CN101684194A - Aromatic polycarbonate resin composition with fire-retardancy - Google Patents

Aromatic polycarbonate resin composition with fire-retardancy Download PDF

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CN101684194A
CN101684194A CN200910173569A CN200910173569A CN101684194A CN 101684194 A CN101684194 A CN 101684194A CN 200910173569 A CN200910173569 A CN 200910173569A CN 200910173569 A CN200910173569 A CN 200910173569A CN 101684194 A CN101684194 A CN 101684194A
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polycarbonate resin
aromatic polycarbonate
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CN101684194B (en
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石田将史
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Teijin Ltd
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Teijin Chemicals Ltd
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Abstract

The invention provides an aromatic polycarbonate resin composition with fire-retardancy, which has improved scratch resistance and color emissivity without reducing mechanical characteristics. Relative to 100 proportions by weight of resin component, the composition contains organophosphorus combustion inhibitor (D component) 5-25 proportions by weight, fluorine-containing drip-proof agent (E component) 0.05-2 proportions by weight, and slide property given agent (F component) 0.01-0.4 proportions by weight; relative to 100 proportions by weight of the aromatic polycarbonate resin (A component), the resin component contains 0.1-10 proportions by weight of graft copolymer (B component) with a mean particle diameter 100-180 nm obtained from emulsion polymerization of latex containing butadiene rubber polymer, unsaturated carboxylic acid alkyl ester and aromatic vinyl monomer whose refractive indexes are above 1.535, and 5-40 proportions by weight of phenylethylene resin (C component) except B component with a weight average molecular weight under 120,000.

Description

Flame-retardant aromatic polycarbonate resin composition
Technical field
The present invention relates to comprise the improved flame-retardant aromatic polycarbonate resin composition of flame retardant resistance of phenylethylene resin series, organic phosphorus flame retardant, fluorine-containing Antidrip agent and the sliding imparting agent of aromatic polycarbonate resin, specific graft copolymer, specific molecular weight range.More particularly, the present invention relates to phenylethylene resin series, sliding imparting agent by cooperating specific above-mentioned graft copolymer, specific molecular weight range, provide have high Chromaticity, the flame-retardant aromatic polycarbonate resin composition of the moulding product of shock resistance, flame retardant resistance, scuff resistance.
Background technology
Aromatic polycarbonate resin is owing to having excellent mechanical characteristics, thermal property, flame retardant resistance, therefore in industrial extensive utilization.And developed the polymer alloy of aromatic polycarbonate resin in a large number with other thermoplastic resins, elastomerics etc., in fields such as office automation (OA) apparatus field, electric/electronic device field, automotive field, other groceries, be extensive use of.
In recent years, particularly lightweight, the miniaturization of goods is remarkable in the electric and electronic field, and the thin-walled property of using the moulding product of aromatic polycarbonate resin is also developing.In such thin molded article,, usually add the caoutchouc elasticity polymkeric substance as the modified impact agent in order to improve intensity, particularly shock strength.
In addition, the recirculation of used goods has become must be indispensable, also attempted the recirculation of resin in every field.For the recirculation that makes resin is easy, in the resin that has in the past carried out application, save application and in only with resin the blended tinting material carry out the desired painted resin of goods and increasing.For this resin, resin is required higher color emissivity.When particularly in aromatic polycarbonate resin, having cooperated rubber elastomer, poor to the tint permanence of black sometimes with degree of depth.For example, disclose the graftomer that in aromatic polycarbonate resin, has cooperated poly organo methane series compounded rubber resin combination, in aromatic polycarbonate resin, cooperated the resin combination (patent documentation 1,2) of the graftomer that the hypertrophy diene series rubber by small particle size forms to have the problem of pitch-dark property difference.In addition owing to save coating process, therefore improve the surperficial scuff resistance of moulding product require surging.
On the other hand, the requirement of halogen-free flame-retardantization that with purposes such as OA equipment, tame electrical articles is the resin material that uses of center is strong, in order to tackle these requirements, in the polymer alloy of aromatic polycarbonate resin and ABS resin, the requirement height of fire-retardantization of thin-walled such as V-0 in as the UL94 of safety requirements particularly.For example, disclose the be combined with graft polymerization ABS of the high rubber of specific refractory power and the resin combination (patent documentation 3) of aromatic copolycarbonate, but had the problem of the fire-proof resin composition that is difficult to be had simultaneously sufficient resistance to impact shock and flame retardant resistance.
That is, in rubber strengthened aromatic copolycarbonate resin composition, reality was also not propose to have thin-wall flame retardance, and shock resistance, scuff resistance, the good resin combination of tint permanence (particularly pitch-dark property).
Patent documentation 1: Japanese kokai publication hei 10-120893 communique
Patent documentation 2: Japanese kokai publication hei 11-140295 communique
Patent documentation 3: TOHKEMY 2007-254507 communique
Summary of the invention
The objective of the invention is to, be provided in the alloy system material of aromatic polycarbonate resin and phenylethylene resin series and use organic phosphorus flame retardant, satisfy the UL94 specification V-0 test of thin-walled, the flame-retardant aromatic polycarbonate resin composition of tint permanence, shock resistance, excellent scratch resistance.
The inventor etc. further investigate in order to solve this problem, found that, contain the graft copolymer of the specified particle diameter of rubber elastomer, the phenylethylene resin series of specific molecular weight range and the combination of sliding imparting agent with specific refractive index, be that the resin that solves above-mentioned problem is formed, go forward side by side one the step study, thereby finished the present invention.
According to the present invention, flame-retardant aromatic polycarbonate resin composition is provided, it contains organic phosphorus flame retardant (D composition) 5～25 weight parts, fluorine-containing Antidrip agent (E composition) 0.05～2 weight part and sliding imparting agent (F composition) 0.01～0.4 weight part with respect to resinous principle 100 weight parts; This resinous principle is with respect to (A) aromatic polycarbonate resin (A composition) 100 weight parts, contain (B) with specific refractory power be the latex that contains butadiene-based rubber matter polymkeric substance, unsaturated carboxylic acid alkyl ester and aromatic vinyl base system monomer more than 1.535 carry out graft copolymer (B composition) 0.1～10 weight part of median size 100nm～180nm that letex polymerization obtains and (C) weight-average molecular weight be B composition phenylethylene resin series (C composition) 5～40 weight parts in addition 120,000 below.
Description of drawings
Fig. 1 is the sketch chart of the device of use in the scuff resistance test.
Embodiment
Below further details of the present invention is described.
(A composition: aromatic copolycarbonate)
Aromatic polycarbonate resin as the A composition of the present invention, make dihydric phenol and carbonate precursor the reaction and obtain.As reaction method, can enumerate the solid phase ester-interchange method of interface polycondensation, melt transesterification process, carbonic ether prepolymer and the ring-opening polymerization method of cyclic carbonate compound etc.
Typical example as use therein dihydric phenol, can enumerate Resorcinol, Resorcinol, 4,4 '-xenol, 1, two (4-hydroxy phenyl) ethane of 1-, 2, two (4-hydroxy phenyl) propane (common name dihydroxyphenyl propane) of 2-, 2, two (the 4-hydroxy-3-methyl phenyl) propane of 2-, 2, two (4-hydroxy phenyl) butane of 2-, 1, two (4-the hydroxy phenyl)-1-diphenylphosphino ethanes of 1-, 1, the 1-bis(4-hydroxyphenyl) cyclohexane, 1, two (the 4-hydroxy phenyls)-3 of 1-, 3, the 5-trimethyl-cyclohexane, 2, two (4-hydroxy phenyl) pentanes of 2-, 4,4 '-(to the phenylene diisopropylidene) biphenol, 4,4 '-(metaphenylene diisopropylidene) biphenol, 1, two (4-the hydroxy phenyl)-4-normenthanes of 1-, two (4-hydroxy phenyl) ether, two (4-hydroxy phenyl) thioether, two (4-hydroxy phenyl) sulfoxide, two (4-hydroxy phenyl) sulfone, two (4-hydroxy phenyl) ketone, two (4-hydroxy phenyl) ester, two (4-hydroxy-3-methyl phenyl) thioether, 9, two (4-hydroxy phenyl) fluorenes and 9 of 9-, two (4-hydroxy-3-methyl phenyl) fluorenes of 9-etc.Preferred dihydric phenol is two (4-hydroxy phenyl) alkane, wherein from the tenacity excellent aspect, and preferred especially dihydroxyphenyl propane (following abbreviate as sometimes " BPA "), general.
As carbonate precursor, use carbonyl halide, carbonic diester or haloformate (Ha ロ ホ Le メ one ト) etc., can enumerate the bishaloformate of phosgene, diphenyl carbonate or dihydric phenol etc. particularly.
When adopting interfacial polymerization to make polycarbonate resin, can use catalyzer, terminal terminator as required, be used to prevent the antioxidant of dihydric phenol oxidation etc. by above-mentioned dihydric phenol and carbonate precursor.In addition, polycarbonate resin of the present invention comprise branched polycarbonate resin that the multi-functional aromatics copolymerization more than the trifunctional is obtained, with two functionality carboxyl acid copolymers of aromatic series or aliphatics (comprising ester ring type) and the polyestercarbonate resin that obtains, the copolymerized panlite that two functionality alcohol (comprising ester ring type) copolymerization are obtained and with this two functionalities carboxylic acid and two functionality alcohol copolymerization together and the polyestercarbonate resin that obtains.In addition, also can be the mixture that mixes more than 2 kinds of the polycarbonate resin that will obtain.
Branched polycarbonate resin can increase the fusion tension force of resin combination of the present invention, based on this characteristic, and the forming process in the time of can improving extrusion moulding, foaming and blow molding.The result can access the more excellent moulding product that formed by these methods of forming of dimensional precision.
