CN102875988A

CN102875988A - Excellent-appearance molded product consisting of aromatic polycarbonate resin composition

Info

Publication number: CN102875988A
Application number: CN2011102017766A
Authority: CN
Inventors: 田中勉; 竹尾充浩; 华国飞; 孟庆民
Original assignee: DIREN HUACHENG COMPOUND PLASTIC (SHANGHAI) Co Ltd; Teijin Chemicals Ltd
Current assignee: DIREN HUACHENG COMPOUND PLASTIC (SHANGHAI) Co Ltd; Teijin Ltd
Priority date: 2011-07-14
Filing date: 2011-07-14
Publication date: 2013-01-16

Abstract

The invention relates to an excellent-appearance molded product consisting of an aromatic polycarbonate resin composition. The invention is characterized in that based on a fact that aromatic polycarbonate resin (a component A) and a grafted copolymer (a component B) which is prepared through graft copolymerization of vinyl cyanide monomer, aromatic vinyl monomer and rubber polymer are 100 weight parts in total, the aromatic polycarbonate resin composition comprises 0.1 to 20 weight parts of polymer (a component C) prepared by copolymerizing (methyl) acrylic acid alkyl ester monomer or a mixture of (methyl) acrylic acid alkyl ester monomer and monomers capable of being copolymerized with the (methyl) acrylic acid alkyl ester monomer by an emulsion polymerization method in the presence of a rubber component, wherein the polymer comprises 0 to 50ppm sodium and 100-1,000ppm phosphorus; and a mold temperature during molding and the glass transition temperature (Tg) of the resin composition meet the condition of a formula 1, namely the mold temperature (DEG C) is more than or equal to (Tg-30) and less than or equal to (Tg+50...).

Description

The products formed that is consisted of by aromatic copolycarbonate resin composition of outward appearance excellence

Technical field

The present invention relates to by will carrying out the products formed that outward appearance that injection-molded moulding obtains is enhanced with die material by aromatic polycarbonate resin, graft copolymer, the resin combination that the rubber acrylic acid polymer consists of of containing with specific remaining amount of metal, described graft copolymer is made of rubber polymer and vinyl cyanide monomer and aromatic vinyl monomer.More specifically, the present invention relates to contain the rubber acrylic acid polymer by what cooperation had a specific remaining amount of metal, improved the white vaporific bad outward appearance that when carrying out injection-molded moulding with die material, produces, and also excellent products formed of humidity resistance, thermostability, the mechanical characteristics take the face shock strength as representative.

Background technology

The polymer alloy of aromatic polycarbonate resin and the graft copolymer take ABS resin as representative is owing to balanced excellent be widely used in business automation equipment (OA equipment) field, electronic electric equipment field and the automotive field etc. of forming process, mechanical properties.In recent years, in the measure for Reduction of the environment load, centered by the purposes such as business automation equipment, family electrical article, automobile, the research plastic molded article without application.Wherein, even in the goods that the individual such as flat-panel monitor, notebook computer also uses, in order to improve its appearance design, also require high gloss, case material that weldless exterior quality is high.

Before known for without application obtain the high products formed of high gloss and weldless exterior quality, having developed and having made die temperature is the die material method of forming that high temperature carries out moulding, adapts to polycarbonate-based resin.For example, propose by using heating medium and heat-eliminating medium control die temperature, the alloy material of glass fiber-reinforced polycarbonate resin, polycarbonate resin and ABS resin is carried out the die material moulding, obtain having the products formed (patent documentation 1, patent documentation 2) of non-filler emersion, weldless high-quality outward appearance.In addition, in other documents, disclose the polycarbonate resin of weighting material reinforcement and the alloy material of ABS resin have been carried out being provided with at die surface the die material moulding of thermal insulation layer, obtained high gloss, weldless products formed (patent documentation 3).Yet, although aforesaid forming method can obtain high gloss, weldless outward appearance concerning major part forms, yet, if in the alloy material of polycarbonate resin and ABS resin, be combined with the composition of the acrylic acid polymer that contains rubber for the improvement shock strength, then have to produce in vain vaporific bad, the problem that can not obtain the products formed of high-quality outward appearance on products formed surface portion ground.

On the other hand, for the material of the implementations such as flat-panel monitor, notebook computer without the parts of application, there is not application to make it further require humidity resistance excellent.

Improvement about the humidity resistance of the alloy material of this polycarbonate resin and ABS resin, can enumerate the method (patent documentation 4) of using the few ABS of specific basic metal amount, the method (patent documentation 5) of adding the few rubber constituent of specific basic metal amount, but there is following problems: if carry out the die material moulding, no matter it is white vaporific bad then to use which kind of composition all to produce on products formed surface portion ground, can not obtain the products formed of high-quality outward appearance.

As mentioned above, either method does not all have open to the resin combination about being made of graft copolymers such as aromatic polycarbonate resin, ABS resin, obtains high gloss, no-welding-seam and not white vaporific bad high-quality outward appearance and the effectively cognition of products formed of humidity resistance excellence.

The prior art document

Patent documentation

Patent documentation 1: Japanese kokai publication hei 10-100216 communique

Patent documentation 2: TOHKEMY 2001-150506 communique

Patent documentation 3: TOHKEMY 2002-275275 communique

Patent documentation 4: TOHKEMY 2000-19186 communique

Patent documentation 5: TOHKEMY 2003-171548 communique

Summary of the invention

In view of the foregoing, the object of the present invention is to provide and keep original humidity resistance, thermostability, and face shock strength and so on mechanical characteristics, do not have white vaporific bad order, a high gloss and the products formed that is made of aromatic copolycarbonate resin composition of high-quality outward appearance is arranged simultaneously.

The inventor is repeatedly attentively research in order to reach above-mentioned purpose, found that by collaboration the aromatic copolycarbonate resin composition of the acrylic acid polymer that contains rubber with specific remaining amount of metal, can reach this purpose, further the present invention has been finished in wholwe-hearted research.

According to the present invention, above-mentioned problem can realize by following aromatic copolycarbonate resin composition is carried out the finished product that injection-molded moulding obtains under the condition of molding of the condition that satisfies following formula (1), in the described aromatic copolycarbonate resin composition, with respect to (A) aromatic polycarbonate resin (A composition) 10～95 weight parts, (B) make vinyl cyanide monomer and aromatic vinyl monomer and rubber polymer graft copolymerization and total 100 weight parts of graft copolymer (B composition) 5～90 weight parts that obtain, contain (C) rubber modified polymers (C composition) 0.1～20 weight part, described rubber modified polymers (C composition) is with (methyl) alkyl acrylate monomer in the presence of rubber constituent, perhaps (methyl) alkyl acrylate monomer and can obtain by the emulsion polymerization copolymerization with the mixture of the monomer of its copolymerization, and sodium content is 0～50ppm, and phosphorus content is 100～1000ppm.

Tg-30≤die temperature (℃)≤Tg+50 ... (1)

(in the formula, Tg is the second-order transition temperature of aromatic copolycarbonate resin composition.)

Wherein, the rubber constituent of C composition is preferably divinyl.

Above-mentioned products formed is the resin combination that contains (E) fluorine-containing anti-dripping agent (E composition) of (D) organic phosphorus flame retardant (D composition) that total 100 weight parts with respect to A composition and B composition are 3～30 weight parts and 0.01～2 weight part by making resin combination, realizes the products formed of excellent in flame retardance.

And then above-mentioned resin combination preferred resin composition is that total 100 weight parts that contain with respect to A composition and B composition are the resin combination of (F) inorganic filling material (F composition) of 0.1～50 weight part.As inorganic filling material, preferably use the packing materials such as talcum, wollastonite, mica, glass fibre, carbon fiber, glass flake.Wherein, particularly preferably be silicate minerals, particularly preferably talcum, wollastonite and mica.Talcum, wollastonite and mica can be realized the good resin combination of rigidity when suppressing impact strength decreased.

Below, further specify details of the present invention.

(A composition: aromatic polycarbonate resin)

Aromatic polycarbonate resin of the present invention (A composition) obtains dihydric phenol and carbonate precursor reaction.As reaction method, can enumerate solid phase ester-interchange method, and the ring-opening polymerization method of cyclic carbonate compound etc. of interface polycondensation, melt transesterification process, carbonic ether prepolymer.

As the typical example of dihydric phenol as used herein, can enumerate Resorcinol, Resorcinol, 4,4 '-xenol, 1, two (4-hydroxy phenyl) ethane of 1-, 2, two (4-hydroxy phenyl) propane (being commonly called as dihydroxyphenyl propane) of 2-, 2, two (the 4-hydroxy-3-methyl phenyl) propane of 2-, 2, two (4-hydroxy phenyl) butane of 2-, 1, two (4-the hydroxy phenyl)-1-diphenylphosphino ethanes of 1-, 1, the 1-bis(4-hydroxyphenyl) cyclohexane, 1, two (the 4-hydroxy phenyls)-3 of 1-, 3, the 5-trimethyl-cyclohexane, 2, two (4-hydroxy phenyl) pentanes of 2-, 4,4 '-(to the phenylene diisopropylidene) xenol, 4,4 '-(metaphenylene diisopropylidene) xenol, 1, two (4-the hydroxy phenyl)-4-normenthanes of 1-, two (4-hydroxy phenyl) ether, two (4-hydroxy phenyl) thioether, two (4-hydroxy phenyl) sulfoxide, two (4-hydroxy phenyl) sulfone, two (4-hydroxy phenyl) ketone, two (4-hydroxy phenyl) ester, two (4-hydroxy-3-methyl phenyl) thioether, 9, two (4-hydroxy phenyl) fluorenes of 9-and two (the 4-hydroxy-3-methyl phenyl) fluorenes of 9,9-etc.Preferred dihydric phenol is two (4-hydroxy phenyl) alkanes, and wherein, from the aspect of tenacity excellent, dihydroxyphenyl propane (following sometimes referred to as " BPA ") particularly preferably, obtains general.

In the present invention, except the dihydroxyphenyl propane as general polycarbonate is polycarbonate, also the special polycarbonate made from other dihydric phenols can be used as the A composition.

For example, as part or all of dihydric phenol composition, use 4,4 '-(metaphenylene diisopropylidene) xenol (following sometimes referred to as " BPM "), 1, the 1-bis(4-hydroxyphenyl) cyclohexane, 1, two (the 4-hydroxy phenyls)-3 of 1-, 3,5-trimethyl-cyclohexane (following sometimes referred to as " Bis-TMC "), 9, the polycarbonate (homopolymer or multipolymer) of two (4-hydroxy phenyl) fluorenes of 9-and two (the 4-hydroxy-3-methyl phenyl) fluorenes (following sometimes referred to as " BCF ") of 9,9-is suitable for the dimensional change that suction is caused, the purposes that the requirement of morphological stability is strict especially.The usage quantity of the dihydric phenol beyond the above-mentioned BPA is preferably more than the 5mol% of the dihydric phenol composition integral body that consists of this polycarbonate, is particularly preferably more than the 10mol%.

When especially requiring high rigidity and better hydrolytic resistance, the A composition that particularly preferably consists of resin combination is the copolymerization polycarbonate of following (1)～(3).

(1) consists of in 100 % by mole of the dihydric phenol compositions of this polycarbonate, BPM is 20～80 % by mole (more preferably 40～75 % by mole, more preferably 45～65 % by mole) and BCF be the copolymerization polycarbonate of 20～80 % by mole (more preferably 25～60 % by mole, more preferably 35～55 % by mole).

(2) consist of in 100 % by mole of the dihydric phenol compositions of this polycarbonate, BPA is 10～95 % by mole (more preferably 50～90 % by mole, more preferably 60～85 % by mole) and BCF be the copolymerization polycarbonate of 5～90 % by mole (more preferably 10～50 % by mole, more preferably 15～40 % by mole).

(3) consist of in 100 % by mole of the dihydric phenol compositions of this polycarbonate, BPM is 20～80 % by mole (more preferably 40～75 % by mole, more preferably 45～65 % by mole) and Bis-TMC be the copolymerization polycarbonate of 20～80 % by mole (more preferably 25～60 % by mole, more preferably 35～55 % by mole).

