CN1370803A - Fire-retardant resin composition and its molded product - Google Patents

Abstract

A flame resistant resin composition, high in heat resistance, excellent in impact resistance, and having a high flame resistance. The polycarbonate based flame resistant resin composition is composed of (A-1) a polycarbonate based resin, (A-2) a thermoplastic resin excepting the polycarbonate based resin, (B) a silicone resin, (C) a phosphate ester represented by chemical formula 1, and (D) an epoxy stabilizer.

Description

Fire-proof resin composition and its moulded product

Invention field

The present invention relates to a kind of flame retardant carbonate polymer.

Background of invention

Polycarbonate resin is used for electricity, electronics, office automation (OA) field as the engineering plastics with the fabulous transparency, shock resistance, thermotolerance and electrical property in the world.In these electricity, electronics and OA field, as the situation of Personal Computer outer packaging part, need high fire resistance (UL94V) or shock resistance.

Polycarbonate resin is the plastic material with high flame retardant and self quenching.But, in electricity, electronics and OA field,, still need higher flame retardant resistance in order to reach the higher degree of safety consistent with UL94V or 94V-1.

Therefore, in the past,, oligopolymer or polymkeric substance and polycarbonate composite methods have been adopted with the polycarbonate derivatives of a large amount of dihydroxyphenyl propane bromides in order to improve the flame retardant resistance of polycarbonate.But this has been subjected to, and shock resistance reduces and the puzzlement of generation problem of cracks easily in moulded product.And because the compound halogen compound that contains a large amount of bromines, producing Halogen gas when burning also is the problem that an environmental protection is paid close attention to.

Phosphoric acid ester and silicone resin are known not halogen-containing fire retardants.For example, in the patent gazette of the open Sho 62-25706 of Japanese Patent, advised phosphoric acid ester is added in the polycarbonate resin.But,, just cause thermotolerance or the problem of shock resistance reduction when preparing moulding material if phosphoric acid ester is added in the polycarbonate compositions.

For this purpose, silicon compound is used for thermoplastic resin as fire retardant, such as polycarbonate, because silicon compound has high heat resistance.When burning, do not produce poisonous gas, and the stability of silicone material is also very high.The silicon compound that uses as fire retardant is a polymkeric substance, by will be in following 4 kinds of siloxane units (M unit, D unit, T unit, Q unit) at least aly carry out polymerization formation.

In another piece reference, the open Sho 62-60421 of Japanese Patent discloses a kind of fire-proof resin composition, has wherein added to have the unitary silicone resin greater than 80 weight %T.Japanese Patent No. Hei 5-86295 discloses fire-proof resin composition, such as polycarbonate, has wherein added and has contained 30-99mol%T unit, 0-80mol%D unit, 1-70mol%M unit and the unitary silicone resin of 0-50mol%Q.

In prior art references, need to add the flame-retardant standard of a large amount of silicone resin with satisfied with electric, that electric mechanical is relevant strictness.As a result, influenced other character of thermoplastic compounds, such as mouldability, kneading property and the required character of other thermoplastics, in addition, because expense, this also becomes and can not carry out.

In addition, as a kind of trial that improves flame retardant effect of silicon compound own and reduction silicon compound aequum, advised metal-salt and silicon compound are used jointly.For example, a day patent application Sho 56-100853 of the present disclosure discloses a kind of fire-proof resin composition, wherein by the D unit with have a silicon compound that the IIa family metal carbonate of 14-20 carbon atom forms and compound such as the polymkeric substance of polycarbonate etc.In another open (Japanese Patent No. Hei 3-48947),, a kind of fire-proof resin composition is disclosed, wherein the IIa family metal-salt of the silicone resin of being made up of M unit and Q unit and other silicone resin and carbonic acid is compound.Even silicon compound and metal-salt are used jointly, for satisfied flame retardant effect is provided, the consumption of silicone resin is still very high.And, also need to use inorganic fire-retarded packing material jointly, such as aluminium hydroxide or halogen or phosphorus compound.

Therefore, in adding the practice of silicone resin, can not obtain sufficient flame retardant effect, unless the amount that adds is very high as the prior art of fire retardant.In addition, if add a large amount of silicone resin, just the outward appearance of various performances such as the mouldability of resin combination, moulded product or physical strength etc. are had a negative impact.And, be expensive as silicone material itself, also there is the Master Cost of great number.Still need to have the silicone additive of high flame retardant effect, or need a kind of additive, it uses to influence flame retardant resistance with silicone resin.

Japanese Patent No. Hei 8-176425 discloses a kind of fire-retardant combination, has wherein added the organopolysiloxane that contains epoxy group(ing) and an alkali metal salt of organic sulfonic acid.Japanese Patent No. Hei 8-176427 discloses a kind of containing by the fire-retardant combination of the polycarbonate resin of organopolysiloxane modification, contains phenolic hydroxyl group and organic alkali metal salt.And, in Japanese Patent No. Hei 9-169914, disclose a kind of by with black petroleum products or multiple pitch and the common composition that uses of silicon compound with improved flame retardant effect.But, in these cases, consider the complicacy that relates in the production phase, need to use expensive silicone resin, and do not obtain enough flame retardant effects.In addition, can not be satisfactory to the dispersiveness and the compatibility of polycarbonate resin.

In Japanese Patent No. Hei 10-139964, fire-retardant combination molecular weight (weight average MW) in the 10000-270000 scope, wherein be shown below to contain D and the unitary silicone resin of T and aromatic polycarbonate compound.

Also have, Japan publication Hei 11-140294 discloses a kind of fire-retarded polycarbonate resin composition, wherein compound contain 50-90mole%T unit, the unitary silicone resin of 10-50mole%D, and the part greater than total organic substituent 80mole% is occupied by phenyl in these unit.

But in these two pieces of reference, the time that burning continues is long, and drip (dripcharacteristic) deficiency, and the flame retardant resistance that obtains in the combustion test of extensively estimating based on UL94 is still unsatisfactory.

In another piece reference, Japanese Patent No. Hei 11-217494 discloses a kind of fire-retarded polycarbonate resin composition, wherein silicon compound has following structure, promptly, has the D unit as its main structure unit, form by D unit and T unit and/or Q unit, and have in addition as the aromatic group of organic functional base and the metal-salt and the polymkeric substance of aromatic sulfur compound.

In following formula, R and X are the organic functional bases.And it is obviously very low as the softening temperature of the silicone resin of essential composition in the above referred-to references, to contain these D unit.Therefore, the easier liquid form that is converted into of silicone resin at room temperature, this makes the compound difficulty especially that becomes with polycarbonate resin.Also have, because the molecular weight height can obtain solid-state silicone resin in room temperature, even the form of its existence is to contain the silicone resin of D unit as essential composition.Therefore, in order to improve the molecular weight of silicone resin, need longer polymerization time, and flame retardant effect is not high.

Japan publication Hei 11-222559 discloses a kind of fire-proof resin composition, contain 100 weight part synthetic resins, this resin contains aromatic ring in molecule, such as having introduced as aromatic polycarbonate resin, phenyl is shown in structural formula: R1mR2nSi (OR3) p (OH) qO (4-m-n-p-q)/2, and the 0.1-10 weight part contains the organo-siloxane of alkoxyl group.In the formula, R1 represents phenyl, R2 represents to have the monovalence alkyl (disregarding phenyl) of 1-6 carbon atom, R3 represents to have the monovalence alkyl of 1-4 carbon atom, and following scope: 0.5＜=m＜=2.0,0＜=n＜=0.9,0.42＜=p＜=2.5,0＜q＜=0.35,0.92＜=+m+n+p+q＜=2.8.

Also have, day, patent application 2000-159996 of the present disclosure disclosed a kind of fire-proof resin composition, contain aromatic polycarbonate, the silicate that is shown below and such as the fire retardant of metals, fire retardant haloid or inorganic family, contain compound, silicone resin, silicone oil, silicon-dioxide, aromatic polyamide resin, polyacrylonitrile fibre, fluorine family tree fat, norvolac resin of three bifurcation piperazine skeletons etc.:

In following formula, R1 to R4 represents to have the hydrocarbon of 1-20 carbon atom, and R1 becomes ring with R4.P and q are 0 or 1, and can not be 0 simultaneously.N is the integer greater than 1.

But, in the fire-proof resin composition of these prior aries, can not obtain having gratifying flame retardant resistance, mobile material and have various gratifying moulded products such as characteristics such as thermotolerance, hydrolytic resistance or shock resistances.

