JPH07113033A - Production of styrenic resin composition containing halogenated epoxy-based flame retardant - Google Patents

Abstract

PURPOSE:To obtain the composition, excellent in flame retardancy, heat resistance, etc., and useful as parts, etc., for household appliances by melt extruding a rubber-modified styrenic resin, a halogenated bisphenolic type epoxy resin and an antimony oxide under specific temperature conditions. CONSTITUTION:This method for producing the objective composition is to melt extrude (A) a rubber-modified styrenic resin (e.g. impact-resistant polystyrene or ABS resin), (B) a halogenated bisphenolic type epoxy resin having preferably a structural formula expressed by formula I [X is Br or Cl; R is lower alkyl; Y is a group expressed by formula II or glycidyl; (i), (j) and (k) are each 0-4; (n) is 0-5] and (C) an antimony oxide at a resin temperature which is a temperature causing the decomposition of the component (B) or below (preferably <=230 deg.C). Furthermore, 5-40 pts.wt. component (B) and 1-20 pts.wt. component (C) are preferably blended with 100 pts.wt. component (A).

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a method for producing a styrene resin composition having excellent flame retardancy. More specifically, it relates to a method for producing a styrene resin composition containing a halogenated epoxy flame retardant having excellent flame retardancy, heat resistance, impact resistance and fluidity.

[0002]

2. Description of the Related Art Styrenic resins have excellent impact resistance in addition to excellent moldability.
It is used in various fields such as home electric appliances and office automation equipment parts, but its use is limited due to the flammability of styrene resins.

As a method of making the styrene resin flame-retardant,
It is known that tetrabromobisphenol A (TBA), decabromodiphenyl oxide (DBDPO), hexabromocyclododecane (HBCD), and other halogen-based flame retardants are added to styrene-based resins, which causes flame retardation to some extent. Has been achieved.

However, the above-mentioned TBA has a drawback that when it is blended with a styrenic resin, the heat resistance is greatly reduced, and the thermal stability is also unfavorable.

The above DBDPO is compounded in a styrene resin together with antimony trioxide (Japanese Patent Laid-Open No. 58-58).
No. 187450), it has excellent heat resistance, but it deteriorates light resistance and impairs impact strength and appearance due to poor dispersibility.

When the above HBCD is blended with a styrene resin (Japanese Patent Publication No. 38-16837, Japanese Patent Publication No. 62).
No. 34784), it has excellent heat resistance, light resistance, and impact resistance, but its decomposition temperature is low, and the thermal stability of the resin is significantly reduced.

Further, it is known to use a halogenated bisphenol type epoxy resin in combination with antimony trioxide as a flame retardant for solving the above problems, as disclosed in JP-A-63-72749.
It is disclosed in the publication. However, when the flame retardant has a low softening temperature and is melt-extruded with a styrene resin, the production stability is low because the viscosity difference between the two is large, and the flame-retardant variation is large depending on the melt-extrusion conditions, which is a problem in production. Was holding.

[0008]

SUMMARY OF THE INVENTION In view of the above situation, the present invention is free from the above-mentioned problems, namely, flame retardancy,
It is an object of the present invention to provide a method for producing a styrene resin composition containing a halogenated epoxy flame retardant having excellent heat resistance, impact resistance and fluidity.

[0009]

Means for Solving the Problems The inventors of the present invention have earnestly studied a technique for improving the flame retardancy of a styrene resin composition containing a halogenated epoxy flame retardant, and as a result, melt extrusion at a specific temperature condition has been performed. As a result, they have surprisingly found that it is possible to dramatically improve flame retardancy, and have reached the present invention.

That is, the present invention provides a method for producing a resin composition containing (A) a rubber-modified styrenic resin, (B) a halogenated bisphenol type epoxy resin, and (C) antimony oxide. Disclosed is a method for producing a styrene-based resin composition containing a halogenated epoxy-based flame retardant, which comprises melt-extruding at a resin temperature below a temperature at which decomposition of the type epoxy resin substantially occurs.

The present invention will be described in detail below.

The resin composition of the present invention contains (A) a rubber-modified styrene resin, a specific (B) flame retardant and a specific (C) flame retardant auxiliary.

The above-mentioned component (A) is a main component of the molding resin composition and plays a role of maintaining the strength of the molded product, and the component (B) together with the component (C) (A). It is a component for imparting flame retardancy to the component.

Here, in producing the above resin composition,
It is essential to control the resin temperature below the temperature at which decomposition of the halogenated bisphenol type epoxy resin occurs.
The halogenated bisphenol type epoxy resin is relatively stable up to 250 ° C. under static conditions, but when melt-extruded under high shearing force over 230 ° C., decomposition reaction is accelerated. The present inventors have found that the flame retardancy and the production stability are significantly improved by controlling the temperature of a specific resin, and have completed the present invention.

The rubber-modified styrenic resin of the component (A) of the present invention includes a rubber-modified product alone or a resin containing a rubber-unmodified styrene-based resin mainly containing the rubber-modified product.

The rubber-modified styrenic resin of the present invention is a polymer in which a rubber-like polymer is dispersed in particles in a matrix composed of a vinyl aromatic polymer, and is aromatic in the presence of the rubber-like polymer. A group vinyl monomer and, if necessary, a vinyl monomer copolymerizable therewith, which is obtained by subjecting the monomer mixture to known bulk polymerization, bulk suspension polymerization, solution polymerization, or emulsion polymerization. Examples of such resins include:
Impact-resistant polystyrene, ABS resin (acrylonitrile-butadiene-styrene copolymer), AAS resin (acrylonitrile-acrylic rubber-styrene copolymer), A
Examples thereof include ES resin (acrylonitrile-ethylene propylene rubber-styrene copolymer).