As the multi-functional aromatics more than the trifunctional that uses in this branched polycarbonate resin, preferred illustration 4,6-dimethyl-2,4,6-three (4-hydroxy phenyl) heptene-2,2,4,6-trimethylammonium-2,4,6-three (4-hydroxy phenyl) heptane, 1,3,5-three (4-hydroxy phenyl) benzene, 1,1,1-three (4-hydroxy phenyl) ethane, 1,1,1-three (3,5-dimethyl-4-hydroxy phenyl) ethane, 2, two (2-hydroxy-5-methyl base benzyl)-4-methylphenol and the 4-{4-[1 of 6-, two (4-hydroxy phenyl) ethyls of 1-] benzene }-α, triphenols such as α-Er Jiajibianji phenol.As other multi-functional aromatics, can illustration Phloroglucinol monomethyl ether, 2,3 ', 4,5 ', 6-penta hydroxy group biphenyl, four (4-hydroxy phenyl) methane, two (2, the 4-dihydroxy phenyl) ketone, 1, two (4,4-dihydroxyl trityl group) benzene and trimellitic acid, Pyromellitic Acid, benzophenone tetracarboxylic acid and their acyl chlorides etc. of 4-, wherein preferred 1,1,1-three (4-hydroxy phenyl) ethane and 1,1,1-three (3,5-dimethyl-4-hydroxy phenyl) ethane, preferred especially 1,1,1-three (4-hydroxy phenyl) ethane.
In the branched polycarbonate resin by multi-functional aromatics deutero-structural unit, by dihydric phenol deutero-structural unit with by this in total 100 molar part of multi-functional aromatics deutero-structural unit, it is 0.03～1 molar part, be preferably 0.07～0.7 molar part, be preferably 0.1～0.4 molar part especially.
In addition, not only derived by multi-functional aromatics in this branched structure unit, and the side reaction can be as melting state transesterification reaction the time, derive under the situation of not using multi-functional aromatics.Should illustrate,, can adopt about the ratio of this branched structure 1H-NMR measures and calculates.
On the other hand, the preferred α of the carboxylic acid of aliphatic two functionalities, alpha, omega-dicarboxylic acid, as its concrete example, can enumerate alicyclic dicarboxylic acids such as straight chain saturated aliphatic dicarboxylic acids such as sebacic acid (decane diacid), dodecanedioic acid, tetradecane diacid, octadecane diacid, octadecane dicarboxylic acid and cyclohexane cyclohexanedimethanodibasic.As two functionality alcohol, more preferably alicyclic diol, can illustration for example cyclohexanedimethanol, cyclohexanediol and tristane dimethanol etc.In addition, the polycarbonate poly organo alkyl copolymer of polyorganosiloxane units that can also use copolymerization.
The A composition can be the product that mixes more than 2 kinds of the polycarbonate that the dihydric phenol composition is different, the polycarbonate that contains branched-chain component, various polyestercarbonate, polycarbonate poly organo alkyl copolymer etc.In addition, can also use the product that mixes more than 2 kinds of different polycarbonate of the polycarbonate that manufacturing process is different, terminal terminator etc.As the reaction formation of interfacial polymerization, melt transesterification process, the solid phase ester-interchange method of carbonic ether prepolymer and the ring-opening polymerization method of cyclic carbonate compound etc. of the manufacture method of polycarbonate resin of the present invention, be known method in various documents and patent gazette etc.
As the aromatic copolycarbonate of A composition of the present invention, not only can use original raw material, can also use by used goods regenerated polycarbonate resin, i.e. so-called aromatic copolycarbonate through material recirculation.As used goods, preferably enumerate sound-proof wall, glass port, printing opacity roof Material and be the container such as transparent component, water bottle such as various glass ports (glazing) material, windshield glass, auto bulb lens of representative and optical recording medium etc. with vehicle dormer window etc.They do not contain a large amount of additives or other resins etc., stably obtain target quality easily.Particularly auto bulb lens, optical recording medium etc. owing to satisfy the more preferably condition of above-mentioned viscosity-average molecular weight, are therefore enumerated as preferred scheme.Have, so-called above-mentioned original raw material is a used raw material on market not as yet after it is made again.
The viscosity-average molecular weight of aromatic copolycarbonate is preferably 1 * 10 4～5 * 10 4, more preferably 1.4 * 10 4～3 * 10 4, more preferably 1.8 * 10 4～2.5 * 10 41.8 * 10 4～2.5 * 10 4Scope, particularly have at the same time good shock resistance and mobile excellent.Most preferably be 1.9 * 10 4～2.4 * 10 4Have, this viscosity-average molecular weight can be used as the A composition and all satisfies, and also comprises the situation that is satisfied this scope by the different mixture more than 2 kinds of molecular weight again.
So-called viscosity-average molecular weight is calculated by the following method among the present invention,, at first, uses Ostwald viscosimeter that is, obtains the specific viscosity (η that is calculated as follows by the solution that aromatic copolycarbonate 0.7g is dissolved in gained among the methylene dichloride 100ml under 20 ℃ Sp),
Specific viscosity (η Sp)=(t-t 0)/t 0
[t 0Be second number that falls of methylene dichloride, t is second number that falls of sample solution]
With the specific viscosity substitution following formula of trying to achieve, obtain viscosity-average molecular weight M.
η Sp/ c=[η]+0.45 * [η] 2C (wherein [η] is limiting viscosity)
[η]＝1.23×10 -4M 0.83
c＝0.7
(B composition: unsaturated carboxylic acid alkyl ester-butadiene-based rubber-aromatic vinyl base system monomer graft copolymer)
The B composition that uses among the present invention is to be unsaturated carboxylic acid alkyl ester-butadiene-based rubber-aromatic vinyl base system monomer graft copolymer that the latex that contains butadiene-based rubber matter polymkeric substance, unsaturated carboxylic acid alkyl ester and aromatic vinyl base system monomer more than 1.535 carries out median size 100nm～180nm that letex polymerization obtains with specific refractory power, is preferably MBS (MBS resin).
As the latex that contains the butadiene-based rubber polymkeric substance of the present invention, can enumerate polyhutadiene, hydrogenation (part) polyhutadiene, and butadiene-styrene copolymer, hydrogenation (part) butadiene-styrene copolymer, styrene-butadiene block copolymer, hydrogenation (part) styrene-butadiene block copolymer, perbutan and with the butadiene-acrylic acid isobutyl ester be main component divinyl such as acrylic rubber multipolymer and can be with the monomeric multipolymer of ethene base system more than a kind of butadiene copolymer etc., wherein, preferably with 1,3-divinyl 50～75 weight parts and the multipolymer that can obtain with ethene base system monomer 25～50 weight part copolymerization more than a kind of 1,3-butadiene copolymerization.
As above-mentioned ethene base system monomer, can use for example aromatic vinyl such as vinylbenzene, alpha-methyl styrene base system monomer; Alkyl methacrylate such as methyl methacrylate, Jia Jibingxisuanyizhi; Alkyl acrylate such as ethyl propenoate, n-butyl acrylate; Unsaturated nitrile such as vinyl cyanide, methacrylonitrile; Vinyl ether such as methylvinylether, butyl vinyl ether; Vinyl halides such as vinylchlorid, bromine ethene; Vinylidene chloride, inclined to one side bromine ethene isogonic halogen ethene; Glycidyl acrylate, glycidyl methacrylate, allyl glycidyl ether, diglycidyl ether of ethylene glycol etc. have the ethene base system monomer of glycidyl etc.
In addition, can also and use aromatic series polyfunctional vinyl compounds such as Vinylstyrene, divinyl toluene; (methyl) acrylate of polyvalent alcohols such as Ethylene glycol dimethacrylate, diacrylate 1,3 butylene glycol ester; Cross-linkable monomers such as allyl carboxylates such as trimethacrylate, triacrylate, allyl acrylate, allyl methacrylate(AMA), Phthalic acid, diallyl ester, sebacic acid diallyl, triallyl triazine etc. two and triallyl compound.
Have, these ethene base system monomers and cross-linkable monomer can use a kind or use more than 2 kinds again.
The specific refractory power that contains the latex of butadiene-based rubber polymkeric substance of the present invention is more than 1.535, and is preferred more than 1.536, more preferably more than 1.538.Specific refractory power was less than 1.535 o'clock, and tint permanence (particularly pitch-dark property) is poor as a result.Have again,, then can't obtain the effect that impact improves if specific refractory power surpasses 1.550, therefore not preferred.The specific refractory power that contains the latex of butadiene-based rubber polymkeric substance can use Abbe refractometer to measure according to JIS K7142.Specifically, thereby can use the value of the specific refractory power of polystyrene (n=1.589) that the film of moulding 300～600 μ m by extrusion forming measures, divinyl rubber (n=1.516), obtain by calculating by the fit rate of styrene butadiene rubbers.
In the latex that contains the butadiene-based rubber matter polymkeric substance as above, the multipolymer that contains acid group can be added, the latex hypertrophyization that contains butadiene-based rubber matter polymkeric substance can be made thus.This latex of hypertrophyization by the multipolymer that contains acid group owing to contain the material of big particle diameter in a large number, therefore can improve the impact resistance of the graft copolymer that obtains, and can access the resin combination of shock resistance excellence.
As the multipolymer that contains acid group, preferably in the presence of at least a kind of anion surfactant, will contain alkyl acrylate and can be with the polymerization of mixtures of unsaturated acid monomer more than at least a kind of alkyl acrylate copolymer latex more than the pH4 that obtains.The carbonatoms of alkyl preferred 1～12 is arranged again.
As alkyl acrylate, can enumerate for example methyl acrylate, ethyl propenoate, propyl acrylate, butyl acrylate, Octyl acrylate, 2-EHA, lauryl acrylate etc.
As unsaturated acid monomer, can enumerate vinylformic acid, methacrylic acid, Ba Dousuan, methylene-succinic acid, styracin, maleic anhydride and butylene tricarboxylic acid etc.
The emulsifying agent that uses when containing the multipolymer of acid group as manufacturing can be enumerated negatively charged ion, positively charged ion, nonionic emulsifying agent, preferred anionic tensio-active agent, the more preferably anion surfactant beyond phosphate ester salt, the alkyl sulfo succinate.
Only the copolymer emulsion that contains acid group that slightly polymerization is as described above obtained adds butadiene-based rubber polymer latex Ruzhong to, just can realize the abundant hypertrophyization of butadiene-based rubber polymkeric substance.The addition that contains the multipolymer of acid group is with respect to butadiene-based rubber polymkeric substance 100 weight parts (as solids component), in order to realize hypertrophyization fully, as solids component, more than preferred 0.01 weight part, below 0.5 weight part.
Monomer a kind or more or monomer mixture and the utilization multipolymer that contain acid group of graft copolymer by will containing aromatic vinyl base system monomer, unsaturated carboxylic acid alkyl ester obtains the latex grafting polymerization that butadiene-based rubber polymkeric substance hypertrophyization obtains.
