JP2001011297A - Flame-retardant synthetic resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a resin composition which has good physical properties, such as good resistances to weather, heat, and impact, and is excellent in flame retardance by compounding a polycarbonate polymer with a phosphoric ester flame retardant and a phosphoric ester metal salt having a specified chemical structure. SOLUTION: The polycarbonate polymer is obtained from a divalent aromatic hydroxy compound and a carbonate precursor, and its structure, etc., are not specifically limited. The phosphoric ester metal salt is represented by formula I (wherein R is H or 1-8C alkyl; R1 and R2 are each 1-8C alkyl; (1)is 1 or 2; and M is an alkali or alkaline earth metal or hydroxyaluminum) and is compounded in an amount of 0.005-5 pts.wt. based on 100 pts.wt. polycarbonate polymer. The phosphoric ester flame retardant is represented by formula II (wherein R3, R4, R6, and R7 are each 1-30C alkyl, alkenyl or the like; R5 is 1-20C alkylene or 6-30C arylene; and (n) is 1-20) and is compounded in an amount of 0.1-30 pts.wt. based on 100 pts.wt. polycarbonate polymer.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a flame-retardant synthetic resin composition having excellent weatherability, heat resistance, impact resistance and formability without containing an organic halogen-based flame retardant. Phosphate ester metal salts having a specific structure in a resin composition comprising a polymer compound or a multicomponent polymer compound comprising a polycarbonate polymer compound and a styrene polymer compound and a phosphate ester flame retardant The present invention relates to a flame-retardant synthetic resin composition containing a flame-retardant aid.

[0002]

2. Description of the Related Art Polycarbonate polymer compounds and multicomponent polymer compounds obtained by mixing a polycarbonate polymer compound with a styrene polymer compound having excellent impact resistance such as ABS and AS are known. Because of its excellent weather resistance, heat resistance, and shock resistance, it is widely applied as a housing material in the OA equipment field such as electric / electronic equipment field, communication equipment field, copier, printer, facsimile, personal computer, etc. It is also expected as a substitute for metal products in the automotive parts field.

[0003] In addition, molded articles using these synthetic resin compositions are required to have flame retardancy, which is described in US Pat. No. 94, Underwriters Laboratories, Inc. UL-94 "). In UL-94,
After igniting the test piece, the flame retardancy is evaluated based on the quenching time until spontaneous extinction, and the presence or absence of resin dripping (drip) due to combustion. The synthetic resin composition for the above application has no drip and short quenching time Is required.

As a flame retardant for imparting flame retardancy to a synthetic resin composition, a system in which a halogen-based organic compound and antimony trioxide are combined has conventionally been used. Due to the toxic gas generated during incineration and environmental problems, those containing no halogen are required.

To solve the above problem, a phosphorus-based flame retardant represented by an aromatic phosphate ester is added to a polycarbonate polymer compound or a multi-component polymer compound comprising a polycarbonate polymer compound and a styrene polymer compound. The method used is being studied. For example, US Pat.
No. 4,394, U.S. Pat. No. 5,112,556, JP-A-5-262940, JP-A-7-2
No. 6,129, JP-A-10-168273 and the like report the use of phosphate ester flame retardants.

However, since a large amount of the phosphoric ester-based flame retardant is required to obtain high flame retardancy, the physical properties of a molded article may be affected. It was difficult to be satisfied.

Further, Japanese Patent No. 2581777 reports a flame-retardant polycarbonate resin composition using a phosphate metal salt for a polycarbonate polymer compound.

[0008] However, the above composition is insufficient in effect when the amount of the phosphoric acid ester metal salt used is small, and is not effective in a multi-component polymer compound further containing a styrene polymer compound. When the amount is insufficient and the amount of use is large, dripping becomes severe.

Therefore, an object of the present invention is to use a polycarbonate-based polymer compound or a multi-component polymer compound comprising a polycarbonate-based polymer compound and a styrene-based polymer compound as a resin component, and to provide weather resistance and heat resistance. Another object of the present invention is to provide a resin composition having good physical properties such as impact resistance and excellent flame retardancy.

[0010]

Means for Solving the Problems As a result of intensive studies, the present inventors have found that by adding a phosphoric acid ester metal salt having a specific structure as a flame retardant auxiliary, a large amount of such a substance as to impair physical properties is obtained. It has been found that the above object can be achieved without using a phosphate ester-based flame retardant.

The present invention has been made on the basis of the above findings. A polycarbonate-based polymer compound (A) is prepared by adding a phosphate ester-based flame retardant (B) and the following [formula 3] (same as the above [formula 1]). The present invention provides a flame-retardant synthetic resin composition containing a compound represented by the general formula (I).

