CN101412844A - Flame-resistant polycarbonate resin composition - Google Patents

Flame-resistant polycarbonate resin composition Download PDF

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Publication number
CN101412844A
CN101412844A CNA2008100989831A CN200810098983A CN101412844A CN 101412844 A CN101412844 A CN 101412844A CN A2008100989831 A CNA2008100989831 A CN A2008100989831A CN 200810098983 A CN200810098983 A CN 200810098983A CN 101412844 A CN101412844 A CN 101412844A
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composition
flame retardant
phenyl
acid
resin composition
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大平洋二
友田琢也
品川佳久
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Teijin Ltd
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Teijin Chemicals Ltd
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Abstract

The invention aims to provide a flame retarding resin compound having transparency in a certain range and excellent flame retarding property, comprising: an aromatic polycarbonate series resin (component A), polytetrafluoroethylene with the fibril forming ability (component B) and a flame retardant (component C), wherein corresponding to the polycarbonate series resin (component A) of 100 parts by weight, the polytetrafluoroethylene with the fibril forming ability (component B) and flame retardant (component C) are 0.1-0.2 and 0.001-20 parts by weight, respectively.

Description

Flame-retardant polycarbonate resin composition
Technical field
The present invention relates to a kind of flame-retardant polycarbonate resin composition.More particularly, the flame-retardant polycarbonate resin composition that relates to a kind of transparency and excellent in flame retardance.
Background technology
Because aromatic polycarbonate resin not only has the transparency or excellent thermotolerance and intensity, but also has certain flame retardant resistance, thereby it is widely used in every field.But, the raising of the flame retardant resistance grade that causes with respect to the thin-walled property of raising that requires because of the flame retardant resistance of electronic apparatus machine part, OA associated components etc. in recent years or goods, the flame retardant resistance of talkative aromatic polycarbonate resin is very inabundant.And, require to have the high flame retardant that meets V-0 among UL specification (American insurance dealer's proof test institute (the Underwriters Laboratories Inc))-94 recently under many circumstances, thereby the PC material of having given high fire resistance seems extremely important.
In order to obtain high flame retardant, for example, drippage (drip) phenomenon of the resin when suppressing combustion test is important.As the method that suppresses drip phenomenon, known have as matrix resin use method, use the method for the polycarbonate resin of copoly type, add as Antidrip agent and have (with reference to the patent documentations 1～3) such as methods that fibril forms the tetrafluoroethylene (below, abbreviate fibrillation PTFE sometimes as) of ability as matrix resin with the unitary aromatic polycarbonate resin of side chain.
Wherein, use has the method for the unitary aromatic polycarbonate resin of side chain as matrix resin, though can expect to keep the transparency and have certain anti-drippage effect, but, the mobile shortcoming that reduces is arranged, if in the time of will suppressing the reduction (minimizing) of flowability, exist the problem that loses anti-drippage effect again with respect to the unitary amount of the side chain of resin total amount.Use the method for the polycarbonate resin of copoly type as matrix resin, because its manufacture method is special, it is poor to make efficient, thereby, not only aspect practicality or the economy problem is being arranged, but also existing the problem that can not obtain anti-fully drippage effect.And the method for adding fibrillation PTFE owing to obtain anti-drippage effect easily, and is added fibrillation PTFE and the reduction of the flowability that causes is also few, thereby it is applicable in the material (material with UL specification V-0, V-1) that requires high flame retardant more.But, the problem that it has the transparency to reduce.
In addition, the reduction of the transparency, the problem that not only has light transmission to reduce also is attended by the defective that the design space of the painted grade of the so-called part that comprises sensation diminishes.See conversely, then we can say the material that keeps the transparency, that is, the material that the total light transmittance in the moulding product is high, its design space of part that comprises sensation is big.Particularly, for the high material of total light transmittance, can use dyestuff is that tinting material is given transparent color (being commonly referred to as bone look (skeleton color)), further, can be coloured material combination or to use pigment separately be coloured material and give translucent color or opaque color also with pigment.And, can make light diffusing obtain to express by adding light diffusing agent, can give the light diffusing of targeted degree by the control addition.Therefore, the reduction of the transparency also is the reduction of transmittance, the painted difficulty that becomes that can make transparent color, thus make the part that comprises sensation and diminish the design space that further comprises the painted integral body of giving light diffusing.
Patent documentation 1:JP spy opens communique 2007-No. 31538
Patent documentation 2:JP spy opens flat 07-No. 258532 communiques
Patent documentation 3:JP spy opens flat 11-No. 323118 communiques
Summary of the invention
The object of the present invention is to provide a kind of flame-retardant polycarbonate resin composition that can satisfy the transparency (total light transmittance) of excellent flame and certain limit simultaneously.
In order to solve the problems referred to above in the method for adding fibrillation PTFE, the inventor etc. have carried out concentrated research, it found that, be limited to the specified range of a small amount of scope by addition with fibrillation PTFE, can satisfy anti-fully drippage effect simultaneously, also promptly can satisfy sufficient flame retardant resistance and certain total light transmittance, can keep the painted design space that comprises the sensation part simultaneously and the appearance design that obtains uniqueness, thereby finish the present invention.Promptly, by adding the transmittance that a spot of fibrillation PTFE expresses (when the time for the thick profiled sheeting of 2mm with limited range, total light transmittance is 74～87%) the aromatic polycarbonate resin material, the little by little atomizing that causes because of its a spot of fibrillation PTFE can bring unique " sending out the transparency of mist " high aesthetic appearance.And, find when this material of use, can keep and comprise painted design space sensation, functional part fully.
According to the present invention, a kind of flame retardant resin composition is provided, this resin combination comprises: aromatic polycarbonate resins (A composition) 100 weight parts; Have fibril form ability tetrafluoroethylene, be preferably the tetrafluoroethylene (B composition) that fibril forms ability that has of mixed style, it is 0.1～0.2 weight part with respect to aromatic polycarbonate resins (A composition) 100 weight parts; And fire retardant (C composition), it is 0.001～20 weight part with respect to aromatic polycarbonate resins (A composition) 100 weight parts.
Flame retardant resin composition with above-mentioned composition, the transparency that can satisfy high flame retardancy and certain limit simultaneously is (in the thick profiled sheeting of 2mm, total light transmittance is 74～87%), the resin combination of the big and outward appearance excellence in the space of comparing painted design with the PC of in the past interpolation fibrillation PTFE can be provided, have the characteristic that conventional art does not have.
Embodiment
Below, illustrate in greater detail the present invention.
(A composition: aromatic polycarbonate resins)
The aromatic polycarbonate resins of using as the A composition is in the present invention reacted binary phenol and carbonic ether presoma and the resin that obtains.As the example of reaction method, can enumerate the solid phase ester-interchange method of interfacial polymerization, melt transesterification process, carbonic ether prepolymer and the ring-opening polymerization method of cyclic carbonate compound etc.
As the representative example of binary phenol as used herein, can enumerate quinhydrones, Resorcinol, 4,4 '-bis-phenol, 1,1-two (4-hydroxy phenyl) ethane, 2,2-two (4-hydroxy phenyl) propane (are referred to as dihydroxyphenyl propane usually, below abbreviate " BPA " sometimes as), 2,2-two (4-hydroxyl-3-aminomethyl phenyl) propane, 2,2-two (4-hydroxy phenyl) butane, 1,1-two (4-hydroxy phenyl)-1-diphenylphosphino ethanes, 1,1-two (4-hydroxy phenyl) hexanaphthene, 1,1-two (4-hydroxy phenyl)-3,3,5-trimethyl-cyclohexane, 2,2-two (4-hydroxy phenyl) pentanes, 4,4 '-(to the phenylene diisopropylidene) diphenol, 4,4 '-(metaphenylene diisopropylidene) diphenol, 1,1-two (4-hydroxy phenyl)-4-normenthanes, two (4-hydroxy phenyl) oxide compound, two (4-hydroxy phenyl) sulfide, two (4-hydroxy phenyl) sulfoxide, two (4-hydroxy phenyl) sulfone, two (4-hydroxy phenyl) ketone, two (4-hydroxy phenyl) ester, two (4-hydroxyl-3-aminomethyl phenyl) sulfide, 9,9-two (4-hydroxy phenyl) fluorenes and 9,9-two (4-hydroxyl-3-aminomethyl phenyl) fluorenes etc.Preferred binary phenol is two (4-hydroxy phenyl) paraffinic hydrocarbonss, wherein, considers from the shock-resistance aspect, and preferred especially dihydroxyphenyl propane is widely used.
In the present invention, except dihydroxyphenyl propane class polycarbonate, can also use the special polycarbonate of making by other binary phenol as the A composition as general polycarbonate.
For example, as part or all of binary phenol composition, use 4,4 '-(metaphenylene diisopropylidene) diphenol (following abbreviate as sometimes " BPM "), 1,1-two (4-hydroxy phenyl) hexanaphthene, 1,1-two (4-hydroxy phenyl)-3,3,5-trimethyl-cyclohexane (following abbreviate as sometimes " Bis-TMC "), 9,9-two (4-hydroxy phenyl) fluorenes and 9, the polycarbonate (homopolymer or multipolymer) of 9-two (4-hydroxyl-3-aminomethyl phenyl) fluorenes (following abbreviate as sometimes " BCF "), the dimensional change or the shape stability that are suitable for suction is caused require on the strict especially purposes.These binary phenol except BPA, preferred 5 moles of the binary phenol composition total amount that constitutes this polycarbonate of using are preferably 10 moles more than the % more than the % especially.
Especially, under the situation that requires to have high rigidity and better hydrolytic resistance, the A composition that especially preferably constitutes resin combination is the Copolycarbonate of following (1)～(3).
(1) in the binary phenol composition of this polycarbonate of formation of 100 moles of %, BPM is 20～80 moles of % (40～75 moles of % more preferably, 45～65 moles of % more preferably) and BCF be the Copolycarbonate of 20～80 moles of % (more preferably 25～60 moles of %, more preferably 35～55 moles of %);
(2) in the binary phenol composition of this polycarbonate of formation of 100 moles of %, BPA is 10～95 moles of % (50～90 moles of % more preferably, 60～85 moles of % more preferably) and BCF be the Copolycarbonate of 5～90 moles of % (more preferably 10～50 moles of %, more preferably 15～40 moles of %);
(3) in the binary phenol composition of this polycarbonate of formation of 100 moles of %, BPM is 20～80 moles of % (40～75 moles of % more preferably, 45～65 moles of % more preferably) and Bis-TMC be the Copolycarbonate of 20～80 moles of % (more preferably 25～60 moles of %, more preferably 35～55 moles of %).
These special polycarbonate both can use separately, also can two or morely suitably mix and use.In addition, also these can be mixed use with general bisphenol A polycarbonate.
About the manufacture method and the characteristic of these special polycarbonate, for example in the flat 6-172508 communique of TOHKEMY, the flat 8-27370 communique of TOHKEMY, TOHKEMY 2001-55435 communique and TOHKEMY 2002-117580 communique etc., detailed record is arranged.
In addition, in above-mentioned various polycarbonate, by adjusting multipolymer composition etc. water-intake rate and Tg (second-order transition temperature) are adjusted at polycarbonate in the following ranges, the hydrolytic resistance of its polymkeric substance self is good, and the low bendability after the moulding is also excellent especially, therefore, be particularly suitable for requiring to have in the field of shape stability.
