JP2013112781A - Black resin composition and resin molded product - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a black resin composition and a black molded article having excellent impact resistance, fluidity, surface hardness and heat resistance and having a jet-black appearance with a texture and transparency like a high-quality lacquer ware, prepared by adding a colorant to a modified polycarbonate resin derived from a specified bisphenol structural unit.SOLUTION: The black resin composition comprises: a resin component (A component) comprising 95 to 60 parts by weight of a copolymerized polycarbonate resin (A-1 component), which contains a 2,2-bis(4-hydroxy-3-methylphenyl)propane component (component a-1) and a 2,2-bis(4-hydroxyphenyl)propane component (component a-2) as an aromatic dihydroxy component, wherein the proportion of the component a-1 is 40 to 90 mol% with respect to 100 mol of the whole aromatic dihydroxy compound, and which has a viscosity average molecular weight of 1.8×10to 3.2×10, and 5 to 40 parts by weight of a styrene resin (A-2); and with respect to 100 parts by weight of the above component A, 0 to 10 parts by weight of an impact modifier (B component) and 0.1 to 5 parts by weight of carbon black (C component).

Description

  The present invention relates to a polycarbonate resin composition and a resin molded article excellent in jetness. More specifically, jet black with excellent impact resistance, fluidity, scratch resistance, and heat resistance, and has a texture and transparency similar to a high-class lacquer ware, in which a colorant is added to a modified polycarbonate resin derived from a specific bisphenol structural unit. The present invention relates to a black resin composition having a black appearance and a black molded product.

  Polycarbonate resin is excellent in transparency, impact resistance, heat resistance, and dimensional stability, so as an engineering plastic, it can be used as an electrical / electronic / OA equipment casing and parts, automotive interior / exterior parts, furniture, and musical instruments. It is used in a wide range of fields such as miscellaneous goods.

  Polycarbonate resin, on the other hand, is a paint general test method described in JIS K5600-5-4-Part 5: Mechanical properties of coating film-Section 4: Pencil hardness measured in accordance with scratch hardness (pencil method) is 2B The surface is soft and easily damaged. In particular, it is represented by casings, interior panels, door handles, steering, car audio / car navigation frames, and shift knobs of electric / electronic / OA devices such as mobile phones, LCD TVs, speakers, portable game machines, and notebook computers. Automotive exterior parts such as automotive interiors, roof spoilers, and window garnishes, furniture, and musical instruments are required to have high-quality lacquer-like texture and translucent blackness in order to bring out a sense of quality. A scratch on the surface is a fatal appearance defect.

  As a method for improving the scratch resistance of the polycarbonate resin, it is generally known to impart jet blackness and scratch resistance by coating the resin surface. However, due to the wettability of the paint to the resin surface and the environmental conditions of the painting process, appearance defects such as pinholes, cracks, repellency, and yuzu skin (orange peel) occur and poor paint adhesion, resulting in a significant decrease in the yield of the painting process. However, productivity is inferior.

  Further, as a technique for improving the scratch resistance of polycarbonate resin without painting, a method of laminating an acrylic resin film or sheet on the resin surface is known (for example, Patent Document 1). However, the acrylic resin has lower heat resistance than the polycarbonate resin and more easily absorbs water, so that the dimensional change due to temperature and humidity is large, and the final product is warped. Furthermore, the appearance distribution is caused by the film thickness distribution of the acrylic resin film or the sheet, and the jet black tone of the high-class feeling is impaired.

  Therefore, it is known to use a resin composition obtained by adding a colorant to a copolymer polycarbonate resin (for example, Patent Document 2) excellent in scratch resistance, and a resin molded body. However, the copolymer polycarbonate resin has a problem that the impact resistance is greatly inferior, and has not been put into practical use.

  Furthermore, when a resin composition in which a PBT resin (polybutylene terephthalate) and an AS resin (acrylonitrile-styrene) are mixed with a polycarbonate resin in which carbon black, which is a black pigment, is dispersed, the surface hardness is improved. While impact property falls remarkably, there exists a subject that jet blackness will fall when an impact modifier is added in order to supplement it. (For example, Patent Document 3)

  Therefore, a black resin composition and a black molded product that do not require painting, have excellent impact resistance, fluidity, scratch resistance, and heat resistance, and have a jet black appearance with a texture and transparency like high-quality lacquerware. Is not yet present.

JP 2007-160892 A Special table 2009-500195 gazette JP-A-11-106518

  An object of the present invention is a modified polycarbonate resin derived from a specific bisphenol structural unit having excellent jet resistance, fluidity, surface hardness, heat resistance, and a jet black appearance with a texture and transparency like a high-class lacquer ware. It is in providing the black resin composition which added the coloring agent to, and a black molded article.

According to the present invention, the above problem is solved by the following configuration.
1. The aromatic dihydroxy component comprises 2,2-bis (4-hydroxy-3-methylphenyl) propane component (component a-1) and 2,2-bis (4-hydroxyphenyl) propane component (component a-2). And a ratio of the component a-1 is 40 to 90 mol% with respect to 100 mol of the wholly aromatic dihydroxy compound, and the viscosity average molecular weight is 1.8 × 10 ^{4 to} 3.2 × 10 ^4. Impact modifier (component B) 0 to 10 with respect to 95 to 60 parts by weight of resin (component A-1) and 100 parts by weight of resin component (component A) consisting of styrene resin (A-2) 5 to 40 A black resin composition comprising 0.1 part by weight of carbon black (component C) by weight.
2. 2. The black resin composition as described in 1 above, which comprises 0.01 to 1 part by weight of two or more kinds of plastic dyes (component D) with respect to 100 parts by weight of the (component A).
3. 3. The black resin composition as described in 1 or 2 above, wherein the impact modifier (component B) contains at least one rubber-modified resin selected from butadiene, acrylic and silicone, or a copolymer thereof. These rubber-modified resins or copolymers are remarkably excellent in impact resistance at low temperatures.
4). The black molded product formed by shape | molding the black resin composition in any one of said 1-3.

  Since the black resin composition and the black molded product of the present invention have excellent jet blackness and are excellent in impact resistance, fluidity, scratch resistance, and heat resistance, they are exterior parts for electronic / electric / OA equipment, automobiles. Applicable to applications that require high-grade appearance such as interior and exterior parts, furniture, and musical instruments. Therefore, the industrial effects that it plays are exceptional.

Hereinafter, the present invention will be described in detail.
<Copolymerized polycarbonate resin (A-1 component)>
The copolymer polycarbonate resin (component A-1) used in the present invention is obtained by reacting a dihydric phenol and a carbonate precursor. Examples of the reaction method include an interfacial polycondensation method, a melt transesterification method, a solid phase transesterification method of a carbonate prepolymer, and a ring-opening polymerization method of a cyclic carbonate compound.

  The polycarbonate resin may be produced by any production method, and in the case of interfacial polycondensation, a terminal stopper of a monohydric phenol is usually used. The polycarbonate resin may be a branched polycarbonate obtained by polymerizing a trifunctional or higher polyfunctional component in addition to the dihydric phenol. Further, it may be a branched polycarbonate resin obtained by polymerizing polyfunctional phenols such as trifunctional phenols, and further, an aliphatic dicarboxylic acid, an aromatic dicarboxylic acid, a polyorganosiloxane component, and a vinyl monomer are copolymerized. It may be a copolymerized polycarbonate.

  As a result of extensive investigations, the copolymeric polycarbonate resin of the present invention has a main aromatic dihydroxy component of 2,2-bis (4-hydroxy-3-methylphenyl) propane component (component a-1) and 2,2 -The bis (4-hydroxyphenyl) propane component (component a-2) is included, and the ratio of the component a-1 is 40-90 mol% with respect to 100 mol of wholly aromatic dihydroxy compounds, and 50-80 mol% Is preferred. When the ratio of the component a-1 is not less than the lower limit of the range, the scratch resistance is excellent, and when it is not more than the upper limit of the range, the impact resistance is excellent. The proportion of component a-1 may be achieved by mixing polycarbonate resins having different composition proportions. Moreover, although it is preferable that 90% or more of all the dihydroxy compound components are the component a-1 and the component a-2, hydroxyl compounds other than the component a-1 and the component a-2 are copolymerized to such an extent that performance is not impaired. be able to.

  In the reaction using, for example, phosgene as the carbonate precursor, the reaction is usually performed in the presence of an acid binder and a solvent. As the acid binder, for example, an alkali metal hydroxide such as sodium hydroxide or potassium hydroxide or an amine compound such as pyridine is used. As the solvent, for example, halogenated hydrocarbons such as methylene chloride and chlorobenzene are used. In order to accelerate the reaction, a catalyst such as a tertiary amine or a quaternary ammonium salt can also be used. In that case, reaction temperature is 0-40 degreeC normally, and reaction time is several minutes-5 hours.

  For example, a transesterification reaction using a carbonic acid diester as a carbonate precursor is carried out by a method in which an aromatic dihydroxy component in a predetermined ratio is stirred with a carbonic acid diester while heating in an inert gas atmosphere to distill the resulting alcohol or phenol. Is called. The reaction temperature varies depending on the boiling point of the alcohol or phenol produced, but is usually in the range of 120 to 300 ° C. The reaction is completed while distilling off the alcohol or phenol produced under reduced pressure from the beginning. Moreover, in order to accelerate | stimulate reaction, the catalyst normally used for transesterification can also be used. Examples of the carbonic acid diester used in the transesterification include diphenyl carbonate, dinaphthyl carbonate, bis (diphenyl) carbonate, dimethyl carbonate, diethyl carbonate, and dibutyl carbonate. Of these, diphenyl carbonate is particularly preferred.