[0012]

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Further, the present invention provides a multi-component polymer compound comprising a polycarbonate polymer compound (A) and a styrene polymer compound (C), a phosphate ester-based flame retardant (B) and the above-mentioned general formula (B). An object of the present invention is to provide a flame-retardant synthetic resin composition containing the compound represented by I).

[0014]

BEST MODE FOR CARRYING OUT THE INVENTION The flame-retardant synthetic resin composition of the present invention will be described in detail below.

In the compound (phosphate metal salt) represented by the above general formula (I) used in the present invention, R,
Examples of the alkyl group having 1 to 8 carbon atoms represented by R ₁ and R ₂ include methyl, ethyl, propyl, isopropyl, butyl, sec-butyl, tert-butyl, isobutyl, amyl, tert-amyl, hexyl, Heptyl, octyl, isooctyl, tertiary octyl, 2-ethylhexyl, and the like. Examples of the alkali metal atom represented by M include sodium, potassium, lithium, and the like. Examples of the alkaline earth metal atom include magnesium and calcium. , Strontium, barium and the like.

Specific examples of the compound represented by the general formula (I) include the following compound No. 1 to 7 and the like. However, the present invention is not limited at all by the following exemplified compounds.

[0017]

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[0018]

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[0019]

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[0020]

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[0021]

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[0022]

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[0023]

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The compound represented by the above general formula (I) is obtained by, for example, reacting phosphorus oxychloride with a 2,2'-methylenebisphenol derivative, hydrolyzing it to form a cyclic acidic phosphate, and then adding water. It is obtained by reacting with a metal hydroxide such as sodium oxide and the like, followed by filtration and drying, and then, if necessary, grinding.

If the amount of the compound represented by the above general formula (I) is less than 0.005 part by weight with respect to 100 parts by weight of the polycarbonate polymer compound (A), the effect is hardly obtained, and 5 parts by weight When the amount exceeds 0.005, not only the improvement of the addition effect is not seen but also the drip becomes easy.
Part by weight is preferred, and 0.05 to 1 part by weight is more preferred.

The polycarbonate polymer compound (A) used in the present invention is a polymer having a carbonate bond, for example, containing two or more hydroxyl groups, each of which is directly bonded to an aromatic carbon atom. It can be obtained from a bonded monocyclic or polycyclic aromatic compound (hereinafter, referred to as “polyvalent hydroxy aromatic compound”) and a carbonate precursor. The polycarbonate polymer compound (A) is not particularly limited in its structure, production method, chain terminator, molecular weight and the like, and may be branched. In addition, one kind or a mixture of two or more kinds may be used, and further, for example, a polymer component such as polyester, which is used by being mixed with a well-known polycarbonate, may be included.

The above-mentioned polycarbonate polymer compound (A) is generally obtained from a divalent hydroxyaromatic compound and a carbonate precursor.
The compound represented by the general formula (III) 1) is preferred.

[0028]

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In the above formula (III), examples of the halogen atom represented by R ₈ , R ₉ and R ₁₀ include fluorine, chlorine, bromine and iodine, and examples of the alkyl group include methyl, ethyl, propyl and Isopropyl, butyl, sec-butyl, tert-butyl, isobutyl, amyl, isoamyl, tert-amyl, hexyl, cyclohexyl, heptyl, isoheptyl, tertiary heptyl, n-octyl, isooctyl, tertiary octyl, 2-ethylhexyl and the like. Examples of the alkoxy group include groups derived from these alkyl groups.Examples of the cycloalkyl group include cyclobutane, cyclopentane, cyclohexane and the like, and aryl and alkylaryl groups include phenyl. , Methylphenyl, dimethylphenyl, ethylphenyl, octane Phenyl, chlorophenyl, bromophenyl, naphthyl and the like; arylalkyl groups include benzyl and phenethyl; and alkylene groups represented by X include methylene, ethylene, ethane-1,1-diyl, propylene , Propane-2,2-diyl, 1-methylethylene, butylene,
1-methylpropylene, 2-methylpropylene, 2,2
-Dimethylpropylene, 1,3-dimethylpropylene,
Butylene, 1-methylbutylene, 2-methylbutylene,
3-methylbutylene, 4-methylbutylene, 2,4-dimethylbutylene, 1,3-dimethylbutylene, pentylene, hexylene, heptylene, octylene and the like, and as the cycloalkylidene group, cyclopentylidene, cyclohexylidene And substituted products thereof.

