CN1330705C

CN1330705C - Flame retardant aromatic poly cabonic ester resin composition and finished products

Info

Publication number: CN1330705C
Application number: CNB021414807A
Authority: CN
Inventors: 小野哲志; 板垣明成; 山谷正明; 小林芳辉
Original assignee: Teijin Chemicals Ltd; Shin Etsu Chemical Co Ltd
Current assignee: Shin Etsu Chemical Co Ltd; Teijin Ltd
Priority date: 2001-08-30
Filing date: 2002-08-30
Publication date: 2007-08-08
Anticipated expiration: 2022-08-30
Also published as: CN1408767A; TWI268949B; DE60206575T2; DE60206575D1

Abstract

The invention relates to a flame retardant aromatic polycarbonate resin composition and molded articles thereof. A halogen-free polycarbonate resin composition having excellent transparency and dripping preventing properties and molded articles thereof are provided according to the present invention. In the composition, 100 parts by weight of resin components comprise 0.1 to 10 parts by weight of a silicone compound which contains an Si-H group with content (Si-H content) of 0.1 to 1.2 mols/100 g and a content of an aromatic group represented by the above general formula (1) (aromatic group content) is 10 to 70 wt%, wherein each symbol is defined in the description.

Description

Flame-retardant aromatic polycarbonate resin composition and moulding product

Technical field

The present invention relates to flame-retardant aromatic polycarbonate resin composition and moulding product thereof.In more detail, the present invention relates to be substantially devoid of bromide and muriate (halogenated flame retardant) or phosphide as fire retardant, and at anti-anti-drop property (preventing property of De リ Star プ) the excellent flame aromatic copolycarbonate resin composition and the moulding product thereof of when burning resin.The invention still further relates to the flame-retardant aromatic polycarbonate resin composition that can obtain the excellent moulding product of the transparency.

Background technology

Fragrance adoption carbon ester resin, aromatic polycarbonate resin/phenylethylene resin series alloy and aromatic polycarbonate resin/aromatic copolycarbonates such as aromatic polyester resins alloy be resin can be by injection molding etc. the simple and high working method of production efficiency make various moulding product, be widely used in branch of industry.Specifically, aromatic polycarbonate resin or its alloy are widely used in the exterior member and the inside components of business automation equipments such as computer, notebook computer, laser printer, ink-jet printer, duplicating machine and facsimile recorder and tame electrical article.In the middle of these were used, resin combination will embody gloss, tone, distinctiveness and the homogeneity of moulding product, the dyeing behavior in the time of will considering emphatically sometimes to cooperate tinting material in resin combination.But also need to adopt good reproducibility, laser printer simple and the required literal of high speed printing, symbol and figure to stamp literal and sign sometimes, at this moment will consider the sharpness of literal and symbol emphatically on moulding product surface.

On the other hand, the moulding product of aromatic polycarbonate resin also are widely used in and require to have excellent transparency and stable on heating branch of industry.Give full play to the excellent transparency of fragrant adoption carbon polycarbonate resin; it is the characteristic of high transmission rate and lowest haze; in the middle of protective guard of various lighting covers, transparent display usefulness etc. requires the field of high transparent, be extensive use of aromatic polycarbonate resin moldings.In the middle of these were used, because the temperature height of light sources such as fluorescent lamp and bulb, in the bathroom or during outdoor use, goods also will expose to the open air in the environment of high humidity, therefore require resin material can keep transparent, color harmony mechanical characteristics in heat and wet environment.Therefore, on the basis of considering the resin combination transparency, also to consider the wet-hot aging performance of resin combination emphatically.

In recent years, in the middle of above-mentioned various application, the flame retardant resistance during the special concern presence of fire.Need a kind ofly have the resin combination that also has high flame retardant on the above-mentioned characteristic basis.As making aromatic polycarbonate resin or its alloy have the method for flame retardant resistance, once proposed halogenide such as interpolation bromide and muriate and phosphide and obtained flame-retardant aromatic polycarbonate resin composition, and be applied in the middle of exigent business automation equipment of flame retardant resistance and the tame electrical article as fire retardant.On the other hand, also developed and substituted the flame-retardant aromatic polycarbonate resin composition of these fire retardants, and be applied in the middle of the said products.Produce corrosive gases when the purpose that changes these fire retardants is to suppress forming process, and improve the recovery utilization rate of goods.

The fire retardant that substitutes above-mentioned fire retardant can be enumerated silicone compounds.Concentrate one's energy in recent years to have studied silicone compounds is coupled to flame retardant resin composition in the aromatic polycarbonate resin, and proposed various schemes.

For example in polycarbonate resin, cooperate perfluoroalkane azochlorosulfonate acid alkali (great soil group) metal-salt and have the method (spy opens flat 6-306265 communique) of the organo-siloxane of alkoxyl group, vinyl and phenyl and in polycarbonate resin, cooperate perfluoroalkane sulfonic acid alkali metal salts or alkali earth metal salt and contain the method (spy opens flat 6-336547 communique) or the like that is combined in the organopolysiloxane of organic silicomethane oxygen (the オ Le ガノキシシリ Le) base on the Siliciumatom by the divalent alkyl.

Also to have proposed in resinous principle to cooperate specific oil be the method (spy opens flat 9-169914 communique) of heavy oil kind or pitch class and silicone compounds and cooperate in containing the non-siloxane resin of aromatic nucleus and contain general formula R ₂SiO _1.0Shown in unit and RSiO _1.5Shown in the method methods such as (spy open flat 10-139964 communique) of unit, weight-average molecular weight silicone resin greater than 10,000, less than 270,000.

But the transparency of the poly carbonate resin composition of aforesaid method, humidity resistance and flame retardant resistance can not be said so well.For example, when thinner thickness, produce drip, the V-0 level requirement that does not reach UL standard 94.And the dispersion of siloxanes is insufficient, produces gonorrhoea in the goods, and perhaps by after the wet heat treatment, the siloxanes cohesion reduces or the like the transparency of material after wet heat treatment.

In addition, in the aromatic copolycarbonate in the special public clear 60-38419 communique, understand the resin combination of forming by organic alkali metal salt and poly-(methyl hydrogen siloxane) specifically.But the own gonorrhoea of the resin of this resin combination, and produce to peel off to wait at product surface and disperse bad defective can not be said so well in the dyeability when embodying cooperation tinting material in goods gloss, tone, distinctiveness and the inhomogeneity resin combination.

Present more use has the anti-drip agent of tetrafluoroethylene conduct that forms the protofibril energy.But when being coupled to tetrafluoroethylene in the aromatic polycarbonate resin, the two is immiscible, so the transparency of goods reduces.

The problem that invention will solve

The 1st purpose of the present invention is to provide a kind of halogenide that is substantially devoid of, and does not preferably also contain the fire resistant aromatic makrolan composition of phosphide.More specifically say to provide a kind of flame-retardant aromatic polycarbonate resin composition, said composition moulding product are clear through the literal and the sign of laser lettering seal, and the anti-anti-drop property excellence of resin during burning, and the dyeability when painted is also fine.

The 2nd purpose of the present invention is to provide a kind of transparency and humidity resistance good, and the also very excellent transparent flame-retarding aromatic copolycarbonate resin composition of anti-anti-drop property of resin during burning.

The 3rd purpose of the present invention is to provide a kind of tracking index (ラ of anti-ト Star キ Application グ) and excellent antistatic property, and when burning resin also excellent flame aromatic polycarbonate composition very of anti-anti-drop property.

Solve the means of problem

In order to achieve the above object, the present inventor has carried out research with keen determination repeatedly, found that the particular silicone compound that in aromatic polycarbonate resin, cooperates specified quantitative, the dyeability that can obtain when painted is good, it is clear with sign to print literal when carrying out the laser lettering, resin is prevented also good flame aromatic copolycarbonate resin composition of anti-drop property during burning, but also can further obtain the transparency and humidity resistance excellent flame aromatic copolycarbonate resin composition, thereby finished the present invention.

That is, if according to the present invention, can provide a kind of flame-retardant aromatic polycarbonate resin composition, said composition comprises:

(1) resinous principle 100 weight parts comprise aromatic polycarbonate resin (A-1 composition) 50～100 weight %, phenylethylene resin series (A-2 composition) 0～50 weight % and aromatic polyester resins (A-3 composition) 0～50 weight %,

(2) at least a silicone compounds (B) 0.1～10 weight part that cooperates in per 100 parts by weight resin compositions, this silicone compounds is the silicone compounds that contains Si-H base and aryl in the molecule, wherein:

1. the content of Si-H base (Si-H amount) be 0.1～1.2mol/100g,

2. the aryl content ratio shown in the following general formula (1) (aryl amount) be 10～70 weight %,

(in the formula (1), X represents that independently of one another OH base, carbon number are 1～20 the organic residue of monovalence.N represents 0～5 integer.And, in the general formula (1),, can choose the X that has nothing in common with each other when n is 2 when above.)

Below specify flame-retardant aromatic carbonate composition of the present invention.At first the order by the silicone compounds (B composition) of resinous principle (A composition) that constitutes said composition and fire retardant describes.

In the resinous principle of resin combination of the present invention (A composition), the aromatic polycarbonate resin that uses as the A-1 composition is except being that common interface polycondensation or the melt transesterification process of passing through reacts the aromatic polycarbonate resin that obtains dihydric phenol and carbonate precursor, can also be to make carbonic ether performed polymer polymeric aromatic polycarbonate resin, or make cyclic carbonate compound carry out the aromatic polycarbonate resin that polymerization obtains by the ring-opening polymerization method by the solid phase ester-interchange method.

The typical example of dihydric phenol used herein has Resorcinol, Resorcinol, 4,4 '-dihydroxyl phenylbenzene biphenyl, two (4-hydroxy phenyl) methane, two { (4-hydroxyls-3, the 5-dimethyl) phenyl } methane, 1, two (4-hydroxy phenyl) ethane of 1-, 1, two (4-the hydroxy phenyl)-1-diphenylphosphino ethanes of 1-, 2, two (4-hydroxy phenyl) propane (common name dihydroxyphenyl propane) of 2-, 2, two { (4-hydroxy-3-methyl) phenyl } propane of 2-, 2, two { (the 4-hydroxyls-3 of 2-, the 5-dimethyl) phenyl } propane, 2, two { (3-sec.-propyl-4-hydroxyl) phenyl } propane of 2-, 2, two { (4-hydroxyl-3-phenyl) phenyl } propane of 2-, 2, two (4-hydroxy phenyl) butane of 2-, 2, two (4-the hydroxy phenyl)-3-methylbutanes of 2-, 2,2-pair-(4-hydroxy phenyl)-3, the 3-dimethylbutane, 2, two (4-the hydroxy phenyl)-2-methylbutanes of 4-, 2, two (4-hydroxy phenyl) pentanes of 2-, 2, two (4-the hydroxy phenyl)-4-methylpentanes of 2-, 1, the 1-bis(4-hydroxyphenyl) cyclohexane, 1, two (4-the hydroxy phenyl)-4-normenthanes of 1-, 1, two (the 4-hydroxy phenyls)-3 of 1-, 3, the 5-trimethyl-cyclohexane, 9, two (4-hydroxy phenyl) fluorenes of 9-, 9, two { (4-hydroxy-3-methyl) phenyl } fluorenes of 9-, α, α '-two (4-hydroxy phenyl-o-diisopropylbenzene(DIPB), α, α '-two (4-hydroxy phenyl)-m-diisopropylbenzene(DIPB), α, α '-two (4-hydroxy phenyl)-p-diisopropylbenzene(DIPB), 1, two (the 4-hydroxy phenyls) 5 of 3-, the 7-dimethyladamantane, 4,4 '-dihydroxy diphenylsulphone, 4,4 '-the dihydroxyl diphenyl sulfoxide, 4,4 '-the dihydroxyl diphenylsulfide, 4,4 '-the dihydroxyl diphenylketone, 4,4 '-dihydroxydiphenyl ether and 4,4 '-the dihydroxyl diphenyl ester or the like, these dihydric phenols can use separately, also can be use mixing two or more.

Wherein, the preferred use by from dihydroxyphenyl propane, 2, two { (4-hydroxy-3-methyl) phenyl } propane, 2 of 2-, two (4-hydroxy phenyl) butane, 2 of 2-, two (4-the hydroxy phenyl)-3-methylbutanes, 2 of 2-, two (the 4-hydroxy phenyls)-3 of 2-, 3-dimethylbutane, 2, two (4-the hydroxy phenyl)-4-methylpentanes, 1 of 2-, two (the 4-hydroxy phenyls)-3,3 of 1-, 5-trimethyl-cyclohexane, 9, two { (4-hydroxy-3-methyl) phenyl } fluorenes and the α of 9-, homopolymer or multipolymer that at least a bis-phenol of selecting in the group that α '-two (4-hydroxy phenyl)-m-diisopropylbenzene(DIPB) constitutes obtains.Especially preferably use the homopolymer and 1 of dihydroxyphenyl propane, two (the 4-hydroxy phenyls)-3,3 of 1-, 5-trimethyl-cyclohexane and dihydroxyphenyl propane, 2, two { (4-hydroxy-3-methyl) phenyl } propane or the α of 2-, the multipolymer of α '-two (4-hydroxy phenyl)-m-diisopropylbenzene(DIPB).

(Ha ロホ Le メ-ト) etc. specifically has bishaloformate of phosgene, diphenyl carbonate or dihydric phenol or the like as the precursor of carbonic ether can to use carbonyl halide (カ Le ボニ Le バライ De), carbonic ether or haloformate.Wherein, phosgene or diphenyl carbonate help industrialization.

When making above-mentioned dihydric phenol and carbonate precursor react the preparation polycarbonate resin, can also use oxidation inhibitor of catalyzer, chain terminator and dihydric phenol or the like as required by interface polycondensation or melt transesterification process.And, polycarbonate resin can also be the branched polycarbonate resin that copolymerization has the above polyfunctionality aromatics of trifunctional, can also be that copolymerization has polyester type polycarbonate, the copolymerization of the difunctionality carboxylic acid of aromatic series or aliphatics (comprising alicyclic) that the copolymerized panlite of difunctionality alcohol (comprising alicyclic) and the polyester type polycarbonate that copolymerization simultaneously has this difunctionality carboxylic acid and difunctionality alcohol are arranged.It can also be the mixture of two or more above-mentioned polycarbonate resins.

The above polyfunctionality aromatics of trifunctional has Phloroglucinol, Gen Pi Portugal phenol, or 4,6-dimethyl-2,4,6-three (4-hydroxy diphenyl) 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 the benzyl)-4-methylphenols of 6-, 4-{4-[1, two (4-hydroxy phenyl) ethyls of 1-] benzene }-α, α-Er Jiajibianji phenol or the like trihydric phenol, four (4-hydroxy phenyl) methane, two (2, the 4-dihydroxy phenyl) ketone, 1, two (4, the 4-dihydroxyl trityl group) benzene of 4-, or trihemellitic acid, pyromellitic acid, benzophenone tetracarboxylic acid and their chloro thing etc.Wherein, preferably use 1,1,1-three (4-hydroxy phenyl) ethane, 1,1,1-three (3,5-dimethyl-4-hydroxy phenyl) ethane, preferred especially 1,1,1-three (4-hydroxy phenyl) ethane.

When containing the polyfunctionality compound that generates branched polycarbonate resin, in the aromatic copolycarbonate total amount, its ratio is 0.001～1 mole of %, preferred 0.005～0.9 mole of %, preferred especially 0.01～0.8 mole of %.When particularly adopting melt transesterification process, sometimes generate branched structure as the side reaction meeting, in the aromatic copolycarbonate total amount, the amount of these branched structures preferably also is 0.001～1 mole of %, preferred 0.005～0.9 mole of %, preferred especially 0.01～0.8 mole of %.This ratio can be passed through ¹H-NMR measures and calculates.

Interfacial polycondensation reacts the normally reaction of dihydric phenol photoreactive gas, is to make its reaction in the presence of acid binding agent and organic solvent.The amine compound that can use alkali-metal oxyhydroxide such as sodium hydroxide, potassium hydroxide or pyridine etc. is as acid binding agent.Can use halogenated hydrocarbons such as methylene dichloride, chlorobenzene as organic solvent.In order to promote reaction, can also use catalyzer such as tertiary amines such as triethyl is pressed, tetra-n-butyl ammonium bromide, tetran-butylphosphonium bromide , quaternary ammonium compound, season  compound simultaneously.At this moment, the pH value in preferred 0～40 ℃ usually of temperature of reaction, preferred about 10 minutes～5 hours of reaction times, the reaction preferably remains on more than 9.

In the interfacial polycondensation reaction, use chain terminator usually.Can use the simple function phenols as chain terminator.Usually using the simple function phenols is in order to regulate molecular weight, generally to use phenol or lower alcohol fortified phenol as the simple function phenols, can using following general formula as chain terminator

(5) expression simple function phenols.

(in the formula, A is that hydrogen atom or carbon number are 1～9 straight or branched alkyl or phenyl substituted alkyl, and r is 1～5, preferred 1～3 integer.)

The concrete example of above-mentioned simple function phenols has phenol, p-tert-butylphenol, right-cumylphenol and isooctyl phenol.

Other monofunctional phenol can be with containing chain alkyl or aliphatic poly ester group as substituent phenols, or represent with the M-nitro benzoic acid chloride-based, or represent with the alkyl carboxylic acid chloride-based of long-chain.Wherein preferred the use has chain alkyl as substituent phenol shown in the following general formula (6) and (7).

(in the formula, X is-R-CO-O-or-R-O-CO-, R represents that singly-bound or carbon number are 1-10, the aliphatic alkyl of preferred 1～5 divalence, n are represented 10～50 integer.)

The substituted benzene phenols of general formula (6), preferred n is 10～30, preferred especially 10～26, concrete example has decyl phenol, dodecyl phenol, tetradecyl phenol, hexadecyl phenol, octadecyl phenol, eicosyl phenol, docosyl phenol and triacontyl phenol etc.

The substituted benzene phenols of general formula (7), preferably X is-R-CO-O-, R is single bonded compound, n is 10～30, preferred 10～26 fortified phenol, concrete example have Para Hydroxy Benzoic Acid ester in the last of the ten Heavenly stems, Para Hydroxy Benzoic Acid dodecyl ester, Para Hydroxy Benzoic Acid tetradecyl ester, Para Hydroxy Benzoic Acid cetyl ester, Para Hydroxy Benzoic Acid eicosyl ester, Para Hydroxy Benzoic Acid docosyl ester and Para Hydroxy Benzoic Acid triacontyl ester or the like.Chain terminator may be used alone, can also be two or more kinds in combination simultaneously.

The melt transesterification process reaction, normally the transesterification reaction of dihydric phenol and carbonic ether in the presence of rare gas element, is mixed dihydric phenol and carbonic ether heating, distillates the alcohol or the phenol of generation.And different, general range is 120～350 ℃ to temperature of reaction with differences such as the boiling points that generates alcohol or phenol.The reaction later stage is decompressed to 1.33 * 10 to reaction system ³About～13.3Pa, the alcohol of generation or phenol are distillated easily.Reaction times was generally about 1～4 hour.

Carbonic ether, having can substituted carbon number be that 6～10 aryl, aralkyl or carbon number are the carbonic ether of alkyl of 1～4 etc.Concrete example has diphenyl carbonate, two (chloro-phenyl-) carbonic ether, dinaphthyl carbonic ether, two (phenylbenzene) carbonic ether, dimethyl carbonate, diethyl carbonate or dibutyl carbonic ether or the like, wherein preferred diphenyl carbonate.

In order to improve polymerization velocity, can also use polymerizing catalyst, as this polymerizing catalyst, specifically can use sodium hydroxide, potassium hydroxide, the sodium salt of dihydric phenol, alkali metal compounds such as sylvite, calcium hydroxide, hydrated barta, alkali earth metallic compounds such as hydrochlorinate magnesium, Tetramethylammonium hydroxide, tetraethyl ammonium hydroxide, Trimethylamine, the basic cpd that triethylamine etc. are nitrogenous, the alkoxide of basic metal and alkaline-earth metal, the organic acid salt of basic metal and alkaline-earth metal, zn cpds, boron compound, aluminum compound, silicon compound, germanium compound, organo-tin compound, lead compound, osmium compound, antimony compounds, manganic compound, titanium compound, used catalyzer in common esterification such as zirconium compounds and the transesterification reaction.Can be used alone catalyzer, also can mix and use two or more catalyzer.The consumption of these polymerizing catalysts, for 1 mole of dihydric phenol raw material, its preferable range is 1 * 10 ^-8～1 * 10 ^-3Equivalent, more preferably 1 * 10 ^-7～5 * 10 ^-4In weight range, select.