(i) water-intake rate is 0.05～0.15%, is preferably 0.06～0.13%; And Tg is 120～180 ℃ a polycarbonate; Perhaps
(ii) Tg is 160～250 ℃, is preferably 170～230 ℃; And water-intake rate is 0.10～0.30%, be preferably 0.13～0.30%, more preferably 0.14～0.27% polycarbonate.
At this, the water-intake rate of polycarbonate is to utilize diameter for 45mm, the thickness discoideus test piece for 3.0mm, according to ISO62-1980, be determined at dipping in 23 ℃ the water after 24 hours moisture content and the numerical value that obtains.In addition, Tg (second-order transition temperature) is according to JIS K7121, the numerical value of trying to achieve with differential scanning calorimeter (DSC) mensuration.
As the carbonic ether precursor, use carboxylic acid halides (Carbonyl halide), carbonic diester or haloformate (Ha ロ ホ Le メ-ト) etc., specifically, can enumerate the bishaloformate etc. of phosgene (Phosgene), diphenyl carbonate or binary phenol.
When by interfacial polymerization, when making aromatic polycarbonate resin, also can use catalyzer, end to stop agent, antioxidant etc. as required by above-mentioned binary phenol and carbonic ether precursor, wherein antioxidant is in order to prevent the oxidation of binary phenol.In addition, the aromatic polycarbonate resin comprises: with the branched polycarbonate resin of copolymerization in addition of the multifunctional aromatics more than the three-functionality-degree; With two functionality carboxylic acids of aromatic series or aliphatics (comprising ester ring type) the polyestercarbonate resin of copolymerization in addition; With two functionality alcohol (the comprising ester ring type) copolymerized panlite of copolymerization in addition; And with this two functionality carboxylic acid and the two official's degree alcohol polyestercarbonate resin of copolymerization in addition.In addition, also can be two or more blended mixtures in addition with resulting aromatic polycarbonate resin.
Branched polycarbonate resin can be given antidrip drop etc. to resin combination of the present invention.As the multifunctional aromatics more than the three-functionality-degree that is used for this branched polycarbonate resin, can enumerate Phloroglucinol monomethyl ether, Gen Pi Portugal phenol or 4,6-dimethyl-2,4,6-three (4-hydroxy phenyl) heptene-2,2,4,6-trimethylammonium-2,4,6-three (4-hydroxy phenyl) heptane, 1,3,5-three (4-hydroxy phenyl) benzene, 1,1,1-three (4-hydroxy phenyl) ethane, 1,1,1-three (3,5-dimethyl-4-hydroxy phenyl) ethane, 2, two (2-hydroxyl-5-the methyl-benzyl)-4-methylphenols of 6-, 4-{4-[1, two (4-hydroxy phenyl) ethyls of 1-] benzene }-α, the triphenol of α-Er Jiajibianji phenol etc.; Four (4-hydroxy phenyl) methane, two (2, the 4-dihydroxy phenyl) ketone, 1, two (4, the 4-dihydroxyl trityl group) benzene of 4-or trimellitic acid, Pyromellitic Acid, benzophenone tetracarboxylic acid (Benzophenone tetracarboxylic) and their sour muriate etc.Wherein, preferred 1,1,1-three (4-hydroxy phenyl) ethane, 1,1,1-three (3,5-dimethyl-4-hydroxy phenyl) ethane is preferably 1,1,1-three (4-hydroxy phenyl) ethane especially.
100 moles of % from binary phenol deutero-structural unit with from the total amount of this polyfunctionality aromatics deutero-structural unit, in the preferred branched polycarbonate is 0.01～1 mole of % from polyfunctionality aromatics deutero-structural unit, is preferably 0.05～0.9 mole of %, is preferably 0.05～0.8 mole of % especially.
In addition, when particularly adopting melt transesterification process, sometimes produce the branched structure unit as side reaction, about the unitary content of this branched structure, also from the total amount of binary phenol deutero-structural unit, accounting for 0.001～1 mole of %, be preferably 0.005～0.9 mole of %, be preferably 0.01～0.8 mole of % especially at 100 moles of %.In addition, the content of above-mentioned branched structure can pass through 1H-NMR measures and calculates.
Two functionality carboxylic acids of preferred aliphat are alpha, omega-dicarboxylic acid.As aliphatic two functionality carboxylic acids, preferably can enumerate direct-connected saturated aliphatic dicarboxylic acids such as sebacic acid (sebacic acid), dodecanedioic acid (Dodecandioic acid), tetradecane diacid, octadecane diacid, octadecane dicarboxylic acid; And the alicyclic dicarboxylic acid of cyclohexane dicarboxylic acid etc.As two functionality alcohol, be preferably alicyclic diol, for example can enumerate cyclohexanedimethanol, cyclohexane diol and tristane dimethanol etc.
In addition, can also use the polyorganosiloxane units polycarbonate-poly organo alkyl copolymer of copolymerization in addition.
As the reactive modes such as ring-opening polymerization method of interfacial polymerization, melt transesterification process, carbonic ether prepolymer solid phase ester-interchange method and the cyclic polycarbonates compound of the manufacture method of polycarbonate resin of the present invention, be by known methods such as various documents and patent gazettes.
When making flame retardant resin composition of the present invention, the viscosity-average molecular weight (M) of aromatic polycarbonate resin is not done special the qualification, but be preferably 1 * 10 4～5 * 10 4, more preferably 1.4 * 10 4～3 * 10 4, more preferably 1.4 * 10 4～2.4 * 10 4
Be lower than 1.0 * 10 in viscosity-average molecular weight 4Aromatic polycarbonate resin in, can't obtain the favorable mechanical characteristic.On the other hand, surpass 5 * 10 by viscosity-average molecular weight 4The resin combination that obtains of aromatic polycarbonate resin, its flowability when injection molding is poor, so versatility is poor.
In addition, aromatic polycarbonate resin also can obtain by viscosity-average molecular weight is mixed at the aromatic polycarbonate resin beyond the above-mentioned scope.Particularly, has the above-mentioned scope (5 * 10 of surpassing 4) the aromatic polycarbonate resin of viscosity-average molecular weight, can improve the entropy-elasticity (entropyelasticity) of resin.Its result in the gas assistant formation and foaming that adopts, can bring into play good forming process when reinforced resin material is shaped to structure unit.This moment, the improvement of forming process was more excellent than above-mentioned branched polycarbonate.As more preferred form, also can use the A composition is 7 * 10 by viscosity-average molecular weight 4～3 * 10 5Aromatic polycarbonate resin (A-1-1 composition) and viscosity-average molecular weight be 1 * 10 4～3 * 10 4Aromatic polycarbonate resin (A-1-2 composition) form, its viscosity-average molecular weight is 1.6 * 10 4～3.5 * 10 4Aromatic polycarbonate resin (A-1 composition) (below, be also referred to as " aromatic polycarbonate resin of pbz polymer amount composition " sometimes).
In the aromatic polycarbonate resin (A-1 composition) of above-mentioned pbz polymer amount composition, the molecular weight of preferred A-1-1 composition is 7 * 10 4～2 * 10 5, more preferably 8 * 10 4～2 * 10 5, more preferably 1 * 10 5～2 * 10 5, be preferably 1 * 10 especially 5～1.6 * 10 5In addition, the molecular weight of A-1-2 composition is preferably 1.0 * 10 4～2.5 * 10 4, more preferably 1.1 * 10 4～2.4 * 10 4, more preferably 1.2 * 10 4～2.4 * 10 4, be preferably 1.2 * 10 especially 4～2.3 * 10 4
The aromatic polycarbonate resin of pbz polymer amount composition (A-1 composition) can be by being mixed above-mentioned A-1-1 composition and A-1-2 composition with various ratios, and it is adjusted into the molecular weight ranges that satisfies regulation and obtains.In the A-1 composition of 100 weight %, preferred A-1-1 composition is 2～40 weight %, 3～30 weight % more preferably, and more preferably 4～20 weight % are preferably 5～20 weight % especially.
In addition, as the preparation method of A-1 composition, can enumerate, (1) is polymerization A-1-1 composition and A-1-2 composition independently respectively, and with they blended methods in addition; (2) adopting with method shown in flat 5-No. 306336 communiques of TOHKEMY is method representative, that will make in same system according to the aromatic polycarbonate resin of a plurality of polymkeric substance peak values of expression in the graph of molecular weight distribution of GPC method, and makes this aromatic polycarbonate resin manufacture the method for the condition that satisfies A-1 composition of the present invention: and the A-1-1 composition of (3) aromatic polycarbonate resin that will obtain by this manufacture method (manufacture method of (2)) and manufacturing separately and/or A-1-2 composition blended method etc. in addition.
The said viscosity-average molecular weight of the present invention can be calculated according to following method.At first, from the solution that under 20 ℃, the 0.7g aromatic copolycarbonate is dissolved in the 100ml methylene dichloride and obtains, use Ostwald viscometer, obtain specific viscosity (η by following formula Sp):
Specific viscosity (η Sp)=(t-t 0)/t 0
[t 0Be drippage number second of methylene dichloride, drippage number second that t is sample solution];
According to resulting specific viscosity (η Sp), calculate viscosity-average molecular weight M by following formula:
η Sp/ c=[η]+0.45 * [η] 2C ([η] is limiting viscosity)
[η]＝1.23×10 -4M 0.83
c＝0.7。
In addition, in the flame retardant resin composition of the present invention, the calculating of the viscosity-average molecular weight of aromatic polycarbonate resin is to carry out according to following method.That is, this resin combination is mixed with 20～30 times methylene dichloride of its weight, thus the solvable composition in the dissolved composition.Obtain this solvable composition by diatomite filtration.Then, the solvent in the removal gained solution.Solid behind the removal solvent is carried out sufficient drying, obtain to be dissolved in the solids component of methylene dichloride.The solution that obtains from this solid of 0.7g is dissolved in the 100ml methylene dichloride, obtain specific viscosity under 20 ℃ with above-mentioned same operation, and, obtain viscosity-average molecular weight M with above-mentioned same operation from this specific viscosity.
(B composition: have the tetrafluoroethylene (fibrillation PTFE) that fibrillation forms function)
The fibrillation PTFE that uses among the present invention both can be independent fibrillation PTFE, also can be the fibrillation PTFE of mixed style,, also can be the tetrafluoroethylene class mixture of fibrillation PTFE particle and organic polymer formation that is.
Fibrillation PTFE has ultra high molecular weight, and the external action that demonstrates by shearing force etc. makes between the PTFE in conjunction with forming fibrous tendency.Its number-average molecular weight is 1,500,000～several scopes of ten million.The lower limit of this number-average molecular weight more preferably 3,000,000.As shown in flat 6-No. 145520 communiques of TOHKEMY, this number-average molecular weight can be calculated according to the melt viscosity of the tetrafluoroethylene under 380 ℃.That is, as the fibrillation PTFE of B composition, the melt viscosity under its 380 ℃ of measuring by the method put down in writing in this communique is 10 7～10 13The scope of poise is preferably 10 8～10 12The scope of poise.
