CN101824213A

CN101824213A - Flame-retardant polycarbonate resin composition

Info

Publication number: CN101824213A
Application number: CN 201010127304
Authority: CN
Inventors: 友田琢也
Original assignee: Teijin Chemicals Ltd
Current assignee: Teijin Ltd
Priority date: 2009-03-05
Filing date: 2010-03-05
Publication date: 2010-09-08
Anticipated expiration: 2030-03-05
Also published as: CN101824213B; JP2010202825A; JP5635239B2

Abstract

The present invention relates to flame-retardant polycarbonate resin composition.The poly carbonate resin composition of transparent and scuff resistance, excellent in flame retardance is provided.Transparent and the scuff resistance of described flame-retardant polycarbonate resin composition, excellent in flame retardance, wherein, with respect to aromatic polycarbonate resin (A composition) 100 weight parts, contain specific refractory power (nd) and be 1.42～1.65 contain phenyl silicone oil (B composition) 0.05～5.0 weight part and fire retardant (C composition) 0.01～30 weight part.

Description

Flame-retardant polycarbonate resin composition

Technical field

The present invention relates to the poly carbonate resin composition of transparent and excellent scratch resistance.Specifically, relate to the also excellent poly carbonate resin composition of flame retardant resistance.

Background technology

Aromatic polycarbonate resin has the transparency, and has excellent flame, thermotolerance and intensity, therefore uses in extensive fields.In addition, therefore aromatic polycarbonate resin and then itself and be that the polymer alloy of the graft copolymer of representative has excellent formability with the ABS resin use in the purposes widely at office equipment, electric/electronic device, automobile etc.

Wherein, in the framework of office equipment such as laser beam printer, duplicating machine and notebook computer, LCD TV, projector apparatus and electric/electronic device, also require is fit to the such high fire resistance of V-0 more in UL standard (safety of America test experience chamber standard)-94, and having proposed at this aromatic polycarbonate resin with the ABS resin is to be combined with the flame-retardant polymer alloy that phosphoric acid ester forms in the graft copolymer of representative.(patent documentation 1)

On the other hand, in recent years for the OA associated components etc., also require to comprise the design of sense organ part.Yet, though this flame-retardant polymer alloy formability, excellent in flame retardance, the problem that exists the transparency to reduce.For the transparency reduced, not only light transmission reduced, and the rough sledding that diminishes and so on of the scope that is accompanied by the design such as painted that comprises the sense organ part.From opposite viewpoint, the material that the transparency obtains keeping, promptly the material that the mist degree in the moulding product is low (material that the transparency is high) we can say that the scope of the design that comprises the sense organ part is big.Specifically, for the low material of mist degree, using dyestuff is that tinting material can be given transparent color (common name basic colors, skeleton color), and then by the combination pigment be colorant, perhaps using pigment separately is colorant, also can give translucent color or opaque color.And then, can present light diffusing by adding light diffusing agent, also can give the light diffusing of target level by the control addition.Therefore, the transparency reduces, and promptly light transmittance reduces, and the painted of transparent color develops to difficult direction, with the part that comprises sense organ and then comprise that also the scope of the design that the painted integral body of having given light diffusing is relevant diminishes.Therefore, the transparency of this flame-retardant polymer alloy can't say that energy is satisfactory.In addition, proposed also to be combined with that not add with the ABS resin be the aromatic polycarbonate resin of graft copolymer of representative and the flame-retardant polymer of phosphoric acid ester.(patent documentation 2)

Yet,,, also require the scuff resistance of excellence from improving the viewpoint of the transparency and weather resistance simultaneously for the OA associated components etc.Therefore, can't say in this motion can be satisfactory aspect weather resistance, also not clear and definite for its solution.

On the other hand, give the method for scuff resistance as the harmless transparency, proposed to be combined with aromatic polycarbonate resin, the specific poly carbonate resin composition that contains phenyl silicone oil, polycaprolactone.(patent documentation 3)

Yet this resin combination still can't be said aspect flame retardant resistance can be satisfactory, and then also can't say to be exactly sufficient for formability.Therefore, can't say the solution that fully discloses above-mentioned technical task.

Patent documentation 1: Japanese kokai publication hei 2-115262 communique

Patent documentation 2: Japanese Unexamined Patent Application Publication 2003-535173 communique

Patent documentation 3: No. 3474329 communique of Japan's special permission

Summary of the invention

In view of the foregoing, the object of the present invention is to provide and keep original transparency and have the polycarbonate-based resin composition that is modified to higher levels of scuff resistance and flame retardant resistance.

The inventor furthers investigate in order to solve above-mentioned problem, found that: the poly carbonate resin composition that is combined with aromatic polycarbonate resin, specific silicone oil and fire retardant is the resin material that solves above-mentioned problem, further study, thereby finished the present invention.

According to the present invention, above-mentioned problem provides a kind of flame-retardant polycarbonate resin composition, it is characterized in that, with respect to aromatic polycarbonate resin (A composition) 100 weight parts, contain specific refractory power (nd) and be 1.42～1.65 contain phenyl silicone oil (B composition) 0.05～3.0 weight part, preferred 0.08～2.0 weight part, further preferred 0.1～1.0 weight part and fire retardant (C composition) 0.01～20 weight part, preferred 0.03～15 weight part, further preferred 0.05～10 weight part.

The flame-retardant polycarbonate resin composition of this formation has the unexistent characteristic of prior art of the transparency and flame retardant resistance and excellent scratch resistance.

Description of drawings

Fig. 1: be use in an embodiment be the edge-on body synoptic diagram of the table of the moulding product of mould (the height 10mm on vertical 250mm * horizontal 300mm * wide 40mm * limit, thick 2.0mm) with frame (bezel).

Fig. 2: be the face side front synoptic diagram that uses in an embodiment, represent the part that cuts out of scuff resistance, transparent test sample with the moulding product of needle-like gate moulding.

Fig. 3: be use in an embodiment with the rear side front synoptic diagram of frame as the moulding product of mould, expression has the situation of projection of band stiffening web.(shape of projection: external diameter 6.5mm, internal diameter 2.5mm, high 10mm)

Nomenclature

1 is the moulding product main body of mould with the frame

2 minute surface portions

3 cast gates (the needle-like gate 4 1.5mm φ of place)

4 anti-scoring tests cut out the position with sample

The projection (external diameter 6.5mm, internal diameter 2.5mm, high 10mm) of 5 band stiffening webs

Embodiment

Below, further the present invention is described in detail.

(the A composition: aromatic copolycarbonate is a resin)

The aromatic polycarbonate resin that uses as the A composition in the present invention reacts dihydric phenol and carbonate precursor and obtains.As one of reaction method example, 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.

Typical example as dihydric phenol used herein, can enumerate Resorcinol, Resorcinol, 4,4 '-dihydroxybiphenyl, 1, two (4-hydroxy phenyl) ethane of 1-, 2, two (4-hydroxy phenyl) propane (common name dihydroxyphenyl propane) of 2-, 2, two (the 4-hydroxy-3-methyl phenyl) propane of 2-, 2, two (4-hydroxy phenyl) butane of 2-, 1, two (4-the hydroxy phenyl)-1-diphenylphosphino ethanes of 1-, 1, the 1-bis(4-hydroxyphenyl) cyclohexane, 1, two (the 4-hydroxy phenyls)-3 of 1-, 3, the 5-trimethyl-cyclohexane, 2, two (4-hydroxy phenyl) pentanes of 2-, 4,4 '-(to phenylene two isopropylidenes) biphenol, 4,4 '-(metaphenylene two isopropylidenes) biphenol, 1, two (4-the hydroxy phenyl)-4-normenthanes of 1-, two (4-hydroxy phenyl) oxygen ether, two (4-hydroxy phenyl) thioether, two (4-hydroxy phenyl) sulfoxide, two (4-hydroxy phenyl) sulfone, two (4-hydroxy phenyl) ketone, two (4-hydroxy phenyl) ester, two (4-hydroxy-3-methyl phenyl) thioether, 9, two (4-hydroxy phenyl) fluorenes and 9 of 9-, two (4-hydroxy-3-methyl phenyl) fluorenes of 9-etc.Preferred dihydric phenol is two (4-hydroxy phenyl) alkane, wherein from the viewpoint of shock-resistance, and preferred especially dihydroxyphenyl propane, general.

In the present invention, except the dihydroxyphenyl propane as general polycarbonate is polycarbonate, the special polycarbonate that uses other dihydric phenols to make can also be used as the A composition.

For example, as part or all of dihydric phenol composition, used 4,4 '-(metaphenylene two isopropylidenes) biphenol (following abbreviate as sometimes " BPM "), 1, the 1-bis(4-hydroxyphenyl) cyclohexane, 1, two (the 4-hydroxy phenyls)-3 of 1-, 3,5-trimethyl-cyclohexane (following abbreviate as sometimes " Bis-TMC "), 9, two (4-hydroxy phenyl) fluorenes and 9 of 9-, the polycarbonate (homopolymer or multipolymer) of two (the 4-hydroxy-3-methyl phenyl) fluorenes (following abbreviate as sometimes " BCF ") of 9-is suitable for the dimensional change to causing because of suction, the purposes that the requirement of morphological stability is strict especially.These dihydric phenols except BPA, preferred 5 moles of the dihydric phenol composition integral body that constitutes this polycarbonate of using are more than the %, particularly 10 moles more than the %.

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

(1) in the 100 moles of % of dihydric phenol composition that constitute this polycarbonate, BPM is 20～80 moles of % (more preferably 40～75 moles of %, more preferably 45～65 moles of %), and BCF is the copolymerization polycarbonate of 20～80 moles of % (more preferably 25～60 moles of %, more preferably 35～55 moles of %).

(2) in the 100 moles of % of dihydric phenol composition that constitute this polycarbonate, BPA is 10～95 moles of % (more preferably 50～90 moles of %, more preferably 60～85 moles of %), and BCF is the copolymerization polycarbonate of 5～90 moles of % (more preferably 10～50 moles of %, more preferably 15～40 moles of %).

(3) in the 100 moles of % of dihydric phenol composition that constitute this polycarbonate, BPM is 20～80 moles of % (more preferably 40～75 moles of %, more preferably 45～65 moles of %), and Bis-TMC is the copolymerization polycarbonate of 20～80 moles of % (more preferably 25～60 moles of %, more preferably 35～55 moles of %).

