CN101519528B - Polycarbonate resin composition with superior appearance - Google Patents

Polycarbonate resin composition with superior appearance Download PDF

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CN101519528B
CN101519528B CN 200910007771 CN200910007771A CN101519528B CN 101519528 B CN101519528 B CN 101519528B CN 200910007771 CN200910007771 CN 200910007771 CN 200910007771 A CN200910007771 A CN 200910007771A CN 101519528 B CN101519528 B CN 101519528B
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CN101519528A (en
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相原哲也
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Teijin 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 byweight 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 products formed 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) section or part in uneven thickness, also have simultaneously excellent impact characteristics and resin combination and the products formed thereof of formability.
Background technology
Take aromatic polycarbonate resin and ABS resin as representative and polymer alloy graft copolymer, have excellent formability and HI high impact characteristic, thereby be 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, take lightweight or reduce costs as purpose, the thin-walled property of this shell products formed, without application (Tu dress レ ス) be developed, affected by it, 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 take aromatic polycarbonate resin and ABS resin in the polymer alloy of the graft copolymer of representative, add the method for core-shell grafting copolymer, relative knowledge has been well-known.
For example, known in the resin combination that the oligopolymer by aromatic copolycarbonate, AS resin, ABS resin, organo phosphorous compounds forms, coordinate the MBS resin as core-shell grafting copolymer, obtain thus the flame retardant resin composition (patent documentation 1, patent documentation 2, patent documentation 3) of mobility, impact, excellent heat resistance.Yet, in this flame retardant resin composition, although by coordinating the MBS resin as core-shell grafting copolymer, can obtain high impact when keeping high workability, but, in the inhomogeneous section of the fusion section of products formed or rib, boss equal thickness, the uneven color of the wire that the flow pattern when producing because of injection moulding causes becomes very large problem in appearance.Its reason is, the form of the products formed that is formed by this polycarbonate-based flame retardant resin composition is in the different cause of part that the flow patterns such as fusion section or in uneven thickness change, and proposed the method for a lot of improvement take aromatic polycarbonate resin and ABS resin as the consistency of the graft copolymer of representative.
For example, in known composition being formed by polycarbonate resin and the styrene resin take ABS resin, HIPS resin as representative, add terpenoid resin as phase solvent, obtain thus the polycarbonate-based thermoplastic resin (patent documentation 4) of fusion section intensity, fusion section outward appearance, melt fluidity excellence.Yet, when using this with terpenoid resin during as the phase solvent of representative, causing the countermeasure of the bad order phenomenon of uneven color as to injection moulding the time because of flow pattern, its effect is little, exists problems such as reducing incendivity.
As mentioned above, need to 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 JP 2003-41114 communique
Patent documentation 3:JP JP 2001-302898 communique
Patent documentation 4:JP JP 2000-63651 communique
Summary of the invention
The object of the invention is to, when a kind of flame retardant resistance, thermotolerance, mobility keeping originally having is provided, 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 take aromatic polycarbonate resin and ABS resin in the graft copolymer of representative, coordinate and have the core-shell grafting copolymer of specific rubber weight average particle diameter, can solve the bad order problem that causes due to the form take aromatic polycarbonate resin and ABS resin as the graft copolymer polymer alloy of representative, thereby complete the present invention.
Above-mentioned problem of the present invention realizes in the following manner.
(1) provide 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 % by weight and 1～99 % by weight, the core-shell grafting copolymer (C composition) that contains 0.1～10 weight part, wherein, the weight average particle diameter that described graft copolymer (B composition) contains rubber particles is the rubber polymer of 0.20～2.0 μ m, vinyl cyanide (シ ア Application PVC ニ Le) monomer and the described core-shell grafting copolymer of aromatic vinyl monomer (C composition) are, be under the existence of polydiene composition of 0.30～0.50 μ m at weight average particle diameter, pass through emulsion polymerization, with (methyl) alkyl acrylate monomer or (methyl) alkyl acrylate monomer with can carry out with (methyl) alkyl acrylate monomer the in addition copolymerization and obtaining of mixture of the monomer of copolymerization.
(2) resin combination as described in (1), wherein, described graft copolymer (B composition) obtains by letex polymerization, and, contain the polydiene of 1～40 % by 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 % by weight.
(4) as the described resin combination of any one in above-mentioned (1)～(3), wherein, with respect to total 100 weight parts of A composition and B composition, contain the inorganic filling material (D composition) of 0.1～50 weight part.
(5) as above-mentioned (4) described resin combination, wherein, inorganic filling material (D composition) is more than one packing materials in the group of selecting free talcum, mica and wollastonite composition.
(6) as the described resin combination of any one 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 more than one fire retardants in the group of selecting free phosphoric acid ester, azochlorosulfonate acid alkali (alkaline earth) metal-salt and silicon compounds composition.
(7) as the described resin combination of any one in above-mentioned (1)～(6), wherein, fire retardant (E composition) is the phosphoric acid ester of following formula (I) expression:
Figure G2009100077712D00031
In formula (I), X is from the derivative divalent phenol residue of dihydroxy compound, and described dihydroxy compound is the dihydroxy compound that selects in the group that free 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 forms; 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 from the derivative bivalent phenol residue of aryl, described aryl be select free phenol, cresols, xylenol, isopropyl-phenol, butylphenol and group that cumyl phenol is formed in aryl.
Description of drawings
Fig. 1 is the surperficial schematic perspective view (long 178mm * high 10mm in wide 245mm * limit, thickness is 2.0mm) of the products formed of the imitation notebook computer casing that uses in embodiment.The cast gate of this products formed is two side gates (long 5mm * wide 8mm, thickness 1.5mm).
Fig. 2 is the surperficial schematic elevational view of the products formed that uses in embodiment, is shown with gate location, the interflow line produces position, anticipation fusion sites.
Fig. 3 is the back side schematic elevational view of the products formed that uses in embodiment, and expression has the state (boss shape: external diameter 6.5mm, internal diameter 2.5mm, height 10mm) of boss with ribbing.
The explanation of Reference numeral
1 imitates the products formed body of notebook computer casing
2 minute surface sections
3 mat surface sections
4 cast gates (side gate two places, long 5mm * wide 8mm, thickness 1.5mm)
The position is envisioned in 5 fusions
6 interflow line A (uneven color of the wire that produces take the part of thinking fusion section as starting point)
7 interflow line B (uneven color of the wire that produces at the flow direction of resin take boss as starting point)
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.
as the representative example of binary phenol, can enumerate quinhydrones, Resorcinol, 4,4 '-bis-phenol, two (4-hydroxy phenyl) ethane of 1,1-, two (4-hydroxy phenyl) propane (usually being referred to as " dihydroxyphenyl propane ") of 2,2-, two (the 4-hydroxy-3-methyl phenyl) propane of 2,2-, two (4-hydroxy phenyl) butane of 2,2-, two (4-the hydroxy phenyl)-1-diphenylphosphino ethanes of 1,1-, two (4-hydroxy phenyl) cyclohexanes of 1,1-, two (the 4-hydroxy phenyls)-3,3 of 1,1-, 5-trimethylammonium cyclohexane, two (4-hydroxy phenyl) pentanes of 2,2-, 4,4 '-(to the phenylene diisopropylidene) diphenol, 4,4 '-(metaphenylene diisopropylidene) diphenol, two (4-the hydroxy phenyl)-4-isopropyl cycloheanes of 1,1-, 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, two (3,5-, the two bromo-4-hydroxy phenyls) propane of 2,2-, two (3,5-, two bromo-4-hydroxy phenyls) sulfone, two (4-hydroxy-3-methyl phenyl) sulfide, two (4-hydroxy phenyl) fluorenes of 9,9-and two (the 4-hydroxy-3-methyl phenyl) fluorenes of 9,9-etc.Preferred binary phenol is two (4-hydroxy phenyl) paraffinic hydrocarbonss, wherein, and from shock-resistance aspect consideration, particularly preferably dihydroxyphenyl propane.
