CN101676331A

CN101676331A - Glass fiber reinforcement aromatic polycarbonate resin composition

Info

Publication number: CN101676331A
Application number: CN200910173841A
Authority: CN
Inventors: 池松龙介
Original assignee: Teijin Chemicals Ltd
Current assignee: Teijin Ltd
Priority date: 2008-09-16
Filing date: 2009-09-14
Publication date: 2010-03-24
Also published as: JP5602997B2; JP2010070590A

Abstract

The present invention provides a glass fiber reinforcement aromatic polycarbonate resin composition, which is reinforced by flat cross section glass fibre and circular cross section staple glass fibre, and has a well mechanical strength, a low aeolotropism and fire retardance, wherein a ratio of an average fibre length and an average fiber diameter of the circular cross section staple glass fibreis less than 10. the resin combination contains 40-99 weight parts of aromatic polycarbonate resin (component A), 1-60 weight parts of reinforced filling material (component B) and 0.001-20 weight parts of flame retardant (component C) relative to 100 weight parts of component A and component B, wherein the reinforced filling material (component B) contains flat cross section glass fibre (component B-1) which fibre sectional long diameter is 10-50[Mu]m, a ratio of the long diameter and the short diameter is 1.5-8, the reinforced filling material also contains fibrous filling material (component B-2), and a proportion by weight of the component B-1 and the component B-2 is 30/70-99/1.

Description

Glass fiber reinforcement aromatic polycarbonate resin composition

Technical field

The present invention relates to the improved glass fiber reinforcement aromatic polycarbonate resin composition of dimensional precision.More particularly, the present invention relates to glass fiber-reinforced resin composition, it strengthens with the fibrous packing material beyond flat cross section glass fibre and the flat cross section glass fibre, has excellent mechanical intensity, less anisotropy, flame retardant resistance simultaneously.

Background technology

, therefore extensively utilize owing to physical strength, excellent in workability with glass fibre enhanced thermoplastic resin.Particularly polycarbonate resin owing to physical strength, dimensional stability, the such excellent specific property of flame retardant resistance, uses in numerous purposes such as mechanical part, trolley part, electrical and electronic parts, office equipment parts.In addition, the reinforced polycarbonate resin that has added various tougheners in polycarbonate resin is using in the purposes widely also owing to its excellent physical strength, thermotolerance.On the other hand, though in polycarbonate resin, cooperated resin combination physical strength, the excellent rigidity of glass fibre, has the anisotropic shortcoming that produces molding shrinkage because of the orientation of fiber.When in moulding product such as precision optical machinery parts such as camera component, office equipment parts, using in recent years, need physical strength, less anisotropy, the good glass fibre of flame retardant resistance to strengthen thermoplastic resin.

For example, the mobile improved aromatic copolycarbonate resin composition that comprises aromatic polycarbonate resin and fiber-filled material and organophosphate is known (with reference to patent documentation 1).But, in this resin combination, the big and problem of warpage easily of the anisotropy that has a molding shrinkage.Comprising aromatic polycarbonate resin and specific non-circular fiber and the improved poly carbonate resin composition of warpage properties of tabular packing material is known (with reference to patent documentation 2).But, flame retardant resistance deficiency in this resin combination.

The resin combination that comprises polycarbonate resin, phenylethylene resin series, cocoon cross section shape glass fibre is known (with reference to patent documentation 3).In addition, the resin combination that comprises polyamide resin, cocoon cross section shape glass fibre is known (with reference to patent documentation 4).

But this communique is not open for improving excellent mechanical intensity, less anisotropy, the effective opinion of flame retardant resistance.

Patent documentation 1: Japanese kokai publication hei 7-3140 communique

Patent documentation 2: Japanese kokai publication hei 6-207089 communique

Patent documentation 3: Japanese kokai publication hei 8-20694 communique

Patent documentation 4: TOHKEMY 2003-82228 communique

Summary of the invention

In view of the above problems, the aromatic polycarbonate resin that the objective of the invention is to have strengthened with the fibrous packing material beyond flat cross section glass fibre and the flat cross section glass fibre is a matrix, has the enhancing resin combination of excellent mechanical intensity, less anisotropy, flame retardant resistance simultaneously.The inventor is further investigation repeatedly to achieve these goals, found that, has the glass fibre and the glassy packing material of specific cross-sectional shape by utilization, can realize this purpose, and the step of going forward side by side is furtherd investigate, thereby has finished the present invention.

According to the present invention, above-mentioned problem realizes by following glass fiber-reinforced resin composition, this glass fiber-reinforced resin composition comprises: thermoplastic resin 40～99 weight parts that contain aromatic polycarbonate resin (A-1 composition), strengthen packing material (B composition) 1～60 weight part, and be the fire retardant (C composition) of 0.001～20 weight part with respect to total 100 weight parts of A composition and B composition, wherein, the mean value that described enhancing packing material (B composition) comprises the major diameter of fibre section is 10～50 μ m, the mean value of the ratio (major diameter/minor axis) of major diameter and minor axis is 1.5～8 flat cross section glass fibre (B-1 composition) and the fibrous packing material except that the B-1 composition (B-2 composition), and the weight ratio of (B-1 composition) and (B-2 composition) (B-1 composition/B-2 composition) is 30/70～99/1.

In addition, above-mentioned problem solves by following synthetic resin, this synthetic resin is by forming the glass fiber-reinforced resin composition moulding, this glass fiber-reinforced resin composition comprises: thermoplastic resin 40～99 weight parts that contain aromatic polycarbonate resin (A-1 composition), strengthen packing material (B composition) 1～60 weight part, and be the fire retardant (C composition) of 0.001～20 weight part with respect to total 100 weight parts of A composition and B composition, wherein, the mean value that described enhancing packing material (B composition) comprises the major diameter of fibre section is 10～50 μ m, the mean value of the ratio (major diameter/minor axis) of major diameter and minor axis is 1.5～8 flat cross section glass fibre (B-1 composition) and the fibrous packing material except that the B-1 composition (B-2 composition), and the weight ratio of (B-1 composition) and (B-2 composition) (B-1 composition/B-2 composition) is 30/70～99/1.

Embodiment

Below, further details of the present invention is described.

(A composition: thermoplastic resin)

(A-1 composition: aromatic polycarbonate resin)

Among the present invention, the aromatic polycarbonate resin that in the thermoplastic resin of A composition, uses, make dihydric phenol and carbonate precursor the reaction and obtain.As an 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.Aromatic polycarbonate resin (A-1 composition) preferably contains more than the 50 weight % in thermoplastic resin (A composition).

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

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

For example, as part or all of dihydric phenol composition, used 4,4 '-(metaphenylene diisopropylidene) 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 fit to for the dimensional change that causes because of suction, the purposes that the requirement of morphological stability is strict especially.Dihydric phenol beyond these BPA, preferred overall 5 moles of the dihydric phenol composition that constitutes this polycarbonate that use be more than the %, preferred especially 10 moles more than the %.

Particularly under the situation that requires high rigidity and better hydrolytic resistance, the A composition that constitutes resin combination is that the copolymerization polycarbonate of following (1)～(3) is particularly suitable.

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

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

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

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

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

Have again, in the above-mentioned various polycarbonate, regulate copolymerization composition etc. and make water-intake rate and the polycarbonate of Tg (second-order transition temperature) in following ranges, the hydrolytic resistance of polymkeric substance self is good, and the low warpage properties after the moulding is also especially excellent, therefore is particularly suitable in the field that requires morphological stability.

(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%, preferred 0.13～0.30%, more preferably 0.14～0.27% polycarbonate.

Wherein, the water-intake rate of polycarbonate is to use the discoideus test film of diameter 45mm, thickness 3.0mm, floods the measured value of moisture rate after 24 hours in 23 ℃ water according to ISO62-1980.In addition, Tg (second-order transition temperature) measures the value of trying to achieve by the differential scanning calorimeter (DSC) according to JIS K7121.

As carbonate precursor, use carbonyl halide, carbonic diester or haloformate (Ha ロホ Le メ one ト) etc., can enumerate the bishaloformate of phosgene, diphenyl carbonate or dihydric phenol etc. particularly.

When adopting interfacial polymerization to make aromatic polycarbonate resin, can use catalyzer, terminal terminator as required, be used to prevent the antioxidant of dihydric phenol oxidation etc. by above-mentioned dihydric phenol and carbonate precursor.In addition, aromatic polycarbonate resin of the present invention comprise branched polycarbonate resin that the multi-functional aromatics copolymerization more than the trifunctional is obtained, with two functionality carboxyl acid copolymers of aromatic series or aliphatics (comprising ester ring type) and the polyestercarbonate resin that obtains, the copolymerized panlite that two functionality alcohol (comprising ester ring type) copolymerization are obtained and with this two functionalities carboxylic acid and two functionality alcohol copolymerization together and the polyestercarbonate resin that obtains.In addition, also can be the mixture that mixes more than 2 kinds of the aromatic polycarbonate resin that will obtain.

Branched polycarbonate resin can be given sag prevention performance etc. to enhancing aromatic copolycarbonate resin composition of the present invention.As the multi-functional aromatics more than the trifunctional that uses in this branched polycarbonate resin, can enumerate Phloroglucinol monomethyl ether, 2,3 ', 4,5 ', 6-penta hydroxy group biphenyl, or 4,6-dimethyl-2,4,6-three (4-hydroxy diphenyl) heptene-2,2,4,6-trimethylammonium-2,4,6-three (4-hydroxy phenyl) heptane, 1,3,5-three (4-hydroxy phenyl) benzene, 1,1,1-three (4-hydroxy phenyl) ethane, 1,1,1-three (3,5-dimethyl-4-hydroxy phenyl) ethane, 2, two (2-hydroxy-5-methyl base the benzyl)-4-methylphenols of 6-, 4-{4-[1, two (4-hydroxy phenyl) ethyls of 1-] benzene }-α, 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.

In the branched polycarbonate by multi-functional aromatics deutero-structural unit, by dihydric phenol deutero-structural unit with by this among 100 moles of % of total of multi-functional aromatics deutero-structural unit, be 0.01～1 mole of %, be preferably 0.05～0.9 mole of %, be preferably 0.05～0.8 mole of % especially.

In addition, particularly under the situation of melt transesterification process, sometimes produce the branched structure unit as side reaction, about this branched structure quantity of units, also preferably with 100 moles of % of total by dihydric phenol deutero-structural unit in, be preferably 0.001～1 mole of %, more preferably 0.005～0.9 mole of % is preferably 0.01～0.8 mole of % especially.Should illustrate that the ratio of this branched structure can adopt ¹H-NMR measures and calculates.

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

In addition, the polycarbonate poly organo alkyl copolymer of polyorganosiloxane units that can also use copolymerization.

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

When making glass fiber-reinforced resin composition of the present invention, the viscosity-average molecular weight of aromatic polycarbonate resin (M) is not particularly limited, and is preferably 10000～50000, and more preferably 14000～30000, more preferably 14000～24000.

Less than 10000 aromatic polycarbonate resin, can't obtain the favorable mechanical characteristic for viscosity-average molecular weight.On the other hand, surpass the resin combination that 50000 aromatic polycarbonate resin obtains by viscosity-average molecular weight, the flowability during injection molding is poor, so versatility is poor.

Have, above-mentioned aromatic polycarbonate resin can obtain its viscosity-average molecular weight in above-mentioned extraneous mixed with resin again.The aromatic polycarbonate resin that particularly has the viscosity-average molecular weight that surpasses above-mentioned scope (50000), the entropy-elasticity of resin improves.In the gas assistant formation and foaming that its result will use sometimes, embody good forming process in the time will strengthening molding resin material for structure unit.The improvement of this forming process is better than above-mentioned branched polycarbonate.As preferred scheme, can also use the A composition to be made up of the aromatic polycarbonate resin (A-1-1 composition) of viscosity-average molecular weight 70000～300000 and the aromatic polycarbonate resin (A-1-2 composition) of viscosity-average molecular weight 10000～30000, its viscosity-average molecular weight is 16000～35000 aromatic polycarbonate resin (A-1 composition) (below be sometimes referred to as " aromatic polycarbonate resin that contains high molecular weight components ").

This contains in the aromatic polycarbonate resin (A-1 composition) of high molecular weight components, the molecular weight of A-1-1 composition preferred 70000～200000, more preferably 80000～200000, more preferably 100000～200000, be preferably 100000～160000 especially.In addition, the molecular weight of A-1-2 composition is preferred 10000～25000, and more preferably 11000～24000, more preferably 12000～24000, be preferably 12000～23000 especially.

