WO2019087653A1 - Thermoplastic resin composition for plated molded article, and molded article and plated molded article both obtained using same - Google Patents
Thermoplastic resin composition for plated molded article, and molded article and plated molded article both obtained using same Download PDFInfo
- Publication number
- WO2019087653A1 WO2019087653A1 PCT/JP2018/036834 JP2018036834W WO2019087653A1 WO 2019087653 A1 WO2019087653 A1 WO 2019087653A1 JP 2018036834 W JP2018036834 W JP 2018036834W WO 2019087653 A1 WO2019087653 A1 WO 2019087653A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- copolymer
- weight
- vinyl
- butadiene
- iii
- Prior art date
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L25/00—Compositions of, homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Compositions of derivatives of such polymers
- C08L25/02—Homopolymers or copolymers of hydrocarbons
- C08L25/04—Homopolymers or copolymers of styrene
- C08L25/08—Copolymers of styrene
- C08L25/14—Copolymers of styrene with unsaturated esters
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
- C08L51/04—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to rubbers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L55/00—Compositions of homopolymers or copolymers, obtained by polymerisation reactions only involving carbon-to-carbon unsaturated bonds, not provided for in groups C08L23/00 - C08L53/00
- C08L55/02—ABS [Acrylonitrile-Butadiene-Styrene] polymers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L69/00—Compositions of polycarbonates; Compositions of derivatives of polycarbonates
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
- C25D5/54—Electroplating of non-metallic surfaces
- C25D5/56—Electroplating of non-metallic surfaces of plastics
Definitions
- the present invention relates to a thermoplastic resin composition for a plated molded article and a molded article using the same.
- Rubber-reinforced styrene resin represented by ABS resin has excellent moldability and mechanical properties, and is excellent in secondary processability such as paintability and plating property, so that it can be used in the automotive field, home appliance field, It is used as a molding material for various components in a wide range of fields such as the OA equipment field.
- polycarbonate resins are widely used in various fields including automobile field, home appliance field, OA equipment field and building materials field because they are excellent in heat resistance and impact resistance.
- a study to melt-mix and alloy polycarbonate resin and ABS resin In particular, in the automotive field, the development of parts that require heat resistance, impact resistance, and secondary processability such as paintability and plating ability is in progress.
- various studies have been advanced to improve the plating characteristics while maintaining the characteristics such as mechanical characteristics and heat resistance.
- Patent Document 1 discloses a polycarbonate resin and a graft having a rubber average particle diameter specified.
- a resin composition for direct plating comprising a copolymer and a vinyl copolymer is disclosed.
- the resin composition described in Patent Document 1 has improved plating properties while maintaining a balance between impact resistance, heat resistance and fluidity, but the effect is not sufficient and the durability after plating is not good. There was an issue that was sufficient.
- Patent Document 2 is composed of a polycarbonate resin, a rubbery polymer-containing copolymer, and a vinyl copolymer, and the content of vinyl cyanide monomer in an acetone-soluble portion in the copolymer is defined.
- a resin composition for plating is disclosed. Although the resin composition described in Patent Document 2 has improved plating properties, its effect is not sufficient, and the balance between the appearance, heat resistance and impact resistance is also insufficient.
- Patent Document 3 discloses a resin composition for electroless plating containing a polycarbonate resin, a vinyl copolymer, and a graft copolymer having a defined graft ratio.
- Patent Document 4 discloses a thermoplastic resin composition which is mainly composed of a graft rubber and is excellent in plating property, impact resistance, and large-size moldability, and further defines an organosilicon compound as a preferred embodiment. Thermoplastic resin compositions are disclosed in amounts. Although the resin composition described in Patent Document 4 is excellent in impact resistance, fluidity, and plating properties, the effect is not sufficient, and the durability after plating is also insufficient.
- An object of the present invention is to provide a thermoplastic resin composition and a molded article thereof which are excellent in the balance of mechanical properties, heat resistance, fluidity, plating properties, durability, and appearance of a plated molded article.
- the present inventors blend polycarbonate resin, graft copolymer, vinyl copolymer and methyl methacrylate-butadiene-styrene copolymer with a specific composition.
- the inventors have found that the mechanical properties, heat resistance, fluidity, plating properties, durability, and the appearance of the plated molded product are excellent in balance, and the present invention has been achieved.
- the present invention provides the following (1) to (6) as the gist.
- (1) It is obtained by graft copolymerization of a monomer mixture containing at least an aromatic vinyl monomer and a vinyl cyanide monomer in the presence of polycarbonate resin (I) and a diene rubber polymer.
- Thermoplastic resin composition for plated molded articles characterized in
- the total content of polycarbonate resin (I), graft copolymer (II), vinyl copolymer (III) and methyl methacrylate-butadiene-styrene copolymer (IV) is 100 parts by weight in total And 0.01 to 0.2 parts by weight of any one or more compounds (V) selected from silicone compounds and fluorine compounds.
- Thermoplastic resin composition for plated molded articles as described above.
- the content ratio of the vinyl cyanide monomer component copolymerized with the vinyl copolymer (III) is from 29 to
- thermoplastic resin composition of the present invention and a molded article thereof will be specifically described.
- Polycarbonate resin (I) is an aromatic dihydroxy compound typically exemplified by 2,2-bis (4-hydroxyphenyl) propane and 2,2-bis (3,5-dimethyl-4-hydroxyphenyl) propane And phosgene are obtained by reaction with a carbonate precursor typically exemplified.
- 2,2-bis (4-hydroxyphenyl) propane (hereinafter sometimes referred to as "bisphenol A"), 1,1-bis (4-hydroxyphenyl) ethane, 2,2, 2-Bis (4-hydroxyphenyl) butane, 2,2-bis (4-hydroxyphenyl) octane, 2,2-bis (4-hydroxy-3-methylphenyl) propane, 1,1-bis (3-tert -Butyl-4-hydroxyphenyl) propane, 2,2-bis (4-hydroxy-3,5-dimethylphenyl) propane, 2,2-bis (3-phenyl-4-hydroxyphenyl) propane, 2,2- Bis (3-cyclohexyl-4-hydroxyphenyl) propane, 1,1-bis (4-hydroxyphenyl) -1-phenylethane, bis Bis (hydroxyaryl) alkanes exemplified by 4-hydroxyphenyl) diphenylmethane and the like; 1,1-bis (4-hydroxyphenyl) cyclopentane, 1,1-bis (4-hydroxyphenyl) cyclopen
- bis (4-hydroxyphenyl) alkanes preferred are bis (4-hydroxyphenyl) alkanes, and particularly preferred is bisphenol A.
- bisphenol A preferred is bisphenol A.
- Carbonyl halides, carbonate esters, haloformates and the like are used as carbonate precursors to be reacted with aromatic dihydroxy compounds, and specifically, phosgene; diaryl carbonates such as diphenyl carbonate, ditolyl carbonate, etc .; dimethyl carbonate, diethyl carbonate etc. Dialkyl carbonates; dihaloformates of dihydric phenol and the like can be mentioned. Among them, phosgene is often preferably used. These carbonate precursors may also be used alone or in combination of two or more.
- the method for producing the polycarbonate resin (I) is not particularly limited, and the polycarbonate resin (I) can be produced by a conventionally known method.
- a conventionally known method for example, an interfacial polymerization method (phosgene method), a melt transesterification method, a solution polymerization method (pyridine method), a ring-opening polymerization method of a cyclic carbonate compound, a solid phase transesterification method of prepolymer, and the like can be mentioned.
- a production method by an interfacial polymerization method is exemplified.
- an organic solvent inert to the reaction, an aqueous alkaline solution, the pH is usually kept at 9 or more, and for preventing oxidation of the aromatic dihydroxy compound and, if necessary, the molecular weight modifier (termination agent) and the aromatic dihydroxy compound
- the reaction product is reacted with phosgene using an antioxidant for polymerization reaction, and then a polymerization catalyst such as tertiary amine or quaternary ammonium salt is added to carry out interfacial polymerization to obtain a polycarbonate resin.
- the addition of the molecular weight modifier is not particularly limited as long as it is from the time of phosgenation to the time of initiation of the polymerization reaction.
- the reaction temperature is, for example, 0 to 40 ° C., and the reaction time is, for example, 2 to 5 hours.
- the organic solvent applicable to the interfacial polymerization is not particularly limited as long as it is inert to the interfacial polymerization reaction, does not mix with water, and can dissolve the polycarbonate resin.
- examples thereof include chlorinated hydrocarbons such as dichloromethane, 1,2-dichloroethane, tetrachloroethane, chloroform, monochlorobenzene and dichlorobenzene, and aromatic hydrocarbons such as benzene, toluene and xylene.
- the hydroxide of alkali metals such as sodium hydroxide and potassium hydroxide, is mentioned.
- molecular weight modifiers include compounds having a monovalent phenolic hydroxyl group and phenyl chloroformate.
- Examples of the compound having a monovalent phenolic hydroxyl group include m-methylphenol, p-methylphenol, m-propylphenol, p-propylphenol, p-tert-butylphenol and p-long chain alkyl-substituted phenol.
- the amount of the molecular weight modifier used is preferably 0.1 to 1 mole relative to 100 moles of the aromatic dihydroxy compound.
- tertiary amines such as trimethylamine, triethylamine, tributylamine, tripropylamine, trihexylamine and pyridine; trimethylbenzyl ammonium chloride, tetrabutyl ammonium chloride, tetramethyl ammonium chloride, triethyl benzyl ammonium chloride, triethyl amine And quaternary ammonium salts such as octyl methyl ammonium chloride.
- the content of the polycarbonate resin (I) is polycarbonate resin (I), graft copolymer (II), vinyl copolymer (III), methyl methacrylate-butadiene-styrene
- the total content of the copolymer (IV) is 100% by weight, it is in the range of 50 to 70% by weight, preferably 52 to 68% by weight, more preferably 55 to 65% by weight. If this proportion is less than 50% by weight, the flow resistance is excellent but the impact resistance and the heat resistance are lowered. On the other hand, when this ratio exceeds 70% by weight, although the impact resistance and the heat resistance are excellent, the flowability is insufficient, and for example, the moldability at the time of injection molding becomes inferior.
- the viscosity-average molecular weight of the polycarbonate resin (I) to (M V) is not particularly limited, preferably 10,000 or more, 21,000 or less, more preferably 12,000 or more, 20,000 or less, and most preferably 15,000 or more and 18,000 or less. If M V is not less than 10,000, mechanical properties such as impact resistance tend to be improved heat resistance, in the case of 21,000 or less improvement in flowability, molded article appearance is improved Prone and preferred.
- the graft copolymer (II) constituting the thermoplastic resin composition of the present invention comprises at least an aromatic vinyl monomer (B) and a vinyl cyanide compound in the presence of a diene rubber polymer (A). It is a graft copolymer formed by graft copolymerization of a monomer mixture containing a monomer (C).
- diene rubber-like polymer (A) which can be used for the graft copolymer (II) one having a glass transition temperature of 0 ° C. or less is suitable, and the lower limit thereof is not particularly limited, but for practical use Is about -80.degree.
- diene rubber polymers that can be used include polybutadiene, styrene-butadiene copolymer, acrylonitrile-butadiene copolymer, styrene-butadiene block copolymer and butyl acrylate-butadiene copolymer. Among them, polybutadiene is preferably used.
- the weight-average particle size of the diene rubber-like polymer (A) is not particularly limited, but is preferably 100 to 1,200 nm, and more preferably 200 to 1,200 nm.
- a diene rubber polymer (A) having a weight average particle diameter of less than 100 nm is used, the impact resistance may be lowered.
- a weight average particle diameter of more than 1200 nm is used May have reduced liquidity.
- diene rubber polymer (A) from the viewpoint of achieving both impact resistance and fluidity, those having a low weight average particle diameter of 200 to 400 nm and a weight average particle diameter of 450 to It is preferable to use two diene rubber polymers having a large particle diameter of 1200 nm in combination, more preferably a combination of one having a weight average particle diameter of 280 to 400 nm and one having a weight average particle diameter of 600 to 1200 nm, still more preferably a weight average particle A combination of one with a diameter of 320 to 380 nm and one with a diameter of 700 to 1100 nm.
- the weight ratio of low particle size to high particle size is 90: 10 to 50 from the viewpoint of impact resistance and flowability.
- the ratio is preferably in the range of 50, more preferably in the range of 80:20 to 60:40, still more preferably in the range of 75:25 to 65:35.
- the weight average particle diameter of the diene rubber polymer (A) is the sodium alginate method described in “Rubbaer Age Vol. 88 p. 484 to 490 (1960) by E. Schmidt, PH Biddison” ( The particle diameter of the cumulative weight fraction of 50% is determined from the concentration ratio of sodium alginate and the cumulative weight fraction of sodium alginate concentration.
- the weight fraction of the part derived from the diene rubber polymer (A) contained in the graft copolymer (II) is preferably adjusted to 40 to 65% by weight, and more preferably the diene rubber polymer (A).
- the weight fraction of the part derived from) is 40 to 60% by weight, more preferably 40 to 50% by weight. When the weight fraction is 40% by weight or more, impact resistance is improved, and when it is 65% by weight or less, the flowability is improved, which is preferable.
- aromatic vinyl monomer (B) used for the graft copolymer (II) examples include styrene, ⁇ -methylstyrene, vinyltoluene, o-ethylstyrene, p-methylstyrene, chlorostyrene and bromostyrene In particular, styrene is preferably employed.
- vinyl cyanide monomer (C) used for the graft copolymer (II) examples include, for example, acrylonitrile, methacrylonitrile and ethacrylonitrile, and in particular, acrylonitrile is preferably employed.
- vinyl monomers of the following include N-phenyl maleimide, N-methyl maleimide, methyl methacrylate and the like, which can be selected according to the respective purposes, and one of these may be used. Also, plural kinds may be used in combination. If the intention is to further improve the heat resistance and the flame retardancy, N-phenylmaleimide is preferably used. In addition, methyl methacrylate is preferably used if importance is given to hardness improvement.
- the weight fraction of the portion derived from the aromatic vinyl monomer (B) in the graft copolymer (II) is 26 to 43% by weight based on 100% by weight of the graft copolymer (II). It is preferably 30 to 41% by weight, particularly preferably 35 to 41% by weight.
- the weight fraction is 26% by weight or more, it tends to be difficult to be colored, while when it is 43% by weight or less, the graft polymerization tends to proceed, the graft ratio is improved, and the impact resistance is improved.
- the weight fraction of the vinyl cyanide monomer (C) -derived portion in the graft copolymer (II) is 9 to 17% by weight based on 100% by weight of the graft copolymer (II). Preferably, it is 10 to 16% by weight, more preferably 12 to 16% by weight.
- the weight fraction is 9% by weight or more, graft polymerization tends to proceed, the grafting ratio is improved, the impact resistance tends to be improved, and when the weight fraction is 17% by weight or less, the coloring tends to be difficult. There is.
- the grafting ratio of the graft copolymer (II) is not particularly limited. From the viewpoint of balance between impact resistance and flowability, the grafting ratio is preferably 7 to 30%, more preferably 20 to 28%, and still more preferably 22 to 26%.
- a graft copolymer (II) an acrylonitrile butadiene styrene graft copolymer (ABS resin), a methyl methacrylate acrylonitrile acrylonitrile butadiene graft copolymer (MABS resin) etc. can be mentioned, for example. Among them, acrylonitrile butadiene styrene graft copolymer (ABS resin) is preferable.
- the content of the graft copolymer (II) is polycarbonate resin (I), graft copolymer (II), vinyl copolymer (III), methyl methacrylate-butadiene
- the total content of styrene copolymer (IV) is 100% by weight, it is in the range of 10 to 30% by weight, preferably 12 to 28% by weight, more preferably 15 to 25% by weight .
- this proportion is less than 10% by weight, impact resistance and plating properties decrease, and when it exceeds 30% by weight, fluidity and heat resistance decrease. .
- the vinyl-based copolymer (III) constituting the thermoplastic resin composition of the present invention is a vinyl-based copolymer obtained by copolymerizing at least an aromatic vinyl-based monomer and a vinyl cyanide-based monomer. . Among them, those containing 29 to 33% by weight of a vinyl cyanide-based monomer (E) -derived portion relative to 100% by weight of the vinyl-based copolymer (III) are preferable.
- the aromatic vinyl monomer (D) and the vinyl cyanide monomer (E) 67 to 71% by weight of the aromatic vinyl monomer (D) and the vinyl cyanide monomer (E)
- the content is preferably 29 to 33% by weight, and more preferably 68 to 70% by weight of the aromatic vinyl monomer (D) and 30 to 32% by weight of the vinyl cyanide monomer (E).
- the etching solution used in the etching step prior to the plating step The affinity to the (strong acid aqueous solution) is improved, the diene rubbery polymer (A) is more easily etched, the anchor effect is increased, and the plating characteristics tend to be improved, which is preferable.
- the average content of the vinyl cyanide-based monomer component is 33% by weight or less, the average content of the aromatic vinyl-based monomer (D) of the vinyl-based copolymer (III) is increased, The compatibility between the vinyl copolymer (III) and the polycarbonate resin (I) is improved, and the characteristics such as heat resistance and impact resistance tend to be improved, which is preferable.
- the vinyl copolymer (III) is a copolymer different from the graft copolymer (II) in that the diene rubber polymer (A) is not contained.
- styrene is the same as the aromatic vinyl monomer (B) in the graft copolymer (II) described above.
- styrene is used. These do not necessarily have to be used alone, and can be used in combination of two or more. Among these, styrene is particularly preferably employed.
- vinyl cyanide-based monomer (E) used for the vinyl-based copolymer (III) for example, similar to the cyanide-based vinyl monomer (C) in the above-mentioned graft copolymer (II), for example, Acrylonitrile, methacrylonitrile, ethacrylonitrile and the like can be mentioned, but in particular acrylonitrile is preferably employed. These do not necessarily have to be used alone, and can be used in combination of two or more.
- the vinyl copolymer (III) also has an aromatic vinyl monomer (D) and a vinyl cyanide monomer to such an extent that the effect of the present invention is not lost.
- Other vinyl monomers copolymerizable with (E) may be used.
- Specific examples of other vinyl monomers include N-phenyl maleimide, N-methyl maleimide, methyl methacrylate and the like, which can be selected according to the respective purposes, and one of these may be used. Also, plural kinds may be used in combination. If it is intended to further improve the heat resistance and the flame retardancy, it is preferable to use N-phenylmaleimide. In addition, methyl methacrylate is preferably used if importance is given to hardness improvement.
- the vinyl copolymer (III) preferably has an intrinsic viscosity of 0.35 to 0.50 dl / g as measured in a methyl ethyl ketone solvent at 30 ° C. with an Ubbelohde viscometer, and more preferably 0.37 to 0. It is preferably in the range of 48 dl / g, more preferably 0.40 to 0.45 dl / g.
- the intrinsic viscosity is 0.35 dl / g or more, the impact resistance tends to be improved, while when it is 0.50 dl / g or less, the flowability tends to be improved, which is preferable.
- Examples of the vinyl-based copolymer (III) include acrylonitrile-styrene copolymer (AS resin), methyl methacrylate-styrene copolymer (MS resin) and the like. Among them, acrylonitrile-styrene copolymer (AS resin) is preferable.
- the content of the vinyl copolymer (III) is polycarbonate resin (I), graft copolymer (II), vinyl copolymer (III), methyl methacrylate-
- the total content of butadiene-styrene copolymer (IV) is 100% by weight, it is in the range of 5 to 20% by weight, preferably 7 to 18% by weight, more preferably 5 to 15% by weight is there. If this proportion is less than 5% by weight, the flowability is reduced, and if it exceeds 20% by weight, the impact resistance and the plating properties are reduced.
- the method for producing graft copolymer (II) and vinyl copolymer (III) is not particularly limited, and bulk polymerization, suspension polymerization, bulk suspension polymerization, solution polymerization, emulsion polymerization, precipitation polymerization And combinations thereof.
- the method of feeding the monomers and batch addition may be carried out at the initial stage, and addition may be performed in several times to polymerize the composition distribution of the copolymer or to prevent it. .
- an initiator used for the polymerization of the graft copolymer (II) and the vinyl copolymer (III) a peroxide or an azo compound is suitably used.
- peroxides include, for example, benzoyl peroxide, cumene hydroperoxide, dicumyl peroxide, diisopropylbenzene hydroperoxide, t-butyl hydroperoxide, t-butylcumyl peroxide, t-butyl peroxy Acetate, t-Butylperoxybenzoate, t-Butylperoxyisopropylcarbonate, Di-t-Butyl Peroxide, t-Butyl Peroxide, 1,1-Bis (t-butylperoxy) 3,3,5 And -trimethylcyclohexane, 1,1-bis (t-butylperoxy) cyclohexane, and t-butylperoxy-2-ethylhexanoate.
- cumene hydroperoxide and 1,1-bis (t-butylperoxy) 3,3,5-trimethylcyclohexane are particularly preferably used.
- azo compound examples include, for example, azobisisobutyronitrile, azobis (2,4 dimethyl valeronitrile), 2-phenylazo-2,4-dimethyl-4-methoxyvaleronitrile, 2-cyano- 2-Propylazoformamide, 1,1'-azobiscyclohexane-1-carbonitrile, azobis (4-methoxy-2,4-dimethylvaleronitrile), dimethyl 2,2'-azobisisobutyrate, 1-t And -butylazo-1-cyanocyclohexane, 2-tert-butylazo-2-cyanobutane, 2-tert-butylazo-2-cyano-4-methoxy-4-methylpentane and the like.
- azobisisobutyronitrile is particularly preferably used.
- one or more may be used in combination.
- a chain transfer agent such as mercaptan or terpene may be used for the purpose of adjusting the degree of polymerization of the graft copolymer (II) or the vinyl copolymer (III).
- the chain transfer agent include n-octyl mercaptan, t-dodecyl mercaptan, n-dodecyl mercaptan, n-tetradecyl mercaptan, n-octadecyl mercaptan and terpinolene.
- n-octyl mercaptan, t-dodecyl mercaptan and n-dodecyl mercaptan are preferably used.
- chain transfer agents it is used in combination of 1 type, or 2 or more types.
- the graft copolymer (II) may exhibit weak alkalinity, and for the purpose of preventing alkaline decomposition and thermal decomposition of the polycarbonate resin (I) which is a component of the present invention, an acidic compound Can be added at the time of graft polymer production or at the time of melt-kneading for producing a resin composition.