Monofunctional phenols usually used as a terminal terminator can be used. Particularly in the case of a reaction using phosgene as a carbonate precursor, monofunctional phenols are generally used as a terminator for controlling the molecular weight, and the resulting aromatic polycarbonate resin has a terminal monofunctional phenol. Since it is blocked by a group based on, it is superior in thermal stability as compared to those not. Specific examples of the monofunctional phenols include, for example, phenol, m-methylphenol, p-methylphenol, m-propylphenol, p-propylphenol, 1-phenylphenol, 2-phenyl. Examples include phenol, p-tert-butylphenol, p-cumylphenol, isooctylphenol, and p-long chain alkylphenol.
In producing the polycarbonate resin, the above dihydric phenols can be used alone or in combination of two or more thereof, and a molecular weight regulator, a branching agent, a catalyst and the like can be used as necessary.

The molecular weight of the copolymer polycarbonate resin of the present invention is 1.8 × 10 ^{4 to} 3.2 × 10 ⁴ , preferably 1.9 × 10 ^{4 to} 3.0 × 10 ⁴ , expressed as a viscosity average molecular weight. more preferably from ^{2.0 × 10 4 ~2.6 × 10 4} . When the molecular weight is not less than the lower limit of the range, sufficient impact resistance is obtained, and when the molecular weight is not more than the upper limit of the range, the fluidity is good, which is preferable. Such molecular weight may be achieved by mixing polycarbonate resins having different molecular weights, but in such mixing, the molecular weight difference is preferably within 1.0 × 10 ⁴ .
The viscosity average molecular weight of the polycarbonate is first determined by using an Ostwald viscometer from a solution in which 0.7 g of polycarbonate is dissolved in 100 ml of methylene chloride at 20 ° C., with a specific viscosity (η _SP ) calculated by the following formula:
Specific viscosity (η _SP ) = (t−t ₀ ) / t ₀
[T ₀ is methylene chloride falling seconds, t is sample solution falling seconds]
The viscosity average molecular weight M is calculated from the determined specific viscosity (η _SP ) by the following formula.
η _SP /c=[η]+0.45×[η] ² c (where [η] is the intrinsic viscosity)
[Η] = 1.23 × 10 ⁻⁴ M ^0.83
c = 0.7

<Styrene resin (component A-2)>
The styrene resin as the component A-2 of the present invention is a resin selected from a polymer or copolymer of an aromatic vinyl compound, or an aromatic vinyl compound and another vinyl monomer and a rubbery polymer. It refers to a resin made of a copolymer obtained by copolymerizing a seed or more. The aromatic vinyl compound preferably contains 10% by weight or more in 100% by weight of the resin.

  Examples of aromatic vinyl compounds include styrene, α-methylstyrene, o-methylstyrene, p-methylstyrene, vinylxylene, ethylstyrene, dimethylstyrene, p-tert-butylstyrene, vinylnaphthalene, methoxystyrene, monobromostyrene, Examples thereof include dibromostyrene, fluorostyrene, and tribromostyrene, and styrene is particularly preferable.

  Preferable examples of the other vinyl monomer copolymerizable with the aromatic vinyl compound include a vinyl cyanide compound and a (meth) acrylic acid ester compound. Examples of the vinyl cyanide compound include acrylonitrile and methacrylonitrile, and acrylonitrile is particularly preferable.

  Specific examples of the (meth) acrylic acid ester compound include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate, butyl (meth) acrylate, amyl (meth) acrylate, Hexyl (meth) acrylate, octyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, cyclohexyl (meth) acrylate, dodecyl (meth) acrylate, octadecyl (meth) acrylate, phenyl (meth) acrylate, benzyl (meth) acrylate, etc. Can be mentioned. The notation of (meth) acrylate indicates that both methacrylate and acrylate are included, and the notation of (meth) acrylic acid ester indicates that both methacrylic acid ester and acrylic acid ester are included. Particularly preferred (meth) acrylic acid ester compounds include methyl methacrylate.

  Other vinyl monomers copolymerizable with aromatic vinyl compounds other than vinyl cyanide compounds and (meth) acrylic acid ester compounds include epoxy group-containing methacrylic acid esters such as glycidyl methacrylate, maleimide, N-methylmaleimide, Examples include maleimide monomers such as N-phenylmaleimide, α, β-unsaturated carboxylic acids such as acrylic acid, methacrylic acid, maleic acid, maleic anhydride, phthalic acid, and itaconic acid, and anhydrides thereof.

  Examples of the rubber polymer include polybutadiene, polyisoprene, and diene copolymers (for example, random copolymers and block copolymers of styrene / butadiene, acrylonitrile / butadiene copolymers, and (meth) acrylic acid alkyl esters. Copolymer of ethylene and α-olefin (eg, ethylene / propylene random copolymer and block copolymer, ethylene / butene random copolymer and block copolymer, etc.) , Copolymers of ethylene and unsaturated carboxylic acid esters (for example, ethylene / methacrylate copolymers and ethylene / butyl acrylate copolymers), copolymers of ethylene and aliphatic vinyl (for example, ethylene / vinyl acetate) Copolymer), ethylene and propylene Non-conjugated diene terpolymers (eg, ethylene / propylene / hexadiene copolymers), acrylic rubbers (eg, polybutyl acrylate, poly (2-ethylhexyl acrylate), and copolymers of butyl acrylate and 2-ethylhexyl acrylate Etc.), as well as silicone rubber (eg, polyorganosiloxane rubber, IPN type rubber composed of a polyorganosiloxane rubber component and a polyalkyl (meth) acrylate rubber component; that is, the two rubber components are entangled with each other so that they cannot be separated. And rubber having a structure, and an IPN type rubber composed of a polyorganosiloxane rubber component and a polyisobutylene rubber component). Of these, polybutadiene, polyisoprene, or diene-based copolymers that are more likely to exhibit the effect are more preferable, and polybutadiene is particularly preferable. These rubbery polymers are preferably 90% by weight or less, more preferably 80% by weight or less, in 100% by weight of the styrene resin.

  Specific examples of the styrene resin include styrene polymers such as polystyrene resin, HIPS resin, MS resin, ABS resin, AS resin, AES resin, ASA resin, MBS resin, MABS resin, MAS resin, and SMA resin. And a styrene-based thermoplastic elastomer (for example, (hydrogenated) styrene-butadiene-styrene copolymer, (hydrogenated) styrene-isoprene-styrene copolymer, etc.). Is meant to include both non-hydrogenated copolymers and hydrogenated copolymers, which are readily available, of which HIPS resins, ABS resins, AS resins are more preferred. Such as AES resin, ASA resin, MBS resin, MABS resin, MAS resin, and styrenic thermoplastic elastomer A reinforced styrene resin.

  Among these, HIPS resin, ABS resin, and AS resin are particularly preferable. ABS resin has excellent moldability for thin-walled molded products, and also has good impact resistance. In particular, favorable characteristics are exhibited in combination with an aromatic polycarbonate resin. Here, MS resin is a copolymer resin mainly composed of methyl methacrylate and styrene, AES resin is a copolymer resin mainly composed of acrylonitrile, ethylene-propylene rubber and styrene, and ASA resin is mainly composed of acrylonitrile, styrene and acrylic rubber. MABS resin is a copolymer resin mainly composed of methyl methacrylate, acrylonitrile, butadiene and styrene, MAS resin is a copolymer resin mainly composed of methyl methacrylate, acrylic rubber and styrene, SMA resin is styrene and anhydrous male A copolymer resin mainly composed of an acid (MA) is shown.

  Styrenic resins can be used alone or in combination of two or more. For example, in an ABS resin, a mixture of an AS polymer (a copolymer of acrylonitrile and styrene) and an ABS copolymer (a copolymer obtained by graft copolymerization of acrylonitrile and styrene on a polybutadiene rubber) is generally used. Is also preferably used in the present invention.

  Furthermore, the styrenic resin may have a high stereoregularity such as syndiotactic polystyrene by using a catalyst such as a metallocene catalyst during the production thereof. Further, in some cases, polymers and copolymers having a narrow molecular weight distribution obtained by methods such as anion living polymerization and radical living polymerization, block copolymers, and polymers and copolymers having high stereoregularity Also good.

  In the ABS resin used in the present invention, the proportion of the diene rubber component is preferably 5 to 80% by weight in 100% by weight of the ABS resin component (that is, in the total of 100% by weight of the ABS polymer and the AS polymer). Preferably it is 8-50 weight%, Most preferably, it is 10-30 weight%.

  Examples of the vinyl cyanide compound used in the ABS resin include those described above, and acrylonitrile is particularly preferable. As the aromatic vinyl compound, those described above can be used as well, and styrene and α-methylstyrene are particularly preferable. The proportion of the component grafted to the diene rubber component is preferably 95 to 20% by weight, more preferably 92 to 50% by weight in 100% by weight of the ABS resin component. Further, it is preferable that the vinyl cyanide compound is 5 to 50% by weight and the aromatic vinyl compound is 95 to 50% by weight with respect to 100% by weight of the total amount of the vinyl cyanide compound and the aromatic vinyl compound. Further, methyl (meth) acrylate, ethyl acrylate, maleic anhydride, N-substituted maleimide and the like can be mixed and used for a part of the components grafted to the diene rubber component, and the content ratio thereof is in the ABS resin component. What is 15 weight% or less is preferable. Furthermore, conventionally well-known various things can be used for the initiator, chain transfer agent, emulsifier, etc. which are used by reaction as needed.

  In the ABS resin, the rubber particle diameter is preferably 0.1 to 5.0 μm, more preferably 0.2 to 3.0 μm, and particularly preferably 0.3 to 1.5 μm. The rubber particle diameter distribution can be either a single distribution or a rubber particle having a plurality of peaks of two or more, and the rubber particles form a single phase in the morphology. Alternatively, it may have a salami structure by containing an occluded phase around the rubber particles.