The aromatic polycarbonate resin (A-1 composition) that contains high molecular weight components can be by mixing above-mentioned A-1-1 composition and A-1-2 composition with various ratios, and regulate with the molecular weight ranges that satisfies regulation and obtain.Preferably, among the 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 A-1-1 composition and the polymerization independently of one another of A-1-2 composition, with they blended methods; (2) use with the spy open the method shown in the flat 5-306336 communique be representative, in same system, be manufactured on 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 measure, make the method for this aromatic polycarbonate resin with the condition that satisfies A-1 composition of the present invention; And (3) will adopt aromatic polycarbonate resin and A-1-1 composition of making separately and/or A-1-2 composition blended method etc. that this manufacture method (manufacturing processs of (2)) obtains.

So-called viscosity-average molecular weight is calculated by the following method among the present invention,, at first, uses Ostwald viscosimeter that is, obtains the specific viscosity (η that is calculated as follows by the solution that aromatic copolycarbonate 0.7g is dissolved in gained among the methylene dichloride 100ml under 20 ℃ _Sp),

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

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

By the specific viscosity (η that tries to achieve _Sp), calculate viscosity-average molecular weight M with 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

Have, the calculating of the viscosity-average molecular weight of the aromatic polycarbonate resin in the glass fiber-reinforced resin composition of the present invention adopts following main points to carry out again.That is, the methylene dichloride of said composition with its 20～30 times of weight mixed, the solvable composition dissolving in the composition.Adopt zeolite filtration to extract this solvable composition.Then the solvent in the solution that obtains is removed.Solid thorough drying after solvent removed obtains being dissolved in the solid of the composition in the methylene dichloride.By the solution that this solid 0.7g is dissolved in gained among the methylene dichloride 100ml, with the above-mentioned specific viscosity of similarly obtaining 20 ℃, by this specific viscosity and the above-mentioned viscosity-average molecular weight M that similarly calculates.

(A-2 composition: phenylethylene resin series)

The phenylethylene resin series that uses in the thermoplastic resin of A composition of the present invention has the thermotolerance and the flame retardant resistance of good forming process and appropriateness, therefore is preferred thermoplastic resin for the harmony that keeps these characteristics.

This phenylethylene resin series be the polymkeric substance of aromatic ethenyl compound or multipolymer and with its be selected from the polymkeric substance that can obtain as required with other vinyl monomers of their copolymerization and the copolymerization more than a kind in the rubber polymer.

As aromatic ethenyl compound, special optimization styrene.As can with other vinyl monomers of aromatic ethenyl compound copolymerization, can preferably enumerate vinyl cyanide based compound and (methyl) acrylic compound.As particularly suitable vinyl cyanide based compound, can enumerate vinyl cyanide, as particularly suitable (methyl) acrylic compound, can enumerate methyl methacrylate.

As beyond vinyl cyanide based compound and (methyl) acrylic compound can with other vinyl monomers of aromatic ethenyl compound copolymerization, can enumerate the methacrylic ester that glycidyl methacrylate etc. contains epoxy group(ing), maleimides such as maleimide, N-methyl maleimide, N-phenylmaleimide are monomer, α such as vinylformic acid, methacrylic acid, toxilic acid, maleic anhydride, fumaric acid, methylene-succinic acid, beta-unsaturated carboxylic acid and acid anhydrides thereof.

As can with the rubber polymer of above-mentioned aromatic ethenyl compound copolymerization, can enumerate polyhutadiene, polyisoprene, diene interpolymer (for example random copolymers of styrene butadiene and segmented copolymer, acrylonitrile butadiene copolymer, and the multipolymer of (methyl) alkyl acrylate and divinyl etc.), the multipolymer of ethene and alpha-olefin (for example ethylene-propylene random copolymer and segmented copolymer, the random copolymers of ethene-butylene and segmented copolymer etc.), the multipolymer of ethene and esters of unsaturated carboxylic acids (ethylene-methyl acrylate multipolymer for example, with ethylene-butyl acrylate copolymer etc.), the multipolymer of ethene and aliphatic ethylene base (for example vinyl-vinyl acetate copolymer etc.), ethene and propylene and non-conjugated diene ter-polymers (for example ethylene-propylene-hexadiene multipolymer etc.), acrylic rubber (butyl polyacrylate for example, poly-(2-EHA), and the multipolymer of butyl acrylate and 2-EHA etc.), and silicon-type rubber (organopolysiloxane rubber for example, the IPN type rubber of forming by organopolysiloxane rubber constituent and poly-(methyl) alkyl acrylate rubber constituent; Have promptly that 2 kinds of rubber constituents are twined mutually and the rubber and IPN type rubber that becomes to be grouped into by organopolysiloxane rubber constituent and polyisobutylene rubber etc. of indissociable structure).

As above-mentioned phenylethylene resin series, specifically can enumerate for example phenylethylene resin series such as polystyrene resin, HIPS resin, MS resin, ABS resin, AS resin, AES resin, ASA resin, MBS resin, MABS resin, MAS resin and SMA resin, and (hydrogenation) styrene-butadiene-styrene copolymer resin, (hydrogenation) styrene-isoprene-styrene copolymer-resin etc.Should illustrate that the souvenir of (hydrogenation) means to comprise does not have hydrogenant resin and hydrogenant resin.Wherein, the MS resin is represented the main copolymer resin of being made up of methyl methacrylate and vinylbenzene, the AES resin is represented mainly by vinyl cyanide, the copolymer resin that ethylene-propylene rubber and vinylbenzene are formed, the ASA resin is represented mainly by vinyl cyanide, the copolymer resin that vinylbenzene and acrylic rubber are formed, the MABS resin is represented mainly by methyl methacrylate, vinyl cyanide, the copolymer resin that divinyl and vinylbenzene are formed, the MAS resin is represented mainly by methyl methacrylate, the copolymer resin that acrylic rubber and vinylbenzene are formed, SMA resin are represented the copolymer resin mainly be made up of vinylbenzene and maleic anhydride (MA).

Have, this phenylethylene resin series by using catalyzer such as metallocene catalyst, can be the resin that syndiotactic polystyrene etc. has high taxis when it is made again.In addition, also can use the polymkeric substance and high polymkeric substance, the multipolymer of multipolymer, segmented copolymer and taxis of the narrow molecular weight distribution that methods such as adopting living anion polymerization, radical living polymerization obtain sometimes.

Wherein, preferred acrylonitritrile-styrene resin resin (AS resin), acrylonitrile-butadiene-styrene copolymer resin (ABS resin).In addition, also styrenic more than 2 kinds can be mixed use.

The AS resin that uses among the present invention is the thermoplastic copolymer that vinyl cyanide based compound and aromatic ethenyl compound copolymerization are formed.As this vinyl cyanide based compound, can especially preferably use vinyl cyanide.In addition, as aromatic ethenyl compound, can preferably use vinylbenzene and alpha-methyl styrene.As each components in proportions in the AS resin, in the time of will totally counting 100 weight %, the vinyl cyanide based compound is 5～50 weight %, is preferably 15～35 weight %, and aromatic ethenyl compound is 95～50 weight %, is preferably 85～65 weight %.In addition, but can also mix other vinyl based compounds of the copolymerization of using above-mentioned record in these vinyl compounds, containing of they is proportional, preferably below the 15 weight % in the AS resinous principle.In addition, the initiator that uses in the reaction, chain-transfer agent etc. can use existing known various materials as required.

This AS resin can adopt any method manufacturing in mass polymerization, suspension polymerization, the letex polymerization, but preferably adopts mass polymerization.In addition, the method for copolymerization also can be any in the copolymerization of employing single stage method or the copolymerization of adopting multistep processes.In addition, as the reduced viscosity of this AS resin, be 0.2～1.0dl/g, be preferably 0.3～0.5dl/g.Reduced viscosity is by accurate weighing AS resin 0.25g, is dissolved among the dimethyl formamide 50ml with 2 hours, uses Ubbelohde viscometer under 30 ℃ environment the solution that obtains to be measured and obtained.Have, the time that flows down of viscometer use solvent is 20～100 seconds viscometer again.Reduced viscosity is by second number (t that flows down of solvent ₀) and second number (t) that flows down of solution obtain according to following formula.

Reduced viscosity (η _Sp/ C)={ (t/t ₀)-1}/0.5

If reduced viscosity less than 0.2dl/g, is then impacted and is reduced, if surpass 1.0dl/g, then mobile variation.

The ABS resin of using among the present invention is to make vinyl cyanide based compound and aromatic ethenyl compound graft polymerization to the diene series rubber composition and the mixture of the multipolymer of the thermoplastic graft copolymer multipolymer that obtains and vinyl cyanide based compound and aromatic ethenyl compound.As the diene series rubber composition that forms this ABS resin, for example can using, second-order transition temperatures such as polyhutadiene, polyisoprene and styrene-butadiene copolymer are the rubber below-30 ℃, its ratio is preferably 5～80 weight % in ABS resin composition 100 weight %, more preferably 8～50 weight % are preferably 10～30 weight % especially.As the vinyl cyanide based compound that is grafted on the diene series rubber composition, can especially preferably use vinyl cyanide.In addition, as the aromatic ethenyl compound that is grafted on the diene series rubber composition, can especially preferably use vinylbenzene and alpha-methyl styrene.This is grafted to the components in proportions on the diene series rubber composition, preferred 95～20 weight % in ABS resin composition 100 weight %, preferred especially 90～50 weight %.In addition, measure 100 weight % with respect to the total of this vinyl cyanide based compound and aromatic ethenyl compound, preferred vinyl cyanide based compound is 5～50 weight %, and aromatic ethenyl compound is 95～50 weight %.In addition, for an above-mentioned part that is grafted to the composition on the diene series rubber composition, also can mix use (methyl) methyl acrylate, ethyl propenoate, maleic anhydride, N substituted maleimide amine etc., they contain proportional in the ABS resin composition, being preferably below the 15 weight %.In addition, the initiator that uses in the reaction, chain-transfer agent, emulsifying agent etc. can use existing known various materials as required.

In the ABS resin of the present invention, rubber size is preferably 0.1～5.0 μ m, and more preferably 0.15～1.5 μ m is preferably 0.2～0.8 μ m especially.The distribution that can use this rubber size is any in the rubber particles of single distribution and the rubber particles with above a plurality of peaks, 2 peaks, can also be the rubber particles that rubber particles also forms single phase in its form, also can be to contain the rubber particles that (オ Network Le one De) has Sa Lami (サラミ) structure mutually by containing around rubber particles.

In addition, it is known so far content that ABS resin contains the vinyl cyanide based compound and the aromatic ethenyl compound that are not grafted on the diene series rubber composition, the free copolymer composition that produces in the time of also can containing this polymerization in the ABS resin of the present invention.The reduced viscosity of the multipolymer of being made up of vinyl cyanide based compound and aromatic ethenyl compound for this free, the reduced viscosity (30 ℃) that adopts the method put down in writing previously to obtain is 0.2～1.0dl/g, more preferably 0.3～0.7dl/g.

In addition, the ratio of grafted vinyl cyanide based compound and aromatic ethenyl compound with respect to the diene series rubber composition, with percentage of grafting (weight %) expression, is preferably 20～200%, more preferably 20～70%.

This ABS resin can adopt any method manufacturing in mass polymerization, suspension polymerization, the letex polymerization.The special ABS resin that preferably adopts mass polymerization to make.In addition, as this mass polymerization, can roll up continuous bulk polymerization method (so-called toray method) and No. 6 423 pages (1989) middle continuous bulk polymerization method of putting down in writing of chemical industry the 53rd volume (so-called Mitsui east platen press) of putting down in writing in No. 6 415 pages (1984) by instantiated electrotechnics the 48th typically.As ABS resin of the present invention, be fit to use any ABS resin.In addition, the method for copolymerization can adopt single stage method to carry out copolymerization, also can adopt multistep processes to carry out copolymerization.In addition, also can preferably use in the ABS resin that adopts this manufacturing process to obtain blend to have with aromatic ethenyl compound and vinyl cyanide composition copolymerization and the blend of the vinyl compound polymer that obtains separately.

