JP2000053851A - Flame retarded thermoplastic resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain highly flame-retarded thermoplastic resin composition without using chlorine or bromine compounds which are excellent in impact resistance, solvent resistance, moist heat resistance, heat stability and molding processability. SOLUTION: The objective flame retarded thermoplastic resin compositions can be obtained by adding to 100 pts.wt. resin composition composed of (A) a polycarbonate based resin and (B) a thermoplastic polyester based resin at an (A) to (B) weight ratio of 95/5-50/50, (C) at least one flame retardant selected from (C1) 0.1-30 pts.wt. organic phosphorus based flame retardant, (C2) 0.1-5 pts.wt. coating-treated, stabilized red phosphorus, (D) 0.5-20 pts.wt. vinyl aromatic/conjugated diene block copolymer or epoxy modified block copolymer, (E) at least one compound selected from (E1) 0.1-50 pts.wt. silicone, (E2) 0.1-100 pts.wt. silicate salt compound and (E3) 0.005-5 pts.wt. fluoroplastic, and (F) 0.1-20 pts.wt. one or more olefin based resins.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a thermoplastic resin composition flame-retarded with compounds other than chlorine and bromine, and more particularly to impact resistance, solvent resistance, wet heat resistance, moldability, heat stability. The present invention relates to a flame-retardant thermoplastic resin composition having excellent heat resistance and exhibiting even higher flame retardancy as compared with conventionally known compositions.

[0002]

2. Description of the Related Art Polycarbonate resin / thermoplastic polyester resin alloys improve the flowability, solvent resistance, etc. of polycarbonate resins and improve the impact resistance, heat resistance, etc. of thermoplastic polyester resins. As an alloy, it has excellent properties, but the alloyed composition is
Generally, there is a problem that impact resistance is low.

Japanese Patent Application Laid-Open No. 49-41442 proposes a technique for improving impact resistance by adding a butadiene graft copolymer rubber to a polycarbonate resin / thermoplastic polyester resin alloy. I have. However, when such a graft rubber is added, the thermal stability is reduced, so that there is a problem that when processed at a high temperature, molding defects such as discoloration and flash are likely to occur.

In recent years, especially in applications of electric and electronic parts, in order to ensure safety against fire, the resin used must conform to UL-94 V-0 or 5VA (US Underwriters Laboratory Standard). In many cases, a high degree of flame retardancy is required, and in order to cope with these, it is necessary to make the composition flame retardant. On the other hand, with increasing interest in environmental issues mainly in Europe, there is a demand for a composition which can exhibit such high flame retardancy without using chlorine or bromine.

As a technique for imparting such high flame retardancy to a resin composition without containing chlorine or bromine, various uses of phosphorus-based flame retardants have been studied. For example, Japanese Patent Application Laid-Open
Japanese Patent Application Laid-Open No. 6-192553 discloses a technique of adding a graft copolymer, a monophosphate flame retardant, and a fluorinated polyolefin to a resin composition comprising a polycarbonate resin and a polyalkylene terephthalate resin.
Japanese Patent Application Laid-Open Publication No. H11-163,055 discloses techniques for adding a graft copolymer, an oligomeric phosphate-based flame retardant, and a fluorinated polyolefin to a resin composition comprising a polycarbonate resin and a polyalkylene terephthalate resin. However, when a phosphate ester-based flame retardant is added to such a polycarbonate-based resin / thermoplastic polyester-based resin alloy, there is a problem that impact resistance, solvent resistance, and wet heat resistance are all significantly reduced. In the above publication, a graft copolymer is added to improve impact resistance.However, when a phosphate ester and a graft copolymer are added in combination, the thermal stability tends to be significantly reduced, and In such a composition, the addition of the organophosphorus flame retardant significantly reduces the solvent resistance and the wet heat resistance. JP-A-10-17760 discloses an epoxy-modified block obtained by epoxidizing a part of a styrene-butadiene block copolymer to a composition comprising a polycarbonate-based resin, a polystyrene-based resin, and an organic phosphorus-based flame retardant. It has been shown that by adding a polymer and a small amount of a polyester resin, flame retardancy can be achieved without using bromine or chlorine, and impact resistance can be improved. However,
In such a composition containing a large amount of polystyrene resin,
Heat resistance and solvent resistance are originally insufficient compared to polycarbonate resin / polyester resin alloys.
In order to obtain sufficient flame retardancy, it is necessary to add a large amount of an organic phosphorus-based flame retardant. Therefore, the addition of the organic phosphorus-based flame retardant greatly reduces the solvent resistance and the wet heat resistance.

[0006]

SUMMARY OF THE INVENTION An object of the present invention is to provide a flame-retardant resin composition obtained by adding an organic phosphorus-based flame retardant to a polycarbonate resin / thermoplastic polyester resin alloy.
An object of the present invention is to improve the impact resistance, thermal stability, solvent resistance, wet heat resistance, molding processability, and obtain a resin composition exhibiting higher flame retardancy as compared with a conventionally known composition. .

[0007]

Means for Solving the Problems As a result of intensive studies, the present inventors have found that a flame retardant resin composition comprising a polycarbonate resin, a thermoplastic polyester resin, and a phosphorus flame retardant has the same Of a block copolymer (3) comprising a polymer block (1) mainly composed of a vinyl aromatic compound and a polymer block (2) mainly composed of a conjugated diene compound, or a partially hydrogenated product (4) thereof An epoxy-modified block copolymer obtained by epoxidizing a double bond derived from a conjugated diene compound, silicone, a silicate compound, at least one compound selected from fluorine-based resins, an olefin-based resin,
The impact resistance, solvent resistance, wet heat resistance, and thermal stability are greatly improved by adding, and the above copolymer is used alone by using an organic phosphorus-based flame retardant and the above copolymer in combination. The present invention has been found to be able to greatly improve the molding processability as compared with the case where the compound is added, and to provide a composition which has good molding processability and can be practically used. That is, in the present invention, the weight ratio (A) / (B) of the (A) polycarbonate resin and the (B) thermoplastic polyester resin is 95/5.
５０50/50, relative to 100 parts by weight of the resin composition,
(C) (C1) 0.1 to 30 parts by weight of organophosphorus flame retardant (C2) 0.1 to 5 parts by weight of coated and stabilized red phosphorus flame retardant 1 selected from (C1) to (C2) More than species,
(D) a block copolymer (3) comprising a polymer block (1) mainly composed of a vinyl aromatic compound and a polymer block (2) mainly composed of a conjugated diene compound in the same molecule, or a partial water thereof. 0.5 to 20 parts by weight of an epoxy-modified block copolymer obtained by epoxidizing a double bond derived from the conjugated diene compound of additive (4), (E) (E1) 0.1 to 50 parts by weight of silicone (E2) Silicate compound 0.1
To 100 parts by weight (E3) 0.005 to 5 parts by weight of a fluorine-based resin, at least one compound selected from (E1) to (E3), and (F) at least one kind of an olefin-based resin 0.1 to 20 parts by weight The composition contains a flame-retardant thermoplastic resin composition obtained by adding a flame-retardant thermoplastic resin composition.

