CN101899205B

CN101899205B - Glass fiber-reinforced resin composition

Info

Publication number: CN101899205B
Application number: CN201010188962.6A
Authority: CN
Inventors: 池松龙介
Original assignee: Teijin Chemicals Ltd
Current assignee: Teijin Ltd
Priority date: 2009-05-26
Filing date: 2010-05-25
Publication date: 2016-01-06
Anticipated expiration: 2030-05-25
Also published as: CN101899205A; JP2010275346A

Abstract

The present invention relates to glass fiber-reinforced resin composition.Its object is to provide with the thermoplastic resin of flat cross section glass fiber reinforcement for matrix, mechanical strength, the anisotropy of molding shrinkage is little, has good outward appearance and the resin combination of sliding properties.Described glass fiber-reinforced resin composition contains: (A) thermoplastic resin containing aromatic polycarbonate resin (A-1 composition) (A composition), (B) the major diameter mean value of fibre section is 10 ~ 50 μm, the mean value of the ratio (major diameter/minor axis) of major diameter and minor axis is the flat cross section glass fibre (B-1 composition) of 1.5 ~ 8 and the packing material except B-1 composition (B-2 composition), and (C) sliding imparting agent (C composition), wherein, relative to A composition 100 weight part, B-1 composition is 1 ~ 150 weight part, B-2 composition is 0 ~ 150 weight part, C composition is 0.1 ~ 30 weight part.

Description

Glass fiber-reinforced resin composition

Technical field

The present invention relates to dimensional precision and the improved glass fiber-reinforced resin composition of sliding properties.More particularly, relate to with flat cross section glass fiber reinforcement containing the thermoplastic resin of polycarbonate resin for matrix, mechanical strength, and the anisotropy of molding shrinkage is little, also has good outward appearance and the glass fiber-reinforced resin composition of sliding properties simultaneously.

Background technology

With the thermoplastic resin of glass fiber reinforcement due to physical strength, excellent in workability, be therefore widely used.Particularly polycarbonate resin, due to the excellent specific property that physical strength, dimensional stability, flame retardant resistance are such, uses in numerous purposes such as mechanical part, trolley part, elec-tric-electronic parts, office equipment part.

At present, the position of sliding properties is needed in these purposes, widely use the method to the products formed coating lubricating grease obtained, slip application all the time, or be used in the aromatic polycarbonate resin with glass fiber reinforcement the method coordinated with the resin combination of the sliding imparting material that is representative such as fluoro-resin, polyvinyl resin and alkene wax.

On the other hand, in aromatic polycarbonate resin, coordinated the resin combination (with reference to patent documentation 1) of glass fibre, although physical strength, excellent rigidity, there is the anisotropic shortcoming producing molding shrinkage because of the orientation of fiber.When using in the products formeds such as the precision mechanical part such as camera component, office equipment part in recent years, need the glass fiber-reinforced resin composition of mechanical strength, less anisotropy, said composition can not meet above-mentioned characteristic.

The improved poly carbonate resin composition of warpage properties be made up of aromatic polycarbonate resin and specific non-round fiber and tabular packing material is known (with reference to patent documentation 2).But mobility, the outward appearance of this resin combination are not enough.

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

The resin combination be made up of aromatic polycarbonate resin and the glass filler and various filler with specific sectional shape is known (with reference to patent documentation 5).

But, although the anisotropy of physical strength, rigidity, molding shrinkage is excellent in this publication, do not meet enough sliding properties.

Patent documentation 1: Japanese Unexamined Patent Publication 2004-256581 publication

Patent documentation 2: Japanese Unexamined Patent Publication 6-207089 publication

Patent documentation 3: Japanese Unexamined Patent Publication 8-20694 publication

Patent documentation 4: Japanese Unexamined Patent Publication 2003-82228 publication

Patent documentation 5: Japanese Unexamined Patent Publication 2007-186571 publication

Summary of the invention

In view of the foregoing, the object of the present invention is to provide with flat cross section glass fiber reinforcement containing the resin combination of polycarbonate resin for matrix, mechanical strength, the anisotropy of molding shrinkage is little, has good outward appearance and the resin combination of sliding properties.The present inventor furthers investigate to achieve these goals repeatedly, found that by utilizing glass fibre and the sliding imparting agent with specific sectional shape, can realize this object, carrying out further furtheing investigate thus completing the present invention.

According to the present invention, above-mentioned problem is realized by following glass fiber-reinforced resin composition, this glass fiber-reinforced resin composition contains: (A) thermoplastic resin containing aromatic polycarbonate resin (A-1 composition) (A composition), (B) the major diameter mean value of fibre section is 10 ~ 50 μm, the mean value of the ratio (major diameter/minor axis) of major diameter and minor axis is the flat cross section glass fibre (B-1 composition) of 1.5 ~ 8 and the packing material except B-1 composition (B-2 composition), and (C) sliding imparting agent (C composition), wherein, relative to A composition 100 weight part, B-1 composition is 1 ~ 150 weight part, B-2 composition is 0 ~ 150 weight part, C composition is 0.1 ~ 30 weight part.

Below, details of the present invention is described further.

(A composition: thermoplastic resin)

(A-1 composition: aromatic polycarbonate resin)

The aromatic polycarbonate resin used in the thermoplastic resin of A-1 composition in the present invention, makes dihydric phenol and carbonate precursor react and obtain.As an example of reaction method, interfacial polymerization, melt transesterification process, the solid phase ester-interchange method of polycarbonate prepolymer thing and the ring-opening polymerization method etc. of cyclic carbonate compound can be enumerated.

As the typical example of the dihydric phenol wherein used, Resorcinol can be enumerated, Resorcinol, 4,4 '-xenol, two (4-hydroxy phenyl) ethane of 1,1-, two (4-hydroxy phenyl) propane (common name dihydroxyphenyl propane) of 2,2-, two (the 4-hydroxy-3-methyl phenyl) propane of 2,2-, two (4-hydroxy phenyl) butane of 2,2-, two (4-the hydroxy phenyl)-1-diphenylphosphino ethane of 1,1-, 1,1-bis(4-hydroxyphenyl) cyclohexane, two (4-hydroxy phenyl)-3,3, the 5-trimethyl-cyclohexanes of 1,1-, two (4-hydroxy phenyl) pentane of 2,2-, 4,4 '-(to phenylenediisopropylidene) biphenol, 4,4 '-(metaphenylene two isopropylidene) biphenol, two (4-the hydroxy phenyl)-4-normenthane of 1,1-, two (4-hydroxy phenyl) oxygen ether, two (4-hydroxy phenyl) thioether, two (4-hydroxy phenyl) sulfoxide, two (4-hydroxy phenyl) sulfone, two (4-hydroxy phenyl) ketone, two (4-hydroxy phenyl) ester, two (4-hydroxy-3-methyl phenyl) thioether, two (4-hydroxy phenyl) fluorenes of 9,9-and two (the 4-hydroxy-3-methyl phenyl) fluorenes of 9,9-etc.Preferred dihydric phenol is two (4-hydroxy phenyl) alkane, wherein from shock resistance aspect, particularly preferably dihydroxyphenyl propane, general.

In the present invention, except the polycarbonate of the dihydroxyphenyl propane system as general polycarbonate, the special polycarbonate using other dihydric phenols to manufacture can also be used as A composition.

Such as, as part or all of dihydric phenol composition, employ 4, 4 '-(metaphenylene two isopropylidene) biphenol (below sometimes referred to as " BPM "), 1, 1-bis(4-hydroxyphenyl) cyclohexane, 1, two (the 4-hydroxy phenyl)-3 of 1-, 3, 5-trimethyl-cyclohexane (below sometimes referred to as " 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 (below sometimes referred to as " BCF ") of 9-is suitable for the dimensional change to causing because of water suction, the purposes that the requirement of morphological stability is strict especially.These dihydric phenols except BPA, preferably use more than 5 % by mole of the dihydric phenol composition entirety forming this polycarbonate, particularly preferably more than 10 % by mole.

Particularly when require high rigidity and better hydrolytic resistance, form the copolymerization polycarbonate that the A composition of resin combination is particularly preferably following (1) ~ (3).

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

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

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

These special polycarbonate can be used alone, and also suitably can mix two or more and use.In addition, also can be used in combination by them and general bisphenol A polycarbonate.

For method for making and the characteristic of these special polycarbonate, such as, be recorded in detail in Japanese Unexamined Patent Publication 6-172508 publication, Japanese Unexamined Patent Publication 8-27370 publication, Japanese Unexamined Patent Publication 2001-55435 publication and Japanese Unexamined Patent Publication 2002-117580 publication etc.

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

I () water-intake rate is 0.05 ~ 0.15%, preferably 0.06 ~ 0.13%, and Tg is the polycarbonate of 120 ~ 180 DEG C, or

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

At this, the water-intake rate of polycarbonate is the discoideus test film using diameter 45mm, thickness 3.0mm, measures moisture rate and the value that obtains according to ISO62-1980 in the water of 23 DEG C after flooding 24 hours.In addition, Tg (second-order transition temperature) is the value measuring according to IJSK7121 differential scanning calorimeter (DSC) and try to achieve.

As carbonate precursor, use carboxylic acid halides, carbonic diester or haloformate (Ha ロホ Le メ mono-ト) etc., the bishaloformate etc. of carbonyl chloride, diphenyl carbonate or dihydric phenol can be enumerated particularly.

When adopting interfacial polymerization to manufacture aromatic polycarbonate resin by above-mentioned dihydric phenol and carbonate precursor, catalyzer, end terminator, antioxidant etc. for preventing dihydric phenol to be oxidized can be used as required.In addition, aromatic polycarbonate resin of the present invention comprise the multi-functional aromatics copolymerization more than by trifunctional branched polycarbonate resin, by the polyestercarbonate resins of two functionality carboxyl acid copolymers of aromatic series or aliphatics (comprising ester ring type), by the copolymerized panlite of two functionality alcohol (comprising ester ring type) copolymerization and by the polyestercarbonate resins of described two functionality carboxylic acids copolymerization together with two functionality alcohol.In addition, can be the mixture mixed by gained aromatic polycarbonate resin of more than two kinds.

Branched polycarbonate resin can give the anti-dropping performance of glass fiber-reinforced resin composition of the present invention etc.As multi-functional the aromatics more than trifunctional used in this branched polycarbonate resin, Phloroglucinol monomethyl ether can be enumerated, 2,3 ', 4,5 ', 6-penta hydroxy group biphenyl, or 4,6-dimethyl-2,4,6-tri-(4-hydroxy phenyl) heptene-2, 2,4,6-trimethylammonium-2,4,6-tri-(4-hydroxy phenyl) heptane, 1,3,5-tri-(4-hydroxy phenyl) benzene, 1,1,1-tri-(4-hydroxy phenyl) ethane, 1,1,1-tri-(3,5-dimethyl-4-hydroxy phenyl) ethane, two (2-hydroxy-5-methyl base the benzyl)-4-methylphenol of 2,6-, 4-{4-[1,1-two (4-hydroxy phenyl) ethyl] benzene } triphenol such as-alpha, alpha-dimethylbenzyl phenol, four (4-hydroxy phenyl) methane, two (2,4-dihydroxy phenyl) ketone, Isosorbide-5-Nitrae-bis-(4,4-dihydroxyl trityl group) benzene, or trimellitic acid, pyromellitic acid, benzophenone tetracarboxylic and their acyl chlorides etc., wherein preferred 1,1,1-tri-(4-hydroxy phenyl) ethane, 1,1,1-tri-(3,5-dimethyl-4-hydroxy phenyl) ethane, particularly preferably 1,1,1-tri-(4-hydroxy phenyl) ethane.