From aspects such as good thermostability, hydrolytic resistances, above-mentioned AS resin and ABS resin that alkali (great soil group) amount of metal reduces are preferred.Alkali in the phenylethylene resin series (great soil group) amount of metal is preferably less than 100ppm, more preferably less than 80ppm, more preferably less than 50ppm, is preferably less than 10ppm especially.From this respect, also preferred AS resin and the ABS resin that obtains by mass polymerization of using.Relevant with this good thermostability, hydrolytic resistance in addition, when using emulsifying agent in AS resin and the ABS resin, this emulsifying agent is preferably Sulfonates, more preferably alkyl sulfonates.In addition, when using peptizer, this peptizer is preferably sulfuric acid or vitriolic alkali earth metal salt.

The use level of phenylethylene resin series with respect to A-1 composition 100 weight parts, is preferably 1～100 weight part, more preferably 5～80 weight parts, further preferred 10～70 weight parts.

(B composition: strengthen packing material)

(B-1 composition: the flat cross section glass fibre)

The glass fibre that uses as B-1 composition of the present invention is the flat cross section glass fibre.As flat cross section glass fibre of the present invention, the mean value that is the major diameter of fibre section is 10～50 μ m, be preferably 15～40 μ m, 20～35 μ m more preferably, and the mean value of the ratio (major diameter/minor axis) of major diameter and minor axis is 1.5～8, be preferably 2～6, more preferably 2.5～5 glass fibre.The mean value of ratio that has used major diameter and minor axis is during for the flat cross section glass fibre of this scope, compare when having used less than 1.5 non-circular section fiber, anisotropy and outward appearance are greatly improved, and with fire retardant and time spent, can significantly improve flame retardant resistance.The reason that this flame retardant resistance improves can be thought: on moulding product surface, the long limit face of flat cross section glass fibre and moulding product surface are orientated abreast, therefore the oxygen barriering effect that the resin charing tunicle except by burning the time produces, compare with the rounded section fiber by the oxygen barriering effect that the flat cross section glass fibre produces, more effectively play a role.In addition, as flattened, except flat, also comprise the non-circular cross sectional shape of ellipticity, silk cocoon shape and tri-lobed or shape similar with it.Wherein, from the aspect of improving of physical strength, less anisotropy, preferred flat shape.In addition, the average fiber of flat cross section glass fibre ratio (length-to-diameter ratio) long and fiber diameter is 2～120, be preferably 2.5～70, more preferably 3～50, less than 2, the effect that physical strength improves is little as the ratio of fruit fiber length and fiber diameter, surpasses 120 as the ratio of fruit fiber length and fiber diameter, it is big that anisotropy becomes, and moulding product outward appearance also worsens.The fiber diameter of so-called this flat cross section glass fibre is meant flattened is scaled positive number average Fibre diameter when circular of the same area.In addition, so-called average fiber is long, is meant that the number average fiber in the glass fiber-reinforced resin composition of the present invention is long.Have again, this number average fiber length is to the high temperature ashing by the moulding product, adopts the dissolving of solvent and adopt the remainder of the packing material that processing such as decomposition of chemical gather to carry out observation by light microscope, the value of being calculated by the image employing image analysis apparatus that obtains.In addition, when calculating this value, being based on following method and the value that obtains, that is, is benchmark, the non-computational length flat cross section glass fibre below it with the Fibre diameter.

The glass of above-mentioned flat cross section glass fibre is formed, and being suitable for A glass, C glass and E glass etc. is the various glass compositions of representative, is not particularly limited.This glass packing material can contain TiO as required ₂, SO ₃And P ₂O ₅Deng composition.More preferably E glass (non-alkali glass) wherein.From the aspect that physical strength improves, this flat cross section glass fibre is preferably used known surface treatment agent, and for example silane coupling agent, titanate coupling agent or aluminate coupling agent etc. have been implemented surface-treated flat cross section glass fibre.In addition, be that resin and polyurethane series resin etc. have carried out the flat cross section glass fibre that boundling is handled preferably with ethylene series resin, phenylethylene resin series, acrylic resin, polyester based resin, epoxy, from the aspect of physical strength, preferred especially epoxy is resin, polyurethane series resin.The collecting agent adhesion amount of the flat cross section glass fibre of handling through boundling in flat cross section glass fibre 100 weight %, is preferably 0.1～3 weight %, more preferably 0.2～2 weight %.

(B-2 composition: fibrous packing material)

In the composition of the present invention, the fibrous packing material as the B-2 composition uses can cooperate the known fibrous packing material except that the B-1 composition.As this fibrous packing material, preferred glass fibre, wollastonite, the carbon of illustration except that the B-1 composition is filler.This fibrous packing material also can utilize to their surface coated the filler of metal oxides such as titanium oxide, zinc oxide, cerium oxide and silicon oxide.As carbon is filler, can enumerate for example carbon fiber, washing carbon fiber, ground carbon fiber, gas-phase growth of carbon fibre and carbon nanotube, carbon black etc.Carbon nanotube can be that Fibre diameter 0.003～0.1 μ m, individual layer, 2 layers and multiwalled are any, preferred multilayer (so-called MWCNT).Wherein, at aspect the physical strength excellence and the aspect that can give good electrical conductivity, preferred carbon fiber and washing carbon fiber.

Above-mentioned fibrous packing material can carry out surface treatment with various surface treatment agents in advance.Can carry out surface treatment as this surface treatment agent 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.In addition, can be with collecting agent granulations such as various resins, high-grade aliphatic ester and waxes and form particulate state.

Enhancing packing material of the present invention (B composition), comprising the thermoplastic resin of aromatic polycarbonate resin (A composition) and strengthening among the total 100 weight % of packing material (B composition), be 1～60 weight %, be preferably 3～60 weight %, more preferably 5～50 weight %.If the B composition is less than 1 weight %, the physical strength deficiency, if surpass 60 weight %, moulding flowability, the reduction of moulding product outward appearance.

As the flat cross section glass fibre (B-1 composition) of enhancing packing material of the present invention (B composition) and the weight ratio of the fibrous packing material except that the B-1 composition (B-2 composition) is 30/70～99/1, be preferably 40/60～99/1, more preferably 50/50～99/1.If the weight ratio of flat cross section glass fibre is more than the 30 weight %, can access good modulus in flexure, the anisotropy of molding shrinkage.

(C composition: fire retardant)

In the glass fiber-reinforced resin composition of the present invention, be combined with as fire retardant and known all cpds.Have, the cooperation of the compound that uses as fire retardant not only improves flame retardant resistance again, and based on the character of each compound, can bring the raising of for example static resistance, flowability, rigidity and thermostability etc.

As this fire retardant, can enumerate (1) organic metal salt flame retardant (organic sulfonic acid alkali (great soil group) metal-salt for example, borate metal salt flame retardant and stannic acid metal-salt flame retardant etc.), (2) organic phosphorus flame retardant (phosplate compound for example, the phosphoric acid ester oligomer compounds, the phosphonate oligomers compound, phosphine nitrile oligomer compounds and Phosphoramido compounds etc.), (3) include the silicone flame retardant of organic silicon compound and (4) halogen flame retardant (brominated epoxy resin for example, brominated Polystyrene, brominated polycarbonate (comprising oligopolymer), bromination polyacrylic ester and bromination polyethylene etc.) etc.

(1) organic metal salt flame retardant

The organic metal salt flame retardant is being kept thermotolerance substantially and just can given on a small quantity aspect the static resistance favourable.The organic metal salt flame retardant that the most advantageously uses among the present invention is fluorine-containing organometalate compound.So-called fluorine-containing organometalate compound of the present invention is meant the metal salt compound of the cation constituent that comprises the anionic component that formed by the organic acid with alkyl that fluorine replaces and formed by metal ion.As preferred concrete example, can replace the metal-salt of organic sulfonic acid, the metal-salt of fluorine replacement organo-sulfate and the metal-salt that fluorine replaces organophosphate by the illustration fluorine.Fluorine-containing organometalate compound can use a kind or will be more than 2 kinds mix and use.Wherein preferred fluorine replaces the metal-salt of organic sulfonic acid, especially preferably has the metal-salt of the sulfonic acid of perfluoroalkyl.The wherein scope of the carbonatoms of perfluoroalkyl preferred 1～18, more preferably 1～10 scope, more preferably 1～8 scope.

The metal that constitutes the metal ion of organic metal salt flame retardant 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 this basic metal, under the higher situation of requirement of the transparency, preferred rubidium and caesium, and because they are not general, and refining also difficulty, the result becomes unfavorable sometimes aspect cost.On the other hand, favourable lithium and sodium are unfavorable sometimes aspect transparent on the contrary aspect cost and flame retardant resistance.Consider these, can distinguish the basic metal that uses in the perfluoro alkyl sulfonic acid an alkali metal salt, but all excellent perfluoro alkyl sulfonic acid sylvite of characteristic harmony in every respect most preferably.Also can be with this sylvite and the perfluoro alkyl sulfonic acid an alkali metal salt and the usefulness that form by other alkali metal.

As this perfluoro alkyl sulfonic acid an alkali metal salt, trifluoromethanesulfonic acid potassium, perfluor fourth potassium sulfonate, the own potassium sulfonate of perfluor, perfluorooctane sulfonate potassium, five fluorine ethyl sulfonic acid sodium, perfluor fourth sodium sulfonate, perfluorooctane sulfonate sodium, trifluoromethanesulfonic acid lithium, perfluor fourth sulfonic acid lithium, perfluor sulfonic acid in heptan lithium, trifluoromethanesulfonic acid caesium, perfluor fourth sulfonic acid caesium, perfluorooctane sulfonate caesium, the own sulfonic acid caesium of perfluor, perfluor fourth sulfonic acid rubidium and the own sulfonic acid rubidium of perfluor etc. can be enumerated, in them a kind or will more than 2 kinds and use can be used.Wherein preferred especially perfluor fourth potassium sulfonate.

Above-mentioned fluorine-containing organic metal salt adopts the content of the fluoride ion of ion-chromatographic determination to be preferably below the 50ppm, more preferably below the 20ppm, more preferably below the 10ppm.The content of fluoride ion is low more, and flame retardant resistance, photostabilization are good more.The lower limit of the content of fluoride ion in fact also can be 0, but takes into account refining step number and effect, in the practicality about preferred 0.2ppm.The perfluoro alkyl sulfonic acid an alkali metal salt of the content of this fluoride ion is for example as described below to be made with extra care.In the scope of 40～90 ℃ (more preferably 60～85 ℃), the perfluoro alkyl sulfonic acid an alkali metal salt is dissolved in the ion exchanged water of 2～10 times of weight of this metal-salt.This perfluoro alkyl sulfonic acid an alkali metal salt adopt with in alkali-metal carbonate or the oxyhydroxide with the method for perfluoro alkyl sulfonic acid or with in alkali-metal carbonate or the oxyhydroxide and the method for perfluoroalkyl sulfonyl fluoride (more preferably adopting the latter's method) and generating.In addition, the special preferably resistance value of this ion exchanged water is the above water of 18M Ω cm.Under said temperature, will be dissolved with the liquid agitation 0.1～3 hour, more preferably 0.5～2.5 hour of metal-salt.Then with this liquid cooling to 0～40 ℃, more preferably 10～35 ℃ scope.Separate out crystallization by cooling.Take out the crystallization of separating out by filtering.Make preferably through purified perfluoro alkyl sulfonic acid an alkali metal salt thus.

The use level of fluorine-containing organometalate compound is a benchmark with total 100 weight parts of A composition and B composition, is preferably 0.005～0.6 weight part, more preferably 0.005～0.2 weight part, more preferably 0.008～0.13 weight part.If be this preferred range, then bring into play effect (for example flame retardant resistance, static resistance etc.) by cooperating fluorine-containing organic metal salt to expect, the detrimentally affect that the photostabilization of poly carbonate resin composition is produced simultaneously also diminishes.

In addition, as the organic metal salt flame retardant beyond the above-mentioned fluorine-containing organometalate compound, preferably do not contain the metal-salt of the organic sulfonic acid of fluorine atom.As this metal-salt, can enumerate for example an alkali metal salt, the alkali earth metal salt of aliphatic sulfonic, an alkali metal salt of aromatic sulphonic acid and (all not the containing fluorine atom) such as alkali earth metal salts of aromatic sulphonic acid of aliphatic sulfonic.

