JPH10168297A - Flame-retardant thermoplastic resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a flame-retardant resin composition which has an excellent molding flow and can give a molding having an excellent flame retardancy and heat resistance and persistent stabilized flame retardancy and deforming little even under high-temperature high-humidity conditions by mixing a mixture comprising a polycarbonate resin and a polyester resin with a limited organophosphorus flame retardant and a stabilized red phosphor flame retardant in a specified ratio. SOLUTION: This composition comprises 100 pts.wt. mixture comprising a polycarbonate resin (A) and a thermoplastic polyester resin (B) in a ratio of 85/15 to 50/50 by weight, 1-11 pts.wt. organophosphorus flame retardant (C) represented by the formula (wherein m1 , m2 , m3 and m4 are each 0-2; and n is 1-15) and 0.05-5 pts.wt. stabilized red phosphorus flame retardant (D). Component A is desirably made from bisphenol A and has desirably a viscosity-average molecular weight of 18.000-35.000. Component B used is exemplified by polyethylene terephthalate. An example of component C is bisphenol A poly(diglycidyl) phosphate. Component D is exemplified by red phosphorus coated with e.g. a thermosetting resin.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a flame-retardant thermoplastic resin composition. More specifically, it is flame retarded with a specific organophosphorus flame retardant and stabilized red phosphorus flame retardant, has excellent molding fluidity, heat resistance and low mold contamination, and can be used at high temperatures for a relatively long time. Even if exposed, there is little decrease in flame retardancy,
Further, the present invention relates to a flame-retardant thermoplastic resin composition that causes less deformation of a molded article even when exposed to high temperature and high humidity.

[0002]

2. Description of the Related Art Polycarbonate resins have high impact resistance,
It is a thermoplastic resin with excellent heat resistance and is widely used as a part in the fields of machinery, automobiles, electricity, electronics and the like.

[0003] Among the polycarbonate resins, aromatic polycarbonate resins have a high glass transition temperature,
Although it has the characteristic of high heat resistance, there are many cases where sufficient fluidity cannot be obtained at the time of processing. Therefore, processing of an aromatic polycarbonate resin requires a relatively high processing temperature of about 300 ° C. In addition, when molding an aromatic polycarbonate resin by injection molding or the like, relatively high injection speed and pressure are required.

On the other hand, thermoplastic polyester resins are excellent in mechanical properties, electrical properties, chemical resistance, etc., and show good molding fluidity when heated to a temperature higher than the crystal melting point of the resin itself. Conventionally, they have been widely used as fibers, films, molding materials and the like.

Attempts have been made to improve the fluidity and other problems of polycarbonate resins, especially aromatic polycarbonate resins, by utilizing such properties of thermoplastic polyester resins. For example,
JP-A-14035, JP-B-39-20434, and JP-A-59-176345 propose compositions in which a polyester resin such as polyethylene terephthalate or polybutylene terephthalate is added to a polycarbonate resin.

By the way, when a thermoplastic resin is used, in order to ensure safety against fire, a sophisticated resin such as one conforming to UL-94 V-0 (US Underwriters Laboratory Standard) is used. In many cases, flame retardancy is required, and various flame retardants have been studied and developed.

[0007] In recent years, with the increasing interest in environmental issues mainly in Europe, various uses of halogen-free flame retardants such as phosphorus-based flame retardants have been studied. Examples of the phosphorus-based flame retardant include an organic phosphorus-based compound and a red phosphorus-based flame retardant.

Examples of the organic phosphorus compounds include, for example, JP-A-63-227632 and JP-A-5-10-10.
79 and JP-A-5-279513.

Japanese Patent Application Laid-Open No. 5-179123 also discloses a composition flame-retarded using the above-mentioned organic phosphorus-based flame retardant, in which a resin composition comprising a polycarbonate resin and a resin other than the polycarbonate resin is used. A flame-retardant resin composition containing a phosphorus-based flame retardant, a boron compound, a polyorganosiloxane, and a fluorine-based resin is disclosed in JP-A-6-192.
No. 553 discloses a flame-retardant resin composition obtained by adding a graft copolymer, an oligomeric organic phosphorus-based flame retardant, and a fluorinated polyolefin to a resin composition comprising a polycarbonate resin and a polyalkylene terephthalate resin. ing.

Examples of the red phosphorus-based flame retardant include red phosphorus-based flame retardants described in JP-B-54-39200, JP-A-55-10463, and JP-B-5-8125. Can be

As the composition flame-retarded by using the above-mentioned red phosphorus-based flame retardant, for example, JP-A-48-85642 and JP-A-50-78651 disclose powdery polycarbonate resin. A flame retardant resin composition to which red phosphorus is added is described.

[0012]

In the field where such a flame-retardant resin composition is used, for example, in the field of electric and electronic parts, simplification of the assembling process and cost reduction are required. Integration and thinning are in progress. Therefore, materials used for such components are required to maintain high heat resistance and high flame retardancy, as well as good molding fluidity.

However, in order to obtain good molding fluidity in a flame-retardant resin composition comprising a polycarbonate-based resin and an organic phosphorus-based flame retardant or a polycarbonate-based resin, a thermoplastic polyester-based resin and an organic phosphorus-based flame retardant. It is necessary to increase the amount of an organic phosphorus-based flame retardant or a thermoplastic polyester-based resin and an organic phosphorus-based flame retardant, but such a composition greatly reduces heat resistance. Further, when the amount of the thermoplastic polyester-based resin is increased, the flame retardancy is reduced, and it is necessary to increase the amount of the organic phosphorus-based flame retardant, which further reduces the heat resistance. Further, the organic phosphorus-based flame retardant has a relatively low decomposition temperature, and a decomposition gas is generated when the flame-retardant resin composition is molded by injection molding or the like, which causes a problem of mold contamination, or a problem. Long-term stable flame retardancy and wet heat resistance, such as deterioration of flame retardancy when a molded body is treated at high temperature for a relatively long time, or deformation of the molded body when exposed to high temperature and high humidity Also occurs.