These special polycarbonate can use separately, also can use suitably mixing more than 2 kinds.In addition, also they can be mixed use with general bisphenol A polycarbonate.

About method for making and the characteristic of these special polycarbonate, at length be recorded in such as in Japanese kokai publication hei 6-172508 communique, Japanese kokai publication hei 8-27370 communique, TOHKEMY 2001-55435 communique and the TOHKEMY 2002-117580 communique etc.

In addition, in above-mentioned various polycarbonate, adjust copolymerization composition etc. and make water-intake rate and the polycarbonate of Tg (second-order transition temperature) in following ranges because the hydrolytic resistance of polymkeric substance self is good, and also especially excellent aspect the low bendability after moulding, therefore be particularly suitable for the field of requirement morphological stability.

(i) water-intake rate be 0.05～0.15%, be preferably 0.06～0.13% and Tg be 120～180 ℃ polycarbonate, perhaps

(ii) Tg is 160～250 ℃, to be preferably 170～230 ℃ and water-intake rate be 0.10～0.30%, be preferably 0.13～0.30%, more preferably 0.14～0.27% polycarbonate.

Herein, the water-intake rate of polycarbonate is for using diameter to be 45mm, the thickness discoideus test film as 3.0mm, is determined at the value of flooding the moisture rate after 24 hours in 23 ℃ the water according to ISO62-1980.In addition, Tg (second-order transition temperature) is for measuring the value of trying to achieve by the differential scanning calorimeter (DSC) according to JIS K7121.

As carbonate precursor, use carbonylic halide, carbonic diester or haloformate etc., can enumerate particularly the bishaloformate of phosgene, diphenyl carbonate or dihydric phenol etc.

When above-mentioned dihydric phenol and carbonate precursor are made polycarbonate resin by interfacial polymerization, can use as required catalyzer, terminator, be used for preventing the antioxidant of dihydric phenol oxidation etc.In addition, the polyestercarbonate resin that polycarbonate resin of the present invention comprises branched polycarbonate resin that the multifunctional aromatics copolymerization more than the trifunctional is formed, form two functional carboxylic acid copolymerization of aromatic series or aliphatics (comprising ester ring type), with the two functional alcohol copolymerized panlite that (comprising ester ring type), copolymerization formed, and the polyestercarbonate resin that this two functional carboxylic acid and two functional alcohol together copolymerization are formed.In addition, can be the polycarbonate that will obtain mix the mixture that forms more than 2 kinds.

Branched polycarbonate resin increases the melting tension force of resin combination of the present invention, can improve forming process in extrusion molding, foaming and blow molding based on this characteristic.The result can access the more excellent products formed that utilizes these methods of forming to form of dimensional precision.

As the multifunctional aromatics more than the trifunctional that in this branched polycarbonate resin, uses, preferably illustration has 4,6-dimethyl-2,4,6-three (4-hydroxy phenyl) heptene-2,2,4,6-trimethylammonium-2,4,6-three (4-hydroxy phenyl) heptane, 1,3,5-three (4-hydroxy phenyl) benzene, 1,1,1-three (4-hydroxy phenyl) ethane, 1,1,1-three (3,5-dimethyl-4-hydroxy phenyl) ethane, two (2-hydroxy-5-methyl base the benzyl)-4-methylphenols of 2,6-, and 4-[4-[1, two (4-hydroxy phenyl) ethyls of 1-] benzene]-triphenols such as alpha, alpha-dimethylbenzyl phenol.In addition, as multifunctional aromatics, illustration has Phloroglucinol, Gen Pi Portugal phenol, four (4-hydroxy phenyl) methane, two (2, the 4-dihydroxy phenyl) ketone, 1, two (4, the 4-dihydroxyl trityl group) benzene of 4-and trimellitic acid, pyromellitic acid, benzophenone tetracarboxylic acid and these sour acyl chlorides etc.Wherein, preferred 1,1,1-three (4-hydroxy phenyl) ethane and 1,1,1-three (3,5-dimethyl-4-hydroxy phenyl) ethane, particularly preferably 1,1,1-three (4-hydroxy phenyl) ethane.

The structural unit of being derived by the multifunctional aromatics in the branched polycarbonate resin, in 100 % by mole of the totals of the structural unit of being derived by dihydric phenol and the structural unit that multifunctional aromatics is derived by this, be preferably 0.03～1 % by mole, more preferably 0.07～0.7 % by mole, be particularly preferably 0.1～0.4 % by mole.

In addition, not only can be derived by multifunctional aromatics in this branched structure unit, do not use multifunctional aromatics and derive the side reaction in the time of also can be such as melting state transesterification reaction to obtain.Should illustrate, for the ratio of this branched structure, can pass through ¹H-NMR measures and calculates.

On the other hand, aliphatic two functional carboxylic acid are preferably α, alpha, omega-dicarboxylic acid, as its concrete example, can enumerate the alicyclic dicarboxylic acids such as the straight chain saturated aliphatic dicarboxylic acids such as sebacic acid (decanedioic acid), dodecanedioic acid, tetradecane diacid, octadecane diacid, octadecane dicarboxylic acid and cyclohexane dicarboxylic acid.As two functional alcohol, preferred alicyclic diol, for example, but illustration cyclohexanedimethanol, cyclohexane diol, tristane dimethanol etc.And then, also can use the polycarbonate poly organo alkyl copolymer that forms with the polyorganosiloxane units copolymerization.

A composition also that the dihydric phenol composition is different polycarbonate, the polycarbonate that contains the branching composition, various polyestercarbonate, polycarbonate poly organo alkyl copolymer etc. mixes the composition that forms more than 2 kinds.And then, also can use the polycarbonate that manufacturing process is different, the different compositions that mixing forms more than 2 kinds such as polycarbonate of terminator.

Utilize the reaction of interface polycondensation to be generally the reaction of dihydric phenol and phosgene, make it in the presence of acid binding agent and organic solvent, to react.As acid binding agent, use the amine compound such as alkali metal hydroxides such as sodium hydroxide, potassium hydroxide or pyridine.As organic solvent, use the halohydrocarbon such as methylene dichloride, chlorobenzene.In addition, in order to promote reaction, also can use triethylamine, four-normal-butyl bromination ammonium, four-normal-butyl bromination

In tertiary amine, quaternary ammonium compound, season

The catalyzer such as compound.Usually preferable reaction temperature is that 0～40 ℃, reaction times are 10 minutes～5 hours, and the pH in the reaction preferably remains on more than 9.

In addition, in this polyreaction, usually use terminator.As this terminator, can use the simple function phenols.As the concrete example of simple function phenols, preferably use the monofunctional phenol class.As this monofunctional phenol class, preferred phenol, p-tert-butylphenol, to cumyl phenol etc., in addition, also can enumerate decyl phenol, dodecyl phenol, tetradecyl phenol, hexadecyl phenol, octadecyl phenol, eicosyl phenol, docosyl phenol, triacontyl phenol etc.These terminators can use separately, also can be also with more than 2 kinds.

Utilize the reaction of melt transesterification process to be the transesterification reaction of dihydric phenol and carbonic ether, usually, undertaken by following method: Yi Bian in the presence of rare gas element, heat dihydric phenol and carbonic ether, Yi Bian mix, the alcohol of generation or phenol are distillated.Temperature of reaction is according to the alcohol that generates or the boiling point of phenol etc. and different, but is roughly 120～350 ℃ scope.In the reaction later stage reaction system is decompressed to about 1.33 * 103～13.3Pa, the alcohol of generation or phenol are distillated easily.Reaction times was generally about 1～4 hour.

As carbonic ether, can enumerate that can to have substituent carbonatoms be that 6～10 aryl, aralkyl or carbonatoms are the ester of 1～4 alkyl etc., wherein preferred diphenyl carbonate.

In reaction, polymerizing catalyst can be used, for example, the alkali metal compound such as sodium salt, sylvite of sodium hydroxide, potassium hydroxide, dihydric phenol can be used; The alkaline earth metal compounds such as calcium hydroxide, hydrated barta, magnesium hydroxide; The nitrogenous basic cpds such as Tetramethylammonium hydroxide, tetraethyl ammonium hydroxide, Trimethylamine, triethylamine; Deng catalyzer.And then organic acid salt, boron compound class, germanium compound class, antimony compounds class, titanium compound class, zirconium compounds class that can use pure salt, alkali (soil) metal of alkali (soil) metal etc. is generally used for the catalyzer of esterification, transesterification reaction.These catalyzer can use separately, and also use capable of being combined is more than 2 kinds.The usage quantity of polymerizing catalyst is 1 * 10 with respect to 1 mole of raw material dihydric phenol usually ^-9～1 * 10 ^-5Equivalent, more preferably 1 * 10 ^-8～5 * 10 ^-6The scope of equivalent.

In melt transesterification process, in order to reduce the phenol end group in the resulting polymers, can after the later stage or end of polycondensation, add the compounds such as 2-chloro-phenyl-carbonic acid phenyl ester, 2-methoxycarbonyl phenyl-carbonic acid phenyl ester, 2-ethoxy carbonyl phenyl-carbonic acid phenyl ester.In addition, in melt transesterification process, preferably use the deactivator of catalyst neutralisation activity.With respect to 1 mole of remaining catalyzer, the usage quantity of this deactivator is preferably 0.5～50 mole ratio.With respect to the aromatic copolycarbonate after the polymerization, usage ratio is preferably 0.01～500ppm, more preferably 0.01～300ppm, 0.01～100ppm more preferably.As preferred deactivator, can enumerate the Witco 1298 Soft Acid tetrabutyl

Salt etc.

The ammonium salts such as salt, dodecylbenzyl sulfuric acid tetraethyl ammonium.

As the aromatic copolycarbonate of A composition of the present invention, not only can use fresh feed, also can use the polycarbonate resin that is obtained by used goods regeneration, i.e. the so-called aromatic copolycarbonate that obtains through material regeneration.As used goods, preferably enumerate take sound-proof wall, glass port, light-transmitting roof material, and automobile sunshade awning top etc. as the container such as transparent component, the water bottles such as various covering materials (glazing material), windscreen or car headlamp lens (head lamp lens) of representative and optical recording medium etc.These goods do not contain a large amount of additives, other resin etc., stably obtain easily target quality.Particularly therefore car headlamp lens, optical recording medium etc. can be used as optimal way and enumerate owing to satisfy the more preferably condition of above-mentioned viscosity-average molecular weight.Should illustrate that above-mentioned fresh feed refers to the raw material that not yet uses in market after it is made.

The viscosity-average molecular weight of aromatic copolycarbonate is preferably 10,000～50, and 000, more preferably 14,000～30,000, more preferably 18,000～25,000.18,000～25, in 000 the scope, good shock-resistance is with mobile and deposit excellent especially.Most preferably be 21,000～24,000.Should illustrate, as long as satisfy this viscosity-average molecular weight as A composition integral body, comprise the A composition that satisfies this scope by the different mixture more than 2 kinds of molecular weight.

Viscosity-average molecular weight of the present invention is following to be obtained: at first, use ostwald's viscometer, try to achieve the specific viscosity of calculating according to following formula by the 0.7g aromatic copolycarbonate is dissolved in the solution that obtains in the 100ml methylene dichloride in 20 ℃,

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

[t ₀Be the number of seconds that falls of methylene dichloride, t is the number of seconds that falls of sample solution]

With the specific viscosity substitution following formula of trying to achieve, try to achieve viscosity-average molecular weight M.

η _Sp/ c=[η]+0.45 * [η] ²C (wherein, [η] is limiting viscosity)

[η]＝1.23×10 ^-4M ^0.83

c＝0.7

(B composition: graft copolymer)

As the graft copolymer of the B composition among the present invention graft copolymer for vinyl cyanide compound and aromatic ethenyl compound and rubber polymer graft copolymerization are formed, also can contain the multipolymer of this graft copolymer, vinyl cyanide compound and aromatic ethenyl compound.