The structural unit derived by multi-functional aromatics in branching polycarbonate, in the structural unit derived by dihydric phenol and the total 100 % by mole of structural unit derived by this multi-functional aromatics, it is 0.01 ~ 1 % by mole, be preferably 0.05 ~ 0.9 % by mole, be particularly preferably 0.05 ~ 0.8 % by mole.

In addition, particularly when melt transesterification process, sometimes branched structure unit can be produced as side reaction, about the amount of this branched structure unit, with the total 100 % by mole of the structural unit derived by dihydric phenol, be 0.001 ~ 1 % by mole, be preferably 0.005 ~ 0.9 % by mole, be particularly preferably 0.01 ~ 0.8 % by mole.Should illustrate, the ratio of this branched structure can be passed through ¹h-NMR measures and calculates.

Aliphatic two functionality carboxylic acids, preferred alpha, omega-dicarboxylic acid.As aliphatic two functionality carboxylic acids, the such as alicyclic dicarboxylic acid such as straight chain saturated aliphatic dicarboxylic acids and cyclohexane cyclohexanedimethanodibasic such as sebacic acid (decane diacid), dodecanedioic acid, tetradecane diacid, octadecane diacid, octadecane dicarboxylic acid preferably can be enumerated.As two functionality alcohol, more preferably alicyclic diols, such as cyclohexanedimethanol, cyclohexanediol and Tricyclodecane Dimethanol etc. can be illustrated.

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

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

When manufacturing glass fiber-reinforced resin composition of the present invention, the viscosity-average molecular weight (M) of aromatic polycarbonate resin is not particularly limited, and is preferably 1 × 10 ⁴~ 5 × 10 ⁴, be more preferably 1.4 × 10 ⁴~ 3 × 10 ⁴, more preferably 1.4 × 10 ⁴~ 2.4 × 10 ⁴.

1 × 10 is less than for viscosity-average molecular weight ⁴aromatic polycarbonate resin, good mechanical characteristics cannot be obtained.On the other hand, by viscosity-average molecular weight more than 5 × 10 ⁴the resin combination that obtains of aromatic polycarbonate resin, from the viewpoint poor universality of poor fluidity during injection molding.

Further, the resin that above-mentioned aromatic polycarbonate resin can be the aromatic polycarbonate resin of mixing viscosity-average molecular weight outside above-mentioned scope and obtain.Particularly viscosity-average molecular weight exceedes above-mentioned scope (5 × 10 ⁴) aromatic polycarbonate resin, the entropy-elasticity of resin improves.Consequently, sometimes by the foaming with gas that strengthens when resin material is used for structural member molding and foaming, good molding processibility is presented.The improvement of this molding processibility is better than above-mentioned branching polycarbonate.As preferred scheme, A composition can also be used to be 7 × 10 by viscosity-average molecular weight ⁴~ 3 × 10 ⁵aromatic polycarbonate resin (A-1-1 composition) and viscosity-average molecular weight be 1 × 10 ⁴~ 3 × 10 ⁴aromatic polycarbonate resin (A-1-2 composition) composition, its viscosity-average molecular weight is 1.6 × 10 ⁴~ 3.5 × 10 ⁴aromatic polycarbonate resin (A-1 composition) (hereinafter sometimes referred to " aromatic polycarbonate resin containing high molecular weight components ").

Should containing in the aromatic polycarbonate resin (A-1 composition) of high molecular weight components, the molecular weight of A-1-1 composition is preferably 7 × 10 ⁴~ 2 × 10 ⁵, be more preferably 8 × 10 ⁴~ 2 × 10 ⁵, more preferably 1 × 10 ⁵~ 2 × 10 ⁵, be particularly preferably 1 × 10 ⁵~ 1.6 × 10 ⁵.In addition, the molecular weight of A-1-2 composition is preferably 1 × 10 ⁴~ 2.5 × 10 ⁴, be more preferably 1.1 × 10 ⁴~ 2.4 × 10 ⁴, more preferably 1.2 × 10 ⁴~ 2.4 × 10 ⁴, be particularly preferably 1.2 × 10 ⁴~ 2.3 × 10 ⁴.

Above-mentioned A-1-1 composition and A-1-2 composition can mix with various ratio by the aromatic polycarbonate resin (A-1 composition) containing high molecular weight components, adjust to the molecular weight ranges of satisfied regulation and obtain.Preferably in A-1 composition 100 % by weight, A-1-1 composition is 2 ~ 40 % by weight, and more preferably A-1-1 composition is 3 ~ 30 % by weight, and preferably A-1-1 composition is 4 ~ 20 % by weight further, and particularly preferably A-1-1 composition is 5 ~ 20 % by weight.

In addition, as the preparation method of A-1 composition, (1) can be enumerated and A-1-1 composition and A-1-2 composition are polymerized independently of one another and the method that they are mixed; (2) use the method showing the aromatic polycarbonate resin at multiple polymkeric substance peak in that be representative with the method shown in Japanese Unexamined Patent Publication 5-306336 publication, that manufacture adopts GPC method to obtain in same system graph of molecular weight distribution, the condition making this aromatic polycarbonate resin meet A-1 composition of the present invention carries out the method manufactured; (3) method etc. that the aromatic polycarbonate resin this manufacture method of employing (manufacturing processs of (2)) obtained mixes with the A-1-1 composition manufactured in addition and/or A-1-2 composition.

In the present invention, said viscosity-average molecular weight is obtained as follows: first, by solution aromatic copolycarbonate 0.7g being dissolved in methylene dichloride 100ml gained at 20 DEG C, uses Ostwald viscosimeter to obtain the specific viscosity (η calculated by following formula _sP),

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

[t ₀be the drippage number of seconds of methylene dichloride, t is the drippage number of seconds of sample solution]

By the specific viscosity (η tried to achieve _sP), calculate viscosity-average molecular weight M by 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

Further, the calculating of viscosity-average molecular weight of aromatic polycarbonate resin adopts following main points to carry out in glass fiber-reinforced resin composition of the present invention.That is, the methylene dichloride of said composition with its 20 ~ 30 times of weight is mixed, the soluble ingredient in composition is dissolved.By diatomite filtration, this soluble ingredient is taken out.Then the solvent in the solution obtained is removed.By fully dry for the solid after desolventizing, obtain the solid of the composition that will be dissolved in methylene dichloride.Be dissolved in by by this solid 0.7g the solution obtained in methylene dichloride 100ml, obtain the specific viscosity of 20 DEG C as described above, calculate viscosity-average molecular weight M as described above by this specific viscosity.

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

(A-2 composition: phenylethylene resin series)

The phenylethylene resin series used in the thermoplastic resin of A-2 composition of the present invention has thermotolerance and the flame retardant resistance of good molding processibility and appropriateness, is therefore to keep the balance of these characteristics and preferred thermoplastic resin.

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

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

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

As can with the rubber polymer of above-mentioned aromatic ethenyl compound copolymerization, can polyhutadiene be enumerated, polyisoprene, diene interpolymer (random copolymers of such as styrene butadiene and segmented copolymer, acrylonitrile butadiene copolymer, and the multipolymer etc. of (methyl) alkyl acrylate and divinyl), multipolymer (the such as ethylene-propylene random copolymer and segmented copolymer of ethene and alpha-olefin, the random copolymers of Ethylene/Butylene and segmented copolymer etc.), multipolymer (the such as ethylene-methyl acrylate multipolymer of ethene and esters of unsaturated carboxylic acids, with ethylene-butyl acrylate copolymer etc.), the multipolymer (such as vinyl-vinyl acetate copolymer etc.) of ethene and aliphatic vinyl compounds, ethene and propylene and non-conjugated diene terpolymer (such as ethylene-propylene-hexadiene multipolymer etc.), acrylic rubber (such as butyl polyacrylate, poly-(2-EHA), and the multipolymer etc. of butyl acrylate and 2-EHA), and silicon-type rubber (such as organopolysiloxane rubber, the IPN type rubber being become to be grouped into poly-(methyl) alkyl acrylate rubbers by organopolysiloxane rubber constituent: namely there are 2 kinds of rubber constituents and be mutually wound around and the rubber of indissociable structure, with the IPN type rubber etc. being become to be grouped into by organopolysiloxane rubber constituent and polyisobutylene rubber).

As above-mentioned phenylethylene resin series, specifically can enumerate the phenylethylene resin series such as such as polystyrene resin, HIPS resin, MS resin, ABS resin, AS resin, AES resin, ASA resin, MBS resin, MABS resin, MAS resin and SMA resin, and (hydrogenation) styrene-butadiene-styrene resin, (hydrogenation) styrene-isoprene-styrene copolymer-resin etc.Should illustrate, the sign of (hydrogenation) means to comprise do not have the resin of hydrogenation and the resin of hydrogenation.Herein, MS resin represents the copolymer resin formed primarily of methyl methacrylate and vinylbenzene, AES resin represents primarily of vinyl cyanide, the copolymer resin that ethylene-propylene rubber and vinylbenzene are formed, ASA resin represents primarily of vinyl cyanide, the copolymer resin that vinylbenzene and acrylic rubber are formed, MABS resin represents primarily of methyl methacrylate, vinyl cyanide, the copolymer resin that divinyl and vinylbenzene are formed, MAS resin represents primarily of methyl methacrylate, the copolymer resin that acrylic rubber and vinylbenzene are formed, SMA resin represents the copolymer resin formed primarily of vinylbenzene and maleic anhydride (MA).

Further, this phenylethylene resin series passes through when it manufactures to use the catalyzer such as metallocene catalyst, it can be the resin that syndiotactic polystyrene etc. has high taxis.In addition, the polymkeric substance of the narrow molecular weight distribution that the method such as living anion polymerization, radical living polymerization of employing according to circumstances also can be used to obtain and high polymkeric substance, the multipolymer of multipolymer, segmented copolymer and taxis.

Wherein, preferred acrylonitritrile-styrene resin resin (AS resin), acrylonitrile-butadiene-styrene copolymer resin (ABS resin).In addition, also can by used in combination for two or more styrenic.

The AS resin used in so-called the present invention is the thermoplastic copolymer by vinyl cyanide based compound and aromatic ethenyl compound copolymerization.As this vinyl cyanide based compound, particularly preferably vinyl cyanide can be used.In addition, as aromatic ethenyl compound, vinylbenzene and alpha-methyl styrene can preferably be used.As the ratio of composition each in AS resin, when being 100 % by weight with entirety, vinyl cyanide based compound is 5 ~ 50 % by weight, and be preferably 15 ~ 35 % by weight, aromatic ethenyl compound is 95 ~ 50 % by weight, is preferably 85 ~ 65 % by weight.In addition, in these vinyl compounds can also above-mentioned record used in combination can other vinyl compounds of copolymerization, they containing less than 15 % by weight in proportional preferably AS resinous principle.In addition, the initiator used in reaction, chain-transfer agent etc. can use existing known various material as required.