- the acidic compound which can be used in the present invention is not particularly limited, and specific examples of the usable compound include hydrochloric acid, sulfuric acid, nitric acid, acetic acid, oxalic acid, malonic acid, succinic acid, maleic acid, adipine Acid, sebacic acid, dodecanedioic acid, maleic anhydride, succinic anhydride, itaconic acid, benzoic acid, methyl benzoate, terephthalic acid, isophthalic acid, orthophthalic acid, naphthalene dicarboxylic acid, diphenic acid, phosphoric acid, dihydrogen phosphate Examples thereof include sodium and the like, preferably maleic anhydride, succinic anhydride, phosphoric acid and sodium dihydrogen phosphate, more preferably phosphoric acid and sodium dihydrogen phosphate.
- the acidic compounds exemplified above are not necessarily used alone, and a plurality of them may be used in combination.
- the amount of the acidic compound added is preferably 1.0 parts by weight or less based on 100 parts by weight of the total of (I) to (III) as a standard. In the case of 1.0 parts by weight or less, appearance defects such as surface defects of the injection molded product tend to be suppressed.
- methyl methacrylate-butadiene-styrene copolymer (IV) is a component different from graft copolymer (II), and in the presence of a butadiene rubbery polymer, It is a core-shell type graft copolymer obtained by graft copolymerization of a monomer mixture containing methyl methacrylate monomer and styrene monomer as main components.
- the methyl methacrylate-butadiene-styrene copolymer (IV) used in the present invention is a copolymer having a butadiene rubber-like polymer as a core component and having a methyl methacrylate-styrene copolymer as a shell component.
- the content of methyl methacrylate-butadiene-styrene copolymer (IV) is polycarbonate resin (I), graft copolymer (II), vinyl copolymer (III)
- the total content of methyl methacrylate-butadiene-styrene copolymer (IV) is 100% by weight, it is in the range of 1 to 10% by weight, preferably 2 to 9% by weight, more preferably 3 ⁇ 8 wt%.
- this ratio is less than 1% by weight, the amount of methyl methacrylate-butadiene-styrene copolymer introduced into the polycarbonate resin (I) matrix phase decreases, and the polycarbonate resin (I) matrix phase is reduced during the etching step.
- the anchor effect is insufficient and sufficient plating characteristics can not be obtained. If it exceeds 10% by weight, the heat resistance and the fluidity will be reduced.
- the content ratio of methyl methacrylate-butadiene-styrene copolymer (IV) to 100 wt% of polycarbonate resin (I) is 3 to 20 wt%, preferably 4 to 18 % By weight, more preferably 5 to 15% by weight. If this content ratio is less than 3% by weight, the amount of methyl methacrylate-butadiene-styrene copolymer (IV) introduced into the polycarbonate resin (I) matrix phase decreases, and the polycarbonate resin (I) matrix phase is The anchor effect is insufficient and sufficient plating characteristics can not be obtained. On the other hand, when it exceeds 20% by weight, heat resistance and fluidity tend to be lowered.
- thermoplastic resin composition of the present invention is substantially composed of polycarbonate resin (I), graft copolymer (II), vinyl copolymer (III) and methyl methacrylate-butadiene-styrene copolymer (IV)
- polycarbonate resin (I), graft copolymer (II), vinyl copolymer (III) and methyl methacrylate-butadiene-styrene copolymer (IV) It will be The meaning of "consisting essentially of” as used herein means that other components may be included as long as the effects of the present invention are not impaired, and as described below, the thermoplastic resin composition of the present invention is Various additives may be included depending on the intended function. Such additives usually have a total content of polycarbonate resin (I), graft copolymer (II), vinyl copolymer (III) and methyl methacrylate-butadiene-styrene copolymer (IV). When it is 100 parts by weight, it is 10
- thermoplastic resin composition of the present invention the content of polycarbonate resin (I), graft copolymer (II), vinyl copolymer (III) and methyl methacrylate-butadiene-styrene copolymer (IV) It is preferable to further contain 0.01 to 0.2 parts by weight of any one or more compounds (V) selected from silicone compounds and fluorine compounds, when the total of the components is 100 parts by weight. .
- the content ratio of the compound (V) is more preferably 0.02 to 0.18 parts by weight, still more preferably 0.03 to 0.15 parts by weight.
- the compound (V) When the compound (V) is contained in an amount of 0.01 parts by weight or more, the stress remaining at the time of injection molding is alleviated, the etching failure in the etching step and the plating failure in the plating step are eliminated. By dispersing the stress applied to the interface between the plating film and the plating film, the durability such as plating peeling or swelling is further improved. In addition, when compound (V) is compounded in an amount of 0.2 parts by weight or less, it is possible to further suppress appearance defects due to suppression of heat resistance deterioration and bleed out of compound (V) onto the surface of a molded article.
- organosiloxanes such as polydimethylsiloxane, polymethylethylsiloxane, polydiethylsiloxane, polymethylphenylsiloxane and the like and selected from them
- silicone rubbers having any one or more kinds as a main component, silanes such as tetraethylsilane and trimethylhexylsilane, and halosilanes such as triethylchlorosilane, diethyldichlorosilane, phenyltrichlorosilane and diphenyldichlorosilane.
- organosiloxanes such as polydimethylsiloxane, polymethylethylsiloxane, polydiethylsiloxane, polymethylphenylsiloxane and the like and any one or more selected from them as a main component
- a silicone rubber is preferred, a compound based on polydimethylsiloxane is more preferred, and a silicone rubber based on polydimethylsiloxane is most preferred.
- the silicone rubber as referred to herein is a product obtained by crosslinking the organosiloxane described above, and refers to one exhibiting rubber properties in the whole or part of the temperature range from normal temperature to 200 ° C.
- a fluorine-type compound used suitably for the thermoplastic resin composition of this invention a polytetrafluoroethylene, a polychloro trifluoro ethylene, a polyvinyl fluoride, a polyvinylidene fluoride, tetrafluoroethylene * hexafluoropropylene is mentioned, for example.
- Copolymers, chlorofluoroethylene / vinylidene fluoride copolymers, etc. may be mentioned, but a compound mainly composed of polytetrafluoroethylene is most preferable.
- impact modifiers can be used in the thermoplastic resin composition of the present invention as long as the characteristics of the present invention are not impaired.
- Impact modifiers which can be used include natural rubber, polyethylene such as low density polyethylene and high density polyethylene, polypropylene, ethylene / propylene copolymer, ethylene / methyl acrylate copolymer, ethylene / ethyl acrylate copolymer , Ethylene / vinyl acetate copolymer, ethylene / glycidyl methacrylate copolymer, ethylene / butyl acrylate copolymer, ethylene / ethyl acrylate / carbon monoxide copolymer, ethylene / glycidyl methacrylate copolymer, ethylene / methyl acrylate / Glycidyl methacrylate copolymer, ethylene / butyl acrylate / glycidyl methacrylate copolymer, ethylene / o
- thermoplastic resin composition of the present invention it is also possible to add an inorganic filler to the thermoplastic resin composition of the present invention as long as the characteristics of the present invention are not impaired.
- the shape of the inorganic filler may be any shape such as fibrous, powdery, granular, and plate-like.
- PAN-based or pitch-based carbon fiber stainless fiber, metal fiber such as aluminum fiber or brass fiber, organic fiber such as aromatic polyamide fiber, gypsum fiber, ceramic fiber, asbestos fiber, zirconia fiber, alumina fiber Fibers, whisker-like fillers such as silica fiber, titanium oxide fiber, silicon carbide fiber, glass fiber, rock wool, potassium titanate whisker, barium titanate whisker, aluminum borate whisker, silicon nitride whisker, silica, calcium carbonate , Glass beads, Glass microballoon, Clay, Molybdenum disulfide, Wallastenite, Montmorillonite, Titanium oxide, Zinc oxide, Barium sulfate, Calcium polyphosphate, Powdered or granular filler such as graphite, Glass flake, Mica, Talc Alumina flakes, kaolin, carbon flakes, metal flakes, scaly carbon, and plate-like fillers such as graphite.
- whisker-like fillers such as silica fiber, titanium oxide fiber, silicon
- the type of glass fiber is not particularly limited as long as it is generally used for reinforcing a resin, and can be selected and used from, for example, chopped strands of long fiber type and short fiber type, and milled fibers.
- the said inorganic filler can also be used, processing the surface with a well-known coupling agent (For example, a silane coupling agent, a titanate coupling agent etc.), and another surface treatment agent.
- the glass fibers may be coated or converged with a thermoplastic resin such as ethylene / vinyl acetate copolymer, or a thermosetting resin such as epoxy resin.
- the inorganic filler may be coated or converged with a thermoplastic resin such as ethylene / vinyl acetate copolymer, or a thermosetting resin such as epoxy resin, and treated with a coupling agent such as aminosilane or epoxysilane. It may be done.
- a thermoplastic resin such as ethylene / vinyl acetate copolymer
- a thermosetting resin such as epoxy resin
- known matting improvers can be used in the thermoplastic resin composition of the present invention as long as the characteristics of the present invention are not impaired.
- a matting modifier which can be used acrylonitrile-butadiene copolymer rubber which is unsaturated nitrile-conjugated diene type copolymer rubber, acrylonitrile-isoprene copolymer rubber, acrylonitrile-butadiene-isoprene copolymer rubber And acrylonitrile-butadiene-acrylic acid copolymer rubbers, and rubbers obtained by hydrogenating conjugated diene units in these rubbers.
- rubbers which may be used in combination with unsaturated nitrile-conjugated diene copolymer rubbers are rubbers which can be crosslinked by a crosslinking agent commonly used in the rubber industry such as sulfur vulcanization type and organic peroxide vulcanization type. It is. Specific examples thereof include conjugated diene-based polymer rubbers such as polybutadiene rubber, styrene-butadiene copolymer rubber (random, block), natural rubber, polyisoprene rubber, polychloroprene rubber and the like, hydrogenated products thereof, EPDM (ethylene, propylene, etc. Diene rubber etc. are illustrated.
- conjugated diene-based polymer rubbers such as polybutadiene rubber, styrene-butadiene copolymer rubber (random, block), natural rubber, polyisoprene rubber, polychloroprene rubber and the like, hydrogenated products thereof, EPDM (ethylene, propylene, etc. Diene rubber
- thermoplastic resin composition of the present invention a hindered phenol-based antioxidant, a sulfur-containing compound-based antioxidant, and a phosphorus-containing organic compound-based antioxidant as long as the characteristics of the present invention are not impaired.
- Thermal antioxidants such as phenols and acrylates, UV absorbers such as benzotriazole, benzophenones and succinates, acrylic acids and their esters, and polymers or copolymers of methacrylic acid and their esters Molding processing aids such as modified polytetrafluoroethylene, decabromobiphenyl ether, tetrabromobisphenol A, chlorinated polyethylene, brominated epoxy oligomers, brominated polycarbonate, antimony trioxide, flame retardants and flame retardants such as condensed phosphates
- Auxiliary agents, antibacterial agents represented by silver antibacterial agents, antifungal agents Carbon black, titanium oxide, release agents, lubricants, and the like can also be added pigments and dyes.
- thermoplastic resin composition of the present invention Next, a method for obtaining the thermoplastic resin composition of the present invention will be described by way of specific examples, but the gist of the present invention is of course not construed as being limited to these examples.
- the thermoplastic resin composition of the present invention can be obtained by melt-mixing the respective resin components that constitute the composition.
- the melting and mixing method is not particularly limited, but a heating device and a method of melting and mixing using a single-screw or twin-screw in a cylinder having a vent may be employed.
- the heating temperature in melt mixing is usually selected from the range of 230 to 320 ° C., but it is also possible to freely set the temperature gradient and the like at the time of melt mixing, as long as the object of the present invention is not impaired.
- a biaxial screw it may be mutually the same direction rotation or different direction rotation. Further, it may be either a meshing type or non meshing type screw.
- the molding method of the thermoplastic resin composition of the present invention is not particularly limited, but it is suitably molded by injection molding.
- the injection molding can be carried out preferably at a temperature range of 240 to 300 ° C., which usually forms a thermoplastic resin set. Further, the mold temperature at the time of injection molding is preferably a temperature range used for normal molding of 30 to 80.degree.
- thermoplastic resin composition of the present invention is suitably used in molded articles to be plated because it is excellent in the balance of mechanical properties, heat resistance, fluidity, plating properties, durability, appearance of plated molded articles, etc.
- the resin composition of the present invention can be required for automobile interior power window panels, center consoles, center clusters, console shutters, lever controllers, console boxes, inner door handles, etc. for automobile interiors where severe plating quality may be required. It can also be applied to materials such as rear spoilers, grills, garnishes, door mirrors, roofs, fenders, bumpers, outer door handles etc.
- electrical and electronic applications OA equipment applications, housing and building materials applications.
- Impact resistance Multi-purpose test specimen type A1 specified in JIS K 7139 is molded using an injection molding machine in which a cylinder temperature is set to 250 ° C. and a mold temperature is set to 60 ° C.
- the Charpy impact strength was measured in accordance with ISO 179/1 eA using a type B2 test piece obtained by cutting
- melt flow rate of the composition pellet was measured at a temperature of 240 ° C. and a load of 98 N.
- Heat resistance Thermal deformation temperature Measured in accordance with ISO 75-2 (measured at 1.8 MPa conditions).
- the test piece was obtained by molding a multipurpose test piece type A1 defined in JIS K 7139 using an injection molding machine in which a cylinder temperature is set to 250 ° C. and a mold temperature is set to 60 ° C.
- test piece of 127 mm ⁇ 76 mm ⁇ 3 mmt was obtained by molding using an injection molding machine in which the cylinder temperature was set to 250 ° C. and the mold temperature was set to 60 ° C. After heat treatment at 80 ° C. for 12 hours, the test piece was immersed in a mixed solution of “Top Placon BOW” 10 ml / L and 98% sulfuric acid 30 ml / L manufactured by Okuno Pharmaceutical Co., Ltd., and degreased and washed. Then, it was immersed in a 68 ° C.
- the plating film formation rate is 100% to the whole test piece area 5
- the plating film formation rate is 80% or more and less than 100% with respect to the entire specimen area ⁇ ⁇ 4
- the plating film formation rate is 60% or more and less than 80% with respect to the entire specimen area ⁇ 3
- the plating film formation rate is 40% or more and less than 60% with respect to the entire test piece area ⁇ 2
- the plating film formation rate is 20% or more and less than 40% with respect to the entire test piece area ... 1.
- the appearance of the plated test piece was evaluated based on the following criteria. There is no abnormality (crack or swelling) in the test piece up to 200 cycles. Abnormality (crack or blister) occurs in the test piece in 150 cycles or more and less than 200 cycles ... Abnormality (crack or blister) occurs in the test piece in 100 cycles or more and less than 150 cycles ... Abnormality (crack or swelling) occurs in the test piece in less than 100 cycles ⁇ ⁇ ⁇ ⁇ .
- the mixture is added to a 0.3% dilute aqueous solution of sulfuric acid at a temperature of 90 ° C., coagulated, neutralized by an aqueous solution of sodium hydroxide, and subjected to washing, dehydration, and drying steps to obtain graft copolymer (II-1).
- graft copolymer (II-1) Prepared.
- the grafting rate was 25%.
- a vinyl-based copolymer (III-1) was prepared by continuous bulk polymerization of a monomer mixture consisting of 69% by weight of styrene and 31% by weight of acrylonitrile.
- the intrinsic viscosity of the resulting vinyl copolymer (III-1) was 0.53 dl / g, and the content of the acrylonitrile-derived portion in the copolymer was 31% by weight.
- a slurry obtained by suspension polymerization of a monomer mixture consisting of 76% by weight of styrene and 24% by weight of acrylonitrile was subjected to washing, dewatering and drying steps to prepare a vinyl-based copolymer (III-2).
- the intrinsic viscosity of the obtained vinyl copolymer (III-2) was 0.42 dl / g, and the content of the acrylonitrile-derived portion was 24% by weight.
- a slurry obtained by suspension polymerization of a monomer mixture consisting of 63.5% by weight of styrene and 36.5% by weight of acrylonitrile is subjected to washing, dehydration and drying steps to obtain a vinyl copolymer (III-3) was prepared.
- the intrinsic viscosity of the resulting vinyl copolymer (III-3) was 0.49 dl / g, and the content of the acrylonitrile-derived portion was 36.5% by weight.
- Silicone compound (V) silicone oil, trade name "SH200”, manufactured by Toray Dow Corning Co., Ltd.
- Silicone compound (V-2) silicone rubber, trade name "EP-2720", manufactured by Toray Dow Corning Co., Ltd.
- Acidic compound 0.5 mol / L phosphoric acid.
- Table 1 shows polycarbonate resin (I), graft copolymer (II), vinyl copolymer (III), methyl methacrylate-butadiene-styrene copolymer (IV), compound (V) and other additives.
- the mixture was compounded at the ratio shown in Table 2 and melt-kneaded using a twin screw extruder (temperature range: 240 to 260 ° C.) of the same direction rotation with a screw diameter of 30 mm to obtain pellets.
- Test pieces were produced from the obtained pellets using an injection molding machine (molding temperature 250 ° C., mold temperature 60 ° C.), and evaluation was performed by the above-mentioned method.
- the proportion (wt.%) Of polycarbonate resin (I), graft copolymer (II), vinyl copolymer (III) and methyl methacrylate-butadiene-styrene copolymer (IV) It is a ratio when the sum total of content of a component is 100 weight%. Further, the content of the compound (V) and other additives is polycarbonate resin (I), graft copolymer (II), vinyl copolymer (III) methyl methacrylate-butadiene-styrene copolymer (IV) Content (parts by weight) based on 100 parts by weight of the total weight of
- thermoplastic resin composition of Examples 1 to 12 that is, the present invention is excellent in the balance of mechanical properties, heat resistance, fluidity, plating properties, durability, appearance of a plated molded product, and the like.
- Examples 1 and 2 and Comparative Examples 1 and 2 when the methyl methacrylate-butadiene-styrene copolymer is not blended, the impact resistance is lowered and the peeling strength which is the plating characteristic is lowered. It can be seen that the appearance after plating is deteriorated and the durability is also inferior.
- thermoplastic resin composition of the present invention is suitably used in molded articles to be plated because it is excellent in the balance of mechanical properties, heat resistance, fluidity, plating properties, durability, appearance of plated molded articles, etc.
- the resin composition of the present invention can be required for automobile interior power window panels, center consoles, center clusters, console shutters, lever controllers, console boxes, inner door handles, etc. for automobile interiors where severe plating quality may be required. It can also be applied to materials such as rear spoilers, grills, garnishes, door mirrors, roofs, fenders, bumpers, outer door handles etc.
- electrical and electronic applications OA equipment applications, housing and building materials applications.
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Polymers & Plastics (AREA)
- Medicinal Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Engineering & Computer Science (AREA)
- Metallurgy (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- General Chemical & Material Sciences (AREA)
- Electrochemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Graft Or Block Polymers (AREA)
Abstract
The present invention addresses the problem of providing: a thermoplastic resin composition having an excellent balance among mechanical properties, heat resistance, flowability, platability, durability, plated-molded-article appearance, etc.; and a molded article. The thermoplastic resin composition for plated molded articles is characterized by consisting substantially of a polycarbonate resin (I), a graft copolymer (II) obtained by graft-copolymerizing a monomer mixture comprising an aromatic vinyl compound monomer and a vinyl cyanide monomer in the presence of a diene-based rubbery polymer, a vinyl-based copolymer (III) obtained by copolymerizing at least an aromatic vinyl compound monomer and a vinyl cyanide monomer, and a methyl methacrylate/butadiene/styrene copolymer (IV), the contents of the polycarbonate resin (I), graft copolymer (II), vinyl-based copolymer (III), and methyl methacrylate/butadiene/styrene copolymer (IV) being 50-70 wt%, 10-30 wt%, 5-20 wt%, and 1-10 wt%, respectively, per 100 wt% the sum of the contents of the polycarbonate resin (I), graft copolymer (II), vinyl-based copolymer (III), and methyl methacrylate/butadiene/styrene copolymer (IV), and the content of the methyl methacrylate/butadiene/styrene copolymer (IV) being 3-20 wt% per 100 wt% the polycarbonate resin (I).
Description
本発明は、めっき成形品用の熱可塑性樹脂組成物およびそれを用いた成形品に関する。
The present invention relates to a thermoplastic resin composition for a plated molded article and a molded article using the same.
ABS樹脂に代表されるゴム強化スチレン樹脂は、優れた成形加工性、機械的特性を有し、また、塗装性やめっき性等の二次加工性にも優れることから、自動車分野、家電分野、OA機器分野など広範な分野において、各種構成部材の成形材料として使用されている。
Rubber-reinforced styrene resin represented by ABS resin has excellent moldability and mechanical properties, and is excellent in secondary processability such as paintability and plating property, so that it can be used in the automotive field, home appliance field, It is used as a molding material for various components in a wide range of fields such as the OA equipment field.
また、ポリカーボネート樹脂は、耐熱性、耐衝撃性に優れていることから、自動車分野、家電分野、OA機器分野、建材分野をはじめとする多岐の分野にわたって幅広く使用されている。近年、ポリカーボネート樹脂の成形加工性や二次加工性等を改善する目的で、また、ABS樹脂の耐熱性や耐衝撃性を改善する目的で、ポリカーボネート樹脂とABS樹脂を溶融混合しアロイ化する検討が進められており、特に自動車分野において、耐熱性、耐衝撃性、および塗装性やめっき性等の二次加工性が必要とされる部品への展開が進んでいる。特に機械特性や耐熱性等の特性を維持したまま、めっき特性を向上させる種々の検討が進められている。
In addition, polycarbonate resins are widely used in various fields including automobile field, home appliance field, OA equipment field and building materials field because they are excellent in heat resistance and impact resistance. In recent years, for the purpose of improving the molding processability and secondary processability of polycarbonate resin, and for the purpose of improving the heat resistance and impact resistance of ABS resin, a study to melt-mix and alloy polycarbonate resin and ABS resin In particular, in the automotive field, the development of parts that require heat resistance, impact resistance, and secondary processability such as paintability and plating ability is in progress. In particular, various studies have been advanced to improve the plating characteristics while maintaining the characteristics such as mechanical characteristics and heat resistance.
