CN101519528A - Polycarbonate resin composition with superior appearance - Google Patents

Polycarbonate resin composition with superior appearance Download PDF

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CN101519528A
CN101519528A CN 200910007771 CN200910007771A CN101519528A CN 101519528 A CN101519528 A CN 101519528A CN 200910007771 CN200910007771 CN 200910007771 CN 200910007771 A CN200910007771 A CN 200910007771A CN 101519528 A CN101519528 A CN 101519528A
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CN101519528B (en
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相原哲也
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Teijin Ltd
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Teijin Chemicals Ltd
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Abstract

The present invention aims to provide a polycarbonate resin composition has superior impact characteristic and moldability, which does not produce confluence pattern at fusion portion or portion having uneven thickness. 100 parts by weight of the resin composition, relative to 99 to 1 by weight of aromatic polycarbonate resin and 1 to 99 by weight of grafting copolymer, contains 0.1 to 10 parts by weight of core-shell type grafting copolymer, wherein the grafting copolymer contains rubber polymer with 0.20 to 2.0 mu m weight average particle diameter of rubber particle, vinyl cyanogen monomer and aromatic ethylene monomer; the core-shell grafting copolymer is obtained by copolymerization of the mixture of (methyl) acrylate monomer or monomer capable of being copolymerized with (methyl) acrylate monomer by emulsion polymerization, with the existence of diene rubber constituent with 0.30 to 0.50 mu m weight average particle diameter.

Description

The poly carbonate resin composition of outward appearance excellence
Technical field
The present invention relates to a kind of poly carbonate resin composition and moulding product thereof of outward appearance excellence.More particularly, relate to a kind of resin combination that contains polycarbonate resin and specific graft copolymer and specific core-shell grafting copolymer by use, not only have the outward appearance that can not produce the excellence of interflow line (flow line) in fusion (weld) portion or part in uneven thickness, also have the excellent impact characteristics and the resin combination and the moulding product thereof of formability simultaneously.
Background technology
With aromatic polycarbonate resin and ABS resin is representative and polymer alloy graft copolymer, has excellent formability and HI high impact characteristic, thereby is widely used in the purposes of office machine, electric appliance and electronic machine, automobile etc.Wherein, the office machine of laser printer, duplicating machine, notebook computer or projector etc. or the shell of electric appliance and electronic machine, it has high impact-resistant and excellent formability strong request, and the polymer alloy that is formed by this aromatic polycarbonate resin and graft copolymer has become main flow.
Especially nearest, with lightweight or to reduce cost be purpose, the thin-walled property of these outer casing forming product, no applicationization (Tu dress レ ス) are developed, and influenced by it, and be more and more higher with the requirement of material to the shell of having given apperance, high impact-resistant.
As this shell material, proposed much in the polymer alloy of graft copolymer that with aromatic polycarbonate resin and ABS resin is representative, add the method for core-shell grafting copolymer, relative knowledge has been well-known.
For example, known in the resin combination of forming by the oligopolymer of aromatic copolycarbonate, AS resin, ABS resin, organo phosphorous compounds, cooperate the MBS resin as core-shell grafting copolymer, obtain the flame retardant resin composition (patent documentation 1, patent documentation 2, patent documentation 3) of flowability, impact, excellent heat resistance thus.Yet, in this flame retardant resin composition, though by cooperating the MBS resin as core-shell grafting copolymer, can when keeping high workability, obtain high impact, but, in the fusion portion of moulding product or rib, the inhomogeneous portion of boss equal thickness, the uneven color of the wire that the flow pattern when producing because of injection moulding causes becomes very big problem in appearance.Its reason is, the form of the moulding product that formed by this polycarbonate-based flame retardant resin composition is in the different cause of part that flow patterns such as fusion portion or in uneven thickness change, and proposed a lot of improvement and with aromatic polycarbonate resin and ABS resin be the method for consistency of the graft copolymer of representative.
For example, known in the composition that the styrene resin that by polycarbonate resin with ABS resin, HIPS resin is representative is formed, add terpenoid resin as phase solvent, obtain the polycarbonate-based thermoplastic resin (patent documentation 4) of fusion portion intensity, fusion portion outward appearance, melt fluidity excellence thus.Yet, when using this with terpenoid resin during, causing the countermeasure of the bad order phenomenon of uneven color as to injection moulding the time because of flow pattern as the phase solvent of representative, its effect is little, exists problems such as reducing incendivity.
As mentioned above, need develop have more high-grade outward appearance, the resin material of impact characteristics, but present situation is also not obtain.
Patent documentation 1:WO2000/001839 communique
Patent documentation 2:JP spy opens the 2003-41114 communique
Patent documentation 3:JP spy opens the 2001-302898 communique
Patent documentation 4:JP spy opens the 2000-63651 communique
Summary of the invention
The objective of the invention is to, provide a kind of the flame retardant resistance that keeps having originally, thermotolerance, mobile in, also have the outward appearance that is improved to higher level, the polycarbonate resin composition of high impact-resistant.
In order to address the above problem, the inventor etc. have carried out concentrated research, found that, by being in the graft copolymer of representative with aromatic polycarbonate resin and ABS resin, cooperate and have the core-shell grafting copolymer of specific rubber weight average particle diameter, can solve the bad order problem that causes owing to the form that with aromatic polycarbonate resin and ABS resin is the graft copolymer polymer alloy of representative, thereby finish the present invention.
Above-mentioned problem of the present invention realizes in the following manner.
(1) provides a kind of resin combination, it is characterized in that, comprise aromatic polycarbonate resin (A composition), graft copolymer (B composition), and core-shell grafting copolymer (C composition), and total 100 weight parts with respect to the graft copolymer (B composition) of the aromatic polycarbonate resin (A composition) of 99～1 weight % and 1～99 weight %, the core-shell grafting copolymer (C composition) that contains 0.1～10 weight part, wherein, to contain the weight average particle diameter of rubber particles be the rubber polymer of 0.20～2.0 μ m to described graft copolymer (B composition), vinyl cyanide (シ ア Application
Figure A200910007771D0006171540QIETU
PVC ニ Le) monomer and aromatic vinyl monomer; Described core-shell grafting copolymer (C composition) is, at weight average particle diameter be 0.30～0.50 μ m the polydiene composition in the presence of, by emulsion polymerization, with the in addition copolymerization and obtaining of (methyl) alkyl acrylate monomer or (methyl) alkyl acrylate monomer and the monomeric mixture that can carry out copolymerization with (methyl) alkyl acrylate monomer.
(2) as (1) described resin combination, wherein, described graft copolymer (B composition) obtains by letex polymerization, and, contain the polydiene of 1～40 weight % as rubber polymer.
(3) as above-mentioned (1) or (2) described resin combination, wherein, described core-shell grafting copolymer (C composition) is the core-shell grafting copolymer that contains the polydiene composition of 40～90 weight %.
(4), wherein,, contain the inorganic filling material (D composition) of 0.1～50 weight part with respect to total 100 weight parts of A composition and B composition as any described resin combination in above-mentioned (1)～(3).
(5) as above-mentioned (4) described resin combination, wherein, inorganic filling material (D composition) is for being selected from more than one packing materials in the group of being made up of talcum, mica and wollastonite.
(6) as any described resin combination in above-mentioned (1)～(5), wherein, total 100 weight parts with respect to A composition and B composition, contain the fire retardant (E composition) of 0.001～25 weight part and the fluorine-containing Antidrip agent (F composition) of 0.05～2 weight part, described fire retardant (E composition) is for being selected from more than one fire retardants in the group of being made up of phosphoric acid ester, azochlorosulfonate acid alkali (alkaline earth) metal-salt and silicon compounds.
(7) as any described resin combination in above-mentioned (1)～(6), wherein, fire retardant (E composition) is the phosphoric acid ester of following formula (I) expression:
Figure A200910007771D00061
In the formula (I), X is from dihydroxy compound deutero-divalent phenol residue, and described dihydroxy compound is the dihydroxy compound that is selected from the group of being made up of quinhydrones, Resorcinol, two (4-hydroxy diphenyl) methane, dihydroxyphenyl propane, dihydroxyl hexichol, dihydroxy naphthlene, two (4-hydroxy phenyl) sulfone, two (4-hydroxy phenyl) ketone and two (4-hydroxy phenyl) sulfide; N is 0～5 integer, and perhaps, when being the mixture of the different phosphoric acid ester of n number, n is their mean value; R 4, R 5, R 6And R 7Represent independently respectively that from aryl deutero-one bivalent phenol residue described aryl is the aryl that is selected from the group of forming by phenol, cresols, xylenol, isopropyl-phenol, butylphenol and to cumyl phenol.
Description of drawings
Fig. 1 is the surperficial schematic perspective view (the long 178mm * high 10mm in wide 245mm * limit, thickness are 2.0mm) of the moulding product of the imitation notebook computer casing that uses among the embodiment.The cast gate of these moulding product is two side gates (long 5mm * wide 8mm, thickness 1.5mm).
Fig. 2 is the surperficial schematic elevational view of the moulding product that use among the embodiment, is shown with gate location, the interflow line produces the position, envisions fusion sites.
Fig. 3 is the back side schematic elevational view of the moulding product that use among the embodiment, and expression has the state (boss shape: external diameter 6.5mm, internal diameter 2.5mm, 10mm highly) of boss with ribbing.
The explanation of Reference numeral
The moulding product body of 1 imitation notebook computer casing
2 minute surface portions
3 mat surface portions
4 cast gates (side gate two places, long 5mm * wide 8mm, thickness 1.5mm)
5 fusion anticipation positions
6 interflow line A (is the uneven color of the wire that produces of starting point with the part of thinking fusion portion)
7 interflow line B (is the uneven color of starting point in the wire of resin flow direction generation with the boss)
8 boss with ribbing (external diameter 6.5mm, internal diameter 2.5mm, height 10mm)
Embodiment
Below, explain the present invention.
(A composition: aromatic polycarbonate resin)
The polycarbonate resin that uses as the A composition in the present invention, binary phenol and carbonic ether presoma are reacted and the aromatic polycarbonate resin that obtains, as the example of reaction method, can enumerate the solid phase ester-interchange method of interfacial polymerization, melt transesterification process, carbonic ether prepolymer and the ring-opening polymerization method of cyclic carbonate compound etc.
Representative example as binary phenol, can enumerate quinhydrones, Resorcinol, 4,4 '-bis-phenol, 1,1-two (4-hydroxy phenyl) ethane, 2,2-two (4-hydroxy phenyl) propane (being referred to as " dihydroxyphenyl propane " usually), 2,2-two (4-hydroxyl-3-aminomethyl phenyl) propane, 2,2-two (4-hydroxy phenyl) butane, 1,1-two (4-hydroxy phenyl)-1-diphenylphosphino ethanes, 1,1-two (4-hydroxy phenyl) hexanaphthene, 1,1-two (4-hydroxy phenyl)-3,3,5-trimethyl-cyclohexane, 2,2-two (4-hydroxy phenyl) pentanes, 4,4 '-(to the phenylene diisopropylidene) diphenol, 4,4 '-(metaphenylene diisopropylidene) diphenol, 1,1-two (4-hydroxy phenyl)-4-normenthanes, two (4-hydroxy phenyl) oxide compound, two (4-hydroxy phenyl) sulfide, two (4-hydroxy phenyl) sulfoxide, two (4-hydroxy phenyl) sulfone, two (4-hydroxy phenyl) ketone, two (4-hydroxy phenyl) ester, 2,2-two (3,5-two bromo-4-hydroxy phenyls) propane, two (3,5-two bromo-4-hydroxy phenyls) sulfone, two (4-hydroxyl-3-aminomethyl phenyl) sulfide, 9,9-two (4-hydroxy phenyl) fluorenes and 9,9-two (4-hydroxyl-3-aminomethyl phenyl) fluorenes etc.Preferred binary phenol is two (4-hydroxy phenyl) paraffinic hydrocarbonss, wherein, considers from the shock-resistance aspect, preferred especially dihydroxyphenyl propane.
As the carbonic ether precursor, use carboxylic acid halides (Carbonyl halide), carbonic ether ester or haloformate (Ha ロ ホ Le メ-ト) etc., specifically, can enumerate the bishaloformate etc. of phosgene (Phosgene), dipheryl carbonate base ester or binary phenol.
When by interfacial polymerization, when making polycarbonate resin, also can use catalyzer, end to stop agent, antioxidant etc. as required by above-mentioned binary phenol and carbonic ether precursor, wherein antioxidant is used to prevent the oxidation of binary phenol.In addition, aromatic polycarbonate resin of the present invention comprises: with the branched polycarbonate resin of copolymerization in addition of the multifunctional aromatics more than the three-functionality-degree; With two functionality carboxylic acids of aromatic series or aliphatics (comprising alicyclic) the polyestercarbonate resin of copolymerization in addition; With two functionality alcohol (the comprising alicyclic) copolymerized panlite of copolymerization in addition; And with this two functionality carboxylic acid and the two official's degree alcohol polyestercarbonate resin of copolymerization in addition.In addition, also can be two or more blended mixtures in addition with resulting polycarbonate resin.
Multifunctional aromatics as more than the three-functionality-degree can use 1,1,1-three (4-hydroxy phenyl) ethane, 1,1,1-three (3,5-dimethyl-4-hydroxy phenyl) ethane etc.
When containing the polyfunctional compound that can produce branched polycarbonate, this polyfunctional compound's content ratio is 0.001～1 mole of %, is preferably 0.005～0.9 mole of %, is preferably 0.01～0.8 mole of % especially in the aromatic copolycarbonate total amount.In addition, when particularly adopting melt transesterification process, sometimes produce branched structure as side reaction, about the content of this branched structure, also in the aromatic copolycarbonate total amount, account for 0.001～1 mole of %, be preferably 0.005～0.9 mole of %, be preferably 0.01～0.8 mole of % especially.In addition, the content of above-mentioned branched structure can pass through 1H-NMR measures and calculates.
Two functionality carboxylic acids of preferred aliphat are alpha, omega-dicarboxylic acid.As aliphatic two functionality carboxylic acids, preferably can enumerate direct-connected saturated aliphatic dicarboxylic acids such as sebacic acid (sebacic acid), dodecanedioic acid (Dodecandioic acid), tetradecane diacid, octadecane diacid, octadecane dicarboxylic acid; And the alicyclic dicarboxylic acid of cyclohexane dicarboxylic acid etc.As two functionality alcohol, be preferably alicyclic diol, for example can enumerate cyclohexanedimethanol, cyclohexane diol and tristane dimethanol etc.