As the carbonic ether precursor, use carboxylic acid halides (Carbonyl halide), carbonic ether ester or haloformate (Ha ロ ホ Le メ one 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 by above-mentioned binary phenol and carbonic ether precursor, also can use as required catalyzer, end to stop agent, antioxidant etc., wherein antioxidant is used for preventing 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 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, can be also two or more mixtures that mixed with resulting polycarbonate resin.
As the multifunctional aromatics more than 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 % by mole, is preferably 0.005～0.9 % by mole, is particularly preferably 0.01～0.8 % by mole 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 account for 0.001～1 % by mole in the aromatic copolycarbonate total amount, be preferably 0.005～0.9 % by mole, be particularly preferably 0.01～0.8 % by mole.In addition, the content of above-mentioned branched structure can pass through 1H-NMR measures to calculate.
Two functionality carboxylic acids of preferred aliphat are alpha, omega-dicarboxylic acid.As aliphatic two functionality carboxylic acids, preferably can enumerate the direct-connected saturated aliphatic dicarboxylic acids such as sebacic acid (sebacic acid), dodecanedioic acid (Dodecandioic acid), tetradecane diacid, octadecane diacid, octadecane dicarboxylic acid; And cyclohexane dicarboxylic acid's etc. alicyclic dicarboxylic acid.As two functionality alcohol, be preferably alicyclic diol, such as enumerating cyclohexane dimethyl carbinol, cyclohexane glycol and tristane dimethanol etc.
And, can also use the polyorganosiloxane units polycarbonate of copolymerization-poly organo alkyl copolymer in addition.
Aromatic polycarbonate resin can be also the two or more resins that mixed in the polycarbonate that above-mentioned binary phenol is different, the polycarbonate that contains branched-chain component, various polyestercarbonate, polycarbonate-various aromatic copolycarbonates such as poly organo alkyl copolymer.Further, polycarbonate, the end that following manufacture method is different stops the different various resins such as polycarbonate of agent also can use the two or more resins that mixed.
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 restriction, but work as molecular weight lower than 1.0 * 10 4The time, be difficult to obtain sufficient intensity as products formed, when surpassing 5.0 * 10 4The time, the forming process reduction.Therefore, when representing with viscosity-average molecular weight, be preferably 1.0 * 10 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 can be 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 products formed that causes for the rheological behaviour of representative because of jet-type etc. is difficult to produce.From suppressing bad order aspect consideration, it is suitable mode.And in STUDY ON AIR INJECTION MOLDING etc., its gas inject amount is also stable, and in addition, foamed cell is stable in foaming, can easily form fine and uniform unit, therefore, is conducive to the present invention.
Be more preferably 8.0 * 10 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 the measuring methods such as GPC (gel permeation chromatography), can observe two with the material of superiors's molecular weight distribution.
The said viscosity-average molecular weight of the present invention can be calculated according to following method.At first, the solution that obtains under 20 ℃, the 0.7g polycarbonate being dissolved in the 100ml methylene dichloride, use Ostwald viscometer, obtain specific viscosity by following formula:
Specific viscosity (η sp)=(t-t 0)/t 0
[t 0Be the drippage number of seconds of methylene dichloride, the drippage number of seconds 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), the weight average particle diameter that refers to contain 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, 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, 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/propene/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 is formed by organopolysiloxane rubber constituent and poly-(methyl) alkyl acrylate rubber constituent namely, thereby has the rubber that two kinds of rubber constituents of structure of mutual complexing can't be separated, and the IPN type rubber that is consisted of 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 particularly preferably polyhutadiene, dienes multipolymer.
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, with the dispersion state variation of polycarbonate resin, cause the phenomenon that impact characteristics reduces, thus not preferred.
The weight average particle diameter of the rubber particles in the present invention is the numerical value by the infiltration type determination of electron microscopy.Specifically, the rubbery polymer of getting an emulsion form is placed in the grid (mesh) that the infiltration type determination of electron microscopy is used, and dyes with the steam of perosmic anhydride or ruthenium tetroxide.Then, with infiltration type electron microscope (TECNAI G2, acceleration voltage 120kv, FEI Co. makes) the rubbery polymer sample after 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., particularly preferably 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, p-tert-butylstyrene, vinyl naphthalene, methoxy styrene, phenyl-monobromide ethene, Dowspray 9, fluorostyrene, phenylstilbene bromide etc., particularly preferably vinylbenzene.
The rubber constituent content of graft copolymer of the present invention (B composition) is 1～40 % by weight, is preferably 5～30 % by weight, more preferably 10～25 % by weight.When content surpasses 40 % by weight, mobility to improve effect insufficient, thereby not preferred.In addition, when this rubber constituent content during lower than 1 % by weight, impact that to improve effect insufficient, thus not preferred.
Manufacture method to graft copolymer of the present invention (B composition) is not done special restriction, but the preferred graft copolymer of making by emulsion polymerization that uses.
As graft copolymer of the present invention (B composition), such as enumerating ABS resin, AES resin, ASA resin etc., these all are easy to obtain particularly.Wherein, more preferably ABS 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 desirable characteristic.
In addition, at this, ABS resin refers to the main graft copolymer that is made of vinyl cyanide, divinyl rubber and vinylbenzene, the AES resin refers to the main graft copolymer that is made of vinyl cyanide, ethylene-propylene rubber(EPR) and vinylbenzene, and the ASA resin refers to the main graft copolymer that 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 % by weight, is preferably 5～30 % by weight, 10～25 % by weight more preferably.When rubber constituent content surpasses 40 % by weight, mobility to improve effect insufficient, thereby not preferred.In addition, when rubber constituent content during lower than 1 % by weight, impact that to improve effect insufficient, thus not preferred.
The mixture of the thermoplastic graft copolymer multipolymer (Acrylonitrile Butadiene—Styrene copolymer) that ABS resin, referred 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, can be both the multipolymer that derives from when making the resin that is consisted of by the thermoplastic graft copolymer multipolymer (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), can be also 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—Styrene copolymer.
In ABS resin, be grafted to the ratio (ratio of the weight of this grafting composition to polydiene composition weight) of vinyl cyanide compound and the aromatic ethylene compound of polydiene composition, be that percentage of grafting (% by weight) is preferably 20～200 % by weight, 20～80 % by weight more preferably.
As the polydiene composition of this ABS resin, such as using the 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 ABS resin, can enumerate foregoing compound, particularly preferably vinylbenzene.As the vinyl cyanide compound in ABS resin, can enumerate foregoing compound, such as enumerating vinyl cyanide, methacrylonitrile etc., particularly preferably vinyl cyanide.