This PTFE both can use the PTFE of solid shape, also can use the PTFE of aqueous liquid dispersion form.In addition, in order to improve the dispersiveness of fibrillation PTFE in resin, and in order to obtain more excellent flame and mechanical characteristics, also can use the PTFE mixture of mixed style of mixed with resin with other.In addition, also preferred utilize as TOHKEMY is put down in 6-No. 145520 communiques disclosedly has with this fibrillation PTFE and is nuclear, is the material of the structure of shell with low-molecular-weight tetrafluoroethylene.
As the commercially available product of this fibrillation PTFE, for example can enumerate DU PONT-MITSUIFLUOROCHEMICALS COMPANY, Port リ Off ロ Application MPAFA500, F-201L etc. that テ Off ロ Application (registered trademark) 6J of LTD, DAIKIN chemical industry (strain) are made.Commercially available product as the aqueous liquid dispersion of fibrillation PTFE, for example can enumerate Off Le オ Application AD-1, AD-936 that rising sun ア イ シ-ア イ Off ロ ロ Port リ マ-ズ (strain) makes, Off Le オ Application D-1, D-2 that DAIKIN industry (strain) is made, DU PONT-MITSUI FLUOROCHEMICALSCOMPANY, テ Off ロ Application (registered trademark) 30J that LTD makes etc.
As the fibrillation PTFE of mixed style, can use the fibrillation PTFE of the mixed style that makes by the method shown in following (1)～(5).That is, (1) is with the aqueous liquid dispersion of the aqueous liquid dispersion of fibrillation PTFE and organic polymer or solution is mixed and carry out co-precipitation and obtain the method (method of record in clear 60-No. 258263 communiques of TOHKEMY, clear 63-No. 154744 communiques of TOHKEMY etc.) of common aggegation mixture; (2) with the aqueous liquid dispersion of fibrillation PTFE and exsiccant organic polymer particle blended method (method of putting down in writing in flat 4-No. 272957 communiques of TOHKEMY) in addition; (3) with aqueous liquid dispersion and the organic polymer particle solution uniform mixing of fibrillation PTFE, the method (method of putting down in writing flat 06-No. 220210 communiques of TOHKEMY, flat 08-No. 188653 communiques of TOHKEMY etc.) of removing medium separately simultaneously from this mixture; (4) polymerization is used to form the monomer methods (method of putting down in writing in flat 9-No. 95583 communiques of TOHKEMY) of organic polymer in the aqueous liquid dispersion of fibrillation PTFE; (5) behind the aqueous liquid dispersion and organic polymer dispersion liquid uniform mixing with PTFE, further polymerising ethylene class monomer in this mixed dispersion liquid obtains the method (methods of record in flat 11-No. 29679 communiques of TOHKEMY etc.) of mixture then.
As the commercially available product of the fibrillation PTFE of these mixed styles, can enumerate [メ Block レ Application A3000] (trade(brand)name), [メ Block レ Application A3700] (trade(brand)name made from Mitsubishi RayonCo.Ltd.), the メ Block レ Application A series that [メ Block レ Application A3800] (trade(brand)name) is representative; The POLY TS AD001 (trade(brand)name) of PIC society; And [BLENDEX B449] (trade(brand)name) of GE ス ペ シ ヤ リ テ イ-ケ ミ カ Le ズ society manufacturing etc.
As the ratio of the fibrillation PTFE of mixed style, in this mixture of 100 weight %, preferred fibrillation PTFE is 1～95 weight %, more preferably 10～90 weight %, more preferably 20～80 weight %.When less than 1 weight %, the organic polymer part shared ratio in flame-retardant copolycarbonate resin of the present invention in the mixed style has the trend that becomes many, thereby transparent easy the reduction, and the effect of improving of flame retardant resistance also becomes beyond expression of words.When surpassing 95 weight %, then be difficult to reach high-caliber appearance.In addition, when surpassing 90 weight %, diminish, thereby considering to use aspect cost is not that the fibrillation PTFE of mixed style is then more favourable with the difference of performance that is not the PTFE of mixed style.
The ratio of fibrillation PTFE in the mixed style can realize the good dispersiveness of fibrillation PTFE when this scope.
With respect to the A composition of 100 weight parts, the content of tetrafluoroethylene (B composition) in resin combination with fibril formation ability is preferably 0.1～0.2 weight part, more preferably 0.1～0.19 weight part, more preferably 0.1～0.18 weight part.In addition, when tetrafluoroethylene of the present invention was mixed style (mixture), the weight part shown in was represented the weight of mixture integral body here.
A composition with respect to 100 weight parts, if the content with tetrafluoroethylene (B composition) of fibril formation ability departs from the scope of 0.1～0.2 weight part, then exist the problem of " the unique mist transparent feel " that can not only be expressed the transparent degree of stipulating in the resin combination of the present invention.In addition, when being lower than 0.10 weight part, can not keep sufficient flame retardant resistance, when surpassing 0.20 weight part, then exist the problem, the particularly shock strength in the test film of specific high-temperature area moulding that the mechanical-physical character of shock strength etc. reduces and reduce.
(C composition: fire retardant)
The fire retardant of C composition is as the fire retardant of polycarbonate resin and known various compound.The cooperation of this compound can bring the raising of flame retardant resistance, in addition, can also be based on the character of each compound, bring raising of for example static electricity resistance, flowability, rigidity and thermostability etc.As above-mentioned fire retardant, can enumerate (i) organic metal salt based flame retardant (for example, organic sulfonic acid alkali (alkali earths) metal-salt, organic boronic metallic salt fire retardant and organotin acid metal salt based flame retardant etc.); (ii) organic phosphates fire retardant (phosplate compound, phosphoric acid ester oligopolymer, phosphonate oligomers, phosphine nitrile oligopolymer and the phosphonic acid amide compound etc. that for example, contain organic group); The (iii) silicon based flame retardant that forms by silicon compound, wherein, preferred organic metallic salt fire retardant.
(i) organic metal salt based flame retardant
Organic metal salt fire retardant among the present invention is that carbonatoms is 1～50, is preferably 1～40 organic acid alkali (alkali earths) metal-salt, more preferably organic sulfonic acid alkali (alkali earths) metal-salt.This organic sulfonic acid alkali (alkali earths) metal-salt comprises: the metal-salt of fluorine substituted alkyl sulfonic acid is 1～10, is preferably 2～8 the perfluoro alkyl sulfonic acid and the metal-salt of basic metal or alkaline-earth metal as carbonatoms; And carbonatoms is 7～50, is preferably 7～40 the aromatic sulphonic acid and the metal-salt of basic metal or alkaline-earth metal.
As the basic metal that constitutes metal-salt of the present invention, can enumerate lithium, sodium, potassium, rubidium and caesium; As alkaline-earth metal, can enumerate beryllium, magnesium, calcium, strontium and barium.Basic metal more preferably.In this basic metal, but then, owing to they are not general and are difficult to make with extra care, therefore, there is defective in preferred bigger rubidium and the caesium of ionic radius that use on cost under the higher situation of the requirement of the transparency.In addition, the metal that lithium and sodium plasma radius are littler is then unfavorable to flame retardant resistance sometimes.Can distinguish the basic metal that uses in the sulfonic acid alkali metal salts according to above-mentioned situation, but no matter consider which aspect, the sulfonic acid potassium salt of balance of properties excellence is best suited for all using.Also can be with this sylvite and sulfonic acid alkali metal salts that forms by other basic metal and usefulness.
As the object lesson of the fluorine-containing organic metal salt based flame retardant of perfluoro alkyl sulfonic acid an alkali metal salt etc., can enumerate trifluoromethayl sulfonic acid potassium, potassium perfluorobutane sulfonate, perflexane potassium sulfonate, Perfluorooctane sulfonates potassium, pentafluoride ethane sodium sulfonate, perfluorinated butane sodium sulfonate, Perfluorooctane sulfonates sodium, trifluoromethayl sulfonic acid lithium, perfluorinated butane sulfonic acid lithium, PF 5070 sulfonic acid lithium, trifluoromethayl sulfonic acid caesium, perfluorinated butane sulfonic acid caesium, Perfluorooctane sulfonates caesium, perflexane sulfonic acid caesium, perfluorinated butane sulfonic acid rubidium and perflexane sulfonic acid rubidium etc.These both can be used alone, also can two or more and usefulness.At this, the carbonatoms of perfluoroalkyl is preferably 1～18 scope, more preferably 1～10 scope, 1～8 scope more preferably.Wherein, be preferably potassium perfluorobutane sulfonate especially.
In perfluoro alkyl sulfonic acid alkali (alkali earths) metal-salt that forms by basic metal, sneak into a lot of fluoride ion (F usually -).Having of this fluoride ion may become the reason that reduces flame retardant resistance, therefore, preferably reduces the existence of fluoride ion as far as possible.The content of this fluoride ion can be measured by ion chromatography.Preferred fluorinated thing ionic content be 100ppm following, more preferably 40ppm following, be preferably below the 10ppm especially.In addition, when considering, more than the preferred 0.2ppm from making efficient.Reduced perfluoro alkyl sulfonic acid alkali (alkali earths) metal-salt of above-mentioned fluoride ion content, its manufacture method adopts known manufacture method, and can make by the following method.That is the method etc. that the gas of the method for the fluoride ion content that contains in the raw material when, reduce making fluorine-containing organic metal salt, generation during with reaction or heating remove by the method for reacting resulting hydrogen fluoride etc. and reduce fluoride ion content when making fluorine-containing organic metal salt with the process for purification of recrystallization and redeposition etc.Particularly, because the C composition relatively dissolves easily in water, therefore, especially preferably make by following operation.This operation is, adopts ion exchanged water, and particularly adopting resistance value is more than the 18M Ω cm, and promptly electric conductivity satisfies and is about the following water of 0.55 μ S/cm, and dissolves under the temperature higher than normal temperature and wash, and cooled off the operation that makes it recrystallization then.
Object lesson as aromatic sulphonic acid alkali (alkali earths) metal-salt, for example, can enumerate diphenyl sulfide-4,4 '-disulfonic acid disodium, diphenyl sulfide-4,4 '-disulfonic acid dipotassium, 5-sulfo group m-phthalic acid potassium, 5-sulfo group m-phthalic acid sodium, the many sodium of the many sulfonic acid of polyethylene terephthalic acid (Port リ エ チ レ Application テ レ Off Le acid Port リ ス Le ホ Application acid Port リ Na ト リ ウ system), 1-methoxynaphthalene-4-calcium sulphonate, 4-lauryl phenyl ether disulfonic acid disodium, poly-(2,6-dimethyl phenylene oxide) the many sodium of many sulfonic acid (Port リ (2,6-ジ メ チ Le Off ェ ニ レ Application オ キ シ De) Port リ ス Le ホ Application acid Port リ Na ト リ ウ system), poly-(1,3-phenylene oxide) the many sodium of many sulfonic acid (Port リ (1,3-Off ェ ニ レ Application オ キ シ De) Port リ ス Le ホ Application acid Port リ Na ト リ ウ system), poly-(1,4-phenylene oxide) the many sodium of many sulfonic acid (Port リ (1,4-Off エ ニ レ Application オ キ シ De) Port リ ス Le ホ Application acid Port リ Na ト リ ウ system), poly-(2,6-phenylbenzene phenylene oxide) the many potassium of many sulfonic acid (Port リ (2,6-ジ Off エ ニ Le Off ェ ニ レ Application オ キ シ De) Port リ ス Le ホ Application acid Port リ カ リ ウ system), poly-(2-fluoro-6-butyl phenylene oxide) poly-sulfonic acid lithium, the potassium sulfonate of benzene sulfonate, benzene sulfonic acid sodium salt, the Phenylsulfonic acid strontium, Phenylsulfonic acid magnesium, to the benzene disulfonic acid dipotassium, naphthalene-2,6-disulfonic acid dipotassium, biphenyl-3,3 '-disulfonic acid calcium, sulfobenzide-3-sodium sulfonate, sulfobenzide-3-potassium sulfonate, sulfobenzide-3,3 '-disulfonic acid dipotassium, sulfobenzide-3,4 '-disulfonic acid dipotassium, α, α, α-trifluoroacetophenone-4-sodium sulfonate, benzophenone-3,3 '-disulfonic acid dipotassium, thiophene-2,5-disulfonic acid disodium, thiophene-2,5-disulfonic acid dipotassium, thiophene-2,5-disulfonic acid calcium, the thionaphthene sodium sulfonate, diphenyl sulfoxide-4-potassium sulfonate, the formalin condenses of sodium naphthalene sulfonate, and the formalin condenses of anthracene sulfonic acid sodium etc.In these aromatic sulphonic acid alkali (alkali earths) metal-salts, preferred especially sylvite.