And, can also use the polyorganosiloxane units polycarbonate-poly organo alkyl copolymer of copolymerization in addition.
Aromatic polycarbonate resin also can be the two or more blended resins in addition in the various aromatic copolycarbonates such as the polycarbonate that above-mentioned binary phenol is different, the polycarbonate that contains branched-chain component, various polyestercarbonate, polycarbonate-poly organo alkyl copolymer.Further, the polycarbonate that following manufacture method is different, end stop various resins such as the different polycarbonate of agent and also can use two or more blended resins in addition.
As the reactive modes such as ring-opening polymerization method of interfacial polymerization, melt transesterification process, carbonic ether prepolymer solid phase ester-interchange method and the cyclic polycarbonates compound of the manufacture method of polycarbonate resin, be by known methods such as various documents and patent gazettes.
The molecular weight of aromatic polycarbonate resin is not done special qualification, be lower than 1.0 * 10 but work as molecular weight 4The time, be difficult to obtain full intensity as the moulding product, when surpassing 5.0 * 10 4The time, the forming process reduction.Therefore, when representing, be preferably 1.0 * 10 with viscosity-average molecular weight 4～5.0 * 10 4, more preferably 1.4 * 10 4～3 * 10 4, more preferably 1.4 * 10 4～2.4 * 10 4In addition, also two or more aromatic polycarbonate resins can be mixed.At this moment, certainly mixed with the aromatic polycarbonate resin of viscosity-average molecular weight outside above-mentioned scope.
Particularly, surpass 5.0 * 10 with viscosity-average molecular weight 4Entropy-elasticity (entropy elasticity) height of mixture of aromatic polycarbonate resin, it is characterized in that the bad order of the moulding product that cause for the rheological behaviour of representative because of jet-type etc. is difficult to produce.Considering from suppressing the bad order aspect, is suitable manner.And in STUDY ON AIR INJECTION MOLDING etc., its gas injection rate is also stable, and in addition, foamed cell is stable in foaming, can easily form fine and uniform unit, therefore, helps the present invention.
Be 8.0 * 10 more preferably with viscosity-average molecular weight 4The mixture of above polycarbonate resin, further preferred with have 1.0 * 10 5The mixture of the polycarbonate resin of above viscosity-average molecular weight.That is, can preferably use in GPC measuring methods such as (gel permeation chromatographies), can observe two materials with superiors's molecular weight distribution.
The said viscosity-average molecular weight of the present invention can be calculated according to following method.At first, from the solution that under 20 ℃, the 0.7g polycarbonate is dissolved in the 100ml methylene dichloride and obtains, use Ostwald viscometer, obtain specific viscosity by following formula:
Specific viscosity (η Sp)=(t-t 0)/t 0
[t 0Be drippage number second of methylene dichloride, drippage number second that t is sample solution];
According to resulting specific viscosity (η Sp), calculate viscosity-average molecular weight M by following formula:
η Sp/ c=[η]+0.45 * [η] 2C ([η] is limiting viscosity)
[η]＝1.23×10 -4M 0.83
c＝0.7。
(B composition: graft copolymer)
Graft copolymer of the present invention (B composition) is meant that the weight average particle diameter that contains rubber particles is the graft copolymer of rubber polymer, vinyl cyanide monomer and the aromatic vinyl monomer of 0.20～2.0 μ m.
As rubber polymer of the present invention, can enumerate polyhutadiene, the dienes multipolymer (for example, the random copolymers of phenylethylene/butadiene and segmented copolymer, the acrylonitrile/butadiene multipolymer, the multipolymer of (methyl) alkyl acrylate and divinyl etc.), polyisoprene, the multipolymer of vinylbenzene and alpha-olefin (for example, ethylene/propylene olefinic random copolymer and segmented copolymer, the random copolymers of ethylene/butylene and segmented copolymer etc.), the multipolymer of ethene and esters of unsaturated carboxylic acids (for example, the ethylene/methacrylic acid ester copolymer, and the multipolymer of ethylene/butyl acrylate etc.), the multipolymer of ethene and aliphatic ethylene (for example, ethylene/vinyl acetate copolymer etc.), the non-conjugated diene terpolymer of ethene and propylene (for example, ethylene/propylene/hexadiene multipolymer etc.), acrylic rubber (for example, butyl polyacrylate, poly-(2-ethylhexyl acrylate), and the multipolymer of butyl acrylate and 2-ethylhexyl acrylate etc.), and silicon class rubber (for example, organopolysiloxane rubber, the IPN type rubber that forms by organopolysiloxane rubber constituent and poly-(methyl) alkyl acrylate rubber constituent, that is, thus the two kinds of rubber constituents of structure with mutual complexing can't isolating rubber, and the IPN type rubber that constitutes by organopolysiloxane rubber constituent and polyisobutylene rubber composition etc.).Wherein, preferably can more easily express the non-conjugated diene ter-polymers of polyhutadiene, dienes multipolymer, polyisoprene, acrylic rubber, ethene and the propylene of its effect, wherein, be preferably polyhutadiene, dienes multipolymer especially.
The weight average particle diameter of the rubber particles of this rubber polymer is 0.20～2.0 μ m, is preferably 0.25～1.5 μ m, more preferably 0.28～1.3 μ m.When the weight average particle diameter of rubber particles during less than 0.2 μ m, it is low that the impact that is brought by the interpolation of graftomer improves effect, thereby not preferred.In addition, when surpassing 2.0 μ m,, cause the phenomenon that impact characteristics reduces with the dispersion state variation of polycarbonate resin, thus not preferred.
The weight average particle diameter of the rubber particles among the present invention is the numerical value by the infiltration type determination of electron microscopy.Specifically, get the grid (mesh) that the rubbery polymer of an emulsion form places the infiltration type determination of electron microscopy to use, and dye with the steam of perosmic anhydride or ruthenium tetroxide.Then, with infiltration type electron microscope (FEI Co. makes for TECNAI G2, acceleration voltage 120kv) the rubbery polymer sample after the dyeing is taken pictures, and by image processing software (NexusNewQube), 200 rubber particles from captured image are calculated weight average particle diameter.
As vinyl cyanide monomer of the present invention, can enumerate vinyl cyanide, methacrylonitrile etc., preferred especially vinyl cyanide.
As aromatic vinyl monomer of the present invention, can enumerate vinylbenzene, alpha-methyl styrene, o-methyl styrene, p-methylstyrene, vinyl-dimethyl benzene, ethyl styrene, dimethyl styrene, to t-butyl styrene, vinyl naphthalene, methoxy styrene, phenyl-monobromide ethene, Dowspray 9, fluorostyrene, tribromo-benzene ethene etc., special optimization styrene.
The rubber constituent content of graft copolymer of the present invention (B composition) is 1～40 weight %, is preferably 5～30 weight %, more preferably 10～25 weight %.When content surpassed 40 weight %, mobile to improve effect insufficient, thereby not preferred.In addition, when this rubber constituent content was lower than 1 weight %, it is insufficient that impact improves effect, thereby not preferred.
Manufacture method to graft copolymer of the present invention (B composition) is not done special qualification, but the preferred graft copolymer that uses by the letex polymerization manufactured.
As graft copolymer of the present invention (B composition), for example can enumerate ABS resin, AES resin, ASA resin etc. particularly, these all are easy to obtain.Wherein, more preferably ADS resin.
ABS resin has excellent forming process in thin molded article, also have good shock-resistance.Especially, with the combination of polycarbonate resin in, show Ideal Characteristics.
In addition, at this, ABS resin is meant the graft copolymer that mainly is made of vinyl cyanide, divinyl rubber and vinylbenzene, the AES resin is meant the graft copolymer that mainly is made of vinyl cyanide, ethylene-propylene rubber(EPR) and vinylbenzene, and the ASA resin is meant the graft copolymer that mainly is made of vinyl cyanide, vinylbenzene and acrylic rubber.
Graft copolymer of the present invention (B composition) both may be used alone, used in two or more.For example, can and use ABS resin and ASA resin, ABS resin and AES resin etc.When and during with a plurality of graft copolymer, the content of rubber constituent is respectively 1～40 weight %, is preferably 5～30 weight %, 10～25 weight % more preferably.When rubber constituent content surpassed 40 weight %, mobile to improve effect insufficient, thereby not preferred.In addition, when rubber constituent content was lower than 1 weight %, it is insufficient that impact improves effect, thereby not preferred.
The mixture of the thermoplastic graft copolymer multipolymer (Acrylonitrile Butadiene) that ABS resin, be meant on polydiene composition graft copolymerization vinyl cyanide compound and aromatic ethylene compound form and the multipolymer (AS multipolymer) of this graft copolymer and vinyl cyanide compound and aromatic ethylene compound.In addition, the multipolymer of this vinyl cyanide compound and aromatic ethylene compound, both can be the multipolymer that when making the resin that constitutes by the thermoplastic graft copolymer multipolymer, derives from (wherein, described thermoplastic graft copolymer multipolymer be in the polydiene composition graft copolymerization thermoplastic graft copolymer multipolymer that forms of vinyl cyanide compound and aromatic ethylene compound), also can be to make aromatic ethylene compound and vinyl cyanide compound copolymerization and material that the vinyl compound interpolymer that obtains is mixed separately respectively.By GPC (gel permeation chromatography) method, conversion polystyrene standard and in the numerical value measured, the weight-average molecular weight of the multipolymer that is formed by this vinyl cyanide compound and aromatic ethylene compound is preferably 3.0 * 10 4～2.0 * 10 5, more preferably 6.0 * 10 4～1.4 * 10 5, more preferably 9.0 * 10 4～1.2 * 10 5In addition, the ratio of this AS multipolymer in the good solvent of this AS multipolymer that can be by ABS resin being dissolved in acetone etc., and is collected its solvable composition by methods such as centrifugations.In addition, its insoluble composition (gel) is real Acrylonitrile Butadiene.
In ABS resin, be grafted to the ratio (weight of this grafting composition is to the ratio of polydiene composition weight) of the vinyl cyanide compound and the aromatic ethylene compound of polydiene composition, be that percentage of grafting (weight %) is preferably 20～200 weight %, 20～80 weight % more preferably.
As the polydiene composition of this ABS resin, for example can use second-order transition temperatures such as polyhutadiene, polyisoprene and styrene-butadiene copolymer to be the rubber constituent below-10 ℃.
As the aromatic ethylene compound in the ABS resin, can enumerate foregoing compound, special optimization styrene.As the vinyl cyanide compound in the ABS resin, can enumerate foregoing compound, for example can enumerate vinyl cyanide, methacrylonitrile etc., preferred especially vinyl cyanide.
Be used for ABS resin of the present invention, the elastoprene components in proportions in the ABS resin composition of 100 weight % is preferably 1～40 weight %, 5～30 weight % more preferably, and more preferably 10～25 weight % are preferably 12～22 weight % especially.In the ABS resin composition of 100 weight %, the ratio of the vinyl cyanide compound beyond the polydiene composition and the multipolymer of aromatic ethylene compound is preferably 99～60 weight %, 95～70 weight % more preferably, more preferably 90～75 weight % are preferably 88～78 weight % especially.And, with respect to this vinyl cyanide compound of 100 weight % and the total 100 weight % of aromatic ethylene compound, vinyl cyanide compound is preferably 5～50 weight % (15～35 weight % more preferably), and aromatic ethylene compound is preferably 95～50 weight % (65～85 weight % more preferably).And, to an above-mentioned part that is grafted to the grafting composition in the polydiene composition, can also mix use (methyl) methyl acrylate, ethyl propenoate, maleic anhydride, N and replace the maleic anhydride imines etc. that contracts, their content ratio is preferably in ABS resin below the 15 weight %.Further, the initiator that uses in reaction, chain-transfer agent, emulsifying agent etc. can adopt known in the past various materials as required.
In ABS resin, the weight average particle diameter of rubber size is preferably 0.20～2.0 μ m, and more preferably 0.25～1.5 μ m especially is preferably 0.28～1.3 μ m.The material that can use the material that is distributed as single distribution of described rubber size or have the above multimodal in two peaks, further in its form, can be the material that rubber particles becomes single phase, also can be to contain to block around rubber particles to have the material that contains (salami) structure mutually.
The manufacture method of this ABS resin is not done special qualification, but the ABS resin by the letex polymerization manufactured more preferably.
(C composition: core-shell grafting copolymer)
Core-shell grafting copolymer of the present invention (C composition) is, with the weight average particle diameter of rubber particles be polydiene composition and (methyl) alkyl acrylate monomer of 0.30～0.50 μ m or (methyl) alkyl acrylate and can with other monomeric mixtures of its copolymerization core-shell grafting copolymer of forming of copolymerization in addition, preferred mainly with methyl methacrylate or methyl methacrylate and the multipolymer that can obtain to the polydiene that with the butadiene-styrene is representative with other monomeric mixture graft copolymerizations of its copolymerization.
The said polydiene composition of the present invention, be meant by letex polymerization, make as primary structure unitary 1, the 3-divinyl is adjusted into 50～100 weight %, is preferably 65～100 weight %, 75～100 weight % more preferably, allows to be adjusted into 50～0 weight % with vinyl monomer this primary structure unit copolymerization, that with vinylbenzene be representative, is preferably 35～0 weight %, the multipolymer that obtains of 25～0 weight % more preferably.If be lower than 50 weight % as the unitary 1,3-butadiene of primary structure, then can not get sufficient impact characteristics, thereby not preferred.
Be 0.30～0.50 μ m when the particle diameter of polydiene composition of the present invention is represented with weight average particle diameter, be preferably 0.30～0.40 μ m, more preferably 0.32～0.38 μ m.When the particle diameter of polydiene during less than 0.30 μ m, it is very dense that fusion portion or in uneven thickness go up the interflow line that produces, and when surpassing 0.50 μ m, causes and disperse badly, lost the effect as impact modifying agent, thereby not preferred.
The weight average particle diameter of rubber particles of the present invention, being to adopt the method identical with the measuring method of the weight average particle diameter of the rubber polymer of B composition and the numerical value measured, is that image with the rubber particles taken by the infiltration type electron microscope is as basic numerical value of calculating.
