-1> Aromatic polycarbonate "Iupilon" S3000 (manufactured by Mitsubishi Engineering Plastics Co., Ltd.) was used.

  <B-2> Aromatic polycarbonate “Iupilon” S2000 (manufactured by Mitsubishi Engineering Plastics) was used.

  <B-3> Aromatic polycarbonate “Iupilon” E2000 (manufactured by Mitsubishi Engineering Plastics) was used.

  <B-4> 24.3% of 2,2′-bis (4-hydroxyphenyl) propane, 30.6% of 2,2′-bis (4-hydroxy-3,5-dimethylphenyl) propane, and diphenyl carbonate 45.1% was charged into a stirring tank and purged with nitrogen and melted at 150 ° C. Tetramethylammonium hydroxide and sodium hydroxide were added thereto, and the reaction was carried out by stirring at 150 ° C. for 1 hour. Next, the temperature was raised to 220 ° C., the pressure was reduced to 27 kPa (200 mmHg), and the mixture was stirred for 1 hour. The temperature was further raised to 250 ° C., the pressure was reduced to 2 kPa (15 mmHg), and the reaction was allowed to proceed by stirring for 1 hour. The obtained reaction product was sent to a centrifugal thin film evaporator and allowed to proceed, and then sent to a horizontal stirring polymerization device to complete the polymerization by staying at 290 ° C. for 30 minutes. Copolymerized aromatic polycarbonate which was made into a strand shape through a die from a horizontal stirrer and pelletized with a cutter was used.

[Reference Example 3] (c1) Modified Styrene Polymer A method for preparing a modified vinyl polymer is shown below. The obtained polymer was dried under reduced pressure at 70 ° C. for 5 hours, then prepared to 0.4 g / 100 ml (methyl ethyl ketone, 30 ° C.), and the intrinsic viscosity was measured using an Ubbelohde viscometer. Moreover, about the content rate of each monomer unit in the obtained modified vinyl polymer, about 30 micrometers film-form sample was created by press molding, and it measured from the peak intensity ratio obtained by FT-IR analysis.

  <C1-1> A modified vinyl copolymer was prepared by suspension polymerization of a monomer mixture composed of 69.7% styrene, 30% acrylonitrile, and 0.3% glycidyl methacrylate. The resulting modified vinyl copolymer has an intrinsic viscosity of 0.53 dl / g of soluble methyl ethyl ketone, the content of each monomer unit is 69.7% by weight of styrene units, 30% by weight of acrylonitrile units, and glycidyl methacrylate. The unit was 0.3% by weight.

  <C1-2> A monomer mixture comprising 67% styrene, 30% acrylonitrile and 3% maleic anhydride was solution polymerized in a methyl ethyl ketone solvent to prepare a vinyl copolymer. The obtained vinyl copolymer had an intrinsic viscosity of 0.53 dl / g of methyl ethyl ketone-soluble component, the content of each monomer unit was 67% by weight of styrene units, 30% by weight of acrylonitrile units, and 3 units of maleic anhydride units. % By weight.

(C2) Polycarbonate-based graft polymer <c2-1> Polycarbonate-graft-styrene / acrylonitrile copolymer (PC-g-SAN) “Modiper CH430” (manufactured by NOF Corporation) was used.

  <C2-2> Polycarbonate-graft-modified styrene / acrylonitrile copolymer (PC-g-mSAN) “Modiper CL440G” (manufactured by NOF Corporation) was used.

  <C2-3> Polycarbonate-graft-polystyrene copolymer (PC-g-PS) “Modiper CL130D” (manufactured by NOF Corporation) was used.

[Reference Example 4] Flame retardant <FR-1> Aromatic bisphosphate "PX200" (manufactured by Daihachi Chemical Industry Co., Ltd.) was used.

  <FR-2> Brominated epoxy resin “SR-T5000” (manufactured by Sakamoto Pharmaceutical Co., Ltd.) was used.

[Reference Example 5] Additive <TZ-1> Acrylic-modified polytetrafluoroethylene “methabrene” A3000 (manufactured by Mitsubishi Rayon Co., Ltd.) was used.