  Further, it is well known that an ABS resin contains a copolymer of a vinyl cyanide compound and an aromatic vinyl compound that is not grafted to a diene rubber component. In the present invention, the ABS resin may contain a free polymer component generated during such polymerization as described above, and a vinyl compound polymer obtained by separately copolymerizing an aromatic vinyl compound and a vinyl cyanide compound. A blended blend may be used. The reduced viscosity (30 ° C.) determined by the method described below is preferably 0.2 to 1 for the reduced viscosity of the copolymer (AS copolymer) comprising such free vinyl cyanide compound and aromatic vinyl compound. 0.0 dl / g, more preferably 0.3 to 0.7 dl / g.

The reduced viscosity is a value obtained by precisely weighing 0.25 g of AS copolymer and measuring a solution dissolved in 50 ml of dimethylformamide over 2 hours in an environment of 30 ° C. using an Ubbelohde viscometer. A viscometer having a solvent flow time of 20 to 100 seconds is used. The reduced viscosity is determined from the following formula from the solvent flow down seconds (t ₀ ) and the solution flow down seconds (t).
Reduced viscosity (η _sp / C) = {(t / t ₀ ) −1} /0.5
The ratio of the free AS copolymer can be obtained by dissolving the ABS resin in a good solvent for the AS copolymer such as acetone and collecting the soluble resin. On the other hand, the insoluble matter (gel) becomes a net ABS copolymer.

The ratio of the vinyl cyanide compound and aromatic vinyl compound grafted to the diene rubber component in the ABS copolymer (the ratio of the weight of the graft component to the weight of the diene rubber component), that is, the graft ratio (% by weight) is 20 -200% is preferable, More preferably, it is 20-80%.
Such ABS resin may be produced by any method such as bulk polymerization, solution polymerization, suspension polymerization, and emulsion polymerization. From the viewpoint of hydrolysis resistance, an ABS resin produced by a bulk polymerization method and a suspension bulk polymerization method is more preferable. Further, the copolymerization may be carried out in one step or in multiple steps.

  In the present invention, the AS resin is a thermoplastic copolymer obtained by copolymerizing a vinyl cyanide compound and an aromatic vinyl compound. Examples of such vinyl cyanide compounds include those described above, and acrylonitrile is particularly preferred. Examples of the aromatic vinyl compound include those described above, and styrene and α-methylstyrene are preferable. The proportion of each component in the AS resin is preferably 5 to 50% by weight of vinyl cyanide compound, more preferably 15 to 35% by weight, and preferably 95% of aromatic vinyl compound when the total is 100% by weight. -50% by weight, more preferably 85-65% by weight. Further, those vinyl compounds may be copolymerized with the above-mentioned other copolymerizable vinyl compounds. These contents are preferably 15% by weight or less in the AS resin component. Moreover, conventionally well-known various things can be used for the initiator, chain transfer agent, etc. which are used by reaction as needed.

  Such an AS resin may be produced by any method such as bulk polymerization, solution polymerization, suspension polymerization, and emulsion polymerization, but is preferably based on bulk polymerization. The copolymerization method may be either one-stage copolymerization or multistage copolymerization. The reduced viscosity of the AS resin is preferably 0.2 to 1.0 dl / g, more preferably 0.4 to 0.7 dl / g (the method for measuring the reduced viscosity is the same as described above).

Such an AS resin has a range of 15 to 35% by weight of acrylonitrile and 85 to 65% by weight of styrene in 100% by weight of the whole AS resin, and is produced by bulk polymerization, and its reduced viscosity is 0.4 to 0.7 dl. / G can be preferably used. In the ABS resin, when the ABS copolymer and the AS copolymer are blended, the ratios of the aromatic vinyl compound and the vinyl cyanide compound in the copolymer may be the same or different. Preferably they are almost the same.
The component A-2 is preferably at least one styrenic resin selected from the group consisting of ABS resin and AS resin.

  The blending amount of the styrene resin (component A-2) is 5 to 40% by weight, preferably 10 to 35% by weight, more preferably based on the total of 100% by weight of the component A-1 and the component A-2. 15 to 30% by weight, most preferably 25 to 30% by weight. A blending amount of at least the lower limit is preferable because excellent moldability is exhibited. Moreover, since the outstanding heat resistance is acquired below an upper limit, it is preferable.

<Impact modifier (component B)>
The impact modifier (component B) used in the present invention has a glass transition temperature other than the styrene resin (A-2) of 10 ° C. or lower, preferably −10 ° C. or lower, more preferably −30 ° C. or lower. Preferred are a polymer composed of a rubber component, and a copolymer obtained by bonding another polymer chain to the polymer composed of the rubber component. Furthermore, the rubber component is preferably a polymer containing at least 35% by weight, more preferably 45% by weight, in 100% by weight of the rubbery polymer. The upper limit of the rubber component content is preferably about 90% by weight in practice.

  The impact modifier is more preferably a copolymer formed by bonding other polymer chains. In the production of a rubbery polymer in which another polymer chain is grafted to a rubber component, it is widely known that not a few polymers or copolymers are not grafted on the rubber component. The component C of the present invention may contain such a free polymer or copolymer.

  More specifically, the impact modifier for component B includes MB (methyl methacrylate-butadiene) copolymer, MA (methyl methacrylate-acrylic rubber) copolymer, methyl methacrylate-acrylic-butadiene rubber copolymer, methyl methacrylate. -(Acrylic / silicone IPN rubber) copolymer and the like. These copolymers are preferably core-shell type graft copolymers in which a polymer chain composed of the above monomer is bonded to a polymer core composed of a rubber component. For example, as rubber components mainly composed of butadiene rubber, acrylic rubber, or butadiene-acrylic composite rubber, Kaneka's Kane Ace B series (for example, B-56 etc.), Mitsubishi Rayon Co., Ltd. Metabrene C series ( For example, C-223A, etc.), W series (eg, W-450A, etc.), Kureha Chemical Co., Ltd. paraloid EXL series (eg, EXL-2602), HIA series (eg, HIA-15, etc.), BTA series (eg, BTA) -III, etc.), KCA series, Rohm & Haas Paraloid EXL series, KM series (eg KM-336P, KM-357P, etc.), Ube modifier's UCL modifier resin series (UMG AB Co., Ltd.) ) UMG AX Resin Series), with acrylic as a rubber component - as consisting mainly of silicone composite rubber include those commercially available under the tradename METABLEN S-2001 or SRK-200 from Mitsubishi Rayon. In particular, a core-shell type graft copolymer in which the rubber component is made of butadiene rubber is a preferred mode in terms of improving impact.

  The rubber particle diameter of the impact modifier is preferably 0.1 to 5.0 μm, more preferably 0.2 to 3.0 μm, and particularly preferably 0.2 to 1.5 μm. As the distribution of the rubber particle diameter, either a single distribution or a rubber particle having two or more peaks can be used, and the rubber particles form a single phase in the morphology. Alternatively, it may have a salami structure by containing an occluded phase around the rubber particles.

  In the rubbery polymer of the graft copolymer, the weight ratio of the grafted component to the rubber substrate (graft ratio (% by weight)) is preferably 10 to 100%, more preferably 15 to 70%, still more preferably. 15-40%.

  Examples of the impact modifier of the present invention include various thermoplastic elastomers composed of a hard segment and a soft segment. Examples of such thermoplastic elastomers include polyester elastomers, polyurethane elastomers, and olefin elastomers.

  In the present invention, when the impact modifier (component B) is contained, the content thereof is 0 to 10 parts by weight, preferably 1 to 10 parts by weight, based on 100 parts by weight of the component A. The amount is more preferably 9 parts by weight, and further preferably 2 to 8 parts by weight. Below the upper limit, problems such as a decrease in fluidity, heat resistance, strength and rigidity are unlikely to occur.

<Carbon black (component C)>
In this invention, content of (C component) is 0.1-5 weight part with respect to 100 weight part of said A component, It is preferable that it is 0.1-3 weight part, 0.1-1 More preferred are parts by weight. When the content of (C component) is not less than the above lower limit, a jet black feeling is obtained, and when it is not more than the above upper limit, it is difficult to cause a decrease in molecular weight and mechanical properties due to thermal decomposition during heating. Further, for the purpose of facilitating handling or improving dispersibility, a master batch may be prepared, granulated, and added with a dispersant.

<Plastic dye (D component)>
The present invention can obtain a deep jetness by adding a plastic dye together with carbon black, which is a black inorganic pigment, as a colorant. In the present invention, a D component comprising a combination of two or more dyes preferably containing 0.01 to 1 part by weight of two or more kinds of plastic dyes (D component) with respect to 100 parts by weight of the above A component. Examples of the constituent dye include anthraquinone, perinone, perylene, azo, methine, and quinoline dyes. By using these dyes in combination, a black resin composition having particularly excellent jetness can be obtained. Any dye can be used as the dye constituting the component D, and is not particularly limited, but specific examples thereof include the following dyes.

  Examples of the anthraquinone dyes include Solvent Red 52, Solvent Red 111, Solvent Red 149, Solvent Red 150, Solvent Red 151, Solvent Red 168, Solvent Red 191, Solvent Red 207, Dispers Red 221, Dispers Red 22 , Solvent Blue 35, Solvent Blue 36, Solvent Blue 63, Solvent Blue 78, Solvent Blue 83, Solvent Blue 87, Solvent Blue 94, Solvent Blue 97, Solvent Blue 97, Solvent Blue 97, Solvent Blue 97, Solvent Blue 97, Solvent Blue 97, Solvent Blue 97, Solvent Blue 97, Solvent Blue 97, Solvent Blue 97, Solvent Blue 97 Examples thereof include commercially available dyes such as Green 28, Disperse Violet 28, Solvent Violet 13, Solvent Violet 14, and Solvent Violet 36.

