JPH0892474A - Flame-retardant resin composition with excellent impact resistance - Google Patents

Abstract

PURPOSE: To obtain a flame-retardant resin composition with excellent impact resistance which does not contain any halogen element causative of a toxic or harmful gas by compounding specific resins with a specific compound. CONSTITUTION: This resin composition comprises 10-85wt.% aromatic polycarbonate, 10-85wt.% rubber-reinforced styrene resin obtained by polymerizing an aromatic vinyl monomer in the presence of a rubbery polymer having a glass transition temp. (Tg) of -30 deg.C or lower, 0.5-20wt.% aromatic vinyl/vinyl cyanide copolymer having an average vinyl cyanide content of 1-10wt.%; 1-30wt.% poly(phenylene ether), and 1-30wt.% organophosphorus compound, especially preferably an aromatic monophosphoric ester or an aromatic condensed phosphoric ester.

Description

Detailed Description of the Invention

[0001]

The present invention relates to a resin composition. More specifically, it relates to a resin composition having excellent impact resistance and flame retardancy.

[0002]

2. Description of the Related Art Polycarbonate resin, rubber-reinforced styrene resin, ABS resin, polycarbonate resin and ABS
As a means for imparting flame retardancy to a resin composition, a method of blending a halogen-based flame retardant is widely used. However, the halogen-based flame retardant has an inherent problem of generating toxic and harmful gas during combustion.

As the flame-retardant resin containing no halogen-based flame retardant, a resin composition obtained by blending a polycarbonate resin and an ABS resin with an organic phosphorus compound, polyphenylene ether.
There are resin compositions in which a telluric resin and a rubber-reinforced styrene resin are blended with an organic phosphorus compound, and among them, a resin composition obtained by blending a polycarbonate resin and an ABS resin with an organic phosphorus compound has impact resistance and difficulty. Various attempts have been made with excellent flammability. For example, in JP-A-2-32154,
It is described that a composition comprising a polycarbonate resin, an ABS resin, an organic phosphorus compound and a tetrafluoroethylene polymer gives excellent impact resistance and flame retardancy.

In Japanese Patent Application Laid-Open No. 2-115262, a composition comprising a polycarbonate resin, an ABS resin and a phosphoric acid ester condensate is a flame-retardant composition without squeezing. Is listed. However, in the evaluation of the flame retardancy test UL-94, it is V-2 because dripping was observed during combustion in the system without the tetrafluoroethylene polymer. German Patent Application Publication No. 420024
No. 7 discloses a resin composition obtained by blending a polycarbonate resin, a polyphenylene ether resin, an ABS resin, a phosphoric acid ester compound and a tetrafluoroethylene polymer, and the resin composition is It is described that it is superior in heat resistance to a resin composition containing no polyphenylene ether resin.

However, a flame-retardant resin composition prepared by blending a polycarbonate resin, a polyphenylene ether resin, an ABS resin, a phosphoric ester compound and a tetrafluoroethylene polymer is also a polyphenylene ether resin. It is described that the resin compositions not blended also have no difference in flame retardancy at V-0 in the combustion test UL-94 evaluation. In order to achieve V-0 and V-1 in the combustion test UL-94 evaluation, it is essential that these resin compositions contain a tetrafluoroethylene polymer as a drip inhibitor during combustion. However, since the tetrafluoroethylene polymer contains fluorine as a halogen-based element, it has a problem that a toxic or harmful gas is generated during combustion.

[0006]

In view of the above situation, an object of the present invention is to provide a resin composition which does not contain any halogen-based element which is a base of generation of toxic or harmful gas, and is excellent. Another object of the present invention is to provide a resin composition having impact resistance and flame retardancy.

[0007]

Means for Solving the Problems The present inventors have made various studies on resin compositions having excellent impact resistance, containing no halogen-based element, and exhibiting flame retardance without dropping during combustion, As a result, they have found that the resin composition shown below exhibits excellent impact resistance and flame retardancy, and have completed the present invention.

That is, according to the present invention, (A) 10 to 85% by weight of aromatic polycarbonate, (B) glass transition temperature (T
g) rubber-reinforced styrene resin obtained by polymerizing an aromatic vinyl monomer in the presence of a rubber-like polymer having a temperature of -30 ° C or less 10
A copolymer composed of an aromatic vinyl monomer and a vinyl cyanide monomer, which contains 1 to 10% by weight of (C) vinyl cyanide monomer as an average composition, is 0.5 to 20% by weight. , (D) 1 to 30% by weight of polyphenylene ether and (E) 1 to 30% by weight of organic phosphorus compound, which is a flame-retardant resin composition having excellent impact resistance.