ポリカーボネート樹脂/ABS樹脂アロイの機械特性や耐熱性等の特性を維持したまま、めっき特性を向上させる従来の技術として、例えば、特許文献1には、ポリカーボネート樹脂、ゴム平均粒子径が規定されたグラフト共重合体およびビニル系共重合体からなるダイレクトめっき用樹脂組成物が開示されている。特許文献1に記載の樹脂組成物は、耐衝撃性、耐熱性、流動性のバランスを取りながら、めっき特性が向上しているものの、その効果は十分ではなく、まためっき後の耐久性も不十分である課題があった。また、特許文献2には、ポリカーボネート樹脂、ゴム質重合体含有共重合体、ビニル系共重合体からなり、共重合体中のアセトン可溶分のシアン化ビニル単量体含有率が規定されたメッキ用樹脂組成物が開示されている。特許文献2に記載の樹脂組成物は、めっき特性が向上しているものの、その効果は十分ではなく、また外観、耐熱性、耐衝撃性のバランスも不十分である課題があった。また、特許文献3には、ポリカーボネート樹脂、ビニル系共重合体、グラフト率を規定したグラフト共重合体を含む無電解メッキ用樹脂組成物が開示されている。特許文献3に記載の樹脂組成物は、めっき密着性に優れると共に、耐衝撃性や剛性のバランスに優れるものの、その効果は十分ではなく、まためっき後の耐久性も不十分である課題があった。また、特許文献4には、グラフトゴムを主成分とする、メッキ性、耐衝撃性、大型成形性に優れた熱可塑性樹脂組成物が開示されており、好ましい態様として、さらに有機ケイ素化合物を規定量配合した熱可塑性樹脂組成物が開示されている。特許文献4に記載の樹脂組成物は、耐衝撃性、流動性、メッキ特性に優れるものの、その効果は十分ではなく、まためっき後の耐久性も不十分である課題があった。
As a conventional technique for improving plating characteristics while maintaining properties such as mechanical properties and heat resistance of polycarbonate resin / ABS resin alloy, for example, Patent Document 1 discloses a polycarbonate resin and a graft having a rubber average particle diameter specified. A resin composition for direct plating comprising a copolymer and a vinyl copolymer is disclosed. The resin composition described in Patent Document 1 has improved plating properties while maintaining a balance between impact resistance, heat resistance and fluidity, but the effect is not sufficient and the durability after plating is not good. There was an issue that was sufficient. Further, Patent Document 2 is composed of a polycarbonate resin, a rubbery polymer-containing copolymer, and a vinyl copolymer, and the content of vinyl cyanide monomer in an acetone-soluble portion in the copolymer is defined. A resin composition for plating is disclosed. Although the resin composition described in Patent Document 2 has improved plating properties, its effect is not sufficient, and the balance between the appearance, heat resistance and impact resistance is also insufficient. Further, Patent Document 3 discloses a resin composition for electroless plating containing a polycarbonate resin, a vinyl copolymer, and a graft copolymer having a defined graft ratio. Although the resin composition described in Patent Document 3 is excellent in plating adhesion and is excellent in the balance of impact resistance and rigidity, the effect is not sufficient and the durability after plating is also insufficient. The Further, Patent Document 4 discloses a thermoplastic resin composition which is mainly composed of a graft rubber and is excellent in plating property, impact resistance, and large-size moldability, and further defines an organosilicon compound as a preferred embodiment. Thermoplastic resin compositions are disclosed in amounts. Although the resin composition described in Patent Document 4 is excellent in impact resistance, fluidity, and plating properties, the effect is not sufficient, and the durability after plating is also insufficient.
本発明は、機械特性、耐熱性、流動性、めっき特性、耐久性、めっき成形品外観等のバランスに優れる、熱可塑性樹脂組成物およびその成形品を提供することを課題とする。
An object of the present invention is to provide a thermoplastic resin composition and a molded article thereof which are excellent in the balance of mechanical properties, heat resistance, fluidity, plating properties, durability, and appearance of a plated molded article.
本発明者らは、上記課題を解決するために鋭意検討を重ねた結果、ポリカーボネート樹脂、グラフト共重合体、ビニル系共重合体、メタクリル酸メチル-ブタジエン-スチレン
共重合体を特定組成で配合することにより、機械特性、耐熱性、流動性、めっき特性、耐久性、めっき成形品外観等のバランスに優れることを見いだし、本発明に到達した。 As a result of intensive studies to solve the above problems, the present inventors blend polycarbonate resin, graft copolymer, vinyl copolymer and methyl methacrylate-butadiene-styrene copolymer with a specific composition. Thus, the inventors have found that the mechanical properties, heat resistance, fluidity, plating properties, durability, and the appearance of the plated molded product are excellent in balance, and the present invention has been achieved.
共重合体を特定組成で配合することにより、機械特性、耐熱性、流動性、めっき特性、耐久性、めっき成形品外観等のバランスに優れることを見いだし、本発明に到達した。 As a result of intensive studies to solve the above problems, the present inventors blend polycarbonate resin, graft copolymer, vinyl copolymer and methyl methacrylate-butadiene-styrene copolymer with a specific composition. Thus, the inventors have found that the mechanical properties, heat resistance, fluidity, plating properties, durability, and the appearance of the plated molded product are excellent in balance, and the present invention has been achieved.
すなわち、本発明は以下の(1)~(6)を要旨とする。
(1)ポリカーボネート樹脂(I)、ジエン系ゴム質重合体の存在下に、少なくとも芳香族ビニル系単量体およびシアン化ビニル系単量体を含有する単量体混合物をグラフト共重合してなるグラフト共重合体(II)、少なくとも芳香族ビニル系単量体およびシアン化ビニル系単量体を共重合してなるビニル系共重合体(III)およびメタクリル酸メチル-ブタジエン-スチレン共重合体(IV)から実質的になり、ポリカーボネート樹脂(I)、グラフト共重合体(II)、ビニル系共重合体(III)、メタクリル酸メチル-ブタジエン-スチレン共重合体(IV)の含有量の合計を100重量%としたときに、ポリカーボネート樹脂(I)が50~70重量%、グラフト共重合体(II)が10~30重量%、ビニル系共重合体(III)が5~20重量%、メタクリル酸メチル-ブタジエン-スチレン共重合体(IV)が1~10重量%であり、かつポリカーボネート樹脂(I)100重量%に対するメタクリル酸メチル-ブタジエン-スチレン共重合体(IV)の含有割合が3~20重量%であることを特徴とするめっき成形品用熱可塑性樹脂組成物。
(2)さらに、ポリカーボネート樹脂(I)、グラフト共重合体(II)、ビニル系共重合体(III)、メタクリル酸メチル-ブタジエン-スチレン共重合体(IV)の含有量の合計を100重量部としたときに、シリコーン系化合物およびフッ素系化合物から選択されるいずれか1種以上の化合物(V)を、0.01~0.2重量部配合してなることを特徴とする上記(1)記載のめっき成形品用熱可塑性樹脂組成物。
(3)化合物(V)が、ポリジメチルシロキサンを主成分とする化合物であることを特徴とする上記(1)または(2)に記載のめっき成形品用熱可塑性樹脂組成物。
(4)ビニル系共重合体(III)を100重量%としたときに、該ビニル系共重合体(III)に共重合されているシアン化ビニル系単量体成分の含有割合が、29~33重量%であることを特徴とする上記(1)~(3)のいずれか1項記載のめっき成形品用熱可塑性樹脂組成物。
(5)上記(1)~(4)のいずれか1項記載のめっき成形品用熱可塑性樹脂組成物を成形してなる成形品。
(6)上記(5)記載の成形品にめっき処理を施してなることを特徴とするめっき成形品。 That is, the present invention provides the following (1) to (6) as the gist.
(1) It is obtained by graft copolymerization of a monomer mixture containing at least an aromatic vinyl monomer and a vinyl cyanide monomer in the presence of polycarbonate resin (I) and a diene rubber polymer. Graft copolymer (II), vinyl copolymer (III) obtained by copolymerizing at least an aromatic vinyl monomer and vinyl cyanide monomer, and methyl methacrylate-butadiene-styrene copolymer ( IV) substantially consisting of polycarbonate resin (I), graft copolymer (II), vinyl copolymer (III) and methyl methacrylate-butadiene-styrene copolymer (IV) in total 50 to 70% by weight of polycarbonate resin (I), 10 to 30% by weight of graft copolymer (II), and 100% by weight of vinyl copolymer (I) I) 5 to 20% by weight, methyl methacrylate-butadiene-styrene copolymer (IV) 1 to 10% by weight, and methyl methacrylate-butadiene-styrene co-weight relative to 100% by weight of polycarbonate resin (I) Thermoplastic resin composition for plated molded articles, characterized in that the content ratio of the combined (IV) is 3 to 20% by weight.
(2) Furthermore, the total content of polycarbonate resin (I), graft copolymer (II), vinyl copolymer (III) and methyl methacrylate-butadiene-styrene copolymer (IV) is 100 parts by weight in total And 0.01 to 0.2 parts by weight of any one or more compounds (V) selected from silicone compounds and fluorine compounds. Thermoplastic resin composition for plated molded articles as described above.
(3) The thermoplastic resin composition for plated molded products according to the above (1) or (2), wherein the compound (V) is a compound containing polydimethylsiloxane as a main component.
(4) When the content of the vinyl copolymer (III) is 100% by weight, the content ratio of the vinyl cyanide monomer component copolymerized with the vinyl copolymer (III) is from 29 to The thermoplastic resin composition for a plated molded product according to any one of the above (1) to (3), which is 33% by weight.
(5) A molded product obtained by molding the thermoplastic resin composition for a plated molded product according to any one of the above (1) to (4).
(6) A plated molded product obtained by subjecting the molded product according to (5) to a plating treatment.
(1)ポリカーボネート樹脂(I)、ジエン系ゴム質重合体の存在下に、少なくとも芳香族ビニル系単量体およびシアン化ビニル系単量体を含有する単量体混合物をグラフト共重合してなるグラフト共重合体(II)、少なくとも芳香族ビニル系単量体およびシアン化ビニル系単量体を共重合してなるビニル系共重合体(III)およびメタクリル酸メチル-ブタジエン-スチレン共重合体(IV)から実質的になり、ポリカーボネート樹脂(I)、グラフト共重合体(II)、ビニル系共重合体(III)、メタクリル酸メチル-ブタジエン-スチレン共重合体(IV)の含有量の合計を100重量%としたときに、ポリカーボネート樹脂(I)が50~70重量%、グラフト共重合体(II)が10~30重量%、ビニル系共重合体(III)が5~20重量%、メタクリル酸メチル-ブタジエン-スチレン共重合体(IV)が1~10重量%であり、かつポリカーボネート樹脂(I)100重量%に対するメタクリル酸メチル-ブタジエン-スチレン共重合体(IV)の含有割合が3~20重量%であることを特徴とするめっき成形品用熱可塑性樹脂組成物。
(2)さらに、ポリカーボネート樹脂(I)、グラフト共重合体(II)、ビニル系共重合体(III)、メタクリル酸メチル-ブタジエン-スチレン共重合体(IV)の含有量の合計を100重量部としたときに、シリコーン系化合物およびフッ素系化合物から選択されるいずれか1種以上の化合物(V)を、0.01~0.2重量部配合してなることを特徴とする上記(1)記載のめっき成形品用熱可塑性樹脂組成物。
(3)化合物(V)が、ポリジメチルシロキサンを主成分とする化合物であることを特徴とする上記(1)または(2)に記載のめっき成形品用熱可塑性樹脂組成物。
(4)ビニル系共重合体(III)を100重量%としたときに、該ビニル系共重合体(III)に共重合されているシアン化ビニル系単量体成分の含有割合が、29~33重量%であることを特徴とする上記(1)~(3)のいずれか1項記載のめっき成形品用熱可塑性樹脂組成物。
(5)上記(1)~(4)のいずれか1項記載のめっき成形品用熱可塑性樹脂組成物を成形してなる成形品。
(6)上記(5)記載の成形品にめっき処理を施してなることを特徴とするめっき成形品。 That is, the present invention provides the following (1) to (6) as the gist.
(1) It is obtained by graft copolymerization of a monomer mixture containing at least an aromatic vinyl monomer and a vinyl cyanide monomer in the presence of polycarbonate resin (I) and a diene rubber polymer. Graft copolymer (II), vinyl copolymer (III) obtained by copolymerizing at least an aromatic vinyl monomer and vinyl cyanide monomer, and methyl methacrylate-butadiene-styrene copolymer ( IV) substantially consisting of polycarbonate resin (I), graft copolymer (II), vinyl copolymer (III) and methyl methacrylate-butadiene-styrene copolymer (IV) in total 50 to 70% by weight of polycarbonate resin (I), 10 to 30% by weight of graft copolymer (II), and 100% by weight of vinyl copolymer (I) I) 5 to 20% by weight, methyl methacrylate-butadiene-styrene copolymer (IV) 1 to 10% by weight, and methyl methacrylate-butadiene-styrene co-weight relative to 100% by weight of polycarbonate resin (I) Thermoplastic resin composition for plated molded articles, characterized in that the content ratio of the combined (IV) is 3 to 20% by weight.
(2) Furthermore, the total content of polycarbonate resin (I), graft copolymer (II), vinyl copolymer (III) and methyl methacrylate-butadiene-styrene copolymer (IV) is 100 parts by weight in total And 0.01 to 0.2 parts by weight of any one or more compounds (V) selected from silicone compounds and fluorine compounds. Thermoplastic resin composition for plated molded articles as described above.
(3) The thermoplastic resin composition for plated molded products according to the above (1) or (2), wherein the compound (V) is a compound containing polydimethylsiloxane as a main component.
(4) When the content of the vinyl copolymer (III) is 100% by weight, the content ratio of the vinyl cyanide monomer component copolymerized with the vinyl copolymer (III) is from 29 to The thermoplastic resin composition for a plated molded product according to any one of the above (1) to (3), which is 33% by weight.
(5) A molded product obtained by molding the thermoplastic resin composition for a plated molded product according to any one of the above (1) to (4).
(6) A plated molded product obtained by subjecting the molded product according to (5) to a plating treatment.
本発明によれば、機械特性、耐熱性、流動性、めっき特性、耐久性、めっき成形品外観等のバランスに優れることから、従来成形できなかった大型成形品や複雑形状成形品、薄肉成形品を射出成形によって得ることができるため、製品の大型化や形状の複雑化に適応でき、また、耐久性の高いめっきによって長期的に意匠性に優れた成形品を得ることができる。
According to the present invention, since it is excellent in the balance of mechanical properties, heat resistance, flowability, plating properties, durability, appearance of plated molded articles, etc., large molded articles, complex shaped molded articles, thin molded articles which could not be molded conventionally Can be obtained by injection molding, so that it can be adapted to the enlargement of the product and the complication of the shape, and a molded article having excellent designability can be obtained in the long term by highly durable plating.
以下、本発明の熱可塑性樹脂組成物とその成形品について、具体的に説明する。
Hereinafter, the thermoplastic resin composition of the present invention and a molded article thereof will be specifically described.
ポリカーボネート樹脂(I)は、2,2-ビス(4-ヒドロキシフェニル)プロパン、2,2-ビス(3,5-ジメチル-4-ヒドロキシフェニル)プロパンで代表的に例示される芳香族ジヒドロキシ化合物と、ホスゲンで代表的に例示されるカーボネート前駆体との反応によって得られる。
Polycarbonate resin (I) is an aromatic dihydroxy compound typically exemplified by 2,2-bis (4-hydroxyphenyl) propane and 2,2-bis (3,5-dimethyl-4-hydroxyphenyl) propane And phosgene are obtained by reaction with a carbonate precursor typically exemplified.
芳香族ジヒドロキシ化合物としては、2,2-ビス(4-ヒドロキシフェニル)プロパン(以下、「ビスフェノールA」と記載することがある。)、1,1-ビス(4-ヒドロキシフェニル)エタン、2,2-ビス(4-ヒドロキシフェニル)ブタン、2,2-ビス(4-ヒドロキシフェニル)オクタン、2,2-ビス(4-ヒドロキシ-3-メチルフェニル)プロパン、1,1-ビス(3-tert-ブチル-4-ヒドロキシフェニル)プロパン、2,2-ビス(4-ヒドロキシ-3,5-ジメチルフェニル)プロパン、2,2-ビス(3-フェニル-4-ヒドロキシフェニル)プロパン、2,2-ビス(3-シクロヘキシル-4-ヒドロキシフェニル)プロパン、1,1-ビス(4-ヒドロキシフェニル)-1-フェニルエタン、ビス(4-ヒドロキシフェニル)ジフェニルメタン等で例示されるビス(ヒドロキシアリール)アルカン類;1,1-ビス(4-ヒドロキシフェニル)シクロペンタン、1,1-ビス(4-ヒドロキシフェニル)シクロヘキサン、1,1-ビス(4-ヒドロキシフェニル)-3,3,5-トリメチルシクロヘキサン等で例示されるビス(ヒドロキシアリール)シクロアルカン類;9,9-ビス(4-ヒドロキシフェニル)フルオレン、9,9-ビス(4-ヒドロキシ-3-メチルフェニル)フルオレン等で例示されるカルド構造含有ビスフェノール類;4,4'-ジヒドロキシジフェニルエーテル、4,4'-ジヒドロキシ-3,3'-ジメチルジフェニルエーテル等で例示されるジヒドロキシジアリールエーテル類;4,4'-ジヒドロキシジフェニルスルフィド、4,4'-ジヒドロキシ-3,3'-ジメチルジフェニルスルフィド等で例示されるジヒドロキシジアリールスルフィド類;4,4'-ジヒドロキシジフェニルスルホキシド、4,4'-ジヒドロキシ-3,3'-ジメチルジフェニルスルホキシド等で例示されるジヒドロキシジアリールスルホキシド類;4,4'-ジヒドロキシジフェニルスルホン、4,4'-ジヒドロキシ-3,3'-ジメチルジフェニルスルホン等で例示されるジヒドロキシジアリールスルホン類;ハイドロキノン、レゾルシン、4,4'-ジヒドロキシジフェニル等が挙げられる。
As the aromatic dihydroxy compound, 2,2-bis (4-hydroxyphenyl) propane (hereinafter sometimes referred to as "bisphenol A"), 1,1-bis (4-hydroxyphenyl) ethane, 2,2, 2-Bis (4-hydroxyphenyl) butane, 2,2-bis (4-hydroxyphenyl) octane, 2,2-bis (4-hydroxy-3-methylphenyl) propane, 1,1-bis (3-tert -Butyl-4-hydroxyphenyl) propane, 2,2-bis (4-hydroxy-3,5-dimethylphenyl) propane, 2,2-bis (3-phenyl-4-hydroxyphenyl) propane, 2,2- Bis (3-cyclohexyl-4-hydroxyphenyl) propane, 1,1-bis (4-hydroxyphenyl) -1-phenylethane, bis Bis (hydroxyaryl) alkanes exemplified by 4-hydroxyphenyl) diphenylmethane and the like; 1,1-bis (4-hydroxyphenyl) cyclopentane, 1,1-bis (4-hydroxyphenyl) cyclohexane, 1,1- Bis (hydroxyaryl) cycloalkanes exemplified by bis (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane and the like; 9,9-bis (4-hydroxyphenyl) fluorene, 9,9-bis (4 Cardo structure-containing bisphenols exemplified by -hydroxy-3-methylphenyl) fluorene and the like; dihydroxy diaryl ethers exemplified by 4,4'-dihydroxydiphenyl ether, 4,4'-dihydroxy-3,3'-dimethyldiphenyl ether and the like ; 4,4'-Dihydroxy dipheny Dihydroxydiaryl sulfides exemplified by sulfide, 4,4'-dihydroxy-3,3'-dimethyldiphenyl sulfide and the like; 4,4'-dihydroxydiphenyl sulfoxide, 4,4'-dihydroxy-3,3'-dimethyldiphenyl Dihydroxydiarylsulfoxides exemplified by sulfoxide etc .; dihydroxydiarylsulfones exemplified by 4,4'-dihydroxydiphenylsulfone, 4,4'-dihydroxy-3,3'-dimethyldiphenylsulfone etc; hydroquinone, resorcinol, 4 , 4'-dihydroxydiphenyl and the like.
これらの中で好ましいのは、ビス(4-ヒドロキシフェニル)アルカン類であり、特に好ましいのは、ビスフェノールAである。これらの芳香族ジヒドロキシ化合物は、1種類を用いても、2種類以上を組み合わせて用いてもよい。
Among these, preferred are bis (4-hydroxyphenyl) alkanes, and particularly preferred is bisphenol A. These aromatic dihydroxy compounds may be used alone or in combination of two or more.
芳香族ジヒドロキシ化合物と反応させるカーボネート前駆体としては、カルボニルハライド、カーボネートエステル、ハロホルメート等が使用され、具体的にはホスゲン;ジフェニルカーボネート、ジトリルカーボネート等のジアリールカーボネート類;ジメチルカーボネート、ジエチルカーボネート等のジアルキルカーボネート類;二価フェノールのジハロホルメート等が挙げられる。中でもホスゲンが好ましく用いられることが多い。これらカーボネート前駆体もまた1種類を用いても、2種類以上を組み合わせて用いてもよい。
Carbonyl halides, carbonate esters, haloformates and the like are used as carbonate precursors to be reacted with aromatic dihydroxy compounds, and specifically, phosgene; diaryl carbonates such as diphenyl carbonate, ditolyl carbonate, etc .; dimethyl carbonate, diethyl carbonate etc. Dialkyl carbonates; dihaloformates of dihydric phenol and the like can be mentioned. Among them, phosgene is often preferably used. These carbonate precursors may also be used alone or in combination of two or more.
ポリカーボネート樹脂(I)を製造する方法としては、特に限定されるものではなく、従来から知られている方法によって製造することができる。例えば、界面重合法(ホスゲン法)、溶融エステル交換法、溶液重合法(ピリジン法)、環状カーボネート化合物の開環重合法、プレポリマーの固相エステル交換法等を挙げることができる。
The method for producing the polycarbonate resin (I) is not particularly limited, and the polycarbonate resin (I) can be produced by a conventionally known method. For example, an interfacial polymerization method (phosgene method), a melt transesterification method, a solution polymerization method (pyridine method), a ring-opening polymerization method of a cyclic carbonate compound, a solid phase transesterification method of prepolymer, and the like can be mentioned.
