CN101142277B - Resin composition - Google Patents

Abstract

The object of the present invention is to provide a polycarbonate containing aromatic polycarbonate and polyethylene terephthalate, which maintains good fluidity and has high chemical resistance, and is excellent in impact resistance, heat resistance, rigidity, and thermal stability. Resin composition of glycol ester, molded article thereof, and method for producing vehicle exterior materials. The present invention relates to a resin composition comprising 50 to 100% by weight of a resin component and 0 to 50% by weight of an inorganic filler (component D), wherein the resin component includes: (i) an aromatic compound having a specific viscosity-average molecular weight Polycarbonate (component A); and (ii) polyterephthalylene glycol having specific intrinsic viscosity (IV), amount of terminal carboxyl groups, ratio of weight average molecular weight (Mw) to number average molecular weight (Mn) (Mw/Mn) Ethylene glycol ester (B component); and (iii) the weight ratio {(A+D)/B} of the total amount of A component and D component to B component is 60/40-85/15. The present invention also relates to a method for manufacturing its molded body and vehicle exterior material.

Description

Resin combination

Technical field

The present invention relates to comprise the resin combination of aromatic copolycarbonate (below, be sometimes referred to as PC) and polyethylene terephthalate (below, be sometimes referred to as PET).In addition, the invention still further relates to the manufacture method of formed bodys such as the outside vehicle material made by said composition and outside vehicle material.

Background technology

In recent years, in automobile and OA equipment, the thin-walled property of parts and lightweight be development rapidly.For example, in automobile,, carried out using resin combination to make with of the trial of car body panel parts such as splash pan as the large component of representative for lightweight.

As the resin combination that in automobile and OA equipment, uses, the resin combination that comprises PC and PET (below, be sometimes referred to as the PC/PET alloy) is arranged.Therefore the PC/PET alloy is useful resin combination, and has proposed various improved plans owing to have the characteristic of PC of shock-resistance, excellent rigidity simultaneously and the characteristic of the PET of resistance to chemical reagents excellence.

For example, in patent documentation 1, put down in writing the automobile side protector that will comprise PC, PET, impact modified material and the injection moulding of micaceous resin combination and make.This resin combination has utilized as the shock-resistance of PC advantage, thermotolerance, and has improved its shortcoming resistance to chemical reagents with PET.But the flowability of this resin combination also has room for improvement, when the moulding large component, produces obstacle sometimes.

In addition, the resin combination that in patent documentation 2, has proposed to comprise PC and reclaimed PET.This resin combination has advantages such as the shock-resistance that derives from PC, rigidity, thermotolerance, but for forming thin-walledization and light-weighted large component, is necessary to improve the flowability of resin combination.This resin combination is owing to used recovery PET, so thermostability is insufficient.

With these similarly, various improvement proposed be the scheme of rerum natura of the resin combination of main component with aromatic polyesters such as PC and PET.For example, in order to improve welding strength, rigidity, shock-resistance, patent documentation 3 has been put down in writing a kind of resin combination, and it comprises PC, aromatic polyester, rubber elastomer and has carried out the surface-treated microfibre with silane compound.Patent documentation 4 has been put down in writing a kind of resin combination, and it comprises the copolymer waxes of PC, aromatic polyester, wollastonite, ethylene-ethyl acrylate copolymer and alpha-olefin and maleic anhydride.Scheme described in the document is for the appearance that improves formed body, resistance to chemical reagents, shock-resistance, rigidity.Patent documentation 5 has been put down in writing a kind of resin combination, and it comprises the wollastonite of PC, aromatic polyester, specified shape.Scheme described in the document is for the shock-resistance of improving resin combination, recovery property and appearance.Patent documentation 6 has put down in writing that the resin combination that will comprise PC and aromatic polyester carries out compression molding and the large-scale formed body that obtains.Scheme described in the document is for the dimensional stability of improving resin combination, impact strength.

But these all are to be conceived to improve mechanical characteristicies such as shock-resistance, rigidity; The scheme of thermal propertys such as thermotolerance, the research of the flowability of the resin combination that requires during for the large component of forming thin-walledization is also insufficient.

As the technology of the flowability of improving resin combination, patent documentation 7 discloses a kind of resin combination, and it comprises low-molecular-weight polybutylene terephthalate, high-molecular weight polyester and specific P contained compound.But, this technology can not be used for the different PC/PET alloy of resinous principle.In addition, for rigidity, shock-resistance, thermotolerance etc., this resin combination also has room for improvement.

As the trolley part resin combination, for example, patent documentation 8 discloses a kind of resin combination, and it comprises PC, ABS and talcum, and satisfies specific coefficient of linear thermal expansion, dart impact strength and load deflection deformation temperature.

As mentioned above, in the PC/PET alloy, proposed much about improving the scheme of shock-resistance, rigidity, thermotolerance, thermostability etc., but the scheme of the resin combination of desired resistance to chemical reagents during the parts of the application outward appearance that desired flowability and moulding will not aspired for stability when having moulding requirement thin-walled property and light-weighted large component simultaneously.

On the other hand, when making large-scale formed body such as trolley part, used sequential valve gate method (below, be called " SVG method "), this method makes a plurality of hot runner valves open or close (with reference to non-patent literature 1) in proper order according to program.Though the SVG method also can be used for by the different a plurality of formed bodys of a plurality of cast gates difference forming shapes, if by formed body of a plurality of cast gate moulding, then can obtain the second best in quality large-scale resin-formed body.The latter normally after the molten resin of coming of flowing from the cast gate of its front passes through, opens cast gate, is following flowing of this molten resin and by this cast gate potting resin.Supply with molten resin owing to carry out this operation at each cast gate interimly, therefore the moulding by the SVG method is commonly called the cascade moulding.Such cascade moulding can be controlled welded bonds, and improves the degree of freedom that cast gate is counted, and the result has can be with the advantage of the lower large-scale formed body of clamp force injection moulding.Therefore, require to be fit to the resin combination with good fluidity of this forming method.

(patent documentation 1) spy opens flat 4-224920 communique

(patent documentation 2) spy opens the 2003-128905 communique

(patent documentation 3) spy opens flat 8-259789 communique

(patent documentation 4) spy opens flat 9-012847 communique

(patent documentation 5) spy opens the 2002-265769 communique

(patent documentation 6) spy opens the 2003-171564 communique

(patent documentation 7) spy opens flat 6-279664 communique

(patent documentation 8) spy opens flat 2-294358 communique

(non-patent literature 1) Plastics Technology, Dec.2003, p38

Summary of the invention

The parts of formed automobile and OA equipment such require thin-walled property and light-weighted parts the time, resin combination must have high workability, in requiring the formed body of excellent appearance, usually carry out application, in order to show stable application outward appearance, must have high resistance to chemical reagents to the organic solvents such as thinner in the coating.In addition, as a rule, demanding rigidity, shock-resistance, thermotolerance, thermostability etc.

Therefore, the object of the present invention is to provide with PC and PET is the resin combination of main component, and it keeps good and mobilely also has high resistance to chemical reagents, and shock-resistance, thermotolerance, rigidity, excellent heat stability.The present invention also aims to provide the formed bodys of making by said composition such as outside vehicle material.The present invention also aims to provide the manufacture method of outside vehicle material.

In general, in order to improve the flowability of resin combination, can reduce the molecular weight that constitutes resin.But if reduce the molecular weight of resin, then mechanical characteristicies such as shock-resistance, rigidity, thermotolerance, thermal property reduce.On the other hand, in the PC/PET alloy,, can increase the content of resistance to chemical reagents than the PET of PC excellence in order to improve resistance to chemical reagents., if increase the content of PET, then mechanical characteristics such as shock-resistance, thermotolerance, thermal property reduce.

Therefore, the inventor makes its mobile method that improves study for the reduction that suppresses shock-resistance, rigidity, thermotolerance and thermostability etc. in the PC/PET alloy simultaneously.Found that,, characteristics such as shock-resistance, thermotolerance, rigidity and thermostability are reduced, and can improve flowability, thereby finish the present invention by use the low viscous PET that did not have in the past as the PET composition in the PC/PET alloy.The inventor also finds, amazingly is, if use low viscous PET, then can increase the content of PET and realizes the raising of resistance to chemical reagents.The inventor also finds, if used the resin combination of low viscous PET by the moulding of SVG method, then can obtain having shock-resistance, the outside vehicle material of low linear expansion coefficient and excellent outward appearance (particularly application outward appearance), thereby finished the present invention.

That is, the present invention is a kind of resin combination, and it comprises the resinous principle of 50～100 weight % and the inorganic filling material of 0～50 weight % (D composition), and wherein, resinous principle comprises:

(i) viscosity-average molecular weight is 16000～23000 aromatic copolycarbonate (A composition); With

(ii) polyethylene terephthalate (B composition), its intrinsic viscosity (IV) is 0.45～0.57dl/g, and the terminal carboxyl(group) amount is 20～35eq/ton, and weight-average molecular weight (Mw) is 1.3～2.1 with the ratio (Mw/Mn) of number-average molecular weight (Mn), and,

(iii) the weight ratio of the total amount of A composition and D composition and B composition (A+D)/B} is 60/40～85/15.The present invention comprises the formed body of being made by this resin combination.Also comprise the outside vehicle material of making by this formed body.

In addition, the present invention is a kind of manufacture method of outside vehicle material, and this method is by making the outside vehicle material with the resin combination injection moulding in mould, wherein,

(i) mould is as described below:

(i-1) have simultaneously cast gate A and cast gate B,

(i-2) cast gate B be the molten resin that the cast gate from other flows into flow pass through after, supply with molten resin and with the cast gate at this interflow of flowing, on the other hand, cast gate A be do not flow the interflow with molten resin and supply with molten resin cast gate,

(i-3) scope of each the cast gate setting in the mould is: externally on the slant range on the material surface at least 20cm with the interior cast gate that does not have other;

(ii) this outside vehicle material is as described below:

(ii-1) mainly constitute by the position that does not need Artistic Design that is arranged on the Artistic Design face on any one face of the positive back side and is selected from the breakthrough part that forms than the depressed part that falls into behind the Artistic Design face and by the face disappearance;

(iii) resin combination is as described below:

(iii-1) comprise the resinous principle of 50～100 weight % and the inorganic filling material of 0～50 weight % (D composition), wherein, resinous principle comprises:

(iii-2) viscosity-average molecular weight is 16000～23000 aromatic copolycarbonate (A composition); With

(iii-3) polyethylene terephthalate (B composition), its intrinsic viscosity (IV) is 0.45～0.57dl/g, and the terminal carboxyl(group) amount is 20～35eq/ton, and weight-average molecular weight (Mw) is 1.3～2.1 with the ratio (Mw/Mn) of number-average molecular weight (Mn), and,

(iii-4) weight ratio of the total amount of A composition and D composition and B composition (A+D)/B} is 60/40～85/15.

The intrinsic viscosity of the PET that uses in the intrinsic viscosity of the PET that uses among the present invention and the common PC/PET alloy is compared extremely low.That is, be about 0.65～1.5dl/g with respect to the intrinsic viscosity of the PET that uses in the common PC/PET alloy, the intrinsic viscosity of the PET that the present invention uses is 0.45～0.57dl/g.Usually, when making formed body, use will further be carried out the PET that solid state polymerization has improved the polymerization degree by the PET that polycondensation obtains., in the present invention,, preferably use the preceding low PET of intrinsic viscosity of solid state polymerization as the B composition.

Description of drawings

Fig. 1 is the sectional skeleton diagram ([C]) of front sketch chart ([A]), side sketch chart ([B]) and the A-A ' axle of the outside vehicle material made among the embodiment.

Nomenclature

1 outside vehicle material body (projecting length: 850mm, horizontal projecting length longitudinally: 1000mm and wall thickness: 4.5mm)

2 Artistic Design faces

3 install the part (inartistic design surface) of window

4 are used to install the depressed part of light fixture

5 are used for the depressed part of mounting knob

11 frame internal upper part cast gates

The 12 notes roads that are connected with cast gate 11 (annotating the top, road is connected with hot runner valve)

Bottom cast gate in 13 frames

The 14 notes roads that are connected with cast gate 13 (annotating the top, road is connected with hot runner valve)

15 are used for the depressed part cast gate (be the drop gate that is positioned on the left-right symmetry axle, its top is connected with hot runner valve) of mounting knob

16 formed body top of tower cast gates (being positioned on the left-right symmetry axle)

The 17 notes roads that are connected with cast gate 16 (annotating the top, road is connected with hot runner valve)

Embodiment

＜resin combination 〉

(A composition: PC)

As the PC of A composition, be the reaction of dihydric phenol and carbonate precursor and the material that obtains.As the method for reaction, can enumerate the solid phase ester-interchange method of interface polycondensation, melt transesterification process, carbonic ether prepolymer and the ring-opening polymerization method of cyclic carbonate compound etc.

As dihydric phenol, can enumerate 2, two (4-hydroxy phenyl) propane (being commonly referred to dihydroxyphenyl propane), 2 of 2-, two { (4-hydroxy-3-methyl) phenyl } propane, 2 of 2-, two (4-hydroxy phenyl) butane, 2 of 2-, two (4-the hydroxy phenyl)-3-methylbutanes, 2 of 2-, two (the 4-hydroxy phenyls)-3 of 2-, 3-dimethylbutane, 2, two (4-the hydroxy phenyl)-4-methylpentanes, 1 of 2-, two (the 4-hydroxy phenyls)-3,3 of 1-, 5-trimethyl-cyclohexane, α, diisopropyl benzene etc. between α '-two (4-hydroxy phenyl).They can separately or mix use more than two kinds.