This AS resin can adopt any one the method manufacture in mass polymerization, suspension polymerization, letex polymerization, but preferably adopts mass polymerization.In addition, the method for copolymerization can be any one in one section of copolymerization or multistage copolymerization.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 measures as follows, that is, precision weighing AS resin 0.25g, was dissolved in dimethyl formamide 50ml with 2 hours, uses Ubbelohde viscometer measure the solution obtained under the environment of 30 DEG C and obtain.Further, the time that flows down of viscometer use solvent is the viscometer of 20 ~ 100 seconds.Reduced viscosity flows down number of seconds (t by solvent ₀) and the number of seconds (t) that flows down of solution obtain according to following formula.

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

If reduced viscosity is less than 0.2dl/g, then impact reduction, if more than 1.0dl/g, then mobility is deteriorated.

The ABS resin used in so-called the present invention, be vinyl cyanide based compound and aromatic ethenyl compound graft polymerization are obtained to diene series rubber composition thermoplastic graft copolymer, and the mixture of multipolymer of vinyl cyanide based compound and aromatic ethenyl compound.As the diene series rubber composition forming this ABS resin, the second-order transition temperatures such as such as polyhutadiene, polyisoprene and styrene-butadiene copolymer can be used to be the rubber of less than-30 DEG C, its ratio is preferably 5 ~ 80 % by weight in ABS resin composition 100 % by weight, be more preferably 8 ~ 50 % by weight, be particularly preferably 10 ~ 30 % by weight.As the vinyl cyanide based compound being grafted to diene series rubber composition, particularly preferably vinyl cyanide can be used.In addition, as the aromatic ethenyl compound being grafted to diene series rubber composition, vinylbenzene and alpha-methyl styrene can particularly preferably be used.This is grafted to the ratio of the composition of diene series rubber composition, in ABS resin composition 100 % by weight preferably 95 ~ 20 % by weight, is particularly preferably 50 ~ 90 % by weight.In addition, relative to the total amount 100 % by weight of this vinyl cyanide based compound and aromatic ethenyl compound, preferred vinyl cyanide based compound is 5 ~ 50 % by weight, and aromatic ethenyl compound is 95 ~ 50 % by weight.In addition, for a part for the above-mentioned composition be grafted on diene series rubber composition, also can (methyl) used in combination methyl acrylate, ethyl propenoate, maleic anhydride, N substituted maleimide amine etc., they in ABS resin composition, be preferably 15 % by weight below containing proportional.In addition, the initiator used in reaction, chain-transfer agent, emulsifying agent etc. can use existing known various material as required.

In ABS resin of the present invention, rubber size preferably 0.1 ~ 5.0 μm, is more preferably 0.15 ~ 1.5 μm, is particularly preferably 0.2 ~ 0.8 μm.The distribution of this rubber size can be used to be the rubber particles of single distribution and size distribution be more than 2 peaks have in the rubber particles at multiple peak any one, can also be the rubber particles that rubber particles forms single-phase in its form, also can be by having containing containing mutually the rubber particles containing (salami) structure around rubber particles.

In addition, ABS resin contains and is not grafted to vinyl cyanide based compound on diene series rubber composition and aromatic ethenyl compound is all the time known, also can containing the free component of polymer produced during this polymerization in ABS resin of the present invention.The reduced viscosity of this free multipolymer formed by vinyl cyanide based compound and aromatic ethenyl compound, the reduced viscosity (30 DEG C) that the method that employing is recorded above is obtained is 0.2 ~ 1.0dl/g, is more preferably 0.3 ~ 0.7dl/g.

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

This ABS resin can adopt any method manufacture in mass polymerization, suspension polymerization, letex polymerization.Particularly preferably adopt mass polymerization manufacture.In addition, as this mass polymerization, the continuous bulk polymerization method (so-called Mitsui east platen press) recorded in the continuous bulk polymerization method (so-called toray method) that can record in Exemplary chemical industry No. 6th, the 48th volume 415 pages (1984) typically and No. 6th, chemical industry the 53rd volume 423 pages (1989).As ABS resin of the present invention, be applicable to using any ABS resin.In addition, the method for copolymerization can be one section of copolymerization, also can be multistage copolymerization.In addition, the blended blend having vinyl compound polymer aromatic ethenyl compound and the other copolymerization of vinyl cyanide based component obtained in the ABS resin adopting this manufacturing process to obtain can be also preferably used in.

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

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

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

The glass fibre used as B-1 composition of the present invention is flat cross section glass fibre.As flat cross section glass fibre of the present invention, be the major diameter mean value of fibre section be 10 ~ 50 μm, be preferably 15 ~ 40 μm, be more preferably 20 ~ 35 μm, the mean value of the ratio (major diameter/minor axis) of major diameter and the minor axis glass fibre that is 1.5 ~ 8, is preferably 2 ~ 6, is more preferably 2.5 ~ 5.When the mean value employing the ratio of major diameter and minor axis is the flat cross section glass fibre of this scope, compared with employing when this mean value is less than the non-circular section fiber of 1.5, anisotropy is greatly improved, and significantly can improve flame retardant resistance.The raising of this flame retardant resistance is considered to caused by following reason: on products formed surface, the face, long limit of flat cross section glass fibre and products formed surface orientation abreast, thus, except the oxygen barriering effect that resin carbonation tunicle during burning produces, the oxygen barriering effect that flat cross section glass fibre produces more effectively plays a role than circular-section fibers.In addition, flattened, except flat, also comprises ellipticity, eyebrow shape and tri-lobed, or the non-circular cross sectional shape of similar shape.Wherein, from the improvement aspect of physical strength, less anisotropy, preferred flat shape.In addition, the average fiber of flat cross section glass fibre ratio (aspect ratio) that is long and fiber diameter is preferably 2 ~ 120, be more preferably 2.5 ~ 70, more preferably 3 ~ 50, ratio as fruit fiber length and fiber diameter is less than 2, then the raising effect of physical strength is little, if the ratio of fruit fiber length and fiber diameter is more than 120, then anisotropy becomes large, and appearance of molded articles also worsens.The fiber diameter of this flat cross section glass fibre refer to flattened is scaled of the same area positive circular time the equal Fibre diameter of number.In addition, so-called average fiber is long, refers to that the equal fiber of number in glass fiber-reinforced resin composition of the present invention is long.Should illustrate, this number equal fiber length carries out observation by light microscope, the value adopting image analysis apparatus to calculate by the image obtained to the residue of the packing material obtained by process such as high temperature ashing, the dissolving that utilizes solvent to carry out of products formed and the decomposition that utilizes chemical reagent to carry out.And, being be standard when calculating this value with Fibre diameter, adopting the value that not computational length obtains in the method for this substandard flat cross section glass fibre.

The various glass compositions that it is representative that the glass composition of above-mentioned flat cross section glass fibre is suitable for A glass, C glass and E glass etc., are not particularly limited.This glass filled material can contain TiO as required ₂, SO ₃and P ₂o ₅deng composition.Wherein more preferably E glass (non-alkali glass).From physical strength raising aspect, this flat cross section glass fibre preferably implements surface treatment with known surface treatment agent such as silane coupling agent, titanate coupling agent or aluminate coupling agent etc.In addition, preferably boundling process has been carried out with ethylene series resin, phenylethylene resin series, acrylic resin, polyester based resin, epoxy system resin and polyurethane series resin etc., from physical strength aspect, particularly preferably epoxy system resin, polyurethane series resin.Through the collecting agent adhesion amount of the flat cross section glass fibre of boundling process, in flat cross section glass fibre 100 % by weight, be preferably 0.1 ~ 3 % by weight, be more preferably 0.2 ~ 1 % by weight.

The content of B-1 composition, relative to A composition 100 weight part, is 1 ~ 150 weight part, more preferably 3 ~ 120 weight parts, further preferred 5 ~ 100 weight parts.If B-1 composition is less than 1 weight part, then the reinforced effects that produces of the glass fibre such as suppression of physical strength, molding shrinkage is not enough, if more than 150 weight parts, then floats significantly at the so-called glass on products formed surface, not preferred from outward appearance aspect.

(B-2 composition: the packing material except except B-1 composition)

(tabular packing material)

As the tabular packing material used in the present invention, the terre verte system mineral etc. such as mica, talcum, clay, graphite, glass flake and montmorillonite can be illustrated.In addition, this tabular packing material comprises the tabular packing material through washing or metal oxide-coated.As tabular packing material of the present invention, be preferably selected from the tabular packing material of at least a kind in mica, talcum, glass flake and graphite, particularly preferably glass flake.The glass flake used as B-2 composition of the present invention is the plate glass filler adopting the methods such as cylinder air blast, sol-gel method to manufacture.The size of the raw material of this glass flake also can select all size according to the degree of pulverizing, classification.The median size of the glass flake used in raw material preferably 10 ~ 1000 μm, more preferably 20 ~ 500 μm, preferably 30 ~ 300 μm further.This is because the treatability of the glass flake of above-mentioned scope and molding processibility are all excellent.Usually, there is fragmentation by processing with the melting mixing of resin in plate glass packing material, its median size diminishes.The number average bead diameter of the glass flake in resin combination preferably 10 ~ 200 μm, more preferably 15 ~ 100 μm, preferably 20 ~ 80 μm further.In addition, this number average bead diameter carries out observation by light microscope, the value adopting image analysis apparatus to calculate by the image obtained to the residue of the plate glass packing material obtained by process such as high temperature ashing, the dissolving that utilizes solvent to carry out of products formed and the decomposition that utilizes chemical reagent to carry out.In addition, being be standard when calculating this value with sheet thickness, adopting the value that not computational length obtains in the method for this substandard glass flake.In addition, as thickness, preferably 0.5 ~ 10 μm, more preferably 1 ~ 8 μm, preferably 1.5 ~ 6 μm further.The glass flake with above-mentioned number average bead diameter and thickness realizes good intensity, rigidity.

As the mica that B-2 composition of the present invention uses, from guaranteeing rigidity aspect, preferred median size is pulverous mica of 10 ~ 700 μm.So-called mica is the crushed material of the silicate minerals comprising aluminium, potassium, magnesium, sodium, iron etc.Have white mica, phlogopite, biotite, micanite etc. in mica, as the mica used in the present invention, can use any one mica, but white mica being compared with phlogopite, biotite, himself is rigidity, from the preferred white mica in rigidity aspect.In addition, phlogopite, biotite compared with white mica, containing a large amount of Fe in principal constituent, therefore himself tone blackout, carry out various painted time preferred white mica.In addition, micanite (the OH base of natural golden mica being replaced into the mica of F) price is high, and Comparatively speaking white mica is favourable.Therefore, in the present invention, set out in all its bearings, preferred white mica.