代表的な製造方法として界面重合法による製造方法を例示する。反応に不活性な有機溶媒、アルカリ水溶液の存在下で、通常pHを9以上に保ち、芳香族ジヒドロキシ化合物、ならびに必要に応じて分子量調整剤(末端停止剤)及び芳香族ジヒドロキシ化合物の酸化防止のための酸化防止剤を用い、ホスゲンと反応させた後、第三級アミン又は第四級アンモニウム塩等の重合触媒を添加し、界面重合を行うことによってポリカーボネート樹脂を得る。分子量調節剤の添加はホスゲン化時から重合反応開始時までの間であれば特に限定されない。なお反応温度は例えば、0~40℃で、反応時間は例えば2~5時間である。
As a representative production method, a production method by an interfacial polymerization method is exemplified. In the presence of an organic solvent inert to the reaction, an aqueous alkaline solution, the pH is usually kept at 9 or more, and for preventing oxidation of the aromatic dihydroxy compound and, if necessary, the molecular weight modifier (termination agent) and the aromatic dihydroxy compound The reaction product is reacted with phosgene using an antioxidant for polymerization reaction, and then a polymerization catalyst such as tertiary amine or quaternary ammonium salt is added to carry out interfacial polymerization to obtain a polycarbonate resin. The addition of the molecular weight modifier is not particularly limited as long as it is from the time of phosgenation to the time of initiation of the polymerization reaction. The reaction temperature is, for example, 0 to 40 ° C., and the reaction time is, for example, 2 to 5 hours.
ここで、界面重合に適用できる有機溶媒としては、界面重合反応に不活性であり、水と混ざり合わず、ポリカーボネート樹脂を溶解することができれば特に制限されるものではない。例えば、ジクロロメタン、1,2-ジクロロエタン、テトラクロロエタン、クロロホルム、モノクロロベンゼン、ジクロロベンゼン等の塩素化炭化水素、ベンゼン、トルエン、キシレン等の芳香族炭化水素等が挙げられる。またアルカリ水溶液に用いられるアルカリ化合物としては、水酸化ナトリウム、水酸化カリウム等のアルカリ金属の水酸化物が挙げられる。
Here, the organic solvent applicable to the interfacial polymerization is not particularly limited as long as it is inert to the interfacial polymerization reaction, does not mix with water, and can dissolve the polycarbonate resin. Examples thereof include chlorinated hydrocarbons such as dichloromethane, 1,2-dichloroethane, tetrachloroethane, chloroform, monochlorobenzene and dichlorobenzene, and aromatic hydrocarbons such as benzene, toluene and xylene. Moreover, as an alkali compound used for aqueous alkali solution, the hydroxide of alkali metals, such as sodium hydroxide and potassium hydroxide, is mentioned.
分子量調節剤としては、一価のフェノール性水酸基を有する化合物やフェニルクロロフォルメートが挙げられる。一価のフェノール性水酸基を有する化合物としては、m-メチルフェノール、p-メチルフェノール、m-プロピルフェノール、p-プロピルフェノール、p-tert-ブチルフェノール及びp-長鎖アルキル置換フェノール等が挙げられる。分子量調節剤の使用量は、芳香族ジヒドロキシ化合物100モルに対して、好ましくは0.1~1モルである。
重合触媒としては、トリメチルアミン、トリエチルアミン、トリブチルアミン、トリプロピルアミン、トリヘキシルアミン、ピリジン等の第三級アミン類;トリメチルベンジルアンモニウムクロライド、テトラブチルアンモニウムクロライド、テトラメチルアンモニウムクロライド、トリエチルベンジルアンモニウムクロライド、トリオクチルメチルアンモニウムクロライド等の第四級アンモニウム塩等が挙げられる。 Examples of molecular weight modifiers include compounds having a monovalent phenolic hydroxyl group and phenyl chloroformate. Examples of the compound having a monovalent phenolic hydroxyl group include m-methylphenol, p-methylphenol, m-propylphenol, p-propylphenol, p-tert-butylphenol and p-long chain alkyl-substituted phenol. The amount of the molecular weight modifier used is preferably 0.1 to 1 mole relative to 100 moles of the aromatic dihydroxy compound.
As a polymerization catalyst, tertiary amines such as trimethylamine, triethylamine, tributylamine, tripropylamine, trihexylamine and pyridine; trimethylbenzyl ammonium chloride, tetrabutyl ammonium chloride, tetramethyl ammonium chloride, triethyl benzyl ammonium chloride, triethyl amine And quaternary ammonium salts such as octyl methyl ammonium chloride.
重合触媒としては、トリメチルアミン、トリエチルアミン、トリブチルアミン、トリプロピルアミン、トリヘキシルアミン、ピリジン等の第三級アミン類;トリメチルベンジルアンモニウムクロライド、テトラブチルアンモニウムクロライド、テトラメチルアンモニウムクロライド、トリエチルベンジルアンモニウムクロライド、トリオクチルメチルアンモニウムクロライド等の第四級アンモニウム塩等が挙げられる。 Examples of molecular weight modifiers include compounds having a monovalent phenolic hydroxyl group and phenyl chloroformate. Examples of the compound having a monovalent phenolic hydroxyl group include m-methylphenol, p-methylphenol, m-propylphenol, p-propylphenol, p-tert-butylphenol and p-long chain alkyl-substituted phenol. The amount of the molecular weight modifier used is preferably 0.1 to 1 mole relative to 100 moles of the aromatic dihydroxy compound.
As a polymerization catalyst, tertiary amines such as trimethylamine, triethylamine, tributylamine, tripropylamine, trihexylamine and pyridine; trimethylbenzyl ammonium chloride, tetrabutyl ammonium chloride, tetramethyl ammonium chloride, triethyl benzyl ammonium chloride, triethyl amine And quaternary ammonium salts such as octyl methyl ammonium chloride.
本発明の熱可塑性樹脂組成物において、ポリカーボネート樹脂(I)の含有量は、ポリカーボネート樹脂(I)、グラフト共重合体(II)、ビニル系共重合体(III)、メタクリル酸メチル-ブタジエン-スチレン共重合体(IV)の含有量の合計を100重量%としたときに、50~70重量%の範囲にあり、好ましくは52~68重量%、より好ましくは55~65重量%である。この割合が50重量%を下回った場合には、流動性は優れるものの、耐衝撃性と耐熱性が低下する。一方、この割合が70重量%を超える場合には、耐衝撃性、耐熱性は優れるものの、流動性が不足し、例えば、射出成形時の成形性に劣るものとなる。
In the thermoplastic resin composition of the present invention, the content of the polycarbonate resin (I) is polycarbonate resin (I), graft copolymer (II), vinyl copolymer (III), methyl methacrylate-butadiene-styrene When the total content of the copolymer (IV) is 100% by weight, it is in the range of 50 to 70% by weight, preferably 52 to 68% by weight, more preferably 55 to 65% by weight. If this proportion is less than 50% by weight, the flow resistance is excellent but the impact resistance and the heat resistance are lowered. On the other hand, when this ratio exceeds 70% by weight, although the impact resistance and the heat resistance are excellent, the flowability is insufficient, and for example, the moldability at the time of injection molding becomes inferior.
ポリカーボネート樹脂(I)の粘度平均分子量(MV)には、特に制限は無いが、好ましくは10,000以上、21,000以下、より好ましくは12,000以上、20,000以下、最も好ましくは15,000以上、18,000以下である。MVが10,000以上の場合には、耐衝撃性などの機械特性、耐熱性などが向上する傾向があり、21,000以下の場合には流動性の向上、成形品外観が良化する傾向があり、好ましい。
The viscosity-average molecular weight of the polycarbonate resin (I) to (M V) is not particularly limited, preferably 10,000 or more, 21,000 or less, more preferably 12,000 or more, 20,000 or less, and most preferably 15,000 or more and 18,000 or less. If M V is not less than 10,000, mechanical properties such as impact resistance tend to be improved heat resistance, in the case of 21,000 or less improvement in flowability, molded article appearance is improved Prone and preferred.
ポリカーボネート樹脂(I)の粘度平均分子量(MV)は、次の方法により求めることができる。まず、塩化メチレン100mlにポリカーボネート樹脂(I)0.7gを20℃で溶解した溶液(濃度c=0.7)から、オストワルド粘度計を用いて、次式にて算出される比粘度(ηSP)を求める。
比粘度(ηSP)=(t-t0)/t0
[t0は塩化メチレンの落下秒数、tは試料溶液の落下秒数] 。 The viscosity-average molecular weight of the polycarbonate resin (I) (M V) can be obtained by the following method. First, from a solution (concentration c = 0.7) obtained by dissolving 0.7 g of polycarbonate resin (I) in 100 ml of methylene chloride at 20 ° C., specific viscosity (η SP calculated by the following equation using an Ostwald viscometer Ask for).
Specific viscosity (η SP ) = (t−t 0 ) / t 0
[T 0 is the number of seconds of methylene chloride falling, t is the number of seconds of falling sample solution].
比粘度(ηSP)=(t-t0)/t0
[t0は塩化メチレンの落下秒数、tは試料溶液の落下秒数] 。 The viscosity-average molecular weight of the polycarbonate resin (I) (M V) can be obtained by the following method. First, from a solution (concentration c = 0.7) obtained by dissolving 0.7 g of polycarbonate resin (I) in 100 ml of methylene chloride at 20 ° C., specific viscosity (η SP calculated by the following equation using an Ostwald viscometer Ask for).
Specific viscosity (η SP ) = (t−t 0 ) / t 0
[T 0 is the number of seconds of methylene chloride falling, t is the number of seconds of falling sample solution].
続いて、求められた比粘度(ηSP)から次のSchnellの式により粘度平均分子量MVを算出することができる。
ηSP/c=[η]+0.45×[η]2c(但し[η]は極限粘度)
[η]=1.23×10-4MV 0.83 。 Then, the equation of the following Schnell from the obtained specific viscosity (eta SP) can be calculated viscosity average molecular weight M V.
η SP /c=[η]+0.45×[η] 2 c (where [[] is the limiting viscosity)
[Η] = 1.23 × 10 -4 M V 0.83.
ηSP/c=[η]+0.45×[η]2c(但し[η]は極限粘度)
[η]=1.23×10-4MV 0.83 。 Then, the equation of the following Schnell from the obtained specific viscosity (eta SP) can be calculated viscosity average molecular weight M V.
η SP /c=[η]+0.45×[η] 2 c (where [[] is the limiting viscosity)
[Η] = 1.23 × 10 -4 M V 0.83.
本発明の熱可塑性樹脂組成物を組成するグラフト共重合体(II)は、ジエン系ゴム質重合体(A)の存在下に、少なくとも芳香族ビニル系単量体(B)およびシアン化ビニル系単量体(C)を含有する単量体混合物をグラフト共重合してなるグラフト共重合体である。
The graft copolymer (II) constituting the thermoplastic resin composition of the present invention comprises at least an aromatic vinyl monomer (B) and a vinyl cyanide compound in the presence of a diene rubber polymer (A). It is a graft copolymer formed by graft copolymerization of a monomer mixture containing a monomer (C).
グラフト共重合体(II)に用いることができるジエン系ゴム質重合体(A)としては、ガラス転移温度が0℃以下のものが好適であり、その下限値には特に制限は無いが実用上は-80℃程度である。使用できるジエン系ゴム質重合体を例示すると、ポリブタジエン、スチレン-ブタジエン共重合体、アクリロニトリル-ブタジエン共重合体、スチレン-ブタジエンブロック共重合体およびアクリル酸ブチル-ブタジエン共重合体などが挙げられるが、なかでも、ポリブタジエンが好ましく用いられる。
As the diene rubber-like polymer (A) which can be used for the graft copolymer (II), one having a glass transition temperature of 0 ° C. or less is suitable, and the lower limit thereof is not particularly limited, but for practical use Is about -80.degree. Examples of diene rubber polymers that can be used include polybutadiene, styrene-butadiene copolymer, acrylonitrile-butadiene copolymer, styrene-butadiene block copolymer and butyl acrylate-butadiene copolymer. Among them, polybutadiene is preferably used.
ジエン系ゴム質重合体(A)の重量平均粒子径は特に制限はないが、100~1200nmであることが好ましく、200~1200nmであることがより好ましい。ジエン系ゴム質重合体(A)として重量平均粒子径が100nmに満たないものを使用すると、耐衝撃性が低下することがあり、一方、重量平均粒子径が1200nmを超えるものを使用する場合には、流動性が低下することがある。
The weight-average particle size of the diene rubber-like polymer (A) is not particularly limited, but is preferably 100 to 1,200 nm, and more preferably 200 to 1,200 nm. When a diene rubber polymer (A) having a weight average particle diameter of less than 100 nm is used, the impact resistance may be lowered. On the other hand, when a weight average particle diameter of more than 1200 nm is used May have reduced liquidity.
また、ジエン系ゴム質重合体(A)としては、耐衝撃性と流動性との両立の観点から、重量平均粒子径が200~400nmの低粒子径のものと、重量平均粒子径が450~1200nmの高粒子径のものの2種類のジエン系ゴム質重合体を併用することが好ましく、より好ましくは重量平均粒子径が280~400nmのものと600~1200nmのものの併用、さらに好ましくは重量平均粒子径が320~380nmのものと700~1100nmのものの併用である。
In addition, as the diene rubber polymer (A), from the viewpoint of achieving both impact resistance and fluidity, those having a low weight average particle diameter of 200 to 400 nm and a weight average particle diameter of 450 to It is preferable to use two diene rubber polymers having a large particle diameter of 1200 nm in combination, more preferably a combination of one having a weight average particle diameter of 280 to 400 nm and one having a weight average particle diameter of 600 to 1200 nm, still more preferably a weight average particle A combination of one with a diameter of 320 to 380 nm and one with a diameter of 700 to 1100 nm.
さらに、前述のとおりジエン系ゴム質重合体(A)を2種類用いる場合、耐衝撃性と流動性の観点から、低粒子径のものと高粒子径のものの重量比率が、90:10~50:50の範囲にあることが好ましく、より好ましくは80:20~60:40、さらに好ましくは75:25~65:35の範囲である。
Furthermore, when two types of diene rubber polymers (A) are used as described above, the weight ratio of low particle size to high particle size is 90: 10 to 50 from the viewpoint of impact resistance and flowability. The ratio is preferably in the range of 50, more preferably in the range of 80:20 to 60:40, still more preferably in the range of 75:25 to 65:35.
なお、ジエン系ゴム質重合体(A)の重量平均粒子径は、「Rubbaer Age Vol.88 p.484~490(1960)by E.Schmidt,P.H.Biddison」に記載のアルギン酸ナトリウム法(アルギン酸ナトリウムの濃度量割合とアルギン酸ナトリウム濃度の累積重量分率より累積重量分率50%の粒子径を求める。)により測定することができる。
The weight average particle diameter of the diene rubber polymer (A) is the sodium alginate method described in “Rubbaer Age Vol. 88 p. 484 to 490 (1960) by E. Schmidt, PH Biddison” ( The particle diameter of the cumulative weight fraction of 50% is determined from the concentration ratio of sodium alginate and the cumulative weight fraction of sodium alginate concentration.
グラフト共重合体(II)に含まれるジエン系ゴム質重合体(A)由来の部分の重量分率は、40~65重量%に調整することが好ましく、より好ましいジエン系ゴム質重合体(A)由来の部分の重量分率は、40~60重量%であり、さらに好ましくは40~50重量%である。重量分率が40重量%以上では耐衝撃性が向上し、一方、65重量%以下では流動性が向上するため好ましい。
The weight fraction of the part derived from the diene rubber polymer (A) contained in the graft copolymer (II) is preferably adjusted to 40 to 65% by weight, and more preferably the diene rubber polymer (A The weight fraction of the part derived from) is 40 to 60% by weight, more preferably 40 to 50% by weight. When the weight fraction is 40% by weight or more, impact resistance is improved, and when it is 65% by weight or less, the flowability is improved, which is preferable.
グラフト共重合体(II)に用いられる芳香族ビニル系単量体(B)としては、例えば、スチレン、α-メチルスチレン、ビニルトルエン、o-エチルスチレン、p-メチルスチレン、クロロスチレンおよびブロモスチレンなどが挙げられるが、特にスチレンが好ましく採用される。
Examples of the aromatic vinyl monomer (B) used for the graft copolymer (II) include styrene, α-methylstyrene, vinyltoluene, o-ethylstyrene, p-methylstyrene, chlorostyrene and bromostyrene In particular, styrene is preferably employed.
グラフト共重合体(II)に用いられるシアン化ビニル系単量体(C)としては、例えば、アクリロニトリル、メタクリロニトリルおよびエタクリロニトリルなどが挙げられるが、特にアクリロニトリルが好ましく採用される。
Examples of the vinyl cyanide monomer (C) used for the graft copolymer (II) include, for example, acrylonitrile, methacrylonitrile and ethacrylonitrile, and in particular, acrylonitrile is preferably employed.
その他、グラフト共重合体(II)を得るにおいては、本発明の効果を失わない程度に芳香族ビニル系単量体(B)およびシアン化ビニル系単量体(C)と共重合可能な他のビニル系単量体を用いうる。他のビニル系単量体の具体例としては、N-フェニルマレイミド、N-メチルマレイミドおよびメタクリル酸メチルなどが挙げられ、それぞれの目的に応じて選択することができ、これらは1種類を用いても複数種を組み合わせて用いても良い。なお、耐熱性や難燃性をさらに向上させる意図があれば、N-フェニルマレイミドを用いることが好ましい。また、硬度向上を重視するのであれば、メタクリル酸メチルが好ましく用いられる。
In addition, in obtaining graft copolymer (II), other copolymerizable with aromatic vinyl monomer (B) and vinyl cyanide monomer (C) to the extent that the effect of the present invention is not lost And vinyl monomers of the following. Specific examples of other vinyl monomers include N-phenyl maleimide, N-methyl maleimide, methyl methacrylate and the like, which can be selected according to the respective purposes, and one of these may be used. Also, plural kinds may be used in combination. If the intention is to further improve the heat resistance and the flame retardancy, N-phenylmaleimide is preferably used. In addition, methyl methacrylate is preferably used if importance is given to hardness improvement.
グラフト共重合体(II)に占める芳香族ビニル系単量体(B)由来部分の重量分率は、グラフト共重合体(II)の重量を100重量%としたとき、26~43重量%であることが好ましく、より好ましくは30~41重量%、特に好ましくは35~41重量%である。この重量分率が26重量%以上の場合には、着色しにくい傾向があり、一方、43重量%以下の場合にはグラフト重合が進行しやすく、グラフト率が向上し、耐衝撃性が向上する傾向がある。
The weight fraction of the portion derived from the aromatic vinyl monomer (B) in the graft copolymer (II) is 26 to 43% by weight based on 100% by weight of the graft copolymer (II). It is preferably 30 to 41% by weight, particularly preferably 35 to 41% by weight. When the weight fraction is 26% by weight or more, it tends to be difficult to be colored, while when it is 43% by weight or less, the graft polymerization tends to proceed, the graft ratio is improved, and the impact resistance is improved. Tend.
グラフト共重合体(II)に占めるシアン化ビニル系単量体(C)由来部分の重量分率は、グラフト共重合体(II)の重量を100重量%としたとき、9~17重量%が好ましく、より好ましくは10~16重量%、さらに好ましくは12~16重量%である。この重量分率が9重量%以上の場合には、グラフト重合が進行しやすく、グラフト率が向上し、耐衝撃性が向上する傾向があり、17重量%以下の場合には、着色しにくい傾向がある。
The weight fraction of the vinyl cyanide monomer (C) -derived portion in the graft copolymer (II) is 9 to 17% by weight based on 100% by weight of the graft copolymer (II). Preferably, it is 10 to 16% by weight, more preferably 12 to 16% by weight. When the weight fraction is 9% by weight or more, graft polymerization tends to proceed, the grafting ratio is improved, the impact resistance tends to be improved, and when the weight fraction is 17% by weight or less, the coloring tends to be difficult. There is.
グラフト共重合体(II)のグラフト率は、特に制限されるものではない。耐衝撃性と流動性のバランスから、グラフト率は7~30%が好ましく、より好ましくは20~28%、さらに好ましくは22~26%である。グラフト率(%)は、次式で示される。
グラフト率(%)=[ジエン系ゴム質重合体にグラフト重合したビニル系単量体の総量(重量)]/[ジエン系ゴム質重合体の重量]×100。 The grafting ratio of the graft copolymer (II) is not particularly limited. From the viewpoint of balance between impact resistance and flowability, the grafting ratio is preferably 7 to 30%, more preferably 20 to 28%, and still more preferably 22 to 26%. The grafting rate (%) is represented by the following formula.
Graft ratio (%) = [total amount (weight) of vinyl-based monomer graft-polymerized to diene-based rubbery polymer] / [weight of diene-based rubbery polymer] × 100.
グラフト率(%)=[ジエン系ゴム質重合体にグラフト重合したビニル系単量体の総量(重量)]/[ジエン系ゴム質重合体の重量]×100。 The grafting ratio of the graft copolymer (II) is not particularly limited. From the viewpoint of balance between impact resistance and flowability, the grafting ratio is preferably 7 to 30%, more preferably 20 to 28%, and still more preferably 22 to 26%. The grafting rate (%) is represented by the following formula.
Graft ratio (%) = [total amount (weight) of vinyl-based monomer graft-polymerized to diene-based rubbery polymer] / [weight of diene-based rubbery polymer] × 100.
グラフト共重合体(II)として、例えばアクリロニトリル・ブタジエン・スチレングラフト共重合体(ABS樹脂)、メチルメタクリレート・アクリロニトリル・ブタジエン・スチレングラフト共重合体(MABS樹脂)等を挙げることができる。なかでもアクリロニトリル・ブタジエン・スチレングラフト共重合体(ABS樹脂)が好ましい。
As a graft copolymer (II), an acrylonitrile butadiene styrene graft copolymer (ABS resin), a methyl methacrylate acrylonitrile acrylonitrile butadiene graft copolymer (MABS resin) etc. can be mentioned, for example. Among them, acrylonitrile butadiene styrene graft copolymer (ABS resin) is preferable.
本発明の熱可塑性樹脂組成物において、グラフト共重合体(II)の含有量は、ポリカーボネート樹脂(I)、グラフト共重合体(II)、ビニル系共重合体(III)、メタクリル酸メチル-ブタジエン-スチレン共重合体(IV)の含有量の合計を100重量%としたときに、10~30重量%の範囲にあり、好ましくは12~28重量%、より好ましくは15~25重量%である。この割合が10重量%未満の場合には、耐衝撃性、めっき特性が低下し、30重量%を超える場合、流動性および耐熱性が低下する。。
In the thermoplastic resin composition of the present invention, the content of the graft copolymer (II) is polycarbonate resin (I), graft copolymer (II), vinyl copolymer (III), methyl methacrylate-butadiene When the total content of styrene copolymer (IV) is 100% by weight, it is in the range of 10 to 30% by weight, preferably 12 to 28% by weight, more preferably 15 to 25% by weight . When this proportion is less than 10% by weight, impact resistance and plating properties decrease, and when it exceeds 30% by weight, fluidity and heat resistance decrease. .