In addition, the secondary multipolymer that the generates when multipolymer of this vinyl cyanide compound and aromatic ethenyl compound also can be vinyl cyanide compound and aromatic ethenyl compound and rubber polymer graft copolymerization, also can be fusion has aromatic ethenyl compound and vinyl cyanide compound separately copolymerization and the multipolymer of the vinyl compound copolymer that obtains.

Rubber polymer of the present invention can be enumerated polyhutadiene, diene interpolymer (for example, vinylbenzene. the random copolymers of divinyl and segmented copolymer, acrylonitrile butadiene copolymer, and the multipolymer of (methyl) alkyl acrylate and divinyl etc.), polyisoprene, the multipolymer of ethene and alpha-olefin (for example, the random copolymers of ethylene, propylene and segmented copolymer, the random copolymers of ethylene butene and segmented copolymer etc.), the multipolymer of ethene and esters of unsaturated carboxylic acids (ethylene methyl acrylate copolymer for example, and the ethylene butyl acrylate multipolymer etc.), the multipolymer of ethene and aliphatic ethylene based compound (for example, ethene vinyl-acetic ester multipolymer etc.), the ter-polymers of ethene and propylene and non-conjugated diene (for example, the multipolymer of ethylene, propylene hexadiene etc.), acrylic rubber (for example, butyl polyacrylate, poly-(2-EHA), and the multipolymer of butyl acrylate and 2-EHA etc.), and silicon be rubber (for example, organopolysiloxane rubber, by the IPN type rubber of organopolysiloxane rubber constituent with poly-(methyl) alkyl acrylate rubber constituent formation, the rubber that namely has the structure that two kinds of rubber constituents twine mutually in indissociable mode, and the IPN type rubber that is consisted of by organopolysiloxane rubber constituent and polyisobutylene rubber composition etc.).Wherein, the more preferably ter-polymers of the easier polyhutadiene that manifests of its effect, diene interpolymer, polyisoprene, acrylic resin, ethene and propylene and non-conjugated diene, wherein, particularly preferably polyhutadiene, diene interpolymer.

The preferable range of the weight average particle diameter of the rubber grain of this rubber polymer is the scope of preferred 0.20～2.0 μ m, and more preferably 0.25～1.5 μ m is particularly preferably 0.28～1.3 μ m.If the weight average particle diameter of rubber grain is less than 0.2 μ m, the modified impact effect of then adding the graft polymerization deposits yields descends, and is not preferred.In addition, then poor with the dispersion state of polycarbonate resin if surpass 2.0 μ m, cause and impact lower degradation, therefore not preferred.

The weight average particle diameter of this rubber grain is the value of measuring with transmission electron microscope.Particularly, measure with the rubbery polymer that drips emulsion state on the net at transmission electron microscope, dye with the steam of perosmic anhydride or ruthenium tetroxide.Then with transmission electron microscope (FEI Co.'s system, TECNAI G2, acceleration voltage 120kv) takes the sample of the rubbery polymer be colored, calculate weight average particle diameter with image processing software (Nexus NewQube) by 200 rubber grains in the image of shooting.

As vinyl cyanide monomer of the present invention, can enumerate vinyl cyanide, methacrylonitrile etc., particularly preferably vinyl cyanide.

As aromatic vinyl monomer of the present invention, can enumerate vinylbenzene, alpha-methyl styrene, o-methyl styrene, p-methylstyrene, vinyl-dimethyl benzene, ethyl styrene, dimethyl styrene, p-tert-butylstyrene, vinyl naphthalene, methoxy styrene, single bromostyrene, dibromo-benzene ethene, fluorostyrene, tribromo-benzene ethene etc., particularly preferably vinylbenzene.

The multipolymer of vinyl cyanide compound of the present invention and aromatic ethenyl compound preferably uses vinyl cyanide and cinnamic multipolymer, the weight-average molecular weight of this multipolymer is being passed through GPC (gel permeation chromatography, gel permeation chromatography) method converts with polystyrene standard and measures in the value that obtains, and is preferably 3.0 * 10 ⁴～2.0 * 10 ⁵Scope, more preferably 6.0 * 10 ⁴～1.4 * 10 ⁵Scope, more preferably 9.0 * 10 ⁴～1.2 * 10 ⁵Scope.

The preferred content of the rubber polymer of graft copolymer of the present invention is the scope of 1～70 % by weight, and more preferably 5～30 % by weight are particularly preferably 10～25 % by weight.If content surpasses 70 % by weight, then mobile improved effect becomes insufficient, and is not preferred.In addition, this rubber mass is during less than 1 % by weight, and the modified impact effect becomes insufficient, and is not preferred.

In addition, be grafted to vinyl cyanide compound on the rubber polymer composition and the ratio (weight of grafting composition is with respect to the ratio of the weight of rubber polymer) of aromatic ethenyl compound, be that percentage of grafting (% by weight) is preferably 20～200%, more preferably 20～80%.

Graft copolymer of the present invention does not specify manufacture method, can preferably use the graftomer that obtains by known polymerization process manufacturings such as emulsion polymerization, mass polymerization, solution polymerization process.

As graft copolymer of the present invention, can enumerate particularly such as ABS resin, AES resin, ASA resin etc., all can easily obtain.More preferably ABS resin wherein.

ABS resin has the forming process for the excellence of thin molded article, also has good shock-resistance.Particularly the combination with polycarbonate resin manifests preferred characteristic.

(C composition: rubber modified polymers)

As the rubber modified polymers of the C composition among the present invention for will (methyl) alkyl acrylate monomer in the presence of rubber constituent or, (methyl) acrylate alkyl ester monomer with can obtain by the emulsion polymerization copolymerization with the mixture of the monomer of its copolymerization, and sodium content is 0～50ppm, and phosphorus content is the polymkeric substance of 100～1000ppm.

Rubber constituent of the present invention is the polymkeric substance with caoutchouc elasticity, as this rubber constituent, can enumerate for example polyhutadiene, polyisoprene, diene interpolymer (for example, the random copolymers of styrene butadiene and segmented copolymer, acrylonitrile butadiene copolymer, and acrylate-butadiene rubber (multipolymer of alkyl acrylate or alkyl methacrylate and divinyl) etc.), the multipolymer of ethene and alpha-olefin (for example, the random copolymers of ethylene, propylene and segmented copolymer, the random copolymers of ethylene butene and segmented copolymer etc.), the multipolymer of ethene and esters of unsaturated carboxylic acids (ethylene methyl acrylate copolymer for example, and the ethylene butyl acrylate multipolymer etc.), the multipolymer of ethene and aliphatic vinyl ester (for example, ethene vinyl-acetic ester multipolymer etc.), the ter-polymers of ethene and propylene and non-conjugated diene (for example, the multipolymer of ethylene, propylene hexadiene etc.), acrylic rubber (for example, butyl polyacrylate, poly-(2-EHA), and the multipolymer of butyl acrylate and 2-EHA etc.), and silicon be rubber (for example, organopolysiloxane rubber, by the IPN type rubber of organopolysiloxane rubber constituent with poly-(methyl) alkyl acrylate rubber constituent formation, the rubber that namely has the structure that two kinds of rubber constituents twine mutually in indissociable mode, and the IPN type rubber that is consisted of by organopolysiloxane rubber constituent and polyisobutene composition etc.).And then, as other rubber constituent, can enumerate urethanes, acid amides rubber, phosphonitrile rubber and fluorine-containing rubber etc.Wherein, preferred polyhutadiene, polyisoprene, diene interpolymer, more preferably polyhutadiene.The second-order transition temperature of rubber constituent is preferably below 10 ℃, more preferably-10 ℃ below, more preferably-30 ℃ below.

The particle diameter of rubber constituent of the present invention is preferably 0.10～0.50 μ m in weight average particle diameter, more preferably 0.15～0.40 μ m, more preferably 0.15～0.35 μ m.If the particle diameter of diene series rubber then be can't see the impact improvement effect less than 0.10 μ m, if surpass 0.50 μ m, cause that then dispersion is bad, cause the decline of outward appearance, shock strength, therefore not preferred.The weight average particle diameter of the rubber particles among the present invention is the value of measuring according to the method identical with the measuring method of the weight average particle diameter of the rubber polymer of B composition, is the value of calculating based on the rubber grain image of taking with transmission electron microscope.

The ratio of the rubber constituent of the rubber modified polymers among the present invention is preferably 40～90 weight parts, more preferably 42～85 weight parts, 45～80 weight parts more preferably in the C composition, relative therewith, the monomer of use or the amount of monomer mixture are preferably following scope: preferred 60～10 mass parts, more preferably 58～15 weight parts, further preferred 55～20 weight parts.In addition, when using monomer mixture, preferably in the summation of monomer mixture, be at least more than 25 % by weight as (methyl) alkyl acrylate monomer that must composition, more preferably more than 40 % by weight.

Can be with the monomer of rubber constituent copolymerization of the present invention (methyl) alkyl acrylate monomer or, (methyl) alkyl acrylate monomer and can with the monomer of its copolymerization, as (methyl) alkyl acrylate monomer, can enumerate methyl methacrylate, β-dimethyl-aminoethylmethacrylate, propyl methacrylate, butyl methacrylate etc., wherein, preferable methyl methyl acrylate, butyl methacrylate.In addition, as can with the monomer of this (methyl) alkyl acrylate monomer copolymerization, can enumerate the alkyl acrylates such as aromatic vinyl monomer, methyl acrylate, ethyl propenoate, propyl acrylate, butyl acrylate, 2-EHA such as vinylbenzene, alpha-methyl styrene, p-methylstyrene, chlorostyrene, dibromo-benzene ethene, tribromo-benzene ethene.Wherein, optimization aromatic vinyl monomer, particularly preferably vinylbenzene.

Above-mentioned vinyl monomer can use respectively a kind of or more than two kinds.

As the rubber modified polymers among the present invention, can enumerate particularly such as MBS resin, MB resin, MABS resin, MAS resin etc., all can easily obtain.Wherein, more preferably MBS resin.

The rubber modified polymers that uses in the present invention by with (methyl) alkyl acrylate monomer or, (methyl) alkyl acrylate and go on foot with the latex one of the rubber constituent of the mixture of other monomer of its copolymerization and above-mentioned formation or the multistep graft polymerization makes.

Should illustrate that monomer or monomer mixture can be once added in graft polymerization itself, one-step polymerization perhaps, also can be divided into monomer or monomer mixture more than 2 times or 2 times and adding, and minute multistep is carried out graft polymerization.

As the method for graft polymerization, use the method for letex polymerization.When carrying out this graft copolymerization, as polymerization starter, can use the persulphates such as Potassium Persulphate, ammonium persulphate, Sodium Persulfate; The organo-peroxides such as tertbutyl peroxide, cumene hydroperoxide, benzoyl peroxide, lauroyl peroxide, hydrogen peroxide diisopropyl benzene; The azo compound such as Diisopropyl azodicarboxylate, 2,2'-Azobis(2,4-dimethylvaleronitrile) etc.In addition, also can be with combinations such as above-mentioned oxidant compound and sulphite, hydrosulphite, thiosulphate, submetallic salt, sodium formaldehyde sulphoxylate, dextroses, as the redox series initiators.

Temperature of reaction in the graft copolymerization can be according to the kind of the polymerization starter that uses, and is for example suitably selecting in 40～80 ℃ the scope.In addition, when letex polymerization, as the emulsifying agent for rubber constituent latex, can suitably use known emulsifying agent.

The gained graft copolymer adds or does not add the additive of suitable antioxidant, as required use etc. in reaction solution, carry out spraying drying (directly powdered); Perhaps in reaction solution, suitably add acid or the condensing agents such as salt such as calcium chloride, sodium-chlor such as sulfuric acid, hydrochloric acid, phosphoric acid, condense, heat-treat again and solidify.Thereafter, through dehydration, clean, final drying and powdered is used.

