JP2001026709A - Flame retardant resin composition and molded article made of the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a flame retardant resin composition having excellent flame retardancy, fluidity and resistance to wet heat, enabling stickiness to a mold to be suppressed and useful in various industrial uses such as an OA equipment field by including a specific aromatic polycarbonate resin, a styrene-based resin and a specific phosphorus-based flame retardant in a specific content ratio. SOLUTION: This composition consists of (A) 40-92 wt.% aromatic polycarbonate having a viscosity average molecular weight of 13,000-17,000, (B) 5-40 wt.% styrene-based resin and (C) 3-20 wt.% phosphorus-based flame retardant of the formula [wherein R1 to R3 are each a 1-8C alkyl or the like; and (n) is 0 or 1]. In addition, (D) silicate-based filler preferably is blended in an amount of 0.1-25 pts.wt. based on 100 pts.wt. of the composition. The ingredient B preferably is a thermoplastic graft copolymer which is obtained by the graft polymerization of diene-based rubber with a vinyl cyanide compound and an aromatic vinyl compound and is produced by a bulk polymerization method.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

[0001] The present invention relates to a flame-retardant resin composition and a molded product obtained by melt-molding the same.

[0002]

2. Description of the Related Art Aromatic polycarbonate resins are widely used industrially because of their excellent mechanical and thermal properties. However, aromatic polycarbonate resins have a high melt viscosity, and therefore have the drawback of poor fluidity and poor moldability. Many polymer alloys with other thermoplastic resins have been developed to improve the flowability of the aromatic polycarbonate resin. Among them, polymer alloys with a styrene-based resin represented by an ABS resin are widely used in the field of automobiles, OA equipment, electronic and electrical equipment, and the like. In recent years, there has been a strong demand for flame-retardant resin materials, mainly for applications such as OA equipment and home appliances, and in order to meet these demands, study of flame-retardant polymer alloys of polycarbonate resin and ABS resin. There have been many.

Conventionally, in such polymer alloys, a halogen-based flame retardant having bromo and a flame retardant auxiliary such as antimony trioxide have been generally used in combination. However, bromo is used due to a problem of generating harmful substances during combustion. Investigations on flame retardancy that does not include halogen compounds have become active. For example, a method of blending triphenyl phosphate and polytetrafluoroethylene having a fibril-forming ability into a polymer alloy of an aromatic polycarbonate resin and an ABS resin (JP-A-2-32154), a phosphate-based oligomer which is a condensed phosphate ester is used. Compounding method (JP-A 2-1)
No. 15262) has been proposed.

[0004] The former method of blending triphenyl phosphate is widely used because it has an effect of achieving good flame retardancy and greatly improving the fluidity of a resin composition. Further, such a method has an advantage that it is excellent also in long-term properties such as wet heat resistance. However, on the other hand, such triphenyl phosphate has the property of being easily vaporized when subjected to a large amount of thermal stress during molding, so that the flame retardant adheres to the surface of the product or the mold, resulting in poor product appearance and reduced productivity. There is a problem of causing.

In the latter method of blending a phosphate oligomer, the flame retardant is less vaporized at the time of molding than triphenyl phosphate, which results in poor product appearance and reduced productivity due to the adhesion of a mold. The problem is solved. However, when the content is the same as that of triphenyl phosphate, there is a disadvantage that flame retardancy is reduced, and the effect of improving the fluidity of the resin composition is not sufficient as compared with triphenyl phosphate.

That is, polycarbonate resin and ABS
The use of a monophosphate compound such as triphenyl phosphate as a flame retardant for a polymer alloy made of a resin has various advantages such as flame retardancy, fluidity, and long-term properties. Therefore, the solution of the problems of productivity and appearance deterioration due to the adhesion of the mold is a strongly demanded problem.

On the other hand, as a method for improving the fluidity of an aromatic polycarbonate resin, a method using a low molecular weight aromatic polycarbonate resin is generally known. However, aromatic polycarbonate resins usually have a sudden drop in properties such as impact resistance at a certain molecular weight, so that they are not actually used except for specific applications. As a resin composition using such a low-molecular-weight aromatic polycarbonate resin, Japanese Patent Application Laid-Open No. 5-287185 discloses that a specific filler is blended at a high concentration, so that both high fluidity and mechanical strength are highly compatible. Resin compositions have been proposed. JP-A-6-345954 proposes a resin composition in which carbon fibers and a bromine-based flame retardant are blended with a low-molecular-weight aromatic polycarbonate. However, a low-molecular-weight aromatic polycarbonate resin and a styrene-based resin are proposed. No specific proposals and recognition of usefulness have been made for the blended material with.

[0008]

SUMMARY OF THE INVENTION An object of the present invention is to provide a resin composition comprising a polymer alloy of an aromatic polycarbonate resin and a styrene resin mixed with a monophosphate ester flame retardant. An object of the present invention is to provide a flame-retardant resin composition with less mold adhesion. The present inventors have conducted intensive studies to achieve the above object, and as a result, when using an aromatic polycarbonate resin having a specific molecular weight,
It has been found that vaporization and mold adhesion can be suppressed very remarkably. As a result, the present invention is a flame-retardant resin composition having good flame retardancy, fluidity and wet heat resistance, and having suppressed mold adhesion. Reached.

[0009]

According to the present invention, there is provided an aromatic polycarbonate resin having a viscosity average molecular weight of 13,000 to 17,000 (component a) of 40 to 92% by weight, and a styrene resin (component b) of 5 to 40% by weight. And a flame-retardant resin composition comprising a total of 100% by weight of 3 to 20% by weight of a phosphorus-based flame retardant (component (c)) represented by the following general formula (1), and melt molding from the flame-retardant resin composition. It relates to the obtained molded article.

[0010]

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Wherein R ₁ , R ₂ and R ₃ independently represent an alkyl group having 1 to 8 carbon atoms or an aryl group which may be substituted by an alkyl group having 6 to 20 carbon atoms; Is 0 or 1)

The aromatic polycarbonate resin in the component (a) of the present invention is usually obtained by reacting a dihydric phenol with a carbonate precursor by an interfacial polycondensation method or a melting method.