The polyvalent hydroxy aromatic compound used as a raw material of the polycarbonate polymer compound (A) is
Examples corresponding to the above general formula (III) include, specifically, resorcin, catechol, hydroquinone, 3-methyl resorcin, 3-ethyl resorcin, 3-propyl resorcin, 3-butyl resorcin, 3-tert-butyl. Resorcin, 3-phenylresorcin, 3-cumylresorcin, 3-methylhydroquinone, 3-ethylhydroquinone, 3-propylhydroquinone, 3-butylhydroquinone, 3-tert-butylhydroquinone, 3-phenylhydroquinone, 3-cumylhydroquinone Dihydroxybenzenes such as 4,4'-dihydroxydiphenyl; 1,1-bis (4
-Hydroxyphenyl) -2,4,4-trimethylcyclopentane, 1,1-bis (4-hydroxyphenyl)
Cyclohexane, 1,1-bis (4-hydroxyphenyl) -3,3-dimethylcyclohexane, 1,1-bis (4-hydroxyphenyl) cyclohexane, 1,1-
Bis (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane, 1,1-bis (4-hydroxy-
3,5-dimethylphenyl) cyclohexane, 1,1-
Bis (4-hydroxyphenyl) cyclododecane, 1,
Bis (hydroxyaryl) cycloalkanes such as 1-bis (4-hydroxy-3,5-dimethylphenyl) cyclododecane and 1,1-bis (4-hydroxyphenyl) cyclododecane; 1,4-bis (4- Bis (hydroxyaryl) aryls such as hydroxyphenylsulfonyl) benzene and 4,4-bis (4-hydroxyphenylsulfonyl) benzene; bis (4-hydroxyphenyl) methane, 1,1-bis (4-hydroxyphenyl) ethane , 1,2-bis (4-hydroxyphenoxy) ethane, 1,4-bis (4-hydroxyphenyl)
Propane, 2,2-bis (4-hydroxyphenyl) propane, 2,2-bis (3-chloro-4-hydroxyphenyl) propane, 2,2-bis (3,5-dichloro-
4-hydroxyphenyl) propane, 2,2-bis (4
-Hydroxy-3,5-dimethylphenyl) propane,
2,2-bis (4-hydroxy-3,5-dibromophenyl) propane, 2,2-bis (4-hydroxyphenyl-3-methylphenyl) propane, 2,2-bis (4
-Hydroxyphenyl-3-cyclohexylphenyl)
Propane, 2,2-bis (4-hydroxy-3-tert-butylphenyl) propane, 2,2-bis (4-hydroxyphenyl-3-methoxyphenyl) propane, 1,1
-Bis (4-hydroxyphenyl) butane, 1,1-bis (4-hydroxyphenyl) isobutane, 2,2-bis (4-hydroxy) butane, 2,4-bis (4-hydroxyphenyl 2-methyl) Bis (hydroxyaryl) alkanes such as butane; dihydroxyaryl ketones such as bis (4-hydroxyphenyl) ketone and bis (4-hydroxy-3-methylphenyl) ketone;
4'-dihydroxydiphenyl ether, 4,4'-dihydroxy-3,3'-dimethylphenyl ether,
Dihydroxyaryl ethers such as 4,4'-dihydroxy-2,5-dihydroxydiphenyl ether;
4,4'-thiodiphenol, bis (4-hydroxyphenyl) sulfide, 4,4'-dihydroxy-3,3 '
-Dimethyldiphenyl sulfide, 4,4'-dihydroxy-3,3'-dimethyldiphenyl sulphoxide,
4,4'-dihydroxy-3,3'-dimethyldiphenylsulfoxide, 2,2-bis (4-hydroxyphenyl) sulfone, 4,4'-dihydroxydiphenylsulfone, 4,4'-dihydroxy-3,3'- Dihydroxyaryl sulfur compounds such as dimethyldiphenylsulfone and phenolphthalein;
Examples other than those corresponding to II) are 2,2,2 ',
2'-tetrahydro-3,3,3 ', 3'-tetramethyl-1,1'-spirobis (1H-indene) -7,
Examples thereof include those having a condensed ring such as 7'-diol, and these may be used alone or in combination of two or more, or may be used in combination with a trivalent or more polyvalent hydroxy aromatic compound.

Examples of the carbonate precursor, which is a raw material of the polycarbonate polymer compound (A), include carbonyl halide, carbonyl ester, haloformate and the like. Preferred specific examples are phosgene, carbonate diester, diphenyl Examples include carbonates, dihaloformates of dihydric phenols, and mixtures thereof.

If the molecular weight of the polycarbonate polymer compound (A) is less than 10,000, the impact strength of the formed product may be reduced, and if it exceeds 200,000, the fluidity may be reduced and processing may become difficult. Therefore, it is preferably from 100,000 to 200,000, and 2
~ 60,000 is more preferable.