本発明の熱可塑性樹脂組成物を組成するビニル系共重合体(III)は、少なくとも芳香族ビニル系単量体およびシアン化ビニル系単量体を共重合してなるビニル系共重合体である。中でも、ビニル系共重合体(III)100重量%に対して、シアン化ビニル系単量体(E)由来部分が29~33重量%含まれたものが好ましい。また、芳香族ビニル系単量体およびシアン化ビニル系単量体の共重合割合としては、芳香族ビニル系単量体(D)67~71重量%およびシアン化ビニル系単量体(E)29~33重量%であることが好ましく、更に好ましくは、芳香族ビニル系単量体(D)68~70重量%およびシアン化ビニル系単量体(E)30~32重量%である。ビニル系共重合体(III)に占めるシアン化ビニル系単量体(E)由来部分の割合が、29重量%以上の場合には、めっき工程の前工程であるエッチング工程で使用されるエッチング液(強酸水溶液)との親和性が向上し、ジエン系ゴム質重合体(A)がよりエッチングされやすくなり、アンカー効果が大きくなり、めっき特性が向上する傾向があり好ましい。シアン化ビニル系単量体成分の平均含有量が、33重量%以下の場合には、ビニル系共重合体(III)の芳香族ビニル系単量体(D)の平均含有量が大きくなり、ビニル系共重合体(III)とポリカーボネート樹脂(I)との相溶性が向上し、耐熱性や耐衝撃性等の特性が向上する傾向があり好ましい。本発明において、ビニル系共重合体(III)は、ジエン系ゴム質重合体(A)を含まない点で、グラフト共重合体(II)とは異なる共重合体である。
The vinyl-based copolymer (III) constituting the thermoplastic resin composition of the present invention is a vinyl-based copolymer obtained by copolymerizing at least an aromatic vinyl-based monomer and a vinyl cyanide-based monomer. . Among them, those containing 29 to 33% by weight of a vinyl cyanide-based monomer (E) -derived portion relative to 100% by weight of the vinyl-based copolymer (III) are preferable. Moreover, as a copolymerization ratio of the aromatic vinyl monomer and the vinyl cyanide monomer, 67 to 71% by weight of the aromatic vinyl monomer (D) and the vinyl cyanide monomer (E) The content is preferably 29 to 33% by weight, and more preferably 68 to 70% by weight of the aromatic vinyl monomer (D) and 30 to 32% by weight of the vinyl cyanide monomer (E). When the proportion of the vinyl cyanide monomer (E) -derived portion in the vinyl copolymer (III) is 29% by weight or more, the etching solution used in the etching step prior to the plating step The affinity to the (strong acid aqueous solution) is improved, the diene rubbery polymer (A) is more easily etched, the anchor effect is increased, and the plating characteristics tend to be improved, which is preferable. When the average content of the vinyl cyanide-based monomer component is 33% by weight or less, the average content of the aromatic vinyl-based monomer (D) of the vinyl-based copolymer (III) is increased, The compatibility between the vinyl copolymer (III) and the polycarbonate resin (I) is improved, and the characteristics such as heat resistance and impact resistance tend to be improved, which is preferable. In the present invention, the vinyl copolymer (III) is a copolymer different from the graft copolymer (II) in that the diene rubber polymer (A) is not contained.
ビニル系共重合体(III)に用いられる芳香族ビニル系単量体(D)としては、前述のグラフト共重合体(II)での芳香族ビニル系単量体(B)と同様に、スチレン、α-メチルスチレン、ビニルトルエン、o-エチルスチレン、p-メチルスチレン、クロロスチレン、ブロモスチレンなどが挙げられる。好ましくはスチレンが用いられる。これらは必ずしも1種類で使用する必要はなく、複数種併用して使用することもできる。これらの中で特にスチレンが好ましく採用される。
As the aromatic vinyl monomer (D) used for the vinyl copolymer (III), styrene is the same as the aromatic vinyl monomer (B) in the graft copolymer (II) described above. Α-methylstyrene, vinyltoluene, o-ethylstyrene, p-methylstyrene, chlorostyrene, bromostyrene and the like. Preferably, styrene is used. These do not necessarily have to be used alone, and can be used in combination of two or more. Among these, styrene is particularly preferably employed.
ビニル系共重合体(III)に用いられるシアン化ビニル系単量体(E)としては、前述のグラフト共重合体(II)でのシアン化ビニル系単量体(C)と同様に、例えば、アクリロニトリル、メタクリロニトリルおよびエタクリロニトリルなどが挙げられるが、特にアクリロニトリルが好ましく採用される。これらは必ずしも1種類で使用する必要はなく、複数種併用して使用することもできる。
As the vinyl cyanide-based monomer (E) used for the vinyl-based copolymer (III), for example, similar to the cyanide-based vinyl monomer (C) in the above-mentioned graft copolymer (II), for example, Acrylonitrile, methacrylonitrile, ethacrylonitrile and the like can be mentioned, but in particular acrylonitrile is preferably employed. These do not necessarily have to be used alone, and can be used in combination of two or more.
また、グラフト共重合体(II)と同様に、ビニル系共重合体(III)においても本発明の効果を失わない程度に芳香族ビニル系単量体(D)およびシアン化ビニル系単量体(E)と共重合可能な他のビニル系単量体を用いても良い。他のビニル系単量体の具体例としては、N-フェニルマレイミド、N-メチルマレイミドおよびメタクリル酸メチルなどが挙げられ、それぞれの目的に応じて選択することができ、これらは1種類を用いても複数種を組み合わせて用いても良い。耐熱性や難燃性をさらに向上させる意図があれば、N-フェニルマレイミドを用いることが好ましい。また、硬度向上を重視するのであれば、メタクリル酸メチルが好ましく用いられる。
Further, as in the case of the graft copolymer (II), the vinyl copolymer (III) also has an aromatic vinyl monomer (D) and a vinyl cyanide monomer to such an extent that the effect of the present invention is not lost. Other vinyl monomers copolymerizable with (E) may be used. Specific examples of other vinyl monomers include N-phenyl maleimide, N-methyl maleimide, methyl methacrylate and the like, which can be selected according to the respective purposes, and one of these may be used. Also, plural kinds may be used in combination. If it is intended to further improve the heat resistance and the flame retardancy, it is preferable to use N-phenylmaleimide. In addition, methyl methacrylate is preferably used if importance is given to hardness improvement.
ビニル系共重合体(III)は、メチルエチルケトン溶媒、30℃、ウベローデ粘度計で測定される固有粘度が0.35~0.50dl/gであることが好ましく、より好ましくは0.37~0.48dl/g、更に好ましくは0.40~0.45dl/gの範囲である。固有粘度が0.35dl/g以上の場合には、耐衝撃性が向上する傾向があり、一方、0.50dl/g以下の場合には流動性が向上する傾向があり好ましい。
The vinyl copolymer (III) preferably has an intrinsic viscosity of 0.35 to 0.50 dl / g as measured in a methyl ethyl ketone solvent at 30 ° C. with an Ubbelohde viscometer, and more preferably 0.37 to 0. It is preferably in the range of 48 dl / g, more preferably 0.40 to 0.45 dl / g. When the intrinsic viscosity is 0.35 dl / g or more, the impact resistance tends to be improved, while when it is 0.50 dl / g or less, the flowability tends to be improved, which is preferable.
ビニル系共重合体(III)として、例えばアクリロニトリル・スチレン共重合体(AS樹脂)、メチルメタクリレート・スチレン共重合体(MS樹脂)等を挙げることができる。なかでもアクリロニトリル・スチレン共重合体(AS樹脂)が好ましい。
Examples of the vinyl-based copolymer (III) include acrylonitrile-styrene copolymer (AS resin), methyl methacrylate-styrene copolymer (MS resin) and the like. Among them, acrylonitrile-styrene copolymer (AS resin) is preferable.
本発明の熱可塑性樹脂組成物において、ビニル系共重合体(III)の含有量は、ポリカーボネート樹脂(I)、グラフト共重合体(II)、ビニル系共重合体(III)、メタクリル酸メチル-ブタジエン-スチレン共重合体(IV)の含有量の合計を100重量%としたときに、5~20重量%の範囲であり、好ましくは7~18重量%、より好ましくは5~15重量%である。この割合が5重量%未満の場合には、流動性が低下し、20重量%を超える場合、耐衝撃性およびめっき特性が低下する。
In the thermoplastic resin composition of the present invention, the content of the vinyl copolymer (III) is polycarbonate resin (I), graft copolymer (II), vinyl copolymer (III), methyl methacrylate- When the total content of butadiene-styrene copolymer (IV) is 100% by weight, it is in the range of 5 to 20% by weight, preferably 7 to 18% by weight, more preferably 5 to 15% by weight is there. If this proportion is less than 5% by weight, the flowability is reduced, and if it exceeds 20% by weight, the impact resistance and the plating properties are reduced.
本発明において、グラフト共重合体(II)、ビニル系共重合体(III)の製造方法には特に制限はなく、塊状重合、懸濁重合、塊状懸濁重合、溶液重合、乳化重合、沈殿重合およびこれらの組み合わせ等が用いられる。単量体の仕込み方法に関しても特に制限はなく、初期に一括添加してもよく、共重合体の組成分布を付けるため、あるいは防止するために添加方法は数回に分けて重合してもよい。
In the present invention, the method for producing graft copolymer (II) and vinyl copolymer (III) is not particularly limited, and bulk polymerization, suspension polymerization, bulk suspension polymerization, solution polymerization, emulsion polymerization, precipitation polymerization And combinations thereof. There is no particular limitation on the method of feeding the monomers, and batch addition may be carried out at the initial stage, and addition may be performed in several times to polymerize the composition distribution of the copolymer or to prevent it. .
本発明において、グラフト共重合体(II)、ビニル系共重合体(III)の重合に使用される開始剤としては、過酸化物またはアゾ系化合物などが好適に用いられる。
In the present invention, as an initiator used for the polymerization of the graft copolymer (II) and the vinyl copolymer (III), a peroxide or an azo compound is suitably used.
過酸化物の具体例としては、例えば、ベンゾイルパーオキサイド、クメンハイドロパーオキサイド、ジクミルパーオキサイド、ジイソプロピルベンゼンハイドロパーオキサイド、t-ブチルハイドロパーオキサイド、t-ブチルクミルパーオキサイド、t-ブチルパーオキシアセテート、t-ブチルパーオキシベンゾエート、t-ブチルパーオキシイソプロピルカルボネート、ジ-t-ブチルパーオキサイド、t-ブチルパーオクテート、1,1-ビス(t-ブチルパーオキシ)3、3、5-トリメチルシクロヘキサン、1,1-ビス(t-ブチルパーオキシ)シクロヘキサン、およびt-ブチルパーオキシ-2-エチルヘキサノエートなどが挙げられる。なかでもクメンハイドロパーオキサイドおよび1,1-ビス(t-ブチルパーオキシ)3、3、5-トリメチルシクロヘキサンが、特に好ましく用いられる。
Specific examples of peroxides include, for example, benzoyl peroxide, cumene hydroperoxide, dicumyl peroxide, diisopropylbenzene hydroperoxide, t-butyl hydroperoxide, t-butylcumyl peroxide, t-butyl peroxy Acetate, t-Butylperoxybenzoate, t-Butylperoxyisopropylcarbonate, Di-t-Butyl Peroxide, t-Butyl Peroxide, 1,1-Bis (t-butylperoxy) 3,3,5 And -trimethylcyclohexane, 1,1-bis (t-butylperoxy) cyclohexane, and t-butylperoxy-2-ethylhexanoate. Among them, cumene hydroperoxide and 1,1-bis (t-butylperoxy) 3,3,5-trimethylcyclohexane are particularly preferably used.
また、アゾ系化合物の具体例としては、例えば、アゾビスイソブチロニトリル、アゾビス(2,4ジメチルバレロニトリル)、2-フェニルアゾ-2,4-ジメチル-4-メトキシバレロニトリル、2-シアノ-2-プロピルアゾホルムアミド、1,1′-アゾビスシクロヘキサン-1-カーボニトリル、アゾビス(4-メトキシ-2,4-ジメチルバレロニトリル)、ジメチル2,2′-アゾビスイソブチレート、1-t-ブチルアゾ-1-シアノシクロヘキサン、2-t-ブチルアゾ-2-シアノブタン、および2-t-ブチルアゾ-2-シアノ-4-メトキシ-4-メチルペンタンなどが挙げられる。なかでもアゾビスイソブチロニトリルが特に好ましく用いられる。
Further, specific examples of the azo compound include, for example, azobisisobutyronitrile, azobis (2,4 dimethyl valeronitrile), 2-phenylazo-2,4-dimethyl-4-methoxyvaleronitrile, 2-cyano- 2-Propylazoformamide, 1,1'-azobiscyclohexane-1-carbonitrile, azobis (4-methoxy-2,4-dimethylvaleronitrile), dimethyl 2,2'-azobisisobutyrate, 1-t And -butylazo-1-cyanocyclohexane, 2-tert-butylazo-2-cyanobutane, 2-tert-butylazo-2-cyano-4-methoxy-4-methylpentane and the like. Among them, azobisisobutyronitrile is particularly preferably used.
これらの開始剤を使用する場合、1種または2種以上を併用して使用される。
When these initiators are used, one or more may be used in combination.
重合を行うに際しては、グラフト共重合体(II)、ビニル系共重合体(III)の重合度調節を目的として、メルカプタンやテルペンなどの連鎖移動剤を使用することも可能である。連鎖移動剤の具体例としては、n-オクチルメルカプタン、t-ドデシルメルカプタン、n-ドデシルメルカプタン、n-テトラデシルメルカプタン、n-オクタデシルメルカプタンおよびテルピノレンなどが挙げられる。なかでも、n-オクチルメルカプタン、t-ドデシルメルカプタンおよびn-ドデシルメルカプタンが好ましく用いられる。これらの連鎖移動剤を使用する場合は、1種または2種以上を併用して使用される。
When the polymerization is carried out, a chain transfer agent such as mercaptan or terpene may be used for the purpose of adjusting the degree of polymerization of the graft copolymer (II) or the vinyl copolymer (III). Specific examples of the chain transfer agent include n-octyl mercaptan, t-dodecyl mercaptan, n-dodecyl mercaptan, n-tetradecyl mercaptan, n-octadecyl mercaptan and terpinolene. Among them, n-octyl mercaptan, t-dodecyl mercaptan and n-dodecyl mercaptan are preferably used. When using these chain transfer agents, it is used in combination of 1 type, or 2 or more types.
本発明の熱可塑性樹脂組成物では、グラフト共重合体(II)が弱アルカリ性を呈することがあり、本発明の構成成分のポリカーボネート樹脂(I)のアルカリ分解、熱分解を防ぐ目的で、酸性化合物をグラフト重合体製造時や樹脂組成物を生産するための溶融混錬時に添加することができる。本発明で使用することができる酸性化合物には、特に制限は無いが、使用できる化合物を具体的に例示すると、塩酸、硫酸、硝酸、酢酸、シュウ酸、マロン酸、コハク酸、マレイン酸、アジピン酸、セバシン酸、ドデカン二酸、無水マレイン酸、無水コハク酸、イタコン酸、安息香酸、安息香酸メチル、テレフタル酸、イソフタル酸、オルトフタル酸、ナフタレンジカルボン酸、ジフェン酸、リン酸、リン酸二水素ナトリウムなどが挙げられ、好ましくは、無水マレイン酸、無水コハク酸、リン酸、リン酸二水素ナトリウムであり、より好ましくは、リン酸、リン酸二水素ナトリウムである。上記の様に例示した酸性化合物は、必ずしも1種で使用する必要は無く、複数種併用して使用することもできる。
In the thermoplastic resin composition of the present invention, the graft copolymer (II) may exhibit weak alkalinity, and for the purpose of preventing alkaline decomposition and thermal decomposition of the polycarbonate resin (I) which is a component of the present invention, an acidic compound Can be added at the time of graft polymer production or at the time of melt-kneading for producing a resin composition. The acidic compound which can be used in the present invention is not particularly limited, and specific examples of the usable compound include hydrochloric acid, sulfuric acid, nitric acid, acetic acid, oxalic acid, malonic acid, succinic acid, maleic acid, adipine Acid, sebacic acid, dodecanedioic acid, maleic anhydride, succinic anhydride, itaconic acid, benzoic acid, methyl benzoate, terephthalic acid, isophthalic acid, orthophthalic acid, naphthalene dicarboxylic acid, diphenic acid, phosphoric acid, dihydrogen phosphate Examples thereof include sodium and the like, preferably maleic anhydride, succinic anhydride, phosphoric acid and sodium dihydrogen phosphate, more preferably phosphoric acid and sodium dihydrogen phosphate. The acidic compounds exemplified above are not necessarily used alone, and a plurality of them may be used in combination.
酸性化合物の添加量は、目安として(I)~(III)の合計100重量部に対し1.0重量部以下が好ましい。1.0重量部以下の場合には、射出成形品の表面れ等の外観不良を抑制できる傾向がある。
The amount of the acidic compound added is preferably 1.0 parts by weight or less based on 100 parts by weight of the total of (I) to (III) as a standard. In the case of 1.0 parts by weight or less, appearance defects such as surface defects of the injection molded product tend to be suppressed.
本発明の熱可塑性樹脂組成物において、メタクリル酸メチル-ブタジエン-スチレン共重合体(IV)とは、グラフト共重合体(II)とは異なる成分であり、ブタジエンゴム質重合体の存在下に、メタクリル酸メチル単量体およびスチレン単量体を主成分とする単量体混合物をグラフト共重合してなるコアシェル型のグラフト共重合体である。
In the thermoplastic resin composition of the present invention, methyl methacrylate-butadiene-styrene copolymer (IV) is a component different from graft copolymer (II), and in the presence of a butadiene rubbery polymer, It is a core-shell type graft copolymer obtained by graft copolymerization of a monomer mixture containing methyl methacrylate monomer and styrene monomer as main components.
本発明に用いるメタクリル酸メチル-ブタジエン-スチレン共重合体(IV)は、コア成分にブタジエンゴム質重合体を有し、シェル成分にメタクリル酸メチル-スチレン共重合体を有する共重合体である。
The methyl methacrylate-butadiene-styrene copolymer (IV) used in the present invention is a copolymer having a butadiene rubber-like polymer as a core component and having a methyl methacrylate-styrene copolymer as a shell component.
本発明の熱可塑性樹脂組成物において、メタクリル酸メチル-ブタジエン-スチレン共重合体(IV)の含有量は、ポリカーボネート樹脂(I)、グラフト共重合体(II)、ビニル系共重合体(III)、メタクリル酸メチル-ブタジエン-スチレン共重合体(IV)の含有量の合計を100重量%としたときに、1~10重量%の範囲であり、好ましくは2~9重量%、より好ましくは3~8重量%である。この割合が1重量%未満であると、ポリカーボネート樹脂(I)マトリクス相へのメタクリル酸メチル-ブタジエン-スチレン共重合体(IV)導入量が少なくなり、エッチング工程時にポリカーボネート樹脂(I)マトリクス相のアンカー効果が不十分となり、十分なめっき特性が得られない。10重量%を超えると、耐熱性や流動性が低下する。
In the thermoplastic resin composition of the present invention, the content of methyl methacrylate-butadiene-styrene copolymer (IV) is polycarbonate resin (I), graft copolymer (II), vinyl copolymer (III) When the total content of methyl methacrylate-butadiene-styrene copolymer (IV) is 100% by weight, it is in the range of 1 to 10% by weight, preferably 2 to 9% by weight, more preferably 3 ~ 8 wt%. When this ratio is less than 1% by weight, the amount of methyl methacrylate-butadiene-styrene copolymer introduced into the polycarbonate resin (I) matrix phase decreases, and the polycarbonate resin (I) matrix phase is reduced during the etching step. The anchor effect is insufficient and sufficient plating characteristics can not be obtained. If it exceeds 10% by weight, the heat resistance and the fluidity will be reduced.
本発明の熱可塑性樹脂組成物において、ポリカーボネート樹脂(I)100重量%に対するメタクリル酸メチル-ブタジエン-スチレン共重合体(IV)の含有割合は、3~20重量%であり、好ましくは4~18重量%、より好ましくは5~15重量%である。この含有割合が3重量%未満の場合、ポリカーボネート樹脂(I)マトリクス相へのメタクリル酸メチル-ブタジエン-スチレン共重合体(IV)導入量が少なくなり、エッチング工程時にポリカーボネート樹脂(I)マトリクス相のアンカー効果が不十分となり、十分なめっき特性が得られない。一方、20重量%を超える場合、耐熱性や流動性が低下する傾向がある。
In the thermoplastic resin composition of the present invention, the content ratio of methyl methacrylate-butadiene-styrene copolymer (IV) to 100 wt% of polycarbonate resin (I) is 3 to 20 wt%, preferably 4 to 18 % By weight, more preferably 5 to 15% by weight. If this content ratio is less than 3% by weight, the amount of methyl methacrylate-butadiene-styrene copolymer (IV) introduced into the polycarbonate resin (I) matrix phase decreases, and the polycarbonate resin (I) matrix phase is The anchor effect is insufficient and sufficient plating characteristics can not be obtained. On the other hand, when it exceeds 20% by weight, heat resistance and fluidity tend to be lowered.
本発明の熱可塑性樹脂組成物は、ポリカーボネート樹脂(I)、グラフト共重合体(II)、ビニル系共重合体(III)およびメタクリル酸メチル-ブタジエン-スチレン共重合体(IV)から実質的になるものである。ここでいう「実質的になる」の意味は本発明の効果を損なわない範囲において他の成分を含みうるとの意であり、以下でも説明されるように、本発明の熱可塑性樹脂組成物は目的とする機能に応じて種々の添加物を含みうる。そのような添加物は通常はポリカーボネート樹脂(I)、グラフト共重合体(II)、ビニル系共重合体(III)、メタクリル酸メチル-ブタジエン-スチレン共重合体(IV)の含有量の合計を100重量部としたとき10重量部以下であり、好ましくは5重量部以下であり、更に好ましくは3重量部以下である。
The thermoplastic resin composition of the present invention is substantially composed of polycarbonate resin (I), graft copolymer (II), vinyl copolymer (III) and methyl methacrylate-butadiene-styrene copolymer (IV) It will be The meaning of "consisting essentially of" as used herein means that other components may be included as long as the effects of the present invention are not impaired, and as described below, the thermoplastic resin composition of the present invention is Various additives may be included depending on the intended function. Such additives usually have a total content of polycarbonate resin (I), graft copolymer (II), vinyl copolymer (III) and methyl methacrylate-butadiene-styrene copolymer (IV). When it is 100 parts by weight, it is 10 parts by weight or less, preferably 5 parts by weight or less, and more preferably 3 parts by weight or less.