The bisphenol A-type PC that the A composition preferably uses basically the dihydric phenol that is made of dihydroxyphenyl propane to make.That is the bisphenol A-type PC that is preferably as follows: preferably use the dihydroxyphenyl propane of 90～100 moles of %, more preferably use the dihydroxyphenyl propane of 95～100 moles of % to make as dihydric phenol.

As carbonate precursor, can use carbonyl halide, carbonic ether or haloformate etc., particularly, can enumerate the bishaloformate of phosgene, diphenyl carbonate or dihydric phenol etc.

The A composition can also be to use other dihydric phenol to carry out the various PC of polymeric high heat resistance or low water absorption except bisphenol A-type PC.PC can pass through manufacture method manufacturing arbitrarily, during interfacial polycondensation, uses the terminal terminator of monobasic phenols usually.PC makes 3 officials can the phenols polymerization and the side chain PC that obtains, can also be to make the aliphatics of aliphatic dicarboxylic acid or aromatic dicarboxylic acid or binary or alicyclic alcohol copolymerization and the copolymerization PC that obtains.But, on excellent this aspect of shock-resistance, the preferred especially PC that makes by the homopolymer of dihydroxyphenyl propane.For the details of A composition, in the WO03/080728 brochure, narrate.

Carry out the object lesson of the PC of polymeric high heat resistance or low water absorption as the dihydric phenol that uses other, preferably enumerate following material.

(1) copolymerization PC, wherein, constitute in the dihydric phenol composition of PC 4 at 100 moles of %, 4 '-(a benzene diisopropylidene) diphenol (being designated hereinafter simply as " BPM ") composition is preferably 20～80 moles of %, 40～75 moles of % more preferably, 45～65 moles of % more preferably, and, 9, two (4-hydroxy-3-methyl phenyl) fluorenes (being designated hereinafter simply as " the BCF ") compositions of 9-are preferably 20～80 moles of %, more preferably 25～60 moles of %, more preferably 35～55 moles of %;

(2) copolymerization PC, wherein, constitute in the dihydric phenol composition of PC at 100 moles of %, the dihydroxyphenyl propane composition is preferably 10～95 moles of %, 50～90 moles of % more preferably, more preferably 60～85 moles of %, and BCF composition are preferably 5～90 moles of %, more preferably 10～50 moles of %, more preferably 15～40 moles of %;

(3) copolymerization PC, wherein, constitute in the dihydric phenol composition of PC at 100 moles of %, the BPM composition is preferably 20～80 moles of %, 40～75 moles of % more preferably, 45～65 moles of % more preferably, and 1, two (the 4-hydroxy phenyls)-3 of 1-, 3,5-trimethyl-cyclohexane composition is preferably 20～80 moles of %, more preferably 25～60 moles of %, more preferably 35～55 moles of %.

These special P C can use separately, also can suitably mix more than 2 kinds and use.In addition, they can also be mixed use with the PC of the bisphenol A-type of using always.

For method for making and the characteristic of these special P C, for example, open flat 6-172508 communique, spy the spy and open flat 8-27370 communique, spy and open 2001-55435 communique and spy and open in the 2002-117580 communique and at length narrate.

As the A composition, not only can use fresh feed, also can use by used goods regenerated PC is so-called recovery PC.As used goods, preferably enumerate insulating board, glass port, printing opacity roof Material and vehicle dormer window etc. for the various glazes of representative with container such as transparent component, water bottles such as material, windscreen or car headlamp glass and optical recording medium etc.These goods can not contain a large amount of additives or other resins etc., stably obtain target quality easily.Particularly car headlamp glass or optical recording medium etc. are owing to by mass consumption and can stably obtain regrowth, therefore enumerated as preferred form.In addition, above-mentioned so-called fresh feed is the raw material that does not also use on market after it is made.

The viscosity-average molecular weight of A composition is 16000～23000, is preferably 16000～22000, more preferably 18000～21000.PC with viscosity-average molecular weight of this preferable range, its flowability, intensity and stable on heating balance excellence.

As long as satisfy this viscosity-average molecular weight, also comprise the situation that satisfies this scope by the different mixture more than 2 kinds of molecular weight as A composition integral body.This point of entropy-elasticity when improving fusion particularly mixes viscosity-average molecular weight sometimes and is preferably 50000, more preferably more than 80000, more preferably the PC more than 100000 is favourable.For example, reducing swirl mark, improving the gas injection moulding, bringing into play effect in foaming (comprising the foaming that adopts supercutical fluid to carry out) and the injection press formability etc.Therefore, when requiring to improve these shortcomings and when using these methods of forming, the PC that mixes viscosity-average molecular weight and be more than 50000 becomes one of preferred selection.The molecular weight of PC is high more, and it is remarkable more that this effect becomes, but from practicality, the upper limit of molecular weight is preferably 2,000,000, and more preferably 300,000, more preferably 200,000.Mix such high molecular weight components,, be preferably the amount that in GPC assay methods such as (gel permeation chromatographies), can observe 2 molecular weight distribution more than the peak according to its cooperation.

In PC (A composition), its phenol amount of hydroxyl groups is preferably below the 30eq/ton, more preferably below the 25eq/ton, more preferably below the 20eq/ton.In addition, fully react by making terminal terminator, this value can be 0eq/ton in fact.The phenol amount of hydroxyl groups can be obtained by the following method: carry out ¹H-NMR measures, and calculates the dihydric phenol unit with carbonic acid ester bond, the dihydric phenol unit with phenol hydroxyl and the unitary mol ratio of terminal terminator, is converted into the phenol amount of hydroxyl groups that is equivalent to polymer weight based on this mol ratio.

Said viscosity-average molecular weight is following among the present invention tries to achieve: at first, the PC with 0.7g under 20 ℃ is dissolved in the methylene dichloride of 100ml, uses your moral viscometer of Oswald to obtain the specific viscosity of being calculated by following formula by the solution that obtains,

Specific viscosity (η SP)=(t-t ₀)/t ₀

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

Again the specific viscosity of obtaining is updated in the following formula, obtains viscosity-average molecular weight M.

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

[η]＝1.23×10 ^-4M ^0.83

c＝0.7

(B composition: PET)

PET (B composition) with terephthalic acid as main dicarboxylic acid composition.PET also can contain terephthalic acid composition dicarboxylic acid composition in addition as copolymer composition.That is, with the total amount of dicarboxylic acid composition during as 100 moles of %, preferred 70～100 moles of PET that % is a terephthalic acid of PET, more preferably 80～100 moles of PET that % is a terephthalic acid, further preferred 90～100 moles of PET that % is a terephthalic acid." aa composition " (" aa " represent compound name) this statement relevant with the structural unit of B composition, expression come from the constitutional unit of this compound " aa " or its ester formation property derivative.For example, so-called dicarboxylic acid composition, expression is from the structural unit of dicarboxylic acid or its ester formation property derivative.

As other the example of dicarboxylic acid composition, can enumerate and come from m-phthalic acid, 2-chlorine terephthalic acid, 2,5-dichloroterephthalicacid acid, 2-methyl terephthalic acid, 4,4-Stilbene dioctyl phthalate, 4,4-biphenyl dicarboxylic acid, phthalic acid, 2,6-naphthalic acid, 2,7-naphthalic acid, diphenic acid, two (to carboxyl phenyl) methane, anthracene dicarboxylic acid, 4,4-phenyl ether dicarboxylic acid, 4,4-biphenoxyl ethane dioctyl phthalate, 5-sodiosulfoisophthalic acid, ethylenebis para Toluic Acid's etc. structural unit.These dicarboxylic acid compositions can use separately, perhaps also can mix more than 2 kinds and use.During as 100 moles of %, other dicarboxylic acid composition is preferably 0～30 mole of %, more preferably 0～20 mole of %, more preferably 0～10 mole of % with the total amount of dicarboxylic acid composition.

Except above-mentioned aromatic dicarboxylic acid composition, can also make aliphatic dicarboxylic acid composition and the copolymerization of B composition less than 30 moles of %.As the object lesson of this composition, can enumerate and come from hexanodioic acid, sebacic acid, nonane diacid, dodecanedioic acid, 1, the structural unit of 3-cyclohexane cyclohexanedimethanodibasic, 1,4 cyclohexanedicarboxylic acid etc.

In addition, PET can also contain glycol component diol component in addition as copolymer composition.With the total amount of diol component during as 100 moles of %, preferred 70～100 moles of PET that % is a glycol component of PET, more preferably 80～100 moles of PET that % is a glycol component, further preferred 90～100 moles of PET that % is a glycol component.

As other diol component, for example can enumerate and come from glycol ether, 1,2-propylene glycol, 1, ammediol, 2,2-dimethyl-1, ammediol, trans-or-2,2,4,4-tetramethyl--1,3-tetramethylene glycol, 1,4-butyleneglycol, neopentyl glycol, 1,5-pentanediol, 1,6-hexylene glycol, 1,4-cyclohexanedimethanol, 1, the structural unit of 3-cyclohexanedimethanol, decamethylene-glycol, cyclohexanediol, terephthalyl alcohol, dihydroxyphenyl propane, tetrabromo-bisphenol, tetrabromo-bisphenol-two (2-hydroxyethyl ether) etc.These can use separately, also can mix more than 2 kinds and use.During as 100 moles of %, other diol component is preferably 0～30 mole of %, more preferably 0～20 mole of %, more preferably 0～10 mole of % with the total amount of diol component.

Can also use the polyethylene terephthalate that a small amount of polyoxyethylene glycol composition is carried out copolymerization as diol component.As the molecular weight of polyoxyethylene glycol composition, preferred 150～6000 scope.

As the proportion of composing of polyoxyethylene glycol composition, in 100 weight % diol components, be preferably below the 5 weight %, more preferably below the 3 weight %, more preferably below the 2 weight %.On the other hand, as lower limit, be preferably more than the 0.5 weight %, more preferably more than the 1 weight %.

In the B composition, the side reaction resultant during usually as polymerization in 100 moles of % diol components, contains the above glycol ether composition of 0.5 mole of % of having an appointment, and this glycol ether composition is preferably 6 moles below the %, more preferably 5 moles below the %.

In the B composition, with the part of terephthalic acid composition change into the m-phthalic acid composition poly terephthalic acid/ethylene isophthalate multipolymer (below, sometimes abbreviate the TA/IA multipolymer as) in terephthalic acid composition and m-phthalic acid components in proportions as follows: with total dicarboxylic acid composition during as 100 moles of %, the terephthalic acid composition is 70～99.9 moles of %, be preferably 75～99 moles of %, more preferably 80～99 moles of %.In addition, the m-phthalic acid composition is 0.1～30 mole of %, is preferably 1～25 mole of %, more preferably 1～20 mole of %.

In this TA/IA multipolymer, except terephthalic acid composition and m-phthalic acid composition, can also 0 mole of % of copolymer-1 following, be preferably the following above-mentioned aromatic dicarboxylic acid compositions such as naphthalic acid of 5 moles of %, perhaps 5 moles of % following, be preferably the following above-mentioned aliphatic dicarboxylic acid compositions such as hexanodioic acid of 3 moles of %, but most preferably only by terephthalic acid composition and m-phthalic acid composition as the dicarboxylic acid composition.As the diol component in the TA/IA multipolymer, most preferably independent glycol component, but also can copolymerization ethylene glycol diol component in addition.

In the B composition, with the part of glycol component change into the neopentyl glycol composition poly terephthalic acid ethylene glycol/neopentyl glycol ester copolymer (below, sometimes abbreviate the EG/NPG multipolymer as) in glycol component and neopentyl glycol components in proportions as follows: with the total diol composition during as 100 moles of %, glycol component is 90～99 moles of %, be preferably 95～99 moles of %, more preferably 97～99 moles of %.In addition, the neopentyl glycol composition is 1～10 mole of %, is preferably 1～8 mole of %, more preferably 1～5 mole of %.Can also copolymerization ethylene glycol and neopentyl glycol diol component in addition.

In this EG/NPG multipolymer, can 0 mole of % of copolymer-1 following, be preferably above-mentioned aromatic dicarboxylic acid compositions such as m-phthalic acid beyond the following terephthalic acid composition of 5 moles of % or naphthalic acid, perhaps 5 moles of % following, be preferably the following above-mentioned aliphatic dicarboxylic acid compositions such as hexanodioic acid of 3 moles of %, but most preferably the dicarboxylic acid composition is independent terephthalic acid composition.In addition, can also copolymerization aliphatic dicarboxylic acid composition.

The B composition can be made in the following way: according to usual method, in the presence of the polycondensation catalyst that contains titanium, germanium, antimony etc., the limit heating edge makes the compound polymerization of the compound of the dicarboxylic acid composition of deriving and the above-mentioned diol component of deriving, and the water or the lower alcohol of by-product is discharged to outside the system.As polycondensation catalyst, preferred germanium class polymerizing catalyst.As germanium class polymerizing catalyst, can enumerate the oxide compound, oxyhydroxide, halogenide, alkoxide, phenates of germanium etc., more specifically, can enumerate germanium dioxide, hydroxide germanium, germanium tetrachloride, tetramethyl alcohol germanium etc.And, also can enumerate insoluble catalyzer such as ANTIMONY TRIOXIDE SB 203 99.8 PCT.Particularly, adopt germanium class polymerizing catalyst to carry out polymeric PET if use, then resistance to chemical reagents, good thermal stability.

In the present invention, can use the compound of the manganese that in transesterification reaction, uses, zinc, calcium, magnesium etc. simultaneously, and can finish the compound of back by phosphoric acid or phosphorous acid etc. in transesterification reaction and make this catalyst deactivation carry out polycondensation as last stage of known polycondensation in the past.The manufacture method of PET can be taked any method in intermittent type, the successive polymerization formula.