  Examples of perinone-based dyes include dyes commercially available with color indexes such as Solvent Orange 60, Solvent Orange 78, Solvent Orange 90, Solvent Violet 29, Solvent Red 135, Solvent Red 162, and Solvent Red 179.

  Examples of perylene dyes include dyes commercially available with color indexes such as Solvent Green 3, Solvent Green 5, Solvent Orange 55, Vat Red 15, Vat Orange 7, F Orange 240, F Red 305, F Red 339, and F Yellow 83.

  Examples of the azo dye include Solvent Yellow 14, Solvent Yellow 16, Solvent Yellow 21, Solvent Yellow 61, Solvent Yellow 81, Solvent Red 23, Solvent Red 24, Solvent Red 27, Solvent Red 27, Solvent Red 8, Solvent Red 121, Solvent Red 132, Solvent Violet 21, Solvent Black 21, Solvent Black 23, Solvent Black 27, Solvent Black 28, Solvent Black 31, Solvent Orange 37 Solvent Orange 37 and dyes commercially available with a color index such as olive Orange 45.

  Examples of methine dyes include dyes commercially available in color indexes such as Solvent Orange 80 and Solvent Yellow 93, and examples of quinoline dyes include Solvent Yellow 33, Solvent Yellow 98, Solvent Yellow 157, Disperse Yellow 54, Yellow 54, Displow Yellow 54, and Displow Yellow 54. Examples thereof include commercially available dyes having a color index of 160 or the like.

  Among the D components used in the present invention, anthraquinone dyes and methine dyes are preferably used. Among them, as anthraquinone dyes, dark dyes such as purple, blue, and green are used, and methine dyes. It is preferable to use a light-colored dye such as yellow as the dye because a black resin composition having high depth and clarity and excellent jetness can be obtained.

<Other ingredients>
In the black resin composition of the present invention, additives can be blended depending on the purpose.
(I) Release agent It is preferable to mix | blend a release agent with the black resin composition of this invention.
Known release agents can be used in the present invention. For example, fatty acid ester, polyolefin wax (polyethylene wax, 1-alkene polymer, etc., which may be modified with a functional group-containing compound such as acid modification), silicone compound, fluorine compound (represented by polyfluoroalkyl ether) Fluorinated oil), paraffin wax, beeswax and the like. Of these, fatty acid esters are preferred from the standpoints of availability, releasability and transparency. Such a release agent is preferably 0.005 to 0.2 parts by weight, more preferably 0.007 to 0.1 parts by weight, still more preferably 0.01 to 0.06 parts per 100 parts by weight of the component A. Parts by weight. When the addition amount is less than the lower limit of the above range, the releasability is not sufficiently improved, and when it exceeds the upper limit, appearance defects such as bleed out are likely to occur.

  Among the above, fatty acid ester is mentioned as a preferable release agent. Such fatty acid esters are esters of aliphatic alcohols and aliphatic carboxylic acids. Such an aliphatic alcohol may be a monohydric alcohol or a dihydric or higher polyhydric alcohol. Moreover, as carbon number of this alcohol, it is the range of 3-32 suitably, More preferably, it is the range of 5-30. Examples of such monohydric alcohols include dodecanol, tetradecanol, hexadecanol, octadecanol, eicosanol, tetracosanol, seryl alcohol, and triacontanol. Examples of such polyhydric alcohols include pentaerythritol, dipentaerythritol, tripentaerythritol, polyglycerol (triglycerol to hexaglycerol), ditrimethylolpropane, xylitol, sorbitol, and mannitol. In the fatty acid ester of the present invention, a polyhydric alcohol is more preferable.

  On the other hand, the aliphatic carboxylic acid preferably has 3 to 32 carbon atoms, and particularly preferably an aliphatic carboxylic acid having 10 to 22 carbon atoms. Examples of the aliphatic carboxylic acid include decanoic acid, undecanoic acid, dodecanoic acid, tridecanoic acid, tetradecanoic acid, pentadecanoic acid, hexadecanoic acid (palmitic acid), heptadecanoic acid, octadecanoic acid (stearic acid), nonadecanoic acid, icosanoic acid, And saturated aliphatic carboxylic acids such as docosanoic acid (behenic acid) and unsaturated aliphatic carboxylic acids such as palmitoleic acid, oleic acid, linoleic acid, linolenic acid, eicosenoic acid, eicosapentaenoic acid, and cetreic acid it can. Among the above, aliphatic carboxylic acids having 14 to 20 carbon atoms are preferable. Of these, saturated aliphatic carboxylic acids are preferred. Such aliphatic carboxylic acids are usually produced from natural fats and oils such as animal fats (such as beef tallow and pork fat) and vegetable fats and oils (such as palm oil). Of other carboxylic acid components. Therefore, in the production of the aliphatic carboxylic acid used in the present invention, it is produced from such natural fats and oils and is in the form of a mixture containing other carboxylic acid components. The acid value in the fatty acid ester is preferably 20 or less (can take substantially 0). However, in the case of all esters (full esters), it is preferable to contain at least free fatty acids in order to improve releasability. In this respect, the acid value in the full esters is preferably in the range of 3 to 15. The iodine value of the fatty acid ester is preferably 10 or less (can take substantially 0). These characteristics can be obtained by a method defined in JIS K 0070.

  The fatty acid ester that can be used in the black resin composition of the present invention may be either a partial ester or a full ester. In the present invention, a partial ester is more preferable in terms of good releasability and durability. Of these, glycerin monoester is preferred. Glycerin monoester is mainly composed of monoester of glycerin and fatty acid. Suitable fatty acids include saturated fatty acids such as stearic acid, palmitic acid, behenic acid, arachidic acid, montanic acid, lauric acid, oleic acid, and linoleic acid. And unsaturated fatty acids such as sorbic acid, and those having glycerin monoesters of stearic acid, behenic acid, and palmitic acid as main components are particularly preferred. Such fatty acids are synthesized from natural fatty acids and become a mixture as described above. The glycerin monoester can be used in combination with other release agents, particularly fatty acid full esters, but even when used in combination, it is preferable that the glycerin monoester is the main component. That is, it is preferably 60% by weight or more in 100% by weight of the release agent.

  In addition, partial esters are often inferior to full esters in terms of thermal stability. In order to improve the thermal stability of such a partial ester, the partial ester preferably has a sodium metal content of less than 20 ppm, more preferably less than 5 ppm, and even more preferably less than 1 ppm. The fatty acid partial ester having a sodium metal content of less than 1 ppm can be produced by producing the fatty acid partial ester by an ordinary method and then purifying it by molecular distillation or the like.

  Specifically, after removing gas components and low-boiling substances with a spray nozzle type degassing apparatus, glycerin is used under the conditions of a distillation temperature of 120 to 150 ° C. and a vacuum degree of 0.01 to 0.03 kPa using a falling film distillation apparatus. For example, a high molecular weight fatty acid ester is distilled off using a centrifugal molecular distillation apparatus at a distillation temperature of 160 to 230 ° C. and a vacuum of 0.01 to 0.2 Torr. The sodium metal can be removed as a distillation residue. By subjecting the resulting distillate to repeated molecular distillation, it is possible to further increase the purity and obtain a fatty acid partial ester having a lower sodium metal content. It is also important to prevent the contamination of the sodium metal component from the external environment by thoroughly washing the inside of the molecular distillation apparatus by an appropriate method in advance and improving airtightness. Such a fatty acid ester is available from a specialist (for example, Riken Vitamin Co., Ltd.).

(Ii) Phosphorus stabilizer It is preferable that the black resin composition of the present invention is further blended with various phosphorus stabilizers mainly for the purpose of improving the thermal stability during the molding process. Examples of such phosphorus stabilizers include phosphorous acid, phosphoric acid, phosphonous acid, phosphonic acid, and esters thereof. In addition, such phosphorus stabilizers include tertiary phosphines.

  Specifically, as the phosphite compound, for example, triphenyl phosphite, tris (nonylphenyl) phosphite, tridecyl phosphite, trioctyl phosphite, trioctadecyl phosphite, didecyl monophenyl phosphite, dioctyl monophenyl Phosphite, diisopropyl monophenyl phosphite, monobutyl diphenyl phosphite, monodecyl diphenyl phosphite, monooctyl diphenyl phosphite, 2,2-methylenebis (4,6-di-tert-butylphenyl) octyl phosphite, tris ( Diethylphenyl) phosphite, tris (di-iso-propylphenyl) phosphite, tris (di-n-butylphenyl) phosphite, tris (2,4-di-tert-butylpheny) ) Phosphite, tris (2,6-di-tert-butylphenyl) phosphite, distearyl pentaerythritol diphosphite, bis (2,4-di-tert-butylphenyl) pentaerythritol diphosphite, bis (2 , 6-Di-tert-butyl-4-methylphenyl) pentaerythritol diphosphite, bis (2,6-di-tert-butyl-4-ethylphenyl) pentaerythritol diphosphite, phenylbisphenol A pentaerythritol diphosphite Phyto, bis (nonylphenyl) pentaerythritol diphosphite, dicyclohexyl pentaerythritol diphosphite, and the like.

  Further, as other phosphite compounds, those which react with dihydric phenols and have a cyclic structure can be used. For example, 2,2′-methylenebis (4,6-di-tert-butylphenyl) (2,4-di-tert-butylphenyl) phosphite, 2,2′-methylenebis (4,6-di-tert- Butylphenyl) (2-tert-butyl-4-methylphenyl) phosphite, 2,2′-methylenebis (4-methyl-6-tert-butylphenyl) (2-tert-butyl-4-methylphenyl) phosphite 2,2′-ethylidenebis (4-methyl-6-tert-butylphenyl) (2-tert-butyl-4-methylphenyl) phosphite.