[0008]

BEST MODE FOR CARRYING OUT THE INVENTION The polycarbonate resin (A) used in the present invention is specifically obtained by reacting a phenol compound having a valency of 2 or more with a carbonic acid diester such as phosgene or diphenyl carbonate. Things.
There are various dihydric phenols.
2,2-bis (4-hydroxyphenyl) propane [commonly known as bisphenol A] is preferred. As the dihydric phenol other than bisphenol A, for example, bis (4-
Bis (4-hydroxyphenyl) phenylmethane; bis (4-hydroxyphenyl) naphthylmethane; bis (4-hydroxyphenyl) methane
-(4-isopropylphenyl) methane; bis (3,5
-Dimethyl-4-hydroxyphenyl) methane; 1,1
-Bis (4-hydroxyphenyl) ethane; 1-naphthyl-1,1-bis (4-hydroxyphenyl) ethane;
1-phenyl-1,1-bis (4-hydroxyphenyl) ethane; 1,2-bis (4-hydroxyphenyl)
Ethane; 2-methyl-1,1-bis (4-hydroxyphenyl) propane; 2,2-bis (3,5-dimethyl-
4-hydroxyphenyl) propane; 1-ethyl-1,
1-bis (4-hydroxyphenyl) propane; 2,2
-Bis (3-methyl-4-hydroxyphenyl) propane; 1,1-bis (4-hydroxyphenyl) butane;
2,2-bis (4-hydroxyphenyl) butane; 1,
4-bis (4-hydroxyphenyl) butane; 2,2-
Bis (4-hydroxyphenyl) pentane; 4-methyl-2,2-bis (4-hydroxyphenyl) pentane;
2,2-bis (4-hydroxyphenyl) hexane;
4,4-bis (4-hydroxyphenyl) heptane;
2,2-bis (4-hydroxyphenyl) nonane; 1,
10-bis (4-hydroxyphenyl) decane; 1,1
Dihydroxydiarylalkanes such as -bis (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane; 1,1-bis (4-hydroxyphenyl)
Dihydroxydiarylcycloalkanes such as 1,1-bis (4-hydroxyphenyl) cyclodecane; bis (4-hydroxyphenyl) sulfone; dihydroxydiaryl such as bis (3,5-dimethyl-4-hydroxyphenyl) sulfone; Dihydroxydiaryl ethers such as sulfones and bis (4-hydroxyphenyl) ether; bis (3,5-dimethyl-4-hydroxyphenyl) ether, 4,4 ′
-Dihydroxybenzophenone; 3,3 ', 5,5'-
Dihydroxydiaryl ketones such as tetramethyl-4,4'-dihydroxybenzophenone, bis (4-hydroxyphenyl) sulfide; bis (3-methyl-4
Dihydroxydiaryl sulfides such as bis (3,5-dimethyl-4-hydroxyphenyl) sulfide, dihydroxy diaryl sulfoxides such as bis (4-hydroxyphenyl) sulfoxide, and 4,4′-dihydroxy diphenyl Dihydroxydiphenyls such as 9,9-bis (4-
And dihydroxyarylfluorenes such as (hydroxyphenyl) fluorene. In addition to dihydric phenols, dihydroxybenzenes such as hydroquinone, resorcinol and methylhydroquinone;
And dihydroxynaphthalenes such as 2,6-dihydroxynaphthalene. These dihydric phenols and the like may be used alone or in combination of two or more.

Examples of the carbonic acid diester compound include diaryl carbonates such as diphenyl carbonate and dialkyl carbonates such as dimethyl carbonate and diethyl carbonate. In the present invention, the polycarbonate resin as the component (A) may contain a branched polycarbonate, if necessary. Examples of the branching agent used to obtain the above-mentioned branched polycarbonate include phloroglucin, melitic acid, trimellitic acid, trimellitic chloride, trimellitic anhydride, gallic acid, n-propyl gallate, protocatechuic acid, pyromellitic acid, and pyromellitic acid Anhydride, α-resorcinic acid, β-resorcinic acid, resorcinaldehyde,
Isatin bis (o-cresol), benzophenonetetracarboxylic acid; 2,4,4'-trihydroxybenzophenone; 2,2 ', 4,4'-tetrahydroxybenzophenone;2,4,4'-trihydroxyphenylether; 2 2,2,4,4'-tetrahydroxyphenyl ether; 2,4,4'-trihydroxydiphenyl-
2-propane; 2,2'-bis (2,4-dihydroxyphenyl) propane; 2,2 ', 4,4'-tetrahydroxydiphenylmethane;2,4,4'-trihydroxydiphenylmethane; 1- [α- Methyl-α- (4′-
Dihydroxyphenyl) ethyl] -3- [α ', α'-
Bis (4 "-hydroxyphenyl) ethyl] benzene;
1- [α-methyl-α- (4′-dihydroxyphenyl) ethyl] -4- [α ′, α′-bis (4 ″ -hydroxyphenyl) ethyl] benzene; α, α ′, α ″ -tris ( 4-hydroxyphenyl) -1,3,5-triisopropylbenzene; 2,6-bis (2-hydroxy-
5'-methylbenzyl) -4-methylphenol; 4,
6-dimethyl-2,4,6-tris (4′-hydroxyphenyl) -2-heptene; 4,6-dimethyl-2,
4,6-tris (4'-hydroxyphenyl) -heptane; 1,3,5-tris (4'-hydroxyphenyl)
Benzene; 1,1,1-tris (4-hydroxyphenyl) ethane; 2,2-bis [4,4-bis (4′-hydroxyphenyl) cyclohexyl] propane; 2,6-
Bis (2'-hydroxy-5'-isopropylbenzyl) -4-isopropylphenol; bis [2-hydroxy-3- (2'-hydroxy-5'-methylbenzyl) -5-methylphenyl] methane; bis [2 -Hydroxy-3- (2'-hydroxy-5'-isopropylbenzyl) -5-methylphenyl] methane; tetrakis (4-hydroxyphenyl) methane; tris (4-hydroxyphenyl) phenylmethane; 2 ', 4', 7-trihydroxyflavan; 2,4,4-trimethyl-
2 ', 4', 7-trihydroxyflavan; 1,3-bis (2 ', 4'-dihydroxyphenylisopropyl)
Benzene; tris (4'-hydroxyphenyl) -amyl-s-triazine;

In some cases, the polycarbonate resin as the component (A) includes a polycarbonate part,
A polycarbonate-polyorganosiloxane copolymer comprising a polyorganosiloxane part may be used. At this time, the degree of polymerization of the polyorganosiloxane portion is preferably 5 or more. In addition, as the polycarbonate resin as the component (A), for example, a linear aliphatic divalent carboxylic acid such as adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, decanedicarboxylic acid and the like may be used as a copolymer monomer. Copolymers can also be used.