For the above reasons, a chain terminator may be used to control the molecular weight of the polycarbonate polymer compound (A) during its production. In this case, as the chain terminator used, for example, phenol, p-chlorophenol, p-tert-butylphenol, 2,4,4
Long-chain alkylphenols such as 6-tribromophenol and 4- (1,3-tetramethylbutyl) phenol;
3,5-di-tert-butylphenol, p-isooctylphenol, p-tert-octylphenol, p-dodecylphenol, 2- (3,5-dimethylheptyl) phenol, 4- (3,5-dimethylheptyl) phenol and the like Phenolic compounds are listed, and the general amount used is
It is 0.5 to 10 mol% of the dihydric hydroxyaromatic compound used.

As the phosphate ester-based flame retardant (B) used in the present invention, any of generally known ones can be used, but the condensation represented by the following general formula (II) can be used. Phosphoric acid ester compounds are preferred in terms of bleeding and juicing during molding.

[0035]

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R ₃ , R ₄ , R in the general formula (II)
Examples of the alkyl group having 1 to 30 carbon atoms represented by ₆ and R ₇ include methyl, ethyl, propyl, isopropyl, butyl, sec-butyl, tert-butyl, pentyl, hexyl, heptyl, octyl, nonyl, Isononyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, eicosyl, behenyl, straight-chain or branched alkyl groups such as tricosyl, and alkenyl groups include vinyl, propenyl, isopropenyl, Butenyl,
Examples thereof include linear or branched alkenyl groups such as isobutenyl, octenyl, decenyl, pentadecenyl, eicosenyl, and tricosenyl. Examples of the aryl group and the alkylaryl group include phenyl, cresyl, 2,6-dimethylphenyl, and 2,4. Di-tert-butylphenyl, 2,
6-di-tert-butylphenyl, 2,4-di-tert-pentylphenyl, 2,4-dicumylphenyl, cyclohexylphenyl, naphthyl, biphenyl and the like, and examples of the arylalkyl group include benzyl and phenylethyl. And the like.

The alkylene group represented by R ₅ includes, for example, ethylene, propylene, tetramethylene and the like, and the arylene group includes 1,2-phenylene,
1,3-phenylene, 1,4-phenylene, 2,5-dimethyl-1,4-phenylene, diphenylmethane-4,
4'-diyl, 2,2-diphenylpropane-4,4 '
-Diyl, diphenylsulfide-4,4'-diyl,
And diphenylsulfone-4,4'-diyl.

As the phosphate ester flame retardant (B), more specifically, the following compound No. 8 to 15 and the like. However, the present invention is not at all limited by the following compounds.

[0039]

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[0040]

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[0041]

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[0042]

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[0043]

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[0044]

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[0045]

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[0046]

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The method for producing the compound preferably used as the phosphate ester flame retardant (B) is not particularly limited, and any known method can be used. For example, a method of performing a dehydrochlorination reaction between phosphorus oxychloride and each phenol compound in the presence of a Lewis acid catalyst, a method of reacting phosphorus oxychloride with 2,6-xylenol, followed by a reaction with dihydric phenol, a method of triphenyl A method of transesterifying a phosphate with a polyhydric phenol such as resorcinol using a catalyst such as magnesium chloride is exemplified. These reactions are preferably carried out in combination with a step of removing excess phenol under reduced pressure as necessary, or deactivating and removing the catalyst by washing with an adsorbent or water.

The amount of the phosphate ester flame retardant (B) used in the flame retardant synthetic resin composition of the present invention is based on 100 parts by weight of the polycarbonate polymer compound (A).
If the amount is less than 0.1 part by weight, the effect is hardly obtained. If the amount exceeds 30 parts by weight, not only the addition effect is hardly improved, but also the processability and the physical properties of the molded product may be adversely affected. The amount is preferably 1 to 30 parts by weight, more preferably 1 to 20 parts by weight.

In the flame-retardant synthetic resin composition of the present invention, a well-known general anti-drip agent can be used in order to prevent dripping of the resin during combustion. Suitable anti-drip agents in the present invention include, for example, fluorine resins such as polytetrafluoroethylene, polyvinylidene fluoride and polyhexafluoropropylene, sodium perfluoromethanesulfonate, potassium perfluoro-n-butanesulfonate Salts, alkali metal perfluoroalkanesulfonates or alkali perfluoroalkanesulfonates such as salts, potassium perfluoro-t-butanesulfonate, sodium perfluorooctanesulfonate and calcium perfluoro-2-ethylhexanesulfonate Examples include earth metal salts and silicone rubbers, which can be used alone or in combination of two or more.