The aromatic polycarbonate (A) used in the present invention is obtained by polymerizing an aromatic vinyl monomer in the presence of a rubbery polymer (B) having a glass transition temperature (Tg) of -30 ° C or lower. With the rubber-reinforced styrene resin thus obtained, the strength of the molded product is maintained, and a carbonized film is formed during combustion to impart flame retardancy. (B) A rubber-reinforced styrene resin obtained by polymerizing an aromatic vinyl monomer in the presence of a rubbery polymer having a glass transition temperature (Tg) of −30 ° C. or lower is (A) an aromatic polycarbonate. It is a component that further improves the impact resistance of.

(D) Polyphenylene ether is (B)
(B) Glass transition temperature (Tg) is compatible with a rubber-reinforced styrene resin obtained by polymerizing an aromatic vinyl monomer in the presence of a rubbery polymer having a temperature of -30 ° C or lower (B) Glass transition temperature (T
g) suppresses thermal decomposition of a rubber-reinforced styrene resin obtained by polymerizing an aromatic vinyl monomer in the presence of a rubber-like polymer having a temperature of -30 ° C or lower, and (A) an aromatic polycarbonate. Similarly, it is a component for forming a carbonized film during combustion and imparting flame retardancy.

The copolymer (C) consisting of the vinyl cyanide monomer and the aromatic vinyl monomer containing 1 to 10% by weight of the vinyl cyanide monomer as an average composition is (A).
Aromatic polycarbonate and (B) glass transition temperature (T
(g) Improving the interfacial strength with the component (D) polyphenylene ether compatible with the rubber-reinforced styrene resin obtained by polymerizing an aromatic vinyl monomer in the presence of a rubbery polymer having a temperature of -30 ° C or less. To produce high impact resistance.

The organic phosphorus compound (E) is a component for imparting flame retardancy. The (A) aromatic polycarbonate used in the present invention is a phosgene method of blowing an aromatic divalent phenol compound in the presence of caustic alkali and a solvent, or an aromatic divalent phenol compound. The aromatic homo- or copolycarbonate is obtained by a transesterification method in which the ester and the diethyl carbonate are transesterified in the presence of a catalyst. The aromatic homo- or copolycarbonate preferably has a viscosity average molecular weight of 10,000 to 1,000,000.

Here, the divalent phenol compound is
2,2'-bis (4-hydroxyphenyl) propane,
2,2'-bis (4-hydroxy-3,5-dimethylphenyl) propane, bis (4-hydroxyphenyl) methane, 1,1'-bis (4-hydroxyphenyl) ethane, 2,2'-bis ( 4-hydroxyphenyl) butane, 2,2'-bis (4-hydroxy-3,5-diphenyl) butane, 2,2'-bis (4-hydroxy-3,
5-dipropylphenyl) propane, 1,1′-bis (4-hydroxyphenyl) cyclohexane, 1-phenyl-1,1′-bis (4-hydroxyphenyl) ethane and the like, especially 2,2′-bis (4-Hydroxyphenyl) propane [bisphenol A] is preferred. The divalent phenol compound of the present invention may be used alone or in combination.

(B) Glass transition temperature (T
g) is a rubber-reinforced styrene resin obtained by polymerizing an aromatic vinyl monomer in the presence of a rubbery polymer having a temperature of −30 ° C. or lower,
As shown below, it is a resin having a rubber-like polymer as dispersed particles and a polymer of an aromatic vinyl monomer as a continuous phase. Examples of the rubber-like polymer to be polymerized include polybutadiene, styrene-butadiene block copolymer, hydrogenated (or partially hydrogenated) polybutadiene, hydrogenated (or partially hydrogenated) styrene-butadiene block copolymer, polyisoprene, styrene. -Isoprene copolymer, acrylic rubber such as polybutyl acrylate, and ethylene-propylene-diene monomer-terpolymer (EPDM).

Examples of the aromatic vinyl monomer to be polymerized include styrene, α-methylstyrene, p-methylstyrene, pt-butylstyrene and the like, which may be used alone or in a mixture. Preferred is styrene. As a method for producing these resins, a known method, for example, a rubber-like polymer is dissolved in a styrene-based monomer or a polymerization solvent thereof, and a catalyst and a chain transfer agent are added to a raw material solution in which the rubber-like polymer is dissolved. The resulting solution is fed to a reactor equipped with a stirrer, and the temperature of 100 ° C ~
Polymerization is performed within a temperature range of 180 ° C., and after the completion of the polymerization, a rubber-reinforced styrene resin is obtained by processing under high temperature vacuum to remove unreacted monomers and a polymerization solvent.

The copolymer of vinyl cyanide monomer and aromatic vinyl monomer having an average composition of 1 to 10% by weight of vinyl cyanide monomer (C) used in the present invention is
Reduced viscosity (0.5 g / dl, methyl ethyl ketone solution,
The measurement (at 30 ° C.) is preferably in the range of 0.3 to 0.8 dl / g, and more preferably 0.4 to 0.7 dl / g. Examples of the aromatic vinyl monomer include styrene, α-methylstyrene, p-methylstyrene, pt-butylstyrene, and the like, and preferably styrene. Examples of the vinyl cyanide monomer include acrylonitrile and methacrylonitrile, and acrylonitrile is preferable.