As the terminal terminator at the time of polymerization of the polycarbonate resin, various known terminators can be used. Specifically, examples of the monohydric phenol include phenol, p-cresol, pt-butylphenol, pt-octylphenol, p-cumylphenol, and nonylphenol. further,
In order to enhance the flame retardancy, a copolymer with a phosphorus compound or a polymer end-blocked with a phosphorus compound can also be used. Further, in order to enhance the weather resistance, a copolymer with a dihydric phenol having a benzotriazole group can be used.

The viscosity average molecular weight of the polycarbonate resin (A) used in the present invention is preferably 10,000 to 10,000.
60000, more preferably 15,000 to 45
000, most preferably from 18,000 to 35,000. When the viscosity average molecular weight is less than 10,000, the strength and heat resistance of the obtained resin composition are often insufficient.
If the viscosity average molecular weight exceeds 60,000, the moldability is often insufficient.

These polycarbonate resins are used alone or in combination of two or more.
When two or more kinds are used in combination, the combination is not limited. For example, those having different monomer units, different copolymerization molar ratios, and / or different molecular weights are arbitrarily combined. The thermoplastic polyester resin (B) used in the present invention is a thermoplastic polyester obtained by polycondensing a divalent or more carboxylic acid component, a divalent or more alcohol and / or a phenol component by a known method. It is. Specific examples of the thermoplastic polyester resin include polyethylene terephthalate, polypropylene terephthalate, polybutylene terephthalate, polyhexamethylene terephthalate, polycyclohexane dimethylene terephthalate, polyethylene naphthalate, and polybutylene naphthalate.

As the divalent or higher valent aromatic carboxylic acid component, a divalent or higher valent aromatic carboxylic acid having 8 to 22 carbon atoms, or an ester-forming derivative thereof is used. Specific examples of these include phthalic acid such as terephthalic acid and isophthalic acid, naphthalenedicarboxylic acid, bis (p-carboxyphenyl) methane, anthracenedicarboxylic acid,
Carboxylic acids such as -4'-diphenyldicarboxylic acid, 1,2-bis (phenoxy) ethane-4,4'-dicarboxylic acid, diphenylsulfonedicarboxylic acid, trimesic acid, trimellitic acid, and pyromellitic acid; Derivatives having an ester-forming ability are exemplified. These may be used alone or in combination of two or more. Preferred are terephthalic acid, isophthalic acid and naphthalenedicarboxylic acid. This is because they are excellent in ease of handling, ease of reaction, physical properties of the obtained resin, and the like.

The dihydric or higher alcohol and / or phenol component includes aliphatic compounds having 2 to 15 carbon atoms, alicyclic compounds having 6 to 20 carbon atoms, and aromatic compounds having 6 to 40 carbon atoms. And compounds having two or more hydroxyl groups therein, as well as ester-forming derivatives thereof. Specific examples of such alcohol and / or phenol components include ethylene glycol, propylene glycol, butanediol, hexanediol,
Decanediol, neopentyl glycol, cyclohexanedimethanol, cyclohexanediol, 2,2 '
-Bis (4-hydroxyphenyl) propane, 2,2 '
Compounds such as -bis (4-hydroxycyclohexyl) propane, hydroquinone, glycerin, pentaerythritol, and the like, and derivatives thereof having an ester-forming ability are exemplified. Preferred alcohol and / or phenol components are ethylene glycol, butanediol,
Cyclohexanedimethanol. Ease of handling,
This is because the easiness of the reaction, the physical properties of the obtained resin, and the like are excellent.

(B) The thermoplastic polyester resin includes:
In addition to the acid component and the alcohol and / or phenol component, known copolymerizable components may be copolymerized as long as the desired properties are not impaired. Examples of such copolymerizable components include carboxylic acids such as divalent or higher valent aliphatic carboxylic acids having 4 to 12 carbon atoms, divalent or higher valent alicyclic carboxylic acids having 8 to 15 carbon atoms, and esters thereof. Forming derivatives. Specific examples thereof include adipic acid, sebacic acid, azelaic acid, dodecanedicarboxylic acid, maleic acid, 1,3-cyclohexanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, and other dicarboxylic acids, or esters thereof. Derivatives having the same.

Oxyacids such as p-hydroxybenzoic acid and their ester-forming derivatives, cyclic esters such as ε-caprolactone, and the like can also be used as the copolymerization component. In addition, polyethylene glycol,
Polypropylene glycol, poly (ethylene oxide / propylene oxide) block and / or random copolymer, bisphenol A copolymerized polyethylene oxide addition polymer, propylene oxide addition polymer,
A thermoplastic polyester resin in which a polyalkylene glycol unit such as the tetrahydrofuran addition polymer and polytetramethylene glycol is partially copolymerized in a polymer chain can also be used. As the copolymerization amount of the above components,
It is generally at most 20% by weight, preferably at most 15% by weight, more preferably at most 10% by weight.

(B) The thermoplastic polyester resin contains an alkylene terephthalate unit, preferably 80% by weight.
The polyalkylene terephthalate is more preferably 85% by weight or more, most preferably 90% by weight or more. This is because the obtained composition has an excellent balance of physical properties (eg, moldability). (B) Phenol / tetrachloroethane = 1/1 of thermoplastic polyester resin
(Weight ratio) Logarithmic viscosity (IV) when measured at 25 ° C. in a mixed solvent is preferably 0.30 to 2.00 dl / g.
Or more, preferably 0.40 to 1.80 dl / g,
More preferably, it is 0.50 to 1.60 dl / g.
If the logarithmic viscosity is less than 0.30, the flame retardancy and mechanical strength of the molded article are often insufficient, and if it exceeds 2.00 dl / g, the molding fluidity tends to decrease.