Be used for ABS resin of the present invention, the ratio of the elastoprene composition in the ABS resin composition of 100 % by weight is preferably 1～40 % by weight, 5～30 % by weight more preferably, and more preferably 10～25 % by weight, be particularly preferably 12～22 % by weight.In the ABS resin composition of 100 % by weight, the ratio of the vinyl cyanide compound beyond the polydiene composition and the multipolymer of aromatic ethylene compound is preferably 99～60 % by weight, 95～70 % by weight more preferably, more preferably 90～75 % by weight, be particularly preferably 88～78 % by weight.And, total 100 % by weight with respect to this vinyl cyanide compound and the aromatic ethylene compound of 100 % by weight, vinyl cyanide compound is preferably 5～50 % by weight (more preferably 15～35 % by weight), and aromatic ethylene compound is preferably 95～50 % by weight (more preferably 65～85 % by weight).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 replacement maleic anhydride contracting imines etc., their content ratio is preferably in ABS resin below 15 % by weight.Further, the initiator that uses in reaction, chain-transfer agent, emulsifying agent etc. can as required, adopt known various material in the past.
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 be 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, can be also to contain to block around rubber particles to have mutually the material that contains (salami) structure.
The manufacture method of this ABS resin is not done special restriction, but the ABS resin of more preferably making by emulsion polymerization.
(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 the mixture of other monomers of its copolymerization core-shell grafting copolymer that forms of copolymerization in addition, preferred mainly with methyl methacrylate or methyl methacrylate and the multipolymer that can obtain to the polydiene take butadiene-styrene as representative with the mixture graft copolymerization of other monomers of its copolymerization.
The said polydiene composition of the present invention, refer to by letex polymerization, make as 1 of primary structure unit, the 3-divinyl is adjusted into 50～100 % by weight, is preferably 65～100 % by weight, 75～100 % by weight more preferably, allow to this primary structure unit copolymerization, vinyl monomer take vinylbenzene as representative is adjusted into 50～0 % by weight, be preferably 35～0 % by weight, the multipolymer that obtains of 25～0 % by weight more preferably.If it is not lower than 50 % by weight, can not get sufficient impact characteristics as the 1,3-butadiene of primary structure unit, thereby preferred.
Be 0.30～0.50 μ m when the particle diameter of polydiene composition of the present invention represents take weight average particle diameter, be preferably 0.30～0.40 μ m, more preferably 0.32～0.38 μ m.During less than 0.30 μ m, fusion section or in uneven thickness the upper interflow line that produces are very dense when the particle diameter of polydiene, when surpassing 0.50 μ m, cause and disperse badly, have 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 vinyl monomer take vinylbenzene as representative of the formation that is used for this polydiene composition, such as the aromatic vinyl monomer that can enumerate vinylbenzene, alpha-methyl styrene, p-methylstyrene, chloro-styrene, Dowspray 9, phenylstilbene bromide etc.; The alkyl methacrylate of methyl methacrylate, β-dimethyl-aminoethylmethacrylate, propyl methacrylate, butyl methacrylate etc.; The alkyl acrylate of methyl acrylate, ethyl propenoate, propyl acrylate, butyl acrylate, vinylformic acid 2-ethylhexyl ester 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, 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 respectively a kind of or use two or more.
In addition, when forming the polydiene composition, as required, can also use the chain-transfer agent (initiator) of uncle's dodecyl mercaptans etc. in polyreaction.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, such as the inorganic salt that can enumerate 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 acetic acid, succsinic acid etc.; And their organic acid anhydride, further, contain in addition carboxylic acid high molecular emulsion etc.
The core-shell grafting copolymer of using in the present invention (C composition), can be by on the latex of the dienes composition with said structure, make (methyl) alkyl acrylate monomer or make (methyl) alkyl acrylate and can carry out with it mixture of other monomers of copolymerization, carry out one or more snippets graft copolymerization and prepare.
That is, as the monomer that uses in above-mentioned graft copolymerization, except (methyl) alkyl-acrylates as the methyl methacrylate of neccessary composition, β-dimethyl-aminoethylmethacrylate 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 become vinyl monomer and the above-mentioned vinyl monomer of cross-linkable monomer and use above-mentioned.When being mixed with (methyl) alkyl acrylate as neccessary composition and using, these vinyl monomers and cross-linkable monomer can use respectively a kind of or use two or more.
In graft polymerization, with polydiene composition latex be adjusted into 40～90 % by weight, be preferably 42～85 % by weight, 45～80 % by weight more preferably, correspondingly, the usage quantity with the monomer that uses or monomer mixture be adjusted into 60～10 % by weight, be preferably 58～15 % by weight, 55～20 % by 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 % by weight, preferably more than 40 % by weight.
In addition, graft copolymer (C composition) both can once add monomer or monomer mixture and carry out one-step polymerization, perhaps, also monomer or monomer mixture can be added more than at twice or twice, thereby a minute multistage carried out graft polymerization.
Adopt the method for letex polymerization as the method for graft copolymerization.When carrying out this graft copolymerization, 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 graft copolymer can according to the kind of the polymerization starter that uses, for example can suitably be chosen in the scope of 40～80 ℃.In addition, when carrying out letex polymerization, as the emulsifying agent for butadiene type rubber polymer latex, can suitably use known emulsifying agent.
Resulting core-shell grafting copolymer (C composition), add suitable antioxidant or add as required additive etc. in reaction solution, perhaps in the situation that do not add and carry out spraying drying (directly powder), perhaps, suitably add condensing agent (such as the acid of sulfuric acid, hydrochloric acid, phosphoric acid etc. or the salt of calcium chloride, sodium-chlor etc.) and condense in reaction solution, further thermal treatment and solidifying in addition.Then, through dehydration, washing, carry out final drying and come into operation after powder.
(D composition: inorganic filling material)
In the present invention, can contain various inorganic filling materials as the D composition.for example, can preferably use talcum, wollastonite, mica, clay, montmorillonite (montmorillonite), montmorillonite (smectite), kaolin, calcium carbonate, carbon fiber, carbon plate, the carbon pearl, milled carbon fiber, tinsel, steel fiber, the metallic coating glass fibre, the metallic coating carbon fiber, the metallic coating sheet glass, silicon-dioxide, ceramic particle, ceramic fiber, Ceramic Balls, the aramid fiber particle, aramid fiber (aramid fiber), the polyarylester fiber, graphite, potassium titanate crystal whisker, aluminium borate whisker, the various whiskers of basic magnesium sulfate etc. etc.Wherein, preferably use the packing material of the 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 in 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 particularly preferably median size is the following talcums of 2 μ m.Can enumerate 0.05 μ m as lower value.In the median size of this said talcum, refer to 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 Sedigraph5100 that Micromeritics company makes 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 degassed compression method (for example, degassed 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 in 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 to flame retardant resistance, also satisfy microdispersed condition in resin, therefore, also can keep good humidity resistance.As the thickness of mica, 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 in 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 refers to, from the image of observing by electron micrograph etc., the random extraction altogether amounts to 1000 parts and measure Fibre diameter, and calculates its number average value and the numerical value obtained.Aspect ratio L/D (the L: number average fiber length, D: be the number average Fibre diameter) more than 5, 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, the PIAS-III system that can enumerate that Byass makes etc.As the wollastonite that the present invention uses, preferably the heat-flash decrement at 1000 ℃ of temperature is below 2 % by weight, more preferably below 1.5 % by weight, more preferably below 1 % by weight.
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 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 large 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 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 with the affinity of resin, and have the compound of the functional group that can react with the surface of strengthening packing material.
