CN101625447A

CN101625447A - Cylinder produced from glass fiber-reinforced resin composition

Info

Publication number: CN101625447A
Application number: CN200910140210A
Authority: CN
Inventors: 池松龙介
Original assignee: Teijin Chemicals Ltd
Current assignee: Teijin Ltd
Priority date: 2008-07-07
Filing date: 2009-07-07
Publication date: 2010-01-13
Also published as: JP2010015091A

Abstract

The object of the invention is to provide a cylinder produced from glass fiber-reinforced resin composition. The cylinder uses thermoplastic resin which is reinforced by glass fiber with flat cross section as substrate, and has the advantages of mechanical intensity, low aeolotropism, good fluidity and excellent appearance. The cylinder is molded by being injected with resin composition, and the resin composition contains: (i) 100 proportion by weight of resin component (A component) containing aromatic polycarbonate resin (A-1 component); (ii) 1-150 proportion by weight of fiberglass (B-1 component) with flat section, whose mean value of long diameter of fibre section is 10-50 mu m, and mean value of ratio between the long diameter and the short diameter (long diameter/short diameter) is 1.5-8; as well as (iii) 0-150 proportion by weight of reinforced filler material, which is one of plate-shaped filler material (B-2 component) and fibrous filler material (B-3 component) besides B-1 component.

Description

The lens barrel of making by glass fiber-reinforced resin composition

Technical field

The present invention relates to the lens barrel made by the improved glass fiber-reinforced resin composition of dimensional accuracy.More particularly, the polycarbonate resin that relates to strengthen with the flat cross section glass fibre is a matrix, physical strength, less anisotropy, mobile excellent also have good surface appearance simultaneously, are assembled into the lens barrel in the optics system of optical elements such as keeping lens, prism and mirror.

Background technology

Therefore the thermoplastic resin that glass fibre strengthens extensively utilizes owing to physical strength, excellent in workability.Particularly polycarbonate resin owing to physical strength, dimensional stability, the such excellent specific property of anti-flammability, uses in numerous purposes such as mechanical part, automobile component, electrical and electronic parts, office equipment parts.

So far, as the resin combination that lens barrel is used, proposed in polycarbonate resin, to cooperate the resin combination (with reference to patent documentation 1) of glass fibre.But, though this resin combination physical strength, excellent rigidity has the anisotropic shortcoming of the molding shrinkage that generation causes by the fiber orientation.When using in moulding product such as precision optical machinery parts such as camera component, office equipment parts in recent years, need the resin combination of physical strength, less anisotropy, good fluidity, this resin combination can not satisfy above-mentioned characteristic.

The improved resin combination of being made up of aromatic polycarbonate resin and specific non-circular fiber and tabular packing material of warpage properties is known (with reference to patent documentation 2).But, this resin combination flowability, outward appearance deficiency.

The resin combination of being made up of polycarbonate resin, phenylethylene resin series, cocoon cross section shape glass fibre is known (with reference to patent documentation 3).In addition, the resin combination of being made up of polyamide, cocoon cross section shape glass fibre and bromide fire retardant is known (with reference to patent documentation 4).

But, this communique is not open for having the lens barrel in the camera, lens barrel and the required characteristic of the lens barrel in the projection TV set in the liquid crystal projection apparatus, be excellent mechanical intensity, outward appearance, flowability, satisfy the effective opinion of resin combination of less anisotropy.

Patent documentation 1: TOHKEMY 2004-256581 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 object of the present invention is to provide the polycarbonate resin to strengthen with the flat cross section glass fibre is matrix, and physical strength, less anisotropy, mobile excellent have the lens barrel of good appearance.The inventor is further investigation repeatedly to achieve these goals, found that the glass fibre that has specific sectional shape by utilization, can realize this purpose, has finished the present invention thereby further further investigate.

According to the present invention, above-mentioned problem realizes that by following lens barrel this lens barrel is by forming resin combination injection moulding, and this resin combination contains:

(i) contain resinous principle (A composition) 100 weight portions of aromatic polycarbonate resin (A-1 composition),

(ii) the mean value of the major diameter of fibre section is 10～50 μ m, and 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) 1～150 weight portion, and

At least a kind that (iii) is selected from tabular packing material (B-2 composition) and the fibrous packing material except that the B-1 composition (B-3 composition) strengthens packing material 0～150 weight portion.

Embodiment

Below details of the present invention is described.

(A composition: resinous principle)

(A-1 composition: aromatic polycarbonate resin)

Aromatic polycarbonate resin (A-1 composition) reacts dihydric phenol and carbonate precursor and obtains.As an example of reaction method, can enumerate the solid phase ester-interchange method of interfacial polymerization, melt transesterification process, carbonic ester prepolymer and the ring-opening polymerization method of cyclic carbonate compound etc.

Typical example as use therein dihydric phenol, can enumerate p-dihydroxy-benzene, resorcinol, 4,4 '-xenol, 1, two (4-hydroxy phenyl) ethane of 1-, 2, two (4-hydroxy phenyl) propane (common name bisphenol-A) 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-isopropyl cyclohexanes 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 impact resistance aspect, and preferred especially bisphenol-A, general.

Among the present invention, beyond the polycarbonate that is as the bisphenol-A of general polycarbonate (below, abbreviate " BPA " sometimes as), 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 change in size that causes because of suction, the purposes that the requirement of morphological stability is strict especially.Dihydric phenol beyond these BPA, preferred all 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 suitably mix use 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 (glass 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 be 0.05～0.15%, preferred 0.06～0.13%, and Tg is 120～180 ℃ polycarbonate, perhaps

(ii) Tg is 160～250 ℃, preferred 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 (glass 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 manufactured 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 potpourri that mixes more than 2 kinds of the polycarbonate resin that will obtain.

Branched polycarbonate resin can be given antidrip fluidity to enhancing aromatic copolycarbonate resin composition of the present invention and can be waited.As the multi-functional aromatics more than the trifunctional that uses in this branched polycarbonate resin, can enumerate 1,3,5-trihydroxybenzene, 2,3 ', 4,5 ', 6-penta hydroxy group biphenyl, or 4,6-dimethyl-2,4,6-three (4-hydroxy phenyl) heptene-2,2,4,6-trimethyl-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, two (4, the 4-dihydroxy trityl group) benzene of 4-, or trimellitic acid, pyromellitic acid, benzophenone tetracarboxylic acid and these 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.