Preference as the aliphatic sulfonic metal-salt, can enumerate alkyl sulfonate alkali (great soil group) metal-salt, can use a kind in them or will also use (wherein, the souvenir of alkali (great soil group) metal-salt uses to comprise an alkali metal salt, both implications of alkali earth metal salt) more than 2 kinds.Preference as the alkane sulfonic acid that uses in this alkyl sulfonate alkali (great soil group) metal-salt, can enumerate methylsulfonic acid, ethyl sulfonic acid, propanesulfonic acid, fourth sulfonic acid, methyl fourth sulfonic acid, own sulfonic acid, heptan sulfonic acid, hot sulfonic acid etc., can use a kind in them or will more than 2 kinds and use.

As the aromatic sulphonic acid that uses in aromatic sulphonic acid alkali (great soil group) metal-salt, 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 of the condensation body that is formed by methylene fundamental mode key of aromatic sulphonic acid can be used a kind in them or will more than 2 kinds and use.

Concrete example as aromatic sulphonic acid alkali (great soil group) metal-salt, can enumerate for example diphenyl sulfide-4,4 '-disulfonic acid disodium, diphenyl sulfide-4,4 '-disulfonic acid dipotassium, m-phthalic acid 5-potassium sulfonate (5-Sulfoisophthalic acid potassium), m-phthalic acid 5-sodium sulfonate, the many sodium of the many sulfonic acid of polyethylene terephthalate (5-Sulfoisophthalic acid sodium), 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, thionyl benzene-4-potassium sulfonate, the formalin condenses of sodium naphthalene sulfonate and the formalin condenses of anthracene sulfonic acid sodium etc.

On the other hand, alkali (great soil group) metal-salt as sulfuric ester, can enumerate alkali (great soil group) metal-salt of the sulfuric ester of monobasic and/or polyalcohols especially, as the sulfuric ester of this monobasic and/or polyalcohols, can enumerate single, two, three, four sulfuric esters of sulfuric ester, the tetramethylolmethane of methyl sulfate, sulfovinic acid, lauryl sulfate, sulfuric acid palm ester, polyoxyethylene alkyl phenyl ether, the sulfuric ester of lauric monoglyceride, the sulfuric ester of hexadecanoic acid direactive glyceride and sulfuric ester of glyceryl monostearate etc.As alkali (great soil group) metal-salt of these sulfuric esters, preferably can enumerate alkali (great soil group) metal-salt of lauryl sulfate.

In addition; as other alkali (great soil group) metal-salt; alkali (great soil group) metal-salt of aromatic sulfonamide can be enumerated, alkali (great soil group) metal-salt of saccharin for example, N-(p-methylphenyl alkylsulfonyl)-right-tolylsulfonyl imines, N-(N '-benzylamino carbonyl) sulfanilyl-imines and N-(phenyl carboxyl) sulfanilyl-imines etc. can be enumerated.

The metal-salt that does not preferably contain the organic sulfonic acid of fluorine atom in above-mentioned is aromatic sulphonic acid alkali (great soil group) metal-salt, preferred especially sylvite.When cooperating this aromatic sulphonic acid alkali (great soil group) metal-salt, its content is benchmark with total 100 weight parts of A composition and B composition, is 0.001～1 weight part, more preferably 0.005～0.5 weight part, more preferably 0.01～0.1 weight part.

(2) organic phosphorus flame retardant

As organic phosphorus flame retardant of the present invention, the preferred aryl groups phosphate compound.Reason is this phosphate compound tone excellence substantially, and is few to light highly reflective generation detrimentally affect.In addition, phosphate compound is owing to having the plasticized effect, and is favourable aspect the forming process that improves resin combination of the present invention.This phosphate compound can use the known various phosphate compound as having fire retardant now, more preferably, can enumerate the phosphate compound more than a kind or 2 kinds of following general formula (1) expression especially.

(X in the formula (1) represents by dihydric phenol deutero-divalent organic group, R ¹, R ², R ³And R ⁴Represent that separately n represents 0～5 integer by monohydric phenol deutero-any monovalent organic radical group).

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

Preferred concrete example as the dihydric phenol of the above-mentioned X that derives, can enumerate 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, wherein preferred Resorcinol, dihydroxyphenyl propane and dihydroxybiphenyl.

As the above-mentioned R that derives ¹, R ², R ³And R ⁴The preferred concrete example of monohydric phenol, can illustration phenol, cresols, xylenol, isopropyl-phenol, butylphenol and to cumyl phenol, wherein preferred phenol and 2,6-xylenol.

Have, this monohydric phenol can be replaced by halogen atom again, as the concrete example that has by the phosphate compound of this monohydric phenol deutero-group, can illustration three (2,4,6-tribromo phenyl) phosphoric acid ester and three (2, the 4-dibromo phenyl) phosphoric acid ester, three (4-bromophenyl) phosphoric acid ester etc.

On the other hand, concrete example as the phosphate compound that is not replaced by halogen atom, preferably phosphoric acid triphenylmethyl methacrylate and three (2, the 6-xylyl) phosplate compound such as phosphoric acid ester, and with Resorcinol two (two (2, the 6-xylyl) phosphoric acid ester) as the phosphoric acid ester oligopolymer of main body, with 4, (wherein what is called is as main body as the phosphoric acid ester oligopolymer of main body with based on the phosphoric acid ester oligopolymer of dihydroxyphenyl propane two (diphenyl phosphate) for 4-dihydroxyl phenylbenzene two (diphenyl phosphates), expression can contain other different compositions of the polymerization degree on a small quantity, and more preferably expression contains more than the 80 weight %, more preferably more than the 85 weight %, the composition of the middle n=1 of above-mentioned formula (1) that further preferred 90 weight % are above).

The use level of organic phosphorus flame retardant is a benchmark with total 100 weight parts of A composition and B composition, is preferably 1～20 weight part, more preferably 2～10 weight parts, more preferably 2～7 weight parts.

(3) silicone flame retardant

As the silicoorganic compound that silicone flame 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.Can think, silicoorganic compound by when it burn himself in conjunction with or combine with composition and to form structure from resin, the reduction reaction when perhaps passing through this structure formation, thus give flame retardant effect to polycarbonate resin.Therefore, preferably contain in this reaction active high group, more specifically, preferably contain at least a kind of group in alkoxyl group and the hydrogen (being the Si-H yl) of being selected from of specified amount.Proportional as containing of this 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 obtained by hydrogen or pure amount that the silicoorganic compound that adopt caustic leaching process to measure per unit weight produce.The alkoxyl group of the preferred carbonatoms 1～4 of alkoxyl group, preferred especially methoxyl group are arranged again.

The structure of silicoorganic compound is generally by constituting 4 kinds of siloxane unit arbitrary combination shown below.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 simple function siloxane unit,

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

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

Q unit: by SiO ₂Four functionality siloxane units of expression.

The structure of the silicoorganic compound that use in the silicone flame retardant particularly, as rational formula, can be enumerated 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 the structure of preferred silicoorganic compound 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

Wherein, 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 silicoorganic compound of coefficient in each rational formula.This mean polymerisation degree is preferably 3～150 scope, 3～80 scope more preferably, and more preferably 3～60 scope is preferably 4～40 scope especially.If be this preferred range, excellence aspect flame retardant resistance.In addition, contain the silicoorganic compound of aromatic group of specified amount as described later in the transparency, also excellent on the tone.

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

Silicoorganic compound can be the straight chain shapes, also can have 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, can enumerate alkyl such as methyl, ethyl, propyl group, butyl, hexyl and decyl particularly, the cycloalkyl of cyclohexyl and so on, the aryl of phenyl and so on, and the aralkyl of tolyl and so on.The more preferably alkyl of carbonatoms 1～8, thiazolinyl or aryl.As alkyl, the alkyl of carbonatomss 1～4 such as special preferable methyl, ethyl and propyl group.

In addition, the silicoorganic compound that use as silicone flame retardant preferably contain aryl.More preferably, the ratio (aromatic group amount) that contains the aromatic group shown in the following general formula (2) is 10～70 weight % (15～60 weight % more preferably).

(in the formula (2), X represents the organic residue of univalent of OH base, carbonatoms 1～20 independently of one another.N represents 0～5 integer.In addition, n is 2 when above in the formula (2), can get mutual separately different types of X).

As the silicoorganic compound that silicone flame retardant uses, can also contain above-mentioned Si-H base and alkoxyl group reactive group in addition, as this reactive group, can illustration amino, carboxyl, epoxy group(ing), vinyl, sulfydryl and methacryloxy etc.

As the silicoorganic compound with Si-H base, preferred illustration contains at least a above silicoorganic compound in the structural unit shown in following general formula (3) and (4).

(in formula (3) and the formula (4), Z ¹～Z ³Represent the organic residue of monovalence of hydrogen atom, carbonatoms 1～20 or the compound of following general formula (5) expression independently of one another.α ¹～α ³Represent 0 or 1 independently of one another.M1 represents the integer more than 0 or 1.In addition, in the formula (3), m1 is that 2 repeating units when above can be got a plurality of repeating unit different from each other.)

(in the formula (5), 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.In addition, in the formula (5), m2 is that 2 repeating units when above can be got a plurality of repeating unit different from each other.)

In the silicoorganic compound that use in the silicone flame retardant,, can enumerate at least a kind of compound that for example is selected from the compound shown in general formula (6) and the general formula (7) as silicoorganic compound with alkoxyl group.

(in the formula (6), 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 1 group is an aryl or aralkyl.δ ¹, δ ²And δ ³The alkoxyl group of expression carbonatoms 1～4.)

(in the formula (7), 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 1 group is an aryl or aralkyl.δ ⁴, δ ⁵, δ ⁶And δ ⁷The alkoxyl group of expression carbonatoms 1～4.)

(4) halogen flame retardant

As halogen flame retardant of the present invention, preferred especially brominated polycarbonate (comprising oligopolymer).The excellent heat resistance of brominated polycarbonate, and can increase substantially flame retardant resistance.The brominated polycarbonate that uses among the present invention is that the structural unit of following general formula (8) expression is the unitary at least 60 moles of % of entire infrastructure, preferably at least 80 moles of %, the brominated polycarbonate compound that especially preferably is made of the structural unit of following general formula (8) expression basically.

(in the formula (8), X is a bromine atoms, R be carbonatoms 1～4 alkylidene group, carbonatoms 1～4 alkylidene or-SO ₂-.)

In addition, in this formula (8), preferred R represent methylene radical, ethylidene, isopropylidene (isopropylidene) ,-SO ₂-, preferred especially isopropylidene.

The chloro-formic ester end group that brominated polycarbonate is preferred remaining is few, and terminal chlorine dose is below the 0.3ppm, more preferably below the 0.2ppm.This end chlorine dose can by with sample dissolution in methylene dichloride, add 4-(to nitrobenzyl) pyridine and with terminal chlorine (terminal chloro-formic ester) reaction, adopt ultraviolet-visible pectrophotometer (the system U-3200 of Hitachi) that it is measured and obtains.If terminal chlorine dose is below the 0.3ppm, the thermostability of poly carbonate resin composition becomes better, and can high-temperature molding, consequently provides the moulding processibility more excellent poly carbonate resin composition.

In addition, the terminal hydroxy group that brominated polycarbonate is preferred remaining is few.More specifically, with respect to 1 mole of the structural unit of brominated polycarbonate, preferred terminal hydroxy group amount is below 0.0005 mole, more preferably below 0.0003 mole.The terminal hydroxy group amount can be passed through sample dissolution to adopt in deuterochloroform ¹The H-NMR method is measured and is obtained.If be this terminal hydroxy group amount, the thermostability of poly carbonate resin composition further improves, thereby preferred.

The specific viscosity of brominated polycarbonate is preferably 0.015～0.1 scope, more preferably 0.015～0.08 scope.The above-mentioned specific viscosity calculating formula that the specific viscosity of brominated polycarbonate is used during according to the viscosity-average molecular weight calculated as the polycarbonate resin of the A composition of the invention described above and calculating.

(D composition: fluorine-containing Antidrip agent)

Can contain fluorine-containing Antidrip agent in the glass fiber-reinforced resin composition of the present invention.By should fluorine-containing Antidrip agent and above-mentioned fire retardant and usefulness, can obtain more excellent flame-retardant performance.As this fluorine-containing Antidrip agent, can enumerate and have the fluoropolymer that fibril forms ability, as this polymkeric substance, can enumerate the partially fluorinated polymkeric substance shown in tetrafluoroethylene, tetrafluoroethylene based copolymer (for example tetrafluoroethylene/hexafluoropropylene copolymer etc.), No. 4379910 communique of United States Patent (USP), by fluoridizing polycarbonate resin that bis-phenol makes etc., but be preferably tetrafluoroethylene (below be sometimes referred to as PTFE).