As the compound low with the affinity of resin, representationally can enumerate various lubricants.As lubricant, such as enumerating the 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 with the affinity of resin, can enumerate (1) this compound direct impregnation maybe is impregnated into solution or the emulsion of this compound the method for strengthening packing material to the method for strengthening packing material; (2) make the reinforcement packing material pass through in the steam of this compound or the method in powder; (3) powder of this compound etc. is exposed at a high speed the method for strengthening packing material; (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, such as enumerating 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 in carboxyl and 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 in carboxyl and 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.In the situation that other functional groups are preferably contained and carboxyl same degree amount.
As the anti-agent that fractures, particularly preferably enumerate the multipolymer of alpha-olefin and maleic anhydride.This multipolymer can according to ordinary method, under the existence of free radical catalyst, be made by melt polymerization or mass polymerization.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 % by weight, the anti-agent that fractures is preferably 0.01～2 % by weight, more preferably 0.05～1.5 % by weight, more preferably 0.1～0.8 % by 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; (ii) 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.); (iii) the silicon based flame retardant that is formed by silicon compound.By coordinating 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 such as the raising of static electricity resistance, mobility, 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, particularly preferably aryl phosphoric acids ester cpds.This phosphate compound is improving aspect flame retardant resistance effectively, and phosphate compound has the plasticity-effect, therefore, although stable on heating reduction is arranged, favourable aspect the forming process that improves resin combination of the present invention.As this phosphate compound, although can use in the past as the known various phosphate compounds of fire retardant, more preferably enumerate one or more the phosphate compound of particularly using following general formula (I) expression.
Figure G2009100077712D00171
(in formula (I), X is from the derivative divalent phenol residue of dihydroxy compound, and described dihydroxy compound is the dihydroxy compound that selects in the group that free 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 forms; 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 from the derivative bivalent phenol residue of aryl, described aryl be select free phenol, cresols, xylenol, isopropyl-phenol, butylphenol and group that cumyl phenol is formed in aryl.)
The phosphate compound of following formula (I), it can be also the 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, be particularly preferably 1～1.14 scope.
As the preferred object lesson of the binary phenol of the X of derivative following formula (I), can enumerate Resorcinol, dihydroxyphenyl propane and dihydroxyl hexichol, wherein, preferred Resorcinol, dihydroxyphenyl propane.
R as derivative following formula (I) 4, R 5, R 6And R 7The preferred object lesson of a bivalent phenol, can enumerate phenol, cresols, xylenol, 2, the 6-xylenol wherein, is preferably phenol and 2,6-xylenol.
As the object lesson of the phosphate compound of following formula (I), can preferably enumerate the phosplate compounds such as Triphenyl phosphate and three (2,6-3,5-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 the phosphoric acid ester oligopolymer of 4,4-dihydroxyl phenylbenzene two (diphenyl phosphoester) as 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 the phosphoric acid ester oligopolymer of 4,4-dihydroxyl phenylbenzene two (diphenyl phosphoester) as 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 is in more preferred scope, the effect of bringing into play by the cooperation of organic phosphates fire retardant (such as flame retardant resistance etc.) just better.
(E-2) organic metal salt based flame retardant
The organic metal salt based flame retardant is favourable aspect the maintenance thermotolerance.In the present invention, most preferred organic metal salt fire retardant is organic sulfonic acid alkali (alkaline earth) metal-salt.Wherein, preferred fluorine replaces alkali (alkaline earth) metal-salt of organic sulfonic acid, particularly 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.
Consist of the metal that fluorine replaces the metal ion of organic sulfonic 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, in the situation that but then, because they are not general and are difficult to make with extra care, therefore, there is defective in higher preferred rubidium and the caesium of using of the requirement of the transparency sometimes on cost.In addition, lithium and sodium are favourable aspect cost or flame retardant resistance, but sometimes unfavorable to the transparency on the contrary.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 from which aspect consider, the perfluoro alkyl sulfonic acid sylvite of balance of properties excellence is best suited for all using.Also can be with this sylvite and the perfluoro alkyl sulfonic acid an alkali metal salt that is formed by other basic metal and use.
As the object lesson of this perfluoro alkyl sulfonic acid an alkali metal salt, can enumerate trifluoromethayl sulfonic acid potassium, potassium perfluorobutane sulfonate, perfluor hexane potassium sulfonate, Perfluorooctane sulfonates potassium, pentafluoride ethane sodium sulfonate, perfluorinated butane sodium sulfonate, Perfluorooctane sulfonates sodium, trifluoromethayl sulfonic acid lithium, perfluorinated butane Sulfonic Lithium, PF 5070 Sulfonic Lithium, trifluoromethayl sulfonic acid caesium, perfluorinated butane sulfonic acid caesium, Perfluorooctane sulfonates caesium, perfluor hexane sulfonic acid caesium, perfluorinated butane sulfonic acid rubidium and perfluor hexane sulfonic acid rubidium etc.These both can be used alone, also can two or more and use.Wherein, be particularly preferably potassium perfluorobutane sulfonate.
In above-mentioned organic metal salt based flame retardant, the content of the fluoride ion by ion-chromatographic determination is preferably below 50ppm, more preferably below 20ppm, more preferably below 10ppm.The content of fluoride ion is lower, and flame retardant resistance or photostabilization are better.In fact, the lower value of fluoride ion content can be adjusted into 0, but considers from process number and the effect of refining step, and in practicality, the preferred lower limit value is the 0.2ppm left and right.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 the method that perfluoro alkyl sulfonic acid is neutralized in alkali-metal carbonate or oxyhydroxide, or generate by the method (the preferred latter's method) that perfluoroalkyl sulfonyl fluoride (パ one Off Le オ ロ ア Le キ Le ス Le ホ ニ Le Off Le オ ラ イ De) is neutralized 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 ℃.By cooling crystallization.Take out the crystallization of separating out by filtration.Thus, produce desirable refining perfluoro alkyl sulfonic acid an alkali metal salt.
When using fluorine to replace organic sulfonic 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 is in more preferred scope, replace by fluorine the effect (such as flame retardant resistance or static resistance etc.) that the cooperation of organic sulfonic acid alkali (alkaline earth) metal brings into play just better.
Replace organic sulfonic 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, such as an alkali metal salt of the alkaline earth salt of an alkali metal salt that can enumerate aliphatic sulfonic, aliphatic sulfonic, aromatic sulphonic acid 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, sulfonic acid, heptan sulfonic acid, hot sulfonic acid etc.These both can use a kind of, also can two or more and use.