As the formation that is used for this polydiene composition be the vinyl monomer of representative with vinylbenzene, for example can enumerate the aromatic vinyl monomer of vinylbenzene, alpha-methyl styrene, p-methylstyrene, chloro-styrene, Dowspray 9, tribromo-benzene ethene etc.; The alkyl methacrylate of methyl methacrylate, Jia Jibingxisuanyizhi, propyl methacrylate, butyl methacrylate etc.; The alkyl acrylate of methyl acrylate, ethyl propenoate, propyl acrylate, butyl acrylate, 2-ethylhexyl acrylate etc.In addition, except above-mentioned monomer, can also enumerate the vinyl monomer with glycidyl of vinyl ethers monomer, halogenation vinylidene monomer, glycidyl acrylate etc. etc.
And, in above-mentioned vinyl monomer, also can become cross-linkable monomer be can with the monomer of divinyl or vinyl monomer copolymerization, be at the compound of C=C key independently more than two at molecular memory, for example, can enumerate the multifunctional vinyl compound of aromatic series of Vinylstyrene, divinyl toluene etc.; The α of the polyvalent alcohol of ethylene glycol dimethacrylate, 1,3 butyleneglycol diacrylate etc., the beta-unsaturated carboxylic acid ester; The α of trimethacrylate or triacrylate, vinylformic acid allyl ester, allyl methacrylate etc., the allyl ester of beta-unsaturated carboxylic acid; The diallyl compound of Phthalic acid, diallyl ester, sebacic acid diallyl, diallyl triazine etc. or triallyl compound etc.
Above-mentioned vinyl monomer and cross-linkable monomer can use a kind of respectively or use two or more.
In addition, when forming the polydiene composition, in polyreaction, as required, can also use the chain-transfer agent (initiator) of uncle's dodecyl mercaptans etc.In this polydiene composition, in preparation during its latex, add loose agent and suppress the weight average particle diameter of polydiene composition.As this hypertrophy agent, for example can enumerate the inorganic salt of sodium-chlor, Repone K, sodium sulfate, sal epsom, Tai-Ace S 150 etc.; The organic salt of lime acetate, magnesium acetate etc.; The mineral acid of sulfuric acid, hydrochloric acid etc.; The organic acid of acetate, succsinic acid etc.; And their organic acid anhydride, further, contain carboxylic acid high molecular emulsion etc. in addition.
The core-shell grafting copolymer of using among the present invention (C composition), can be by on the latex of dienes composition with said structure, make (methyl) alkyl acrylate monomer or make (methyl) alkyl acrylate and other monomeric mixtures that can carry out copolymerization, carry out one or more snippets graft copolymerization and prepare with it.
That is, as the monomer that in above-mentioned graft copolymerization, uses, except (methyl) alkyl-acrylates as the methyl methacrylate of neccessary composition, Jia Jibingxisuanyizhi etc.; And beyond the alkyl-acrylates of methyl acrylate, ethyl propenoate, butyl acrylate etc., can also enumerate that vinylbenzene, alpha-methyl styrene or various halogen replace and/or the styrenic of alkyl-substituted styrene etc.; The vinyl monomer with glycidyl of glycidyl acrylate, glycidyl methacrylate, glycidyl allyl ether etc.Further, also can be with above-mentioned vinyl monomer and above-mentioned vinyl monomer and the usefulness that becomes cross-linkable monomer.When being mixed with (methyl) alkyl acrylate as neccessary composition and using, these vinyl monomers and cross-linkable monomer can use a kind of respectively or use two or more.
In graft polymerization, with polydiene composition latex be adjusted into 40～90 weight %, be preferably 42～85 weight %, 45～80 weight % more preferably, correspondingly, the usage quantity with employed monomer or monomer mixture be adjusted into 60～10 weight %, be preferably 58～15 weight %, 55～20 weight % more preferably.In addition, when using monomer mixture, in the total amount of monomer mixture, as the content of (methyl) alkyl acrylate monomer of neccessary composition at least more than 25 weight %, preferably more than 40 weight %.
In addition, graft copolymer (C composition) both can once add monomer or monomer mixture and carried out one-step polymerization, perhaps, also can be at twice or twice above interpolation with monomer or monomer mixture, thus divide multistage to carry out graft polymerization.
Method as graft copolymerization adopts method of emulsion polymerization.This graft copolymerization is fashionable carrying out, and as polymerization starter, can use the persulphate of Potassium Persulphate, ammonium persulphate, Sodium Persulfate etc.; The organo-peroxide of tertbutyl peroxide, isopropyl benzene hydroperoxide, benzoyl hydrogen peroxide, lauric acid superoxide, diisopropyl benzene hydrogen peroxide etc.; The azo compound of Diisopropyl azodicarboxylate, azo isovaleronitrile etc. etc.In addition, above-mentioned oxidant compound and sulphite, hydrosulphite, thiosulphate, submetallic salt, sodium sulfoxylate formaldehyde, dextrose etc. are mixed and used as redox class initiator.
Temperature of reaction in the graft copolymer can for example can suitably be chosen in 40～80 ℃ scope according to the kind of employed polymerization starter.In addition, when carrying out letex polymerization,, can suitably use known emulsifying agent as emulsifying agent at butadiene type rubber polymer latex.
Resulting core-shell grafting copolymer (C composition), in reaction solution, add suitable antioxidant or add additive etc. as required, perhaps under the situation of not adding, carry out spraying drying (directly powderization), perhaps, in reaction solution, suitably add condensing agent (for example salt of the acid of sulfuric acid, hydrochloric acid, phosphoric acid etc. or calcium chloride, sodium-chlor etc.) and condense, further thermal treatment and solidifying in addition.Then, through dehydration, washing, carry out final drying and come into operation after the powderization.
(D composition: inorganic filling material)
In the present invention, can contain various inorganic filling materials as the D composition.For example, can preferably use the various whiskers etc. of talcum, wollastonite, mica, clay, montmorillonite (montmorillonite), montmorillonite (smectite), kaolin, lime carbonate, carbon fiber, carbon plate, carbon pearl, milled carbon fiber, tinsel, steel fiber, metallic coating glass fibre, metallic coating carbon fiber, metallic coating sheet glass, silicon-dioxide, ceramic particle, ceramic fiber, Ceramic Balls, aramid fiber particle, aramid fiber (aramid fiber), polyarylester fiber, graphite, potassium titanate crystal whisker, aluminium borate whisker, basic magnesium sulfate etc.Wherein, preferably use the packing material of silicates such as talcum, wollastonite, mica.These inorganic filling materials both can use one or more and use.
(D-1 composition: talcum)
The talcum that uses among the present invention (D-1 composition), can enumerate median size is the following talcums of 5 μ m.More preferably median size is the following talcums of 3 μ m, and preferred especially median size is the following talcums of 2 μ m.Can enumerate 0.05 μ m as lower value.In this said steatitic median size, be meant the D50 (mid-diameter of size distribution) that measures by as the X ray penetrant method of one of liquid-phase precipitation method.As the object lesson of the device of implementing this mensuration, can enumerate the Sedigraph5100 of Micromeritics company manufacturing etc.
Talcum preferably uses with the granulation state.As prilling process, situation and the in fact obsolete situation of using tackiness agent are arranged.More preferably do not use the talcum of tackiness agent.Prilling process when not using tackiness agent, can enumerate degassing compression method (for example, the degassing on one side under vacuum state, on one side carry out the method for roll compaction with briquetting machine etc.) and rotating granulation or cohesion prilling process etc.
(D-2 composition: mica)
As the mica that uses among the present invention (D-2 composition), can enumerate median size is pulverous mica of 1～80 μ m.Further preferred median size is the mica of 2～50 μ m.This median size is the value of measuring by the laser diffraction and scattering method.When median size is 1～80 μ m, when can play better effect, also satisfy microdispersed condition in the resin to flame retardant resistance, therefore, also can keep good humidity resistance.As micaceous thickness, can use the thickness of surveying by the observation of electron microscope is the mica of 0.01～1 μ m.Preferred thickness is 0.03～3 μ m.And, also can implement surface treatment to this mica with silane coupling agent etc., further, also can use the wedding agent enforcement granulation of epoxies, polyurethanes, acrylic acid or the like etc., thereby become particulate state.
(D-3 composition: wollastonite)
The wollastonite that uses among the present invention (D-3 composition), preferred number average Fibre diameter is the wollastonite of 0.5～5 μ m.This number average Fibre diameter is meant, from the image of observing by electron micrograph etc., extracts altogether at random and amounts to 1000 parts and measure Fibre diameter, and calculate its number average value and the numerical value obtained.Aspect ratio L/D (the L: number average fiber length, D: be more than 5 the number average Fibre diameter), more preferably more than 6 of preferred wollastonite.Number average fiber length is obtained in accordance with the following methods: by opticmicroscope or electron microscope etc., almost can observe the multiplying power of wollastonite all images fully, observe wollastonite, this image is input to image analysis apparatus, calculate number average fiber length.As image analysis apparatus, can enumerate the PIAS-III system of Byass manufacturing etc.As the wollastonite that the present invention uses, be below the 2 weight % preferably, more preferably below the 1.5 weight %, more preferably below the 1 weight % in the heat-flash decrement under 1000 ℃ of temperature.
Resin combination of the present invention can contain to be useful on suppress to strengthen the anti-agent that fractures that packing material fractures.The anti-agent that fractures hinders the tack between matrix resin and the reinforcement packing material, acts on the stress of strengthening packing material when reducing melting mixing, thereby suppresses fractureing of packing material.As the effect of the anti-agent that fractures, can enumerate (1) and improve rigidity (it is big that the aspect ratio of packing material becomes); (2) improve toughness (easily bring into play the toughness of matrix resin, especially, the aromatic polycarbonate resin that will have an excellent toughness is effective during as main body); (3) improve electroconductibility (when being the electroconductibility packing material) etc.Specifically, the anti-agent that fractures is a compound as described below: (i) will be with the affinity of resin low compound is directly overlayed on this compound when strengthening the packing material surface; (ii) have the structure low, and have the compound of the functional group that can react with the surface of strengthening packing material with the affinity of resin.
As the compound low, representationally can enumerate various lubricants with the affinity of resin.As lubricant, for example can enumerate fluorocarbon oils such as mineral oil, synthetic oil, high-grade aliphatic ester, higher fatty acid amides, organopolysiloxane (silicone oil, silicon rubber etc.), olefines wax (paraffin, polyolefin-wax etc.), polyalkylene glycol, fluoride fat acid esters, trifluorochloroethylene, poly-hexafluoro propylene glycol etc.
As will directly being overlayed on the method for strengthening the packing material surface by low compound, can enumerate (1) this compound direct impregnation maybe is impregnated into the method for strengthening packing material with the solution or the emulsion of this compound to the method for strengthening packing material with the affinity of resin; (2) make the reinforcement packing material pass through in the steam of this compound or the method in the powder; (3) powder of this compound etc. is exposed to the method for strengthening packing material at a high speed; (4) make the chemomotive force method of strengthening packing material and the friction of this compound etc.
As have with the low structure of the affinity of resin and have can with the compound of the functional group of the surface reaction of strengthening packing material, can enumerate the above-mentioned lubricant of being crossed by various modified with functional group.As this functional group, for example can enumerate carboxyl, acid anhydride, epoxy group(ing), oxazolinyl, isocyanate group, ester group, amino, alkoxysilyl etc.
Fracture agent more preferably as anti-, have the polyolefin-wax that is selected from least a functional group among carboxyl and the acid anhydride.Be preferably 500～20000 as molecular weight in weight-average molecular weight, more preferably 1000～15000.In this polyolefin-wax, have the lubricant that is selected from least a functional group among carboxyl and the acid anhydride with respect to 1g, carboxyl and acid anhydride's amount is preferably 0.05～10meq/g, more preferably 0.1～6meq/g, more preferably 0.5～4meq/g.Under the situation of other functional groups, preferably contain and carboxyl same degree amount.
As the anti-agent that fractures, especially preferably enumerate the multipolymer of alpha-olefin and maleic anhydride.This multipolymer can in the presence of free radical catalyst, be made by melt polymerization or mass polymerization according to ordinary method.At this, as alpha-olefin, the mean value that can preferably enumerate its carbonatoms is 10～60 alpha-olefin.As alpha-olefin, more preferably the mean value of its carbonatoms is 16～60 alpha-olefin, more preferably 25～55 alpha-olefin.In the resin combination of the present invention of 100 weight %, the anti-agent that fractures is preferably 0.01～2 weight %, more preferably 0.05～1.5 weight %, more preferably 0.1～0.8 weight %.
(E composition: fire retardant)
Resin combination of the present invention can use as the known various fire retardants of the fire retardant of aromatic polycarbonate resin (E composition).As more preferably (i) organic phosphates fire retardant (for example, phosplate compound, phosphoric acid ester oligopolymer, phosphonate oligomers, phosphine nitrile oligopolymer and phosphonic acid amide compound etc.) of E composition; The (ii) silicon based flame retardant that (iii) forms of organic metal salt based flame retardant (for example, organic sulfonic acid alkali (alkaline earth) metal-salt, borate metal salt based flame retardant and stannic acid metallic salt fire retardant etc.) by silicon compound.By cooperating the compound that uses as fire retardant, the raising that not only can bring flame retardant resistance can also be based on the character of each compound, brings the raising of for example static electricity resistance, flowability, rigidity and thermostability etc.
(E-1) organic phosphates fire retardant
As the organic phosphates fire retardant that can use in the present invention, preferably phosphoric acid ester cpds, special preferred aryl groups phosphate compound.This phosphate compound is improving aspect the flame retardant resistance effectively, and phosphate compound has the plasticity-effect, therefore, though stable on heating reduction is arranged, favourable aspect the forming process that improves resin combination of the present invention.As this phosphate compound,, more preferably enumerate one or more the phosphate compound of particularly using following general formula (I) expression though can use in the past as the known various phosphate compounds of fire retardant.
(in the formula (I), X is from dihydroxy compound deutero-divalent phenol residue, and described dihydroxy compound is the dihydroxy compound that is selected from the group of being made up of quinhydrones, Resorcinol, two (4-hydroxy diphenyl) methane, dihydroxyphenyl propane, dihydroxyl hexichol, dihydroxy naphthlene, two (4-hydroxy phenyl) sulfone, two (4-hydroxy phenyl) ketone and two (4-hydroxy phenyl) sulfide; N is 0～5 integer, and perhaps, when being the mixture of the different phosphoric acid ester of n number, n is their mean value; R 4, R 5, R 6And R 7Represent independently respectively that from aryl deutero-one bivalent phenol residue described aryl is the aryl that is selected from the group of forming by phenol, cresols, xylenol, isopropyl-phenol, butylphenol and to cumyl phenol.)