As the unsaturated carboxylic acid alkyl ester that uses among the present invention, can enumerate methyl methacrylate, Jia Jibingxisuanyizhi, ethyl propenoate, n-butyl acrylate etc., wherein the preferable methyl methyl acrylate.
As the aromatic vinyl base system monomer that uses among the present invention, can enumerate vinylbenzene, alpha-methyl styrene, the replacement of various halogen and alkyl-substituted styrene etc., wherein optimization styrene.
The polymerization process of graft copolymer of the present invention is letex polymerization, preferred especially multi-step emulsion polymerization.As this multi-step emulsion polymerization, can enumerate for example special method of putting down in writing among the 2003-261629 of opening.
Polymerization is different because of the kind of polymerization starter, can carry out in the scope about 40～80 ℃.That is, preferably add or add continuously with the monomeric mode that contains the latex grafting of butadiene-based rubber polymkeric substance and carry out polymerization with gradation.By taking such polymerization methods, can obtain having the graft copolymer of desired structure with comparalive ease.Have, when taking multi-step emulsion polymerization, it is identical with reinforced afterwards monomer composition that reinforced monomer of initial stage is formed, and also can change again.The latex, unsaturated carboxylic acid alkyl ester and the monomeric ratio of components of aromatic vinyl base system that contain the butadiene-based rubber polymkeric substance in the graft copolymer are preferably 40～90%: 10～60%: 0～60%, more preferably 50～80%: 10～40%: 10～40%.
The median size of graft copolymer is 100nm～180nm among the present invention, is preferably 120nm～175nm, more preferably 150nm～170nm.If median size surpasses 180nm, then become the reason that total light transmittance reduces, tint permanence worsens of fire-proof resin composition.If opposite median size can't obtain sufficient shock resistance sometimes less than 100nm.Here said median size is the semi-invariant (weight part) when measuring that contrasts its little particle for each particle diameter, the particle diameter corresponding with the semi-invariant of 50 weight parts.This median size is by impregnated in OsO with graft copolymer 4Or RuO 4Solution and after dyeing, observe with transmission electron microscope, average and try to achieve for the particle diameter of the particle assay more than 1000.
The rubber constituent amount of graft copolymer is 40～90 weight %, is preferably 50～80 weight %.
The content of B composition is 0.1～10 weight parts with respect to A composition 100 weight parts, preferred 1～8 weight part, more preferably 2～7 weight parts.Content is during greater than 10 weight parts, and flame retardant resistance reduces.
＜C composition: the phenylethylene resin series beyond the B composition 〉
In order to improve flowability, to improve scuff resistance, it is that B composition phenylethylene resin series in addition 120,000 below is as the C composition that fire resistant aromatic makrolan resin of the present invention contains weight-average molecular weight.The weight-average molecular weight of C composition is preferably below 115,000, more preferably below 110,000.If weight-average molecular weight surpasses 120,000, can't obtain sufficient scuff resistance, therefore not preferred.Have, the lower limit of weight-average molecular weight is not particularly limited again, but preferred more than 80,000.Should illustrate that weight-average molecular weight can adopt GPC to use polystyrene standard (Polymer Laboratories system), the relation of elution time and elution amount is converted to molecular weight and obtains.
As phenylethylene resin series of the present invention, can enumerate vinyl cyanide-acrylic rubber-styrol copolymer (AAS resin) particularly, vinyl cyanide-ethylene, propylene is rubber-styrene multipolymer (AES resin), acrylonitrile-butadiene-styrene copolymer (ABS resin), acrylonitritrile-styrene resin (AS resin) etc., wherein preferred ABS resin, AS resin.Below for describing as the preferred ABS resin of C composition, AS resin.
As the diene series rubber composition that forms ABS resin, using second-order transition temperature such as polyhutadiene and styrene-butadiene copolymer, acrylonitrile-butadiene for example is rubber below 10 ℃.As with diene series rubber composition grafted vinyl cyanide based compound, can enumerate for example vinyl cyanide, methacrylonitrile etc., in addition, as with diene series rubber composition grafted aromatic ethenyl compound, for example can enumerate nuclear substituted phenylethylenes such as vinylbenzene, alpha-methyl styrene and p-methylstyrene.
In the ABS resin of using among the present invention, the elastoprene components in proportions is preferably 0.1～30 weight part in ABS resin composition 100 weight parts, and more preferably 0.2～25 weight part is preferably 0.3～20 weight part especially.
In the ABS resin, rubber size is preferably 0.05～5 μ m in weight average particle diameter, more preferably 0.1～2.0 μ m, further preferred 0.2～0.5 μ m.The distribution that can use this rubber size is any in the rubber particles of single distribution and the rubber particles with above a plurality of peaks, 2 peaks, both can be the rubber particles that rubber particles also becomes single phase in its form, also can be to contain the rubber particles that (オ Network Le one De) has Sa Lami (サ ラ ミ) structure mutually by containing around rubber particles.
In addition, ABS resin contains the vinyl cyanide based compound that is not grafted on the diene series rubber composition and the multipolymer of aromatic ethenyl compound is known so far content.The free copolymer composition that ABS resin of the present invention produces in the time of also can containing this polymerization as mentioned above can also be blend with aromatic ethenyl compound and vinyl cyanide based compound copolymerization and blend that the vinyl compound polymer that obtains forms separately.Have, the ratio of this free AS resin can be dissolved in ABS resin in the good solvent of these AS resins such as acetone, obtains from its solvable composition again.On the other hand, its insoluble composition (gel) is real ABS resin.
In the ABS resin with the ratio (weight of this grafting composition is with respect to the ratio of the weight of diene series rubber composition) of diene series rubber composition grafted vinyl cyanide based compound and aromatic ethenyl compound, be that percentage of grafting (weight %) is preferably 20～200%, more preferably 20～80%.
This ABS resin can adopt any method manufacturings such as mass polymerization, solution polymerization, suspension polymerization and letex polymerization.
As each components in proportions in the AS resin, in the time of will all counting 100 weight parts, vinyl cyanide is 5～50 weight parts, is preferably 15～35 weight parts, and phenylethylene resin series is 95～50 weight parts, is preferably 85～65 weight parts.In addition, can also with can with other styrene copolymerized vinyl based compounds and styrene copolymerized.Containing below 15 weight parts in the proportional preferably AS resin of they.In addition, the initiator that uses in the reaction, chain-transfer agent etc. can use existing known various materials as required.
This AS resin can adopt any method manufacturings such as mass polymerization, solution polymerization, suspension polymerization, suspension mass polymerization and letex polymerization, but preferably adopts mass polymerization.In addition, the method for copolymerization can be any in the copolymerization of employing single stage method or the copolymerization of adopting multistep processes.
About the reduced viscosity of this AS resin, the reduced viscosity (30 ℃) that adopts the method for following record to obtain is 0.2～1.0dl/g, more preferably 0.3～0.7dl/g.
Reduced viscosity obtains by the following method: accurate weighing AS resin 0.25g, be dissolved among the dimethyl formamide 50ml with 2 hours, and the use Ubbelohde viscometer is measured the solution that obtains under 30 ℃ environment.Have, the time that flows down of viscometer use solvent is 20～100 seconds viscometer again.Reduced viscosity is by second number (t that flows down of solvent 0) and second number (t) that flows down of solution obtain according to following formula.
Reduced viscosity (η Sp/ C)={ (t/t 0)-1}/0.5
The content of C composition with respect to A composition 100 weight parts, is 5～40 weight parts, preferred 18～38 weight parts, more preferably 20～35 weight parts.Content can't manifest sufficient scuff resistance during less than 5 weight parts, and when bigger than 40 weight parts, flame retardant resistance significantly reduces.
(D composition: organic phosphorus flame retardant)
As organic phosphorus flame retardant of the present invention (D composition), can enumerate the phosphate compound of following formula (1) expression.
Figure G2009101735697D00111
(hydroxyl that the X in the above-mentioned formula represents to be selected from the dihydroxy compound in Resorcinol, Resorcinol, dihydroxyphenyl propane and the dihydroxybiphenyl is removed and the divalent group that obtains, R 1, R 2, R 3And R 4The aryl of representing carbonatoms 6～12 independently of one another, j, k, l and m are 0 or 1 independently of one another, and n represents 0～5 integer).
The phosphate compound of above-mentioned formula (1) can be the mixture with compound of different n numbers, under the situation of this mixture, average n number is preferably 0.5～1.5, more preferably 0.8～1.2, more preferably 0.95～1.15, be preferably 1～1.14 scope especially.
X in the above-mentioned formula is by the dihydroxy compound deutero-divalent group that is selected from Resorcinol, Resorcinol, dihydroxyphenyl propane and the dihydroxybiphenyl, wherein is preferably by Resorcinol, dihydroxyphenyl propane and dihydroxybiphenyl deutero-divalent group.
R in the above-mentioned formula 1, R 2, R 3And R 4, can illustration by phenol, cresols, xylenol, isopropyl-phenol, butylphenol with to oxy-compound deutero-univalent perssads such as cumyl phenols, wherein preferred phenol and 2,6-xylenol.
Have, this monohydric phenol can be replaced by halogen atom again, as the concrete example that has by the phosphate compound of this monohydric phenol deutero-group, can illustration three (2,4,6-tribromo phenyl) phosphoric acid ester and three (2, the 4-dibromo phenyl) phosphoric acid ester, three (4-bromophenyl) phosphoric acid ester etc.
On the other hand, concrete example as the phosphate compound that is not replaced by halogen atom, preferably phosphoric acid triphenylmethyl methacrylate and three (2, the 6-xylyl) phosplate compound such as phosphoric acid ester and with Resorcinol two (two (2, the 6-xylyl) phosphoric acid ester) as the phosphoric acid ester oligopolymer of main body, 4,4-dihydroxyl phenylbenzene two (diphenyl phosphates) is as the phosphoric acid ester oligopolymer of main body and (wherein so-called as main body as the phosphoric acid ester oligopolymer of main body with dihydroxyphenyl propane two (diphenyl phosphate), expression can contain other different compositions of the polymerization degree on a small quantity, and more preferably expression contains more than 80 weight parts, more preferably more than 85 weight parts, the composition of the middle n=1 of above-mentioned formula (1) that further preferred 90 weight parts are above).