  Examples of the phosphate compound include tributyl phosphate, trimethyl phosphate, tricresyl phosphate, triphenyl phosphate, trichlorophenyl phosphate, triethyl phosphate, diphenyl cresyl phosphate, diphenyl monoorxenyl phosphate, tributoxyethyl phosphate, dibutyl phosphate, dioctyl phosphate, Examples thereof include diisopropyl phosphate, and triphenyl phosphate and trimethyl phosphate are preferable.

  Examples of the phosphonite compound include tetrakis (2,4-di-tert-butylphenyl) -4,4′-biphenylenediphosphonite, tetrakis (2,4-di-tert-butylphenyl) -4,3′-biphenylenedi. Phosphonite, tetrakis (2,4-di-tert-butylphenyl) -3,3′-biphenylenediphosphonite, tetrakis (2,6-di-tert-butylphenyl) -4,4′-biphenylenediphosphonite Tetrakis (2,6-di-tert-butylphenyl) -4,3′-biphenylene diphosphonite, tetrakis (2,6-di-tert-butylphenyl) -3,3′-biphenylene diphosphonite, bis (2,4-di-tert-butylphenyl) -4-phenyl-phenylphosphonite, bis (2,4-di tert-butylphenyl) -3-phenyl-phenylphosphonite, bis (2,6-di-n-butylphenyl) -3-phenyl-phenylphosphonite, bis (2,6-di-tert-butylphenyl)- 4-phenyl-phenylphosphonite, bis (2,6-di-tert-butylphenyl) -3-phenyl-phenylphosphonite, and the like, and tetrakis (di-tert-butylphenyl) -biphenylenediphosphonite, bis (Di-tert-butylphenyl) -phenyl-phenylphosphonite is preferred, tetrakis (2,4-di-tert-butylphenyl) -biphenylenediphosphonite, bis (2,4-di-tert-butylphenyl)- More preferred is phenyl-phenylphosphonite. Such a phosphonite compound is preferable because it can be used in combination with a phosphite compound having an aryl group in which two or more alkyl groups are substituted.

  Examples of the phosphonate compound include dimethyl benzenephosphonate, diethyl benzenephosphonate, and dipropyl benzenephosphonate.

  Tertiary phosphine includes triethylphosphine, tripropylphosphine, tributylphosphine, trioctylphosphine, triamylphosphine, dimethylphenylphosphine, dibutylphenylphosphine, diphenylmethylphosphine, diphenyloctylphosphine, triphenylphosphine, tri-p-tolyl. Examples include phosphine, trinaphthylphosphine, and diphenylbenzylphosphine. A particularly preferred tertiary phosphine is triphenylphosphine.

  The phosphorus stabilizer can be used not only in one kind but also in a mixture of two or more kinds. Among the phosphorus stabilizers, phosphite compounds or phosphonite compounds are preferable. In particular, tris (2,4-di-tert-butylphenyl) phosphite, tetrakis (2,4-di-tert-butylphenyl) -4,4′-biphenylenediphosphonite and bis (2,4-di-) tert-Butylphenyl) -phenyl-phenylphosphonite is preferred. A combination of these and a phosphate compound is also a preferred embodiment.

(Iii) Hindered phenol-based stabilizer The black resin composition of the present invention contains a hindered phenol-based stabilizer mainly for the purpose of improving the heat stability and heat aging resistance during the molding process. Can do. Examples of such hindered phenol stabilizers include α-tocopherol, butylhydroxytoluene, sinapyl alcohol, vitamin E, n-octadecyl-β- (4′-hydroxy-3 ′, 5′-di-tert-butylfel). ) Propionate, 2-tert-butyl-6- (3′-tert-butyl-5′-methyl-2′-hydroxybenzyl) -4-methylphenyl acrylate, 2,6-di-tert-butyl-4- ( N, N-dimethylaminomethyl) phenol, 3,5-di-tert-butyl-4-hydroxybenzylphosphonate diethyl ester, 2,2′-methylenebis (4-methyl-6-tert-butylphenol), 2,2 ′ -Methylenebis (4-ethyl-6-tert-butylphenol), 4,4'-methylenebis (2 , 6-di-tert-butylphenol), 2,2′-methylenebis (4-methyl-6-cyclohexylphenol), 2,2′-dimethylene-bis (6-α-methyl-benzyl-p-cresol) 2, 2′-ethylidene-bis (4,6-di-tert-butylphenol), 2,2′-butylidene-bis (4-methyl-6-tert-butylphenol), 4,4′-butylidenebis (3-methyl-6) -Tert-butylphenol), triethylene glycol-N-bis-3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionate, 1,6-hexanediol bis [3- (3,5- Di-tert-butyl-4-hydroxyphenyl) propionate], bis [2-tert-butyl-4-methyl 6- (3-tert- Butyl-5-methyl-2-hydroxybenzyl) phenyl] terephthalate, 3,9-bis {2- [3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionyloxy] -1,1, -Dimethylethyl} -2,4,8,10-tetraoxaspiro [5,5] undecane, 4,4'-thiobis (6-tert-butyl-m-cresol), 4,4'-thiobis (3- Methyl-6-tert-butylphenol), 2,2′-thiobis (4-methyl-6-tert-butylphenol), bis (3,5-di-tert-butyl-4-hydroxybenzyl) sulfide, 4,4 ′ -Di-thiobis (2,6-di-tert-butylphenol), 4,4'-tri-thiobis (2,6-di-tert-butylphenol), 2,2-thio Ethylenebis- [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], 2,4-bis (n-octylthio) -6- (4-hydroxy-3 ′, 5′-di -Tert-butylanilino) -1,3,5-triazine, N, N'-hexamethylenebis- (3,5-di-tert-butyl-4-hydroxyhydrocinnamide), N, N'-bis [3 -(3,5-di-tert-butyl-4-hydroxyphenyl) propionyl] hydrazine, 1,1,3-tris (2-methyl-4-hydroxy-5-tert-butylphenyl) butane, 1,3,3 5-trimethyl-2,4,6-tris (3,5-di-tert-butyl-4-hydroxybenzyl) benzene, tris (3,5-di-tert-butyl-4-hydroxyphenyl) Isocyanurate, tris (3,5-di-tert-butyl-4-hydroxybenzyl) isocyanurate, 1,3,5-tris (4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl) isocyanurate 1,3,5-tris 2 [3 (3,5-di-tert-butyl-4-hydroxyphenyl) propionyloxy] ethyl isocyanurate and tetrakis [methylene-3- (3 ′, 5′-di- tert-butyl-4-hydroxyphenyl) propionate] methane and the like. All of these are readily available. The said hindered phenolic antioxidant can be used individually or in combination of 2 or more types.

  The amount of the (ii) phosphorus stabilizer and (iii) hindered phenol antioxidant is preferably 0.0001 to 1 part by weight, more preferably 0.001 to 100 parts by weight of the component A. 0.1 parts by weight, more preferably 0.005 to 0.1 parts by weight. If the stabilizer is too small than the above range, it is difficult to obtain a good stabilizing effect. If the stabilizer exceeds the above range, the appearance of the material may be deteriorated or the appearance may be poor, such as bleed out. There is.

  In the black resin composition of the present invention, an antioxidant other than the hindered phenol antioxidant can be used as appropriate. Examples of such other antioxidants include pentaerythritol tetrakis (3-mercaptopropionate), pentaerythritol tetrakis (3-lauryl thiopropionate), and glycerol-3-stearyl thiopropionate. The amount of these other antioxidants used is preferably 0.001 to 0.05 parts by weight with respect to 100 parts by weight of the polycarbonate resin.

  In addition, the polycarbonate resin of the present invention includes UV absorbers, light stabilizers, antistatic agents, heat ray absorbers, flame retardants, hydrolysis improvers, inorganic fillers, antibacterial agents, photocatalytic antifouling agents, and light diffusion. An agent, a white pigment for light high reflection, and the like can be contained. These can be contained by appropriately selecting agents and blending amounts that do not hinder the effects of the present invention.

(Iv) Ultraviolet Absorber The black resin composition of the present invention can contain an ultraviolet absorber. Specific examples of the ultraviolet absorber of the present invention include, for example, 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-octoxybenzophenone, 2-hydroxy-4 in the benzophenone series. -Benzyloxybenzophenone, 2-hydroxy-4-methoxy-5-sulfoxybenzophenone, 2-hydroxy-4-methoxy-5-sulfoxytrihydridolate benzophenone, 2,2'-dihydroxy-4-methoxybenzophenone, 2, 2 ′, 4,4′-tetrahydroxybenzophenone, 2,2′-dihydroxy-4,4′-dimethoxybenzophenone, 2,2′-dihydroxy-4,4′-dimethoxy-5-sodiumsulfoxybenzophenone, bis (5-Benzoyl-4-hydroxy-2- Examples include methoxyphenyl) methane, 2-hydroxy-4-n-dodecyloxybenzophenone, and 2-hydroxy-4-methoxy-2′-carboxybenzophenone.