The feature of B composition is that intrinsic viscosity is lower than the PET that uses in the common PC/PET alloy.That is, the intrinsic viscosity of B composition (IV) is 0.45～0.57dl/g, is preferably 0.47～0.55dl/g, more preferably 0.49～0.52dl/g.When the IV value is high, except flowability reduces, also there is the problem of the raising effect that is difficult to show resistance to chemical reagents.In addition, when IV was too low, except intensity reduced greatly, because the many influences of the end group amount of PET, the thermostability of thermoplastic resin reduced.When producing the low PET of IV value, because the fragmentation of line material, so also there is the problem of pelletizing difficulty.

The intrinsic viscosity of B composition (IV) is in the value of 25 ℃ of mensuration in ortho chloro phenol.That is, with 1.2gPET at 15cm ³Ortho chloro phenol in the heating for dissolving postcooling, and calculate by the soltion viscosities of measuring down at 25 ℃.The density of the PET that obtains after the polycondensation operation is preferably 1.35～1.41g/cm ³, 1.37～1.39g/cm more preferably ³In the present invention, the density of PET is based on the D method of JIS K7112, measures under 23 ℃ temperature by the density gradient tube method of using ca nitrate soln.

Usually, when making formed body, use will further be carried out the PET that solid state polymerization has improved the polymerization degree by the PET that polycondensation obtains., in the present invention,, can use the low PET of the polymerization degree that does not carry out solid state polymerization as the B composition.

The ratio (Mw/Mn) of the weight-average molecular weight of B composition (Mw) and number-average molecular weight (Mn) is 1.3～2.1, is preferably 1.5～2.1, more preferably 1.7～2.0.

Mw/Mn can try to achieve by GPC (gel permeation chromatography).Promptly, use is placed on 23 ℃ of temperature, GPC determinator under the air ambient of the cleaning of relative humidity 50%, MIXED-C (the length 300mm that uses Port リ マ one ラ ボ ラ ト リ one ズ company to make, internal diameter 7.5mm) as post, use chloroform as mobile phase, the イ one ジ one キ ヤ Le PS-2 that uses the manufacturing of Port リ マ one ラ ボ ラ ト リ one ズ company is as reference material, and use UV detector (wavelength 254nm) as detector, use chloroform as launching solvent, the PET test portion is dissolved in chloroform: in hexafluoroisopropanol=1: 1 (vol) mixing solutions, dilute with chloroform then, solution with the concentration 0.3mg/ml that obtains is injected into 100 μ l in the GPC determinator again, under the condition of 35 ℃ of column temperatures and flow 1ml/min, carry out GPC and measure, calculate the number-average molecular weight (Mn) of test portion, weight-average molecular weight (Mw) and Mw/Mn.At this moment, GPC measures in the peak, gets rid of to come from the unreacted monomer of lower molecular weight zone generation or the fine peak of impurity, only uses the main peak from polymkeric substance to calculate.

In recent years, will reclaim PET is used in the resin combination again.The Mw/Mn that reclaims PET is very big sometimes, should be noted that when using as B composition of the present invention.

The terminal carboxyl(group) amount of B composition is 20～35eq/ton, is preferably 22～30eq/ton, more preferably 23～28eq/ton.

The containing ratio of the dioxy ethylidene terephthalate units of B composition is preferably 1.0～5.0 moles of %, the more preferably scope of 1.0～2.5 moles of %.The PET that obtains by polycondensation adopts usually and melt extrudes the method for forming and be shaped to granular (sheet).Such granulous PET preferably has the median size of 2～5mm, more preferably has the median size of 2.2～4mm.PET preferably directly utilizes so granular PET that has passed through the liquid polycondensation operation.

(C composition: rubber polymer)

The rubber polymer of said C composition, be meant comprise second-order transition temperature be preferably below 10 ℃, more preferably-10 ℃ below, the polymkeric substance of the rubber constituent below more preferably-30 ℃; And comprising the multipolymer that combines other polymer chain on the polymkeric substance of this rubber constituent and form.Further be meant this rubber constituent of in 100 weight % rubber polymers, preferably containing more than the 35 weight %, more preferably contain the polymkeric substance of this rubber constituent more than the 45 weight %.In practicality, it is suitable being limited to about 90 weight % on the content of rubber constituent.

Rubber polymer more preferably combines other polymer chain and the multipolymer that forms.In the manufacturing of the rubber polymer that grafting forms in conjunction with other polymer chain on rubber constituent, extensively be known that to generate polymkeric substance or the multipolymer that much is not grafted on the rubber constituent.C composition of the present invention can contain such free polymkeric substance or multipolymer.

Rubber polymer as the C composition, particularly, can enumerate SB (styrene butadiene) multipolymer, ABS (acrylonitrile-butadiene-styrene (ABS)) multipolymer, MBS (methyl methacrylate-butadiene-styrene) multipolymer, MABS (methyl methacrylate-acrylonitrile-butadiene-styrene (ABS)) multipolymer, MB (methyl methacrylate-divinyl) multipolymer, ASA (acrylonitrile-styrene-acrylic rubber) multipolymer, AES (vinyl cyanide-ethylene-propylene rubber-styrene-alkene) multipolymer, MA (methyl methacrylate-acrylic rubber) multipolymer, MAS (methyl methacrylate-acrylic rubber-vinylbenzene) multipolymer, methyl methacrylate-acrylate-butadiene rubber multipolymer, methyl methacrylate-acrylate-butadiene rubber-styrol copolymer, methyl methacrylate-(vinylformic acid silica alkane IPN rubber) multipolymer etc.These multipolymers all preferably combine the graft copolymer of the core-shell that comprises above-mentioned polymer of monomers chain on the core of the multipolymer that comprises rubber constituent.Wherein, be preferably selected from least a rubber polymer in styrene-butadiene copolymer, acrylonitrile-butadiene-styrene copolymer, MBS and methyl methacrylate-(vinylformic acid silica alkane IPN rubber) multipolymer.

The rubber size of rubber polymer is preferably 0.05～2 μ m in weight average particle diameter, and more preferably 0.1～1 μ m is preferably 0.1～0.5 μ m especially.Can use the rubber polymer that is distributed as single distribution of this rubber size and have in the rubber polymer at above a plurality of peaks, 2 peaks any, and, for its form, can form the form of single phase for rubber particles, also can be to contain by the periphery at rubber particles to contain the form that has the salami structure mutually.

In the rubber polymer of graft copolymer, this grafted composition is preferably 10～100% with respect to the weight ratio (percentage of grafting (weight %)) of rubber matrix, and more preferably 15～70%, more preferably 15～40%.

As rubber polymer, can enumerate the various thermoplastic elastomers that constitute by hard segment and soft chain segment.As such thermoplastic elastomer, can enumerate polyester elastomer, polyurethane elastomer, styrenic elastomerics and olefin type elastomer etc.

(D composition: inorganic filling material)

Inorganic filling material as D composition of the present invention, can freely select sheet, fibrous, spherical, hollow form, for the intensity of resin combination or the raising and the dimensional stability of shock-resistance, preferred sheet packing material and/or fibrous packing material.Inorganic filling material (D composition) can carry out surface treatment with various surface treatment agents such as silane coupling agent (comprising alkylalkoxy silane or poly-organohydrogensiloxanes etc.), high-grade aliphatic ester, acid compound (for example, phosphorous acid, phosphoric acid, carboxylic acid and carboxylic acid anhydride etc.) and waxes.In addition, also can be and make particulate state with collecting agent granulations such as various resins, high-grade aliphatic ester and waxes.

(sheet packing material)

As the sheet packing material, can enumerate sheet glass, tinsel, graphite flake, terre verte, kaolinton, mica and talcum etc.Hollow packing materials such as glass hollow ball sometimes by with the fragmentation of resin melting mixing, thereby similarly obtain the effect that rigidity improves with tabular inorganic filling material.Comprise the packing material that shows such effect in the sheet packing material.These inorganic filling materials have comprised the inorganic filling material of kinds of materials surface-coated.As kinds of materials, representational is metal, alloy, metal oxide etc.Coated metal or alloy etc. can be given high electroconductibility, can also improve Artistic Design sometimes.Coated metal oxide can be given functions such as photoconductivity sometimes, can also improve Artistic Design in addition.

The median size (D50 (median particle diameter of size distribution)) of the sheet packing material of measuring with the laser diffraction and scattering method is preferably 0.1～50 μ m, more preferably 0.3～30 μ m, more preferably 0.5～10 μ m.Averaged particles thickness is preferably 0.01～1 μ m, more preferably 0.01～0.8 μ m, more preferably 0.05～0.5 μ m.

(mica)

The micaceous median size of measuring with the laser diffraction and scattering method (D50 (median particle diameter of size distribution)) is preferably 1～50 μ m, more preferably 2～20 μ m, more preferably 2～10 μ m.The micaceous median size is during less than 1 μ m, and it is insufficient that inflexible is improved effect, even and surpass 50 μ m, it is also insufficient that inflexible improves, the reduction of physical strengths such as impact characteristics also clearly, and is not preferred.The micaceous thickness of the observation practical measurement by electron microscope is preferably 0.01～1 μ m, more preferably 0.03～0.3 μ m.Length-to-diameter ratio is preferably 5～200, and more preferably 10～100.Mica can be the crushed material of natural mineral, also can be synthetics.In addition, as the micaceous comminuting method, can make with any method of dry type comminuting method and case of wet attrition method.The dry type comminuting method normally cheaply, and on the other hand, the case of wet attrition method is for thinner and carefully mica to be pulverized be effective.Its result, the rigidity of resin combination improves effect and further improves.

(talcum)

The steatitic chemical constitution is a hydrous magnesium silicate, uses chemical formula 4SiO usually ₂3MgO2H ₂O represents normally have the flakey particle of laminate structure.Talcum is by the SiO of 56～65 weight % ₂, the MgO of 28～35 weight % and the H of about 5 weight % ₂O constitutes.As other minor constituent, contain the Fe of 0.03～1.2 weight % ₂O ₃, 0.05～1.5 weight % Al ₂O ₃, 0.05～1.2 weight % the following K of CaO, 0.2 weight % ₂The Na that O, 0.2 weight % are following ₂O.Form as preferred steatitic, be SiO ₂: 62～63.5 weight %, MgO:31～32.5 weight %, Fe ₂O ₃: 0.03～0.15 weight %, Al ₂O ₃: 0.05～0.25 weight % and CaO:0.05～0.25 weight %.In addition, the heat-flash decrement is preferably 2～5.5 weight %.

The steatitic median size that adopts settling process to measure is preferably 0.1～50 μ m, 0.1～10 μ m more preferably, and more preferably 0.2～5 μ m is preferably 0.2～3.5 μ m especially.Preferred volume density is 0.5g/cm ³Talcum.The steatitic median size is meant the D50 (median particle diameter of size distribution) that employing is measured as the X ray penetrant method of one of liquid phase settling process.As the object lesson of the device that carries out this mensuration, can enumerate the Sedigraph5100 of マ イ Network ロ メ リ ラ イ Star Network ス company manufacturing etc.

Method for making when pulverizing talcum from raw ore is not particularly limited, and can utilize axial flow type mill method, ring-like mill method, roller mill method, ball milled, jet mill method and the rotary compression shear type of container mill method etc.Talcum after preferred the pulverizing carries out stage treatment by various grading machines again makes the size distribution unanimity.As grading machine, be not particularly limited, can enumerate impact mill formula intertia force classifier (variable impact mill etc.), attached wall effect utilization type intertia force classifier (bend pipe spraying machine etc.), centrifuge field grading machine (multi-cyclone, microplex, dispersion separator, ア キ ユ カ Star ト, turbine classifier, turboplex, micron separator and super separator etc.) etc.

From aspects such as its operability, talcum is the talcum of state of aggregation more preferably, as this method for making, method, use collecting agent that adopts degassing compression and the method for compressing etc. is arranged.Adopt the method for degassing compression easy and unwanted collecting agent resinous principle can be blended in the resin combination of the present invention, so preferred especially.

(fibrous packing material)

The fiber diameter of fibrous packing material is preferably 0.1～30 μ m, more preferably 0.1～20 μ m, more preferably 0.5～15 μ m.Average fiber length is preferably 1～500 μ m, more preferably 1～400 μ m, more preferably 5～350 μ m.

Fiber diameter is to strengthen filler with electron microscope observation, obtains Fibre diameter separately, calculates the number average Fibre diameter by this measured value again.Use electron microscope to be owing to be difficult to the correct size of measuring as the level of object with opticmicroscope.The object filler of Fibre diameter is measured in random extraction the image that obtains from all electron microscope observations, at the position finding Fibre diameter near the central part of each filler.Calculate the number average Fibre diameter by the measured value that obtains.Observe multiplying power and be about 1000 times, measuring radical is (in operation, to be preferably below 600) more than 500.

Average fiber length is to use the observation by light microscope filler, obtains length separately, calculates number average fiber length by this measured value again.The observation of opticmicroscope makes less overlapping and dispersive sample between the filler from being prepared as.Under the condition of 20 times on object lens, observe, be about 250,000 CCD photographic camera in pixel and obtain it with the form of view data and observe image.Use image analysis apparatus to obtain ultimate range between 2 of view data by the view data that obtains, use such program to calculate staple length.Under such condition, the sizableness of per 1 pixel is in the length of 1.25 μ m, and measuring radical is (in operation, to be preferably below 600) more than 500.

As fibrous packing material, can enumerate glass fibre, carbon fiber, steel fiber, ceramic fiber, slag fibre, asbestos, zonotolite, wollastonite and various whisker class (calcium titanate whisker, aluminium borate whisker, boron whisker and alkali magnesium sulfate crystal whisker etc.) etc.