Typical examples of the dihydric phenol used here include hydroquinone, resorcinol, 4,4
4'-dihydroxydiphenyl, bis (4-hydroxyphenyl) methane, bis {(4-hydroxy-3,5-
Dimethyl) phenyl @ methane, 1,1-bis (4-hydroxyphenyl) ethane, 1,1-bis (4-hydroxyphenyl) -1-phenylethane, 2,2-bis (4
-Hydroxyphenyl) propane (commonly known as bisphenol A), 2,2-bis} (4-hydroxy-3-methyl)
Phenyl {propane, 2,2-bis {(4-hydroxy-3,5-dimethyl) phenyl} propane, 2,2-bis {(3-isopropyl-4-hydroxy) phenyl}
Propane, 2,2-bis {(4-hydroxy-3-phenyl) phenyl} propane, 2,2-bis (4-hydroxyphenyl) butane, 2,2-bis (4-hydroxyphenyl) -3-methylbutane, 2,2-bis (4-hydroxyphenyl) -3,3-dimethylbutane, 2,4
-Bis (4-hydroxyphenyl) -2-methylbutane, 2,2-bis (4-hydroxyphenyl) pentane, 2,2-bis (4-hydroxyphenyl) -4-methylpentane, 1,1-bis (4 -Hydroxyphenyl) cyclohexane, 1,1-bis (4-hydroxyphenyl) -4-isopropylcyclohexane, 1,1-
Bis (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane, 9,9-bis (4-hydroxyphenyl) fluorene, 9,9-bis {(4-hydroxy-3-methyl) phenyl} fluorene, α , Α'-bis (4-hydroxyphenyl) -o-diisopropylbenzene, α, α'-bis (4-hydroxyphenyl) -m
-Diisopropylbenzene, α, α'-bis (4-hydroxyphenyl) -p-diisopropylbenzene, 1,
3-bis (4-hydroxyphenyl) -5,7-dimethyladamantane, 4,4′-dihydroxydiphenylsulfone, 4,4′-dihydroxydiphenylsulfoxide, 4,4′-dihydroxydiphenylsulfide,
4,4'-dihydroxydiphenyl ketone, 4,4'-
Examples thereof include dihydroxydiphenyl ether and 4,4′-dihydroxydiphenyl ester, and these can be used alone or as a mixture of two or more.

Among them, bisphenol A, 2,2-bis {(4-hydroxy-3-methyl) phenyl} propane, 2,2-bis (4-hydroxyphenyl) butane,
2,2-bis (4-hydroxyphenyl) -3-methylbutane, 2,2-bis (4-hydroxyphenyl)-
3,3-dimethylbutane, 2,2-bis (4-hydroxyphenyl) -4-methylpentane, 1,1-bis (4
A homopolymer obtained from at least one bisphenol selected from the group consisting of -hydroxyphenyl) -3,3,5-trimethylcyclohexane and α, α'-bis (4-hydroxyphenyl) -m-diisopropylbenzene, or Copolymers are preferred. In particular, bisphenol A homopolymer and 1,1-bis (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane and bisphenol A, 2,2-bis {(4-hydroxy- Copolymers with 3-methyl) phenyl} propane or α, α′-bis (4-hydroxyphenyl) -m-diisopropylbenzene are preferably used.

As the carbonate precursor, carbonyl halide, carbonate ester or haloformate is used, and specific examples include phosgene, diphenyl carbonate, dihaloformate of dihydric phenol and the like.

In producing the polycarbonate resin by reacting the dihydric phenol with the carbonate precursor by an interfacial polycondensation method or a melting method, if necessary, a catalyst, a terminal stopper and an antioxidant for the dihydric phenol may be used. Etc. may be used. Further, the polycarbonate resin may be a branched polycarbonate resin obtained by copolymerizing a trifunctional or higher polyfunctional aromatic compound, or a polyester carbonate resin obtained by copolymerizing an aromatic or aliphatic bifunctional carboxylic acid, In addition, 2 of the obtained polycarbonate resin
It may be a mixture of more than one species.

The reaction by the interfacial polycondensation method is usually a reaction between dihydric phenol and phosgene, and is carried out in the presence of an acid binder and an organic solvent. As the acid binder, for example, an alkali metal hydroxide such as sodium hydroxide or potassium hydroxide or an amine compound such as pyridine is used.
As the organic solvent, for example, halogenated hydrocarbons such as methylene chloride and chlorobenzene are used. Further, for promoting the reaction, for example, a catalyst such as a tertiary amine such as triethylamine, tetra-n-butylammonium bromide, or tetra-n-butylphosphonium bromide, a quaternary ammonium compound, or a quaternary phosphonium compound may be used. it can. At that time, the reaction temperature is usually 0 to 40 ° C., the reaction time is preferably about 10 minutes to 5 hours, and the pH during the reaction is preferably maintained at 9 or more.

In such a polymerization reaction, a terminal stopper is usually used. Monofunctional phenols can be used as such a terminal stopper. Monofunctional phenols are commonly used as molecular terminators for molecular weight control, and the resulting polycarbonate resins are capped by groups based on monofunctional phenols, so that Excellent heat stability. Such a monofunctional phenol is generally a phenol or a lower alkyl-substituted phenol, and may be a monofunctional phenol represented by the following general formula (2).

[0019]

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(Wherein A is a hydrogen atom or a group having 1 to 9 carbon atoms)
Is a linear or branched alkyl group or a phenyl group-substituted alkyl group, and r is an integer of 1 to 5, preferably 1 to 3. )

Specific examples of the above monofunctional phenols include phenol, p-tert-butylphenol, p-cumylphenol and isooctylphenol.