The applicant has been surprised to find a kind of resin combination, it has high flame retardancy, and above-mentioned all problems all by collaborative use the phosphoric acid ester of silicone resin and ad hoc structure and in addition by coupling collar oxygen stabilizer and anti-drip agent and with compound solution of polycarbonate family tree fat.Composition of the present invention has thermotolerance, excellent impact and hydrolytic resistance, and has excellent flame retardancy.

Summary of the invention

The present invention relates to a kind of flame retardant polycarbonate composition, contain polycarbonate (A-1); A kind of thermoplastic resin (A-2) that is different from polycarbonate; A kind of silicone resin (B); With a kind of phosphate compound (C) shown in the following formula: Wherein, each R1, R2, R3 and R4 represent to have the hydrocarbon of 1-30 carbon atom respectively; X represents to have the divalent organic group of 1-30 carbon atom, itself in addition can contain Sauerstoffatom and/or nitrogen-atoms; Represent the integer of 0-5 with m; With a kind of epoxy stabilizer (D),

Described composition be characterized as polycarbonate family tree fat (A-1) and thermoplastic resin (A-2) weight ratio (A-1: A-2) 99: 1-1: in 99 scopes, and

Described silicon family resin (B) is the ratio of 0.1-15 weight part with respect to the polycarbonate family tree fat (A-1) and the thermoplastic resin (A-2) of total amount 100 weight parts,

The ratio that described phosphate compound (C) is the 1-30 weight part with respect to the polycarbonate family tree fat (A-1) and the thermoplastic resin (A-2) of total amount 100 weight parts and

Described epoxy stabilizer (D) is the ratio of 0.01-10 weight part with respect to the polycarbonate family tree fat (A-1) and the thermoplastic resin (A-2) of total amount 100 weight parts, and wherein said silicone resin (B), described phosphate compound (C) and described epoxy stabilizer (D) provide synergy.

In one embodiment, thermoplastic resin (A-2) is selected from following one group:

A) contain the polymkeric substance of (a) aromatic vinyl strand joint (unimer) composition as its constituent;

B) contain (a) aromatic vinyl strand joint composition and (b) vinyl cyanide strand joint composition as the multipolymer of its constituent;

C) contain (a) aromatic vinyl strand joint composition, (b) vinyl cyanide strand joint composition and

(c) rubber polymer is as the multipolymer of its constituent;

D) aromatic polyester;

E) polyphenylene oxide (polyphenylene ether);

F) polyetherimide; With

G) poly phenylene sulfoether (polyphenylene sulfide).

In another embodiment, thermoplastic resin (A-2) is selected from ABS resin, AES resin, ACS resin, AAS resin and polystyrene resin.

In another embodiment, silicone resin (B) is the silicone resin that contains at least 2 types siloxane unit, described siloxane unit is selected from the siloxane unit (Q unit) that siloxane unit (T unit) that RSiO1.5 represents, siloxane unit (D unit) that R3SiO1.0 represents, siloxane unit (M unit) that R3SiO0.5 represents and SiO2.0 represent, wherein R represents the monovalent unsubstituted or alkyl that 1-10 carbon atom arranged that replaces.Above-mentioned this class silicone resin (B) is an ideal as the silicone resin of being made up of T unit and M unit or as the silicone resin existence by T unit and M unit and SiO2.0 (Q unit, wherein R represents the alkyl that 1-10 carbon atom arranged monovalent non-replacement or that replace) composition.In another embodiment, the aromatic group that in above-mentioned silicone resin (B), has the 20mole% ratio among the contained organic functional base R at least.

In another embodiment, phosphate compound (C) is dihydroxyphenyl propane-tetraphenyldiphosphate or dihydroxyphenyl propane-four cresyl bisphosphate; Epoxy group(ing) stablizer (D) is 3,4-epoxy group(ing) cyclohexyl methyl-3 ', 4 '-epoxy-cyclohexane carbonic ether or two (3,4-epoxy group(ing) cyclohexyl) adipic acid ester; Among the present invention, anti-drip agent (E) is a polytetrafluoroethylene (PTFE), and with respect to polycarbonate family tree fat (A-1) or total polycarbonate family tree fat (A-1) and 100 weight parts of thermoplastic resin (A-2), its ratio with the 0.01-10 weight part exists.

The invention still further relates to above-mentioned fire-proof resin composition form comprise electricity with the machinery of electronics and the goods of home decorating.Detailed Description Of The Invention

The fire-proof resin composition that the present invention relates to is characterised in that and contains polycarbonate family tree fat (A-1), thermoplastic resin (A-2), silicone resin (B), phosphate compound (C) and epoxy stabilizer (D).

Polycarbonate family tree fat (A-1).The aromatics Copolycarbonate that is used for polycarbonate family tree fat of the present invention (A) and is the aromatics homo-polycarbonate or obtain by the reaction between aromatic dihydroxy compound and the carbonate precursor.

Polycarbonate family tree fat has the repeated structural unit shown in the following formula (1) usually,

 O-A-O-C ... (1) wherein A is by aromatic dihydroxy compound deutero-residue of divalent.

Aromatic dihydroxy compound exists as monokaryon or multi-nucleus aromatic compound, have 2 hydroxyl-functional group unit and wherein the direct key of each hydroxyl link on the carbon atom of virtue nuclear.

The example that bisphenol cpd shown in the following formula (2) can be used as aromatic dihydroxy compound provides.

Wherein Ra and Rb can be identical or different, are respectively halogen atom or monovalence alkyl, and m and n are the integers of 0-4.X is

Rc and Rd are hydrogen atom or monovalence alkyl, and Rc and Rd can form ring structure, and Re is a bivalent hydrocarbon radical.

The example of the aromatic dihydroxy compound shown in these formulas (2) comprises two (hydroxyaryl) alkane, such as two (4-hydroxy phenyl) methane, 1, two (4-hydroxy phenyl) ethane of 1-, 2, two (4-hydroxy phenyl) propane (being called dihydroxyphenyl propane) of 2-, 2, two (4-hydroxy phenyl) butane of 2-, 2, two (4-hydroxy phenyl) octanes of 2-, two (4-hydroxy phenyl) phenylmethane, 2, two (4-hydroxyl-1-aminomethyl phenyl) propane of 2-, 1, two (4-hydroxyl-tert-butyl-phenyl) propane of 1-, 2, two (4-hydroxyl-3-bromophenyl) propane of 2-, 2, two (4-hydroxyl-3,5-dibromo phenyl) propane of 2-etc.; Two (hydroxyaryl) naphthenic hydrocarbon, such as 1, two (4-hydroxy phenyl) pentamethylene, 1 of 1-, 1-bis(4-hydroxyphenyl) cyclohexane etc.; The dihydroxyl aryl ethers, such as 4,4 '-dihydroxydiphenyl ether, 4,4 '-dihydroxyl-3,3 '-diphenyl ether etc.; The dihydroxyl diaryl sulfide, such as 4,4 '-dihydroxyl diphenylsulfide, 4,4 '-dihydroxyl-3,3 '-diphenylsulfide etc.; The dihydroxyl diaryl sulphoxide, such as 4,4 '-dihydroxyl diphenyl sulfoxide, 4,4 '-dihydroxyl-3,3 '-diphenyl sulfoxide etc.; Dihydroxyl diaryl sulfone, such as 4,4 '-dihydroxy-diphenyl sulfone, 4,4 '-dihydroxyl-3,3 '-sulfobenzide etc.But, it should be noted that aromatic dihydroxy compound is not limited only to above-mentioned example.

In one embodiment, aromatic dihydroxy compound is 2, two (4-hydroxy phenyl) propane (being called dihydroxyphenyl propane) of 2-.Also have, except shown in the above-mentioned formula (2) those, the aromatic dihydroxy compound shown in the following formula (3) also can be used as aromatic dihydroxy compound and uses.

Wherein each R1 is C independently ₁-C ₁₀Alkyl, halogen atom or halo alkyl, wherein at least one described alkyl is replaced by halogen atom, and p is the integer of 0-4.

The example of these compounds comprises Resorcinol; The Resorcinol that replaces is such as 3-methylresorcinol, 3-ethyl resorcinol, 3-propyl group Resorcinol, 3-butyl Resorcinol, 3-tert-butyl resorcin, 3-phenyl Resorcinol, 3-cumyl Resorcinol, 2,3,4,6-tetrafluoro Resorcinol and 2,3,4,6-tetrabromo Resorcinol; Pyrocatechol; With the quinhydrones of quinhydrones and replacement, such as 3-toluhydroquinone, 3-ethyl quinhydrones, 3-propyl group quinhydrones, 3-butylhydroquinone, 3-tertiary butylated hydroquinone, 3-phenyl quinhydrones, 3-cumyl quinhydrones, 2,3,5,6-duroquinol, 2,3,5,6-tetra-tert quinhydrones, 2,3,5,6-tetrafluoro quinhydrones and 2,3,5,6-tetrabromo quinhydrones.