In this polyreaction, in order to reduce the phenols end group, after polycondensation later stage or reaction end, can add as compounds such as two (chloro-phenyl-) carbonic ether, two (bromophenyl) carbonic ether, two (nitrophenyl) carbonic ether, two (phenyl) carbonic ether, chloro-phenyl-benzol carbonate, bromophenyl benzol carbonate, nitrophenyl benzol carbonate, phenyl carbonic ether, methoxycarbonyl phenyl carbonic ether and ethoxy carbonyl phenyl carbonic ethers.Wherein, preferably use 2-chloro-phenyl-benzol carbonate, 2-methoxycarbonyl phenyl carbonic ether and 2-ethoxy carbonyl phenyl carbonic ether, especially preferably use 2-methoxycarbonyl phenyl carbonic ether.

In this polyreaction, preferably use the active deactivator of catalyst neutralisation.The concrete example of this deactivator has benzene sulfonates such as Phenylsulfonic acid, p-toluenesulphonic acids, methyl benzenesulfonate, ethyl benzenesulfonat, Phenylsulfonic acid butyl ester, Phenylsulfonic acid monooctyl ester, Phenylsulfonic acid phenyl ester, p-toluenesulphonic acids methyl esters, p-toluenesulphonic acids ethyl ester, p-toluenesulphonic acids butyl ester, p-toluenesulphonic acids monooctyl ester, p-phenyl toluene-sulphonate; Also has trifluoromethanesulfonic acid, naphthene sulfonic acid, sulfonated polystyrene, methyl acrylate-sulfonated phenylethylene copolymer, Witco 1298 Soft Acid-2-phenyl-2-propyl ester, Witco 1298 Soft Acid-2-phenyl-2-butyl ester, octyl group sulfonic acid tetrabutyl  salt, decyl sulfonic acid tetrabutyl  salt, Phenylsulfonic acid tetrabutyl  salt, Witco 1298 Soft Acid tetraethyl- salt, Witco 1298 Soft Acid tetrabutyl  salt, Witco 1298 Soft Acid four hexyl  salt, Witco 1298 Soft Acid four octyl group  salt, decyl ammonium butyl sulfuric ester, decyl ammonium decyl sulfuric ester, dodecyl ammonium methylsulfuric acid ester, dodecyl QAE quaternary aminoethyl sulfuric ester, dodecyl first ammonium methylsulfuric acid ester, dodecyl dimethyl ammonium tetradecyl sulfuric ester, tetradecyl Dimethyl Ammonium methylsulfuric acid ester, the tetramethyl-ammonium hexyl sulfate, decyl trimethyl ammonium hexadecyl hydrosulfate ester, TBuA dodecylbenzyl sulfuric ester, tetraethyl ammonium dodecylbenzyl sulfuric ester, compounds such as tetramethyl-ammonium dodecylbenzyl sulfuric ester, but be not limited in this scope.Also can mix and use two or more above-claimed cpds.

Preferred  salt or the ammonium salt of using in deactivator.Concerning 1 mole of remaining catalyzer, the consumption of deactivator is 0.5～50 mol ratio preferably, and the polycarbonate resin after polymerization, the consumption of deactivator is 0.01～500ppm, more preferably 0.01～300ppm, preferred especially 0.01～100ppm.

Molecular weight to polycarbonate resin is not particularly limited.Be lower than at 10,000 o'clock but work as its viscosity-average molecular weight, the hot properties of resin reduces, when it surpasses 50,000 o'clock, the forming process reduction of resin was so the viscosity-average molecular weight of optimization polycarbonate resin is 10,000～50,000, more preferably 14,000～30,000, further preferred 14,000～24,000.Might as well mix in addition and use two or more polycarbonate resins, can certainly mix the not polycarbonate resin in above-mentioned scope of viscosity-average molecular weight.

Preferred especially and viscosity-average molecular weight surpasses 50,000 polycarbonate resin mixing.Because the anti-drip performance of such mixture is good, can more effective acquisition effect of the present invention.More can preferably use and the mixture of viscosity-average molecular weight at the polycarbonate resin more than 80,000, further preferred and viscosity-average molecular weight is at the mixture of the polycarbonate resin more than 100,000.Just preferably use and obviously have the polycarbonate resin lipoprotein mixture that two peaks distribute when measuring by GPC methods such as (gel permeation chromatographies).

Said viscosity-average molecular weight among the present invention is at first made solution to polycarbonate resin 0.7g being dissolved in the methylene dichloride 100ml under 20 ℃.Obtain specific viscosity with the ostwald's viscometer test and by following formula,

Specific viscosity (η _SP)=(t-t ₀)/t ₀

[t ₀: drippage number second of methylene dichloride, t: drippage number second of sample solution] specific viscosity of obtaining is updated in the following formula, obtain viscosity-average molecular weight M.

η _SP/ c=[η]+0.45 * [η] ²C is (in the formula [η]: limiting viscosity)

[η]＝123×10 ^-4M ^0.83

c＝0.7

The aromatic copolycarbonate of A-1 composition of the present invention is above-mentioned aromatic polycarbonate resin, and is the resin that is substantially devoid of halogen atom.What is called is substantially devoid of halogen atom, is illustrated in not contain halogen replacement dihydric phenol etc. in the molecule, is not meant trace solvent (halohydrocarbon) and carbonate precursor residual in the above-mentioned aromatic copolycarbonate preparation process.

The aforementioned aromatic polycarbonate resin of A-1 composition of the present invention, further the acid number scope of optimization aromatic polycarbonate resin (PC)-0.5～5.0 (mg angelic acid/10kgPC).(in the scope of mg angelic acid/10kgPC) time, silicone compounds of the present invention (B composition) can play a role acid number effectively, demonstrates tracking index easily, the anti-anti-drop property of the resin when static resistance and burning at-0.5-5.0.More preferably acid number 0.0～3.0 (aromatic polycarbonate resin of scope of mg angelic acid/10kgPC).If (mg angelic acid/10kgPC) then the alkalescence of aromatic polycarbonate resin itself is high, the thermostability of composition reduces acid number less than-0.5.If greater than 5.0 (the mg angelic acid/10kgPC), then free acid in the aromatic polycarbonate resin or phenols end group combine with the Si-H in the silicone compounds (B composition) is basic, then tracking index and static resistance reduce, and resin is difficult to demonstrate anti-anti-drop property during burning.

Here said acid number is meant the acid contained in every 10kg polycarbonate resin (representing with 10kgPC) or the amount of alkali, be in methylene dichloride 100ml, add methyl alcohol 3ml, again add polycarbonate resin sample 10.0g 20 ℃ down dissolving make solution, in this solution, add C ₁₅H ₁₇CN ₄-C ₁₆H ₁₈CIN ₃SnH ₂O 1ml is as indicator, with the sodium methylate (CH of 0.01mol/l ₃ONa) titration, titer when adding sample and the titer when not adding sample are updated in the following calculating formula, obtain acid number.

V＝N×k×(X-Y)×10000/W

V: acid number (the mg angelic acid/10kgPC)

N: sodium methylate (CH ₃ONa) mol/l

K:0.01mol/lCH ₃The coefficient of ONa

X: the titer when adding the polycarbonate resin sample (ml)

Y: the titer when not adding the polycarbonate resin sample (ml)

W: sample size (g)

Acid number is-0.5～5.0 (aromatic polycarbonate resin of mg angelic acid/10kgPC), when preparing aromatic polycarbonate resin with interface polycondensation, sometimes to remove catalyzer such as triethylamine into promoting that reaction is used, and use hydrochloric acid, but for the sour composition that neutralizes and cause by hydrochloric acid, add alkali, addition that can be by suitable control alkali composition or strengthen the method for purification procedures such as the washing, (scope of mg angelic acid/10kgPC) that acid number is controlled at-0.5～5.0.In addition, in the aromatic polycarbonate resin preparation process of the interface polycondensation that does not use catalyzer, in order to neutralize and the alkali composition that produces by acid binding agents such as sodium hydroxide, add suitable sour composition, addition that can be by the sour composition of suitable control or the method for strengthening purification procedures such as washing are controlled at acid number-0.5～5.0 (in the scope of mg angelic acid/10kgPC).

In the resin combination of the present invention, the phenylethylene resin series that can be used as the A-2 composition that resinous principle (A composition) uses is by styrene monomer polymerization or the phenylethylene resin series that obtained by more than one copolymerization of selecting in other vinyl monomer of styrene monomer and copolymerization with it and the rubber mass polymer as required.

Used styrenic monomers has styrene derivativess such as vinylbenzene, alpha-methyl styrene, neighbour-vinyl toluene, p-methylstyrene, vinyl-dimethyl benzene, ethyl styrene, dimethyl styrene, right-t-butyl styrene, vinyl naphthalene, methoxy styrene in the aforementioned phenylethylene resin series composition, special optimization styrene, these monomers can be used alone, but also also mix together two or more monomers.

Can vinyl cyanide based compounds such as vinyl cyanide, methacrylonitrile, acrylic acid aryl esters such as phenyl acrylate, benzyl acrylate be arranged with other vinyl monomer of aforementioned styrenic monomers copolymerization; Acrylic acid alkyl esters such as methyl acrylate, ethyl propenoate, propyl acrylate, butyl acrylate, vinylformic acid pentyl ester, Ethyl acrylate, 2-EHA, Octyl acrylate, cyclohexyl acrylate, dodecylacrylate; Aryl methacrylate such as phenyl methacrylate, benzyl methacrylate; Alkyl methacrylates such as methyl methacrylate, Jia Jibingxisuanyizhi, propyl methacrylate, butyl methacrylate, methacrylic acid pentyl ester, N-Hexyl methacrylate, methacrylic acid 2-ethylhexyl, Octyl methacrylate, cyclohexyl methacrylate, methyl-propyl acid dodecyl ester; Glycidyl methacrylate etc. contain the methacrylic ester of epoxy group(ing); Maleic anhydride imines, N-methyl maleic anhydride imines, N-phenyl maleic anhydride maleic anhydrides such as the imines imines that contracts that contracts that contracts that contracts is a monomer; α such as vinylformic acid, methacrylic acid, toxilic acid, maleic anhydride, phthalic acid, methylene-succinic acid, beta-unsaturated carboxylic acid and acid anhydrides thereof or the like.

Can polyhutadiene be arranged with the rubber mass polymer of aforementioned styrenic monomers copolymerization, polyisoprene, the random copolymer of styrene butadiene and the embedding interpolymer that breaks, the acrylonitrile butadiene interpolymer, the interpolymer of alkyl acrylate or alkyl methacrylate and divinyl, diolefin series interpolymers such as butadiene-isoprene interpolymer, the random copolymer of ethylene, propylene and the embedding interpolymer that breaks, the interpolymer of ethene such as the disconnected interpolymer of the random copolymer of ethylene butene and embedding and alpha-olefin, the ethylene methacrylate interpolymer, the interpolymer of ethene such as ethylene butyl acrylate interpolymer and unsaturated carboxylic ester, the interpolymer of ethene such as ethylene-vinyl acetate interpolymer and aliphatic ethylene base, the terpolymers of ethene such as ethylene, propylene hexadiene interpolymer and propylene and non-conjugated diene, acrylic rubber such as butyl polyacrylate and have the organopolysiloxane rubber constituent and poly-(methyl) alkyl acrylate rubber constituent is twined not compounded rubber of separable structure (hereinafter referred to as IPN type rubber) or the like mutually.

The concrete example of this styrene resin (A-2 composition) has polystyrene, styrene butadiene styrene multipolymer (SBS), hydrogenation styrene butadiene styrene multipolymer (hydrogenation SBS), hydrogenation styrene isoprene styrol copolymer (SEPS), impact resistant polystyrene (HIPS), acrylonitrile styrene copolymer (AS resin), acrylonitrile butadient styrene (ABS resin), MMB methyl methacrylate butadiene styrol copolymer (MBS resin), methyl methacrylate acrylonitrile butadient styrene (MABS resin), vinyl cyanide acrylic rubber styrol copolymer (AAS resin), vinyl cyanide second third is resin and their mixtures such as rubber styrol copolymer (AES resin) and the rare IPN type of benzene second rubbery copolymer.These polystyrene resins also can be when it prepares, and the high stereotaxis polystyrene by using catalyzer such as metalloscene catalyst to make has high stereospecific phenylethylene resin series.And can also use the narrow polymkeric substance of the molecular weight distribution that obtains by methods such as living anion polymerization, free radical activity polymerizations and multipolymer, segmented copolymer and high stereospecific polymer, multipolymer sometimes.Wherein, preferred polystyrene (PS), impact resistant polystyrene (HIPS), acrylonitrile styrene copolymer (AS resin), MMB methyl methacrylate butadiene styrol copolymer (MBS resin), acrylonitrile butadient styrene (ABS resin), ABS resin most preferably.Also can mix and use two or more phenylethylene resin series.

So-called ABS resin is meant graft polymerization vinyl cyanide based compound and the thermoplastic graft copolymer multipolymer of aromatic ethenyl compound and the mixture of vinyl cyanide based compound and aromatic vinyl copolymer on the diene series rubber composition.The diene series rubber composition that forms this ABS resin can use the rubber of second-order transition temperature below 10 ℃ such as polyhutadiene, polyisoprene and styrene-butadiene copolymer, in 100 weight %ABS resins, the usage ratio of diene series rubber composition is preferably 5～80 weight %, preferred especially 10～50 weight %.Grafted vinyl cyanide based compound can be enumerated aforesaid compound, especially preferably use vinyl cyanide on the diene series rubber composition.Be grafted on the aromatic ethenyl compound on the diene series rubber composition, can use aforesaid compound equally, preferably use vinylbenzene and alpha-methyl styrene.In the 100 weight %ABS resinous principles, the grafting component proportions on the diene series rubber composition is preferably 95～20 weight %, preferred especially 50～90 weight %.Concerning cyaniding (シア Applicationization) vinyl compound and aromatic ethenyl compound total amount were 100 weight %, the amount of vinyl cyanide based compound was preferably 5～50 weight %, and the amount of aromatic ethenyl compound is preferably 95～50 weight %.In partially grafted composition to the diene series rubber composition, also can mix and use methyl methacrylate, ethyl propenoate, maleic anhydride, N to replace the maleic anhydride imines etc. that contracts.Containing of this compounds is proportional in the ABS resin composition below the preferred 15 weight %.As required, various additives known such as operable initiator, chain-transfer agent, emulsifying agent in the reaction.

In ABS resin, rubber particles diameter, preferred 0.1～5.0 μ m, more preferably 0.15～1.5 μ m aspect weight average particle diameter, preferred especially 0.2～1 μ m.The distribution of rubber particles diameter can be that single distribution also can be to have the above multimodal in two peaks to distribute, and the rubber constituent of two kinds of size distribution all can be used.Aspect form, can be the structure that rubber particles forms homogeneous phase, also can be by around rubber particles, containing the island shape structure (サラミ Agencies makes) that sealing phase (オ Network Le-De phase) forms.

As everyone knows, contain vinyl cyanide based compound and the aromatic ethenyl compound that is not grafted on the diene series rubber composition in the ABS resin.In ABS resin of the present invention, also can contain the free polymer composition that produces in the polymerization.The molecular weight of the interpolymer that is formed by this free vinyl cyanide based compound and aromatic ethenyl compound calculates with reducing viscosity (dl/g), is preferably 0.2～1.0, and more preferably 0.25～0.5.

Concerning the diene series rubber composition, the vinyl cyanide based compound in the grafting and the ratio of aromatic ethenyl compound are preferably 20～200 weight %, more preferably the percentage of grafting of 20～70 weight %.

This ABS resin can adopt any one method preparation of mass polymerization, suspension polymerization, letex polymerization, and copolymerization process also is to adopt single stage method copolymerization and multistep processes copolymerization.But also can use in the ABS resin that aforesaid method obtains the blending resin of the aromatic ethenyl compound that blending obtains by other copolymerization approach and the vinyl compound copolymer of vinyl cyanide based compound copolymerization.

In the resin combination of the present invention, the aromatic polyester resins that can be used as the A-3 composition that resinous principle (A composition) uses is polymkeric substance or the multipolymer that obtains through polycondensation as main component with aromatic dicarboxylic acid or its reactive derivatives and dibasic alcohol or its ester derivative.

Here said aromatic dicarboxylic acid can use terephthalic acid, m-phthalic acid, phthalic acid, 1, the 5-naphthalene dicarboxylic acids, 2, the 6-naphthalene dicarboxylic acids, 4,4 '-the xenyl dicarboxylic acid, 4,4 '-xenyl ether dicarboxylic acid, 4,4 '-the xenyl propanedioic acid, 4,4 '-xenyl sulfonation dicarboxylic acid, 4,4 '-xenyl isopropylidene dicarboxylic acid, 1,2-joins (phenoxy group) ethane-4,4 '-dicarboxylic acid, 2,5-anthryl dicarboxylic acid, 2,6-anthryl dicarboxylic acid, 4,4 '-p-connection triphenylenyl dicarboxylic acid, 2, fragrant family dicarboxylic acid such as 5-pyridine dicarboxylic acid especially preferably use terephthalic acid or 2,6-naphthyl dicarboxylic acid.

Aromatic dicarboxylic acid also can be use mixing two or more.If amount is few, alicyclic dicarboxylic acids such as aliphatic dicarboxylic acid, cyclohexane dicarboxylic acid such as this dicarboxylic acid and more than one hexanodioic acid, nonane diacid, sebacic acid, dodecyl diacid etc. can also be mixed and use.

The dibasic alcohol of aromatic polyester composition of the present invention has ethylene glycol, propylene glycol, butyleneglycol, hexylene glycol, neopentyl glycol, pentanediol, hexa-methylene glycol, decanediol, 2-methyl isophthalic acid, aliphatic diols, 1 such as ammediol, Diethylene Glycol, triethylene glycol, alicyclic diols such as 4-cyclohexanedimethanol etc., 2,2-connection (beta-hydroxy ethoxyl phenenyl) propane etc. contains glycol of aromatic nucleus etc. and composition thereof.If amount is few, can also to use molecular weight be 400～6,000 long chain diol, promptly more than one polyoxyethylene glycol, poly--1, and ammediol, polytetramethylene glycol etc. carries out the long chain diol of copolymerization.

The fragrant adoption ester of benzene of the present invention can also make it have side chain by introducing a spot of branching agent.To the kind of branching agent without limits, can use trimesic acid, trihemellitic acid, trimethylolethane, TriMethylolPropane(TMP), tetramethylolmethane or the like.

The concrete example of aromatic polyester resins (A-3 composition) has polyethylene terephthalate (PET), Poly(Trimethylene Terephthalate), polybutylene terephthalate (PBT), poly terephthalic acid hexylene glycol ester, PEN (PEN), PBN (PBN), polyethylene-1,2-connection (phenoxy group) ethane-4,4 '-dicarboxylic ester or the like.In addition, can also use poly-m-phthalic acid/ethylene glycol terephthalate, poly terephthalic acid/copolyester and their mixtures such as m-phthalic acid butanediol ester.In order to obtain the over-all properties of better thermal characteristics and mechanical property, preferably make polyethylene terephthalate, the PEN of spent glycol as dibasic alcohol.In the aromatic polyester resins of 100 weight %, the consumption of polyethylene terephthalate, PEN is preferably more than 50 weight %.Particularly the consumption of polyethylene terephthalate is preferably more than 50 weight %.In addition, when requiring processibility and mechanical over-all properties, preferably use with polybutylene terephthalate, the PBN of butyleneglycol as dibasic alcohol, and by weight, the amount ranges of polybutylene terephthalate/polyethylene terephthalate preferably 2～10.

Terminal group structure to the gained aromatic polyester resins is not particularly limited, and the hydroxyl in the terminal group and the ratio of carboxyl can be roughly the same, and a kind of end group that also can be wherein is more.For these terminal group, also can be by reacting end-blocking with reactive compounds.