The phosphate compound of following formula (I), it also can be mixture with compound of different n numerical value, when being this mixture, the mean value of preferred n is 0.5～1.5, more preferably 0.8～1.2, more preferably 0.95～1.15, is preferably 1～1.14 scope especially.
As the preferred object lesson of the binary phenol of the X of the following formula of deriving (I), can enumerate Resorcinol, dihydroxyphenyl propane and dihydroxyl hexichol, wherein, preferred Resorcinol, dihydroxyphenyl propane.
R as the following formula of deriving (I) 4, R 5, R 6And R 7The preferred object lesson of a bivalent phenol, can enumerate phenol, cresols, xylenol, 2,6-xylenol, wherein, be preferably phenol and 2,6-xylenol.
As the object lesson of the phosphate compound of following formula (I), can preferably enumerate phosplate compounds such as Triphenyl phosphate and three (2, the 6-3,5-dimethylphenyl) phosphoric acid ester; And with the phosphoric acid ester oligopolymer of two two (2, the 6-3,5-dimethylphenyl) phosphoric acid ester of Resorcinol as main body; With 4,4-dihydroxyl phenylbenzene two (diphenyl phosphoester) is as the phosphoric acid ester oligopolymer of main body; And with the phosphoric acid ester oligopolymer of dihydroxyphenyl propane two (diphenyl phosphoester) as main body, wherein, preferably with the phosphoric acid ester oligopolymer of two two (2, the 6-3,5-dimethylphenyl) phosphoric acid ester of Resorcinol as main body; With 4,4-dihydroxyl phenylbenzene two (diphenyl phosphoester) is as the phosphoric acid ester oligopolymer of main body; And with the phosphoric acid ester oligopolymer of dihydroxyphenyl propane two (diphenyl phosphoester) as main body.
When using the organic phosphates fire retardant as fire retardant, its use level is with respect to total 100 weight parts of A composition and B composition, is preferably 1～25 weight part, more preferably 2～25 weight parts, 3～20 weight parts more preferably.When use level was in more preferred range, the effect of bringing into play by the cooperation of organic phosphates fire retardant (for example flame retardant resistance etc.) was just good more.
(E-2) organic metal salt based flame retardant
The organic metal salt based flame retardant is favourable aspect the maintenance thermotolerance.Most preferred organic metal salt fire retardant is organic sulfonic acid alkali (alkaline earth) metal-salt among the present invention.Wherein, preferred fluorine replaces alkali (alkaline earth) metal-salt of organic sulfonic acid, especially preferably has alkali (alkaline earth) metal-salt of the sulfonic acid of perfluoroalkyl.At this moment, the carbonatoms of perfluoroalkyl is preferably 1～18 scope, more preferably 1～10 scope, more preferably 1～8 scope.
Constitute the metal that fluorine replaces the metal ion of organic azochlorosulfonate acid alkali (alkaline earth) metal-salt, be basic metal or alkaline-earth metal, can enumerate lithium, sodium, potassium, rubidium and caesium as basic metal; As alkaline-earth metal, can enumerate beryllium, magnesium, calcium, strontium and barium.Basic metal more preferably.Therefore, preferred organic metal salt based flame retardant is the perfluoro alkyl sulfonic acid an alkali metal salt.In this basic metal, but then, owing to they are not general and are difficult to make with extra care, therefore, there is defective in preferred rubidium and the caesium of using sometimes on cost under the higher situation of the requirement of the transparency.In addition, lithium and sodium are favourable aspect cost or flame retardant resistance, but unfavorable to the transparency on the contrary sometimes.Can distinguish the basic metal that uses in the perfluoro alkyl sulfonic acid an alkali metal salt according to above-mentioned situation, but no matter which aspect consider that the perfluoro alkyl sulfonic acid sylvite of balance of properties excellence all is best suited for using from.Also can be with this sylvite and perfluoro alkyl sulfonic acid an alkali metal salt that forms by other basic metal and usefulness.
As the object lesson of this perfluoro alkyl sulfonic acid an alkali metal salt, can enumerate trifluoromethayl sulfonic acid potassium, potassium perfluorobutane sulfonate, perflexane potassium sulfonate, Perfluorooctane sulfonates potassium, pentafluoride ethane sodium sulfonate, perfluorinated butane sodium sulfonate, Perfluorooctane sulfonates sodium, trifluoromethayl sulfonic acid lithium, perfluorinated butane sulfonic acid lithium, PF 5070 sulfonic acid lithium, trifluoromethayl sulfonic acid caesium, perfluorinated butane sulfonic acid caesium, Perfluorooctane sulfonates caesium, perflexane sulfonic acid caesium, perfluorinated butane sulfonic acid rubidium and perflexane sulfonic acid rubidium etc.These both can be used alone, also can two or more and usefulness.Wherein, be preferably potassium perfluorobutane sulfonate especially.
In the above-mentioned organic metal salt based flame retardant, the content of the fluoride ion by ion-chromatographic determination is preferably below the 50ppm, more preferably below the 20ppm, more preferably below the 10ppm.The content of fluoride ion is low more, and flame retardant resistance or photostabilization are then good more.In fact, the lower value of fluoride ion content can be adjusted into 0, but takes all factors into consideration from the process number and the effect of refining step, and the preferred lower limit value is about 0.2ppm in the practicality.Perfluoro alkyl sulfonic acid an alkali metal salt with this fluoride ion content for example can be refining by following method.That is, under 40～90 ℃ (more preferably at 60～85 ℃), an alkali metal salt of perfluoro alkyl sulfonic acid is dissolved in the ion exchanged water of 2～10 times of weight of this metal-salt.This perfluoro alkyl sulfonic acid an alkali metal salt, by perfluoro alkyl sulfonic acid is carried out the neutral method in alkali-metal carbonate or oxyhydroxide, or, perfluoroalkyl sulfonyl fluoride (パ-Off Le オ ロ ア Le キ Le ス Le ホ ニ Le Off Le オ ラ イ De) generates by being carried out neutral method (the preferred latter's method) at alkali-metal carbonate or oxyhydroxide.In addition, this ion exchanged water, particularly preferably adopting resistance value is the above water of 18M Ω cm.The solution that has dissolved metal-salt was stirred under said temperature 0.1～3 hour, preferably stirred 0.5～2.5 hour.Then, this solution is cooled to 0～40 ℃, preferably is cooled to 10～35 ℃.Separate out crystallization by cooling.Take out the crystallization of separating out by filtering.Thus, produce the refining perfluoro alkyl sulfonic acid an alkali metal salt of ideal.
When using fluorine to replace organic azochlorosulfonate acid alkali (alkaline earth) metal-salt as fire retardant, its use level is with respect to total 100 weight parts of A composition and B composition, be preferably 0.01～1.0 weight part, more preferably 0.05～0.8 weight part, more preferably 0.08～0.6 weight part.When use level was in more preferred range, it was just good more to replace the effect (for example flame retardant resistance or static resistance etc.) that the cooperation of organic azochlorosulfonate acid alkali (alkaline earth) metal brings into play by fluorine.
Replace organic azochlorosulfonate acid alkali (alkaline earth) metal-salt organic metal salt based flame retardant in addition as fluorine, the preferred not metal-salt of the organic sulfonic acid of contain fluorine atoms.As this metal-salt, for example can enumerate an alkali metal salt of alkaline earth salt, aromatic sulphonic acid of an alkali metal salt, the aliphatic sulfonic of aliphatic sulfonic and alkaline earth salt of aromatic sulphonic acid (all not contain fluorine atoms) etc.
Preferred example as the aliphatic sulfonic metal-salt, can enumerate alkyl sulfonate alkali (alkaline earth) metal-salt, these both can use a kind of, also can be two or more and with (at this, the mark of alkali (alkaline earth) metal-salt represents to comprise any one of an alkali metal salt, alkaline earth salt).As the preferred example of the paraffinic hydrocarbons sulfonic acid that uses in this alkyl sulfonate alkali (alkaline earth) metal-salt, can enumerate methylsulfonic acid, ethyl sulfonic acid, propanesulfonic acid, fourth sulfonic acid, methyl fourth sulfonic acid, own sulfonic acid, heptan sulfonic acid, hot sulfonic acid etc.These both can use a kind of, also can two or more and usefulness.
As the aromatic sulphonic acid that is used for aromatic sulphonic acid alkali (alkaline earth) metal-salt, can enumerate monomer shape or polymkeric substance shape aromatic series sulfide sulfonic acid, aromatic carboxylic acid and ester sulfonic acid, monomer shape or polymkeric substance shape aromatic ether sulfonic acid, aromatic sulfonic acid ester sulfonic acid, monomer shape or polymkeric substance shape aromatic sulphonic acid, monomer shape or polymkeric substance shape aromatic series sulfone sulfonic acid, aromatic ketone sulfonic acid, hetero ring type sulfonic acid, aromatic series sulfoxide sulfonic acid, be selected from least a acid in the group that the condenses that formed by the alkylene base key by aromatic sulphonic acid forms.These both can use a kind of, or two or more and usefulness.
Object lesson as aromatic sulphonic acid alkali (alkaline earth) metal-salt, for example, can enumerate diphenyl sulfide-4,4 '-disulfonic acid disodium, diphenyl sulfide-4,4 '-disulfonic acid dipotassium, 5-sulfo group m-phthalic acid potassium, 5-sulfo group m-phthalic acid sodium, the many sodium of the many sulfonic acid of polyethylene terephthalic acid (Port リ エ チ レ Application テ レ Off Le
Figure A200910007771D0023081341QIETU
Port リ ス Le ホ Application
Figure A200910007771D0023081341QIETU
Port リ Na ト リ ウ system), 1-methoxynaphthalene-4-calcium sulphonate, 4-lauryl phenyl ether disulfonic acid disodium, the poly-many sodium of (2,6-dimethyl phenylene oxide) many sulfonic acid (Port リ (2,6-ジ メ チ Le Off エ, two レ Application オ キ シ De) Port リ ス Le ホ Application
Figure A200910007771D0023081341QIETU
Port リ Na ト リ ウ system), the poly-many sodium of (1,3-phenylene oxide) many sulfonic acid (Port リ (1,3-Off エ, two レ Application オ キ シ De) Port リ ス Le ホ Application
Figure A200910007771D0023081341QIETU
Port リ Na ト リ ウ system), the poly-many sodium of (1,4-phenylene oxide) many sulfonic acid (Port リ (1,4-Off エTwo レ Application オ キ シ De) Port リ ス Le ホ Application
Figure A200910007771D0023081341QIETU
Port リ Na ト リ ウ system), the poly-many potassium of (2,6-phenylbenzene phenylene oxide) many sulfonic acid (Port リ (2,6-ジ Off エTwo Le Off エTwo レ Application オ キ シ De) Port リ ス Le ホ Application
Figure A200910007771D0023081341QIETU
Port リ カ リ ウ system), poly-(2-fluoro-6-butyl phenylene oxide) poly-sulfonic acid lithium, the potassium sulfonate of benzene sulfonate, benzene sulfonic acid sodium salt, the Phenylsulfonic acid strontium, Phenylsulfonic acid magnesium, to the benzene disulfonic acid dipotassium, naphthalene-2,6-disulfonic acid dipotassium, biphenyl-3,3 '-disulfonic acid calcium, sulfobenzide-3-sodium sulfonate, sulfobenzide-3-potassium sulfonate, sulfobenzide-3,3 '-disulfonic acid dipotassium, sulfobenzide-3,4 '-disulfonic acid dipotassium, α, α, α-trifluoroacetophenone-4-sodium sulfonate, benzophenone-3,3 '-disulfonic acid dipotassium, thiophene-2,5-disulfonic acid disodium, thiophene-2,5-disulfonic acid dipotassium, thiophene-2,5-disulfonic acid calcium, the thionaphthene sodium sulfonate, diphenyl sulfoxide-4-potassium sulfonate, the formalin condenses of sodium naphthalene sulfonate, and the formalin condenses of anthracene sulfonic acid sodium etc.
In the metal-salt of the organic sulfonic acid of contain fluorine atoms not, optimization aromatic azochlorosulfonate acid alkali (alkaline earth) metal-salt, preferred especially sylvite.When cooperating aromatic sulphonic acid alkali (alkaline earth) metal-salt as fire retardant, its use level is with respect to total 100 weight parts of A composition and B composition, be preferably 0.01～1.0 weight part, more preferably 0.05～0.8 weight part, more preferably 0.08～0.6 weight part.
(E-3) silicon based flame retardant
In the present invention, as the silicon compound that the silicon based flame retardant uses, the chemical reaction when being meant by burning improves the compound of flame retardant resistance.As this compound, all cpds that can use in the past the fire retardant as aromatic polycarbonate resin to propose.Silicon compound is considered to be in when burning, forms structure (structure) by the combination of himself or by combining with composition from resin, and perhaps the reduction reaction when forming this structure is given flame retardant effect to polycarbonate resin.Therefore, preferably contain active high group in above-mentioned reaction.More particularly, at least a group in alkoxyl group and the hydrogen base (イ De ロ ジ エ Application) (being the Si-H yl) of being selected from that preferably contains specified amount.The content of preferred this group (alkoxyl group, Si-H yl) is than being the scope of 0.1～1.2mol/100g, more preferably scope, the scope of 0.15～0.6mol/100g more preferably of 0.12～1mol/100g.This content ratio can utilize caustic leaching process, obtains by hydrogen or pure amount that the silicon compound of measuring per unit weight produces.In addition, preferred alkoxyl group is that carbonatoms is 1～4 alkoxyl group, is preferably methoxyl group especially.
Usually, the structure of silicon compound is to constitute by the following four kinds of siloxane units of arbitrary combination.That is,
M unit: (CH 3) 3SiO 1/2, H (CH 3) 2SiO 1/2, H 2(CH 3) SiO 1/2, (CH 3) 2(CH 2=CH) SiO 1/2, (CH 3) 2(C 6H 5) SiO 1/2, (CH 3) (C 6H 5) (CH 2=CH) SiO 1/2Deng the single functionality siloxane unit;
D unit: (CH 3) 2SiO, H (CH 3) SiO, H 2SiO, H (C 6H 5) SiO, (CH 3) (CH 2=CH) SiO, (C 6H 5) 2The two functionality siloxane units of SiO etc.;
T unit: (CH 3) SiO 3/2, (C 3H 7) SiO 3/2, HSiO 3/2, (CH 2=CH) SiO 3/2, (C 6H 5) SiO 3/2Deng the three-functionality-degree siloxane unit;
Q unit: use SiO 2Four functionality siloxane units of expression.