In addition, the sodium content of the rubber modified polymers among the present invention is that 0～50ppm, phosphorus content are 100～1000ppm, and preferred sodium content is that 1～45ppm, phosphorus content are 120～800ppm, and more preferably sodium content is that 3～40ppm, phosphorus content are 150～600ppm.If sodium content surpasses 50ppm, produce white vaporific bad order when then carrying out injection-molded moulding with die material, not preferred.In addition, if phosphorus content is below the 100ppm, then because thermostability is not enough, produce white vaporific bad order when carrying out injection-molded moulding with die material, undesirable.When phosphorus surpassed 1000ppm, humidity resistance descends, and was undesirable.

Should illustrate, impurity when the sodium of the rubber modified polymers among the present invention is letex polymerization, can carry out acid out by the latex with the rubber constituent after the letex polymerization or saltout and make after the slurries, clean these slurries and remove with paraffinic hydrocarbons series solvents such as pentane, hexane, heptane.

This sodium content is following quantitatively: with mixed solution under 300 ℃ * 2 hour condition the thermal degradation of 0.3g sample with sulfuric acid and nitric acid, then, make inspection liquid with the ultrapure water constant volume, implement quantitatively by the ICP-AES method.

The antioxidant that adds when in addition, the phosphorus of the rubber modified polymers among the present invention depends on polymerization.By after sample being solidified into the tablet shape, measure this phosphorus content with fluorescent x-ray analyzer.

(D composition: organic phosphorus flame retardant)

As organic phosphorus flame retardant of the present invention, the preferably phosphoric acid aromatic ester compound.This phosphate compound is effective to the raising of flame retardant resistance, and phosphate compound has plasticization effect, although therefore thermotolerance descends, is being favourable aspect the forming process of raising resin combination of the present invention.This phosphate compound can use in the past as the known various phosphate compounds of fire retardant, can more preferably enumerate the one kind or two or more phosphate compound of following general formula (1) expression.

(wherein, the X in the above-mentioned formula represents the binary organic group of being derived by dihydric phenol, R ¹¹, R ¹², R ¹³, and R ¹⁴Represent respectively the monobasic organic group of being derived by monohydric phenol, n represents 0～5 integer.)

The phosphate compound of above-mentioned formula (1) can be the mixture of the compound with different n numbers, under the situation of this mixture, the scope of average n number is preferably 0.5～1.5, and more preferably 0.8～1.2, more preferably 0.95～1.15, be particularly preferably 1～1.14.

Preferred concrete example as the dihydric phenol of the above-mentioned X that derives, but illustration Resorcinol, Resorcinol, two (4-hydroxy diphenyl) methane, dihydroxyphenyl propane, dihydroxybiphenyl, dihydroxy naphthlene, two (4-hydroxy phenyl) sulfone, two (4-hydroxy phenyl) ketone, and two (4-hydroxy phenyl) thioethers, wherein, preferred Resorcinol, dihydroxyphenyl propane, and dihydroxybiphenyl.

As the above-mentioned R that derives ¹¹, R ¹², R ¹³, and R ¹⁴The preferred concrete example of monohydric phenol, but illustration phenol, cresols, xylenol, isopropyl-phenol, butylphenol, and to cumyl phenol, wherein, preferred phenol and 2,6-xylenol.

Should illustrate that this monohydric phenol can replace halogen atom, as the concrete example of the phosphate compound with the group of being derived by this monohydric phenol, but illustration tricresyl phosphate (2,4,6-tribromo phenyl) ester and tricresyl phosphate (2,4-dibromo phenyl) ester, tricresyl phosphate (4-bromophenyl) ester etc.

On the other hand, as the concrete example that does not replace the phosphate compound that halogen atom is arranged, preferably phosphoric acid triphenylmethyl methacrylate and tricresyl phosphate (2, the 6-xylyl) the phosplate compound such as ester and with Resorcinol two (two (2, the 6-xylyl) is the phosphoric acid ester oligopolymer of main body phosphoric acid ester), be phosphoric acid ester oligopolymer, and the phosphoric acid ester oligopolymer take dihydroxyphenyl propane pair (diphenyl phosphate) as main body of main body with 4,4-dihydroxyl phenylbenzene two (diphenyl phosphates).

As the use level of organic phosphorus flame retardant, total 100 weight parts with respect to A composition and B composition are preferably 3～30 weight parts, more preferably 3～25 weight parts, more preferably 5～20 weight parts.Content during less than 3 weight part flame retardant resistance not enough, thermotolerance declines to a great extent during greater than 30 weight part, and is therefore not preferred.

In addition, also can and use other fire retardant such as this organic phosphorus flame retardant and organic metal salt flame retardant, silicon-series five-retardant.Concrete example as the organic metal salt flame retardant, preferred potassium perfluorobutane sulfonate salt (large Japanese ink chemical industrial company system, MEGAFAC F-114P (trade(brand)name)), concrete example as silicon-series five-retardant, the organo-siloxane flame retardant (chemical industrial company of SHIN-ETSU HANTOTAI system, X-40-2600J (trade(brand)name)) that preferably contains Si-H base and methyl and phenyl.

Take total 100 weight parts of A composition and B composition as benchmark, the use level of organic metal salt flame retardant, silicon-series five-retardant is preferably 0.005～1 weight part, more preferably 0.01～0.7 weight part, more preferably 0.02～0.5 weight part.

(E composition: fluorine-containing anti-dripping agent)

Melting drippage when the fluorine-containing anti-dripping agent that uses among the present invention is used for preventing from burning further improves flame retardant resistance, and preferred the use has the tetrafluoroethylene that protofibril forms ability.Need to prove that following tetrafluoroethylene simply is called PTFE sometimes.Molecular weight with PTFE of protofibril formation ability has high molecular weight, demonstrates by external actions such as shearing forces PTFE is bonded to each other, becomes fibrous tendency.Its molecular weight is 1,000,000～1,000 ten thousand aspect the number-average molecular weight of being tried to achieve by standard specific gravity, more preferably 2,000,000～9,000,000.This PTFE also can use the PTFE of aqueous liquid dispersion form except solid shape.In addition, improve in order to make this have PTFE dispersiveness in resin that protofibril forms ability, obtain better flame retardant resistance and mechanical characteristics, also can use the PTFE mixture with the form of other mixed with resin.

Have the commercially available product that protofibril forms the PTFE of ability as this, can enumerate the Polyflon MPA FA500 of Teflon (registered trademark) 6J such as Dupont-Mitsui Fluorochemicals company, DAIKIN chemical industrial company and F-201L etc.Typical example as the commercially available product of the aqueous liquid dispersion of PTFE, can enumerate FLUON AD-1, the AD-936 of Asahi-ICI Fluoropolymers company system, Teflon (registered trademark) 30J of FLUON D-1, the D-2 of DAIKIN chemical industrial company system, Dupont-Mitsui Fluorochemicals company system etc.

PTFE as mixed style, can use the mixed style PTFE:(1 that obtains by the following method) aqueous liquid dispersion of PTFE is mixed, carries out co-precipitation with aqueous liquid dispersion or the solution of organic polymer, obtain the method (method of record in Japanese kokai publication sho 60-258263 communique, the Japanese kokai publication sho 63-154744 communique etc.) of common cohesion mixture; The method (method of putting down in writing in the Japanese kokai publication hei 4-272957 communique) of (2) aqueous liquid dispersion of PTFE being mixed with dry organic polymer particle; (3) aqueous liquid dispersion with PTFE evenly mixes with organic polymer particle solution, removes simultaneously the method (method of record in Japanese kokai publication hei 06-220210 communique, the Japanese kokai publication hei 08-188653 communique etc.) of medium separately from this mixture; (4) in the aqueous liquid dispersion of PTFE, will be formed with the method (method of putting down in writing in the Japanese kokai publication hei 9-95583 communique) of the monomer polymerization of organic polymer; And (5) with the aqueous liquid dispersion of PTFE with after the organic polymer dispersion liquid evenly mixes, again with vinyl monomer polymerization in this mixed dispersion liquid, obtain thereafter the method (method of putting down in writing among the Japanese kokai publication hei 11-29679 etc.) of mixture.As the commercially available product of the PTFE of these mixed styles, can enumerate MITSUBISHI RAYON company " METABLEN A3800 " etc.

As the ratio of the PTFE in the mixed style, in PTFE mixture 100 % by weight, PTFE is preferably 1～60 % by weight, more preferably 5～55 % by weight.When the ratio of PTFE is in this scope, can reach the good dispersion of PTFE.

With respect to total 100 weight parts of A composition and B composition, the content of fluorine-containing anti-dripping agent is preferably 0.01～2 weight part, more preferably 0.05～1 weight part, more preferably 0.1～0.6 weight part.Content drips during burning during less than 0.01 weight part, when surpassing 2 weight part, can see forming process decline, and is therefore not preferred.

(F composition: inorganic filling material)

In the present invention, can comprise various inorganic filling materials as the F composition.As this inorganic filling material, can enumerate for example talcum, wollastonite, mica, clay, montmorillonite, terre verte, kaolin, calcium carbonate, glass fibre, granulated glass sphere, glass sphere, milled glass fiber, glass flake, carbon fiber, the kish carbon sheet, the carbon pearl, ground carbon fiber, tinsel, steel fiber, cover metallic glass fiber, cover the metal carbon fiber, cover the metallic glass scale, silicon-dioxide, ceramic particle, ceramic fiber, Ceramic Balls, the aromatic polyamide particle, Kevlar, the polyarylate fiber, graphite, potassium titanate crystal whisker, aluminium borate whisker, the various whiskers such as basic magnesium sulfate etc.Wherein, preferably use the silicate packing materials such as talcum, wollastonite, mica, glass fibre, milled glass fiber.Wherein, particularly preferably be talcum, wollastonite, mica.These strengthen weighting materials can comprise a kind or and with comprising more than 2 kinds.

As preferred wollastonite in the present invention, preferred number average Fibre diameter is the wollastonite of 0.5～5 μ m.This number average Fibre diameter is from the image with observations such as electron micrographs, measures the Fibre diameter of 1000 parts of total of random sampling, calculates its arithmetic mean value and obtains.In addition, long-width ratio L/D (L: number average fiber length, D: the number average Fibre diameter) be preferably more than 5, more preferably more than 6.Should illustrate, number average fiber length can followingly be calculated: by opticmicroscope or electron microscope etc., under the multiplying power of the general image that can roughly fully observe wollastonite, observe wollastonite, with this image input picture resolver, calculate number average fiber length.As image analysis apparatus, can enumerate PIAS-III system such as PIAS company system etc.Wollastonite as using in the present invention is preferably below 2 % by weight in the scorching hot decrement under 1000 ℃, more preferably below 1.5 % by weight, more preferably below 1 % by weight.

And then as preferred talcum in the present invention, can enumerate median size is the following talcums of 5 μ m.And then can enumerate preferred median size is the following talcums of 3 μ m, particularly preferably the following talcum of 2 μ m.As lower limit, can enumerate 0.05 μ m.Herein, the median size of talcum refers to be used as the D50 (median particle diameter of size distribution) that a kind of X-ray transmission method of liquid phase settling process is measured.As the concrete example of the device that carries out this mensuration, can enumerate the Sedigraph5100 of Micromeritics company system etc.

Talcum preferably uses with the form after the granulation.As prilling process, the situation of using tackiness agent and the situation of not using in fact tackiness agent are arranged.More preferably do not use the situation of tackiness agent.As the prilling process of the situation of not using tackiness agent, can enumerate method (such as the method etc. of carrying out on one side roller-type compression at the vacuum state lower pumping on one side with briquetting press etc.), and the method for rolling granulation, cohesion granulation etc. of the compression of bleeding.

Preferred mica in the present invention, can enumerate median size is the Powdered mica of 1～80 μ m.Preferredly enumerate the mica that median size is 2～50 μ m.The value of this median size for measuring by the laser diffraction and scattering method.When median size is 1～80 μ m, give better effect in flame retardant resistance, and owing to the loose condition of differential that also satisfies in the resin, therefore also can keep well humidity resistance.As the thickness of mica, the thickness that can use the practical measurement by electron microscope observation is the mica of 0.01～1 μ m.Preferred thickness is 0.03～3 μ m.Can further carry out surface treatment with silane coupling agent etc. to this mica, and then also the tackiness agents such as epoxy available system, polyurethane series, acrylic acid series carry out granulation, the granulation shape.