Preparation method about these aromatic polyester resins, can be according to usual way, containing in the presence of the polycondensation catalysts such as titanium, germanium, antimony, the limit heating edge makes dicarboxylic acid and aforementioned glycol component polymerization, and water, lower alcohol or the dibasic alcohol that pair generates be discharged to outside the reaction system, produce aromatic polyester resins.The example that contains the polymerizing catalyst of germanium has the oxide compound of germanium, oxyhydroxide, halogenide, alcoholate, phenolate or the like, and concrete example has germanium oxide, hydroxide germanium, germanium tetrachloride, tetramethoxy germanium or the like.

In this process, can also be used in the known polycondensation last stage transesterification reaction, compounds such as the manganese of use, zinc, calcium, magnesium after transesterification reaction finishes, can also pass through phosphoric acid or phosphorons acid compound, make catalyst deactivation carry out polycondensation.

Molecular weight for aromatic polyester resins is not particularly limited, and making solvent with the o-chlorophenol is 0.4～1.2 in the intrinsic viscosity of 35 ℃ of mensuration, and preferred 0.6～1.15.

About the cooperate ratio of aromatic polycarbonate resin (A-composition) in the aromatic copolycarbonate resin composition of the present invention (A) with phenylethylene resin series (A-2 composition) and/or aromatic polyester resins (A-3 composition), total amount in aromatic polycarbonate resin and phenylethylene resin series and/or aromatic polyester resins is 100 weight %, aromatic polycarbonate resin is 100～50 weight %, preferred 99.5～50 weight %, and phenylethylene resin series and/or aromatic polyester resins are 0～50 weight %, preferred 0.5～50 weight %.The cooperation ratio of aromatic polycarbonate resin (A-1) is lower than 50 weight %, when just the cooperation ratio of phenylethylene resin series (A-2) and/or aromatic polyester resins (A-3) is greater than 50 weight %, the flame retardant resistance of resin combination is not enough, so should not adopt.

In the resin combination of the present invention, the silicone compounds (B composition) that uses as fire retardant is the silicone compounds with specific Si-H key.Promptly from molecule, contain the silicone compounds (B) more than select in the silicone compounds of Si-H base and aryl at least a, wherein 1. the content of Si-H base (Si-H amount) be 0.1～1.2mol/100g, 2. the aryl shown in the following general formula (1) contain ratio (aryl amount) be 10～70 weight %,

(in the formula (1), X represents that independently of one another OH base, carbon number are 1～20 the organic residue of monovalence.N represents 0～5 integer.In the general formula (1),, can choose the X that has nothing in common with each other when n is 2 when above.)。

Preferably at least a structural unit from contain the structural unit shown in following general formula (2) and (3) is as the silicone compounds of selecting in the silicone compounds that contains the Si-H key unit more than at least a.

(in formula (2) and the formula (3), Z ¹～Z ³Represent that independent separately hydrogen atom, carbon number are 1～20 organic residue of monovalence and the compound shown in the following general formula (4).α 1～α 3 is separately independently, represents 0 or 1 respectively.M1 represents the integer more than 0 or 1.In the formula (3), when m1 is 2 when above, repeating unit can be chosen the multiple repeating unit that has nothing in common with each other),

(in the formula (4), Z ⁴～Z ⁸Independent separately expression hydrogen atom, carbon number are 1～20 the organic residual machine of monovalence.α 4～α 8 is separately independently, represents 0 or 1 respectively.M2 represents the integer more than 0 or 1.In the formula (4), when m2 is that 2 repeating units when above can be chosen the multiple repeating unit that has nothing in common with each other.)

With M be single functionality siloxane unit, D be the difunctionality siloxane unit, when T is the three-functionality-degree siloxane unit, the preferred silicone compounds that constitutes by MD unit or MDT unit.

The Z of structural unit shown in above-mentioned general formula (2), (3) and (4) ¹～Z ⁸And carbon number is that 1～20 the organic residue of monovalence can be enumerated alkyl such as methyl, ethyl, propyl group, butyl, hexyl, decyl among the X of general formula (1), alkenyls such as cycloalkyl such as cyclohexyl, vinyl, allyl group, aryl such as phenyl, tolyl and aralkyl and these groups can also contain various functional groups such as epoxy group(ing), carboxyl, acid anhydride, amino and sulfydryl.Preferably contain carbon number and be 1～8 alkyl, alkenyl or aryl, carbon numbers such as special preferable methyl, ethyl, propyl group are 1～4 alkyl, vinyl or phenyl.

In the silicone compounds that contains at least a above structural unit in the structural unit shown in aforementioned formula (2) and (3), when having multiple siloxane bond repeating unit, can choose any form of random copolymerization, the disconnected copolymerization of embedding or trapezoidal copolymerization (テ-パ-De overlaps altogether).

Among the present invention, in the conduct aforementioned silicone compounds of (B) composition, the Si-H amount in the silicone compounds must be in the scope of 0.1～1.2mol/100g.The Si-H amount forms siloxane structure easily during burning in 0.1～1.2mol/100g scope.More preferably the Si-H amount is at the silicone compounds of 0.2～1.0mol/100g scope.When Si-H amount is lower than 0.1mol/100g, be difficult to form siloxane structure, and when being higher than 1.2mol/100g, the thermostability of composition reduces, and during wet heat treatment, superfluous Si-H base reacts with airborne moisture, generate hydrogen, produce bubble, the moulding product gonorrhoea that becomes.Here said siloxane structure is meant that silicone compounds reacts to each other or the reticulated structure of resin and siloxane reactions generation.

Here said Si-H amount is meant the mol number of Si-H structure contained in every 100g silicone compounds.Can obtain by the hydrogen volume that produces with caustic leaching process analytical unit weight siloxane compound.For example when 25 ℃ of following 1g silicone compound deposits yields 122ml hydrogen, obtain the Si-H amount by following calculating formula and be 0.5mol/100g.

122×273/(273+25)÷22400×1000.5

On the other hand, at resinous principle (A composition), particularly in the A-1 composition, cooperate in the resin combination of silicone compounds, in order to suppress moulding product gonorrhoea, or the transparency that causes by wet heat treatment reduction, the dispersion state of siloxanes is very important.This is that the then gonorrhoea of resin combination, and product surface own produces and peels off because if the siloxanes dispersion is inhomogeneous, or silicone compounds migration when wet heat treatment, disperses inequality, the transparent reduction.Be difficult to obtain the good moulding product of the transparency.The important factor that determines this dispersion state is aryl amount and the mean polymerisation degree in the silicone compounds.Particularly in transparent resin combination, mean polymerisation degree is even more important.

According to this viewpoint, as silicone compounds of the present invention, aryl weight range wherein must be at 10～70 weight %.More preferably the aryl amount is at the silicone compounds of 15～60 weight % scopes.If the aryl amount is lower than 10 weight %, then the silicone compounds skewness causes disperseing bad, is difficult to obtain the good moulding product of the transparency.If the aryl amount is higher than 70 weight %, then the molecule stiffness of silicone compounds itself improves, and skewness still occurs, causes disperseing bad, also is difficult to obtain the good molding of the transparency.

Here said aryl amount is meant in the silicone compounds that containing of aryl shown in the following general formula (1) is proportional, can obtain according to following calculating formula.

Aryl amount=[A/M] * 100 (weight %)

A in the aforementioned calculation formula, M represent following numerical value respectively.

The total molecular weight of aryl moiety shown in contained all general formulas (1) in A=1 silicone compounds molecule

The molecular weight of M=silicone compounds

As silicone compounds of the present invention (B composition) preferably the ranges of indices of refraction 25 ℃ the time 1.40～1.60, more preferably ranges of indices of refraction is 1.42～1.59, most preferably ranges of indices of refraction is at 1.44～1.59 silicone compounds.Specific refractory power is in above-mentioned scope the time, and silicone compounds is dispersed in the aromatic copolycarbonate imperceptibly, can obtain that gonorrhoea is lower, the better resin combination of dyeability.

As silicone compounds of the present invention (B composition), it is preferred below 18% to be used in the volatile quantity that 105 ℃/3 hours loss on heating method measures.The more preferably silicone compounds of volatile quantity below 10%.If volatile quantity is greater than 18%, when the preparation resin combination, the volatile quantity of silicone compounds increases, and makes troubles for sometimes the moulding of resin combination moulding product.

As the silicone compounds that contains structural unit shown in the above-mentioned general formula, as long as can satisfy above-mentioned condition, then the structure of compound promptly can be a straight chain structure, also can be the structure with side chain.Can also use any one position of side chain, end and branch point in molecular structure or all cpds that a plurality of position has the Si-H base.

The structure of general silicone compounds is combined together formation to following four kinds of siloxane units.

M unit: (CH ₃) ₃SiO _1/2, H (CH ₃) ₂SiO _1/2, H ₂(CH ₃) SiO _1/2, (CH ₃) ₂(CH ₂=CH) SiO _1/2, (CH ₃) ₂(C ₆H ₆) SiO _1/2, (CH ₃) (C ₆H ₅) (CH ₂=CH) SiO _1/2Deng the single functionality siloxane unit

D unit: (CH ₃) ₂SiO, H (CH ₃) SiO, H ₂SiO, H (C ₆H ₅) SiO, (CH ₃) (CH ₂=CH) SiO, (C ₆H ₅) ₂Difunctionality siloxane units such as SiO

T unit: (CH ₃) SiO _3/2, (C ₃H ₇) SiO _3/2, HSiO _3/2, (CH ₂=CH) SiO _3/2, (C ₆H ₅) SiO _3/2Deng the three-functionality-degree siloxane unit

Q unit: SiO ₂Four shown functionality siloxane units

The concrete rational formula of silicone compounds structure used in the present invention has D _n, T _p, M _mD _n, M _mT _p, M _mQ _q, M _mD _nT _p, M _mD _nQ _q, M _mT _pQ _q, M _mD _nT _pQ _q, D _nT _p, D _nQ _q, D _nT _pQ _qWherein, preferred silicone compounds structure is M _mD _n, M _mT _p, M _mD _nT _p, M _mD _nQ _q, more preferably structure is M _mD _nOr M _mD _nT _p

(the inferior horn Coefficient m in the above-mentioned rational formula, n, p, q are the integer of each siloxane polymerization degree of expression, the mean polymerisation degree that the following angle factor sum in each rational formula is a silicone compounds.Among the present invention, the scope of this mean polymerisation degree preferably 3～150, more preferably scope is 3～80, further preferable range is 3～60.When any one of m, n, p, q is numerical value more than 2, can think to have down that the siloxane unit of angle factor is the siloxane unit that is connected with two or more different hydro atoms and organic residue.)

Above-mentioned silicone compounds can be distinguished separately and use, and also can be used two or more.

Silicone compounds with this Si-H key can prepare with the currently known methods of itself.For example according to the structure of required silicone compounds, corresponding organochlorosilane class put together to be hydrolyzed, and removes secondary hydrochloric acid and low boiling component of giving birth to, and can obtain the purpose product.In addition, make initial feed with silicon (oxygen) oil, annular siloxane and the alkoxyl silicone alkanes that contain the aryl shown in Si-H key and the general formula (1) and other organic residue in the molecule, use acid catalysts such as hydrochloric acid, sulfuric acid, methylsulfonic acid, sometimes in order to be hydrolyzed, also to add water, after making it carry out polyreaction, remove used acid catalyst and low boiling point component equally, can obtain needed silicone compounds.

The silicone compounds of aforementioned (B) composition, concerning 100 parts by weight resin compositions (A composition), its amount is 0.1～10 weight part, preferred 0.3～7 weight part, more preferably 0.5～5 weight part cooperates.

In the resin combination of the present invention, can also cooperate at least a compound of from free radical generating agent, organic alkali metal salt and organic alkali earth metal salt, selecting as (C) composition.By cooperating (C) composition, can further improve flame retardant resistance, particularly anti-anti-drop property is improved.In the present invention (C) composition is called the flame retardant resistance modifying agent.(C) composition is as the use level of flame retardant resistance modifying agent, and concerning 100 parts by weight resin compositions (A composition), its optimum range is 0.001～0.3 weight part, preferred 0.005～0.3 weight part, more preferably 0.005～0.2 weight part.

The free radical generating agent that uses as the present invention (C) composition has 2,5-dimethyl-2, organo-peroxides, 2 such as 5-two (t-butylperoxy) 3-hexin, dicumyl peroxide, 3-dimethyl-2,3-diphenyl butane (diisopropylbenzene(DIPB)) or the like, these superoxide are on sale on market, and Japanese grease (strain) is made, commodity are called パ one ヘキシ Application 25B, パ one Network ミ Le D, ノ Off マ one BC etc., are easy to obtain.It would be desirable when melting mixing, seldom to produce free radical, and the time can effectively produce free radical with certain stability in burning, so more preferably 2,3-dimethyl-2,3-diphenyl butane (diisopropylbenzene(DIPB)) is as free radical generating agent.

As the employed an alkali metal salt of the present invention (C) composition, alkaline earth salt, can use fire-retardant used various metal-salts, particularly metal organic sulfonate of polycarbonate resin or sulfuric ester metal-salt in the past.These metal-salts not only can use separately, but also can use two or more mixing.As basic metal of the present invention lithium, sodium, potassium, rubidium, caesium are arranged, alkaline-earth metal has beryllium, magnesium, calcium, strontium, barium, special preferred lithium, sodium, potassium.

Aforementioned metal organic sulfonate has an alkali metal salt of aliphatic sulfonic, the alkali earth metal salt of aliphatic sulfonic, an alkali metal salt of aromatic sulphonic acid, the alkali earth metal salt of aromatic sulphonic acid etc.Azochlorosulfonate acid alkali (great soil group) metal-salt and perfluoroalkane azochlorosulfonate acid alkali (great soil group) metal-salt that the preference of this aliphatic sulfonic metal-salt has the part alkyl of alkansulfonic acid alkali (great soil group) metal-salt, this alkansulfonic acid alkali (great soil group) metal-salt to be replaced by fluorine atom, these alkali (great soil group) metal-salt, can use a kind ofly, perhaps use two or more simultaneously.(expression method of said here alkali (great soil group) metal-salt uses from the meaning that comprises an alkali metal salt and alkali earth metal salt).

The preference of used alkansulfonic acid has methylsulfonic acid, ethyl sulfonic acid, propanesulfonic acid, fourth sulfonic acid, methyl fourth sulfonic acid, own sulfonic acid, heptan sulfonic acid, hot sulfonic acid etc. in chain azochlorosulfonate acid alkali (great soil group) metal-salt.These sulfonic acid can use a kind ofly, also can use two or more simultaneously.The metal-salt that also has the part alkyl to be replaced by fluorine atom.

The preference of perfluoroalkane sulfonic acid has perfluor methylsulfonic acid, perfluor ethyl sulfonic acid, perfluor propanesulfonic acid, perfluor fourth sulfonic acid, perfluoro-methyl fourth sulfonic acid, the own sulfonic acid of perfluor, perfluor sulfonic acid in heptan, perfluorooctane sulfonate or the like, and preferred especially carbon number is 1～8 perfluoroalkane sulfonic acid.These perfluoroalkane sulfonic acid can use a kind ofly, also can use two or more simultaneously.

The preferred b sodium salt of this alkansulfonic acid alkali (great soil group) metal-salt, the preferred perfluor fourth of perfluoroalkane alkali (great soil group) metal-salt sulfonic acid potassium salt.

Employed aromatic sulphonic acid is the aromatic thioether sulfonic acid from monomer shape or polymkeric substance shape in aromatic sulphonic acid alkali (great soil group) metal-salt, aromatic carboxylic acid and ester sulfonic acid, monomer shape or polymkeric substance shape aromatic ether sulfonic acid, aromatic sulfonic acid ester sulfonic acid, monomer shape or polymkeric substance shape aromatic sulphonic acid, monomer shape or polymkeric substance shape aromatic series sulfone sulfonic acid, aromatic ketone sulfonic acid, many annular sulfonic acid, aromatic series sulfoxide sulfonic acid, at least a acid of selecting in the group that the condenses that aromatic sulphonic acid connects with methene key constitutes.These aromatic sulphonic acids can use a kind ofly, perhaps use two or more simultaneously.

The azochlorosulfonate acid alkali of the aromatic thioether of monomer shape or polymkeric substance shape (great soil group) metal-salt, open the spy report is arranged in the clear 50-98539 communique, for example diphenylsulfide-4,4 '-disulfonic acid disodium, diphenylsulfide-4,4 '-disulfonic acid dipotassium or the like.

The azochlorosulfonate acid alkali of aromatic carboxylic acid and ester (great soil group) metal-salt, opening in the clear 50-98540 communique the spy has report, for example: 5-sulfoisophthalic acid potassium, 5-sulfoisophthalic acid sodium, the poly-sodium of the poly-sulfonic acid of poly-ethylidene terephthalic acid or the like.

The azochlorosulfonate acid alkali of the aromatic ether of monomer shape or polymkeric substance shape (great soil group) metal-salt, opening in the clear 50-98542 communique the spy has report, for example: 1-methoxynaphthalene-4-calcium sulphonate, 4-dodecyl phenylate disulfonic acid disodium, poly-(2, the inferior phenoxy group of 6-dimethyl) the poly-sodium of poly-sulfonic acid, poly-(1, the inferior phenoxy group of 3-) the poly-sodium of poly-sulfonic acid, poly-(1, the inferior phenoxy group of 4-) poly-sodium of poly-sulfonic acid, poly-(2, the inferior phenoxy group of 6-phenylbenzene) poly-potassium of poly-sulfonic acid, poly-(the inferior phenoxy group of 2-fluoro-6-butyl) poly-sulfonic acid lithium or the like.

The azochlorosulfonate acid alkali of aromatic sulfonic acid ester (great soil group) metal-salt is opened in the clear 50-98544 communique the spy report, for example: the potassium sulfonate of benzene sulfonate etc.

Aromatic sulphonic acid alkali (great soil group) metal-salt of monomer shape or polymkeric substance shape is opened in the clear 50-98546 communique the spy report, for example: benzene sulfonic acid sodium salt, Phenylsulfonic acid strontium, Phenylsulfonic acid magnesium, p-Phenylsulfonic acid dipotassium, naphthalene-2,6-disulfonic acid dipotassium, xenyl-3,3 '-disulfonic acid calcium or the like.

Monomer shape or polymkeric substance shape aromatic series sulfone azochlorosulfonate acid alkali (great soil group) metal-salt are opened in the clear 52-54746 communique the spy report, for example: sulfobenzide-3-sodium sulfonate, sulfobenzide-3-potassium sulfonate, sulfobenzide-3,3 '-disulfonic acid dipotassium, sulfobenzide-3,4 '-the disulfonic acid dipotassium etc.

The azochlorosulfonate acid alkali of aromatic ketone (great soil group) metal-salt is opened in the clear 50-98547 communique the spy report, for example: α, α, α-trifluoroacetophenone-4-sodium sulfonate, benzophenone-3,3 '-the disulfonic acid dipotassium etc.

Many annular azochlorosulfonate acid alkalis (great soil group) metal-salt is opened in the clear 50-116542 communique the spy report, thiophene-2 for example, 5-disulfonic acid disodium, thiophene-2,5-disulfonic acid dipotassium, thiophene-2,5-disulfonic acid calcium, thionaphthene sodium sulfonate or the like.

The azochlorosulfonate acid alkali of aromatic series sulfoxide (great soil group) metal-salt is opened in the clear 52-54745 communique the spy report, for example: diphenyl sulfoxide-4-potassium sulfonate etc.

Aromatic sulphonic acid alkali (great soil group) metal-salt condensation body with the methene key condensation has the formaldehyde condensation products of sodium naphthalene sulfonate, the formaldehyde condensation products of anthracene sulfonic acid sodium etc.

The alkali of sulfuric ester (great soil group) metal-salt has sulfuric ester alkali (great soil group) metal-salt of monobasic and/or polyvalent alcohol, the sulfuric ester of this monobasic and/or polyalcohols, the sulfuric ester of methylsulfuric acid ester, ethylsulfuric acid ester, laurilsulfate, hexadecyl hydrosulfate ester, polyoxyethylene alkyl phenyl ether, single, two, three, four sulfuric esters of tetramethylolmethane are arranged, the sulfuric ester of the sulfuric ester of dodecylic acid direactive glyceride, the sulfuric ester of hexadecanoic acid direactive glyceride, glyceryl monostearate etc.Preferably use alkali (great soil group) metal-salt of laurilsulfate as alkali (great soil group) metal-salt of these sulfuric esters.