The acid number of phosphate compound is preferably 0.2mgKOH/g, more preferably below the 0.15mgKOH/g, more preferably below the 0.1mgKOH/g, is preferably below the 0.05mgKOH/g especially.The lower limit of this acid number in fact also can be 0, in the practicality more than the preferred 0.01mgKOH/g.On the other hand, the content of half ester is more preferably below 1.1 weight parts, further below preferred 0.9 weight part.As lower limit, in the practicality more than preferred 0.1 weight part, more preferably more than 0.2 weight part.When acid number surpassed 0.2mgKOH/g, when perhaps half ester content surpassed 1.5mg, the poor heat stability during moulding was accompanied by the decomposition of aromatic copolycarbonate, and the hydrolytic resistance of resin combination reduces.Above-mentioned C composition also can mix the different phosphate compounds more than 2 kinds.
The content of D composition is benchmark with total 100 weight parts of A composition, B composition and C composition, is 5～25 weight parts, preferred 6～23 weight parts, preferred especially 7～20 weight parts.By this preferred proportion of composing, provide aromatic copolycarbonate resin composition with good flame-retardance.
(E composition: fluorine-containing Antidrip agent)
The fluorine-containing Antidrip agent of E composition that uses among the present invention is meant the fusion drippage when being used to prevent to burn and further improves the additive of flame retardant resistance that preferred the use has the tetrafluoroethylene that fibril forms ability.Should illustrate, below abbreviate tetrafluoroethylene as PTFE sometimes.Have the molecular weight that fibril forms the PTFE of ability and have high molecular weight, under the external action of shearing force etc. between the PTFE in conjunction with and show into and be fibrous tendency.The number-average molecular weight of its molecular weight to be tried to achieve by standard specific gravity is 1,000,000～1,000 ten thousand, more preferably 2,000,000～9,000,000.This PTFE also can use the aqueous liquid dispersion form except solid shape.In addition, this has the PTFE that fibril forms ability, improves in order to make the dispersiveness in resin, obtains more excellent flame-retardant performance and mechanical characteristics, also can use the PTFE mixture with the mixed style of other resins.
Have the commercially available product that fibril forms the PTFE of ability as this, can enumerate the POLYFLONMPA FA500 of teflon (registered trademark) 6J of fluorine chemistry company of Mitsui Du Pont for example, big aurification industrial and F-201L etc.As the commercially available product of the aqueous liquid dispersion of PTFE, can enumerate Off Le オ Application AD-1, AD-936, FLUON D-1, the D-2 of Daikin Industries corporate system, teflon (registered trademark) 30J of Mitsui Du Pont fluorine chemistry corporate system etc. of ASAHI-ICI FLUORO POLYMERS corporate system as representative.
PTFE as mixed style, can use the product that adopts following method to obtain, promptly, (1) aqueous liquid dispersion of the aqueous liquid dispersion of PTFE and organic polymer or solution are mixed carries out co-precipitation and obtain the method for common cohesion mixture (spy opens clear 60-258263 communique, the spy opens the method for middle records such as clear 63-154744 communique), (2) with aqueous liquid dispersion and the exsiccant organic polymer particle blended method (spy opens the method for putting down in writing in the flat 4-272957 communique) of PTFE, (3) aqueous liquid dispersion and the organic polymer particle solution with PTFE mixes, (spy opens flat 06-220210 communique to remove the method for medium separately simultaneously by this mixture, the method of record in the Te Kaiping 08-188653 communique etc.), (4) after the monomer methods of polymerization organic polymer to be formed (spy opens the method for putting down in writing in the flat 9-95583 communique) and (5) mix the aqueous liquid dispersion of PTFE and organic polymer dispersion liquid in the aqueous liquid dispersion of PTFE, polymerising ethylene base system monomer in this mixed dispersion liquid again obtains the product that the method (spy opens the method for putting down in writing in the flat 11-29679 grade) of mixture obtains then.As the commercially available product of the PTFE of these mixed styles, " metablen A3800 " (trade(brand)name), " metablen A3700 " (trade(brand)name) and GESpecialty Chemicals corporate system " BLENDEX B449 " (trade(brand)name) etc. that can the illustration mitsubishi rayon.
As the ratio of PTFE in the mixed style, in PTFE mixture 100 weight parts, PTFE is preferably 1～60 weight part, more preferably 5～55 weight parts.The ratio of PTFE can realize the good dispersion of PTFE when this scope.The content of E composition is benchmark with total 100 weight parts of A composition, B composition and C composition, is 0.05～2 weight part, is preferably 0.05～1 weight part, more preferably 0.1～0.6 weight part.By this preferred proportion of composing, provide aromatic copolycarbonate resin composition with good flame-retardance.
(F composition: the sliding imparting agent)
Fire resistant aromatic makrolan resin of the present invention in order to improve scuff resistance, contains the sliding imparting agent as the F composition.As sliding imparting agent of the present invention, can enumerate silicone oil, silicone resin particulate, polyethylene etc. particularly, wherein preferred silicone oil, polyethylene.Below for describing as the preferred silicone oil of F composition, polyethylene.
(F-1: silicone oil)
As the silicone oil that is used as the F composition among the present invention, can enumerate straight chain shape or cyclic polydimethyl siloxane oil, PSI oil, in the part of methyl, import the modified silicon oil of organic group etc., the wherein preferred poly-organopolysiloxane that uses following (2) expression.
[n in the formula (2) represents 700～1,050 integer.]
Such silicone oil is comparatively ideal 25 ℃ kinematic viscosity to be 8,000～35,000mm 2/ s, preferably 10,000～30,000mm 2The scope of/s.If kinematic viscosity is low excessively, after mixing in resin combination, silicone oil is separated out on the formed body surface easily, if molecular weight is too high, and the dispersed variation of silicone oil in resin, perhaps scuff resistance variation sometimes.
(F-2: polyethylene)
Be used as the polyvinyl resin of F composition among the present invention, can use commercially available polyvinyl resin usually, but its viscosity-average molecular weight be below 10,000, preferred 2,000～7,000 scope.Surpass 10,000 polyvinyl resin for viscosity-average molecular weight, be easy to generate layer in the moulding product and peel off degraded appearance.Particularly by using the polyethylene of above-mentioned scope, can access at first outward appearance excellence and shock strength, the also excellent moulding product of heat seal strength.In order to increase the affinity with polycarbonate resin, the polar group that this polyvinyl resin can import acid, ester, anhydride group, epoxy group(ing) and so on carries out modification and uses, and it also is preferred doing like this.
The content of F composition is benchmark with total 100 weight parts of A composition, B composition and C composition, is 0.01～0.4 weight part, preferred 0.05～0.3 weight part, more preferably 0.1～0.3 weight part.Content can't manifest sufficient scuff resistance during less than 0.01 weight part, and during greater than 0.4 weight part, color emissivity, flame retardant resistance significantly reduce.
(G composition: the high-grade aliphatic ester of monobasic or polyvalent alcohol)
G composition among the present invention is the higher fatty acid of the ester of monobasic or polyvalent alcohol and higher fatty acid.Higher fatty acid preferably contains the lipid acid of the above carbonatoms of 60 weight parts 20 or more (more preferably carbonatoms 20～32, further preferred carbonatoms 26～32).As this higher fatty acid, preferred illustration is the higher fatty acid of main component with the montanic acid.This higher fatty acid is usually by making the montanin wax oxidation.On the other hand, as monohydroxy-alcohol, can illustration for example dodecanol, tetradecanol, cetyl alcohol, Stearyl alcohol, eicosanol, Tetracosyl alcohol, the pure and mild triacontanol price quote of hexacosane etc.
As polyvalent alcohol, can enumerate for example glycerine, Glycerol dimer, Polyglycerine (for example ten Polyglycerine etc.), tetramethylolmethane, Dipentaerythritol, TriMethylolPropane(TMP), glycol ether and propylene glycol etc.Pure composition in the E composition, more preferably polyvalent alcohol.Wherein more preferably glycerine, tetramethylolmethane, Dipentaerythritol and TriMethylolPropane(TMP), special preferably glycerine.
With the montanic acid is the higher fatty acid of main component and the ester of monobasic or polyvalent alcohol (preferred polyol), preferred density: 0.94～1.10g/cm 3, acid number: 1～200, saponification value: 50～200 scope.
The content of G composition is benchmark with total 100 weight parts of A composition, B composition and C composition, is preferably 0.1～1 weight part, more preferably 0.15～0.7 weight part, more preferably 0.30～0.65 weight part.By this preferred proportion of composing, provide aromatic copolycarbonate resin composition with good release property.
(about other additives)
In the poly carbonate resin composition of the present invention, the molecular weight when making forming process, tone are stable, can use various stablizers, look material.As this stablizer, can to enumerate phosphorus and be stablizer, hindered phenol be stablizer, UV light absorber, dye pigment, thermo-stabilizer, static inhibitor etc.
(i) phosphorus is stablizer
As phosphorus is stablizer, can illustration phosphorous acid, phosphoric acid, phosphonous acid, phosphonic acids and their ester and tertiary phosphine etc.
Specifically, as bi-ester of phosphite, can enumerate for example triphenyl phosphite, tricresyl phosphite (nonyl phenyl) ester, tridecyl phosphite, the tricresyl phosphite monooctyl ester, tricresyl phosphite (octadecyl) ester, phosphorous acid didecyl list phenylester, phosphorous acid dioctyl list phenylester, phosphorous acid di-isopropyl list phenylester, phosphorous acid monobutyl diphenyl, phosphorous acid list decyl diphenyl, phosphorous acid list octyl group diphenyl, tricresyl phosphite (diethyl phenyl) ester, tricresyl phosphite (diisopropyl phenyl) ester, tricresyl phosphite (di-n-butyl phenyl) ester, tricresyl phosphite (2, the 4-di-tert-butyl-phenyl) ester, tricresyl phosphite (2, the 6-di-tert-butyl-phenyl) ester, distearyl pentaerythrityl diphosphite, two (2, the 4-di-tert-butyl-phenyl) pentaerythritol diphosphites, two (2,6-di-t-butyl-4-aminomethyl phenyl) pentaerythritol diphosphites, two (2,6-di-t-butyl-4-ethylphenyl) pentaerythritol diphosphites, two { 2, two (1-methyl isophthalic acid-phenylethyl) phenyl of 4-} pentaerythritol diphosphites, phenyl dihydroxyphenyl propane pentaerythritol diphosphites, two (nonyl phenyl) pentaerythritol diphosphites and dicyclohexyl pentaerythritol diphosphites etc.