When cooperating inorganic filling material, fracture, improve the thermostability of resin combination in order to suppress inorganic filling material, in resin combination of the present invention, can comprise the silane compound of alkylalkoxy silane or alkyl hydrogen silane, carboxyl etc.; Comprise the top coats such as ethylene series wax of the acidic groups such as carboxylic acid anhydride group, sulfonic group with lubricator.

With respect to total 100 weight parts of A composition and B composition, the content of (F) inorganic filling material among the present invention is preferably 0.1～50 weight part, more preferably 0.5～40 weight part, more preferably 1～30 weight part.If this use level less than 0.1 weight part, does not then have the reinforced effects of packing material, if surpass 50 weight parts, then shock strength significantly descends, and is therefore not preferred.

(about the content of each composition)

About the ratio of the A composition in the aromatic copolycarbonate resin composition of the present invention, B composition, take total 100 weight parts of A composition, B composition as benchmark, the A composition is 10～95 weight parts, and the B composition is 5～90 weight parts.The A composition is preferably 50～95 weight parts, 60～93 weight parts more preferably, and the B composition is preferably 5～50 weight parts, more preferably 7～40 weight parts.

When the B composition surpasses 95 weight part less than 5 weight parts or A composition, mobile insufficient, when the B composition surpasses 90 weight parts or A composition less than 10 weight part, thermotolerance, impact strength decreased, not preferred.

With respect to total 100 weight parts of A composition and B composition, the content of C composition is 0.1～20 weight part, is preferably 0.5～15 weight part, more preferably 1～10 weight part.The C composition is during less than 0.1 weight part, and the modified impact effect is insufficient, if surpass 20 weight parts, then thermotolerance, humidity resistance, flame retardant resistance descend, and be therefore not preferred.

(about other additive)

In aromatic copolycarbonate resin composition of the present invention, the molecular weight when making forming process, tone are stable, can use various stablizers, colorant.As this stablizer, can enumerate phosphorus and be stablizer, hindered phenol and be stablizer, UV light absorber, and photostabilizer etc.

(i) phosphorus is stablizer

Be stablizer as phosphorus, but illustration phosphorous acid, phosphoric acid, phosphonous acid, phosphonic acids and their ester and tertiary phosphine etc.

Particularly as bi-ester of phosphite, can enumerate for example triphenyl phosphite, tricresyl phosphite (nonyl phenyl) ester, tridecyl phosphite, the tricresyl phosphite monooctyl ester, tricresyl phosphite (octadecyl) ester, phosphorous acid didecyl monophenyl, phosphorous acid dioctyl monophenyl, phosphorous acid di-isopropyl monophenyl, phosphorous acid monobutyl diphenyl ester, phosphorous acid list decyl diphenyl ester, phosphorous acid list octyl group diphenyl ester, tricresyl phosphite (diethyl phenyl) ester, tricresyl phosphite (diisopropyl phenyl) ester, tricresyl phosphite (di-n-butyl phenyl) ester, tricresyl phosphite (2, the 4-di-tert-butyl-phenyl) ester, tricresyl phosphite (2, the 6-di-tert-butyl-phenyl) ester, distearyl pentaerythritol diphosphite, diphosphorous acid two (2, the 4-di-tert-butyl-phenyl) pentaerythritol ester, diphosphorous acid two (2,6-di-t-butyl-4-aminomethyl phenyl) pentaerythritol ester, diphosphorous acid two (2,6-di-t-butyl-4-ethylphenyl) pentaerythritol ester, diphosphorous acid two [two (1-methyl isophthalic acid-phenylethyl) phenyl of 2,4-] pentaerythritol ester, diphosphorous acid phenyl dihydroxyphenyl propane pentaerythritol ester, two (nonyl phenyl) pentaerythritol esters of diphosphorous acid, and diphosphorous acid dicyclohexyl pentaerythritol ester etc.

And then, as other bi-ester of phosphite, also can use the bi-ester of phosphite with ring texture with the dihydric phenols reaction.For example, but illustration phosphorous acid 2,2 '-methylene-bis (4, the 6-di-tert-butyl-phenyl) (2, the 4-di-tert-butyl-phenyl) ester, phosphorous acid 2,2 '-methylene-bis (4,6-di-tert-butyl-phenyl) (the 2-tertiary butyl-4-aminomethyl phenyl) ester, and phosphorous acid 2,2-methylene-bis (4,6-di-tert-butyl-phenyl) monooctyl ester etc.

As phosphate compound, can enumerate tributyl phosphate, trimethyl phosphite 99, Tritolyl Phosphate, triphenylphosphate, trichlorophenyl phosphate, triethyl phosphate, diphenyl tolyl phosphate, diphenyl mono-orthoxenyl phosphate, tributoxyethyl phosphate, dibutyl phosphate, dioctylphosphoric acid ester, diisopropyl phosphate etc., preferably phosphoric acid triphenylmethyl methacrylate, trimethyl phosphite 99.

As phosphinate compound, can enumerate two phosphonous acid four (2, the 4-di-tert-butyl-phenyl)-4,4 '-Ya Biphenyl Ester, two phosphonous acid four (2, the 4-di-tert-butyl-phenyl)-4,3 '-Ya Biphenyl Ester, two phosphonous acid four (2, the 4-di-tert-butyl-phenyl)-3,3 '-two inferior phenyl esters, two phosphonous acid four (2, the 6-di-tert-butyl-phenyl)-4,4 '-Ya Biphenyl Ester, two phosphonous acid four (2, the 6-di-tert-butyl-phenyl)-4,3 '-Ya Biphenyl Ester, two phosphonous acid four (2, the 6-di-tert-butyl-phenyl)-3,3 '-Ya Biphenyl Ester, phosphonous acid two (2, the 4-di-tert-butyl-phenyl)-4-phenyl-phenyl ester, phosphonous acid two (2, the 4-di-tert-butyl-phenyl)-3-phenyl-phenyl ester, phosphonous acid two (2,6-di-n-butyl phenyl)-3-phenyl-phenyl ester, phosphonous acid two (2, the 6-di-tert-butyl-phenyl)-4-phenyl-phenyl ester, phosphonous acid two (2, the 6-di-tert-butyl-phenyl)-3-phenyl-phenyl ester etc., preferred two phosphonous acid four (di-tert-butyl-phenyl)-Ya Biphenyl Esters, two (di-tert-butyl-phenyl)-phenyl-phenyl esters of phosphonous acid, more preferably two phosphonous acid four (2, the 4-di-tert-butyl-phenyl) inferior Biphenyl Ester, two (2, the 4-di-tert-butyl-phenyl)-phenyl-phenyl esters of phosphonous acid.This phosphonous compound can with above-mentioned bi-ester of phosphite and usefulness with the aryl that has replaced 2 above alkyl, be preferred.

As phosphonate compound, can enumerate phosphenylic acid dimethyl ester, phosphenylic acid diethyl ester, reach phosphenylic acid dipropyl etc.

As tertiary phosphine, but illustration triethyl phosphine, tripropyl phosphine, tributylphosphine, tri octyl phosphine, three amyl group phosphines, dimethylphenylphosphine, dibutyl Phenylphosphine, diphenyl methyl phosphine, phenylbenzene octyl group phosphine, triphenylphosphine, three-p-methylphenyl phosphine, three naphthyl phosphines, and phenylbenzene benzyl phosphine etc.Particularly preferred tertiary phosphine is triphenylphosphine.

Above-mentioned phosphorus is not only available a kind of stablizer, also can be mixed with two or more.Be in the stablizer at above-mentioned phosphorus, preferred phosphinate compound or the bi-ester of phosphite that represents with following general formula (2).

(in the formula (2), R and R ' expression carbonatoms is that 6～30 alkyl or carbonatoms are 6～30 aryl, can be mutually the same, and also can be different.)

As the phosphinate compound, preferred two phosphonous acid four (2, the 4-di-tert-butyl-phenyl)-the Ya Biphenyl Ester, stablizer take this phosphinate as main component is as Sandostab P-EPQ (trade mark, Clariant company system) and Irgafos P-EPQ (trade mark, CIBA SPECIALTY CHEMICALS company system) commercially available, all can utilize.

In addition, in above-mentioned formula (2), preferred bi-ester of phosphite is distearyl pentaerythritol diphosphite, diphosphorous acid two (2, the 4-di-tert-butyl-phenyl) pentaerythritol ester, diphosphorous acid two (2,6-di-t-butyl-4-aminomethyl phenyl) pentaerythritol ester, and diphosphorous acid two [two (1-methyl isophthalic acid-phenylethyl) phenyl of 2,4-] pentaerythritol ester.

Distearyl pentaerythritol diphosphite is commercially available as ADK STAB PEP-8 (trade mark, Asahi Electro-Chemical Co. Ltd's system), JPP681S (trade mark, north of the city chemical industrial company system), all can utilize.Diphosphorous acid two (2, the 4-di-tert-butyl-phenyl) pentaerythritol ester is as ADK STAB PEP-24G (trade mark, Asahi Electro-Chemical Co. Ltd's system), Alkanox P-24 (trade mark, Great Lakes company system), Ultranox P 626 (trade marks, GE Specialty Chemicals company system), Doverphos S-9432 (trade mark, Dover Chemical company system) and Irgaofos 126 and 126FF (trade mark, CIBA SPECIALTY CHEMICALS company system) etc. commercially available, all can utilize.Two (2, the 6-di-t-butyl-4-aminomethyl phenyl) pentaerythritol esters of diphosphorous acid are commercially available as ADK STAB PEP-36 (trade mark, Asahi Electro-Chemical Co. Ltd's system), can easily utilize.In addition, diphosphorous acid two [two (1-methyl isophthalic acid-phenylethyl) phenyl of 2,4-] pentaerythritol ester is as ADK STAB PEP-45 (trade mark, Asahi Electro-Chemical Co. Ltd's system), and Doverphos S-9228 (trade mark, Dover Chemical company system) commercially available, all can utilize.