Here, the rubbery polymer needs to have a glass transition temperature (Tg) of -30 ° C. or lower,
If it exceeds -30 ° C, the impact resistance will decrease.

Examples of such rubbery polymers include diene rubbers such as polybutadiene, poly (styrene-butadiene), poly (acrylonitrile-butadiene), and saturated rubbers obtained by hydrogenating the above diene rubbers, isoprene rubbers, chloroprene rubbers. , An acrylic rubber such as polybutyl acrylate, an ethylene-propylene-diene monomer terpolymer (EPDM), and the like, and a diene rubber is particularly preferable.

The aromatic vinyl monomer, which is an essential component in the graft-polymerizable monomer mixture to be polymerized in the presence of the above rubbery polymer, is, for example, styrene, α-methylstyrene, paramethylstyrene or p-methylstyrene. -Chlorostyrene, p-bromostyrene, 2,4,5-tribromostyrene and the like, and styrene is most preferable, but styrene may be the main component and other aromatic vinyl monomers may be copolymerized.

If desired, one or more monomer components copolymerizable with the aromatic vinyl monomer may be introduced as a component of the rubber-modified styrene resin. When it is necessary to enhance oil resistance, unsaturated nitrile monomers such as acrylonitrile and methacrylonitrile can be used.

When it is necessary to reduce the melt viscosity at the time of blending, an acrylate ester composed of an alkyl group having 1 to 8 carbon atoms can be used. Furthermore, when it is necessary to further increase the heat resistance of the resin composition, α-methylstyrene, acrylic acid, methacrylic acid,
Monomers such as maleic anhydride and N-substituted maleimide may be copolymerized. The content of the vinyl monomer copolymerizable with the vinyl aromatic monomer in the monomer mixture is 0-40.
% By weight.

The rubber-like polymer in the rubber-modified styrene resin of the present invention is preferably 5 to 80% by weight, particularly preferably 10 to 50% by weight, and the graft-polymerizable monomer mixture is preferably 95 to 20%. %, More preferably 90 to 50% by weight. Outside this range, the impact resistance and rigidity of the desired resin composition cannot be balanced. Furthermore, the rubber particle size of the styrene-based polymer is
0.1 to 5.0 μm is preferable, especially 0.2 to 3.0 μm
m is preferred. Within the above range, impact resistance is particularly improved.

The reduced viscosity ηsp / c (0.5 g / dl, toluene solution, measured at 30 ° C.), which is a measure of the molecular weight of the rubber-modified styrenic resin of the present invention, is 0.30 to 0.80 dl.
/ G is preferably in the range of 0.40 to 0.60
More preferably, it is in the range of dl / g. As means for satisfying the above requirements regarding the reduced viscosity ηsp / c of the rubber-modified styrene resin, the amount of the polymerization initiator, the polymerization temperature,
Adjustment of the amount of chain transfer agent can be mentioned.

The structure of the halogenated bisphenol type epoxy resin (B) of the present invention is not particularly limited, but it is generally represented by the following structural formula.

[0025]

[Chemical 1]

[0026]

[Chemical 2]

(Where X is a bromine atom or chlorine atom, R is
Is a lower alkyl group, and Y is (2) or (3) (glycidyl group), i, j, and k are integers of 0 to 4,
And n is an integer of 0-5 and shows the number of repetitions. ) Specific examples of the halogenated bisphenol include dibromobisphenol A, tetrabromobisphenol A, dichlorobisphenol A, tetrachlorobisphenol A, dibromobisphenol F, tetrabromobisphenol F, dichlorobisphenol F, tetrachlorobisphenol F, dibromobisphenol S, Tetrabromobisphenol S, dichlorobisphenol S, tetrachlorobisphenol S and the like can be mentioned, but tetrabromobisphenol A is preferred.

Further, Y which is an end group of the halogenated bisphenol type epoxy resin (B) is preferably a substituent represented by (2) which is tribromophenyl as an aromatic ring, or a glycidyl group (3).

The halogenated bisphenol type epoxy resin used in the present invention can be obtained, for example, by subjecting a halogenated bisphenol and epichlorohydrin to a dehydrochlorination reaction in the presence of an alkali.

The antimony oxide (C) of the present invention is antimony trioxide, antimony tetroxide, antimony pentoxide, etc., and acts as a flame retardant aid for the component (B).

When imparting light resistance to the resin composition of the present invention, (D) a light resistance improver can be added.

The light resistance improver (D) is a UV absorber, a hindered amine light stabilizer, an antioxidant,
It is a halogen scavenger, a light-shielding agent, a metal deactivator, or a quencher, and also includes agents in which one or more of them are combined.