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

For the method for making and the characteristic of these special polycarbonate, for example, at length be recorded in the spy and open that flat 6-172508 communique, spy are opened flat 8-27370 communique, the spy opens in 2001-55435 communique and the Te Kai 2002-117580 communique etc.

It should be noted that, in above-mentioned various polycarbonate, make water-intake rate and the polycarbonate of Tg (second-order transition temperature) in following ranges by adjusting copolymerization composition etc., because the hydrolytic resistance of polymkeric substance self is good, and also especially excellent on the low warpage properties after the moulding, therefore in requiring the field of morphological stability, be particularly suitable for.

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

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

Here, the water-intake rate of polycarbonate is to use the discoideus test film of diameter 45mm, thick 3.0mm, according to ISO62-1980 in 23 ℃ water, flood measure moisture rate after 24 hours and value.In addition, Tg (second-order transition temperature) is the value of obtaining with differential scanning calorimeter (DSC) mensuration according to JIS K7121.

As carbonate precursor, use carboxylic acid halides, carbonic diester or haloformate (Ha ロホ Le メ one ト) etc., specifically can enumerate the bishaloformate of carbonyl chloride, diphenyl carbonate or dihydric phenol etc.

When making aromatic polycarbonate resin by above-mentioned dihydric phenol and carbonate precursor, as required, can use catalyzer, terminal terminator, be used to prevent the antioxidant of dihydric phenol generation oxidation etc. by interfacial polymerization.In addition, aromatic polycarbonate resin comprise branched polycarbonate resin that the multi-functional aromatics copolymerization more than the trifunctional is formed, polyestercarbonate resin that two functionality carboxyl acid copolymers of aromatic series or aliphatics (comprising ester ring type) are formed, with two functionality alcohol (comprising ester ring type) copolymerized panlites that copolymerization forms and polyestercarbonate resin that described two functionality carboxylic acids and two functionality alcohol copolymerization are together formed.In addition, can be the mixture that the gained aromatic polycarbonate resin more than 2 kinds is mixed.

Branched polycarbonate resin can be given anti-drippage performance etc. to reinforcement aromatic copolycarbonate resin composition of the present invention.As the multi-functional aromatics more than the trifunctional that uses in the described branched polycarbonate resin, can enumerate Phloroglucinol, 2,3 ', 4,5 ', 6-penta hydroxy group biphenyl, perhaps 4,6-dimethyl-2,4,6-three (4-hydroxy diphenyl) heptene-2,2,4,6-trimethylammonium-2,4,6-three (4-hydroxy phenyl) heptane, 1,3,5-three (4-hydroxy phenyl) benzene, 1,1,1-three (4-hydroxy phenyl) ethane, 1,1,1-three (3,5-dimethyl-4-hydroxy phenyl) ethane, 2, two (2-hydroxy-5-methyl base the benzyl)-4-methylphenols of 6-, 4-{4-[1, two (4 hydroxy phenyl) ethyls of 1-] benzene }-α, triphenols such as α-Er Jiajibianji phenol, four (4-hydroxy phenyl) methane, two (2, the 4-dihydroxy phenyl) ketone, 1,4-two (4,4-dihydroxyl trityl group) benzene, or trimellitic acid, pyromellitic acid, benzophenone tetracarboxylic acid and their acyl chlorides etc., wherein, preferred 1,1,1-three (4-hydroxy phenyl) ethane, 1,1,1-three (3,5-dimethyl-4-hydroxy phenyl) ethane, preferred especially 1,1,1-three (4-hydroxy phenyl) ethane.

For in the branched polycarbonate resin by multi-functional aromatics deutero-structural unit, in by dihydric phenol deutero-structural unit and 100 moles of % of total, be 0.01～1 mole of %, preferred 0.05～0.9 mole of %, preferred especially 0.05～0.8 mole of % by this multi-functional compounds's deutero-structural unit.

In addition, the situation of melt transesterification process particularly, generate the branched structure unit sometimes as side reaction, for the unitary amount of described branched structure, also preferably with 100 moles of % of total by dihydric phenol deutero-structural unit in, be 0.001～1 mole of %, be preferably 0.005～0.9 mole of %, be preferably 0.01～0.8 mole of % especially.In addition, for the amount of described branched structure, can pass through ¹H-NMR measures and calculates.

The preferred alpha, omega-dicarboxylic acid of aliphatic two functionality carboxylic acids.As aliphatic two functionality carboxylic acids, can preferably exemplify alicyclic dicarboxylic acids such as straight chain saturated aliphatic dicarboxylic acids such as sebacic acid (decane diacid), dodecanedioic acid, tetradecane diacid, octadecane diacid, octadecane dicarboxylic acid and cyclohexane dicarboxylic acid.As two functionality alcohol, more preferably alicyclic diol, but illustration for example cyclohexanedimethanol, cyclohexane diol and tristane dimethanol etc.

And then, can also use polyorganosiloxane units is carried out polycarbonate-poly organo alkyl copolymer that copolymerization forms.

As the reaction formation of interfacial polymerization, melt transesterification process, the solid phase ester-interchange method of carbonic ether prepolymer and the ring-opening polymerization method of cyclic carbonate compound etc. of the manufacture method of polycarbonate resin of the present invention, be to be recorded in known method in various documents and the patent gazette etc.

When making flame-retardant polycarbonate resin composition of the present invention, the viscosity-average molecular weight of aromatic polycarbonate resin (M) is not particularly limited, and is 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

For viscosity-average molecular weight less than 1 * 10 ⁴Aromatic polycarbonate resin, 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, the viewpoint versatility of the flowability difference during from injection molding is poor.

In addition, above-mentioned aromatic polycarbonate resin can be mix viscosity-average molecular weight outside above-mentioned scope aromatic polycarbonate resin and the resin that obtains.Particularly viscosity-average molecular weight surpasses above-mentioned scope (5 * 10 ⁴) aromatic polycarbonate resin, the entropy-elasticity of resin improves.Consequently, gas assistant formation and foaming when sometimes reinforced resin material being used for structural member molding present good forming process.The improvement of described forming process is better than above-mentioned branching polycarbonate.As preferred mode, can also 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) constitute, its viscosity-average molecular weight is 1.6 * 10 ⁴～3.5 * 10 ⁴Aromatic polycarbonate resin (A-1 composition) (below, be sometimes referred to as " aromatic polycarbonate resin of pbz polymer amount composition ").

For the aromatic polycarbonate resin (A-1 composition) of described pbz polymer amount composition, the molecular weight of A-1-1 composition is preferably 7 * 10 ⁵～2 * 10 ⁵, more preferably 8 * 10 ⁴～2 * 10 ⁵, further preferred 1 * 10 ⁵～2 * 10 ⁵, preferred especially 1 * 10 ⁵～1.6 * 10 ⁵In addition, the molecular weight of A-1-2 composition is preferably 1 * 10 ⁴～2.5 * 10 ⁴, more preferably 1.1 * 10 ⁴～2.4 * 10 ⁴, further preferred 1.2 * 10 ⁴～2.4 * 10 ⁴, preferred especially 1.2 * 10 ⁴～2.3 * 10 ⁴

The aromatic polycarbonate resin of pbz polymer amount composition (A-1 composition) can be with above-mentioned A-1-1 composition and A-1-2 composition with various mixed, adjust to the molecular weight ranges that satisfies regulation and obtain.Preferably in A-1 composition 100 weight %, the A-1-1 composition is 2～40 weight %, and more preferably the A-1-1 composition is 3～30 weight %, and further preferred A-1-1 composition is 4～20 weight %, and preferred especially A-1-1 composition is 5～20 weight %.

In addition, as the preparation method of A-1 composition, can enumerate (1) with the polymerization and with they blended methods independently respectively of A-1-1 composition and A-1-2 composition; (2) use with the spy open the method that provides in the flat 5-306336 communique be representative, in same system, make the method that shows the aromatic polycarbonate resin at a plurality of polymkeric substance peak in the graph of molecular weight distribution that adopts the GPC method to obtain, the method that the condition that makes this aromatic polycarbonate resin satisfy A-1 composition of the present invention is made; And (3) will adopt aromatic polycarbonate resin that described manufacture method (manufacture method of (2)) obtains, with A-1-1 composition of making in addition and/or A-1-2 composition blended method etc.

Said viscosity-average molecular weight is following among the present invention obtains: at first use Ubbelohde viscometer, at the solution that is formed by dissolving aromatic copolycarbonate 0.7g in methylene dichloride 100ml under 20 ℃, obtain the specific viscosity (η that calculates with following formula _SP),

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

[t ₀Be drippage number second of methylene dichloride, t is drippage number second of sample solution]

By the specific viscosity (η that is obtained _SP) calculate viscosity-average molecular weight M according to following mathematical expression.

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

[η]＝1.23×10 ^-4M ^0.83

c＝0.7

In addition, the calculating of the viscosity-average molecular weight of the aromatic polycarbonate resin in the flame-retardant polycarbonate resin composition of the present invention is undertaken by following main points.That is,, make the solvable composition dissolving in the composition with the methylene dichloride mixing of said composition and its 20～30 times of weight.Should take out by solvable composition by diatomite filtration.Then the solvent in the solution that obtains is removed.To obtain to be dissolved in the solid of the composition in the methylene dichloride except that the solid thorough drying after desolvating.By in methylene dichloride 100ml, dissolving the solution that this solid 0.7g forms, with the above-mentioned specific viscosity of similarly obtaining under 20 ℃, by this specific viscosity and the above-mentioned viscosity-average molecular weight M that similarly calculates.

(B composition: contain phenyl silicone oil)

The specific refractory power (nd) that contains phenyl silicone oil of the present invention is 1.42～1.65, and preferred index is 1.43～1.59, more preferably 1.44～1.56, most preferably 1.46～1.54.In addition, phenyl content is preferably 7～80 weight %, this liquid phase 30～70 weight %.Be added with in polycarbonate resin when containing phenyl silicone oil, specific refractory power (nd) was less than 1.42 o'clock, and it is opaque that resultant composition becomes, and specific refractory power (nd) surpasses at 1.65 o'clock, and it is opaque that composition also becomes.Preferred especially following formula (1)～(4) are represented contains phenyl silicone oil, and the repeating unit in the represented structure of following formula (1), (2) and (4) can be that random form also can be a block form.