In these aromatic sulphonic acid alkali (alkali earths) metal-salts, preferred sulfobenzide-3-potassium sulfonate and sulfobenzide-3,3 '-disulfonic acid dipotassium, preferred especially their mixture (the former and the latter's weight ratio is 15/85～30/70).
As the organic metal salt beyond azochlorosulfonate acid alkali (alkali earths) metal-salt, can preferably enumerate alkali (alkali earths) metal-salt of sulfuric ester and alkali (alkali earths) metal-salt of aromatic sulfonamide etc.Alkali (alkali earths) metal-salt as sulfuric ester, can enumerate alkali (alkali earths) metal-salt of monobasic and/or polyalcohols sulfuric ester especially, as this monobasic and/or polyalcohols sulfuric ester, can enumerate the sulfuric ester of methyl sulfate, sulfovinic acid, lauryl sulfate, hexadecyl hydrosulfate ester, poly-hydroxyalkyl vinyl base alkyl phenyl ether, one, two, three, four sulfuric esters of tetramethylolmethane, sulfuric ester, the sulfuric ester of hexadecanoic acid direactive glyceride and the sulfuric ester of glyceryl monostearate etc. of month silicic acid direactive glyceride.As alkali (alkali earths) metal-salt of these sulfuric esters, preferably enumerate alkali (alkali earths) metal-salt of lauryl sulfate.
As alkali (alkali earths) metal-salt of aromatic sulfonamide, for example can enumerate alkali (alkali earths) metal-salt of asccharin, N-p-toluenesulfonyl-tolysulfonyl imines, N-(N '-benzylamino carbonyl) sulfimide and N-(phenyl carboxyl) sulfimide etc.
With respect to the A composition of 100 weight parts, the content of organic metal salt based flame retardant is 0.001～1 weight part, be preferably 0.005～0.5 weight part, more preferably 0.01～0.3 weight part, more preferably 0.03～0.15 weight part.
(ii) organic phosphates fire retardant
As the organic phosphates fire retardant, the preferred aryl groups phosphate compound.This is because all very excellent cause of the common color and luster of this phosphate compound.In addition, phosphate compound has the plasticity-effect, and is therefore, favourable aspect the forming process that improves resin combination of the present invention.As this phosphate compound,, more preferably enumerate one or more the phosphate compound of particularly using following general formula (i) expression though can use in the past as the known various phosphate compounds of fire retardant.
Figure A200810098983D00151
(in the formula (i), X 1For from binary phenol deutero-divalent organic group; R 1, R 2, R 3And R 4Distinguish independence and expression from monobasic phenol deutero-any monovalent organic radical group; J, k, l and m are independent respectively and be 0 or 1; N is 0～5 integer, and under the situation that is the different phosphate mixture of the polymerization degree, n represents its mean value, is 0～5 numerical value.)
The phosphate compound of above-mentioned formula, it also can be mixture with compound of different n numerical value, when being this mixture, the mean value of preferred n is 0.5～1.5, more preferably 0.8～1.2, more preferably 0.95～1.15, is preferably 1～1.14 scope especially.
As the above-mentioned X that derives 1The preferred object lesson of binary phenol, can enumerate by quinhydrones, Resorcinol, two (4-hydroxy diphenyl) methane, dihydroxyphenyl propane, dihydroxyl phenylbenzene, remove two hydroxyls in the dihydroxy compound of selecting among the group that dihydroxy naphthlene, two (4-hydroxy phenyl) sulfone, two (4-hydroxy phenyl) ketone and two (4-hydroxy phenyl) sulfide are formed and the divalent group that obtains.
As R 1, R 2, R 3And R 4Object lesson, can enumerate respectively a hydroxyl of removal in the monohydroxy compound of selecting among independent and the group that can be replaced by more than one halogen atom, forms and the univalent perssad that obtains by phenol, cresols, xylenol, isopropyl-phenol, butylphenol and to cumyl phenol.
As the above-mentioned R that derives 1, R 2, R 3And R 4The preferred object lesson of a bivalent phenol, can enumerate phenol, cresols, xylenol, isopropyl-phenol, butylphenol and, wherein, be preferably phenol and 2,6-xylenol cumyl phenol.
In addition, this monobasic phenol can be replaced by halogen atom, as the object lesson that contains by the phosphate compound of this monobasic phenol deutero-group, can enumerate three (2,4,6-tribromo phenyl) phosphoric acid ester, three (2, the 4-bromophenyl) phosphoric acid ester and three (4-bromophenyl) phosphoric acid ester etc.
On the other hand, as the object lesson of the phosphate compound that is not replaced by halogen atom, can preferably enumerate phosplate compounds such as triphenyl and three (2, the 6-3,5-dimethylphenyl) phosphoric acid ester; And two two (2, the 6-3,5-dimethylphenyl) phosphoric acid ester of Resorcinol are as the phosphoric acid ester oligopolymer of main body; With 4,4-dihydroxyl phenylbenzene two (diphenyl phosphoester) is as the phosphoric acid ester oligopolymer of main body; And with dihydroxyphenyl propane two (diphenyl phosphoesters) as main body the phosphoric acid ester oligopolymer (said as main body at this, be that expression can contain other different compositions of the polymerization degree on a small quantity, preferably represent in the above-mentioned formula (1) component content of n=1 be 80 weight % above, more preferably 85 weight % above, more preferably more than the 90 weight %.)
With respect to the A composition of 100 weight parts, the content of organic phosphates fire retardant is 0.01～20 weight part, be preferably 2～10 weight parts, 2～7 weight parts more preferably.
(iii) silicon based flame retardant
As the silicon compound that the silicon based flame retardant uses, the chemical reaction when being meant by burning improves the compound of flame retardant resistance.As this compound, all cpds that can use in the past the fire retardant as aromatic polycarbonate resin to propose.Silicon compound is considered to be in when burning, forms structure (structure) by the combination of himself or by combining with composition from resin, and perhaps the reduction reaction when forming this structure is given flame retardant effect to polycarbonate resin.Therefore, preferably contain active high group in above-mentioned reaction.More particularly, preferably contain at least a group that is selected from alkoxyl group and the hydrogen base (Ha イ De ロ ジ エ Application) (being the Si-H yl).The content of preferred this group (alkoxyl group, Si-H yl) is than being the scope of 0.1～1.2mol/100g, more preferably scope, the scope of 0.15～0.6mol/100g more preferably of 0.12～1mol/100g.This content ratio can utilize caustic leaching process, obtains by hydrogen or pure amount that the silicon compound of measuring per unit weight produces.In addition, preferred alkoxyl group is that carbonatoms is 1～4 alkoxyl group, is preferably methoxyl group especially.
Usually, the structure of silicon compound is to constitute by the following four kinds of siloxane units of arbitrary combination.That is,
M unit: (CH 3) 3SiO 1/2, H (CH 3) 2SiO 1/2, H 2(CH 3) SiO 1/2, (CH 3) 2(CH 2=CH) SiO 1/2, (CH 3) 2(C 6H 5) SiO 1/2, (CH 3) (C 6H 5) (CH 2=CH) SiO 1/2Deng the single functionality siloxane unit;
D unit: (CH 3) 2SiO, H (CH 3) SiO, H 2SiO, H (C 6H 5) SiO, (CH 3) (CH 2=CH) SiO, (C 6H 5) 2The two functionality siloxane units of SiO etc.;
T unit: (CH 3) SiO 3/2, (C 3H 7) SiO 3/2, HSiO 3/2, (CH 2=CH) SiO 3/2, (C 6H 5) SiO 3/2Deng the three-functionality-degree siloxane unit;
Q unit: use SiO 2Four functionality siloxane units of expression.
The structure that is used for the silicon compound of silicon based flame retardant can be enumerated the structure of representing with following signal formula particularly, that is, and and D n, T p, M mD n, M mT p, M mQ q, M mD nT p, M mD nQ q, M mT pQ q, M mD nT pQ q, D nT p, D nQ q, D nT pQ qWherein, preferred silicon compound structure is M mD n, M mT p, M mD nT p, M mD nQ q, preferred structure is M mD nOr M mD nT p
At this, the Coefficient m in the above-mentioned signal formula, n, p, q are the integer more than 1 of the polymerization degree of each siloxane unit of expression, and the summation of coefficient is the mean polymerisation degree of silicon compound in each signal formula.Preferred this mean polymerisation degree 3～150 scope, more preferably 3～80 scope, more preferably 3～60 scope, be preferably 4～40 scope especially.This mean polymerisation degree is in preferred range more, and its flame retardant resistance is then excellent more.And, containing the silicon compound of the aromatic group of specified amount as described later, its transparency or color and luster are also excellent.Consequently, can access good reflected light.
In addition, when among m, n, p, the q any one is numerical value more than 2,, can be that institute's bonded hydrogen atom or organic residue are different two or more siloxane units with the siloxane unit of this coefficient.
Silicon compound both can be a linear chain structure, also can be the silicon compound with branched structure.In addition, being preferably carbonatoms with the organic residue of Siliciumatom bonded is organic residue of 1～30, more preferably 1～20.As this organic residue, can enumerate the alkyl of methyl, ethyl, propyl group, butyl, hexyl and decyl etc. particularly; The cycloalkyl of cyclohexyl etc.; The aryl of phenyl etc.; The aralkyl of tolyl etc. etc.More preferably carbonatoms is 1～8 alkyl, thiazolinyl or aryl.As alkyl, the carbonatoms that is preferably methyl, ethyl, propyl group etc. especially is 1～4 alkyl.
And the silicon compound that uses as the silicon based flame retardant preferably contains aryl.On the other hand, silane compound and silicone compounds as organic surface treatment agent of TiO 2 pigment can access the ideal effect when it does not contain aryl, therefore, can be differentiated clearly in its preferred form with the silicon based flame retardant.Preferred silicon based flame retardant is that the ratio (aromatic group amount) of the aromatic group (ii) represented with following general formula is the silicon compound of 10～70 weight % (15～60 weight % more preferably).