As the aromatic sulphonic acid that is used for aromatic sulphonic acid alkali (alkaline earth) metal-salt, can enumerate at least a acid in the group of condenses composition of sulfonic acid, alkylene base key formation that aromatic sulphonic acid freely pass through in choosing of sulfonic acid, hetero ring type sulfonic acid, aromatic series sulfoxide of aromatic series sulfone sulfonic acid, aromatic ketone of aromatic sulphonic acid, monomer shape or polymkeric substance shape of sulfonic acid, monomer shape or polymkeric substance shape of sulfonic acid, aromatic sulfonic acid ester of aromatic ether of sulfonic acid, monomer shape or polymkeric substance shape of sulfonic acid, aromatic carboxylic acid and ester of aromatic series sulfide of monomer shape or polymkeric substance shape.These both can use a kind of, or two or more and use.
as the object lesson of 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 タ Le acid Port リ ス Le ホ Application acid Port リ Na ト リ ウ system), 1-methoxynaphthalene-4-calcium sulphonate, 4-lauryl phenyl ether disulfonic acid disodium, poly-(2,6-dimethyl phenylene oxide) many sodium of many sulfonic acid (Port リ (2,6-ジ メ チ Le Off エ ニ レ Application オ キ シ De) Port リ ス Le ホ Application acid 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 ニ レ Application オ キ シ De) Port リ ス Le ホ Application acid Port リ Na ト リ ウ system), the poly-many sodium of (Isosorbide-5-Nitrae-phenylene oxide) many sulfonic acid (Port リ (Isosorbide-5-Nitrae-Off エ ニ レ Application オ キ シ De) Port リ ス Le ホ Application acid Port リ Na ト リ ウ system), poly-(2,6-phenylbenzene phenylene oxide) many potassium of many sulfonic acid (Port リ (2,6-ジ Off エ ニ Le Off エ ニ レ Application オ キ シ De) Port リ ス Le ホ Application acid Port リ カ リ ウ system), poly-(2-fluoro-6-butyl phenylene oxide) poly-Sulfonic 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, BP-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, particularly preferably sylvite.When coordinating 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 referring to by burning improves the compound of flame retardant resistance.As this compound, the various compounds that can use in the past the fire retardant as aromatic polycarbonate resin to propose.Silicon compound is considered to be in when burning, and by the combination of himself or by forming structure (structure) with being combined from the composition of resin, perhaps the reduction reaction when forming this structure, give 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 hydrogen base (Ha 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, the utility alkali decomposition method is obtained 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 particularly preferably methoxyl group.
Usually, the structure of silicon compound is to consist of 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.
Be used for the structure of the silicon compound of silicon based flame retardant, can enumerate particularly the structure that represents with following signal formula, that is, 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 above-mentioned signal formula, n, p, q are the integer more than 1 of the polymerization degree of each siloxane unit of expression, and in each signal formula, the summation of coefficient is the mean polymerisation degree of silicon compound.Preferred this mean polymerisation degree 3～150 scope, more preferably 3～80 scope, more preferably 3～60 scope, be particularly preferably 4～40 scope.This mean polymerisation degree is in more preferred scope, and its flame retardant resistance is more excellent.And, containing as described later the silicon compound of the aromatic group of specified amount, its transparency or color and luster are also excellent.
In addition, when any one in m, n, p, q is numerical value more than 2, with the siloxane unit of this coefficient, can be hydrogen atom or the different two or more siloxane unit of organic residue of institute's combination.
Silicon compound can be both linear chain structure, can be also the silicon compound with branched structure.It is organic residue of 1～30, more preferably 1～20 that organic residue of being combined with Siliciumatom in addition, is preferably carbonatoms.As this organic residue, can enumerate particularly methyl, ethyl, propyl group, butyl, the alkyl of base and decyl etc.; 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 particularly preferably methyl, ethyl and propyl group etc. 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 % by weight (more preferably 15～60 % by weight).
Figure G2009100077712D00221
(in 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), when n is 2 when above, can get respectively mutual different types of X.)
Silicon compound as the silicon based flame retardant uses can also contain reactive group, as this reactive group, such as enumerating amino, carboxyl, epoxy group(ing), vinyl, sulfydryl and methacryloxy etc. except above-mentioned Si-H base and alkoxyl group.
As the silicon compound with Si-H base, preferably enumerate at least a above silicon compound in the structural unit that contains useful following general formula (III) and (IV) represent:
(in formula (III) and formula (IV), Z 1～Z 3Represent independently that respectively hydrogen atom, carbonatoms are 1～20 the organic residue of monovalence or the compound that represents with following logical formula V; α 1～α 3 represents respectively 0 or 1 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 respectively different a plurality of repeating units mutually.)
(in 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 respectively 0 or 1 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 respectively different a plurality of repeating units mutually.)
At the silicon compound that is used for the silicon based flame retardant, as the silicon compound with alkoxyl group, for example can enumerate at least a compound that is selected from in the compound of general formula (VI) and general formula (VII) expression:
Figure G2009100077712D00232
(in 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 aryl or aralkyl; δ 1, δ 2And δ 3The expression carbonatoms is 1～4 alkoxyl group.)
Figure G2009100077712D00241
(in 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 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 in 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, the below sometimes with tetrafluoroethylene referred to as " PTFE ".Have the PTFE that protofibril forms ability and have high molecular weight, the external action that demonstrates by shearing force etc. makes between 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 retardant resistance and mechanical characteristics, this has the PTFE mixture that PTFE that protofibril forms ability can also use the mixed style that is mixed with other resin.
Have as this commercially available product that protofibril forms the PTFE of ability, for example can enumerate DUPONT-MITSUI FLUOROCHEMICALS COMPANY, the Port リ Off ロ Application MPA FA500 that テ Off ロ Application (registered trademark) 6J, the DAIKIN industry (strain) of LTD is 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-1, the AD-936 that make, FluonD-1, 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 the clear 60-258263 communique of TOHKEMY, the clear 63-154744 communique of TOHKEMY etc.) that co-precipitation obtains common aggegation mixture; The method (method of putting down in writing in the flat 4-272957 communique of TOHKEMY) of (2) aqueous liquid dispersion of PTFE being mixed with dry organic polymer particle; (3) aqueous liquid dispersion with PTFE evenly mixes with organic polymer particle solution, the method (the flat 06-220210 communique of TOHKEMY, the flat 08-188653 communique of TOHKEMY etc. record method) of removing simultaneously medium separately from this mixture; (4) polymerization is used to form the method (method of putting down in writing in the flat 9-95583 communique of TOHKEMY) of the monomer of organic polymer in the aqueous liquid dispersion of PTFE; And (5) with the aqueous liquid dispersion of PTFE with after the organic polymer dispersion liquid evenly mixes, then further polymerising ethylene class monomer in this mixed dispersion liquid obtains the method (method of record in the flat 11-29679 communique of TOHKEMY etc.) of mixture.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 mixed form, in the PTFE of 100 % by weight mixture, the content ratio of PTFE is preferably 1～60 % by weight, more preferably 5～55 % by 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 total 100 % by weight of A composition and B composition, the A component content is 99～1 % by weight, be preferably 98～20 % by weight, more preferably 97～40 % by weight, be particularly preferably 95～60 % by weight, the B component content is 1～99 % by weight, be preferably 2～80 % by weight, more preferably 3～60 % by weight, be particularly preferably 5～40 % by weight.
During lower than 1 % by weight, physical strength, the thermotolerance of shock strength etc. are insufficient when the A component content, in addition, when surpassing 99 % by weight, reduce 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 lower than 0.1 weight part, produce interflow line or impact characteristics insufficient, in addition, when surpassing 10 weight part, 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 part, produce the reduction of mobility 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 lower than 0.001 weight part, flame retardant resistance is insufficient, and in addition, when surpassing 25 weight part, 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.During lower than 0.05 weight part, flame retardant resistance is insufficient when the content of F composition, and in addition, when surpassing 2 weight part, 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, Distearyl pentaerythritol, two (2,4-di-tert-butyl-phenyl) pentaerythritol diphosphites, two (2,6-di-t-butyl-4-aminomethyl phenyl) pentaerythritol diphosphites, two (2,6-di-t-butyl-4-ethylphenyl) pentaerythritol diphosphites, two { two (1-methyl isophthalic acid-phenylethyl) phenyl of 2,4-} pentaerythritol diphosphites, phenyl dihydroxyphenyl propane pentaerythritol diphosphites, two (nonyl phenyl) pentaerythritol diphosphites, and two cyclohexyl 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 (4,6-di-tert-butyl-phenyl) (the 2-tertiary butyl-4-aminomethyl phenyl) phosphorous acid ester and 2,2-methylene-bis (4,6-di-tert-butyl-phenyl) octyl group phosphorous acid ester etc.