(ii) hindered phenol is antioxidant

As the hindered phenol based compound, can use the various compounds that usually are engaged in the resin.As this hindered phenol based compound; but illustration is alpha-tocopherol for example; butylhydroxy toluene; sinapyl alcohol; vitamin E; octadecyl-3-(3; the 5-di-tert-butyl-hydroxy phenyl) propionic ester; the 2-tertiary butyl-6-(3 '-tertiary butyl-5 '-methyl-2 '-hydroxybenzyl)-4-aminomethyl phenyl acrylate; 2; 6-di-t-butyl-4-(N; the N-dimethylaminomethyl) phenol; 3; 5-di-tert-butyl-4-hydroxyl benzyl diethyl phosphonate; 2; 2 '-methylene-bis (4-methyl-6-tert-butylphenol); 2; 2 '-methylene-bis(4-ethyl-6-t-butyl phenol); 4; 4 '-methylene-bis (2; the 6-DI-tert-butylphenol compounds); 2; 2 '-methylene-bis(4-methyl-6-cyclohexyl phenol); 2; 2 '-dimethylene-two (6-Alpha-Methyl-benzyl-p-cresol); 2; 2 '-ethylidene-two (4; the 6-DI-tert-butylphenol compounds); 2; 2 '-butylidene-two (4-methyl-6-tert-butylphenol); 4; 4 '-butylidene-bis(3-methyl-6-t-butyl phenol); triethylene glycol-N-pair-3-(3-tertiary butyl-4-hydroxy-5-aminomethyl phenyl) propionic ester; 1; the 6-hexylene glycol is two, and [3-(3; the 5-di-tert-butyl-hydroxy phenyl) propionic ester]; two [the 2-tertiary butyl-4-methyl-6-(the 3-tertiary butyl-5-methyl-2-hydroxybenzyl) phenyl] terephthalate; 3; 9-pair 2-[3-(3-tertiary butyl-4-hydroxy-5-aminomethyl phenyl) propionyloxy]-1; 1;-dimethyl ethyl }-2; 4; 8; 10-four oxo spiral shells [5; 5] undecane; 4; 4 '-thiobis (the 6-tertiary butyl-meta-cresol); 4; 4 '-thiobis (3 methy 6 tert butyl phenol); 2; 2 '-thiobis (4-methyl-6-tert-butylphenol); two (3; the 5-di-tert-butyl-4-hydroxyl benzyl) thioether; 4; 4 '-two-thiobis (2; the 6-DI-tert-butylphenol compounds); 4; 4 '-three-thiobis (2; the 6-DI-tert-butylphenol compounds); 2,2-sulfo-di ethylene bis-[3-(3,5-, two-tert-butyl-hydroxy phenyl) propionic ester]; 2; two (positive hot sulfenyl)-6-(the 4-hydroxyls-3 of 4-; 5-di-tert-butyl amido)-1,3,5-triazines; N; N '-hexa-methylene two-(3; 5-di-t-butyl-4-hydroxyl hydrocinnamamide); N, N '-two [3-(3,5-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 (3,5-di-tert-butyl-4-hydroxyl benzyl) benzene; three (3,5-di-tert-butyl-hydroxy phenyl) isocyanuric acid ester; three (3; the 5-di-tert-butyl-4-hydroxyl benzyl) isocyanuric acid ester; 1; 3,5-three (the 4-tertiary butyl-3-hydroxyl-2,6-dimethyl benzyl) isocyanuric acid ester; 1; 3; 5-three 2[3 (3,5-di-tert-butyl-hydroxy phenyl) propionyloxy] the ethyl isocyanuric acid ester; four [methylene radical-3-(3,5-di-tert-butyl-hydroxy phenyl) propionic ester] methane; triethylene glycol-N-pair-3-(3-tertiary butyl-4-hydroxy-5-aminomethyl phenyl) propionic ester; triethylene glycol-N-pair-3-(3-tertiary butyl-4-hydroxy-5-aminomethyl phenyl) acetic ester; 3; two [2-[3-(3-tertiary butyl-4-hydroxy-5-aminomethyl phenyl) acetoxyl groups]-1 of 9-; the 1-dimethyl ethyl]-2,4,8; 10-four oxaspiros [5; 5] undecane; four [methylene radical-3-(3-tertiary butyl-4-hydroxy-5-aminomethyl phenyl) propionic ester] methane; 1,3,5-trimethylammonium-2; 4,6-three (3-tertiary butyl-4-hydroxy-5-methyl-benzyl) benzene; and three (3-tertiary butyl-4-hydroxy-5-methyl-benzyl) isocyanuric acid ester etc.

In above-claimed cpd, preferably utilize four [methylene radical-3-(3-tertiary butyl-4-hydroxy-5-aminomethyl phenyl) propionic ester] methane, octadecyl-3-(3 among the present invention, the 5-di-tert-butyl-hydroxy phenyl) propionic ester, and 3, two [2-[3-(3-tertiary butyl-4-hydroxy-5-aminomethyl phenyl) propionyloxies]-1 of 9-, the 1-dimethyl ethyl]-2,4,8,10-four oxaspiros [5,5] undecane.Particularly preferably 3, two [2-[3-(3-tertiary butyl-4-hydroxy-5-aminomethyl phenyl) propionyloxies]-1 of 9-, 1-dimethyl ethyl]-2,4,8,10-four oxaspiros [5,5] undecane.Above-mentioned hindered phenol is that antioxidant can be used singly or in combination more than 2 kinds.

Preferred cooperation phosphorus is that stablizer and hindered phenol are any in the antioxidant.Particularly preferably cooperating phosphorus is stablizer, more preferably cooperates three organophosphorus compoundss.Take total 100 weight parts of A composition and B composition as benchmark, phosphorus is that stablizer and hindered phenol are that the use level of oxidation inhibitor is preferably respectively 0.005～1 weight part, more preferably 0.01～0.3 weight part.

(iii) releasing agent

In aromatic copolycarbonate resin composition of the present invention, the productivity when improving its moulding, reduce products formed and be deformed into purpose, the preferred releasing agent that further cooperates.As this releasing agent, can use known releasing agent.Can enumerate such as polyunsaturated fatty acid ester, unsaturated fatty acid ester, polyolefin wax (polyethylene wax, 1-olefin polymerization thing etc.Also can use the quilts such as sour modification to contain the compound modified wax of functional group), silicon compound, fluorine cpd (with Polyfluoroalkyl ether as fluorocarbon oil of representative etc.), paraffin, beeswax etc.

Wherein, as preferred releasing agent, can enumerate fatty acid ester.This fatty acid ester is the ester of fatty alcohol and aliphatic carboxylic acid.This fatty alcohol can be 1 yuan of alcohol, also can be the polyvalent alcohol more than 2 yuan.In addition, this pure carbonatoms is 3～32 scope, more preferably 5～30 scope.As this monohydroxy-alcohol, but illustration such as dodecanol, tetradecanol, cetyl alcohol, Stearyl alcohol, eicosanol, Tetracosyl alcohol, n-Hexacosanol, triacontanol price quote etc.As this polyvalent alcohol, can enumerate tetramethylolmethane, Dipentaerythritol, tripentaerythritol, Polyglycerine (triglycerin～six glycerine), two (trishydroxymethyl) propane, Xylitol, sorbyl alcohol, reach N.F,USP MANNITOL etc.More preferably polyvalent alcohol in fatty acid ester of the present invention.

On the other hand, the preferred carbonatoms of aliphatic carboxylic acid is 3～32, particularly preferably carbonatoms is 10～22 aliphatic carboxylic acid.As this aliphatic carboxylic acid, can enumerate the representative examples of saturated aliphatic carboxylic such as capric acid, undecanoic acid, dodecylic acid, tridecanoic acid, tetradecanoic acid, pentadecylic acid, hexadecanoic acid (palmitinic acid), margaric acid, octadecanoic acid (stearic acid), nondecylic acid, docosoic acid, arachic acid, Ji docosoic and Zoomeric acid, oleic acid, linolic acid, linolenic acid, eicosenoic acid, timnodonic acids, and the unsaturated aliphatic carboxylic acid such as cetoleic acid.Wherein, the preferred carbonatoms of aliphatic carboxylic acid is 14～20 aliphatic carboxylic acid.Wherein, preferred representative examples of saturated aliphatic carboxylic.Particularly preferably stearic acid and palmitinic acid.

The above-mentioned aliphatic carboxylic acid such as stearic acid, palmitinic acid is usually by the animal raw fat take butter, lard etc. as representative and the natural oil lipid manufacturings such as vegetative grease take plam oil, sunflower oil as representative, so these aliphatic carboxylic acids are generally the mixture that comprises other different carboxylic acid composition of carbonatoms.Therefore, in the manufacturing of fatty acid ester of the present invention also preferred use by this natural oil lipid manufacturing, by morphotic fatty acid carboxylate, particularly stearic acid, the palmitinic acid of the mixture that comprises other carboxylic acid composition.

Fatty acid ester of the present invention can be any in partial ester and the full ester (full ester).Yet if partial ester, hydroxyl value uprises usually, and therefore the resin decomposition when bringing out high temperature easily etc. are more preferably full ester.Acid number in the fatty acid ester of the present invention see from the viewpoint of thermostability be preferably below 20, more preferably 4～20 scope, more preferably 4～12 scope.Should illustrate that acid number can get 0 in fact.In addition, the hydroxyl value of fatty acid ester 0.1～30 scope more preferably.And then iodine number is preferably below 10.Should illustrate that iodine number can get 0 in fact.Can try to achieve these characteristics by the method for regulation among the JIS K 0070.

Take total 100 weight parts of A composition and B composition as benchmark, the content of releasing agent is preferably 0.005～2 weight part, more preferably 0.01～1 weight part, more preferably 0.05～0.5 weight part.In this scope, aromatic copolycarbonate resin composition has good release property and roll release.Particularly the fatty acid ester of this amount provides and does not damage good tone and have good release property and the aromatic copolycarbonate resin composition of roll release.

(iv) UV light absorber

Aromatic copolycarbonate resin composition of the present invention can contain UV light absorber.Resin combination of the present invention is the weathering resistance variation owing to the impact of rubber constituent, fire retardant sometimes, and therefore deteriorated in order to prevent this, the combined with ultraviolet radiation absorption agent is effective.

As UV light absorber of the present invention; particularly; as benzophenone series; but illustration for example 2; the 4-dihydroxy benaophenonel; ESCALOL 567; 2-hydroxyl-4-octyloxy benzophenone; 2-hydroxyl-4-benzyloxy benzophenone; 2-hydroxyl-4-methoxyl group-5-sulphur oxygen base benzophenone; 2-hydroxyl-4-methoxyl group-5-sulphur oxygen base benzophenone trihydrate; 2; 2 '-dihydroxyl-4-methoxy benzophenone; 2; 2 '; 4; 4 '-tetrahydroxybenzophenone; 2; 2 '-dihydroxyl-4; 4 '-dimethoxy-benzophenone; 2; 2 '-dihydroxyl-4,4 '-dimethoxy-5-sodium sulfonate benzophenone; two (5-benzoyl-4-hydroxyl-2-p-methoxy-phenyl) methane; 2-hydroxyl-4-positive 12-alkoxy benzophenone; and 2-hydroxyl-4-methoxyl group-2 '-carboxyl benzophenone etc.

As benzotriazole be, but illustration is 2-(2-hydroxy-5-methyl base phenyl) benzotriazole for example, 2-(2-hydroxyl-uncle's 5-octyl phenyl) benzotriazole, 2-(2-hydroxyl-3, the 5-dicumylphenyl) phenyl benzotriazole, 2-(the 2-hydroxyl-3-tertiary butyl-5-aminomethyl phenyl)-5-chlorinated benzotriazole, 2, [4-(1 for 2 '-methylene-bis, 1,3, the 3-tetramethyl butyl)-6-(2H-benzotriazole-2-yl) phenol], 2-(2-hydroxyl-3, the 5-di-tert-butyl-phenyl) benzotriazole, 2-(2-hydroxyl-3, the 5-di-tert-butyl-phenyl)-the 5-chlorinated benzotriazole, 2-(2-hydroxyl-3, the 5-di-tert-pentyl-phenyl) benzotriazole, 2-(2-hydroxyl-uncle's 5-octyl phenyl) benzotriazole, 2-(2-hydroxyl-5-tert-butyl-phenyl) benzotriazole, 2-(2-hydroxyl-4-octyloxyphenyl) benzotriazole, 2,2 '-methylene-bis (4-cumyl-6-benzotriazole benzene), 2,2 '-TOPOT 2,2′ p phenylenebis (1,3-benzo

Piperazine-4-ketone), reach 2-[2-hydroxyl-3-(3,4,5,6-tetrahydro-phthalimide methyl)-and the 5-aminomethyl phenyl] benzotriazole and 2-(2 '-hydroxy-5-methyl base acryloxy ethylphenyl)-2H-benzotriazole and can and can have with the multipolymer of the vinyl monomer of this monomer copolymerization etc. the polymkeric substance etc. of 2-hydroxy phenyl-2H-benzotriazole skeleton with the multipolymer of the vinyl monomer of this monomer copolymerization, 2-(2 '-hydroxyl-5-acryloxy ethylphenyl)-2H-benzotriazole.

As hydroxyphenyltriazinuv system, but illustration 2-(4,6-phenylbenzene-1 for example, 3,5-triazine-2-yl)-5-hexyloxy phenol, 2-(4,6-phenylbenzene-1,3,5-triazine-2-yl)-5-methoxyphenol, 2-(4,6-phenylbenzene-1,3,5-triazine-2-yl)-5-thanatol, 2-(4,6-phenylbenzene-1,3,5-triazine-2-yl)-5-propoxy-phenol, and 2-(4,6-phenylbenzene-1,3,5-triazine-2-yl)-5-butoxy phenol etc.And then, but the phenyl of illustration 2-(two (2,4-the 3,5-dimethylphenyl)-1,3,5-triazines of 4,6--2-yl)-above-mentioned exemplary compounds such as 5-hexyloxy phenol becomes 2, the compound of 4-3,5-dimethylphenyl.