A composition obtained by adding a red phosphorus flame retardant to a polycarbonate resin often has insufficient molding fluidity, and the flame retardant resin composition is molded by injection molding or the like. At this time, there is a problem that a gas having a peculiar odor is generated, which has an adverse effect on the human body.

[0015] In order to solve the above-mentioned problems, the present inventors first added an organic phosphorus-based flame retardant and a red phosphorus-based flame retardant to a resin composition comprising a polycarbonate-based resin and a thermoplastic polyester-based resin. -Based resins, flame-retardant resin compositions with the addition of flame-retardant aids such as silicone resins, with less mold contamination, good molding fluidity,
A composition with high flame retardancy and high heat resistance has been obtained, but when treated for a relatively long time at high temperature, the flame retardancy of the molded product decreases, or when exposed to high temperature and high humidity, the molded product becomes There are problems such as deformation.

The present invention has been made in order to solve the above-mentioned problems, and has an object to have good molding fluidity, high flame retardancy, high heat resistance, and a relatively long time under high temperature. Flame retardancy of molded body after time treatment (long-term stable flame retardancy)
An object of the present invention is to provide a flame-retardant resin composition having excellent heat and moisture resistance and low mold contamination.

[0017]

Means for Solving the Problems As a result of intensive studies, the present inventors have found that a specific organic phosphorus flame retardant and a stabilized red phosphorus flame retardant are added to a resin mixture comprising a polycarbonate resin and a polyester resin. Has a high molding fluidity, has high flame retardancy and high heat resistance, and more surprisingly, it is difficult to treat the molded body at a high temperature for a relatively long time. The present inventors have found that a flame-retardant resin composition with little decrease in flammability, little deformation of a molded article even when exposed to high temperature and high humidity, and little mold contamination can be obtained, and have completed the present invention.

That is, the present invention relates to 100 parts (parts by weight, hereinafter referred to as "parts by weight") of a resin mixture (AB) containing (A) a polycarbonate resin and (B) a thermoplastic polyester resin in a weight ratio of 85/15 to 50/50. (C) general formula (I):

[0019]

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(Wherein, m ₁ , m ₂ , m ₃ , and m ₄ are each an integer of 0 to 2 and n is an integer of 1 to 15), and 1 to 11 parts of an organic phosphorus-based flame retardant; (D) a flame-retardant thermoplastic resin composition containing 0.05 to 5 parts of a stabilized red phosphorus flame retardant (Claim 1); and (E) a glass transition temperature of 0 ° C.
A rubber-like elastic body comprising 1 to 15 parts of the following:
The flame-retardant thermoplastic resin composition according to claim 1 or 2, further comprising (F) a fluororesin and / or 0.01 to 5 parts of silicone. The flame-retardant thermoplastic resin composition (Claim 4) according to Claim 1, 2, or 3, further comprising (G) 0.5 to 100 parts of a reinforcing filler, and a resin composition (Claim 3). Furthermore, the present invention relates to the flame-retardant thermoplastic resin composition according to claim 1, containing (H) 0.01 to 5 parts of an epoxy compound (claim 5).

[0021]

DETAILED DESCRIPTION OF THE INVENTION The polycarbonate resin (A), which is the component (A) used in the present invention, is specifically a phenolic compound having a valency of 2 or more and a carbonic acid diester compound such as phosgene or diphenyl carbonate. And a component used for imparting properties such as impact resistance, heat deformation resistance, and mechanical strength to the composition of the present invention.

There are various kinds of the above-mentioned phenolic compounds having two or more valences. In particular, 2,2-bis (4-hydroxyphenyl) propane (commonly called bisphenol A) which is a divalent phenolic compound is economical and mechanical. It is preferable from the point of strength. Examples of dihydric phenol compounds other than bisphenol A include, for example, bis (4-hydroxyphenyl) methane, bis (4-hydroxyphenyl) phenylmethane, bis (4-hydroxyphenyl) naphthylmethane, bis (4-hydroxyphenyl) -(4-isopropylphenyl) methane, bis (3,5-dichloro-4-hydroxyphenyl) 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 (3,5-dichloro-4-hydroxyphenyl) propane, 2,2-bis (3,5-dibromo-4-hydroxyphenyl) propane, 2,2 -Bis (3-chloro-4
-Hydroxyphenyl) propane, 2,2-bis (3-
Methyl-4-hydroxyphenyl) propane, 2,2-
Bis (3-fluoro-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 and 2,2-bis (4-hydroxyphenyl) -1,1,1,3,3,3-hexafluoropropane Kind;
Dihydroxydiarylcycloalkanes such as 1,1-bis (4-hydroxyphenyl) cyclohexane, 1,1-bis (3,5-dichloro-4-hydroxyphenyl) cyclohexane and 1,1-bis (4-hydroxyphenyl) cyclodecane Dihydroxydiaryl sulfones such as bis (4-hydroxyphenyl) sulfone, bis (3,5-dimethyl-4-hydroxyphenyl) sulfone and bis (3-chloro-4-hydroxyphenyl) sulfone; bis (4-hydroxy Dihydroxydiaryl ethers such as phenyl) ether and bis (3,5-dimethyl-4-hydroxyphenyl) ether; 4,4′-dihydroxybenzophenone,
Dihydroxydiaryl ketones such as 3 ', 5,5'-tetramethyl-4,4'-dihydroxybenzophenone; bis (4-hydroxyphenyl) sulfide, bis (3-methyl-4-hydroxyphenyl) sulfide,
Dihydroxydiaryl sulfides such as bis (3,5-dimethyl-4-hydroxyphenyl) sulfide;
Dihydroxydiarylsulfoxides such as bis (4-hydroxyphenyl) sulfoxide; dihydroxydiphenyls such as 4,4'-dihydroxydiphenyl;
And dihydroxyarylfluorenes such as 9,9-bis (4-hydroxyphenyl) fluorene. In addition to dihydric phenol compounds, dihydroxybenzenes such as hydroquinone, resorcinol, and methylhydroquinone; 1,5-dihydroxynaphthalene;
Dihydroxynaphthalenes such as 2,6-dihydroxynaphthalene can be used as the divalent phenol compound.