The structural unit of deriving by multi-functional aromatics in the branched polycarbonate, in 100 moles of % of total of structural unit of deriving and the structural unit that multi-functional aromatics is derived by this by dihydric phenol, 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 subsidiary reaction, about this branched structure quantity of units, with 100 moles of % of total of the structural unit of deriving by dihydric phenol 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 aliphatic two functionality carboxylic acids.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 decanedioic acid (decane diacid), dodecanedioic acid, tetracosandioic acid, octadecane diacid, eicosane diacid 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 ring-opening polymerization method of interfacial polymerization, melt transesterification process, carbonic ester prepolymer solid phase ester-interchange method and the cyclic carbonate compound of the manufacture method of polycarbonate resin etc., be known method in various documents and patent gazette etc.

During resin combination that manufacturing has strengthened with glass fibre, the viscosity average molecular weigh of aromatic polycarbonate resin (M) is not particularly limited, be preferably 1 * 10 ⁴～5 * 10 ⁴, more preferably 1.4 * 10 ⁴～3 * 10 ⁴, more preferably 1.4 * 10 ⁴～2.4 * 10 ⁴

For viscosity average molecular weigh less than 1 * 10 ⁴Aromatic polycarbonate resin, can't obtain the favorable mechanical characteristic.On the other hand, surpass 5 * 10 by viscosity average molecular weigh ⁴The resin combination that obtains of aromatic polycarbonate resin, the flowability during injection moulding is poor, so versatility is poor.

Have, aromatic polycarbonate resin can obtain its viscosity average molecular weigh in above-mentioned extraneous mixed with resin again.Particularly has the above-mentioned scope (5 * 10 of surpassing ⁴) the aromatic polycarbonate resin of viscosity average molecular weigh, the entropic elasticity of resin improves.In the gas assistant formation and foaming that its result will use sometimes, embody good processing and forming in the time will strengthening molding resin material for structure member.The improvement of this processing and forming is better than above-mentioned branched polycarbonate.As preferred scheme, can also use the A composition by viscosity average molecular weigh 7 * 10 ⁴～3 * 10 ⁵Aromatic polycarbonate resin (A-1-1 composition) and viscosity average molecular weigh 1 * 10 ⁴～3 * 10 ⁴Aromatic polycarbonate resin (A-1-2 composition) form, its viscosity average molecular weigh is 1.6 * 10 ⁴～3.5 * 10 ⁴Aromatic 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 7 * 10 ⁴～2 * 10 ⁵, more preferably 8 * 10 ⁴～2 * 10 ⁵, more preferably 1 * 10 ⁵～2 * 10 ⁵, be preferably 1 * 10 especially ⁵～1.6 * 10 ⁵In addition, the molecular weight of A-1-2 composition preferred 1 * 10 ⁴～2.5 * 10 ⁴, more preferably 1.1 * 10 ⁴～2.4 * 10 ⁴, more preferably 1.2 * 10 ⁴～2.4 * 10 ⁴, be preferably 1.2 * 10 especially ⁴～2.3 * 10 ⁴

The aromatic polycarbonate resin (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,, can enumerate (1), with the method for their mixing with A-1-1 composition and the polymerization independently of one another of A-1-2 composition as the preparation method of A-1 composition; (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 the method for this manufacture method (autofrettages of (2)) aromatic polycarbonate resin that obtains and the A-1-1 composition of making in addition and/or the mixing of A-1-2 composition etc.

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

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

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

By the specific viscosity (η that tries to achieve _Sp), calculate viscosity average molecular weigh 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 viscosity average molecular weigh of aromatic polycarbonate resin adopts following main points to carry out in the resin combination that has strengthened with glass fibre again.That is, the methylene chloride of this resin combination with its 20～30 times of weight mixed, the solvable composition dissolving in the resin combination.Adopt zeolite filtration to extract this solvable composition.Then the solvent in the solution that obtains is removed.Will be fully dry except that the solid after desolvating, obtain being dissolved in the solid of the composition in the methylene chloride.By the solution that this solid 0.7g is dissolved in gained among the methylene chloride 100ml, with the above-mentioned specific viscosity of similarly obtaining 20 ℃, by this specific viscosity and the above-mentioned viscosity average molecular weigh (M) of similarly calculating.

The content of the A-1 composition in the A composition is preferably more than the 50 weight %, more preferably more than the 55 weight %, further more than the preferred 60 weight %.

(A-2 composition: phenylethylene resin series)

The phenylethylene resin series (A-2 composition) that uses as resinous principle has the thermotolerance and the anti-flammability of good processing and forming and appropriateness, so is preferred resin for the harmony that keeps these characteristics.

This phenylethylene resin series (A-2 composition) 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) acrylate compounds.As particularly suitable vinyl cyanide based compound, can enumerate vinyl cyanide, as particularly suitable (methyl) acrylate compounds, can enumerate methyl methacrylate.

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

As can with the rubber polymer of above-mentioned aromatic ethenyl compound copolymerization, can enumerate polybutadiene, polyisoprene, diene interpolymer (for example random copolymers of styrene-butadiene and segmented copolymer, acrylonitrile-butadiene copolymer, and the multipolymer of (methyl) alkyl acrylate and butadiene 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 (polysiloxane rubber for example, the IPN type rubber of forming by polysiloxane 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 polysiloxane rubber constituent and Oppanol etc. of indissociable structure).

As phenylethylene resin series (A-2 composition), 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) s-B-S copolymer resin, (hydrogenation) styrene-isoprene-styrene copolymer-resin etc.Should illustrate that the souvenir of (hydrogenation) means and comprises the resin that do not have hydrogenation and the resin of hydrogenation.Wherein, the MS resin is represented the main copolymer resin of being made up of methyl methacrylate and styrene, the AES resin is represented mainly by vinyl cyanide, the copolymer resin that ethylene-propylene rubber and styrene are formed, the ASA resin is represented mainly by vinyl cyanide, the copolymer resin that styrene and acrylic rubber are formed, the MABS resin is represented mainly by methyl methacrylate, vinyl cyanide, the copolymer resin that butadiene and styrene are formed, the MAS resin is represented mainly by methyl methacrylate, the copolymer resin that acrylic rubber and styrene are formed, SMA resin are represented the copolymer resin mainly be made up of styrene and maleic anhydride (MA).

Have, this phenylethylene resin series (A-2 composition) by using catalyzer such as metallocene catalyst, can be the resin that syndiotactic polystyrene etc. has high stereoregularity when it is made again.In addition, according to circumstances also can use the polymkeric substance and high polymkeric substance, the multipolymer of multipolymer, segmented copolymer and stereoregularity of the narrow molecular weight distribution that methods such as adopting living anion polymerization, radical living polymerization obtain.