Except above-mentioned formula (2), those other aromatic dihydroxy compound be following formula represent 2,2,2 ', 2 '-tetrahydrochysene-3,3,3 ', 3 '-tetramethyl--1,1 '-spiral shell-two [1H-indenes]-7,7 '-glycol:

These aromatic dihydroxy compounds can use separately, or two kinds are united use.Polycarbonate can be linear or branching.It can also be the mixture of the polycarbonate of linear polycarbonate and branching.

The polycarbonate of branching can obtain by multifunctional aromatic substance and aromatic dihydroxy compound and carbonate precursor reaction.Listed the exemplary of the multifunctional aromatic substance of this class in the United States Patent (USP) 3028385,3334154,4001124 and 4131576.Specific example comprises 1,1,1-three (4-hydroxy phenyl) ethane, 2,2 ', 2 " three (4-hydroxy phenyl) diisopropyl benzene, (Alpha-Methyl-α, α '; α '-three (4-hydroxy phenyl)-1,4-diethylbenzene, α, α '; α " three (4-hydroxy phenyls)-1,3,5-triisopropylbenzene, fluoro glycine, 4,6-dimethyl-2,4,6-three (4-hydroxy phenyl) heptane-2,1,3,5-three (4-hydroxy phenyl) benzene, 2, two [4,4-(4,4 '-dihydroxy phenyl) the cyclohexyl]-propane, 1 of 2-, 2,4-benzenetricarboxylic acid, 1,3,5-benzene tricarbonic acid and pyromellitic acid.Wherein, preferably use 1,1,1-three (4-hydroxy phenyl) ethane, α, α ', α " three (4-hydroxy phenyls)-1,3,5-triisopropylbenzene etc.

For there is no particular limitation in the limiting viscosity of the polycarbonate-base resin of 25 ℃ of mensuration in methylene dichloride, can suitably select according to required purposes and moldability, but be at least 0.26dL/g usually, preferred 0.30-0.98dL/g, more preferably 0.34-0.64dL/g.When calculating molecular-weight average viscosity, should be at least 10000 usually, preferred 12000-50000, more preferably 14000-30000.The mixture of the polycarbonate resin that all right service performance viscosity is different.By in methylene dichloride, measuring limiting viscosities (limiting viscosity [number] η) in 20 ℃, calculate molecular-weight average viscosity (Mv) according to Mark-Houwink viscosity formula then:

η＝K×(Mv) ^a(K＝1.23×10 ^-4，a＝0.83)

The polycarbonate-base resin that uses in the present invention with currently known methods production.The example that comprises is as follows:

(1) a kind of method is wherein carried out transesterification reaction polycarbonate synthesis (scorification) when the fusion with aromatic dihydroxy compound and carbonate precursor (such as carbonic diester).

(2) a kind of method, wherein aromatic dihydroxy compound and carbonate precursor (such as phosgene) react (interfacial) in solution.

These production methods are described in for example Japanese patent application H2-175723 and H2-124934, United States Patent (USP) 4001184,4238569,4238597 and 4474999 etc.Thermoplastic resin (A-2) except polycarbonate family tree fat

In the present invention, the thermoplastic resin except carbonic ether (hereinafter only being called thermoplastic resin) can be included in above-mentioned polycarbonate.Any thermoplastic resin except polycarbonate can use as thermoplastic resin (A-2), and it is not had specific restriction, but preferred the use is selected from one or more following resins:

(1) comprises the polymkeric substance of (a) aromatic vinyl monomer composition as constituent

(2) comprise (a) aromatic vinyl monomer composition and (b) the vinyl cyanide monomers composition as the multipolymer of constituent

(3) comprise (a) aromatic vinyl monomer composition, (b) vinyl cyanide monomers composition and (c) the class rubber polymer as the multipolymer of constituent

(4) aromatic polyester

(5) polyphenylene oxide

(6) polyester-imide

(7) poly phenylene sulfoether

All above-mentioned resins can be used as commodity purchasing, have no particular limits for production method etc.

(being total to) polymkeric substance (1) is at first described the polymkeric substance that comprises (a) aromatic vinyl monomer composition (1).The example of aromatic vinyl monomer composition (a) comprises vinylbenzene, alpha-methyl styrene, o-, m-or p-vinyl toluene, vinyl-dimethyl benzene, monochlorostyrene, dichlorostyrene, phenyl-monobromide ethene, Dowspray 9, fluorobenzene ethene, to t-butyl styrene, the rare and vinyl naphthalene of ethylbenzene second.The polymkeric substance that uses among the present invention can be the homopolymer of one of these monomers, maybe can be the multipolymer of two or more different monomers.In these monomers, special optimization styrene and alpha-methyl styrene.In one embodiment, use styrene resin.

Have no particular limits for the method for producing this class (being total to) polymkeric substance, can use any common currently known methods, such as mass polymerization, solution polymerization, body suspension polymerization, suspension polymerization and letex polymerization.Also can obtain (being total to) polymkeric substance by the resin of mixed polymerization respectively.

Polymkeric substance (2) describes below and comprises (a) aromatic vinyl monomer composition and (b) multipolymer of vinyl cyanide monomers composition (2).The example of aromatic vinyl monomer composition (a) is same as described above.The example of vinyl cyanide monomers composition (b) comprises vinyl cyanide and methacrylonitrile.In multipolymer, can contain one or more of these compositions.

(a)/(b) there is no particular limitation for proportion of composing, and it is selected according to application.(a)/(b) be preferably (a) for 50-95 weight % with (b) for 5-50 weight %, more preferably (a) be 65-92 weight % and (b) is 8-35 weight %.

The preferred example of above-mentioned polymkeric substance is SAN resin (styrene-acrylonitrile copolymer).Production method for this multipolymer has no particular limits, and can use any common currently known methods, such as mass polymerization, solution polymerization, body suspension polymerization, suspension polymerization and letex polymerization.Can also obtain the multipolymer of needs by the resin of mixed polymerization respectively.

Multipolymer (3) describes below and comprises (a) aromatic vinyl monomer composition, (b) vinyl cyanide monomers composition and (c) multipolymer of class rubber polymer.The example of aromatic vinyl monomer composition (a) and vinyl cyanide monomers composition (b) is same as described above.

The example of class rubber polymer (c) comprises polyhutadiene, polyisoprene, styrene butadiene random copolymer and segmented copolymer, butadiene isoprene copolymer and other rubber based on diene; The multipolymer of the multipolymer of ethylene-propylene random copolymer and segmented copolymer, ethene and alpha-olefin, ethylene-methyl acrylate, ethylene-propylene acid butyl ester and other ethene and esters of unsaturated carboxylic acids; Acrylate-butadienecopolymer is such as butyl acrylate-butadienecopolymer and other acrylic elastomer polymkeric substance; The multipolymer of ethylene-vinyl acetate and other ethene and fatty acid vinyl [salt]; Ethylene-propylene-hexadiene multipolymer and the non-trimer of gripping diene altogether of other ethylene-propylene; Butylene-isoprene copolymer and chlorating polyethylene.These can use or unite use separately.Preferred class rubber polymer is non-trimer, elastoprene and the acrylic elastomer polymkeric substance of gripping diene altogether of ethylene-propylene, preferred especially polyhutadiene and styrene-butadiene copolymer.In one embodiment, vinylbenzene is 50 weight % or still less.

This multipolymer (3) is the graft copolymer by in the presence of class rubber polymer (3) other composition graft polymerization being obtained preferably.Be preferably selected from the resin of ABS resin (acrylonitrile-butadiene-styrene copolymer), AES resin (acrylonitrile ethylene styrene copolymer), ACS resin (acrylonitrile-chlorianted polyethylene-styrene terpolymer) and AAS resin (vinyl cyanide-acrylic elastomer-styrol copolymer) especially.

The weight-average molecular weight (Mw) of above-mentioned (being total to) polymkeric substance (1) and multipolymer (2) and (3) is preferably 30000-200000, and 30000-150000 is better, and 30000-110000 is good especially.

In one embodiment of the invention, can with the mentioned component (a) and (b) and (c) copolymerization monomer also can with the copolymerization in above-mentioned (being total to) polymkeric substance (1) and multipolymer (2) and (3) of these compositions.The example of this class copolymerisable monomer comprises vinylformic acid, methacrylic acid and other α, beta-unsaturated carboxylic acid, (methyl) methyl acrylate, (methyl) ethyl propenoate, (methyl) propyl acrylate, (methyl) butyl acrylate, (methyl) vinylformic acid 2-ethyl ester, methacrylic acid 2-(ethyl hexyl) ester and other α, the beta-unsaturated carboxylic acid ester; Maleic anhydride, itaconic anhydride and other α, β-unsaturated dicarboxylic acid acid anhydrides; And maleimide, N-methyl maleimide, N-ethyl maleimide, N-phenylmaleimide, N-o-chloro-phenyl-maleimide and other α, β-unsaturated dicarboxylic acid imide compound.These monomers can separately or be united use.