(in the formula, Ph represents phenyl, and x, y are respectively the integers of 0≤x≤10,1≤y≤100 scopes)

(in the formula, Ph represents phenyl, and m, n are respectively the integers of 0≤m≤10,1≤n≤100 scopes)

(in the formula, Ph represents phenyl)

(in the formula, Ph represents phenyl, and p, q are respectively 0≤p≤25,0≤q≤100 and the value of giving the phenyl content of 7～80 weight %)

In addition, these contain phenyl silicone oil and can use more than 2 kinds.And then, as the representative commercially available product that contains phenyl silicone oil of above-mentioned formula (1), the methyl phenyl silicone oil SH-710 (specific refractory power 1.533) of eastern beautiful DOW CORNING organosilicon corporate system being arranged, can easily obtain.

(C composition: fire retardant)

Fire retardant of the present invention (C composition) can use in the past as the known all cpds of the fire retardant of aromatic polycarbonate resin, more preferably (i) organic phosphorus flame retardant (for example phosplate compound, phosphoric acid ester oligomeric compound, phosphonic acid ester oligomeric compound, phosphonitrile oligomeric compound and phosphonic acid amide compound etc.), (ii) organic metal salt flame retardant (for example organic sulfonic acid alkali (great soil group) metal-salt, borate metal salt flame retardant and stannic acid metal-salt flame retardant etc.), the silicone-based fire retardant that (iii) formed by silicone compounds.In addition, the cooperation of the compound that uses as fire retardant not only improves flame retardant resistance, and according to the character of each compound, can also bring the raising of for example static electricity resistance, flowability, rigidity and thermostability etc.

(C-1 composition: organic phosphorus flame retardant)

As organic phosphorus flame retardant of the present invention, preferably phosphoric acid ester cpds, particularly aryl phosphate ester cpds.This phosphate compound is improving aspect the flame retardant resistance effectively, and phosphate compound has plasticization effect, though therefore there is thermotolerance to reduce, is being favourable aspect the forming process of raising resin combination of the present invention.This phosphate compound can use in the past as the known various phosphate compounds of fire retardant, more preferably can enumerate the represented phosphate compound more than a kind or 2 kinds of particularly following general formula (I).

(X in the formula is by the dihydroxy compound deutero-dihydric phenol residue that is selected from Resorcinol, Resorcinol, two (4-hydroxy diphenyl) methane, dihydroxyphenyl propane, dihydroxybiphenyl, dihydroxy naphthlene, two (4-hydroxy phenyl) sulfone, two (4-hydroxy phenyl) ketone and two (4-hydroxy phenyl) thioether, n is 0～5 integer, perhaps when the time for the mixture of the different phosphoric acid ester of the number of n, n is their mean value, R ¹, R ², R ³And R ⁴Serve as reasons independently of one another and be selected from phenol, cresols, xylenol, isopropyl-phenol, butylphenol and the aryl deutero-monohydric phenol residue in the cumyl phenol.)

The phosphate compound of above-mentioned formula (I) can be the mixture with compound of different n numbers, during for such mixture, average n number is preferably 0.5～1.5, and more preferably 0.8～1.2, further preferred 0.95～1.15, preferred especially 1～1.14 scope.

As the preferred concrete example of the dihydric phenol of the X that induces above-mentioned formula (I), be Resorcinol, dihydroxyphenyl propane and dihydroxybiphenyl, wherein preferably Resorcinol, dihydroxyphenyl propane.

As the R that induces above-mentioned formula (I) ¹, R ², R ³And R ⁴The preferred concrete example of monohydric phenol, be phenol, cresols, xylenol, 2,6-xylenol, phenol and 2 preferably wherein, 6-xylenol.

Concrete example as the phosphate compound of above-mentioned formula (I), triphenylphosphate and tricresyl phosphate (2, the 6-xylyl) phosplate compound such as ester, with with the two [di(2-ethylhexyl)phosphates (2 of Resorcinol, the 6-xylyl) ester] be the phosphoric acid ester oligopolymer of main body, with 4,4-dihydroxybiphenyl two (diphenyl phosphate) is the phosphoric acid ester oligopolymer of main body, and be fit to based on the phosphoric acid ester oligopolymer of dihydroxyphenyl propane two (diphenyl phosphates), wherein preferably with the two (di(2-ethylhexyl)phosphates (2 of Resorcinol, the 6-xylyl) ester) is the phosphoric acid ester oligopolymer of main body, with 4,4-dihydroxybiphenyl two (diphenyl phosphate) is the phosphoric acid ester oligopolymer of main body, and based on the phosphoric acid ester oligopolymer of dihydroxyphenyl propane two (diphenyl phosphates).

When using organic phosphorus flame retardant as fire retardant, its use level is 1～20 weight part with respect to A composition 100 weight parts, preferred 2～15 weight parts, further preferred 3～10 weight parts.In this preferred range, wave effect all the more by cooperating organic phosphorus flame retardant to expect.

(C-2 composition: the organic metal salt flame retardant)

The organic metal salt flame retardant is favourable keeping substantially aspect the thermotolerance.The organic metal salt flame retardant that most preferably uses is azochlorosulfonate acid alkali (great soil group) metal-salt in the present invention.Wherein preferably fluorine replaces alkali (great soil group) metal-salt of organic sulfonic acid, particularly preferably is alkali (great soil group) metal-salt of the sulfonic acid with perfluoroalkyl.At this, the scope of the carbonatoms of perfluoroalkyl preferred 1～18, more preferably 1～10 scope, further preferred 1～8 scope.

Constituting the metal that fluorine replaces the metal ion of organic azochlorosulfonate acid alkali (great soil group) metal-salt, is basic metal or alkaline-earth metal.As basic metal, can enumerate lithium, sodium, potassium, rubidium and caesium.As alkaline-earth metal, can enumerate beryllium, magnesium, calcium, strontium and barium.Basic metal more preferably.Therefore, preferred organic metal salt flame retardant is the perfluoro alkyl sulfonic acid an alkali metal salt.In described basic metal, when the requirement of the transparency is higher, preferred rubidium and caesium, on the other hand because they are not general and refining yet difficulty, so the result is unfavorable on cost sometimes.On the other hand, favourable lithium and sodium is unfavorable sometimes on the transparency on the contrary on cost and flame retardant resistance.Consider these situations, can separately use the basic metal in the perfluoro alkyl sulfonic acid an alkali metal salt, but all excellent perfluoro alkyl sulfonic acid sylvite of the balance of characteristic from which aspect no matter most preferably.Can also be with described sylvite and the perfluoro alkyl sulfonic acid an alkali metal salt and the usefulness that form by other alkali metal.

As described perfluoro alkyl sulfonic acid an alkali metal salt, 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., they can use a kind or will be more than 2 kinds and use.Wherein preferred especially potassium perfluorobutane sulfonate.

Above-mentioned organic metal salt flame retardant is preferably below the 50ppm by the content of the fluoride ion of ion-chromatographic determination, more preferably below the 20ppm, below the further preferred 10ppm.The content of fluoride ion is low more, and flame retardant resistance and photostabilization are good more.The lower limit of the content of fluoride ion in fact also may reach 0, but keeps in balance from refining man-hour and effect, in the practical application about preferred 0.2ppm.The perfluoro alkyl sulfonic acid an alkali metal salt of this fluoride ion content is for example refining as follows.Scope at 40～90 ℃ (more preferably 60～85 ℃) is dissolved in the perfluoro alkyl sulfonic acid an alkali metal salt in the ion exchanged water of these metal-salt 2～10 times of weight.This perfluoro alkyl sulfonic acid an alkali metal salt is by with in alkali-metal carbonate or the oxyhydroxide and the method for perfluoro alkyl sulfonic acid, perhaps uses in alkali-metal carbonate or the oxyhydroxide and method (more preferably adopting the latter's the method) generation of perfluoroalkyl sulfonyl fluoride.In addition, the special preferably water of resistance value more than 18M Ω cm of this ion exchanged water.Under said temperature, will be dissolved with the solution stirring 0.1～3 hour of metal-salt, more preferably 0.5～2.5 hour.Then this solution is cooled to 0～40 ℃, more preferably 10～35 ℃ scope.Separate out by crystallisation by cooling.Isolate the crystallization of being separated out by filtration.Make the perfluoro alkyl sulfonic acid an alkali metal salt after preferably making with extra care thus.

When using fluorine to replace organic azochlorosulfonate acid alkali (great soil group) metal-salt as fire retardant, its use level is 0.01～1.0 weight part with respect to A composition 100 weight parts, preferred 0.03～0.8 weight part, further preferred 0.05～0.5 weight part.In this preferred range, wave all the more by cooperating fluorine to replace the effect (for example flame retardant resistance, static electricity resistance etc.) that organic azochlorosulfonate acid alkali (great soil group) metal-salt is expected.

Replace organic azochlorosulfonate acid alkali (great soil group) metal-salt organic metal salt flame retardant in addition as fluorine, the preferred not metal-salt of the organic sulfonic acid of contain fluorine atoms.As this metal-salt, for example can enumerate an alkali metal salt of aliphatic sulfonic, the alkali earth metal salt of aliphatic sulfonic, an alkali metal salt of aromatic sulphonic acid and the alkali earth metal salt of aromatic sulphonic acid etc. (all not contain fluorine atoms).

Preference as an alkali metal salt of aliphatic sulfonic, can enumerate alkyl sulfonate alkali (great soil group) metal-salt, they can use a kind or will be more than 2 kinds and with (at this, the statement of alkali (great soil group) metal-salt is used to comprise an alkali metal salt, the whole meaning of alkali earth metal salt).Preference as the alkane sulfonic acid that in this alkyl sulfonate alkali (great soil group) metal-salt, uses, can enumerate methanesulfonic, ethane sulfonic acid, propane sulfonic acid, butane sulfonic acid, methylbutane sulfonic acid, hexane sulfonic acid, heptanesulfonic acid, perfluoroetane sulfonic acid etc., they can use a kind or will be more than 2 kinds and use.