As UV light absorber, particularly, as cyclic imide ester system, but illustration for example 2,2 '-

TOPOT

2,2′ p phenylenebis (3,1-benzo

Piperazine-4-ketone), 2,2 '-(4,4-diphenylene) two (3,1-benzos

Piperazine-4-ketone), reach 2,2 '-(2,6-naphthalene) two (3,1-benzos

Piperazine-4-ketone) etc.

As cyanoacrylate be; but illustration for example 1; two [(the 2 '-cyano group-3 ' of 3-; 3 '-diphenylprop enoyl-) oxygen base]-2; two [(the 2-cyano group-3 of 2-; 3-diphenylprop enoyl-) oxygen base] methyl) propane, and 1,3-two-[(2-cyano group-3,3-diphenylprop enoyl-) oxygen base] benzene etc.

And then, above-mentioned UV light absorber is by obtaining the structure that can carry out the monomeric compound of radical polymerization, can be the polymer-type UV light absorber that the monomer copolymerizations such as this ultraviolet-absorbing monomer and/or light stability monomer with the structure of hindered amine and (methyl) alkyl acrylate are formed.As above-mentioned ultraviolet-absorbing monomer, preferably be illustrated in and contain benzotriazole skeleton, benzophenone skeleton, triazine skeleton, cyclic imide ester skeleton, and the compound of cyanoacrylate skeleton in the ester substituting group of (methyl) acrylate.

In above-mentioned UV light absorber, consider that from the ultraviolet absorption ability aspect preferred benzotriazole system and hydroxyphenyltriazinuv system consider from thermotolerance, tone (transparency) aspect, preferred cyclic imide ester system and cyanoacrylate system.Above-mentioned UV light absorber can be used separately or use with the form of the mixture more than 2 kinds.

Take total 100 weight parts of A composition and B composition as benchmark, the content of UV light absorber is preferably 0.01～2 weight part, 0.02～2 weight part more preferably, and more preferably 0.03～1 weight part is particularly preferably 0.05～0.5 weight part.

(v) dye pigment

Aromatic copolycarbonate resin composition of the present invention can provide further to contain and variously dye pigment and manifest the products formed of various appearance design.

As the fluorescence dye that uses among the present invention (comprising white dyes), can enumerate such as coumarin series fluorescence dye, chromene be fluorescence dye, perylene be fluorescence dye, anthraquinone be fluorescence dye, thioindigo be fluorescence dye, xanthene be fluorescence dye, xanthone be fluorescence dye, thioxanthene be fluorescence dye, thioxanthone be fluorescence dye, thiazine be fluorescence dye, and diaminostilbene be fluorescence dye etc.Among these fluorescence dyes, deteriorated few coumarin series fluorescence dye, the chromene during the good and polycarbonate resin forming process of preferred thermotolerance be fluorescence dye, and perylene be fluorescence dye.

As the dyestuff beyond above-mentioned bluing agent and the fluorescence dye, can enumerate perylene based dye, coumarin series dyestuff, thioindigo based dye, anthraquinone based dye, thioxanthone based dye, yellow prussiate, pyrene ketone based dye, quinoline based dye, the quinacridone based dye, two such as Prussian blue

Piperazine based dye, isoindolinone based dye, and phthalocyanine based dye etc.And then resin combination of the present invention also can cooperate with metallic pigment and obtain better metal color.As metallic pigment, preferably have the metallic pigment of metal coating or metal oxide coating at various tabular weighting agents.

Take total 100 weight parts of A composition and B composition as benchmark, the above-mentioned content that dyes pigment is preferably 0.00001～1 weight part, more preferably 0.00005～0.5 weight part.

(vi) other thermo-stabilizer

In aromatic copolycarbonate resin composition of the present invention, also can cooperate above-mentioned phosphorus is that stablizer and hindered phenol are other thermo-stabilizer beyond the antioxidant.This other thermo-stabilizer preferably with aforementioned stable agent and antioxidant in any and usefulness, particularly preferably with both and use.As this other thermo-stabilizer, preferably illustration is for example with 3-hydroxyl-5, and the reaction product of 7-di-t-butyl-furans-2-ketone and o-Xylol is that the lactone of representative is stablizer (details of this stablizer is recorded in the Japanese kokai publication hei 7-233160 communique).This compound is commercially available as Irganox HP-136 (trade mark, CIBA SPECIALTY CHEMICALS company system), can utilize this compound.And then, sell the stablizer that this compound and various bi-ester of phosphite and hindered phenol compound are mixed on the market.The illustration Irganox HP-2921 of above-mentioned company system for example preferably.Also can utilize the stablizer that is pre-mixed in the present invention.Take total 100 weight parts of A composition and B composition as benchmark, lactone is that the use level of stablizer is preferably 0.0005～0.05 weight part, more preferably 0.001～0.03 weight part.

In addition, as other stablizer, illustration has tetramethylolmethane four (3-mercaptopropionic acid ester), tetramethylolmethane four (3-lauryl thiopropionate), reaches glycerol-sulphur-containing stabilizers such as 3-stearyl thiopropionate.This stablizer is effective especially when resin combination is applicable to rotoforming.Take total 100 weight parts of A composition and B composition as benchmark, the use level of this sulphur-containing stabilizer is preferably 0.001～0.1 weight part, more preferably 0.01～0.08 weight part.

As the thermoplastic resin beyond A composition～C composition, illustration has aromatic polyester resins (pet resin (PET resin), polybutylene terephthalate resin (PBT resin), cyclohexanedimethanol copolymerization pet resin (so-called PET-G resin), the PEN resin, and the PBN resin etc.), plexiglass (PMMA resin), cyclic polyolefin resin, polylactic resin, the polycaprolactone resin, thermoplastic fluorocarbon resin (take polyvinylidene fluoride resin for example as representative), and polyolefin resin (polyvinyl resin for example, ethene-(alpha-olefin) copolymer resin, acrylic resin, and propylene-(alpha-olefin) copolymer resin etc.).Take total 100 weight parts of A composition and B composition as benchmark, the content of above-mentioned other thermoplastic resin is preferably below 20 weight parts, more preferably below 10 weight parts.

(manufacturing of aromatic copolycarbonate resin composition)

In order to make aromatic copolycarbonate resin composition of the present invention, can adopt any means.For example; can enumerate following methods: with A composition, B composition, C composition and after other additive fully mixes with pre-mixing means such as V-type blending machine, Henschel mixer, mechanochemistry device, extruding mixing machines arbitrarily; carry out as required the granulation of this premixture with Squeezinggranulator, briquetting press etc.; then; be that the melt kneading machine of representative carries out melt kneading in order to the aeration type twin-screw extruder, granulate with tablets press thereafter.

In addition, also can enumerate each composition is supplied to respectively method in the melt kneading machine take the aeration type twin-screw extruder as representative independently; After a part of pre-mixing with each composition, supply to independently method in the melt kneading machine etc. with remaining composition.As with the premixed method of the part of each composition, can enumerate after the composition pre-mixing beyond the A composition, mix with the aromatic polycarbonate resin of A composition or directly supply to method in the forcing machine.

As premixed method, also can enumerate for example following methods: comprising the material during as the A composition with powder morphology, the part of this powder and the additive that cooperates are mixed, make the masterbatch with the additive of powder dilution, utilize this masterbatch.And then also can enumerate from beginning method of supplying with independently a kind of composition etc. midway to the melt extruded machine.In addition, when in the composition that cooperates, fluent meterial being arranged, can use priming device or add liquid device to the supply of melt extruded machine.

As extrusion machine, can preferably use the extrusion machine of the ventilation hole of the volatilization gas that has the moisture that to discharge in the raw material, produced by the melt kneading resin.Preferably be provided for the moisture that to produce, volatilization gas efficient is discharged to the extrusion machine outside well from ventilation hole vacuum pump.In addition, also the sieve that is used for removing the foreign matter of sneaking into extruding raw material etc. can be arranged on the zone before the extruder mold section, foreign matter is removed from resin combination.As this sieve, can enumerate wire cloth, net-changing device, sintered metal plates (disc filter etc.) etc.

As the melt kneading machine, except twin-screw extruder, can enumerate the above multishaft extruder of Banbury, nip roll, single shaft extrusion machine, 3 axles etc.

The resin of as described above extruding directly cut off and granulate, perhaps after forming strand with this strand with the tablets press cut-out and granulate.When needs reduce to be granulated in the situation of the impact of the dust of outside etc., preferably purify the atmosphere around the extrusion machine.And then, when this grain is made, can use the whole bag of tricks that has proposed in polycarbonate resin at CD, carry out aptly the distribution of shapes of grain narrow and smallization, reduce to leak and cut (miss cut) thing, reduce the micro mist that transports or produce when carrying and reduce the bubble (bubbles of vacuum) that produces in strand or intragranular section.By these treatment processs, can carry out high all moulding, reach the proportion that reduces silver color and so on unfavorable condition.In addition, the shape of grain can get cylinder, prism, reach the general shapes such as spherical, is more preferably cylinder.The diameter of this cylinder is preferably 1～5mm, more preferably 1.5～4mm, more preferably 2～3.3mm.On the other hand, the length of cylinder is preferably 1～30mm, more preferably 2～5mm, more preferably 2.5～3.5mm.

(manufacturing of products formed)

Products formed of the present invention carries out injection-molded moulding with above-mentioned aromatic copolycarbonate resin composition and obtains under the condition of molding of the condition of the condition that satisfies following formula (1), preferred following formula (2).

Tg-30≤die temperature (℃)≤Tg+50 ... (1)

Tg-25≤die temperature (℃)≤Tg+30 ... (2)

When die temperature surpasses 30 ℃ than Tg is low, because die temperature is low, produce a large amount of current marks in the products formed, therefore not preferred.In addition, when die temperature surpassed 50 ℃ than Tg is high, it was long to become cooling time, and shaping cycle is elongated, and is therefore not preferred.

The second-order transition temperature of the formula among the present invention (1), formula (2) is for measuring the second-order transition temperature that each resin combination obtains according to ISO3146, exist when a plurality of in second-order transition temperature, and the side's that use temperature is low second-order transition temperature is calculated.

Should illustrate, make this die temperature satisfy the temperature shown in formula (1), the formula (2) time so long as from aromatic copolycarbonate resin composition is expelled to mould inside begin till the end-of-fill during get final product, do not limit especially the die temperature of other times.

Method as heating mould, can enumerate in the past making of the proposing method that the heating mediums such as hot water, water vapour, heat hot water circulate in pipe arrangement in the mould temperature adjustment, with the radiant heat of halogen lamp be radiated at mold cavity surface method, electrothermal heater etc. is imbedded method in the mould, the method for the low thermal insulation layer of thermal conductivity etc. is set in mold cavity surface, the method that the heating mediums such as hot water, water vapour, heat hot water are circulated in pipe arrangement in the mould temperature adjustment.These methods can be used separately, also multiple use capable of being combined.

As the concrete example of the products formed that utilizes resin combination of the present invention, can enumerate the case, vehicle part etc. of business automation equipment, family's electrical article.As these goods, such as Personal Computer, notebook computer, flat-panel monitor, printer, portable terminal, mobile phone, duplicating machine, facsimile recorder, auto navigation parts, automobile audio parts etc. can be enumerated, in their the various parts such as housing, the resin that is formed by thermoplastic resin composition of the present invention can be used.Wherein, the case of preferred flat-panel monitor, notebook computer.

[invention effect]

Aromatic copolycarbonate resin composition of the present invention is kept forming process that aromatic polycarbonate resin and graft copolymer take ABS resin as representative had originally, and face shock strength and so on mechanical characteristics, improved simultaneously the white vaporific bad order that produces when carrying out injection-molded moulding with die material, as mentioned above, be widely used in office automation, electric/electronic device, automobile, and other various fields.Therefore, the effect on the industry that obtains of the present invention is very big.

Description of drawings

Fig. 1 is the face side schematic side view (vertical 250mm * horizontal 300mm * brim height 10mm, thickness 1.5mm) of the products formed of the imitative notebook computer case that uses among the embodiment.