There is no particular limitation for the production method of these multipolymers, and it can use mass polymerization, body suspension polymerization or solution polymerization production.

Aromatic polyester (4) aromatic polyester itself is known, is the polyester that has aromatic ring on the chain unit of polymkeric substance.These polymkeric substance and multipolymer obtain by polycondensation, and wherein principal constituent is aromatic dicarboxylic acid and glycol (or it becomes ester derivative).

The example of aromatic dicarboxylic acid comprises terephthalic acid, m-phthalic acid, phthalic acid, 1,5-naphthalene dicarboxylic acids, naphthalene-2,5-dicarboxylic acid, naphthalene-2,6-dicarboxylic acid, biphenyl-2,2 '-dicarboxylic acid, biphenyl-3,3 '-dicarboxylic acid, biphenyl-4,4 '-dicarboxylic acid, biphenyl sulfone-4,4 '-dicarboxylic acid, diphenylisopylidene-4,4 '-dicarboxylic acid, 1,2-two (phenoxy group) ethane-4,4 '-dicarboxylic acid, anthracene-2,5-dicarboxylic acid, anthracene-2,6-dicarboxylic acid, p-terphenyl-4,4 '-dicarboxylic acid and pyridine-2, the 5-dicarboxylic acid.Terephthalic acid is preferred.

These aromatic dicarboxylic acids can also two or more mixture use.Also have, as long as consumption is little, one or more aliphatic dicarboxylic acids------or one or more alicyclic dicarboxylic acids---such as cyclohexane dicarboxylic acid such as hexanodioic acid, nonane diacid, dodecanedioic acid and sebacic acid-can mix with above-mentioned aromatic dihydroxy carboxylic acid.

The example of diol component comprises ethylene glycol, propylene glycol, butyleneglycol, hexylene glycol, neopentyl glycol, 2-methyl-prop-1,3-glycol, glycol ether, triglycol and other aliphatic diol, and hexanaphthene-1,4-dimethanol and other alicyclic diol, and the mixture of these glycol.Also have, as long as consumption is little, but one or more molecular weight are the long chain diol copolymerization of 400-6000, such as polyoxyethylene glycol, poly--1, and ammediol or poly-1,4-butyleneglycol.

The specific examples of aromatic polyester resin comprises polyethylene terephthalate (PET), polytrimethylene terephthalate, polybutylene terephthalate (PBT), poly-naphthalene diacid second diester, poly-naphthalene diacid fourth diester, poly-1,2-two (phenoxy group) ethane-4,4 '-dicarboxylic acid second diester and poly terephthalic acid cyclohexanedimethanoester esters.In one embodiment, use PBT or PET.

Polyphenylene oxide (5) polyphenylene oxide (PPE) is known resin, has replacement or unsubstituted phenylate repeating unit.Specific example comprises poly-(2,6-dimethyl-1,4-phenylene) ether, poly-(2,6-diethyl-1, the 4-phenylene) ether, poly-(2-methyl-6-ethyl-1,4-phenylene) ether, poly-(2-methyl-6-propyl group-1, the 4-phenylene) ether, poly-(2,6-dipropyl-1, the 4-phenylene) ether, poly-(2-ethyl-6-propyl group-1,4-phenylene) ether, poly-(2,6-dimethoxy-1, the 4-phenylene) ether, poly-(2,6-dichloromethyl-1,4-phenylene) ether, poly-(2,6-dibromo methyl isophthalic acid, the 4-phenylene) ether, poly-(2,6-phenylbenzene-1,4-phenylene) ether, poly-(2,6-xylyl-1, the 4-phenylene) ether, poly-(2,6-chloryl (dichloroyl)-1,4-phenylene) ether, poly-(2,6-dibenzyl-1, the 4-phenylene) ether and poly-(2,6-dimethyl-1,4-phenylene) ether.

The PPE multipolymer can be to contain in some phenylate repeating units by the trisubstituted phenol of alkyl---such as 2,3, the 6-pseudocuminol---multipolymer.Can also be that wherein distyryl compound has been grafted to multipolymer on the PPE.Distyryl compound grafted polyphenylene oxide comprises the multipolymer that the distyryl compound graft polymerization a kind of and such as vinylbenzene, alpha-methyl styrene, Vinyl toluene or chlorostyrene among the above-mentioned PPE is obtained.PPE is that Noryl can buy from market as the trade mark that GE Plastics Japan produces.

Polyetherimide (6) polyetherimide is known resin, and for example the trade mark of GE Plastics Japan is the resin of Ultem.

Poly phenylene sulfoether (7) poly phenylene sulfoether (PPS) is known resin, has replacement or unsubstituted diphenyl sulfide repeating unit.Example comprises those that can buy from Phillips Petroleum, Tosoh Susteel Tohpren, Kureha Chemical etc.

Multipolymer (1) and (3) preferably are used for the present invention as thermoplastic resin, more preferably use the resin that is selected from HIPS (high impact polystyrene rigidity), ABS resin (acrylonitrile-butadiene-styrene copolymer), AES resin (acrylonitrile ethylene styrene copolymer), ACS resin (acrylonitrile-chlorianted polyethylene-styrene terpolymer) and AAS resin (vinyl cyanide-acrylic elastomer-styrol copolymer).Preferred especially ABS resin and HIPS.

For this thermoplastic resin (A-2), and the weight ratio of itself and polycarbonate-base resin (A-1) (A-1: be 99 A-2): 1-1: the 99th, favourable, preferred 30: 70-70: 30.

Composition B-silicone resin has no particular limits for the silicone resin as the composition (B) that exists in the present invention.In one embodiment, the silicone resin that uses contains at least 2 kinds of siloxane units, and it is selected from the siloxane unit (M unit) that siloxane unit (T unit) that RSiO1.5 represents, siloxane unit (D unit) that R3SiO1.0 represents, siloxane unit (Q unit) that SiO2.0 represents and R3SiO0.5 represent (wherein R represents the alkyl that 1-10 carbon atom arranged of the unsubstituted or replacement of unit price).

The organic group of forming silicone resin can be identical or different.In one embodiment, used alkyl such as methyl, ethyl, propyl group, butyl etc., such as the alkenyl of vinyl, allyl group etc., such as the aryl of phenyl, toluyl etc.

In the organic group R of these types, consider from dispersiveness and flame retardant resistance aspect polycarbonate family tree fat, having methyl and/or phenyl is special ideal as the silicone resin of organic group R, and because it is bought easily as silicone resin in this case.Especially the silicone resin that has phenyl also has good especially flame retardant resistance except outstanding consistency is arranged with respect to polycarbonate, and has improved the transparency of polycarbonate.It is ideal that this class phenyl exists with the ratio greater than 20 moles of % with respect to whole organic group in silicone resin, and better is to exist with the ratio greater than 40 moles of % with respect to whole organic group.

The molecular weight of the silicone resin that uses in fire-proof resin composition of the present invention is an ideal in the 1000-50000 scope, more desirably should be in the 2000-20000 scope, the special ideal molecular weight of this silicone resin that uses in fire-proof resin composition of the present invention is in the 3000-10000 scope.If molecular weight is less than 1000, under the condition that adopts, be difficult to keep solid-state, if molecular weight surpass 50000 processibility reduce, the dispersiveness of polycarbonate is descended.

In one embodiment, the silicone resin silicone resin (B) that acts among the present invention of the silicone resin of T and M unit composition or T, M and Q unit composition.

The M unit that contains the 0.03-1 mole with respect to 1 mole of T unit in silicone resin is an ideal, and the amount of 0.05-0.3 mole is better.Also have, contain in silicone resin under the unitary situation of Q, these Q unit are ideal with respect to 1 mole of unitary content of T for the 0.001-0.5 mole, and the amount of 0.01-0.05 mole is better.The Q unit that contains the high oxidation degree with higher amount is favourable for reaching flame retardant resistance, if but the unitary quantitative change height of Q in the siloxanes, dispersiveness to polycarbonate family tree fat becomes unsatisfactory, becomes very strong because become the material behavior of inorganic particles.Thus, need the control compositely proportional, thereby it is in the above-mentioned scope.