  Specific examples of the ultraviolet absorber include benzotriazole-based compounds such as 2- (2-hydroxy-5-methylphenyl) benzotriazole, 2- (2-hydroxy-5-tert-octylphenyl) benzotriazole, 2 -(2-hydroxy-3,5-dicumylphenyl) phenylbenzotriazole, 2- (2-hydroxy-3-tert-butyl-5-methylphenyl) -5-chlorobenzotriazole, 2,2'-methylenebis [ 4- (1,1,3,3-tetramethylbutyl) -6- (2H-benzotriazol-2-yl) phenol], 2- (2-hydroxy-3,5-di-tert-butylphenyl) benzo Triazole, 2- (2-hydroxy-3,5-di-tert-butylphenyl) -5-chlorobenzotriazol 2- (2-hydroxy-3,5-di-tert-amylphenyl) benzotriazole, 2- (2-hydroxy-5-tert-octylphenyl) benzotriazole, 2- (2-hydroxy-5-tert- Butylphenyl) benzotriazole, 2- (2-hydroxy-4-octoxyphenyl) benzotriazole, 2,2′-methylenebis (4-cumyl-6-benzotriazolephenyl), 2,2′-p-phenylenebis ( 1,3-benzoxazin-4-one), and 2- [2-hydroxy-3- (3,4,5,6-tetrahydrophthalimidomethyl) -5-methylphenyl] benzotriazole, and 2- (2 ′ -Hydroxy-5-methacryloxyethylphenyl) -2H-benzotriazole and copolymer with the monomer 2 such as a copolymer with a possible vinyl monomer and a copolymer of 2- (2′-hydroxy-5-acryloxyethylphenyl) -2H-benzotriazole with a vinyl monomer copolymerizable with the monomer. Examples include polymers having a -hydroxyphenyl-2H-benzotriazole skeleton.

  Specific examples of the ultraviolet absorber include 2- (4,6-diphenyl-1,3,5-triazin-2-yl) -5-hexyloxyphenol and 2- (4) in hydroxyphenyltriazine series. , 6-Diphenyl-1,3,5-triazin-2-yl) -5-methyloxyphenol, 2- (4,6-diphenyl-1,3,5-triazin-2-yl) -5-ethyloxy Phenol, 2- (4,6-diphenyl-1,3,5-triazin-2-yl) -5-propyloxyphenol, and 2- (4,6-diphenyl-1,3,5-triazine-2- Yl) -5-butyloxyphenol and the like. Furthermore, the phenyl group of the above exemplary compounds such as 2- (4,6-bis (2,4-dimethylphenyl) -1,3,5-triazin-2-yl) -5-hexyloxyphenol is 2,4-dimethyl. Examples of the compound are phenyl groups.

  As the ultraviolet absorber, specifically, in the cyclic imino ester type, for example, 2,2′-p-phenylenebis (3,1-benzoxazin-4-one), 2,2 ′-(4,4′-diphenylene) ) Bis (3,1-benzoxazin-4-one), 2,2 ′-(2,6-naphthalene) bis (3,1-benzoxazin-4-one) and the like.

  Further, as the ultraviolet absorber, specifically, for cyanoacrylate, for example, 1,3-bis-[(2′-cyano-3 ′, 3′-diphenylacryloyl) oxy] -2,2-bis [(2- Examples include cyano-3,3-diphenylacryloyl) oxy] methyl) propane and 1,3-bis-[(2-cyano-3,3-diphenylacryloyl) oxy] benzene.

  Further, the ultraviolet absorber has a structure of a monomer compound capable of radical polymerization, whereby the ultraviolet-absorbing monomer and / or the light-stable monomer having a hindered amine structure, and an alkyl (meth) acrylate. A polymer type ultraviolet absorber obtained by copolymerization with a monomer such as may be used. Preferred examples of the UV-absorbing monomer include compounds containing a benzotriazole skeleton, a benzophenone skeleton, a triazine skeleton, a cyclic imino ester skeleton, and a cyanoacrylate skeleton in the ester substituent of (meth) acrylate. The

Among them, benzotriazole and hydroxyphenyltriazine are preferable from the viewpoint of ultraviolet absorption ability, and cyclic imino ester and cyanoacrylate are preferable from the viewpoint of heat resistance and hue. You may use the said ultraviolet absorber individually or in mixture of 2 or more types.
The content of the ultraviolet absorber is 0.01 to 2 parts by weight, preferably 0.03 to 2 parts by weight, more preferably 0.04 to 1 part by weight, more preferably 0, based on 100 parts by weight of the component A. 0.05 to 0.5 parts by weight.

(V) Flame Retardant The black resin composition of the present invention may contain various compounds known as flame retardants for polycarbonate resins. The compounding of the compound used as the flame retardant not only improves the flame retardancy but also provides, for example, an improvement in antistatic properties, fluidity, rigidity, and thermal stability based on the properties of each compound.
Examples of such flame retardants include (i) organometallic salt flame retardants (for example, alkali (earth) organic sulfonate metal salts, borate metal salt flame retardants, stannate metal salt flame retardants, etc.), and (ii) Organophosphorous flame retardants (for example, monophosphate compounds, phosphate oligomer compounds, phosphonate oligomer compounds, phosphonitrile oligomer compounds, and phosphonic acid amide compounds), (iii) silicone flame retardants comprising silicone compounds, and (iv) halogens And flame retardant (for example, brominated epoxy resin, brominated polystyrene, brominated polycarbonate (including oligomers), brominated polyacrylate, chlorinated polyethylene, etc.).

(Vi) Anti-dripping agent The black resin composition of the present invention may contain an anti-dripping agent. By using such an anti-dripping agent in combination with the above flame retardant, better flame retardancy can be obtained. Examples of the anti-dripping agent include a fluorinated polymer having a fibril-forming ability. Examples of such a polymer include polytetrafluoroethylene, tetrafluoroethylene copolymers (for example, tetrafluoroethylene / hexafluoropropylene copolymers). , Etc.), partially fluorinated polymers as shown in U.S. Pat. No. 4,379,910, polycarbonate resins produced from fluorinated diphenols, etc., preferably polytetrafluoroethylene (hereinafter referred to as PTFE). Is).

Polytetrafluoroethylene (fibrillated PTFE) having fibril-forming ability has a very high molecular weight, and exhibits a tendency to bind PTFE to each other by an external action such as shearing force to form a fiber. Its number average molecular weight ranges from 1.5 million to tens of millions. The lower limit is more preferably 3 million. The number average molecular weight is calculated based on the melt viscosity of polytetrafluoroethylene at 380 ° C. as disclosed in JP-A-6-145520. That is, the fibrillated PTFE has a melt viscosity at 380 ° C. measured by the method described in this publication in the range of 10 ⁷ to 10 ¹³ poise, preferably in the range of 10 ⁸ to 10 ¹² poise.

  Such PTFE can be used in solid form or in the form of an aqueous dispersion. In addition, PTFE having such fibril-forming ability can improve the dispersibility in the resin, and it is also possible to use a PTFE mixture in a mixed form with other resins in order to obtain better flame retardancy and mechanical properties. is there. Further, as disclosed in JP-A-6-145520, those having a structure having such a fibrillated PTFE as a core and a low molecular weight polytetrafluoroethylene as a shell are also preferably used.

  Examples of commercially available fibrillated PTFE include Teflon (registered trademark) 6J from Mitsui DuPont Fluorochemical Co., Ltd., Polyflon MPA FA500, F-201L from Daikin Chemical Industries, Ltd., and the like. Commercially available aqueous dispersions of fibrillated PTFE include: Fluon AD-1, AD-936 manufactured by Asahi IC Fluoropolymers, Fluon D-1, D-2 manufactured by Daikin Industries, Ltd., Mitsui A representative example is Teflon (registered trademark) 30J manufactured by DuPont Fluorochemical Co., Ltd.

  As a mixed form of fibrillated PTFE, (1) a method in which an aqueous dispersion of fibrillated PTFE and an aqueous dispersion or solution of an organic polymer are mixed and co-precipitated to obtain a co-agglomerated mixture (JP-A-60-258263). (2) A method of mixing an aqueous dispersion of fibrillated PTFE and dried organic polymer particles (Japanese Patent Laid-Open No. 4-272957). Described method), (3) A method in which an aqueous dispersion of fibrillated PTFE and an organic polymer particle solution are uniformly mixed, and the respective media are simultaneously removed from the mixture (Japanese Patent Laid-Open Nos. 06-220210, (Method described in Japanese Patent Application Laid-Open No. 08-188653), (4) A method of polymerizing monomers forming an organic polymer in an aqueous dispersion of fibrillated PTFE (Method described in JP-A-9-95583), and (5) an aqueous dispersion of PTFE and an organic polymer dispersion are uniformly mixed, and then a vinyl monomer is further polymerized in the mixed dispersion. Thereafter, those obtained by a method for obtaining a mixture (a method described in JP-A No. 11-29679) can be used. Examples of commercially available fibrillated PTFE in a mixed form include “Metablene A3800” (trade name) manufactured by Mitsubishi Rayon Co., Ltd. and “BLENDEX B449” (trade name) manufactured by GE Specialty Chemicals.

In order to more effectively utilize the good mechanical properties and surface appearance properties of the black resin composition of the present invention, the fibrillated PTFE is preferably finely dispersed as much as possible. As a means of achieving such fine dispersion, the above mixed form of fibrillated PTFE is advantageous. A method of directly supplying an aqueous dispersion in a melt kneader is also advantageous for fine dispersion. However, in the case of the aqueous dispersion form, consideration is required in that the hue is slightly deteriorated. The proportion of fibrillated PTFE in the mixed form is preferably 10 to 80% by weight, more preferably 15 to 75% by weight, in 100% by weight of the mixture. When the ratio of fibrillated PTFE is in such a range, good dispersibility of fibrillated PTFE can be achieved.
The content of the fibrillated PTFE in the polycarbonate resin composition is preferably 0.001 to 1 part by weight, more preferably 0.1 to 0.7 part by weight based on 100 parts by weight of the component A.