The structure that is used for the silicon compound of silicon based flame retardant can be enumerated the structure of representing with following signal formula particularly, that is, and and D n, T p, M mD n, M mT p, M mQ q, M mD nT p, M mD nQ q, M mT pQ q, M mD nT pQ q, D nT p, D nQ q, D nT pQ qWherein, preferred silicon compound structure is M mD n, M mT p, M mD nT p, M mD nQ q, preferred structure is M mD nOr M mD nT p
At this, the Coefficient m in the above-mentioned signal formula, n, p, q are the integer more than 1 of the polymerization degree of each siloxane unit of expression, and the summation of coefficient is the mean polymerisation degree of silicon compound in each signal formula.Preferred this mean polymerisation degree 3～150 scope, more preferably 3～80 scope, more preferably 3～60 scope, be preferably 4～40 scope especially.This mean polymerisation degree is in preferred range more, and its flame retardant resistance is then excellent more.And, containing the silicon compound of the aromatic group of specified amount as described later, its transparency or color and luster are also excellent.
In addition, when among m, n, p, the q any one is numerical value more than 2,, can be the different two or more siloxane unit of institute's bonded hydrogen atom or organic residue with the siloxane unit of this coefficient.
Silicon compound both can be a linear chain structure, also can be the silicon compound with branched structure.In addition, being preferably carbonatoms with the organic residue of Siliciumatom bonded is organic residue of 1～30, more preferably 1～20.As this organic residue, can enumerate the alkyl of methyl, ethyl, propyl group, butyl, hexyl and decyl etc. particularly; The cycloalkyl of cyclohexyl etc.; The aryl of phenyl etc.; The aralkyl of tolyl etc. etc.More preferably carbonatoms is 1～8 alkyl, thiazolinyl or aryl.As alkyl, the carbonatoms that is preferably methyl, ethyl and propyl group etc. especially is 1～4 alkyl.
And the silicon compound that uses as the silicon based flame retardant preferably contains aryl.More preferably using the content ratio (aromatic group amount) of the aromatic group of following general formula (II) expression is the silicon compound of 10～70 weight % (15～60 weight % more preferably).
Figure A200910007771D00251
(in the formula (II), X represents independently that respectively OH base, carbonatoms are 1～20 the organic residue of monovalence; N represents 0～5 integer.And in formula (II),, can get mutual different types of X respectively when n is 2 when above.)
Silicon compound as the silicon based flame retardant uses can also contain reactive group except above-mentioned Si-H base and alkoxyl group, as this reactive group, for example can enumerate amino, carboxyl, epoxy group(ing), vinyl, sulfydryl and methacryloxy etc.
As silicon compound, preferably enumerate at least a above silicon compound in the structural unit that contains useful following general formula (III) and (IV) represent with Si-H base:
Figure A200910007771D00252
Figure A200910007771D00253
(in formula (III) and the formula (IV), Z 1～Z 3Represent independently that respectively hydrogen atom, carbonatoms are 1～20 organic residue of monovalence or the compound represented with following logical formula V; α 1～α 3 represents 0 or 1 respectively independently; M1 represents the integer more than 0 or 1; And in formula (III), when m1 is 2 when above, its repeating unit can be got different a plurality of repeating units mutually respectively.)
(in the formula V, Z 4～Z 8Represent independently that respectively hydrogen atom, carbonatoms are 1～20 the organic residue of monovalence; α 4～α 8 represents 0 or 1 respectively independently; M2 represents the integer more than 0 or 1; And in formula V, when m2 is 2 when above, its repeating unit can be got different a plurality of repeating units mutually respectively.)
At the silicon compound that is used for the silicon based flame retardant,, for example can enumerate at least a compound that is selected from in the compound of general formula (VI) and general formula (VII) expression as silicon compound with alkoxyl group:
Figure A200910007771D00262
(in the formula (VI), β 1Expression vinyl, carbonatoms are that 1～6 alkyl, carbonatoms are that 3～6 cycloalkyl, carbonatoms are 6～12 aryl and aralkyl; γ 1, γ 2, γ 3, γ 4, γ 5And γ 6The expression carbonatoms is that 1～6 alkyl and cycloalkyl and carbonatoms are 6～12 aryl and aralkyl, and wherein at least one group is an aryl or aralkyl; δ 1, δ 2And δ 3The expression carbonatoms is 1～4 alkoxyl group.)
Figure A200910007771D00271
(in the formula (VII), β 2And β 3Expression vinyl, carbonatoms are that 1～6 alkyl, carbonatoms are that 3～6 cycloalkyl and carbonatoms are 6～12 aryl and aralkyl; γ 7, γ 8, γ 9, γ 10, γ 11, γ 12, γ 13And γ 14The expression carbonatoms is that 1～6 alkyl, carbonatoms are that 3～6 cycloalkyl, carbonatoms are 6～12 aryl and aralkyl, and wherein at least one group is an aryl or aralkyl; δ 4, δ 5, δ 6And δ 7The expression carbonatoms is 1～4 alkoxyl group.)
When using the silicon based flame retardant as fire retardant, with respect to total 100 weight parts of A composition and B composition, the use level of silicon based flame retardant is preferably 0.1～5 weight part, more preferably 0.2～4 weight part, 0.3～3 weight part more preferably.
Above-mentioned fire retardant (E-1), (E-2) and (E-3) can use separately, perhaps two or more and use.
(F composition: fluorine-containing Antidrip agent)
The fluorine-containing Antidrip agent that uses among the present invention (F composition) is the fluorochemicals that can prevent the solution drippage and further improve flame retardant resistance when burning, as representational example, can enumerate the tetrafluoroethylene with protofibril formation ability.In addition, sometimes tetrafluoroethylene is abbreviated as " PTFE " below.Have the PTFE that protofibril forms ability and have high molecular weight, the external action that demonstrates by shearing force etc. makes between the PTFE in conjunction with forming fibrous tendency.As its molecular weight, the number-average molecular weight of obtaining by standard specific gravity is 1,000,000～1,000 ten thousand, preferred 2,000,000～9,000,000.This PTFE can also use the PTFE of aqueous liquid dispersion form except using solid shape.In addition, in order to improve the dispersiveness in resin, and in order to obtain more excellent flame and mechanical characteristics, this has PTFE that protofibril forms ability and can also use and other the resin PTFE mixture of blended mixed style in addition.
Has the commercially available product that protofibril forms the PTFE of ability as this, for example can enumerate DUPONT-MITSUI FLUOROCHEMICALS COMPANY, the Port リ Off ロ Application MPA FA500 that テ Off ロ Application (registered trademark) 6J of LTD, DAIKIN industry (strain) are made and F-201L etc.Commercially available product as the aqueous liquid dispersion of PTFE, representationally for example can enumerate Asahi-ICIFluoropolymers Co., Ltd. the FluonAD of Zhi Zaoing-1, AD-936, FluonD-1, the D-2 that DAIKIN industry (strain) is made, DUPONT-MITSUI FLUOROCHEMICALSCOMPANY, Teflon (registered trademark) 30J that LTD makes etc.
As the PTFE of mixed style, can use the PTFE:(1 of the mixed style that obtains by following method) with the aqueous liquid dispersion of the aqueous liquid dispersion of PTFE and organic polymer or solution is mixed and carry out the method (method of record in clear 60-No. 258263 communiques of TOHKEMY, clear 63-No. 154744 communiques of TOHKEMY etc.) that co-precipitation obtains common aggegation mixture; (2) with the aqueous liquid dispersion of PTFE and exsiccant organic polymer particle blended method (method of putting down in writing in flat 4-No. 272957 communiques of TOHKEMY) in addition; (3) with aqueous liquid dispersion and the organic polymer particle solution uniform mixing of PTFE, the method (method of putting down in writing flat 06-No. 220210 communiques of TOHKEMY, flat 08-No. 188653 communiques of TOHKEMY etc.) of removing medium separately simultaneously from this mixture; (4) polymerization is used to form the monomer methods (method of putting down in writing in flat 9-No. 95583 communiques of TOHKEMY) of organic polymer in the aqueous liquid dispersion of PTFE; And behind (5) aqueous liquid dispersion and organic polymer dispersion liquid uniform mixing with PTFE, further polymerising ethylene class monomer in this mixed dispersion liquid obtains the method (methods of record in flat 11-No. 29679 communiques of TOHKEMY etc.) of mixture then.As the commercially available product of the PTFE of these mixed forms, can enumerate [BLENDEX B449] (trade(brand)name) that [metablen A3800] (trade(brand)name) made with Mitsubishi Rayon Co.Ltd. and GE Specialty Chemicals company make etc.
As the ratio of the PTFE in the mixed form, in the PTFE mixture of 100 weight %, the content ratio of PTFE is preferably 1～60 weight %, more preferably 5～55 weight %.When the content ratio of PTFE is in this scope, can realize the good dispersiveness of PTFE.
(about the content of each composition)
Resin combination of the present invention, in the total 100 weight % of A composition and B composition, the A component content is 99～1 weight %, be preferably 98～20 weight %, more preferably 97～40 weight %, be preferably 95～60 weight % especially, the B component content is 1～99 weight %, be preferably 2～80 weight %, more preferably 3～60 weight %, be preferably 5～40 weight % especially.
When the A component content was lower than 1 weight %, physical strength, the thermotolerance of shock strength etc. were insufficient, in addition, when surpassing 99 weight %, reduced formability, thereby undesirable.
With respect to total 100 weight parts of A composition and B composition, the content of C composition is 0.1～10 weight part, be preferably 0.5～9 weight part, 1～8 weight part more preferably.When being lower than 0.1 weight part, it is insufficient to produce interflow line or impact characteristics, and in addition, when surpassing 10 weight parts, thermotolerance or flame retardant resistance significantly reduce, thereby not preferred.
With respect to total 100 weight parts of A composition and B composition, the content of D composition is for being preferably 0.1～50 weight part, more preferably 0.5～40 weight part, 1～30 weight part more preferably.When the D component content surpasses 50 weight parts, produce the mobile reduction or the remarkable reduction of shock strength, thereby not preferred.
With respect to total 100 weight parts of A composition and B composition, the content of E composition is preferably 0.001～25 weight part, more preferably 0.05～23 weight part, 0.1～20 weight part more preferably.When being lower than 0.001 weight part, flame retardant resistance is insufficient, and in addition, when surpassing 25 weight parts, thermotolerance or physical strength significantly reduce, thereby not preferred.
With respect to total 100 weight parts of A composition and B composition, the content of F composition is preferably 0.05～2 weight part, more preferably 0.07～1.5 weight part, 0.1～1 weight part more preferably.When the content of F composition was lower than 0.05 weight part, flame retardant resistance was insufficient, and in addition, when surpassing 2 weight parts, the mechanical characteristics of shock strength etc. reduces, thereby not preferred.
(about other additive)
(i) Phosphorus stablizer
As Phosphorus stablizer, can enumerate phosphorous acid, phosphoric acid, phosphonous acid, phosphonic acids and their ester and tertiary phosphine etc.
As concrete phosphorous acid ester (phosphite) compound, for example can enumerate, triphenyl phosphite, three (nonyl phenyl) phosphorous acid ester, the tricresyl phosphite decyl ester, tricresyl phosphite octyl group ester, three (octadecyl) phosphorous acid ester, didecyl list phenyl phosphites, dioctyl list phenyl phosphites, di-isopropyl list phenyl phosphites, monobutyl phenylbenzene phosphorous acid ester, single decyl phenylbenzene phosphorous acid ester, single octyl group phenylbenzene phosphorous acid ester, three (diethyl phenyl) phosphorous acid ester, three (diisopropyl phenyl) phosphorous acid ester, three (di-n-butyl phenyl) phosphorous acid ester, three (2,4-di-tert-butyl-phenyl) phosphorous acid ester, three (2,6-di-tert-butyl-phenyl) phosphorous acid ester, the distearyl pentaerythritol diphosphites, two (2,4-di-tert-butyl-phenyl) pentaerythritol diphosphites, two (2,6-di-t-butyl-4-aminomethyl phenyl) pentaerythritol diphosphites, two (2,6-di-t-butyl-4-ethylphenyl) pentaerythritol diphosphites, two { 2,4-two (1-methyl-1-phenylethyl) phenyl } pentaerythritol diphosphites, phenyl dihydroxyphenyl propane pentaerythritol diphosphites, two (nonyl phenyl) pentaerythritol diphosphites, and the dicyclohexyl pentaerythritol diphosphites etc.
Further, as other bi-ester of phosphite, can use the bi-ester of phosphite that reacts and have ring texture with the binary phenol.For example, can enumerate 2,2 '-methylene-bis (4, the 6-di-tert-butyl-phenyl) (2, the 4-di-tert-butyl-phenyl) phosphorous acid ester, 2,2 '-methylene-bis (4, the 6-di-tert-butyl-phenyl) (the 2-tertiary butyl-4-aminomethyl phenyl) phosphorous acid ester and 2,2-methylene-bis (4, the 6-di-tert-butyl-phenyl) octyl group phosphorous acid ester etc.
As phosphoric acid ester (phosphate) compound, can enumerate tributyl phosphate, trimethyl phosphite 99, Tritolyl Phosphate, triphenylphosphate, trichlorophenyl phosphoric acid ester, triethyl phosphate, diphenylmethyl benzenephosphonic acid ester, the adjacent xenyl phosphoric acid ester of phenylbenzene list, three butoxyethyl group phosphoric acid ester, dibutyl phosphate, dioctylphosphoric acid ester, diisopropyl phosphate etc., preferably phosphoric acid triphenylmethyl methacrylate, trimethyl phosphite 99.