The above-mentioned ultraviolet absorber absorbs light energy and becomes a keto-type molecule by intramolecular proton transfer (benzophenone, benzotriazole type), or cis-trans isomerization (cyanoacrylate type). ), Released as heat energy,
It is a component to make it harmless. Specific examples are 2,4-
2-hydroxybenzophenones such as dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-octoxybenzophenone and 5,5'-methylenebis (2-hydroxy-4-methoxybenzophenone), 2- (2 ′ -Hydroxy-5 ′
-Methylphenyl) benzotriazole, 2- (2'-
Hydroxy-5'-t-octylphenyl) benzotriazole, 2- (2'-hydroxy-3 ', 5'-di-
t-butylphenyl) benzotriazole, 2- (2 '
-Hydroxy-3 ', 5'-di-t-butylphenyl)
-5-chlorobenzotriazole, 2- (2'-hydroxy-3'-t-5'-methylphenyl) -5-chlorobenzotriazole, 2- (2'-hydroxy-3 ',
5'-dicumylphenyl) benzotriazole, 2,
2- (2'-hydroxyphenyl) benzotriazoles such as 2'-methylenebis (4-t-octyl-6-benzotriazolyl) phenol, phenyl salicylate, resorcinol monobenzoate, 2,4-di-t.
-Butylphenyl-3 ', 5'-di-t-butyl-4'
-Hydroxybenzoates, hexadecyl-3,5-di-t-butyl-4-hydroxybenzoates and other benzoates, 2-ethyl-2'-atoxyoxanilide,
Substituted oxanilides such as 2-ethoxy-4'-dodecyl oxanilide and ethyl-α-cyano-β, β-diphenyl acrylate, methyl-2-cyano-3-methyl-3- (p-methoxyphenyl) acrylate And cyanoacrylates.

The hindered amine light stabilizer is a component for decomposing hydroperoxide generated by light energy to generate stable N—O.radicals, N—OR and N—OH for stabilization. A specific example is
2,2,6,6-tetramethyl-4-piperidyl stearate, 1,2,2,6,6-pentamethyl-4-piperidyl stearate, 2,2,6,6-tetramethyl-
4-piperidyl benzoate, bis (2,2,6,6-
Tetramethyl-4-piperidyl sebacate, bis (1,
2,2,6,6-Pentamethyl-4-piperidyl) sebacate, tetrakis (2,2,6,6-tetramethyl-
4-piperidyl) 1,2,3,4-butanetetracarboxylate, tetrakis (1,2,2,6,6-pentamethyl-4-piperidyl) 1,2,3,4-butanetetracarboxylate, bis ( 1,2,2,6,6-pentamethyl-4-piperidyl) .di (tridecyl) -1,
2,3,4-butane tetracarboxylate, bis (1,2,2,6,6-pentamethyl-4-piperidyl) -2-butyl-2- (3 ', 5'-di-t-butyl-4 -Hydroxybenzyl) malonate, 1- (2-hydroxyethyl) -2,2,6,6-tetramethyl-4
-Piperidinol / diethyl succinate polycondensate, 1,6
-Bis (2,2,6,6-tetramethyl-4-piperidylamino) hexane / dibromoethane polycondensate, 1,6
-Bis (2,2,6,6-tetramethyl-4-piperidylamino) hexane / 2,4-dichloro-6-t-octylamino-s-triazine polycondensate, 1,6-bis (2,2,2 6,6-Tetramethyl-4-piperidylamino) hexane / 2,4-dichloro-6-morpholino-s
-Triazine polycondensation products and the like.

The above-mentioned antioxidant is a component for stabilizing peroxide radicals such as hydroperoxy radicals generated or for decomposing peroxides such as hydroperoxide generated during thermoforming or by exposure to light. Is.
Specific examples thereof are hindered phenolic antioxidants and / or peroxide decomposers. The former serves as a radical chain inhibitor, and the latter decomposes the peroxide generated in the system into more stable alcohols to prevent autoxidation.

The above-mentioned hindered phenol-based antioxidants are 2,6-di-tert-butyl-4-methylphenol, styrenated phenol, n-octadecyl 3
-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate, 2,2'-methylenebis (4-
Methyl-6-tert-butylphenol), 2-ter
Charbutyl-6- (3-tert-charbutyl-2-hydroxy-5-methylbenzyl) -4-methylphenyl acrylate, 2- [1- (2-hydroxy-3,5-di-charpentylphenyl) ethyl]- 4,6-di-Charpentylphenyl acrylate, 4,4'-butylidene bis (3-methyl-6-tert-butylbutylphenol), 4,4'-thiobis (3-methyl-6-ter-
(Charlebutylphenol), alkylated bisphenol, tetrakis [methylene 3- (3,5-ditertiarybutyl-4-hydroxyphenyl) propionate] methane, 3,9-bis [2- [3- (3-tertiarybutyl- 4-hydroxy-5-methylphenyl) -propionyloxy] -1,1-dimethylethyl] -2,
4,8,10-tetraoxaspiro [5.5] undecane and the like.

The peroxide decomposer is trisnonylphenylphosphite, triphenylphosphite,
Organophosphorus peroxide decomposers such as tris (2,4-di-tert-butylphenyl) phosphite or dilauryl 3,3'-thiodipropionate, dimyristyl 3,
3'-thiodipropionate, distearyl 3,3'-
Organic sulfur peroxide decomposers such as thiodipropionate, pentaerythrityl tetrakis (3-lauryl thiopropionate), ditridecyl 3,3'-thiodipropionate and 2-mercaptobenzimidazole.

The above-mentioned halogen scavenger is a component for scavenging free halogen generated during thermoforming or light exposure. Specific examples thereof include hydrotalcite, zeolite, magnesium oxide, calcium stearate, basic metal salts such as zinc stearate, organic tin compounds, and organic epoxy compounds.