In addition, as other bi-ester of phosphite, can use the compound that has ring texture with the dihydric phenols reaction.Can illustration for example 2,2 '-methylene-bis (4, the 6-di-tert-butyl-phenyl) (2, the 4-di-tert-butyl-phenyl) phosphorous acid ester, 2,2 '-methylene-bis (4, the 6-di-tert-butyl-phenyl) (the 2-tertiary butyl-4-aminomethyl phenyl) phosphorous acid ester and 2,2 '-methylene-bis (4, the 6-di-tert-butyl-phenyl) octyl group phosphorous acid ester etc.
As phosphate compound, can enumerate tributyl phosphate, trimethyl phosphite 99, Tritolyl Phosphate, triphenylphosphate, trichlorophenyl phosphate, triethyl phosphate, di(2-ethylhexyl)phosphate phenyltolyl base ester, the adjacent biphenyl ester of di(2-ethylhexyl)phosphate phenyl list, tributoxyethyl phosphate, dibutyl phosphate, dioctylphosphoric acid ester, diisopropyl phosphate etc., preferably phosphoric acid triphenylmethyl methacrylate, trimethyl phosphite 99.
As phosphinate compound, can enumerate four (2, the 4-di-tert-butyl-phenyl)-4,4 '-biphenylene, two phosphinates, four (2, the 4-di-tert-butyl-phenyl)-4,3 '-biphenylene, two phosphinates, four (2, the 4-di-tert-butyl-phenyl)-3,3 '-biphenylene, two phosphinates, four (2, the 6-di-tert-butyl-phenyl)-4,4 '-biphenylene, two phosphinates, four (2, the 6-di-tert-butyl-phenyl)-4,3 '-biphenylene, two phosphinates, four (2, the 6-di-tert-butyl-phenyl)-3,3 '-biphenylene, two phosphinates, two (2, the 4-di-tert-butyl-phenyl)-4-phenyl-phenyl-phosphonite ester, two (2, the 4-di-tert-butyl-phenyl)-3-phenyl-phenyl-phosphonite ester, two (2,6-di-n-butyl phenyl)-3-phenyl-phenyl-phosphonite ester, two (2, the 6-di-tert-butyl-phenyl)-4-phenyl-phenyl-phosphonite ester, two (2, the 6-di-tert-butyl-phenyl)-3-phenyl-phenyl-phosphonite ester etc., preferred four (di-tert-butyl-phenyl)-biphenylenes, two phosphinates, two (di-tert-butyl-phenyls)-phenyl-phenyl-phosphonite ester, more preferably four (2, the 4-di-tert-butyl-phenyl)-biphenylene two phosphinates, two (2, the 4-di-tert-butyl-phenyl)-phenyl-phenyl-phosphonite esters.This phosphinate compound can also be used with above-mentioned bi-ester of phosphite with the aryl that is substituted with 2 above alkyl.
As phosphonate compound, can enumerate phosphenylic acid dimethyl ester, phosphenylic acid diethyl ester and phosphenylic acid dipropyl etc.
As tertiary phosphine, can the illustration triethyl phosphine, tripropyl phosphine, tributylphosphine, tri octyl phosphine, three amyl group phosphines, dimethylphenylphosphine, dibutyl Phenylphosphine, diphenyl methyl phosphine, phenylbenzene octyl group phosphine, triphenylphosphine, three (p-methylphenyl) phosphine, three naphthyl phosphines and phenylbenzene benzyl phosphine etc.Particularly preferred tertiary phosphine is a triphenylphosphine.
Above-mentioned phosphorus is that stablizer can only use a kind, also can use mixing more than 2 kinds.Above-mentioned phosphorus is in the stablizer, the bi-ester of phosphite of preferred phosphinate compound or following general formula (3) expression.
Figure G2009101735697D00161
(in the formula (3), R 5And R 6The expression alkyl of carbonatoms 6～30 or the aryl of carbonatoms 6～30, can be mutually the same also can be different.)
As mentioned above, as phosphinate compound, preferred four (2, the 4-di-tert-butyl-phenyl)-biphenylene two phosphinates, the stablizer that with this phosphinate is main component is commercially available with Sandostab P-EPQ (trade mark, Clariant corporate system) and Irgafos P-EPQ (trade mark, CIBA SPECIALTYCHEMICALS corporate system), all can utilize.
In addition, in the above-mentioned formula (3), preferred bi-ester of phosphite is a distearyl pentaerythrityl diphosphite, two (2, the 4-di-tert-butyl-phenyl) pentaerythritol diphosphites, two (2,6-di-t-butyl-4-aminomethyl phenyl) pentaerythritol diphosphites and two { 2, two (1-methyl isophthalic acid-phenylethyl) phenyl of 4-} tetramethylolmethane two phosphinates.
Distearyl pentaerythrityl diphosphite is commercially available with ADK STAB PEP-8 (trade mark, Asahi Electro-Chemical Co. Ltd's system), JPP681S (trade mark, north of the city chemical industrial company system), all can utilize.Two (2, the 4-di-tert-butyl-phenyl) pentaerythritol diphosphites is commercially available with ADK STAB PEP-24G (trade mark, Asahi Electro-Chemical Co. Ltd's system), Alkanox P-24 (trade mark, Great Lakes corporate system), UltranoxP626 (trade mark, GE Specialty Chemicals corporate system), Doverphos S-9432 (trade mark, Dover Chemical corporate system) and Irgaofos126 and 126FF (trade mark, CIBASPECIALTY CHEMICALS corporate system) etc., all can utilize.Two (2,6-di-t-butyl-4-aminomethyl phenyl) pentaerythritol diphosphites is commercially available with ADK STAB PEP-36 (trade mark, Asahi Electro-Chemical Co. Ltd's system), can easily utilize.In addition, two { 2, two (1-methyl isophthalic acid-phenylethyl) phenyl of 4-} pentaerythritol diphosphites is commercially available with ADK STAB PEP-45 (trade mark, Asahi Electro-Chemical Co. Ltd's system) and Doverphos S-9228 (trade mark, Dover Chemical corporate system), all can utilize.
(ii) hindered phenol is an oxidation inhibitor
As hindered phenol compound, can use all cpds that in resin, cooperates usually.As this hindered phenol compound; can illustration alpha-tocopherol for example; butylhydroxy toluene; sinapyl alcohol; vitamin-E; octadecyl-3-(3; the 5-di-tert-butyl-hydroxy phenyl) propionic ester; the 2-tertiary butyl-6-(3 '-tertiary butyl-5 '-methyl-2 '-hydroxybenzyl)-4-aminomethyl phenyl acrylate; 2; 6-di-t-butyl-4-(N; the N-dimethylaminomethyl) phenol; 3; 5-di-tert-butyl-4-hydroxyl benzyl phosphonic acid ester diethyl ester; 2; 2 '-methylene-bis (4-methyl-6-tert butyl phenol); 2; 2 '-methylene-bis(4-ethyl-6-t-butyl phenol); 4; 4 '-methylene-bis (2; the 6-DI-tert-butylphenol compounds); 2; 2 '-methylene-bis(4-methyl-6-cyclohexyl phenol); 2; 2 '-dimethylene-two (6-Alpha-Methyl-benzyl-p-cresol); 2; 2 '-ethidine-two (4; the 6-DI-tert-butylphenol compounds); 2; 2 '-Ding fork base-two (4-methyl-6-tert butyl phenol); 4; 4 '-Ding fork base-two (3 methy 6 tert butyl phenols); triglycol-N-pair-3-(3-tertiary butyl-4-hydroxy-5-aminomethyl phenyl) propionic ester; 1; the 6-hexylene glycol is two, and [3-(3; the 5-di-tert-butyl-hydroxy phenyl) propionic ester]; two [the 2-tertiary butyl-4-methyl 6-(the 3-tertiary butyl-5-methyl-2-hydroxybenzyl) phenyl] terephthalate; 3; 9-pair 2-[3-(3-tertiary butyl-4-hydroxy-5-aminomethyl phenyl) propionyloxy]-1; the 1-dimethyl ethyl }-2; 4; 8; 10-four oxaspiros [5; 5] undecane; 4; 4 '-thiobis (the 6-tertiary butyl-meta-cresol); 4; 4 '-thiobis (3 methy 6 tert butyl phenol); 2; 2 '-thiobis (4-methyl-6-tert butyl phenol); two (3; the 5-di-tert-butyl-4-hydroxyl benzyl) thioether; 4; 4 '-two-thiobis (2; the 6-DI-tert-butylphenol compounds); 4; 4 '-three-thiobis (2; the 6-DI-tert-butylphenol compounds); 2; 2-sulfo-di ethylene bis-[3-(3; the 5-di-tert-butyl-hydroxy phenyl) propionic ester]; 2, two (positive hot the sulfenyl)-6-(4-hydroxyl-3,5-di-tert-butyl amido)-1 of 4-; 3; the 5-triazine; N, N '-hexa-methylene is two-(3,5-di-t-butyl-4-hydroxyl hydrocinnamamide); N; [3-(3 for N '-two; the 5-di-tert-butyl-hydroxy phenyl) propionyl] hydrazine; 1,1,3-three (2-methyl-4-hydroxyl-5-tert-butyl-phenyl) butane; 1; 3; 5-trimethylammonium-2,4,6-three (3; the 5-di-tert-butyl-4-hydroxyl benzyl) benzene; three (3; the 5-di-tert-butyl-hydroxy phenyl) isocyanuric acid ester; three (3, the 5-di-tert-butyl-4-hydroxyl benzyl) isocyanuric acid ester; 1,3; 5-three (the 4-tertiary butyl-3-hydroxyl-2; the 6-dimethyl benzyl) isocyanuric acid ester; 1,3,5-three 2[3 (3; the 5-di-tert-butyl-hydroxy phenyl) propionyloxy] the ethyl isocyanuric acid ester; four [methylene radical-3-(3; the 5-di-tert-butyl-hydroxy phenyl) propionic ester] methane; triglycol-N-pair-3-(3-tertiary butyl-4-hydroxy-5-aminomethyl phenyl) propionic ester; triglycol-N-pair-3-(3-tertiary butyl-4-hydroxy-5-aminomethyl phenyl) acetic ester; 3,9-pair [2-{3-(3-tertiary butyl-4-hydroxy-5-aminomethyl phenyl) acetoxyl group }-1, the 1-dimethyl ethyl]-2; 4; 8,10-four oxaspiros [5,5] undecane; four [methylene radical-3-(3-tertiary butyl-4-hydroxy-5-aminomethyl phenyl) propionic ester] methane; 1; 3; 5-trimethylammonium-2,4,6-three (3-tertiary butyl-4-hydroxy-5-methyl-benzyl) benzene and three (3-tertiary butyl-4-hydroxy-5-methyl-benzyl) isocyanuric acid ester etc.