As phosphinate compound (phosphonite), can enumerate four (2,4-di-tert-butyl-phenyl)-4,4 '-diphenylene, two phosphinates, four (2,4-di-tert-butyl-phenyl)-4,3 '-diphenylene, two phosphinates, four (2,4-di-tert-butyl-phenyl)-3,3 '-diphenylene, two phosphinates, four (2,6-di-tert-butyl-phenyl)-4,4 '-diphenylene, two phosphinates, four (2,6-di-tert-butyl-phenyl)-4,3 '-diphenylene, two phosphinates, four (2,6-di-tert-butyl-phenyl)-3,3 '-diphenylene, two phosphinates, two (2,4-di-tert-butyl-phenyl)-4-phenyl-phenyl-phosphonite ester, two (2,4-di-tert-butyl-phenyl)-3-phenyl-phenyl-phosphonite ester, two (2,6-di-n-butyl phenyl)-3-phenyl-phenyl-phosphonite ester, two (2,6-di-tert-butyl-phenyl)-4-phenyl-phenyl-phosphonite ester, two (2,6-di-tert-butyl-phenyl)-3-phenyl-phenyl-phosphonite ester etc.Wherein, preferred four (di-tert-butyl-phenyl)-diphenylenes, two phosphinates, two (di-tert-butyl-phenyls)-phenyl-phenyl-phosphonite ester, more preferably four (2,4-di-tert-butyl-phenyl)-diphenylene two phosphinates, two (2,4-di-tert-butyl-phenyls)-phenyl-phenyl-phosphonite ester.This phosphinate compound can have the bi-ester of phosphite and the usefulness of two above substituted aryls with abovementioned alkyl, and preferably adopts this mode.
As phosphonate compound (phosphonate), can enumerate phosphenylic acid dimethyl ester, phosphenylic acid diethyl ester and phosphenylic acid dipropyl etc.
As tertiary phosphine, can enumerate triethyl phosphine, tripropyl phosphine, tributylphosphine, tri octyl phosphine, three amyl group phosphines, dimethylphenylphosphine, dibutyl Phenylphosphine, diphenyl methyl phosphine, phenylbenzene octyl group phosphine, triphenylphosphine, three p-methylphenyl phosphines, three naphthyl phosphines and phenylbenzene benzyl phosphine etc.Particularly preferred tertiary phosphine is a triphenylphosphine.
Above-mentioned Phosphorus stablizer not only can only use a kind of, and it is two or more to mix use.In the above-mentioned Phosphorus stablizer, the bi-ester of phosphite of preferred phosphinate compound or following general formula (VIII) expression.
Figure A200910007771D00311
(in the formula (VIII), R and R ' expression carbonatoms is 6～30 the alkyl or the aryl of carbonatoms 6～30, and they both can be identical mutually, also difference) mutually.
As mentioned above, as phosphinate compound, preferred four (2, the 4-di-tert-butyl-phenyl)-diphenylene two phosphinates.As being the stablizer of principal constituent with this phosphinate, commercially available have Sandostab P-EPQ (trade mark, Clariant company make) and an Irgafos P-EPQ (trade mark, CIBASPECIALTY CHEMICALS company make), all can use.
In addition; in above-mentioned formula (VIII); preferred bi-ester of phosphite is two hard ester acyl group pentaerythritol diphosphites, two (2; the 4-di-tert-butyl-phenyl) pentaerythritol diphosphites, two (2; 6-di-t-butyl-4-aminomethyl phenyl) pentaerythritol diphosphites and two { 2, two (1-methyl isophthalic acid-phenylethyl) phenyl of 4-} pentaerythritol diphosphites.
As two hard ester acyl group pentaerythritol diphosphites, commercially available have ア デ カ ス Block PEP-8 (trade mark, rising sun electrochemical industry (strain) are made), a JPP681S (trade mark, north of the city chemical industry (strain) are made), all can use.As two (2, the 4-di-tert-butyl-phenyl) pentaerythritol diphosphites, commercially available have ア デ カ ス Block PEP-24G (trade mark, rising sun electrochemical industry (strain) are made), AlkanoxP-24 (trade mark, Great Lakes company make), Ultranox P626 (trade mark, GE SpecialtyChemicals company make), Doverphos S-9432 (trade mark, Dover Chemical company make) and Irgaofos126 and a 126FF (trade mark, CIBA SPECIALTYCHEMICALS company make) etc., all can use.As two (2,6-di-t-butyl-4-aminomethyl phenyl) pentaerythritol diphosphites, commercially available have a ア デ カ ス Block PEP-36 (trade mark, rising sun electrochemical industry (strain) are made), can easily use.In addition, as two { 2,4-two (1-methyl isophthalic acid-phenylethyl) phenyl } pentaerythritol diphosphites, commercially available have ア デ カ ス Block PEP-45 (trade mark, rising sun electrochemical industry (strain) are made) and a Doverphos S-9228 (trade mark, Dover Chemical company make), all can use.
(ii) Hinered phenols antioxidant
As hindered phenol compound, can use all cpds that is matched with usually in the resin.As this hindered phenol compound; for example can the illustration alpha-tocopherol; butylhydroxy toluene; sinapyl alcohol; vitamin-E; octadecyl-3-(3; 5-two-tert-butyl-hydroxy phenyl) propionic ester; the 2-tertiary butyl-6-(3 '-tertiary butyl-5 '-methyl 2 '-hydroxybenzyl)-4-aminomethyl phenyl acrylate; 2; 6-di-t-butyl 4-(N; the N-dimethylaminomethyl) phenol; 3; 5-di-tert-butyl-4-hydroxyl benzyl phosphonic acids diethyl ester; 2; 2 '-methylene-bis (4-methyl-6-tert butyl phenol); 2; 2 '-methylene-bis(4-ethyl-6-t-butyl phenol); 4; 4 '-methylene-bis (2; the 6-DI-tert-butylphenol compounds); 2; 2 '-methylene-bis(4-methyl-6-cyclohexyl phenol); 2; 2 '-dimethylene-two (6-α-Jia Jibianji-p-cresol); 2; 2 '-ethylidene-two (4; the 6-DI-tert-butylphenol compounds); 2; 2 '-butylidene-two (4-methyl-6-tert butyl phenol); 4; 4 '-butylidene-two (3 methy 6 tert butyl phenol); triethylene glycol-N-pair-3-(3-tertiary butyl-4-hydroxy-5-aminomethyl phenyl) propionic ester; 1; [3-(3 for 6-hexylene glycol-two; the 5-di-tert-butyl-hydroxy phenyl) propionic ester]; two [the 2-tertiary butyl-4-methyl-6-(the 3-tertiary butyl-5-methyl-2-hydroxybenzyl) phenyl] terephthalate; 3; 9-pair 2-[3-(3-tertiary butyl-4-hydroxy-5-aminomethyl phenyl) propionyloxy]-1; the 1-dimethyl ethyl }-2; 4; 8; 10-four oxaspiros [5; 5] undecane; 4; 4 '-thiobis (the 6-tertiary butyl-meta-cresol); 4; 4 '-thiobis (3 methy 6 tert butyl phenol); 2; 2 '-thiobis (4-methyl-6-tert butyl phenol); two (3; the 5-di-tert-butyl-4-hydroxyl benzyl) sulfide; 4; 4 '-dithio two (2; the 6-DI-tert-butylphenol compounds); 4; 4 '-trithio two (2; the 6-DI-tert-butylphenol compounds); 2; 2-sulfo-divinyl is two, and [3-(3; the 5-di-tert-butyl-hydroxy phenyl) propionic ester]; 2, two (n-octyl the sulfo-)-6-(4-hydroxyl-3,5-di-t-butyl phenylamino)-1 of 4-; 3; the 5-triazine; N, N '-hexa-methylene is two-(3,5-di-t-butyl-4-hydroxyl hydrocinnamamide); N; [3-(3 for N '-two; the 5-di-tert-butyl-hydroxy phenyl) propionyl] hydrazine; 1,1,3-three (2-methyl-4-hydroxyl-5-tert-butyl-phenyl) butane; 1; 3; 5-trimethylammonium-2,4,6-three (3; the 5-di-tert-butyl-4-hydroxyl benzyl) benzene; three (3; the 5-di-tert-butyl-hydroxy phenyl) chlorinated isocyanurates; three (3, the 5-di-tert-butyl-4-hydroxyl benzyl) chlorinated isocyanurates; 1,3; 5-three (the 4-tertiary butyl-3-hydroxyl-2; the 6-dimethyl benzyl) chlorinated isocyanurates; 1,3,5-three 2[3 (3; the 5-di-tert-butyl-hydroxy phenyl) propionyloxy] the ethyl chlorinated isocyanurates; four [methylene radical-3-(3; the 5-di-tert-butyl-hydroxy phenyl) propionic ester] methane; triethylene glycol-N-pair-3-(3-tertiary butyl-4-hydroxy 5-aminomethyl phenyl) propionic ester; triethylene glycol-N-pair-3-(3-tertiary butyl-4-hydroxy-5-aminomethyl phenyl) acetic ester; 3,9-pair 2-[3-(3-tertiary butyl-4-hydroxy-5-aminomethyl phenyl) acetoxyl group] and-1, the 1-dimethyl ethyl }-2; 4; 8,10-four oxaspiros [5,5] undecane; four [methylene radical-3-(3-tertiary butyl-4-hydroxy-5-aminomethyl phenyl) propionic ester] methane; 1; 3; 5-trimethylammonium-2,4,6-three (3-tertiary butyl-4-hydroxy-5-methyl-benzyl) benzene; and three (3-tertiary butyl 4-hydroxy-5-methyl base benzyl) isocyanuric acid ester etc.
In above-claimed cpd, the present invention preferably uses four [methylene radical-3-(3-tertiary butyl-4-hydroxy-5-aminomethyl phenyl) propionic ester] methane, octadecyl-3-(3, the 5-di-tert-butyl-hydroxy phenyl) propionic ester and 3,9-pair 2-[3-(3-tertiary butyl-4-hydroxy-5-aminomethyl phenyl) propionyloxy]-1, the 1-dimethyl ethyl }-2,4,8,10-four oxaspiros [5,5] undecane.Especially preferably use 3,9-pair 2-[3-(3-tertiary butyl-4-hydroxy-5-aminomethyl phenyl) propionyloxy] and-1, the 1-dimethyl ethyl }-2,4,8,10-four oxaspiros [5,5] undecane.Above-mentioned Hinered phenols antioxidant both can use separately, or was used in combination.
In preferred Phosphorus stablizer of cooperation and the Hinered phenols antioxidant any one.Especially preferred and use them.With respect to total 100 weight parts of A composition and B composition, the use level of Phosphorus stablizer and Hinered phenols antioxidant is 0.001～3 weight part, is preferably 0.005～2 weight part, more preferably 0.01～1 weight part.When and the time spent, with respect to total 100 weight parts of A composition and B composition, preferably cooperate the Phosphorus stablizer of 0.01～0.3 weight part and the Hinered phenols antioxidant of 0.01～03 weight part.
(iii) releasing agent
In resin combination of the present invention, the productivity when improving moulding or reduce the distortion of moulding product, preferred further cooperation releasing agent.Can use known releasing agent as this releasing agent.For example, can enumerate polyunsaturated fatty acid ester, unsaturated fatty acid ester, polyolefins wax (polyethylene wax, 1-alkene polymers etc. also can use the material that functional compounds is able to modification that contains by sour modification etc.), silicon compound, fluorine cpd (with poly-fluoroalkyl ether as the fluorocarbon oil of representative etc.), paraffin, beeswax etc.Wherein, can enumerate fatty acid ester as preferred releasing agent.This fatty acid ester is the ester of aliphatics alcohols and fatty carboxylic acids.This fatty alcohol both can be monohydroxy-alcohol, also can be the above polyvalent alcohol of binary.In addition, as this pure carbonatoms in 3～32 scope, 5～30 scope more preferably.As this monohydroxy-alcohol, for example can enumerate 12 carbon alcohol, ten four carbon alcohols, 16 carbon alcohol, octadecanol, eicosanol, tetracosa carbon alcohol, 26 carbon alcohol and 30 carbon alcohol etc.As this polyvalent alcohol, can enumerate tetramethylolmethane, Dipentaerythritol, tripentaerythritol, Polyglycerine (triglycerin～six glycerine), two (trishydroxymethyl) propane, Xylitol, Sorbitol Powder and mannitol etc.In fatty acid ester of the present invention, polyvalent alcohol more preferably.
On the other hand, the carbonatoms of preferred aliphat carboxylic acid is 3～32, particularly preferably is carbonatoms and is 10～22 aliphatic carboxylic acid.As this aliphatic carboxylic acid, for example can enumerate the representative examples of saturated aliphatic carboxylic of capric acid, hendecoic acid, lauric acid, ficocerylic acid, ten tetra-carbonics, 15 carbonic acid, 16 carbonic acid (palmitinic acid), 17 carbonic acid, 18 carbonic acid (stearic acid), 19 carbonic acid, docosoics, 20 carbonic acid and behenic acid etc. and the unsaturated aliphatic carboxylic acid of Zoomeric acid, oleic acid, linolic acid, linolenic acid, eicosenoic acid, timnodonic acid and cetoleic acid etc.In above-mentioned, as the preferred carbonatoms of aliphatic carboxylic acid 14～20 aliphatic carboxylic acid.Wherein, representative examples of saturated aliphatic carboxylic preferably.Preferred especially stearic acid and palmitinic acid.
Because the above-mentioned aliphatic carboxylic acid of stearic acid or palmitinic acid etc. is normally by with shea butter or pig fat etc. being the animal raw fat of representative and by the natural oil lipid manufacturing that with plam oil or sunflower seed oil is the vegetative grease etc. of representative, so these aliphatic carboxylic acids normally contain other different carboxylic acid compositions of carbonatoms mixture.Therefore, in the manufacturing of fatty acid ester of the present invention, also by these natural lipid manufacturings, the aliphatic carboxylic acid that the mixture mode that preferred use contains other carboxylic acid compositions forms especially preferably uses stearic acid or palmitinic acid.
Fatty acid ester can be any in part ester and the full ester (full ester).But in the part ester, common hydroxyl value height, the decomposition of resin etc. when bringing out high temperature easily, therefore more preferably full-cream.Consider that from the viewpoint of thermostability the acid number in the fatty acid ester of the present invention is preferably below 20, more preferably 4～20, more preferably 4～12.In addition, in fact acid number can get 0.In addition, the hydroxyl value of fatty acid ester is preferably 0.1～30.And iodine number is preferably below 10.In fact iodine number can get 0.These characteristics can be obtained according to the method for regulation among the JIS K 0070.