The copolymer of the above-mentioned aromatic vinyl monomer and the above-mentioned vinyl cyanide monomer used in the present invention has a uniform composition of the vinyl cyanide monomer in the copolymer. ,
It may be uneven. Further, it may be a blend of a copolymer of an aromatic vinyl monomer having a different content of vinyl cyanide monomer and a vinyl cyanide monomer, but preferably the vinyl cyanide monomer is continuously composed. It is a copolymer with distribution.

When the average composition of the vinyl cyanide monomer in the copolymer of the aromatic vinyl monomer and the vinyl cyanide monomer is less than 1% by weight, the aromatic polycarbonate (A) is used. The interfacial strength with and decreases, and the impact resistance is poor. When the average composition of vinyl cyanide monomer is 10% by weight or more,
(B) The rubber-reinforced styrene resin obtained by polymerizing an aromatic vinyl monomer in the presence of a rubber-like polymer having a glass transition temperature (Tg) of −30 ° C. or less reduces the interfacial strength and reduces the impact resistance. descend.

If necessary as a component of the copolymer,
One or more monomer components copolymerizable with the aromatic vinyl monomer and the vinyl cyanide monomer can be introduced. The above-mentioned copolymerizable monomer component is an acrylic acid ester monomer composed of an alkyl group having 1 to 8 carbon atoms such as methyl acrylate and butyl acrylate, and has 1 to 8 carbon atoms such as methyl methacrylate. Α, β such as methacrylic acid ester monomer consisting of alkyl group, maleic anhydride, itaconic anhydride
An unsaturated carboxylic acid anhydride monomer or a maleimide-based monomer such as maleimide, N-methylmaleimide or N-phenylmaleimide.

As a method for producing these resins, a known method, for example, a styrene-based monomer, a vinyl cyanide monomer, a polymerization solvent, and a liquid in which a catalyst and a chain transfer agent are added are stirred to form a laminar flow reaction. Supply to a vessel or a complete mixing type reactor, 100 ℃ ~
Polymerization is carried out in a temperature range of 180 ° C., and after the completion of the polymerization, a copolymer is obtained by treating under a high temperature vacuum in order to remove unreacted monomers, a polymerization solvent and the like. A laminar flow reactor produces a copolymer having a compositional distribution and a non-uniform composition, and a complete mixing reactor produces a copolymer having a non-uniform compositional composition.

Reduced viscosity of the above copolymer (0.5 g / d
1, methyl ethyl ketone solution, measured at 30 ° C.) is 0.3
To 0.8 dl / g, preferably 0.4
More preferably, it is in the range of 0.7 dl / g. (D) polyphenylene ether used in the present invention (hereinafter referred to as P
PE is abbreviated as PE) is a homopolymer and / or a copolymer composed of a bonding unit represented by the following formula.

[0022]

[Chemical 1]

However, R1, R2, R3, and R4 are each selected from the group consisting of hydrogen, hydrocarbons, and substituted hydrocarbon groups, and may be the same or different from each other. As a specific example of this PPE, poly (2,6-
Dimethyl-1,4-phenylene ether), a copolymer of 2,6-dimethylphenol and 2,3,6-trimethylphenol, and the like are preferable, and among them, poly (2,6-dimethyl-1,4-phenylene ether). Is preferred.

The method for producing such PPE is not particularly limited, and for example, US Pat. No. 3,306,874 is used.
Can be easily produced by oxidative polymerization of 2,6 xylenol, for example, by using a complex of a cuprous salt and an amine as a catalyst according to the method described in U.S. Pat. No. 3,3061075, U.S. Pat. Patent No. 3,257,357, US Pat. No. 3,257,3
It can be easily produced by the method described in Japanese Patent No. 58, Japanese Patent Publication No. 52-17880 and Japanese Patent Publication No. 50-51197.

Reduced viscosity of the above PPE used in the present invention (0.5 g / dl, chloroform solution, measured at 30 ° C.)
Is preferably in the range of 0.20 to 0.70 dl / g, more preferably in the range of 0.30 to 0.60 dl / g. Examples of means for satisfying the above requirements regarding the reduced viscosity of PPE include adjustment of the amount of catalyst during production of the PPE.

The (E) organophosphorus compound used in the present invention is
For example, phosphine, phosphine oxide, biphosphine, phosphonium salt, phosphinate, phosphoric acid ester, phosphorous acid ester and the like. More specifically, triphenyl phosphate, methyl neopentyl phosphite, hentaerythritol diethyldiphosphite, methyl neopentyl phosphate, phenyl neopentyl phosphate, pentaerythritol. Diphenyl diphosphate, dicyclopentyl hypophosphite, dineopentyl hypophosphite,
Phenyl pyrocatechol phosphite, ethyl pyrocatechol phosphate and dipyrrocatechol hypophosphite. In particular, as the organic phosphorus compound, aromatic monophosphoric acid ester (Chemical Formula 2) and aromatic condensed phosphoric acid ester (Chemical Formula 3) are preferable.