Figure A200810098983D00181
(formula (ii) in, X represents independently that respectively OH base, carbonatoms are 1～20 the organic residue of monovalence; N represents 0～5 integer.And formula (ii) in, when n is 2 when above, can get mutual different types of X respectively.)
Silicon compound as the silicon based flame retardant uses can also contain reactive group except above-mentioned Si-H base and alkoxyl group, as this reactive group, for example can enumerate amino, carboxyl, epoxy group(ing), vinyl, sulfydryl, methacryloxy etc.
As silicon compound, preferably enumerate and contain (iii) and the (iv) at least a above silicon compound in the structural unit of expression of useful following general formula with Si-H base:
Figure A200810098983D00182
(formula (iii) and formula (iv) in, Z 1～Z 3Represent independently that respectively hydrogen atom, carbonatoms are 1～20 the organic residue of monovalence or with following general formula (v) Biao Shi compound; α 1～α 3 represents 0 or 1 respectively independently; M1 represents the integer more than 0 or 1; Further, formula (iii) in, when m1 is 2 when above, its repeating unit can be got different a plurality of repeating units mutually respectively.)
Figure A200810098983D00191
(formula (v), Z 4～Z 8Represent independently that respectively hydrogen atom, carbonatoms are 1～20 the organic residue of monovalence; α 4～α 8 represents 0 or 1 respectively independently; M2 represents the integer more than 0 or 1; Further, (v), when m2 is 2 when above, its repeating unit can be got different a plurality of repeating units mutually respectively in formula.)
At the silicon compound that is used for the silicon based flame retardant, as silicon compound with alkoxyl group, for example can enumerate be selected from general formula (vi) and general formula (the vii) at least a compound in Biao Shi the compound:
Figure A200810098983D00192
(formula (vi), β 1Expression vinyl, carbonatoms are that 1～6 alkyl, carbonatoms are that 3～6 cycloalkyl, carbonatoms are 6～12 aryl and aralkyl; γ 1, γ 2, γ 3, γ 4, γ 5And γ 6The expression carbonatoms is that 1～6 alkyl and cycloalkyl and carbonatoms are 6～12 aryl and aralkyl, and wherein at least one group is an aryl or aralkyl; δ 1, δ 2, δ 3The expression carbonatoms is 1～4 alkoxyl group.)
Figure A200810098983D00201
(formula (vii), β 2, β 3Expression vinyl, carbonatoms are that 1～6 alkyl, carbonatoms are that 3～6 cycloalkyl and carbonatoms are 6～12 aryl and aralkyl; γ 7, γ 8, γ 9, γ 10, γ 11, γ 12, γ 13And γ 14The expression carbonatoms is that 1～6 alkyl, carbonatoms are that 3～6 cycloalkyl, carbonatoms are 6～12 aryl and aralkyl, and wherein at least one group is an aryl or aralkyl; δ 4, δ 5, δ 6, δ 7The expression carbonatoms is 1～4 alkoxyl group.)
With respect to the A composition of 100 weight parts, the content of silicon based flame retardant is 0.01～20 weight part, be preferably 0.5～10 weight part, 1～5 weight part more preferably.
(other composition)
Can cooperate the various additives that cooperate usually in a spot of reinforcement packing material, the polycarbonate resin in the flame-retardant polycarbonate resin composition of the present invention.
(I) strengthen packing material
Can cooperate at least a reinforcement packing material that is selected among the group who forms by tabular inorganic filling material and fibrous inorganic filling material as strengthening packing material.But,, therefore preferably adopt little silicate minerals class packing material of shape or category of glass packing material as strengthening packing material because resin combination of the present invention requires to have good surface appearance.As this silicate minerals class packing material, can preferably enumerate talcum, white mica, synthetic fluorine mica, montmorillonite and wollastonite.As the category of glass packing material, can enumerate glass fibre, sheet glass and glass milled fiber etc.Silicate minerals class packing material and category of glass packing material can adopt the packing material of coating of metal oxides such as its surperficial oxidized titanium, zinc oxide, cerium oxide and silicon oxide.
Above-mentioned reinforcement packing material can be implemented surface treatment by surface treatment agent in advance.As this surface treatment agent, can enumerate the various surface treatment agents of silane coupling agent (comprising alkylalkoxy silane or poly-organohydrogensiloxanes etc.), high-grade aliphatic ester, acid compound (for example, phosphorous acid, phosphoric acid, carboxylic acid, carboxylic acid anhydride etc.) and wax etc.Further, also can carry out granulation and make it to become particulate state by the collecting agent of various resins, high-grade aliphatic ester and wax etc.
With respect to the A composition of 100 weight parts, the content of strengthening packing material is 1～50 weight part, be preferably 1～20 weight part, 1～3 weight part more preferably.
(II) Phosphorus stablizer
In the flame retardant resin composition of the present invention, can not promote preferably to cooperate Phosphorus stablizer in the extent and scope of hydrolysis.This Phosphorus stablizer can improve when making or the thermostability during forming process, and improves mechanical characteristics, color and luster and forming stability.As Phosphorus stablizer, can enumerate phosphorous acid, phosphoric acid, phosphonous acid, phosphonic acids and these sour esters and tertiary phosphine etc.
As concrete phosphorous acid ester (phosphite) compound, can enumerate, triphenyl phosphite, three (nonyl phenyl) phosphorous acid ester, three decyl phosphorous acid esters, the trioctylphosphine phosphorous acid ester, three (octadecyl) phosphorous acid ester, didecyl list phenyl phosphites, dioctyl list phenyl phosphites, di-isopropyl list phenyl phosphites, monobutyl phenylbenzene phosphorous acid ester, single decyl phenylbenzene phosphorous acid ester, single octyl group phenylbenzene phosphorous acid ester, 2,2-methylene-bis (4,6-di-tert-butyl-phenyl) octyl group phosphorous acid ester, three (diethyl phenyl) phosphorous acid ester, three (diisopropyl phenyl) phosphorous acid ester, three (di-n-butyl phenyl) phosphorous acid ester, three (2,4-di-tert-butyl-phenyl) phosphorous acid ester, three (2,6-di-tert-butyl-phenyl) phosphorous acid ester, the distearyl pentaerythritol diphosphites, two (2,4-di-tert-butyl-phenyl) pentaerythritol diphosphites, two (2,6-di-t-butyl-4-aminomethyl phenyl) pentaerythritol diphosphites, two (2,6-di-t-butyl-4-ethylphenyl) pentaerythritol diphosphites, phenyl dihydroxyphenyl propane pentaerythritol diphosphites, two (nonyl phenyl) pentaerythritol diphosphites, dicyclohexyl pentaerythritol diphosphites etc.
Further, as other bi-ester of phosphite, can use the bi-ester of phosphite that reacts and have ring texture with the binary phenol.For example, can enumerate 2,2 '-methylene-bis (4, the 6-di-tert-butyl-phenyl) (2, the 4-di-tert-butyl-phenyl) phosphorous acid ester, 2,2 '-methylene-bis (4, the 6-di-tert-butyl-phenyl) (the 2-tertiary butyl-4-aminomethyl phenyl) phosphorous acid ester, 2,2 '-methylene-bis (4-methyl-6-tert butyl phenyl) (the 2-tertiary butyl-4-aminomethyl phenyl) phosphorous acid ester, 2,2 '-ethylenebis (4-methyl-6-tert butyl phenyl) (the 2-tertiary butyl-4-aminomethyl phenyl) phosphorous acid ester etc.
As phosphoric acid ester (phosphate) compound, can enumerate tributyl phosphate, trimethyl phosphite 99, Tritolyl Phosphate, triphenylphosphate, trichlorophenyl phosphoric acid ester, triethyl phosphate, diphenylmethyl benzenephosphonic acid ester, the adjacent xenyl phosphoric acid ester of phenylbenzene list, three butoxyethyl group phosphoric acid ester, dibutyl phosphate, dioctylphosphoric acid ester, diisopropyl phosphate etc., preferably phosphoric acid triphenylmethyl methacrylate, trimethyl phosphite 99.
As phosphinate compound (phosphonite), can enumerate four (2,4-di-tert-butyl-phenyl)-4,4 '-diphenylene, two phosphinates, four (2,4-di-tert-butyl-phenyl)-4,3 '-diphenylene, two phosphinates, four (2,4-di-tert-butyl-phenyl)-3,3 '-diphenylene, two phosphinates, four (2,6-di-tert-butyl-phenyl)-4,4 '-diphenylene, two phosphinates, four (2,6-di-tert-butyl-phenyl)-4,3 '-diphenylene, two phosphinates, four (2,6-di-tert-butyl-phenyl)-3,3 '-diphenylene, two phosphinates, two (2,4-di-tert-butyl-phenyl)-4-phenyl-phenyl-phosphonite ester, two (2,4-di-tert-butyl-phenyl)-3-phenyl-phenyl-phosphonite ester, two (2,6-di-n-butyl phenyl)-3-phenyl-phenyl-phosphonite ester, two (2,6-di-tert-butyl-phenyl)-4-phenyl-phenyl-phosphonite ester, two (2,6-di-tert-butyl-phenyl)-3-phenyl-phenyl-phosphonite ester etc.Wherein, preferred four (di-tert-butyl-phenyl)-diphenylenes, two phosphinates, two (di-tert-butyl-phenyls)-phenyl-phenyl-phosphonite ester, more preferably four (2,4-di-tert-butyl-phenyl)-diphenylene two phosphinates, two (2,4-di-tert-butyl-phenyls)-phenyl-phenyl-phosphonite ester.This phosphinate compound can have the bi-ester of phosphite and the usefulness of two above substituted aryls with abovementioned alkyl, and preferably adopts this mode.
As phosphonate compound (phosphonate), can enumerate phosphenylic acid dimethyl ester, phosphenylic acid diethyl ester and phosphenylic acid dipropyl etc.
As tertiary phosphine, can enumerate triethyl phosphine, tripropyl phosphine, tributylphosphine, tri octyl phosphine, three amyl group phosphines, dimethylphenylphosphine, dibutyl Phenylphosphine, diphenyl methyl phosphine, phenylbenzene octyl group phosphine, triphenylphosphine, three pairs of toluene phosphines, three naphthyl phosphines and phenylbenzene benzyl phosphines etc.Particularly preferred tertiary phosphine is a triphenylphosphine.
Above-mentioned Phosphorus stablizer both can use separately, also can two or more mixing use.In above-mentioned Phosphorus stablizer, preferably cooperating with the trimethyl phosphite 99 is the alkyl acid phosphate ester cpds of representative.In addition, also preferably with this alkyl acid phosphate ester cpds and bi-ester of phosphite and/or phosphinate compound and usefulness.