(Vii) Antistatic agent The black resin composition of the present invention may require antistatic performance, and in such a case, it is preferable to include an antistatic agent. Examples of the antistatic agent include (1) aryl sulfonic acid phosphonium salts represented by dodecylbenzenesulfonic acid phosphonium salts, organic sulfonic acid phosphonium salts such as alkyl sulfonic acid phosphonium salts, and tetrafluoroboric acid phosphonium salts. Examples thereof include phosphonium borate salts. The content of the phosphonium salt is suitably 5 parts by weight or less, preferably 0.05 to 5 parts by weight, more preferably 1 to 3.5 parts by weight, based on a total of 100 parts by weight of component A and component B. Parts, more preferably in the range of 1.5 to 3 parts by weight.

  Examples of the antistatic agent include: (2) lithium organic sulfonate, organic sodium sulfonate, organic potassium sulfonate, cesium organic sulfonate, rubidium organic sulfonate, calcium organic sulfonate, magnesium organic sulfonate, and barium organic sulfonate. And organic sulfonate alkali (earth) metal salts. Such metal salts are also used as flame retardants as described above. More specific examples of such metal salts include metal salts of dodecylbenzene sulfonic acid and metal salts of perfluoroalkane sulfonic acid. The content of the organic sulfonate alkali (earth) metal salt is suitably 0.5 parts by weight or less based on the total of 100 parts by weight of component A and component B, preferably 0.001 to 0.3 weights. Parts, more preferably 0.005 to 0.2 parts by weight. In particular, alkali metal salts such as potassium, cesium, and rubidium are preferable.

  Examples of the antistatic agent include (3) organic sulfonic acid ammonium salts such as alkyl sulfonic acid ammonium salt and aryl sulfonic acid ammonium salt. The ammonium salt is suitably 0.05 parts by weight or less based on a total of 100 parts by weight of the component A and the component B. Examples of the antistatic agent include (4) a polymer containing a poly (oxyalkylene) glycol component such as polyether ester amide as a constituent component. The polymer is suitably 5 parts by weight or less based on a total of 100 parts by weight of the component A and the component B.

<Other additives>
In addition to the additives described above, the black resin composition of the present invention includes a fluorescent dye, a fluorescent brightening agent, an inorganic phosphor (for example, a phosphor having aluminate as a mother crystal), a bluing agent, a flow A dispersant such as paraffin, a heat ray absorbent, a photochromic agent, and the like can be blended.

<Manufacture of black resin composition and molded product>
In producing the black resin composition of the present invention, the production method is not particularly limited, and a known production method can be used. Usually, polycarbonate resin, additives, and colorants are premixed, then put into an extruder and melt-kneaded, and then the extruded thread is cooled and cut by a pelletizer to produce a pellet-shaped molding material . As the extruder, any of a single screw extruder and a twin screw extruder can be used, but a twin screw extruder is preferable from the viewpoint of productivity and kneadability. A typical example of such a twin screw extruder is ZSK (trade name, manufactured by Werner & Pfleiderer). Specific examples of similar types include TEX (trade name, manufactured by Nippon Steel Works, Ltd.), TEM (trade name, manufactured by Toshiba Machine Co., Ltd.), KTX (product name, manufactured by Kobe Steel, Ltd.), and the like. Can be mentioned. As the extruder, one having a vent capable of degassing moisture in the raw material and volatile gas generated from the melt-kneaded resin can be preferably used. From the vent, a vacuum pump is preferably installed for efficiently discharging generated moisture and volatile gas to the outside of the extruder. It is also possible to remove a foreign substance from the resin composition by installing a screen for removing the foreign substance mixed in the extrusion raw material in the zone in front of the extruder die. Examples of such a screen include a wire mesh, a screen changer, a sintered metal plate (such as a disk filter), and the like.

  Further, the additive and the colorant can be independently supplied to the extruder, but it is preferable to premix with the resin raw material as described above. Examples of such premixing means include a Nauter mixer, a V-type blender, a Henschel mixer, a mechanochemical apparatus, and an extrusion mixer. A more suitable method is to prepare a master agent by mixing a part of the raw material and an additive with a high-speed stirrer such as a Henschel mixer, and then leave the total amount of the resin raw material and the high-speed component such as a Nauter mixer. It is a method of mixing with a stirrer that is not.

The resin extruded from the extruder is directly cut into pellets, or after forming strands, the strands are cut with a pelletizer and pelletized. When it is necessary to reduce the influence of external dust or the like, it is preferable to clean the atmosphere around the extruder. Furthermore, in the production of such pellets, various methods that have already been proposed are used to narrow the pellet shape distribution, further reduce miscuts, further reduce fine powder generated during transportation or transportation, and It is preferable to reduce bubbles (vacuum bubbles) generated in the strands and pellets. Miscuts can be reduced by controlling the thread temperature during cutting with a pelletizer, blowing ionic air during cutting, optimizing the rake angle of the pelletizer, and properly blending the release agent, and cutting. And a method of filtering the mixture of the pellets and water to separate the pellets, water and miscuts. An example of the measuring method is disclosed in, for example, Japanese Patent Application Laid-Open No. 2003-200421. By these prescriptions, it is possible to increase the molding cycle and reduce the occurrence rate of defects such as silver.
The black resin composition of the present invention can also obtain a desired molded product by a method such as injection molding, injection compression molding, injection blow molding, extrusion molding or blow molding.

  Hereinafter, although an example is given and explained in detail, the present invention is not limited to this unless it exceeds the purpose. In addition, the physical-property evaluation and jet black evaluation in an Example and a comparative example followed the following method.

<Physical property evaluation>
(1) The viscosity-average molecular weight viscosity average molecular weight, determined using an Ostwald viscometer specific viscosity of (eta _SP) from a solution prepared by dissolving polycarbonate resin 0.7g methylene chloride 100ml at 20 ° C., from the specific viscosity (eta _SP) The viscosity average molecular weight (Mv) was calculated by the following formula.
Specific viscosity (η _SP ) = (t−t ₀ ) / t ₀
[T ₀ is methylene chloride falling seconds, t is sample solution falling seconds]
η _SP /c=[η]+0.45×[η] ² c (where [η] is the intrinsic viscosity)
[Η] = 1.23 × 10 ⁻⁴ Mv ^0.83
c = 0.7

(2) Pencil hardness Using a mold having a cavity surface with an arithmetic average roughness (Ra) of 0.03 μm, using a J-75E3 injection molding machine manufactured by Nippon Steel Works, cylinder temperature 280 ° C., mold temperature Under the conditions of 80 ° C., with a holding pressure of 20 seconds and a cooling time of 20 seconds, the width is 50 mm, the length is 90 mm, the thickness is 3 mm (length 20 mm), 2 mm (length 45 mm), 1 mm (length 25 mm) from the gate side. A three-stage plate was formed. The pencil hardness at a thickness of 2 mm of the three-stage plate was measured according to JIS K5600.

(3) Impact resistance evaluation (notched Charpy impact strength)
The notched Charpy impact strength of the test piece at 23 ° C. was measured according to ISO179.

(4) Fluidity Using a Sumitomo Heavy Industries, Ltd. SG-150U molding machine, the flow length was evaluated with an Archimedes spiral flow mold (channel thickness 2 mm, channel width 8 mm). The conditions were a cylinder temperature of 280 ° C., a mold temperature of 70 ° C., and an injection pressure of 100 MPa.

(5) Heat resistance After the pellets are dried at 110 ° C. for 5 hours, the deflection temperature under load is measured according to ISO 178 using a test piece injection-molded at a cylinder temperature of 280 ° C. using an injection molding machine J-75E3 manufactured by Nippon Steel Works. did. Load: 1.80 MPa. (Specimen shape: length 80 mm x width 10 mm x thickness 4 mm)

(6) Jetness The jetness evaluation was performed by glossiness evaluation and color difference evaluation. The glossiness at an incident light reception angle of 20 degrees is 75 or more, the glossiness at an incident light reception angle of 60 degrees is 85 or more, the color difference L * is 3.0 or more and 13.0 or less, and a * is −1.0 or more and −0 0.1 or less and b * of 1.0 or more and 4.0 or less are excellent in jet blackness.
(6-1) Evaluation of Glossiness The obtained black molded product (three-stage plate, 2 mm thickness) was measured with a gloss meter (HORIBA IG-331, manufactured by HORIBA) with an incident light receiving angle of 20 degrees and 60 degrees. It was measured.
(6-2) Color difference evaluation The obtained black molded product (three-stage plate, thickness 2 mm part) is in accordance with JIS K7373 (light source D65, transmission), integrating sphere spectrophotometer CE-7000A (X-Rite) Then, the color difference was measured using a D65 light source, a reflection method, a viewing angle of 10 °, and a color difference formula CIE1976 (L * a * b *).

(Examples 1-16, Comparative Examples 1-16)
Tris (2,4-di-tert-butylphenyl) phosphite was added to the powder obtained with the composition shown in Table 1 at 0.05% by weight and stearic acid monoglyceride at 0.1% by weight. After mixing (A-2 component), (B component), (C component), and (D component) with the composition described in 2-3, the powder was mixed with a vent type twin screw extruder [Corporation] A polycarbonate resin was obtained after melt-kneading while degassing with KTX-46 manufactured by Kobe Steel. About the obtained resin, pencil hardness, impact resistance, fluidity, heat resistance, jet blackness were evaluated by the method described above. The results are shown in Tables 2-3.