[0027]

[Chemical 2]

[0028]

[Chemical 3]

(However, Ar1, Ar2, Ar3, Ar4
, Ar5 and Ar6 are aromatic groups selected from a phenyl group, a xylenyl group, an ethylphenyl group, an isopropylphenyl group, a butylphenyl group and a 4,4'-dioxydiarylalkane group. Further, n represents an integer of 0 to 3, and m represents an integer of 1 or more. The resin composition of the present invention has (A) 10 to 85% by weight of aromatic polycarbonate and (B) a glass transition temperature (Tg) of −.
10 to 85% by weight of a rubber-reinforced styrene resin obtained by polymerizing an aromatic vinyl monomer in the presence of a rubbery polymer at 30 ° C. or less, and (C) a vinyl cyanide monomer as an average composition of 1
0.5 to 20% by weight of a copolymer comprising an aromatic vinyl monomer and a vinyl cyanide monomer, the content of which is 10 to 10% by weight,
(D) 1 to 30% by weight of PPE, (E) organic phosphorus compound 1
It is a flame-retardant resin composition, characterized in that it contains 30 wt%.

Further, the composition ratio of the resin composition of the present invention is
Preferably, (A) aromatic polycarbonate 25 to 7
5% by weight, (B) 15 to 70% by weight of a rubber-reinforced styrene resin obtained by polymerizing an aromatic vinyl monomer in the presence of a rubber-like polymer having a glass transition temperature (Tg) of -30 ° C or less,
(C) The vinyl cyanide monomer has an average composition of 1 to 10
1 to 15% by weight of a copolymer composed of an aromatic vinyl monomer and a vinyl cyanide monomer contained in an amount of (D) PPE2
.About.20 wt%, and (E) an organic phosphorus compound 2 to 30 wt%.

(A) The aromatic polycarbonate is 10
If it is less than 10% by weight, impact resistance and flame retardancy will decrease, and
Even if it exceeds 85% by weight, impact resistance and flame retardancy are deteriorated. (B) When the rubber-reinforced styrene resin obtained by polymerizing an aromatic vinyl monomer in the presence of a rubber-like polymer having a glass transition temperature (Tg) of -30 ° C or less is less than 10% by weight, impact resistance is lowered. However, the flame retardancy exceeding 85% by weight is reduced. (C) Vinyl cyanide monomer having an average composition of 1 to 1
If the content of the copolymer containing 0% by weight of an aromatic vinyl monomer and a vinyl cyanide monomer is less than 0.5% by weight, the impact resistance decreases, and if it exceeds 20% by weight, the impact resistance decreases. descend. (D) If the PPE is less than 1% by weight, the flame retardancy decreases,
If it exceeds 30% by weight, the impact resistance decreases.

If the organic phosphorus compound (E) is less than 1% by weight, the flame retardancy is lowered, and if it exceeds 30% by weight, the impact resistance is lowered. The resin composition of the present invention may be blended with (F) polystyrene resin, if necessary. If necessary, the resin composition of the present invention may be blended with (G) a thermoplastic elastomer, and examples thereof include polystyrene-based, polyolefin-based, polyester-based, polyurethane-based, 1,2-polybutadiene-based, and polyvinyl chloride. In this case, polystyrene-based thermoplastic elastomer is particularly preferable.

The above polystyrene-based thermoplastic elastomer
Is a block copolymer composed of an aromatic vinyl unit and a conjugated diene unit, or a block copolymer partially hydrogenated at the conjugated diene unit portion. The aromatic vinyl monomer constituting the block copolymer is obtained by polymerizing the aromatic vinyl monomer in the presence of the rubber-like polymer (B) having a glass transition temperature (Tg) of −30 ° C. or lower. Among the aromatic vinyl monomers described in the description of the rubber-reinforced styrene resin, styrene is most preferable, but styrene may be the main component and other 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 partially hydrogenated unit is represented by B. In this case, SB, S (BS) n, (where n is an integer of 1 to 3), S (BSB) n, (where n is an integer of 1 to 2)
Linear block copolymer of (SB) nX (however,
n is an integer of 3 to 6. X is a coupling agent residue such as silicon tetrachloride, tin tetrachloride and polyepoxy compound. It is preferable that it is a star-shaped block copolymer having a B portion as a bond center, which is represented by (4). Among them, SB type 2,
SBS type 3 and SBBS type 4 linear-block copolymers are preferred.