In the above-claimed cpd, preferably utilize four [methylene radical-3-(3-tertiary butyl-4-hydroxy-5-aminomethyl phenyl) propionic ester] methane, octadecyl-3-(3 among the present invention, the 5-di-tert-butyl-hydroxy phenyl) propionic ester and 3,9-pair [2-{3-(3-tertiary butyl-4-hydroxy-5-aminomethyl phenyl) propionyloxy }-1, the 1-dimethyl ethyl]-2,4,8,10-four oxaspiros [5,5] undecane.Preferred especially 3,9-two [2-{3-(3-tertiary butyl-4-hydroxy-5-aminomethyl phenyl) propionyloxy }-1,1-dimethyl ethyl]-2,4,8,10-four oxaspiros [5,5] undecane.Above-mentioned hindered phenol is that oxidation inhibitor can use separately or will be used in combination more than 2 kinds.
Phosphorus is that stablizer and hindered phenol are that oxidation inhibitor preferably cooperates any.Especially preferably cooperating phosphorus is stablizer, more preferably cooperates three organophosphorus compoundss.Phosphorus is that stablizer and hindered phenol are the use level of oxidation inhibitor, and total 100 weight parts with A composition, B composition and C composition are benchmark respectively, are preferably 0.005～1 weight part, more preferably 0.01～0.3 weight part.
(iii) UV light absorber
Poly carbonate resin composition of the present invention can contain UV light absorber.Resin combination of the present invention is because poor because of the influence weathering resistance of rubber constituent, fire retardant sometimes, and therefore in order to prevent this deterioration, it is effective cooperating UV light absorber.
As UV light absorber of the present invention; specifically; in benzophenone series; can illustration for example 2; the 4-dihydroxy benaophenonel; 2-hydroxyl-4-methoxy benzophenone; 2-hydroxyl-4-octyloxy benzophenone; 2-hydroxyl-4-benzyloxy benzophenone; 2-hydroxyl-4-methoxyl group-5-sulfonic group benzophenone (2-ヒ De ロ キ シ-4-メ ト キ シ-5-ス Le ホ キ シ ベ ソ ソ ゾ Off エ ノ Application); 2-hydroxyl-4-methoxyl group-5-sulfonic group three hydrogenation benzophenone (2-ヒ De ロ キ シ-4-メ ト キ シ-5-ス Le ホ キ シ ト リ Ha イ De ラ イ De レ イ ト ベ ソ ゾ Off エ ノ ソ); 2; 2 '-dihydroxyl-4-methoxy benzophenone; 2; 2 '; 4; 4 '-tetrahydroxybenzophenone; 2; 2 '-dihydroxyl-4; 4 '-dimethoxy-benzophenone; 2; 2 '-dihydroxyl-4; 4 '-dimethoxy-benzophenone-5-sodium sulfonate (2; 2 '-ジ ヒ De ロ キ シ-4,4 '-ジ メ ト キ シ-5-ソ ジ ウ system ス Le ホ キ シ ベ ソ ゾ Off エ ノ ソ); two (5-benzoyl-4-hydroxyl-2-p-methoxy-phenyl) methane; 2-hydroxyl-4-positive 12-alkoxy benzophenone and 2-hydroxyl-4-methoxyl group-2 '-carboxyl benzophenone etc.
As UV light absorber, specifically, in benzotriazole system, can illustration 2-(2-hydroxy-5-methyl base phenyl) benzotriazole for example, 2-(2-hydroxyl-uncle's 5-octyl phenyl) benzotriazole, 2-(2-hydroxyl-3, the 5-dicumylphenyl) phenyl benzotriazole, 2-(the 2-hydroxyl-3-tertiary butyl-5-aminomethyl phenyl)-5-chlorobenzotriazole, 2, [4-(1 for 2 '-methylene-bis, 1,3, the 3-tetramethyl butyl)-6-(2H-benzotriazole-2-yl) phenol], 2-(2-hydroxyl-3, the 5-di-tert-butyl-phenyl) benzotriazole, 2-(2-hydroxyl-3, the 5-di-tert-butyl-phenyl)-the 5-chlorobenzotriazole, 2-(2-hydroxyl-3, the 5-di-tert-pentyl-phenyl) benzotriazole, 2-(2-hydroxyl-uncle's 5-octyl phenyl) benzotriazole, 2-(2-hydroxyl-5-tert-butyl-phenyl) benzotriazole, 2-(2-hydroxyl-4-octyloxyphenyl) benzotriazole, 2,2 '-methylene-bis (4-cumyl-6-benzotriazole phenyl), 2,2 '-TOPOT 2,2 (1,3-benzoxazine-4-ketone) and 2-[2-hydroxyl-3-(3,4,5,6-tetrahydric phthalimide methyl)-the 5-aminomethyl phenyl] benzotriazole, and 2-(2 '-hydroxy-5-methyl base acryloxy ethylphenyl)-2H-benzotriazole and can with the monomeric multipolymer of ethene base system of this monomer copolymerization, 2-(2 '-hydroxyl-5-acryloxy ethylphenyl)-2H-benzotriazole and can have the polymkeric substance etc. of 2-hydroxy phenyl-2H-benzotriazole skeleton with the monomeric multipolymer of ethene base system of this monomer copolymerization etc.
As UV light absorber, specifically, in hydroxyphenyltriazinuv system, can illustration 2-(4 for example, 6-phenylbenzene-1,3,5-triazines-2-yl)-5-hexyloxy phenol, 2-(4,6-phenylbenzene-1,3,5-triazines-2-yl)-5-methoxyphenol, 2-(4,6-phenylbenzene-1,3,5-triazines-2-yl)-5-thanatol, 2-(4,6-phenylbenzene-1,3,5-triazines-2-yl)-5-propoxy-phenol and 2-(4,6-phenylbenzene-1,3,5-triazines-2-yl)-5-butoxy phenol etc.In addition, but also the phenyl of illustration 2-(4,6-two (2, the 4-3,5-dimethylphenyl)-1,3,5-triazines-2-yls)-above-mentioned exemplary compounds such as 5-hexyloxy phenol become 2, the compound of 4-3,5-dimethylphenyl.
As UV light absorber, specifically, in cyclic imide acid esters system, can illustration for example 2,2 '-TOPOT 2,2 (3,1-benzoxazine-4-ketone), 2,2 '-(4,4 '-biphenylene) two (3,1-benzoxazine-4-ketone) and 2,2 '-(2, the 6-naphthylidene) two (3,1-benzoxazine-4-ketone) etc.
In addition; as UV light absorber; specifically, in cyanoacrylate system, can illustration for example 1; 3-pair-[(2 '-cyano group-3 '; 3 '-diphenylprop enoyl-) oxygen base]-2, two [(2-cyano group-3, the 3-diphenylprop enoyl-) oxygen base] methyl of 2-] propane and 1; 3-pair-[(2-cyano group-3,3-diphenylprop enoyl-) oxygen base] benzene etc.
In addition, the above-mentioned UV light absorber polymer-type UV light absorber that can be the structure of the monomeric compound by the taking free redical polymerization light stability monomer that makes this ultraviolet-absorbing monomer and/or have the structure of hindered amine form with monomer copolymerization such as (methyl) alkyl acrylate.As above-mentioned ultraviolet-absorbing monomer, preference is shown in the compound that contains benzotriazole skeleton, benzophenone skeleton, triazine skeleton, cyclic imide acid esters skeleton and cyanoacrylate skeleton in the ester substituting group of (methyl) acrylate.
In above-mentioned, aspect ultraviolet absorption ability, preferred benzotriazole system and hydroxyphenyltriazinuv system, aspect thermotolerance, tone (transparency), preferred cyclic imide acid esters system and cyanoacrylate system.Above-mentioned UV light absorber can be used separately or use with the mixture more than 2 kinds.
The content of UV light absorber is benchmark with total 100 weight parts of A composition, B composition and C composition, is preferably 0.01～2 weight part, 0.03～2 weight part more preferably, and more preferably 0.02～1 weight part is preferably 0.05～0.5 weight part especially.
(iv) dye pigment
Poly carbonate resin composition of the present invention also contains the various pigment that dye, and the moulding product that embody various designability can be provided.
As the fluorescence dye that uses among the present invention (comprising white dyes), for example can enumerating, coumarin series fluorescence dye, chromene are that fluorescence dye, perylene are that fluorescence dye, anthraquinone are that fluorescence dye, thioindigo are that fluorescence dye, xanthene are that fluorescence dye, xanthone are that fluorescence dye, thioxanthene are that fluorescence dye, thioxanthone are that fluorescence dye, thiazine are that fluorescence dye and diamino stibene are fluorescence dye etc.Wherein, few coumarin series fluorescence dye, the chromene of deterioration the during forming process of the good and polycarbonate resin of preferred thermotolerance is that fluorescence dye and perylene are fluorescence dye.
As the dyestuff beyond above-mentioned blue light agent and the fluorescence dye, can enumerate perylene based dye, coumarin series dyestuff, thioindigo based dye, anthraquinone based dye, thioxanthone based dye, yellow prussiate, purple cyclic ketones based dye, quinoline based dye, quinacridone based dye, dioxazine based dye, isoindolinone based dye and phthalocyanine based dye etc. such as dark purple.In addition, all right complexed metal pigment of resin combination of the present invention obtains more good metal color.As metallic pigment, preferably on various plate-like fillers, have the metallic pigment of metal tunicle or metal oxide coating.
The above-mentioned content that dyes pigment is benchmark with total 100 weight parts of A composition, B composition and C composition, preferred 0.00001～1 weight part, more preferably 0.00005～0.5 weight part.