As the aromatic sulphonic acid that in aromatic sulphonic acid alkali (great soil group) metal-salt, uses, can enumerate the sulfonic acid of the aromatic thioether that is selected from monomer shape or polymkeric substance shape, the sulfonic acid of aromatic carboxylic acid and ester, the sulfonic acid of the aromatic ether of monomer shape or polymkeric substance shape, the sulfonic acid of aromatic sulfonic acid ester, the aromatic sulphonic acid of monomer shape or polymkeric substance shape, the aromatic series sulfone sulfonic acid of monomer shape or polymkeric substance shape, the sulfonic acid of aromatic ketone, hetero ring type sulfonic acid, the sulfonic acid of aromatic series sulfoxide, at least a kind of acid in the condensation body that the methylene fundamental mode key of aromatic sulphonic acid forms, they can use a kind or will more than 2 kinds and use.

Concrete example as aromatic sulphonic acid alkali (great soil group) metal-salt, can enumerate for example diphenylsulfide-4,4 '-disulfonic acid disodium, diphenylsulfide-4,4 '-disulfonic acid dipotassium, 5-sulfoisophthalic acid potassium, 5-sulfoisophthalic acid sodium, the many sodium of the many sulfonic acid of polyethylene terephthalate, 1-methoxynaphthalene-4-calcium sulphonate, 4-dodecylphenyl ether disulfonic acid disodium, poly-(2,6-dimethyl phenylate) the many sodium of many sulfonic acid, poly-(1, the 3-phenylate) the many sodium of many sulfonic acid, poly-(1, the 4-phenylate) the many sodium of many sulfonic acid, poly-(2,6-phenylbenzene phenylate) the many potassium of many sulfonic acid, poly-(2-fluoro-6-butyl phenylate) many 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 formaldehyde condensation products of the formaldehyde condensation products of sodium naphthalene sulfonate and anthracene sulfonic acid sodium etc.

In the metal-salt of the organic sulfonic acid of contain fluorine atoms not, optimization aromatic azochlorosulfonate acid alkali (great soil group) metal-salt, preferred especially sylvite.When cooperating this aromatic sulphonic acid alkali (great soil group) metal-salt as fire retardant, its content is 0.01～1 weight part with respect to A composition 100 weight parts, preferred 0.03～0.8 weight part, further preferred 0.05～0.5 weight part.

(C-3 composition: the silicone-based fire retardant)

As the silicone compounds that silicone-based fire retardant of the present invention uses, be the compound that the chemical reaction during by burning improves flame retardant resistance.As this compound, all cpds that can use in the past the fire retardant as aromatic polycarbonate resin to propose.Think silicone compounds by when it burns, himself take place in conjunction with or combine with the composition that derives from resin and to form structure, perhaps pass through the reduction reaction when this structure formation, and give flame retardant effect polycarbonate resin.Therefore preferably comprise the high group of activity in this reaction, more particularly, preferably contain at least a group in alkoxyl group and the hydrogen (being the Si-H yl) of being selected from of specified amount.Proportional as containing of described group (alkoxyl group, Si-H yl), the scope of preferred 0.1～1.2mol/100g, the more preferably scope of 0.12～1mol/100g, the further scope of preferred 0.15～0.6mol/100g.This ratio is measured the hydrogen that silicone compounds produced of per unit weight or the amount of alcohol and is obtained by caustic leaching process.In addition, the alkoxyl group of the preferred carbonatoms 1～4 of alkoxyl group, preferred especially methoxyl group.

In general, the structure of silicone compounds constitutes by 4 kinds of siloxane unit arbitrary combination that illustrate below inciting somebody to action.Promptly

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 1 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) ₂2 functionality siloxane units such as SiO;

T unit: (CH ₃) SiO _3/2, (C ₃H ₇) SiO _3/2, HSiO _3/2, (CH ₂=CH) SiO _3/2, (C ₆H ₅) SiO _3/2Deng 3 functionality siloxane units;

Q unit: use SiO ₂4 functionality siloxane units of expression.

The structure of the silicone compounds that uses in the silicone-based fire retardant specifically, can be enumerated D as rational formula _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 the structure of preferred silicone compounds is M _mD _n, M _mT _p, M _mD _nT _p, M _mD _nQ _q, further preferred construction is M _mD _nOr M _mD _nT _p

At this, the Coefficient m in the above-mentioned rational formula, n, p, q are the integers more than 1 of the polymerization degree of each siloxane unit of expression, the mean polymerisation degree that adds up to silicone compounds of the coefficient in each rational formula.The scope of this mean polymerisation degree preferred 3～150, more preferably 3～80 scope, further preferred 3～60 scope, preferred especially 4～40 scope.In this preferred range, it is excellent more that flame retardant resistance becomes.And then as described later, the transparency of silicone compounds and the tone of aromatic group that contains specified amount is also excellent.

In addition, when any among m, n, p, the q was numerical value more than 2, the siloxane unit that has this coefficient can become institute's bonded hydrogen atom, the different siloxane unit more than 2 kinds of organic residue.

Silicone compounds can be that the straight chain shape also can be a branched structure.In addition, with the organic residue of Siliciumatom bonded preferably carbonatoms 1～30, more preferably organic residue of 1～20.As this organic residue, specifically can enumerate alkyl such as methyl, ethyl, propyl group, butyl, hexyl and decyl, as the cycloalkyl the cyclohexyl, as aryl the phenyl and the aralkyl as tolyl.Alkyl, alkenyl or the aryl of further preferred carbonatoms 1～8.As alkyl, the alkyl of carbonatomss 1～4 such as special preferable methyl, ethyl and propyl group.

Further the silicone compounds that preferably uses as the silicone-based fire retardant contains aryl.Containing of the aromatic group that more preferably following general formula (II) is represented proportional (amount of aromatic group) is 10～70 weight % (more preferably 15～60 weight %).

(in the formula (II), X represents the organic residue of monovalence of OH base, carbonatoms 1～20 independently of one another.N represents 0～5 integer.And then n is 2 when above in formula (II), can get the X of mutually different kind separately.)

Silicone compounds as the silicone-based fire retardant uses can also contain reactive group except above-mentioned Si-H base and alkoxyl group, as this reactive group, illustration has for example amino, carboxyl, oxyethyl group, vinyl, sulfydryl and methacryloxy etc.

As the silicone compounds with Si-H base, preferred illustration contains following general formula (III) and (IV) silicone compounds more than at least a in the represented structural unit.

(in formula (III) and the formula (IV), Z ¹～Z ³Organic residue of monovalence or the represented compound of following logical formula V of representing hydrogen atom, carbonatoms 1～20 independently of one another.α ¹～α ³Represent 0 or 1 independently of one another.M1 represents the integer more than 0 or 1.And then m1 is that 2 repeating units when above can be got mutually different separately a plurality of repeating units in formula (IV).)

(in the formula V, Z ⁴～Z ⁸The organic residue of monovalence of representing hydrogen atom, carbonatoms 1～20 independently of one another.α ⁴～α ⁸Represent 0 or 1 independently of one another.M2 represents the integer more than 0 or 1.And then m2 is that 2 repeating units when above can be got mutually different separately a plurality of repeating units in formula V.)

In the silicone compounds that in the silicone-based fire retardant, uses,, for example can enumerate at least a compound of from the represented compound of general formula (VI) and general formula (VII), selecting as silicone compounds with alkoxyl group.

(in the formula (VI), β ¹Expression vinyl, the alkyl of carbonatoms 1～6, the cycloalkyl of carbonatoms 3～6 and the aryl and the aralkyl of carbonatoms 6～12.γ ¹, γ ², γ ³, γ ⁴, γ ⁵And γ ⁶The alkyl of expression carbonatoms 1～6 and the aryl and the aralkyl of cycloalkyl and carbonatoms 6～12, at least one group is an aryl or aralkyl.δ ¹, δ ²And δ ³The alkoxyl group of expression carbonatoms 1～4.)

(in the formula (VII), β ²And β ³Expression vinyl, the alkyl of carbonatoms 1～6, the cycloalkyl of carbonatoms 3～6 and the aryl and the aralkyl of carbonatoms 6～12.γ ⁷, γ ⁸, γ ⁹, γ ¹⁰, γ ¹¹, γ ¹², γ ¹³And γ ¹⁴Alkyl, the cycloalkyl of carbonatoms 3～6 and the aryl and the aralkyl of carbonatoms 6～12 of expression carbonatoms 1～6, at least one group is an aryl or aralkyl.δ ⁴, δ ⁵, δ ⁶And δ ⁷The alkoxyl group of expression carbonatoms 1～4.)

When using the silicone-based fire retardant as fire retardant, its use level is 0.01～5 weight part with respect to A composition 100 weight parts, preferred 0.1～4 weight part, further preferred 0.3～3 weight part.

Above-mentioned fire retardant (C-1 composition), (C-2 composition) and (C-3 composition) may be used singly or in combination of two or more kinds.From the viewpoint of formability and flame retardant resistance, the phosphorus flame retardant of preferred (C-1 composition).

(D composition: fluorine-containing Antidrip agent)

The so-called fluorine-containing Antidrip agent (D composition) that uses in the present invention is to prevent that fusion is dripped and made the further fluorochemicals that improves of flame retardant resistance when burning, and representational can enumerating has the tetrafluoroethylene that fibril forms ability.Need to prove, below abbreviate tetrafluoroethylene as PTFE sometimes.PTFE with fibril formation ability has high molecular weight, will be fibrous trend in conjunction with showing between the PTFE by external force effects such as shearing forces.The number-average molecular weight of its molecular weight to be obtained by standard specific gravity is 1,000,000～1,000 ten thousand, more preferably 2,000,000～9,000,000.This PTFE can also use the PTFE of aqueous liquid dispersion form except solid shape.In addition, this has the PTFE that fibril forms ability, improves, obtains better flame retardant resistance and mechanical characteristics in order to make the dispersiveness in resin, can also use the PTFE mixture with the mixed style of other mixed with resin.