Other alkali (great soil group) metal-salt has alkali (great soil group) metal-salt of aromatic sulfonamide, for example: alkali (great soil group) metal-salt of benzoic sulfimide, N-(p-tolylsulfonyl)-p-tolylsulfonyl imines, N-(N '-benzyl aminocarbonyl) sulfanilyl-imines and N-(phenyl carboxyl) sulfanilyl-imines etc.

In the above-mentioned alkali of enumerating (great soil group) metal-salt, preferred composition is alkali (great soil group) metal-salt of aromatic sulphonic acid and alkali (great soil group) metal-salt of perfluoroalkane base sulfonic acid etc.

As previously mentioned, flame retardant resin composition of the present invention is the resinous principle (A composition) based on aromatic polycarbonate resin, cooperates specific silicone compounds (B composition) to obtain as fire retardant by specified proportion in this resinous principle.

Just can provide a kind of flame-retardant aromatic polycarbonate resin composition according to the present invention, it is by being used with aromatic polycarbonate resin as main resinous principle (A composition), silicone compounds (B composition) with cooperate flame retardant resistance modifying agent (C) composition to obtain as required, and it does not contain halogen flame such as bromide as the agent of anti-burning anti-drop property excellent fire retardant (following abbreviate as sometimes " Halogen ").In the resin combination of the present invention, the same with common cooperation, can also in poly carbonate resin composition, cooperate other resin, weighting agent or various additive.About other resin, weighting agent or additive, will be elaborated in the back.

The following describes the representative preferred embodiment of the present invention.This preferred embodiment is the halogen-free flame-retardance aromatic copolycarbonate resin composition, is to obtain resin combination transparent and the moulding product that humidity resistance is good.

Halogen-free flame-retardance poly carbonate resin composition in the past obtains by simple combination, also can't see have practical value aspect the transparency and the humidity resistance.

According to the present invention, transparent flame-retardant aromatic polycarbonate resin composition can be provided, it is that the silicone compounds (B composition) that contains 0.1～10 weight part in 100 weight part aromatic polycarbonate resins (A-1 composition) is formed.This silicone compounds is selected from the silicone compounds that contains Si-H base and aryl in the molecule, wherein 1. the content of Si-H base (Si-H amount) be 0.1～1.2mol/100g, 2. the content of the aryl shown in the following general formula (1) (aryl amount) be 10～70 weight %,

(in the formula (1), X represents independently that separately OH base, carbon number are 1～20 the organic residue of univalent.N represents 0～5 integer.In the general formula (1),, can choose mutually different X when n is 2 when above.)。

In the following description, this transparent flame-retarding aromatic copolycarbonate resin composition is abbreviated as " transparent resin composition ".In this manual, the two is referred to as " resin combination " or " flame retardant resin composition " transparent composition and opaque composition.

Aforementioned transparent resin composition of the present invention is to be resinous principle with aromatic polycarbonate resin (A-1 composition), in this resinous principle of 100 weight parts, cooperate silicone compounds 0.1～10 weight part, though its composition is simple, is a kind of halogen-free resin composition that has flame retardant resistance, the transparency and humidity resistance simultaneously.

The resinous principle of this transparent resin composition is made of aromatic polycarbonate fat resin (A-1 composition) basically, but only otherwise the influence transparency also can contain a spot of other resin (A-2 composition, A-3 composition or other resin).In transparent resin composition, as the silicone compounds of B composition, preferably use its structure, mean polymerisation degree, Si-H amount, aryl amount and the foregoing compound of specific refractory power, the same preferred preferred exemplary of using in the narration of front.The average polymerization scope is preferably 3～80, and preferable range is 3～60, and more preferably scope is 4～40, and special preferable range is 4～20.

The cooperation proportional range of aromatic polycarbonate resin (A-1 composition) and silicone compounds (B composition) can be identical with the proportional range of resinous principle of narrating previously (A composition) and silicone compounds (B composition).In aforementioned transparent resin composition, also can be used aforesaid flame retardant resistance modifying agent (C composition).Flame retardant resistance modifying agent (C composition) as previously mentioned, by a small amount of cooperation, just can be brought into play the effect of improvement flame retardant resistance, so there is not the problem that produces transparency reduction by cooperating the flame retardant resistance modifying agent under most of situation.

In transparent resin composition of the present invention,, can also cooperate other resin and weighting agent so long as do not damage the transparency.Most of other resin and weighting agent all can influence the transparency, so when selecting its kind and consumption, should fully take into account this point.

Use transparent resin composition of the present invention, can obtain the moulding product of the transparency and wet-hot aging performance excellence.As described later, the mist degree of the thick moulding product of 2mm is 0.3～20%, preferred 0.5～15%.Simultaneously as described later, in the environment of 65 ℃ of temperature and 85% humidity, kept the mist degree (H of the thick moulding product of 2mm 300 hours ₁) and initial mist degree (H ₀) difference Δ H (H ₁-H ₀) be 0.01～10%, preferred 0.02～7%, like this, transparent resin composition of the present invention just is suitable for producing the transparency and all good moulding product of humidity resistance.

Because transparent resin composition of the present invention still is the flame-retardant composition of Halogen, so also can effectively be applied to require among the various moulding product of the transparency and humidity resistance.

The transparency of transparent resin composition of the present invention is excellent, thus good by cooperating pigment and dyestuff can obtain the transparency, and bright moulding product.

A composition, B composition and C composition in the resin combination of the present invention more than have been described.Below further specify weighting agent, other resin and the various additive that can be engaged in the said composition.

In the resin combination of the present invention, can also further cooperate weighting agent as (D) composition.By cooperating this weighting agent (D) composition, can be modified to the physical strength of type product.As this weighting agent, can use to improving the weighting agent that synthetic resin intensity cooperates.The use level of D composition, concerning 100 parts by weight resin compositions (A composition), it is 1～100 weight part, preferred 3～80 weight parts, more preferably 5～60 weight parts.

Can enumerate talcum, mica, white clay, wollastonite, lime carbonate, glass fibre, glass microballon, hollow glass micropearl, flexible fiber, glass flake, carbon fiber, kish carbon sheet, carbon microballon, flexible carbon fiber, metal scale, steel fiber as the D composition, materials such as metallic cover glass fibre, metallic cover carbon fiber, metallic cover glass flake, silicon-dioxide, ceramic particle, ceramic fiber, aromatic polyamide particle, aromatic polyamide fibre, polyarylester fiber, graphite, electrical conductivity Carbon black and various whiskers.

In the resin combination of the present invention, for the Physical Mechanical, chemical property and the electrical property that improve the moulding product, can cooperate the thermoplastic resin beyond the A composition.The use level of this thermoplastic resin, it is different and different with purpose to look its kind, and in per 100 parts by weight resin compositions (A composition), the use level of other thermoplastic resin is 1～30 weight part, preferred 2～20 weight parts usually.

It is the thermoplastic resin that the general-purpose plastics of representative, the engineering plastics, polyether-ether-ketone, polyetherimide, polysulfones, polyethersulfone, polyphenylene sulfide that are representative with poly (phenylene ether) resin, polyformaldehyde resin, polyamide resin, cyclic polyolefin resin, polyarylate resin (amorphism polyarylester, liquid crystal liquid crystal property polyarylester) etc. etc. are known as super engineering plastics that other thermoplastic resin can be enumerated with polyvinyl resin, acrylic resin, polyalkyl methacrylate resin etc.In addition, can also use thermoplastic elastomers such as the thermoplastic elastomer of ethylene series, polyamide-based thermoplastic elastomer, polyurethane series thermoplastic elastomer.

In the resin combination of the present invention, in order to give the various functions of goods and to improve characteristic, can also cooperate itself original additive on a small quantity, so long as do not influence purpose of the present invention, these additives can cooperate by general quantity.

These additives comprise B composition fire retardant (phosphoric acid ester in addition, red phosphorus, metal hydroxides etc.), anti-drip agent (have and to form fibriilar fluoropolymer etc.), thermo-stabilizer, UV light absorber, photostabilizer, releasing agent, lubricant, antiseize paste (PTFE particle etc.), tinting material (carbon black, pigment such as titanium oxide, dyestuff), light diffusing agent (acrylate cross linked particle, the silicon crosslinked particle, glass flake as thin as a wafer, calcium carbonate particles etc.), fluorescent bleaches, phosphorescent pigment, fluorescent dye, static inhibitor, fluidity amendment, the nucleus agent, inorganic or organic antibacterial agent, photocatalyst stain control agent (titanium oxide microparticle, zinc oxide fine particles etc.), with the graft rubber be the shock-resistance modifying agent of representative, infrared absorbent and photochromic agent.

In the resin combination of the present invention, aromatic polycarbonate resin accounts for 50～100 weight % as resinous principle.Therefore thermostability, antioxygen, light stability (UV stable) and the release property in order to improve resin combination uses the additive that helps improving these performances in aromatic polycarbonate resin.Below specify the situation of these additives.

Can cooperate phosphorus-containing stabilizers as thermo-stabilizer in the resin combination of the present invention, can use the how a kind of of phosphoric acid ester (ホス Off アイト) compound, phosphorous acid ester (ホスホ Na イト) compound and phosphonic acid ester (ホス Off エト) compound as this phosphorus-containing stabilizers.

Can use various phosphate compounds as thermo-stabilizer, concrete example has the phosphate compound shown in the general formula (8).

[in the formula, R ⁸Expression hydrogen atom or carbon number are that 1～20 alkyl, carbon number are that 6～20 aryl or alkaryl, carbon number are 7～30 aralkyl or their halogen, alkylthio (carbon number of alkyl is 1～30) or hydroxyl substituent, can select 3 R ⁸Be identical or different, can also select by dihydric phenols deutero-ring texture.]

Also has the phosphate compound shown in the general formula (9).

[in the formula, R ⁹, R ¹⁰Represent that respectively hydrogen atom, carbon number are that 1～20 alkyl, carbon number are that 6～20 aryl or alkaryl, carbon number are that 7～30 aralkyl, carbon number are that 4～20 cycloalkyl, carbon number are 15～25 2-(4-hydroxy phenyl) propyl group substituted aryl.Cycloalkyl and aryl can be selected to be replaced by alkyl, perhaps the group that do not replaced by alkyl.]

Can also enumerate the phosphate compound shown in the general formula (10).

[in the formula, R ¹¹, R ¹²Be that carbon number is 12～25 alkyl.R ¹¹And R ¹²Can be identical, also can be different]

The phosphonate compound that uses as thermo-stabilizer has the phosphonate compound shown in phosphonate compound shown in the following general formula (11) and the following general formula (12).

[in the formula, Ar ¹, Ar ²The expression carbon number is that 6～20 aryl or alkaryl or carbon number are 15～25 2-(4-hydroxyphenyl) propyl group substituted aryl, can select four Ar ¹Be identical, or different.Also can select two Ar ²Be identical, or different.]

Preference corresponding to the phosphate compound of above-mentioned general formula (8) has phenylbenzene isooctyl phosphoric acid ester, 2,2 '-methylene-bis (4, the 6-di-tert-butyl-phenyl) octyl group phosphorous acid ester, phenylbenzene list (tridecyl) phosphoric acid ester, phenyl two isodecyl alkyl phosphates, phenyl two (tridecyl) phosphoric acid ester etc.

Preferred example corresponding to the phosphate compound of above-mentioned general formula (9) has distearyl pentaerythritol diphosphate, two (2, the 4-di-tert-butyl-phenyl) pentaerythritol diphosphate, two (2,6-di-t-butyl-4-aminomethyl phenyl) pentaerythritol diphosphate, phenyl dihydroxyphenyl propane pentaerythritol diphosphate, dicyclohexyl pentaerythritol diphosphate etc., preference is a distearyl pentaerythritol diphosphate, two (2, the 4-di-tert-butyl-phenyl) pentaerythritol diphosphate, two (2,6-di-t-butyl-4-aminomethyl phenyl) pentaerythritol diphosphate or the like.These phosphate compounds can use a kind ofly, perhaps use two or more.

Corresponding to the preference of the phosphate compound of above-mentioned general formula (10) have 4,4 '-isopropylidene biphenol four (tridecyl) phosphoric acid ester etc.

Concrete preference corresponding to the phosphonate compound of above-mentioned general formula (11) has four (2, the 4-diisopropyl phenyl)-4,4 '-the biphenylene bisphosphonates, four (2,4-di-n-butyl phenyl)-4,4 '-the biphenylene bisphosphonates, four (2, the 4-di-tert-butyl-phenyl)-4,4 '-the biphenylene bisphosphonates, four (2, the 4-di-tert-butyl-phenyl)-4,3 '-the biphenylene bisphosphonates, four (2, the 4-di-tert-butyl-phenyl)-3,3 '-the biphenylene bisphosphonates, four (2, the 6-diisopropyl phenyl)-4,4 '-the biphenylene bisphosphonates, four (2,6-di-n-butyl phenyl)-4,4 '-the biphenylene bisphosphonates, four (2, the 6-di-tert-butyl-phenyl)-4,4 '-the biphenylene bisphosphonates, four (2, the 6-di-tert-butyl-phenyl)-4,3 '-the biphenylene bisphosphonates, four (2, the 6-di-tert-butyl-phenyl)-3,3 '-the biphenylene bisphosphonates or the like.Wherein preferred four (di-tert-butyl-phenyl)-biphenylene bisphosphonates, more preferably four (2, the 4-di-tert-butyl-phenyl)-biphenylene bisphosphonates.This four (2, the 4-di-tert-butyl-phenyl)-biphenylene bisphosphonates, preferred two or more mixture, concrete example has four (2, the 4-di-tert-butyl-phenyl)-4,4 '-biphenylene bisphosphonates (E2-1 composition), four (2, the 4-di-tert-butyl-phenyl)-4,3 '-biphenylene bisphosphonates (E2-2 composition) and four (2, the 4-di-tert-butyl-phenyl)-3,3 '-biphenylene bisphosphonates (E2-3 composition), these phosphonic acid esters, can use a kind ofly, or use two or more simultaneously.The preferred mixture that uses these three kinds of phosphonic acid esters.Ratio of mixture when using three kinds of phosphonic acid ester mixtures, the preferable range of E2-1 composition, E2-2 composition and E2-3 composition is 100: 37～64: 4～14 by weight, more preferably scope is 100: 40～60: 5～11.

Concrete preference corresponding to the phosphonate compound of above-mentioned general formula (12) is two (2, the 4-diisopropyl phenyl)-4-phenyl-Phenylphosphine acid esters, two (2,4-di-n-butyl phenyl)-3-phenyl-Phenylphosphine acid esters, two (2, the 4-di-tert-butyl-phenyl)-4-phenyl-Phenylphosphine acid esters, two (2, the 4-di-tert-butyl-phenyl)-3-phenyl-Phenylphosphine acid esters, two (2, the 6-diisopropyl phenyl)-4-phenyl-Phenylphosphine acid esters, two (2,6-di-n-butyl phenyl)-3-phenyl-Phenylphosphine acid esters, two (2, the 6-di-tert-butyl-phenyl)-4-phenyl-Phenylphosphine acid esters, two (2, the 6-di-tert-butyl-phenyl)-3-phenyl-Phenylphosphine acid esters or the like, preferred two (2 tert-butyl-phenyl)-phenyl-Phenylphosphine acid esters, more preferably two (2, the 4-di-tert-butyl-phenyl)-phenyl-Phenylphosphine acid esters.This pair (2, the 4-di-tert-butyl-phenyl)-phenyl-Phenylphosphine acid esters, preferred two or more mixture, concrete example have (2, the 4-di-tert-butyl-phenyl)-4-phenyl-Phenylphosphine acid esters and two (2, the 4-di-tert-butyl-phenyl) 3-phenyl-Phenylphosphine acid esters.These phosphonates can use a kind of or use two kinds simultaneously.The preferred mixture that uses these two kinds of phosphonic acid esters.When using the mixture of these two kinds of phosphonic acid esters, by weight, the preferable range of its ratio of mixture is 5: 1～4, more preferably 5: 2～3.

The phosphate compound that uses as thermo-stabilizer has Tributyl phosphate ester, trimethyl phosphate, Tritolyl Phosphate, triphenylphosphate, trichlorophenyl phosphoric acid ester, triethyl phosphate, diphenylmethyl phenyl phosphate ester, the positive xenyl phosphoric acid ester of phenylbenzene list, three butoxyethyl group phosphoric acid ester, dibutylphosphoric acid ester, dioctyl phosphoric acid ester, di-isopropyl phosphoric acid ester etc., preferred trimethyl phosphate.

The more preferably compound of above-mentioned phosphorous thermo-stabilizer also has the compound shown in following general formula (13) and (14).

(in the formula (13), R ¹³And R ¹⁴Be separately independently, the expression carbon number is 1～12 alkyl, cycloalkyl, aryl or aralkyl.)

(in the formula (14), R ¹⁵, R ¹⁶, R ¹⁷, R ¹⁸, R ²¹, R ²²And R ²³Be separately independently, expression hydrogen atom, carbonatoms are 1～12 alkyl, cycloalkyl, aryl or aralkyl, R ¹⁹Expression hydrogen atom or carbonatoms are 1～4 alkyl, R ²⁰Expression hydrogen atom or methyl.)

In the general formula (13), preferred R ¹³And R ¹⁴Be that carbonatoms is 1～12 alkyl, more preferably carbonatoms is 1～8 alkyl.The object lesson of general formula (13) compound can be enumerated three (3,5-dimethylphenyl) phosphorous acid ester, three (diethyl phenyl) phosphorous acid ester, three (diisopropyl phenyl) phosphorous acid esters, three (di-n-butyl phenyl) phosphorous acid ester, three (2, the 4-di-tert-butyl-phenyl) phosphorous acid ester, three (2, the 6-di-tert-butyl-phenyl) phosphorous acid ester etc.Preferred especially three (2, the 4-di-tert-butyl-phenyl) phosphorous acid ester.

Compound shown in the general formula (14) can prepare with own perception method.For example: make the reaction of bisphenol cpd shown in the following general formula (15) and phosphorus trichloride, obtain corresponding chlorophosphate, and then the phenol shown in itself and the following general formula (16) is reacted.

(in the formula (15), R ¹⁵, R ¹⁶, R ¹⁷And R ¹⁸Represent that respectively hydrogen atom, carbonatoms are 1～12 alkyl, chloro alkyl, aryl or aralkyl, R ¹⁹Expression hydrogen atom or carbonatoms are 1～4 alkyl, R ²⁰Expression hydrogen atom or methyl.)

(in the formula (16), R ²¹, R ²²And R ²³Represent that respectively hydrogen atom, carbonatoms are 1～12 alkyl, cycloalkyl, aryl or aralkyl.)

The concrete example of compound can enumerate 2 shown in the above-mentioned general formula (15), 2 '-the methylene radical bis-phenol, 2,2 '-methylene-bis (4-sylvan), 2,2 '-methylene-bis (6-sylvan), 2,2 '-methylene-bis (4, the 6-dimethyl phenol), 2,2 '-the ethylidene bis-phenol, 2,2 '-ethylenebis (4-sylvan), 2,2 '-the isopropylidene bis-phenol, 2,2 '-methylene-bis (4-methyl-6 tert-butyl phenol), 2,2 '-methylene-bis (4-ethyl-6 tert-butyl phenol), 2,2 '-methylene-bis (4, the 6-di-tert-butylphenol), 2,2 '-methylene-bis (4-methyl-6-cyclohexyl phenol), 2,2 '-dihydroxyl-3,3 '-two (Alpha-Methyl cyclohexyl)-5,5 '-the dimethyl benzene methylmethane, 2,2 '-methylene-bis (6-Alpha-Methyl-benzyl-p-cresols), 2,2 '-ethylidene-two (4, the 6-di-tert-butylphenol) and 2,2 '-butylidene-two (4-methyl-6 tert-butyl phenols) etc., and can preferably use.

Compound shown in the general formula (15) more preferably uses 2,2 '-methylene-bis (4-methyl-6 tert-butyl phenol), 2,2 '-methylene-bis (4-ethyl-6 tert-butyl phenol), 2,2 '-methylene-bis (4, the 6-di-tert-butylphenol), 2,2 '-ethylidene-two (4, the 6-di-tert-butylphenol) and 2,2 '-butylidene-two (4-methyl-6 tert-butyl phenols).