[Examples 1 to 28, Comparative Examples 1 to 13]
The raw material which consists of a composition of the Example of Tables 1-4 and a comparative example is supplied to the twin screw extruder (Ikegai Kogyo Co., Ltd. PCM-30) set to the extrusion temperature of 250 degreeC, and the gut after discharge from die | dye is supplied. Immediately cooled in ice water to fix the structure, a pellet-like polymer was produced.

  Using the obtained pellet-shaped polymer, each test piece was molded with an injection pressure (lower limit pressure + 1 MPa) by an injection molding machine (manufactured by Sumitomo Heavy Industries, Promat 40/25), and the physical properties were measured under the following conditions. .

  [Impact Resistance]: Impact resistance was evaluated according to ASTM D256-56A. It is set as the average value of six measurements.

  [Bending strength]: The bending strength was evaluated according to ASTM D790.

  [Bending elastic modulus]: The bending elastic modulus was evaluated according to ASTM D790.

  [Tensile strength]: Tensile strength was evaluated according to ASTM D638.

  [Tensile Elongation]: The tensile elongation was evaluated according to ASTM D638.

  [Heat resistance]: Heat resistance was evaluated according to ASTM D648 (load: 1.82 MPa).

  [Flowability]: The flow length (spiral flow length) of spiral flow (cross-sectional shape: width 10 mm × thickness 2 mm) was measured at a cylinder temperature of 240 ° C., a mold temperature of 60 ° C., and an injection pressure of 50 MPa.

  [Limiting oxygen index]: The limiting oxygen index was evaluated according to JIS K7021.

  [Adhesion strength of plating film]: 15) The square plate subjected to electroplating (bright copper plating) is baked at 80 ° C. for 2 hours and then allowed to cool for 1 hour, and then the plating film is 10 mm wide and 20 mm long. It evaluated by measuring the power (Kg) at the time of peeling.

  [Plating thermal cycle test]: 19) A square plate subjected to electroplating (chromium plating) at 90 ° C. (1 hr) → room temperature (15 min) → −35 ° C. (1 hr) → room temperature (15 min) as one cycle. Three cycles were performed, and the presence or absence of abnormality (swelling, peeling, cracking) on the plating surface was observed and evaluated.

(Plating conditions)
An 80 mm × 80 mm × 3 mm thick square plate molded product molded at a mold temperature of 60 ° C. was plated under the following conditions.
1) The degreasing test piece was immersed at 55 ° C. for 4 minutes using “A Screen A-220” (Okuno Pharmaceutical Co., Ltd.).
2) Washing with water 3) Etching 98% by weight sulfuric acid and dipping at 60 ° C. for 10 minutes.
4) Washing with water 5) Acid treatment 5% by weight hydrochloric acid soaked at 30 ° C. for 2 minutes.
6) Washing with water 7) Immerse in a solution consisting of 150 ml of catalyst concentrated hydrochloric acid, 50 ml of catalyst C (produced by Okuno Pharmaceutical Co., Ltd.) and 1000 ml of water at 20 ° C. for 2 minutes.
8) Washing with water 9) Immersion at 40 ° C. for 3 minutes using 10% by weight of sulfuric acid accelerator.
10) Washing with water 11) Immersion at 30 ° C. for 8 minutes using electroless copper plating OPC-750 (Okuno Pharmaceutical Co., Ltd.).
12) Washing with water 13) Immersion for 30 seconds using activated 5% by weight sulfuric acid.
14) Washing with water 15) An electroplating (bright copper plating) test piece consists of 50 g of concentrated sulfuric acid, 200 g of copper sulfate (pentahydrate), SCB-MU 10 ml, SCB-I 1 ml (Okuno Pharmaceutical Co., Ltd.) and 1000 ml of water. Place in an acidic copper plating bath and form a copper plating film with a thickness of about 30 μm under conditions of a temperature of 20 to 25 ° C. and a current density of 4 A / dm ² .
16) Washing with water 17) Electroplating (bright nickel plating) 40 g of boric acid, 50 g of nickel chloride (hexahydrate), 300 g of nickel sulfate (7 hydrate), 1 ml of monolite (Okuno Pharmaceutical Co., Ltd.), A nickel plating film having a thickness of about 15 μm was formed in a plating bath consisting of 20 ml of Acuna B-I (Okuno Pharmaceutical Co., Ltd.) and 1000 ml of water under conditions of a temperature of 50 ° C. and a current density of 5 A / dm ² .
18) Washing with water 19) Electroplating (chromium plating) Chromium plating with a thickness of about 0,2 μm in a plating bath consisting of 5 g of concentrated sulfuric acid, 250 g of chromium oxide and 1000 ml of water at a temperature of 45 ° C. and a current density of 20 A / dm ^2. Form a film.