When the amount of the anti-drip agent is less than 0.05 part by weight, the anti-drip effect is small with respect to 100 parts by weight of the polycarbonate polymer compound (A). Heat shrinkage increases,
The dimensional accuracy may decrease and the cost may increase.
0.05 to 5 parts by weight is preferable, and 0.1 to 2 parts by weight is more preferable.

In the case where the flame-retardant synthetic resin composition of the present invention is further provided with stabilization, if necessary, at the time of mixing the resin,
At any stage such as molding, a general-purpose ultraviolet absorber,
Additives such as antioxidants and light stabilizers can be added.

As the above-mentioned ultraviolet absorber, for example,
4-dihydroxybenzophenone, 2-hydroxy-4
-Methoxybenzophenone, 2-hydroxy-4-octoxybenzophenone, 5,5'-methylenebis (2-
2-hydroxybenzophenones such as hydroxy-4-methoxybenzophenone); 2- (2-hydroxy-5)
-Methylphenyl) benzotriazole, 2- (2-hydroxy-5-tert-octylphenyl) benzotriazole, 2- (2-hydroxy-3,5-ditert-butylphenyl) -5-chlorobenzotriazole, 2- (2-
Hydroxy-3-tert-butyl-5-methylphenyl)-
5-chlorobenzotriazole, 2- (2-hydroxy-3,5-dicumylphenyl) benzotriazole,
2,2'-methylenebis (4-tert-octyl-6-benzotriazolylphenol), 2- (2-hydroxy-
Polyethylene glycol ester of 3-tert-butyl-5-carboxyphenyl) benzotriazole, 2- [2
-Hydroxy-3- (2-acryloyloxyethyl)
-5-methylphenyl] benzotriazole, 2- [2
-Hydroxy-3- (2-methacryloyloxyethyl) -5-tert-butylphenyl] benzotriazole,
2- [2-hydroxy-3- (2-methacryloyloxyethyl) -5-tert-octylphenyl] benzotriazole, 2- [2-hydroxy-3- (2-methacryloyloxyethyl) -5-tert-butylphenyl ] -5
Chlorobenzotriazole, 2- [2-hydroxy-5
-(2-methacryloyloxyethyl) phenyl] benzotriazole, 2- [2-hydroxy-3-tert-butyl-5- (2-methacryloyloxyethyl) phenyl] benzotriazole, 2- [2-hydroxy-3-
Tertiary amyl-5- (2-methacryloyloxyethyl)
Phenyl] benzotriazole, 2- [2-hydroxy-3-tert-butyl-5- (3-methacryloyloxypropyl) phenyl] -5-chlorobenzotriazole,
2- [2-hydroxy-4- (2-methacryloyloxymethyl) phenyl] benzotriazole, 2- [2-
Hydroxy-4- (3-methacryloyloxy-2-hydroxypropyl) phenyl] benzotriazole, 2
2- [2 such as-[2-hydroxy-4- (3-methacryloyloxypropyl) phenyl] benzotriazole;
-Hydroxyphenyl) benzotriazoles; 2-
(2-hydroxy-4-methoxyphenyl) -4,6-
Diphenyl-1,3,5-triazine, 2- (2-hydroxy-4-hexyloxyphenyl) -4,6-diphenyl-1,3,5-triazine, 2- (2-hydroxy-4-octoxyphenyl ) -4,6-bis (2,4-
Dimethylphenyl) -1,3,5-triazine, 2-
[2-hydroxy-4- (3-C12-13 mixed alkoxy-2-hydroxypropoxy) phenyl] -4,6
-Bis (2,4-dimethylphenyl) -1,3,5-triazine, 2- [2-hydroxy-4- (2-acryloyloxyethoxy) phenyl] -4,6-bis (4-
Methylphenyl) -1,3,5-triazine, 2-
(2,4-dihydroxy-3-allylphenyl) -4,
6-bis (2,4-dimethylphenyl) -1,3,5-
Triazine, 2,4,6-tris (2-hydroxy-3
-Methyl-4-hexyloxyphenyl) -1,3,5-
2- (2-hydroxyphenyl) -4 such as triazine,
6-diaryl-1,3,5-triazines; phenyl salicylate, resorcinol monobenzoate, 2,
4-di-tert-butylphenyl-3,5-di-tert-butyl-4
Benzoates such as -hydroxybenzoate, hexadecyl-3,5-ditert-butyl-4-hydroxybenzoate; 2-ethyl-2'-ethoxyoxanilide, 2
Substituted oxanilides such as -ethoxy-4'-dodecyloxanilide; ethyl-α-cyano-β, β-diphenylacrylate, methyl-2-cyano-3-methyl-3-
Cyanoacrylates such as (p-methoxyphenyl) acrylate; various metal salts or metal chelates, particularly nickel or chromium salts or chelates.