Further, other monofunctional phenols include:
Phenols or benzoic acid chlorides having a long-chain alkyl group or aliphatic polyester group as a substituent, or long-chain alkylcarboxylic acid chlorides can also be used. Among them, phenols having a long-chain alkyl group represented by the following general formulas (3) and (4) as a substituent are preferably used.

[0023]

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[0024]

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(Wherein X is -RO-, -R-CO-O
— Or —RO—CO—, wherein R represents a single bond or a divalent aliphatic hydrocarbon group having 1 to 10, preferably 1 to 5 carbon atoms, and n represents an integer of 10 to 50. Show. )

As the substituted phenols of the general formula (3), those having n of 10 to 30, especially 10 to 26 are preferred. Specific examples thereof include decylphenol, dodecylphenol, tetradecylphenol, hexadecylphenol and Octadecylphenol, eicosylphenol, docosylphenol, triacontylphenol and the like can be mentioned.

As the substituted phenols of the general formula (4), a compound in which X is -R-CO-O- and R is a single bond is suitable, and n is 10 to 30, especially 10 to 26.
Are preferred, and specific examples thereof include, for example, decyl hydroxybenzoate, dodecyl hydroxybenzoate,
Examples include tetradecyl hydroxybenzoate, hexadecyl hydroxybenzoate, eicosyl hydroxybenzoate, docosyl hydroxybenzoate and triacontyl hydroxybenzoate.

The terminal terminator is desirably introduced at least at 5 mol%, preferably at least 10 mol%, based on all terminals of the obtained polycarbonate resin. More preferably, the terminal terminator is introduced in an amount of at least 80 mol% with respect to all terminals, that is, the terminal hydroxyl group (OH group) derived from dihydric phenol is more preferably at most 20 mol%, particularly preferably. This is the case when 90 mol% or more of the terminal terminator is introduced to all the terminals, that is, when the OH group is 10 mol% or less. Further, the terminal stoppers may be used alone or in combination of two or more.

The reaction by the melting method is usually a transesterification reaction between a dihydric phenol and a carbonate ester,
The method is carried out by a method in which a dihydric phenol and a carbonate ester are mixed while heating in the presence of an inert gas to distill off the produced alcohol or phenol. The reaction temperature varies depending on the boiling point of the produced alcohol or phenol, but is usually in the range of 120 to 350 ° C.
In the latter stage of the reaction, the pressure of the system is reduced to about 10 to 0.1 Torr to facilitate the distillation of the alcohol or phenol produced. The reaction time is usually about 1 to 4 hours.

Examples of the carbonate ester include an optionally substituted ester such as an aryl group having 6 to 10 carbon atoms, an aralkyl group, or an alkyl group having 1 to 4 carbon atoms. Specifically, diphenyl carbonate, ditolyl carbonate, bis (chlorophenyl) carbonate, m-cresyl carbonate, dinaphthyl carbonate, bis (diphenyl) carbonate, dimethyl carbonate, diethyl carbonate, dibutyl carbonate, etc. Is preferred.

A polymerization catalyst can be used to increase the polymerization rate. Examples of the polymerization catalyst include sodium hydroxide, potassium hydroxide, alkali metal compounds such as sodium salts and potassium salts of dihydric phenol, and water. Alkaline earth metal compounds such as calcium oxide, barium hydroxide and magnesium hydroxide; nitrogen-containing basic compounds such as tetramethylammonium hydroxide, tetraethylammonium hydroxide, trimethylamine and triethylamine; alkoxides of alkali metals and alkaline earth metals Manganese, organic acid salts of alkali metals and alkaline earth metals, zinc compounds, boron compounds, aluminum compounds, silicon compounds, germanium compounds, organic tin compounds, lead compounds, osmium compounds, antimony compounds Compounds, titanium compounds, usually the esterification reaction, such as zirconium compounds, there can be used a catalyst used in the transesterification reaction. The catalyst may be used alone or in combination of two or more. The amount of the polymerization catalyst used is preferably 1 × 10 ⁻⁸ to 1 ×, based on 1 mol of the dihydric phenol used as the raw material.
It is selected in the range of 10 ⁻³ equivalents, more preferably 1 × 10 ^{−7 to} 5 × 10 ⁻⁴ equivalents.

In order to reduce the number of phenolic terminal groups in such a polymerization reaction, for example, bis (chlorophenyl) carbonate, bis (bromophenyl) carbonate, bis (nitrophenyl) carbonate is used later or after completion of the polycondensation reaction. , Bis (phenylphenyl)
Carbonate, chlorophenylphenyl carbonate,
It is preferable to add compounds such as bromophenylphenyl carbonate, nitrophenylphenyl carbonate, phenylphenyl carbonate, methoxycarbonylphenylphenyl carbonate, and ethoxycarbonylphenylphenyl carbonate. Of these, 2-chlorophenylphenyl carbonate, 2-methoxycarbonylphenylphenyl carbonate and 2-ethoxycarbonylphenylphenyl carbonate are preferred, and 2-methoxycarbonylphenylphenyl carbonate is particularly preferred.

The molecular weight of the polycarbonate resin is 13,000 to 17,000 in terms of viscosity average molecular weight (M),
14,000 to 16,000 is preferred. The viscosity average molecular weight is determined by inserting the specific viscosity (η _SP ) obtained from a solution obtained by dissolving 0.7 g of a polycarbonate resin in 100 mL of methylene chloride at 20 ° C. into the following equation. η _SP /c=[η]+0.45×[η] ² c (where [η]
Is the intrinsic viscosity) [η] = 1.23 × 10 ⁻⁴ M ^0.83 c = 0.7

When an aromatic polycarbonate resin having a viscosity average molecular weight of more than 17,000 is used, the fluidity is reduced, and the molding temperature is increased accordingly. It adheres to the mold surface, resulting in poor product appearance and reduced productivity. In addition, when a material having a viscosity average molecular weight of less than 13,000 is used, sufficient flame retardancy cannot be obtained, and the mechanical strength decreases.