Have the tetrafluoroethylene (fibrillation PTFE) that fibril forms ability and have high molecular weight, under the external action of shearing force etc. between the PTFE in conjunction with and show into and be fibrous tendency.Its number-average molecular weight is 1,500,000～tens million of scope.Its lower limit more preferably 3,000,000.This number-average molecular weight is disclosed in the spy and opens flat 6-145520 communique, calculates according to the melt viscosity of 380 ℃ of following tetrafluoroethylene.That is the melt viscosity when, fibrillation PTFE adopts 380 ℃ that the method put down in writing in this communique measures is 10 ⁷～10 ¹³The scope of pool, more preferably 10 ⁸～10 ¹²The scope of pool.

This PTFE also can use the aqueous liquid dispersion form except solid shape.In addition, this has the PTFE that fibril forms ability, improves in order to make the dispersiveness in resin, obtains more excellent flame-retardant performance and mechanical characteristics, also can use the PTFE mixture with the mixed style of other resins.In addition, also preferably utilize as disclosed open flat 6-145520 communique the spy in, have with this fibrillation PTFE and be core, be the form of the structure of shell with low-molecular-weight tetrafluoroethylene.

As the commercially available product of fibrillation PTFE, can enumerate for example teflon (registered trademark) 6J, POLYFLON MPAFA500, the F-201L etc. of big aurification industrial of fluorine chemistry company of Mitsui Du Pont as representative.As the commercially available product of the aqueous liquid dispersion of fibrillation PTFE, can enumerate Off Le オ Application AD-1, AD-936, FLUON D-1, the D-2 of Daikin Industries corporate system, teflon (registered trademark) 30J of Mitsui Du Pont fluorine chemistry corporate system etc. of rising sun アイシ one アイ Off ロロ Port リマ one ズ corporate system.

Fibrillation PTFE as mixed style, can use the product that adopts following method to obtain, promptly, (1) aqueous liquid dispersion of the aqueous liquid dispersion of fibrillation PTFE and organic polymer or solution are mixed carries out co-precipitation and obtain the method for common cohesion mixture (spy opens clear 60-258263 communique, the spy opens the method for middle records such as clear 63-154744 communique), (2) with aqueous liquid dispersion and the exsiccant organic polymer particle blended method (spy opens the method for putting down in writing in the flat 4-272957 communique) of fibrillation PTFE, (3) aqueous liquid dispersion and the organic polymer particle solution with fibrillation PTFE mixes, (spy opens flat 06-220210 communique to remove the method for medium separately simultaneously by this mixture, the method of record in the Te Kaiping 08-188653 communique etc.), (4) after the monomer methods of polymerization organic polymer to be formed (spy opens the method for putting down in writing in the flat 9-95583 communique) and (5) mix the aqueous liquid dispersion of PTFE and organic polymer dispersion liquid in the aqueous liquid dispersion of fibrillation PTFE, polymerising ethylene base system monomer in this mixed dispersion liquid again 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 fibrillation PTFE of these mixed styles, " metablen A3800 " (trade(brand)name), GESpecialty Chemicals corporate system " BLENDEX B449 " (trade(brand)name) and PacificInterchem Corporation corporate system " POLY TS AD001 " (trade(brand)name) etc. that can the illustration mitsubishi rayon.

For the good mechanical strength of more effectively utilizing glass fiber reinforced flame retardant resin composition of the present invention to have, preferably as far as possible above-mentioned fibrillation PTFE differential is loose.As this microdispersed method of realization, the fibrillation PTFE of above-mentioned mixed style is favourable.In addition, the method that the fibrillation PTFE of aqueous liquid dispersion form directly is supplied in the melting mixing machine is loose also favourable for differential.But the fibrillation PTFE of water-based dispersing morphology slightly should be noted that aspect the deterioration at tone.As the ratio of fibrillation PTFE in the mixed style, among this mixture 100 weight %, fibrillation PTFE is preferably 10～80 weight %, more preferably 15～75 weight %.The ratio of fibrillation PTFE can realize the good dispersion of fibrillation PTFE when this scope.

The content of D composition of the present invention is benchmark with total 100 weight parts of A composition and B composition, is preferably 0.01～3 weight part, more preferably 0.01～2 weight part, further preferred 0.05～1.5 weight part.If the D composition surpasses 3 weight parts, moulding product outward appearance worsens, if less than 0.01 weight part, can not obtain effectively anti-drippage effect.In addition, as the content of the fibrillation PTFE of D composition, be benchmark with total 100 weight parts of A composition and B composition, preferred 0.01～1 weight part, more preferably 0.1～0.7 weight part.

(about other additives)

In the glass fiber-reinforced resin composition of the present invention, can use the molecular weight when being used to make forming process to reduce, make the stable various stablizers of tone, releasing agent, look material and fire retardant etc.

(i) stablizer

Can cooperate known various stablizer in the glass fiber-reinforced resin composition of the present invention.As stablizer, can enumerate phosphorus is that stablizer, hindered phenol are oxidation inhibitor, UV light absorber and photostabilizer etc.

(i-1) phosphorus is stablizer

As phosphorus is stablizer, can illustration phosphorous acid, phosphoric acid, phosphonous acid, phosphonic acids and their ester and tertiary phosphine etc.Wherein preferred especially phosphorous acid, phosphoric acid, phosphonous acid and phosphonic acids, three organophosphorus compoundss and phosphate ester acid compound.Have, the organic group in the phosphate ester acid compound comprises any in a replacement, two replacements and their mixture again.Comprise in them any in the following exemplary compounds corresponding too with this compound.

As three organophosphorus compoundss, can the illustration trimethyl phosphite 99, triethyl phosphate, tributyl phosphate, trioctyl phosphate, tridecyl phosphate, tricresyl phosphate (dodecyl) ester, tricresyl phosphate lauryl, tricresyl phosphate stearyl ester, Tritolyl Phosphate, triphenylphosphate, trichlorophenyl phosphate, di(2-ethylhexyl)phosphate phenyltolyl base ester, the adjacent biphenyl ester of di(2-ethylhexyl)phosphate phenyl list and tributoxyethyl phosphate etc.Preferably phosphoric acid trialkyl ester wherein.The carbonatoms of this trialkylphosphate is preferably 1～22, and more preferably 1～4.Particularly preferred trialkylphosphate is a trimethyl phosphite 99.

As the phosphate ester acid compound, can illustration acid methyl orthophosphoric acid, acid phosphate ester, acid butyl phosphate, acid phosphoric acid butoxy ethyl ester, acid octyl phosphate, acid phosphoric acid ester in the last of the ten Heavenly stems, acid lauryl phosphate, acid phosphoric acid stearyl ester, acid phosphoric acid oleyl alcohol ester, acid di(2-ethylhexyl)phosphate dodecyl ester, acid phenyl-phosphate, acid phosphoric acid nonyl phenylester, acid phosphoric acid cyclohexyl, acid phosphoric acid phenoxy ethyl, alkoxyl group polyoxyethylene glycol phosphate ester acid and dihydroxyphenyl propane phosphate ester acid etc.Wherein, the long-chain dialkyl group phosphate ester acid of carbonatoms more than 10 is effective to the raising of thermostability, and the stability of this phosphate ester acid self is high, and be therefore preferred.

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

In addition, as other bi-ester of phosphite, can also use the compound that has ring texture with the dihydric phenols reaction.Can illustration for example 2,2 '-methylene-bis (4, the 6-di-tert-butyl-phenyl) (2, the 4-di-tert-butyl-phenyl) phosphorous acid ester, 2,2 '-methylene-bis (4, the 6-di-tert-butyl-phenyl) (the 2-tertiary butyl-4-aminomethyl phenyl) phosphorous acid ester and 2,2-methylene-bis (4, the 6-di-tert-butyl-phenyl) octyl group phosphorous acid ester etc.

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

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

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

Preferred phosphorus is that stablizer is the bi-ester of phosphite of three organophosphorus compoundss, phosphate ester acid compound and following general formula (9) expression.Especially preferably cooperate three organophosphorus compoundss.

(in the formula (9), the alkyl of R and R ' expression carbonatoms 6～30 or the aryl of carbonatoms 6～30, can be mutually the same also can be different.)

As mentioned above, as phosphinate compound, preferred four (2, the 4-di-tert-butyl-phenyl)-biphenylene two phosphinates, the stablizer that with this phosphinate is main component is commercially available with SandostabP-EPQ (trade mark, Clariant corporate system) and Irgafos P-EPQ (trade mark, CIBA SPECIALTYCHEMICALS corporate system), all can utilize.

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

(i-2) hindered phenol is an oxidation inhibitor

As hindered phenol compound, can use all cpds that in resin, cooperates usually.As this hindered phenol compound; can illustration alpha-tocopherol for example; butylhydroxy toluene; sinapyl alcohol; vitamin-E; octadecyl-3-(3; the 5-di-tert-butyl-hydroxy phenyl) propionic ester; the 2-tertiary butyl-6-(3 '-tertiary butyl-5 '-methyl-2 '-hydroxybenzyl)-4-aminomethyl phenyl acrylate; 2; 6-di-t-butyl-4-(N; the N-dimethylaminomethyl) phenol; 3; 5-di-tert-butyl-4-hydroxyl benzyl phosphonic acid ester diethyl ester; 2; 2 '-methylene-bis (4-methyl-6-tert butyl phenol); 2; 2 '-methylene-bis(4-ethyl-6-t-butyl phenol); 4; 4 '-methylene-bis (2; the 6-DI-tert-butylphenol compounds); 2; 2 '-methylene-bis(4-methyl-6-cyclohexyl phenol); 2; 2 '-dimethylene-two (6-Alpha-Methyl-benzyl-p-cresol); 2; 2 '-ethidine-two (4; the 6-DI-tert-butylphenol compounds); 2; 2 '-Ding fork base-two (4-methyl-6-tert butyl phenol); 4; 4 '-Ding fork base-two (3 methy 6 tert butyl phenols); triglycol-N-pair-3-(3-tertiary butyl-4-hydroxy-5-aminomethyl phenyl) propionic ester; 1; the 6-hexylene glycol is two, and [3-(3; the 5-di-tert-butyl-hydroxy phenyl) propionic ester]; two [the 2-tertiary butyl-4-methyl 6-(the 3-tertiary butyl-5-methyl-2-hydroxybenzyl) phenyl] terephthalate; 3; 9-pair 2-[3-(3-tertiary butyl-4-hydroxy-5-aminomethyl phenyl) propionyloxy]-1; the 1-dimethyl ethyl }-2; 4; 8; 10-four oxaspiros [5; 5] undecane; 4; 4 '-thiobis (the 6-tertiary butyl-meta-cresol); 4; 4 '-thiobis (3 methy 6 tert butyl phenol); 2; 2 '-thiobis (4-methyl-6-tert butyl phenol); two (3; the 5-di-tert-butyl-4-hydroxyl benzyl) thioether; 4; 4 '-two-thiobis (2; the 6-DI-tert-butylphenol compounds); 4; 4 '-three-thiobis (2; the 6-DI-tert-butylphenol compounds); 2; 2-sulfo-di ethylene bis-[3-(3; the 5-di-tert-butyl-hydroxy phenyl) propionic ester]; 2, two (positive hot the sulfenyl)-6-(4-hydroxyl-3,5-di-tert-butyl amido)-1 of 4-; 3; the 5-triazine; N, N '-hexa-methylene is two-(3,5-di-t-butyl-4-hydroxyl hydrocinnamamide); N; [3-(3 for N '-two; the 5-di-tert-butyl-hydroxy phenyl) propionyl] hydrazine; 1,1,3-three (2-methyl-4-hydroxyl-5-tert-butyl-phenyl) butane; 1; 3; 5-trimethylammonium-2,4,6-three (3; the 5-di-tert-butyl-4-hydroxyl benzyl) benzene; three (3; the 5-di-tert-butyl-hydroxy phenyl) isocyanuric acid ester; three (3, the 5-di-tert-butyl-4-hydroxyl benzyl) isocyanuric acid ester; 1,3; 5-three (the 4-tertiary butyl-3-hydroxyl-2; the 6-dimethyl benzyl) isocyanuric acid ester; 1,3,5-three 2[3 (3; the 5-di-tert-butyl-hydroxy phenyl) propionyloxy] the ethyl isocyanuric acid ester; four [methylene radical-3-(3; the 5-di-tert-butyl-hydroxy phenyl) propionic ester] methane; triglycol-N-pair-3-(3-tertiary butyl-4-hydroxy-5-aminomethyl phenyl) propionic ester; triglycol-N-pair-3-(3-tertiary butyl-4-hydroxy-5-aminomethyl phenyl) acetic ester; 3,9-pair [2-{3-(3-tertiary butyl-4-hydroxy-5-aminomethyl phenyl) acetoxyl group }-1, the 1-dimethyl ethyl]-2; 4; 8,10-four oxaspiros [5,5] undecane; four [methylene radical-3-(3-tertiary butyl-4-hydroxy-5-aminomethyl phenyl) propionic ester] methane; 1; 3; 5-trimethylammonium-2,4,6-three (3-tertiary butyl-4-hydroxy-5-methyl-benzyl) benzene and three (3-tertiary butyl-4-hydroxy-5-methyl-benzyl) isocyanuric acid ester etc.