If the amount of these ultraviolet absorbers is less than 0.005 parts by weight with respect to 100 parts by weight of the polycarbonate polymer compound (A), a sufficient stabilizing effect cannot be obtained and 30 parts by weight. If the amount is more than 0.1%, it is difficult to improve the effect of addition, and there is a possibility of waste.
It is preferably from 0.5 to 30 parts by weight, more preferably from 0.05 to 20 parts by weight.

Examples of the antioxidant include triphenyl phosphite, tris (2,4-ditert-butylphenyl) phosphite, tris (nonylphenyl) phosphite, tris (dinonylphenyl) phosphite, tris (Mono, di-mixed nonylphenyl) phosphite, bis (2-tert-butyl-4,6-dimethylphenyl) .ethyl phosphite, diphenyl acid phosphite,
2,2'-methylenebis (4,6-di-tert-butylphenyl) octyl phosphite, diphenyldecyl phosphite, phenyldiisodecyl phosphite, tributyl phosphite, tris (2-ethylhexyl) phosphite, tridecyl phosphite, tridecyl phosphite Lauryl phosphite, dibutyl acid phosphite, dilauryl acid phosphite, trilauryl trithiophosphite, bis (neopentyl glycol) -1,4-cyclohexanedimethyldiphosphite, bis (2,4-di-tert-butylphenyl) Pentaerythritol diphosphite, bis (2,6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphite, distearylpentaerythritol diphosphite, phenyl-
4,4'-isopropylidene diphenol pentaerythritol diphosphite, tetra (C12-15 mixed alkyl) -4,4'-isopropylidene diphenyl phosphite, bis [2,2'-methylenebis (4,6-
Diamylphenyl)] • isopropylidenediphenylphosphite, hydrogenated-4,4′-isopropylidenediphenol polyphosphite, bis (octylphenyl)
Bis [4,4'-n-butylidenebis (2-tert-butyl-5-methylphenol)]-1,6-hexanediol diphosphite, tetratridecyl-4,4'-butylidenebis (2-tert-butyl- 5-methylphenol)
Diphosphite, hexa (tridecyl) -1,1,3-
Tris (2-methyl-5-tert-butyl-4-hydroxyphenyl) butane triphosphonite, 9,10-dihydro-9-oxa-10-phosphaphenanthrene-
Phosphorus antioxidants such as 10-oxide, 2-butyl-2-ethylpropanediol, 2,4,6-tri-tert-butylphenol monophosphite;

2,6-di-tert-butyl-p-cresol,
2,6-diphenyl-4-octadecyloxyphenol, stearyl (3,5-ditert-butyl-4-hydroxyphenyl) propionate, distearyl (3,5-
Di-tert-butyl-4-hydroxybenzyl) phosphonate, tridecyl-3,5-di-tert-butyl-4-hydroxybenzylthioacetate, thiodiethylenebis [(3,5-di-tert-butyl-4-hydroxyphenyl)
Propionate], 4,4'-thiobis (6-tert-butyl-m-cresol), 2-octylthio-4,6-di (3,5-di-tert-butyl-4-hydroxyphenoxy)
-S-triazine, 2,2'-methylenebis (4-methyl-6-tert-butylphenol), bis [3,3-bis (4-hydroxy-3-tert-butylphenyl) butyric acid] glycol ester, 4 , 4'-butylidenebis (4,6-di-tert-butylphenol), 2,2 '
-Ethylidenebis (4,6-di-tert-butylphenol), 1,1,3-tris (2-methyl-4-hydroxy-5-tert-butylphenyl) butane, bis [2-tert-butyl-4-methyl -6- (2-hydroxy-3-tert-butyl-5-methylbenzyl) phenyl] terephthalate, 1,3,5-tris (2,6-dimethyl-3-hydroxy-4-tert-butylbenzyl) isocyanurate ,
1,3,5-tris (3,5-di-tert-butyl-4-hydroxybenzyl) isocyanurate, 1,3,5-tris (3,5-di-tert-butyl-4-hydroxybenzyl)
-2,4,6-trimethylbenzene, 1,3,5-tris [(3,5-ditert-butyl-4-hydroxyphenyl) propionyloxyethyl] isocyanurate, tetrakis [methylene-3- (3,5 -Di-tert-butyl-4
-Hydroxyphenyl) propionate] methane, 2-
Tert-butyl-4-methyl-6- (2-acryloyl-3-tert-butyl-5-methylbenzyl) phenol,
3,9-bis [2- (3-tert-butyl-4-hydroxy-5-methylhydrocinnamoyloxy) -1,1-dimethylethyl] -2,4,8,10-tetraoxaspiro [5. 5] undecane], phenolic antioxidants such as triethylene glycol bis [β- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionate];

Dialkylthiodipropionates such as dilauryl, dimyristyl, myristylstearyl and distearyl esters of thiodipropionic acid, and β-alkylmercaptopropionates of polyols such as pentaerythritol tetra (β-dodecylmercaptopropionate) And other sulfur-based antioxidants.