The thermoplastic polyester resin (B) can be used alone or in combination of two or more.
When two or more kinds are used in combination, the combination is not limited. For example, those having different copolymer components and different molar ratios and / or those having different molecular weights are arbitrarily combined. In the present invention, the mixing ratio of the (A) polycarbonate resin and the (B) thermoplastic polyester resin is 95/5 to 50/50 by weight, preferably 90/10 to 55/45. More preferably, it is in the range of 85/15 to 60/40. When the weight ratio of (B) the thermoplastic polyester resin in the mixture of (A) the polycarbonate resin and (B) the thermoplastic polyester resin is less than 5, the moldability and the moldability of the obtained molded article are reduced. Solvent properties are decreased, and if it exceeds 50, impact resistance and flame retardancy are undesirably decreased. In the present invention, a compound containing bromine or chlorine can be obtained by using at least one flame retardant selected from (C) (C1) an organic phosphorus flame retardant, and (C2) a coated stabilized red phosphorus. High flame retardancy can be provided without using it. The component (C) may be used alone for each of the components (C1) and (C2),
The components (C1) and (C2) may be used in combination. (C
1) Specific examples of the organic phosphorus-based flame retardant include phosphate, phosphonate, phosphinate, phosphine oxide, phosphite, phosphonite, phosphinite, phosphazene, and the like. More specifically, trimethyl phosphate, triethyl phosphate, tributyl phosphate, tributyl phosphate, and the like. (2-ethylhexyl) phosphate, tributoxyethyl phosphate, triphenyl phosphate, tricresyl phosphate, trixylenyl phosphate, tris (isopropylphenyl) phosphate, trinaphthyl phosphate, cresyl diphenyl phosphate, xylenyl diphenyl phosphate, diphenyl ( 2-ethylhexyl) phosphate, di (isopropylphenyl) phenyl phosphate, phenyldicresyl phosphate DOO, di 2-ethylhexyl phosphate, monoisodecyl phosphate, 2-acryloyloxyethyl acid phosphate, 2-methacryloyloxyethyl acid phosphate, diphenyl -
2-acryloyloxyethyl phosphate, diphenyl-2-methacryloyloxyethyl phosphate, triphenyl phosphite, trisnonylphenyl phosphite, tristridecyl phosphite, dibutyl hydrogen diene phosphite, triphenyl phosphine oxide, tricresyl phosphine oxide, methane Phosphorus compounds such as diphenyl phosphonate, diethyl phenylphosphonate, phenoxyphosphazene, propoxyphosphazene, and the like. Here, in particular, the following general formula (2):

[0020]

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(Wherein R1 to R4 are monovalent aromatic groups or aliphatic groups, R5 is a divalent aromatic group, n is 0 to 16, and n R3 and R5 are different from each other. The phosphoric acid ester represented by the general formula (2) is preferred because the moldability can be greatly improved, the flame retardancy is excellent, and the handling is easy. The condensed phosphoric acid ester having a molecular weight of from 16 to 16 is more preferable from the viewpoint of low contamination to metal parts such as a mold during molding. Specific examples of the phosphate ester (n = 0) represented by the general formula (2) include triphenyl phosphate, tricresyl phosphate, trixylenyl phosphate, cresyl diphenyl phosphate, xyenyl diphenyl phosphate, and the like. Can be Specific examples of the condensed phosphate represented by the above general formula (2) include resorcinol bis (diphenyl) phosphate
(3)

[0022]

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(N = 0 to 15) Resorcinol bis (di-2,6-xylyl) phosphate (4)

[0024]

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(N = 0 to 15) bisphenol A bis (dicresyl) phosphate (5)

[0026]

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(N = 0 to 15) Hydroquinone bis (di-2,6-xylyl) phosphate (6)

[0028]

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(N = 0 to 15) and condensates obtained by combining them. These organic phosphorus flame retardants may be used alone or in combination of two or more. When the organic phosphorus-based flame retardant (C1) is used alone, the amount added is based on 100 parts by weight of the resin composed of the polycarbonate resin (A) and the thermoplastic polyester resin (B).
0.1 to 30 parts by weight, preferably 0.2 to 25 parts by weight, more preferably 0.3 to 20 parts by weight.
(C1) When the addition amount of the organic phosphorus-based flame retardant is less than 0.1 part by weight, the effect of improving flame retardancy and molding processability is poor, and
If the amount exceeds 0 parts by weight, the resulting molded article tends to have reduced impact resistance, heat resistance and solvent resistance.