(v) other thermo-stabilizers
In the poly carbonate resin composition of the present invention, also can cooperate above-mentioned phosphorus is that stablizer and hindered phenol are other thermo-stabilizers beyond the oxidation inhibitor.These other thermo-stabilizer, preferably with these stablizers and oxidation inhibitor in any and usefulness, preferred especially and both and usefulness.As these other thermo-stabilizer, the preference example is as with 3-hydroxyl-5, and the resultant of reaction of 7-di-t-butyl-furans-2-ketone and o-Xylol is that the lactone of representative is stablizer (details of this stablizer is recorded in the spy and opens in the flat 7-233160 communique).This compound is commercially available as Irganox HP-136 (trade mark, CIBA SPECIALTYCHEMICALS corporate system), can utilize this compound.In addition, the stablizer that this compound and various bi-ester of phosphite and hindered phenol compound are mixed is also commercially available.The Irganox HP-2921 of preference example such as above-mentioned corporate system.The stablizer that also can utilize this to be pre-mixed among the present invention.Lactone is the use level of stablizer, is benchmark with total 100 weight parts of A composition, B composition and C composition, is preferably 0.0005～0.05 weight part, more preferably 0.001～0.03 weight part.
In addition, as other stablizers, can illustration tetramethylolmethane four (3-mercaptopropionic acid ester), tetramethylolmethane four (3-lauryl thiopropionate) and glycerine-3-stearyl thiopropionate etc. contain the stablizer of sulphur.This stablizer is effective especially when resin combination is applied to rotoforming.This contains the use level of the stablizer of sulphur, is benchmark with total 100 weight parts of A composition, B composition and C composition, is preferably 0.001～0.1 weight part, more preferably 0.01～0.08 weight part.
(vi) static inhibitor
In the poly carbonate resin composition of the present invention, require antistatic property sometimes, preferably contain static inhibitor this moment.As this static inhibitor, can enumerate (1) ten dialkyl benzene sulfonic acid phosphonium salt for example and be the boron acid phosphonium salt that the fragrant basic sulfonic acid phosphonium salt of representative and alkane base sulfonic acid phosphonium salt etc. have machine sulfonic acid phosphonium salt and four fluorine boron acid phosphonium salt and so on.The content of Gai phosphonium salt is benchmark with total 100 weight parts of A composition, B composition and C composition, is to be fit to below 5 weight parts, is preferably 0.05～5 weight part, more preferably 1～3.5 weight part, the more preferably scope of 1.5～3 weight parts.
As static inhibitor, for example can enumerate organic sulfonic acid alkali (great soil group) metal-salts such as (2) organic sulfonic acid lithium, organic sulfonic acid sodium, organic sulfonic acid potassium, organic sulfonic acid caesium, organic sulfonic acid rubidium, organic sulfonic acid calcium, organic sulfonic acid magnesium and organic sulfonic acid barium.This metal-salt also uses as fire retardant as previously mentioned.This metal-salt more specifically can illustration for example metal-salt, the metal-salt of perfluoroalkane sulfonate etc. of Witco 1298 Soft Acid.The content of organic sulfonic acid alkali (great soil group) metal-salt is benchmark with total 100 weight parts of A composition, B composition and C composition, is fit to preferred 0.001～0.3 weight part, more preferably 0.005～0.2 weight part below 0.5 weight part.An alkali metal salts such as preferred especially potassium, caesium and rubidium.
As static inhibitor, for example can enumerate organic sulfonic acid ammonium salts such as (3) alkylsulphonic acid ammonium salt and aryl sulfonic acid ammonium salt.This ammonium salt is a benchmark with total 100 weight parts of A composition, B composition and C composition, is to be fit to below 0.05 weight part.As static inhibitor, for example can enumerate (4) polyether ester amides and so on the polymkeric substance of poly-(oxygen alkene) diol component for its constituent.This polymkeric substance is a benchmark with total 100 weight parts of A composition, B composition and C composition, is to be fit to below 5 weight parts.
(vii) other additives
Can cooperate A composition, B composition and C composition such dispersion agent, the photocatalyst of thermoplastic resin, other flow ability modifying agents, antiseptic-germicide, whiteruss in addition in the poly carbonate resin composition of the present invention is stain control agent, infrared absorbent and photochromic agent etc.
As the A composition, thermoplastic resin beyond B composition and the C composition can illustration aromatic polyester resins (pet resin (PET resin), polybutylene terephthalate resin (PBT resin), cyclohexanedimethanol copolymerization pet resin (so-called PET-G resin), PEN resin and PBN resin etc.), plexiglass (PMMA resin), cyclic polyolefin resin, polylactic resin, the polycaprolactone resin, thermoplastic fluorocarbon resin (for example being representative) with the polyvinylidene fluoride resin, and polyolefin resin (polyvinyl resin, ethene-(alpha-olefin) copolymer resin, acrylic resin and propylene-(alpha-olefin) copolymer resin etc.).Above-mentioned other thermoplastic resins are benchmark with total 100 weight parts of A composition, B composition and C composition, below preferred 20 weight parts, more preferably below 10 weight parts.
(manufacturing of poly carbonate resin composition)
When making flame-retardant aromatic polycarbonate resin composition of the present invention, adopt arbitrary method.Can enumerate for example following method: use V-type mixing machine, Henschel mixer, mechanochemistry device and extrude premixing mechanism such as mixing machine with A composition and even F composition with arbitrarily behind other additive thorough mixing (so-called doing mixed); adopt the granulation of the premixture that extruding pelletization device, compound stalk forming machine (briquettingmachine) etc. obtain as required; use then with ventage formula biaxial extruder and carry out melting mixing as the melting mixing machine of representative, the composition after using equipment such as tablets press to melting mixing then carries out granulation.
In addition, can also enumerate that to supply to each composition with ventage formula biaxial extruder independently of one another be method in the melting mixing machine of representative; After a part of pre-mixing with each composition, supply to method in the melting mixing machine etc. independently with remaining composition.As premixed method, for example can enumerate the additives dry blended that is cooperated beyond the part of the powder of A composition and D composition and the D composition, make method with the masterbatch of the additive of powder dilution.In addition, also can further enumerate a composition independently from the method for supplying with that melt extrudes machine midway etc.Heating temperature during these melting mixings is selected 250～300 ℃ scope usually.
Have, when containing aqueous composition in the composition of cooperation, the supply in melt extruding machine can be used so-called fluid infusion apparatus or liquid appending apparatus again.Preferred this fluid infusion apparatus or the liquid appending apparatus that is provided with heating unit that use.The phosphoric acid ester oligopolymer that contains in the D composition particularly of the present invention is because of the distribution difference of condensation degree n, is not solid state but aqueous sometimes.Therefore, adopt method from liquid appending apparatus to the supply of forcing machine that use so-called fluid infusion apparatus or.Therefore, the forcing machine that uses among the present invention, the preferred use has the forcing machine that liquid injects the raw material supplying mouth of usefulness.In addition, the interpolation of this phosphoric acid ester oligopolymer is pressed above pressure feed with known liquid transporting apparatus such as toothed gear pumps with the discharge in the forcing machine from the opening for feed of the barrel that is arranged on forcing machine usually.Have, the phosphoric acid ester oligopolymer during this supply uses the phosphoric acid ester oligopolymer of the temperature that is heated to 20 ℃～100 ℃, preferred 30 ℃～90 ℃, more preferably 40 ℃～80 ℃ again.Below 20 ℃ the time, the viscosity of phosphoric acid ester is too high, is difficult to carry out the high interpolation of quantitative accuracy, if be more than 100 ℃, causes volatilization, decomposition or the deterioration of phosphoric acid ester in the secular manufacturing sometimes.
In addition, the resin of extruding can directly cut off and carry out granulation, perhaps forms behind the tow with tablets press this tow to be cut off to carry out granulation.In the time of need alleviating the influencing of external dust etc. during granulation, preferably the environment around the forcing machine is cleaned.The shape of the pellet that obtains can be cylinder, square column and general shape such as spherical, more preferably cylinder.The diameter of this cylinder is preferably 1～5mm, more preferably 1.5～4mm, more preferably 2～3.3mm.On the other hand, the length of cylinder is preferably 1～30mm, more preferably 2～5mm, more preferably 2.5～3.5mm.
Flame-retardant aromatic polycarbonate resin composition of the present invention can obtain the moulding product by the pellet injection molding that will make as mentioned above usually, thereby make various goods.In this injection molding, not only common forming method can be used, injection compression molding, injection extrusion forming, air-auxiliary injection forming, foaming (comprising the method for injecting supercutical fluid), insert moulding, in-mould coating moulding, heat insulation mould molding, heating cooling mould molding, dual-color forming, sandwich moulding and ultra-high speed injection molding etc. rapidly can also be enumerated.In addition, moulding can be selected cold runner mode and hot runner mode.
In addition, poly carbonate resin composition of the present invention also can use with forms such as various special-shaped extrusion molding articles, sheet material, films by extrusion moulding.In addition, also can use inflation method, rolling process, teeming practice etc. in the moulding of sheet material, film.Can also be shaped to heat-shrinkable tube by applying specific stretched operation.In addition, also can adopt rotoforming, blow molding etc. that poly carbonate resin composition of the present invention is made the moulding product.
As the concrete example of the moulding product that utilize flame-retardant aromatic polycarbonate resin composition of the present invention, be fit to be applied in the internal part, housing (housing) etc. of OA equipment, tame electrical article.As these goods, can in the various parts of the framework of for example duplicating machine, printer, LCD TV etc., use the resin that forms by fire-retardant thermoplastic resin composite of the present invention.
Flame-retardant aromatic polycarbonate resin composition of the present invention, owing under the situation that flame retardant resistance, mechanical characteristics are reduced, manifest high Chromaticity, therefore particularly pitch-dark property can be used as the formed material in the wide field such as OA field, field of household appliances such as duplicating machine, printer.The industrial effect that the present invention produces is very big.
The inventor thinks that the solution of the present invention of present the best summed up the preferable range of above-mentioned each important document, for example, its typical example is recorded among the following embodiment.Certainly, the present invention is not limited to these schemes.
Embodiment
Estimate and adopt following method to implement.