The concrete example of compound can be enumerated phenol, 2-methylphenol, 3-methylphenol, 4-methylphenol, 2 shown in the general formula (16), 4-xylenol, 2,6-xylenol, 2 tertiary butyls-4-methylphenol, 2, the 4-DI-tert-butylphenol compounds, 2,6-DI-tert-butylphenol compounds, 2,6-di-tert-butyl-4-methy phenol, 2,4-dimethyl-6 tert.-butyl phenol, 2,6-di-t-butyl-4-ethylphenol, 2,4,6-tri-butyl-phenol and 2,6-di-t-butyl-4-sec-butyl phenol or the like, and can preferably use.The concrete example of compound more preferably has the compound of two above alkyl substituents shown in the general formula (16).

It is oxidation inhibitor that the antioxygen base that can cooperate in resin combination of the present invention can be enumerated phenol.By using phenol is oxidation inhibitor, can the variable color of control exposure under heat condition, for improving flame retardant resistance certain effect is arranged also simultaneously.Can use various phenol is oxidation inhibitor as this phenol.

This phenol is that the concrete example of oxidation inhibitor can be enumerated vitamin E; Octadecane base-β-(4 '-hydroxyl-3 '; 5 '-di-tert-butyl-phenyl (Off エ Le)) 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; N-two-methylamino methyl) phenol; 3; 5-di-tert-butyl-4-hydroxyl benzyl phosphonic acids 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-benzyls-p-cresols) 2; 2 '-ethylidene-two (4; the 6-DI-tert-butylphenol compounds); 2; 2 '-butylidene-two (4-methyl-6 tert.-butyl phenols); 4; 4 '-butylidene two (3-methyl-6 tert.-butyl phenol); triethylene glycol-N-pair-3-(3 tertiary butyl-4-hydroxies-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 [2 tertiary butyls-4-methyl-6-(3 tertiary butyls-5-methyl-2-hydroxybenzyl) phenyl] terephthalate; 3; 9-pair 2-[3-(3 tertiary butyl-4-hydroxies-s-aminomethyl phenyl) propionyloxy]-1; the 1-dimethyl ethyl }-2; 4; 8; 10-four oxaspiros [5; 5] undecane; 4; 4 '-thiobis (6 tertiary butyls-m-cresols); 4; 4 '-thiobis (3-methyl-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; two (the hot sulfenyl of the n-)-6-of 4-(4-hydroxyl-3 '; 5 '-the di-tert-butyl amido)-1; 3; the 5-triazine; N; N '-hexa-methylene 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) isocyanic ester; three (3; the 5-di-tert-butyl-4-hydroxyl benzyl) isocyanic ester; 1; 3; 5-three (4 tertiary butyls-3-hydroxyl-2; the 6-dimethyl benzyl) isocyanic ester; 1; 3; 5-32 [3 (3; the 5-di-tert-butyl-hydroxy phenyl) propionyloxy] ethyl isocyanate; four [methylene radical-3-(3 '; 5 '-di-tert-butyl-hydroxy phenyl) propionic ester] methane or the like, all can preferably use.

More preferably use n-octadecyl-β-(4 '-hydroxyl-3 ', 5 '-di-tert-butyl-phenyl (Off エ Le)) propionic ester, the 2-tertiary butyl-6-(3 '-tertiary butyl-5 '-methyl-2 '-hydroxybenzyl)-4-aminomethyl phenyl acrylate, 3,9-pair 2-[3-(3 tertiary butyl-4-hydroxies-5-aminomethyl phenyl) propionyloxy]-1, the 1-dimethyl ethyl }-2,4,8,10-four oxaspiros [5,5] undecane and four [methylene radical-3-(3 ', 5 '-di-tert-butyl-hydroxy phenyl) propionic ester] methane, further preferred n-octadecyl-β-(4 '-hydroxyl-3 ', 5 '-di-tert-butyl-phenyl (Off エ Le)) propionic ester.

Oxidation inhibitor can also use the oxidation inhibitor of sulfur-bearing.Particularly when resin combination is used for rotoforming and compressed moulding, be more suitable for using sulfur-bearing oxidation inhibitor.The object lesson of this sulfur-bearing oxidation inhibitor has two dodecyls-3,3 '-thiodipropionate, double tridecyl-3,3 '-thiodipropionate, two tetradecyls-3,3 '-thiodipropionate, two octadecyls-3,3 '-thiodipropionate, dodecyl octadecyl-3,3 '-thiodipropionate, tetramethylolmethane four (β-dodecyl thiopropionate) ester, two [2-methyl-4-(3-dodecyl sulfo-propionyloxy)-5 tert-butyl-phenyls] thioether, the octadecyl disulfide, mercaptobenzimidazole, 2-sulfydryl-6-tolimidazole, 1,1 '-thiobis (beta naphthal) or the like.More preferably tetramethylolmethane four (β-dodecyl thiopropionate) ester etc.

Above-mentioned phosphorous thermo-stabilizer, the phenol of enumerating is that oxidation inhibitor and sulfur-bearing oxidation inhibitor can use separately separately, or mixes and use two or more additives.More preferably use phosphorous thermo-stabilizer, especially preferably contain the phosphorous thermo-stabilizer of compound shown in the above-mentioned general formula (13).

The cooperation ratio of these stablizers in composition, in per 100 parts by weight resin compositions (A composition), phosphorus-containing stabilizers, phenol are that the cooperation ratio of oxidation inhibitor or sulfur-bearing oxidation inhibitor is advisable with 0.0001～1 weight part respectively.In more preferably per 100 parts by weight resin compositions, its cooperation ratio is 0.0005～0.5 weight part, further preferred 0.001～0.2 weight part.

In the resin combination of the present invention, can also cooperate remover as required.Because among the present invention, the B composition has flame retardant resistance,, also still can obtain flame retardant properties preferably so flame retardant resistance is produced dysgenic releasing agent even cooperation is general easy.The releasing agent that this releasing agent can use oneself to know.For example: polyunsaturated fatty acid ester, unsaturated fatty acid ester, polyolefin wax (polyethylene wax or 1-chain olefin polymer.Also can use with sour modification etc. and contain compound modified polyethylene wax of functional group or 1-chain olefin polymer), the silicone compounds (siloxanes beyond the B composition of the present invention.For example: straight chain shape or X 2-1401 oil and polyphenylmethyl base silicone oil or the like.Also can use usefulness such as sour modification to contain the compound modified siloxanes of functional group), fluorochemical (with poly-fluoroalkyl ether as the fluorocarbon oil of representative etc.), paraffin, beeswax (yellow wax) etc.Wherein, can enumerate polyunsaturated fatty acid ester class, straight chain shape or ring-type polymethyl siloxane oil and polyphenylmethyl base silicone oil, and fluorocarbon oil etc.Concerning 100 parts by weight resin compositions (A composition), the consumption of this releasing agent is preferably 0.01～0.3 weight part.

The ideal releasing agent is polyunsaturated fatty acid ester, for example can uses red moss four alkoxides such as senior fatty acid esters such as low-grade fatty acid ester classes such as fatty acid polyglycerol ester class, stearyl stearyl ester, V-1326 sebate, tetramethylolmethane four stearyl esters such as direactive glyceride class, ten stearic acid, ten glyceryl ester and four stearic acid, ten glyceryl ester of glyceryl monostearate etc.

Constituent of the present invention is used for the housing of business automation equipment more, so preferably contain UV light absorber.As UV light absorber; can enumerate with 2; the 4-dihydric benzophenone; 2-hydroxyl-4-methoxyl group benzophenone; 2-hydroxyl-4 n-octyloxy benzophenone; 2-hydroxyl-4 n-dodecane oxygen base benzophenone; 2-hydroxyl-4-benzyloxy benzophenone; 2; 2 '-dihydroxyl-4-methoxyl group benzophenone; 2-hydroxyl-4-methoxyl group-2 '-the carboxyl benzophenone; 2-hydroxyl-4-methoxyl group-5-sulfoxide group benzophenone; 2; 2 '-dihydroxyl-4; 4 '-the dimethoxy benzophenone; 2; 2 '; 4; 4 '-the tetrahydroxy benzophenone; 2; 2 '-dihydroxyl-4,4 '-dimethoxy-5--sulfinic acid sodium benzophenone; two (5-benzoyl-4-hydroxyl-2-p-methoxy-phenyl) methane etc. are UV light absorber for the benzophenone of representative.

As UV light absorber also have with 2-(2 '-hydroxyl-5 '-aminomethyl phenyl) benzotriazole, 2-(2 '-hydroxyl-5 ' tert-butyl-phenyl) benzotriazole, 2-(2 '-hydroxyl-5 ' uncle octyl phenyl) benzotriazole, 2-(2 '-hydroxyl-3 ', 5 '-di-tert-butyl-phenyl) benzotriazole, 2-(2 '-hydroxyl-3 ', 5 '-di-tert-pentyl-phenyl) benzotriazole, 2-(2 '-hydroxyl-3 '-dodecyl-5 '-aminomethyl phenyl) benzotriazole, 2-(2 '-hydroxyl-3 ', 5 '-two (α, α '-dimethyl benzyl) phenyl benzotriazole, 2-[2 '-hydroxyl-3 '-(3 "; 4 " 5 "; 6 "-four phthalimide methyl)-5 '-aminomethyl phenyl] benzotriazole, 2-(2 '-hydroxyl-3 ' tertiary butyl-5 '-aminomethyl phenyl]-the 5-chlorobenzotriazole, 2-(2 '-hydroxyl-3 ', 5 '-di-tert-butyl-phenyl)-the 5-chlorobenzotriazole, 2,2 '-[4-(1 for methylene-bis, 1,3, the 3-tetramethyl butyl)-6-(2H-benzotriazole-2-yl) phenol, (condenses of the 3-tertiary butyl-5-(2H-benzotriazole-2-yl)-4-hydroxy phenyl propionic ester and polyoxyethylene glycol is that the benzotriazole of representative is a UV light absorber to methyl-3-.

(4,6-is two-(2,4-3,5-dimethylphenyl-1,3,5-triazines-2-yl)-hydroxyphenyltriazinuv based compounds such as 5-hexyloxy-phenol to also have 2-(4,6-phenylbenzene-1,3,5-triazines-2-yl)-5-hexyloxy-phenol, 2-as UV light absorber.

In the resin combination of the present invention, can also cooperate photostabilizer.The concrete example of this photostabilizer has with two (2,2,6,6-tetramethyl--4-piperidyl) sebate, two (1,2,2,6,6-penta methyl-4-piperidyl) sebate, two (1,2,2,6,6-penta methyl-4-piperidyl)-2-(3, the 5-di-tert-butyl-4-hydroxyl benzyl)-2n-butyl malonic acid ester, 1,2,3,4-butane carboxylic acid and 2,2,6, the condenses of 6-tetramethyl--pure and mild tridecyl alcohol of 4-piperidines, 1,2,3,4-butane carboxylic acid and 1,2,2,6, the condenses of 6-penta methyl-pure and mild tridecyl alcohol of 4-piperidines, four (2,2,6,6-tetramethyl--4-piperidyl)-1,2,3,4-butane tetracarboxylic acid esters, four (1,2,2,6,6-penta methyl-4-piperidyl)-1,2,3,4-butane tetracarboxylic acid esters, it is poly-that { [6-(1,1,3, the 3-tetramethyl butyl) amino-1,3,5-triazine-2,4-two bases] [(2,2,6, the 6-tetramethyl-piperidyl) imino-] hexa-methylene [(2,2,6, the 6-tetramethyl-piperidyl) imino-], poly-{ [6-morpholino-s-triazine-2,4-two bases] [(2,2,6, the 6-tetramethyl-piperidyl) imido] hexa-methylene [(2,2,6, the 6-tetramethyl-piperidyl) imino-] }, 1,2,3,4-BTCA and 2,2,6,6-tetramethyl--pure and mild the β of 4-piperidines, β, β ', β '-tetramethyl--3,9-(2,4,8,10-four oxaspiros [5,5] undecane) condenses of di-alcohol, N, N '-two (3-aminopropyl) ethylene diamine and 2, the two [N-butyl-N-(1,2 of 4-, 2,6,6-penta methyl-4-piperidyl) amino]-chloro-1,3, the condenses of 5-triazine, 1,2,3,4-BTCA and 1,2,2,6, the 6-penta methyl-pure and mild β of 4-piperidines, β, β ', β '-tetramethyl--3,9-(2,4,8,1 0-oxaspiro [5,5] condenses of di-alcohol undecane), it is poly-that methyl-propyl-the 3-hydroxyl-[4-(2,2,6,6-tetramethyl-piperidyl] siloxanes is the hindered amine of representative.

The ratio of aforementioned UV light absorber and photostabilizer, in per 100 parts of resinous principles (A composition), usage ratio separately is respectively 0.01～5 weight part, more preferably 0.02～1 weight part.

In the resin combination of the present invention,, can add (Block Le-イ Application グ) agent of turning blue for the yellowing that prevents to cause by UV light absorber.So long as the general blueing agent that uses in polycarbonate resin does not then have special detrimentally affect.General preferred use anthraquinone based dye, it is easy to obtain.Concrete blueing agent can be enumerated general solubility violet (SolvenViolet) 13[CA.No (color index No) 60725 by name: trade name, Beyer Co., Ltd makes, " sieve's Marko Simon Rex Bai Aolaite (マ Network ロレ Star Network スバイオレ Star ト) B ", Mitsubishi Chemical's (strain) make, " the blue G of Da Yialaijin (ダイアレジ Application) ", Sumitomo Chemical (strain) are made, " this meter Prast Bai Aolaite (スミプラストバイオレ Star ト) B "]; General solubility violet (Solvent Villet) 31[CA.No.68210 by name: trade name, Mitsubishi Chemical's (strain) makes, " Da Yialaijinbai Aurion spy (ダイアレジ Application バイオレ Star ト) D "]; General solubility violet (Solvent Violet) 33[CA.No.60725 by name: trade name, Mitsubishi Chemical's (strain) makes " Da Yialaijin (ダイアレジ Application) indigo plant-J "]; General soluble blue (Solvent Blue) 94[CA.No.6150 by name: trade name, Mitsubishi Chemical's (strain) makes " Da Yialaijin (ダイアレジ Application) indigo plant-N "]; General solubility violet (Solvent Violet) 36[CA.No.68210 by name: trade name, Beyer Co., Ltd makes " sieve's mark Simon Rex Bai Aolaite (マ Network ロレ Star Network スバイオレ Star ト) 3R "]; General soluble blue (Solvent Blue) 97[trade(brand)name by name, Beyer Co., Ltd makes " sieve's mark Simon Rex (マ Network ロレ Star Network ス) indigo plant-RR "] and general soluble blue (Solvent Blue) 45 [CA.No.61110: trade name by name, サ Application De company make " you (テラゾ one Le) indigo plant-RLS "] of Anthony Terlazzo or the like, your (テラゾ one Le) indigo plant-RLS of preferred especially sieve's mark Simon Rex (マ Network ロレ Star Network ス) blue RR, sieve's mark Simon Rex Bai Aolaite (マ Network ロレ Star Network スバイオレ Star ト) B and Anthony Terlazzo] etc. blueing agent.

The anti-drip performance of resin combination of the present invention is good, in order further to improve this performance, can also use common anti-drip agent simultaneously.But preferred plan of the present invention is transparent resin composition.In order not damage the transparency, the use level of common anti-drip agent suits below 0.1 weight part concerning 100 weight part A compositions, preferably is lower than 0.08 weight part, more preferably less than 0.05 weight part.Should can enumerate fluoropolymer by anti-drip agent, special preferably polytetrafluoroethylene (hereinafter referred to as PTFE) with formation protofibril energy.

Have the PTFE that forms the protofibril energy and have high molecular weight, have the fibrous tendency of formation of interosculating under the external force effects such as shearing force between the PTFE.Its molecular weight calculates by the number-average molecular weight of obtaining according to standard specific gravity, 1,000,000～1,000 ten thousand, and preferred 2,000,000～9,000,000.This kind PTFE resin can also use the resin of aqueous liquid dispersion except can using solid resin.Have the dispersing property of PTFE in resin that forms the protofibril energy in order to improve this kind, further obtain the excellent flame and the transparency, also can use PTFE mixture with other mixed with resin.The mixing shape PTFE that sells on the market has " BLENDEX B449 " (trade(brand)name) that mitsubishi rayon's's (strain) " Mai Tebulian (メ Block レ Application) A3000 " (trade(brand)name) and the special chemical preparations of GE company make or the like.

Prepare resin combination of the present invention, can adopt any means.Can be with V-Mixer, Han Xieer mixing machine, chemomotive force equipment, extrude pre-blend approach such as mixing machine to A composition, B composition with arbitrarily behind other composition thorough mixing; carry out granulation by extruding granulator and tablets press etc. as required, and then be that the melting mixing machine of representative carries out melting mixing and with process for granulating such as tablets presss in order to the exhaust twin screw extruder.

Other method handlebar A composition, B composition and other composition supply to individually respectively with the exhaust twin screw extruder be in the melting mixing machine of representative method, after A composition and other composition pre-mixing of part, respectively pre-mixing composition and remaining other composition are supplied to method, water or organic solvent in the melting mixing machine again and supply with the melting mixing machine or will offer method of melting mixing machine or the like behind this diluted mixture thing and other composition premix after B composition diluted mixture.In addition, when in the gradation composition liquid component being arranged, need to use fluid infusion apparatus or the liquid appending apparatus of in the melting mixing machine, carrying liquid.

Resin combination of the present invention is normally by using particle to produce various goods through the method that injection molding obtains the moulding product.In injection molding, not only can adopt the forming method of common cold runner formula, can also adopt the hot runner mode of not expecting handle.In injection molding, not only can use common forming method, can also the injection molding of using gas assist type, injection compression molding, ultra-high speed injection molding, injection-molding moulding, dual-color forming, interlayer moulding, the moulding of mould internal coated layer, insert molding moulding, foaming (comprise and utilize supercutical fluid), the moulding of rapid heating cooling die, heat insulation mould molding and Mo Nei melt molding and be used in combination these forming methods etc. again.

Resin combination of the present invention can also be made various special-shaped extrusion molding articles by extrusion moulding, uses with forms such as sheet material, films.In the moulding of sheet material, film, can adopt method moulding such as inflation and curtain coating.Can also make the thermal contraction flexible pipe by carrying out specific extension operation.Can also adopt and need not the moulding product are produced in the rotoforming of resin melting mixing.

Can also carry out various surface treatments to the moulding product that formed by resin combination, surface treatment includes decorative coating, hard coat, waterproof and oilproof coating, hydrophilic coating, ultraviolet radiation absorption coating, infrared ray absorption coating, absorption of electromagnetic wave coating, heating coating, antistatic coating, insulating coating, conductive coating and metalized coated (() plating, chemical vapor deposition (CVD), physical vapor deposition (PVD), flame plating) or the like.Be specially adapted to attached lid transparency conducting layer on clear sheet.

The effect of invention

Flame-retardant aromatic polycarbonate resin composition of the present invention contains silicone compounds (B composition) as fire retardant, have excellent anti-drip performance, and the dyeability when painted and during by laser lettering method printing word and sign the sharpness of literal and sign all fine.These characteristics be in the past the fire resistant aromatic makrolan resin can't be obtained, and this resin combination has high thermal stability when high temperature fusions such as injection molding simultaneously.Therefore in each industrial circle such as business automation equipment, electronic and electrical equipment, be very useful.

Particularly, can obtain transparent excellent flame aromatic copolycarbonate resin composition according to preferred version of the present invention.This flame retardant resin composition is owing to contain specific silicone compounds (B composition) as fire retardant, so it has anti-anti-drop property, the transparency and humidity resistance simultaneously.The resin combination that has these several specific characters simultaneously just is not a common poly carbonate resin composition in the past.The resin combination that this kind transparency is good can be used as clear sheet and uses after moulding; not only can be used as the protective guard of illuminating lamp shade, transparent display usefulness; also can be used as light guide member, among solar cell cover body and base material, lens, set of lenses, junctor, touch switchboard, resin window, recreational machine parts (front panel of pinball machine, circuit cover etc.), prism, reflective mirror etc. are used.Just all has great using value at each industrial circles such as business automation equipment, electronic and electrical equipment, vehicle, agricultural, fishery and civil construction fields.