In addition, as comminuting method during manufacture mica, the dry type comminuting method that former for mica stone is pulverized by useful Dry-crusher, with with Dry-crusher by after former for mica stone coarse reduction, add the grinding aids such as water, carry out main pulverizing with slurry form wet crushing mill, then carry out dewatering, dry case of wet attrition method.Further, the lower limit of the median size of mica, the median size preferably adopting Microtrack laser diffractometry to measure is more than 10 μm, on the other hand, above limits the use of the median size meter adopting oscillatory type method of sieving to measure, preferably less than 700 μm.The mica that Microtrack laser diffractometry is applicable to employing oscillatory type method of sieving 325 order throughput is more than 95 % by weight carries out.Oscillatory type method of sieving is generally used for the mica of particle diameter more than it.Oscillatory type method of sieving of the present invention is following method: first use vibration cribellum, adopt, by the standard sieve of the JIS specification of the order overlap of width of mesh, screening in 10 minutes is carried out to the mica powder 100g used, be determined at the weight of powder residual on each sieve, obtain size-grade distribution.The weight average particle diameter adopting oscillatory type method of sieving to measure the preferably scope of 50 ~ 700 μm, the scope of 50 ~ 400 μm because shock strength is excellent more preferably.The effect of this particle diameter is being particularly play well in the mica that obtains of raw material with white mica.Few more than the mica of 700 μm, and cast gate obstruction when easily producing shaping etc. is shaping bad, therefore not preferred.On the other hand, the pulverizing being less than 10 μm needs extremely many man-hours at present, therefore uneconomical.As the thickness of mica, the thickness that employing electron microscope observation can be used to survey is the mica of 0.01 ~ 10 μm.In addition, this mica can carry out surface treatment with silane coupling agent etc., also can become particulate state with collecting agent granulations such as various resin, the high-grade aliphatic esters such as polyurethane series resin.

As the talcum that B-2 composition of the present invention uses, being the flakey particle with laminate structure, chemical constitution is hydrous magnesium silicate, generally uses chemical formula 4SiO ₂3MgO2H ₂o represents, usually by 56 ~ 65 % by weight SiO ₂, the MgO of 28 ~ 35 % by weight, the H of about 5 about % by weight ₂o is formed.As other a small amount of composition, containing the Fe of 0.03 ~ 1.2 % by weight ₂o ₃, 0.05 ~ 1.5 % by weight Al ₂o ₃, the CaO of 0.05 ~ 1.2 % by weight, the K of less than 0.2 % by weight ₂o, less than 0.2 % by weight Na ₂o etc., proportion is about 2.7.The particle diameter of the talcum is here particle diameter when being 50% according to the cumulative weight percentage obtained by the size-grade distribution adopting Andreasen pipet method to measure of JISM8016 mensuration.Its particle diameter preferably 0.3 ~ 15 μm, more preferably 0.5 ~ 10 μm.In addition, manufacture method for making during this talcum about being pulverized by former stone, there is no particular restriction, and axial flow type polishing, ring abrasive method, roller can be utilized to grind method, ball milled, jet mill method and container rotary compression shear-type polishing etc.Various grading machine is preferably adopted to carry out stage treatment, the talcum that size distribution is neat to the talcum after pulverizing further.As grading machine, there is no particular restriction, can enumerate impingement intertia force classifier (variable impactor etc.), wall attachment effect utilizes type intertia force classifier (bend pipe injection etc.), centrifugal field grading machine (multi-cyclone, air classifier (microplex), dispersion separator, AccuCut, turbine classifier, ultrafine powder grading machine (turboplex), particle separator (microseparater) and ultramicro separator etc.) etc.In addition, from aspects such as its treatability, preferably this talcum is state of aggregation, as its method for making, has and utilizes the method for degassed compression, uses collecting agent to carry out the method etc. compressed.From easy and do not make unwanted collecting agent resinous principle be mixed into aspect in the present composition, particularly preferably utilize the method for degassed compression.

As the graphite that B-2 composition of the present invention uses, it is flaky graphite.Coordinate the resin combination of this flaky graphite to have good electroconductibility, there is good physical strength, less anisotropy simultaneously.The particle diameter of graphite of the present invention is the scope of 5 ~ 300 μm.This particle diameter is preferably 5 ~ 70 μm, is more preferably 7 ~ 40 μm, more preferably 7 ~ 35 μm.By meeting this scope, realize good flame retardant resistance.On the other hand, if median size is less than 5 μm, then the improvement effect of dimensional precision easily reduces, if median size is more than 300 μm, then shock resistance also slightly reduces, and the so-called graphite on products formed surface floats obviously simultaneously, therefore not preferred.Floating of this surface is because graphite comes off from products formed surface, caused by electronic unit conducting and possibility defective component.In addition, if above-mentioned preferred median size, then the outward appearance with products formed becomes good, also easily obtains the advantage of good sliding simultaneously.The fixing carbon amounts of graphite of the present invention is preferably more than 80 % by weight, is more preferably more than 90 % by weight, and more preferably more than 98 % by weight.In addition, the volatile component of graphite of the present invention is preferably less than 3 % by weight, is more preferably less than 1.5 % by weight, and more preferably less than 1 % by weight.In the present invention, the median size of graphite refers to the particle diameter becoming composition graphite self in the past, and this particle diameter refers to the particle diameter adopting laser diffractometry to obtain.In addition, only otherwise damage the characteristic of composition of the present invention, in order to increase the affinity with thermoplastic resin, surface treatment, such as epoxy finishes, carbamate process, silane coupled process and oxide treatment etc. can be implemented to the surface of graphite.

(fibrous filler material)

In composition of the present invention, as the fibrous filler material that B-2 composition uses, the known fibrous filler material except B-1 composition can be enumerated.As this fibrous filler material, preferably illustrate glass fibre, glass milled fiber, wollastonite, the carbon system filler beyond B-1 composition.This fibrous filler material also can utilize the filler having carried out the metal oxide-coated such as titanium oxide, zinc oxide, cerium oxide and silicon oxide on their surface.As carbon system filler, such as carbon fiber, washing carbon fiber, carbon milled fiber, gas-phase growth of carbon fibre and carbon nanotube, carbon black etc. can be enumerated.Carbon nanotube can be Fibre diameter 0.003 ~ 0.1 μm, individual layer, 2 layers and multilayer any one, preferred multilayer (so-called MWCNT).Wherein, from mechanical strength aspect and the aspect that good electroconductibility can be given, preferred carbon fiber and washing carbon fiber.

Above-mentioned fibrous filler material can carry out surface treatment with various surface treatment agent in advance.As this surface treatment agent, surface treatment can be carried out with the various surface treatment agent such as silane coupling agent (comprising alkylalkoxy silane, poly-organohydrogensiloxanes etc.), high-grade aliphatic ester, acid compound (such as phosphorous acid, phosphoric acid, carboxylic acid and carboxylic acid anhydride etc.) and wax.In addition, can granulation be carried out with collecting agents such as various resin, high-grade aliphatic ester and waxes and form particulate state.

The content of B-2 composition, relative to A composition 100 weight part, is 0 ~ 150 weight part, is preferably 1 ~ 150 weight part, is more preferably 3 ~ 100 weight parts, more preferably 5 ~ 75 weight parts.

(C composition: sliding imparting agent)

The sliding imparting material used as C composition of the present invention can widely use the sliding imparting material usually used in resin.At least a kind of sliding be selected from ethylene series wax, fluorine resin, fluorine system oil, silicon-type oily, silicon-type powder, polyolefin-based resins, mineral oil, synthetic oil, high-grade aliphatic ester, higher fatty acid amides and molybdenumdisulphide can be enumerated particularly and give material, from sliding aspect, at least a kind of sliding be selected from ethylene series wax, fluorine resin, fluorine system oil, oily, the silicon-type powder of silicon-type and polyolefin-based resins can be preferably used to give material.Being more preferably ethylene series wax, fluorine resin, silicon-type oil, silicon-type powder, is most preferably ethylene series wax, fluorine resin, silicon-type powder.

As the ethylene series wax used in the present invention, be preferably molecular weight be 1000 ~ 10000, the multipolymer of the alpha-olefin of Alathon or ethene and carbonatoms 3 ~ 60.This molecular weight is the number-average molecular weight adopting GPC (gel permeation chromatography) method to measure.The upper limit of number-average molecular weight is more preferably 6000, and more preferably 4000.If molecular weight is less than 1000, then the characteristic of wax is not enough.On the other hand, if molecular weight is more than 10000, be then difficult to products formed surface transport, therefore sliding easily becomes not enough.In addition, if molecular weight is more than 10000, then outward appearance is also easily deteriorated.By the ethylene series wax of above-mentioned molecular weight ranges, obtain the products formed of outward appearance, shock strength and welding strength excellence.This GPC measures by under the environment of the clean air of temperature 23 DEG C, relative humidity 50%, use and be post with ShodexAC800 and (ShodexK-805L × 2 piece), be moving phase with chloroform, take polystyrene standard as standard substance and the GPC determinator counting detector with differential refraction rate, use chloroform as developing solvent, carry out under the condition of column temperature 40 DEG C with flow 1ml/ minute.

The carbon number of alpha-olefin composition is preferably 4 ~ 50, is more preferably 5 ~ 40.As preferred concrete example, exemplary propylene, 1-butylene, 1-hexene, 4-methyl-1-pentene and 1-octene etc.Preferred ethylene series wax of the present invention is the multipolymer of the alpha-olefin of Alathon or ethene and carbonatoms 3 ~ 60.The wherein ratio of the alpha-olefin of carbonatoms 3 ~ 60 in this multipolymer, using whole Component units of multipolymer be 100 % by mole as benchmark, be preferably less than 20 % by mole, be more preferably less than 10 % by mole.

In addition, the ethylene series wax used in the present invention, is preferably 1 ~ 10 by the molecular weight distribution that weight-average molecular weight/number-average molecular weight represents, is more preferably 1.2 ~ 5, more preferably the scope of 1.5 ~ 4.If this molecular weight distribution is too wide, then make products formed surface easily produce to be clamminess because of low molecular weight compositions so bad.In addition, its density is preferably 0.880 ~ 0.965g/cm ³scope.Its lower limit is preferably 0.890, is more preferably 0.920.Easily become favourable in the sliding properties of highdensity ethylene series wax when high loading.In addition, its fusing point is preferably the scope of 80 ~ 135 DEG C, is more preferably the scope of 100 ~ 130 DEG C.In addition, the degree of branching etc. are not particularly limited.Polyolefin-wax can be mixture of more than two kinds, also can import acidic functionality, functional group containing ester bond and epoxy group(ing) isopolarity group.The preference degree of this import volume is as follows, and such as, if acidic functionality, its acid value (JISK5902) is preferably below 20mgKOH/g (more preferably below 10mgKOH/g, further preferred below 2mgKOH/g).For other functional groups, be preferably the content with degree.

Ethylene series wax of the present invention can adopt known method manufacture, can use known Z-type catalyst, philip catalyst or metallocene catalyst, adopts the polymerization manufactures such as solution polymerization, slurry polymerization and vapour phase polymerization.In addition, also by the polyolefine thermolysis of the high molecular of this manufacturing process manufacture will be adopted, or can be manufactured by the separation and purification carrying out its low molecular weight compositions.