The resin composition of the present invention, if necessary,
One or more (H) light resistance improvers selected from ultraviolet absorbers, hindered amine light stabilizers, antioxidants, light-shielding agents, metal deactivators, and quenchers can be added. 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). ), And is a component for releasing and detoxifying as heat energy. A specific example is
2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-
Octoxybenzophenone, 5,5′-methylenebis (2-hydroxy-4-methoxybenzophenone), etc. 2-hydroxybenzophenones, 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-chlorobenzotriazol, 2- (2'-hydroxy-3 ', 5'-dicumylphenyl) benzotriazole, 2 , 2'-methylenebis (4-t-octyl-6-benzotriazolyl) phenol and the like, 2- (2 '
-Hydroxyphenyl) benzotriazoles, phenyl salicylates, resorcinol monobenzoates,
2,4-di-t-butylphenyl-3 ′, 5′-di-t
-Butyl-4'-hydroxybenzoate, hexadecyl-3,5-di-t-butyl-4-hydroxybenzoate, and other benzoates, 2-ethyl-2'-atoxyoxanilide , 2-ethoxy-4′-dodecyl oxanilide and other substituted oxanilides, and ethyl-α-cyano-β, β-diphenyl acrylate, methyl-2-cyano-3-methyl-3- (p- Cyanoacrylates such as methoxyphenyl) acrylate.

The hindered amine-based 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. Is. 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-
Butane tetracarboxylate, bis (1, 2, 2,
6,6-Pentamethyl-4-piperidyl) -di (tridecyl) -1,2,3,4-butanetetracarboxylate
G., 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 (2,2,6,6-tetramethyl-4-piperidylamino) hexane / 2,4-dichloro-6-morpholino-s-triazine polycondensate and the like.

The above-mentioned antioxidant stabilizes peroxide radicals such as hydroperoxy radicals produced by thermoforming or exposure to light, or produces hydroperoxide.
It is a component for decomposing peroxides such as oxides.
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 formed in the system into more stable alcohols to prevent autoxidation.

The hindered phenol type antioxidant is 2,6-di-tert-butyl-4-methylphenol.
Le, styrenate dephenol, n-octadecyl 3
-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate, 2,2'-methylenerubbis (4
-Methyl-6-tert-butylbutylphenol), 2-tert-butyl-6- (3-tert-butyl-2-hydroxy-5-methylbenzyl) -4-methylphenyl acrylate, 2- [1- (2-hydroxy-3,5-
Di-charpentylphenyl) ethyl] -4,6-di-charpentylphenyl acrylate, 4,4'-
Butylidenebis (3-methyl-6-tert-butylbutylphenol), 4,4'-thiobis (3-methyl-6-tert-butylbutylphenol), alkylated bisphenol, tetrakis [methylene 3- (3,5-dither
Charbutyl-4-hydroxyphenyl) propione
To] methane, 3,9-bis [2- [3- (3-tert-butyl-4-hydroxy-5-methylphenyl) -propionyloxy] -1,1-dimethylethyl] -2,
4,8,10-tetraoxaspiro [5.5] undecane and the like.

The peroxide decomposer is trisnonylphenyl phosphite, triphenyl phosphite,
Organophosphorus peroxide decomposers such as tris (2,4-di-tert-butylphenyl) phosphite or dilauryl 3,3′-thiodipropionate, dimyristyl 3,
3'-thiodipropionate, distearyl 3,3'-
It is an organic sulfur-based peroxide decomposing agent such as thiodipropione, pentaerythrityl tetrakis (3-laurylthiopropionate), ditridecyl 3,3′-thiodipropionate, and 2-mercaptobenzimidazole.

The light-shielding agent is a component for preventing light from reaching the polymer bulk. Specific examples thereof include rutile type titanium oxide (TiO2), zinc oxide (ZnO), chromium oxide (Cr2 O3), cerium oxide (CeO2) 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 derivatives thereof. The quencher is
Organic nickel or the like is a component for deactivating photoexcited functional groups such as hydroperoxide and carbonyl groups in polymers by energy transfer.

Examples of the apparatus for producing the resin composition of the present invention include an extruder, a Banbury mixer, a roller and a kneader. A method using an extruder is preferable, and the melt extrusion method may be such that all the components are melt-extruded at the same time, or first, the resin component [(A) aromatic polycarbonate, (B) glass transition temperature is used. A rubber-reinforced styrene resin obtained by polymerizing an aromatic vinyl monomer in the presence of a rubbery polymer having a (Tg) of -30 ° C or less, and (C) a vinyl cyanide monomer having an average composition of 1 to 10% by weight. %, A copolymer comprising an aromatic vinyl monomer and a vinyl cyanide monomer, (D) PPE is melt-extruded, and then a polymer additive is melt-extruded again, or a sequential extrusion method or a plurality of There is a one-stage extrusion method in which a resin component is melted in the former stage by an extruder composed of a resin and a polymer additive other than the resin component is melt-extruded in the latter stage.