Embodiment

Below further specify the present invention with embodiment, but the present invention should not be confined to carry out assessment of performance by following project among this scope of embodiments.

(1) material behavior

(1-I) anti-anti-drop property

Use the thickness made according to the UL standard test film, test by UL standard 94 as 1.6mm.Measure once catch fire and twice ignition happens in combustion process after produce drip time, evaluate with the shortest time (second).

(1-II) dyeability

Being of a size of 150mm * 150mm, thickness is that the square sheet metal forming product of 2.0mm are divided into 9 parts, measure the L value of nine positions respectively with the color discriminator TCM-1800 of Tokyo electricity look industry (strain), among the L value of nine positions mensuration, deduct minimum value with maximum value and obtain difference (Δ L), by this difference and the moulding product outward appearance that detects by an unaided eye, evaluate by following standard.

Zero: good.Do not have peel off, glossy, tone good, outward appearance is even.

*: bad.Peel off, matt, tone is bad, outward appearance is inhomogeneous.

(1-III) laser lettering

The laser printer SL475E that uses NEC (strain) to make, the 2.00mm thick test film lettering of byte speed with the 100mm/ sweep velocity of second, 30 μ m to making according to the UL standard, with minimum current value that can lettering and the trace sharpness that detects by an unaided eye, evaluate by following standard.

Zero: good.Can assert that literal is clear.

*: bad.Be coated with in the literal and phenomenon such as rub.

(1-IV) transparency

According to JIS K7105 size up is that 150mm * 150mm, thickness are the transparency of the square moulding product of 2.0mm, the haze value that usefulness records and the moulding product tone that detects by an unaided eye, and evaluates its transparency.

(1-V) humidity resistance

The square moulding product of in 1-IV, measuring usefulness in temperature: 65 ℃, humidity: 85% environment was placed down after 500 hours, according to the method mensuration haze value of JIS K7105.Evaluate humidity resistance with the moulding product tone after poor (the Δ H) of gained haze value and initial haze value and the wet heat treatment that observes with the naked eye.(gonorrhoea " the degree of the light transmission that being meant detects by an unaided eye confirms." opaque " is to can't see the light transmission phenomenon with detecting by an unaided eye.Do not measure its mist degree).

[embodiment 1～25 and comparative example 1～18]

By following main points, make the resin combination of listing in table 1～9.Describe by number order in the following table.

In the ratio that list table 1～9 each composition being measured, is antioxygen base (IRGAFOS168 that Japanese チバガイギ-company makes) to phosphorous acid ester: 0.01 weight part again; Phenol is antioxygen base (IRGANOX1076 that Japanese チバガイギ-company makes): 0.01 weight part; UV light absorber (ケミプロ changes into the Kai Misuobu (ケミソ one Block) 79 that industry (strain) is made): 0.3 weight part; Remover (reason is ground Li Kaimaer (the リケマ one Le) SL900 that vitamin b6 usp (strain) is made): after 0.3 weight part measures,, then this mixture is transported in the forcing machine, makes resin combination with drum mixing machine uniform mixing.

Forcing machine uses the exhaust twin screw extruder ((strain) Kobe Steel, Ltd KTX-30) of screw diameter as φ 30mm.Screw-rod structure, be provided with first kneading block (constituting) in the past at exhaust position, be provided with second kneading block (constituting) later on by feeding rotor * 1 and feed back rotor * 2 at exhaust position by feeding kneading disk * 2, feeding rotor * 1, feed back rotor * 1 and feed back kneading disk * 1.Barrel zone temperature and head temperature are that 280 ℃, the swabbing pressure of venting port are 3, extrude the line material under the condition of 000Pa, cool off in water-bath, with grain-making machine the line material are cut into particle then, finish granulating working procedure.

The gained particle 110 ℃ with the heated air circulation type drying machine dry 5 hours, use injection moulding machine [method nanogram (strain) T-150D] to be injected into test film then.Injection molding condition: barrel zone temperature: 290 ℃, die temperature: 70 ℃.

Corresponding to table 1～table 9 respectively number used starting material etc. following shown in.(also representing same content in the narrating content of raw-material numbering beyond table).

(A) composition

(A-1 composition)

PC-1: straight chain shape polycarbonate resin (is made with the phosgene method, by dihydroxyphenyl propane and the aromatic polycarbonate resin that constitutes as chain terminator with the p tert.-butyl phenol.This aromatic polycarbonate resin does not use in preparation in the end group of amine series catalysts, aromatic polycarbonate resin, the hydroxyl end groups ratio is 10 moles of %, the phosphonic acid ester that contains 25ppm in this aromatic polycarbonate resin is oxidation inhibitor [manufacturing of Clariant (Network ラリア Application ト) company, Sand stab P-EPQ], viscosity-average molecular weight is 22,500)

PC-2: a chain aromatic polycarbonate resin (bright dipping petroleum chemistry (strain) manufacturing, Ta Fulong ( Off ロ Application) IB2500)

PC-3: under the condition that methylene dichloride, 10% aqueous sodium hydroxide solution, triethylamine exist, make dihydroxyphenyl propane, chain terminator p-tert-butylphenol photoreactive gas prepared in reaction polycarbonate resin with usual way.In this process, concerning dihydroxyphenyl propane, use the p-tert-butylphenol of 0.058 mol ratio, make viscosity-average molecular weight and be 15,500 polycarbonate resin

PC-4: under the condition that methylene dichloride, 10% aqueous sodium hydroxide solution, triethylamine exist, make dihydroxyphenyl propane, chain terminator p-tert-butylphenol photoreactive gas prepared in reaction polycarbonate resin with usual way.In this process, concerning dihydroxyphenyl propane, use the p-tert-butylphenol of 0.0004 mol ratio, make viscosity-average molecular weight and be 121,000 polycarbonate resin.

(A-2 composition)

ABS: styrene butadiene-acrylonitrile copolymer (Japanese A﹠amp; L (エイア Application De エ Le) (strain) makes, Sang Take (サ Application Star Network) UT-61)

AS: styrene-acrylonitrile copolymer (Asahi Chemical Industry's industry (strain) is made, Si Tayi clarke (スイラ Star Network)-AS 767 R27)

MBS: MBS (clock deep pool chemical industry (strain) is made, Ka Naiaisi (カネエ one ス) B-56)

(A-3 composition)

PET: (Supreme Being people's (strain) makes TR-8580, intrinsic viscosity: 0.8) to pet resin

PBT: (Supreme Being people's (strain) makes TRB-H, intrinsic viscosity: 1.07) to the polybutylene terephthalate resin

(B composition)

Synthesis example-1

In the 1L flask of whipping appts, refrigerating unit and thermometer is installed, the hexamethyldisiloxane of packing into 15.9g, 1,3,5,7-tetramethyl-ring tetrasiloxane 147.3g, octamethylcyclotetrasiloxane 14.5g and dimethoxydiphenylsilane 395.1g add vitriol oil 25.0g while stirring.After temperature in the system is cooled to 10 ℃, in flask, splash into water 29.7g with 30 fens clock times while stirring.In this process, continue cooling, the interior temperature of system is remained on below 20 ℃.After titration finishes, keep system temperature, continue to stir 5 hours at 10～20 ℃, add water 8.5g and toluene 300g after the slaking, stir static placement after 30 minutes, remove isolated water layer, and then wash four times, confirm that toluene layer is neutral with 5% aqueous sodium persulfate solution.Under reduced pressure, make system temperature reach 120 ℃ to the heating of this toluene solution, remove toluene and low boiling point component after, remove by filter insolubles, obtain silicone compounds B-1.

Synthesis example-2

In the 1L flask of whipping appts, refrigerating unit, thermometer was installed, pack into water 538.2g and toluene 120g were cooled to 5 ℃.In dropping funnel, pack into the mixture of trimethylchlorosilane 22.6g, dimethyl dichlorosilane (DMCS) 119.6g and diphenyl dichlorosilane 34.2g, stir material in the flask on the limit, and the limit splashes into said mixture in flask, and the time of splashing into is 2 hours.In this process, continue cooling, the interior temperature of system is remained on below 20 ℃.After titration finishes, continue to stir down at 20 ℃ and made its slaking in 4 hours, the static placement in back then, remove isolating hydrochloric acid water layer, add 10% aqueous sodium carbonate and stir after 5 minutes, isolating water layer is removed in static placement.Further use ion-exchange water washing 3 times then, confirm that toluene layer is neutral.Under reduced pressure to the heating of this toluene solution, make that temperature reaches 120 ℃ in the system, remove toluene and low boiling point component after, remove by filter insolubles and obtain silicone compounds B-2.

Synthesis example-3

Water 452.8g and toluene 120g pack in flask, splash into the mixture of trimethylchlorosilane 21.7g, dimethyl dichlorosilane (DMCS) 23.0g, dimethyldichlorosilane(DMCS) 80.0g and diphenyl dichlorosilane 32.9g, in addition, carry out and synthesis example-2 identical operations, obtain silicone compounds B-3.

Synthesis example-4

In flask, pack 1 into, 1,3,3-tetramethyl disiloxane 100.7g, 1,3,5,7-tetramethyl-ring tetrasiloxane 60.1g, octamethylcyclotetrasiloxane 129.8g, octaphenyl cyclotetrasiloxane 143.8g and phenyltrimethoxysila,e 99.1g add vitriol oil 25.0g again, splash into water 13.8g, in addition, carry out identical operations, obtain silicone compounds B-4 with synthesis example 1-.

Synthesis example-5

In flask, pack into water 454.9g and toluene 140g, splash into the mixture of dimethylchlorosilane 47.3g, dimethyl dichlorosilane (DMCS) 34.5g, dimethyldichlorosilane(DMCS) 1.4g, diphenyl dichlorosilane 11.3g and phenyl-trichloro-silicane 63.5g, in addition, carry out and synthesis example-2 identical operations, obtain silicone compounds B-5.

Synthesis example-6

The hexamethyldisiloxane of in flask, packing into 26.0g, 1,3,5,7-tetramethyl-ring tetrasiloxane 57.7g, octamethylcyclotetrasiloxane 26.1g and dimethoxydiphenylsilane 456.3g, add vitriol oil 25.0g again, splash into water 34.3g, in addition, carry out and synthesis example-1 identical operations, obtain silicone compounds B-6.

Synthesis example-7

The hexamethyldisiloxane of in flask, packing into 81.2g, 1,3,5,7-tetramethyl-ring tetrasiloxane 30.1g, octamethylcyclotetrasiloxane 129.8g and dimethoxydiphenylsilane 317.7g, add vitriol oil 25.0g again, splash into water 23.9g, in addition, carry out and synthesis example-1 identical operations, obtain silicone compounds B-7.

Synthesis example-8

Water 511.3g and toluene 120g pack in flask, splash into dimethylchlorosilane 14.8g, dimethyl dichlorosilane (DMCS) 17.9g, the mixture of dimethyldichlorosilane(DMCS) 112.7g and diphenyl dichlorosilane 19.7g, in addition, carry out and synthesis example-2 identical operations, obtain silicone compounds B-8.

Synthesis example-9

In flask, pack 1 into, 1,3,3-tetramethyl disiloxane 6.7g, 1,3,5,7-tetramethyl-ring tetrasiloxane 60.1g and dimethoxydiphenylsilane 533.9g add vitriol oil 40.0g again, splash into water 40.2g, in addition, carry out and synthesis example-1 identical operations, obtain silicone compounds B-9.

B-1: the Si-H amount that makes according to synthesis example-1 is that 50 weight %, specific refractory power are 1.5313 silicone compounds for 0.49mol/100g, aryl amount

B-2: the Si-H amount that makes according to synthesis example-2 is that 20 weight %, specific refractory power are 1.4480 silicone compounds for 1.00mol/100g, aryl amount

B-3: the Si-H amount that makes according to synthesis example-3 is that 20 weight %, specific refractory power are 1.4502 silicone compounds for 0.20mol/100g, aryl amount

B-4: the Si-H amount that makes according to synthesis example-4 is that 30 weight %, specific refractory power are 1.4750 silicone compounds for 0.50mol/100g, aryl amount

B-5: the Si-H amount that makes according to synthesis example-5 is that 30 weight %, specific refractory power are 1.4770 silicone compounds for 0.80mol/100g, aryl amount

B-6: the Si-H amount that makes according to synthesis example-6 is that 60 weight %, specific refractory power are 1.5583 silicone compounds for 0.20mol/100g, aryl amount

B-7: the Si-H amount that makes according to synthesis example-7 is that 40 weight %, specific refractory power are 1.4970 silicone compounds for 0.10mol/100g, aryl amount

B-8: the Si-H amount that makes according to synthesis example-8 is that 12 weight %, specific refractory power are 1.4188 silicone compounds for 0.31mol/100g, aryl amount

B-9: the Si-H amount that makes according to synthesis example-9 is that 67 weight %, specific refractory power are 1.5839 silicone compounds for 0.22mol/100g, aryl amount

Other (B) composition

Synthesis example-10

The hexamethyldisiloxane of in flask, packing into 97.4g, 1,3,5,7-tetramethyl-ring tetrasiloxane 180.4g and octamethylcyclotetrasiloxane 222.5g add vitriol oil 25.0g again, do not splash into water, in addition, carry out and synthesis example-1 identical operations, obtain silicone compounds B-10.

Synthesis example-11

The hexamethyldisiloxane of in flask, packing into 39.9g, 1,3,5,7-tetramethyl-ring tetrasiloxane 14.8g, octamethylcyclotetrasiloxane 200.6g and dimethoxydiphenylsilane 300.6g, add vitriol oil 25.0g again, splash into water 22.6g, in addition, carry out and synthesis example-1 identical operations, obtain silicone compounds B-11.

Synthesis example-12

Pack in flask water 560.6g and toluene 140g splash into the mixture of dimethylchlorosilane 18.9g, dimethyl dichlorosilane (DMCS) 126.5g and diphenyl dichlorosilane 25.3g.In addition, carry out and synthesis example-2 identical operations, obtain silicone compounds B-12.

B-10 (comparison): the Si-H amount that makes according to synthesis example-10 is that 0 weight %, specific refractory power are 1.3956 silicone compounds for 0.60mol/100g, aryl amount

B-11 (comparison): the Si-H amount that makes according to synthesis example-11 is that 38 weight %, specific refractory power are 1.4915 silicone compounds for 0.05mol/100g, aryl amount.

B-12 (comparison): the Si-H amount that makes according to synthesis example-12 is that 16 weight %, specific refractory power are 1.4419 silicone compounds for 1.31mol/100g, aryl amount

The rational formula of＜each silicone compounds 〉

B-1：M ₂D ^H ₂₅D ₂D ^φ2 _16.5

B-2：M ₂D ^H ₁₀D ^φ2 _1.3

B-3：M ₂D ^H ₂D _6.2D ^φ2 _1.3

B-4：M ^H ₃D ^H ₂D _3.5D ^φ2 _1.45T ^φ ₁

B-5：M ^H ₅D ^H ₃D _0.107D ^φ2 _0.445T ^φ ₃

B-6：M ₂D ^H ₆D _2.2D ^φ2 _11.67

B-7：M ₂D ^H ₁D _3.5D ^φ2 _2.6

B-8：M ^H ₂D ^H ₂D _11.2D ^φ2 ₁

B-9：M ^H ₂D ^H ₂₀D ^φ2 _43.7

B-10:M ₂D ^H ₅D ₅(comparison)

B-11:M ₂D ^H ₁D ₁₁D ^{φ 2} ₅(comparison)

B-12:M ^H ₂D ^H ₁₁D ^{φ 2} ₁(comparison)

Siloxane unit below each symbolic representation in the above-mentioned rational formula, the inferior horn coefficient of each symbol are represented the polymerization degree of each siloxane units in the molecule.

M：(CH ₃) ₃SiO _1/2

M ^H：H(CH ₃) ₂SiO _1/2

D：(CH ₃) ₂SiO

D ^H：H(CH ₃)SiO

D ^φ2：(C ₆H ₅) ₂SiO

T ^φ：(C ₆H ₅)SiO _3/2

(C) composition

C-1:2,3-dimethyl-2,3-diphenyl butane (common name diisopropylbenzene(DIPB), Japanese grease (strain) is made, Nuo Fuma (ノ Off マ one) BC)

C-2: potassium perfluorobutane sulfonate salt (big Japanese ink chemical industry (strain) is made, Meccah method gram (メガ Off ア Star Network) F-114P)

C-3: (UCB (ユ one シ one PVC one) Japan makes the sulfobenzide sulfonic acid potassium salt, KSS)

Table 1

		Unit	Embodiment 1	Embodiment 2	Embodiment 3	Embodiment 4	Embodiment 5
		Unit	Embodiment 1	Embodiment 2	Embodiment 3	Embodiment 4	Embodiment 5	(A) composition	PC-1	Weight part	100		70	80	97
PC-2	″		100						PC-1	Weight part	100		70	80	97
PC-2	″		100				ABS		″			30
AS	″				20		ABS		″			30
AS	″				20		MBS		″					3
(B) composition	B-4	″	2	2	2	2	MBS		″					3	2
(B) composition	B-4	″	2	2	2	2	Produce the time of drip	After catching fire for 1 time	Second	No drip	No drip	No drip	No drip	No drip	2
After catching fire for 2 times	Second	8	15	6	6	8		After catching fire for 1 time	Second	No drip	No drip	No drip	No drip	No drip
After catching fire for 2 times	Second	8	15	6	6	8		Dyeability	Boldness	-	○	○	○	○	○
ΔL	-	0.1	0.1	0.1	0.1	0.1			Boldness	-	○	○	○	○	○
ΔL	-	0.1	0.1	0.1	0.1	0.1	The laser lettering		Sharpness	-	○	○	○	○	○
Current value	A	19.0	19.3	19.5	19.0	19.2			Sharpness	-	○	○	○	○	○
Current value	A	19.0	19.3	19.5	19.0	19.2		The transparency	Tone	-	Water white transparency	Water white transparency	Opaque	Opaque	Opaque
Mist degree	-	1.1	1.1	-	-	-			Tone	-	Water white transparency	Water white transparency	Opaque	Opaque	Opaque

Table 2

		Unit	Embodiment 6	Embodiment 7	Embodiment 8	Embodiment 9	Embodiment 10
		Unit	Embodiment 6	Embodiment 7	Embodiment 8	Embodiment 9	Embodiment 10	(A) composition	PC-1	Weight part	90	90	100	100	100
PET	″	10							PC-1	Weight part	90	90	100	100	100
PET	″	10					PBT		″		10
(B) composition	B-1	″			2		PBT		″		10
	B-1	″			2		B-2	″				2
	B-3	″					B-2	″				2		2
	B-3	″					B-4	″	2	2				2
	Produce the time of drip	After catching fire for 1 time	Second	No drip	No drip	No drip	B-4	″	2	2				No drip	No drip
After catching fire for 2 times		After catching fire for 1 time	Second	No drip	No drip	No drip	Second	7	7	10	14	6		No drip	No drip
After catching fire for 2 times		Dyeability	Boldness	-	○	○	Second	7	7	10	14	6	○	○	○
ΔL	-		Boldness	-	○	○	0.1	0.1	0.1	0.5	0.4		○	○	○
ΔL	-		The laser lettering	Sharpness	-	○	0.1	0.1	0.1	0.5	0.4	○	○	○	○
Current value	A	19.6		Sharpness	-	○	19.4	19.2	18.8	19.6		○	○	○	○
Current value	A	19.6		The transparency	Tone	-	19.4	19.2	18.8	19.6	Opaque	Opaque	Water white transparency	Water white transparency	Water white transparency
Mist degree	-	-	-		Tone	-	1.6	1.6	1.6		Opaque	Opaque	Water white transparency	Water white transparency	Water white transparency