The amount of these antioxidants used is based on 100 parts by weight of the polycarbonate polymer compound (A).
When the amount is less than 0.01 part by weight, it is difficult to sufficiently obtain the stabilizing effect, and even when used in an amount exceeding 50 parts by weight, it is difficult to increase the effect of addition. Therefore, 0.01 to 50 parts by weight is preferable.
0.5 to 30 parts by weight is more preferred.

The flame-retardant synthetic resin composition of the present invention may further contain, if necessary, reinforcing fiber materials such as glass fiber, carbon fiber, polyamide fiber, and aromatic polyester fiber, calcium carbonate, talc, silica, and carbon. Black, fillers such as titanium oxide, pigments, coloring agents such as dyes, lubricants, antistatic agents, release agents, well-known general additives such as fluidity improvers, etc. at the time of resin mixing, molding, etc. It can be blended in stages.

The flame-retardant synthetic resin composition of the present invention comprises
It is used for housing materials in the fields of electronic equipment, communication equipment, and OA equipment, such as copiers, printers, facsimiles, personal computers, and alternative materials for metal products in the automotive parts field.

The flame-retardant synthetic resin composition of the present invention comprises
Instead of the polycarbonate polymer compound (A),
A multi-component polymer compound comprising the polycarbonate polymer compound (A) and the styrene polymer compound (C) can also be used. In this case, the reference of the amount of each component used is the above-mentioned multi-component polymer compound instead of the above-mentioned polymer compound (A).

In the multi-component polymer compound composed of the polycarbonate polymer compound (A) and the styrene polymer compound (C), the styrene polymer compound (C) constituting the multi-component polymer compound is represented by styrene. A polymer compound obtained by using an aromatic vinyl compound as an essential raw material and another resin raw material as an optional component, and these can be used without any particular restrictions on the structure, production method, molecular weight and the like.

The aromatic vinyl compound used as an essential raw material of the styrene polymer compound (C) includes, for example, styrene, vinylnaphthalene, α-methylstyrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, Methyl styrene, ethyl styrene, monochlorostyrene,
Substituted styrene substituted with 1 to 5 halogen atoms and / or alkyl groups and / or alkenyl groups such as dichlorostyrene, monobromostyrene, dibromostyrene, fluorostyrene, p-tert-butylstyrene, etc., and optional components Examples of resin raw materials used include: vinyl cyanides such as acrylonitrile and methacrylonitrile; α, β-unsaturated carboxylic acids such as acrylic acid and methacrylic acid; alkyl acrylates having 1 to 8 carbon atoms;
Α, β-unsaturated carboxylic acid esters such as alkyl methacrylates of No. 8 to 8; α, β-unsaturated dicarboxylic acid anhydrides such as maleic anhydride and itaconic anhydride and derivatives thereof; maleimide, N-maleimide, N- Methylmaleimide, N-ethylmaleimide, N-phenylmaleimide,
Α, β-unsaturated carboxylic imides such as No-chlorophenylmaleimide; conjugated diene compounds such as isoprene, butadiene and chloroprene; epoxy-modified conjugated diene compounds; olefins such as ethylene and propylene;
Vinyl acetate.

The styrenic polymer compound (C) may be at least one kind of aromatic vinyl compound, and may be a mixture of two or more kinds of polymer compounds. As a method for producing a mixture of two or more kinds, a blending method such as a melt blending method, a kneading blending method, a melt casting method, a solution method, a copolymerization method such as a grafting method, a block method, a random method, a mutual method, a melt grafting method, etc. And a block graft copolymerization method.

Specific examples of the styrene polymer compound (C) include polystyrene, high impact polystyrene (HIPS) resin, acrylonitrile butadiene styrene (ABS) resin, polyethylene chloride acrylonitrile styrene (ACS) resin, and styrene acrylonitrile (SAN). Resin, acrylonitrile butyl acrylate styrene (AAS) resin, butadiene styrene resin, styrene maleic resin, styrene maleimide resin, ethylene propylene acrylonitrile styrene (AES) resin, butadiene methyl methacrylate (MBS)
Resins.