The (C2) coated stabilized red phosphorus used in the present invention is red phosphorus stabilized by coating the surface by various methods, preferably a thermosetting resin coating. And red phosphorus coated with at least one compound selected from metal hydroxide coatings and metal plating coatings. The thermosetting resin is not particularly limited as long as it can coat red phosphorus, and specific examples thereof include a phenol-formalin-based resin, a urea-formalin-based resin,
Melamine-formalin-based resins, alkyd-based resins, and the like. The metal hydroxide is not particularly limited as long as it can cover red phosphorus, and specific examples thereof include aluminum hydroxide, magnesium hydroxide, zinc hydroxide, and titanium hydroxide. The electroless plating film is not particularly limited as long as it can cover red phosphorus, but is not limited to Fe, Ni, Co, Cu, Zn, Mn, Ti, and Z.
r, Al or alloys thereof. Further, these coatings may be used in combination of two or more or two or more layers. The stabilized red phosphorus is preferably red phosphorus that has been treated with one or more compound coatings selected from thermosetting resin coatings, metal hydroxide coatings, and metal plating coatings. This is because the stabilized red phosphorus-based flame retardant is easy to handle and the odor is also improved. The stabilized red phosphorus is used alone or in combination of two or more. 2
When used in combination of more than one kind, the combination is not limited. For example, different coatings and / or different coatings having different particle sizes can be arbitrarily combined.
(C2) When the stabilized red phosphorus is used alone, the content is as follows:
With respect to 100 parts by weight of the total amount of (A) the polycarbonate resin and (B) the thermoplastic polyester resin, 0.
The amount is 1 to 5 parts by weight, preferably 0.3 to 4 parts by weight, and more preferably 0.5 to 3 parts by weight. If the amount is less than 0.1 part by weight, the resulting molded article has insufficient flame retardancy. If the amount exceeds 5 parts by weight, odor is generated during molding, which is not preferable. The preferable addition amount when the above (C1) and (C2) are added together is the same as the addition amount when the above (C1) and (C2) are individually added. (C
1) By adding (C2) in combination, excellent flame retardancy can be obtained without deteriorating the excellent properties such as the impact resistance and heat resistance of the polycarbonate resin and the solvent resistance of the polyester resin. And can improve moldability at the same time. The epoxy-modified block copolymer (D) used in the present invention comprises a polymer block (1) mainly composed of a vinyl aromatic compound and a polymer block (2) mainly composed of a conjugated diene compound in the same molecule. The double bond derived from the conjugated diene compound of the block copolymer (3) or its partially hydrogenated product (4) is epoxidized. As the “vinyl aromatic compound” which is the main component of the polymer block (1) constituting the block copolymer (3),
Styrene, α-methylstyrene, vinyltoluene, p-
Tertiary butylstyrene, divinylbenzene, p-methylstyrene, 1,1-diphenylstyrene and the like can be exemplified,
Styrene is preferably used. These are one or two
More than one species can be used in combination. Examples of the “conjugated diene compound” which is the main component of the polymer block (2) constituting the block copolymer (3) include butadiene, isoprene, 1,3-pentadiene, 2,3-dimethyl-
1,3-butadiene, piperylene, 3-butyl-1,3
-Octadiene, phenyl-1,3-butadiene and the like. One or more of these can be used in combination. Among them, butadiene, isoprene and a combination thereof are preferred. The block copolymer (3) is composed of a polymer block (1) composed of a vinyl aromatic compound and a polymer block (2) composed of a conjugated diene compound. The copolymerization (weight) ratio of the vinyl aromatic compound and the conjugated diene compound is such that the vinyl aromatic compound / conjugated diene compound is in the range of 5/95 to 70/30,
In particular, it is preferably in the range of 10/90 to 60/40. The molecular structure of the block copolymer (3) may be linear, branched, radial, or any combination thereof. For example, the polymer block (1) and the polymer block (2) are 1-2-1, 2-1-2-1,
A case having a structure such as (1-2-) 4Si or 1-2-1-2-1 can be exemplified. The unsaturated bond derived from the conjugated diene compound of the block polymer (3) may be partially hydrogenated (4). The number average molecular weight of the block copolymer (3) is from 5,000 to 600,000.
And particularly preferably 10,000 to
It is in the range of 500,000. In addition, the molecular weight distribution [the ratio of the weight average molecular weight (Mw) to the number average molecular weight (Mn) (M
w / Mn)] is preferably 10 or less. This is because within this range, appropriate compatibility with each component can be obtained. The epoxy-modified block copolymer (D) is obtained by reacting the block polymer (3) or its partially hydrogenated product (4) with an epoxidizing agent such as hydroperoxides and peracids in an inert solvent. can get. By blending the epoxy-modified block copolymer (D), a suitable impact resistance can be imparted to the thermoplastic resin composition. The amount of the epoxidizing agent used in the epoxidation is not strictly limited, and is appropriately selected depending on the type of the epoxidizing agent, the desired degree of epoxidation, and the individual block copolymer (3) or (4) used. . (D) It is preferable to use an epoxy-modified block copolymer having an epoxy equivalent of 250 or more and 3000 or less. If the epoxy equivalent is less than 250, a gel may be formed due to the reaction of the epoxy group at the time of molding, or the moldability of the composition tends to be reduced. If the epoxy equivalent exceeds 3000, the effect of improving the impact resistance is poor. There is a tendency that the surface of the molded product is peeled off during molding. (D) the epoxy-modified block copolymer,
It is preferable to use those having a weight ratio of the aromatic vinyl compound to the epoxidized diene compound of from 30/70 to 80/20. When the weight ratio of the aromatic vinyl compound is less than 30%, the thermal stability at the time of molding at a high temperature tends to decrease, and when it exceeds 80%, the effect of improving the impact resistance is poor, or during molding. There is a tendency for the surface of the molded article to peel off. In the present invention, (E) (E1) silicone,
By using at least one compound selected from the group consisting of (E2) a silicate compound and (E3) a fluororesin, it is possible to prevent a dripping phenomenon that occurs during a combustion test and to impart high flame retardancy to a thin-walled molded product. Can be. The component (E) is (E1)
To (E3) may be used alone, and (E1)
The components (E3) to (E3) may be arbitrarily used in combination of two kinds, or all the components (E1) to (E3) may be used. The (E1) silicone used in the present invention is not particularly limited. For example, R ₃ SiO _0.5 , R ₂ SiO, RSiO _1.5 ,
_{R'R 2 SiO 0.5, R'RSiO, R} '2 SiO, R'
SiO _1.5 , SiO ₂ units and mixtures thereof (wherein R
Is independently a substituted or unsubstituted saturated or unsaturated monovalent hydrocarbon group, R ′ is each independently the same as R or a hydrogen atom, represents a group such as hydroxyl, alkoxyl, aryl, vinyl, allyl, Furthermore, R, R '
Some of the groups of epoxy group, amino group, hydroxyl group, carboxyl group, mercapto group, vinyl group, phenol group,
Which may be substituted with a reactive group such as an acryl group or a methacryl group), or a liquid, a gum, a varnish, a powder, Flaky polymers and the like.
Specific examples include polydimethylsiloxane, polymethylphenylsiloxane, and polydiorganosiloxane having R ₂ SiO as a main structural unit, such as polydiphenylsiloxane, and some of the hydrogen atoms contained in the hydrocarbon group of the polydiorganosiloxane are epoxy. Group, amino group, hydroxyl group, carboxyl group, mercapto group, vinyl group, phenol group, acrylic group, modified polydiorganosiloxane substituted with reactive group such as methacryl group, polymethylsilsesquioxane, polymethylphenylsilsesquioxane Polyorganosilsesquioxane having RSiO _1.5 as a main constituent unit, such as oxane, _0.5 unit of R ₃ SiO and Si
Examples thereof include a silicone resin having an O ₂ unit as a main component and a polyorganosiloxane rubber having rubber elasticity. The amount of the silicone (E1) used is 0.1 to 50 parts by weight, preferably 0.1 to 50 parts by weight, based on 100 parts by weight of the total of the polycarbonate resin (A) and the thermoplastic polyester resin (B). It is 40 parts by weight, more preferably 0.5 to 30 parts by weight. The amount used is 0.
If the amount is less than 1 part by weight, the flame retardancy is insufficient, and if it exceeds 50 parts by weight, the mechanical strength of the flame retardant resin composition of the present invention tends to decrease, which is not preferable. Silicone (E