Have the commercially available product that fibril forms the PTFE of ability as this, can enumerate the POLYFLON MPA FA500 of TEFLON (registered trademark) 6J of Mitsui-fluorine chemistry company of Du Pont for example, big aurification industrial and F-201L etc.As the commercially available product of the aqueous liquid dispersion of PTFE, can enumerate FLUONAD-1, AD-936, the big system FLUON D-1 of aurification industrial, the D-2 of ASAHI-ICI FLUORO POLYMERS corporate system, TEFLON (registered trademark) 30J of Mitsui-fluorine chemistry company of Du Pont etc. as representing.

PTFE as mixed style, can use the mixture that obtains by the following method: mix the aqueous liquid dispersion of PTFE (1) with the aqueous liquid dispersion or the solution of organic polymer, carries out co-precipitation and obtain the method (spy opens the method that clear 60-258263 communique, spy are opened record in the clear 63-154744 communique etc.) of common cohesion mixture; (2) with aqueous liquid dispersion and the exsiccant organic polymer particle blended method (spy opens the method for putting down in writing in the flat 4-272957 communique) of PTFE; (3) aqueous liquid dispersion with PTFE mixes equably with organic polymer particle solution, the method for from this mixture various media being removed simultaneously (spy opens flat 06-220210 communique, the spy opens the method for middle records such as flat 08-188653 communique); (4) in the aqueous liquid dispersion of PTFE, the monomer of organic polymer to be formed is carried out polymeric method (spy opens the method for putting down in writing in the flat 9-95583 communique); And (5) with the aqueous liquid dispersion of PTFE with after the organic polymer dispersion liquid mixes equably, further polymerising ethylene base system monomer in this mixed dispersion liquid obtains the method (spy opens the method for putting down in writing in the flat 11-29679 grade) of mixture then.As the commercially available product of the PTFE of these mixed styles, can enumerate " BLENDEX B449 " (trade(brand)name), the PIC corporate system " POLY TS AD001 " (trade(brand)name) of " METABLEN A3800 " (trade(brand)name), " METABLENA3700 " (trade(brand)name), " METABLEN A3750 " (trade(brand)name), GE Specialty Chemicals corporate system of Li Yang company of Mitsubishi and SHINE POLYMER corporate system " SN3307 " etc.

As the ratio of the PTFE of mixed style, in PTFE mixture 100 weight %, preferred PTFE is 1～60 weight %, more preferably 5～55 weight %.The ratio of PTFE can realize the dispersiveness that PTFE is good when described scope.

(content of each composition)

In the poly carbonate resin composition of the present invention, with respect to A composition 100 weight parts, the content of B composition is 0.05～3.0 weight part, is preferably 0.08～2.0 weight part, more preferably 0.1～1.0 weight part.The B composition is during less than 0.05 weight part, and the sliding of moulding product is not enough, and when surpassing 3.0 weight parts, the transparency is not enough and be not suitable for.

The content of C composition is 0.01～20 weight part with respect to A composition 100 weight parts, preferred 0.03～15 weight part, further preferred 0.05～10 weight part.The C composition is during less than 0.01 weight part, and flame retardant resistance and formability are not enough, and during greater than 20 weight parts, thermotolerance, physical strength significantly reduce and be not suitable for.

The content of D composition is preferably 0.03～1 weight part with respect to A composition 100 weight parts, more preferably 0.04～0.5 weight part, further preferred 0.05～0.3 weight part.The D composition is during less than 0.03 weight part, and flame retardant resistance is not enough, and during greater than 1 weight part, and the transparency is not enough and be not suitable for.

(other additive)

In flame-retardant polycarbonate resin composition of the present invention, except above-mentioned A composition～D composition, can cooperate the various additives that in polycarbonate resin, cooperate usually.

(I) phosphorus is stablizer

In flame-retardant polycarbonate resin composition of the present invention, under the degree that does not promote hydrolysis, preferably being combined with phosphorus is stablizer.This phosphorus is that stablizer makes when making or the thermostability during forming process improves, makes mechanical characteristics, color harmony forming stability to improve.As phosphorus is stablizer, and illustration has phosphorous acid, phosphoric acid, phosphonous acid, phosphonic acids and their ester and tertiary phosphine etc.

Specifically, as bi-ester of phosphite, can enumerate for example triphenyl phosphite, tricresyl phosphite (nonyl phenyl) ester, tridecyl phosphite, the tricresyl phosphite monooctyl ester, tricresyl phosphite (octadecyl) ester, phosphorous acid didecyl list phenylester, phosphorous acid dioctyl list phenylester, phosphorous acid di-isopropyl list phenylester, phosphorous acid monobutyl diphenyl, phosphorous acid list decyl diphenyl, phosphorous acid list octyl group diphenyl, 2,2-methylene-bis (4, the 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, the 4-di-tert-butyl-phenyl) phosphorous acid ester, three (2, the 6-di-tert-butyl-phenyl) phosphorous acid ester, distearyl pentaerythrityl diphosphite, two (2, the 4-di-tert-butyl-phenyl) pentaerythritol diphosphites, two (2,6-di-t-butyl-4-aminomethyl phenyl) pentaerythritol diphosphites, two (2,6-di-t-butyl-4-ethylphenyl) pentaerythritol diphosphites, phenyl dihydroxyphenyl propane pentaerythritol diphosphites, two (nonyl phenyl) pentaerythritol diphosphites, dicyclohexyl pentaerythritol diphosphites etc.

And then, as other bi-ester of phosphite, can also use the bi-ester of phosphite that has ring texture with the dihydric phenols reaction.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, two (4-methyl-6-tert butyl phenyl) (the 2-tertiary butyl-4-aminomethyl phenyl) phosphorous acid esters of 2 '-ethidine etc.

As phosphate compound, can enumerate tributyl phosphate, trimethyl phosphite 99, Tritolyl Phosphate, triphenylphosphate, trichlorophenyl phosphate, triethyl phosphate, di(2-ethylhexyl)phosphate phenyltolyl base ester, the adjacent biphenyl ester of di(2-ethylhexyl)phosphate phenyl list, tricresyl phosphate (butoxyethyl group) ester, dibutyl phosphate, dioctylphosphoric acid ester, diisopropyl phosphate etc.Preferably phosphoric acid triphenylmethyl methacrylate, trimethyl phosphite 99.

As phosphinate compound, can enumerate four (2, the 4-di-tert-butyl-phenyl)-4,4 '-biphenylene, two phosphinates, four (2, the 4-di-tert-butyl-phenyl)-4,3 '-biphenylene, two phosphinates, four (2, the 4-di-tert-butyl-phenyl)-3,3 '-biphenylene, two phosphinates, four (2, the 6-di-tert-butyl-phenyl)-4,4 '-biphenylene, two phosphinates, four (2, the 6-di-tert-butyl-phenyl)-4,3 '-biphenylene, two phosphinates, four (2, the 6-di-tert-butyl-phenyl)-3,3 '-biphenylene, two phosphinates, two (2, the 4-di-tert-butyl-phenyl)-4-phenyl-phenyl-phosphonite ester, two (2, the 4-di-tert-butyl-phenyl)-3-phenyl-phenyl-phosphonite esters, two (2,6-di-n-butyl phenyl)-3-phenyl-phenyl-phosphonite esters, two (2, the 6-di-tert-butyl-phenyl)-4-phenyl-phenyl-phosphonite ester, two (2, the 6-di-tert-butyl-phenyl)-3-phenyl-phenyl-phosphonite esters etc.Preferred four (di-tert-butyl-phenyl)-biphenylenes, two phosphinates, two (di-tert-butyl-phenyls)-phenyl-phenyl-phosphonite ester, more preferably four (2, the 4-di-tert-butyl-phenyl)-biphenylene two phosphinates, two (2, the 4-di-tert-butyl-phenyl)-phenyl-phenyl-phosphonite ester.Described phosphinate compound preferably can also be used with above-mentioned bi-ester of phosphite with the aryl that is substituted with 2 above alkyl.

As phosphonate compound, can enumerate Phenylsulfonic acid dimethyl ester, Phenylsulfonic acid diethyl ester and Phenylsulfonic acid dipropyl etc.

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

Above-mentioned phosphorus is in the stablizer, can only use a kind of or mixes more than 2 kinds and to use.Above-mentioned phosphorus is in the stablizer, and preferably cooperating with the trimethyl phosphite 99 is the alkyl acid phosphate ester cpds of representative.In addition, this alkyl acid phosphate ester cpds and bi-ester of phosphite and/or phosphinate compound and with also being preferred mode.

(II) hindered phenol is a stablizer

It is stablizer that flame-retardant polycarbonate resin composition of the present invention can further cooperate hindered phenol.The effect of the tone deterioration during the tone when this cooperation performance for example suppresses forming process worsens, uses for a long time etc.As hindered phenol is stablizer; for example; illustration has 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 acid ester diethyl ester; 2; 2 '-methylene-bis (4-methyl-6-tert butyl phenol); 2; 2 '-methylene-bis(4-ethyl-6-t-butyl phenol); 4; 4 '-methylene-bis (2; the 6-DI-tert-butylphenol compounds); 2; 2 '-methylene-bis(4-methyl-6-cyclohexyl phenol); 2; 2 '-dimethylene-two (6-Alpha-Methyl-benzyl-p-cresol); 2; 2 '-ethidine-two (4; the 6-DI-tert-butylphenol compounds); 2; 2 '-Ding fork base-two (4-methyl-6-tert butyl phenol); 4; 4 '-Ding fork base two (3 methy 6 tert butyl phenol); triethylene glycol-N-pair-3-(3-tertiary butyl-4-hydroxy-5-aminomethyl phenyl) propionic ester; 1; the 6-hexylene glycol is two, and [3-(3; the 5-di-tert-butyl-hydroxy phenyl) propionic ester]; two [the 2-tertiary butyl-4-methyl-6-(the 3-tertiary butyl-5-methyl-2-hydroxybenzyl) phenyl] terephthalate; 3; 9-pair 2-[3-(3-tertiary butyl-4-hydroxy-5-aminomethyl phenyl) propionyloxy]-1; the 1-dimethyl ethyl }-2; 4; 8; 10-four oxaspiros [5; 5] undecane; 4; 4 '-thiobis (the 6-tertiary butyl-meta-cresol); 4; 4 '-thiobis (3 methy 6 tert butyl phenol); 2; 2 '-thiobis (4-methyl-6-tert butyl phenol); two (3; the 5-di-tert-butyl-4-hydroxyl benzyl) thioether; 4; 4 '-two-thiobis (2; the 6-DI-tert-butylphenol compounds); 4; 4 '-three-thiobis (2; the 6-DI-tert-butylphenol compounds); 2; [3-(3 for 2-sulfo-di ethylene bis; the 5-di-tert-butyl-hydroxy phenyl) propionic ester]; 2; two (positive hot sulfenyl)-6-(the 4-hydroxyls-3 ' of 4-; 5 '-di-tert-butyl amido)-1; 3; the 5-triazine; N; N '-hexa-methylene two-(3; 5-di-t-butyl-4-hydroxyl hydrocinnamamide); N; N '-two-[3-(3; the 5-di-tert-butyl-hydroxy phenyl) propionyl] hydrazine; 1; 1; 3-three (2-methyl-4-hydroxyl-5-tert-butyl-phenyl) butane; 1; 3; 5-trimethylammonium-2; 4; 6-three (3; the 5-di-tert-butyl-4-hydroxyl benzyl) benzene; three (3; the 5-di-tert-butyl-hydroxy phenyl) isocyanuric acid ester; three (3; the 5-di-tert-butyl-4-hydroxyl benzyl) isocyanuric acid ester; 1; 3; 5-three (the 4-tertiary butyl-3-hydroxyl-2; the 6-dimethyl benzyl) isocyanuric acid ester; 1; 3; 5-three 2[3 (3; the 5-di-tert-butyl-hydroxy phenyl) propionyloxy] the ethyl isocyanuric acid ester; and four [methylene radical-3-(3 ', 5 '-di-tert-butyl-hydroxy phenyl) propionic ester] methane etc.They all obtain easily.Above-mentioned hindered phenol is that antioxidant may be used singly or in combination of two or more.