The above-mentioned hydrotalcite does not include a water-containing basic carbonate such as magnesium, calcium, zinc, aluminum or bismuth or its crystal water,
Includes natural and synthetic products. As a natural product, Mg ₆
Examples thereof include those having a structure of Al ₂ (OH) ₁₆ CO ₃ .4H ₂ O. In addition, as a synthetic product, Mg _0.7 Al _0.3 (OH)
₂ (CO ₃ ) _0.15・ 0.54H ₂ O, Mg _4.5 Al ₂ (O
H) ₁₃ CO ₃ · 3.5H ₂ O, Mg _4.2 Al ₂ (OH) _{12.4
CO 3, Zn 6 Al 2 (} OH) 16 CO 3 · 4H 2 O, Ca 6 A
l ₂ (OH) ₁₆ CO ₃ .4H ₂ O, Mg ₁₄ Bi ₂ (OH)
_29.6 · 4.2H ₂ O and the like can be mentioned.

The above zeolite is Na ₂ O.Al ₂ O ₃
It is an A-type zeolite represented by 2SiO ₂ .XH ₂ O or a metal-substituted zeolite containing at least one metal selected from the metals of Group II and Group IV of the periodic table. And as the substitution metal, Mg, Ca, Zn, Sr,
Ba, Zr, Sn and the like are preferable, and Ca, Zn and Ba are particularly preferable.

The organic epoxy compound is epoxidized soybean oil, tris (epoxypropyl) isocyanurate,
Hydroquinone diglycidyl ether, terephthalic acid diglycidyl ester, 4,4′-sulfobisphenol polyglycidyl ether, N-glycidyl phthalimide, or hydrogenated bisphenol A glycidyl ether,
3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, 2- (3,4-
Epoxy cyclohexyl spiro [5,5] -3,4-epoxy) cyclohexane-m-dioxane, bis (3,3
4-epoxycyclohexylmethyl) adipate, vinylcyclohexenedioxide, 4-vinylepoxycyclohexane, bis (3,4-epoxy-6-methylcyclohexylmethyl) adipate, 3,4-epoxy-
6-methylcyclohexyl-3,4-epoxy-6-methylcyclohexanecarboxylate, methylenebis (3,4-epoxycyclohexane), dicyclopentadienebepoxide, di (3,4) ethylene glycol.
Alicyclic epoxy compounds such as epoxyepoxycyclohexylmethyl) ether, ethylenebis (3,4-epoxycyclohexanecarboxylate), dioctyl epoxyhexahydrophthalate, and di-2-ethylhexyl epoxyhexahydrophthalate.

The light-shielding agent is a component for preventing light from reaching the bulk of the polymer. Specific examples thereof include rutile type titanium oxide (TiO ₂ ), zinc oxide (ZnO), chromium oxide (Cr ₂ O ₃ ), cerium oxide (CeO ₂ ), and the like.

The metal deactivator is a component for deactivating heavy metal ions in the resin with a chelate compound. Specific examples thereof include acid amine derivatives, benzotriazole, and their derivatives.

The above-mentioned quencher is a component for deactivating photoexcited functional groups such as hydroperoxide and carbonyl group in a polymer by energy transfer, and organic nickel and the like are known.

When imparting fluidity to the resin composition of the present invention, (E) a fluidity improver may be added.

The (E) fluidity improver is a copolymer resin containing an aromatic vinyl unit and an acrylate unit,
It is an aliphatic hydrocarbon, a higher fatty acid, a higher fatty acid ester, a higher fatty acid amide, a higher aliphatic alcohol, or a metal soap, and also contains an agent in which one or more of them are combined.

The aromatic vinyl unit of the above copolymer resin is
The aromatic vinyl unit shown in the description of the component (A), and the acrylic acid ester unit is an acrylic acid ester composed of an alkyl group having 1 to 8 carbon atoms such as methyl acrylate and butyl acrylate. Here, the content of acrylic acid ester units in the copolymer resin is preferably 3 to 40% by weight, and more preferably 5 to 20% by weight. Also,
Solution viscosity, which is an index of the molecular weight of the copolymer resin (resin 1
0 wt% MEK solution, measurement temperature 25 ° C) is 2-10
It is preferably cP (centipoise). If the solution viscosity is less than 2 cP, the impact strength will decrease, while 10 cP
If it exceeds, the effect of improving the fluidity decreases.

The above-mentioned aliphatic hydrocarbon processing aid is liquid paraffin, natural paraffin, microwax, polyolefin wax, synthetic paraffin, and partial oxides thereof, fluorides, chlorides and the like.

The above-mentioned higher fatty acids include saturated fatty acids such as caproic acid, hexadecanoic acid, palmitic acid, stearic acid, phenylstearic acid and ferronic acid, and unsaturated fatty acids such as ricinoleic acid, lysine veridic acid and 9-oxy12 octadecenoic acid. Fatty acids and the like.