Fig. 2 is the face side front schematic view of the products formed that uses among the embodiment, and expression produces the position of white vaporific bad order.

Fig. 3 is the rear side front schematic view of the products formed that uses among the embodiment, and expression has a mouthful position, with the situation of the protruding hub of rib.

[nomenclature]

The products formed main body of 1 imitative notebook computer casing

2 minute surface sections

3 white vaporific bad roughly occurrence positions

4 mouthfuls (sprue 5mm φ, 1 place)

5 protruding hubs

6 ribs

Embodiment

The inventor thinks that now best the solution of the present invention compiled the preferable range of above-mentioned each important document, for example, puts down in writing in the following embodiments its typical example.Certainly the present invention is not limited to these modes.

Embodiment

The evaluation of＜aromatic copolycarbonate resin composition 〉

(i) second-order transition temperature

According to ISO3146, measure the second-order transition temperature of each resin combination of table 1, table 2 record with the DSC device.

(ii) Charpy impact intensity

According to ISO 179, implement the mensuration of the Charpy impact intensity of tool breach.

(iii) load deflection deformation temperature

According to ISO 75-1 and 75-2, measuring load deflection deformation temperature.Should illustrate, be to implement under the 1.80MPa at measuring load.

(iv) flowability

Measuring stream with injection moulding forming machine " SG150U processed of Sumitomo Heavy Industries ", thick to be that 2mm, stream are wide be the archimedes type helicoidal flow length of 8mm.Should illustrate, be that cylinder temperature is that 260 ℃, die temperature are that 70 ℃, injection pressure are to implement under the condition of 98MPa at condition of molding.

(v) face shock strength

Under following condition of molding, make the dihedral plate of 150mm * 150mm * 2mmt, measure with the high speed surface shock-testing machine and destroy required energy (failure energy: E1) and collapse state.Should illustrate that ductile failure is preferred result.Trier uses high speed surface shock-testing machine Hydro Shot HTM-1 (company of Shimadzu Seisakusho Ltd. system), test conditions is made as: the impact velocity of hitting core is 7m/ second, and front end is that semicircle shape, radius are that the bore dia that hits core and bear platform of 6.35mm is 25.4mm.

260 ℃ of [condition of molding] cylinder temperatures, 60 ℃ of die temperatures, injection speed 30mm/s

(vi) flame retardant resistance

According to UL standard 94V, implement combustion experiment with thickness 1.5mm.

(vii) humidity resistance (face shock strength)

Under above-mentioned condition of molding, make the dihedral plate of 150mm * 150mm * 2mmt, under 65 ℃, the condition of 85%RH, process 500 hours with constant temperature and humidity cabinet [PSL-2FPH processed of TABAI ESPEC company] after, enforcement high speed surface impact experiment.Should illustrate that the high speed surface shock test uses the method identical with (v) to measure failure energy (E2), the measurement result (E1) of (v) as the value before the wet heat treatment, is calculated according to the following formula conservation rate.Wherein, consider from practical aspect that the conservation rate of preferred failure energy is more than 70%, particularly preferably in more than 75%.

Failure energy conservation rate (%)=(E2/E1) * 100

(viii) outward appearance

[use equipment]

[injection moulding forming machine] MITSUBISHI HEAVY INDUSTRIES PLASTIC TECHNOLOGY 450ME II-50U processed of company

260 ℃ of [condition of molding] cylinder temperatures, injection speed 20mm/s

Die temperature is put down in writing in table 1, table 2

40 seconds cooling times

1) white mist

Under above-mentioned condition of molding, make the products formed of the imitative notebook computer case shown in Fig. 1 to Fig. 3, by the state of range estimation comparative evaluation in the white vaporific bad order of products formed surface generation.

[decision method] judges the outward appearance of products formed by range estimation.(zero: without white mist, *: white mist is arranged)

2) current mark

By visual observations 1) in the having or not of the current mark that produces at protruding hub portion periphery of the products formed of moulding.

[decision method] judges the outward appearance of products formed by range estimation.(zero: without current mark, *: current mark is arranged)

[embodiment 1～16, comparative example 1～10]

From the composition shown in the 1st supplying opening supply schedule 1～table 2 of forcing machine, by the mixture that consists of except the composition D composition (phosphoric acid ester of FR-1) and the F composition (reinforcement weighting material).This mixture is that the premixture of following (i) and other composition are mixed to get in the V-type blending machine.Wherein, premixture (i) is the mixture of the aromatic copolycarbonate of E composition (fluorine-containing Antidrip agent) and A composition, account for the mode of 2.5 % by weight of mixture with the F composition, this bag of vibration integral body evenly mixes it and the mixture that obtains in polyethylene bag.In addition, the F composition is all supplied with the side feeding device from the 3rd supplying opening.And then, the FR-1 of C composition is being heated under 80 ℃ the state with priming device (the Fuji Techno Industries HYM-JS-08 processed of company), from cylinder the 2nd supplying opening (position between the 1st supplying opening and the 2nd supplying opening) midway, supply in the extrusion machine with reaching respectively the regulation ratio.It is a certain amount of that priming device is set as supply, gauger (CWF processed of the KUBOTA company) precision measurement of the feed rate of other raw material.The aeration type twin-screw extruder of extruding use diameter 30mm φ (the company's T EX30 α of JSW-38.5BW-3V), be that 150rpm, spray volume are that the vacuum tightness of 20kg/h, ventilation hole is melt kneading under the condition of 3kPa at screw speed, obtain particle.Should illustrate, about extrusion temperature, implement under 260 ℃ from the 1st supplying opening to mould part.

With the part of the particle that obtains with hot air circulation type drying machine under the situation of embodiment 12～16 in 80～90 ℃ of dryings 5 hours, under the situation of embodiment 1～11, comparative example 1～10 in 100～110 ℃ of dryings 5 hours, afterwards, use injection moulding forming machine, make to estimate and use the test film moulding.

Each composition of sign flag in table 1～table 2 is as described below.

(A composition)

PC-1: aromatic polycarbonate resin [viscosity-average molecular weight of being made by ordinary method by dihydroxyphenyl propane and phosgene is 22,500 polycarbonate resin powder, and Supreme Being people changes into company's system, Panlite L-1225WP]

PC-2: aromatic polycarbonate resin [viscosity-average molecular weight of being made by ordinary method by dihydroxyphenyl propane and phosgene is 19,700 polycarbonate resin powder, and Supreme Being people changes into company's system, Panlite L-1225WX]

(B composition)

ABS-1:ABS resin [Japanese A﹠amp; L company system, KRALASTIC SXH-330 (trade(brand)name), the divinyl rubber composition is about 17.5 % by weight, the weight average rubber size is 0.40 μ m, by the letex polymerization manufacturing]

The ABS-2:ABS resin [GT-A-250 processed of DENKA company (trade(brand)name), the divinyl rubber composition is about 18 % by weight, the weight average rubber size is 0.30 μ m, by the letex polymerization manufacturing]

(C composition)

MBS-1:MBS[Rohm and Haas company system: Paraloid EXL2620 (trade(brand)name); By the letex polymerization manufacturing, nuclear is that polyhutadiene, the shell of 70 % by weight is the graft copolymer of vinylbenzene and methyl methacrylate, sodium content is 15ppm, phosphorus content is 235ppm]

MBS-2:MBS[Rohm and Haas company system: Paraloid EXL2678 (trade(brand)name); By the letex polymerization manufacturing, nuclear is that polyhutadiene, the shell of 60 % by weight is the graft copolymer of vinylbenzene and methyl methacrylate, sodium content is 10ppm, phosphorus content is 350ppm]

MBS-3: core-shell grafting copolymer [by the letex polymerization manufacturing, nuclear is that divinyl rubber composition, the shell of 70 % by weight is the graft copolymer of vinylbenzene and methyl methacrylate, sodium content is 40ppm, phosphorus content is 310ppm]

MBS-4:MBS[MITSUBISHI RAYON company system: METABLEN C-223A (trade(brand)name); By the letex polymerization manufacturing, nuclear is that polyhutadiene, the shell of 70 % by weight is the graft copolymer of vinylbenzene and methyl methacrylate, sodium content is 83ppm, phosphorus content is 5ppm]

MBS-5:MBS[KANEKA company system: Kane Ace M-901 (trade(brand)name); By the letex polymerization manufacturing, nuclear is that polyhutadiene, the shell of 70 % by weight is the graft copolymer of vinylbenzene and methyl methacrylate, sodium content is 46ppm, phosphorus content is 8ppm]

MBS-6: core-shell grafting copolymer [by the letex polymerization manufacturing, nuclear is that divinyl rubber composition, the shell of 70 % by weight is the graft copolymer of vinylbenzene and methyl methacrylate, sodium content is 40ppm, phosphorus content is 1,100ppm]

MBS-7: core-shell grafting copolymer [by the letex polymerization manufacturing, nuclear is that divinyl rubber composition, the shell of 70 % by weight is the graft copolymer of vinylbenzene and methyl methacrylate, sodium content is 20ppm, phosphorus content is 90ppm]

(D composition)

FR-1: the phosphoric acid ester (large eight chemical industrial company's system: CR-741 (trade(brand)name)) take dihydroxyphenyl propane two (diphenyl phosphate) as main component

FR-2: the phosphoric acid ester take Resorcinol (diphenyl phosphate) as main component (large eight chemical industrial company's system: CR-733S (trade(brand)name))

(E composition)

PTFE: tetrafluoroethylene [the Polyflon MP processed FA500 of DAIKIN industrial (trade(brand)name)]

(F composition)

WSN: wollastonite (clear water industrial system: H-1250F (trade(brand)name))

Talcum: talcum (Lin Huacheng company system: HST 0.8 (trade(brand)name))

(other composition)

DC30M: ethylene series wax (the Mitsubishi Chemical Ind's system: Diacarna 30M (trade(brand)name)) that is formed by alpha-olefin and maleic anhydride copolymerization

SL: fatty acid ester is releasing agent (RIKEN VITAMIN company system: Rikemal SL900 (trade(brand)name))

IRGX: phenol is thermo-stabilizer (Ciba Specialty Chemicals K.K. system: IRGANOX1076 (trade(brand)name))

[table 1]

[table 2]

As seen from the above table, by applicable rubber modified polymers with specific remaining amount of metal of the present invention, can can't harm shock strength, humidity resistance, flame retardant resistance, mobile the white vaporific bad order that produces when in being heated to the mould of high temperature, carrying out injection-molded moulding of improving.

Claims

1. products formed is by with condition of molding hemostasis molded obtain of aromatic copolycarbonate resin composition in the condition that satisfies following formula (1),

In the described aromatic copolycarbonate resin composition, with respect to (A) aromatic polycarbonate resin, be that A composition 10～95 weight parts, (B) make vinyl cyanide monomer and aromatic vinyl monomer and rubber polymer graft copolymerization and the graft copolymer that obtains, be total 100 weight parts of B composition 5～90 weight parts, contain (C) rubber modified polymers, be C composition 0.1～20 weight part

Described C composition is with (methyl) alkyl acrylate monomer or (methyl) alkyl acrylate monomer with can obtain by the emulsion polymerization copolymerization with the mixture of the monomer of its copolymerization in the presence of rubber constituent, and sodium content is 0～50ppm, phosphorus content is 100～1000ppm

Tg-30≤die temperature (℃)≤Tg+50 ... (1)

In the formula, Tg is the second-order transition temperature of aromatic copolycarbonate resin composition.

2. products formed according to claim 1, wherein, the rubber constituent of C composition is divinyl.

3. products formed according to claim 1 and 2, wherein, described resin combination contain with respect to total 100 weight parts of A composition and B composition be 3～30 weight parts (D) organic phosphorus flame retardant, be D composition and 0.01～2 weight part (E) fluorine-containing anti-dripping agent, be the E composition.

4. each described products formed according to claim 1～3, wherein, described resin combination contain with respect to total 100 weight parts of A composition and B composition be 0.1～50 weight part (F) inorganic filling material, be the F composition.

5. each described products formed according to claim 1～4, wherein, products formed is the case of flat-panel monitor, notebook computer.