As the fluorine resin in the present invention, low molecular weight polytetrafluoroethylene, polyvinylidene difluoride (PVDF), tetrafluoroethylene-perfluoro methyl vinyl ether copolymer, tetrafluoraoethylene-hexafluoropropylene copolymer, tetrafluoroethylene-ethylene copolymer etc. can be enumerated, all can use, wherein from sliding aspect, preferably use low molecular weight polytetrafluoroethylene.Also the situation containing a small amount of copolymer composition in this low molecular weight polytetrafluoroethylene is comprised.As low molecular weight polytetrafluoroethylene, the low molecular weight polytetrafluoroethylene used usually used as dry lubricant can be used, be preferably micronized.Measuring at employing optical transmission method makes micropowder be scattered in the method for the dispersion liquid in tetrachloroethylene, the preferred average out to of particle diameter 0.1 ~ 100 μm of micropowder.In addition, the fusing point at ptfe micropowder end, is preferably more than 320 DEG C in DSC method measures.Ptfe micropowder end easily re-unites, and therefore also have the ptfe micropowder end implementing to not easily re-unite and burn till the process such as process, they also can preferably use.Teflon resin by Daikin Industries (strain) as LubronL-5, L-2, L-7, by ASAHI-ICIFLUOROPOLYMERS (strain) as FLUONL-150J, L-169J, L-170J, L-172J, by Mitsui-Du Pont's fluorine chemistry (strain) as TLP-10F-1, sold as HostaflonTF9202, TF9205 by HoechstJapan (strain), can easily obtain.

As the fluorine system oil in the present invention, can enumerate voltalef, poly-hexafluoro propylene glycol etc., from process aspect, particularly preferably the kinematic viscosity of 20 DEG C is the fluorine system oil of below 10000cst.Fluorocarbon oil is also requiring resin combination of the present invention to be particularly suitable for during flame retardant resistance.

As the silicon-type oil in the present invention, dimethyl silicone oil, methyl phenyl silicone oil, methyl hydrogen silicone oil, ring-type dimethyl silicone oil, the dimethyl silicone oil with the functional group of reacting with aromatic copolycarbonate and methyl phenyl silicone oil, polyether modified silicon oil, high-grade aliphatic ester modified silicon wet goods can be enumerated.As this silicone oil, from process aspect, preferably the kinematic viscosity of 20 DEG C is the silicon-type oil of below 10000cst.

As the silicon-type powder in the present invention, can enumerate and make silicone oil support particulate matter in the product of inorganic Substrates, silicone resin and modified organic silicon, organo-silicone rubber.

As the polyolefin-based resins in the present invention, ldpe resin, high-density polyethylene resin, straight-chain ldpe resin etc. can be enumerated, to the degree of branching, be not particularly limited as the alpha-olefin composition of copolymer composition.In addition, manufacture method is also not particularly limited, adopt high-pressure free radical process, use the method for Z-type catalyst, use the method that magnesium chloride supports Z-type catalyst, the polyvinyl resin using any methods such as the method for metallocene catalyst to obtain, all can use.In addition, the characteristic such as molecular weight, taxis is not particularly limited.

The content of C composition, relative to A composition 100 weight part, is 0.1 ~ 30 weight part, is more preferably 0.5 ~ 20 weight part, more preferably 1 ~ 15 weight part.If C composition is less than 0.1 weight part, then sliding properties is not enough, if more than 30 weight parts, be then peeling, not preferred from outward appearance aspect.

(about other additives)

In glass fiber-reinforced resin composition of the present invention, molecular weight during in order to make forming process, tone are stablized, and can use various stablizer, releasing agent, look material.

(i) stablizer

Known various stablizer can be coordinated in glass fiber-reinforced resin composition of the present invention.As stablizer, phosphorus system stablizer, hindered phenol system antioxidant, UV light absorber and photostabilizer etc. can be enumerated.

(i-1) phosphorus system stablizer

As phosphorus system stablizer, illustrate and have phosphorous acid, phosphoric acid, phosphonous acid, phosphonic acids and their ester and tertiary phosphine etc.Wherein particularly preferably phosphorous acid, phosphoric acid, phosphonous acid and phosphonic acids, three organophosphorus compoundss and acidic phosphate ester compounds.Further, the organic group in acidic phosphate ester compounds comprises any one in a replacement, two replacements and their mixture.Any one in them is comprised too in the following exemplary compounds corresponding with this Compound Phase.

As three organophosphorus compoundss, illustrate and have trimethyl phosphite 99, triethyl phosphate, tributyl phosphate, trioctyl phosphate, tridecyl phosphate, tricresyl phosphate (dodecyl) ester, tricresyl phosphate lauryl, tricresyl phosphate stearyl ester, Tritolyl Phosphate, triphenylphosphate, trichlorophenyl phosphate, diphenyl phosphate tolyl ester, diphenyl phosphate list adjacent biphenyl ester and tricresyl phosphate (butoxyethyl group) ester etc.Wherein preferably phosphoric acid trialkyl ester.The carbon number of this trialkylphosphate is preferably 1 ~ 22, is more preferably 1 ~ 4.Particularly preferred trialkylphosphate is trimethyl phosphite 99.

As acidic phosphate ester compounds, illustrate and have acid phosphate methyl esters, acid phosphate ester, acid butyl phosphate, acid phosphate butoxyethyl, acid phosphate monooctyl ester, acid phosphate ester in the last of the ten Heavenly stems, acid phosphate lauryl, acid phosphate stearyl ester, acid phosphate grease, acid phosphate docosyl ester, acid phosphate phenyl ester, acid phosphate nonyl phenylester, acid phosphate cyclohexyl, acid phosphate phenoxy ethyl, alkoxyl group polyoxyethylene glycol acid phosphoric acid ester and dihydroxyphenyl propane phosphate ester acid etc.Wherein, carbon number be more than 10 long-chain dialkyl group phosphate ester acid effective to the raising of thermostability, the stability of this phosphate ester acid self is high, therefore preferably.

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

In addition, as other bi-ester of phosphite, can use and react with dihydric phenols and there is the compound of ring texture.Such as 2 can be enumerated, 2 '-methylene-bis (4,6-di-tert-butyl-phenyl) (2,4-di-tert-butyl-phenyl) phosphorous acid ester, 2,2 '-methylene-bis (4,6-di-tert-butyl-phenyl) (the 2-tertiary butyl-4-aminomethyl phenyl) phosphorous acid ester and 2,2-methylene-bis (4,6-di-tert-butyl-phenyl) octyl group phosphorous acid ester etc.

As phosphinate compound, four (2 can be enumerated, 4-di-tert-butyl-phenyl)-4, 4 '-biphenylen, four (2, 4-di-tert-butyl-phenyl)-4, 3 '-biphenylen, four (2, 4-di-tert-butyl-phenyl)-3, 3 '-biphenylen, four (2, 6-di-tert-butyl-phenyl)-4, 4 '-biphenylen, four (2, 6-di-tert-butyl-phenyl)-4, 3 '-biphenylen, four (2, 6-di-tert-butyl-phenyl)-3, 3 '-biphenylen, two (2, 4-di-tert-butyl-phenyl)-4-phenyl-phenyl phosphinate, two (2, 4-di-tert-butyl-phenyl)-3-phenyl-phenyl phosphinate, two (2, 6-di-n-butyl phenyl)-3-phenyl-phenyl phosphinate, two (2, 6-di-tert-butyl-phenyl)-4-phenyl-phenyl phosphinate, two (2, 6-di-tert-butyl-phenyl)-3-phenyl-phenyl phosphinate etc., preferably four (di-tert-butyl-phenyl)-biphenylen, two (di-tert-butyl-phenyl)-phenyl-phenyl phosphinate, more preferably four (2, 4-di-tert-butyl-phenyl)-biphenylen, two (2, 4-di-tert-butyl-phenyl)-phenyl-phenyl phosphinate.This phosphinate compound can with above-mentioned have to replace have the bi-ester of phosphite of the aryl of more than 2 alkyl and use.

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

As tertiary phosphine, illustrate and have triethyl phosphine, tripropyl phosphine, tributylphosphine, tri octyl phosphine, three amyl group phosphines, dimethylphenylphosphine, dibutylphenylphosphine, diphenyl methyl phosphine, phenylbenzene octyl group phosphine, triphenylphosphine, three (p-methylphenyl) phosphine, three naphthyl phosphines and diphenylbenzyl phosphine etc.Particularly preferred tertiary phosphine is triphenylphosphine.

The bi-ester of phosphite that preferred phosphorus system stablizer is three organophosphorus compoundss, acidic phosphate ester compounds and following general formula (1) represent.Particularly preferably coordinate three organophosphorus compoundss.

[changing 1]

(in formula (1), R and R ' represents the alkyl of carbon number 6 ~ 30 or the aryl of carbon number 6 ~ 30, can be the same or different each other.)

As mentioned above, as phosphinate compound, preferably four (2,4-di-tert-butyl-phenyl)-biphenylen, the stablizer being principal constituent with this phosphinate is commercially available with SandostabP-EPQ (trade mark, Clariant Inc.) and IrgafosP-EPQ (trade mark, CIBASPECIALTYCHEMICALS Inc.), all can utilize.