Phosphorus is that stablizer and hindered phenol are the use level of stablizer, with respect to A composition 100 weight parts, is preferably 0.0001～1 weight part, more preferably 0.001～0.5 weight part, more preferably 0.005～0.3 weight part.

(reinforcement filler)

Can cooperate in the poly carbonate resin composition of the present invention as strengthening the known various packing materials of filler.Yet because resin combination of the present invention is required the transparency, therefore preferably the silicate mine system filler or the glass of the harmless transparency are filler as strengthening filler.As described silicate mine system filler, preference is shown with talcum, white mica, synthetic fluorine mica, montmorillonite and wollastonite.As glass is filler, and illustration has glass fibre, glass flake (glass flake) and glass powder debris etc.Silicate mine system filler and glass are the filler that filler also can utilize has metal oxides such as titanium oxide, zinc oxide, cerium oxide and silicon oxide to form in their surface coated.

Described reinforcement filler can carry out surface treatment with various surface treatment agents in advance.As this surface treatment agent, can carry out surface treatment with various surface treatment agents such as silane coupling agent (comprising alkylalkoxy silane, poly-organohydrogensiloxanes etc.), high-grade aliphatic ester, acid compound (for example phosphorous acid, phosphoric acid, carboxylic acid and carboxylic acid anhydride etc.) and waxes.And then, can also carry out granulation and form particulate state with collecting agents such as various resins, high-grade aliphatic ester and waxes.

Strengthening filler is benchmark with A composition 100 weight parts, and the upper limit that can cooperate is 100 weight parts.Preferred 25 weight parts of this upper limit, more preferably 20 weight parts.

(IV) thermo-stabilizer outside above-mentioned

In flame-retardant polycarbonate resin composition of the present invention, can also cooperate except above-mentioned phosphorus be that stablizer and hindered phenol are other thermo-stabilizers the stablizer.As described other thermo-stabilizers, the preference example is as with 3-hydroxyl-5, and the reaction product of 7-di-t-butyl furans-2-ketone and o-Xylol is that the lactone of representative is a stablizer.The write up of this stablizer is opened in the flat 7-233160 communique in the spy.This compound has commercially available as Irganox HP-136 (trade mark, CIBA SPECIALTYCHEMICALS corporate system), can utilize this compound.And then, also commercially available have this compound mixed with various bi-ester of phosphite and hindered phenol compound and stablizer.For example, preference is shown with the Irganox HP-2921 that above-mentioned company makes.Lactone is that the use level of stablizer is preferably 0.0005～0.05 weight part with respect to A composition 100 weight parts, more preferably 0.001～0.03 weight part.

In addition, as these other stablizer, illustration has tetramethylolmethane four (3-mercaptopropionic acid ester), tetramethylolmethane four (3-lauryl thiopropionate) and glycerol-sulphur-containing stabilizers such as 3-stearyl thiopropionate.The use level of this sulphur-containing stabilizer is preferably 0.001～0.1 weight part with respect to A composition 100 weight parts, more preferably 0.01～0.08 weight part.

(V) UV light absorber

In flame-retardant polycarbonate resin composition of the present invention,, can also cooperate UV light absorber in order to give photostabilization.

As UV light absorber; specifically; for benzophenone series; illustration for example has 2; the 4-dihydroxy benaophenonel; 2-hydroxyl-4-methoxy benzophenone; 2-hydroxyl-4-octyloxy benzophenone; 2-hydroxyl-4-benzyloxy benzophenone; 2-hydroxyl-4-methoxyl group-5-sulfonic group benzophenone (2-ヒ De ロキシ-4-メトキシ-5-ス Le ホキシベ Application ゾ Off エノ Application); 2-hydroxyl-4-methoxyl group-5-sulfonic group three hydrogenation benzophenone (2-ヒ De ロキシ-4-メトキシ-5-ス Le ホキシトリ Ha イ De ライ De レイトベ 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-benzophenone-5-sodium sulfonate (2; 2 '-ジヒ De ロキシ-4,4 '-ジメトキシ-5-ソジウ system ス Le ホキシベ Application ゾ Off エノ Application); two (5-benzoyl-4-hydroxyl-2-p-methoxy-phenyl) methane; 2-hydroxyl-4-positive 12-alkoxy benzophenone and 2-hydroxyl-4-methoxyl group-2 '-carboxyl benzophenone etc.

As UV light absorber, specifically, for benzotriazole be, illustration has for example 2-(2-hydroxy-5-methyl base phenyl) benzotriazole, 2-(2-hydroxyl-uncle's 5-octyl phenyl) benzotriazole, 2-(2-hydroxyl-3, the 5-dicumylphenyl) phenyl benzotriazole, 2-(the 2-hydroxyl-3-tertiary butyl-5-aminomethyl phenyl)-5-chlorobenzotriazole, 2, [4-(1 for 2 '-methylene-bis, 1,3, the 3-tetramethyl butyl)-6-(2H-benzotriazole-2-yl) phenol], 2-(2-hydroxyl-3, the 5-di-tert-butyl-phenyl) benzotriazole, 2-(2-hydroxyl-3, the 5-di-tert-butyl-phenyl)-the 5-chlorobenzotriazole, 2-(2-hydroxyl-3, the 5-di-tert-pentyl-phenyl) benzotriazole, 2-(2-hydroxyl-uncle's 5-octyl phenyl) benzotriazole, 2-(2-hydroxyl-5-tert-butyl-phenyl) benzotriazole, 2-(2-hydroxyl-4-octyloxyphenyl) benzotriazole, 2,2 '-methylene-bis (4-cumyl-6-benzotriazole phenyl), 2,2 '-TOPOT 2,2 (1,3-benzoxazine-4-ketone) and 2-[2-hydroxyl-3-(3,4,5,6-tetrahydrochysene phthalic diamide methyl)-the 5-aminomethyl phenyl] benzotriazole, and 2-(2 '-hydroxy-5-methyl base acryloxy ethylphenyl)-2H-benzotriazole and can with the multipolymer of the vinyl monomer of this monomer copolymerization, 2-(2 '-hydroxyl-5-acryloxy ethylphenyl)-2H-benzotriazole and can have the polymkeric substance etc. of 2-hydroxy phenyl-2H-benzotriazole skeleton with the multipolymer of the vinyl monomer of this monomer copolymerization etc.

As UV light absorber, specifically, for hydroxyphenyltriazinuv system, illustration has for example 2-(4,6-phenylbenzene-1,3,5-triazines-2-yl)-5-hexyloxy phenol, 2-(4,6-phenylbenzene-1,3,5-triazines-2-yl)-5-methoxyphenol, 2-(4,6-phenylbenzene-1,3,5-triazines-2-yl)-5-thanatol, 2-(4,6-phenylbenzene-1,3,5-triazines-2-yl)-5-propoxy-phenol and 2-(4,6-phenylbenzene-1,3,5-triazines-2-yl)-5-butoxy phenol etc.And then also the phenyl of 2-(4, two (2, the 4-3,5-dimethylphenyl)-1,3,5-triazines-2-yls of 6-)-5-hexyloxy phenol etc., above-mentioned exemplary compounds is arranged is 2 to illustration, the compound of 4-3,5-dimethylphenyl.

As UV light absorber, specifically, for cyclic imide acid esters system, illustration for example has 2,2 '-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; as UV light absorber; specifically, for cyanoacrylate system, illustration for example has 1; two [(the 2 '-cyano group-3 ' of 3-; 3 '-diphenylprop enoyl-) oxygen base]-2, two [(2-cyano group-3, the 3-diphenylprop enoyl-) oxygen base] methyl of 2-) propane and 1; two [(2-cyano group-3,3-diphenylprop enoyl-) oxygen base] benzene of 3-etc.

And then, above-mentioned UV light absorber can also be by forming the structure of monomeric compound that can radical polymerization, and monomers such as this ultraviolet-absorbing monomer and/or light stability monomer and (methyl) alkyl acrylate are carried out the polymer-type UV light absorber that copolymerization forms.As above-mentioned ultraviolet-absorbing monomer, preference is shown with the compound that contains benzotriazole skeleton, benzophenone skeleton, triazine skeleton, cyclic imide acid esters skeleton and cyanoacrylate skeleton in the ester substituting group of (methyl) acrylate.

Wherein, from the viewpoint of ultraviolet absorption ability, preferred benzotriazole system and hydroxyphenyltriazinuv system, from the viewpoint of thermotolerance, tone, preferred cyclic imide acid esters system and cyanoacrylate system.Above-mentioned UV light absorber can be used separately or use with the mixture more than 2 kinds.