  Furthermore, for a sample obtained by cutting a 100 μm-thick section from a molded product obtained by the above injection molding, the sample obtained by dyeing polycarbonate by iodine staining and then cutting an ultrathin section was magnified 50,000 times with a transmission electron microscope. And observed.

In addition, with respect to a sample obtained by cutting a 100 μm-thick section from the molded product obtained by the injection molding, the structure period in the case of a biphasic continuous structure or the interparticle distance in the case of a dispersed structure is expressed by small-angle X-ray scattering (less than 0.4 μm). It was measured by a structure period or interparticle distance) or light scattering (in the case of a structure period or interparticle distance of 0.4 μm or more). Peaks were observed in all samples, and the structural period or interparticle distance (Λm) calculated from the peak position (θm) by the following equation was obtained.
Λm = (λ / 2) / sin (θm / 2)

  From the transmission electron micrograph of each sample, the state of the structure, from small-angle X-ray scattering or light scattering to the structure period or interparticle distance, as well as impact resistance, bending properties, tensile properties, heat resistance, fluidity, plating properties and limitations The measurement results of the oxygen index are shown in Tables 1 to 4.

  From Examples 1 to 16, by using (c) modified styrene polymer and (c2) polycarbonate graft polymer in combination with (A) styrene resin and (b) polycarbonate resin as in the present invention, 1 μm The following two-phase continuous structure and fine phase structure, which is a dispersed structure, can be stably obtained in practical injection molding, and mechanical properties, heat resistance, fluidity, plating properties, and even flame retardance are dramatically improved. I was able to improve it. In particular, when the styrene resin having <A-2-4> α-methylstyrene unit described in Examples 5 and 10 and the <B-4> copolymer aromatic polycarbonate described in Examples 9 and 10 are used. In addition, the compatibility due to a decrease in the free volume under shear during melt-kneading was improved, the desired phase structure was easily obtained, and a marked improvement in properties was observed. Further, when the vinyl copolymer having a high <A2-5> acrylonitrile content described in Example 6 was used, and when the amount of the <A-1-1> graft polymer described in Examples 15 and 16 was increased In addition, the plating property could be improved while maintaining the mechanical properties.

  Further, from Examples 17 to 21, even when the types and addition ratios of (c1) modified styrene polymer and (c2) polycarbonate graft polymer were changed, the same excellent characteristics as described above could be expressed. .

  On the other hand, as in Comparative Examples 1 to 8, (c1) the modified styrene polymer and (c2) the polycarbonate graft polymer not added, or (c1) the modified styrene polymer and (c2) the polycarbonate graft polymer. When it was added alone, the desired phase structure could not be obtained by general-purpose injection molding, and the mechanical properties, fluidity and plating properties were low.

  From the comparison between Example 12 and Comparative Example 7, when the amount of polycarbonate resin required for high impact is as small as 30 parts by weight, the impact resistance is greatly reduced as in Comparative Example 7, whereas (c1) modification By adding the styrene-based polymer and (c2) the polycarbonate-based graft polymer in combination, a fine structure having a biphasic continuous structure is obtained, and the same resistance to resistance as in Comparative Examples 1 to 6 in which 50 parts by weight of the polycarbonate resin is added. While exhibiting impact properties, fluidity, chemical resistance, and plating properties can be dramatically improved.

  From Examples 22 to 28, even when a flame retardant and an additive are added to the styrenic resin composition, it has a fine phase structure that is a two-phase continuous structure of 1 μm or less as in the present invention. The flame retardancy was drastically improved while maintaining the properties, fluidity and plating properties. In particular, when the amount of <FR-1> flame retardant described in Example 23 is increased and when the amount of <B-3> polycarbonate resin described in Example 28 is increased, the limiting oxygen index (LOI) is about 30%. Thus, it becomes a level at which V-0 can be expressed in the UL standard vertical combustion test which is a general flame retardant index.