With respect to total 100 weight parts of A composition and B composition, the content of releasing agent is preferably 0.005～2 weight part, more preferably 0.01～1 weight part, more preferably 0.05～0.5 weight part.In this scope, poly carbonate resin composition has good release property and roll release.Particularly, the fatty acid ester of this content can be provided under the situation of not damaging good color and luster, has the excellent release property and the poly carbonate resin composition of roll release type.
(iv) UV light absorber
Can also contain UV light absorber in the resin combination of the present invention.Because resin combination of the present invention has the excellent transparency, therefore, is suitable for very much making in the purposes of light transmission.
As UV light absorber, can enumerate benzophenone particularly, for example can enumerate 2, the 4-dihydroxy benaophenonel, 2-hydroxyl-4-methoxy benzophenone, 2-hydroxyl-4-octyloxy benzophenone, 2-hydroxyl-4-benzyloxy benzophenone, 2-hydroxyl-4-methoxyl group-5-sulphur oxygen base benzophenone, 2-hydroxyl-4-methoxyl group-5-sulphur oxygen base Trihydride benzophenone (2-ヒ De ロ キ シ-4-メ ト キ シ-5-ス Le ホ キ シ ト リ Ha イ De ラ イ De レ イ ト ベ Application ゾ Off エ ノ Application), 2,2 '-dihydroxyl-4-methoxy benzophenone, 2,2 ', 4,4 '-tetrahydroxybenzophenone, 2,2 '-dihydroxyl-4,4 '-dimethoxy-benzophenone, 2,2 '-dihydroxyl-4,4 '-dimethoxy-5-sulphur oxygen acid sodium benzophenone, two (5-benzoyl-4-hydroxyl-2-p-methoxy-phenyl) methane, 2-hydroxyl-4-positive 12-alkoxy benzophenone and 2-hydroxyl-4-methoxyl group-2 '-carboxyl benzophenone etc.
Benzotriazole category as UV light absorber, for example can enumerate 2-(2-hydroxy-5-methyl base phenyl) benzotriazole, 2-(2-hydroxyl-uncle's 5-octyl phenyl) benzotriazole, 2-(2-hydroxyl-3, the 5-dicumylphenyl) phenyl benzotriazole, 2-(the 2-hydroxyl-3-tertiary butyl-5-aminomethyl phenyl)-5-chlorobenzotriazole, 2, [4-(1 for 2 '-methylene-bis, 1,3, the 3-tetramethyl butyl)-6-(2H-benzotriazole-2-yl) phenol], 2-(2-hydroxyl-3, the 5-di-tert-butyl-phenyl) benzotriazole, 2-(2-hydroxyl-3, the 5-di-tert-butyl-phenyl)-the 5-chlorobenzotriazole, 2-(2-hydroxyl-3, the 5-di-tert-pentyl-phenyl) benzotriazole, 2-(2-hydroxyl-uncle's 5-octyl phenyl) benzotriazole, 2-(2-hydroxyl-5-tert-butyl-phenyl) benzotriazole, 2-(2-hydroxyl-4-octyloxyphenyl) benzotriazole, 2,2 '-methylene-bis (4-cumyl-6-benzotriazole phenyl), 2,2 '-TOPOT 2,2 (1,3-benzoxazine-4-ketone), 2-[2-hydroxyl-3-(3,4,5,6-tetrahydrochysene phthalic diamide methyl)-the 5-aminomethyl phenyl] benzotriazole, 2-(2 '-hydroxy-5-methyl base acrylyl oxy-ethyl phenyl)-2H-benzotriazole and can with the multipolymer of the vinyl monomer of this monomer copolymerizable or 2-(2 '-hydroxyl-5-acrylyl oxy-ethyl phenyl)-2H-benzotriazole and can be with the polymkeric substance with 2-hydroxy phenyl-2H-benzotriazole skeleton of the multipolymer of the vinyl monomer of this monomer copolymerizable etc. etc.
As the hydroxyphenyltriazinuv class of UV light absorber, can enumerate 2-(4,6-phenylbenzene-1,3,5-triazine-2-yl)-and 5-hexyl oxy phenol, 2-(4,6-phenylbenzene-1,3,5-triazine-2-yl)-and 5-methyl oxy phenol, 2-(4,6-phenylbenzene-1,3,5-triazine-2-yl)-and 5-ethyl oxy phenol, 2-(4,6-phenylbenzene-1,3,5-triazine-2-yl)-and 5-propyl group oxy phenol and 2-(4,6-phenylbenzene-1,3,5-triazine-2-yl)-5-butyl oxy phenol etc.Further, the phenyl that can also enumerate in 2-(4, two (2, the 4-3,5-dimethylphenyl)-1,3,5-triazines-2-yls of 6-)-above-mentioned example compound such as 5-hexyl oxy phenol becomes 2, the compound of 4-3,5-dimethylphenyl.
As the cyclic imide base ester class of UV light absorber, for example can enumerate 2,2 '-TOPOT 2,2 (3,1-benzoxazine-4-ketone), 2,2 '-(4,4 '-diphenylene) two (3,1-benzoxazine-4-ketone) and 2,2 '-(2, the 6-naphthalene) two (3,1-benzoxazine-4-ketone) etc.
In addition; cyanoacrylate as UV light absorber; particularly as enumerating 1; 3-pair-[(2 '-cyano group-3 '; 3 '-diphenylprop enoyl-) oxygen]-2,2-pair-[(2-cyano group-3,3-diphenylprop enoyl-) oxygen] methylpropane and 1; 3-pair-[(2-cyano group-3,3-diphenylprop enoyl-) oxygen] benzene etc.
Further, above-mentioned UV light absorber also can be, by adopting the monomeric compound structure to carry out radical polymerization, the monomer of this ultraviolet-absorbing monomer and/or light stability monomer with the structure of hindered amine and (methyl) alkyl acrylate etc. carried out copolymerization and the aggretion type UV light absorber that obtains.As above-mentioned ultraviolet-absorbing monomer, can preferably enumerate the compound that contains benzotriazole skeleton, benzophenone skeleton, triazine skeleton, cyclic imino ester skeleton and cyanoacrylate skeleton in the ester substituting group of (methyl) acrylate.
In above-mentioned, when considering ultraviolet absorption ability, preferably adopt benzotriazole category and hydroxyphenyltriazinuv class, and when considering thermotolerance and color and luster (transparency), then preferably adopt cyclic imino ester class and cyanoacrylate.Above-mentioned UV light absorber both can be used separately, can also use two or more mixtures.
With respect to total 100 weight parts of A composition and B composition, the content of UV light absorber is 0.01～2 weight part, is preferably 0.02～2 weight part, more preferably 0.03～1 weight part, more preferably 0.05～0.5 weight part.
(v) dye pigment
Resin combination of the present invention can further contain the various pigment that dye, and the moulding product of performance various appearances are provided.Because resin combination of the present invention has the excellent transparency, therefore, is suitable for very much making in the purposes of light transmission.Therefore, for example, can give the transparent feel of higher photopermeability or nature to resin combination of the present invention by cooperating white dyes, and, by cooperating white dyes or other luminous fluorescent dyestuff, can give the more excellent appearance effect of utilizing illuminant colour.In addition, dying pigment and can providing and have delicate paintedly of denier and has the more resin combination of high transparent.
As the fluorescence dye that uses among the present invention (comprising white dyes), for example can enumerate coumarins fluorescence dye, chromene fluorochrome, perylene fluorochrome, anthraquinone fluorochrome, thioindigo fluorochrome, xanthene fluorochrome, xanthone fluorochrome, thioxanthene fluorochrome, thioxanthone fluorochrome, thiazides fluorescence dye and diaminobenzil fluorochrome etc.Wherein, the coumarins fluorescence dye that preferred thermotolerance is good and deterioration is few in the forming process of polycarbonate resin, chromene fluorochrome, with and the perylene fluorochrome.
As the dyestuff beyond above-mentioned bluing agent and the fluorescence dye, can lift out perylene class dyestuff, coumarins dyestuff, thioindigo class dyestuff, anthraquinone dyes, thioxanthene ketone dyestuff, Prussian blue etc. yellow prussiate, purple cyclic ketones class dyestuff, quinoline dyestuff, quinoline a word used for translation ketone dyestuff, dioxazines dyestuff, isoindoline ketone dyestuff and phthalocyanines dye etc.Further, resin combination of the present invention passes through hybrid metal pigment, and can access more good metal color.As metallic pigment, preferably in various plate-like fillers, has the material of metal tunicle or metal oxide coating.
With respect to total 100 weight parts of A composition and B composition, the above-mentioned content that dyes pigment is preferably 0.00001～1 weight part, more preferably 0.00005～0.5 weight part.
(vi) other thermo-stabilizer
In resin combination of the present invention, except above-mentioned Phosphorus stablizer and Hinered phenols antioxidant, can also cooperate other thermo-stabilizer.Described other thermo-stabilizers, preferably with these stablizers and oxidation inhibitor in any one and usefulness, especially preferred and both and usefulness.As these other thermo-stabilizer, for example can preferably enumerate with 3-hydroxyl-5, the resultant of reaction of 7-di-t-butyl-furans-2-ketone and o-Xylol is the lactone stablizer (about the detailed content of this stablizer, on the books in the flat 7-233160 communique of TOHKEMY) of representative.This compound can utilize this compound as Irganox HP-136 (trade mark, CIBA SPECIALTYCHEMICALS company make) and commercially available.In addition, commercially available in addition with this compound and various bi-ester of phosphite and hindered phenol compound blended stablizer in addition.For example, can preferably enumerate the Irganox HP-2921 of above-mentioned company.In the present invention, also can use the described stablizer that mixes in advance.With respect to total 100 weight parts of A composition and B composition, the use level of preferred lactone stablizer is 0.0005～0.05 weight part, more preferably 0.001～0.03 weight part.
In addition, as other stablizers, can enumerate the sulphur-containing stabilizer of tetramethylolmethane four (3-mercaptopropionic acid ester), tetramethylolmethane four (3-lauryl thiopropionate) and glycerol-3-stearyl thiopropionate etc.This stablizer is effective especially when resin combination is used for rotoforming.With respect to total 100 weight parts of A composition and B composition, preferably the use level of this sulphur-containing stabilizer is 0.001～0.1 weight part, more preferably 0.01～0.08 weight part.
(vii) high reflection of light used white pigment
In resin combination of the present invention, can give the luminous reflectance effect with white pigment by cooperating the high reflection of light.As this white pigment, preferred titanium dioxide (the particularly titanium dioxide of being handled by organic surface treatment agents such as organo-siloxanes) pigment.The high reflection of this light content of white pigment, total 100 weight parts with respect to A composition and B composition are preferably 3～30 weight parts, more preferably 8～25 weight parts.In addition, the high reflection of light is preferred also with two or more with white pigment.
(viii) other additives
In resin combination of the present invention, can contain dispersion agent, photochemical catalysis class stain control agent, hot line absorption agent and the photochromic agent etc. of thermoplastic resin beyond A composition and the B composition, other mobile modification agents, antiseptic-germicide, whiteruss etc.
As the thermoplastic resin beyond A composition and the B composition, can enumerate plexiglass (PMMA resin), ring-type polyolefin resin, polylactic resin, polycaprolactone resin, thermoplastic fluorocarbon resin (for example, with the polyvinylidene fluoride resin being representative) and polyolefin resin (polyvinyl resin, acrylic resin etc.).
(manufacturing of resin combination)
When making resin combination of the present invention, can adopt arbitrary method.For example; can enumerate pre-mixing device such as adopting V-Mixer, Henschel mixer, chemomotive force device and extrusion mixing machine; thorough mixing is from A composition～F composition and arbitrarily after other additives; with extrusion tablets press or briquetting machine etc. premixture is carried out granulation as required; be that the melting mixing machine of representative carries out melting mixing in order to the exhaust biaxial extruder then, then carry out the method for granulationization by tablets press etc.
In addition, can also enumerate with each composition supply to independently respectively be the method or the part in each composition of pre-mixing of melting mixing machine of representative with the exhaust biaxial extruder after, supply to method of melting mixing machine etc. independently with remaining composition.As the part of each composition is carried out premixed ten thousand methods, for example can enumerate in advance the composition beyond the A composition is carried out pre-mixing after, mix or directly be supplied to the method for forcing machine with the polycarbonate resin of A composition.
As pre-blend approach, for example can also enumerate, when containing as the A composition under the situation of powdery substance, the part of this powder mixed with the additive that is cooperated and prepared the parent sizing material (マ ス -バ ッ チ) of the additive that has diluted by powder, utilized the method for this parent sizing material again.In addition, can also enumerate a composition independently from the method for supplying with that melt extrudes machine midway etc.Further, when having in the composition that is cooperated under the situation of aqueous material, can use so-called fluid infusion apparatus or liquid appending apparatus to the supply that melt extrudes machine.
As forcing machine, the preferred forcing machine that uses with venting port, this forcing machine with venting port can remove moisture in the raw material or the volatile gases that is produced by the melting mixing resin.Preferably be provided with and be used for the vacuum pump that the moisture that will be produced or volatilization gas drain into the forcing machine outside effectively at venting port.In addition, the zone before forcing machine mould portion is provided with and is used to remove the filtering net of sneaking into extruding impurities in raw materials etc., also impurity can be removed from resin combination thus.As this filtering net, can enumerate wire netting, screen replacing device, sintered metal plates (disc filter etc.) etc.
As the melting mixing machine, except biaxial extruder, can also enumerate mixing machine, mixing roller, single shaft forcing machine, the multiple screw extruder more than three etc. of closing of Banbury.
The resin of extruding as mentioned above can directly cut off and carries out granulating, or after forming strand, this strand is cut off with tablets press and carries out granulating.In addition, when when carrying out granulating,, then preferably the environmental gas around the forcing machine carry out cleaningization if be necessary to reduce outside influence as dust etc.Further, in this particulate is made, can be by the whole bag of tricks that has proposed in polycarbonate resin at CD, suitably carry out the minimizing of the bubble (bubbles of vacuum) that the minimizing of narrow and smallization that particle shape distributes, the short small powder of cutting minimizing, the transportation of thing (ミ ス カ ッ ト thing) or producing when carrying and strand or granule interior produce.According to these methods, the generation ratio that can carry out the height circulationization of moulding and reduce the bad phenomenon of silver-colored spot (シ Le バ-) etc.In addition, coating of particles can be the general shape of cylindrical, corner post shape and sphere etc., and is more preferably cylindrical.The diameter of preferred this cylinder is 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.