The use level of UV light absorber is preferably 0.01～2 weight part with respect to A composition 100 weight parts, more preferably 0.02～2 weight part, further preferred 0.03～1 weight part, most preferably 0.05～0.5 weight part.

(VI) releasing agent

In poly carbonate resin composition of the present invention, the productivity when improving its moulding, reduce the distortion of moulding product, further preferred cooperation releasing agent.As this releasing agent, can use known releasing agent.For example, polyunsaturated fatty acid ester, unsaturated fatty acid ester, polyolefin wax (can use polyethylene wax, 1-olefin polymer etc., usefulness such as sour modification contain the material that functional compounds has carried out modification), silicone compounds, fluorine cpd (with the poly-fluoroalkyl ether fluorocarbon oil that is representative etc.), paraffin, beeswax etc.Wherein, as preferred releasing agent, can enumerate fatty acid ester.This fatty acid ester is the ester of fatty alcohol and aliphatic carboxylic acid.This fatty alcohol can be that monohydroxy-alcohol also can be the above polyvalent alcohol of binary.In addition, as this pure carbonatoms, be 3～32 scope, more preferably 5～30 scope.As this monohydroxy-alcohol, illustration has for example dodecanol, tetradecanol, cetyl alcohol, Stearyl alcohol, eicosanol, Tetracosyl alcohol, the pure and mild triacontanol price quote of hexacosane etc.As this polyvalent alcohol, can enumerate tetramethylolmethane, Dipentaerythritol, tripentaerythritol, Polyglycerine (triglycerin～six glycerine), two (TriMethylolPropane(TMP)s), Xylitol, Sorbitol Powder and N.F,USP MANNITOL etc.More preferably polyvalent alcohol in the fatty acid ester of the present invention.

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

Above-mentioned aliphatic carboxylic acid such as stearic acid, palmitinic acid is usually by being the animal raw fat of representative with butter, lard etc. and being the natural oil lipid manufacturings such as vegetative grease of representative with plam oil, sunflower wet goods, so these aliphatic carboxylic acids normally contain other different carboxylic acid compositions of carbonatoms mixture.Therefore, in the manufacturing of fatty acid ester of the present invention, preferred use by this natural oil lipid manufacturing, by morphotic aliphatic carboxylic acid, especially stearic acid, the palmitinic acid of the mixture that contains other carboxylic acid compositions.

Fatty acid ester of the present invention can be any in part ester and the full ester (full ester).Yet, the resin decomposition when bringing out high temperature easily etc., therefore more preferably full ester because the common hydroxyl value of part ester is high.From the viewpoint of thermostability, the acid number of fatty acid ester of the present invention is preferably below 20, more preferably 4～20 scope, more preferably 4～12 scope.In addition, acid number can be 0 in fact.In addition, more preferably 0.1～30 scope of the hydroxyl value of fatty acid ester.And then iodine value is preferred below 10.In addition, iodine value can be 0 in fact.These characteristics can be obtained by the method for stipulating among the JIS K0070.

With respect to A composition 100 weight parts, the content of releasing agent is preferably 0.005～2 weight part, more preferably 0.01～1 weight part, further preferred 0.05～0.5 weight part.When this scope, poly carbonate resin composition has good release property and roll release.Particularly the fatty acid ester of this amount provides the poly carbonate resin composition with good release property and roll release with can can't harm good tone.

(VII) above-mentioned other compositions in addition

Except mentioned component, in flame-retardant polycarbonate resin composition of the present invention, in order the moulding product to be given various functions and to be improved characteristic, can cooperate on a small quantity itself is known additive.These additives are as long as harmless purpose of the present invention then is common use level.

As this additive, can enumerate antiseize paste (for example PTFE particle), tinting material (carbon black for example, pigment such as titanium oxide, dyestuff), light diffusing agent (vinylformic acid crosslinked particle for example, the silicone crosslinked particle, calcium carbonate particles), fluorescence dye, white dyes, photostabilizer (is representative with the hindered amine), inorganic is fluor (for example being the fluor of crystallization parent nucleus with the aluminate), antistatic agent, crystallization nucleating agent, inorganic and organic antiseptic-germicide, photocatalyst is a stain control agent (particulate titanium dioxide for example, particulate oxide zinc), flow ability modifying agent, free-radical generating agent, infrared absorbent (hot line absorption agent), and photochromic agent etc.

(manufacturing of poly carbonate resin composition)

When making poly carbonate resin composition of the present invention, its manufacture method is not particularly limited.But in order to realize the good dispersion of silicone oil, therefore the preferable production process of resin combination of the present invention is to adopt the method for the such multiple screw extruder of biaxial extruder with each composition melting mixing.

As the typical example of biaxial extruder, can enumerate ZSK (Werner ﹠amp; Pfleiderer corporate system, trade(brand)name).As the concrete example of same-type, can enumerate TEX ((strain) JSW system, trade(brand)name), TEM (toshiba machine (strain) system, trade(brand)name), KTX (made, the trade(brand)name of (strain) Kobe Steel) etc.In addition, can also enumerate FCM (Farrel corporate system, trade(brand)name), Ko-Kneader (Buss corporate system, trade(brand)name) and DSM melting mixing machines such as (Krauss-Maffei corporate system, trade(brand)names) as typical example.Wherein, more preferably be the type of representative with ZSK.In the biaxial extruder of this ZSK type, its screw rod is complete occlusal pattern, and screw rod is made of the different various kneading disks of length various spiro rod sections different with pitch and width (or be equivalent to its mixing fragment of using).

The preferred mode of biaxial extruder is as follows.The screw rod shape can be used 1,2 and 3 thread screw, particularly can preferably use molten resin transport capacity, shear 2 wide thread screws of range of application of mixing these both sides of ability.Spiro rod length in the biaxial extruder (L) is preferably 20～45 with the ratio (L/D) of diameter (D), and further preferred 28～42.Realize easily when L/D is big disperseing uniformly, and when excessive because thermal degradation when and cause the decomposition of resin easily.Having the mixing zone that constitutes by kneading disk fragment (or be equivalent to its mixing fragment) that is used to improve mixing property more than 1 place on the screw rod, preferably has 1～3 place.

And then, as forcing machine, can preferably use forcing machine with the ventilation hole that can outgas to the moisture in the raw material, the volatilization gas that produces by the melting mixing resin.Preferably be provided for to produce the vacuum pump that moisture, volatilization gas are discharged to the forcing machine outside efficiently from ventilation hole.In addition, can also be provided for foreign matter being removed from resin combination in extruding dies portion region in front with sneaking into the screen cloth that foreign matter of extruding in the raw material etc. is removed.As described screen cloth, can enumerate wire netting, net-changing device (screen changer), sintered metal plates (dish filter etc.) etc.

Be not particularly limited to the supply method of forcing machine as B composition～D composition and other additives (abbreviating " additive " in following illustration as), representational illustration has following method.(i) additive and polycarbonate resin are supplied in independently method in the forcing machine respectively.After (ii) using mixing machines such as super mixing roll with additive and the pre-mixing of polycarbonate resin powder, be supplied to the method for forcing machine.(iii) additive and polycarbonate resin are carried out in advance the method for masterbatch pelletization behind the melting mixing.

Aforesaid method one of (ii) is to supply with the method for forcing machine after the whole pre-mixings of essential raw material.And other method is to make earlier the masterbatch agent that is combined with additive with high density, with this masterbatch agent separately or with the further pre-mixing of remaining polycarbonate resin after, supply with the method for forcing machine.In addition, this masterbatch agent can be selected powder morphology and this powder is compressed in the form that granulation etc. forms any.And other premixing mechanism for example has nauta mixer, V-mixer, Henschel mixer, mechanochemistry device and extrudes mixing machine etc., preferably the mixing machine of the high-speed stirring type as super mixing machine.And then other pre-blend approach is for example to make polycarbonate resin and additive are scattered in after the solution that forms in the solvent equably, removes the method for this solvent.

The resin that the machine of being extruded is extruded directly cuts off and granulating, perhaps after forming tow this tow is cut off and granulating with tablets press.And then, when need reducing the influencing of outside dust etc., preferably with the clean environmentization around the forcing machine.And then, in this particulate is made, employing is at the whole bag of tricks of CD with motion in the polycarbonate resin, the minimizing that can suitably carry out stricturization that coating of particles distributes, leak the bubble (bubbles of vacuum) that minimizing, the transportation of cutting thing or the minimizing of carrying the micro mist that produces constantly and tow and granule interior produce.Can carry out the height circulationization of moulding and reduce the generation ratio of the such unfavorable condition of silver color by these treatment processs.This and, coating of particles can be cylinder, square column and general shape such as spherical, more preferably cylinder.The diameter of described cylinder is preferably 1～5mm, more preferably 1.5～4mm, more preferably 2～3.3mm.On the other hand, the length of cylinder is preferably 1～30mm, more preferably 2～5mm, more preferably 2.5～3.5mm.

(the moulding product that form by resin combination of the present invention)

The flame-retardant polycarbonate resin composition of the present invention that obtains as mentioned above can carry out the particle of as above making injection molding usually and make various products.And then, can be without particle, but will directly form sheet, film, special-shaped extrusion molding article, directly blow molding product and injection-molded article with the resin of forcing machine melting mixing.

In this injection molding, not only can adopt common forming method, according to appropriate purpose, can also adopt coated and molded in injection compression molding, injection extrusion forming, air-auxiliary injection forming, foaming (comprising the method for injecting supercutical fluid), insert moulding, the mould, heat insulation mould molding, heating is cooled off injection mouldings such as mould molding, dual-color forming, sandwich moulding and ultra-high speed injection molding and obtained the moulding product rapidly.The advantage of these various methods of forming is well-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 can also form the shape of various special-shaped extrusion molding articles, sheet and film etc. by extrusion moulding.In addition, the moulding of sheet, film can also be used inflation method, rolling process, casting method etc.And then, by applying specific stretched operation, can also be shaped to heat-shrinkable tube.In addition, can also resin combination of the present invention be made the moulding product by rotoforming, blow molding etc.