(wollastonite)

The fiber diameter of wollastonite is preferably 0.1～10 μ m, more preferably 0.1～5 μ m, more preferably 1～2 μ m.Its length-to-diameter ratio (average fiber length/fiber diameter) is preferably 3～30, and more preferably 5～9.The measuring method of fiber diameter, average fiber length is identical with the said determination method.

Because the whiteness that wollastonite has originally is reflected in the resin combination fully, therefore, preferably do one's utmost to remove iron branch that is blended in the raw ore and the iron branch of when raw ore is pulverized, sneaking into owing to the wearing and tearing of machine by magnet separator.Preferably handling by such magnet separator makes the content of the iron in the wollastonite be converted into Fe ₂O ₃Be below the 0.5 weight %.In addition, wollastonite can be the crushed material of natural mineral, also can be synthetic products.

(glass fibre)

As glass fibre, be not particularly limited glass such as A glass, C glass, E glass and form, according to circumstances also can contain TiO ₂, SO ₃, P ₂O ₅Deng composition.But, more preferably E glass (non-alkali glass).Glass fibre is in all sorts of ways the stretching limit quenching of melten glass limit, thereby becomes the specific fibre shape.Quenching and stretching condition for this moment are not particularly limited.In addition, the shape in cross section can also be used positive circular shape in addition such as ellipticity, cocoon shape, trilobal except positive circle.It can also be the fiber that has mixed the glass fibre of positive circular glass fiber and positive circular shape in addition.

The fiber diameter of glass fibre is not particularly limited, but is preferably 1～25 μ m, more preferably 3～17 μ m, more preferably 10～15 μ m.When use has the glass fibre of fiber diameter of this scope, can not damage the formed body outward appearance, and can show good thermotolerance etc.In addition, as the preferred staple length of glass reinforced material, in resin composition pellet of the present invention or formed body,, be preferably 50～500 μ m, more preferably 100～400 μ m, more preferably 230～270 μ m as average fiber length.

Average fiber length is after formed body being dissolved in the solvent or with basic cpd resin being decomposed, the value of utilizing observation by light microscope etc. and being calculated by the residue of the glass fibre of taking by image analysis apparatus.When calculating this value, adopt the method for the fiber of not counting the following length of Fibre diameter.In order to reduce the anisotropy that comes from glass fibre, fiber and the above-mentioned glass fibre that is called as L/D≤10 of milled fiber can be added separately.

Glass fibre can be by surface-coated dose of lining.Here, surface-coated dose preferably includes the compound that (i) contains epoxide group.The compound that contains epoxide group is rich reactive to various resins, and effective for improving tack, on the other hand, also can not produce decomposition reaction etc. for the polymkeric substance of the high condensation class of reactivity etc., can bring into play good characteristic.The raising of such tack when forming process to being present in the high shearing force of polymkeric substance effect between the glass fibre.Thus, except the reinforced effects of fiber, under the situation of crystalline polymer, can improve crystallinity, the result can realize good thermotolerance and reduction size through the time change.

As the compound that contains epoxide group, can use the various compounds that contain epoxide group, preferably its molecular weight is the material that contains a plurality of epoxide groups in the compound that contains epoxide group with macromolecular structure, especially 1 molecule more than 500.From stable on heating viewpoint, the preferred structure that mainly constitutes by aromatic nucleus.

As the compound that preferably contains epoxide group, can enumerate phenol novolak type epoxy resin, line style cresols phenolic resin varnish type epoxy resin.Can enumerate phenol novolak type epoxy resin especially.That is, preferred phenol novolak type epoxy resin and/or line style cresols phenolic resin varnish type epoxy resin are that the resin of main body is as the compound that contains epoxide group.Promptly, can preferably be set forth in 100 weight % and contain in the compound of epoxide group, contain 70 weight % above, preferably contain 80 weight % above, more preferably contain 90 weight % above phenol novolak type epoxy resin and/or line style cresols phenolic resin varnish type epoxy resin.

The (ii) glass fibre that is equivalent to 100 weight %, surface-coated dose amount are preferably 0.1～2 weight %, more preferably 0.5～1.5 weight %, more preferably 0.6～1.2 weight %.During less than 0.1 weight %, surface-coated insufficient and make the assembly of fiber become insufficient.For the unfavorable condition of so inadequate boundling, narration in the back.On the other hand, if surpass 2 weight %, then tack is saturated, and produces the situation that characteristic that collecting agent has thermoplastic resin reduces.

As the characteristic of glass fibre, the preferred 3mm length chopped strands that (iii) in 1 liter beaker, adds the 200g glass fibre, the flyings generating capacity when stirring 5 minutes with stirrer with 2000rpm down for 23 ℃ is below the 10g.Here said flyings are to make the chopped strands of boundling open fibre by stirring to pass through 30 purpose amounts.In addition, as stirrer, preferably show rotating speed and can feedback control to the stirrer (that is, rotating speed often keeps constant) of the rotating speed of set(ting)value.The blade of stirrer uses the type peculiar to vessel of 3 pieces of blades of diameter 50mm φ.This flyings generating capacity is more preferably below the 5g, more preferably below the 3g.

Usually, the resin combination that contains the such glass fibre of the present invention is made by glass fibre is supplied in the melting mixing machine.At this moment, the glass fibre of raw material is owing to following principal element is subjected to suitable external force, and described principal element is: (1) carries with the pre-blend of material resin, (2) air and (3) use supply machine (screw or oscillatory type etc.) and side feeder to supply to melting mixing machine etc. independently.

Here, adopt under the situation of the many glass fibre of the flyings generating capacity of above-mentioned test, when supplying to the melting mixing machine, owing to flyings produce can not stable supplying problem.In addition,, can not bite in the melting mixing machine, and produce problem such as backflow because the volume density of these flyings is low.These problems cause the irregular delay of resin in the melting mixing machine, and the result makes the resin thermal degradation when.

In addition, when supplying to glass fibre in the melting mixing machine, in conveying, produce flyings and in carrying pipe arrangement, stop up, thereby produce problems such as to carry out the air conveying with air conveying etc.Under the many situations of flyings generating capacity, when thermoplastic resin and glass fibre melting mixing, be easy to generate fractureing of glass fibre, thereby the problems such as each characteristic of expectations such as can not showing rigidity or thermotolerance are arranged.

In order to satisfy the characteristic of above-mentioned flyings generating capacity, preferably, also use surface-coated dose that contains compositions such as urethane, polyacrylic ester or polymeric amide simultaneously except as its compound that contains epoxy of surface-coated dose.More preferably use simultaneously with urethane.Therefore, as preferred surface-coated dose, can enumerate with phenol novolak type epoxy resin and/or line style cresols phenolic resin varnish type epoxy resin and be principal constituent and contain surface-coated dose of urethane.Wherein, phenol novolak type epoxy resin and/or line style cresols phenolic resin varnish type epoxy resin preferably contain 50～95 weight % in surface-coated dose of 100 weight %, more preferably contain 60～90 weight %.Particularly, in 100 weight % binder constituents, preferably contain the above phenol novolak type epoxy resin of 50 weight %, more preferably contain more than the 60 weight %.

When being covered with so surface-coated dose, preferably with aminosilane class coupling agent or epoxy silane class coupling agent surface treatment is carried out on the surface of glass fibre in advance, and then handled with phenol novolak type epoxy resin and/or line style cresols phenolic resin varnish type epoxy resin and urethane.In addition, in the collecting agent of glass fibre, except the composition (surface-coated dose) of assembling fiber enhancer in fact, also contain composition or other emulsifying agents of giving oilness usually, but so various compositions can certainly be included in the collecting agent.Coating contains the milky solution of these various compositions and carries out drying treatment, remains on the fiber enhancer based on surface-coated dose composition.In drying treatment or heat treatment step, promoted surface-coated dose polymer quantification and formed surface-coated dose fully.

In addition, be the method that in the liquid that has mixed phenol novolak type epoxy resin and/or line style cresols phenolic resin varnish type epoxy resin and both emulsions of urethane, makes the glass fibre coating basically.But also can be the method that independently both is coated with.

Usually, when only phenol novolak type epoxy resin being arranged, the flyings generation increases.But, in the present invention, amount by the regulating ring epoxy resins and with other collecting agent combination, it is good and contain a large amount of epoxide groups to obtain surface-coated dose thermotolerance, the few glass fibre of while flyings generation, because the flyings generation is lowered, therefore can realize effects such as excellent thermotolerance, dimensional stability.

In the present invention, from viewpoints such as shock-resistance, outward appearance, dimensional stability and costs, be preferably selected from least a inorganic filling material in mica, talcum, wollastonite and the glass fibre.Preferred especially wollastonite or glass fibre.

(the E composition: inhibitor fractures)

For suppress inorganic filling material (D composition) fracture or broken, and in order further to improve the thermostability of resin combination, resin combination of the present invention can contain the inhibitor that fractures.In such inhibitor that fractures, comprise: (i) comprise and silicate minerals between have the lubricant of reactive functional group and the (ii) surface-coated in advance lubricant on silicate minerals.The inhibitor that preferably fractures is alkylalkoxy silane or the alkyl hydrogen silane that contains the lubricant of acidic-group or have the alkyl of carbonatoms below 60.

As the lubricant that contains acidic-group, the olefines wax that preferably contains the carboxyl class, wherein every 1g contains the lubricant of carboxyl class, preferably with the concentration of 0.05～10meq/g, more preferably with the concentration of 0.1～6meq/g, further preferably contain the carboxyl class with the concentration of 0.5～4meq/g.In addition, the molecular weight of olefines wax is preferably 1000～10000.Further preferably satisfy the alpha-olefin of condition of such concentration and molecular weight and the multipolymer of maleic anhydride.Such multipolymer can according to usual method in the presence of free radical catalyst with melt polymerization or mass polymerization manufactured.Wherein, as alpha-olefin, the mean value that can preferably enumerate its carbonatoms is 10～60 alpha-olefin.As alpha-olefin, the mean value of more preferably enumerating its carbonatoms is 16～60, more preferably 25～55 alpha-olefin.

(each components in proportions)

Each components in proportions among the present invention is narrated.

Resin combination of the present invention comprises 50～100 weight %, is preferably 70～95 weight %, more preferably 55～65 weight % resinous principle and 50～0 weight %, be preferably 30～5 weight %, the inorganic filling material of 45～35 weight % (D composition) more preferably.

In the resin combination of the present invention, the total amount of PC (A composition) and inorganic filling material (D composition) and the weight ratio of PET (B composition), promptly (A+D)/B is 60/40～85/15, is preferably 65/35～85/15, more preferably 65/35～80/20.

The weight ratio of A composition and B composition (A/B) is preferably 40/60～90/10, and more preferably 65/35～75/25.The addition of A composition after a little while, it is insufficient that shock strength, thermotolerance become easily, addition is difficult to show resistance to chemical reagents for a long time.

With respect to total amount 100 weight parts of A composition and B composition, rubber polymer (C composition) is preferably 1～50 weight part, more preferably 1～10 weight part, more preferably 2～7 weight parts.Addition after a little while, it is insufficient that the performance of shock strength becomes easily, and too much the time, thermotolerance or rigidity reduce.

With respect to total amount 100 weight parts of A composition and B composition, the inhibitor that fractures (E composition) is preferably 0.01～10 weight part, more preferably 0.1～5 weight part, more preferably 0.3～3 weight part.The only amount of E composition changes according to the content of D composition, and content 10 weight parts of every D composition are preferably 0.05～5 weight part, more preferably 0.1～3 weight part, more preferably 0.1～1 weight part.

Based on the resin combination of the present invention of ISO1133 standard test melt volume speed (the MVR value: the cm of unit under 280 ℃, 2.16kg load ³/ 10 minutes) be preferably 10～150, more preferably 13～150, more preferably 18～100, be preferably 20～80 especially.MVR value hour can not show sufficient flow characteristics, and when excessive, sometimes poor impact resistance.

Based on the bending elastic modulus of the resin combination of ASTM D-790 standard test (unit: MPa) be preferably 2000～25000, more preferably 8000～25000.

The cracking frequency of resin combination in resistance to chemical reagents test is preferably 0～20%, and more preferably 0～10%.Resistance to chemical reagents is that 10 test films of making based on ASTM D-638 standard are applied 0.5% strain with 3 bending jigs respectively, and impregnated in gasoline under 23 ℃ (エ Star ソ manufacturing, regular grade gasoline) 10 minutes and the sheet number that do not crack etc.

Resin combination is 1.0 * 10 at the linear expansivity-30～80 ℃ scope that the central part of the test film of making based on the ISO527-1 standard is in that flow direction measures ^-5～12.0 * 10 ^-5/ ℃ scope.The lower limit of this linear expansivity is preferably 1.2 * 10 ^-5/ ℃.The upper limit of this linear expansivity is preferably 5.5 * 10 ^-5/ ℃, more preferably 3.5 * 10 ^-5/ ℃.When linear expansivity was bigger than this scope, formed body was big for the dimensional change of the temperature variation in the environment for use, is not suitable as the outside vehicle material.Linear expansivity hour though there is not special problem, is difficult to take into account other characteristic, particularly formed body outward appearance in fact.

The load deflection deformation temperature that resin combination is measured under 0.45MPa load based on ASTM D-648 standard is in 110～145 ℃ scope, is preferably 120 ℃～145 ℃, is preferably 130 ℃～145 ℃ especially.When load deflection deformation temperature is hanged down, when coating baking, be easy to generate distortion.In addition, under environment for use, for example remarkable deflection during applied load under the weather of sweltering heat makes the product texture of vehicle reduce easily.