In addition, phenolic compounds having a valency of 3 or more also include
The obtained polycarbonate resin (A) can be used in a range where the thermoplasticity is maintained. Examples of the trivalent or higher phenolic compound include 2,4,4'-trihydroxybenzophenone, 2,2 ', 4,4'-tetrahydroxybenzophenone, 2,4,4'-trihydroxyphenyl ether, 2,2 ', 4,4'-tetrahydroxyphenyl ether, 2,4,4'-trihydroxydiphenyl-2-propane, 2,2'-bis (2,4-dihydroxy) 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) -2-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 and the like.

These divalent or higher phenolic compounds may be used alone or in combination of two or more.

If necessary, the polycarbonate resin (A) may contain, in addition to the phenolic compound having a valency of 3 or more, a component for forming a branched polycarbonate resin having chemical resistance, heat stability, and mechanical properties. It can be contained within a range not to impair. Components (branching agents) other than the trivalent or higher phenolic compound used to obtain the branched polycarbonate resin include, for example, phloroglucin, melitic acid, trimellitic acid, trimellitic acid chloride, trimellitic anhydride, gallic acid, and gallic acid. n-propyl, protocatechuic acid, pyromellitic acid, pyromellitic dianhydride, α-
Examples include resorcinic acid, β-resorcinic acid, resorcinaldehyde, trimethyl chloride, isatin bis (o-cresol), trimethyl trichloride, 4-chloroformylphthalic anhydride, benzophenonetetracarboxylic acid, and the like.

In addition, as a copolymer component of the polycarbonate resin (A), for example, adipic acid, pimelic acid,
A linear aliphatic dicarboxylic acid such as suberic acid, azelaic acid, sebacic acid, and decanedicarboxylic acid may be used.

As the component of the polycarbonate resin (A), if necessary, various known compounds used as a terminal stopper at the time of polymerization may be replaced with those having impaired chemical resistance, thermal stability and mechanical properties. You may use it in the range which does not know. In particular,
A monohydric phenolic compound, for example, phenol,
p-cresol, pt-butylphenol, pt-
Octylphenol, p-cumylphenol, bromophenol, tribromophenol, nonylphenol and the like can be mentioned.

Examples of the carbonic acid diester compound include diaryl carbonates such as diphenyl carbonate, and the like.
Examples thereof include dialkyl carbonates such as dimethyl carbonate and diethyl carbonate.

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 15000-4500
0, particularly preferably 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. When the viscosity average molecular weight exceeds 60,000, molding processability is often insufficient.

Specific examples of the polycarbonate resin (A) as described above include, for example, a polycarbonate resin obtained by reacting bisphenol A with diphenyl carbonate, and a reaction between bis (4-hydroxyphenyl) methane and diphenyl carbonate. And the like obtained polycarbonate resin.

As the polycarbonate resin (A), a polycarbonate-polyorganosiloxane copolymer comprising a polycarbonate part and a polyorganosiloxane part may be used. The degree of polymerization of the polyorganosiloxane moiety is preferably 5 or more. Further, in order to enhance the flame retardancy, a copolymer with a phosphorus compound or a polymer whose terminal is blocked with a phosphorus compound may be used. Further, a copolymer with a dihydric phenol having a benzotriazole group may be used in order to enhance weather resistance.

Such polycarbonate resins may be used alone or in combination of two or more. When two or more kinds are used in combination, there is no particular limitation on the combination, and for example, those having different monomer units, different copolymerization molar ratios, different molecular weights, and the like can be arbitrarily combined.

The thermoplastic polyester resin (B) as the component (B) used in the present invention comprises a divalent or higher valent aromatic carboxylic acid component and a divalent or higher valent alcohol and / or
A thermoplastic aromatic polyester-based resin obtained by polycondensation with a phenol component by a known method, and is a component used to enhance molding fluidity and chemical resistance.

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 the divalent or higher aromatic carboxylic acid component include, for example, terephthalic acid, isophthalic acid, phthalic acid, naphthalenedicarboxylic acid, bis (p-carbodiphenyl) methane,
Anthracenedicarboxylic acid, 4,4'-diphenyldicarboxylic acid, 1,2-bis (phenoxy) ethane-4,
Examples thereof include divalent aromatic carboxylic acids such as 4'-dicarboxylic acid and diphenylsulfone dicarboxylic acid, and trivalent or more aromatic carboxylic acids such as trimesic acid, trimellitic acid and pyromellitic acid, and derivatives having ester forming ability thereof. Can be Of these, terephthalic acid, isophthalic acid, and naphthalenedicarboxylic acid are preferred because they are easy to handle, easy to react, and excellent in properties of the obtained resin (for example, heat resistance, moisture resistance, mechanical properties, and the like). .
These may be used alone or in combination of two or more.