1) may be used alone or in combination of two or more. When two or more types are used in combination, the combination is not particularly limited. The (E2) silicate compound used in the present invention has an effect of improving the flame retardancy. In addition, the addition of the silicate compound can improve the heat resistance and the elastic modulus. it can. Such a silicate compound is typically a compound having a chemical composition of SiO2 units. Although the shape is not particularly limited, it is typically in the form of powder, granule, needle, plate, or the like. These silicate compounds may be natural products or synthesized products. Specific examples of the silicate compound include magnesium silicate, aluminum silicate, calcium silicate, talc, mica, wollastonite, kaolin, diatomaceous earth, and smectite. Among them, mica, talc, kaolin, and smectite are excellent in the effect of remarkably increasing the flame retardancy of the molded product, and also have the effect of suppressing the anisotropy of the molded product when it is formed, as well as its heat resistance and mechanical properties. It is preferable because it also has an excellent effect of improving strength. They are,
They may be used alone or in combination of two or more. When two or more types are used in combination, the combination is not particularly limited. The silicate compound (E2)
It may be treated with a surface treatment agent such as a silane coupling agent or a titanate coupling agent. Examples of the silane coupling agent include epoxy silane, amino silane, and vinyl silane. Examples of the titanate coupling agent include monoalkoxy type, chelate type, and coordinate type. The amount of the silicate compound (E2) is 0.1 to 10 parts by weight based on 100 parts by weight of the resin composed of the polycarbonate resin (A) and the thermoplastic polyester resin (B).
0 parts by weight, preferably 0.2 to 70 parts by weight, more preferably 0.3 to 50 parts by weight. (E2) When the added amount of the silicate compound is less than 0.1 part by weight, the obtained molded article has poor flame retardancy improving effect, and when it exceeds 100 parts by weight, the impact resistance of the obtained molded article, Thermal stability and surface properties are reduced, and handling tends to be difficult such that kneading with a resin during melt kneading becomes difficult. The fluororesin (E3) used in the present invention is a resin having a fluorine atom. Is a resin having a fluorine atom in the resin. Specifically, polymonofluoroethylene, polydifluoroethylene, polytrifluoroethylene, polytetrafluoroethylene, tetrafluoroethylene / hexafluoropropylene copolymer, ethylene / tetrafluoroethylene copolymer, polyvinylidene fluoride, etc. Can be mentioned. Further, if necessary, the monomer used in the production of the fluororesin and the copolymerizable monomer may be used in combination to polymerize, if necessary, to the extent that physical properties such as flame retardancy of the obtained molded article are not impaired. The obtained copolymer may be used. One of these fluorine resins may be used alone, or two or more thereof may be used in combination. The molecular weight of the fluororesin is preferably from 1,000,000 to 20,000,000, more preferably from 2,000,000 to
10 million. The method for producing these fluororesins can be obtained by a generally known method such as emulsion polymerization, suspension polymerization, bulk polymerization, and solution polymerization. The fluorinated resin (E3) is preferably a fluorinated polyolefin resin, and more preferably a fluorinated polyolefin resin having an average particle size of 700 μm or less. Here, the average particle size refers to an average particle size of secondary particles formed by aggregation of primary particles of a fluorinated polyolefin resin. Furthermore, a fluorinated polyolefin resin is preferably a fluorinated polyolefin resin having a density-to-bulk density ratio (density / bulk density) of 6.0 or less. Here, the density and bulk density are J
It was measured by the method described in IS-K6891. The fluorinated resin (E3) may be used alone or in combination of two or more. When two or more kinds are used in combination, the combination is not limited. For example, different types are used arbitrarily. The amount of the fluororesin (E3) used is 0.005 to 5 parts per 100 parts by weight of the total amount of the polycarbonate resin (A) and the thermoplastic polyester resin (B).
Parts by weight, preferably 0.01 to 1 part by weight, more preferably 0.02 to 0.5 part by weight. If the amount is less than 0.005, the effect of improving the flame retardancy is small, and if it exceeds 5 parts by weight, the molding fluidity and the surface appearance of the molded article of the flame retardant resin composition of the present invention tend to decrease. Therefore, it is not preferable. In the present invention, (F) an olefin-based resin is used to improve the impact resistance, toughness, and solvent resistance of the obtained molded article. As these resins, those having at least one glass transition point at 0 ° C. or lower, more preferably −20 ° C. or lower, are preferable in order to improve the impact resistance of the obtained resin. Olefin-based resins include, in addition to polyolefins in a narrow sense, polydienes, mixtures of two or more thereof, copolymers of two or more olefin monomers and diene monomers, and other vinyl copolymerizable with olefin monomers and olefins. It is used as a broad concept including a copolymer comprising at least one type of monomer. For example, ethylene, propylene, 1-butene, 1-pentene, isobutene, butadiene, isoprene, phenylpropadiene, cyclopentadiene, 1,
5-norbornadiene, 1,3-cyclohexadiene,
A single polymer selected from one or a combination of two or more of monomers such as 1,4-cyclohexadiene, 1,5-cyclooctadiene, 1,3-cyclooctadiene, α, ω-nonconjugated dienes, and the like. Examples thereof include a mixture comprising a copolymer or a copolymer, a homopolymer thereof, and a mixture of two or more copolymers. Among these, polyethylene, polypropylene and the like are preferably used because the solvent resistance of the obtained composition is improved. In addition, these olefin components, (meth) acrylic acid, (meth)
A copolymer of a vinyl monomer copolymerizable with an olefin such as alkyl acrylate, glycidyl (meth) acrylate, vinyl acetate, maleic anhydride, N-phenylmaleimide, carbon monoxide, etc. Is also good.
Specific examples of these copolymers include polyethylene / alkyl (meth) acrylate copolymer, ethylene / alkyl (meth) acrylate / carbon monoxide copolymer, and ethylene / glycidyl methacrylate. Copolymer, ethylene-glycidyl methacrylate-vinyl acetate copolymer, ethylene-glycidyl methacrylate-alkyl (meth) acrylate copolymer, ethylene-vinyl acetate copolymer, ethylene-vinyl acetate-carbon monoxide copolymer And ethylene / (meth) acrylic acid copolymer, ethylene / maleic anhydride copolymer, ethylene / maleic anhydride / N-phenylmaleimide copolymer, and the like. Equivalent copolymers can be produced with other olefin resins. The method for polymerizing these polyolefin resins is not particularly limited, and can be polymerized by various methods. As long as it is polyethylene, high-density polyethylene, medium-density polyethylene, low-density polyethylene, linear low-density polyethylene, and the like can be obtained by a polymerization method, and any of them can be preferably used. (F) The addition amount of the olefin resin is preferably 0.1 to 20 parts by weight, more preferably 0 to 20 parts by weight, based on 100 parts by weight of the resin composed of the polycarbonate resin (A) and the thermoplastic polyester resin (B). 0.2 to 15 parts by weight, most preferably 0.3 to 10 parts by weight. If the amount is less than 0.1 part by weight, the effect of improving the impact resistance and solvent resistance of the composition is small,
Exceeding the weight parts is not preferred because the flame retardancy, rigidity, heat resistance and the like of the obtained composition are reduced. The flame-retardant resin composition of the present invention further includes any other thermoplastic or thermosetting resin within a range not to impair the present invention, such as an unsaturated polyester resin, a polyamide resin, a polystyrene resin, and a rubber-like resin. Elastic copolymer polystyrene resin, acrylonitrile / styrene compound copolymer, polyalkyl (meth) acrylate resin, polyphenylmaleimide resin, polyphenylene sulfide resin, polyphenylene ether resin, polyacetal resin, polysulfone resin, A rubber-like elastic body, a graft-modified rubber-like elastic body, or the like may be added alone or in combination of two or more. Further, in order to make the flame-retardant resin composition of the present invention a higher-performance one, an antioxidant such as a phenol-based antioxidant, a thioether-based antioxidant, a heat stabilizer such as a phosphorus-based stabilizer, and the like. Are preferably used alone or in combination of two or more. Further, if necessary, generally well-known stabilizers, lubricants, release agents, plasticizers, non-phosphorus-based flame retardants, flame retardant aids, ultraviolet absorbers, light stabilizers, pigments, dyes, antistatics Additives such as an agent, a conductivity imparting agent, a dispersant, a compatibilizer, and an antibacterial agent can be used alone or in combination of two or more. The method for producing the composition of the present invention is not particularly limited. For example, it can be produced by a method of drying and kneading the above components, other additives, resins, etc., and then using a melt kneading machine such as a single screw or twin screw extruder. When the compounding agent is a liquid, it can be produced by adding the compounding agent to the extruder midway using a liquid supply pump or the like. The molding method of the thermoplastic resin composition produced by the present invention is not particularly limited, and molding methods generally used for thermoplastic resins, for example, injection molding, blow molding, extrusion molding, vacuum molding, press Molding, calendar molding, etc. can be applied.