The resin composition of the present invention can be obtained by melt-kneading according to the above-mentioned method. At that time, other antioxidants, other ultraviolet absorbers, lubricants such as stearic acid and zinc stearate, and fillers. A reinforcing agent such as glass fiber, a coloring agent such as a dye or a pigment, and the like can be added as necessary. The resin composition of the present invention thus obtained,
For example, by injection molding or extrusion molding, a molded product having excellent moldability, flame retardancy and impact resistance can be obtained.

[0043]

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 performed using the following methods or measuring machines. (1) The average composition of (C) vinyl cyanide monomer is 1
Reduced Viscosity of Copolymer Consisting of Aromatic Vinyl Monomer and Vinyl Cyanide Monomer Containing 10 to 10% by Weight The copolymer is dissolved in methyl ethyl ketone to give a concentration of 0.5 g.
/ Dl solution, 10 ml of this solution was placed in a Canon-Fenske viscometer, and the solution was allowed to flow at a temperature of 30 ° C for several seconds t1.
Was measured. On the other hand, the flowing down time t0 of pure methyl ethyl ketone 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)

(2) Reduced viscosity of PPE ηsp / C PPE was dissolved in chloroform to give a solution having a concentration of 0.5 g / dl, 10 ml of this solution was placed in a Canon-Fenske viscometer, and the solution was allowed to flow at 30 ° C. The number of seconds t1 was measured. On the other hand, the flowing seconds t0 of pure chloroform 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) The average composition of (C) vinyl cyanide monomer is 1
Amount of average acrylonitrile unit of copolymer consisting of aromatic vinyl monomer and vinyl cyanide monomer contained by 10% by weight (% by weight) A film was prepared by compression of the copolymer, and an infrared absorption meter was used. An infrared absorption spectrum was obtained at -CN group (2
220 cm-1) It was calculated from the absorption intensity ratio of the phenyl group (1600 cm-1).

(4) Composition of acrylonitrile units in a copolymer composed of an aromatic vinyl monomer and a vinyl cyanide monomer containing (C) 1 to 10% by weight of a vinyl cyanide monomer as an average composition. Presence of distribution Dissolve the copolymer in tetrahydrofuran (THF) and
Prepare a 125% solution and measure by liquid chromatography. Liquid Chromatography (manufactured by Shimadzu) Column ZORBAK-CN 45 ° C Solvent THF / Heptane Gradient THF / Heptane (20/80) → THF / Heptane (100/0) Detector UV (254 nm) (5) Izod impact strength ASTM-D256 Was measured at 23 ° C. (V notch, 1/8 inch test piece)

(6) Flame retardance VB (Vertical Bur) compliant with UL-94
(1/8 inch test piece). V- ○: Flame-extinguishing time (sec) Average ≤ 5 Maximum 10 drops None V-1: Flame-extinguishing time (sec) Average ≤ 25 Max 30 Drops None V-2: Flame-extinguishing time (sec) Average ≤ 25 Max 30 Drops None PUT: Flame-extinguishing time (sec) Average ≤25 Maximum 30 (when not corresponding to V-0, V-1, V-2) (1) (A) Aromatic polycarbonate (hereinafter referred to as PC) A commercially available bisphenol A type polycarbonate (trade name: Panlite L1250, manufactured by Teijin Chemicals Ltd.) was used. (2) (B) A rubber-reinforced styrene resin (referred to as HIPS) obtained by polymerizing an aromatic vinyl monomer in the presence of a rubbery polymer having a glass transition temperature (Tg) of −30 ° C. or less, commercially available HIPS ( Asahi Kasei Kogyo Co., Ltd. product name Asahi Kasei polystyrene H8117) was used.

(3) (C) Copolymer of aromatic vinyl monomer and vinyl cyanide monomer [styrene-acrylonitrile copolymer, (hereinafter referred to as AS)] C-1; styrene 81. A mixed solution prepared by blending 100 parts by weight of a mixed solution of 6% by weight, 3.4% by weight of acrylonitrile, and 15.0% by weight of ethylbenzene with 0.03 parts by weight of t-butylperoxypropylisopropyl carbonate as a polymerization catalyst. It is fed at a rate of 0.7 liter / HR to a polymerization apparatus in which three 1.3 liter laminar flow type reactors are arranged in series, polymerization is carried out at a polymerization temperature of 120 to 160 ° C., and a polymerization solution is added (final reactor). (The solid content of the polymerized solution was 69% by weight) 23
The polymer was introduced into an extruder equipped with a vacuum vent, which was heated to 0 ° C., and the unreacted monomer and solvent were separated by evaporation to obtain a polymer.
The acrylonitrile (hereinafter, AN)% in the copolymer is
It has a composition distribution of 4.4% by weight according to liquid chromatography analysis. The reduced viscosity (30 ° C.) of the polymer dissolved in methyl ethyl ketone was 0.49 dl / g.