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 6 to 4 carbon atoms.
0 aromatic compounds having two or more hydroxyl groups in the molecule and ester-forming derivatives thereof are used. Specific examples of the dihydric or higher alcohol and / or phenol component include, for example, dihydric aliphatic alcohols such as ethylene glycol, propylene glycol, butanediol, hexanediol, decanediol and neopentyl glycol, cyclohexanedimethanol, cyclohexane Divalent alicyclic alcohols such as diols, aromatic diols such as 2,2'-bis (4-hydroxyphenyl) propane, 2,2'-bis (4-hydroxycyclohexyl) propane, hydroquinone,
Examples thereof include trihydric or higher alcohol or phenolic compounds such as glycerin and pentaerythritol, and derivatives thereof having an ester forming ability. Among them, ethylene glycol and butanediol are preferred because they are easy to handle, easy to react, and have excellent properties (eg, moisture resistance, heat resistance, etc.) of the obtained resin. These may be used alone or in combination of two or more.

The thermoplastic polyester resin (B) includes:
In addition to the acid component and the alcohol and / or phenol component, known copolymerizable components may be copolymerized as long as 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. Sex derivatives. Specific examples thereof include dicarboxylic acids such as adipic acid, sebacic acid, azelaic acid, dodecanedioic acid, maleic acid, 1,3-cyclohexanedicarboxylic acid, and 1,4-cyclohexanedicarboxylic acid, and their ester-forming ability. Derivatives. Also, oxyacids such as p-oxybenzoic acid and p-hydroxybenzoic acid, their ester-forming derivatives, and cyclic esters such as ε-caprolactone can be used as the copolymerization component. Furthermore, 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, tetrahydrofuran addition polymer, poly A polymer obtained by partially copolymerizing a polyalkylene glycol unit such as tetramethylene glycol in a polymer chain can also be used. As the copolymerization amount of the components,
It is generally preferably at most 20%, more preferably at most 15%, particularly preferably at most 10%.

The thermoplastic polyester resin (B) contains 80% or more of alkylene terephthalate units,
A polyalkylene terephthalate-based resin having 5% or more, particularly 90% or more, is preferred because the resulting composition has a good balance of physical properties such as heat resistance and crystallinity.

The logarithmic viscosity (IV) of the thermoplastic polyester resin (B) measured at 25 ° C. in a mixed solvent of phenol / tetrachloroethane = 1/1 (weight ratio) is preferably 0.30-2. 00 dl / g, more preferably 0.40 to 1.80 dl / g, and particularly preferably 0.1 dl / g.
It is 50 to 1.60 dl / g. Logarithmic viscosity 0.30d
If it is less than 1 / g, the heat resistance and mechanical strength of the molded article are often insufficient, and if it exceeds 2.00 dl / g, the molding fluidity tends to decrease.

Specific examples of the thermoplastic polyester resin (B) include, for example, polyethylene terephthalate, polypropylene terephthalate, polybutylene terephthalate, polyhexamethylene terephthalate, polycyclohexane dimethylene terephthalate, polyethylene naphthalate, polybutylene naphthalate and the like. Can be These may be used alone or in combination of two or more. When two or more kinds are used in combination, there is no particular limitation on the way of combining them. For example, those having different copolymer components and different molar ratios and / or different molecular weights can be arbitrarily combined.

The proportion of the polycarbonate resin (A) and the thermoplastic polyester resin (B) used is 85/15 to 50/50, preferably 82/18 to 55, by weight.
/ 45, more preferably 80/20 to 60/40. When the use ratio is more than 85/15, the obtained composition is often insufficient in molding fluidity, and the ratio of 50/50 is insufficient.
If it is less than this, it is not preferable because excellent flame retardancy and heat resistance cannot be obtained.

The component (C) used in the present invention is represented by the general formula (I):

[0042]

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(Wherein m ₁ , m ₂ , m ₃ and m ₄ are integers of 0 to 2, and n is an integer of 1 to 15). It is a component used to enhance flammability and molding fluidity.

The organophosphorus flame retardant (C) comprises a specific monofunctional phenol, ie, at least one of phenol, monomethylphenol and dimethylphenol, and a specific bifunctional phenol, ie, 2,2-bis (4-hydroxyphenyl). ) It is obtained by reacting propane with phosphorus oxychloride, but is not limited by this method.

In the formula (I), m _{1 to} m ₄ are preferably 1 or 2 from the viewpoint of thermal stability. Also, n is 1 to 15,
It is preferably an integer of 1 to 10, and more preferably an integer of 1 to 7, and heat resistance and workability vary depending on the number.

As specific examples of the organophosphorus flame retardant (C), m _{1 to} m ₄ in the general formula (I) are all 1 and n is 1
Bisphenol A poly (dicresyl) phosphate, m _{1 to} m ₄ are all 0 and n is 1 bisphenol A poly (diphenyl) phosphate, m _{1 to} m ₄ are all 2 and n is 1 bisphenol A poly ( Dixylenyl) phosphate or n in the above compound is 1 to 15
And the like. Further, the organic phosphorus-based flame retardant (C) may be a mixture of n-mers. These may be used alone or in combination of two or more. When two or more kinds are used in combination, there is no limitation on the combination, and for example, those having different structures, different molecular weights, and the like can be arbitrarily combined.

The amount of the organophosphorus flame retardant (C) is 1 to 11 parts, preferably 1 to 11 parts, based on 100 parts of the resin mixture (AB) comprising the polycarbonate resin (A) and the thermoplastic polyester resin (B). 1.5 to 10 parts, more preferably 2 to 9 parts. If the amount is less than 1 part,
The molding fluidity of the obtained molded product is insufficient, and if it exceeds 11 parts, heat resistance, long-term stable flame retardancy, wet heat resistance and the like are inferior.

The stabilized red phosphorus flame retardant (D), which is the component (D) used in the present invention, is a component used to enhance the flame retardancy. Red phosphorus coated with at least one coating selected from a resin coating, a metal hydroxide coating and a metal plating coating can be given. By coating the red phosphorus with a film in this way, the handleability is excellent and the deterioration of the physical properties of the composition is reduced.

The thermosetting resin, the metal hydroxide, and the metal constituting the metal plating forming the film are not particularly limited as long as they can coat red phosphorus.