[0031]

EXAMPLES Hereinafter, the present invention will be described in detail with reference to Examples, but the present invention is not limited thereto. In the following, “parts” means parts by weight and “%” means% by weight, unless otherwise specified. The evaluation of the resin composition was performed by the following method. Evaluation method The obtained pellet was dried at 100 ° C. for 4 hours, and then dried at 150 ° C.
t Using a injection molding machine, at a cylinder temperature of 270 ° C. and a mold temperature of 50 ° C., a thickness of 1.6 mm, 2.5 mm, 3.2 m
m, bar (width 12 mm, length 127 mm), thickness 3.
2 mm ASTM No. 1 dumbbell test piece, 150 mm square x
A flat plate having a thickness of 2.5 mm was obtained, and the following evaluation was performed. Flame retardancy: Flame retardancy of a 1.6 mm thick bar was evaluated by a V test according to UL-94 standard. In this evaluation, the flame retardancy was V-
Those having a rating of 0 were evaluated for flame retardancy by a 5V test using a 2.5 mm-thick bar and a 150 mm-square 2.5 mm-thick flat plate according to the UL-94 standard. Impact resistance: Using a 3.2 mm thick bar, ASTM D-
According to 256, notched IZOD impact strength was measured at 23 ° C. to evaluate impact resistance. Solvent resistance: (1) A 3.2 mm-thick bar was given 1% bending strain, gasoline (regular gasoline manufactured by Nippon Oil Co., Ltd.) was applied, and then left at 23 ° C. for 48 hours. (2) A 3.2 mm bar was given 1% bending strain, applied with salad oil, and then treated in an oven maintained at 80 ° C. for 72 hours. (3) A 3.2 mm bar was subjected to 1% bending strain, dioctyl phthalate (reagent) was applied, and the bar was treated in an oven maintained at 80 ° C. for 24 hours. These three types of treatments were separately performed, and changes in surface appearance were visually evaluated according to the following criteria. ：: No change in appearance in any of the tests. ：: Cracks occurred in the sample in any one or two of the tests. X: Cracks occurred in the sample in any of the three tests. Thermal stability: Obtained pellets After drying at 100 ° C for 4 hours, the cylinder temperature was 310 ° C using a 75t injection molding machine.
With a molding cycle of 3 minutes, a mold temperature of 50 ° C. and 150
Twenty plate-shaped molded products of mm × 150 mm × 2.5 mm were molded, and the surface appearance was visually evaluated for ten molded products from the tenth to the twentieth. ：: good appearance ：: poor appearance due to flash, silver, resin burn, discoloration, etc. is observed in a part of the molded product. ×: Poor appearance due to flash, silver, resin burning, discoloration, etc. is observed on the entire surface of the molded product. Moisture and heat resistance: ASTM No. 1 test piece was treated at 65 ° C. and 85% humidity for 1000 hours, and the test piece before and after the treatment was subjected to AST.
23 ° C., tensile speed 10 mm / m according to MD638
A tensile test was performed under the conditions of “in”, and a tensile strength retention was calculated from a difference in tensile strength before and after the treatment. The higher the retention, the better the resistance to moist heat. Moldability According to JIS K-6730, the value of the melt index at 280 ° C. and a load of 2160 g was measured. (Unit g /
Example 1-A polyethylene terephthalate resin (B1) polymerized using 85 parts by weight of a bisphenol A type polycarbonate resin (A1) having a viscosity average molecular weight of about 23500 and germanium dioxide having an logarithmic viscosity of about 0.75 dl / g. ) Epoxy-modified block copolymer (D1) obtained by epoxidizing 15 parts by weight of a styrene-butadiene block copolymer [Epofriend A-1020: trade name, manufactured by Daicel Chemical Industries, Ltd.]
Butadiene / styrene weight ratio 60/40, epoxy equivalent of about 510] 2.0 parts by weight, talc (E2-1) (talcan PK: trade name, manufactured by Hayashi Kasei) having an average particle diameter of 13 μm 0.5
Part, polytetrafluoroethylene (E3-1) (Polyflon FA-500: trade name, manufactured by Daikin) 0.3 part, ethylene / ethyl acrylate copolymer [ethyl acrylate content = 35% by weight] (F1) (Evaflex EE
AA709: trade name, manufactured by Du Pont-Mitsui Polychemicals) 2.
0 parts, as a stabilizer, HP which is a phosphite-based stabilizer
0.2 parts by weight of -10 (trade name of Asahi Denka) and 0.2 parts of AO-60 (trade name of Asahi Denka) which is a phenolic stabilizer.
Parts by weight in advance, and a twin-screw extruder [TEX4
4: Trade name of Nippon Steel Works Co., Ltd.] and 7.5 parts of bisphenol A bis (dicresyl phosphate) as an organic phosphorus-based flame retardant (C1) was added on the way from the liquid addition pump of the extruder. And melt-extruded to obtain a resin composition. Table 1 shows the evaluation results of the resin composition. Examples 2 to 18: Resin compositions were obtained in the same manner as in Example 1 except that the amounts of each compounding agent were changed to those shown in Tables 1 and 2. However, the following compounding agents were used. The evaluation results are shown in Tables 1 and 2. (A) Bisphenol A having a viscosity average molecular weight of about 26500 as a polycarbonate resin
-Type polycarbonate resin (A2) (B) As a thermoplastic polyester resin ・ Polyethylene terephthalate resin having a logarithmic viscosity of 0.6 (B2) ・ Polybutylene terephthalate resin having a logarithmic viscosity of 0.85 (B3) (C1) Organic Phosphorus-based flame retardant triphenyl phosphate (C1-2) tri (2,6-xylyl) phosphate (C1-3) resorcinol bis (di-2,6-xylyl) phosphate (C1-4) hydroquinone bis (Di-2,6-xylyl) phosphate (C1-5) resorcinol bis (diphenyl) phosphate (C
1-6) Among these, those that were liquid at room temperature were added on the way from the liquid addition pump of the extruder, and those that were solid at room temperature were added from the hopper of the extruder. (C2) As coated stabilized red phosphorus: Stabilized red phosphorus [Nova Excel F5: trade name of Rin Kagaku Kogyo] Stabilized red phosphorus whose surface is coated with a phenolic resin (C
2-1) (D) As a copolymer, (D2) Epofriend A1010: Daicel Chemical Industries, Ltd., trade name: butadiene / styrene weight ratio 60/4
0, epoxy equivalent about 1000] (E1) As silicone: Silicone (E1-1) [Si powder DC4-70
51: Trade name of Toray Dow Corning Silicone) (E2) As a silicate compound ・ Mica having an average particle diameter of about 20 μm [A-21S: trade name of Mika Yamaguchi] (E2-2) (F) As an olefin resin, Ethylene / methyl acrylate / glycidyl methacrylate copolymer [methyl acrylate content = 30% by weight, glycidyl methacrylate content = 6% by weight] (F
2) (Bond First 7M: trade name of Sumitomo Chemical) ・ Linear low-density polyethylene (F3) (moretech 016)
8N: trade name of Idemitsu Petrochemical) Ethylene glycidyl methacrylate copolymer [glycidyl methacrylate content = 12% by weight] (F4)
(Bond First E: trade name, manufactured by Sumitomo Chemical) Comparative Examples 1 to 10 Example 1 except that the amount of each compounding agent was changed to the amount shown in Table 3.
In the same manner as in the above, a resin composition was obtained. Table 3 shows the evaluation results. The following compounding agents were used except for those shown in the examples. MBS rubber: Kaneace M-511 (trade name, manufactured by Kanegafuchi Chemical Industry Co., Ltd.) ABS rubber: graft copolymer of 50 wt% of butadiene, 10 wt% of acrylonitrile and 40 wt% of styrene. In Comparative Example 1, since the (B) polyester was not used, the solvent resistance and the moldability deteriorated. In Comparative Example 2, since the ratio of (A) polycarbonate to (B) polyester is out of the range of the present patent, impact resistance and flame retardancy are reduced. In Comparative Example 3, no flame retardancy was obtained because the flame retardant (C) was not used. In Comparative Example 4,
(C) Since the amount of the flame retardant is out of the range of the present patent, solvent resistance, thermal stability, wet heat resistance, and the like are reduced. In Comparative Example 5, since the copolymer (D) was not used, the impact resistance, the wet heat resistance, and the solvent resistance were reduced, and the thermal stability and flame retardancy were slightly deteriorated. In Comparative Example 6, since none of (E) was used, the flame retardancy was reduced. In Comparative Example 7, since the (F) olefin-based resin was not used, impact resistance and solvent resistance were reduced. In Comparative Example 8, since the amount of the copolymer (D) was out of the range of the present invention, molding was difficult. In Comparative Example 9, since the graft rubber was used in place of the copolymer (D), the wet heat resistance, the heat stability, and the solvent resistance were reduced, and the flame retardancy also tended to be slightly reduced. As is clear from the comparison between Tables 1 and 2 as Examples and Table 3 as Comparative Examples, all of the compositions of the present invention have flame resistance, impact resistance and solvent resistance. It can also be seen that they are excellent in wet heat resistance and heat stability.