The raw material polycarbonate resin is produced by a conventionally known method (such as an interfacial polycondensation method or a melt polymerization method), and then subjected to a microfiltration treatment in a solution state, or a granulated raw material after granulation (desolvation). For example, it is preferable to remove impurities and foreign substances such as low molecular weight components and unreacted components by washing with a poor solvent such as acetone under heating conditions. In the extrusion step (pelletization step) for obtaining a pellet-like polycarbonate resin, it is preferable to remove foreign substances by passing through a sintered metal filter having a filtration accuracy of 10 μm in a molten state. If necessary, it is also preferable to add an additive such as a phosphorus-based antioxidant. While these phosphorus-based antioxidants have an antioxidant effect, they affect the moist heat resistance of the polycarbonate resin, and thus are preferably incorporated in the polycarbonate resin at 0.0001 to 0.1% by weight, more preferably 0.0005-0.05
%, Particularly preferably 0.001 to 0.01% by weight. In any case, in order to improve the wet heat resistance, it is necessary that the content of the raw material resin such as foreign matter, impurities, and solvent is minimized.

The aromatic polycarbonate resin of the present invention may further contain, if necessary, a release agent, an ultraviolet absorber such as a triazole, acetophenone or salicylate ester; a bluing agent such as an anthraquinone dye; Coloring agents such as black and titanium oxide (0.001 to 10
% By weight), a light-diffusing agent, a lubricant, a fluorescent whitening agent such as coumarin, naphthalimide, or an oxazole compound (0.01 to
0.1% by weight) and the like.

The styrene resin used as the component b in the present invention is a resin containing styrene or a styrene derivative such as α-methylstyrene or vinyltoluene in an amount of 20% by weight or more based on 100% by weight of the styrene resin. . Accordingly, as the styrene resin, homopolymers or copolymers of such styrene derivatives, copolymers of these monomers with vinyl monomers such as acrylonitrile and methyl methacrylate, and diene rubbers such as polybutadiene, ethylene・ Propylene rubber, acrylic rubber, polyorganosiloxane component and poly (meth)
Styrene and / or a styrene derivative, or styrene and / or a styrene derivative and another vinyl monomer are graft-polymerized onto a rubber component such as a composite rubber having a structure entangled with each other so that the alkyl acrylate component cannot be separated. Things can be mentioned. Specific examples of these styrene resins include polystyrene,
High impact polystyrene (HIPS), acrylonitrile-styrene copolymer (AS resin), acrylonitrile
Butadiene / styrene copolymer (ABS resin), methyl methacrylate / butadiene / styrene copolymer (MB
S resin), methyl methacrylate, acrylonitrile,
Butadiene / styrene copolymer (MABS resin), acrylonitrile / ethylene propylene rubber / styrene copolymer (AES resin), acrylonitrile / styrene
A resin such as an acrylic rubber copolymer (ASA resin), or a mixture thereof is mentioned. In the copolymer and the mixture, a styrene-based derivative component contains 20% by weight or more in 100% by weight of the styrene-based resin. is there. Such various polymers, bulk polymerization, suspension polymerization, emulsion polymerization, those produced by various polymerization methods such as bulk suspension polymerization can be used, and even if the copolymerization method is copolymerized in one step,
Copolymerization may be carried out in multiple stages.

In the present invention, among these, polystyrene, high impact polystyrene (HIPS), acrylonitrile / styrene copolymer (AS resin), acrylonitrile / butadiene / styrene copolymer (ABS resin), acrylonitrile / styrene / acrylic rubber Copolymer (A
SA resin) is preferable. Above all, AB is preferred from the viewpoint of impact resistance.
S resin is most preferred. Further, among these, those produced by the bulk polymerization method can be preferably used in that the wet heat resistance can be further improved. These b-components can be used alone or in combination of two or more.

The ABS resin referred to in the present invention is a thermoplastic graft copolymer obtained by graft-polymerizing a vinyl cyanide compound and an aromatic vinyl compound to a diene rubber component, and is usually produced as a by-product during the graft polymerization of an AS resin or the like. To form a mixture with other polymers. Further AB
A mixture of S resin and separately polymerized AS resin is widely used industrially. As the diene rubber component forming the ABS resin, a rubber having a glass transition point of 10 ° C. or less, such as polybutadiene, polyisoprene, and styrene-butadiene copolymer, is used. 5 to 75% by weight
It is preferred that Examples of the vinyl cyanide compound grafted to the diene rubber component include acrylonitrile and methacrylonitrile, and examples of the aromatic vinyl compound grafted to the diene rubber component include styrene and α-methylstyrene. And nucleus-substituted styrene. The content ratio of the vinyl cyanide compound and the aromatic vinyl compound is such that the vinyl cyanide compound is 5 to 50% by weight and the aromatic vinyl compound is 100% by weight of the total amount of the vinyl cyanide compound and the aromatic vinyl compound. Is 95-5
0% by weight. Further, methyl acrylate, methyl methacrylate, ethyl acrylate, maleic anhydride, N
Substituted maleimides and the like can be mixed and used, but their content should be 15% by weight or less in the component b.

The ABS resin of the present invention may be produced by any method of bulk polymerization, suspension polymerization, and emulsion polymerization. As described above, the ABS resin produced by the bulk polymerization method has poor wet heat resistance. This is more preferable in that it is further improved.

Further, the preferred ABS resin satisfies the condition that the amount of acrylonitrile monomer remaining in the ABS resin is 200 ppm or less, more preferably 100 ppm or less, particularly preferably 50 ppm or less. When the amount of the residual acrylonitrile monomer satisfies these amounts, better moisture and heat resistance can be satisfied. When the amount of the acrylonitrile monomer is less than 5 ppm, the wet heat resistance is not significantly improved, but the economic disadvantage due to an increase in the number of steps for reducing the amount of the monomer is increased. It is.

The phosphorus-based flame retardant used as the component c in the present invention is represented by the following formula (1).