In addition; can also enumerate the mode that contains E composition of the present invention in advance with high density ground; with the melting mixing machine A composition and B composition are carried out melting mixing; and carry out granulating and make the parent sizing material; this parent sizing material is mixed with residual A composition and other additives, and carry out granular method by the melting mixing machine.
(the moulding product that form by resin combination of the present invention)
Resin combination of the present invention obtains the moulding product by the particle of as above making is carried out injection molding usually, thereby produces various goods.In described injection molding, be not only common forming method, can suitably use compression molding, injection extrusion forming, air-auxiliary injection forming, foaming (comprising the moulding of injecting), insert moulding, in-mold coating (In-Mold Coating) moulding, heat insulation mould molding, heating cooling mould molding, dual-color forming, interlayer moulding and ultra-high speed injection molding etc. rapidly according to purpose by supercutical fluid.The advantage of these various forming methods has been well-known.In addition, moulding can be selected any in cold runner mode and the hot runner mode.
Resin combination of the present invention can become forms such as various special-shaped extrusion molding articles, sheet, film like and be used by extrusion moulding.In addition, in sheet, film like moulding, can also use blow moulding, rolling process, casting method etc.And, by implementing specific stretched operation, also can be shaped to heat-shrinkable tube.In addition, also can resin combination of the present invention be manufactured the moulding product by rotoforming or blow molding etc.
As the object lesson of the moulding product that utilized resin combination of the present invention, be fit to be applied in the purposes of the internal part of OA machine or tame electrical article or housing etc.As these goods, for example can enumerate computer, notebook computer, CRT monitor, printer, portable terminal, mobile telephone, duplicating machine, facsimile recorder, recording medium (CD, CD-ROM, DVD, PD, FDD etc.) drive, parabolic antenna (parabola antenna), power tool, VTR, TV, flatiron, blower, electric cooker, microwave oven, sound machine, the voice machine of audio frequency/compact video disc/laser disc etc., the illumination machine, refrigerator, air-conditioning, type-writer, word processors etc. can use the resin that is formed by flame retardant resin composition of the present invention in their the various parts of framework etc.In addition, as other resins, can enumerate the automobile parts of guide plate parts, auto navigation parts, automobile audio parts etc.
The inventor thinks best embodiments of the present invention at present, and the embodiment for the preferable range that combines above-mentioned each important document for example, is recorded in its typical example among the following embodiment.Certainly, the present invention is not limited to these embodiments.
Embodiment
Below, illustrate in greater detail the present invention by embodiment.Under situation about not indicating especially, " part " expression " weight part " among the embodiment, " % " expression " weight % ".In addition, evaluation is to carry out according to following method.
(evaluation of resin combination)
(i) flame retardant resistance: with thickness is the test piece of 1.5mm, carries out combustion test according to UL specification 94.
In addition, more than the preferred V-1 grade of the grade of flame retardant resistance.
(ii) the summer is than shock strength:
According to ISO 179, implement the mensuration of band breach summer than shock strength.
(iii) thermotolerance
According to ISO 75-1 and 75-2, measure the load deflection temperature.In addition, measuring with the load is that 1.80MPa implements.
(iv) mobile
With injection moulding machine (SG150U, Sumitomo Heavy Industries, Ltd makes), measure the Archimedean screw length of flow of the thick 2mm of stream, the wide 8mm of stream.At center housing temperature is that 260 ℃, die temperature are that 70 ℃, injection pressure are to carry out under the condition of 98MPa.
(v) outward appearance
The framework moulding product of the notebook computer of moulding Fig. 1～shown in Figure 3 are confirmed whether to produce the uneven color (interflow line A) of wire and are the uneven color (interflow line B) whether starting point produces wire with the boss on the extended line of fusion portion.
Zero: no uneven color produces
*: produce uneven color
Embodiment 1～19, comparative example 1～10
According to forming shown in table 1～table 3, supply with mixture from first supplying opening of forcing machine, this mixture is made of the composition except that FR-1 (phosphoric acid ester), D composition (reinforcement packing material) and the B composition (ABS-1, ABS-2, ABS-3, ABS-4) of E composition.The premixture that mixes following (i) in V-Mixer becomes to assign to obtain described mixture with other.Promptly, (i) be the mixture of the aromatic copolycarbonate of F composition (fluorine-containing Antidrip agent) and A composition, wherein, become the mode of 2.5 weight % with the F component content, described F composition and A composition are dropped in the polyethylene bag, and rock this bag integral body and make its mixed uniformly mixture.When containing B composition (ABS-1, ABS-2, ABS-3, ABS-4) and D composition (reinforcement packing material), then adopt the side feeder, supply with from second supplying opening.Further, when adding the FR-1 of E composition, be heated under 80 ℃ the state, adopt fluid infusion apparatus (HYM-JS-08, Fuji's science and technology industry (strain) are made), from cylinder body the 3rd supplying opening (position between the 1st supplying opening and venting port) midway, supply with to forcing machine, to be adjusted into the ratio of regulation.Fluid infusion apparatus be set to weight feed, the feed rate of other raw materials is then by gauger (CWF, make in (strain) Kubo field) delicate metering.Use the exhaust biaxial extruder (5BW-3V of diameter 30mm Φ, the TEX30 α-38 of (strain) JSW) extrudes, and be that 150rpm, extrusion capacity are that the vacuum tightness of 20kg/h, exhaust portion is to carry out melting mixing under the 3kPa to obtain particle in the screw rod rotation number.In addition, for extrusion temperature, it is 260 ℃ from first supplying opening to mould part.
To resulting granules under 80～90 degree, by the heated air circulation type drying machine after dry 6 hours, by injection moulding machine, the test piece of moulding evaluation usefulness (according to UL94, ISO179, ISO75-1 and ISO 75-2).
In addition, the content of each composition of the symbolic representation in table 1～3 is as follows.
(A composition)
PC-1: aromatic polycarbonate resin (パ Application ラ イ ト L-1225WP is 22500 polycarbonate resin powder by common method by the viscosity-average molecular weight of dihydroxyphenyl propane photoreactive gas manufacturing, and Supreme Being people changes into (strain) and makes)
PC2: aromatic polycarbonate resin (パ Application ラ イ ト L-1225WX is 19700 polycarbonate resin powder by common method by the viscosity-average molecular weight of dihydroxyphenyl propane photoreactive gas manufacturing, and Supreme Being people changes into (strain) and makes)
(B composition)
ABS-1:ABS resin (Network ラ ラ ス チ ッNetwork SXH-330 (trade(brand)name), the about 17.5 weight % of divinyl rubber composition, rubber weight average particle diameter 0.40 μ m, by the letex polymerization manufacturing, Japanese A﹠amp; L (strain) makes)
(rubber weight average particle diameter 0.56 μ m is by block polymerization manufacturing, Japanese A﹠amp for UT-61 (trade(brand)name), the about 14 weight % of divinyl rubber composition for the ABS-2:ABS resin; L (strain) makes)
ABS-5: the ABS resin of making by letex polymerization (CHT (trade(brand)name), by the about 58 weight % of rubber constituent amount that polyhutadiene constitutes, rubber weight average particle diameter 0.31 μ m, CHEIL INDUSTRYINC makes)
(C composition)
MBS-1: core-shell grafting copolymer (nuclear by the letex polymerization manufacturing is the divinyl rubber composition of 70 weight %, and shell is the vinylbenzene of 30 weight % and the graft copolymer of methyl methacrylate, and the weight average particle diameter of rubber constituent is 0.32 μ m)
MBS-2: core-shell grafting copolymer (nuclear by the letex polymerization manufacturing is the divinyl rubber composition of 70 weight %, and shell is the vinylbenzene of 30 weight % and the graft copolymer of methyl methacrylate, and the weight average particle diameter of rubber constituent is 0.41 μ m)
MBS-3: core-shell grafting copolymer (パ ラ ロ イ De EXL-2678 (trade(brand)name), nuclear is the polyhutadiene of 60 weight %, shell is the vinylbenzene of 40 weight % and the graft copolymer of methyl methacrylate, the weight average particle diameter of rubber constituent is 0.35 μ m, by the letex polymerization manufacturing, Rohm and Haas company makes)
(D composition)
WSN: wollastonite (H-1250F (trade(brand)name), clear water Industrial Co., Ltd makes)
Talcum: talcum (HST0.8 (trade(brand)name), woods changes into Co., Ltd. and makes)
Mica: white mica (A-41 (trade(brand)name), (strain) mountain pass mica industry manufacturing)
(E composition)
FR-1: with the phosphoric acid ester (CR-741 (trade(brand)name), Daihachi Chemical Industry Co., Ltd. make) of dihydroxyphenyl propane two (diphenyl phosphoester) as principal constituent
FR-2: potassium perfluorobutane sulfonate salt (メ ガ Off ァ ッ Network F-114P (trade(brand)name), Dainippon Ink. ﹠ Chemicals Inc makes)
FR-3: the organo-siloxane based flame retardant (X-40-2600J (trade(brand)name), Shin-Etsu Chemial Co., Ltd makes) that contains Si-H base and methyl and phenyl
(F composition)
PTFE: tetrafluoroethylene (Port リ Off ロ Application MP FA500 (trade(brand)name), Daikin Industries (strain) is made)
(other compositions)
ABS-3: by the ABS resin (by the about 15 weight % of rubber constituent amount that polyhutadiene constitutes, rubber weight average particle diameter 0.18 μ m) of letex polymerization manufacturing
ABS-4: by the ABS resin (by the about 21 weight % of rubber constituent amount that polyhutadiene constitutes, rubber weight average particle diameter 2.2 μ m) of letex polymerization manufacturing
MBS-4: core-shell grafting copolymer (metablenC-223A (trade(brand)name), nuclear is the polyhutadiene of 70 weight %, shell is the vinylbenzene of 30 weight % and the graft copolymer of methyl methacrylate, the weight average particle diameter of rubber constituent is 0.23 μ m, and Mitsubishi Rayon Co.Ltd makes)
MBS-5: core-shell grafting copolymer (nuclear by the letex polymerization manufacturing is the divinyl rubber composition of 70 weight %, and shell is the vinylbenzene of 30 weight % and the graft copolymer of methyl methacrylate, and the weight average particle diameter of rubber constituent is 0.55 μ m)
DC30M: the olefines wax that the copolymerization of alpha-olefin and maleic anhydride obtains (ダ イ ヤ カ Le Na 30M (trade(brand)name), Mitsubishi chemical Co., Ltd makes)
SL900: fatty acid ester releasing agent (リ ケ マ-Le SL900 (trade(brand)name), reason is ground VITAMIN (strain) manufacturing)
IRGX: phenol thermo-stabilizer (IRGANOX1076 (trade(brand)name), Ciba SpecialtyChemicals company makes)
TMP: phosphoric acid ester thermo-stabilizer (TMP (trade(brand)name), Daihachi Chemical Industry Co., Ltd. makes)
Figure A200910007771D00451
Figure A200910007771D00471
Figure A200910007771D00481
As can be known from the above table, the polydiene of the specific weight average particle diameter of the application of the invention, can access and have the outward appearance that does not produce the excellence of interflow line in fusion portion or part in uneven thickness, and have the excellent impact characteristics and the poly carbonate resin composition of formability simultaneously.
Industrial applicibility
Because resin combination of the present invention does not produce the interflow line in fusion section or part in uneven thickness, and Therefore impact characteristics and mouldability excellence, are widely used in OA purposes and other various uses. Therefore, the industrial effect that reaches of the present invention is very big.

Claims (8)

1. resin combination, it is characterized in that, comprise aromatic polycarbonate resin as the A composition, as the graft copolymer of B composition and as the core-shell grafting copolymer of C composition, and total 100 weight parts with respect to the B composition of the A composition of 99～1 weight % and 1～99 weight %, the C composition that contains 0.1～10 weight part
Wherein, described B composition contains rubber polymer, vinyl cyanide monomer and the aromatic vinyl monomer that the weight average particle diameter of rubber particles is 0.20～2.0 μ m; Described C composition is, at weight average particle diameter be 0.30～0.50 μ m the polydiene composition in the presence of, by emulsion polymerization, with (methyl) alkyl acrylate monomer or (methyl) alkyl acrylate monomer and can with the in addition copolymerization and obtaining of the monomeric mixture of this (methyl) alkyl acrylate monomer copolymerization.
2. resin combination as claimed in claim 1, wherein, described B composition obtains by letex polymerization, and, contain the polydiene of 1～40 weight % as rubber polymer.
3. resin combination as claimed in claim 1 or 2, wherein, described C composition is the core-shell grafting copolymer that contains the polydiene composition of 40～90 weight %.
4. as any described resin combination in the claim 1～3, wherein, contain inorganic filling material, and, contain the D composition of 0.1～50 weight part with respect to total 100 weight parts of A composition and B composition as the D composition.
5. resin combination as claimed in claim 4, wherein, described D composition is more than one the inorganic filling material that is selected from the group of being made up of talcum, mica and wollastonite.
6. as any described resin combination in the claim 1～5, wherein, contain as the fire retardant of E composition and as the fluorine-containing Antidrip agent of F composition, and total 100 weight parts with respect to A composition and B composition, contain the E composition of 0.001～25 weight part and the F composition of 0.05～2 weight part, described E composition is more than one the fire retardant that is selected from the group of being made up of phosphoric acid ester, sulfonic acid alkali metal salts or azochlorosulfonate acid alkali earth metal salt and silicon compounds.
7. as any described resin combination in the claim 1～6, wherein, the E composition is the phosphoric acid ester of following formula (I) expression:
In the formula (I), X is from dihydroxy compound deutero-divalent phenol residue, and described dihydroxy compound is the dihydroxy compound that is selected from the group of being made up of quinhydrones, Resorcinol, two (4-hydroxy diphenyl) methane, dihydroxyphenyl propane, dihydroxyl hexichol, dihydroxy naphthlene, two (4-hydroxy phenyl) sulfone, two (4-hydroxy phenyl) ketone and two (4-hydroxy phenyl) sulfide; N is 0～5 integer, and perhaps when for the mixture of the different phosphoric acid ester of n number, n is their mean value; R 4, R 5, R 6And R 7Represent independently respectively that from aryl deutero-one bivalent phenol residue described aryl is the aryl that is selected from the group of forming by phenol, cresols, xylenol, isopropyl-phenol, butylphenol and to cumyl phenol.
8. moulding product, it is to be formed by any described resin combination moulding in the claim 1～7.
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