Table 3

		Unit	Embodiment 11	Embodiment 12	Embodiment 13	Embodiment 14	Embodiment 15	Embodiment 16
		Unit	Embodiment 11	Embodiment 12	Embodiment 13	Embodiment 14	Embodiment 15	Embodiment 16	(A) composition	PC-1	Weight part	100	100	100	100	100	100
(B) composition	B-4	″			1	3	5	2	(A) composition	PC-1	Weight part	100	100	100	100	100	100
	B-4	″			1	3	5	2	B-5	″	2		1
	B-6	″		2					B-5	″	2		1
	B-6	″		2					(C) composition	C-1	″						0.1
Produce the time of drip	After catching fire for 1 time	Second	No drip	No drip	No drip	No drip	No drip	No drip	(C) composition	C-1	″						0.1
	After catching fire for 1 time	Second	No drip	No drip	No drip	No drip	No drip	No drip	After catching fire for 2 times	Second	11	9	10	15	17	No drip
	Dyeability	Boldness	-	○	○	○	○	○	After catching fire for 2 times	Second	11	9	10	15	17	No drip	○
ΔL		Boldness	-	○	○	○	○	○	-	0.1	0.1	0.1	0.1	0.1	0.1		○
ΔL		The laser lettering	Sharpness	-	○	○	○	○	-	0.1	0.1	0.1	0.1	0.1	0.1	○	○
Current value	A		Sharpness	-	○	○	○	○	19.0	19.2	19.5	19.0	18.5	19.6		○	○
Current value	A		The transparency	Tone	-	Water white transparency	Water white transparency	Water white transparency	19.0	19.2	19.5	19.0	18.5	19.6	Water white transparency	Water white transparency	Water white transparency
Mist degree	-	1.3		Tone	-	Water white transparency	Water white transparency	Water white transparency	0.8	1.1	1.2	1.3	1.2		Water white transparency	Water white transparency	Water white transparency

Table 4

		Unit	Embodiment 17	Embodiment 18	Embodiment 19	Embodiment 20	Embodiment 21	Embodiment 22
		Unit	Embodiment 17	Embodiment 18	Embodiment 19	Embodiment 20	Embodiment 21	Embodiment 22	(A) composition	PC-1	Weight part	100	100	100	100
PC-2	″					80				PC-1	Weight part	100	100	100	100
PC-2	″					80		PC-3		″					20	85
PC-4	″						15	PC-3		″					20	85
PC-4	″						15	(B) composition		B-4	″	2	1	2	1	1	1
B-5	″				1					B-4	″	2	1	2	1	1	1
B-5	″				1				(C) composition	C-2	″	0.1	0.1		0.1	0.1	0.1
C-3	″			0.1						C-2	″	0.1	0.1		0.1	0.1	0.1
C-3	″			0.1				Produce the time of drip		After catching fire for 1 time	Second	No drip	No drip	No drip	No drip	No drip	No drip
After catching fire for 2 times	Second	No drip	No drip	No drip	No drip	No drip	No drip			After catching fire for 1 time	Second	No drip	No drip	No drip	No drip	No drip	No drip
After catching fire for 2 times	Second	No drip	No drip	No drip	No drip	No drip	No drip		Dyeability	Boldness	-	○	○	○	○	○	○
ΔL	-	0.1	0.1	0.5	0.4	0.1	0.1			Boldness	-	○	○	○	○	○	○
ΔL	-	0.1	0.1	0.5	0.4	0.1	0.1	The laser lettering		Sharpness	-	○	○	○	○	○	○
Current value	A	19.4	19.8	19.4	19.3	19.2	19.2			Sharpness	-	○	○	○	○	○	○
Current value	A	19.4	19.8	19.4	19.3	19.2	19.2		The transparency	Tone		Water white transparency	Water white transparency	Water white transparency	Water white transparency	Water white transparency	Water white transparency
Mist degree		2.8	1.9	1.1	2.8	1.9	1.9			Tone		Water white transparency	Water white transparency	Water white transparency	Water white transparency	Water white transparency	Water white transparency

Table 5

		Unit	Comparative example 1	Comparative example 2	Comparative example 3	Comparative example 4	Comparative example 5
		Unit	Comparative example 1	Comparative example 2	Comparative example 3	Comparative example 4	Comparative example 5	(A) composition	PC-1	Weight part	100		70	80	97
PC-2	″		100						PC-1	Weight part	100		70	80	97
PC-2	″		100				ABS		″			30
AS	″				20		ABS		″			30
AS	″				20		MBS		″					3
(B) beyond the composition	B-12	″	2	2	2	2	MBS		″					3	2
(B) beyond the composition	B-12	″	2	2	2	2	Produce the time of drip	After catching fire for 1 time	Second	No drip	No drip	No drip	No drip	No drip	2
After catching fire for 2 times	Second	13	20	11	9	14		After catching fire for 1 time	Second	No drip	No drip	No drip	No drip	No drip
After catching fire for 2 times	Second	13	20	11	9	14		Dyeability	Boldness	-	○	○	○	○	○
ΔL	-	0.1	0.1	0.1	0.1	0.1			Boldness	-	○	○	○	○	○
ΔL	-	0.1	0.1	0.1	0.1	0.1	The laser lettering		Sharpness	-	×	×	×	×	×
Current value	A	18.8	19.0	18.9	18.8	19.0			Sharpness	-	×	×	×	×	×
Current value	A	18.8	19.0	18.9	18.8	19.0		The transparency	Tone	-	Water white transparency	Water white transparency	Opaque	Opaque	Opaque
Mist degree	-	1.8	1.8	-	-	-			Tone	-	Water white transparency	Water white transparency	Opaque	Opaque	Opaque

Table 6

		Unit	Comparative example 6	Comparative example 7	Comparative example 8	Comparative example 9
		Unit	Comparative example 6	Comparative example 7	Comparative example 8	Comparative example 9	(A) composition	PC-1	Weight part	90	90	100	100
PET	″	10						PC-1	Weight part	90	90	100	100
PET	″	10				PBT		″		10
Add up to (A)		″	100	100	100	PBT		″		10			100
Add up to (A)		″	100	100	100	(B) beyond the composition	B-10	″			2		100
B-11	″				2		B-10	″			2
B-11	″				2		B-12	″	2	2
Add up to (B)		″	2	2	2		B-12	″	2	2			2
Add up to (B)		″	2	2	2	Produce the time of drip	After catching fire for 1 time	Second	No drip	No drip	No drip	1	2
After catching fire for 2 times	Second	10	9	9	1		After catching fire for 1 time	Second	No drip	No drip	No drip	1
After catching fire for 2 times	Second	10	9	9	1		Dyeability	Boldness	-	○	○	×	○
ΔL	-	0.1	0.1	3.8	0.1			Boldness	-	○	○	×	○
ΔL	-	0.1	0.1	3.8	0.1	The laser lettering		Sharpness	-	×	×	×	×
Current value	A	19.1	19.2	19.2	22.0			Sharpness	-	×	×	×	×
Current value	A	19.1	19.2	19.2	22.0		The transparency	Tone	-	Opaque	Opaque	Gonorrhoea	Water white transparency
Mist degree	-	-	-	61.0	1.1			Tone	-	Opaque	Opaque	Gonorrhoea	Water white transparency

Table 7

		Unit	Comparative example 10	Comparative example 11	Comparative example 12	Comparative example 13
		Unit	Comparative example 10	Comparative example 11	Comparative example 12	Comparative example 13	(A) composition	PC-1	Weight part	100	100	100	100
(B) composition	B-4	″		0.05	15		(A) composition	PC-1	Weight part	100	100	100	100
(B) composition	B-4	″		0.05	15		(B) beyond the composition	B-12	″	5
Produce the time of drip	After catching fire for 1 time	Second	No drip	2	No drip	1	(B) beyond the composition	B-12	″	5
	After catching fire for 1 time	Second	No drip	2	No drip	1	After catching fire for 2 times	Second	28	1	36	1
	Dyeability	Boldness	-	○	○	○	After catching fire for 2 times	Second	28	1	36	1	○
ΔL		Boldness	-	○	○	○	-	0.1	0.1	0.1	0.1		○
ΔL		The laser lettering	Sharpness	-	×	×	-	0.1	0.1	0.1	0.1	×	×
Current value	A		Sharpness	-	×	×	18.1	21.9	18.0	22.2		×	×
Current value	A		The transparency	Tone	-	Water white transparency	18.1	21.9	18.0	22.2	Water white transparency	Water white transparency	Water white transparency
Mist degree	-	9.9		Tone	-	Water white transparency	0.4	6.5	0.3		Water white transparency	Water white transparency	Water white transparency

Table 8

		Unit	Comparative example 14	Comparative example 15	Comparative example 16	Comparative example 17	Comparative example 18
		Unit	Comparative example 14	Comparative example 15	Comparative example 16	Comparative example 17	Comparative example 18	(A) composition	PC-1	Weight part	70	97	90	30	40
ABS	″	30			70				PC-1	Weight part	70	97	90	30	40
ABS	″	30			70		MBS		″		3
PET	″			10		60	MBS		″		3
PET	″			10		60	(B) composition		B-4	″				2	2
Produce the time of drip	After catching fire for 1 time	Second	1	1	1	3	(B) composition	2	B-4	″				2	2
	After catching fire for 1 time	Second	1	1	1	3	After catching fire for 2 times	2	Second	1	1	1	1	1
	Dyeability	Boldness	-	○	○	○	After catching fire for 2 times	○	Second	1	1	1	1	1	○
ΔL		Boldness	-	○	○	○	-	○	0.1	0.1	0.1	0.1	0.1		○
ΔL		The laser lettering	Sharpness	-	×	×	-	×	0.1	0.1	0.1	0.1	0.1	○	○
Current value	A		Sharpness	-	×	×	21.7	×	22.2	22.3	18.8	19.0		○	○
Current value	A		The transparency	Tone	-	Opaque	21.7	Opaque	22.2	22.3	18.8	19.0	Opaque	Opaque	Opaque
Mist degree	-	-		Tone	-	Opaque	-	Opaque	-	-	-		Opaque	Opaque	Opaque

Table 9

		Unit	Embodiment 23	Embodiment 24	Embodiment 25
		Unit	Embodiment 23	Embodiment 24	Embodiment 25	(A) composition	PC-1	Weight part	100	100	100
(B) composition	B-7	″	2			(A) composition	PC-1	Weight part	100	100	100
	B-7	″	2			B-8	″		2	1
	B-9	″			2	B-8	″		2	1
	B-9	″			2	(C) composition	C-2	″	0.1	0.1	0.1
Produce the time of drip	After catching fire for 1 time	Second	No drip	No drip	No drip	(C) composition	C-2	″	0.1	0.1	0.1
	After catching fire for 1 time	Second	No drip	No drip	No drip	After catching fire for 2 times	Second	No drip	No drip	No drip
	Dyeability	Boldness	-	○	○	After catching fire for 2 times	Second	No drip	No drip	No drip	○
ΔL		Boldness	-	○	○	-	0.1	0.1	0.1		○
ΔL		The laser lettering	Sharpness	-	○	-	0.1	0.1	0.1	○	○
Current value	A		Sharpness	-	○	19.4	19.4	19.4		○	○
Current value	A		The transparency	Tone	-	19.4	19.4	19.4	Water white transparency	Water white transparency	Water white transparency
Mist degree	-	2.3		Tone	-	2.8	3.1		Water white transparency	Water white transparency	Water white transparency

[embodiment 26～38 and comparative example 19～24]

Each composition that his-and-hers watches 10～14 are listed measures in the cooperation ratio shown in the table, and other composition of not listing in the his-and-hers watches is according to the component proportions metering identical with embodiment 1, and uses the method identical with embodiment 1 to make resin combination and test film.

Shown in the starting material that list table 10～14 etc. are following.

(B) composition

Synthesis example-13

Water 301.9g and toluene 150g pack in flask, splash into the mixture of trimethylchlorosilane 21.7g, dimethyl dichlorosilane (DMCS) 23.0g, dimethyldichlorosilane(DMCS) 12.9g and diphenyl dichlorosilane 76.0g, in addition, carry out and synthesis example 2 identical operations, obtain silicone compounds B-13.

Synthesis example-14

The hexamethyldisiloxane of in flask, packing into 16.2g, 1,3,5,7-tetramethyl-ring tetrasiloxane 61.0g, octamethylcyclotetrasiloxane 103.8g and dimethoxydiphenylsilane 391.0g, add vitriol oil 25.0g again, splash into water 29.4g, in addition, carry out and synthesis example-1 identical operations, obtain silicone compounds B-14.

Synthesis example-15

In flask, pack 1 into, 1,3,3-tetramethyl disiloxane 167.9g, octamethylcyclotetrasiloxane 92.7g, octaphenyl cyclotetrasiloxane 49.6g and phenyltrimethoxysila,e 297.4g, add vitriol oil 25.5g again, splash into water 41.3g, in addition, carry out and synthesis example-1 identical operations, obtain silicone compounds B-15.

Synthesis example-16

Water 403.2g and toluene 120g pack in flask, splash into the mixture of dimethylchlorosilane 48.3g, dimethyldichlorosilane(DMCS) 43.9g, diphenyl dichlorosilane 21.5g and phenyl-trichloro-silicane 36.0g, in addition, carry out and synthesis example-2 identical operations, obtain silicone compounds B-16.

Synthesis example-17

In flask, pack 1 into, 1,3,3-tetramethyl disiloxane 70.5g, 1,3,5,7-tetramethyl-ring tetrasiloxane 126.3g and dimethoxydiphenylsilane 243.8g add vitriol oil 25.0g again, splash into water 18.3g, in addition, carry out and synthesis example-1 identical operations, obtain silicone compounds B-17.

Synthesis example-18

In flask, pack 1 into, 1,3,3-tetramethyl disiloxane 87.3g, hexamethyldisiloxane 211.1g, 1,3,5,7-tetramethyl-ring tetrasiloxane 31.3g and phenyltrimethoxysila,e 257.8g add vitriol oil 25.0g again, splash into water 35.8g, in addition, carry out and synthesis example-1 identical operations, obtain the silane oxidation and close B-18.

Synthesis example-19

Water 447.2g and toluene 200g pack in flask, splash into the mixture of trimethylchlorosilane 22.2g, dimethyl dichlorosilane (DMCS) 39.1g, dimethyldichlorosilane(DMCS) 21.9g, diphenyl dichlorosilane 43.0g, METHYL TRICHLORO SILANE 12.7g and phenyl-trichloro-silicane 18.0g, in addition, carry out and synthesis example-2 identical operations, obtain silicone compounds B-19.

Synthesis example-20

The hexamethyldisiloxane of in flask, packing into 8.1g, 1,3,5,7-methyl cyclotetrasiloxane 120.3g, octamethylcyclotetrasiloxane 111.2g and dimethoxydiphenylsilane 195.5g, add vitriol oil 20.0g again, splash into water 14.7g, in addition, carry out and synthesis example-1 identical operations, obtain silicone compounds B-20.

B-13: the Si-H amount that makes according to synthesis example-13 is that 49 weight %, mean polymerisation degree are 8.0 silicone compounds for 0.21mol/100g, aryl amount

B-14: the Si-H amount that makes according to synthesis example-14 is that 50 weight %, mean polymerisation degree are 42.0 silicone compounds for 0.20mol/100g, aryl amount

B-15: the Si-H amount that makes according to synthesis example-15 is that 31 weight %, mean polymerisation degree are 11.0 silicone compounds for 0.50mol/100g, aryl amount

B-16: the Si-H amount that makes according to synthesis example-16 is that 27 weight %, mean polymerisation degree are 6.5 silicone compounds for 0.52mol/100g, aryl amount

B-17: the Si-H amount that makes according to synthesis example-17 is that 39 weight %, mean polymerisation degree are 7.9 silicone compounds for 0.80mol/100g, aryl amount

B-18: the Si-H amount that makes according to synthesis example-18 is that 20 weight %, mean polymerisation degree are 4.4 silicone compounds for 0.37mol/100g, aryl amount

B-19: the Si-H amount that makes according to synthesis example-19 is that 33 weight %, mean polymerisation degree are 62.0 silicone compounds for 0.34mol/100g, aryl amount

B-20: the Si-H amount that makes according to synthesis example-20 is that 31 weight %, mean polymerisation degree are 88.0 silicone compounds for 0.50mol/100g, aryl amount

Other (B) composition

Synthesis example-21

Pack 1,1,3 in flask into, 3-tetramethyl disiloxane 39.0g and dimethoxydiphenylsilane 566.9g add vitriol oil 25.0g again, splash into water 42.6g, in addition, carry out and synthesis example-1 identical operations, obtain silicone compounds B-21.

Synthesis example-22

Water 560.6g and toluene 130g pack in flask, splash into the mixture of trimethylchlorosilane 21.2g, dimethyl dichlorosilane (DMCS) 52.3g, dimethyldichlorosilane(DMCS) 83.9g and phenyl-trichloro-silicane 13.8g, in addition, carry out and synthesis example-2 identical operations, obtain silicone compounds B-22.

B-21 (comparison): the Si-H amount that makes according to synthesis example-21 is that 72 weight %, mean polymerisation degree are 10.0 silicone compounds for 0.12mol/100g, aryl amount

B-22 (comparison): the Si-H amount that makes according to synthesis example-22 is the silicone compounds of 5 weight %, mean polymerisation degree 21.0 for 0.45mol/100g, aryl amount

The rational formula of＜each silicone compounds 〉

B-13：M ₂D ^H ₂D ₁D ^φ2 ₃

B-14：M ₂D ^H ₁₀D ₁₄D ^φ2 ₁₆

B-15：M ^H ₅D _2.5D ^φ2 _0.5T ^φ ₃

B-16：M ^H ₃D ₂D ^φ2 _0.5T ^φ ₁

B-17：M ^H ₂D ^H ₄D ^φ2 _1.9

B-18：M ₂M ^H ₁D ^H _0.4T ^φ ₁

B-19：M ₁₂D ^H ₂₀D ₁₀D ^φ2 ₁₀T ₅T ^φ ₅

B-20：M ₂D ^H ₄₀D ₃₀D ^φ2 ₁₆

B-21:M ^H ₂D ^{φ 2} ₈(comparison)

B-22:M ₃D ^H ₇D ₁₀T ^φ ₁(comparison)

The inferior horn coefficient of the siloxane unit in the above-mentioned rational formula below each symbolic representation, each symbol back is represented the polymerization degree of each siloxane unit in the molecule.