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 styrene and α-Jia Jibenyixi.As each components in proportions in the AS resin, in the time of will all 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 in these vinyl compounds, can also mix other vinyl based compounds of the copolymerization of using above-mentioned record, they contain below the 15 weight % in the proportional preferably AS resinous principle.In addition, the initiating agent that uses in the reaction, chain-transferring agent etc. can use existing known various materials as required.

This AS resin can adopt any method manufacturing in bulk polymerization, suspension polymerization, the emulsion polymerization, but preferably adopts bulk 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 in 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 viscosity meter use solvent is 20～100 seconds viscosity meter again.

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 the potpourri that makes the multipolymer of thermoplastic graft copolymer multipolymer that vinyl cyanide based compound and aromatic ethenyl compound graft polymerization obtain to the diene series rubber composition and vinyl cyanide based compound and aromatic ethenyl compound.As the diene series rubber composition that forms this ABS resin, for example can using, glass transition temperatures such as polybutadiene, polyisoprene and Styrene-Butadiene 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, optimization styrene and α-Jia Jibenyixi especially.This is grafted to the components in proportions on the diene series rubber composition, is preferably 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 acrylate, maleic anhydride, N substituted maleimide amine etc., they contain proportional in the ABS resin composition, being preferably below the 15 weight %.In addition, the initiating agent that uses in the reaction, chain-transferring agent, emulsifying agent etc. can use existing known various materials as required.

In the ABS resin, 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.For the reduced viscosity of this free multipolymer of being made up of vinyl cyanide based compound and aromatic ethenyl compound, the reduced viscosity (30 ℃) that the method that employing is put down in writing is previously obtained is 0.2～1.0dl/g, more preferably 0.3～0.7dl/g.

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

This ABS resin can adopt any method manufacturing in bulk polymerization, suspension polymerization, the emulsion polymerization.The special ABS resin that preferably adopts bulk 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 engineering 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 be to adopt the copolymerization of single stage method, also can be the copolymerization of adopting multistep processes.In addition, also can preferably use in the ABS resin that adopts this autofrettage 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 thermal stability, 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.Related with this good thermal stability, 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 coagulating agent, the alkali earth metal salt of this coagulating agent preferably sulfuric acid or sulfuric acid.

Phenylethylene resin series (A-2 composition) preferably is selected from least a kind of resin in polystyrene, ABS resin, AS resin and the HIPS resin.

The content of phenylethylene resin series (A-2 composition), with respect to A-1 composition 100 weight portions, preferred 1～100 weight portion, more preferably 5～80 weight portions, further preferred 10～70 weight portions.

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

Lens barrel of the present invention contains flat cross section glass fibre (B-1 composition).The mean value of the major diameter of the fibre section of flat cross section glass fibre (B-1 composition) is 10～50 μ m, is preferably 15～40 μ m, more preferably 20～35 μ m.In addition, the mean value of the ratio (major diameter/minor axis) of major diameter and minor axis is 1.5～8, is preferably 2～6, more preferably 2.5～5.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, compares when having used less than 1.5 non-circular section fiber, and anisotropy is greatly improved, and can significantly improve anti-flammability.The reason that this anti-flammability improves can be thought: on moulding product surface, the long limit face and the moulding product surface of flat cross section glass fibre (B-1 composition) are orientated abreast, therefore the oxygen barriering effect that the resin charing tunicle except by burning the time produces, compare with the round section fiber by the oxygen barriering effect that flat cross section glass fibre (B-1 composition) produces, more effectively play a role.

In addition, flattened also comprises the non-circular cross sectional shape of ellipticity, silk cocoon shape, tri-lobed or shape similar with it except flat.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 (B-1 composition) ratio (length-diameter ratio) long and fiber diameter is preferably 2～120, and more preferably 2.5～70, more preferably 3～50.Less than 2, the raising effect of physical strength is little as the ratio of fruit fiber length and fiber diameter, surpasses 120 as the ratio of fruit fiber length and fiber diameter, and it is big that anisotropy becomes, and moulding product outward appearance also worsens.

The fiber diameter of this flat cross section glass fibre (B-1 composition) 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 that uses among 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 chemicals 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 flat cross section glass fibre (B-1 composition) 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 (alkali-free glass) wherein.

From the aspect that physical strength improves, this flat cross section glass fibre is preferably used known surface conditioning agent, and for example silane coupling agent, titanate coupling agent or aluminate coupling agent etc. are implemented surface treatment.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 0.2～1 weight %.

The content of flat cross section glass fibre (B-1 composition) with respect to A composition 100 weight portions, is 1～150 weight portion, more preferably 3～100 weight portions, further preferred 5～70 weight portions.If the B-1 composition is less than 1 weight portion, the physical strength deficiency, if surpass 150 weight portions, particularly moulding flowability, the decline of moulding product outward appearance are not suitable as the lens barrel purposes.

(B-2 composition: tabular packing material)

As the tabular inorganic filling material that uses among the present invention (B-2 composition), can the illustration mica, talcum, clay, graphite, glass sheet and polynite smectites (smectite) such as (montmorillonite) be mineral etc.In addition, this tabular inorganic filling material (B-2 composition) comprises the tabular inorganic filling material that applied through washing or burning.Among the present invention,, preferably be selected from least a kind of tabular inorganic filling material in glass sheet, mica, graphite and the talcum, special preferred glass sheet as the B-2 composition.The glass sheet that uses as the B-2 composition is the plate glass filler that adopts methods such as cylinder air blast, sol-gel process to make.The size of the raw material of this glass sheet also can be selected all size according to the degree of pulverizing, classification.Preferred 10～1000 μ m of the mean grain size of the glass sheet that uses in the raw material, more preferably 20～500 μ m, further preferred 30～300 μ m.This is because the processing of the glass sheet of above-mentioned scope and processing and forming are all excellent.Usually, fragmentation takes place because of the melting mixing processing with resin in the plate glass packing material, and its mean grain size diminishes.Preferred 10～200 μ m of the number average bead diameter of the glass sheet in the resin combination, more preferably 15～100 μ m, further preferred 20～80 μ m.In addition, this number average bead diameter is to the high temperature ashing by the moulding product, adopts the dissolving of solvent and adopt the remainder of the tabular packing material that processing such as decomposition of chemicals 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 with the sheet thickness, not the glass sheet of computational length below it.In addition, as thickness, preferred 0.5～10 μ m, more preferably 1～8 μ m, further preferred 1.5～6 μ m.Glass sheet with above-mentioned number average bead diameter and thickness is realized good intensity, rigidity.