The higher fatty acid esters are monohydric alcohol esters of fatty acids such as methyl phenylstearate and butyl phenylstearate, and monobasic alcohol esters of polybasic acids such as diphenylstearyl phthalate diester. , Sorbitan monolaurate, sorbitan monostearate, sorbitan monooleate, sorbitan sesquioleate, sorbitan trioleate, polyoxyethylene sorbitan monolaurate, polyoxyethylene sorbitan monopalmitate, polyoxyethylene sorbitan monostearate,
Sorbitan esters such as polyoxyethylene sorbitan monooleate, stearic acid monoglyceride, oleic acid monoglyceride, capric acid monoglyceride,
Fatty acid ester of glycerin monomer such as behenic acid monoglyceride, polyglycerin stearate,
Polyglycerin oleic acid ester, polyglycerin fatty acid ester such as polyglycerin lauric acid ester, polyoxyethylene monolaurate, polyoxyethylene monostearate, fatty acid ester having a polyalkylene ether unit such as polyoxyethylene monooleate, and Examples include neopentyl polyol distearate and other neopentyl polyol fatty acid esters.

The above-mentioned higher fatty acid amides include monoamides of saturated fatty acids such as phonyl stearic acid amide, methylol stearic acid amide, and methylol behenic acid amide, coconut oil fatty acid diethanolamide, lauric acid diethanolamide, and coconut oil fatty acid diethanolamide, olein. N, N′-2 substituted monoamides such as acid diethanolamide, and methylenebis (12-hydroxyphenyl) stearic acid amide, ethylenebisstearic acid amide, ethylenebis (12-hydroxyphenyl) stearic acid amide, hexamethylene Screw (12-
Saturated fatty acid bisamides such as hydroxyphenyl) stearic acid amide, and aromatic bisamides such as m-xylylenebis (12-hydroxyphenyl) stearic acid amide.

The higher aliphatic alcohols are monohydric alcohols such as stearyl alcohol and cetyl alcohol, polyhydric alcohols such as sorbitol and mannitol,
And polyoxyethylene dodecylamine, polyoxyethylene voctadecylamine and the like, and further allylated ether having a polyalkylene ether unit such as polyoxyethylene allyl ether, and polyoxyethylene lauryl ether, polyoxyethylene tridodecyl Ether, polyoxyethylene cetyl ether,
Polyoxyethylene stearyl ether, polyoxyethylene alkyl ether such as polyoxyethylene oleyl ether, polyoxyethylene octyl phenyl ether, polyoxyethylene alkyl phenyl ether such as polyoxyethylene nonyl phenyl ether, polyepichlorohydrin ether, polyoxyethylene bisphenol A It is a dihydric alcohol having a polyalkylene ether unit such as ether, polyoxyethylene ethylene glycol, polyoxypropylene bisphenol A ether, and polyoxyethylene polyoxypropylene glycol ether.

The metal soap is a metal salt of the higher fatty acid such as stearic acid such as barium, calcium, zinc, aluminum or magnesium.

The resin composition of the present invention may contain a flame retardant other than the component (B) and a flame retardant auxiliary other than the component (C).

The flame retardants other than the component (B) of the present invention are halogen type, phosphorus type and inorganic type flame retardants.

Examples of the halogen-based flame retardant include aromatic halogen compounds, halogenated polycarbonates, halogenated aromatic vinyl polymers, halogenated cyanurate resins, halogenated polyphenylene ethers, and the like.
Preferably decapromodiphenyl oxide, tetrabromobisphenol A, tetrabromobisphenol A
Oligomer, brominated bisphenol phenoxy resin, brominated bisphenol polycarbonate, brominated polystyrene, brominated cross-linked polystyrene, brominated polyphenylene oxide, polydibromophenylene oxide, decabromodiphenyl oxide bisphenol condensate, halogen-containing phosphate ester and It is a fluororesin or the like.

Examples of the phosphorus-based flame retardants include organic phosphorus compounds, red phosphorus, inorganic phosphates and the like.

Examples of the above-mentioned organic phosphorus compound include phosphine, phosphine oxide, biphosphine, phosphonium salt, phosphinic acid salt, phosphoric acid ester, and phosphorous acid ester. More specifically, triphenyl phosphate, methyl neobenthyl phosphite, hentaerythritol diethyl diphosphite, methyl neopentyl phosphate, phenyl neopentyl phosphate, pentaerythritol diphenyl phosphate, didicyclopentyl hibodiphosphate. , Gineo Pentyl Hibophos Fight,
Examples thereof include phenylpyrocatechol phosphite, ethylpyrocatechol phosphate, and dipyrocatechol hibodiphosphate.

Here, a hydroxyl group-containing aromatic phosphoric acid ester is particularly preferable in terms of the balance of fluidity, heat resistance and impact resistance, and the above-mentioned organic phosphorus compound containing no hydroxyl group may be used in combination.

The above-mentioned hydroxyl group-containing aromatic phosphoric acid ester means phosphoresidue containing one or more phenolic hydroxyl groups in tricresyl phosphate, triphenyl phosphate, condensed phosphoric acid ester thereof and the like. An acid ester, for example, the following compounds.

[0061]

[Chemical 3]

[0062]

[Chemical 4]

(However, Ar ₁ , Ar ₂ , Ar ₃ , Ar ₄ , A
r ₅ and Ar ₆ are aromatic groups selected from a phenyl group, a xylenyl group, an ethylphenyl group, an isopropylphenyl group and a butylphenyl group, and at least one hydroxy group is substituted with the above aromatic group in the phosphoric acid ester. Has been done. Further, n represents an integer of 0 to 3, and m represents an integer of 1 or more. Among the hydroxyl group-containing aromatic phosphoric acid esters, diphenylresorcinyl phosphate represented by the following formula (5) or diphenylhydroquinonyl phosphate represented by the following formula (6) is particularly preferable. It is disclosed in JP-A 1-223158 and is obtained by the reaction of phenol, hydroxyphenol, aluminum chloride and phosphorus chloride.