Consider the balance between flame retardant resistance, processibility and the moulded product characteristic, it is desirable to from the content range of above-mentioned siloxane unit, select a scope, thereby make that the shared ratio in T unit is the 50-97 mole % of whole silicone resin weight.

Available known method is synthesized this class silicone resin.For example by organochlorosilane or organoalkoxysilane are obtained with the condensation reaction that is hydrolyzed of excessive water.In one embodiment, contain the silicone resin of silanol group by the silane compound water that T, Q and D unit the are formed condensation reaction preparation that is hydrolyzed, then, prepare silicone resin if this silanol group is carried out three organic-silylations by the compound that uses the M unit to form, control molecular weight so in this case and become and carry out easily, because this situation is an ideal.

In the example of a production method of the silicone resin that forms in T and M unit, wherein (wherein R1 is replacement or the unsubstituted monovalence alkyl that is same to each other or different to each other to the 5-100 weight part shown in (R13Si) aZ, a is the integer of 1-3, when a is 1, Z is hydrogen atom, halogen atom, hydroxyl or hydrolization group, when a was 2, Z was-O-,-NX-or-S-, when a was 3, Z was-N-.Also have, X is hydrogen atom, the monovalence alkyl of 1-4 carbon atom is arranged) silicon compound (b) and the 100 weight parts silicone resin that contains the silanol group that (a) [RSiO1.5] T unit forms react.The above-mentioned silicone resin that contains the silanol groups of composition (a) can be synthetic with known method.The condensation reaction that is hydrolyzed of for example that usefulness such as organochlorosilane or organoalkoxysilane is excessive water obtains.In the reaction of this class, the amount by regulating pondage or control hydrolysis catalyzer and the time length of type, condensation reaction or temperature etc. can obtain the silicone resin of different extent of polymerizations.The silicone resin that obtains like this contains silanol groups (SiOH) usually.

(R13Si) silicon compound of the composition shown in the aZ (b) is the compound that the silanol groups that wherein exists in the composition (a) has been silylated.Example about the Z hydrolysising group can provide such as methoxyl group, oxyethyl group, propoxy-, isopropoxy, the alkoxyl group of butoxy, such as chlorine, the halogen of bromine etc., alkenyloxy such as propenyloxy group etc., such as acetoxyl group, the acyloxy of benzoyloxy, such as the acetone oximido, organic oximido of butanone oximido etc., such as the dimethyl aminooxy, organic aminooxy of diethyl aminooxy etc., such as dimethylamino, organic amino of cyclohexyl amino etc., organic amide base such as N-methyl kharophen etc.

Example about composition (b) can provide such as trimethyl silane, the hydrogen diene silane (hydrodiene silane) of triethyl silicane etc., such as trimethylchlorosilane, chlorotriethyl silane, the chlorosilane of tri-phenyl chloride etc., silanol such as trimethyl silyl alcohol etc., such as the trimethylammonium methoxy silane, the organoalkoxysilane of triethyl methoxy silane etc., such as (CH3) 3SiNHCH3, (CH3) 3SiNHC2H5, (CH3) 3SiNH (CH3) 2, (CH3) aminosilane of 3SiNH (C2H5) 2 grades, acyloxy silane such as (CH3) 3SiOCOCH3 etc., such as [(CH3) 3Si] NH, 1, two silazanes of 3-divinyl tetramethyl-two silazanes etc., three silazanes such as nine methyl trimethoxy silazane [(CH3) 3Si] 3N etc.In these examples, silazane class or chlorosilane class are desirable the employings, because be easy to the control reaction or remove unreacted compound.

Reaction between mentioned component (a) and the composition (b) can be carried out under the known condition that silanol is converted into silyl (silylation).For example, be under the situation of silazane or chlorosilane at composition (b), reaction is only by heating blended composition (a) and (b) and easily carrying out.At this moment, the ratio of employing is with respect to 100 weight part compositions (a), and composition (b) is an ideal in 5-100 weight part scope.And, if the ratio of composition (b) less than 5 weight parts, the silanol groups of composition (a) can not be by silanization satisfactorily and distortion during reaction so, such as producing gel.Also have, if the ratio of composition (b) is greater than 100 weight parts, the economy from the raw material angle just becomes bad so, because a large amount of unreacted composition exists as residue, and need the longer time to be used to remove unreacted composition (b), complicated thereby technology becomes.

In addition, it is desirable to above-mentioned Silanization reaction and carry out in organic solvent, control reaction temperature is so that the generation of the side reaction of control dehydrating condensation simultaneously.About this class representative examples of organic of using can provide hydrocarbon system's solvent such as toluene, dimethylbenzene, hexane, industrial gasoline, solvent oil, kerosene etc., such as the ether solvent of tetrahydrofuran (THF), dioxan etc., such as the chlorinated hydrocarbon solvent of methylene dichloride, ethylene dichloride etc.Have no particular limits for temperature of reaction, but in the highest 120 ℃ of scopes, be fit in room temperature.The hydrochloric acid that generates in reaction, ammonia, ammonium chloride, alcohol etc. can be removed by washing with water, or remove simultaneously with solvent.

The silicone resin that aforesaid method obtains exists in the form of room temperature with the liquid or solid material usually.With polycarbonate family tree fat compound silicone resin be ideal with solid-state the existence because it can disperse in polycarbonate family tree fat equably.Softening temperature greater than 400C, be desirably the solid state si resin particularly suitable of 70-2500C.In addition, can regulate the softening temperature of silicone resin by mixing two kinds of different silicone resin of softening temperature.

By control as the molecular weight of the silicone resin that contains silanol groups of composition (a), carry out the silanol groups of silanization and become the molecular weight of kind controllable silicon resin of the composition (b) of silylating reagent by control.

If the silicone resin of Shi Yonging has the D unit in the present invention, because it is easy to be converted into fluent meterial in room temperature, the softening temperature of silicone resin significantly reduces so.As a result, with the compound difficulty that becomes of itself and polycarbonate.Also have, if molecular weight improves, can obtain in room temperature is the silicone resin of solid matter form, even it exists with the form with the unitary silicone resin of D.But, elongated for improving the required polymerization time of molecular weight in this case, compare final flame retardant effect reduction with the silicone resin that the Q unit is formed with the silicone resin of forming by T and M unit or by T, M.

The silicone resin of Shi Yonging can contain a small amount of silanol groups in the present invention, but from storage stability, when melt-processed stability or consider that from the flame retardant resistance aspect amount of silanol groups is ideal more for a short time.The amount of contained silanol groups is an ideal less than 0.5 weight % in silicone resin, and better is that its content is less than 0.3 weight %.

In fire-proof resin composition of the present invention, polycarbonate family tree fat (A-1) and thermoplastic resin (A-2) with respect to total amount 100 weight parts, by the amount of compound silicone resin is the 0.1-15 weight part, and the polycarbonate family tree fat (A-1) and thermoplastic resin (A-2) content that it is desirable to respect to total amount 100 weight parts are the 0.1-5 weight part.If the amount of silicone resin, then can not obtain satisfied flame retardant resistance less than 0.1 weight part, if surpass 15 weight parts, then not only can not reach the raising flame retardant resistance, and the outward appearance of moulded product and optical clarity or intensity are had a negative impact.In addition, any can not produce obnoxious flavour in these silicone resin when burning.

The compound that phosphate compound (C) following formula is represented uses as phosphoric acid ester:

In formula, R ¹, R ², R ³And R ⁴Be the alkyl that 1-30 carbon atom arranged independently of one another, preferably have 1-5 carbon atom, preferably that replace or unsubstituted aromatic hydrocarbyl.If replace, substituent example comprises alkyl, alkoxyl group, alkylthio, halogen, aryl and aryloxy.

At this R ¹, R ², R ³And R ⁴Example comprise phenyl, cresyl, xylyl (such as 2, the 6-xylyl), trimethylphenyl, ethylphenyl, cumyl and butyl phenyl.If therefore contain alkyl, the resin combination that obtains is outstanding especially aspect flame retardant resistance.

X is the C that can contain Sauerstoffatom and/or nitrogen-atoms ₁-C ₃₀Divalent organic group.This X be for example-O-Y ¹-O-(Y wherein ¹Be that replace or unsubstituted aromatic hydrocarbyl, preferred 1,4-phenylene, 1,3-phenylene etc.) or-O-Y ²-R ⁵-Y ³-O-(Y wherein ²And Y ³Be bivalent substituted or unsubstituted aromatic hydrocarbyl, its special example comprises phenylene replacement or unsubstituted; R ⁵Be C ₁-C ₈Bivalent hydrocarbon radical or oxygen alkyl (R ⁶-O-; R wherein ⁶Be C ₁-C ₈Bivalent hydrocarbon radical), C more particularly ₁-C ₉Divalent aliphatic alkyl, such as 2,2 '-propylidene).X can be an organic group, and wherein the direct key of nitrogen-atoms is linked on the phosphorus atom, for example 1, and 4-piperidines two bases (following formula):

M is the integer of 0-5.