[0043]

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(Wherein R ₁ , R ₂ and R ₃ independently represent an alkyl group having 1 to 8 carbon atoms or an aryl group which may be substituted with an alkyl group having 6 to 20 carbon atoms; Is 0 or 1)

The phosphorus-based flame retardants of the formula (1) include, for example, trimethyl phosphate, triethyl phosphate, tributyl phosphate, trioctyl phosphate, tributoxyethyl phosphate, triphenyl phosphate,
Tricresyl phosphate, cresyl diphenyl phosphate, octyl diphenyl phosphate and the like can be mentioned. Among such phosphorus-based flame retardants, triphenyl phosphate can be preferably used. This is because triphenyl phosphate has a low melting point and thus is easy to vaporize, but even if it adheres to a mold, it is relatively easy to remove. Furthermore, it can be preferably used in that it has good flame retardancy, good fluidity at the time of molding, and a good effect on wet heat resistance.

In the present invention, the silicate-based filler used as the component d means that the SiO ₂ component is 3 in terms of its chemical composition.
An inorganic filler containing 5% by weight or more, preferably an inorganic filler containing 40% by weight or more. Such silicate-based fillers include kaolin, talc, clay, pyrophyllite, mica, montmorillonite, bentonite, wollastonite, sepiolite, zonotolite, natural silica, synthetic silica, various glass fillers, zeolites, diatomaceous earth, halloysite And the like.

Among them, in the present invention, it is possible to increase the number of action points for suppressing the hydrolysis by finely dispersing such a filler, and also from the viewpoint of imparting flame retardancy, the reinforcing effect on the resin is important. From the viewpoint, talc, mica and wollastonite can be mentioned as preferable fillers. Among them, talc is most preferable.

The mica used in the present invention is preferably a powder having an average particle diameter of 1 to 80 μm from the viewpoint of securing the reinforcing effect. Mica is a crushed silicate mineral containing aluminum, potassium, magnesium, sodium, iron and the like. Mica includes muscovite, phlogopite, biotite, artificial mica and the like, and any mica can be used as the mica of the present invention. In particular, OH groups of phlogopite, biotite and phlogopite are replaced by F atoms. than was artificial mica, SiO ₂
Higher content muscovite is preferred. The pulverization method for producing mica includes a dry pulverization method in which raw mica is pulverized by a dry pulverizer and a coarse pulverization of mica ore in a dry pulverizer, and then adding water to a wet pulverizer in a slurry state. In the present invention, there is a wet pulverization method in which dewatering and drying are performed, and a dry pulverization method is more common at a lower cost, but it is difficult to pulverize mica thinly and finely. It is preferable to use mica manufactured by the following method.

The average particle size of mica is from 1 to 80 as measured by a microtrack laser diffraction method.
μm can be preferably used. More preferably, the average particle size is 2 to 50 μm. In the case of 1 to 80 μm, a good effect on the flame retardancy is obtained, and the condition for fine dispersion in the resin is satisfied, so that the wet heat resistance can be maintained well.

As for the thickness of mica, those having a thickness actually measured by observation with an electron microscope of 0.01 to 1 μm can be used. Preferably, the thickness is 0.03-0.3 μm.
Further, such mica may be surface-treated with a silane coupling agent or the like, and may be granulated with a binder such as an epoxy-based, urethane-based, or acrylic-based binder to form granules. Specific examples of mica include mica powder (mica powder) A-41, A-21, and A-11 manufactured by Yamaguchi Mica Industrial Co., Ltd., and these are easily available on the market.

The talc used in the present invention is preferably a powder having an average particle size of 0.5 to 20 μm from the viewpoint of securing rigidity. Since talc is thicker than mica, it is preferable that talc has a smaller particle size in order to have the same dispersion in the resin. Here, the average particle size of talc means a value measured by a microtrack laser diffraction method.

The talc of the present invention is not particularly limited to the place of production, but more preferably, the talc has a higher SiO ₂ component, for example, 60% by weight or more. In the case of such an SiO ₂ component amount, the content of Fe ₂ O ₃ which is an impurity tends to be relatively large, and therefore, such talc is also advantageous in terms of hue. Also, there is no particular limitation on the production method when such talc is crushed from a rough stone, such as an axial flow mill method, an annular mill method, a roll mill method, a ball mill method, a jet mill method, and a container rotating compression shearing mill method. Can be used. Further, such talc is preferably in an agglomerated state in terms of handling properties and the like. Examples of such a production method include a method using deaeration compression, a method using a binder resin and compression, and the method using deaeration compression is particularly simple. Moreover, it is preferable because unnecessary binder resin components are not mixed into the composition of the present invention.

[0053] and wollastonite in the present invention, the fibrous inorganic filler mainly composed of calcium silicate is a natural white mineral having needle-like crystals, substantially formula CaSiO ₃
And usually contains about 50% by weight of SiO ₂ , about 47% by weight of CaO, Fe ₂ O ₃ , Al ₂ O _3, etc., and has a specific gravity of about 2.9.

The wollastonite of the present invention preferably has a number average length of 10 to 50 μm and a number average diameter of 1 to 10 μm, and more preferably has a number average length of 5 to 25 μm at least 50%, More preferably, it is 60% or more. The fiber diameter is 0.5 to 2.5
Those having a fiber diameter of μm are at least 40% or more, more preferably 50% or more. Further, those having a number average aspect ratio of 6 or more, more preferably 8 or more can be more preferably used. In particular, when the aspect ratio is 8 or more, the reinforcing effect is sufficient, which is preferable. However, considering the working environment, those having an aspect ratio of 50 or less are more preferable.

The fiber length and fiber diameter are calculated from values measured for 200 or more randomly extracted wollastonite images from an optical microscope, an electron microscope, or the like. The wollastonite may be subjected to a surface treatment with a normal surface treatment agent, for example, a coupling agent such as a silane coupling agent or a titanate coupling agent.