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

(i-2) hindered phenol system antioxidant

As hindered phenol compound, the various compounds usually coordinated in resin can be used.As this hindered phenol compound, such as alpha-tocopherol can be illustrated, butylhydroxy toluene, sinapyl alcohol, vitamin-E, octadecyl-3-(3,5-di-tert-butyl-hydroxy phenyl) propionic ester, the 2-tertiary butyl-6-(3 '-tertiary butyl-5 '-methyl-2 '-hydroxybenzyl)-4-aminomethyl phenyl acrylate, 2,6-di-t-butyl-4-(N, N-dimethylaminomethyl) phenol, 3,5-di-tert-butyl-4-hydroxyl benzyl phosphonic acid ester diethyl ester, 2,2 '-methylene-bis (4-methyl-6-tert-butylphenol), 2,2 '-methylene-bis(4-ethyl-6-t-butyl phenol), 4,4 '-methylene-bis (2,6 di t butyl phenol), 2,2 '-methylene-bis(4-methyl-6-cyclohexyl phenol), 2,2 '-dimethylene-bis-(6-Alpha-Methyl-benzyl-p-cresol), 2,2 '-ethidine-bis-(4,6-DI-tert-butylphenol compounds), 2,2 '-Ding pitches base two (4-methyl-6-tert-butylphenol), 4,4 '-Ding pitches base two (3 methy 6 tert butyl phenol), two-3-(3-tertiary butyl-4-hydroxy-5-aminomethyl phenyl) propionic ester of triglycol-N-, 1,6-hexylene glycol two [3-(3,5-di-tert-butyl-hydroxy phenyl) propionic ester], two [the 2-tertiary butyl-4-methyl-6-(the 3-tertiary butyl-5-methyl-2-hydroxybenzyl) phenyl] terephthalate, two { 2-[3-(3-tertiary butyl-4-hydroxy-5-aminomethyl phenyl) propionyloxy]-1,1-dimethyl ethyl }-2,4,8,10-tetra-oxaspiro [5, the 5] undecanes of 3,9-, 4,4 '-thiobis (the 6-tertiary butyl-meta-cresol), 4,4 '-thiobis (3 methy 6 tert butyl phenol), 2,2 '-thiobis (4-methyl-6-tert-butylphenol), two (3,5-di-tert-butyl-4-hydroxyl benzyl) thioether, 4,4 '-two-thiobis (2,6 di t butyl phenol), 4,4 '-three-thiobis (2,6 di t butyl phenol), 2,2-thiodiethylene is two-and [3-(3,5-di-tert-butyl-hydroxy phenyl) propionic ester], two (just pungent sulfenyl)-6-(4-hydroxyl-3,5-di-tert-butyl the amido)-1,3,5-triazines of 2,4-, N, N '-hexa-methylene is two-(3,5-di-t-butyl-4-hydroxyhydrocinnamamide), N, N '-bis-[3-(3,5-di-tert-butyl-hydroxy phenyl) propionyl] hydrazine, 1,1,3-tri-(2-methyl-4-hydroxyl-5-tert-butyl-phenyl) butane, 1,3,5-trimethylammonium-2,4,6-tri-(3,5-di-tert-butyl-4-hydroxyl benzyl) benzene, three (3,5-di-tert-butyl-hydroxy phenyl) isocyanuric acid ester, three (3,5-di-tert-butyl-4-hydroxyl benzyl) isocyanuric acid ester, 1,3,5-tri-(the 4-tertiary butyl-3-hydroxyl-2,6-dimethyl benzyl) isocyanuric acid ester, 1,3,5-32 [3 (3,5-di-tert-butyl-hydroxy phenyl) propionyloxy] ethyl isocyanurate, four [methylene radical-3-(3,5-di-tert-butyl-hydroxy phenyl) propionic ester] methane, two-3-(3-tertiary butyl-4-hydroxy-5-aminomethyl phenyl) propionic ester of triglycol-N-, two-3-(3-tertiary butyl-4-hydroxy-5-aminomethyl phenyl) acetic ester of triglycol-N-, 3,9-pair [2-{3-(3-tertiary butyl-4-hydroxy-5-aminomethyl phenyl) acetoxyl group }-1,1-dimethyl ethyl]-2,4,8,10-tetra-oxaspiro [5,5] undecanes, four [methylene radical-3-(3-tertiary butyl-4-hydroxy-5-aminomethyl phenyl) propionic ester] methane, 1,3,5-trimethylammonium-2,4,6-tri-(3-tertiary butyl-4-hydroxy-5-methyl-benzyl) benzene and three (3-tertiary butyl-4-hydroxy-5-methyl-benzyl) isocyanuric acid ester etc.

In above-claimed cpd, four [methylene radical-3-(3-tertiary butyl-4-hydroxy-5-aminomethyl phenyl) propionic ester] methane, octadecyl-3-(3 is preferably utilized in the present invention, 5-di-tert-butyl-hydroxy phenyl) propionic ester and 3,9-pair [2-{3-(3-tertiary butyl-4-hydroxy-5-aminomethyl phenyl) propionyloxy }-1,1-dimethyl ethyl]-2,4,8,10-tetra-oxaspiro [5,5] undecane.Particularly preferably 3,9-pairs [2-{3-(3-tertiary butyl-4-hydroxy-5-aminomethyl phenyl) propionyloxy }-1,1-dimethyl ethyl]-2,4,8,10-tetra-oxaspiro [5,5] undecanes.Above-mentioned hindered phenol system antioxidant can be used alone or two or more combinationally used.

Any one in preferred cooperation phosphorus system's stablizer and hindered phenol system antioxidant.Particularly preferably coordinate phosphorus system stablizer, more preferably coordinate three organophosphorus compoundss.The use level of phosphorus system stablizer and hindered phenol system antioxidant, respectively with A composition 100 weight part for benchmark, be preferably 0.005 ~ 1 weight part, be more preferably 0.01 ~ 0.3 weight part.

(i-3) UV light absorber

Glass fiber-reinforced resin composition of the present invention can contain UV light absorber.Resin combination of the present invention, also can this tone of long term maintenance in outdoor application even if therefore pass through combined with ultraviolet radiation absorption agent owing to also having good tone.

As UV light absorber of the present invention, particularly, in benzophenone series, such as 2 can be illustrated, 4-dihydroxy benaophenonel, ESCALOL 567, 2-hydroxyl-4-octyloxybenzophenone, 2-hydroxyl-4-behzyloxybenzophenone, 2-hydroxyl-4-methoxyl group-5-sulfonic group benzophenone, 2-hydroxyl-4-methoxyl group-5-sulfonic group three hydrogenation benzophenone, 2, 2 '-dihydroxyl-4-methoxy benzophenone, 2, 2 ', 4, 4 '-tetrahydroxybenzophenone, 2, 2 '-dihydroxyl-4, 4 '-dimethoxy-benzophenone, 2, 2 '-dihydroxyl-4, 4 '-dimethoxy-benzophenone-5-sodium sulfonate, two (5-benzoyl-4-hydroxyl-2-p-methoxy-phenyl) methane, 2-hydroxyl-4-positive 12-alkoxy benzophenone and 2-hydroxyl-4-methoxyl group-2 '-carboxyl benzophenone etc.

As UV light absorber, particularly, in benzotriazole system, such as 2-(2-hydroxy-5-methyl base phenyl) benzotriazole can be illustrated, 2-(the tertiary octyl phenyl of 2-hydroxyl-5-) benzotriazole, 2-(2-hydroxyl-3, 5-dicumylphenyl) phenyl benzotriazole, 2-(the 2-hydroxyl-3-tertiary butyl-5-aminomethyl phenyl)-5-chlorobenzotriazole, 2, 2 '-methylene-bis [4-(1, 1, 3, 3-tetramethyl butyl)-6-(2H-benzotriazole-2-base) phenol], 2-(2-hydroxyl-3, 5-di-tert-butyl-phenyl) benzotriazole, 2-(2-hydroxyl-3, 5-di-tert-butyl-phenyl)-5-chlorobenzotriazole, 2-(2-hydroxyl-3, 5-di-tert-pentyl-phenyl) benzotriazole, 2-(the tertiary octyl phenyl of 2-hydroxyl-5-) benzotriazole, 2-(2-hydroxyl-5-tert-butyl-phenyl) benzotriazole, 2-(2-hydroxyl-4-octyloxyphenyl) benzotriazole, 2, 2 '-methylene-bis (4-cumyl-6-benzotriazole phenyl), 2, 2 '-TOPOT 2,2′ p phenylenebis (1, 3-benzoxazine-4-ketone) and 2-[2-hydroxyl-3-(3, 4, 5, 6-tetrahydric phthalimide methyl)-5-aminomethyl phenyl] benzotriazole, and 2-(2 '-hydroxy-5-methyl base acryloyl-oxyethyl phenyl)-2H-benzotriazole and can with the multipolymer of the ethene base system monomer of this monomer copolymerization, 2-(2 '-hydroxyl-5-acryloyl-oxyethyl phenyl)-2H-benzotriazole and the polymkeric substance etc. of 2-hydroxy phenyl-2H-benzotriazole skeleton can be had with the multipolymer etc. of the ethene base system monomer of this monomer copolymerization.

As UV light absorber, particularly, in hydroxyphenyltriazinuv system, such as 2-(4,6-phenylbenzene-1 can be illustrated, 3,5-triazine-2-base)-5-hexyloxy-phenol, 2-(4,6-phenylbenzene-1,3,5-triazine-2-base)-5-methoxyphenol, 2-(4,6-phenylbenzene-1,3,5-triazines-2-base)-5-thanatol, 2-(4,6-phenylbenzene-1,3,5-triazine-2-base)-5-propoxy-phenol and 2-(4,6-phenylbenzene-1,3,5-triazine-2-base)-5-butoxy phenol etc.In addition, the phenyl that also can illustrate the above-mentioned exemplary compounds such as 2-(two (2, the 4-3,5-dimethylphenyl)-1,3,5-triazines-2-base of 4,6-)-5-hexyloxy-phenol becomes the compound of 2,4-3,5-dimethylphenyls.

As UV light absorber, particularly, in cyclic imide acid esters system, such as 2 can be illustrated, 2 '-TOPOT 2,2′ p phenylenebis (3,1-benzoxazine-4-ketone), 2,2 '-(4,4 '-biphenylene) two (3,1-benzoxazine-4-ketone) and 2,2 '-(2,6-naphthylidene) two (3,1-benzoxazine-4-ketone) etc.

In addition; as UV light absorber; particularly, in cyanoacrylate system, such as 1 can be illustrated; 3-pair-[(2 '-cyano group-3 '; 3 '-diphenylacryloyl) oxygen base]-2,2-two [(2-cyano group-3,3-diphenylacryloyl) oxygen base] methyl] propane and 1; 3-pair-[(2-cyano group-3,3-diphenylacryloyl) oxygen base] benzene etc.

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

In above-mentioned, in ultraviolet absorption ability, preferred benzotriazole system and hydroxyphenyltriazinuv system, in thermotolerance, tone, preferred cyclic imide acid esters system and cyanoacrylate system.Above-mentioned UV light absorber can be used alone or uses with mixture of more than two kinds.

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

(i-4) other thermo-stabilizers

In glass fiber-reinforced resin composition of the present invention, also can coordinate other thermo-stabilizers except above-mentioned phosphorus system stablizer and hindered phenol system antioxidant.These other thermo-stabilizers preferably with any one in these stablizers and antioxidant use, particularly preferably also use with both.As these other thermo-stabilizers, preference example is as the lactone system stablizer (details of this stablizer is recorded in Unexamined Patent 7-233160 publication) taking the reaction product of 3-hydroxyl-5,7-di-t-butyls-furans-2-ketone and o-Xylol as representative.This compound is commercially available as IrganoxHP-136 (trade mark, CIBASPECIALTYCHEMICALS Inc.), can utilize this compound.In addition, commercially available have the stablizer this compound and various bi-ester of phosphite and hindered phenol compound mixed.Preference example is as the IrganoxHP-2921 of above-mentioned Inc..Also this stablizer be pre-mixed can be utilized in the present invention.The use level of lactone system stablizer, with A composition 100 weight part for benchmark, is preferably 0.0005 ~ 0.05 weight part, is more preferably 0.001 ~ 0.03 weight part.

In addition, as other stablizers, the stablizer containing sulphur such as tetramethylolmethane four (3-mercaptopropionic acid ester), tetramethylolmethane four (3-lauryl thiopropionate) and glycerol-3-stearyl-thio propionic ester can be illustrated.This stablizer is effective especially when resin combination being applied to rotoforming.The use level of the stablizer of sulphur should be contained, with A composition 100 weight part for benchmark, be preferably 0.001 ~ 0.1 weight part, be more preferably 0.01 ~ 0.08 weight part.

(ii) releasing agent

Glass fiber-reinforced resin composition of the present invention in order to improve its shaping time productivity and improve the dimensional precision of products formed, except sliding imparting agent, can also the known releasing agents such as fatty acid ester, paraffin, beeswax be contained.Pressure propagation is good owing to having good mobility for glass fiber-reinforced resin composition of the present invention, can obtain being out of shape uniform products formed.On the other hand, because its molding shrinkage is low, therefore ejection resistance easily becomes large, the distortion of products formed when its result easily causes the demoulding.Above-mentioned special component be engaged in the characteristic not damaging glass fiber-reinforced resin composition when can solve this problem.