本発明の熱可塑性樹脂組成物においては、ポリカーボネート樹脂(I)、グラフト共重合体(II)、ビニル系共重合体(III)、メタクリル酸メチル-ブタジエン-スチレン共重合体(IV)の含有量の合計を100重量部としたときに、さらに、シリコーン系化合物およびフッ素系化合物から選択されるいずれか1種以上の化合物(V)を、0.01~0.2重量部含有することが好ましい。化合物(V)の含有割合はより好ましくは、0.02~0.18重量部、さらに好ましくは0.03~0.15重量部である。化合物(V)を、0.01重量部以上含有した場合、射出成形時に残留する応力が緩和され、エッチング工程でのエッチング不良やめっき工程でのめっき不良が解消され、さらにめっき後成形品の樹脂とめっき皮膜の界面にかかる応力が分散されることで、めっき剥がれや膨れ等の耐久性が更に改善される。また、化合物(V)を、0.2重量部以下配合した場合、耐熱性低下の抑制や化合物(V)の成形品表面へのブリードアウトによる外観不良を更に抑制できることができる。
In the thermoplastic resin composition of the present invention, the content of polycarbonate resin (I), graft copolymer (II), vinyl copolymer (III) and methyl methacrylate-butadiene-styrene copolymer (IV) It is preferable to further contain 0.01 to 0.2 parts by weight of any one or more compounds (V) selected from silicone compounds and fluorine compounds, when the total of the components is 100 parts by weight. . The content ratio of the compound (V) is more preferably 0.02 to 0.18 parts by weight, still more preferably 0.03 to 0.15 parts by weight. When the compound (V) is contained in an amount of 0.01 parts by weight or more, the stress remaining at the time of injection molding is alleviated, the etching failure in the etching step and the plating failure in the plating step are eliminated. By dispersing the stress applied to the interface between the plating film and the plating film, the durability such as plating peeling or swelling is further improved. In addition, when compound (V) is compounded in an amount of 0.2 parts by weight or less, it is possible to further suppress appearance defects due to suppression of heat resistance deterioration and bleed out of compound (V) onto the surface of a molded article.
本発明の熱可塑性樹脂組成物に好適に使用されるシリコーン系化合物としては、例えば、ポリジメチルシロキサン、ポリメチルエチルシロキサン、ポリジエチルシロキサン、ポリメチルフェニルシロキサン等のオルガノシロキサン類およびそれらから選択されるいずれか1種類以上を主成分とするシリコーンゴム、テトラエチルシラン、トリメチルヘキシルシラン等のシラン類あるいはトリエチルクロルシラン、ジエチルジクロルシラン、フェニルトリクロルシラン、ジフェニルジクロルシラン等のハロシラン類が挙げられる。成形品表面へのブリードアウト抑制の観点から、ポリジメチルシロキサン、ポリメチルエチルシロキサン、ポリジエチルシロキサン、ポリメチルフェニルシロキサン等のオルガノシロキサン類およびそれらから選択されるいずれか1種類以上を主成分とするシリコーンゴムが好ましく、ポリジメチルシロキサンを主成分とする化合物がさらに好ましく、ポリジメチルシロキサンを主成分とするシリコーンゴムが最も好ましい。ここでいうシリコーンゴムとは、上記オルガノシロキサン類を架橋反応させたものであり、常温から200℃の範囲の温度域の全部または一部の温度域においてゴム性状を示すものを指す。 また、本発明の熱可塑性樹脂組成物に好適に使用されるフッ素系化合物としては、例えば、ポリテトラフルオロエチレン、ポリクロロトリフルオロエチレン、ポリフッ化ビニル、ポリフッ化ビニリデン、テトラフルオロエチレン・ヘキサフルオロプロピレン共重合体、クロロフルオロエチレン・フッ化ビニリデン共重合体などが挙げられるが、ポリテトラフルオロエチレンを主成分とする化合物が最も好ましい。
As silicone type compounds suitably used for the thermoplastic resin composition of the present invention, for example, organosiloxanes such as polydimethylsiloxane, polymethylethylsiloxane, polydiethylsiloxane, polymethylphenylsiloxane and the like and selected from them Examples thereof include silicone rubbers having any one or more kinds as a main component, silanes such as tetraethylsilane and trimethylhexylsilane, and halosilanes such as triethylchlorosilane, diethyldichlorosilane, phenyltrichlorosilane and diphenyldichlorosilane. From the viewpoint of suppression of bleed-out to the surface of a molded article, organosiloxanes such as polydimethylsiloxane, polymethylethylsiloxane, polydiethylsiloxane, polymethylphenylsiloxane and the like and any one or more selected from them as a main component A silicone rubber is preferred, a compound based on polydimethylsiloxane is more preferred, and a silicone rubber based on polydimethylsiloxane is most preferred. The silicone rubber as referred to herein is a product obtained by crosslinking the organosiloxane described above, and refers to one exhibiting rubber properties in the whole or part of the temperature range from normal temperature to 200 ° C. Moreover, as a fluorine-type compound used suitably for the thermoplastic resin composition of this invention, a polytetrafluoroethylene, a polychloro trifluoro ethylene, a polyvinyl fluoride, a polyvinylidene fluoride, tetrafluoroethylene * hexafluoropropylene is mentioned, for example. Copolymers, chlorofluoroethylene / vinylidene fluoride copolymers, etc. may be mentioned, but a compound mainly composed of polytetrafluoroethylene is most preferable.
また、本発明の熱可塑性樹脂組成物には本発明の特性を損なわない範囲で、公知の耐衝撃改良材を使用することができる。使用することができる耐衝撃改良材としては、天然ゴム、低密度ポリエチレンや高密度ポリエチレンなどのポリエチレン、ポリプロピレン、エチレン/プロピレン共重合体、エチレン/メチルアクリレート共重合体、エチレン/エチルアクリレート共重合体、エチレン/酢酸ビニル共重合体、エチレン/グリシジルメタクリレート共重合体、エチレン/ブチルアクリレート共重合体、エチレン/エチルアクリレート/一酸化炭素共重合体、エチレン/グリシジルメタクリレート共重合体、エチレン/メチルアクリレート/グリシジルメタクリレート共重合体、エチレン/ブチルアクリレート/グリシジルメタクリレート共重合体、エチレン/オクテン-1共重合体、エチレン/ブテン-1共重合体などのエチレン系エラストマ、ポリエチレンテレフタレート/ポリ(テトラメチレンオキシド)グリコールブロック共重合体、ポリエチレンテレフタレート/イソフタレート/ポリ(テトラメチレンオキシド)グリコールブロック共重合体などのポリエステルエラストマ、アクリル系のコアシェルエラストマ、スチレン系エラストマが例示される。これらは、必ずしも1種類で使用する必要はなく、2種類以上混合して使用することもできる。
Further, known impact modifiers can be used in the thermoplastic resin composition of the present invention as long as the characteristics of the present invention are not impaired. Impact modifiers which can be used include natural rubber, polyethylene such as low density polyethylene and high density polyethylene, polypropylene, ethylene / propylene copolymer, ethylene / methyl acrylate copolymer, ethylene / ethyl acrylate copolymer , Ethylene / vinyl acetate copolymer, ethylene / glycidyl methacrylate copolymer, ethylene / butyl acrylate copolymer, ethylene / ethyl acrylate / carbon monoxide copolymer, ethylene / glycidyl methacrylate copolymer, ethylene / methyl acrylate / Glycidyl methacrylate copolymer, ethylene / butyl acrylate / glycidyl methacrylate copolymer, ethylene / octene-1 copolymer, ethylene-based elastomer such as ethylene / butene-1 copolymer, polyethylene Terephthalate / poly (tetramethylene oxide) glycol block copolymer, a polyester elastomer such as polyethylene terephthalate / isophthalate / poly (tetramethylene oxide) glycol block copolymer, an acrylic core-shell elastomer, a styrene based elastomer are exemplified. These do not have to be used in one kind, and two or more kinds can be used in combination.
また、本発明の熱可塑性樹脂組成物には本発明の特性を損なわない範囲で、無機充填材を添加することも可能である。無機充填材の形状としては、繊維状、粉末状、粒状、板状などのいずれの形状であってもよい。具体的には、PAN系やピッチ系の炭素繊維、ステンレス繊維、アルミニウム繊維や黄銅繊維などの金属繊維、芳香族ポリアミド繊維などの有機繊維、石膏繊維、セラミック繊維、アスベスト繊維、ジルコニア繊維、アルミナ繊維、シリカ繊維、酸化チタン繊維、炭化ケイ素繊維、ガラス繊維、ロックウール、チタン酸カリウムウィスカー、チタン酸バリウムウィスカー、ホウ酸アルミニウムウィスカー、窒化ケイ素ウィスカーなどの繊維状、ウィスカー状充填材、シリカ、炭酸カルシウム、ガラスビーズ、ガラスマイクロバルーン、クレー、二硫化モリブデン、ワラステナイト、モンモリロナイト、酸化チタン、酸化亜鉛、硫酸バリウム、ポリリン酸カルシウム、グラファイトなどの粉状、粒状の充填材、ガラスフレーク、マイカ、タルク、アルミナフレーク、カオリン、カーボンフレーク、金属フレーク、鱗片状カーボン、黒鉛などの板状充填材が挙げられる。特にガラス繊維の種類は、一般に樹脂の強化用に用いるものなら特に限定はなく、例えば長繊維タイプや短繊維タイプのチョップドストランド、ミルドファイバーなどから選択して用いることができる。なお、上記無機充填材はその表面を公知のカップリング剤(例えば、シラン系カップリング剤、チタネート系カップリング剤など)、その他の表面処理剤で処理して用いることもできる。また、ガラス繊維はエチレン/酢酸ビニル共重合体などの熱可塑性樹脂、エポキシ樹脂などの熱硬化性樹脂で被覆あるいは集束されていてもよい。無機充填材は、エチレン/酢酸ビニル共重合体などの熱可塑性樹脂や、エポキシ樹脂などの熱硬化性樹脂で被覆または集束処理されていてもよく、アミノシランやエポキシシランなどのカップリング剤などで処理されていてもよい。
Moreover, it is also possible to add an inorganic filler to the thermoplastic resin composition of the present invention as long as the characteristics of the present invention are not impaired. The shape of the inorganic filler may be any shape such as fibrous, powdery, granular, and plate-like. Specifically, PAN-based or pitch-based carbon fiber, stainless fiber, metal fiber such as aluminum fiber or brass fiber, organic fiber such as aromatic polyamide fiber, gypsum fiber, ceramic fiber, asbestos fiber, zirconia fiber, alumina fiber Fibers, whisker-like fillers such as silica fiber, titanium oxide fiber, silicon carbide fiber, glass fiber, rock wool, potassium titanate whisker, barium titanate whisker, aluminum borate whisker, silicon nitride whisker, silica, calcium carbonate , Glass beads, Glass microballoon, Clay, Molybdenum disulfide, Wallastenite, Montmorillonite, Titanium oxide, Zinc oxide, Barium sulfate, Calcium polyphosphate, Powdered or granular filler such as graphite, Glass flake, Mica, Talc Alumina flakes, kaolin, carbon flakes, metal flakes, scaly carbon, and plate-like fillers such as graphite. In particular, the type of glass fiber is not particularly limited as long as it is generally used for reinforcing a resin, and can be selected and used from, for example, chopped strands of long fiber type and short fiber type, and milled fibers. In addition, the said inorganic filler can also be used, processing the surface with a well-known coupling agent (For example, a silane coupling agent, a titanate coupling agent etc.), and another surface treatment agent. The glass fibers may be coated or converged with a thermoplastic resin such as ethylene / vinyl acetate copolymer, or a thermosetting resin such as epoxy resin. The inorganic filler may be coated or converged with a thermoplastic resin such as ethylene / vinyl acetate copolymer, or a thermosetting resin such as epoxy resin, and treated with a coupling agent such as aminosilane or epoxysilane. It may be done.
また、本発明の熱可塑性樹脂組成物には本発明の特性を損なわない範囲で、公知の艶消し改良材を使用することができる。使用することができる艶消し改良材としては、不飽和ニトリル-共役ジエン形共重合体ゴムであるアクリロニトリル-ブタジエン共重合体ゴム、アクリロニトリル-イソプレン共重合体ゴム、アクリロニトリル-ブタジエン-イソプレン共重合体ゴム、アクリロニトリル-ブタジエン-アクリル酸共重合体ゴム等、及びこれらのゴム中の共役ジエン単位を水素化したゴムなどが例示される。また、不飽和ニトリル-共役ジエン系共重合体ゴムと併用してもよい他のゴムは、硫黄加硫系や有機過酸化物加硫系等のゴム工業で常用される架橋剤で架橋できるゴムである。その具体例として、ポリブタジエンゴム、スチレン-ブタジエン共重合体ゴム(ランダム、ブロック)、天然ゴム、ポリイソプレンゴム、ポリクロロプレンゴムなどの共役ジエン系重合体ゴム及びその水素化物、EPDM(エチレン・プロピレン・ジエンゴム)等が例示される。
In addition, known matting improvers can be used in the thermoplastic resin composition of the present invention as long as the characteristics of the present invention are not impaired. As a matting modifier which can be used, acrylonitrile-butadiene copolymer rubber which is unsaturated nitrile-conjugated diene type copolymer rubber, acrylonitrile-isoprene copolymer rubber, acrylonitrile-butadiene-isoprene copolymer rubber And acrylonitrile-butadiene-acrylic acid copolymer rubbers, and rubbers obtained by hydrogenating conjugated diene units in these rubbers. In addition, other rubbers which may be used in combination with unsaturated nitrile-conjugated diene copolymer rubbers are rubbers which can be crosslinked by a crosslinking agent commonly used in the rubber industry such as sulfur vulcanization type and organic peroxide vulcanization type. It is. Specific examples thereof include conjugated diene-based polymer rubbers such as polybutadiene rubber, styrene-butadiene copolymer rubber (random, block), natural rubber, polyisoprene rubber, polychloroprene rubber and the like, hydrogenated products thereof, EPDM (ethylene, propylene, etc. Diene rubber etc. are illustrated.
また、本発明の熱可塑性樹脂組成物には本発明の特性を損なわない範囲で、必要に応じて、ヒンダードフェノール系酸化防止剤、含硫黄化合物系酸化防止剤、含リン有機化合物系酸化防止剤、フェノール系、アクリレート系などの熱酸化防止剤、ベンゾトリアゾール系、ベンゾフェノン系、サクシレート系などの紫外線吸収剤、アクリル酸およびそのエステルや、メタクリル酸およびそのエステルからなる重合体または共重合体や変性ポリテトラフルオロエチレンなどの成形加工助剤、デカブロモビフェニルエーテル、テトラブロモビスフェノールA、塩素化ポリエチレン、臭素化エポキシオリゴマー、臭素化ポリカーボネート、三酸化アンチモン、縮合リン酸エステルなどの難燃剤・難燃助剤、銀系抗菌剤に代表される抗菌剤、抗カビ剤、カーボンブラック、酸化チタン、離型剤、潤滑剤、顔料および染料などを添加することもできる。
In the thermoplastic resin composition of the present invention, as required, a hindered phenol-based antioxidant, a sulfur-containing compound-based antioxidant, and a phosphorus-containing organic compound-based antioxidant as long as the characteristics of the present invention are not impaired. , Thermal antioxidants such as phenols and acrylates, UV absorbers such as benzotriazole, benzophenones and succinates, acrylic acids and their esters, and polymers or copolymers of methacrylic acid and their esters Molding processing aids such as modified polytetrafluoroethylene, decabromobiphenyl ether, tetrabromobisphenol A, chlorinated polyethylene, brominated epoxy oligomers, brominated polycarbonate, antimony trioxide, flame retardants and flame retardants such as condensed phosphates Auxiliary agents, antibacterial agents represented by silver antibacterial agents, antifungal agents Carbon black, titanium oxide, release agents, lubricants, and the like can also be added pigments and dyes.
次に本発明の熱可塑性樹脂組成物を得る方法について具体的に例を挙げて説明するが、もちろん本発明の要旨はこの例に限定して解釈されるものではない。
Next, a method for obtaining the thermoplastic resin composition of the present invention will be described by way of specific examples, but the gist of the present invention is of course not construed as being limited to these examples.
本発明の熱可塑性樹脂組成物は、構成する各樹脂成分を溶融混合して得ることができる。溶融混合方法に関しては、特に制限は無いが、加熱装置、ベントを有するシリンダーで単軸または二軸のスクリューを使用して溶融混合する方法などが採用可能である。溶融混合の際の加熱温度は、通常230~320℃の範囲から選択されるが、本発明の目的を損なわない範囲で、溶融混合時の温度勾配等を自由に設定することも可能である。また、二軸のスクリューを用いる場合は、互いに同方向回転でも異方向回転でも良い。また噛み合い型、非噛み合い型のスクリューのいずれでもよい。
The thermoplastic resin composition of the present invention can be obtained by melt-mixing the respective resin components that constitute the composition. The melting and mixing method is not particularly limited, but a heating device and a method of melting and mixing using a single-screw or twin-screw in a cylinder having a vent may be employed. The heating temperature in melt mixing is usually selected from the range of 230 to 320 ° C., but it is also possible to freely set the temperature gradient and the like at the time of melt mixing, as long as the object of the present invention is not impaired. Moreover, when using a biaxial screw, it may be mutually the same direction rotation or different direction rotation. Further, it may be either a meshing type or non meshing type screw.
本発明の熱可塑性樹脂組成物の成形方法については特に限定されないが、射出成形により好適に成形される。射出成形は、好ましくは240~300℃の通常、熱可塑性樹脂組を成形する温度範囲で実施することができる。また、射出成形時の金型温度は、好ましくは30~80℃の通常成形に使用される温度範囲である。
The molding method of the thermoplastic resin composition of the present invention is not particularly limited, but it is suitably molded by injection molding. The injection molding can be carried out preferably at a temperature range of 240 to 300 ° C., which usually forms a thermoplastic resin set. Further, the mold temperature at the time of injection molding is preferably a temperature range used for normal molding of 30 to 80.degree.
本発明の熱可塑性樹脂組成物は、機械特性、耐熱性、流動性、めっき特性、耐久性、めっき成形品外観等のバランスに優れることから、めっきが施される成形品において好適に用いられ、また、大型または形状の複雑な成形品に好適である。すなわち、本発明の樹脂組成物は、厳しいめっき品位が要求されうる自動車内装用のパワーウインドパネル、センターコンソール、センタークラスター、コンソールシャッター、レバーコントローラー、コンソールボックス、インナードアハンドルなどや、自動車用の外装材、すなわちリアスポイラー、グリル、ガーニッシュ、ドアミラー、ルーフ、フェンダー、バンパー、アウタードアハンドルなどへも応用することができる。また電気電子用途、OA機器用途、住宅・建材用途にも好適に使用することができる。
The thermoplastic resin composition of the present invention is suitably used in molded articles to be plated because it is excellent in the balance of mechanical properties, heat resistance, fluidity, plating properties, durability, appearance of plated molded articles, etc. In addition, it is suitable for large sized or complex shaped articles. That is, the resin composition of the present invention can be required for automobile interior power window panels, center consoles, center clusters, console shutters, lever controllers, console boxes, inner door handles, etc. for automobile interiors where severe plating quality may be required. It can also be applied to materials such as rear spoilers, grills, garnishes, door mirrors, roofs, fenders, bumpers, outer door handles etc. In addition, it can be suitably used for electrical and electronic applications, OA equipment applications, housing and building materials applications.
本発明をさらに具体的に説明するため、以下に実施例を挙げるが、これらの実施例は本発明を何ら制限するものではなく、種々の変形が可能である。まず、実施例および比較例において用いられた各種物性の評価方法を下記する。
EXAMPLES The present invention will be further illustrated by way of the following examples, which should not be construed as limiting the present invention in any way, and various modifications may be made. First, evaluation methods of various physical properties used in Examples and Comparative Examples will be described below.
(1)耐衝撃性
組成物ペレットを、シリンダー温度を250℃、金型温度を60℃に設定した射出成形機を用いて、JIS K 7139に規定される多目的試験片タイプA1を成形し、これを切り出したタイプB2試験片を用いて、ISO179/1eAに準拠してシャルピー衝撃強度を測定した。 (1) Impact resistance Multi-purpose test specimen type A1 specified in JIS K 7139 is molded using an injection molding machine in which a cylinder temperature is set to 250 ° C. and a mold temperature is set to 60 ° C. The Charpy impact strength was measured in accordance with ISO 179/1 eA using a type B2 test piece obtained by cutting
組成物ペレットを、シリンダー温度を250℃、金型温度を60℃に設定した射出成形機を用いて、JIS K 7139に規定される多目的試験片タイプA1を成形し、これを切り出したタイプB2試験片を用いて、ISO179/1eAに準拠してシャルピー衝撃強度を測定した。 (1) Impact resistance Multi-purpose test specimen type A1 specified in JIS K 7139 is molded using an injection molding machine in which a cylinder temperature is set to 250 ° C. and a mold temperature is set to 60 ° C. The Charpy impact strength was measured in accordance with ISO 179/1 eA using a type B2 test piece obtained by cutting
(2)流動性
組成物ペレットをISO1133に準拠して、温度240℃、98N荷重条件でメルトフローレートを測定した。 (2) Flowability Based on ISO 1133, the melt flow rate of the composition pellet was measured at a temperature of 240 ° C. and a load of 98 N.
組成物ペレットをISO1133に準拠して、温度240℃、98N荷重条件でメルトフローレートを測定した。 (2) Flowability Based on ISO 1133, the melt flow rate of the composition pellet was measured at a temperature of 240 ° C. and a load of 98 N.
(3)耐熱性
熱変形温度:ISO75-2(1.8MPa条件で測定)に準拠して測定した。試験片は、シリンダー温度を250℃、金型温度を60℃に設定した射出成形機を用いて、JIS K 7139に規定される多目的試験片タイプA1を成形して得た。 (3) Heat resistance Thermal deformation temperature: Measured in accordance with ISO 75-2 (measured at 1.8 MPa conditions). The test piece was obtained by molding a multipurpose test piece type A1 defined in JIS K 7139 using an injection molding machine in which a cylinder temperature is set to 250 ° C. and a mold temperature is set to 60 ° C.