M：(CH ₃) ₃SiO _1/2

M ^H：H(CH ₃) ₂SiO _1/2

D：(CH ₃) ₂SiO

D ^H：H(CH ₃)SiO

D ^φ2：(C ₆H ₅) ₂SiO

T：(CH ₃)SiO _3/2

T ^φ：(C ₆H ₅)SiO _3/2

Table 10

		Unit	Embodiment 26	Embodiment 27	Embodiment 28	Embodiment 29	Embodiment 30	Embodiment 31
		Unit	Embodiment 26	Embodiment 27	Embodiment 28	Embodiment 29	Embodiment 30	Embodiment 31	(A) composition	PC-1	Weight part	100			100	100	100
PC-2	″		100	100						PC-1	Weight part	100			100	100	100
PC-2	″		100	100				(B) composition		B-13	″	2
B-14	″		2	5						B-13	″	2
B-14	″		2	5					B-15	″				2	5
B-16	″						2		B-15	″				2	5
B-16	″						2		Produce the time of drip	After catching fire for 1 time	Second	No drip	No drip	No drip	No drip	No drip	No drip
After catching fire for 2 times	Second	7	18	22	9	18	7			After catching fire for 1 time	Second	No drip	No drip	No drip	No drip	No drip	No drip
After catching fire for 2 times	Second	7	18	22	9	18	7	The transparency		Tone	-	Water white transparency	Water white transparency	Water white transparency	Water white transparency	Water white transparency	Water white transparency
Mist degree	-	0.3	1.6	9.1	1.1	1.3	0.8			Tone	-	Water white transparency	Water white transparency	Water white transparency	Water white transparency	Water white transparency	Water white transparency
Mist degree	-	0.3	1.6	9.1	1.1	1.3	0.8		Humidity resistance	Tone	-	Water white transparency	Water white transparency	Water white transparency	Water white transparency	Water white transparency	Water white transparency
The Δ mist degree	-	1.0	0.9	2.6	1.9	2.5	0.8			Tone	-	Water white transparency	Water white transparency	Water white transparency	Water white transparency	Water white transparency	Water white transparency
The Δ mist degree	-	1.0	0.9	2.6	1.9	2.5	0.8	The laser lettering		Sharpness	-	○	○	○	○	○	○
Current value	A	19.2	19.4	18.6	19.6	18.5	19.7			Sharpness	-	○	○	○	○	○	○

Table 11

		Unit	Embodiment 32	Embodiment 33	Embodiment 34	Embodiment 35
		Unit	Embodiment 32	Embodiment 33	Embodiment 34	Embodiment 35	(A) composition	PC-1	Weight part	100	100	100	100
(B) composition	B-13	″		1			(A) composition	PC-1	Weight part	100	100	100	100
	B-13	″		1			B-15	″	2	1	2	2
	(C) composition	C-1	″	0.1			B-15	″	2	1	2	2
C-2		C-1	″	0.1			″		0.1	0.1
C-2		C-3	″				″		0.1	0.1		0.1
Produce the time of drip		C-3	″				After catching fire for 1 time	Second	No drip	No drip	No drip	0.1	No drip
	After catching fire for 2 times	Second	No drip	No drip	No drip	No drip	After catching fire for 1 time	Second	No drip	No drip	No drip		No drip
	After catching fire for 2 times	Second	No drip	No drip	No drip	No drip	The transparency	Tone	-	Water white transparency	Water white transparency	Water white transparency	Water white transparency
Mist degree	-	1.2	2.6	2.8	1.1			Tone	-	Water white transparency	Water white transparency	Water white transparency	Water white transparency
Mist degree	-	1.2	2.6	2.8	1.1	Drawing property of moisture-proof		Tone	-	Water white transparency	Water white transparency	Water white transparency	Water white transparency
The Δ mist degree	-	2.0	1.6	1.6	4.1			Tone	-	Water white transparency	Water white transparency	Water white transparency	Water white transparency
The Δ mist degree	-	2.0	1.6	1.6	4.1		The laser lettering	Sharpness	-	○	○	○	○
Current value	A	19.6	19.2	19.4	19.4			Sharpness	-	○	○	○	○

Table 12

		Unit	Comparative example 19	Comparative example 20	Comparative example 21
		Unit	Comparative example 19	Comparative example 20	Comparative example 21	(A) composition	PC-1	Weight part	100	100	100
(B) composition	B-15	″	0.05	20		(A) composition	PC-1	Weight part	100	100	100
(B) composition	B-15	″	0.05	20		(B) beyond the composition	B-22	″			2
Produce the time of drip	After catching fire for 1 time	Second	1	No drip	No drip	(B) beyond the composition	B-22	″			2
	After catching fire for 1 time	Second	1	No drip	No drip	After catching fire for 2 times	Second	1	30	11
	The transparency	Tone	-	Water white transparency	Water white transparency	After catching fire for 2 times	Second	1	30	11	Gonorrhoea
Mist degree		Tone	-	Water white transparency	Water white transparency	-	0.4	7.9	77.7		Gonorrhoea
Mist degree		Humidity resistance	Tone	-	Water white transparency	-	0.4	7.9	77.7	Water white transparency	Gonorrhoea
The Δ mist degree	-		Tone	-	Water white transparency	0.3	11.3	1.8		Water white transparency	Gonorrhoea
The Δ mist degree	-		The laser lettering	Sharpness	-	0.3	11.3	1.8	×	×	×
Current value	A	21.9		Sharpness	-	17.5	19.1		×	×	×

Table 13

		Unit	Comparative example 22	Comparative example 23	Comparative example 24
		Unit	Comparative example 22	Comparative example 23	Comparative example 24	(A) composition	PC-1	Weight part	100	100	100
(B) beyond the composition	B-11	″		10		(A) composition	PC-1	Weight part	100	100	100
	B-11	″		10		B-21	″	2
	Produce the time of drip	After catching fire for 1 time	Second	No drip	3	B-21	″	2			1
After catching fire for 2 times		After catching fire for 1 time	Second	No drip	3	Second	13	1	1		1
After catching fire for 2 times		The transparency	Tone	-	Gonorrhoea	Second	13	1	1	Water white transparency	Water white transparency
Mist degree	-		Tone	-	Gonorrhoea	31.6	0.9	0.3		Water white transparency	Water white transparency
Mist degree	-		Humidity resistance	Tone	-	31.6	0.9	0.3	Gonorrhoea	Water white transparency	Water white transparency
The Δ mist degree	-	2.0		Tone	-	1.3	0.3		Gonorrhoea	Water white transparency	Water white transparency
The Δ mist degree	-	2.0		The laser lettering	Sharpness	1.3	0.3	-	×	×	×
Current value	A	19.1	21.6		Sharpness	22.2		-	×	×	×

Table 14

		Unit	Embodiment 36	Embodiment 37	Embodiment 38
		Unit	Embodiment 36	Embodiment 37	Embodiment 38	(A) composition	PC-1	Weight part	100	100	100
(B) composition	B-17	″	2			(A) composition	PC-1	Weight part	100	100	100
	B-17	″	2			B-18	″		2
	B-19	″			2	B-18	″		2
	B-19	″			2	(C) composition	C-2	″	0.1	0.1	0.1
Produce the time of drip	After catching fire for 1 time	Second	No drip	No drip	No drip	(C) composition	C-2	″	0.1	0.1	0.1
	After catching fire for 1 time	Second	No drip	No drip	No drip	After catching fire for 2 times	Second	No drip	No drip	No drip
	The transparency	Tone	-	Water white transparency	Water white transparency	After catching fire for 2 times	Second	No drip	No drip	No drip	Water white transparency
Mist degree		Tone	-	Water white transparency	Water white transparency	-	2.4	1.6	2.9		Water white transparency
Mist degree		Humidity resistance	Tone	-	Water white transparency	-	2.4	1.6	2.9	Water white transparency	Water white transparency
The Δ mist degree	-		Tone	-	Water white transparency	1.4	2.1	2.0		Water white transparency	Water white transparency
The Δ mist degree	-		The laser lettering	Sharpness	-	1.4	2.1	2.0	○	○	○
Current value	A	18.7		Sharpness	-	19.1	19.1		○	○	○

[embodiment 39～42]

According to the ratio shown in the table 15 each composition is measured, it is oxidation inhibitor (the Japanese チバガイギ manufacturing IRGAFOS168 of one company) to phosphorous acid ester again: 0.01 weight part, phenol is oxidation inhibitor (the vapour Bart plants chemical (Ciba Specialty Chemicals) IRGANOX1076): 0.05 weight part, releasing agent (make by コグニスジヤパ Application (strain), Lip river Ji Xiaoer (ロキシオ one Le) VPG861): 0.3 weight part, after sieve's Marko Simon Rex Bai Aolaite of Beyer Co., Ltd (マ Network ロレ Star Network スバイオレ Star ト) B:0.00005 weight part measures, with drum mixing machine uniform mixing, use the method identical that this mixture is made resin combination and test film with embodiment 1.

Starting material shown in the table 15 are as follows.

(D) composition

D-1: talcum (woods changes into (strain) and makes UPN HS-T0.8)

Table 15

		Unit	Embodiment 39	Embodiment 40	Embodiment 41	Embodiment 42
		Unit	Embodiment 39	Embodiment 40	Embodiment 41	Embodiment 42	(A) composition	PC-1	Weight part	100			100
PC-2	″		80					PC-1	Weight part	100			100
PC-2	″		80			PC-3		″		20	85
PC-4	″			15		PC-3		″		20	85
PC-4	″			15		(B) composition		B-13	″	1	1	1	1
(C) composition	C-2	″	0.1	0.1	0.1	(B) composition		B-13	″	1	1	1	1
	C-2	″	0.1	0.1	0.1	C-3		″				0.05
	(D) composition	D-1	″			C-3		″				0.05	1
Produce the time of drip	(D) composition	D-1	″			After catching fire for 1 time		Second	No drip	No drip	No drip	No drip	1
	After catching fire for 2 times	Second	No drip	No drip	No drip	After catching fire for 1 time	No drip	Second	No drip	No drip	No drip	No drip
	After catching fire for 2 times	Second	No drip	No drip	No drip	The laser lettering	No drip	Sharpness	-	○	○	○	○
Current value	A	19.1	19.2	19.2	19.2			Sharpness	-	○	○	○	○
Current value	A	19.1	19.2	19.2	19.2		The transparency	Tone	-	Water white transparency	Water white transparency	Water white transparency	Water white transparency
Mist degree	-	1.7	1.6	1.6	10.2			Tone	-	Water white transparency	Water white transparency	Water white transparency	Water white transparency

[embodiment 43]

In the ratio shown in the table 16 each composition is measured, it is oxidation inhibitor (IRGAFOS168 that Japanese チバガイギ-company makes) to phosphorous acid ester again: 0.01 weight part, phenol is oxidation inhibitor (the vapour Bart plants chemical (Ciba Specialty Chemicals) IRGANOX1076): 0.05 weight part, releasing agent (make by コグニスジヤパ Application (strain), Lip river Ji Xiaoer (ロキシオ one Le) VPG816:0.3 weight part, having the tetrafluoroethylene concentration that forms the protofibril energy is the masterbatch pellet (the masterbatch pellet of the poly-fluorine dragon of above-mentioned PC-1:97.5 weight % and Daikin Industries system (Port リ Off ロ Application) MPA FA500:2.5 weight % by twin screw extruder granulation same as described above) of the polycarbonate resin of 2.5 weight %: 2 weight parts, sieve's Marko Simon Rex Bai Aolaite of Beyer Co., Ltd (マ Network ロレ Star Network スバイオレ Star ト) B:0.00003 weight part measures, with drum mixing machine uniform mixing, use the method identical that this mixture is made resin combination and test film with embodiment 1.

[embodiment 44]

By PC-1: B-20=100: 10 weight ratio is dissolved in above-mentioned PC-1 and above-mentioned B-20 in the methylene dichloride, is modulated into the dichloromethane solution of 10 weight %.This dichloromethane solution is sprayed with the special type spray-dryer of GS-310 with the organic solvent that ヤマトラボテ Star Network is made, obtain the mixed powder of polycarbonate resin and organo-siloxane.Operational condition: thermophore: nitrogen, thermophore enter the temperature in spraying chamber: 70 ℃, and thermophore flow: 0.5m ³/ minute, spray pressure 100kPa, the input speed of dichloromethane solution: 40g/ minute, spraying bottom surface, chamber temperature: 70 ℃.

According to the cooperation ratio shown in the table 16 this mixed powder and PC-1 are measured,, use the method identical to make resin combination and test film with embodiment 39 again in other composition metering that does not illustrate in ratio identical and the composition his-and-hers watches 16 with embodiment 39.

Table 16

		Unit	Embodiment 43	Embodiment 44
		Unit	Embodiment 43	Embodiment 44	(A) composition	PC-1	Weight part	100	100
(B) composition	B-13	″	1		(A) composition	PC-1	Weight part	100	100
	B-13	″	1		B-20	″		2
	(C) composition	C-2	″	0.1	B-20	″		2
Produce the time of drip	(C) composition	C-2	″	0.1	After catching fire for 1 time	Second	No drip	No drip
	After catching fire for 2 times	Second	No drip	No drip	After catching fire for 1 time	Second	No drip	No drip
	After catching fire for 2 times	Second	No drip	No drip	The laser lettering	Sharpness	-	○	○
Current value	A	19.2	19.7			Sharpness	-	○	○
Current value	A	19.2	19.7	The transparency		Tone	-	Water white transparency	Water white transparency
Mist degree	-	5.4	12.2			Tone	-	Water white transparency	Water white transparency
Mist degree	-	5.4	12.2		Appendix			Add PTFE	Use the premixture of A and B

The foregoing description can illustrate the following fact.Flame-retardant aromatic polycarbonate resin composition of the present invention is when stamping literal and sign by the laser lettering, the sharpness height of literal and sign, and by adding silicone compounds of the present invention, prolonged catch fire after to the time that produces drip, the anti-drip performance of resin is also fine during burning.

Can also further specify the following fact.The transparency of transparent flame-retarding aromatic copolycarbonate resin composition of the present invention, humidity resistance excellence.And by add silicone compounds of the present invention, prolonged catch fire after to the time that produces drip, the anti-anti-drop property of resin is also fine during burning.Particularly when the polymerization degree of silicone compounds satisfies prescribed condition, can obtain the excellent transparency and anti-anti-drop property.

[embodiment 45]

Use the particulate material of embodiment 39,120 ℃ through hot air circular drying machine after dry 5 hours, with the front portion sheet material being installed is that the single screw extrusion machine of φ 40mm is extruded with the diameter of T shape head, screw speed is 40rpm, by the casting roller of contact head face, extrude the sheet material that obtains 100 μ m.This sheet material transparent fabulous, the surface smoothing excellence.This sheet material is cut into the moulding product that are of a size of 50mm * 50mm, these sheet forming product are put in the dc magnetron sputtering device.Laminated in order metal oxide layer 40nm, silver and gold alloy layer 9nm, this metal oxide layer 40nm that is made of indium and tin-oxide makes the transparent conductivity sheet material.

Claims

1. flame-retardant aromatic polycarbonate resin composition, composition comprises:

(1) as resinous principle 100 weight parts of A composition, comprise A-1 component aromatic adoption carbonate resin 50～100 weight %, A-2 composition phenylethylene resin series 0～50 weight % and A-3 component aromatic adoption ester resin 0～50 weight %,

(2) as at least a above silicone compounds 0.1～10 weight part with respect to per 100 parts by weight resin components matching of B composition, this silicone compounds is the silicone compounds that contains Si-H base and aryl in the molecule, wherein

1. the content that is called the Si-H base of Si-H amount is 0.1～1.2mol/100g,

2. being called the aryl content ratio shown in the following general formula (1) of aryl amount is 10～70 weight %,

In the formula (1), X represents that independently of one another OH base, carbon number are 1～20 the organic residue of monovalence, and n represents 0～5 integer,

3. be selected from the silicone compounds that contains at least a above structural unit among the structural unit shown in following general formula (2) and (3),

In formula (2) and (3), Z ¹～Z ³Represent that independently of one another hydrogen atom, carbon number are 1～20 organic residue of monovalence or the compound shown in the following general formula (4); α 1～α 3 is separately independently, represents 0 or 1 respectively; M1 represents 0 or be integer more than 1;

In the formula (4), Z ⁴～Z ⁸Represent that independently of one another hydrogen atom, carbon number are 1～20 the organic residue of monovalence; α 4～α 8 is separately independently, represents 0 or 1 respectively; M2 represents the integer more than 0 or 1.

2. flame-retardant aromatic polycarbonate resin composition according to claim 1, wherein, in following formula (1), when n is 2 when above, X differs from one another.

3. flame-retardant aromatic polycarbonate resin composition according to claim 1, wherein, in following formula (2), when m1 is 2 when above, repeating unit is chosen mutually different multiple repeating unit.

4. flame-retardant aromatic polycarbonate resin composition according to claim 1, wherein, in following formula (4), when m2 is 2 when above, repeating unit is chosen the multiple heavy again unit that has nothing in common with each other.

5. flame-retardant aromatic polycarbonate resin composition according to claim 1, wherein, the mean polymerisation degree of this B composition silicone compounds is 3～150.

6. flame-retardant aromatic polycarbonate resin composition according to claim 1, wherein, the Si-H base unit weight that this B composition silicone compounds is contained, promptly the Si-H amount is 0.2～1.0mol/100g.

7. flame-retardant aromatic polycarbonate resin composition according to claim 1, wherein, the aryl amount of this B composition silicone compounds is 15～60 weight %.

8. flame-retardant aromatic polycarbonate resin composition according to claim 1, wherein, the specific refractory power of this B composition silicone compounds in the time of 25 ℃ is 1.40～1.60.

9. flame-retardant aromatic polycarbonate resin composition according to claim 1, wherein, this B composition silicone compounds is the silicone compounds that is made of MD unit or MDT unit, wherein, M represents that single functionality siloxane unit, D represent that difunctionality siloxane unit, T represent the three-functionality-degree siloxane unit.

10. flame-retardant aromatic polycarbonate resin composition according to claim 1, wherein, with respect to these A composition resinous principle 100 weight parts, also contain as the C composition from free radical generating agent, organic alkali metal salt and organic alkali earth metal salt, select at least a more than compound 0.001～0.3 weight part.

11. flame-retardant aromatic polycarbonate resin composition according to claim 1 wherein, with respect to these A composition resinous principle 100 weight parts, also contains weighting agent 1～100 weight part as the D composition.

12. flame-retardant aromatic polycarbonate resin composition according to claim 1, wherein, this A composition resinous principle is made up of A-1 component aromatic adoption carbonate resin 50～99.5 weight %, A-2 composition phenylethylene resin series 0～50 weight % and/or A-3 component aromatic adoption ester resin 0～50 weight %, and the total amount of A-2 composition and A-3 composition is 0.5～50 weight %.

13. flame-retardant aromatic polycarbonate resin composition according to claim 1 wherein, is substantially devoid of halogenide as fire retardant.

14. flame-retardant aromatic polycarbonate resin composition according to claim 1, described composition is the transparent flame-retarding aromatic copolycarbonate resin composition, it contains relative 100 weight part A-1 component aromatic adoption carbonate resins, at least a above silicone compounds 0.1～10 weight part as the B composition, this silicone compounds is the silicone compounds that contains Si～H base and aryl in the molecule, wherein

1. the Si-H base content that is called Si-H amount be 0.1～1.2mol/100g and

2. be called containing of the aryl shown in the following general formula (1) of aryl amount proportional be 10～70 weight %,

In the formula (1), X represents that independently of one another OH base, carbon number are 1～20 the organic residue of monovalence; N represents 0～5 integer;

In formula (2) and (3), Z ¹～Z ³Represent that independently of one another hydrogen atom, carbon number are that 1～20 monovalence has the compound shown in basic residue or the following general formula (4); α 1～α 3 is separately independently, represents 0 or 1 respectively; M1 represents 0 or be integer more than 1;

15. flame-retardant aromatic polycarbonate resin composition according to claim 14, wherein, in following formula (1), when n is 2 when above, X differs from one another.

16. flame-retardant aromatic polycarbonate resin composition according to claim 14, wherein, in following formula (2), when m1 is 2 when above, repeating unit is chosen mutually different multiple repeating unit.

17. flame-retardant aromatic polycarbonate resin composition according to claim 14, wherein, in following formula (4), when m2 is 2 when above, repeating unit is chosen and is equipped with multiple heavy again unit inequality.

18. flame-retardant aromatic polycarbonate resin composition according to claim 14, wherein, the mean polymerisation degree of this B composition silicone compounds is 3～80.

19. flame-retardant aromatic polycarbonate resin composition according to claim 14, wherein, the Si-H base unit weight that this B composition silicone compounds is contained, promptly the Si-H amount is 0.2～1.0mol/100g.

20. flame-retardant aromatic polycarbonate resin composition according to claim 14, wherein, the aryl amount of this B composition silicone compounds is 15～60 weight %.

21. flame-retardant aromatic polycarbonate resin composition according to claim 14, wherein, the mean polymerisation degree of this B composition silicone compounds is 3～60.

22. flame-retardant aromatic polycarbonate resin composition according to claim 14, wherein, the specific refractory power of this B composition silicone compounds in the time of 25 ℃ is 1.40～1.60.

23. flame-retardant aromatic polycarbonate resin composition according to claim 14, wherein, this B composition silicone compounds is the silicone compounds that is made of MD unit or MDT unit, wherein, M is that single functionality siloxane unit, D are that difunctionality siloxane unit, T are the three-functionality-degree siloxane unit.

24. flame-retardant aromatic polycarbonate resin composition according to claim 14 wherein, is 0.3～20% with the thick haze value of the 2mm of JIS K7105 standard test.

25. flame-retardant aromatic polycarbonate resin composition according to claim 14, wherein, in temperature: 65 ℃, humidity: placing under 85% the environment after 300 hours, is 0.01～10% with the thick haze value of the 2mm of JIS K7105 standard test with the initial poor Δ H of haze value.

26. flame-retardant aromatic polycarbonate resin composition according to claim 14, wherein, with respect to A-1 component aromatic adoption carbonate resin 100 weight parts, cooperate at least a above compound 0.001～0.3 weight part in free radical generating agent, organic alkali metal salt and the organic alkali earth metal salt of being selected from again as the C composition.

27. flame-retardant aromatic polycarbonate resin composition according to claim 11 wherein, is substantially devoid of halogenide as fire retardant.

28. moulding product are made with claim 1 or the described aromatic copolycarbonate resin composition of claim 14.

29. a clear sheet is made by the described aromatic copolycarbonate resin composition of claim 14.