[0064]

[Chemical 5]

The above-mentioned red phosphorus used in the present invention includes, in addition to general red phosphorus, its surface in advance.
Metals selected from aluminum hydroxide, magnesium hydroxide, zinc hydroxide and titanium hydroxide, coated with a metal hydroxide coating, metals selected from aluminum hydroxide, magnesium hydroxide, zinc hydroxide and titanium hydroxide. A thermosetting resin coated on a liquid film of a metal hydroxide selected from aluminum hydroxide, magnesium hydroxide, zinc hydroxide and titanium hydroxide, which has been coated with a film consisting of a hydroxide and a thermosetting resin. Those double-coated with the above coating can also be preferably used.

The above-mentioned inorganic phosphate used in the present invention is typically ammonium polyphosphate.

Further, as the inorganic flame retardant, aluminum hydroxide, magnesium hydroxide, dolomite, hydrotalcite, calcium hydroxide, barium hydroxide, basic magnesium carbonate, zirconium hydroxide, hydrate of tin oxide, etc. Inorganic metal compound hydrate, zinc borate, zinc metaborate, barium metaborate, zinc carbonate, magnesium carbonate, mu calcium, calcium carbonate, barium carbonate, magnesium oxide, molybdenum oxide, zirconium oxide, tin oxide, antimony oxide , Red phosphorus and the like. These may be used alone or in combination of two or more. Among them, those selected from the group consisting of magnesium hydroxide, aluminum hydroxide, basic magnesium carbonate and hydrotalcite have a good flame retarding effect and are economically advantageous.

Examples of the flame retardant aid other than the above-mentioned component (C) include triazine skeleton-containing compounds, antimony trioxide,
Examples thereof include metal oxides such as copper oxide, magnesium oxide, zinc oxide, molybdenum oxide, iron oxide, manganese oxide, aluminum oxide, tin oxide and titanium oxide, and silicone resins such as polydiorganosiloxane.

The triazine skeleton-containing compound is particularly preferable as the flame retardant aid for the phosphorus-based flame retardant. Specific examples thereof include melamine, melam, melon, melamine silanurate, succinoguanamine, adivoguanamine, methylglutaloganamin, melamine phosphate, melamine resin, and BT resin, but particularly volatility-resistant. From the viewpoint of, melamine cyanurate is preferable.

In order to further improve the impact strength of the resin composition of the present invention, an impact resistance improver which is a styrene thermoplastic elastomer and / or silicone oil can be blended, if necessary.

The styrene thermoplastic elastomer is
It is a block copolymer composed of an aromatic vinyl unit and a conjugated diene unit, or a block copolymer in which the conjugated diene unit portion is hydrogenated.

The aromatic vinyl monomer constituting the block copolymer is the aromatic vinyl monomer described in the explanation of the component (A), and styrene is the most preferable, but styrene is the main component and the other aromatic vinyl monomers are the same. Aromatic vinyl monomers may be copolymerized.

Examples of the conjugated diene monomer which constitutes the above block copolymer include 1,3-butadiene and isoprene.

In the block structure of the block copolymer, a polymer block composed of an aromatic vinyl unit is represented by S, and a polymer block composed of a conjugated diene and / or its hydrogenated unit is represented by B. If SB, S
(BS) n, (where n is an integer of 1 to 3), S (BS
B) n, (where n is an integer of 1 to 2) linear-block copolymer, (SB) n X (where n is an integer of 3 to 6, X is silicon tetrachloride, tin tetrachloride, A coupling agent residue such as a polyepoxy compound), which is a star block copolymer having a B portion as a bond center, is preferable. Among them, SB type 2 and SBS type 3
SBBS type 4 linear-block copolymers are preferred.

The resin composition of the present invention contains 5 to 40 parts by weight of (B) halogenated bisphenol type epoxy resin, based on 100 parts by weight of (A) rubber-modified styrene resin.
1 to 20 parts by weight of (C) antimony oxide is compounded, and if necessary, 0 to 10 parts by weight of (D) light resistance improver,
It is preferable to mix 0 to 30 parts by weight of the (E) fluidity improver. Within the above range, the balance characteristics of flame retardancy, molding processability (fluidity), impact resistance and heat resistance are excellent.

The resin composition of the present invention can be produced by melt-kneading the above components with a commercially available single-screw extruder, twin-screw extruder or the like. In addition, as a method of feeding each component, the resin, the flame retardant, and other additives may be added in a batch feed, or the resin may be added by the top feed and the flame retardant and the other additives may be added by the side feed. Good. At that time, other antioxidants, other ultraviolet absorbers, tin-based heat stabilizers, other inorganic or halogen-based flame retardants, lubricants such as stearic acid and zinc stearate, fillers, reinforcing agents such as glass fibers. A coloring agent such as a dye or a pigment may be added as necessary.

What is important in this decomposition is to melt-extrude at a temperature below the temperature at which decomposition of the component (B), which does not show a decrease in flame retardance, substantially occurs. It is practical to control this temperature as follows. That is, if
When the component (B) is decomposed, the decomposed product is produced in the obtained resin composition, which is due to GPC of the resin composition.
It can be grasped by analysis. Specifically, it can be evaluated by the ratio of peak 1 having an elution time of 18 minutes, as described in Examples described later. In the present invention, the ratio of the peak 1 in the obtained resin composition is preferably 5% or less. Further, in order to satisfy these conditions in a practical extrusion process, setting the melt extrusion temperature of the resin composition to 230 ° C. or lower is a simple index.