This fatty acid ester is the ester of aliphatics alcohols and fatty carboxylic acids.This fatty alcohol can be 1 yuan of alcohol, also can be the polyvalent alcohol of more than 2 yuan.In addition, the carbon number of this alcohol is preferably 3 ~ 32, is more preferably 5 ~ 30.On the other hand, the preferred carbon number of aliphatic carboxylic acid be 3 ~ 32, more preferably carbon number be the aliphatic carboxylic acid of 10 ~ 30.Wherein preferred representative examples of saturated aliphatic carboxylic.From the aspect of excellent heat stability during high temperature, fatty acid ester of the present invention is full ester (complete ester) preferably.Acid value in fatty acid ester of the present invention is preferably less than 20 (can get 0 in fact).In addition, the hydroxyl valency of fatty acid ester, the more preferably scope of 0.1 ~ 30.In addition, the iodine value of fatty acid ester preferably less than 10 (can 0 be got in fact).These characteristics can adopt the method specified in JISK0070 to try to achieve.

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

(iii) pigment is contaminated

Glass fiber-reinforced resin composition of the present invention, also containing various dye pigment, can provide the products formed embodying various designability.As the dye pigment used in the present invention, perylene series pigments, coumarin series dyestuff, thioindigo based dye, anthraquinone based dye, thioxanthone based dye, yellow prussiate, purple cyclic ketones based dye, quinoline based dye, quinacridone based dye, dioxazine based dye, isoindolinone based dye and the phthalocyanine based dye etc. such as dark purple can be enumerated.In addition, resin combination of the present invention can also obtain better metal color by complexed metal pigment.As metallic pigment, preferred aluminium powder.In addition, by coordinate white dyes, in addition can be luminous fluorescence dye, the better design effect producing illuminant colour can be given.

As the fluorescence dye used in the present invention (comprising white dyes), such as coumarin series fluorescence dye, chromene system fluorescence dye, perylene system fluorescence dye, anthraquinone system fluorescence dye, thioindigo system fluorescence dye, xanthene system fluorescence dye, xanthone system fluorescence dye, thioxanthene system fluorescence dye, thioxanthone system fluorescence dye, thiazine system fluorescence dye and diaminostilbene system fluorescence dye etc. can be enumerated.Wherein, preferred thermotolerance good and that deterioration is few when the forming process of polycarbonate resin coumarin series fluorescence dye, chromene system fluorescence dye and perylene system fluorescence dye.

The content of above-mentioned dye pigment, with A composition 100 weight part for benchmark, preferably 0.00001 ~ 1 weight part, more preferably 0.00005 ~ 0.5 weight part.

(iv) there is the compound of infrared ray absorption ability

Glass fiber-reinforced resin composition of the present invention can containing the compound with infrared ray absorption ability.As this compound, preferred illustration phthalocyanine system near infrared ray absorption, the burning system near infrared ray absorptions such as ATO, ITO, iridium oxide and ruthenium oxide, the various metallic compounds of the near-infrared absorbing 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 system near infrared ray absorption, such as the commercially available MIR-362 having Mitsui Chemicals (strain) to make, can easily obtain.As carbon filler, carbon black, graphite (comprise natural and artificial both) and soccerballene etc. can be illustrated, preferably carbon black and graphite.They can be used alone or be two kinds or more.The content of phthalocyanine system near infrared ray absorption, with A composition 100 weight part for benchmark, preferably 0.0005 ~ 0.2 weight part, more preferably 0.0008 ~ 0.1 weight part, further preferred 0.001 ~ 0.07 weight part.The content of burning system near infrared ray absorption, metal diboride system near infrared ray absorption and carbon filler, in resin combination of the present invention, the preferably scope of 0.1 ~ 200ppm (part by weight), the more preferably scope of 0.5 ~ 100ppm.

(v) light diffusing agent

In glass fiber-reinforced resin composition of the present invention, can light diffusing agent be coordinated thus give light diffusion effect.As this light diffusing agent, inorganic particles and their mixture etc. of the such low-refraction of high molecular particle, calcium carbonate can be illustrated.This high molecular particle is the known particulate of light diffusing agent as polycarbonate resin.More preferably, can to illustrate particle diameter be the vinylformic acid crosslinked particle of several μm and poly organic silicon sesquioxyalkane is the organosilicon crosslinked particle etc. of representative.The shape of light diffusing agent can illustrate spherical, disc, cylindricality and amorphous etc.Described spherical may not be full spherical, also comprise the spherical of distortion, described cylindricality comprises cubes.Preferred light diffusing agent is spherical, and its particle diameter is more evenly better.The content of light diffusing agent, with A composition 100 weight part for benchmark, is preferably 0.005 ~ 20 weight part, is more preferably 0.01 ~ 10 weight part, more preferably 0.01 ~ 3 weight part.Further, light diffusing agent may be two kinds or more.

(vi) light high reverse--bias white pigment

In glass fiber-reinforced resin composition of the present invention, light high reverse--bias white pigment can be coordinated thus give luminous reflectance effect.As this white pigment, particularly preferably titanium dioxide (particularly with the titanium dioxide of the organic surface treatment process such as organosilicon) pigment.The content of this light high reverse--bias white pigment, becomes subtotaling 100 weight part for benchmark with A, preferably 3 ~ 30 weight parts, more preferably 8 ~ 25 weight parts.Further, light high reverse--bias white pigment may be two kinds or more.

(vii) static inhibitor

In glass fiber-reinforced resin composition of the present invention, sometimes require antistatic property, now preferably containing static inhibitor.As this static inhibitor, can enumerate fragrant base sulfonic acid phosphonium salt that such as (1) ten dialkyl benzene sulfonic acid phosphonium salt is 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, with A composition 100 weight part for benchmark, is applicable below 5 weight parts, is preferably 0.05 ~ 5 weight part, is more preferably 1 ~ 3.5 weight part, more preferably the scope of 1.5 ~ 3 weight parts.

As static inhibitor, organic sulfonic acid alkali (great soil group) metal-salts such as (2) organic sulfonic acid lithium, organic sulfonic acid sodium, organic sulfonic acid potassium, organic sulfonic acid caesium, organic sulfonic acid rubidium, organic sulfonic acid calcium, organic sulfonic acid magnesium and organic sulfonic acid barium can be enumerated such as.This metal-salt as previously mentioned, also uses as fire retardant.This metal-salt, more specifically, can illustrate the metal-salt of such as Witco 1298 Soft Acid, the metal-salt etc. of perfluoroalkane sulfonate.The content of organic sulfonic acid alkali (great soil group) metal-salt, becoming subtotaling 100 weight part for benchmark with A, is applicable below 0.5 weight part, is preferably 0.001 ~ 0.3 weight part, more preferably 0.005 ~ 0.2 weight part.The particularly preferably an alkali metal salt such as potassium, caesium and rubidium.

As static inhibitor, the organic sulfonic acid ammonium salts such as (3) alkylsulphonic acid ammonium salt and aryl sulfonic acid ammonium salt can be enumerated such as.This ammonium salt for benchmark, is applicable with A composition 100 weight part below 0.05 weight part.As static inhibitor, such the containing of (4) polyether ester amides can be enumerated such as and gather the polymkeric substance of (oxidation alkylene) diol component as its constituent.This polymkeric substance for benchmark, is applicable with A composition 100 weight part below 5 weight parts.

(viii) other additives

Dispersion agent, photocatalyst system stain control agent and photochromic agent etc. that the thermoplastic resin except A-1 composition, A-2 composition, rubber polymer, other flow ability modifying agents, antiseptic-germicide, whiteruss are such can be coordinated in glass fiber-reinforced resin composition of the present invention.

As the thermoplastic resin except A composition, 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), polylactic resin, polycaprolactone resin can be illustrated.As rubber polymer, various core-shell grafting copolymer and thermoplastic elastomer can be illustrated.Other thermoplastic resins above-mentioned and rubber polymer, with A composition 100 weight part for benchmark, preferably below 20 weight parts, more preferably below 10 weight parts.

(manufacture of glass fiber-reinforced resin composition)

When manufacturing glass fiber-reinforced resin composition of the present invention, adopt arbitrary method.Can enumerate and such as use V-mixer, Henschel mixer, mechanochemistry device, extrude the premixing mechanisms such as mixing machine by A composition, B component, C composition with after other additives fully mix arbitrarily; extruding pelletization device, briquetting machine etc. is adopted to carry out the granulation of this premixture as required; then the melting mixing machine that to use with ventage formula twin screw extruder be representative carries out melting mixing, then uses tablets press to carry out the method for granulation.

In addition, the method be supplied to independently of one another by each composition with in the ventage formula twin screw extruder melting mixing machine that is representative can also be enumerated; After a part of pre-mixing of each composition, be supplied to the method etc. in melting mixing machine independently with remaining composition.As the method for a part for each composition being carried out pre-mixing, can enumerate such as in advance by the composition pre-mixing beyond A composition, then be mixed in A composition or the method be directly supplied in forcing machine.

As the method for carrying out pre-mixing, can enumerate such as, when containing the material with powder morphology as A composition, by a part for this powder and the blended masterbatch manufacturing the additive diluted with powder of the additive of cooperation, then utilize the method for this masterbatch.The method etc. supplied independently by single component from the midway of melt extruder can also be enumerated.Further, when having liquid substance in the composition coordinated, so-called priming device can be used to the supply in melt extruder or add liquid device.

As forcing machine, preferably use that have can by the forcing machine of ventage degassed to the moisture in raw material, the volatilization gas that produced by melting mixing resin.Preferred setting is used for the vacuum pump producing moisture, volatilization gas is discharged to forcing machine outside efficiently from ventage.In addition, the screen cloth be used for extruding the removings such as the foreign matter that is mixed in raw material can also be set for region before extruding dies portion, from resin combination, foreign matter be removed.As described screen cloth, wire netting, net-changing device (screenchanger), sintered metal plates (dish filter etc.) etc. can be enumerated.

As melting mixing machine, except twin screw extruder, the multiple screw extruder etc. of more than banbury mixers, mixing roller, single screw extrusion machine, 3 screw rods can also be enumerated.

The resin extruded as mentioned above, directly cuts off and carries out granulation, or with tablets press, granulation is carried out in the cut-out of this tow after forming tow.When needing to alleviate the affecting of external dust etc. during granulation, preferably the environment around forcing machine is cleaned.In the manufacture of this this pellet external, be used in polycarbonate for optical disks resin the various methods proposed, the minimizing of micro mist produced when narrowing, the leakage that suitably can carry out the distribution of shapes of pellet are cut the minimizing of thing, transport or carry and the minimizing of the bubble (bubbles of vacuum) of tow or pellet interior generation.Shaping height circulationization can be carried out by these treatment processs and reduce the proportion of the such unfavorable condition of crazing.In addition, the shape of pellet can be cylinder, square column and the general shape such as spherical, is more preferably cylinder.The diameter of this cylinder is preferably 1 ~ 5mm, is more preferably 1.5 ~ 4mm, more preferably 2 ~ 3.3mm.On the other hand, the length of cylinder is preferably 1 ~ 30mm, is more preferably 2 ~ 5mm, more preferably 2.5 ~ 3.5mm.