Specific examples of the thermosetting resin include a phenol-formalin resin, a urea-formalin resin,
Melamine-formalin resin, alkyd resin, etc.
Specific examples of the metal hydroxide include aluminum hydroxide, magnesium hydroxide, zinc hydroxide, titanium hydroxide, and the like. Specific examples of the metal that forms the metal plating film, for example, an electroless plating film, include Fe, Ni, Co, C
u, Zn, Mn, Ti, Zr, Al or alloys thereof.

The coating for coating the red phosphorus may be a coating of a single material, a coating of a combination of two or more materials, or a coating laminated two or more times. .

The content of red phosphorus in the stabilized red phosphorus-based flame retardant (D) is preferably 70% or more from the viewpoint of flame retarding efficiency, and more preferably 80% or more.
The upper limit of the content of red phosphorus is preferably 99.5% from the viewpoint of working environment safety, and more preferably 99.0%.

The average particle size of the stabilized red phosphorus flame retardant (D) is preferably 1 to 70 μm from the viewpoint of the appearance of the molded article and the safety of the working environment, and more preferably 3 to 60 μm.
Are preferred.

The stabilized red phosphorus flame retardant (D) may be used alone or in combination of two or more. When two or more kinds are used in combination, there is no particular limitation on the combination, and for example, different coatings and different particles having different particle sizes can be arbitrarily combined.

The compounding amount of the stabilized red phosphorus-based flame retardant (D)
It is 0.05 to 5 parts, preferably 0.07 to 100 parts with respect to 100 parts of the resin mixture (AB) composed of the polycarbonate resin (A) and the thermoplastic polyester resin (B).
4 parts, more preferably 0.1 to 3 parts. If the amount is less than 0.05 part, the resulting molded article has insufficient flame retardancy. If the amount exceeds 5 parts, odor is generated during molding and mold contamination is poor.

In the present invention, the impact strength of the obtained molded article
In order to enhance toughness, chemical resistance, and the like, a rubber-like elastic body (E) having a glass transition temperature (Tg) of 0 ° C. or less as a component (E) may be added.

The rubber-like elastic body (E) has a Tg of 0 ° C. or lower, and more preferably -20 ° C. or lower, because the resulting resin has improved impact strength.

The rubber-like elastic body (E) is not particularly limited as long as the rubber-like elastic body has a Tg of 0 ° C. or less. For example, polybutadiene, styrene-butadiene rubber, acrylonitrile-butadiene rubber, alkyl (meth) acrylate, -Rubbers such as diene rubbers such as butadiene rubber, acrylic rubber, ethylene-propylene rubber and siloxane rubber; graft polymers obtained by graft copolymerizing a vinyl monomer with the rubber; olefin resins. These may be used alone or in combination of two or more. Among these, it is preferable to use at least one of a graft polymer and an olefin-based resin.

The vinyl monomers used in the production of the graft polymer include aromatic vinyl compounds, vinyl cyanide compounds, alkyl (meth) acrylates, and other vinyl compounds that can be graft-polymerized to rubber. That is.

Examples of the aromatic vinyl compound include styrene, o-methylstyrene, m-methylstyrene and p-methylstyrene.
-Methylstyrene, α-methylstyrene, chlorostyrene, bromostyrene, vinyltoluene, etc .; examples of vinyl cyanide compounds; acrylonitrile, methacrylonitrile, etc .; and examples of alkyl (meth) acrylate, butyl. Examples of other vinyl compounds include acrylate, butyl methacrylate, ethyl acrylate, ethyl methacrylate, methyl acrylate, and methyl methacrylate. Examples of other vinyl compounds include (meth) such as unsaturated acids such as acrylic acid and methacrylic acid, glycidyl acrylate, and glycidyl methacrylate. Examples include glycidyl acrylate, vinyl acetate, maleic anhydride, and N-phenylmaleimide.

The copolymerization ratio when the rubber and the vinyl monomer are copolymerized is not particularly limited. However, in order to further increase the impact strength, a preferable ratio is 10/10 by weight.
90-90 / 10, further 30 / 70-80 / 20
It is. If the copolymerization ratio is less than 10/90, the effect of improving impact resistance is reduced, and if it exceeds 90/10, the compatibility with the resin mixture (AB) tends to decrease.

The olefin resin in the rubber-like elastic body (E) is a polydiene, a mixture of two or more thereof, or a copolymer of an olefin monomer and at least one diene monomer, in addition to polyolefin in a narrow sense. The term is used in a broad sense including a copolymer of an olefin monomer and one or more other vinyl monomers copolymerizable therewith. For example, ethylene, propylene, 1-butene, 1-pentene, isobutene, butadiene, isoprene, chloroprene, phenylpropadiene, cyclopentadiene, 1,5-norbornadiene, 1,3-cyclohexadiene, 1,4-cyclohexadiene, , 5-cyclooctadiene, 1,3
-Homopolymers or copolymers selected from one or a combination of two or more of monomers such as -cyclooctadiene and α, ω-non-conjugated dienes; Mixtures of two or more are mentioned. Among them, polyethylene, polypropylene and the like are preferably used from the viewpoint of improving the chemical resistance of the obtained composition.

The copolymer comprising the olefin monomer and at least one other vinyl monomer copolymerizable therewith includes olefin monomer, (meth) acrylic acid and alkyl (meth) acrylate. And copolymers of glycidyl (meth) acrylate, vinyl acetate, maleic anhydride, N-phenylmaleimide, and carbon monoxide.

Specific examples of the copolymer include ethylene / ethyl acrylate copolymer, ethylene / butyl acrylate / carbon monoxide terpolymer, ethylene / glycidyl methacrylate copolymer, ethylene / glycidyl methacrylate / vinyl acetate Copolymer, ethylene / vinyl acetate copolymer, ethylene / vinyl acetate / carbon monoxide copolymer, ethylene / acrylic acid copolymer, ethylene / maleic anhydride copolymer, ethylene / maleic anhydride / N-
And phenylmaleimide copolymers.