The example of phosphoric acid ester comprises dihydroxyphenyl propane tetraphenyldiphosphate (BPADP), triphenylphosphate, tritolyl phosphate, cresyl diphenyl phosphate, dihydroxyphenyl propane tetramethyl phenol bisphosphate, Resorcinol four (2, the 6-3,5-dimethylphenyl) phosphoric acid ester and four (xylyl) piperidines phosphoamide.Wherein preferred dihydroxyphenyl propane tetraphenyldiphosphate (BPADP) and dihydroxyphenyl propane tetramethyl phenol bisphosphate are as phosphoric acid ester.

If this phosphate compound (C) adds with above-mentioned silicone resin (B), can form moulded product so with excellent impact and thermotolerance and excellent flame retardancy.

The amount of compound phosphate compound (C) is the 1-30 weight part with respect to the polycarbonate family tree fat (A-1) and the thermoplastic resin (A-2) of total amount 100 weight parts in fire-proof resin composition of the present invention, and the polycarbonate family tree fat (A-1) and the thermoplastic resin (A-2) that it is desirable to respect to total amount 100 weight parts are the 1-10 weight part.If the amount of phosphate compound (C) is less than 1 weight part, (can not obtain enough flame retardant resistances), however if surpass 30 weight parts, lost thermotolerance.

Epoxy stabilizer (D) epoxy stabilizer (D) further adds according in the fire-proof resin composition of the present invention.The example of this epoxy stabilizer comprises epoxidised soybean oil, epoxidised Toenol 1140, phenylglycidyl ether, allyl glycidyl ether, the tert-butyl-phenyl glycidyl ether, 3,4-epoxycyclohexyl methyl-3 ', 4 '-epoxycyclohexyl carboxylicesters, 3,4-epoxy-6-methyl cyclohexane ylmethyl-3 ', 4 '-epoxy-6 "-the methylcyclohexyl carboxylicesters; 2; 3-epoxycyclohexyl methyl-3 '; 4 '-epoxycyclohexyl carboxylicesters; 4-(3; 4-epoxy-5-methylcyclohexyl) butyl-3 ', 4 '-epoxycyclohexyl carboxylicesters, 3,4-epoxycyclohexyl oxyethane, cyclohexyl methyl-3,4-epoxycyclohexyl carboxylicesters, 3,4-epoxy-6-methyl cyclohexane ylmethyl-6 "-the methylcyclohexyl carboxylicesters; bisphenol A diglycidyl ether; tetrabromo-bisphenol glycidyl ether; phthalic acid diglycidylether; the diglycidylether of hexahydrophthalic acid; two-epoxy Dicyclopentadiene (DCPD) ether, two-ethylene oxide glycol, two-the epoxycyclohexyl adipic acid ester, the divinyl diepoxide, tetraphenyl oxyethane, octyl group epoxy phthalic ester, epoxidised polyhutadiene, 3,4-dimethyl-1, the 2-epoxy cyclohexane, 3,5-dimethyl-1, the 2-epoxy cyclohexane, 3-methyl-5-the tertiary butyl-1, the 2-epoxy cyclohexane, octadecyl-2,2-dimethyl-3,4-epoxycyclohexyl carboxylicesters, N-butyl-2,2-dimethyl-3,4-epoxycyclohexyl carboxylicesters, cyclohexyl-2-methyl-3,4-epoxycyclohexyl carboxylicesters, N-butyl-2-sec.-propyl-3,4-epoxy-5-methylcyclohexyl carboxylicesters, octadecyl-3,4-epoxycyclohexyl carboxylicesters, 2-ethylhexyl-3 ', 4 '-epoxycyclohexyl carboxylicesters, 4,6-dimethyl-2,3-epoxycyclohexyl-3 ', 4 '-epoxycyclohexyl carboxylicesters, 4, the anhydrous tetrahydrophthalic acid of 5-epoxy, the 3-tertiary butyl-4, the anhydrous tetrahydrophthalic acid of 5-epoxy, diethyl-4,5-epoxy-suitable-1,2-cyclohexane carboxylic acid ester, di-n-butyl-3-the tertiary butyl-4,5-epoxy-suitable-1,2-cyclohexane carboxylic acid ester etc.

In one embodiment, epoxy stabilizer (D) is an alicyclic hydrocarbon Resins, epoxy.In another embodiment, be 3,4-epoxycyclohexyl methyl-3 ', 4 '-epoxycyclohexane carboxylate or two (3, the 4-epoxycyclohexyl) adipic acid ester.

This alicyclic hydrocarbon epoxy stabilizer can be bought with the trade mark of R-51 from Asahi Denka Kogyo Kabushiki Kaisha (AsahiElectrochemicals Co.Ltd.), or buys as Celoxide 2021P or Celoxide 2080 from Daicel Kagaku KogyoKabushiki Kaisha (Daicel Chemical Industries Co.Ltd.).

The hydrolytic resistance of finding resin combination is improved by adding epoxy stabilizer.In one embodiment, the amount of the epoxy stabilizer that adds under the situation of using polycarbonate family tree fat (A-1) separately with respect to the polycarbonate family tree fat (A-1) of 100 weight parts, or under the situation that polycarbonate resin (A-1) and thermoplastic resin (A-2) use together, with respect to (A-1) of 100 weight parts and (A-2) be about 0.01-10 weight part.In one embodiment, this amount is the 0.1-5 weight part.For optimized hydrolytic resistance, the amount of epoxy stabilizer is greater than 0.01 weight part.But if should amount surpass 10 weight parts, the physical strength of moulded product will be influential so.

Anti-drip agent (E) resin combination of the present invention can comprise anti-drip agent.Anti-drip agent is a kind of additive that suppresses drip when burning, can use any known reagent.In one embodiment, anti-drip agent forms the O-fiber structure in the resin of polycarbonate-base, uses polytetrafluoroethylene (PTFE) and TFE copolymer (such as tetrafluoroethylene/hexafluoropropylene copolymer) typically.

In available various types of polytetrafluoroethylene (PTFE)s, preferably have a kind of of fabulous dispersiveness, emulsified and be dispersed in the aqueous solution or the analogue such as PTFE wherein, or wherein PTFE is wrapped up by the resin of for example polycarbonate and styrene-acrylonitrile copolymer, or the master batch of the resin of PTFE and for example polycarbonate and styrene-acrylonitrile copolymer, because it provides the surface of good outward appearance for the moulded product of being made up of polycarbonate compositions.If use a kind of material, wherein PTFE disperses by emulsification in such as the solution of water etc., and then there is no particular limitation, but average particulate diameter is an ideal less than 1 micron PTFE material, it is desirable to especially to use less than 0.5 micron.

Specific example about commercially available PTFE material, can provide Teflon 30J (trade mark, Mitsubishi DuponFluoro Chemicals (Kabushiki Kaisha (Mitsubishi Dupon Fluoro Chemicals Co.Ltd.)), Polyflon D-2C (trade mark, Daikin Kagaku Kogyo (Kabushiki Kaisha (KaikinChemical Industries Co.Ltd.)), Aflon AD1 (trade mark, Asahi Glass (Kabushiki Kaisha (Asahi Glass Co.Ltd.)).

The amount of the anti-drip agent of adding is ideal with respect to the polycarbonate family tree fat (A-1) and the thermoplastic resin (A-2) of total amount 100 weight parts for the 0.01-10 weight part, and better is to add 0.05-2 weight part, the amount of optimal adding 0.1-0.5 weight part.

If the amount of composition (E) less than above-mentioned scope, so just can not obtain having the poly carbonate resin composition of fabulous flame retardant resistance,, so just lost flowability if greater than above-mentioned scope.

Also have, the molecular weight of this tetrafluoroethylene should it is desirable at 1000000-5000000 greater than 500000.

The generation of drip when the resin combination of compound tetrafluoroethylene has been controlled burning.And, if tetrafluoroethylene and silicone resin together use, so just further controlled drip, in addition, to compare with the situation that only adds tetrafluoroethylene, the incendiary time has shortened.