By subjecting the composition of the present invention thus obtained to, for example, an injection molding machine or extrusion molding, thermal stability, molding processability (flowability), flame retardancy, heat resistance and impact resistance are obtained. It is possible to obtain an excellent molded product.

[0079]

EXAMPLES The present invention will be described in more detail with reference to examples below, but the present invention is not limited thereto.

The measurements in Examples and Comparative Examples were carried out using the following methods or measuring machines.

(1) Weight average particle diameter of rubber The weight average particle diameter of the rubber-modified aromatic vinyl resin is determined by the particle diameter of the butadiene polymer in the transmission electron micrograph taken by the ultrathin section method of the resin composition. , Calculated by the following formula.

Weight average particle diameter = ΣNi · Di ₄ / ΣNi · Di ₃ (where Ni is the number of butadiene-based polymer particles whose particles are Di). (2) Reduced viscosity ηsp / c per 1 g of resin A mixed solvent of 18 ml of methyl ethyl ketone (MEK) and 2 ml of methanol is added, the mixture is shaken at 25 ° C. for 2 hours, and then centrifuged at 5 ° C. and 18000 rpm for 3 minutes.
The supernatant was taken out and the resin component was precipitated with methanol, and then dried.

0.1 g of the resin thus obtained was added to M
Dissolve in EK to obtain a solution having a concentration of 0.5 g / dl, and put 10 ml of this solution in a Canon-Fenske viscometer.
At 0 ° C., the number of seconds t1 during which the solution flowed was measured. On the other hand, the flowing down time t0 of pure MEK was separately measured with the same viscometer and calculated by the following mathematical formula.

Ηsp / c = (t1 / t0-1) / c
(C: Polymer concentration g / dl) (3) Izod impact strength It was measured at 23 ° C. by a method according to ASTM-D256. (V notch, 1/8 inch test piece) (4) Vicat softening temperature It was measured by a method according to ASTM-D1525 and used as a scale of heat resistance. (5) Melt flow rate (MFR) The melt flow rate was measured by a method according to ASTM-D1238 as an index of fluidity. 1 under a load of 5 kg and a melting temperature of 200 ° C
It was determined from the extrusion rate per 0 minutes (g / 10 minutes). (6) Flame retardance VB (Vertical Bur) compliant with UL-94
Ning) method. (1/8 inch test piece) (7) Pyrolysis behavior (thermogravimetric balance test) Using a Shimadzu thermal analyzer DT-40 under an air stream, 10
The temperature was raised to 550 ° C at a rate of ° C / min, and the thermal decomposition behavior was measured.
Here, the thermal decomposition initiation temperature is the temperature at which the composition decreases by 1% by weight.

Further, the weight loss was measured by standing still at 200 ° C. and 250 ° C. in an air stream.

(8) Analysis of flame retardant composition A. Molecular weight (GPC analysis) 1 g of the resin composition was added to 20 ml of methyl ethyl ketone, stirred for 2 hours, separated by a centrifuge, and the supernatant was measured by gel permeation chromatography (GPC) under the following conditions. It was

Mobile phase: Tetrahydrofuran column: TSK-GEL GMHXL [Tosoh Corp.]
Made] Shodex GPC KF801 [Showa Denko KK]
Device] Device: HLC-8020 manufactured by Tosoh Corp. B. NMR analysis Each of the fractions obtained by the above GPC analysis was fractionated, and a sample was dissolved in deuterated chloroform using a Fourier transform nuclear magnetic resonance apparatus (FT-NMR) [AC200P type 200 MHz manufactured by Bruker Co., Ltd.] to obtain protons. It was identified from the peak intensity and chemical shift.

The following components were used as the components used in Examples and Comparative Examples.

(A) Rubber-modified styrene-based resin (component A) Rubber-modified styrene-based resin (HIPS-1) Commercially available rubber-modified aromatic vinyl resin [Asahi Kasei Co., Ltd. polystyrene / polybutadiene (cis 1,4 bond / Transformer 1,4 bond / vinyl 1,2 bond weight ratio = 95/2
/ 3) = 88/12 (weight ratio) Weight average rubber particle diameter
1.25 μm ηsp / c 0.79] was used. (HI
PS-1) Rubber modified styrene resin (HIPS-2) Commercially available rubber modified aromatic vinyl resin [Asahi Kasei Corporation polystyrene / polybutadiene (cis 1,4 bond / trans 1,4 bond / vinyl 1, 2 bond weight ratio = 95/2
/ 3) = 90/10 (weight ratio) Weight average rubber particle size
1.8 μm ηsp / c 0.60 Liquid paraffin 2
% Content] was used. (Referred to as HIPS-2) Rubber-unmodified styrenic resin (GPPS) Commercially available polystyrene (weight average molecular weight 210,000, number average molecular weight 66,000, no liquid paraffin) [(Asahi Chemical Industry Co., Ltd.) (hereinafter, It is called GPPS)].