C-2: Styrene 79.0% by weight, AN
In 100 parts by weight of a mixed solution of 6.0% by weight and 15.0% by weight of ethylbenzene, 0.03 parts by weight of t-butyl peroxyisopropyl carbonate as a polymerization catalyst and 0.05 parts by weight of α-methylstyrene dimer were used. The mixed solution containing 1 part was fed at a rate of 0.7 liter / HR to a polymerization apparatus in which three liter laminar flow reactors were arranged in series, and polymerization was performed at a polymerization temperature of 120 to 160 ° C. The polymerization liquid (the solid content in the polymerization liquid discharged from the final reactor was 69% by weight) was introduced into an extruder with a vacuum vent heated to 230 ° C., and an unreacted monomer was introduced.
And the solvent was evaporated to obtain a polymer.

The AN% in the copolymer is 8.3% by weight,
It has a composition distribution by liquid chromatography analysis. Also, reduced viscosity (30%) obtained by dissolving a polymer in methyl ethyl ketone.
C.) was 0.52 dl / g. C-3; styrene 83.3% by weight, AN 1.7% by weight,
A laminar flow reactor of 1.3 liters was prepared by mixing 100 parts by weight of a mixed solution of 15.0% by weight of ethylbenzene with 0.03 part by weight of t-butyl peroxyisopropyl carbonate as a polymerization catalyst. Was supplied at a rate of 0.7 liter / HR to a polymerization apparatus in which 3 units were arranged in series, polymerization was carried out at a polymerization temperature of 120 to 160 ° C., and the polymerization liquid was added (solid content in the polymerization liquid discharged from the final reactor was 69 (Wt%) was introduced into an extruder equipped with a vacuum vent, which was heated to 230 ° C., and the unreacted monomer and the solvent were separated by evaporation to obtain a polymer.

AN% in the copolymer is 2.0% by weight,
It has a composition distribution by liquid chromatography analysis. Also, reduced viscosity (30%) obtained by dissolving a polymer in methyl ethyl ketone.
C.) was 0.45 dl / g. C-4: 100 parts by weight of a mixed solution of 69.6% by weight of styrene, 10.4% by weight of AN and 20.0% by weight of ethylbenzene, and 0.03 part by weight of t-butyl peroxyisopropyl carbonate as a polymerization catalyst. And 0.1 part by weight of α-methyl styrene dimer were mixed at a rate of 0.7 liter / HR to a polymerization apparatus in which three 1.3 liter laminar flow reactors were arranged in series. , Polymerization temperature 120
Polymerization is carried out at ˜160 ° C., and the polymerization liquid (solid content in the polymerization liquid discharged from the final reactor is 69% by weight) is introduced into an extruder with a vacuum vent heated to 230 ° C. to evaporate unreacted monomers and solvent. Separation gave a polymer.

AN% in the copolymer is 13.3% by weight.
Therefore, it has a composition distribution by liquid chromatography analysis. In addition, the reduced viscosity of a polymer dissolved in methyl ethyl ketone (3
(0 ° C.) was 0.52 dl / g. C-5; styrene 81.6% by weight, AN 3.4% by weight,
A 2.2-liter complete mixing type reactor was prepared by mixing 100 parts by weight of a mixed solution of 15.0% by weight of ethylbenzene with 0.03 part by weight of t-butyl peroxyisopropyl carbonate as a polymerization catalyst. To 1.0 liter /
It is supplied at a rate of HR and polymerized at a polymerization temperature of 140 ° C. to obtain a polymerization liquid (the solid content in the polymerization liquid discharged from the final reactor is 46% by weight).
Introduced into an extruder with a vacuum vent heated to 230 ° C,
The unreacted monomer and the solvent were separated by evaporation to obtain a polymer.

The AN% in the copolymer is 4.9% by weight,
The composition is uniform by liquid chromatography analysis. The reduced viscosity (30 ° C.) of the polymer dissolved in methyl ethyl ketone was 0.53 dl / g. C-6; 73.3% by weight of styrene, 4.7% by weight of AN,
A mixed solution of 100 parts by weight of 22.0% by weight of ethylbenzene and 0.02 parts by weight of t-butyl peroxyisopropyl carbonate as a polymerization catalyst was added to a 5.0-liter complete mixing reactor. To 2.4 liters /
It is fed at a rate of HR and polymerized at a polymerization temperature of 142 ° C. to obtain a polymerization liquid (solid content in the polymerization liquid discharged from the final reactor is 46% by weight).
Introduced into an extruder with a vacuum vent heated to 230 ° C,
The unreacted monomer and the solvent were separated by evaporation to obtain a polymer.