Next, the mixing ratio of each component in the resin composition of the present invention will be described. The mixing ratio of the components a to c in the resin composition is represented based on the total weight of the three components.
The component a is 40 to 92% by weight, the component b is 5 to 40% by weight, and the component c is 3 to 20% by weight per 100% by weight of the total of the three.
It is. When the component a is less than 40% by weight or the component b exceeds 40% by weight, sufficient flame retardancy cannot be obtained, and heat resistance (particularly, deflection temperature under load) and mechanical strength are reduced. In addition, the component a exceeds 92% by weight or b
If the content of the component is less than 5% by weight, the fluidity is reduced, and the molding temperature is increased accordingly, so that the flame retardant vaporizes and adheres to the product or the mold surface, resulting in poor appearance of the product and reduced productivity. Become like Further, when the component c is less than 3% by weight, sufficient flame retardancy cannot be obtained, and when it exceeds 20% by weight, mechanical strength and heat resistance (particularly, deflection temperature under load) are remarkably reduced, and wet heat resistance is also significantly reduced. .

In the present invention, the compounding ratio of the component d is in the range of 0.1 to 25 parts by weight, preferably 0.5 to 20 parts by weight per 100 parts by weight of the total of the components a to c. If the compounding ratio of this d component is less than 0.1 part by weight, there is no effect of improving the moist heat resistance, and 25 parts by weight lowers the fluidity, so that a higher molding temperature is required, the vaporization of the flame retardant becomes large, and Problems such as mold adhesion occur. Further, the impact strength is lowered and the surface appearance of the obtained molded product is deteriorated, which is not preferable.

The composition of the present invention may further contain polytetrafluoroethylene having a fibril-forming ability in order to further improve the flame retardancy. Polytetrafluoroethylene having a fibril-forming ability is classified into type 3 in the ASTM standard. Further, the polytetrafluoroethylene having a fibril-forming ability preferably has a primary particle diameter in the range of 0.05 to 10 μm, and more preferably has a secondary particle diameter of 50 to 700 μm. Such a polytetrafluoroethylene has a drip-preventing performance at the time of a combustion test of a test piece in a UL standard vertical combustion test, and such a polytetrafluoroethylene having a fibril-forming ability is, for example, Mitsui-Dupont Fluorochemical Co. Teflon 6J
Alternatively, it is commercially available from Daikin Chemical Industries, Ltd. as Polyflon and can be easily obtained. The compounding amount of polytetrafluoroethylene having a fibril forming ability is 0.1 to 100 parts by weight based on a total of 100 parts by weight of the three components a to c.
One part by weight is preferred. When the content is in the range of 0.1 to 1 part by weight, it is possible to obtain a satisfactory appearance and mechanical properties together with a sufficient melting dripping prevention performance.

As the polytetrafluoroethylene, in addition to a usual solid form, an aqueous emulsion and a dispersion form can be used. In addition, polytetrafluoroethylene having a fibril-forming ability improves dispersibility in a resin, and in order to obtain better appearance and mechanical properties, a polytetrafluoroethylene emulsion and a vinyl polymer emulsion are mixed. Aggregated mixtures can also be mentioned as a preferred form.

Here, as the vinyl polymer, polypropylene, polyethylene, polystyrene, HIPS, AS
Resin, ABS resin, MBS resin, MABS resin, ASA
Resin, polymethyl (meth) acrylate, block copolymer composed of styrene and butadiene and its hydrogenated copolymer, block copolymer composed of styrene and isoprene, and its hydrogenated copolymer, acrylonitrile-butadiene copolymer, Ethylene-propylene random copolymer and block copolymer, ethylene-butene random copolymer and block copolymer, ethylene and α-olefin copolymer, ethylene-unsaturated carboxylic acid such as ethylene-butyl acrylate A copolymer with an ester, an acrylate-butadiene copolymer such as butyl acrylate-butadiene, a rubbery polymer such as polyalkyl (meth) acrylate, a composite rubber containing polyorganosiloxane and polyalkyl (meth) acrylate, More heels It can be exemplified styrene compound rubber, acrylonitrile, a copolymer obtained by grafting a vinyl monomer of polyalkyl methacrylate or the like.

Among these, from the viewpoint of compatibility with the component b, a composite rubber containing polystyrene, HIPS, ABS resin, ASA resin, polymethyl methacrylate, polyorganosiloxane and polyalkyl (meth) acrylate, and further, such a composite rubber A copolymer obtained by grafting a vinyl-based monomer such as styrene, acrylonitrile, or polyalkyl methacrylate is more preferable, and a polymer of the same type as the component b is more preferably used.

In order to prepare such an agglomerated mixture, the average particle diameter is preferably 0.01 to 1 μm, particularly 0.05 to 0.5 μm.
An aqueous emulsion of the component (b) having an average particle size of 0.1.
It is mixed with an aqueous emulsion of polytetrafluoroethylene having a size of from 0.05 to 10 μm, in particular from 0.05 to 1.0 μm. Such an emulsion of polytetrafluoroethylene is obtained by polymerizing polytetrafluoroethylene by emulsion polymerization using a fluorinated surfactant.
In the emulsion polymerization, other copolymer components such as hexafluoropropylene can be copolymerized in an amount of 10% by weight or less of the whole polytetrafluoroethylene.

In order to obtain such an agglomerated mixture, a suitable polytetrafluoroethylene emulsion is usually prepared by adding
The styrene resin emulsion having a solid content of 0 to 70% by weight, especially 50 to 65% by weight,
Those having a solids content of 5 to 60% by weight, in particular 30 to 45% by weight, are used. Furthermore, the proportion of polytetrafluoroethylene in the aggregated mixture is 5 to 40% by weight in a total of 100% by weight with the vinyl polymer used in the aggregated mixture.
In particular, 10 to 30% by weight can be preferably used. After mixing the emulsions described above, a production method in which the mixture is stirred and mixed, poured into hot water in which a metal salt such as calcium chloride, magnesium sulfate or the like is dissolved, and subjected to salting out and coagulation to thereby separate and recover the mixture can be preferably mentioned. Other examples include a method of recovering the stirred mixed emulsion by a method such as spray drying or freeze drying.