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 are obtained depending on the polymerization method, and any of them can be preferably used.

By adding a graft polymer and an olefin resin together as the rubber-like elastic body (E), effects such as impact resistance and chemical resistance can be further enhanced.

The compounding amount of the rubber-like elastic body (E) is preferably 1 to 15 parts, more preferably 1.5 to 12 parts, especially preferably 2 to 100 parts of the resin mixture (AB).
10 parts. When the amount is more than 15 parts, the rigidity, heat resistance, and the like tend to decrease, and in order to obtain a clear effect by using the rubber-like elastic body (E),
It is preferable to use one or more parts.

In the present invention, a fluorine resin and / or silicone (F) as the component (F) can be used for the purpose of further improving flame retardancy.

The fluorine-based resin is a resin containing 5% or more, more preferably 10% or more, of fluorine atoms in the resin. Specific examples include polymonofluoroethylene,
Polydifluoroethylene, polytrifluoroethylene,
Examples include polytetrafluoroethylene, tetrafluoroethylene / hexafluoropropylene copolymer, and the like. In addition, if necessary, a single amount used for the production of the fluororesin within a range that does not impair the physical properties such as the flame retardancy of the obtained molded article (usually a range in which the fluorine atom content is 5% or more). A copolymer obtained by polymerizing a polymer together with a copolymerizable monomer (for example, α-olefin or the like) may be used. These fluororesins may be used alone.
A combination of more than one species may be used.

The molecular weight of the fluororesin is 1,000,000 to
20 million is preferred, and more preferably 2 million to 1
10 million.

These fluorine-based resins can be produced by generally known production methods such as emulsion polymerization, suspension polymerization, bulk polymerization, and solution polymerization.

The silicone refers to (poly) organosiloxane, and includes monoorganosiloxane such as dimethylsiloxane and phenylmethylsiloxane, and polydimethylsiloxane obtained by polymerizing these.
Specific examples include polyphenylmethylsiloxane and organopolysiloxanes such as copolymers thereof.

In the case of the above-mentioned organopolysiloxane, a modified silicone having a molecular terminal substituted by an epoxy group, a hydroxyl group, a carboxyl group, a mercapto group, an amino group or a polyether group bonded by an ether bond is also useful. Among them, a polymer having a number average molecular weight of 200 or more, and more preferably 1000 to 5,000,000 is preferable because the flame retardancy can be further improved.

The form of the silicone is not particularly limited, and any form such as oil, gum, varnish, powder, and pellet can be used.

When the fluororesin and / or the silicone (F) are compounded, the amount of the resin mixture (A
B) Based on 100 parts, preferably 0.01 to 5 parts, more preferably 0.03 to 4 parts, particularly preferably 0.0 to 4 parts.
5 to 3.5 parts. If the amount is less than 0.01 part, the effect of further improving the flame retardancy is small, and if it exceeds 5 parts, the moldability and the like tend to decrease.

The composition of the present invention may further contain a reinforcing filler (G) as a component (G) in order to further improve heat resistance, mechanical strength and the like.

Specific examples of the reinforcing filler (G) include fibrous fillers such as glass fiber, carbon fiber and potassium titanate fiber, glass beads, glass flake, talc, mica, kaolin, wollastonite, smectite. Diatomaceous earth, calcium carbonate, calcium sulfate, barium sulfate and the like. Among these, silicate compounds and / or fibrous reinforcing agents are preferred in terms of heat resistance, mechanical properties, and the like.

The silicate compound is represented by the chemical composition S
It is a compound having a shape such as powder, granule, needle, plate, etc. containing iO ₂ units. Specific examples include magnesium silicate, aluminum silicate, calcium silicate, talc, mica, wollastonite, kaolin Diatomaceous earth, smectite and the like. These may be natural products or synthetic ones. Among them, talc, mica, kaolin, and smectite are preferred in terms of moisture resistance and the like, and mica and talc are particularly preferred.

The preferred average diameter of the silicate compound (particle diameter when converted to a circle determined by image processing of a micrograph) is not particularly limited, but is preferably 0.01 to 100 μm, and more preferably 0.01 to 100 μm. Is 0.1-50μ
m, especially 0.3 to 40 μm. Average diameter is 0.0
If the thickness is less than 1 μm, the strength improvement effect is not sufficient,
If the ratio exceeds the range, the toughness tends to decrease.

The silicate compound may be treated with a surface treating agent such as a silane coupling agent and a titanate coupling agent. As the silane coupling agent, for example, epoxy silane, amino silane,
Examples of titanate-based coupling agents such as vinyl-based silanes include monoalkoxy-type, chelate-type, and coordinate-type coupling agents.

The method for treating the silicate compound with a surface treating agent is not particularly limited, and can be carried out by a usual method.
For example, it can be carried out by adding the surface treating agent to the layered silicate and stirring or mixing the solution as it is or while heating.

As the fibrous reinforcing agent, glass fiber,
Carbon fiber. When a fibrous reinforcing agent is used, it is preferable to use chopped strand glass fibers treated with a sizing agent from the viewpoint of workability. Further, in order to enhance the adhesion between the resin and the fibrous reinforcing agent, those obtained by treating the surface of the fibrous reinforcing agent with a coupling agent are preferable,
A binder may be used. Examples of the coupling agent include the same compounds as described above.

When glass fiber is used as the reinforcing filler (G), the diameter is 1 to 20 μm and the length is 0.01 to 50 mm
Are preferred. If the fiber length is too short, the reinforcing effect is not sufficient, and if it is too long, the surface properties, extrusion processability, and processability of the molded product deteriorate.