In the above-claimed cpd, preferably utilize four [methylene radical-3-(3-tertiary butyl-4-hydroxy-5-aminomethyl phenyl) propionic ester] methane, octadecyl-3-(3 among the present invention, the 5-di-tert-butyl-hydroxy phenyl) propionic ester and 3,9-pair [2-{3-(3-tertiary butyl-4-hydroxy-5-aminomethyl phenyl) propionyloxy }-1, the 1-dimethyl ethyl]-2,4,8,10-four oxaspiros [5,5] undecane.Preferred especially 3,9-two [2-{3-(3-tertiary butyl-4-hydroxy-5-aminomethyl phenyl) propionyloxy }-1,1-dimethyl ethyl]-2,4,8,10-four oxaspiros [5,5] undecane.Above-mentioned hindered phenol is that oxidation inhibitor can use separately or will be used in combination more than 2 kinds.

Phosphorus is that stablizer and hindered phenol are that oxidation inhibitor preferably cooperates any.Especially preferably cooperating phosphorus is stablizer, more preferably cooperates three organophosphorus compoundss.Phosphorus is that stablizer and hindered phenol are the use level of oxidation inhibitor, and total 100 weight parts with A composition and B composition are benchmark respectively, are 0.005～1 weight part, are preferably 0.01～0.3 weight part.

(i-3) UV light absorber

Glass fiber-reinforced resin composition of the present invention can contain UV light absorber.Therefore resin combination of the present invention passes through to cooperate UV light absorber owing to also have good color tone, also can this tone of long term maintenance even use without.

As UV light absorber of the present invention; particularly; in benzophenone series; can illustration for example 2; the 4-dihydroxy benaophenonel; 2-hydroxyl-4-methoxy benzophenone; 2-hydroxyl-4-octyloxy benzophenone; 2-hydroxyl-4-benzyloxy benzophenone; 2-hydroxyl-4-methoxyl group-5-sulfonic group benzophenone (2-ヒ De ロキシ-4-メトキシ-5-ス Le ホキシベ 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, particularly, in benzotriazole system, can illustration 2-(2-hydroxy-5-methyl base phenyl) benzotriazole for example, 2-(2-hydroxyl-uncle's 5-octyl phenyl) benzotriazole, 2-(2-hydroxyl-3, the 5-dicumylphenyl) phenyl benzotriazole, 2-(the 2-hydroxyl-3-tertiary butyl-5-aminomethyl phenyl)-5-chlorobenzotriazole, 2, [4-(1 for 2 '-methylene-bis, 1,3, the 3-tetramethyl butyl)-6-(2H-benzotriazole-2-yl) phenol], 2-(2-hydroxyl-3, the 5-di-tert-butyl-phenyl) benzotriazole, 2-(2-hydroxyl-3, the 5-di-tert-butyl-phenyl)-the 5-chlorobenzotriazole, 2-(2-hydroxyl-3, the 5-di-tert-pentyl-phenyl) benzotriazole, 2-(2-hydroxyl-uncle's 5-octyl phenyl) benzotriazole, 2-(2-hydroxyl-5-tert-butyl-phenyl) benzotriazole, 2-(2-hydroxyl-4-octyloxyphenyl) benzotriazole, 2,2 '-methylene-bis (4-cumyl-6-benzotriazole phenyl), 2,2 '-TOPOT 2,2 (1,3-benzoxazine-4-ketone) and 2-[2-hydroxyl-3-(3,4,5,6-tetrahydric phthalimide methyl)-the 5-aminomethyl phenyl] benzotriazole, and 2-(2 '-hydroxy-5-methyl base acryloxy ethylphenyl)-2H-benzotriazole and can with the monomeric multipolymer of ethene base system of this monomer copolymerization, 2-(2 '-hydroxyl-5-acryloxy ethylphenyl)-2H-benzotriazole and can have the polymkeric substance etc. of 2-hydroxy phenyl-2H-benzotriazole skeleton with the monomeric multipolymer of ethene base system of this monomer copolymerization etc.

As UV light absorber, particularly, in hydroxyphenyltriazinuv system, can illustration 2-(4 for example, 6-phenylbenzene-1,3,5-triazines-2-yl)-5-hexyloxy phenol, 2-(4,6-phenylbenzene-1,3,5-triazines-2-yl)-5-methoxyphenol, 2-(4,6-phenylbenzene-1,3,5-triazines-2-yl)-5-thanatol, 2-(4,6-phenylbenzene-1,3,5-triazines-2-yl)-5-propoxy-phenol and 2-(4,6-phenylbenzene-1,3,5-triazines-2-yl)-5-butoxy phenol etc.In addition, but also the phenyl of illustration 2-(4,6-two (2, the 4-3,5-dimethylphenyl)-1,3,5-triazines-2-yls)-above-mentioned exemplary compounds such as 5-hexyloxy phenol become 2, the compound of 4-3,5-dimethylphenyl.

As UV light absorber, particularly, in cyclic imide acid esters system, can illustration for example 2,2 '-TOPOT 2,2 (3,1-benzoxazine-4-ketone), 2,2 '-(4,4 '-biphenylene) two (3,1-benzoxazine-4-ketone) and 2,2 '-(2, the 6-naphthylidene) two (3,1-benzoxazine-4-ketone) etc.

In addition; as UV light absorber; particularly, in cyanoacrylate system, can illustration for example 1; 3-pair-[(2 '-cyano group-3 '; 3 '-diphenylprop enoyl-) oxygen base]-2, two [(2-cyano group-3, the 3-diphenylprop enoyl-) oxygen base] methyl of 2-] propane and 1; 3-pair-[(2-cyano group-3,3-diphenylprop enoyl-) oxygen base] benzene etc.

In addition, the UV light absorber of the above-mentioned UV light absorber polymer-type that can be the structure of the monomeric compound by the taking free redical polymerization light stability monomer that makes this ultraviolet-absorbing monomer and/or have the structure of hindered amine form with monomer copolymerization such as (methyl) alkyl acrylate.As above-mentioned ultraviolet-absorbing monomer, preference is shown in the compound that contains benzotriazole skeleton, benzophenone skeleton, triazine skeleton, cyclic imide acid esters skeleton and cyanoacrylate skeleton in the ester substituting group of (methyl) acrylate.

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

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

(i-4) other thermo-stabilizers

In the glass fiber-reinforced resin composition of the present invention, also can cooperate above-mentioned phosphorus is that stablizer and hindered phenol are other thermo-stabilizers beyond the oxidation inhibitor.These other thermo-stabilizer preferably with these stablizers and oxidation inhibitor in any and usefulness, preferred especially and both and usefulness.As these other thermo-stabilizer, the preference example is as with 3-hydroxyl-5, and the resultant of reaction of 7-di-t-butyl-furans-2-ketone and o-Xylol is that the lactone of representative is stablizer (details of this stablizer is recorded in the spy and opens in the flat 7-233160 communique).This compound is commercially available as Irganox HP-136 (trade mark, CIBA SPECIALTYCHEMICALS society system), can utilize this compound.In addition, the stablizer that this compound and various bi-ester of phosphite and hindered phenol compound are mixed is also commercially available.The Irganox HP-2921 of preference example such as above-mentioned society system.The stablizer that also can utilize this to be pre-mixed among the present invention.Lactone is the use level of stablizer, is benchmark with total 100 weight parts of A composition and B composition, is preferably 0.0005～0.05 weight part, more preferably 0.001～0.03 weight part.

In addition, as other stablizers, can illustration tetramethylolmethane four (3-mercaptopropionic acid ester), tetramethylolmethane four (3-lauryl thiopropionate) and glycerine-3-stearyl thiopropionate etc. contain the stablizer of sulphur.This stablizer is effective especially when resin combination is applied to rotoforming.This contains the use level of the stablizer of sulphur, is benchmark with total 100 weight parts of A composition and B composition, is preferably 0.001～0.1 weight part, more preferably 0.01～0.08 weight part.

(ii) releasing agent

Glass fiber-reinforced resin composition of the present invention, productivity when improving its moulding, improve the dimensional precision of moulding product, can also further cooperate known releasing agents such as fatty acid ester, polyolefin wax, silicoorganic compound, fluorine cpd (to gather the fluorocarbon oil etc. that fluoro-alkyl ether is representative), paraffin, beeswax.Therefore glass fiber-reinforced resin composition of the present invention owing to have a good flowability, obtains that pressure propagation is good, the uniform moulding product of distortion.On the other hand, because its molding shrinkage is low, so demoulding opposing becomes big, the distortion of moulding product when its result causes the demoulding easily easily.Address this problem under the situation that is engaged in the characteristic of not damaging glass fiber-reinforced resin composition of above-mentioned special component.

This fatty acid ester is the ester of aliphatics alcohols and fatty carboxylic acids.This fatty alcohol can be 1 yuan of alcohol, also can be the polyvalent alcohol more than 2 yuan.In addition, this pure carbonatoms is preferably 3～32, and more preferably 5～30.On the other hand, aliphatic carboxylic acid is preferred carbonatoms 3～32, the more preferably aliphatic carboxylic acid of carbonatoms 10～30.Wherein preferred representative examples of saturated aliphatic carboxylic.The aspect of the excellent heat stability during from high temperature, the preferred full ester (full ester) of fatty acid ester of the present invention.Acid number in the fatty acid ester of the present invention is preferably below 20 (can get 0 in fact).In addition, more preferably 0.1～30 scope of the hydroxyl value of fatty acid ester.In addition, the iodine number of fatty acid ester is preferred (can get 0 in fact) below 10.These characteristics can adopt the method for regulation among the JIS K 0070 to try to achieve.

As polyolefin wax, can the illustration molecular weight be 1000～10000, the multipolymer of the alpha-olefin of the homopolymer of the alpha-olefin of Alathon, carbonatoms 3～60 or multipolymer or ethene and carbonatoms 3～60.This molecular weight is to adopt GPC (gel permeation chromatography) method to convert and the number-average molecular weight of mensuration with polystyrene standard.The upper limit of this number-average molecular weight more preferably 6000, more preferably 3000.The carbonatoms of alpha-olefin composition is preferably below 60 in the polyolefin wax, more preferably below 40.As preferred concrete example, can the illustration propylene, 1-butylene, 1-hexene, 4-methyl-1-pentene and 1-octene etc.Preferred polyolefin wax is the multipolymer of the alpha-olefin of Alathon or ethene and carbonatoms 3～60.The ratio of the alpha-olefin of carbonatoms 3～60 is preferably 20 moles below the %, more preferably 10 moles below the %.As so-called polyethylene wax, the commercially available product of preferred utilization.

The content of above-mentioned releasing agent is benchmark with total 100 weight parts of A composition and B composition, preferred 0.005～5 weight part, more preferably 0.01～4 weight part, more preferably 0.02～3 weight part.

(iii) dye pigment

Glass fiber-reinforced resin composition of the present invention also contains the various pigment that dye, and the moulding product that embody various designability can be provided.As the pigment that dyes that uses among the present invention, can enumerate perylene series pigments, coumarin series dyestuff, thioindigo based dye, anthraquinone based dye, thioxanthone based dye, yellow prussiate, purple cyclic ketones based dye, quinoline based dye, quinacridone based dye, dioxazine based dye, isoindolinone based dye and phthalocyanine based dye etc. such as dark purple.In addition, all right complexed metal pigment of resin combination of the present invention obtains more good metal color.As metallic pigment, preferred aluminium powder.In addition, by cooperating white dyes, luminous fluorescence dye outside it, can give the better design effect that produces illuminant colour.