Preferred mode as resin combination of the present invention has following resin combination.

(1) aspect 1 described resin combination, it comprises the resinous principle of 70～95 weight % and the fiber diameter of 30～5 weight % is that 1～2 μ m, length-to-diameter ratio are 5～9 wollastonite (D composition), and wherein, resinous principle comprises:

(i) viscosity-average molecular weight is 16000～23000 bisphenol A-type aromatic copolycarbonate (A composition); With

(ii) use the polyethylene terephthalate (B composition) of germanium class polymerization polymerization catalyst, its intrinsic viscosity (IV) is 0.49～0.57dl/g, and the terminal carboxyl(group) amount is 23～28eq/ton, and weight-average molecular weight (Mw) is 1.9～2.1 with the ratio (Mw/Mn) of number-average molecular weight (Mn), and

(iii) the weight ratio of the total amount of A composition and D composition and B composition (A+D)/B} is 70/30～80/20;

(iv) the weight ratio (A/B) of A composition and B composition is 65/35～75/25.

(2) aspect 1 described resin combination, it comprises the resinous principle of 55～65 weight % and the fiber diameter of 45～35 weight % is that 10～15 μ m, average fiber length are the glass fibre (D composition) of 230～270 μ m, and wherein, resinous principle comprises:

(i) viscosity-average molecular weight is 16000～23000 bisphenol A-type aromatic copolycarbonate (A composition); With

(ii) use the polyethylene terephthalate (B composition) of germanium class polymerization polymerization catalyst, its intrinsic viscosity (IV) is 0.49～0.52dl/g, and the terminal carboxyl(group) amount is 23～28eq/ton, and weight-average molecular weight (Mw) is 1.9～2.1 with the ratio (Mw/Mn) of number-average molecular weight (Mn), and

(iii) the weight ratio of the total amount of A composition and D composition and B composition (A+D)/B} is 65/35～75/25;

(iv) the weight ratio (A/B) of A composition and B composition is 45/55～55/45.

(3) a kind of liquid resin composition, it comprises at least a inorganic filling material (D composition) in mica, talcum and the wollastonite of being selected from of the resinous principle of 50～100 weight % and 0～50 weight %, and wherein, resinous principle comprises:

(i) polycarbonate (A1 composition), it is selected from viscosity-average molecular weight is 16000～23000 bisphenol A polycarbonate; With

(ii) polyethylene terephthalate (B1 composition), it is selected from intrinsic viscosity (IV) is 0.45～0.57dl/g, and the terminal carboxyl(group) amount is 20～35eq/ton, and the ratio (Mw/Mn) of weight-average molecular weight (Mw) and number-average molecular weight (Mn) is 1.3～2.1 polyethylene terephthalate, and

(iii) the weight ratio of the total amount of A1 composition and D composition and B1 composition (A1+D)/B1} is 60/40～85/15;

(iv) the melt volume speed (MVR value) under 280 ℃, 2.16kg load based on the ISO1133 standard is 23～150cm ³/ 10 minutes be 2000～25000MPa based on the bending elastic modulus of ASTM D-790 standard test, and the cracking frequency in the resistance to chemical reagents evaluation is 0～20%.

(4) a kind of liquid resin composition, it comprises the resinous principle of 50～100 weight % and the glass fibre of 0～50 weight % (D composition), and wherein, resinous principle comprises:

(i) polycarbonate (A1 composition), it is selected from viscosity-average molecular weight is 16000～23000 bisphenol A polycarbonate; With

(ii) polyethylene terephthalate (B1 composition), it is selected from intrinsic viscosity (IV) is 0.45～0.57dl/g, and the terminal carboxyl(group) amount is 20～35eq/ton, and the ratio (Mw/Mn) of weight-average molecular weight (Mw) and number-average molecular weight (Mn) is 1.3～2.1 polyethylene terephthalate, and

(iii) the weight ratio of the total amount of A1 composition and D composition and B1 composition (A1+D)/B1} is 60/40～85/15;

(iv) the melt volume speed (MVR value) under 280 ℃, 2.16kg load based on the ISO1133 standard is 10～150cm ³/ 10 minutes be 8000～25000MPa based on the bending elastic modulus of ASTM D-790 standard test, and the cracking frequency in the resistance to chemical reagents evaluation is 0～10%.

(other compositions)

In addition, in satisfying the scope of above-mentioned characteristic, in resin combination of the present invention, can also cooperate B composition aromatic polyester in addition, fire retardant, flame retardant (for example, sodium antimonate and ANTIMONY TRIOXIDE SB 203 99.8 PCT etc.), チ ヤ one (for example forms compound, novolac-type resol, the condenses of pitch class and formaldehyde etc.), nucleator (for example, sodium stearate and ethylene-acrylic acid sodium etc.), Antidrip agent (having the fluorinated polyolefin of protofibril formation ability etc.), thermo-stabilizer, oxidation inhibitor (for example, Hinered phenols antioxidant and sulfur type antioxidant etc.), UV light absorber, photostabilizer, releasing agent, antistatic agent, whipping agent, flow ability modifying agent, antiseptic-germicide, photocatalyst class stain control agent (particulate titanium dioxide, particulate oxide zinc etc.), lubricant, tinting material, white dyes, light-storing paint, fluorescence dye, infrared absorbent, photochromic agent etc.

(i) aromatic polyester

Can also in resin combination of the present invention, add polyethylene terephthalate aromatic polyester in addition.As an example, can enumerate Poly(Trimethylene Terephthalate), polybutylene terephthalate (PBT), poly terephthalic acid hexylene glycol ester, PEN (PEN), PBN (PBN), poly-1, two (phenoxy group) ethane-4 of 2-, copolyesters such as 4 '-dioctyl phthalate glycol ester etc. and poly-m-phthalic acid/ethylene glycol terephthalate, poly-m-phthalic acid/mutual-phenenyl two acid bromide two alcohol ester.With respect to the PET of 100 weight part B compositions, be preferably 1～100 weight part as the addition of these aromatic polyesters, more preferably 10～90 weight parts, more preferably 30～60 weight parts.

(ii) thermo-stabilizer

Preferably in resin combination of the present invention, cooperate various thermo-stabilizers.As such thermo-stabilizer, preferred Phosphorus stablizer.As Phosphorus stablizer, can enumerate phosphorous acid, phosphoric acid, phosphonous acid, phosphonic acids and their ester and tertiary phosphine etc.Phosphorus stablizer like this can only use a kind, also can mix more than 2 kinds and use.

Particularly, as bi-ester of phosphite, can enumerate the such trialkyl phosphite of tridecyl phosphite; The dialkyl group list aromatic yl phosphite that didecyl list phenyl phosphites is such; The monoalkyl diaryl phosphorous acid ester that monobutyl phenylbenzene phosphorous acid ester is such; Triphenyl phosphite and three (2, the 4-di-tert-butyl-phenyl) the such triaryl phosphites of phosphorous acid ester; Distearyl pentaerythrityl diphosphite, two (2, the 4-di-tert-butyl-phenyl) pentaerythritol diphosphites, two (2, the 4-dicumylphenyl) pentaerythritol phosphite such as pentaerythritol diphosphites and two (2,6-di-t-butyl-4-aminomethyl phenyl) pentaerythritol diphosphites; And 2,2-methylene-bis (4, the 6-di-tert-butyl-phenyl) octyl group phosphorous acid ester and 2, cyclic phosphites such as 2 '-methylene-bis (4, the 6-di-tert-butyl-phenyl) (2, the 4-di-tert-butyl-phenyl) phosphorous acid ester.

As phosphate compound, can enumerate tributyl phosphate, trimethyl phosphite 99, Tritolyl Phosphate, triphenylphosphate, triethyl phosphate, diphenylmethyl phenyl phosphate ester, the adjacent xenyl phosphoric acid ester of phenylbenzene list, tri butylethyl phosphate and di-isopropyl phosphoric acid ester etc., preferably phosphoric acid triphenylmethyl methacrylate, trimethyl phosphite 99.

As phosphinate compound, can preferably enumerate four (di-tert-butyl-phenyl) biphenylene two phosphinates and two (di-tert-butyl-phenyl) phenyl phosphinate, more preferably four (2, the 4-di-tert-butyl-phenyl) biphenylene two phosphinates and two (2, the 4-di-tert-butyl-phenyl) phenyl phosphinate.Such phosphinate compound can use simultaneously with the bi-ester of phosphite with aryl that abovementioned alkyl replaces more than 2, is preferred.

As phosphonate compound, can enumerate phosphenylic acid dimethyl ester, phosphenylic acid diethyl ester and phosphenylic acid dipropyl etc.As tertiary phosphine, for example can enumerate triphenylphosphine.

In 100 weight % resin combination of the present invention, the use level of Phosphorus stablizer is preferably 0.0001～1 weight %, more preferably 0.0005～0.5 weight %, more preferably 0.002～0.3 weight %.

(iii) oxidation inhibitor

Can also in resin combination of the present invention, cooperate oxidation inhibitor.Thermostability when oxidation inhibitor can improve the resin combination forming process and heat-resistant aging.The preferred Hinered phenols antioxidant of oxidation inhibitor.As Hinered phenols antioxidant, can enumerate octadecyl-3-(3, the 5-di-tert-butyl-hydroxy phenyl) propionic ester, the 2-tertiary butyl-6-(3 '-tertiary butyl-5 '-methyl-2 '-hydroxybenzyl)-4-aminomethyl phenyl acrylate, 4,4 '-butylidene-bis(3-methyl-6-t-butyl phenol), triethylene glycol-N-pair-3-(3-tertiary butyl-4-hydroxy-5-aminomethyl phenyl) propionic ester, 3,9-pair 2-[3-(3-tertiary butyl-4-hydroxy-5-aminomethyl phenyl) propionyloxy]-1, the 1-dimethyl ethyl }-2,4,8,10-four oxaspiros [5,5] hendecane, N, N '-hexa-methylene two-(3,5-di-t-butyl-4-hydroxyl hydrocinnamamide), 1,3,5-trimethylammonium-2,4,6-three (3, the 5-di-tert-butyl-4-hydroxyl benzyl) benzene, and four [methylene radical-3-(3, the 5-di-tert-butyl-hydroxy phenyl) propionic ester] methane etc.These all obtain easily.Wherein, preferably use octadecyl-3-(3, the 5-di-tert-butyl-hydroxy phenyl) propionic ester.Hinered phenols antioxidant can use more than 2 kinds alone or in combination.In 100 weight % resin combinations, the use level of oxidation inhibitor is preferably 0.0001～0.05 weight %.

(iv) UV light absorber

As UV light absorber, can enumerate as the known benzophenone compound of UV light absorber, benzotriazole compound, hydroxyphenyltriazinuv compounds, cyclic imide acid esters compound and aminoacrylic acid ester compound etc.More specifically, for example can enumerate 2-(2H-benzotriazole-2-yl) p-cresol, 2-(2H-benzotriazole-2-yl)-4-(1,1,3, the 3-tetramethyl butyl) phenol, 2-(2H-benzotriazole-2-yl)-4, two (1-methyl isophthalic acid-phenylethyl) phenol of 6-, 2-[5-chlorine (2H)-benzotriazole-2-yl]-4-methyl-6-tert butyl phenol, 2,2 '-methylene-bis [6-(2H-benzotriazole-2-yl)-4-(1,1,3, the 3-tetramethyl butyl) phenol], 2-(4,6-phenylbenzene-1,3,5-triazines-2-yl)-and the 5-[(hexyl) oxygen] phenol, 2,2 '-TOPOT 2,2 (3, the 1-benzo Piperazine-4-ketone) and 1, two [(2-cyano group-3,3-phenylbenzene propylene acyl) the oxygen bases]-2 of 3-, two [[(2-cyano group-3,3-phenylbenzene propylene acyl) oxygen base] methyl] propane of 2-etc.In addition, can also use two (2,2,6,6-tetramethyl--4-piperidyl) sebates, two (1,2,2,6,6-pentamethyl--4-piperidyl) sebate etc. to be the hindered amine light stabilizer of representative.In 100 weight % resin combinations, the use level of UV light absorber, photostabilizer is preferably 0.01～1 weight %.

(v) releasing agent

As releasing agent, can enumerate ester, paraffin and the beeswax etc. of olefines wax, silicone oil, fluorocarbon oil, organopolysiloxane, monobasic or polyvalent alcohol and higher fatty acid.Wherein, the ester of preferred monobasic or polyvalent alcohol and higher fatty acid.It is lipid acid more than 17 that higher fatty acid preferably contains the above carbonatoms of 60 weight %, more preferably contain the above carbonatoms of 60 weight % and be 17～32 lipid acid, further preferably contain the above carbonatoms of 60 weight % and be 26～32 lipid acid.As such higher fatty acid, can enumerate with the montanic acid is the higher fatty acid of principal constituent.Such higher fatty acid is made by the oxidation montanin wax usually.On the other hand, as monohydroxy-alcohol, for example can enumerate dodecanol, tetradecanol, cetyl alcohol, Stearyl alcohol, eicosanol, Tetracosyl alcohol, n-Hexacosanol and triacontanol price quote etc.

As polyvalent alcohol, for example can enumerate glycerine, two glycerine, Polyglycerine (for example ten glycerine etc.), tetramethylolmethane, Dipentaerythritol, TriMethylolPropane(TMP), glycol ether and propylene glycol etc.Pure composition in the ester of monobasic or polyvalent alcohol and higher fatty acid is polyvalent alcohol more preferably.In addition, in the middle of these, preferably glycerine, tetramethylolmethane, Dipentaerythritol and TriMethylolPropane(TMP), special preferably glycerine.