A variety of aggregated mixtures of a polytetrafluoroethylene emulsion having a fibril-forming ability and a vinyl-based polymer emulsion can be used in various forms. For example, a vinyl-based emulsion may be formed around polytetrafluoroethylene particles. Examples include a form in which a polymer is surrounded, a form in which a polytetrafluoroethylene is surrounded around a vinyl-based polymer, and a form in which several particles are aggregated with respect to one particle.

Further, a product obtained by graft polymerization of the same or another type of vinyl monomer on the outer layer of the aggregated mixture can also be used. Such vinyl monomers include styrene, α-methylstyrene, methyl methacrylate, cyclohexyl acrylate, dodecyl methacrylate, dodecyl acrylate, acrylonitrile, acrylic acid-2-
Preference is given to ethylhexyl, which can be used alone or copolymerized.

As a commercially available coagulated mixture of the above-mentioned polytetrafluoroethylene emulsion having a fibril-forming ability and an emulsion of a vinyl polymer, methabrene “A3000” may be mentioned as a representative example from Mitsubishi Rayon Co., Ltd. It can be used preferably in the present invention.

The resin composition of the present invention may be used in addition to the above-mentioned styrene-based resin, particularly for the purpose of improving low-temperature impact properties.
A rubbery polymer can be blended. Such rubbery polymers include (meth) acrylate-based core-shell graft copolymers, polyurethane-based elastomers,
Examples include polyester-based elastomers.

Examples of the (meth) acrylate-based core-shell graft copolymer include rubber-like alkyl (meth) acrylate polymers having 2 to 8 alkyl groups and copolymers with diene-based rubbery polymers. Alternatively, a core-shell type polymer in which a shell formed by polymerizing an alkyl (meth) acrylate and optionally a copolymerizable vinyl monomer on a core with a mixture, and a multi-stage core-shell type polymer in the same manner may be used. Can be used. Also, a core composed solely of a diene rubbery polymer can be used.
As such a (meth) acrylic acid ester core-shell graft polymer, a product name "HI" is available from Kureha Chemical Industry Co., Ltd.
Resins commercially available as "A-15" and "HIA-28" can be mentioned, and those having only a diene rubbery polymer as a core include Kureha Chemical Industry Co., Ltd.
And a resin commercially available under the trade name "PARALOID EXL-2602".

Further, a composite rubber having a structure in which the polyorganosiloxane component and the poly (meth) alkyl acrylate component are entangled with each other so as to be inseparable from each other is added to an alkyl (meth) acrylate and optionally a copolymerizable vinyl monomer. A polymer obtained by graft polymerization of a monomer (hereinafter referred to as an IPN-type polymer) can also be used. As such an IPN type polymer, “METABLEN S-
It is commercially available under the trade name "2001" and is easily available.

The thermoplastic polyurethane elastomer which can be used in the present invention includes an organic polyisocyanate, a polyol and two or three functional groups having a molecular weight of 5 or less.
It is obtained by the reaction of a chain extender of 0 to 400, and various known thermoplastic polyurethane elastomers can be used. As such a thermoplastic polyurethane elastomer, for example, "Kuramilon U" manufactured by Kuraray Co., Ltd.
(Product name) etc. can be easily obtained.

The thermoplastic polyester elastomer usable in the present invention is obtained by polycondensing a difunctional carboxylic acid component, an alkylene glycol component and a polyalkylene glycol component. Can be used.
Such thermoplastic polyester elastomers are easily available, for example, "Pelprene" (trade name) manufactured by Toyobo Co., Ltd. and "Nouvellen" (trade name) manufactured by Teijin Limited.

The resin composition of the present invention can be produced by mixing the above components with a mixer such as a tumbler, a V-type blender, a Nauta mixer, a Banbury mixer, a kneading roll, and an extruder. Further, polyester, polyamide, other thermoplastic resins such as polyphenylene ether may be mixed as long as the object of the present invention is not impaired,
It is also possible to incorporate a polyorganosiloxane flame retardant.

Further, as long as the object of the present invention is not impaired, a stabilizer (for example, a phosphoric ester, a phosphite, etc.), an antioxidant (for example, a hindered phenol compound, etc.), a light stabilizer (for example, For example, benzotriazole-based compounds, hindered amine-based compounds, benzophenone-based compounds), coloring agents, blowing agents, antistatic agents and the like can be blended with various generally-mixed additives.
These may be used alone or in the form of master pellets of various resins.

Examples of the heat stabilizer include phosphorous acid, phosphoric acid, phosphonous acid, phosphonic acid and esters thereof, which are known as heat stabilizers for aromatic polycarbonate resins. Phyto, tris nonylphenyl phosphite, tris (2,4-di-t
tert-butylphenyl) phosphite, tridecyl phosphite, trioctyl phosphite, trioctadecyl phosphite, didecyl monophenyl phosphite, dioctyl monophenyl phosphite, diisopropyl monophenyl phosphite, monobutyl diphenyl phosphite, monodecyl Diphenyl phosphite, monooctyl diphenyl phosphite, bis (2,6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphite, 2,2-methylenebis (4,6-di-tert-butylphenyl) Phosphite ester compounds such as octyl phosphite, bis (nonylphenyl) pentaerythritol diphosphite, bis (2,4-di-tert-butylphenyl) pentaerythritol diphosphite , Tri-butyl phosphate,
Trimethyl phosphate, tricresyl phosphate,
Phosphoric ester compounds such as triphenyl phosphate, trichlorophenyl phosphate, triethyl phosphate, diphenylcresyl phosphate, diphenyl monoorthoxenyl phosphate, tributoxyethyl phosphate, dibutyl phosphate, dioctyl phosphate, diisopropyl phosphate, and other phosphorus-based heat stable substances As an agent, tetrakis (2,4-di-ter
t-butylphenyl) -4,4′-biphenylenediphosphonite, tetrakis (2,4-di-tert-butylphenyl) -4,3′-biphenylenediphosphonite,
Tetrakis (2,4-di-tert-butylphenyl)
-3,3'-biphenylenediphosphonite, bis (2,
Examples thereof include phosphonite compounds such as 4-di-tert-butylphenyl) -4-biphenylenediphosphonite. Of these, trisnonylphenyl phosphite, distearylpentaerythritol diphosphite, bis (2,4-di-tert-butylphenyl) pentaerythritol diphosphite, tris (2,4-di-tert-butylphenyl) Phosphite, triphenyl phosphate, trimethyl phosphate tetrakis (2,4-di-tert-butylphenyl) -4,4′-biphenylenediphosphonite is preferred. These heat stabilizers may be used alone or in combination of two or more.