  On the other hand, as in Comparative Examples 9 to 13, (c1) modified styrene-based polymer and (c2) polycarbonate-based graft polymer not added, or (c1) modified styrene-based polymer and (c2) polycarbonate-based graft polymer alone When a flame retardant and an additive are added to the composition added in step 1, the desired phase structure is not obtained, the mechanical properties are low, and the flame retardancy is significantly reduced compared to the product of the present invention. In order to develop the properties, it is necessary to add a large amount of a flame retardant and (b) increase the amount of the polycarbonate resin.

  It can be used for various applications such as electric / electronic parts, automobile parts, machine mechanism parts, OA equipment, home appliances and other housings, their parts, and sundry goods.

Claims (13)

A styrene resin composition comprising (A) a styrene resin, (B) a thermoplastic resin other than the styrene resin, (c1) a modified styrene polymer, and (c2) a polycarbonate graft polymer. The thermoplastic resin other than (A) styrene resin and (B) styrene resin has a biphasic continuous structure with a structural period of 0.001 to 1 μm, or a dispersed structure with a distance between particles of 0.001 to 1 μm. The styrenic resin composition as described. A thermoplastic resin other than (A) a styrene resin and (B) a styrene resin has a biphasic continuous structure with a structural period of 0.01 to 0.5 μm or a dispersed structure with a distance between particles of 0.01 to 0.5 μm. The styrenic resin composition according to claim 2. (C1) The modified styrene polymer comprises a vinyl monomer unit containing at least one functional group selected from a carboxyl group, a hydroxyl group, an epoxy group, an amino group, and an oxazoline group. Styrenic resin composition. (C2) The styrene resin composition according to claim 1, wherein the polycarbonate graft polymer includes a polycarbonate resin segment and a vinyl polymer segment. (A) The styrenic resin composition according to claim 1, wherein the styrenic resin contains a styrenic monomer unit substituted with an alkyl group having 1 to 4 carbon atoms. The styrenic resin composition according to claim 1, wherein the thermoplastic resin other than (B) the styrenic resin is (b) a polycarbonate resin. The (b) polycarbonate resin comprises (b1) 2,2′-bis (4-hydroxyphenyl) propane and (b2) 2,2′-bis (4-hydroxy-3,5-dimethylphenyl) propane, At least one bifunctional phenolic compound selected from 2'-bis (4-hydroxy-3,5-diethylphenyl) propane and 2,2'-bis (4-hydroxy-3,5-dipropylphenyl) propane The styrene resin composition according to claim 7, comprising an aromatic copolymer polycarbonate obtained by copolymerizing (A) Styrenic resin is present in the presence of (r) 5 to 80% by weight of a rubbery polymer, (a1) 5 to 90% by weight of styrenic monomer units, (a2) vinyl cyanide monomer Graft-polymerize 1 to 50% by weight of a monomer mixture and 20 to 95% by weight of a monomer mixture composed of 0 to 80% by weight of other vinyl monomer units (a3) copolymerizable therewith (A- 1) 5 to 100 parts by weight of graft (co) polymer, (a1) 5 to 90% by weight of styrene monomer units, (a2) 1 to 50% by weight of vinyl cyanide monomer units, and (A3) copolymerizable (a3) obtained by polymerizing a monomer mixture comprising 0 to 80% by weight of another vinyl monomer unit (A-2) 0 to 95 parts by weight of a vinyl (co) polymer A styrene resin composition according to claim 1, which is a rubber-modified styrene resin comprising a1) a total of 100 wt% respectively of ~ (a3)). The melt-kneading of (A) styrene resin, (B) thermoplastic resin other than styrene resin, (c1) modified styrene polymer, and (c2) polycarbonate graft polymer. A method for producing a styrene-based resin composition. The component (A), the component (B), the component (c1) and the component (c2) are compatible with each other under shear during the melt kneading and phase-separated under non-shear after discharge. The manufacturing method of the styrene resin composition as described in any one of. A molded article comprising the styrenic resin composition according to any one of claims 1 to 9. The molded article according to claim 12, which is subjected to painting or plating treatment.