In 100 weight % resin combinations, the use level of releasing agent is preferably 0.001～2 weight %, 0.005～1 weight % more preferably, and more preferably 0.01～1 weight % is preferably 0.01～0.5 weight % especially.

(vi) antistatic agent

As antistatic agent, for example can enumerate polyether ester amides, Zerol, the high condenses alkali of naphthalenesulfonateformaldehyde formaldehyde (soil) metal-salt, Witco 1298 Soft Acid alkali (soil) metal-salt, Witco 1298 Soft Acid ammonium salt, Witco 1298 Soft Acid

Salt, maleic anhydride direactive glyceride and maleic anhydride two glyceryl ester etc.In 100 weight % resin combinations, the use level of antistatic agent is preferably 0.01～10 weight %.

(vii) flow ability modifying agent

As flow ability modifying agent, for example (for example can enumerate softening agent, representational have a phosphoric acid ester, the phosphoric acid ester oligopolymer, the phosphonitrile oligopolymer, fatty acid ester, aliphatic polyester and aliphatic polycarbonate etc.), other thermoplastic resins of high rigidity and high workability or thermoplastic resin oligopolymer are (for example, representational have and will be selected from vinylbenzene, at least a composition polymerization in vinyl cyanide and the polymethylmethacrylate and the weight-average molecular weight that obtains are less than 40000 polymkeric substance, the oligopolymer of high rigidity polycarbonate etc.), liquid crystalline polymers (for example, representational liquid crystal polyester etc. arranged), upright and outspoken type molecule (for example, representational poly(p-phenylene) based compound etc. arranged), and lubricant (for example, representationally has mineral oil, synthetic oil, high-grade aliphatic ester, high fatty acid amide, organopolysiloxane, olefines wax, polyalkylene glycol and fluorocarbon oil etc.) etc.

In 100 weight % resin combinations, flow ability modifying agent can preferably cooperate 0.1～10 weight %, more preferably cooperates 1～8 weight %.

(viii) fire retardant

As fire retardant, can enumerate with red phosphorus or use known thermosetting resin and/or inorganic materials is carried out the stabilization of micro encapsulation to the red phosphorus surface red phosphorus is the red phosphorus based flame retardant of representative; With the oligopolymer of tetrabromo-bisphenol, tetrabromo-bisphenol, brominated bisphenol based epoxy resin, brominated bisphenol class phenoxy resin, brominated bisphenol class polycarbonate, brominated Polystyrene, bromination crosslinked polystyrene, brominated polyphenylether, poly-dibromobenzene aether, decabromodiphynly oxide bis-phenol condenses and contain the halogen based flame retardant that halophosphate is representative; Being the organophosphate based flame retardant of representative as the triphenylphosphate of phosplate compound, as Resorcinol two (two (xylyl) phosphoric acid ester) and the dihydroxyphenyl propane two (diphenyl phosphoester) and the tetramethylolmethane phenylbenzene bisphosphate etc. of condensed phosphoric acid esters; The hydrate of inorganic metal compounds such as mineral-type phosphoric acid salt, aluminium hydroxide, magnesium hydroxide such as polyphosphoric acid ammonium salt, aluminum phosphate, zirconium phosphate, zinc borate, zinc metaborate, magnesium oxide, molybdenum oxide, zirconium white, stannic oxide, weisspiessglanz etc. are the mineral-type fire retardant of representative; Potassium perfluorobutane sulfonate, perfluorinated butane calcium sulphonate, perfluorinated butane sulfonic acid caesium, sulfobenzide-3-potassium sulfonate, sulfobenzide-3,3 '-disulfonic acid potassium are organic bases (soil) the metallic salt fire retardant of representative; The multipolymer that contains (gathering) organosilicone compounds of aryl and alkoxyl group, (gathering) organosilicone compounds that contains aryl and Si-H group or (gathering) organo-siloxane and polycarbonate resin is the type siloxane fire retardant of representative; It with phenoxy phosphazene oligopolymer or ring-type phenoxy phosphazene oligopolymer phosphazene flame retardant of representative etc.

In 100 weight % resin combinations, the content of fire retardant is preferably 0.1～50 weight %, more preferably 0.1～20 weight %.

(ix) Antidrip agent

Fusion when Antidrip agent prevents to burn is dripped and flame retardant resistance is further improved.As Antidrip agent, preferred fluorine-containing Antidrip agent.

As the fluorine-containing Antidrip agent that is suitable as Antidrip agent, can enumerate fluoropolymer with protofibril formation ability.As such polymkeric substance, can enumerate the polycarbonate resin of making by partially fluorinated polymkeric substance, fluorinated biphenyl phenol shown in tetrafluoroethylene, tetrafluoroethylene copolymer (for example, tetrafluoroethylene/hexafluoropropylene copolymer etc.), No. 4379910 communique of United States Patent (USP) etc.Wherein, preferably polytetrafluoroethylene (below, be sometimes referred to as PTFE).

Have the PTFE that protofibril forms ability and have ultra high molecular weight, thereby and because external actions such as shearing force make the PTFE demonstration that is bonded to each other become the material of fibrous tendency.Its number-average molecular weight is 1,500,000～several scopes of ten million.Lower limit more preferably 3,000,000.It is disclosed that this number-average molecular weight such as spy open flat 6-145520 communique, calculates based on the melt viscosity of the tetrafluoroethylene under 380 ℃.That is, the melt viscosity under the fibrillation PTFE measure with the method for this communique record 380 ℃ is 10 ⁷～10 ¹³The scope of pool is preferably 10 ⁸～10 ¹²The scope of pool.This PTFE can also use the aqueous liquid dispersion form except solid shape.In order to improve dispersed in resin and to obtain excellent flame-retardant performance and mechanical characteristics, this has PTFE that protofibril forms ability can also use PTFE mixture with the mixed style of other resins.

As having the commercially available product that protofibril forms the PTFE of ability, for example can enumerate teflon (registered trademark) 6J of Mitsui デ ユ Port Application Off ロ ロ ケ ミ カ Le (strain), Port リ Off ロ Application MPA FA500, the F-201L etc. of ダ イ キ Application chemical industry (strain).As the commercially available product of the aqueous liquid dispersion of PTFE, representationally enumerate Off Le オ Application AD-1, the AD-936 that rising sun ア イ シ one ア イ Off ロ ロ Port リ マ one ズ (strain) makes; Off Le オ Application D-1, D-2 that ダ イ キ Application industry (strain) is made; Teflon (registered trademark) 30J that Mitsui デ ユ Port Application Off ロ ロ ケ ミ カ Le (strain) is made etc.

PTFE as mixed style, can obtain by the following method: (1) is mixed the aqueous liquid dispersion of the aqueous liquid dispersion of PTFE and organic polymer or solution and is carried out co-precipitation, thereby (spy opens clear 60-258263 communique to obtain the method for common cohesion mixture, the spy opens the method for records such as clear 63-154744 communique), (2) with the aqueous liquid dispersion of PTFE and exsiccant organic polymer particle blended method (spy opens the method for flat 4-272957 communique record), (3) with aqueous liquid dispersion and the organic polymer particle solution uniform mixing of PTFE, (spy opens flat 06-220210 communique to remove the method for medium separately again from this mixture simultaneously, the method of record such as Te Kaiping 08-188653 communique), (4) in the aqueous liquid dispersion of PTFE, will be formed with the method (spy opens the method for flat 9-95583 communique record) of the monomer polymerization of organic polymer, and behind (5) aqueous liquid dispersion and organic polymer dispersion liquid uniform mixing with PTFE, polymerising ethylene base class monomer in this mixed dispersion liquid again obtains the method (spy opens the method that waits record for flat 11-29679 number) of mixture then.As the commercially available product of the PTFE of these mixed styles, can enumerate " メ タ Block レ Application A3800 " (trade(brand)name) of Mitsubishi's レ イ ヨ Application (strain) and " BLENDEXB449 " (trade(brand)name) that GE ス ペ シ ヤ リ ラ イ one ケ ミ カ Le ズ company makes etc.

As the ratio of the PTFE in the mixed style, in 100 weight %PTFE mixtures, PTFE is preferably 1～60 weight %, more preferably 5～55 weight %.When the ratio of PTFE is in this scope, can realize the good dispersiveness of PTFE.

In 100 weight % resin combinations, the content of Antidrip agent is preferably 0.01～10 weight %, more preferably 0.1～3 weight %.

(manufacturing of resin combination)

Resin combination of the present invention can be made by the following method, for example, A composition, B composition and other compositions is carried out pre-mixing, then melting mixing, granulating.As premixed device, can enumerate nauta mixer, V-type mixing machine, Henschel mixing tank, power chemical devices, extrude mixing machine etc.When pre-mixing, as required, can carry out granulation by extruding pelletization device or material cake preformer etc.After pre-mixing, the preferred employing with the exhaust biaxial extruder is that the melting mixing machine of representative carries out melting mixing, carries out granulating by machines such as tablets presss.As the melting mixing machine, also can enumerate banbury mixers, mixing roller, permanent heat agitated container etc., but preferred exhaust biaxial extruder.

In addition, can also take each composition pre-mixing not to be supplied to independently with the biaxial extruder respectively is method in the melting mixing machine of representative.Also can enumerate after the pre-mixing of part composition, supply to method in the melting mixing machine independently with remaining component.Particularly, when cooperating inorganic filling material, inorganic materials preferably uses the such feedway of side charger to be supplied in the molten resin by forcing machine supplying opening midway.About premixed device and granulation, same as described above.When the composition that cooperates has liquid material, can use so-called fluid infusion apparatus or liquid appending apparatus to supply with to the melting mixing machine.

Further the moisture that preferably contains in A composition and the B composition before melting mixing is few.Therefore, more preferably by carrying out melting mixing again after methods such as various warm air dryings, hertzian wave drying, vacuum-drying any or both dryings with A composition or B composition.Exhaust air suction degree in the melting mixing is preferably 1～60kPa, more preferably the scope of 2～30kPa.

The resin combination of extruding as mentioned above is preferred directly to cut off and granulating, perhaps after forming the line material, utilizes tablets press line material to cut off and granulating.When granulating, being necessary to reduce the influencing of outside dust etc., preferably with the atmosphere cleaning gasization around the forcing machine.In addition, in such particulate is made, the preferred stricturization that uses the whole bag of tricks that has proposed in polycarbonate resin at CD suitably to carry out coating of particles to distribute, reduce and wrongly cut thing, reduce the micro mist that transports or produce when carrying and reduce the line material or the bubble (bubbles of vacuum) of granule interior generation.Can carry out the height periodization of moulding and reduce the so bad generation ratio of crazing by these processing.In addition, coating of particles can be taked cylinder, prism and general shape such as spherical, but more preferably cylinder.The diameter of this cylinder is preferably 1～5mm, more preferably 1.5～4mm, more preferably 2～3.3mm.On the other hand, the length of cylinder is preferably 1～30mm, more preferably 2～5mm, more preferably 2.5～3.5mm.

By injection moulding resin composition pellet of the present invention, can obtain formed bodys such as outside vehicle material of the present invention.In addition, particle preferably contains the single particle of all the components that constitutes formed body, but particle that also can mixing element is different when injection moulding and obtain formed body.

＜formed body 〉

The present invention comprises the formed body of being made by above-mentioned resin combination.As formed body, can enumerate the parts of the such trolley part of outside vehicle material, OA equipment.

＜outside vehicle material 〉

The present invention comprises the outside vehicle material of being made by above-mentioned formed body.The outside vehicle material mainly is made of the position that does not need Artistic Design that is arranged on the Artistic Design face on any one face of the positive back side and is selected from the breakthrough part that forms than the depressed part that falls into behind the Artistic Design face and by the face disappearance.

The surfaceness (Ra) based on JIS B0601-1994 measured of outside vehicle material in the Artistic Design face is preferably 0.001～3 μ m, 0.01～1 μ m more preferably, the energy-to-break in 23 ℃ of high speed face shock tests of measuring down is preferably the scope of 3～70J.

The surfaceness on formed body surface depends on die surface smoothness, condition of molding and heat insulation mould or heats die apparatus such as cooling die and formed material etc. rapidly.Surfaceness (Ra) is than above-mentioned scope hour, and it is superfluous that these equipment become, and shortcoming forming stability easily perhaps becomes.On the other hand, when surfaceness (Ra) is bigger than above-mentioned scope, become insufficient easily, perhaps need superfluous application as the outside vehicle material.When Ra was 0.01～1 μ m, these balance was excellent especially.

The outside vehicle material preferably has on the Artistic Design face at least films.That is, the outside vehicle material is preferably at coating composition on its Artistic Design face at least after the moulding, then is cured 100～140 ℃ temperature range and handles and form the outside vehicle material of filming.More preferably 105～135 ℃ of this temperature ranges, more preferably 115～135 ℃.The storing temperature of coating is high more, and few more with the tone difference of steel plate part, gloss is also good, and the result can have the application of feeling of high class.In the preferred mode of the present invention, outside vehicle material of the present invention can fully tolerate application.In addition, because environmental problem has in recent years also been studied new coating (water-borne coatings and powder coating etc.), in formed body of the present invention, can preferably use these new coatings.In addition, in order not carry out application, broad research the film produced by insert molding, formed body of the present invention is compared with common injection-molded article, the adaptability excellence of film produced by insert molding is particularly suitable for the film produced by insert molding of deep drawn shape.

Artistic Design face among the present invention in the said outside vehicle material is meant when observing under the state that vehicle can travel at least, can be from the face of outside identification.