Glass fiber-reinforced resin composition of the present invention usually can by obtaining products formed by the pellet injection molding manufactured as mentioned above.In this injection molding, not only can enumerate common forming method, injection compression molding, the taking shape by injection and press, air-auxiliary injection forming, the foaming method of supercutical fluid (comprise inject), shaping, the heat insulation mould molding of insert moulding, in-mould coating can also be enumerated, instant heating cooling die is shaping, dual-color forming, sandwich are shaping and ultra-high speed injection molding etc.In addition, any one can selection in cold runner mode and hot runner mode shaping.The products formed that glass fiber-reinforced resin composition that is little by the anisotropy of mechanical strength, molding shrinkage, that have good sliding is formed is provided thus.Namely, according to the present invention, following products formed is provided, this products formed is by forming glass fiber-reinforced resin composition melt molding, this glass fiber-reinforced resin composition contains: (A) thermoplastic resin containing aromatic polycarbonate resin (A-1 composition) (A composition), (B) the major diameter mean value of fibre section is 10 ~ 50 μm, the mean value of the ratio (major diameter/minor axis) of major diameter and minor axis is the flat cross section glass fibre (B-1 composition) of 1.5 ~ 8 and the packing material except B-1 composition (B-2 composition), and (C) sliding imparting agent (C composition), wherein relative to A composition 100 weight part, B-1 composition is 1 ~ 150 weight part, B-2 composition is 0 ~ 150 weight part, C composition is 0.1 ~ 30 weight part.In addition, various surface treatment can also be carried out to the products formed be made up of resin combination of the present invention.Surface treatment mentioned here, be evaporation (physical vapor deposition, chemical vapor deposition etc.), plating (plating, electroless plating, melting plating etc.), application, coating, printing etc. form the process of new layer on the surface of synthetic resin, the method used in common polycarbonate resin can be applied.As surface treatment, the various surface treatments such as hard coat, waterproof-oil-repellent, ultraviolet absorbing coatings, infrared ray absorption coating and metallization (evaporation etc.) can be illustrated particularly.

According to the present invention, the mechanical strength of the products formed formed by glass fiber-reinforced resin composition of the present invention, the anisotropy of molding shrinkage is little, and there is good outward appearance and sliding properties simultaneously, therefore useful in the various uses such as mechanical part, trolley part, elec-tric-electronic parts, office equipment part, the effect in industry is very big.

Embodiment

The present inventor thinks that the solution of the present invention best has at present converged the preferable range of above-mentioned each important document, such as, is recorded in following embodiment by its typical example.Certainly, the present invention is not limited to these schemes.

Embodiment

(I) evaluation of glass fiber-reinforced resin composition

(i) bending elastic modulus: measure according to ISO178 (condition determination 23 DEG C).Further, test film uses injection moulding machine (Sumitomo hoisting machinery industry (strain) SG-150U processed) to carry out shaping at barrel temperature 310 DEG C, die temperature 100 DEG C.

(ii) molding shrinkage: a short brink is had the minor face 50mm of the film cast gate of thick 1.5mm, long limit 100mm, thick 2mm flat-plate molded, 23 DEG C, carry out 24 hours status adjustment under 50%RH after, use the flow direction of flowing and the size of right angle orientation of three-dimensional measurement device (Mitutoyo Mfg. Co., Ltd.'s (strain) MICROPAK550 processed) assay plate, obtain the molding shrinkage of flow direction and right angle orientation.Further, test film uses injection moulding machine (Sumitomo hoisting machinery industry (strain) SG-150U processed) to carry out shaping at barrel temperature 310 DEG C, die temperature 100 DEG C.

(iii) anisotropy: the flow direction of the above-mentioned molding shrinkage obtained and the ratio of right angle orientation are obtained as anisotropy.Anisotropic value is more close to 1, then the anisotropy of molding shrinkage is less, more preferably.

(iv) frictional coefficient: the reciprocal kinetic friction wear testing machine AFT-15M that use Orientec (strain) is made is as valuator device.By by circular section part, the pin-shaped test film (material: PC) that the front end that the cylinder of the hemisphere of diameter 5mm φ and diameter 5mm φ, long 30mm combines has sphere is installed to fixation side test film support.On the other hand, injection molding is adopted to make the tabular test film (cast gate is the pin-shaped cast gate of the wide 40mm × thick 1mm of the one end on inclined limit) of long 150mm × wide 150mm × thick 2mm by the resin combination of embodiment and comparative example, central part is cut as long 50mm × wide 100mm, this cutting test sheet is fixed on reciprocating pedestal.Further, test film uses injection moulding machine (Sumitomo hoisting machinery industry (strain) SG-150U processed) to carry out shaping at barrel temperature 310 DEG C, die temperature 100 DEG C.Under the state that the cylinder axis direction of pin-shaped test film is parallel with the plane normal direction of tabular test film, under the state of the load of applied load loading 9.8N, the front end land portions of above-mentioned pin-shaped test film is contacted with the planar section of the cutting test sheet of this tabular test film.Under this contact condition, 23 DEG C, in the atmosphere of relative humidity 50%RH, with the distance that to-and-fro movement one way on the speed of 25mm/s 1 straight line is planar 25mm, maximum frictional force when measuring motion 1 ~ 50 time by the dynamometry load transducer of the capacity 49N be connected with pin-shaped test film side, calculates frictional coefficient by the relation of its mean value and above-mentioned load loading.

(v) outward appearance: the square plate of the wide 50mm of visual mensuration × long 80mm × thick 2mm.Little for floating of glass, that appearance is good situation is represented with zero, by large for floating of glass, that appearance is poor situation with × represent.Further, test film uses injection moulding machine (Sumitomo hoisting machinery industry (strain) SG-150U processed) to carry out shaping at barrel temperature 310 DEG C, die temperature 100 DEG C.

[embodiment 1 ~ 18, comparative example 1 ~ 6]

With each use level that table 1, table 2 are recorded, after polycarbonate resin, phenylethylene resin series, sliding imparting agent and various additive being mixed with stirrer, use ventage formula twin screw extruder to carry out melting mixing, obtain pellet.The various additives used, with 10 ~ 100 of respective use level times of concentration for after target makes the premixture with polycarbonate resin in advance, adopt stirrer to carry out overall mixing.Ventage formula twin screw extruder uses (strain) JSW system: TEX-30XSST (completely occlusion, equidirectional rotation, 2 thread screws).Extrusion condition is the vacuum tightness 3kPa of output 20kg/h, screw rod revolution 150rpm, ventage, and in addition, extrusion temperature: be 280 DEG C from the first supplying opening to the second supplying opening is 290 DEG C from the second supplying opening to mouth mould part.Use the side feeder of above-mentioned forcing machine to supply from the second supplying opening further, strengthen packing material, remaining polycarbonate resin and additive are supplied to forcing machine from the first supplying opening.First supplying opening mentioned here is distance mouth mould supplying opening farthest, and so-called second supplying opening is the supplying opening between the mouth mould and the first supplying opening of forcing machine.

At 120 DEG C, using hot air circulation type drying machine by the pellet that obtains, after dry 5 hours, uses injection moulding machine by shaping for the test film evaluated.Each evaluation result is shown in table 1, table 2.

Each composition that mark in table 1,2 indicates is as described below.

(A composition)

PC: (Supreme Being people changes into (strain) makes the straight-chain polycarbonate resin powder of viscosity-average molecular weight 22400: PanliteL-1225WP)

AS: acrylonitritrile-styrene resin (the first woolens (strain) system " STAREXHF5670 " (trade(brand)name), GPC measures the weight-average molecular weight of the polystyrene standard conversion obtained: 95000, acrylonitrile content content: 28.5 % by weight, styrene content content: 71.5 % by weight)

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

(B component)

(B-1 composition)

HGF-1: flat cross section short glass fiber (day east weaving (strain) makes: CSG3PA-830, major diameter 27 μm, minor axis 4 μm, Cutting Length 3mm, epoxy collecting agent)

HGF-2: flat cross section short glass fiber (day east weaving (strain) makes: CSG3PA-820, major diameter 27 μm, minor axis 4 μm, Cutting Length 3mm, polyurethane series collecting agent)

(B-2 composition)

GFL: granular glass scale (the intermediate value median size that NHTechno (strain) FlekaREFG-301 processed, standard sieve method measure be 140 μm, thickness 5 μm, epoxy collecting agent)

TALC: ((strain) wins Guanshan Mountain mining industry made " VictoriliteTK-RC " (trade(brand)name), tap density: 0.80g/cm to talcum ³, median size: 2 μm)

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

MF: milled fiber (day east weaving (strain) PFE-301S processed, Fibre diameter: 13 μm, Cutting Length 40 μm, silane coupling agent process)

CF: carbon fiber (eastern nation artificial silk (strain) BESFIGHTHTA-C6-U processed, diameter 7 μm)

(C composition)

Wax: polyolefin-wax (Mitsui Chemicals (strain) HI-WAX310MP processed)

PTFE: teflon resin (Daikin Industries (strain) LubronL-5 processed)

Silicone oil: silicone oil (eastern beautiful DOW CORNING organosilicon (strain) SH-710 processed)

(other compositions)

PCL: polycaprolactone [Daicel chemical industry (strain) PlaccelH1P processed]

TMP: trimethyl phosphite 99 (large eight chemical industry (strain) TMP processed)

CB: carbon black

Table 1

Table 2

Claims

1. a glass fiber-reinforced resin composition, it contains:

(A) thermoplastic resin and A composition, containing aromatic polycarbonate resin and A-1 composition,

(B) the major diameter mean value of fibre section be 10 ~ 50 μm, major diameter and the ratio of minor axis and the mean value of major diameter/minor axis be 1.5 ~ 8 flat cross section glass fibre and B-1 composition, and fibrous filler material and B-2 composition, and

(C) sliding imparting agent and C composition, it is selected from least a kind of sliding imparting agent in ethylene series wax, fluorine system oil, oily, the silicon-type powder of silicon-type and polyolefin-based resins,

Wherein, relative to A composition 100 weight part, B-1 composition is 1 ~ 150 weight part, and B-2 composition is 1 ~ 150 weight part, and C composition is 1 ~ 15 weight part,

The fibrous filler material of described B-2 composition is selected from least a kind in glass fibre beyond B-1 composition, that do not comprise glass milled fiber, wollastonite and carbon system filler.

2. glass fiber-reinforced resin composition according to claim 1, wherein, the mean value of the major diameter of B-1 composition and the ratio of minor axis and major diameter/minor axis is 2.5 ~ 6.

3. glass fiber-reinforced resin composition according to claim 1, wherein, sliding imparting agent and C composition are number-average molecular weights is 1,000 ~ 10, the ethylene series wax of 000.

4. glass fiber-reinforced resin composition according to claim 1, wherein, thermoplastic resin and A composition are the thermoplastic resins containing phenylethylene resin series and A-2 composition 1 ~ 100 weight part relative to A-1 composition 100 weight part.

5. a synthetic resin, it is by forming shaping for the glass fiber-reinforced resin composition according to any one of Claims 1 to 4.

6. a lens barrel, it is by forming shaping for the glass fiber-reinforced resin composition according to any one of Claims 1 to 4.