The type and amount of the styrenic polymer compound (C) are appropriately selected depending on the physical properties of the desired molded product.
Resins are suitable, and the amount of use is preferably 1 to 50 parts by weight, more preferably 10 to 40 parts by weight, based on 100 parts by weight of the polycarbonate polymer compound (A).

Further, the production method, molecular weight and the like of the multicomponent polymer compound comprising the polycarbonate polymer compound (A) and the styrene polymer compound (C) are not particularly limited.

[0067]

EXAMPLES Hereinafter, the present invention will be described more specifically with reference to Examples and Comparative Examples, but the present invention is not limited to the following Examples.

(Example 1) Polycarbonate (PC) resin (Iupilon E-2000F: manufactured by Mitsubishi Gas Chemical Company) 1
00 parts by weight, the flame retardant and the flame retardant auxiliary described in Table 1 were dry blended and pelletized at 280 ° C. using a single screw extruder. The obtained pellets were dried in an oven at 120 ° C. for 6 hours, and then 5 inches × 1/2 inch × 1 at a mold temperature of 100 ° C. using an injection molding machine at a cylinder temperature of 300 ° C.
A / 8 inch test piece was prepared. UL-94 test (extinguishing time measurement) and bleed evaluation were performed on the obtained test pieces. Table 1 shows the results.

[0069]

[Table 1]

(Example 2) Polycarbonate (PC) resin (Iupilon E-2000F: manufactured by Mitsubishi Gas Chemical Company) 8
0 parts by weight and 20 parts by weight of ABS resin (Styrac 100: manufactured by Asahi Kasei Kogyo Co., Ltd.) were mixed with a Henschel mixer, dried in an oven at 120 ° C. for 6 hours, and then polytetrafluoroethylene (an anti-drip agent) was added. 0.12 parts by weight of Teflon 6J: manufactured by DuPont Fluorochemicals Co., Ltd.)
Pelletized at 60 ° C. using a single screw extruder. After drying the obtained pellets in an oven at 120 ° C. for 6 hours, 2
Using an injection molding machine at a cylinder temperature of 60 ° C., a test piece of 5 inch × １ ／ inch × １ ／ inch was prepared at a mold temperature of 100 ° C. UL-94 about the obtained test piece
A test (extinguishment time, drip evaluation) and bleed evaluation were performed. The results are shown in Table 2 (comparison of flame retardant aids), Table 3
(Comparison of flame retardants) and Table 4 (Comparison of concentrations). still,
In Tables 2 to 4, there are some examples that are partially overlapped for clarity of the respective comparisons.

[0071]

[Table 2]

[0072]

[Table 3]

[0073]

[Table 4]

(Example 3) Polycarbonate (PC) resin (Iupilon E-2000F: manufactured by Mitsubishi Gas Chemical Company) 6
A test piece was prepared in the same manner as in Example 2 except that 0 part by weight, 40 parts by weight of ABS resin (Stylac 100: manufactured by Asahi Kasei Kogyo Co., Ltd.), and the flame retardant and flame retardant auxiliary shown in Table 5 were used. ,
Each evaluation was performed. Table 5 shows the results.

[0075]

[Table 5]

[0076]

According to the present invention, there is provided a resin composition containing a polycarbonate polymer compound or a multi-component polymer compound comprising a polycarbonate polymer compound and a styrene polymer compound. It has good physical properties such as heat resistance and impact resistance and has excellent flame retardancy.

 ──────────────────────────────────────────────────続 き Continued on the front page (72) Inventor Ryoji Kimura 5-2-13-1 Shirahata, Urawa-shi, Saitama F-term in Asahi Denka Kogyo Co., Ltd. 4J002 BC032 BC062 BC072 BC082 BC092 BC112 BH012 BN102 BN122 BN142 BN152 BN162 CG011 CG021 CG031 EW066 FD010 FD050 FD070 FD130 FD136 GN00 GQ00

Claims (4)

[Claims] 1. A polycarbonate polymer compound (A)
A flame-retardant synthetic resin composition comprising a phosphate ester-based flame retardant (B) and a compound represented by the following general formula (I). Embedded image 2. Polycarbonate polymer compound (A)
Flame-retardant synthetic resin comprising a multi-component polymer compound consisting of a styrene-based polymer compound (C) and a phosphate ester-based flame retardant (B) and a compound represented by the above general formula (I) Composition. 3. The phosphoric ester-based flame retardant (B),
The flame-retardant synthetic resin composition according to claim 1 or 2, which is a condensation-type phosphate compound represented by the following general formula (II). Embedded image 4. The method according to claim 1, wherein the styrenic polymer compound (C) is
The flame-retardant synthetic resin composition according to claim 2 or 3, which is an acrylonitrile butadiene styrene (ABS) resin.