In the present invention, about anti-drip agent, polyphenylene oxide (PPE) can use with above-mentioned tetrafluoroethylene.The example of PPE can provide and comprise poly-(2,6-dimethyl-1,4-phenylene) ether, poly-(2,6-diethyl-1, the 4-phenylene) ether, poly-(2-methyl-6-ethyl-1,4-phenylene) ether, poly-(2-methyl-6-propyl group-1,4-phenylene) ether, poly-(2,6-dipropyl-1, the 4-phenylene) ether, poly-(2,6-phenylbenzene-1,4-phenylene) ether, poly-(2,6-xylyl-1, the 4-phenylene) ether etc.Special ideal PPE family tree fat is poly-(2,6-dimethyl-1,4-phenylene) ether.Also have, about polyphenylene ether copolymer, multipolymer has the trisubstituted phenol of alkyl in the phenylate repeating unit, for example, particularly has 2,3, the 6-pseudocuminol.In one embodiment, multipolymer wherein the vinylbenzene compounds of group be grafted in this polyphenylene oxide.About having of can providing of vinylbenzene compounds of group grafted polyphenylene oxide by the multipolymer that obtains of the vinylbenzene compounds of group of vinylbenzene, alpha-methyl styrene, Vinyl toluene, chloro-styrene etc. for example of graft polymerization in above-mentioned polyphenylene oxide.

In addition, about anti-drip agent, the anti-drip agent of inorganic family also can be used with above-mentioned tetrafluoroethylene.Can provide silicon-dioxide, quartz, pure aluminium silicate, mica, vanadine, aluminum oxide, lime carbonate, talcum, silicon carbide, silicon nitride, titanium dioxide, ferric oxide, carbon black etc. about the anti-drip agent of above-mentioned inorganic family.

Other composition resin combination of the present invention can also contain the UV absorption agent, based on the oxidation inhibitor of hindered phenol, releasing agent etc.The example of UV absorption agent comprises UV absorption agent based on benzotriazole, based on the UV absorption agent of benzophenone with based on the UV absorption agent of salicylate (ester).

In fire-proof resin composition of the present invention, can also not make and add known additive under its condition of losing its material behavior at blended resin composition or when it is molded as goods.For example, can add tinting material (decorations is such as the pigment of carbon black, titanium dioxide etc.), weighting agent, strengthening agent (glass fibre, carbon fiber, talcum, clay, mica, glass flake, grind glass, granulated glass sphere), lubricant, softening agent, fire retardant, flow characteristics improving agent etc.

Have no particular limits for the method for preparing resin combination of the present invention, can use any known method.But being to use the melting mixing method is special ideal.When producing resin combination, also can add a small amount of solvent.

About spendable device, can provide extruding machine especially as an example, impact mixing machine (bombardingmixer), roll, kneader etc., can be intermittently or the successive mode operate.At this moment, have no particular limits for composition blended order.

This fire-proof resin composition that the present invention relates to has excellent flame retardancy, and when burning drip does not take place.

For example, the fire-proof resin composition that the present invention relates to satisfies UL-94 V-0 level in UL-94 V evaluation, UL-94 V evaluation is 1/16 o'clock a test panel according to carrying out in the test method of Bleten 94 " Combustion test for material classification " of theUnder Writer Laboratory Incorporation (UL-94 hereinafter referred to as) indication, wherein preparing a thickness.In addition, the standard of each V level is as shown in table 1 below in UL-94: table 1

Rank	????V-0	????V-1	????V-1
				The time that each specimen flame is residual	Less than 10 seconds	Less than 30 seconds	Less than 30 seconds
5 residual total times of specimen flame	Less than 50 seconds	Less than 250 seconds	Less than 250 seconds
				By the drip cotton of igniting	Do not exist	Do not exist	Exist

The fire-proof resin composition that the present invention relates to can be molded as the form of any needs with the molding methods of any hope, such as using injection moulding, extrusion molding, blowing etc.

The moulded product that obtains like this has excellent impact and high heat resistance, and has excellent flame retardancy.Therefore, the moulded product of resin combination of the present invention can be aptly as the outside plate of OA equipment or household electrical appliance or as house decoraton parts, electronics and electric mechanical parts.

Fire-proof resin composition of the present invention has high flame retardancy because containing special phosphate and silicone resin and does not lose shock resistance or mouldability simultaneously, need not in addition to worry that corresponding fire retardant produces Halogen gas when burning, because it does not contain the fire retardant that is formed by chlorine, bromine compounds etc., therefore say to have fabulous function from environmental angle.Also have owing to wherein added specific epoxy stabilizer, the hydrolytic resistance of polycarbonate family tree fat itself is improved, and can produce the moulded product with fabulous shock resistance.

Therefore, this fire-proof resin composition is particularly useful in the application that needs high heat resistance, the material that uses such as the parts that are used for for example household electrical appliance, house decoraton and the OA equipment of televisor, printer, duplicating machine, facsimile recorder, PC etc., at the inner member of series of cells, liquid crystal reflector, automobile etc.

Embodiment

By embodiment the present invention is described in more detail hereinafter.But the present invention is not subjected to the restriction of these embodiment.

In addition, in an embodiment, except as otherwise noted, part is a weight part, and % is weight %.In addition, following compounds is as each composition.

Polycarbonate family tree fat (PC): the polycarbonate of dihydroxyphenyl propane: LEXAN (trade mark, NipponGE:Plastics Kabushiki Kaisha (Japan GE Plastics Co.Ltd.) produces), at limiting viscosity=0.49dl/g that 250C measures in methylene dichloride, viscosity-average molecular weight (Mv)=21760 (calculating).

ABS resin: the material of rubber content=20%, MI=2.5g/10 second.

Phosphate compound (C) compounds of group: dihydroxyphenyl propane-tetraphenylphosphonium acid esters, CR741S (trade mark, Daihachi Kagaku Kabushiki Kaisha (Daihachi Chemical Co.Ltd.) produces).

Epoxy stabilizer: 3,4-epoxycyclohexyl methyl-3 ', 4 '-epoxy cyclohexane carbonic ether (Daicel Kagaku Kogyo Kabushiki Kaisha (Daicel Chemical IndustriesCo.Ltd.) produces for Celoxide2021P, trade mark).

Polytetrafluoroethylene (PTFE): Polyflon D-2C (trade mark, Daikin Kagaku Kogyo (KabushikiKaisha (Daikin Chemical Industreis Co.Ltd.))).PTFE emulsification in water disperses in this material, and PTFE content is 60 weight %.In addition, Polyflon D-2C adds with respect to the amount of polycarbonate family tree fat with 0.5 weight %, because the actual add-on of PTFE is 0.3%.Also have, water is evaporated when the preparation resin combination.

Silicone resin: use the silicone material shown in the table 2 composed as follows.Table 2

Silicone resin		????A-1	??A-2	????B-1
					Character	Structural unit	T and M	T and M	??T、D、M
The Ph/Me mol ratio	????65/35	???70/30	????70/30
				Weight-average molecular weight		????7800	???7500	????75000
Softening temperature [℃]	????160	???140	??????85
				The OH residue		????0	????0	???????0

The Ph/Me mol ratio: in silicone resin except the phenyl that exists in M unit (T, D unit) and the mol ratio of methyl.

Embodiment 1

Mix 90 weight part polycarbonates, 10 weight part ABS resin, 1 weight part silicone resin (A-1), 6 weight part phosphoric acid ester (CR741S), 0.3 weight part epoxy stabilizer and 0.5 weight part PTFE, with twin shaft extruding machine (TEX44aII, Nippon Sei Kojo (Kabushiki Kaisha) (Japan SteelManufacturing Works Ltd.) produces) to mould at the thorax warm extrusion of 250-260 0C with the screw speed of 300rpm, cutting obtains the particle of length-specific.With the test panel of these particles by 100t injection moulding machine injection moulding specific dimensions under the condition of moulding of thorax temperature 260 0C and metal die temperature 50 0C.The performance test of the moulded product that obtains is carried out as follows.

(1) estimates shock resistance.Based on ASTM-1, the test panel during with thickness 1/8 is estimated cantilever-type impact strength.

(2) temperature (thermotolerance) is subdued in load.Based on ASTM-D-648, the submissive temperature during test panel test load 18.6kg when the thickness 1/4.

(3) hydrolytic resistance.Measurement keeps after 48 hours the weight-average molecular weight of polycarbonate in the resin combination under the original weight-average molecular weight of polycarbonate and the 100RH normal atmosphere at 121 ℃ in the resin combination of preparation.Carry out the measurement of weight-average molecular weight with GPC.And the low expression of weight-average molecular weight hydrolytic resistance is low.

(4) estimate flame retardant resistance.According to test based on above-mentioned UL-94, promptly, according to the testing method of pointing out at Bleten 94 " Combustion test for material classification " of the Under Writer LaboratoryIncorporation (UL-94 hereinafter referred to as), measure the flame retardant resistance of the moulded product of thickness 1.6mm.And be total combustion time of 5 test materials combustion time.