As the fluorescence dye that uses among the present invention (comprising white dyes), for example can enumerating, coumarin series fluorescence dye, chromene are that fluorescence dye, perylene are that fluorescence dye, anthraquinone are that fluorescence dye, thioindigo are that fluorescence dye, xanthene are that fluorescence dye, xanthone are that fluorescence dye, thioxanthene are that fluorescence dye, thioxanthone are that fluorescence dye, thiazine are that fluorescence dye and diamino stibene are fluorescence dye etc.Wherein, few coumarin series fluorescence dye, the chromene of deterioration the during forming process of the good and polycarbonate resin of preferred thermotolerance is that fluorescence dye and perylene are fluorescence dye.

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

The compound that (iv) has the infrared ray absorption ability

Glass fiber-reinforced resin composition of the present invention can contain the compound with infrared ray absorption ability.As this compound, preferred illustration phthalocyanine is a near infrared ray absorption, burning system near infrared ray absorptions such as ATO, ITO, iridium oxide and ruthenium oxide, the various metallic compounds of near infrared absorption ability excellences such as metal diboride system near infrared ray absorption such as lanthanum boride, cerium boride and tungsten boride, and carbon filler.As this phthalocyanine is near infrared ray absorption, and for example Mitsui Chemicals corporate system MIR-362 is commercially available, can easily obtain.As carbon filler, can the illustration carbon black, graphite (comprise natural and artificial both) and soccerballene etc., be preferably carbon black and graphite.They can use separately or will also use more than 2 kinds.Phthalocyanine is the content of near infrared ray absorption, is benchmark with total 100 weight parts of A composition and B composition, preferred 0.0005～0.2 weight part, more preferably 0.0008～0.1 weight part, further preferred 0.001～0.07 weight part.The content of burning system near infrared ray absorption, metal diboride system near infrared ray absorption and carbon filler, in resin combination of the present invention, the scope of preferred 0.1～200ppm (part by weight), the more preferably scope of 0.5～100ppm.

(v) light diffusing agent

In the glass fiber-reinforced resin composition of the present invention, thereby can cooperate light diffusing agent to give the light diffusion effect.As this light diffusing agent, can the illustration high molecular particle, the inorganic particles of the low-refraction of lime carbonate and so on and their mixture etc.This high molecular particle is as the known particulate of the light diffusing agent of polycarbonate resin.More preferably, can the illustration particle diameter count the vinylformic acid crosslinked particle of μ m and organosilicon crosslinked particle that poly organic silicon sesquioxyalkane is representative etc.The shape of light diffusing agent can the illustration sphere, disc, cylindricality and unsetting etc.This sphere may not be positive ball, also comprises the distortion ball, and this cylindricality comprises cubes.Preferred light diffusing agent is spherical, and its particle diameter homogeneous more is preferred more.The content of light diffusing agent is benchmark with total 100 weight parts of A composition and B composition, is preferably 0.005～20 weight part, more preferably 0.01～10 weight part, more preferably 0.01～3 weight part.Have, light diffusing agent can will also be used more than 2 kinds again.

(vi) high reflection of light used white pigment

In the glass fiber-reinforced resin composition of the present invention, thereby can cooperate the high reflection of light to give the luminous reflectance effect with white pigment.As this white pigment, preferred especially titanium dioxide (the particularly titanium dioxide of handling with organic surface treatment agents such as organosilicons) pigment.The high reflection of this light is with the content of white pigment, is benchmark with total 100 weight parts of A composition and B composition, preferred 3～30 weight parts, more preferably 8～25 weight parts.Have, the high reflection of light can will also be used more than 2 kinds with white pigment again.

(vii) static inhibitor

In the glass fiber-reinforced resin composition of the present invention, require antistatic property sometimes, preferably contain static inhibitor this moment.As this static inhibitor, can enumerate (1) ten dialkyl benzene sulfonic acid phosphonium salt for example and be the boron acid phosphonium salt that the fragrant basic sulfonic acid phosphonium salt of representative and alkane base sulfonic acid phosphonium salt etc. have machine sulfonic acid phosphonium salt and four fluorine boron acid phosphonium salt and so on.The content of Gai phosphonium salt is benchmark with total 100 weight parts of A composition and B composition, is to be fit to below 5 weight parts, preferred 0.05～5 weight part, more preferably 1～3.5 weight part, the further scope of preferred 1.5～3 weight parts.

As static inhibitor, for example can enumerate organic sulfonic acid alkali (great soil group) metal-salts such as (2) organic sulfonic acid lithium, organic sulfonic acid sodium, organic sulfonic acid potassium, organic sulfonic acid caesium, organic sulfonic acid rubidium, organic sulfonic acid calcium, organic sulfonic acid magnesium and organic sulfonic acid barium.This metal-salt also uses as fire retardant as previously mentioned.This metal-salt more specifically can illustration for example metal-salt, the metal-salt of perfluoroalkane sulfonate etc. of Witco 1298 Soft Acid.The content of organic sulfonic acid alkali (great soil group) metal-salt is benchmark with total 100 weight parts of A composition and B composition, is fit to preferred 0.001～0.3 weight part, more preferably 0.005～0.2 weight part below 0.5 weight part.An alkali metal salts such as preferred especially potassium, caesium and rubidium.

As static inhibitor, for example can enumerate organic sulfonic acid ammonium salts such as (3) alkylsulphonic acid ammonium salt and aryl sulfonic acid ammonium salt.This ammonium salt is a benchmark with total 100 weight parts of A composition and B composition, is to be fit to below 0.05 weight part.As static inhibitor, for example can enumerate (4) polyether ester amides and so on the polymkeric substance of poly-(oxygen alkene) diol component for its constituent.This polymkeric substance is a benchmark with total 100 weight parts of A composition and B composition, is to be fit to below 5 weight parts.

(viii) other additives

In the glass fiber-reinforced resin composition of the present invention, can cooperate dispersion agent, the photocatalyst of thermoplastic resin beyond the A composition, rubber polymer, other flow ability modifying agents, antiseptic-germicide, whiteruss and so on is stain control agent and photochromic agent etc.

As the thermoplastic resin beyond the A composition, can illustration aromatic polyester resins (pet resin (PET resin), polybutylene terephthalate resin (PBT resin), cyclohexanedimethanol copolymerization pet resin (so-called PET-G resin), PEN resin and PBN resin etc.), plexiglass (PMMA resin), cyclic polyolefin resin, polylactic resin, the polycaprolactone resin, thermoplastic fluorocarbon resin (for example being representative) with the polyvinylidene fluoride resin, and polyolefin resin (polyvinyl resin, ethene-(alpha-olefin) copolymer resin, acrylic resin and propylene-(alpha-olefin) copolymer resin etc.).As rubber polymer, can various core-shell grafting copolymer of illustration and thermoplastic elastomer.Above-mentioned other thermoplastic resins and rubber polymer are benchmark with total 100 weight parts of A composition and B composition, below preferred 10 weight parts, more preferably below 5 weight parts.

(manufacturing of glass fiber-reinforced resin composition)

When making glass fiber-reinforced resin composition of the present invention, adopt arbitrary method.

Can enumerate for example following method: use V-type mixing machine, Henschel mixer, mechanochemistry device, extrude premixing mechanism such as mixing machine with A composition, B composition, C composition with arbitrarily behind other additive thorough mixing; adopt extruding pelletization device, compound stalk forming machine (briquettingmachine) etc. to carry out the granulation of this premixture as required; use then with ventage formula biaxial extruder and carry out melting mixing, use tablets press to carry out granulation then as the melting mixing machine of representative.

In addition, can also enumerate that to supply to each composition with ventage formula biaxial extruder independently of one another be method in the melting mixing machine of representative; After a part of pre-mixing with each composition, supply to method in the melting mixing machine etc. independently with remaining composition.As with the premixed method of the part of each composition, for example can enumerate in advance with after the composition pre-mixing beyond the A composition, be mixed in the A composition or directly supply to method in the forcing machine.

As premixed method, for example, when containing composition, can enumerate the part of this powder and additive blend to be cooperated with powder morphology as the A composition, make masterbatch with the additive of powder dilution, utilize the method for this masterbatch.Can also enumerate from method of a composition being supplied with independently of melt extruding machine etc. midway.Have, when containing aqueous composition in the composition of cooperation, the supply in melt extruding machine can be used so-called fluid infusion apparatus or liquid appending apparatus again.

As forcing machine, can preferably use the forcing machine of ventage with the volatilization gas degassing that can produce with the moisture in the raw material, by the melting mixing resin.Preferably be provided for generation moisture, volatilization gas are discharged to from ventage efficiently the vacuum pump of forcing machine outside.In addition, can also be provided in the zone before the extruding dies portion from resin combination, foreign matter being removed with extruding the screen cloth that the foreign matter of sneaking in the raw material etc. is removed.As this screen cloth, can enumerate wire netting, net-changing device (screenchanger), sintered metal plates (dish filter etc.) etc.

As the melting mixing machine, except biaxial extruder, can also enumerate banbury mixers, mixing roller, single shaft forcing machine, the multiple screw extruder more than 3 etc.

The resin of extruding as mentioned above can directly cut off and carry out granulation, perhaps forms behind the tow with tablets press this tow to be cut off to carry out granulation.In the time of need alleviating the influencing of external dust etc. during granulation, preferably the environment around the forcing machine is cleaned.In addition in the manufacturing of this pellet, the whole bag of tricks that has proposed in polycarbonate resin at CD be can use, minimizing, transportation or the minimizing of the micro powder that produces when carrying and the minimizing of tow or the inner bubble (bubbles of vacuum) that produces of pellet of narrow and smallization, the mistake cut substrate of the distribution of shapes of pellet suitably carried out.Can carry out the reduction of the bad generation ratio of the height circulationization of moulding and crazing (silver) and so on by these treatment processs.In addition, the shape of pellet can be cylinder, square column and general shape such as spherical, more preferably cylinder.The diameter of this cylinder is preferably 1～5mm, more preferably 1.5～4mm, more preferably 2～3.3mm.On the other hand, the length of cylinder is preferably 1～30mm, more preferably 2～5mm, more preferably 2.5～3.5mm.

Glass fiber-reinforced resin composition of the present invention can obtain the moulding product by the pellet injection molding that will make as mentioned above usually, thereby make various goods.In this injection molding, not only common forming method can be used, injection compression molding, injection extrusion forming, air-auxiliary injection forming, foaming (comprising the method for injecting supercutical fluid), insert moulding, in-mould coating moulding, heat insulation mould molding, heating cooling mould molding, dual-color forming, sandwich moulding and ultra-high speed injection molding etc. rapidly can also be enumerated.In addition, moulding can be selected cold runner mode and hot runner mode.

In addition, glass fiber-reinforced resin composition of the present invention also can use with forms such as various special-shaped extrusion molding articles, sheet material, films by extrusion moulding.In addition, the moulding of sheet material, film also can be used inflation method, rolling process, teeming practice etc.In addition, also can be shaped to heat-shrinkable tube by implementing specific stretched operation.In addition, also can adopt rotoforming, blow molding etc. that glass fiber-reinforced resin composition of the present invention is made the moulding product.

The glass fiber-reinforced resin composition and the moulding product that have excellent mechanical intensity, less anisotropy, flame retardant resistance simultaneously are provided thus.Promptly, according to the present invention, the moulding product are provided, these moulding product are by forming the resin combination melt molding, this resin combination comprises: thermoplastic resin (A composition) 40～99 weight parts that contain aromatic polycarbonate resin (A-1 composition), strengthen packing material (B composition) 1～60 weight part, and be the fire retardant (C composition) of 0.001～20 weight part with respect to total 100 weight parts of A composition and B composition, described enhancing packing material (B composition) comprises that the mean value of the major diameter of fibre section is 10～50 μ m, the mean value of the ratio (major diameter/minor axis) of major diameter and minor axis is 1.5～8 flat cross section glass fibre (B-1 composition) and the fibrous packing material except that the B-1 composition (B-2 composition), and the weight ratio of (B-1 composition) and (B-2 composition) is 30/70～99/1.