As the mica that B-2 composition of the present invention uses, from guaranteeing the rigidity aspect, preferred mean grain size is pulverous mica of 10～700 μ m.So-called mica is the crushed material that comprises the silicate mineral of aluminium, potassium, magnesium, sodium, iron etc.White mica, phlogopite, black mica, micanite etc. are arranged in the mica, as the mica that uses among the present invention, can use any mica, but white mica comparing with phlogopite, black mica, himself is rigidity, and white mica is preferred aspect rigidity.In addition, phlogopite, black mica are compared with white mica, contain Fe in the principal ingredient in a large number, so the tone of himself blackout, carry out various also preferred white micas when painted.In addition, micanite (the OH base of natural phlogopite being replaced into the mica of F) price height, Comparatively speaking white mica is favourable.Therefore, set out preferred white mica among the present invention in all its bearings.

In addition, comminuting method during as the manufacturing of mica, the dry type comminuting method that useful Dry-crusher is pulverized the former stone of mica and with Dry-crusher with the former stone coarse crushing of mica after, add grinding aids such as entry, in wet crushing mill, lead pulverizing with slurry form, dewater then, dry case of wet attrition method.

Have, for the lower limit of the mean grain size of mica, the mean grain size that preferably adopts the Microtrack laser diffractometry to measure is more than the 10 μ m again, and on the other hand, for the upper limit, the mean grain size meter of measuring with the oscillatory type sieve method is below the preferred 700 μ m.It is that mica more than the 95 weight % carries out that the Microtrack laser diffractometry is fit to for adopting oscillatory type sieve method 325 order throughputs.Mica for the particle diameter more than it generally uses the oscillatory type sieve method.Oscillatory type sieve method of the present invention is following method: at first use the vibration cribellum, adopt the standard sieve by the overlapping JIS specification of the order of width of mesh that the mica powder 100g that uses is carried out screening in 10 minutes.Be determined at each sieve and go up the weight of residual powder, obtain size-grade distribution.Adopt the scope of preferred 50～700 μ m of weight average particle diameter of oscillatory type sieve method mensuration, because impact strength excellence, the more preferably scope of 50～400 μ m.The effect of this particle diameter is being to be fit to performance in the mica that obtains of raw material with the white mica particularly.The mica that surpasses 700 μ m is few, and the moulding such as cast gate obstruction when being easy to generate moulding are bad, therefore not preferred.On the other hand, need extremely many time less than the pulverizing of 10 μ m is present, therefore uneconomical.

As the thickness of mica, can use the thickness of the observation actual measurement of adopting electron microscope is the mica of 0.01～10 μ m.In addition, this mica can carry out surface treatment with silane coupling agent etc., also can be with collecting agent granulations such as various resins, high-grade aliphatic esters such as polyurethane series resin and become graininess.

As the talcum that B-2 composition of the present invention uses, be flakey particle with layer structure, on the chemical composition hydrous magnesium silicate, generally use chemical formula 4SiO ₂3MgO2H ₂O represents, common SiO by 56～65 weight % ₂, the MgO of 28～35 weight %, the H about about 5 weight % ₂O constitutes.As other minor constituents, contain the Fe of 0.03～1.2 weight % ₂O ₃, 0.05～1.5 weight % Al ₂O ₃, 0.05～1.2 weight % the following K of CaO, 0.2 weight % ₂The Na that O, 0.2 weight % are following ₂O etc., proportion is about 2.7.The particle diameter of the talcum here is a heavily rate of the cumulative weight percent (Plot that obtained by the size-grade distribution that employing Anderson (sedimentation)pipet (Andreasen pipet) method of measuring according to JISM8016 is measured) be 50% o'clock particle diameter.Preferred 0.3～15 μ m of its particle diameter, more preferably 0.5～10 μ m.In addition, the method for making when this talcum being pulverized by former stone, there is no particular restriction, can utilize axial flow type polishing, ring polishing, roller mill method, ball-milling method, jet mill method and the rotary compression shear type of container polishing etc.In addition, adopt various graders that the talcum after pulverizing is carried out classification and handle the talcum that the preferable particle size distribution is neat.As grader; there is no particular restriction, can enumerate impact type intertia force classifier (variable impactor etc.), utilize wall attachment effect type intertia force classifier (bend pipe injection etc.), centrifugal field grader (multistage cyclone classifier, differentiating stage device (MICROPLEX), disperse polarity splitter, Ah ask'sing card special clasfficiator (ACCUCUT), turbine clasfficiator, turbine air classifier (TURBOPLEX), centrifugal classifier and super separator) etc.

In addition, from aspects such as its property handled, this talcum is preferably state of aggregation, as its method for making, the method for utilizing degassing compression, the method that the use collecting agent compresses etc. is arranged.From easy and do not make unwanted collecting agent resinous principle sneak into aspect the composition of the present invention, the preferred especially method of utilizing degassing compression.

The graphite that uses as the B-2 composition among the present invention is flaky graphite.Cooperate the resin combination of this flaky graphite to have good electrical conductivity, had excellent mechanical intensity, less anisotropy simultaneously.

The particle diameter of graphite is the scope of 5～300 μ m.This particle diameter is preferably 5～70 μ m, more preferably 7～40 μ m, more preferably 7～35 μ m.By satisfying this scope, realize excellent flame-retardant performance.On the other hand, if mean grain size less than 5 μ m, the effect of improving of dimensional accuracy reduces easily, if mean grain size surpasses 300 μ m, impact resistance also slightly reduces, the so-called graphite on the product of moulding simultaneously surface floats obviously, so not preferred.Floating of this surface is because graphite comes off from moulding product surface, has the possibility of defective component with the electronic unit conducting.In addition, if above-mentioned preferred mean grain size, the outward appearance with moulding product becomes well, also obtains the advantage of good sliding simultaneously easily.

The fixed carbon amount of graphite is preferably more than the 80 weight %, more preferably more than the 90 weight %, more preferably more than the 98 weight %.In addition, the volatile ingredient of graphite of the present invention is preferably below the 3 weight %, more preferably below the 1.5 weight %, more preferably below the 1 weight %.

The mean grain size of graphite is meant the particle diameter that becomes composition B-2 composition self in the past among the present invention, and this particle diameter is meant the particle diameter that adopts laser diffractometry to obtain.