As 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, the 4-di-tert-butyl-phenyl)-4, 4 '-diphenylene, two phosphinates, four (2, the 4-di-tert-butyl-phenyl)-4, 3 '-diphenylene, two phosphinates, four (2, the 4-di-tert-butyl-phenyl)-3, 3 '-diphenylene, two phosphinates, four (2, the 6-di-tert-butyl-phenyl)-4, 4 '-diphenylene, two phosphinates, four (2, the 6-di-tert-butyl-phenyl)-4, 3 '-diphenylene, two phosphinates, four (2, the 6-di-tert-butyl-phenyl)-3, 3 '-diphenylene, two phosphinates, two (2, the 4-di-tert-butyl-phenyl)-4-phenyl-phenylphosphite ester, two (2, the 4-di-tert-butyl-phenyl)-3-phenyl-phenylphosphite ester, two (2, 6-di-n-butyl phenyl)-3-phenyl-phenylphosphite ester, two (2, the 6-di-tert-butyl-phenyl)-4-phenyl-phenylphosphite ester, two (2, the 6-di-tert-butyl-phenyl)-3-phenyl-phenylphosphite ester etc.Wherein, preferred four (di-tert-butyl-phenyl)-diphenylene two phosphinates, two (di-tert-butyl-phenyl)-phenyl-phenylphosphite ester, more preferably four (2, the 4-di-tert-butyl-phenyl)-diphenylene two phosphinates, two (2,4-di-tert-butyl-phenyl)-phenyl-phenylphosphite ester.This phosphinate compound can have with abovementioned alkyl bi-ester of phosphite and the use of two above substituted aryls, 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 triphenylphosphine.
Above-mentioned Phosphorus stablizer not only can only use a kind of, can also mix use two or more.In above-mentioned Phosphorus stablizer, the bi-ester of phosphite of preferred phosphinate compound or following general formula (VIII) expression.
Figure G2009100077712D00281
(in formula (VIII), R and R ' expression carbonatoms is 6～30 alkyl or the aryl of carbonatoms 6～30, and they both can be mutually identical, also difference) mutually.
As mentioned above, as phosphinate compound, preferred four (2,4-di-tert-butyl-phenyl)-diphenylene two phosphinates.As the stablizer take this phosphinate as principal constituent, 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 { two (1-methyl isophthalic acid-phenylethyl) phenyl of 2,4-} pentaerythritol diphosphites.
As two hard ester acyl group pentaerythritol diphosphites, commercially available have ア デ カ ス タ 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 a ア デ カ ス タ Block PEP-24G (trade mark, rising sun electrochemical industry (strain) is made), AlkanoxP-24 (trade mark, Great Lakes company makes), Ultranox P626 (trade mark, GE SpecialtyChemicals company makes), Doverphos S-9432 (trade mark, Dover Chemical company makes), and Irgaofos126 and 126FF (trade mark, CIBA SPECIALTYCHEMICALS company makes) etc., all can use.As two (2,6-di-t-butyl-4-aminomethyl phenyl) pentaerythritol diphosphites, commercially available have a ア デ カ ス タ 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 タ 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 the various compounds that usually are matched with in 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, N-dimethylaminomethyl) phenol, 3,5-di-tert-butyl-4-hydroxyl benzyl phosphonic acids diethyl ester, 2,2 '-methylene-bis (4-methyl-6-tert-butylphenol), 2,2 '-methylene-bis(4-ethyl-6-t-butyl phenol), 4,4 '-methylene-bis (2,6 di t butyl phenol), 2,2 '-methylene-bis (4-methyl-6-cyclohexyl phenol), 2,2 '-dimethylene-two (6-α-methylbenzyl-p-cresol), 2,2 '-ethylidene-two (4,6-DI-tert-butylphenol compounds), 2,2 '-butylidene-two (4-methyl-6-tert-butylphenol), 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, 1,6-hexylene glycol-two [3-(3,5-di-tert-butyl-hydroxy phenyl) propionic ester], two [the 2-tertiary butyl-4-methyl-6-(the 3-tertiary butyl-5-methyl-2-hydroxybenzyl) phenyl] terephthalate, 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, 4,4 '-thiobis (the 6-tertiary butyl-meta-cresol), 4,4 '-thiobis (3 methy 6 tert butyl phenol), 2,2 '-thiobis (4-methyl-6-tert-butylphenol), two (3,5-di-tert-butyl-4-hydroxyl benzyl) sulfide, 4,4 '-dithio two (2,6 di t butyl phenol), 4,4 '-trithio two (2,6 di t butyl phenol), 2,2-sulfo-divinyl two [3-(3,5-di-tert-butyl-hydroxy phenyl) propionic ester], two (n-octyl the sulfo-)-6-(4-hydroxyl-3,5-di-t-butyl phenylamino) of 2,4--1,3,5-triazines, N, N '-hexa-methylene is two-(3,5-di-t-butyl-4-hydroxyl hydrocinnamamide), N, N '-two [3-(3,5-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 (3,5-di-tert-butyl-4-hydroxyl benzyl) benzene, three (3,5-di-tert-butyl-hydroxy phenyl) chlorinated isocyanurates, three (3,5-di-tert-butyl-4-hydroxyl benzyl) chlorinated isocyanurates, 1,3,5-three (the 4-tertiary butyl-3-hydroxyl-2,6-dimethyl benzyl) chlorinated isocyanurates, 1,3,5-, three 2[3 (3,5-di-tert-butyl-hydroxy phenyl) propionyloxy] the ethyl chlorinated isocyanurates, four [methylene radical-3-(3,5-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-two { 2-[3-(3-tertiary butyl-4-hydroxy-5-aminomethyl phenyl) propionyloxy]-1,1-dimethyl ethyl }-2,4,8,10-four oxaspiros [5,5] undecane.Above-mentioned Hinered phenols antioxidant both can use separately, or was used in combination.
Any one in the Phosphorus stablizer of preferred cooperation and Hinered phenols antioxidant.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 used time, with respect to total 100 weight parts of A composition and B composition, preferably coordinate 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 products formed, the preferred releasing agent that further coordinates.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 can be both 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, such as enumerating Lauryl 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, such as the representative examples of saturated aliphatic carboxylic that can enumerate capric acid, hendecoic acid, lauric acid, ficocerylic acid, ten tetra-carbonics, 15 carbonic acid, Palmitic 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, be 14～20 aliphatic carboxylic acid as the preferred carbonatoms of aliphatic carboxylic acid.Wherein, representative examples of saturated aliphatic carboxylic preferably.Particularly preferably stearic acid and palmitinic acid.
Due to the above-mentioned aliphatic carboxylic acid of stearic acid or palmitinic acid etc. normally by the animal raw fat take shea butter or pig fat etc. as representative and by the natural oil lipid manufacturing of vegetative grease take plam oil or sunflower seed oil as representative etc., 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 particularly preferably uses stearic acid or palmitinic acid.