The reinforcing filler (G) may be used alone.
A combination of more than one species may be used. When two or more kinds are used in combination, there is no particular limitation on the combination, but a preferable combination includes a combination of two or more kinds of reinforcing fillers selected from mica, talc and glass fiber.

When the reinforcing filler (G) is compounded, the compounding amount is preferably 0.5 to 100 parts, more preferably 1 to 60 parts with respect to 100 parts of the resin mixture (AB).
Parts, particularly preferably 2 to 40 parts. The blending amount is 0.
When the amount is less than 5 parts, the effect of improving heat resistance is small,
Exceeding the part deteriorates the surface properties, extrusion processability, and moldability of the molded product.

The composition of the present invention may further contain an epoxy compound (H) in order to suppress mold contamination and dripping during combustion, and to improve heat stability and wet heat resistance.

The epoxy compound (H) is a compound having at least one, preferably two to three epoxy groups in a molecule, and preferably having an epoxy equivalent of 100 to 2,000 and containing no halogen atom in the molecule. Specific examples thereof include N-glycidyl phthalimide, N-glycidyl tetrahydrophthalimide, phenyl glycidyl ether,
p-butylphenyl glycidyl ether, neohexene oxide, ethylene glycol diglycidyl ether,
Polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, tetramethylene glycol diglycidyl ether, polytetramethylene glycol diglycidyl ether, bisphenol A type epoxy compound, bisphenol S type epoxy compound, resorcinol type epoxy compound, Phenol novolak epoxy compound, ortho-cresol novolak epoxy compound, diglycidyl adipate, diglycidyl sebacate, diglycidyl phthalate, glycidyl methacrylate, glycidyl acrylate, ethylene-glycidyl methacrylate copolymer, ethylene-glycidyl methacrylate- Vinyl acetate copolymer, etc. . Of these, bisphenol A type epoxy compounds are preferred from the viewpoint of heat resistance, low volatility, heat stability, and moisture resistance. These may be used alone,
Two or more kinds may be used in combination.

When the epoxy compound (H) is blended, the amount is preferably 0.01 to 5 parts, more preferably 0.05 parts, per 100 parts of the resin mixture (AB).
The amount is 5 to 4.5 parts, particularly preferably 0.1 to 4 parts.
When the amount is less than 0.01 part, the effect of improving mold contamination, heat stability and wet heat resistance is small, and when it exceeds 5 parts, the flame retardancy is reduced.

The flame-retardant thermoplastic resin composition of the present invention comprises
Any other thermoplastic or thermosetting resin within a range not to impair the object of the present invention, such as a liquid crystal polyester resin, a polyamide resin, a polystyrene resin, a polyphenylene sulfide resin, a polyphenylene ether resin, and a polyacetal resin. Resin, polysulfone resin,
A rubber-like elastic body or the like may be added alone or in combination of two or more.

In order to improve the performance of the flame-retardant thermoplastic resin composition of the present invention, a phenolic antioxidant,
Antioxidants such as thioether-based antioxidants and heat stabilizers such as phosphorus-based stabilizers may be used alone or in combination of two or more. Further, if necessary, usually other well-known stabilizers, lubricants, mold release agents, plasticizers, non-phosphorus-based flame retardants, flame retardant aids, ultraviolet absorbers, light stabilizers, pigments, dyes, Additives such as antistatic agents, conductivity-imparting agents, dispersants, compatibilizers, and antibacterial agents may 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 the above-mentioned components, other additives, resins and the like, followed by melt-kneading using a melt-kneading machine such as a single-screw extruder or a twin-screw extruder. In addition, when the compounding agent is a liquid, it can be manufactured by adding the compounding agent to a melt kneader using a liquid supply pump or the like.

The method for forming the flame-retardant thermoplastic resin composition of the present invention is not particularly limited, and molding methods generally used for thermoplastic resins, for example, injection molding, blow molding, extrusion molding, and the like. A vacuum forming method, a press forming method, a calendar forming method, and the like can be applied.

The flame-retardant thermoplastic resin composition of the present invention is suitably used for various uses. Preferred applications include
Injection molded products, blow molded products, extruded products, etc. of home electric appliances, OA equipment parts, automobile parts, and the like.

As a preferred embodiment of the present invention, for example, a viscosity average molecular weight of 2 obtained by reacting bisphenol A with diphenyl carbonate as the component (A) is used.
5000 polycarbonate resin has 95% of polyethylene terephthalate unit as a component (B), and has a logarithmic viscosity (IV) of 0 when measured at 25 ° C. in a phenol / tetrachloroethane = 1/1 (weight ratio) mixed solvent. .7d
pentamer as a component (C) for 100 parts of a resin mixture (AB) having a component ratio (A) / (B) = 70/30 (weight ratio) using a polyethylene terephthalate resin having a weight of 1 / g. Flame-retardant heat containing 5 parts of a certain bisphenol A poly (diphenyl) phosphate and 3.5 parts of a stabilized red phosphorus-based flame retardant coated with a phenol resin as a component (D) and having a red phosphorus content of 95%. And a plastic resin composition. In this case, it has excellent properties in all of fluidity, flame retardancy, heat resistance, mold contamination, long-term stable flame retardancy and wet heat resistance.

[0095]

The composition of the present invention will be described in more detail with reference to the following examples, but it should not be construed that the invention is limited thereto.

The components used in Examples and Comparative Examples are shown in Table 1.

[0097]

[Table 1]

The evaluation in Examples and Comparative Examples was performed by the following method.

(Preparation of Sample) After the pellets were dried at 120 ° C. for 5 hours, the cylinder temperature was set to 2 using a 35 t injection molding machine.
80mm, mold temperature 70 ° C, thickness 1.0mm, 1.6m
m, 3.2 mm, and 6.4 mm bars (each having a width of 12.
7 mm, length 127 mm).