In addition, only otherwise damage the characteristic of composition of the present invention, in order to increase the compatibility with thermoplastic resin, surface treatment can be implemented in the surface of graphite, and for example epoxy finishes, polyurethane are handled, silane coupled processing and oxidation processes etc.

(B-3 composition: fibrous packing material)

Lens barrel of the present invention can contain fibrous packing material (B-3 composition).As fibrous packing material (B-3 composition), glass milled fiber, wollastonite, carbon beyond the glass fibre beyond the preferred illustration B-1 composition, glass hollow microsphere, beaded glass, the B-1 composition are filler.It is at least a kind of fibrous packing material in the filler that the B-3 composition preferably is selected from glass fibre, glass milled fiber, wollastonite and carbon beyond the B-1 composition.

This fibrous packing material (B-3 composition) also can utilize the filler that has carried out metal oxide-coated such as titanium dioxide, zinc paste, cerium oxide and monox on their surface.As carbon is filler, can enumerate for example carbon fiber, washing carbon fiber, carbon milled fiber, gas-phase growth of carbon fibre and carbon nano-tube, carbon black etc.Carbon nano-tube can be any in fibre diameter 0.003～0.1 μ m, individual layer, 2 layers and the multilayer, preferred multilayer (so-called MWCNT).Wherein, from mechanical excellent strength aspect and the aspect that can give good electrical conductivity, preferred carbon fiber and washing carbon fiber.

Fibrous packing material (B-3 composition) can carry out surface treatment with various surface conditioning agents in advance.Can carry out surface treatment as this surface conditioning agent with various surface conditioning agents such as silane coupling agent (comprising alkylalkoxy silane, poly-Organhydridosiloxaneresins etc.), high-grade aliphatic ester, acid compound (for example phosphorous acid, phosphoric acid, carboxylic acid and carboxylic acid anhydrides etc.) and waxes.In addition, can carry out granulation and form graininess with collecting agents such as various resins, high-grade aliphatic ester and waxes.

Being selected from least a kind of content that strengthens packing material in B-2 composition and the B-3 composition, with respect to A composition 100 weight portions, is 0～150 weight portion, is preferably 0～100 weight portion, more preferably 0～75 weight portion, more preferably 1～75 weight portion.

(about other adjuvants)

In the resin combination that strengthens with glass fibre that uses among the present invention, molecular weight, tone when making processing and forming are stable, can use various stabilizing agents, release agent, look material.

(i) stabilizing agent

Can cooperate known various stabilizing agent in the resin combination that uses among the present invention.As stabilizing agent, can enumerate phosphorus is that stabilizing agent, hindered phenol are antioxidant, ultraviolet light absorber and light stabilizer etc.

(i-1) phosphorus is stabilizing agent

As phosphorus is stabilizing agent, 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 potpourri again.Comprise in them any in the following exemplary compounds corresponding too with this compound.

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

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, alkoxy polyglycol phosphate ester acid and bisphenol-A phosphate ester acid etc.Wherein, the long-chain dialkyl group phosphate ester acid of carbon number more than 10 is effective to the raising of thermal stability, 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 diisopropyl 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 bisphenol-A pentaerythritol diphosphites, two (nonyl phenyl) pentaerythritol diphosphites and dicyclohexyl pentaerythritol diphosphites etc.

In addition, as other bi-ester of phosphite, can use the compound that has ring texture with the dihydric phenols reaction.For example can enumerate 2,2 '-di-2-ethylhexylphosphine oxide (4, the 6-di-tert-butyl-phenyl) (2, the 4-di-tert-butyl-phenyl) phosphite ester, 2,2 '-di-2-ethylhexylphosphine oxide (4, the 6-di-tert-butyl-phenyl) (the 2-tert-butyl group-4-aminomethyl phenyl) phosphite ester and 2,2-di-2-ethylhexylphosphine oxide (4, the 6-di-tert-butyl-phenyl) octyl group phosphite 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 phenyl-phosphonic acid dimethyl ester, phenyl-phosphonic acid diethylester and phenyl-phosphonic 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, diphenyl octyl group phosphine, triphenylphosphine, three (p-methylphenyl) phosphine, three naphthyl phosphines and diphenyl benzyl phosphine etc.Particularly preferred tertiary phosphine is a triphenylphosphine.

Preferred phosphorus is that stabilizing agent is the bi-ester of phosphite of three organophosphorus compoundss, phosphate ester acid compound and following general formula (1) expression.Especially preferably cooperate three organophosphorus compoundss.

(in the formula (1), the alkyl of Ar and Ar ' expression carbon number 6～30 or the aryl of carbon number 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 stabilizing agent that with this phosphinate is principal ingredient is commercially available with Sandostab P-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-} pentaerythrite two phosphinates.

(i-2) hindered phenol is an antioxidant

As hindered phenol compound, can use all cpds that in resin, cooperates usually.As this hindered phenol compound; can the illustration alpha-tocopherol; butylated hydroxytoluene; sinapinic alcohol; vitamin E; octadecyl-3-(3; the 5-di-tert-butyl-hydroxy phenyl) propionic ester; the 2-tert-butyl group-6-(3 '-tert-butyl group-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 phosphonate ester diethyl ester; 2; 2 '-di-2-ethylhexylphosphine oxide (4-methyl-6-tert butyl phenol); 2; 2 '-methylene-bis(4-ethyl-6-t-butyl phenol); 4; 4 '-di-2-ethylhexylphosphine oxide (2; the 6-DI-tert-butylphenol compounds); 2; 2 '-methylene-bis(4-methyl-6-cyclohexyl phenol); 2; 2 '-dimethylene-two (6-Alpha-Methyl-benzyl-paracresol); 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); triethylene glycol-N-pair-3-(3-tertiary butyl-4-hydroxy-5-aminomethyl phenyl) propionic ester; 1; the 6-hexanediol is two, and [3-(3; the 5-di-tert-butyl-hydroxy phenyl) propionic ester]; two [the 2-tert-butyl group-4-methyl 6-(the 3-tert-butyl group-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-tert-butyl group-metacresol); 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-t-butyl-butyl benzene 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) propiono] hydrazine; 1,1,3-three (2-methyl-4-hydroxyl-5-tert-butyl-phenyl) butane; 1; 3; 5-trimethyl-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-tert-butyl group-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-3-(3; the 5-di-tert-butyl-hydroxy phenyl) propionic ester] methane; triethylene glycol-N-pair-3-(3-tertiary butyl-4-hydroxy-5-aminomethyl phenyl) propionic ester; triethylene glycol-N-pair-3-(3-tertiary butyl-4-hydroxy-5-aminomethyl phenyl) acetic acid esters; 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-3-(3-tertiary butyl-4-hydroxy-5-aminomethyl phenyl) propionic ester] methane; 1; 3; 5-trimethyl-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-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 antioxidant can use separately or will be used in combination more than 2 kinds.