熱変形温度:ISO75-2(1.8MPa条件で測定)に準拠して測定した。試験片は、シリンダー温度を250℃、金型温度を60℃に設定した射出成形機を用いて、JIS K 7139に規定される多目的試験片タイプA1を成形して得た。 (3) Heat resistance Thermal deformation temperature: Measured in accordance with ISO 75-2 (measured at 1.8 MPa conditions). The test piece was obtained by molding a multipurpose test piece type A1 defined in JIS K 7139 using an injection molding machine in which a cylinder temperature is set to 250 ° C. and a mold temperature is set to 60 ° C.
(4)めっき特性
シリンダー温度を250℃、金型温度を60℃に設定した射出成形機を用いて、127mm×76mm×3mmtの試験片を成形して得た。80℃で12時間熱処理後、試験片を奥野製薬工業株式会社製「トッププラコンBOW」10ml/Lおよび98%硫酸30ml/Lの混液に浸漬、脱脂洗浄した。その後、三酸化クロム溶液400g/Lおよび98%硫酸220ml/Lの68℃混液に15分間浸漬し、エッチング処理した。その後、奥野製薬工業株式会社製「トップキャッチCR-200」220ml/Lおよび35%塩酸50ml/Lの25℃混液に2分間浸漬し、中和処理した。その後、奥野製薬工業株式会社製「キャタリストC-7」20ml/Lおよび35%塩酸200ml/Lの35℃混液に5分間浸漬し、キャタリスト(触媒吸着)処理した。その後、35%塩酸100ml/Lの40℃水溶液に5分間浸漬し、アクセレーター(パラジウム還元)処理した。その後、奥野製薬工業株式会社製「化学ニッケルSEP」の35℃溶液に6分間浸漬し、ニッケル金属層を形成させた。その後、奥野製薬工業株式会社製「ANCアクチ」10ml/Lおよび98%硫酸30ml/Lの25℃混液に30秒浸漬し、同置換した。最後に奥野製薬工業株式会社製「トップダンクCuX」の25℃溶液に浸漬し、3A/dm2の電流値で、2.5時間硫酸銅めっきした。めっき後試験片に関して、試験片中央部に、カッターにて、長さ60mm、幅10mmの切れ込みを入れ、JIS H 8630に従い、50mm/分のクロスヘッド速度にて、ピーリング(90°引き剥がし)強度測定を実施した。ピーリング強度が大きい方が、めっき皮膜と樹脂の密着性に優れると言える。また、めっき後試験片の外観を下記の基準にて、5段階で評価した。なお、数字が大きいほど、めっき皮膜形成に優れると言える。
めっき皮膜形成率が試験片面積全体に対して100% ・・・ 5
めっき皮膜形成率が試験片面積全体に対して80%以上、100%未満 ・・ 4
めっき皮膜形成率が試験片面積全体に対して60%以上、80%未満 ・・・ 3
めっき皮膜形成率が試験片面積全体に対して40%以上、60%未満 ・・・ 2
めっき皮膜形成率が試験片面積全体に対して20%以上、40%未満 ・・・ 1 。 (4) Plating characteristics A test piece of 127 mm × 76 mm × 3 mmt was obtained by molding using an injection molding machine in which the cylinder temperature was set to 250 ° C. and the mold temperature was set to 60 ° C. After heat treatment at 80 ° C. for 12 hours, the test piece was immersed in a mixed solution of “Top Placon BOW” 10 ml / L and 98% sulfuric acid 30 ml / L manufactured by Okuno Pharmaceutical Co., Ltd., and degreased and washed. Then, it was immersed in a 68 ° C. mixture of a chromium trioxide solution 400 g / L and a 98% sulfuric acid 220 ml / L for 15 minutes for etching. Thereafter, the resultant was immersed for 2 minutes in a mixed solution of 220 ml / L "Top Catch CR-200" manufactured by Okuno Pharmaceutical Co., Ltd. and 50 ml / L of 35% hydrochloric acid for 2 minutes for neutralization treatment. Then, it was immersed for 5 minutes in a mixed solution of 20 ml / L of "Catalyst C-7" manufactured by Okuno Pharmaceutical Industry Co., Ltd. and 200 ml / L of 35% hydrochloric acid for 5 minutes to perform catalyst (catalyst adsorption) treatment. Then, it was immersed in a 40 ° C. aqueous solution of 100 ml / L of 35% hydrochloric acid for 5 minutes to perform accelerator (palladium reduction) treatment. Thereafter, it was immersed in a 35 ° C. solution of “chemical nickel SEP” manufactured by Okuno Pharmaceutical Co., Ltd. for 6 minutes to form a nickel metal layer. Then, it was immersed in a 25 ° C. mixture of 10 ml / L of “ANC Act” manufactured by Okuno Pharmaceutical Industry Co., Ltd. and 30 ml / L of 98% sulfuric acid for 30 seconds for substitution. Finally, it was immersed in a 25 ° C. solution of “Top Dunk CuX” manufactured by Okuno Pharmaceutical Co., Ltd., and plated with copper sulfate at a current value of 3 A / dm 2 for 2.5 hours. For the test piece after plating, insert a 60 mm long and 10 mm wide cut with a cutter in the center of the test piece and peel (90 ° peel) strength at a crosshead speed of 50 mm / min according to JIS H 8630 The measurement was performed. It can be said that the larger the peeling strength, the better the adhesion between the plating film and the resin. Moreover, the external appearance of the test piece after plating was evaluated in five steps by the following reference | standard. In addition, it can be said that it is excellent in plating film formation, so that a number is large.
The plating film formation rate is 100% to the whole test piece area 5
The plating film formation rate is 80% or more and less than 100% with respect to the entire specimen area · · 4
The plating film formation rate is 60% or more and less than 80% with respect to the entire specimen area ··· 3
The plating film formation rate is 40% or more and less than 60% with respect to the entire test piece area ··· 2
The plating film formation rate is 20% or more and less than 40% with respect to the entire test piece area ... 1.
シリンダー温度を250℃、金型温度を60℃に設定した射出成形機を用いて、127mm×76mm×3mmtの試験片を成形して得た。80℃で12時間熱処理後、試験片を奥野製薬工業株式会社製「トッププラコンBOW」10ml/Lおよび98%硫酸30ml/Lの混液に浸漬、脱脂洗浄した。その後、三酸化クロム溶液400g/Lおよび98%硫酸220ml/Lの68℃混液に15分間浸漬し、エッチング処理した。その後、奥野製薬工業株式会社製「トップキャッチCR-200」220ml/Lおよび35%塩酸50ml/Lの25℃混液に2分間浸漬し、中和処理した。その後、奥野製薬工業株式会社製「キャタリストC-7」20ml/Lおよび35%塩酸200ml/Lの35℃混液に5分間浸漬し、キャタリスト(触媒吸着)処理した。その後、35%塩酸100ml/Lの40℃水溶液に5分間浸漬し、アクセレーター(パラジウム還元)処理した。その後、奥野製薬工業株式会社製「化学ニッケルSEP」の35℃溶液に6分間浸漬し、ニッケル金属層を形成させた。その後、奥野製薬工業株式会社製「ANCアクチ」10ml/Lおよび98%硫酸30ml/Lの25℃混液に30秒浸漬し、同置換した。最後に奥野製薬工業株式会社製「トップダンクCuX」の25℃溶液に浸漬し、3A/dm2の電流値で、2.5時間硫酸銅めっきした。めっき後試験片に関して、試験片中央部に、カッターにて、長さ60mm、幅10mmの切れ込みを入れ、JIS H 8630に従い、50mm/分のクロスヘッド速度にて、ピーリング(90°引き剥がし)強度測定を実施した。ピーリング強度が大きい方が、めっき皮膜と樹脂の密着性に優れると言える。また、めっき後試験片の外観を下記の基準にて、5段階で評価した。なお、数字が大きいほど、めっき皮膜形成に優れると言える。
めっき皮膜形成率が試験片面積全体に対して100% ・・・ 5
めっき皮膜形成率が試験片面積全体に対して80%以上、100%未満 ・・ 4
めっき皮膜形成率が試験片面積全体に対して60%以上、80%未満 ・・・ 3
めっき皮膜形成率が試験片面積全体に対して40%以上、60%未満 ・・・ 2
めっき皮膜形成率が試験片面積全体に対して20%以上、40%未満 ・・・ 1 。 (4) Plating characteristics A test piece of 127 mm × 76 mm × 3 mmt was obtained by molding using an injection molding machine in which the cylinder temperature was set to 250 ° C. and the mold temperature was set to 60 ° C. After heat treatment at 80 ° C. for 12 hours, the test piece was immersed in a mixed solution of “Top Placon BOW” 10 ml / L and 98% sulfuric acid 30 ml / L manufactured by Okuno Pharmaceutical Co., Ltd., and degreased and washed. Then, it was immersed in a 68 ° C. mixture of a chromium trioxide solution 400 g / L and a 98% sulfuric acid 220 ml / L for 15 minutes for etching. Thereafter, the resultant was immersed for 2 minutes in a mixed solution of 220 ml / L "Top Catch CR-200" manufactured by Okuno Pharmaceutical Co., Ltd. and 50 ml / L of 35% hydrochloric acid for 2 minutes for neutralization treatment. Then, it was immersed for 5 minutes in a mixed solution of 20 ml / L of "Catalyst C-7" manufactured by Okuno Pharmaceutical Industry Co., Ltd. and 200 ml / L of 35% hydrochloric acid for 5 minutes to perform catalyst (catalyst adsorption) treatment. Then, it was immersed in a 40 ° C. aqueous solution of 100 ml / L of 35% hydrochloric acid for 5 minutes to perform accelerator (palladium reduction) treatment. Thereafter, it was immersed in a 35 ° C. solution of “chemical nickel SEP” manufactured by Okuno Pharmaceutical Co., Ltd. for 6 minutes to form a nickel metal layer. Then, it was immersed in a 25 ° C. mixture of 10 ml / L of “ANC Act” manufactured by Okuno Pharmaceutical Industry Co., Ltd. and 30 ml / L of 98% sulfuric acid for 30 seconds for substitution. Finally, it was immersed in a 25 ° C. solution of “Top Dunk CuX” manufactured by Okuno Pharmaceutical Co., Ltd., and plated with copper sulfate at a current value of 3 A / dm 2 for 2.5 hours. For the test piece after plating, insert a 60 mm long and 10 mm wide cut with a cutter in the center of the test piece and peel (90 ° peel) strength at a crosshead speed of 50 mm / min according to JIS H 8630 The measurement was performed. It can be said that the larger the peeling strength, the better the adhesion between the plating film and the resin. Moreover, the external appearance of the test piece after plating was evaluated in five steps by the following reference | standard. In addition, it can be said that it is excellent in plating film formation, so that a number is large.
The plating film formation rate is 100% to the whole test piece area 5
The plating film formation rate is 80% or more and less than 100% with respect to the entire specimen area · · 4
The plating film formation rate is 60% or more and less than 80% with respect to the entire specimen area ··· 3
The plating film formation rate is 40% or more and less than 60% with respect to the entire test piece area ··· 2
The plating film formation rate is 20% or more and less than 40% with respect to the entire test piece area ... 1.
(5)めっき後成形品耐久性
シリンダー温度を250℃、金型温度を60℃に設定した射出成形機を用いて、50mm×90mm、厚さ1mmと2.5mmの段付き試験片を成形して得た。エッチング処理およびめっき処理は、上記(4)項の条件と同条件で実施し、めっき後試験片を得た。得られためっき後試験片を、-30℃で1時間処理後、40分かけて70℃まで昇温、70℃で1時間処理後、40分かけて-30℃まで降温した。このサイクルを1サイクルとして、200サイクルまでのヒートサイクル耐久性試験を実施した。耐久性については、めっき試験片の外観を、下記の基準にて、評価した。
200サイクルまで、試験片に異常(クラックや膨れ)なし ・・・ ◎
150サイクル以上、200サイクル未満で試験片に異常(クラックや膨れ)発生
・・・ ○
100サイクル以上、150サイクル未満で試験片に異常(クラックや膨れ)発生
・・・ △
100サイクル未満で試験片に異常(クラックや膨れ)発生 ・・・ × 。 (5) Durability of molded articles after plating Using an injection molding machine with a cylinder temperature of 250 ° C. and a mold temperature of 60 ° C., 50 mm × 90 mm, 1 mm thick and 2.5 mm thick stepped test pieces are molded I got it. The etching treatment and the plating treatment were carried out under the same conditions as the condition (4) above to obtain a post-plating test piece. The obtained post-plating test piece was treated at -30.degree. C. for 1 hour, heated to 70.degree. C. in 40 minutes, treated at 70.degree. C. for 1 hour, and cooled to -30.degree. C. in 40 minutes. The heat cycle durability test up to 200 cycles was carried out with this cycle as one cycle. With respect to the durability, the appearance of the plated test piece was evaluated based on the following criteria.
There is no abnormality (crack or swelling) in the test piece up to 200 cycles.
Abnormality (crack or blister) occurs in the test piece in 150 cycles or more and less than 200 cycles ...
Abnormality (crack or blister) occurs in the test piece in 100 cycles or more and less than 150 cycles ...
Abnormality (crack or swelling) occurs in the test piece in less than 100 cycles · · · ×.
シリンダー温度を250℃、金型温度を60℃に設定した射出成形機を用いて、50mm×90mm、厚さ1mmと2.5mmの段付き試験片を成形して得た。エッチング処理およびめっき処理は、上記(4)項の条件と同条件で実施し、めっき後試験片を得た。得られためっき後試験片を、-30℃で1時間処理後、40分かけて70℃まで昇温、70℃で1時間処理後、40分かけて-30℃まで降温した。このサイクルを1サイクルとして、200サイクルまでのヒートサイクル耐久性試験を実施した。耐久性については、めっき試験片の外観を、下記の基準にて、評価した。
200サイクルまで、試験片に異常(クラックや膨れ)なし ・・・ ◎
150サイクル以上、200サイクル未満で試験片に異常(クラックや膨れ)発生
・・・ ○
100サイクル以上、150サイクル未満で試験片に異常(クラックや膨れ)発生
・・・ △
100サイクル未満で試験片に異常(クラックや膨れ)発生 ・・・ × 。 (5) Durability of molded articles after plating Using an injection molding machine with a cylinder temperature of 250 ° C. and a mold temperature of 60 ° C., 50 mm × 90 mm, 1 mm thick and 2.5 mm thick stepped test pieces are molded I got it. The etching treatment and the plating treatment were carried out under the same conditions as the condition (4) above to obtain a post-plating test piece. The obtained post-plating test piece was treated at -30.degree. C. for 1 hour, heated to 70.degree. C. in 40 minutes, treated at 70.degree. C. for 1 hour, and cooled to -30.degree. C. in 40 minutes. The heat cycle durability test up to 200 cycles was carried out with this cycle as one cycle. With respect to the durability, the appearance of the plated test piece was evaluated based on the following criteria.
There is no abnormality (crack or swelling) in the test piece up to 200 cycles.
Abnormality (crack or blister) occurs in the test piece in 150 cycles or more and less than 200 cycles ...
Abnormality (crack or blister) occurs in the test piece in 100 cycles or more and less than 150 cycles ...
Abnormality (crack or swelling) occurs in the test piece in less than 100 cycles · · · ×.
<ポリカーボネート系樹脂(I)>
・ポリカーボネート系樹脂(I-1);商品名「“ユーピロン”(登録商標)S-2000」、粘度平均分子量:24,000、三菱エンジニアリングプラスチック(株)製。 <Polycarbonate resin (I)>
-Polycarbonate resin (I-1); trade name "" Eupilon "(registered trademark) S-2000", viscosity average molecular weight: 24,000, manufactured by Mitsubishi Engineering Plastics Co., Ltd.
・ポリカーボネート系樹脂(I-1);商品名「“ユーピロン”(登録商標)S-2000」、粘度平均分子量:24,000、三菱エンジニアリングプラスチック(株)製。 <Polycarbonate resin (I)>
-Polycarbonate resin (I-1); trade name "" Eupilon "(registered trademark) S-2000", viscosity average molecular weight: 24,000, manufactured by Mitsubishi Engineering Plastics Co., Ltd.
<グラフト共重合体(II)の調製>
ポリブタジエンラテックス(重量平均粒子径350nmと800nmの2種併用し、比率8:2)45重量%(固形分換算)の存在下で、スチレン40重量%とアクリロニトリル15重量%からなる単量体混合物を、ステアリン酸カリウムを使用して乳化重合してゴム強化スチレン・アクリロニトリル共重合体ラテックスを得た。これを、90℃の温度の0.3%希硫酸水溶液中に添加して凝集後、水酸化ナトリウム水溶液により中和後に洗浄・脱水・乾燥工程を経て、グラフト共重合体(II-1)を調製した。グラフト率は25%であった。 <Preparation of Graft Copolymer (II)>
A monomer mixture comprising 40% by weight of styrene and 15% by weight of acrylonitrile in the presence of 45% by weight (in terms of solid content) of polybutadiene latex (2 types of weight average particle diameters of 350 nm and 800 nm used in combination, ratio 8: 2) Emulsion polymerization was carried out using potassium stearate to obtain a rubber-reinforced styrene-acrylonitrile copolymer latex. The mixture is added to a 0.3% dilute aqueous solution of sulfuric acid at a temperature of 90 ° C., coagulated, neutralized by an aqueous solution of sodium hydroxide, and subjected to washing, dehydration, and drying steps to obtain graft copolymer (II-1). Prepared. The grafting rate was 25%.
ポリブタジエンラテックス(重量平均粒子径350nmと800nmの2種併用し、比率8:2)45重量%(固形分換算)の存在下で、スチレン40重量%とアクリロニトリル15重量%からなる単量体混合物を、ステアリン酸カリウムを使用して乳化重合してゴム強化スチレン・アクリロニトリル共重合体ラテックスを得た。これを、90℃の温度の0.3%希硫酸水溶液中に添加して凝集後、水酸化ナトリウム水溶液により中和後に洗浄・脱水・乾燥工程を経て、グラフト共重合体(II-1)を調製した。グラフト率は25%であった。 <Preparation of Graft Copolymer (II)>
A monomer mixture comprising 40% by weight of styrene and 15% by weight of acrylonitrile in the presence of 45% by weight (in terms of solid content) of polybutadiene latex (2 types of weight average particle diameters of 350 nm and 800 nm used in combination, ratio 8: 2) Emulsion polymerization was carried out using potassium stearate to obtain a rubber-reinforced styrene-acrylonitrile copolymer latex. The mixture is added to a 0.3% dilute aqueous solution of sulfuric acid at a temperature of 90 ° C., coagulated, neutralized by an aqueous solution of sodium hydroxide, and subjected to washing, dehydration, and drying steps to obtain graft copolymer (II-1). Prepared. The grafting rate was 25%.
<ビニル系共重合体(III)の調製>
・スチレン69重量%とアクリロニトリル31重量%からなる単量体混合物を連続塊状重合して、ビニル系共重合体(III-1)を調製した。得られたビニル系共重合体(III-1)の固有粘度は0.53dl/gであり、共重合体中のアクリロニトリル由来部分の含有量は、31重量%であった。
・スチレン76重量%とアクリロニトリル24重量%からなる単量体混合物を懸濁重合して得られたスラリーを洗浄・脱水・乾燥工程を経て、ビニル系共重合体(III-2)を調製した。得られたビニル系共重合体(III-2)の固有粘度は0.42dl/gであり、アクリロニトリル由来部分の含有量は、24重量%であった。
・スチレン63.5重量%とアクリロニトリル36.5重量%からなる単量体混合物を懸濁重合して得られたスラリーを洗浄・脱水・乾燥工程を経て、ビニル系共重合体(III-3)を調製した。得られたビニル系共重合体(III-3)の固有粘度は0.49dl/gであり、アクリロニトリル由来部分の含有量は、36.5重量%であった。 <Preparation of vinyl copolymer (III)>
A vinyl-based copolymer (III-1) was prepared by continuous bulk polymerization of a monomer mixture consisting of 69% by weight of styrene and 31% by weight of acrylonitrile. The intrinsic viscosity of the resulting vinyl copolymer (III-1) was 0.53 dl / g, and the content of the acrylonitrile-derived portion in the copolymer was 31% by weight.
A slurry obtained by suspension polymerization of a monomer mixture consisting of 76% by weight of styrene and 24% by weight of acrylonitrile was subjected to washing, dewatering and drying steps to prepare a vinyl-based copolymer (III-2). The intrinsic viscosity of the obtained vinyl copolymer (III-2) was 0.42 dl / g, and the content of the acrylonitrile-derived portion was 24% by weight.
A slurry obtained by suspension polymerization of a monomer mixture consisting of 63.5% by weight of styrene and 36.5% by weight of acrylonitrile is subjected to washing, dehydration and drying steps to obtain a vinyl copolymer (III-3) Was prepared. The intrinsic viscosity of the resulting vinyl copolymer (III-3) was 0.49 dl / g, and the content of the acrylonitrile-derived portion was 36.5% by weight.
・スチレン69重量%とアクリロニトリル31重量%からなる単量体混合物を連続塊状重合して、ビニル系共重合体(III-1)を調製した。得られたビニル系共重合体(III-1)の固有粘度は0.53dl/gであり、共重合体中のアクリロニトリル由来部分の含有量は、31重量%であった。
・スチレン76重量%とアクリロニトリル24重量%からなる単量体混合物を懸濁重合して得られたスラリーを洗浄・脱水・乾燥工程を経て、ビニル系共重合体(III-2)を調製した。得られたビニル系共重合体(III-2)の固有粘度は0.42dl/gであり、アクリロニトリル由来部分の含有量は、24重量%であった。
・スチレン63.5重量%とアクリロニトリル36.5重量%からなる単量体混合物を懸濁重合して得られたスラリーを洗浄・脱水・乾燥工程を経て、ビニル系共重合体(III-3)を調製した。得られたビニル系共重合体(III-3)の固有粘度は0.49dl/gであり、アクリロニトリル由来部分の含有量は、36.5重量%であった。 <Preparation of vinyl copolymer (III)>
A vinyl-based copolymer (III-1) was prepared by continuous bulk polymerization of a monomer mixture consisting of 69% by weight of styrene and 31% by weight of acrylonitrile. The intrinsic viscosity of the resulting vinyl copolymer (III-1) was 0.53 dl / g, and the content of the acrylonitrile-derived portion in the copolymer was 31% by weight.
A slurry obtained by suspension polymerization of a monomer mixture consisting of 76% by weight of styrene and 24% by weight of acrylonitrile was subjected to washing, dewatering and drying steps to prepare a vinyl-based copolymer (III-2). The intrinsic viscosity of the obtained vinyl copolymer (III-2) was 0.42 dl / g, and the content of the acrylonitrile-derived portion was 24% by weight.