Fatty acid ester can be any in part ester and full ester (full ester).But in the part ester, usually hydroxyl value is high, and the decomposition of resin etc. when easily bringing out high temperature is therefore more preferably full-cream.Consider from the viewpoint of thermostability, the acid number in fatty acid ester of the present invention is preferably below 20, and 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 in 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 in the situation of not damaging good color and luster, has excellent release property and the poly carbonate resin composition of roll release type.
(iv) UV light absorber
Can also contain UV light absorber in resin combination of the present invention.Because resin combination of the present invention has the excellent transparency, therefore, be 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, ESCALOL 567, 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.
as the benzotriazole category of 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-3,5-dicumylphenyl) phenyl benzotriazole, 2-(the 2-hydroxyl-3-tertiary butyl-5-aminomethyl phenyl)-5-chlorobenzotriazole, 2,2 '-methylene-bis [4-(1,1,3,3-tetramethyl butyl)-6-(2H-benzotriazole-2-yl) phenol], 2-(2-hydroxyl-3,5-di-tert-butyl-phenyl) benzotriazole, 2-(2-hydroxyl-3,5-di-tert-butyl-phenyl)-5-chlorobenzotriazole, 2-(2-hydroxyl-3,5-di-tert-pentyl-phenyl) benzotriazole, 2-(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′ p phenylenebis (1,3-benzoxazine-4-ketone), 2-[2-hydroxyl-3-(3,4,5,6-tetrahydrochysene phthalic diamide methyl)-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) the basic oxy phenol of-5-, 2-(4,6-phenylbenzene-1,3,5-triazine-2-yl)-5-methyl oxy phenol, 2-(4,6-phenylbenzene-1,3,5-triazine-2-yl)-5-ethyl oxy phenol, 2-(4,6-phenylbenzene-1,3,5-triazine-2-yl)-5-propyl group oxy phenol and 2-(4,6-phenylbenzene-1,3,5-triazine-2-yl)-5-butyl oxy phenol etc.Further, can also enumerate 2-(4,6-two (2,4-3,5-dimethylphenyl)-1,3,5-triazines-2-yl)-5-the phenyl in the above-mentioned example compound such as basic oxy phenol become 2, the compound of 4-3,5-dimethylphenyl.
Cyclic imide base ester class as UV light absorber, for example can enumerate 2,2 '- TOPOT 2,2′ p phenylenebis (3,1-benzoxazine-4-ketone), 2,2 '-(4,4 '-diphenylene) two (3,1-benzoxazine-4-ketone) and 2,2 '-(2,6-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 can be also, 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. is 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), 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 products formed of performance various appearances is provided.Because resin combination of the present invention has the excellent transparency, therefore, be suitable for very much making in the purposes of light transmission.Therefore, for example by coordinating white dyes, can give to resin combination of the present invention the transparent feel of higher photopermeability or nature, and, by coordinating 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 in the present invention (comprising white dyes), such as enumerating Fluorescent Brightening agents based on Coumarin, chromene fluorochrome, perylene fluorochrome, Anthraquinones fluorescence dye, thioindigo fluorochrome, xanthene fluorochrome, xanthone fluorochrome, thioxanthene fluorochrome, thioxanthone fluorochrome, thiazides fluorescence dye and diaminobenzil fluorochrome etc.Wherein, preferred thermotolerance good and in the forming process of polycarbonate resin deteriorated few Fluorescent Brightening agents based on Coumarin, chromene fluorochrome, with and the perylene fluorochrome.
As the dyestuff beyond above-mentioned bluing agent and 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 Azone class 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 better metal color.As metallic pigment, preferably has the material of metal tunicle or metal oxide coating in various plate-like fillers.
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 coordinate other thermo-stabilizer.Described other thermo-stabilizers, preferably with these stablizers and oxidation inhibitor in any one and use, especially preferred and both and use.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, the commercially available stablizer that in addition this compound is mixed with various bi-ester of phosphite and hindered phenol compound.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) the high reflection white pigment of light
In resin combination of the present invention, can give the luminous reflectance effect with white pigment by coordinating the high reflection of light.As this white pigment, preferred titanium dioxide (titanium dioxide of particularly being processed 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 B composition, other mobile modification agents, antiseptic-germicide, whiteruss etc.
As the thermoplastic resin beyond A composition and B composition, can enumerate plexiglass (PMMA resin), ring-type polyolefin resin, polylactic resin, pla-pcl resin, thermoplastic fluorocarbon resin (for example, take polyvinylidene fluoride resin as representative) and polyolefin resin (polyvinyl resin, acrylic resin etc.).
(manufacturing of resin combination)
When making resin combination of the present invention, can adopt method arbitrarily.For example; can enumerate pre-mixing device such as adopting V-Mixer, Henschel mixer, chemomotive force device and extrusion mixing machine; fully mix 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; then the melting mixing machine that is representative in order to the exhaust biaxial extruder carries out melting mixing, then carries out the method for granulation by tablets press etc.
In addition, can also enumerate each composition is supplied to respectively the method or the part in each composition of pre-mixing of the melting mixing machine take the exhaust biaxial extruder as representative independently after, supply to independently method of melting mixing machine etc. 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 in the situation of powdery substance, the part of this powder mixed with the additive that coordinates and prepared the parent sizing material (マ ス タ one バ Star チ) of the additive that has been diluted by powder, being recycled the method for this parent sizing material.In addition, can also enumerate a composition independently from the method for supplying with of melt extruder midway etc.Further, when having in the composition that coordinates in the situation of aqueous material, can use so-called fluid infusion apparatus or liquid appending apparatus to the supply of melt extruder.
As forcing machine, the preferred forcing machine with venting port that uses, this forcing machine with venting port can remove the moisture in raw material or the volatile gases that is produced by the melting mixing resin.Preferably be provided with at venting port the vacuum pump that effectively drains into the forcing machine outside for the moisture that will produce or volatilization gas.In addition, the region division before extruding machine mold section is useful on the filtering net of removing the impurity of sneaking in extruding raw material 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 the mixing above multiple screw extruder of machine, mixing roller, single axle extruding machine, three axles etc. that closes 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, if be necessary to reduce outside impact as dust etc., preferably the environmental gas around forcing machine is carried out cleaning.Further, in the manufacturing of this particle, can be by the whole bag of tricks that has proposed in polycarbonate resin at CD, suitably carry out minimizing, the transportation of narrow and smallization that particle shape distributes, chopped thing (ミ ス カ Star ト thing) or the minimizing of the bubble (bubbles of vacuum) that the minimizing of the small powder that produces 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 one) etc.In addition, the shape of particle can be cylindrical, corner post shape and spherical etc. common shape, 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 in advance the mode that contains E composition of the present invention 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 remaining A composition and other additives, and carry out granular method by the melting mixing machine.
(products formed that is formed by resin combination of the present invention)
Resin combination of the present invention obtains products formed 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 according to purpose, suitably use compression molding, injection extrusion forming, air-auxiliary injection forming, foaming (comprising the moulding of injecting by supercutical fluid), insert moulding, in-mold coating (In-Mold Coating) moulding, heat insulation mould molding, the moulding of instant heating cooling die, dual-color forming, interlayer moulding and ultra-high speed injection molding etc.The advantage of these various forming methods has been well-known.In addition, moulding can be selected any in cold runner mode and hot runner mode.