Phosphorus is that stabilizing agent and hindered phenol are that antioxidant preferably cooperates any.Especially preferably cooperating phosphorus is stabilizing agent, more preferably cooperates three organophosphorus compoundss.Phosphorus is that stabilizing agent and hindered phenol are the use level of antioxidant, is benchmark with A composition 100 weight portions respectively, is 0.005～1 weight portion, is preferably 0.01～0.3 weight portion.

(i-3) ultraviolet light absorber

The resin combination that uses among the present invention can contain ultraviolet light absorber.Therefore this resin combination passes through to cooperate ultraviolet light absorber owing to also have good color tone, also can this tone of long term maintenance even use without.

As ultraviolet light absorber; particularly; for 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-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-5-sulfonic group benzophenone trihydrate (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 '-dihydroxy-4-methoxy benzophenone; 2; 2 '; 4; 4 '-tetrahydroxybenzophenone; 2; 2 '-dihydroxy-4; 4 '-dimethoxy-benzophenone; 2; 2 '-dihydroxy-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-methoxyphenyl) methane; 2-hydroxyl-4-positive 12-alkoxy benzophenone and 2-hydroxyl-4-methoxyl-2 '-carboxyl benzophenone etc.

As ultraviolet light absorber, particularly, for benzotriazole be, 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-tert-butyl group-5-aminomethyl phenyl)-5-chlorobenzotriazole, 2, [4-(1 for 2 '-di-2-ethylhexylphosphine oxide, 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 '-di-2-ethylhexylphosphine oxide (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 multipolymer of the ethene base system monomer of this monomer copolymerization, 2-(2 '-hydroxyl-5-acryloxy ethylphenyl)-2H-benzotriazole and can have the polymkeric substance etc. of 2-hydroxy phenyl-2H-benzotriazole skeleton with the multipolymer of the ethene base system monomer of this monomer copolymerization etc.

As ultraviolet light absorber, particularly, for hydroxyphenyltriazinuv system, can illustration 2-(4 for example, 6-diphenyl-1,3,5-triazines-2-yl)-the own oxygen base of 5-phenol, 2-(4,6-diphenyl-1,3,5-triazines-2-yl)-5-metoxyphenol, 2-(4,6-diphenyl-1,3,5-triazines-2-yl)-5-thanatol, 2-(4,6-diphenyl-1,3,5-triazines-2-yl)-5-propoxyl group phenol and 2-(4,6-diphenyl-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 the own oxygen base of 5-phenol become 2, the compound of 4-3,5-dimethylphenyl.

As ultraviolet light absorber, particularly, for 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-naphthylene) two (3,1-benzoxazine-4-ketone) etc.

In addition; as ultraviolet light absorber; particularly, for 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 ultraviolet light absorber of the ultraviolet 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 the 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 ultraviolet light absorber can use separately or use with the potpourri more than 2 kinds.

The content of ultraviolet light absorber is benchmark with A composition 100 weight portions, preferred 0.01～2 weight portion, and 0.02～2 weight portion more preferably, more preferably 0.03～1 weight portion is preferably 0.05～0.5 weight portion especially.

(i-4) other thermal stabilizers

In the resin combination that uses among the present invention, also can cooperate above-mentioned phosphorus is that stabilizing agent and hindered phenol are other thermal stabilizers beyond the antioxidant.These other thermal stabilizer preferably with these stabilizing agents and antioxidant in any and usefulness, preferred especially and both and usefulness.As these other thermal 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-xylene is that the lactone of representative is stabilizing agent (details of this stabilizing agent 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 corporate system), can utilize this compound.In addition, the stabilizing agent 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 corporate system.The stabilizing agent that also can utilize this to be pre-mixed among the present invention.Lactone is the use level of stabilizing agent, is benchmark with A composition 100 weight portions, is preferably 0.0005～0.05 weight portion, more preferably 0.001～0.03 weight portion.

In addition, as other stabilizing agents, can illustration pentaerythrite four (3-mercaptopropionic acid ester), pentaerythrite four (3-lauryl thiopropionate) and glycerine-3-stearyl thiopropionate etc. contain the stabilizing agent of sulphur.This stabilizing agent is effective especially when resin combination is applied to rotational forming.This contains the use level of the stabilizing agent of sulphur, is benchmark with A composition 100 weight portions, is preferably 0.001～0.1 weight portion, more preferably 0.01～0.08 weight portion.

(ii) release agent

The resin combination that uses among the present invention, throughput rate when improving its moulding, improve the dimensional accuracy of moulding product, can also contain known release agents such as fatty acid ester, polyolefin wax, organo-silicon compound, fluorine compounds (to gather the fluorocarbon oil etc. that fluoro-alkyl ether is representative), paraffin, beeswax.The resin combination that uses among the present invention, owing to have good flowability, it is good therefore to obtain pressure propagation, is out of shape uniform moulding product.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 resin combination of above-mentioned special component.

This fatty acid ester is the ester of aliphatics alcohols and fatty carboxylic acids.This aliphatic alcohol can be 1 yuan of alcohol, also can be the polyvalent alcohol more than 2 yuan.In addition, this pure carbon number is preferably 3～32, and more preferably 5～30.On the other hand, preferably carbon number 3～32, the more preferably aliphatic carboxylic acid of carbon number 10～30 of aliphatic carboxylic acid.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.Acid number in the fatty acid ester 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, carbon number 3～60 or multipolymer or ethene and carbon number 3～60.This molecular weight is the number-average molecular weight that adopts GPC (gel permeation chromatography) method to convert and measure with polystyrene standard.The upper limit of this number-average molecular weight more preferably 6000, more preferably 3000.The carbon number 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 carbon number 3～60.The ratio of the alpha-olefin of carbon number 3～60 is preferably 20 moles below the %, more preferably 10 moles below the %.As so-called Tissuemat E, the commercially available product of preferred utilization.

The content of above-mentioned release agent is benchmark with A composition 100 weight portions, preferred 0.005～5 weight portion, more preferably 0.01～4 weight portion, more preferably 0.02～3 weight portion.