The outside vehicle material preferably is attached to material on the framework by the rubber mass binding agent.The rubber mass binding agent can use known binding agent, but can preferably use two component polyurethane adhesive.As the object lesson of preferred two component polyurethane adhesive, the BETAMATE2810 (trade(brand)name, the combination of A agent and B/S agent) that for example has DOW AUTOMOTIVE company to make.The preferred wash primer that uses as the preferred object lesson of wash primer, for example can be enumerated the BETAPRIME5404 (trade(brand)name) that DOW AUTOMOTIVE company makes in this binding agent.

The outside vehicle material has preferably been installed photopermeability parts or means of illumination at least one part of its depressed part or breakthrough part.Thus, the outside vehicle material can have the higher function as modular unit simultaneously.

The maximal projection area of outside vehicle material is preferably 1500～40000cm ², 2000～20000cm more preferably ², 2200～15000cm more preferably ²

As the outside vehicle material, can enumerate squab panel, splash pan, collision bumper, car door, column, side protector, side rubbing strip, back protector, back rubbing strip, various turbulence generator, hood, top cover, luggage-boot lid, removable top cover and vehicle window reflective mirror etc.Outside vehicle material of the present invention is applicable to splash pan and so-called vertical outside plates such as car door.The wheel house that also can enumerate the guard shield of two-wheeled motor vehicle and tractor is with dashboard etc.

The resin combination that constitutes the outside vehicle material preferably contains the rubber polymer (C composition) of PET (B composition), 1～8 weight % of PC (A composition), 5～35 weight % of 40～90 weight % and the inorganic filling material (D composition) of 3～25 weight % in 100 weight % resin combinations.

The manufacture method of＜outside vehicle material 〉

The present invention comprises the method for having used above-mentioned resin combination to make the outside vehicle material.This method has been utilized the cascade moulding of adopting the SVG method.In the method, (ii) outside vehicle material and (iii) resin combination is as mentioned above.(i) mould has following feature.

(i) mould is as described below:

(i-1) have simultaneously cast gate A and cast gate B,

(i-2) cast gate B be the molten resin that the cast gate from other flows into flow pass through after, supply with molten resin and with the cast gate at this interflow of flowing, on the other hand, cast gate A be do not flow the interflow with molten resin and supply with molten resin cast gate,

(i-3) scope of each the cast gate setting in the mould is: externally on the slant range on the material surface at least 20cm with the interior cast gate that does not have other.

Mould preferably all cast gates is arranged at least a position that does not need Artistic Design that is selected from depressed part, breakthrough part end and the formed body end.

Also preferred (i-4) cast gate B of mould is after supplying with resin by cast gate A, and the supply variable valve that is arranged on the stream that is communicated with cast gate B by control is supplied with molten resin, so that the molten resin that flows into from other cast gates flows by the back and the interflow of should flowing.The control of such variable valve can use commercially available device to carry out with arbitrary method.For example can enumerate time control, screw position control and the control of die cavity internal pressure etc.If the supply of the molten resin among the cast gate B is too fast, then produce the backflow of molten resin, make the resin flow disorder, therefore produce bad order or welded bonds.This was supplied with when slow, produced the big density difference with the resin of cast gate B from the molten resin cooling of other cast gates, thereby still was easy to generate bad order.Therefore, be necessary to control the opening/closing timing of the suitable cast gate that does not produce these unfavorable conditions.In addition, preferably determine this gate location, so that such switching condition on opportunity has permission as far as possible.

In the cascade moulding of adopting the SVG method,, all be necessary to make molten resin to flow to other cast gate at least from the resin of any cast gate except its molten resin the cast gate of the last supply molten resin by other cast gates.In addition, in the end supply with in the cast gate of molten resin, molten resin is necessary to flow to its goods end.

In the present invention, if each cast gate satisfies above-mentioned (i-3), then its configuration is not particularly limited, but in portion gate, compare the cast gate configuration that becomes short especially or because this configuration etc. are former thereby when supply amount of resin from portion gate is tailed off, be easy to generate following drawback with other in the distance between the cast gate of supplying with molten resin and the cast gate that passes through from the molten resin of this cast gate.(a) control that opens and closes of cast gate becomes difficulty, (b) easily because the amount of resin of supplying with is compared with other tails off, thereby elongated in the residence time of this partial melting resin, resin generation thermal degradation when.In addition, after a little while, also produce the drawback of above-mentioned (b) from the supply amount of resin of the cast gate of last supply molten resin.

Therefore, the resin capacity of being supplied with by each cast gate (Vi) preferably satisfies the relation of 0.5≤Vi/Vave≤1.5 with respect to the average capacity (Vave) that the total amount that is filled into the resin capacity in the mould obtains divided by the cast gate number, more preferably satisfy the relation of 0.6≤Vi/Vave≤1.4, the further preferred relation that satisfies 0.7≤Vi/Vave≤1.3.

On the other hand, when satisfying so preferred relation, the part of the wall thickness distance between cast gate that is necessary to extend.Therefore, in the cascade moulding of adopting the SVG method, need be than the necessary good flowability that is far away in the common moulding of manying cast gate.By satisfying such prerequisite, resin combination of the present invention can be made good outside vehicle material in the cascade moulding of adopting the SVG method.In addition, when satisfying above-mentioned preferred relation, its formed body wall thickness is preferably even as far as possible on the whole.Therefore, preferred its wall thickness of outside vehicle material of the present invention is in average wall thickness ± 50%, more preferably in ± 30%.Average wall thickness is meant formed body volume (mm ³) divided by the surface-area (mm of formed body ²) and the value that obtains.

In addition, supply with the cast gate of molten resin and the cast gate that passes through from the molten resin of this cast gate between hypertelorism the time, flowing of molten resin becomes not enough easily.Therefore, above-mentioned condition (i-3): each cast gate in the mould preferably is set to following scope: in the slant range on the outside material surface, at least 20cm with interior do not have other cast gates and at 80cm with interior other cast gates that exists; More preferably be set at least 25cm with interior do not have other cast gates and at 70cm with the interior scope that has other cast gates; Further preferably be set at least 25cm with interior do not have other cast gates and at 60cm with the interior scope that has other cast gates.

Injection moulding also can partly or entirely using injection compression molding, slush molding, heat known shaping such as cooling forming and dual-color forming rapidly the outside vehicle material simultaneously.Particularly, to formed body wall thickness part use simultaneously slush molding, the breakthrough part of outside vehicle material or depressed part with transparent resin material carry out dual-color forming, the transparent component that carries out dual-color forming adopts injection compression molding to carry out moulding, the position that needs Artistic Design especially used to heat cooling forming etc. rapidly be effective.

According to the manufacture method of outside vehicle material of the present invention, the welded bonds of the formed body that can suppress to obtain.According to the manufacture method of outside vehicle material of the present invention, can improve the degree of freedom of cast gate number, the result can be with the lower large-scale formed body of clamp force injection moulding.

Embodiment

Below, narrate the present invention in more detail by embodiment.

I. raw material

(A composition)

PC1: the straight chain aromatic copolycarbonate powder of viscosity-average molecular weight 19700 (Supreme Being people changes into the パ Application ラ イ ト L-1225WX (trade(brand)name) that (strain) makes)

PC2: the straight chain aromatic copolycarbonate powder of viscosity-average molecular weight 16000 (Supreme Being people changes into the パ Application ラ イ ト CM-1000 (trade(brand)name) that (strain) makes)

PC3: the straight chain aromatic copolycarbonate powder of viscosity-average molecular weight 20900 (Supreme Being people changes into the パ Application ラ イ ト L-1225WS (trade(brand)name) that (strain) makes)

PC4: the straight chain aromatic copolycarbonate particle of viscosity-average molecular weight 19700 (Supreme Being people changes into the パ Application ラ イ ト L-1225L (trade(brand)name) that (strain) makes)

(B composition)

PET1: the polymerizing catalyst polymeric IV value of using germanium compound is 0.51, the terminal carboxyl(group) amount is that (Supreme Being people changes into (strain) and makes, TR-MB) for 2.0 polyethylene terephthalate as 26.3eq/ton, Mw/Mn

PET2: the polymerizing catalyst polymeric IV value of using germanium compound is 0.56, the terminal carboxyl(group) amount is that (Supreme Being people changes into (strain) and makes, TR-L) for 2.1 polyethylene terephthalate as 23.2eq/ton, Mw/Mn

(beyond the B composition)

PET3: the polymerizing catalyst polymeric IV value of using germanium compound is 0.70, the terminal carboxyl(group) amount as 22.0eq/ton, Mw/Mn is 1.9 polyethylene terephthalate (Supreme Being people changes into (strain) and makes, TR-4550 (trade(brand)name))

PET4: the polymerizing catalyst polymeric IV value of using germanium compound is 0.83, the terminal carboxyl(group) amount as 18.0eq/ton, Mw/Mn is 2.1 polyethylene terephthalate (Supreme Being people changes into (strain) and makes, TR-8580 (trade(brand)name))

(C composition)

IM1: divinyl alkyl methacrylate styrol copolymer (ロ one system ア Application De Ha one ス company makes, BTA712 (trade(brand)name))

IM2: divinyl alkyl acrylate alkyl methacrylate multipolymer (ロ one system ア Application De Ha one ス company makes, パ ラ ロ イ De EXL2602 (trade(brand)name))

(D composition)

WSN1: wollastonite (NYCO company makes, NYGLOS4 (trade(brand)name))

WSN2: wollastonite (river ironworker industry (strain) is made, PH-330 (trade(brand)name))

GF: glass fibre (day east is spun (strain) and made, 3PE-944 (trade(brand)name))

(E composition)

WAX:1-alkene copolymer-maleic anhydride (the ダ イ ヤ カ Le Na 30M (trade(brand)name) that Mitsubishi Chemical's (strain) makes)

(other)

The PBT1:IV value is 0.87 polybutylene terephthalate (Port リ プ ラ ス チ Star Network ス (strain) makes, ジ ユ ラ ネ Star Network ス 500FP (trade(brand)name))

ST1: Phosphorus stablizer (rising sun electrochemical industry (strain) is made, ア デ カ ス タ Block PEP-8 (trade(brand)name))

ST2: Phosphorus stablizer (rising sun electrochemical industry (strain) is made, ア デ カ ス タ Block PEP-24G (trade(brand)name))

UV: UV light absorber (シ プ ロ changes into (strain) and makes, シ one ソ one Block 701 (trade(brand)name))

CB: black masterbatch (paddy changes into industry (strain) manufacturing, ロ イ ヤ Le Block ラ Star Network 904S (trade(brand)name) more)

COL: (タ イ オ キ サ イ De ジ ヤ パ Application (strain) is made to add 25 weight % titanium dioxide in above-mentioned PC1, RTC30) and 0.5 weight % carbon black (Mitsubishi Chemical's (strain) make #970) and to make total amount be 100 weight %, do mixed and finely dispersed material with super mixing tank

II. the making of test film

Utilize hot air dryer to make the particle drying 4 hours of the resin combination of manufacturing under 120 ℃, (FANUC company makes: T-150D) at 270 ℃ of barrel temperatures, 70 ℃ of compacted unders of die temperature with the shaper of clamp force 1470kN.Make the test film shape based on the test film of standard separately.

III. the evaluating characteristics of resin combination

(i) MVR (unit: cm ³/ 10 minutes): use the resin particle of making, based on the melt volume speed under 280 ℃ of ISO1133 standard tests, the 2.16kg load (MVR value).Particle passed through hot air dryer down dry 4 hours at 120 ℃ in advance during mensuration.Measure メ Le ト イ Application デ Network サ one 2A that uses the smart machine of (strain) Japan to make.

(ii) load deflection deformation temperature (unit: ℃): make test film with above-mentioned method, under 0.45MPa load, measure load deflection deformation temperature based on ASTM D-648 standard.

(iii) bending elastic modulus (unit: MPa): make test film with above-mentioned method, based on ASTM D-790 standard test bending elastic modulus.

(iv) shock-resistance (unit: J/m): make test film with above-mentioned method, based on the izod impact value (band breach) of 23 ℃ of ASTM D-256 standard tests.

(v) resistance to chemical reagents: make the tension test sheet based on ASTM D-638 standard with above-mentioned method.With 3 bending jigs test film is applied 0.5% strain, and under 23 ℃, impregnated in gasoline (エ Star ソ (strain) make, regular grade gasoline) 10 minutes.Implement each 10 test, the sheet number that record does not crack etc.

(vi) thermostability: except barrel temperature being set at 280 ℃, adopt the method identical with the making item of above-mentioned test film, injection molding 20 power plates (after 150 * 150 * 3mmt), make shaping cycle stop wittingly, implement delay in 10 minutes continuously.Confirm to be detained the formed body outward appearance of the 1st the material feeding～3rd time material feeding in back, implement following evaluation.

◎ is the generation to crazing etc. unconfirmed on formed body surface.

Though zero has confirmed crazing in the 1st material feeding, in the 2nd and the 3rd material feeding, do not confirm the generation of crazing etc.

＜embodiment 1～6 (manufacturing of resin combination) 〉

Use the raw material of kind shown in the table 1 and amount, utilize forcing machine to make the particle of resin combination (E1)～(E6).The TEM-48SS (L/D=50, machine barrel several 13) that forcing machine uses toshiba machine (strain) to make.Pulverous A composition uses paddle dryer and granular A composition uses Hopper Dryer dry down more than 4 hours, again by main feeder input at 120 ℃ in advance.The B composition is dry down more than 4 hours, again by main feeder input at 120 ℃ in Hopper Dryer in advance.D composition and wax are pre-mixed, and use the weigher that is independent of the B composition, from the side feeder input.For the composition beyond these, use the Henschel mixer premix in advance, again by main feeder input.Set exhaust at the 10th machine barrel place, implement suction with the vacuum tightness that 6kPa is following.Other extrusion condition is: 260 ℃ of barrel design temperatures, 270 ℃ of die head design temperatures, extrude rate 200kg/ hour and screw speed 250rpm.The characteristic of the particle that obtains (E1)～(E6) is as shown in table 1.