A slurry obtained by suspension polymerization of a monomer mixture consisting of 63.5% by weight of styrene and 36.5% by weight of acrylonitrile is subjected to washing, dehydration and drying steps to obtain a vinyl copolymer (III-3) Was prepared. The intrinsic viscosity of the resulting vinyl copolymer (III-3) was 0.49 dl / g, and the content of the acrylonitrile-derived portion was 36.5% by weight.
<メタクリル酸メチル-ブタジエン-スチレン共重合体(IV)>
・MBS樹脂(IV-1);商品名「“カネエース”M732」、(株)カネカ製。 <Methyl methacrylate-butadiene-styrene copolymer (IV)>
-MBS resin (IV-1); brand name "" Kane ace "M732, Kaneka Co., Ltd. make.
・MBS樹脂(IV-1);商品名「“カネエース”M732」、(株)カネカ製。 <Methyl methacrylate-butadiene-styrene copolymer (IV)>
-MBS resin (IV-1); brand name "" Kane ace "M732, Kaneka Co., Ltd. make.
<化合物(V)>
・シリコーン系化合物(V-1);シリコーンオイル、商品名「SH200」、東レ・ダウコーニング(株)製。
・シリコーン系化合物(V-2);シリコーンゴム、商品名「EP-2720」、東レ・ダウコーニング(株)製。 <Compound (V)>
Silicone compound (V-1); silicone oil, trade name "SH200", manufactured by Toray Dow Corning Co., Ltd.
Silicone compound (V-2): silicone rubber, trade name "EP-2720", manufactured by Toray Dow Corning Co., Ltd.
・シリコーン系化合物(V-1);シリコーンオイル、商品名「SH200」、東レ・ダウコーニング(株)製。
・シリコーン系化合物(V-2);シリコーンゴム、商品名「EP-2720」、東レ・ダウコーニング(株)製。 <Compound (V)>
Silicone compound (V-1); silicone oil, trade name "SH200", manufactured by Toray Dow Corning Co., Ltd.
Silicone compound (V-2): silicone rubber, trade name "EP-2720", manufactured by Toray Dow Corning Co., Ltd.
<その他添加剤>
・酸性化合物;0.5mol/Lリン酸。 <Other additives>
Acidic compound: 0.5 mol / L phosphoric acid.
・酸性化合物;0.5mol/Lリン酸。 <Other additives>
Acidic compound: 0.5 mol / L phosphoric acid.
(実施例1~12、比較例1~9)
ポリカーボネート系樹脂(I)、グラフト共重合体(II)、ビニル系共重合体(III)、メタクリル酸メチル-ブタジエン-スチレン共重合体(IV)、化合物(V)およびその他添加剤を、表1または表2に示した比で配合し、スクリュー径30mmの同方向回転の二軸押出機(温度範囲:240~260℃)で溶融混練を行い、ペレットを得た。得られたペレットから、射出成形機(成形温度250℃、金型温度60℃)を用いて試験片を作製し、前述の方法により評価を行った。なお、表中ポリカーボネート系樹脂(I)、グラフト共重合体(II)、ビニル系共重合体(III)、メタクリル酸メチル-ブタジエン-スチレン共重合体(IV)の割合(wt.%)はこれら成分の含有量の合計を100重量%としたときの割合である。また、化合物(V)およびその他添加剤の含有量は、ポリカーボネート樹脂(I)、グラフト共重合体(II)、ビニル系共重合体(III)メタクリル酸メチル-ブタジエン-スチレン共重合体(IV)の合計重量を100重量部としたときの含有量(重量部)である。 (Examples 1 to 12, Comparative Examples 1 to 9)
Table 1 shows polycarbonate resin (I), graft copolymer (II), vinyl copolymer (III), methyl methacrylate-butadiene-styrene copolymer (IV), compound (V) and other additives. Alternatively, the mixture was compounded at the ratio shown in Table 2 and melt-kneaded using a twin screw extruder (temperature range: 240 to 260 ° C.) of the same direction rotation with a screw diameter of 30 mm to obtain pellets. Test pieces were produced from the obtained pellets using an injection molding machine (molding temperature 250 ° C., mold temperature 60 ° C.), and evaluation was performed by the above-mentioned method. In the table, the proportion (wt.%) Of polycarbonate resin (I), graft copolymer (II), vinyl copolymer (III) and methyl methacrylate-butadiene-styrene copolymer (IV) It is a ratio when the sum total of content of a component is 100 weight%. Further, the content of the compound (V) and other additives is polycarbonate resin (I), graft copolymer (II), vinyl copolymer (III) methyl methacrylate-butadiene-styrene copolymer (IV) Content (parts by weight) based on 100 parts by weight of the total weight of
ポリカーボネート系樹脂(I)、グラフト共重合体(II)、ビニル系共重合体(III)、メタクリル酸メチル-ブタジエン-スチレン共重合体(IV)、化合物(V)およびその他添加剤を、表1または表2に示した比で配合し、スクリュー径30mmの同方向回転の二軸押出機(温度範囲:240~260℃)で溶融混練を行い、ペレットを得た。得られたペレットから、射出成形機(成形温度250℃、金型温度60℃)を用いて試験片を作製し、前述の方法により評価を行った。なお、表中ポリカーボネート系樹脂(I)、グラフト共重合体(II)、ビニル系共重合体(III)、メタクリル酸メチル-ブタジエン-スチレン共重合体(IV)の割合(wt.%)はこれら成分の含有量の合計を100重量%としたときの割合である。また、化合物(V)およびその他添加剤の含有量は、ポリカーボネート樹脂(I)、グラフト共重合体(II)、ビニル系共重合体(III)メタクリル酸メチル-ブタジエン-スチレン共重合体(IV)の合計重量を100重量部としたときの含有量(重量部)である。 (Examples 1 to 12, Comparative Examples 1 to 9)
Table 1 shows polycarbonate resin (I), graft copolymer (II), vinyl copolymer (III), methyl methacrylate-butadiene-styrene copolymer (IV), compound (V) and other additives. Alternatively, the mixture was compounded at the ratio shown in Table 2 and melt-kneaded using a twin screw extruder (temperature range: 240 to 260 ° C.) of the same direction rotation with a screw diameter of 30 mm to obtain pellets. Test pieces were produced from the obtained pellets using an injection molding machine (molding temperature 250 ° C., mold temperature 60 ° C.), and evaluation was performed by the above-mentioned method. In the table, the proportion (wt.%) Of polycarbonate resin (I), graft copolymer (II), vinyl copolymer (III) and methyl methacrylate-butadiene-styrene copolymer (IV) It is a ratio when the sum total of content of a component is 100 weight%. Further, the content of the compound (V) and other additives is polycarbonate resin (I), graft copolymer (II), vinyl copolymer (III) methyl methacrylate-butadiene-styrene copolymer (IV) Content (parts by weight) based on 100 parts by weight of the total weight of
実施例1~12、すなわち本発明の熱可塑性樹脂組成物は、機械特性、耐熱性、流動性、めっき特性、耐久性、めっき成形品外観等のバランスに優れる。一方、実施例1~2と比較例1~2の比較から、メタクリル酸メチル-ブタジエン-スチレン共重合体を配合しないと、耐衝撃性が低下すると共に、めっき特性であるピーリング強度が低下し、めっき後外観が悪化し、さらに耐久性にも劣ることがわかる。また、実施例2~6と比較例3~4の比較から、ポリカーボネート系樹脂(I)の含有量が本発明で規定する範囲より少ないと耐衝撃性、耐熱性が低下し、多いとめっき特性であるピーリング強度が低下し、めっき後外観が悪化し、さらに耐久性にも劣ることがわかる。また、実施例2~6と比較例5、9との比較から、ビニル系共重合体(III)の含有量が本発明で規定する範囲を外れると、めっき特性であるピーリング強度が低下し、めっき後外観が悪化し、さらに耐久性にも劣ることがわかる。また、実施例2~6と比較例6との比較から、メタクリル酸メチル-ブタジエン-スチレン共重合体(IV)配合量およびポリカーボネート系樹脂(I)に対するメタクリル酸メチル-ブタジエン-スチレン共重合体(IV)の含有割合が本発明で規定する範囲よりも大きいと、耐衝撃性および耐熱性が低下する。実施例2~6と比較例7~8との比較から、グラフト共重合体(II)の含有量が本発明で規定する範囲よりも小さいと、めっき特性であるピーリング強度が低下し、めっき後外観が悪化し、さらに耐久性にも劣り、大きいと耐衝撃性、耐熱性とめっき特性、耐久性のバランスにおとることがわかる。また、実施例5と実施例12との比較から、化合物(V)を(V-1)から、(V-2)に変更することによって、ピーリング強度、外観、耐久性にさらに優れることがわかる。
The thermoplastic resin composition of Examples 1 to 12, that is, the present invention is excellent in the balance of mechanical properties, heat resistance, fluidity, plating properties, durability, appearance of a plated molded product, and the like. On the other hand, from the comparison of Examples 1 and 2 and Comparative Examples 1 and 2, when the methyl methacrylate-butadiene-styrene copolymer is not blended, the impact resistance is lowered and the peeling strength which is the plating characteristic is lowered. It can be seen that the appearance after plating is deteriorated and the durability is also inferior. Further, from the comparison of Examples 2 to 6 and Comparative Examples 3 to 4, when the content of the polycarbonate resin (I) is less than the range specified in the present invention, the impact resistance and the heat resistance decrease, and when it is large, the plating characteristics It is understood that the peeling strength is lowered, the appearance after plating is deteriorated, and the durability is also deteriorated. Further, from the comparison of Examples 2 to 6 and Comparative Examples 5 and 9, when the content of the vinyl copolymer (III) is out of the range specified in the present invention, the peeling strength which is the plating property is lowered, It can be seen that the appearance after plating is deteriorated and the durability is also inferior. Further, from the comparison of Examples 2 to 6 and Comparative Example 6, the blending amount of methyl methacrylate-butadiene-styrene copolymer (IV) and the methyl methacrylate-butadiene-styrene copolymer to polycarbonate resin (I) ( When the content ratio of IV) is larger than the range specified in the present invention, the impact resistance and the heat resistance are lowered. From the comparison of Examples 2 to 6 and Comparative Examples 7 to 8, when the content of the graft copolymer (II) is smaller than the range specified in the present invention, the peeling strength which is the plating property decreases, and after plating The appearance is deteriorated and further the durability is inferior, and when it is large, it is understood that the balance between the impact resistance, the heat resistance, the plating characteristics and the durability is taken. Further, from the comparison of Example 5 and Example 12, it is understood that the peeling strength, the appearance and the durability are further excellent by changing the compound (V) from (V-1) to (V-2). .
本発明の熱可塑性樹脂組成物は、機械特性、耐熱性、流動性、めっき特性、耐久性、めっき成形品外観等のバランスに優れることから、めっきが施される成形品において好適に用いられ、また、大型または形状の複雑なめっき成形品に好適である。すなわち、本発明の樹脂組成物は、厳しいめっき品位が要求されうる自動車内装用のパワーウインドパネル、センターコンソール、センタークラスター、コンソールシャッター、レバーコントローラー、コンソールボックス、インナードアハンドルなどや、自動車用の外装材、すなわちリアスポイラー、グリル、ガーニッシュ、ドアミラー、ルーフ、フェンダー、バンパー、アウタードアハンドルなどへも応用することができる。また電気電子用途、OA機器用途、住宅・建材用途にも好適に使用することができる。
The thermoplastic resin composition of the present invention is suitably used in molded articles to be plated because it is excellent in the balance of mechanical properties, heat resistance, fluidity, plating properties, durability, appearance of plated molded articles, etc. In addition, it is suitable for large-sized or shaped complex plated articles. That is, the resin composition of the present invention can be required for automobile interior power window panels, center consoles, center clusters, console shutters, lever controllers, console boxes, inner door handles, etc. for automobile interiors where severe plating quality may be required. It can also be applied to materials such as rear spoilers, grills, garnishes, door mirrors, roofs, fenders, bumpers, outer door handles etc. In addition, it can be suitably used for electrical and electronic applications, OA equipment applications, housing and building materials applications.
Claims (6)
- ポリカーボネート樹脂(I)、ジエン系ゴム質重合体の存在下に、少なくとも芳香族ビニル系単量体およびシアン化ビニル系単量体を含有する単量体混合物をグラフト共重合してなるグラフト共重合体(II)、少なくとも芳香族ビニル系単量体およびシアン化ビニル系単量体を共重合してなるビニル系共重合体(III)およびメタクリル酸メチル-ブタジエン-スチレン共重合体(IV)から実質的になり、ポリカーボネート樹脂(I)、グラフト共重合体(II)、ビニル系共重合体(III)、メタクリル酸メチル-ブタジエン-スチレン共重合体(IV)の含有量の合計を100重量%としたときに、ポリカーボネート樹脂(I)が50~70重量%、グラフト共重合体(II)が10~30重量%、ビニル系共重合体(III)が5~20重量%、メタクリル酸メチル-ブタジエン-スチレン共重合体(IV)が1~10重量%であり、かつポリカーボネート樹脂(I)100重量%に対するメタクリル酸メチル-ブタジエン-スチレン共重合体(IV)の含有割合が3~20重量%であることを特徴とするめっき成形品用熱可塑性樹脂組成物。 Graft copolymer obtained by graft copolymerization of a monomer mixture containing at least an aromatic vinyl monomer and a vinyl cyanide monomer in the presence of a polycarbonate resin (I) and a diene rubber polymer From a vinyl copolymer (III) obtained by copolymerizing at least an aromatic vinyl monomer and a vinyl cyanide monomer (II) from methyl methacrylate-butadiene-styrene copolymer (IV) Substantially, the total content of polycarbonate resin (I), graft copolymer (II), vinyl copolymer (III) and methyl methacrylate-butadiene-styrene copolymer (IV) is 100% by weight in total 50% to 70% by weight of polycarbonate resin (I), 10 to 30% by weight of graft copolymer (II), and vinyl copolymer (III) 5 to 20% by weight, methyl methacrylate-butadiene-styrene copolymer (IV) 1 to 10% by weight, and methyl methacrylate-butadiene-styrene copolymer based on 100% by weight of polycarbonate resin (I) (IV The thermoplastic resin composition for plated molded articles, wherein the content ratio of 3) to 20% by weight.
- さらに、ポリカーボネート樹脂(I)、グラフト共重合体(II)、ビニル系共重合体(III)、メタクリル酸メチル-ブタジエン-スチレン共重合体(IV)の含有量の合計を100重量部としたときに、シリコーン系化合物およびフッ素系化合物から選択されるいずれか1種以上の化合物(V)を、0.01~0.2重量部配合してなることを特徴とする請求項1記載のめっき成形品用熱可塑性樹脂組成物。 Furthermore, when the total content of polycarbonate resin (I), graft copolymer (II), vinyl copolymer (III) and methyl methacrylate-butadiene-styrene copolymer (IV) is 100 parts by weight The plating and forming according to claim 1, wherein 0.01 to 0.2 parts by weight of any one or more compounds (V) selected from silicone compounds and fluorine compounds are blended. Product thermoplastic resin composition.
- 化合物(V)が、ポリジメチルシロキサンを主成分とする化合物であることを特徴とする請求項1または2に記載のめっき成形品用熱可塑性樹脂組成物。 The compound (V) is a compound which has a polydimethylsiloxane as a main component, The thermoplastic resin composition for metal-plating molded articles of Claim 1 or 2 characterized by the above-mentioned.
- ビニル系共重合体(III)を100重量%としたときに、該ビニル系共重合体(III)に共重合されているシアン化ビニル系単量体成分の含有割合が、29~33重量%であることを特徴とする請求項1~3のいずれか1項記載のめっき成形品用熱可塑性樹脂組成物。 The content of the vinyl cyanide-based monomer component copolymerized with the vinyl-based copolymer (III) is 29 to 33% by weight, based on 100% by weight of the vinyl-based copolymer (III). The thermoplastic resin composition for a plated molded product according to any one of claims 1 to 3, which is characterized in that
- 請求項1~4のいずれか1項記載のめっき成形品用熱可塑性樹脂組成物を成形してなる成形品。 A molded product obtained by molding the thermoplastic resin composition for a plated molded product according to any one of claims 1 to 4.
- 請求項5記載の成形品にめっき処理を施してなることを特徴とするめっき成形品。 A plated molded product obtained by subjecting the molded product according to claim 5 to a plating treatment.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2018557065A JPWO2019087653A1 (en) | 2017-10-30 | 2018-10-02 | Thermoplastic resin composition for plating molded products, molded products using it, plating molded products |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2017208977 | 2017-10-30 | ||
JP2017-208977 | 2017-10-30 |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2019087653A1 true WO2019087653A1 (en) | 2019-05-09 |
Family
ID=66333488
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/JP2018/036834 WO2019087653A1 (en) | 2017-10-30 | 2018-10-02 | Thermoplastic resin composition for plated molded article, and molded article and plated molded article both obtained using same |
Country Status (2)
Country | Link |
---|---|
JP (1) | JPWO2019087653A1 (en) |
WO (1) | WO2019087653A1 (en) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN111393820A (en) * | 2019-11-29 | 2020-07-10 | 东风汽车有限公司 | Electroplating material |
Citations (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS5614549A (en) * | 1979-07-12 | 1981-02-12 | Sumitomo Naugatuck Co Ltd | Thermoplastic resin composition with excellent heat cycle property |
JPS59155436A (en) * | 1983-02-22 | 1984-09-04 | Teijin Chem Ltd | Plated resin article |
JPH1046019A (en) * | 1996-08-01 | 1998-02-17 | Idemitsu Petrochem Co Ltd | Resin composition for plating |
JP2000017138A (en) * | 1998-06-30 | 2000-01-18 | Sumika Abs Latex Kk | Resin composition for plating and plated moldings |
JP2002294059A (en) * | 2001-03-28 | 2002-10-09 | Mitsubishi Engineering Plastics Corp | Polycarbonate resin composition and plated molded article of polycarbonate resin |
JP2002322356A (en) * | 2001-04-26 | 2002-11-08 | Nippon A & L Kk | Resin composition for plating and plated molded article |
JP2015168814A (en) * | 2014-03-11 | 2015-09-28 | 東レ株式会社 | Thermoplastic resin composition and molded article |
EP3202850A1 (en) * | 2015-11-05 | 2017-08-09 | LG Chem, Ltd. | Polycarbonate-abs-based alloy resin composition having excellent plating adhesive strength, and molded product comprising same |
-
2018
- 2018-10-02 WO PCT/JP2018/036834 patent/WO2019087653A1/en active Application Filing
- 2018-10-02 JP JP2018557065A patent/JPWO2019087653A1/en active Pending
Patent Citations (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS5614549A (en) * | 1979-07-12 | 1981-02-12 | Sumitomo Naugatuck Co Ltd | Thermoplastic resin composition with excellent heat cycle property |
JPS59155436A (en) * | 1983-02-22 | 1984-09-04 | Teijin Chem Ltd | Plated resin article |
JPH1046019A (en) * | 1996-08-01 | 1998-02-17 | Idemitsu Petrochem Co Ltd | Resin composition for plating |
JP2000017138A (en) * | 1998-06-30 | 2000-01-18 | Sumika Abs Latex Kk | Resin composition for plating and plated moldings |
JP2002294059A (en) * | 2001-03-28 | 2002-10-09 | Mitsubishi Engineering Plastics Corp | Polycarbonate resin composition and plated molded article of polycarbonate resin |
JP2002322356A (en) * | 2001-04-26 | 2002-11-08 | Nippon A & L Kk | Resin composition for plating and plated molded article |
JP2015168814A (en) * | 2014-03-11 | 2015-09-28 | 東レ株式会社 | Thermoplastic resin composition and molded article |
EP3202850A1 (en) * | 2015-11-05 | 2017-08-09 | LG Chem, Ltd. | Polycarbonate-abs-based alloy resin composition having excellent plating adhesive strength, and molded product comprising same |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN111393820A (en) * | 2019-11-29 | 2020-07-10 | 东风汽车有限公司 | Electroplating material |
Also Published As
Publication number | Publication date |
---|---|
JPWO2019087653A1 (en) | 2020-09-24 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
JP3454515B2 (en) | Flame retardant thermoplastic resin composition | |
JP6610680B2 (en) | Thermoplastic resin composition and molded article thereof | |
TW200407385A (en) | Polycarbonate resin composition and molded article thereof | |
JP2010536947A (en) | Aromatic polycarbonate composition | |
JP6279420B2 (en) | Polycarbonate molding composition | |
JP3655979B2 (en) | Thermoplastic resin composition | |
WO2019087653A1 (en) | Thermoplastic resin composition for plated molded article, and molded article and plated molded article both obtained using same | |
WO2006062032A1 (en) | Thermoplastic resin composition and molded body | |
JP4766909B2 (en) | Resin composition for direct plating and plated decoration products. | |
KR20180136962A (en) | Antistatic thermoplastic molding material | |
EP3775039B1 (en) | Glass fiber reinforced thermoplastic compositions with good mechanical properties | |
CN110785465B (en) | Thermoplastic resin composition, resin molded article thereof, and coated article | |
JP2022187748A (en) | Thermoplastic resin composition and molded article | |
CN107690453A (en) | The polycarbonate moulding compound through glass fiber reinforcement with improved toughness | |
JP2015168814A (en) | Thermoplastic resin composition and molded article | |
TW201840707A (en) | Composition and thermoplastic moulding compound having good low-temperature toughness, high gloss and high processing stability | |
JP2012177088A (en) | Thermoplastic resin composition, and molding thereof | |
US11174384B2 (en) | Polycarbonate composition and polycarbonate molding material having improved flowability | |
US20240043684A1 (en) | Thermoplastic composition with good plating performance | |
JP2014181279A (en) | Natural rubber-containing thermoplastic resin composition and its molded article | |
JP5024754B2 (en) | Thermoplastic elastomer resin composition for composite molding and composite molded body | |
JP2008189716A (en) | Thermoplastic elastomer resin composition for composite molding and molded article | |
JP2014133780A (en) | Impact resistant sheet | |
MXPA01001017A (en) | Flame retardant polycarbonate/rubber-modified graft copolymer resin blend having a metallic appearance |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
ENP | Entry into the national phase |
Ref document number: 2018557065 Country of ref document: JP Kind code of ref document: A |
|
121 | Ep: the epo has been informed by wipo that ep was designated in this application |
Ref document number: 18873320 Country of ref document: EP Kind code of ref document: A1 |
|
NENP | Non-entry into the national phase |
Ref country code: DE |
|
122 | Ep: pct application non-entry in european phase |
Ref document number: 18873320 Country of ref document: EP Kind code of ref document: A1 |