(iii) dye pigment

The resin combination that uses among the present invention also contains the various pigment that dye, and the moulding product that embody various designability can be provided.As dying pigment, can enumerate perylene series pigments, coumarin series dyestuff, thioindigo based dye, anthraquinone based dye, thioxanthones based dye, ferrocyanide, 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 obtains more good metal color.As metallic pigments, preferred aluminium powder.In addition, by cooperating fluorescer, luminous fluorescent dye outside it, can give the better design effect that produces illuminant colour.

As the fluorescent dye that uses among the present invention (comprising fluorescer), for example can enumerating, coumarin series fluorescent dye, chromene are that fluorescent dye, perylene are that fluorescent dye, anthraquinone are that fluorescent dye, thioindigo are that fluorescent dye, xanthene are that fluorescent dye, xanthone are that fluorescent dye, thioxanthene are that fluorescent dye, thioxanthones are that fluorescent dye, thiazine are that fluorescent dye and diamido stibene are fluorescent dye etc.Wherein, few coumarin series fluorescent dye, the chromene of deterioration the during processing and forming of good, the polycarbonate resin of preferred thermotolerance is that fluorescent dye and perylene are fluorescent dye.

The above-mentioned content that dyes pigment is benchmark with A composition 100 weight portions, preferred 0.00001～1 weight portion, more preferably 0.00005～0.5 weight portion.

The compound that (iv) has the heat ray receptivity

The resin combination that uses among the present invention can contain the compound with heat ray receptivity.As this compound, preferred illustration phthalocyanine is a near infrared ray absorption, burning system near infrared ray absorptions such as ATO, ITO, yttrium 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 fullerene 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 portions of A composition and B composition, preferred 0.0005～0.2 weight portion, more preferably 0.0008～0.1 weight portion, further preferred 0.001～0.07 weight portion.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 resin combination that uses among 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 such low-refraction of lime carbonate and their compound 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 acrylic acid crosslinked particle of μ m and organosilicon crosslinked particle that Polyorganosilsesquioande 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 cube.Preferred light diffusing agent is spherical, and its particle diameter homogeneous more is preferred more.The content of light diffusing agent is benchmark with A composition 100 weight portions, is preferably 0.005～20 weight portion, more preferably 0.01～10 weight portion, more preferably 0.01～3 weight portion.Have, light diffusing agent can will also be used more than 2 kinds again.

(vi) high reflection of light used Chinese white

In the resin combination that uses among the present invention, thereby can cooperate the high reflection of light to give the light reflecting effect with Chinese white.As this Chinese white, preferred especially titania (the particularly titania of handling with organic surface conditioning agents such as organosilicons) pigment.The high reflection of this light is benchmark with the content of Chinese white with A one-tenth subtotaling 100 weight portions, preferred 3～30 weight portions, more preferably 8～25 weight portions.Have, the high reflection of light can will also be used more than 2 kinds with Chinese white again.

(vii) antistatic agent

In the resin combination that uses among the present invention, require antistatic property sometimes, preferably contain antistatic agent this moment.As this antistatic agent, can enumerate (1) ten dialkyl benzene sulfonic acid phosphonium salt for example and be the fragrant basic sulfonic acid phosphonium salt of representative and alkane base sulfonic acid phosphonium salt etc. has machine sulfonic acid phosphonium salt and the such boron acid phosphonium salt of four fluorine boron acid phosphonium salt.The content of Gai phosphonium salt is benchmark with total 100 weight portions of A composition and B composition, is fit to preferred 0.05～5 weight portion, more preferably 1～3.5 weight portion, the further scope of preferred 1.5～3 weight portions below 5 weight portions.

As antistatic agent, for example can enumerate organic sulfonic acid alkali (great soil group) slaines 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 slaine also uses as fire retardant as previously mentioned.This slaine more specifically can illustration for example slaine, the slaine of perfluoroalkane sulfonate etc. of dodecylbenzene sulfonic acid.The content of organic sulfonic acid alkali (great soil group) slaine, becoming subtotaling 100 weight portions with A is benchmark, is fit to preferred 0.001～0.3 weight portion, more preferably 0.005～0.2 weight portion below 0.5 weight portion.Alkali metal salts such as preferred especially potassium, caesium and rubidium.

As antistatic agent, for example can enumerate organic sulfonic acid ammonium salts such as (3) alkyl sulfonic acid ammonium salt and aryl sulfonic acid ammonium salt.This ammonium salt is a benchmark with A composition 100 weight portions, is fit to below 0.05 weight portion.As antistatic agent, for example can enumerate (4) polyether ester amides such with the polymkeric substance of poly-(oxyalkylene) diol component for its constituent.This polymkeric substance is a benchmark with A composition 100 weight portions, is fit to below 5 weight portions.

(viii) other adjuvants

Can cooperate A composition such spreading agent, the photocatalyst of thermoplastic resin, rubber polymer, other flow ability modifying agents, antiseptic, whiteruss in addition in the resin combination that uses among the present invention is anti fouling 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 A composition 100 weight portions, below preferred 10 weight portions, more preferably below 5 weight portions.

(manufacturing of glass fiber-reinforced resin composition)

During resin combination that manufacturing strengthens with glass fibre, adopt arbitrary method.Can enumerate for example following method: use V-type mixing machine, Henschel mixer, mechanochemistry device, extrude premixed means such as mixer with A composition, B-1 composition with after other adjuvants fully mix arbitrarily; adopt extruding pelletization device, compound stalk forming machine (briquetting machine) etc. to carry out the granulation of this premix as required; use then with blow vent formula biaxial extruder and carry out melting mixing, use granulating machine to carry out granulation then as the melting mixing machine of representative.

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

As premixed method, when containing composition, for example can enumerate the part of this powder and the adjuvant blend of cooperation with powder morphology as the A composition, make masterbatch with the adjuvant 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 extruder, can preferably use the extruder of blow vent 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 blow vent efficiently the vacuum pump of extruder 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 extruder, 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 granulating machine 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 extruder 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 so bad generation ratio of the height circulationization of moulding and crazing (silver) by these disposal routes.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.

Lens barrel of the present invention can obtain by the pellet injection moulding that will make as mentioned above usually.In this injection moulding, not only common forming method can be used, injection compression molding, injection extrusion forming, air-auxiliary injection forming, foaming (comprising the method for injecting supercritical fluid), insert moulding, in-mould coating moulding, heat insulation mould molding, heating cooling mould molding, dual-color forming, sandwich moulding and hypervelocity injection moulding etc. rapidly can also be enumerated.In addition, moulding can be selected any in cold runner mode and the hot flow path mode.