[0032]

Industrial Applicability The flame-retardant resin composition of the present invention is characterized by the impact resistance, solvent resistance, wet heat resistance and heat stability of a polycarbonate resin composition flame-retarded without using compounds such as chlorine and bromine. It is possible to provide a composition having improved flame retardancy, exhibiting higher flame retardancy as compared with conventionally known compositions, and having good moldability. These are very useful industrially.

[0033]

【table 1】

[0034]

[Table 2]

[0035]

[Table 3]

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) C08L 27/12 C08L 27/12 53/02 53/02 67/02 67/02 83/04 83/04 F Term (reference) 4J002 AC085 BB034 BB054 BB064 BB074 BB094 BB124 BB154 BB164 BC065 BD124 BD144 BD154 BD164 BG035 BK004 BL024 BP014 CB005 CD204 CF042 CF052 CF062 CF072 CF082 CF215 CG010 CG020 CG04 CH0 014 EW156 FB077 FB108 FB138 FB148 FB168 FB267 FD020 FD030 FD040 FD050 FD090 FD100 FD110 FD130 FD133 FD136 FD160 FD170 FD180 FD200

Claims (4)

[Claims] 1. 100 parts by weight of a resin composition comprising (A) a polycarbonate resin and (B) a thermoplastic polyester resin, wherein the weight ratio (A) / (B) of both is 95/5 to 50/50. (C) at least one phosphorus-based flame retardant selected from the following (C1) and (C2): (C1) 0.1 to 30 parts by weight of an organic phosphorus-based flame retardant (C2) coated stabilized red phosphorus 0.1 to 5 parts by weight (D) A block copolymer comprising a polymer block (1) mainly composed of a vinyl aromatic compound and a polymer block (2) mainly composed of a conjugated diene compound in the same molecule. A double bond derived from the conjugated diene compound of (3) or its partially hydrogenated product (4) is partially or entirely epoxidized,
0.5 to 20 parts by weight of epoxy-modified block copolymer (E) One or more compounds selected from the following (E1) to (E3) (E1) 0.1 to 50 parts by weight of silicone (E2) silicate compound 0 0.1 to 100 parts by weight (E3) 0.005 to 5 parts by weight of a fluorinated resin (F) 0.1 to 20 parts by weight of one or more olefinic resins 2. The flame-retardant thermoplastic resin composition according to claim 1, wherein (C) the organic phosphorus-based flame retardant is a phosphoric ester represented by the following general formula (I). (Wherein, R1 to R4 are monovalent aromatic groups or aliphatic groups,
R5 represents a divalent aromatic group and n represents 0 to 16, and n R3 and R5 may be different from each other. ) 3. The epoxy-modified block copolymer (D) has an epoxy equivalent of 250 or more and 3000 or less and a weight ratio of the aromatic vinyl compound to the epoxidized diene compound of 30/70 to 80/20. Claim 1 which is
2. The flame-retardant thermoplastic resin composition according to item 2. 4. The method according to claim 1, wherein (B) the thermoplastic polyester resin is
The flame-retardant thermoplastic resin composition according to claim 1, which is a polyalkylene terephthalate having an alkylene terephthalate unit of 80% by weight or more.