Provide thus have the more excellent transparency and scuff resistance, the moulding product of the poly carbonate resin composition of flame retardant resistance.Promptly, according to the present invention, provide following flame-retardant polycarbonate resin composition is carried out the moulding product that melt molding forms, described flame-retardant polycarbonate resin composition is with respect to (A) aromatic polycarbonate resin (A composition) 100 weight parts, contain (B) specific refractory power (nd) and be 1.42～1.65 contain phenyl silicone oil (B composition) 0.05～3.0 weight part and (C) fire retardant (C composition) 0.01～20 weight part.

And then, can also carry out various surface treatments to the moulding product that form by flame-retardant polycarbonate resin composition of the present invention.Said herein surface treatment, be meant by evaporation (physical vapor deposition, chemical vapor deposition etc.), plating (plating, electroless plating, fusion plating etc.), coating, coating, printing etc. on the top layer of synthetic resin, to form new layer, can use the method for in polycarbonate resin, using usually.As surface treatment, concrete example is shown with firmly and is coated with, hydrophobic-oleophobic is coated with, ultraviolet radiation absorption is coated with, infrared ray absorption is coated with, metalized various surface treatments such as (evaporations etc.).

Flame-retardant polycarbonate resin composition of the present invention is owing to transparency excellence and then have excellent scuff resistance and excellent flame, therefore useful in various uses such as various electronics-electric installations (particularly TV use frame), OA equipment, vehicle part, mechanical part, other agriculture goods, materials and equipments, transport container, game machine and the small articles of daily use, the effect on the industry of its performance is especially good.

The inventor thinks that the mode of the present invention of present the best is the mode that has converged the preferable range of above-mentioned each important document, for example, is recorded in its typical example among the following embodiment.That is, the invention is not restricted to these modes.

Embodiment

Below enumerate embodiment and further specify the present invention.In addition, estimate the following method that adopts.

(1) scuff resistance:, use the reciprocal dynamic friction wear testing machine AFT-15M of ORIENTEC corporate system as estimating machine.The test film (material: polyester 50%, nylon 50%) that the front end of the cylinder of diameter 10mm φ, long 30mm is had the wiping clean-cloth (あつ Chi こつ Chi ふ I ん) of Teijin Ltd's system is installed on the fixation side test film support.

On the other hand, with hot air dryer at 100 ℃ with the particle drying that obtains after 6 hours, adopt injection moulding machine (Sumitomo heavy-duty machine tool industry (strain) system SG-150U), frame moulding product shown in Figure 1 (be uniform wall thickness roughly, its average wall thickness is 2.0mm) are carried out moulding under the condition of 260 ℃ of barrel temperatures, 60 ℃ of die temperatures, injection speed 30mm/sec.In addition, the cast gate of frame moulding product is with 4 place's needle-like gates (gate diameter φ 1.5mm, sectional area 1.77mm ²) implement.Then cut out profiled sheeting (long 40mm * wide 50mm), this profiled sheeting is fixed on the reciprocating base by these moulding product.Cylinder axis direction at test film becomes under the parallel state with the plane normal direction of profiled sheeting, under the state that has applied load loading 200g, the fore-end of above-mentioned test film is contacted with the planar section of described profiled sheeting.Under this contact condition, on 1 straight line in 23 ℃, the atmosphere of relative humidity 50%RH in the plane once back and forth being that 2 seconds ratio moves back and forth the distance 50 times that one way is 10mm, for the condition of surface of the profiled sheeting after the test, (based on ISO/FDIS 3668) has or not scratch from the distance of 30cm with visual observations under the source of artificial light of 2000～4000lx.

Need to prove, estimate and carry out according to following benchmark.

Zero: do not have scratch △ takes place: have slightly scratch take place *: have scratch to take place

(2) transparency: use and " (1) scuff resistance " identical profiled sheeting, the mensuration machine uses the reflective-transmissive rate meter (HR-100 type) of color technical institute system in the village, measures mist degree according to ASTM D-1003.

(3) flame retardant resistance:, estimate its grade with the testing vertical flammability that thickness 0.8mm and 2.4mm carry out UL standard 94.

[embodiment 1～15 and comparative example 1～8]

In the polycarbonate resin powder that adopts interface polycondensation to make by the dihydroxyphenyl propane photoreactive gas, the various additives that cooperate table 1～table 2 record with each use level, after the mixing roll mixing, with exhaust biaxial extruder ((strain) JSW system: TEX30 α (interlock fully, equidirectional rotation, 2 thread screws)) carry out melting mixing, obtain particle.With Henschel mixer make additive with 10 times of concentration of use level separately in advance with the premixture of polycarbonate resin powder after, adopt mixing roll to carry out whole mixing.Extrusion condition is that spray volume is that 20kg/h, screw rod revolution are that 150rpm, deflated vacuum tightness are 3kPa, and in addition, extrusion temperature is divided into 260 ℃ from the 1st supplying opening to die section.

With the particle that obtains at 100 ℃ with the heated air circulation type drying machine after dry 6 hours, use injection moulding machine, under the condition of 260 ℃ of barrel temperatures, 60 ℃ of die temperatures and injection speed 50mm/sec, with the flame retardant resistance evaluation profiled sheeting moulding of long 125mm, wide 13mm, thick 0.8mm and 2.4mm.In addition, use Sumitomo heavy-duty machine tool industry (strain) system: SG-150U as injection moulding machine.In addition, adopt the method for record in " (1) scuff resistance " and " (2) transparency " to be made into template.Each evaluation result of the profiled sheeting that obtains is shown in table 1～table 2.

In addition, the theing contents are as follows of each composition of sign flag in table 1～table 2.

(A composition)

PC-1: adopt interface polycondensation to stop the p-tert-butylphenol photoreactive gas synthetic straight chain shape aromatic polycarbonate resin powder (Supreme Being people changes into (strain) system: L-1225WS (trade(brand)name), viscosity-average molecular weight 20900) of agent by dihydroxyphenyl propane, as end

PC-2: adopt interface polycondensation to stop the p-tert-butylphenol photoreactive gas synthetic straight chain shape aromatic polycarbonate resin powder (Supreme Being people changes into (strain) system PanliteL-1225WX (trade(brand)name), viscosity-average molecular weight 19700) of agent by dihydroxyphenyl propane, as end

(B composition)

B-1: specific refractory power (nd) is 1.533 methyl phenyl silicone oil (eastern beautiful DOW CORNING organosilicon corporate system, SH710)

B-2: specific refractory power (nd) is 1.404 dimethyl silicone oil (eastern beautiful DOW CORNING organosilicon corporate system, SH200)

(C composition)

C-1: with dihydroxyphenyl propane two (diphenyl phosphate) is the phosphoric acid ester (big eight chemical industry (strain) system, CR-741 (trade(brand)name)) of principal constituent

C-2:MEGAFAC F-114P (trade(brand)name) (big Japanese ink chemistry (strain) system, potassium perfluorobutane sulfonate salt)

(D composition)

D-1:POLYFLON MPA FA500 (trade(brand)name) (Daikin Industries (strain) system, tetrafluoroethylene)

D-2: contain tetrafluoroethylene mixed powder METABLEN A3750 (trade(brand)name) (the beautiful sun of Mitsubishi (strain) system, this tetrafluoroethylene are that mixture is the mixture (polytetrafluoroethylene content 50 weight %) that is made of tetrafluoroethylene and acrylic copolymer)

(other)

SL:RIKEMAL SL900 (trade(brand)name) (reason grind VITAMIN (strain) system polyunsaturated fatty acid ester be releasing agent)

TMP:TMP (trade(brand)name) (big eight chemical industry (strain) system phosphorus is stablizer)

Table 1

Table 2

By above-mentioned table 1～table 2 as can be known, the transparency of flame-retardant polycarbonate resin composition of the present invention and excellent scratch resistance, and then also have excellent flame.

Claims

1. flame-retardant polycarbonate resin composition, it is characterized in that, with respect to aromatic polycarbonate resin is A composition 100 weight parts, and containing refractive index n d and be 1.42～1.65 the phenyl silicone oil that contains is that B composition 0.05～3.0 weight part and fire retardant are C composition 0.01～20 weight part.

2. poly carbonate resin composition as claimed in claim 1 wherein, contains phenyl silicone oil and is the B composition and be to be selected from and contain phenyl silicone oil more than a kind in the represented compound in following formula [1]～[4],

In the formula, Ph represents phenyl, and x, y are respectively the integers of 0≤x≤10,1≤y≤100 scopes;

In the formula, Ph represents phenyl, and m, n are respectively the integers of 0≤m≤10,1≤n≤100 scopes;

In the formula, Ph represents phenyl;

In the formula, Ph represents phenyl, and p, q are respectively 0≤p≤25,0≤q≤100 and the integer of having given the phenyl content of 7～80 weight %.

3. flame-retardant polycarbonate resin composition as claimed in claim 1 or 2, wherein, fire retardant is that the C composition is that to be selected from phosphate compound be that C-1 composition, azochlorosulfonate acid alkali (great soil group) metal-salt are that C-2 composition and silicone compound are the fire retardant more than a kind in the C-3 composition.

4. flame-retardant polycarbonate resin composition as claimed in claim 3, wherein, fire retardant is that the C composition is the represented phosphate compound of following formula (I),

X in the formula is by the dihydroxy compound deutero-dihydric phenol residue that is selected from Resorcinol, Resorcinol, two (4-hydroxy diphenyl) methane, dihydroxyphenyl propane, dihydroxybiphenyl, dihydroxy naphthlene, two (4-hydroxy phenyl) sulfone, two (4-hydroxy phenyl) ketone and two (4-hydroxy phenyl) thioether, n is 0～5 integer, perhaps when the time for the mixture of the different phosphoric acid ester of n number, n is their mean value, R ¹, R ², R ³And R ⁴Serve as reasons independently of one another and be selected from phenol, cresols, xylenol, isopropyl-phenol, butylphenol and the aryl deutero-monohydric phenol residue in the cumyl phenol.

5. as each described flame-retardant polycarbonate resin composition in the claim 1～4, wherein, with respect to A composition 100 weight parts, containing fluorine-containing Antidrip agent is D composition 0.03～1 weight part.

6. a formed body obtains with each described flame-retardant polycarbonate resin composition moulding in the claim 1～5.

7. the frame that TV is used forms with each described flame-retardant polycarbonate resin composition in the claim 1～5.