(I) evaluation of flame-retardant aromatic polycarbonate resin composition
(i) Sha Erpi (Charpy) shock strength
According to ISO 179, implement the mensuration of notched Charpy shock strength.
(ii) scuff resistance test
According to Fig. 1 scuff resistance test method of the present invention is described.Measure and use the trier that test cloth has been installed in reciprocal kinetic friction wear testing machine [the accurate system AFT-15-M of industrial is surveyed in east] on the cylinder of diameter 10mm.Use this device, add specific load, make test sample reciprocal 50 times, implement the scuff resistance test.
Test a machine: reciprocal kinetic friction wear testing machine
Test cloth: Supreme Being people makes あ つ Chi こ つ Chi ふ I ん (rag, trade(brand)name) (polyester 50% nylon 50%)
Number of times: 50 times back and forth
Stroke: 15mm
Speed: 10mm/s
Load: 400g
Under the source of artificial light of decision method: 2000～4000lx (according to ISO/FDIS 3668), from 30cm the distance with visual judgement not damaged is arranged.
(iii) flame retardant resistance
According to UL specification 94V, implement combustion test with thickness 1.8mm.
(iv) L value
According to JIS K 7105, use the D65 light source to implement reflection measurement.In color solid (color space), used the 3-D walls and floor of the such performance of Lab.L value representation L lightness (lightness) in the table, L=0 represents the darkest (black), L=100 represents the brightest state (white).If Δ L=0～1.5 are very little luminosity equation, if Δ L=1.5～3.0, be can perception luminosity equation, if more than the Δ L=3, be tangible luminosity equation.Having, is to implement under the 2.0mm at the thickness of test film again.The L value preferred when not adding MBS the value no change of (comparative example 1).
[embodiment 1～6, comparative example 1～14]
With the composition shown in table 1 and the table 2, supply with the mixture that is grouped into by the one-tenth that does not comprise C composition, D composition from the 1st supplying opening of forcing machine.This mixture mixes the premixture of following (i) by V-type mixing machine and obtains with other compositions.That is, be the mixture of the aromatic copolycarbonate of E composition (fluorine-containing Antidrip agent) and A composition (i), be in polyethylene bag with this bag body vibration and uniform mixing so that the E composition is the mixture of 2.5 weight parts of this mixture.Have, the C composition uses the side feeder to supply with from the 2nd supplying opening again.And the D composition uses 3rd supplying opening (2nd supplying opening and ventage formula venting port between) of fluid infusion apparatus (Fuii Techno Industries corporate system HYM-JS-08) from the barrel way to supply to forcing machine with the state that is heated to 80 ℃, to reach the ratio of regulation separately.It is a certain amount of that fluid infusion apparatus is set at supply, and the feed rate of other raw material adopts gauger [KUBOTA corporate system CWF] critically to measure.Extrude ventage formula biaxial extruder (the TEX30 α of JSW-38.5BW-3V), obtain carrying out under the vacuum tightness 3kPa with screw rod revolution 200rpm, output 20kg/h, ventage the pellet of melting mixing that uses diameter 30mm φ.Have again,, partly be 260 ℃ from the 1st supplying opening to the mouth mould for extrusion temperature.
Use down the heated air circulation type drying machine that the pellet that obtains after dry 6 hours, is used injection moulding machine [the system SG150U of Sumitomo Heavy Industries] at 80-90 ℃, at the test film of the condition compacted under evaluation usefulness of 240 ℃ of barrel temperatures, 60 ℃ of die temperatures.
Each composition of mark souvenir in table 1 and the table 2 is as described below.
(A composition)
PC: aromatic polycarbonate resin [adopt polycarbonate resin powder, the Supreme Being people of the viscosity-average molecular weight 22,400 of ordinary method preparation to change into corporate system PANLITEL-1225WP by the dihydroxyphenyl propane photoreactive gas)
(B composition)
IM-1: nuclear-shell graft copolymer; Nuclear is the graft copolymer of vinylbenzene and methyl methacrylate for latex, the shell that contains vinylbenzene and butadiene-based rubber polymkeric substance.The specific refractory power (calculated value) of nuclear part is 1.538.The median size of graftomer is 160nm.(mitsubishi rayon system metablen C-215A (trade(brand)name))
IM-2: nuclear-shell graft copolymer; Nuclear is the graft copolymer of vinylbenzene and methyl methacrylate for latex, the shell that contains vinylbenzene and butadiene-based rubber polymkeric substance.The specific refractory power (calculated value) of nuclear part is 1.545.The median size of graftomer is 100nm.
IM-3: nuclear-shell graft copolymer; Nuclear is the graft copolymer of vinylbenzene and methyl methacrylate for latex, the shell that contains vinylbenzene and butadiene-based rubber polymkeric substance.The specific refractory power (calculated value) of nuclear part is 1.531.The median size of graftomer is 200nm.
IM-4: nuclear-shell graft copolymer; Nuclear is the graft copolymer of vinylbenzene and methyl methacrylate for latex, the shell that contains vinylbenzene and butadiene-based rubber polymkeric substance.The specific refractory power (calculated value) of nuclear part is 1.538.The median size of graftomer is 200nm.
IM-5: nuclear-shell graft copolymer; Nuclear is the graft copolymer of vinylbenzene and methyl methacrylate for latex, the shell that contains vinylbenzene and butadiene-based rubber polymkeric substance.The specific refractory power (calculated value) of nuclear part is 1.538.The median size of graftomer is 80nm.
(C composition)
AS-1:AS resin (Japanese A﹠amp; L corporate system LITAC-A BS207 (trade(brand)name)) letex polymerization AS resin.Weight-average molecular weight is 109,000.
AS-2:AS resin (CHEIL INDUSTRIES INC. system: HR5330 (trade(brand)name)).Weight-average molecular weight is 129,000.
AS-3:AS resin (CHEIL INDUSTRIES INC. system: HR5330S (trade(brand)name)).Weight-average molecular weight is 147,000.
ABS-1:ABS resin (CHEIL INDUSTRIES INC. system: CH-T (trade(brand)name)).Weight-average molecular weight is 60,000.
ABS-2:ABS resin (the system GT-A-200 (trade(brand)name) of Denki Kagaku Kogyo kabushiki) letex polymerization ABS resin.Weight-average molecular weight is 101,000.
(D composition)
FR: with dihydroxyphenyl propane two (diphenyl phosphate) is the phosphoric acid ester (big eight chemical industrial company's system: CR-741 (trade(brand)name)) of main component
(E composition)
PTFE1: tetrafluoroethylene (Daikin Industries corporate system POLYFLON MP FA500 (trade(brand)name))
PTFE2: the mixed powder (mitsubishi rayon system metablenA3750 (trade(brand)name)) that contains tetrafluoroethylene
(F composition)
Si: silicone oil (system KF-96-1 ten thousand cs of chemical company of SHIN-ETSU HANTOTAI)
PE: polyvinyl resin (the system Hi-wax 310MP (trade(brand)name) of Mitsui Petrochemical Ind., Ltd.) viscosity-average molecular weight is 3,000.
(G composition)
SL: fatty acid ester is that (reason is ground the VITAMIN corporate system to releasing agent; RIKEMAL SL900 (trade(brand)name))
(other compositions)
IRG: phenol is thermo-stabilizer (Ciba Specialty Chemicals K.K. system; IRGANOX1076 (trade(brand)name))
CB: black masterbatch (paddy changes into industrial's system, ロ イ ヤ Le Block ラ Star Network 904S (trade(brand)name) more)
[table 1]
Figure G2009101735697D00291
[table 2]
Figure G2009101735697D00301
By above-mentioned table as can be known, by adding the of the present invention specific MBS resin of specified quantitative, under the situation that shock strength, flame retardant resistance are reduced, can improve tint permanence significantly, particularly pitch-dark property.In addition as can be known, by adding the sliding imparting agent of specified quantitative, scuff resistance improves.

Claims (7)

1. flame-retardant aromatic polycarbonate resin composition, with respect to resinous principle 100 weight parts, contain (D) organic phosphorus flame retardant and be D composition 5～25 weight parts, (E) fluorine-containing Antidrip agent and be E composition 0.05～2 weight part and (F) the sliding imparting agent be F composition 0.01～0.4 weight part; Described resinous principle is A composition 100 weight parts with respect to (A) aromatic polycarbonate resin, contain (B) with specific refractory power be graft copolymer that the latex that contains butadiene-based rubber matter polymkeric substance, unsaturated carboxylic acid alkyl ester and aromatic vinyl base system monomer more than 1.535 carries out median size 100nm～180nm that letex polymerization obtains be B composition 0.1～10 weight part and (C) weight-average molecular weight be that phenylethylene resin series beyond the B composition below 120,000 is C composition 5～40 weight parts.
2. flame-retardant aromatic polycarbonate resin composition according to claim 1, wherein, the B composition is that the rubber constituent amount is the graft copolymer of 40～90 weight %.
3. flame-retardant aromatic polycarbonate resin composition according to claim 1 and 2, wherein, the C composition is that to be selected from the rubber constituent amount be that the acrylonitrile-butadiene-styrene copolymer of 0.1～30 weight % is that ABS resin and acrylonitritrile-styrene resin are at least a kind of multipolymer in the AS resin.
4. according to each described flame-retardant aromatic polycarbonate resin composition in the claim 1～3, wherein, the D composition is that the acid number of following formula (1) expression is the following organic phosphorus flame retardant of 0.2mgKOH/g,
Figure A2009101735690002C1
The hydroxyl that X in the formula represents to be selected from the dihydroxy compound of Resorcinol, Resorcinol, dihydroxyphenyl propane and dihydroxybiphenyl is removed and the divalent group that obtains, R 1, R 2, R 3And R 4The aryl of representing carbonatoms 6～12 independently of one another, j, k, l and m are 0 or 1 independently of one another, and n represents 0～5 integer.
5. according to each described flame-retardant aromatic polycarbonate resin composition in the claim 1～4, wherein, the F composition is a silicone oil.
6. flame-retardant aromatic polycarbonate resin composition according to claim 5, wherein, the F composition is the silicone oil of following formula (2) expression,
Figure A2009101735690003C1
N in the formula represents 700～1,050 integer.
7. according to each described flame-retardant aromatic polycarbonate resin composition in the claim 1～4, wherein, the F composition is the polyethylene of viscosity-average molecular weight below 10,000.
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