The result is as shown in table 3.

Embodiment 2-3

In embodiment 1, with silicone resin (A-2) or (B-1) replace silicone resin (A-1).Except this variation, react with being similar to embodiment 1 method, the particulate character that obtains is thus estimated.

The result is as shown in table 3.Comparing embodiment 1-4

Use the composition shown in the table 3.Except this variation, react with being similar to embodiment 1 method, the particulate character that obtains is thus estimated.

The result is as shown in table 3.

Table 3

		Embodiment 1	Embodiment 2	Embodiment 3	Comparing embodiment 1	Comparing embodiment 2	Comparing embodiment 3	Comparing embodiment 4
									Form	PC	????90	????90	????90	????90	????90	????90	????90
ABS	????10	????10	????10	????10	????10	????10	????10
								CR741S (phosphoric acid ester)		????6	????5	????6	????6	????6	????6	????-
Silicone resin (A-1)	????1	????-	????-	????-	????-	????1	????5
								Silicone resin (A-2)		????-	????1	????-	????-	????-		????-
Silicone resin (B-1)	????-	????-	????1	????-	????-	?????-	????-
								?PTFE		????0.5	????0.5	????0.5	????0.5	????0.5	????0.5	????0.5
Epoxy stabilizer	????0.3	????0.3	????0.3	?????-	????0.3	????-	????0.3
								Shock resistance IZOD (kg/cm)		????80	????85	????80	????75	????75	????80	????80
Load subdue temperature (℃)		????106	????109	????106	????106	????106	????106										????120
								?UL	?UL94-1.6 *1 the combustion time-second	????8	????24	????23	????50	????50	????11	????240
The UL level	??V-0	??V-0	??V-0	????V-1	????V-1	????V-0	????V-2
									Hydrolytic resistance	Initial	??45000	??45000	??45000	????45000	????45000	????45000	????45000
After aging	??43000	??43000	??42000	????30000	????42000	????29000	????43000

^*1) the 1.6th, 1.6mm thickness

As shown in table 3, resin combination of the present invention is short combustion time, because wherein added epoxy stabilizer and anti-drip agent with polycarbonate family tree fat, silicone resin and phosphate compound (C) compound, and it has controlled the generation of drip, and has high fire resistance (UL-94 V-0).Also have, resin combination of the present invention has fabulous hydrolytic resistance because itself in addition when heating, be not hydrolyzed yet.

The flame retardant resistance of comparative example 1 the resin combination that does not contain silicone resin and epoxy stabilizer and hydrolytic resistance deficiency.And the flame retardant resistance deficiency of comparative example 2 the resin combination that does not contain silicone resin.In addition, comparative example 3 the resin combination hydrolytic resistance deficiency that does not contain epoxy stabilizer.Also have, still low even the resin combination of comparative example 4 not phosphorous acid esters has increased the amount flame retardant resistance of silicone resin.Therefore, by adding the multiple effect that can realize in polycarbonate family tree fat to the resin combination flame retardant resistance in conjunction with phosphoric acid ester and silicone resin and with it.

Claims (13)

1. fire-retardant combination, contain:

A) polycarbonate resin (A-1);

B) a kind of thermoplastic resin (A-2) that is different from polycarbonate;

C) a kind of silicone resin (B);

D) a kind of phosphate compound (C) shown in the following formula:

Wherein, each R ¹, R ², R ³And R ⁴Represent C respectively ₁-C ₃₀Hydrocarbon; X represents C ₁-C ₃₀Divalence can contain the organic group of Sauerstoffatom and/or nitrogen-atoms; Represent the integer of 0-5 with m; With

E) a kind of epoxy stabilizer (D),

The weight ratio of wherein said polycarbonate family tree fat (A-1) and described thermoplastic resin (A-2) (A-1: A-2) 99: 1-1: in 99 scopes,

Described silicone resin (B) exists with respect to the polycarbonate family tree fat (A-1) of total amount 100 weight parts and thermoplastic resin (A-2) amount with the 0.1-15 weight part,

Described phosphate compound (C) exist with the amount of 1-30 weight part with respect to the polycarbonate family tree fat (A-1) of total amount 100 weight parts and thermoplastic resin (A-2) and

Described epoxy stabilizer (D) exists with respect to the polycarbonate family tree fat (A-1) of total amount 100 weight parts and thermoplastic resin (A-2) amount with the 0.01-10 weight part.

2. the fire-retardant combination of claim 1, wherein said thermoplastic resin (A-2) is selected from following one group:

A) contain the polymkeric substance of (a) aromatic vinyl strand joint (unimer) composition as its constituent;

B) contain (a) aromatic vinyl strand joint composition and (b) vinyl cyanide strand joint composition as the multipolymer of its constituent;

C) contain (a) aromatic vinyl strand joint composition, (b) vinyl cyanide strand joint composition and (c) rubber polymer as the multipolymer of its constituent;

D) aromatic polyester;

E) polyphenylene oxide;

F) polyetherimide; With

G) poly phenylene sulfoether.

3. the fire-retardant combination of claim 1, wherein said thermoplastic resin (A-2) is selected from: ABS resin (acrylonitrile-butadiene-styrene copolymer), AES resin (acrylonitrile ethylene styrene copolymer), ACS resin (acrylonitrile-chlorianted polyethylene-styrene terpolymer) and AAS resin (vinyl cyanide-acrylic elastomer-styrol copolymer).

4. the fire-retardant combination of claim 1, wherein silicone resin (B) contains at least two kinds and is selected from following siloxane unit:

A) siloxane unit (T unit) represented of RSiO1.5,

B) siloxane unit (D unit) represented of R2SiO1.0,

C) siloxane unit (M unit) represented of R3SiO0.5 and

D) siloxane unit (Q unit) represented of SiO2.0,

Wherein R represents the alkyl that 1-10 carbon atom arranged that unit price is unsubstituted or replace.

5. the fire-retardant combination of claim 4, wherein said silicone resin (B) they are a) silicone resin or the b that form of T unit and M unit) silicone resin formed of the siloxane unit represented of T unit and M unit and Q unit.

6. the fire-retardant combination of claim 4, wherein said silicone resin molecular weight is about 1000-50000.

7. the fire-retardant combination of claim 5, wherein in above-mentioned silicone resin (B) among the contained monovalence alkyl R, the shared ratio of aryl is at least 20 moles of %.

8. the fire-retardant combination of claim 1, wherein phosphate compound (C) is dihydroxyphenyl propane-tetraphenyldiphosphate or dihydroxyphenyl propane four cresyl bisphosphates.

9. the fire-retardant combination of claim 1, wherein epoxy stabilizer (D) is 3,4-epoxycyclohexyl methyl-3 ', 4 '-epoxycyclohexane carboxylate or two-(3, the 4-epoxycyclohexyl) adipic acid ester.

10. the fire-retardant combination of claim 1 further contains anti-drip agent (E).

11. the fire-retardant combination of claim 10, wherein anti-drip agent (E) exists with respect to the polycarbonate family tree fat (A-1) of the polycarbonate family tree fat (A-1) of 100 weight parts or total amount 100 weight parts and thermoplastic resin (A-2) amount with about 0.01-10 weight part.

12.. comprising, a method for preparing fire-retardant combination, described method merge and mix following ingredients:

A) polycarbonate (A-1);

B) a kind of thermoplastic resin (A-2) that is different from polycarbonate;

C) a kind of silicone resin (B);

D) a kind of phosphate compound (C) shown in the following formula:

Wherein, each R ¹, R ², R ³And R ⁴Represent C respectively ₁-C ₃₀Hydrocarbon; X represents C ₁-C ₃₀Divalence can contain the organic group of Sauerstoffatom and/or nitrogen-atoms; Represent the integer of 0-5 with m; With

E) a kind of epoxy stabilizer (D),

The weight ratio of wherein said polycarbonate family tree fat (A-1) and described thermoplastic resin (A-2) (A-1: A-2) 99: 1-1: in 99 scopes,

Described silicone resin (B) exists with respect to the polycarbonate family tree fat (A-1) of total amount 100 weight parts and thermoplastic resin (A-2) amount with the 0.1-15 weight part,

Described phosphate compound (C) exist with the amount of 1-30 weight part with respect to the polycarbonate family tree fat (A-1) of total amount 100 weight parts and thermoplastic resin (A-2) and

Described epoxy stabilizer (D) exists with respect to the polycarbonate family tree fat (A-1) of total amount 100 weight parts and thermoplastic resin (A-2) amount with the 0.01-10 weight part.

13. the method for claim 12, thereby comprise that further the reduction composition forms the step of particulate form.