The AN% in the copolymer is 9.0% by weight,
The composition is uniform by liquid chromatography analysis. The reduced viscosity (30 ° C.) of the polymer dissolved in methyl ethyl ketone was 0.43 dl / g. C-7: 100 parts by weight of a mixed solution of 65.0% by weight of styrene, 10.0% by weight of AN and 25.0% by weight of ethylbenzene, and 0.02 parts by weight of t-butyl peroxyisopropyl carbonate as a polymerization catalyst. The mixed solution containing 1 part was fed to a 1.9-liter complete mixing type reactor at a rate of 1.2 liters / HR and polymerized at a polymerization temperature of 140 ° C. to obtain a polymerization liquid (in the polymerization liquid of the final reactor). (Solid content of 33% by weight) is introduced into an extruder equipped with a vacuum vent, which is heated to 230 ° C., the unreacted monomer and the solvent are separated by evaporation, and the polymer is added.
Got

AN% in the copolymer is 12.0% by weight.
Therefore, the composition is uniform by liquid chromatography analysis. In addition, the reduced viscosity of a polymer dissolved in methyl ethyl ketone (30
C.) was 0.54 dl / g. (4) The following were used as (D) PPE. After fully replacing the inside of a stainless steel reactor having an oxygen blowing port at the bottom of the reactor with a cooling coil and stirring blades with nitrogen, 54.8 g of cupric bromide and 1110 g of di-n-butylamine. , And toluene, 20 liters, n-butanol, 16 liters, and methanol, 4 liters, were dissolved in a mixed solvent of 8.75 kg of 2,6-xylenol and charged into a reactor. Oxygen was continuously blown into the reactor while stirring, and polymerization was performed for 180 minutes while controlling the internal temperature to 30 ° C.

After completion of the polymerization, the precipitated polymer was filtered off. A methanol / hydrochloric acid mixture was added to this to decompose the residual catalyst in the polymer, which was further thoroughly washed with methanol and dried to obtain a powdery PPE. Reduced viscosity η
SP was 0.55 dl / g. Since PPE resin has a high melting temperature, polystyrene resin (Asahi Kasei Corp. product name Asahi Kasei polystyrene 685) / PPE = 30
Master extruded / 70 at 300 ° C in advance
Pellets were used (hereinafter referred to as M-PPE).

(5) (E) Organophosphorus compound Triphenyl phosphate as a commercially available aromatic monophosphate ester [trade name: TPP manufactured by Daihachi Chemical Industry Co., Ltd.]
(Referred to as TPP)] and phenylresorcin polyphosphate [trade name CR733S (hereinafter referred to as 733S) manufactured by Daihachi Chemical Industry Co., Ltd.] were used as the aromatic condensed phosphoric acid ester. (6) (G) Polystyrene resin Commercially available polystyrene resin (Asahi Kasei Kogyo KK, trade name Asahi Kasei Polystyrene 685)

[0057]

[Examples 1 to 12, Comparative Examples 1 to 8] PC / HIPS / AS
/ M-PPE / TPP were mixed in the weight ratios shown in Tables 1 and 2 and a twin-screw extruder (manufactured by Nakatani Co., Ltd.) at a temperature of 260 ° C.
Melt kneading with 30 mmΦ). The pellets thus obtained are injected into an injection molding machine (trade name IS manufactured by Toshiba Machine Co., Ltd.).
Cylinder temperature at 55 EPN) 240 ° C, mold temperature 60
Test pieces were prepared under the condition of ° C and various physical properties were evaluated. The results are shown in Tables 1 and 2. According to Table 1 and Table 2, the resin composition of the present invention has excellent impact resistance and flame retardancy.

[0058]

[Table 1]

[0059]

[Table 2]

[0060]

INDUSTRIAL APPLICABILITY The resin composition of the present invention has higher impact resistance and flame retardancy than conventional resin compositions which do not contain any halogen-based element which is a base for generating toxic or harmful gas. It is excellent. This resin composition is used for home electric appliances, O
It is suitable for A equipment parts, etc., and plays a large role in these industries.

[Brief description of drawings]

FIG. 1 shows a chart of liquid chromatography measurement of C-1.
It is observed from the chart that the copolymer has a composition distribution.

FIG. 2 shows a chart of liquid chromatography measurement of C-5.
It is observed from the chart that the copolymer has a uniform composition.

Claims (1)

[Claims] 1. (A) Aromatic polycarbonate 10 to 8
5% by weight, (B) 10 to 85% by weight of a rubber-reinforced styrene resin obtained by polymerizing an aromatic vinyl monomer in the presence of a rubbery polymer having a glass transition temperature (Tg) of −30 ° C. or less,
(C) The vinyl cyanide monomer has an average composition of 1 to 10
0.5% to 20% by weight of a copolymer composed of an aromatic vinyl monomer and a vinyl cyanide monomer, 1 to 30% by weight of (D) polyphenylene ether, and (E) an organophosphorus compound 1 A flame-retardant resin composition containing 30 to 30% by weight.