＜comparative example 1～7 〉

Except the raw material that uses kind shown in the table 1 and amount, carry out the operation same with embodiment 1～6, make the particle (CE1)～(CE7) of resin combination.The characteristic of particle (CE1)～(CE7) is as shown in table 1.

Table 1

[0299]As shown in table 1, resin combination of the present invention has high flowability (MVR), and has high resistance to chemical reagents, and modulus, shock-resistance, thermostability are also excellent.

＜embodiment 7～12 (manufacturing of formed body) 〉

Particle (E1)～(E6) was descended the outside vehicle material formed body that moulding is shown in Figure 1 dry 4 hours at 120 ℃.The J1300E-C5 that moulding uses (strain) JSW to make.The barrel design temperature is 270 ℃, and die temperature is 60 ℃.The front end of annotating the road all is connected with the valve gate of hot-runner mould, opens in the following sequence with the valve gate that each cast gate is connected.That is, at first open the cast gate (16) of formed body top of tower and be present in the cast gate (15) of the bottom on the symmetry axis.Then, opening valve after just by cast gate 11, molten resin is supplied with from cast gate 11 from the molten resin of cast gate 16.In addition, opening valve after just by cast gate 14, molten resin is supplied with from cast gate 14 from the molten resin of cast gate 15.Outer material is lip-deep, and 11 slant range is about 33.5cm from cast gate 16 to cast gate, and outer material is lip-deep, and 14 slant range is about 26.8cm from cast gate 15 to cast gate.The particulate numbering of using among each embodiment is as shown in table 2.

Table 2

The embodiment numbering

7?

8?

9?

10?

11?

12?

The particle numbering

(E1)?

(E2)?

(E3)?

(E4)?

(E5)?

(E6)?

＜comparative example 8～14 〉

Except using particle (CE1)～(CE7), carry out the operation same, the formed body that moulding is shown in Figure 1 with embodiment 7～12.The particulate numbering of using in each comparative example is as shown in table 3.

Table 3

The comparative example numbering

8?

9?

10?

11?

12?

13?

14?

The particle numbering

(CE1)?

(CE2)?

(CE3)?

(CE4)?

(CE5)?

(CE6)?

(CE7)?

(evaluation of formability)

In embodiment 7～12, comparative example 8～9,, obtain on the Artistic Design face, almost not finding the formed body of welded bonds by adopting the cascade moulding of SVG method.The welded bonds of Artistic Design face is an identifiable degree when observing under strong light source, and its length is about 1cm.In addition, based on JIS B0601-1994 standard, when sampling 5 places measure surfaceness (Ra) on the Artistic Design face, be between 0.15～0.20 μ m.Because the outward appearance of Artistic Design face is even, therefore judge that arbitrary portion all can satisfy this value.For embodiment 12,, can obtain formed body by mold temperature being set at 300 ℃.

On the other hand, in the comparative example 10～13 that uses particle (CE3)～(CE6), because the illiquidity of resin combination, even, on the Artistic Design face, also produce tangible welded bonds therefore at same condition compacted under.If the barrel design temperature is set to 300 ℃, then this welded bonds disappears, but produces crazing on the Artistic Design face, can not obtain the good formed body of outward appearance.

For the comparative example 14 that has used particle (CE7), under 300 ℃ of mold temperatures, flowability is also insufficient, can not obtain formed body.

(evaluation of coating)

For the embodiment 7～12{ particle (E1)～(E6) that obtains good formed body }, comparative example 8～9{ particle (CE1)～(CE2) formed body implement application.The storing temperature of application is 120 ℃.After this application, the formed body of comparative example 8～9 cracks at gate part, is coated with to be contained in this part and to be inhaled into, and produces so-called application and sucks, and outward appearance reduces.For the formed body of embodiment 7～12, can obtain the good application product of application outward appearance.

The effect of invention

Resin combination of the present invention has kept good flowability and has had high resistance to chemical reagents, and resistance to impact, heat resistance, rigidity, heat endurance are also excellent. In addition, the resistance to impact of formed body of the present invention, heat resistance, rigidity, heat endurance, resistance to chemical reagents and outward appearance excellence. According to the manufacture method of outside vehicle material of the present invention, the generation of the melt run that can be inhibited also has excellent outward appearance and the outside vehicle material on surface.

Industrial applicability

Resin combination of the present invention therefore can be in the widely industrial field use such as automotive field, OA apparatus field, electronic electric equipment field, building materials field, Agricultural Materials field, fishery Material Field owing to resistance to impact, rigidity, excellent heat resistance.

Claims (24)

1. A resin composition comprising 50 to 100% by weight of a resin component and 0 to 50% by weight of an inorganic filler as component D, wherein the resin component comprises: (i) bisphenol A aromatic polycarbonate with a viscosity average molecular weight of 16,000 to 23,000 as component A; and (ii) As component B, polyethylene terephthalate has an intrinsic viscosity IV of 0.45 to 0.57 dl/g, an amount of terminal carboxyl groups of 20 to 35 eq/ton, and a ratio Mw of the weight average molecular weight Mw to the number average molecular weight Mn /Mn is 1.3 to 2.1, and, (iii) The weight ratio (A+D)/B of the total amount of A component and D component to B component is 60/40-85/15. 2. The resin composition according to claim 1, wherein the weight ratio A/B of the A component and the B component is 40/60 to 90/10. 3. The resin composition according to claim 1, wherein the intrinsic viscosity IV of component B is 0.47 to 0.55 dl/g. 4. The resin composition according to claim 1, which contains 1 to 50 parts by weight of a rubbery polymer as the C component with respect to 100 parts by weight of the total amount of the A component and the B component. 5. The resin composition according to claim 4, wherein, the C component is selected from styrene-butadiene copolymer, acrylonitrile-butadiene-styrene copolymer, methyl methacrylate-butadiene- At least one rubbery polymer selected from a styrene copolymer and a methyl methacrylate-(acrylic-siloxane IPN rubber) copolymer. 6 . The resin composition according to claim 1 , which contains 0.01 to 10 parts by weight of a fracture inhibitor as the E component with respect to 100 parts by weight of the total amount of the A component and the B component. 7. The resin composition according to claim 1, wherein component D is a sheet-like filler and/or a fibrous filler. 8. The resin composition according to claim 1, wherein component D is at least one inorganic filler selected from mica, talc, wollastonite, and glass fiber. 9. The resin composition according to claim 1, wherein component D is wollastonite or glass fiber. 10. The resin composition according to claim 1, wherein the component B is polyethylene terephthalate polymerized using a germanium-based polymerization catalyst. 11. The resin composition according to claim 1, which comprises 70 to 95% by weight of the resin component and 30 to 5% by weight of wollastonite with an average fiber diameter of 1 to 2 μm and an aspect ratio of 5 to 9 as D Composition, wherein, resin composition comprises: (i) bisphenol A aromatic polycarbonate with a viscosity average molecular weight of 16,000 to 23,000 as component A; and (ii) Polyethylene terephthalate polymerized with a germanium-based polymerization catalyst is used as component B, and its intrinsic viscosity IV is 0.49-0.57dl/g, the amount of terminal carboxyl groups is 23-28eq/ton, and the weight-average molecular weight Mw and The ratio Mw/Mn of the number average molecular weight Mn is 1.9 to 2.1, and, (iii) The weight ratio (A+D)/B of the total amount of components A and D to component B is 70/30 to 80/20; (iv) Weight ratio A/B of A component and B component is 65/35-75/25. 12. The resin composition according to claim 1, comprising 55 to 65% by weight of resin components and 45 to 35% by weight of glass fibers having an average fiber diameter of 10 to 15 μm and an average fiber length of 230 to 270 μm as component D , wherein the resin component contains: (i) bisphenol A aromatic polycarbonate with a viscosity average molecular weight of 16,000 to 23,000 as component A; and (ii) Polyethylene terephthalate polymerized with a germanium-based polymerization catalyst is used as the B component, and its intrinsic viscosity IV is 0.49 to 0.52dl/g, the amount of terminal carboxyl groups is 23 to 28eq/ton, and the weight average molecular weight Mw and The ratio Mw/Mn of the number average molecular weight Mn is 1.9 to 2.1, and, (iii) The weight ratio (A+D)/B of the total amount of components A and D to component B is 65/35 to 75/25; (iv) Weight ratio A/B of A component and B component is 45/55-55/45. 13. A fluid resin composition comprising 50 to 100% by weight of a resin component and 0 to 50% by weight of at least one inorganic filler selected from mica, talc and wollastonite as component D, wherein the resin component Include: (i) polycarbonate as A1 component, which is selected from bisphenol A polycarbonate with a viscosity average molecular weight of 16000-23000; and (ii) Polyethylene terephthalate is used as the B1 component, which is selected from the group with an intrinsic viscosity IV of 0.45-0.57dl/g, an amount of terminal carboxyl groups of 20-35eq/ton, a weight-average molecular weight Mw and a number-average molecular weight Mn. A polyethylene terephthalate having a ratio Mw/Mn of 1.3 to 2.1, and, (iii) The weight ratio (A1+D)/B1 of the total amount of components A1 and D to component B1 is 60/40 to 85/15; (iv) The melt volume rate measured based on the ISO1133 standard at 280°C and under a load of 2.16kg, that is, the MVR value is 23 to 150 cm ³ /10 minutes, and the flexural modulus measured based on the ASTM D-790 standard is 2000 to 25000 MPa, In addition, the occurrence rate of cracks in the chemical resistance evaluation was 0 to 20%. 14. A fluid resin composition comprising 50 to 100% by weight of a resin component and 0 to 50% by weight of glass fibers as component D, wherein the resin component comprises: (i) polycarbonate as the A1 component, which is selected from bisphenol A polycarbonates with a viscosity-average molecular weight of 16,000 to 23,000; and (ii) Polyethylene terephthalate is used as the B1 component, which is selected from the group with an intrinsic viscosity IV of 0.45 to 0.57 dl/g, an amount of terminal carboxyl groups of 20 to 35 eq/ton, a weight average molecular weight Mw and a number average molecular weight Mn. A polyethylene terephthalate having a ratio Mw/Mn of 1.3 to 2.1, and, (iii) The weight ratio (A1+D)/B1 of the total amount of components A1 and D to component B1 is 60/40 to 85/15; (iv) The melt volume rate measured based on the ISO1133 standard at 280°C under a load of 2.16kg, that is, the MVR value, is 10 to 150 cm ³ /10 minutes, and the flexural modulus measured based on the ASTM D-790 standard is 8000 to 25000 MPa, In addition, the occurrence rate of cracks in the chemical resistance evaluation was 0 to 10%. 15. A molded article comprising the resin composition according to claim 1. 16. A vehicle exterior material comprising the molded body according to claim 15. 17. The vehicle exterior material according to claim 16, wherein the surface roughness Ra measured based on JIS B0601-1994 in the artistic design surface is 0.001 to 3 μm, and the fracture energy in the high-speed surface impact test measured at 23° C. is The range of 3 ~ 70J. 18. The vehicle exterior material according to claim 16, which has a coating film on at least the artistic design surface. 19. The vehicle exterior material according to claim 16, which is attached to the frame by a rubbery adhesive. 20. The vehicle exterior material according to claim 16, wherein a light-transmitting member or a lighting device is attached to at least one portion of the recessed portion or the penetrating portion. 21. The vehicle exterior material according to claim 16, wherein the maximum projected area is in the range of 1500 to 40000 cm ² . 22. A manufacturing method of a vehicle exterior material, which manufactures a vehicle exterior material by injection molding a resin composition in a mold, wherein, (i) The molds are as follows: (i-1) There are both gate A and gate B, (i-2) Gate B is a gate that supplies molten resin and merges with the flow of molten resin flowing in from other gates, and gate A supplies molten resin without merging with the flow of molten resin. the gate, (i-3) The setting range of each gate in the mold is: there are no other gates within at least 20cm of the linear distance on the surface of the external material; (ii) The exterior material of the vehicle is as follows: (ii-1) It is mainly composed of an artistic design surface provided on either side of the front and back, and a part that does not require artistic design selected from a recessed portion that is recessed from the artistic design surface and a penetrating portion formed by a missing surface ; (iii) The resin composition is as follows: (iii-1) Containing 50 to 100% by weight of a resin component and 0 to 50% by weight of an inorganic filler as component D, wherein the resin component includes: (iii-2) Bisphenol A aromatic polycarbonate with a viscosity average molecular weight of 16,000 to 23,000 as component A; and (iii-3) As component B, polyethylene terephthalate has an intrinsic viscosity IV of 0.45 to 0.57 dl/g, an amount of terminal carboxyl groups of 20 to 35 eq/ton, and a weight-average molecular weight between Mw and number-average molecular weight Mn. The ratio Mw/Mn is 1.3 to 2.1, and, (iii-4) The weight ratio (A+D)/B of the total amount of A component and D component to B component is 60/40-85/15. 23. The manufacturing method according to claim 22, wherein the mold also has the following characteristics: (i-4) After the gate B is supplied with resin from gate A, the molten resin is supplied by controlling the supply regulating valve provided on the flow path communicating with gate B so that after the molten resin flowing in from other gates flows through Merge with the flow. 24. The manufacturing method according to claim 22, wherein all the gates of the mold are provided in at least one site that does not require artistic design selected from a recessed portion, a through portion, an end portion, and an end portion of a molded body.

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