(III) Hinered phenols stablizer
In the flame retardant resin composition of the present invention, can also cooperate the Hinered phenols stablizer.By cooperating this Hinered phenols stablizer, can bring into play that color and luster when for example suppressing forming process worsens or life-time service in the effect that worsens of color and luster.As the Hinered phenols stablizer; for example can enumerate alpha-tocopherol; butylhydroxy toluene; sinapyl alcohol; vitamin-E; Octadecane base-β-(4 '-hydroxyl-3 '; 5 '-di-tert-butyl-phenyl) propionic ester; the 2-tertiary butyl-6-(3 '-tertiary butyl-5 '-methyl 2 '-hydroxybenzyl)-4-aminomethyl phenyl acrylate; 2; 6-di-t-butyl 4-(N; the N-dimethylaminomethyl) phenol; 3; 5-di-tert-butyl-4-hydroxyl benzyl phosphonic acids diethyl ester; 2; 2 '-methylene-bis (4-methyl-6-tert butyl phenol); 2; 2 '-methylene-bis(4-ethyl-6-t-butyl phenol); 4; 4 '-methylene-bis (2; the 6-DI-tert-butylphenol compounds); 2; 2 '-methylene-bis(4-methyl-6-cyclohexyl phenol); 2; 2 '-methylene-bis (6-α-Jia Jibianji-p-cresol); 2; 2 '-ethylidene-two (4; the 6-DI-tert-butylphenol compounds); 2; 2 '-butylidene-two (4-methyl-6-tert butyl phenol); 4; 4 '-butylidene-two (3 methy 6 tert butyl phenol); triethylene glycol-N-pair-3-(3-tertiary butyl-4-hydroxy-5-aminomethyl phenyl) propionic ester; 1; [3-(3 for 6-hexylene glycol-two; the 5-di-tert-butyl-hydroxy phenyl) propionic ester]; two [the 2-tertiary butyl-4-methyl-6-(the 3-tertiary butyl-5-methyl-2-hydroxybenzyl) phenyl] terephthalate; 3; 9-pair 2-[3-(3-tertiary butyl-4-hydroxy-5-aminomethyl phenyl) propionyloxy]-1; the 1-dimethyl ethyl }-2; 4; 8; 10-four oxaspiros [5; 5] undecane; 4; 4 '-thiobis (the 6-tertiary butyl-meta-cresol); 4; 4 '-thiobis (3 methy 6 tert butyl phenol); 2; 2 '-thiobis (4-methyl-6-tert butyl phenol); two (3; the 5-di-tert-butyl-4-hydroxyl benzyl) sulfide; 4; 4 '-dithio two (2; the 6-DI-tert-butylphenol compounds); 4; 4 '-trithio two (2; the 6-DI-tert-butylphenol compounds); 2; 2-sulfo-divinyl is two, and [3-(3; the 5-di-tert-butyl-hydroxy phenyl) propionic ester]; 2; two (n-octyl sulfo-)-6-(the 4-hydroxyls-3 ' of 4-; 5 '-di-t-butyl phenylamino)-1; 3; the 5-triazine; N; N '-hexa-methylene two-(3; 5-di-t-butyl-4-hydroxyl hydrocinnamamide); N; [3-(3 for N '-two; the 5-di-tert-butyl-hydroxy phenyl) propionyl] hydrazine; 1; 1; 3-three (2-methyl-4-hydroxyl-5-tert-butyl-phenyl) butane; 1; 3; 5-trimethylammonium-2; 4; 6-three (3; the 5-di-tert-butyl-4-hydroxyl benzyl) benzene; three (3; the 5-di-tert-butyl-hydroxy phenyl) chlorinated isocyanurates; three (3; the 5-di-tert-butyl-4-hydroxyl benzyl) chlorinated isocyanurates; 1; 3; 5-three (the 4-tertiary butyl-3-hydroxyl-2; the 6-dimethyl benzyl) chlorinated isocyanurates; 1; 3; 5-three 2[3 (3; the 5-di-tert-butyl-hydroxy phenyl) propionyloxy] the ethyl chlorinated isocyanurates; four [methylene radical-3-(3 ', 5 '-di-tert-butyl-hydroxy phenyl) propionic ester] methane etc.These all are easy to obtain.Above-mentioned Hinered phenols stablizer both can use separately, also can be used in combination.
With respect to the A composition of 100 weight parts, the content of Phosphorus stablizer and Hinered phenols stablizer is 0.0001～1 weight part, be preferably 0.001～0.5 weight part, 0.005～0.3 weight part more preferably.
(IV) above-mentioned thermo-stabilizer in addition
In flame retardant resin composition of the present invention, except above-mentioned Phosphorus stablizer and Hinered phenols stablizer, can also cooperate other thermo-stabilizer.As these other thermo-stabilizer, for example can preferably enumerate with 3-hydroxyl-5, the resultant of reaction of 7-di-t-butyl-furans-2-ketone and o-Xylol is the lactone stablizer of representative.About the detailed content of this stablizer, on the books in the flat 7-233160 communique of TOHKEMY.This compound can utilize this compound as Irganox HP-136 (trade mark, CIBA SPECIALTYCHEMICALS company make) and commercially available.In addition, commercially available in addition with this compound and various bi-ester of phosphite and hindered phenol compound blended stablizer in addition.For example, can enumerate the Irganox HP-2921 of above-mentioned company.With respect to the A composition of 100 weight parts, the content of preferred lactone stablizer is 0.0005～0.05 weight part, more preferably 0.001～0.03 weight part.
In addition, as other stablizers, can enumerate the sulphur-containing stabilizer of tetramethylolmethane four (3-mercaptopropionic acid ester), tetramethylolmethane four (3-lauryl thiopropionate) and glycerol-3-stearyl thiopropionate etc.With respect to the A composition of 100 weight parts, preferably the content of this sulphur-containing stabilizer is 0.001～0.1 weight part, more preferably 0.01～0.08 weight part.
(V) UV light absorber
In flame retardant resin composition of the present invention, can cooperate UV light absorber in order to give photostabilization.
As UV light absorber, can enumerate benzophenone particularly, for example can enumerate 2, the 4-dihydroxy benaophenonel, 2-hydroxyl-4-methoxy benzophenone, 2-hydroxyl-4-octyloxy benzophenone, 2-hydroxyl-4-benzyloxy benzophenone, 2-hydroxyl-4-methoxyl group-5-sulphur oxygen base benzophenone, 2-hydroxyl-4-methoxyl group-5-sulphur oxygen base Trihydride benzophenone (2-ヒ De ロ キ シ-4-メ ト キ シ-5-ス Le ホ キ シ ト リ Ha イ De ラ イ De レ イ ト ベ Application ゾ Off エ ノ Application), 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-sulphur oxygen acid sodium 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.
Benzotriazole category as UV light absorber, can enumerate 2-(2-hydroxy-5-methyl base phenyl) benzotriazole particularly, 2-(2-hydroxyl-uncle's 5-octyl phenyl) benzotriazole, 2-(2-hydroxyl-3, the 5-dicumylphenyl) phenyl benzotriazole, 2-(the 2-hydroxyl-3-tertiary butyl-5-aminomethyl phenyl)-5-chlorobenzotriazole, 2, [4-(1 for 2 '-methylene-bis, 1,3, the 3-tetramethyl butyl)-6-(2H-benzotriazole-2-yl) phenol], 2-(2-hydroxyl-3, the 5-di-tert-butyl-phenyl) benzotriazole, 2-(2-hydroxyl-3, the 5-di-tert-butyl-phenyl)-the 5-chlorobenzotriazole, 2-(2-hydroxyl-3, the 5-di-tert-pentyl-phenyl) benzotriazole, 2-(2-hydroxyl-uncle's 5-octyl phenyl) benzotriazole, 2-(2-hydroxyl-5-tert-butyl-phenyl) benzotriazole, 2-(2-hydroxyl-4-octyloxyphenyl) benzotriazole, 2,2 '-methylene-bis (4-cumyl-6-benzotriazole phenyl), 2,2 '-TOPOT 2,2 (1,3-benzoxazine-4-ketone), 2-[2-hydroxyl-3-(3,4,5,6-tetrahydrochysene phthalic diamide methyl)-the 5-aminomethyl phenyl] benzotriazole, 2-(2 '-hydroxy-5-methyl base acrylyl oxy-ethyl phenyl)-2H-benzotriazole and can with the multipolymer of the vinyl monomer of this monomer copolymerizable or 2-(2 '-hydroxyl-5-acrylyl oxy-ethyl phenyl)-2H-benzotriazole and can be with the polymkeric substance with 2-hydroxy phenyl-2H-benzotriazole skeleton of the multipolymer of the vinyl monomer of this monomer copolymerizable etc. etc.
As the hydroxyphenyltriazinuv of UV light absorber, for example, can enumerate 2-(4 particularly, 6-phenylbenzene-1,3,5-triazines-2-yl)-5-hexyl oxy phenol, 2-(4,6-phenylbenzene-1,3,5-triazines-2-yl)-5-methyl oxy phenol, 2-(4,6-phenylbenzene-1,3,5-triazines-2-yl)-5-ethyl oxy phenol, 2-(4,6-phenylbenzene-1,3,5-triazines-2-yl)-5-propyl group oxy phenol and 2-(4,6-phenylbenzene-1,3,5-triazines-2-yl)-5-butyl oxy phenol etc.Further, the phenyl that can also enumerate in 2-(4, two (2, the 4-3,5-dimethylphenyl)-1,3,5-triazines-2-yls of 6-)-above-mentioned example compound such as 5-hexyl oxy phenol becomes 2, the compound of 4-3,5-dimethylphenyl.
As the cyclic imide base ester of UV light absorber, for example can enumerate 2 particularly, 2 '-TOPOT 2,2 (3,1-benzoxazine-4-ketone), 2,2 '-metaphenylene two (3,1-benzoxazine-4-ketone) and 2,2 '-p, p '-diphenylene two (3,1-benzoxazine-4-ketone) etc.
In addition; cyanoacrylate as UV light absorber; for example can enumerate 1 particularly; 3-pair-[(2 '-cyano group-3 '; 3 '-diphenylprop enoyl-) oxygen]-2,2-pair-[(2-cyano group-3,3-diphenylprop enoyl-) oxygen] methylpropane and 1; 3-pair-[(2-cyano group-3,3-diphenylprop enoyl-) oxygen] benzene etc.
Further, above-mentioned UV light absorber also can be, by adopting the monomeric compound structure to carry out radical polymerization, the monomer of this ultraviolet-absorbing monomer and/or light stability monomer and (methyl) alkyl acrylate etc. carried out copolymerization and the aggretion type UV light absorber that obtains.As above-mentioned UV light absorber monomer, can preferably enumerate the compound that contains benzotriazole skeleton, benzophenone skeleton, triazine skeleton, cyclic imino ester skeleton and cyanoacrylate skeleton in the ester substituting group of (methyl) acrylate.
In above-mentioned, when considering ultraviolet absorption ability, preferably adopt benzotriazole category and hydroxyphenyltriazinuv class, and when considering thermotolerance and color and luster, then preferably adopt cyclic imino ester class and cyanoacrylate.Above-mentioned UV light absorber both can be used separately, can also use two or more mixtures.
With respect to the A composition of 100 weight parts, the content of UV light absorber is 0.01～2 weight part, is preferably 0.02～2 weight part, more preferably 0.03～1 weight part, more preferably 0.05～0.5 weight part.
(VI) other
Except above-mentioned, in order to give various functions to the moulding product or to improve characteristic, can also cooperate in the flame retardant resin composition of the present invention a spot of himself by known additive.These additives can be cooperated according to common use level in the scope of not damaging the object of the invention.