(B) Halogenated bisphenol type epoxy resin (component B) Brominated modified epoxy resin (FR-1), manufactured by Dainippon Ink and Chemicals, Inc., trade name Plum E
C-14 was used. (Referred to as FR-1)

[0091]

[Chemical 6]

(C) Antimony Oxide (Component C) Antimony trioxide was used as a flame retardant aid. (FR-
2) (d) Fluidity improver (component E) Liquid paraffin was used as the fluidity improver. (MO
(E) Impact resistance improver Silicone oil (polydimethylsiloxane viscosity 100 cp) was used as an impact resistance improver. (TH-1
The styrene-based thermoplastic elastomer [styrene / butadiene block polymer (40/6
0 weight ratio) manufactured by Asahi Kasei Co., Ltd.] was used. (TH-2
Examples 1 to 12 Comparative Examples 1 to 8 HIPS-1 / HIPS-2 / GPPS / FR-1 / F
R-2 / MO / TH-1 / TH-2 = 50/40/10
A resin composition consisting of /22/5/2/0.05/2 (weight ratio) was produced. That is, a twin-screw extruder capable of side feed (ZS manufactured by Werner Pfleiderer)
K-40 mmφ) was melt-kneaded under the conditions shown in Table 1 at a rotation speed of 295 rpm to produce a resin composition. At that time, the resin temperature is controlled by changing the cylinder temperature, or by changing the shape or number of the screw barts while keeping the cylinder temperature constant at 200 ° C, shear heat generation is performed by using screws with different kneading levels. Controlled by quantity. The resin temperature was measured by inserting a thermocouple thermometer into the resin at the outlet of the die.

Then, a test piece was prepared from the obtained composition by an injection molding machine (resin temperature: 200 ° C.), and the composition was made flame-retardant and MF.
The R and Izod impact strength were evaluated. Table 1,
2 and FIGS. 1 and 2 show the results.

[0094]

[Table 1]

[0095]

[Table 2]

According to Tables 1 and 2 and FIGS.
It can be seen that when the resin is melt-extruded at the following resin temperatures, flame retardancy and impact strength are excellent.

Here, the halogenated bisphenol type epoxy resin (FR-1) is relatively excellent in thermal stability under static conditions. (In air, the weight reduction start temperature at 10 ° C./min and the 1% weight reduction temperature are 255 and 30, respectively.
Weight loss of 5 ° C and 200 ° C and 250 ° C for 30 minutes in air are 0.27 and 1.4, respectively.
It is 3% by weight. ) However, melt extrusion under conditions of 230 ° C. or higher and high shear force causes flame retardancy, particularly drastic addition of fire species, increases MFR, and decreases Izod impact strength. From this fact, it is considered that FR-1 is decomposed.

FIG. 3 shows the GPC analysis results of the compositions having a resin temperature of 230 ° C. or higher (Comparative Example 6) and 230 ° C. or lower (Example 1). Here, the ratio of peak 1 having an elution time of 18 minutes is 7.4% in the former and 3.3% in the latter, and FR-1 decomposes to produce peak 1 at 230 ° C or higher. Conceivable.

FIG. 4 shows the GPC peak 1 and FR-1.
The results of proton-FT-NMR analysis of are shown. FR-1
Has a terminal end capped with a tribromophenyl group,
Detected in pm, the GPC peak 1 is 7.6 pp.
It is not detected in m.

From the above results, it is shown that the tribromophenyl group at the terminal of FR-1 is cleaved by the melt extrusion under the condition of 230 ° C. or higher and high shearing force, and the flame retardancy is lowered.

[0101]

According to the production method of the present invention, a styrene resin composition containing a halogenated epoxy flame retardant having excellent flame retardancy can be obtained. This composition is suitable for home electric appliance parts, OA crisis parts, etc., because the amount of fire drops during combustion is extremely small and it has excellent flame retardancy, impact resistance, heat resistance, and fluidity. The role played by these industries is significant.

[Brief description of drawings]

FIG. 1 is a diagram showing the relationship between resin temperature and flame retardancy during melt extrusion. The horizontal axis represents the resin temperature, and the vertical axis represents the extinction time and the number of drops in 5 molded products.

FIG. 2 is a diagram showing the relationship between resin temperature and physical properties during melt extrusion. The horizontal axis represents the resin temperature, and the vertical axis represents the Izod impact strength and MFR.

FIG. 3 shows a resin temperature of 230 ° C. or higher (Comparative Example 6), 230.
The GPC analysis results of the composition at a temperature of not more than C (Example 1) and the halogenated bisphenol type epoxy resin (FR-1) are shown. Here, the ratio of peak 1 having an elution time of 18 minutes is 7.4% for the former and 3.3% for the latter.

FIG. 4 Broton-F of GPC peak 1 and FR-1
The T-NMT analysis results are shown. The end of FR-1 is capped with a tribromophenyl group and is detected at 7.6 ppm, but the GPC peak 1 is not detected at 7.6 ppm.

Claims (2)

[Claims] 1. A rubber-modified styrene resin, (B)
Halogenated bisphenol type epoxy resin, and (C)
In a method for producing a resin composition containing antimony oxide, a halogenated epoxy flame retardant characterized by melt-extruding at a resin temperature below a temperature at which decomposition of the halogenated bisphenol type epoxy resin substantially occurs. The manufacturing method of the styrene resin composition containing. 2. The method for producing a styrene resin composition according to claim 1, wherein the resin composition is melt-extruded at a resin temperature of 230 ° C. or lower.