<Copolymerized polycarbonate resin component (component A-1)>
(Production of copolymer polycarbonate resin (PC-1))
A reactor equipped with a thermometer, a stirrer and a reflux condenser was charged with 3844 parts of a 48% aqueous sodium hydroxide solution and 22,380 parts of ion-exchanged water, and 2,2-bis (4-hydroxy-3-methyl) was added thereto. Phenyl) propane (Bis-C, manufactured by Honshu Chemical) 1,992 parts, 2,2-bis (4-hydroxyphenyl) propane (Bis-A, manufactured by Nippon Steel Chemical) 1,773 parts, and hydrosulfite 7 After dissolving 53 parts (manufactured by Wako Pure Chemical Industries, Ltd.), 13,210 parts of methylene chloride was added, and 2,000 parts of phosgene was blown in at about 15-25 ° C. over about 60 minutes with stirring. After completion of the phosgene blowing, 640 parts of a 48% aqueous sodium hydroxide solution and 93.2 parts of p-tert-butylphenol were added and stirring was resumed. After emulsification, 3.24 parts of triethylamine was added and further stirred at 28 to 33 ° C. for 1 hour. The reaction was terminated. After completion of the reaction, the product is diluted with methylene chloride, washed with water, acidified with hydrochloric acid, washed with water, and further washed with water until the conductivity of the aqueous phase becomes substantially the same as that of ion-exchanged water. Obtained. Next, this solution is passed through a filter having an aperture of 0.3 μm, and further dropped into warm water in a kneader with an isolation chamber having a foreign matter outlet at the bearing, and the polycarbonate resin is flaked while distilling off methylene chloride. The liquid-containing flakes were pulverized and dried to obtain a powder.

(Production of copolymer polycarbonate resin (PC-2))
A polycarbonate resin was obtained in the same manner as in Example 1 except that p-tert-butylphenol was changed to 81.6 parts by weight. The results are shown in Table 1.
(Production of copolymer polycarbonate resin (PC-3))
A polycarbonate resin was obtained in the same manner as in Example 1 except that p-tert-butylphenol was changed to 69.9 parts by weight. The results are shown in Table 1.
(Production of copolymer polycarbonate resin (PC-4))
The same procedure as in Example 1 except that 1,593 parts of 2,2-bis (4-hydroxy-3-methylphenyl) propane and 2,128 parts of 2,2-bis (4-hydroxyphenyl) propane were changed. A polycarbonate resin was obtained. The results are shown in Table 1.
(Production of copolymer polycarbonate resin (PC-5))
In the same manner as in Example 1 except that 3,187 parts of 2,2-bis (4-hydroxy-3-methylphenyl) propane and 709 parts of 2,2-bis (4-hydroxyphenyl) propane were changed. A polycarbonate resin was obtained. The results are shown in Table 1.
(Production of copolymer polycarbonate resin (PC-6))
The same procedure as in Example 1 was performed except that Teijin Chemicals Panlite L-1225WX was used as the polycarbonate resin. The results are shown in Table 1.
(Production of copolymer polycarbonate resin (PC-7))
The same procedure as in Example 1 except that 1,195 parts of 2,2-bis (4-hydroxy-3-methylphenyl) propane and 2,483 parts of 2,2-bis (4-hydroxyphenyl) propane were changed. A polycarbonate resin was obtained. The results are shown in Table 1.
(Production of copolymer polycarbonate resin (PC-8)) C homo, Mv = 20,000
The same procedure as in Example 1 except that 2,2-bis (4-hydroxyphenyl) propane was not used and the amount was changed to 3,984 parts of 2,2-bis (4-hydroxy-3-methylphenyl) propane. A polycarbonate resin was obtained. The results are shown in Table 1.
(Production of copolymer polycarbonate resin (PC-9)) Mv = 16,000
A polycarbonate resin was obtained in the same manner as in Example 1 except that p-tert-butylphenol was changed to 116.6 parts by weight. The results are shown in Table 1.
(Production of copolymer polycarbonate resin (PC-10)) Mv = 34,000
A polycarbonate resin was obtained in the same manner as in Example 1 except that p-tert-butylphenol was changed to 46.4 parts by weight. The results are shown in Table 1.

(Production of copolymer polycarbonate resin (PC-11))
A reactor equipped with a thermometer, a stirrer and a reflux condenser was charged with 5236 parts of a 48% aqueous sodium hydroxide solution and 20,000 parts of ion-exchanged water, and 1,1-bis (4-hydroxy-3-methyl) was added thereto. After dissolving 4704 parts of phenyl) cyclohexane (Bis-OC-Z) and 9.4 parts of hydrosulfite, 17,540 parts of methylene chloride was added, and 2,200 parts of phosgene were added at 15-25 ° C. with stirring. Blowed over 60 minutes. After completion of the phosgene blowing, 654 parts of a 48% aqueous sodium hydroxide solution and 81.6 parts of p-tert-butylphenol were added and stirring was resumed. After emulsification, 4.32 parts of triethylamine was added and further stirred at 28 to 33 ° C. for 1 hour. The reaction was terminated. After completion of the reaction, the product is diluted with methylene chloride, washed with water, acidified with hydrochloric acid, washed with water, and further washed with water until the conductivity of the aqueous phase becomes substantially the same as that of ion-exchanged water. Obtained. Next, this solution is passed through a filter having an aperture of 0.3 μm, and further dropped into warm water in a kneader with an isolation chamber having a foreign matter outlet at the bearing, and the polycarbonate resin is flaked while distilling off methylene chloride. The liquid-containing flakes were pulverized and dried to obtain a powder.

(Production of copolymer polycarbonate resin (PC-12))
A reactor equipped with a thermometer, a stirrer and a reflux condenser was charged with 5236 parts of a 48% aqueous sodium hydroxide solution and 20,000 parts of ion-exchanged water, and 1,1-bis (4-hydroxy-3-methyl) was added thereto. Phenyl) cyclohexane (Bis-OC-Z) 2,533 parts, bisphenol A 1948 parts and hydrosulfite 9.4 parts were dissolved, methylene chloride 17,540 parts was added, and phosgene was added at 15-25 ° C. with stirring. 2,200 parts were blown in over about 60 minutes. After completion of the phosgene blowing, 654 parts of a 48% aqueous sodium hydroxide solution and 102 parts of p-tert-butylphenol were added and stirring was resumed. After emulsification, 4.32 parts of triethylamine was added, and the mixture was further stirred at 28 to 33 ° C. for 1 hour. The reaction was terminated. After completion of the reaction, the product is diluted with methylene chloride, washed with water, acidified with hydrochloric acid, washed with water, and further washed with water until the conductivity of the aqueous phase becomes substantially the same as that of ion-exchanged water. Obtained. Next, this solution is passed through a filter having an aperture of 0.3 μm, and further dropped into warm water in a kneader with an isolation chamber having a foreign matter outlet at the bearing, and the polycarbonate resin is flaked while distilling off methylene chloride. The liquid-containing flakes were pulverized and dried to obtain a powder.

<Styrenic resin component (A-2 component)>
ABS resin: UT-61 (trade name) manufactured by Japan A & L Co., Ltd. (butadiene rubber component: about 14% by weight, weight average rubber particle diameter: 0.56 μm) was used.
AS resin: Japan A & L Co., Ltd. Lightac-ABS-207 (trade name) (weight average molecular weight 109,000) was used.
<Impact modifier component (component B)>
B-1: Core-shell graft copolymer (Rohm and Haas: Paraloid EXL-2602 (trade name))
B-2: Core-shell graft copolymer (Mitsubishi Rayon Co., Ltd .: Metablen S-2001 (trade name)
B-3: Core-shell graft copolymer (Mitsubishi Rayon Co., Ltd. product: Metablen W-450A (trade name)
<Carbon black (component C)>
Component C: carbon black (Mitsubishi Kasei Kogyo Co., Ltd. # 3600)
<Plastic dye (component D)
D component: NUBIAN BLACK PC-5857 (made by Orient Chemical Industry Co., Ltd.)

  As is clear from the results in Tables 2 and 3, the black resin molded article made of the black resin composition of the present invention is excellent in impact resistance, fluidity, surface hardness, heat resistance and jet blackness. On the other hand, it can be seen that the polycarbonate resin that is widely used cannot provide useful properties that are poor in surface hardness. Moreover, in the modified polycarbonate of patent document 2, it was confirmed that fluidity | liquidity and impact resistance are inferior. That is, according to this invention, it turns out that the black resin composition and black resin molded product which cannot be obtained with the polycarbonate resin generally used or the modified polycarbonate of patent document 2 are obtained.

  The black resin composition and the black resin molded product of the present invention are a casing, interior panel, door handle, steering, etc. of electric / electronic / OA equipment represented by a mobile phone, a liquid crystal television, a speaker, a portable game machine, and a notebook computer. It can be used for car audio / car navigation frames, automotive interiors such as shift knobs, exterior parts such as roof spoilers and window garnishes, furniture and musical instruments.

Claims (4)

The aromatic dihydroxy component comprises 2,2-bis (4-hydroxy-3-methylphenyl) propane component (component a-1) and 2,2-bis (4-hydroxyphenyl) propane component (component a-2). A copolymer polycarbonate resin (A) in which the proportion of component a-1 is 40 to 90 mol in 100 mol of the wholly aromatic dihydroxy component and the viscosity average molecular weight is 1.8 × 10 ^{4 to} 3.2 × 10 ⁴ -1 component) 95 to 60 parts by weight and styrene-based resin (A-2) 5 to 40 parts by weight of resin component (A component) 100 parts by weight, impact modifier (B component) 0 to 10 parts by weight Part, carbon black (C component) 0.1-5 weight part black resin composition formed.   The black resin composition according to claim 1, comprising 0.01 to 1 part by weight of two or more kinds of plastic dyes (D component) with respect to 100 parts by weight of the resin component (A component).   The black resin composition according to claim 1 or 2, wherein the impact modifier (component B) contains at least one rubber-modified resin selected from butadiene, acrylic and silicone, or a copolymer thereof.   The black molded product formed by shape | molding the black resin composition in any one of Claims 1-3.