Utilize the moulding product of resin combination of the present invention, can be used for various uses such as various electronic electric equipment parts, camera component, OA equipment unit, precision optical machinery parts, mechanical part, vehicle part, other agriculture goods, materials and equipments, conveyance container, game machine and groceries, especially for lens barrel, the effect on the industry of its generation is remarkable.

In addition, can also carry out various surface treatments to the moulding product of making by resin combination of the present invention.Here said surface treatment, be evaporation (physical vapor deposition, chemical vapor deposition etc.), plating (plating, electroless plating, fusion plating etc.), spray paint, coating, printing etc. form new layer on the top layer of synthetic resin processing, can use the method for using in the common polycarbonate resin.As surface treatment, particularly can the illustration hard coat, waterproof-anti-oil coating, ultraviolet radiation absorption coating, infrared ray absorption coating and metallization various surface treatments such as (evaporations etc.).Hard coat is preferred especially and thinks necessary surface treatment.

In addition, resin combination of the present invention owing to have improved metal adaptation, therefore also preferably uses vapor deposition treatment and plating to handle.The moulding product that are provided with metal level like this can be used in electromagnetic wave shielding member, conductive component and antenna element etc.The preferred especially sheet and membranaceous of these parts.

Glass fiber-reinforced resin composition of the present invention, because physical strength, less anisotropy excellence, and has good flame-retardance simultaneously, therefore widespread use in buildings, construction equipment, agriculture equipment, ocean equipment, vehicle, electric-electronics, machinery, other various fields as mentioned above particularly can be used for lens barrel.Therefore, the effect on the industry of the present invention's generation is very big.

The inventor thinks that the solution of the present invention of present the best summed up the preferable range of above-mentioned each important document, for example, its typical example is recorded among the following embodiment.Certainly, the present invention is not limited to these schemes.

Embodiment

(I) evaluation of glass fiber-reinforced resin composition

(i) bending elastic modulus: measure according to ASTM D790 (23 ℃ of condition determinations).Have, test film uses injection moulding machine (the system SG-150U of Sumitomo Heavy Industries) to carry out moulding under 100 ℃ of 310 ℃ of barrel temperatures, die temperature again.

(ii) flexural strength (welded bonds, no welded bonds are arranged): use the test film of ASTM D638I type, thereby the test film with welded bonds is to fill from the side gate that is arranged on the test film both sides to make welded bonds at the test film central part.In addition, the test film of no welded bonds is with the sealing of the cast gate of a side and make.Measure the test film that obtains according to ASTM D790 (23 ℃ of condition determinations).Have, test film uses injection moulding machine (the system SG-150U of Sumitomo Heavy Industries) to carry out moulding under 100 ℃ of 310 ℃ of barrel temperatures, die temperature again.

(iii) weld line strength conservation rate: the form with (flexural strength that welded bonds is arranged)/(flexural strength of no welded bonds) * 100=weld line strength conservation rate (%) is obtained.

(iv) molding shrinkage: short brink of moulding has the minor face 50mm of thick 1.5mm film cast gate, the flat board of long limit 100mm, thick 4mm, behind 23 ℃, 50%RH, 24 hours status adjustment, use the size of three-dimensional measurement device (the system MICROPAK 550 of Mitutoyo Mfg. Co., Ltd.) assay plate mobile flow direction and right angle orientation, obtain the molding shrinkage of flow direction and right angle orientation.

(v) anisotropy: likening to anisotropy of the flow direction of the above-mentioned molding shrinkage of obtaining and right angle orientation obtained.Anisotropic value is more near 1, and is then preferred.

(vi) out of roundness: use the SG-150U of Sumitomo Heavy Industries shaper, lens barrel mould (long 15mm, internal diameter 20mm, wall thickness 2.5mm) with tubular, at 300 ℃ of barrel temperatures, 80 ℃ of compacted under lens barrels of die temperature formed body, use the system RONDCOM41A of Tokyo Micronics Inc. to measure the out of roundness of internal diameter.With the longest portion of the internal diameter of cylindrical molding and the difference of the length of short portion as out of roundness.This difference is more little, and then out of roundness is high more.

(vii): outward appearance: visual judgement has tarnish, is designated as zero with floating of glass is little and glossiness, with floating of glass is big and lacklustre is designated as *.

(viii): flame retardant resistance:, estimate maximum combustion number second and UL94 grade with thick 0.8mm and 1.6mm according to the UL94 standard.Maximum combustion number second is short more, and then flame retardant resistance is excellent more.Have, test film uses injection moulding machine (the system SG-150U of Sumitomo Heavy Industries) to carry out moulding under 100 ℃ of 310 ℃ of barrel temperatures, die temperature again.

[embodiment 1～8, comparative example 1～7]

With each use level, after of the various additives mixing of blending machine, use ventage formula biaxial extruder to carry out melting mixing with polycarbonate resin, table 1 record, obtain pellet.The various additives that use are after benchmark makes premixture with polycarbonate resin in advance, to adopt mixing machine to carry out all mixing with 10-100 times of concentration of use level separately.Ventage formula biaxial extruder uses JSW's system: TEX-30XSST (interlock fully, equidirectional rotation, 2 screw rods).Extrusion condition is the vacuum tightness 3kPa of output 20kg/h, screw rod revolution 150rpm, ventage, and in addition, extrusion temperature is made as: from first supplying opening to second supplying opening is 270 ℃, partly is 280 ℃ from second supplying opening to the mouth mould.Have, strengthen packing material and use the side feeder of above-mentioned forcing machine to supply with from second supplying opening, remaining polycarbonate resin and additive are supplied to forcing machine from first supplying opening.Here said first supplying opening is a distance mouthful mould supplying opening farthest, and so-called second supplying opening is at the mouth mould of forcing machine and the supplying opening between first supplying opening.

Use the heated air circulation type drying machines that the pellet that obtains after dry 5 hours, is used the test film of injection moulding machine moulding evaluation usefulness at 120 ℃.Each evaluation result is shown in table 1.

Each composition of mark souvenir in the table 1 is as described below.

(A composition)

PC: (Supreme Being people changes into corporate system to the straight chain shape polycarbonate resin powder of viscosity-average molecular weight 22400: PANLITE L-1225WP)

ABS: acrylonitrile-styrene-butadienecopolymer (Japanese I﹠amp; L corporate system " SANTACUT-61 " (trade(brand)name), mass polymerization, the about 80 weight % of free AS component of polymer and the about 20 weight % of abs polymer composition (the insoluble gel component of acetone), divinyl rubber component content are overall about 15 weight %)

(B composition)

(B-1 composition)

HGF-1: flat cross section short glass fiber (day eastern textile company system: CSG 3PA-830, major diameter 27 μ m, minor axis 4 μ m, Cutting Length 3mm, epoxy are collecting agent)

HGF-2: flat cross section short glass fiber (day eastern textile company system: CSG 3PA-820, major diameter 27 μ m, minor axis 4 μ m, Cutting Length 3mm, polyurethane series collecting agent)

(B-2 composition)

GF: rounded section short glass fiber (NEG corporate system; ECS-03T-511, diameter 13 μ m, Cutting Length 3mm, aminosilane-treated surface treatment and polyurethane series collecting agent)

CF: carbon fiber [the eastern artificial silk corporate system BESFIGHT HTA-C6-U of nation, diameter 7 μ m]

(C composition)

FR-1: based on the phosphoric acid ester of dihydroxyphenyl propane two (diphenyl phosphates) (big eight chemical industrial company's systems " CR-741 " (trade(brand)name), TGA5% weight minimizing temperature=335.9 ℃)

FR-2 perfluor fourth sulfonic acid potassium salt (the big system MEGAFACE F-114P of Japanese ink chemical company)

(D composition)

PTFE: have the tetrafluoroethylene (Daikin Industries corporate system " POLYFLON MPA FA500 " (trade(brand)name)) that fibril forms ability

(other compositions)

TMP: trimethyl phosphite 99 (the big system TMP of eight chemical industrial companies)

CB: the total 100 weight parts use biaxial extruder of 4 compositions of the bisphenol A polycarbonate resin (Supreme Being people changes into corporate system CM-1000, viscosity-average molecular weight 16000) of the montanic acid ester type waxes (Clariant Japan corporate system Licolub WE-1 powder) of the carbon black (MA-100 is deceived in Mitsubishi Chemical Ind's charcoal processing) of 30 weight parts, the white mineral oil of 3 weight parts (Exxon Mobil system Crystol N352), 0.2 weight part and 66.8 weight parts carried out melting mixing and the carbon black master batch made.

[table 1]

Claims

1. glass fiber-reinforced resin composition comprises:

The thermoplastic resin that contains aromatic polycarbonate resin and be the A-1 composition is A composition 40～99 weight parts;

Strengthening packing material is B composition 1～60 weight part, described enhancing packing material is that the mean value of the B composition major diameter that comprises the fibre section is that the ratio of 10～50 μ m, major diameter and minor axis is that the mean value of major diameter/minor axis is that 1.5～8 flat cross section glass fibre is that B-1 composition and the fibrous packing material except that the B-1 composition are the B-2 composition, and the weight ratio B-1 composition/B-2 composition of B-1 composition and B-2 composition is 30/70～99/1; And

With respect to total 100 weight parts of A composition and B composition is that the fire retardant of 0.001～20 weight part is the C composition.

2. glass fiber-reinforced resin composition according to claim 1, wherein, the ratio of the major diameter of B-1 composition and minor axis is that the mean value of major diameter/minor axis is 2.5～5.

3. glass fiber-reinforced resin composition according to claim 1 and 2, wherein, the average fiber length of B-1 composition is that length-to-diameter ratio is 2～120 with the ratio of fiber diameter.

4. according to each described glass fiber-reinforced resin composition in the claim 1～3, wherein, the B-2 composition is that to be selected from glass fibre, wollastonite, carbon except that the B-1 composition be at least a kind of fibrous packing material in the filler.

5. according to each described glass fiber-reinforced resin composition in the claim 1～4, wherein, the C composition is at least a kind of fire retardant that is selected from organic metal salt flame retardant and the organic phosphorus flame retardant.

6. resin combination according to claim 5, wherein, the C composition is an organic phosphorus flame retardant.

7. glass fiber-reinforced resin composition according to claim 5, wherein, the organic metal salt flame retardant is organic sulfonic acid alkali (great soil group) metal-salt.

8. glass fiber-reinforced resin composition according to claim 7, wherein, organic sulfonic acid alkali (great soil group) metal-salt is perfluoro alkyl sulfonic acid alkali (great soil group) metal-salt.

9. glass fiber-reinforced resin composition according to claim 6, wherein, organic phosphorus flame retardant is the fire retardant of following general formula (1) expression,

X in the above-mentioned formula can enumerate by Resorcinol, Resorcinol, two (4-hydroxy diphenyl) methane, dihydroxyphenyl propane, dihydroxybiphenyl, dihydroxy naphthlene, two (4-hydroxy phenyl) sulfone, two (4-hydroxy phenyl) ketone, two (4-hydroxy phenyl) thioether deutero-divalent group, j, k, l, m are 0 or 1 independently of one another, n is 0～5 integer, perhaps under situation 0～5 mean value for the mixture of the different phosphoric acid ester of n number, R ¹, R ², R ³And R ⁴Independently of one another for the halogen atom more than 1 replacement or unsubstituted phenol, cresols, xylenol, isopropyl-phenol, butylphenol, to cumyl phenol deutero-univalent perssad.

10. according to each described glass fiber-reinforced resin composition in the claim 1～9, wherein, with respect to A-1 composition 100 weight parts, it is A-2 composition 1～100 weight part that thermoplastic resin contains phenylethylene resin series.

11. glass fiber-reinforced resin composition according to claim 10, wherein, phenylethylene resin series is the resin more than a kind that is selected from polystyrene, ABS resin, AS resin and the HIPS resin.

12. according to each described glass fiber-reinforced resin composition in the claim 1～11, wherein, the A composition contains the above aromatic polycarbonate resin of 50 weight %.

13. according to each described resin combination in the claim 1～12, wherein, with respect to total 100 weight parts of A composition and B composition, the fluorine-containing Antidrip agent that contains 0.01～3 weight part is the D composition.

14. a synthetic resin forms each described injection moulding of glass fibre reinforced resin composition in the claim 1～13.

15. synthetic resin according to claim 14 is characterized in that, synthetic resin is a lens barrel.