Resin combination of the present invention can become the 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 by rotoforming or blow molding etc., resin combination of the present invention be manufactured products formed.
As the object lesson of the products formed that has utilized resin combination of the present invention, be fit to be applied in the purposes of the internal part of OA machine or family's 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 speech robot of audio frequency/compact video disc/laser disc etc., the illumination machine, refrigerator, air-conditioning, type-writer, word processor 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 automotive part 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 in following embodiment.Certainly, the present invention is not limited to these embodiments.
Embodiment
Below, illustrate in greater detail the present invention by embodiment.In the situation that do not indicate especially " part " expression " weight part " in embodiment, " % " expression " % by weight ".In addition, evaluation is to carry out by the following method.
(evaluation of resin combination)
(i) flame retardant resistance: be the test piece of 1.5mm with thickness, carry 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) Charpy impact intensity:
According to ISO 179, implement the mensuration with breach Charpy impact intensity.
(iii) thermotolerance
According to ISO 75-1 and 75-2, measure the load deflection temperature.In addition, mensuration is implemented take load as 1.80MPa.
(iv) mobility
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.Be that 260 ℃, die temperature are that 70 ℃, injection pressure are to carry out under the condition of 98MPa at center housing temperature.
(v) outward appearance
The framework products formed of the notebook computer of moulding Fig. 1～shown in Figure 3, the uneven color (interflow line B) of confirming whether to produce the uneven color (interflow line A) of wire and whether produce wire take boss as starting point on the extended line of fusion section.
Zero: produce without uneven color
*: produce uneven color
Embodiment 1～19, comparative example 1～10
According to forming shown in table 1～table 3, supply with mixture from the first supplying opening of forcing machine, this mixture is made of the composition except 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.Namely, (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 % by weight with the F component content, described F composition and A composition are dropped in 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), adopt the side feeder, supply with from the second supplying opening.Further, when adding the FR-1 of E composition, be heated under the state of 80 ℃, 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 by gauger (CWF, (strain) Kubo field make) delicate metering.Use the exhaust biaxial extruder (5BW-3V of diameter 30mm Φ, the TEX30 α-38 of (strain) JSW) extrude, and be that 150rpm, extrusion capacity are that the vacuum tightness of 20kg/h, exhaust portion is to carry out melting mixing under 3kPa to obtain particle in the screw rod rotation number.In addition, for extrusion temperature, from the first supplying opening to mould part be 260 ℃.
To resulting particle under 80～90 degree, by hot air circulation type drying machine after dry 6 hours, by injection moulding machine, the test piece of moulding evaluation use (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 the viscosity-average molecular weight of dihydroxyphenyl propane photoreactive gas manufacturing by common method, 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 the viscosity-average molecular weight of dihydroxyphenyl propane photoreactive gas manufacturing by common method, and Supreme Being people changes into (strain) and makes)
(B composition)
The ABS-1:ABS resin (Network ラ ラ ス チ Star Network SXH-330 (trade(brand)name), the divinyl rubber composition is 17.5 % by weight approximately, rubber weight average particle diameter 0.40 μ m, by the letex polymerization manufacturing, Japanese A﹠amp; L (strain) makes)
The ABS-2:ABS resin (UT-61 (trade(brand)name), the divinyl rubber composition is 14 % by weight approximately, and rubber weight average particle diameter 0.56 μ m is by block polymerization manufacturing, Japanese A﹠amp; L (strain) makes)
ABS-5: the ABS resin of making by letex polymerization (CHT (trade(brand)name), the rubber constituent amount that is made of polyhutadiene is 58 % by weight approximately, rubber weight average particle diameter 0.31 μ m, CHEIL INDUSTRYINC makes)
(C composition)
MBS-1: core-shell grafting copolymer (core by the letex polymerization manufacturing is the divinyl rubber composition of 70 % by weight, and shell is the vinylbenzene of 30 % by 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 (core by the letex polymerization manufacturing is the divinyl rubber composition of 70 % by weight, and shell is the vinylbenzene of 30 % by 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), core is the polyhutadiene of 60 % by weight, shell is the vinylbenzene of 40 % by 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 make)
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 ア Star 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: the ABS resin of making by letex polymerization (the rubber constituent amount that is made of polyhutadiene is 15 % by weight approximately, rubber weight average particle diameter 0.18 μ m)
ABS-4: the ABS resin of making by letex polymerization (the rubber constituent amount that is made of polyhutadiene is 21 % by weight approximately, rubber weight average particle diameter 2.2 μ m)
MBS-4: core-shell grafting copolymer (metablenC-223A (trade(brand)name), core is the polyhutadiene of 70 % by weight, shell is the vinylbenzene of 30 % by 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 (core by the letex polymerization manufacturing is the divinyl rubber composition of 70 % by weight, and shell is the vinylbenzene of 30 % by 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 one Le SL900 (trade(brand)name), reason is ground VITAMIN (strain) manufacturing)
IRGX: phenol thermo-stabilizer (IRGANOX1076 (trade(brand)name), Ciba SpecialtyChemicals company make)
TMP: phosphoric acid ester thermo-stabilizer (TMP (trade(brand)name), Daihachi Chemical Industry Co., Ltd. makes)
Figure G2009100077712D00421
Figure G2009100077712D00431
Figure G2009100077712D00441
Figure G2009100077712D00451
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 section or part in uneven thickness, and have simultaneously excellent impact characteristics and the poly carbonate resin composition of formability.
Industrial applicibility
Because resin combination of the present invention does not produce the interflow line in fusion section or part in uneven thickness, and impact characteristics and formability excellence, therefore, be widely used in OA purposes and other various uses.Therefore, the industrial effect that reaches of the present invention is very large.

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 % by weight and 1～99 % by 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, be under the existence of polydiene composition of 0.30～0.50 μ m at weight average particle diameter, by emulsion polymerization, with (methyl) alkyl acrylate monomer or (methyl) alkyl acrylate monomer and can with the in addition copolymerization and obtaining of the mixture of the monomer 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 % by 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 % by weight.
4. resin combination as claimed in claim 1, wherein, contain the inorganic filling material as the D composition, and with respect to total 100 weight parts of A composition and B composition, contain the D composition of 0.1～50 weight part.
5. resin combination as claimed in claim 4, wherein, described D composition is more than one the inorganic filling material in the group that forms of the free talcum of choosing, mica and wollastonite.
6. resin combination as claimed in claim 1, 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 in the group that forms of the free phosphoric acid ester of choosing, sulfonic acid alkali metal salts or azochlorosulfonate acid alkali earth metal salt and silicon compounds.
7. resin combination as claimed in claim 6, wherein, the E composition is the phosphoric acid ester of following formula (I) expression:
Figure FSB00000906316300021
In formula (I), X is from the derivative divalent phenol residue of dihydroxy compound, and described dihydroxy compound is the dihydroxy compound that selects in the group that free 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 forms; 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 from the derivative bivalent phenol residue of aryl, described aryl is the aryl in the free phenol of choosing, cresols, xylenol, isopropyl-phenol, butylphenol and group that cumyl phenol is formed.
8. products formed, it is to be formed by the described resin combination moulding of any one in claim 1～7.
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CN101787194B (en) * 2009-10-28 2012-05-30 上海锦湖日丽塑料有限公司 Flame retardant PC/ABS composition with high rigidity and high stability
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