As this additive, can enumerate antiseize paste (for example PTFE particle), tinting material (carbon black for example, the pigment of titanium oxide etc., dyestuff), light diffusing agent (vinylformic acid crosslinked particle for example, the polysiloxane crosslinked particle, calcium carbonate particles), fluorescence dye, white dyes, photostabilizer (is representative with the hindered amine compound), mineral-type fluor (for example with the fluor of aluminate) as the crystallization masterbatch, static inhibitor, crystallization nucleating agent, inorganic or organic antibacterial agent, photocatalyst class stain control agent (micropartical titanium oxide for example, micropartical zinc oxide), releasing agent, modification agent flows, free radical generating agent, infrared absorbent (hot line absorption agent) and photochromic agent etc.
The transparency of＜resin combination of the present invention 〉
Resin combination of the present invention, owing to contain fibrillation PTFE, though can not keep the original transparency of polycarbonate resin fully, but owing to the addition with fibrillation PTFE is limited in a spot of specified range, thereby have certain transparency.For example,, when measuring its total light transmittance, then be limited at 74.0%～87.0%, be preferably 75.0%～87.0%, more preferably 76.0%～87.0% scope by the thick profiled sheeting of resin combination moulding 2mm of the present invention.The transparency of this limited range promptly, produces unique " sending out the transparency of mist " high appearance property.And, comprise painted design space sensation, functional part and also have the wide space that is equal to mutually with polycarbonate resin material with original transparency.
In the situation of not using coloured material, resin combination of the present invention can create " a unique mist transparent feel " of only expressing the transparent degree of stipulating in the resin combination of the present invention.In addition, be the situation of coloured material using various dyestuffs, by suppressing its addition, pigmentable goes out the color of generation " a unique mist transparent feel ", can strengthen painted unique mist sense that suppresses by increasing addition.In addition, by with pigment be that coloured material is used in combination, or to use pigment separately be coloured material, pigmentable becomes translucent colour or opaque colored, can keep very wide painted design space.In flame-retardant polycarbonate resin composition of the present invention, if the total light transmittance of the profiled sheeting that moulding 2mm is thick departs from 74.0%～87.0% scope, then can not create " a unique mist transparent feel " of only expressing the transparent degree of stipulating in the resin combination of the present invention, in other words, can not create " unique send out mist transparent feel " who is limited to by addition that specific scope brings with fibrillation PTFE.
＜about the manufacture method of resin combination 〉
When making resin combination of the present invention, its manufacture method is not done special qualification.But, in order to realize the good dispersion of fibrillation PTFE or fibrillation PTFE class mixture (mixed style), the preferred manufacture method of resin combination of the present invention is for adopting as the multiple screw extruder of biaxial extruder each composition method of melting mixing in addition.
As the representative example of biaxial extruder, can enumerate ZSK (trade(brand)name, Wemer ﹠amp; Pfleiderer company makes).As the object lesson of same model, can enumerate TEX (trade(brand)name, (strain) JSW makes), TEM (trade(brand)name, toshiba machine (strain) is made), KTX (trade(brand)name, the manufacturing of (strain) Kobe Steel) etc.In addition, as object lesson, can also enumerate the melting mixing machine of FCM (trade(brand)name, Farrel company makes), Ko-Kneader (trade(brand)name, Buss company makes) and DSM (trade(brand)name, Krauss-Maffei company makes) etc.In above-mentioned, preferably be the model of representative with ZSK.In the biaxial extruder of this ZSK model, its screw rod is complete meshing type, and screw rod is made up of length various screw portions and the different various kneading disks (kneader disc) (or the mixing part of using suitable with it) of width different with spacing.
In biaxial extruder, preferred mode is as described below.Promptly, the screw rod shape can adopt the screw-type screw rod (ネ ジ ス Network リ ユ-) of single thread, double thread and triple thread, preferably especially uses the transporting power of molten resin or shears all wide double thread screw rod of the two aspect scope of applications of mixing ability.The ratio (L/D) of spiro rod length in the biaxial extruder (L) and diameter (D) is preferably 20～45, and more preferably 28～42.The L/D value is big more reaches uniform dispersion state easily more, but when too big, is easy to generate the decomposition of resin because of thermal ageing.Screw rod must have more than one mixing district, preferably has 1～3, and wherein, described mixing district is by kneading disk part (perhaps suitable with it the mixing part) formation that is used to improve mixing property.
Further, as forcing machine, the preferred forcing machine that uses with the venting port that can remove the moisture in the raw material or the volatile gases that produces by the melting mixing resin.Preferably be provided with and be used for the vacuum pump that the moisture that produced or volatilization gas drained into the forcing machine outside effectively from venting port.In addition, the zone before forcing machine mould portion is provided with and is used to remove the filtering net of sneaking into extruding impurities in raw materials etc., also impurity can be removed from resin combination thus.As this filtering net, can enumerate wire netting, screen replacing device, sintered metal plates (disc filter etc.) etc.
And, to with C composition and other additives (in the following illustration, only be called " additive ") there is no particular limitation to supply with the method for forcing machine, but can enumerate following method as its representational example: the method for (i) additive and polycarbonate resin being supplied with independently forcing machine respectively; (ii) adopt the mixing machine of super mixing machine etc., in advance additive and polycarbonate resin powder are carried out pre-mixing after, resupply the method for forcing machine; And (iii) in advance additive and polycarbonate resin are carried out melting mixing, make the method for host grain (マ ス -ペ レ Star ト).
Aforesaid method one of (ii), for needed starting material all being carried out resupply after the pre-mixing method of forcing machine.Other method is host (the マ ス one that is combined with additive with making high density earlier
Figure A200810098983D0028170312QIETU
), this host further carried out pre-mixing individually or with remaining polycarbonate resin after, resupply the method for forcing machine.In addition, this host can be selected arbitrary shape Powdered and that this powder is compressed granulation etc.In addition,, for example can enumerate Nautamixer, V-type mixing tank, Henschel mixing tank, chemomotive force device and extrude mixing tank etc. as other pre-blend approach, but the mixing tank of the high-speed stirring type of preferred super mixing tank etc.Further, other pre-blend approach for example is that polycarbonate resin and additive are dispersed in solvent and behind the obtain solution, remove the method for this solvent.
By the resin that forcing machine is extruded, can directly cut off and carry out granulating, or after forming strand, this strand is cut off with tablets press and carried out granulating.In addition, outside during when being necessary to reduce as the influencing of dust etc., preferably the environmental gas around the forcing machine carry out cleaningization.Further, in this particulate is made, can be by the whole bag of tricks that has proposed in polycarbonate resin at CD, suitably carry out the minimizing of the bubble (bubbles of vacuum) that the minimizing of narrow and smallization that particle shape distributes, the short small powder of cutting minimizing, the transportation of thing (ミ ス カ Star ト thing) or producing when carrying and strand or granule interior produce.According to these prescriptions, the generation ratio that can carry out the height circulationization of moulding and reduce the bad phenomenon of silver-colored spot (シ Le バ-) etc.In addition, coating of particles can be the general shape of cylindrical, corner post shape, sphere etc., and is more preferably cylindrical.The diameter of preferred this cylinder is 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.
＜moulding product〉about forming by resin combination of the present invention
The flame retardant resin composition of the present invention that obtains as mentioned above can produce various products by the particle of making is as mentioned above carried out injection molding usually.And, also can be without granulation, with forcing machine directly with the resin manufacture slabbing behind the melting mixing, film like, special-shaped extrusion molding article, blowing (direct blow) moulding product and injection-molded article.
In above-mentioned injection molding, not only can adopt common forming method, can also be according to purpose, suitably adopt injection compression molding, injection pressure moulding, air-auxiliary injection forming, foaming (comprising the moulding of injecting), insert moulding by supercutical fluid, in-mold coating (In-Mold Coating) moulding, heat insulation mould molding, the injection moulding of heating cooling mould molding, dual-color forming, interlayer moulding, ultra-high speed injection molding etc. rapidly, thereby obtain the moulding product.The advantage of these various manufacturing process is all known.In addition, moulding can be selected any in cold runner mode and the hot runner mode.
In addition, resin combination of the present invention also can become forms such as various special-shaped extrusion molding articles, sheet, film like and be used by extrusion moulding.In addition, in sheet, film like moulding, can also use blow moulding, rolling process, casting method etc.And, by implementing specific extension operation, also can be shaped to heat-shrinkable tube.In addition, also can resin combination of the present invention be manufactured the moulding product by rotoforming or blow molding etc.
The moulding product of the resin combination with excellent outward appearance and hydrolytic resistance so, can be provided.That is, according to the present invention, provide flame retardant resin composition melt molding and the moulding product that form in addition, described resin combination is made of the A composition of 100 weight parts, the B composition of 0.1～0.2 weight part and the C composition of 0.001～20 weight part.
And, to the moulding product that form by flame retardant resin composition of the present invention, can carry out various surface treatments.In this said surface treatment, be meant that the surface at synthetic resin of evaporation (physical vapor deposition, chemical vapor deposition etc.), plating (electric plating, plated by electroless plating, fusion plating etc.), application, coating, printing etc. forms the processing of new coating, can use the method that is generally used for polycarbonate resin.As surface treatment, can enumerate the various surface treatments of hard coat, hydrophobic oleophobic coating, ultraviolet radiation absorption coating, infrared ray absorption coating, metallic coating (evaporation) etc. particularly.
Embodiment
The present inventor thinks best embodiments of the present invention at present, and the embodiment for the preferable range that satisfies above-mentioned each important document for example, is recorded in its typical example among the following embodiment.Certainly, the present invention is not limited to these embodiments.
Below, describe the present invention in detail by embodiment.In addition, evaluation is to carry out according to following method.(1) flame retardant resistance: use hot air dryer, under 120 ℃ to carry out 6 hours drying by following method resulting granules.Then, by injection moulding machine (IS150EN-5Y, toshiba machine (strain) make), be that 280 ℃, die temperature are under 60 ℃ the condition at barrel temperature, molding thickness is the test film that the UL94 combustion test of 2mm is used, and implements the testing vertical flammability of UL specification 94 and estimates.To not meeting the test film of any one grade among V-0, V-1, the V-2, be designated as not V.
(2) total light transmittance: use hot air dryer, under 120 ℃ to carry out 6 hours drying by following method resulting granules.Then, with injection moulding machine (SG-150U, Sumitomo Heavy Industries, Ltd makes), at barrel temperature is that 290 ℃, die temperature are under 80 ℃ the condition, with 50 seconds moulding circulation make wide 50mm, long 90mm, thick be that (it is the syllogic plate of 3mm (long 20mm), 2mm (long 45mm), 1mm (long 25mm) that the side of ゲ-ト) begins from spout.Use the reflecting ﹠ transmitting rate instrument HR-100 of Murakami K. K.'s dye technology institute system, measure the total light transmittance of the thickness 2.0mm profiled sheeting partly of this syllogic plate according to JIS K 7105-1.
(3) summer is than shock strength: use hot air dryer, under 120 ℃ to carry out 6 hours drying by following method resulting granules.Then, by injection moulding machine (SG-150U, Sumitomo Heavy Industries, Ltd make), be that 330 ℃, die temperature are under 80 ℃ of conditions at barrel temperature, make mensuration with 50 seconds moulding circulation and use test film, carry out the mensuration of breach summer than shock strength according to ISO 179.