The lens barrel that has physical strength, less anisotropy, flow characteristics and good appearance and anti-flammability simultaneously is provided thus.Promptly, according to the present invention, lens barrel is provided, this lens barrel is by forming resin combination injection moulding, this resin combination contains: resinous principle (A composition) 100 weight portions that (i) contain aromatic polycarbonate resin (A-1 composition), (ii) 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 be 1.5～8 flat cross section glass fibre (B-1 composition) 1～150 weight portion and (iii) be selected from tabular packing material (B-2 composition) and the fibrous packing material except that the B-1 composition (B-3 composition) at least a kind strengthen packing material 0～150 weight portion.

In addition, can also carry out various surface treatments to the lens barrel of making by resin combination of the present invention.Here the processing that said surface treatment is 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 surface of synthetic resin.Can use the method for using in the common polycarbonate resin.As surface treatment, particularly can the illustration hard conating, waterproof-anti-oil coating, UVA coating, infrared ray absorbing coating and metallization various surface treatments such as (evaporations etc.).

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) modulus of elasticity in static bending

Measure according to ASTM D790 (23 ℃ of condition determinations).Have, test film uses injection (mo(u)lding) machine (the system SG-150U of Sumitomo Heavy Industries) to carry out moulding under 80 ℃ of 300 ℃ of barrel temperatures, mold temperature again.

(ii) bending strength (melt run, no melt run are arranged)

Use the test film of ASTM D638I type, thereby the test film with melt run is to fill from the side gate that is arranged on the test film both sides to make melt run at the test film central portion.In addition, the test film of no melt run 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 (mo(u)lding) machine (the system SG-150U of Sumitomo Heavy Industries) to carry out moulding under 80 ℃ of 300 ℃ of barrel temperatures, mold temperature again.

(iii) weld line strength conservation rate

Form with (bending strength that melt run is arranged)/(bending strength of no melt run) * 100=weld line strength conservation rate (%) is obtained.

(iv) molding shrinkage

Short brink of moulding has the minor face 50mm of the film cast gate of thick 1.5mm, the flat board of long limit 100mm, thick 4mm, behind 23 ℃, 50%RH, 24 hours status adjustment, use the mobile flow direction of three-dimensional measurement device (the corporate system MICROPAK of Mitutoyo Mfg. Co., Ltd. 550) assay plate and the size of 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 then the anisotropy of molding shrinkage is more little and preferred.

(vi) circularity

Use the SG-150U of Sumitomo Heavy Industries make-up machine, 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 mold temperature formed body, use the system RONDCOM41A of Tokyo Micronics Inc. to measure the circularity of internal diameter.With the longest portion of the internal diameter of cylindrical molding and the difference of the length of short portion as circularity.This difference is more little, and then circularity is high more.

(vii) mobile

Use the SG-150U of Sumitomo Heavy Industries make-up machine, estimate length of flow with archimedes type helical flow mould (the thick 2mm of stream, the wide 8mm of stream).Condition is 290 ℃ of barrel temperatures, 60 ℃ of mold temperatures, injection pressure 98.1MPa.

Embodiment 1-14, comparative example 1-11

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

Use down the heated air circulation type dryers that the pellet that obtains after dry 5 hours, is used the test film of injection (mo(u)lding) machine moulding evaluation usefulness at 120 ℃.Each evaluation result is shown in table 1-table 2.

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 weigh 22400: PANLITE L-1225WP)

AS: acrylonitritrile-styrene resin (the first woolens corporate system " STAREXHF5670 " (trade name), is measured the weight-average molecular weight that converts by polystyrene standard obtain: 95000 by GPC, vinyl cyanide component content: 28.5 weight %, styrene component content: 71.5 weight %)

ABS: acrylonitrile-styrene-butadiene copolymer (Japanese I﹠amp; L corporate system " SANTAC " (trade name), bulk polymerization, the free about 80 weight % of AS component of polymer and the about 20 weight % of abs polymer composition (the insoluble gel component of acetone), butadiene rubber component content are all 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)

GFL: granular glass sheet (NHTechno corporate system Off レカ REFG-301, intermediate value mean grain size 140 μ m, the thickness 5 μ m, the epoxy that adopt the standard sieve method to measure are collecting agent)

MICA: mean grain size 250 μ m マスコバイト (woods changes into corporate system " MC-40 " (trade name))

TALC: talcum (wins Guanshan Mountain mining industry made " PVC Network トリライト TK-RC " (trade name), bulk density: 0.80g/cm ³, mean grain size: 2 μ m)

(B-3 composition)

GF: round 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)

MF: milled fiber (day eastern textile company system PFE-301S, fibre diameter: 13 μ m, Cutting Length 40 μ m, silane coupling agent are handled)

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

(other compositions)

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

CB: black masterbatch (the polystyrene resin masterbatch of carbon black 40% is contained in Gu Huacheng company more)

The invention effect

According to the present invention, can access mechanical strength, less anisotropy, mobile excellent, and with The time have the excellent lens barrel of good appearance, so the effect on the industry is very big.

Claims

1. a lens barrel is characterized in that, by resin combination injection moulding is formed, this resin combination contains:

(i) containing aromatic polycarbonate resin is that the resinous principle of A-1 composition is A composition 100 weight portions,

(ii) the mean value of the major diameter of 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 B-1 composition 1～150 weight portion, and

(iii) being selected from tabular packing material is that B-2 composition and the fibrous packing material except that the B-1 composition are at least a kind of enhancing packing material 0～150 weight portion in the B-3 composition.

2. lens barrel according to claim 1, wherein, the B-2 composition is at least a kind of tabular packing material that is selected from glass sheet, mica, graphite and the talcum.

3. lens barrel according to claim 2, wherein, the B-3 composition is that to be selected from glass fibre, glass milled fiber, wollastonite and carbon beyond the B-1 composition be at least a kind of fibrous packing material in the filler.

4. according to each described lens barrel in the claim 1～3, 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.

5. according to each described lens barrel in the claim 1～4, wherein, the average fiber of B-1 composition ratio long and fiber diameter is that length-diameter ratio is 2～120.

6. according to each described lens barrel in the claim 1～5, wherein, with respect to A-1 composition 100 weight portions, the phenylethylene resin series that resinous principle contains 1～100 weight portion is the A-2 composition.

7. lens barrel according to claim 6, wherein, phenylethylene resin series is that the A-2 composition is at least a kind of resin that is selected from polystyrene, ABS resin, AS resin and the HIPS resin.

8. according to each described lens barrel in the claim 1～7, wherein, the A composition contains the above aromatic polycarbonate resin of 50 weight %.