(Fluidity) The pellets were dried at 120 ° C. for 5 hours, and the melt index (MI) was measured at 280 ° C. under a load of 2160 g according to JIS K6730.

(Flame Retardancy) Bars of 1.0 mm and 1.6 mm were evaluated for flame retardancy according to the UL-94 V standard.

(Heat resistance) Using a 6.4 mm bar, AS
The deflection temperature under load was measured at a load of 0.45 MPa according to TM D-648.

(Mold Contamination Resistance)
After drying for a time, using a 75 t injection molding machine, 50 flat plates of 120 × 120 × 2 mm were continuously formed at a cylinder temperature of 300 ° C., and changes in the mold surface were visually observed and evaluated.

◎: No change, glossy ○: Slightly cloudy, slightly reduced in gloss Δ: Cloudy, reduced in gloss ×: Large cloudy, no gloss

(Long-term stable flame retardancy) 1.0 mm, 1.6 m
m was treated at 70 ° C. for 400 hours, and then the sample after the treatment was evaluated for flame retardancy according to UL-94V standard.

The flame retardancy after the treatment was higher than that before the treatment.
も の indicates that the flame retardancy did not change, and x indicates that the flame retardancy was reduced.

(Moisture and heat resistance) A 6.4 mm bar was heated at 121 ° C.
Was held under saturated pressurized steam for 60 hours to perform a wet heat treatment, the thickness of the central portion of the bar before and after the wet heat treatment was measured, and the thickness change rate was obtained and evaluated by the following equation.

[0108]

(Equation 1)

(Impact strength) A bar of 3.2 mm was subjected to ASTM.
Izod impact strength was measured and evaluated according to D-256.

Example 1 80 parts of PC (A1), 20 parts of PET (B1), 1 part of stabilized red phosphorus (D1), ADK STAB H as a phosphorus-based stabilizer
After dry-blending 0.3 parts of P-10 (trade name, manufactured by Asahi Denka Kogyo KK), the cylinder temperature was set to 280 ° C.
To a hopper of a twin-screw extruder with vent (TEX44, manufactured by Nippon Steel Works, Ltd.), and add 4 parts of a phosphorus compound (C1) from a liquid addition pump of the extruder to perform melt extrusion. The resin composition was obtained and evaluated. Table 1 shows the results.

Examples 2 to 10 and Comparative Examples 1 to 9 Resin compositions were obtained in the same manner as in Example 1 except that the components shown in Tables 2 and 3 were used in the amounts shown in Tables 2 and 3 and evaluated. did. However, the reinforcing filler was added during melt kneading. The results are shown in Tables 2 and 3. NotV in Table 3 is UL-
Indicates that it is out of the 94 V standard.

[0112]

[Table 2]

[0113]

[Table 3]

In Comparative Examples 1, 2, and 3, the organophosphorus compound is out of the range of the present invention, so that the long-term stable flame retardancy is inferior to that of the examples, and the deformation of the molded article after the wet heat resistance test is small. Is big. In Comparative Example 4, since a large amount of the organic phosphorus compound was added, heat resistance was lowered, and mold contamination, long-term stable flame retardancy, and wet heat resistance were poor. In Comparative Example 5, since a large amount of stabilized red phosphorus was added, an odor was generated and mold contamination was poor. In Comparative Example 6, since no stabilized red phosphorus-based flame retardant was added,
Poor long-term stable flame retardancy. Comparative Example 7 was inferior in fluidity and flame retardancy because no organic phosphorus compound was added. Comparative Example 8 is inferior in flame retardancy and heat resistance because the weight ratio of polycarbonate resin / thermoplastic polyester resin is out of the range of the present invention. In Comparative Example 9, since no thermoplastic polyester resin was contained, the fluidity was poor and no flame retardancy was obtained.

As is evident from the above, all of the compositions of the present invention are excellent in fluidity, flame retardancy, heat resistance, mold contamination, long-term stable flame retardancy, and wet heat resistance. You can see that there is.

[0116]

According to the present invention, a flame-retardant thermoplastic resin composition having excellent properties in any of fluidity, flame retardancy, heat resistance, mold contamination, long-term stable flame retardancy and wet heat resistance. A product is obtained, which is very useful industrially.

Continuation of the front page (51) Int.Cl. ⁶ Identification code FI C08L 67/00 C08L 67/00 // (C08L 69/00 67:00 21:00 27:12 83:04) (72) Inventor Hiroshi Koyama (72) Inventor Kazushi Hirobe 3-2-25-307 Honjo Nishi, Kita-ku, Osaka-shi

Claims (5)

[Claims] (1) 85/15 to 50/50 of (A) a polycarbonate resin and (B) a thermoplastic polyester resin.
(A) 100 parts by weight of a resin mixture (AB) contained in a weight ratio of / 50, (C) a general formula (I): (In the formula, m ₁ , m ₂ , m ₃ , and m ₄ are integers of 0 to 2, and n is 1
Organophosphorus flame retardant 1 represented by the following formula:
To 11 parts by weight and (D) a stabilized red phosphorus flame retardant.
A flame-retardant thermoplastic resin composition containing 0.5 to 5 parts by weight. 2. The flame-retardant thermoplastic resin composition according to claim 1, further comprising (E) 1 to 15 parts by weight of a rubber-like elastic body having a glass transition temperature of 0 ° C. or lower. 3. The flame-retardant thermoplastic resin composition according to claim 1, further comprising (F) 0.01 to 5 parts by weight of a fluororesin and / or silicone. 4. The method according to claim 1, further comprising:
The flame-retardant thermoplastic resin composition according to claim 1, containing 0 parts by weight. 5. The method according to claim 1, further comprising:
The flame-retardant thermoplastic resin composition according to claim 1, containing from 5 to 5 parts by weight.