Embodiment 1～22 and comparative example 1～5
In the polycarbonate resin powder of making by the dihydroxyphenyl propane photoreactive gas by interface polycondensation, each use level by record in the table cooperates various additives, after being mixed with mixing machine, (TEX30 α is (meshing fully with the exhaust biaxial extruder, equidirectional rotation, the double thread screw rod), Japan Steel Co., Ltd makes) carry out melting mixing, thus obtain particle.Additive with 10 times concentration of use level, behind the premixture with Henschel mixer making and polycarbonate resin powder, all mixes with mixing machine respectively in advance.Extrusion condition is extrusion capacity: 20kg/h; Screw rod rotation number: 150rpm; Exhaust portion vacuum tightness: 3KPa; Extrusion temperature: from first supplying opening to overflow mould is 260 ℃.
Shown in the theing contents are as follows of each composition of the symbolic representation in the table.
(A composition)
PC-1: pass through interface polycondensation, stop p-tert-butylphenol, phosgene synthetic straight chain aromatic polycarbonate resin powder (the パ Application ラ イ ト L-1225WP (trade(brand)name) of agent by dihydroxyphenyl propane, as end, viscosity-average molecular weight is 22400, and Teijin Chemicals, Ltd. makes)
PC-2:, stop p-tert-butylphenol, the phosgene synthetic straight chain aromatic polycarbonate resin powder (L-1225WX (trade(brand)name), viscosity-average molecular weight is 19700, Teijin Chemicals, Ltd.'s manufacturing) of agent by dihydroxyphenyl propane, as end by interface polycondensation
PC-3: by melting state transesterification reaction, (viscosity-average molecular weight is 22500, and this chain link components in proportions is passed through to prop up the chain link composition is about 0.1 mole of % in repeating unit weight polycarbonate resin particle by dihydroxyphenyl propane and diphenyl carbonate synthetic 1H-NMR measures and calculates, and is 0 mole of % (not having corresponding peak) in the PC-1 polycarbonate resin with the same manner mensuration)
PC-4:, stop p-tert-butylphenol, the phosgene synthetic straight chain aromatic polycarbonate resin powder (CM-1000 (trade(brand)name), viscosity-average molecular weight is 16000, Teijin Chemicals, Ltd.'s manufacturing) of agent by dihydroxyphenyl propane, as end by interface polycondensation
(B composition)
B-1: Port リ Off ロ Application MPAFA500 (trade(brand)name) (ltd. makes for tetrafluoroethylene, DAIKININDUSTRIES)
B-2:POLY TS AD001 (trade(brand)name) (PIC society makes, the mixture (polytetrafluoroethylene content be 50 weight %s) of this tetrafluoroethylene class mixture for being made of polytetrafluoroethylparticle particle and vinylbenzene-acrylonitrile copolymer particle)
B-3:Blendex449 (trade(brand)name) (Cronpton makes, the mixture (polytetrafluoroethylene content be 50 weight %s) of this tetrafluoroethylene class mixture for being made of polytetrafluoroethylparticle particle and vinylbenzene-acrylonitrile copolymer particle)
B-4: メ Block レ Application A3700 (trade(brand)name) (Mitsubishi Rayon Co.Ltd. makes, the mixture (content of tetrafluoroethylene be 50 weight %s) of this tetrafluoroethylene class mixture for being made up of the tetrafluoroethylene acrylic copolymer)
(C composition)
C-1: メ ガ Off ア Star Network F-114P (trade(brand)name) (potassium perfluorobutane sulfonate salt, Dainippon Ink and Chemicals, Inc makes)
C-2:KSS (trade(brand)name) (sulfobenzide-3,3 '-disulfonic acid di-potassium and sulfobenzide-3-single disulfonic acid potassium salt are with 2:8 blended mixture, and コ-シ-PVC-ジ ヤ パ Application is made)
C-3: the straight chain shape silicon compound that contains Si-H and phenyl
(manufacture method of C-3)
In the 1L flask that has agitator, refrigerating unit, thermometer, add entry 301.9g and toluene 150g, and interior temperature is cooled to 5 ℃.In dropping funnel, drop into the mixture of trimethylchlorosilane 21.7g, dimethyl dichlorosilane (DMCS) 23.0g, dimethyldichlorosilane(DMCS) 12.9g and diphenyl dichlorosilane 76.0g, and when stirring, in flask, dripped with 2 hours.In the meantime, continue to cool off, so that interior temperature maintains below 20 ℃.Drip after the end, continuation is stirred down for 20 ℃ in interior temperature and was carried out slaking in 4 hours.Then, leave standstill and remove isolating hydrochloric acid water layer, add 10% aqueous sodium carbonate and stir after 5 minutes, leave standstill and remove isolating water layer.Then, further clean 3 times, confirm that toluene layer becomes neutrality with ion exchanged water.This toluene solution under reduced pressure is heated to 120 ℃ of interior temperature, thereby after removing toluene and low boilers,, obtains silicon compound C-3 by removing by filter insolubles.
Among this silicon compound C-3, Si-H amount is that 49 weight %, mean polymerisation degree are 8.0 for 0.21mol/100g, aromatic series base unit weight.
C-4: the silicon compound that contains Si-H, phenyl, branched structure
(manufacture method of C-4)
In the 1L flask that has agitator, refrigerating unit, thermometer, add 1,1,3,3-tetramethyl disiloxane 100.7g, 1,3,5,7-tetramethyl-ring tetrasiloxane 60.1g and octamethylcyclotetrasiloxane 129.8g, octaphenyl cyclotetrasiloxane 143.8g and phenyltrimethoxysila,e 99.1g, and add vitriol oil 25.0g while stirring.After interior temperature is cooled to 10 ℃, while stirring with 30 fens water 13.8g that drip in the clockwise flask.In the meantime, continue to cool off, so that interior temperature maintains below 20 ℃.Drip after the end, continuation is stirred down for 10～20 ℃ in interior temperature and was carried out slaking in 5 hours.Then, add water 8.5g and toluene 300g and stir after 30 minutes, leave standstill and remove isolating water layer.Then, further clean 4 times, confirm that toluene layer becomes neutrality with 5% aqueous sodium persulfate solution.This toluene solution under reduced pressure is heated to 120 ℃ of interior temperature, thereby after removing toluene and low boilers,, obtains silicon compound C-4 by removing by filter insolubles.
Among this silicon compound C-4, Si-H amount is that 30 weight %, mean polymerisation degree are 10.95 for 0.50mol/100g, aromatic series base unit weight.
The signal formula of＜each silicon compound 〉
C-3：M 2D H 2D 1D φ2 3
C-4：M H 3D H 2D 3.5D φ2 1.45T φ 1
In addition, the following siloxane unit of each symbolic representation in the above-mentioned signal formula, the coefficient of each symbol (index number) are the quantity (polymerization degree) of each siloxane unit in expression 1 molecule.
M：(CH 3) 3SiO 1/2
M H：H(CH 3) 2SiO 1/2
D：(CH 3) 2SiO
D H：H(CH 3)SiO
D φ2：(C 6H 5) 2SiO
T φ：(C 6H 5)SiO 3/2
C-5:PX-200 (trade(brand)name) (Resorcinol two (two xylyl phosphoric acid ester), big eight chemical industry (strain) are made)
(other)
SL: リ ケ マ-Le SL900 (trade(brand)name) (LTD makes for polyunsaturated fatty acid ester class releasing agent, RIKENVITAMIN CO.)
CS:ECS-03T-511 (trade(brand)name) (NEG (strain) is made for glass fibre, diameter 13 μ m, cutting length 3mm)
MF:PEF-301S (trade(brand)name) (day east is spun (strain) and made for glass chopped strand, diameter 9 μ m, number average fiber length 30 μ m)
TMP:TMP (trade(brand)name) (Phosphorus stablizer, big eight chemical industry (strain) are made)
Figure A200810098983D00351
Figure A200810098983D00361
Figure A200810098983D00371
As can be known clear and definite from above-mentioned table 1 and table 2, flame retardant resin composition of the present invention has the transparency (total light transmittance of certain limit) of specified range, compares the shock strength excellence during high-temperature molding with comparative example.
Industrial applicibility
Flame retardant resin composition of the present invention has the transparency of certain limit, and anti-flammability, outer See excellently, can create the high outward appearance of delicate mist degree that the transparency of certain limit is brought, therefore, Be applicable to various electronic apparatus, OA machine, vehicle part, mechanical part, other Agricultural Materials, In the various uses of cask, game machine and groceries etc., it reaches very special effect industrial Really.

Claims (10)

1. flame retardant resin composition, it is characterized in that, described flame retardant resin composition comprise as the aromatic polycarbonate resin of A composition, as the B composition have that fibril forms the tetrafluoroethylene of ability and as the fire retardant of C composition, wherein, aromatic polycarbonate resin with respect to 100 weight parts as the A composition, as the B composition to have the tetrafluoroethylene that fibril forms ability be 0.1～0.2 weight part, be 0.001～20 weight part as the fire retardant of C composition.
2. flame retardant resin composition as claimed in claim 1, wherein, the B composition is the tetrafluoroethylene that fibril forms ability that has of mixed style.
3. flame retardant resin composition as claimed in claim 1 or 2, wherein, the total light transmittance of the profiled sheeting that the 2mm that the described resin combination of moulding obtains is thick is 74～87%.
4. as any described flame retardant resin composition in the claim 1～3, wherein, the content of C composition is 0.001～5 weight part.
5. as any described flame retardant resin composition in the claim 1～3, wherein, the content of C composition is 0.01～0.3 weight part.
6. as any described flame retardant resin composition in the claim 1～5, wherein, the C composition is the organic metal salt based flame retardant.
7. flame retardant resin composition as claimed in claim 6, wherein, the organic metal salt based flame retardant is organic acid an alkali metal salt or alkali earth metal salt.
8. flame retardant resin composition as claimed in claim 7, wherein, organic acid an alkali metal salt or alkali earth metal salt are organic sulfonic acid an alkali metal salt or organic sulfonic acid alkali earth metal salt.
9. flame retardant resin composition as claimed in claim 6, wherein, the C composition is fluorine-containing organic metal salt based flame retardant.
10. moulding product, it is to be formed by any described flame retardant resin composition in the claim 1～9.
CNA2008100989831A 2007-05-31 2008-05-26 Flame-resistant polycarbonate resin composition Pending CN101412844A (en)

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JP5679693B2 (en) * 2010-05-07 2015-03-04 帝人株式会社 Flame retardant polycarbonate resin composition
JP5558926B2 (en) * 2010-06-01 2014-07-23 帝人株式会社 Flame retardant polycarbonate resin composition
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CN102844377A (en) * 2010-04-20 2012-12-26 三菱瓦斯化学株式会社 Transparent, fire-retardant aromatic polycarbonate resin composition and molded product
CN102844377B (en) * 2010-04-20 2015-02-04 三菱瓦斯化学株式会社 Transparent, fire-retardant aromatic polycarbonate resin composition and molded product
WO2020151552A1 (en) * 2019-01-24 2020-07-30 金发科技股份有限公司 Makrolon composition and use of sulfonate and phosphorous compound in reducing fuming and heat release of makrolon

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