As the heat stabilizer of the present invention, in addition to the above, it is also preferable to add a hindered phenol compound or a sulfur compound generally known as an antioxidant. Such a compound is particularly preferable in that the thermal stability of the styrenic resin is maintained and the thermal decomposition of the resin is suppressed. Specific examples of such a compound include n-octadecyl-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate, 4,4′-butylidenebis (3-methyl-6-tert-butylphenol), 4,4'-thiobis (3-methyl-6-tert
-Butylphenol), 2,2'-methylenebis (4-
Methyl-6-tert-butylphenol), tris (3,5-di-tert-butyl-4-hydroxybenzyl) isocyanurate, 2,6-di-tert-butyl-4-methylphenol, 2,4-di- tert-amyl-6- [1- (3,5-di-tert-amyl-2)
-Hydroxyphenyl) ethyl] phenyl acrylate, and pentaerythrityltetrakis (3-laurylthiopropionate), dilauryl-3,3'-thiodipropionate, dimyristyl-3,3'-thiodipropionate, Stearyl-3,3'-thiodipropionate and the like can be mentioned.

The resin composition thus obtained is extruded,
It can be easily molded by injection molding, compression molding, etc.
It is particularly suitable for injection molding. Also, it can be applied to blow molding, vacuum molding and the like. In particular, it is most suitable as a material for electrical and electronic parts that require UL94V-0 and exterior use of OA.

[0077]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be further described below with reference to examples. The parts in the examples are parts by weight, and the evaluation was made by the following method.

(1) Moisture / heat resistance-1: About 50 g of pellets were treated with an environmental tester (platinum sub-zero lucifer manufactured by Tabai Espec Co., Ltd.) under the conditions of 65 ° C. and 85% RH.
After the treatment for 0 hour, the apparent viscosity average molecular weight was measured by the same method as that for measuring the molecular weight of the aromatic polycarbonate resin. That is, after dissolving the pellets in methylene chloride, the insoluble content was removed by filtration, and the specific viscosity of the solution obtained as a solution was measured in the same manner as the viscosity average molecular weight measurement of the polycarbonate resin described in the text, and the same calculation formula was used. The value of the apparent viscosity average molecular weight was calculated.

(2) Moisture / heat resistance-2: ASTM D790
A bending test was performed in accordance with the above-mentioned standards, and a change in strength before and after the heat treatment was observed. That is, the test piece was placed in an environment of 23 ° C. and 50% RH after molding and subjected to a bending test 24 hours later. The value before the wet heat treatment was used. After performing the bending test for 500 hours under the conditions of 65 ° C. and 85% RH, the value after the treatment was taken as the value after the treatment.

(3) Flame retardancy: A combustion test was conducted at a thickness of 1.6 mm in accordance with UL standard 94V.

(4) Mold contamination: Injection molding machine [FANU
C-T-150D] (box size: 100 mm (length) x 150 mm (width) x 15
mm (height) × the product thickness box-shaped article is a mobile terminal housing of 1.5 mm), injection pressure 800 kg / cm nearly good molded article cylinder temperature and mold temperature of 70 ° C. obtained in ² And the presence or absence of deposits on the mold surface was checked every 100 shots, and the number of molding shots in which deposits occurred was counted.

Reference Example 1 A reactor equipped with a thermometer, a stirrer and a reflux condenser was charged with 219.4 parts of ion-exchanged water and 40.2 parts of a 48% aqueous sodium hydroxide solution.
After dissolving 57.5 parts of bis (4-hydroxyphenyl) propane and 0.12 parts of hydrosulfite,
181 parts of methylene chloride were added, and 28.3 parts of phosgene were blown in at 15 to 25 ° C for 40 minutes with stirring. After completion of the phosgene blowing, 7.2 parts of a 48% aqueous sodium hydroxide solution and 2.42 parts of p-tert-butylphenol were added, stirring was started. After emulsification, 0.06 part of triethylamine was added, and the mixture was further heated at 28 to 33 ° C. for 1 hour. The reaction was completed by stirring. After the completion of the reaction, the product was diluted with methylene chloride, washed with water, acidified with hydrochloric acid, and washed with water.When the conductivity of the aqueous phase became almost the same as that of ion-exchanged water, an isolation chamber having a foreign substance take-out port in the bearing was formed. The methylene chloride was evaporated by the provided kneader to obtain a powder having a viscosity average molecular weight of 15,000. This was designated as PC-1.

Reference Example 2 A reactor equipped with a stirrer and a distillation column was charged with 228 parts of 2,2-bis (4-hydroxyphenyl) propane and diphenyl carbonate (manufactured by Bayer).
220 parts (about 1.03 mol / bisphenol A 1 mol)
And, as a catalyst, 0.000024 parts of sodium hydroxide (about 6 × 10 ⁻⁷ mol / 1 mol of bisphenol A) and 0.0073 parts of tetramethylammonium hydroxide (about 8 × 10 ⁻⁵ mol / 1 mol of bisphenol A) were charged.
It was replaced with nitrogen. This mixture was heated to 200 ° C. and dissolved with stirring. Next, most of the phenol was distilled off in 1 hour while heating at a reduced pressure of 30 Torr,
When the temperature was further increased to 270 ° C. and the polymerization reaction was carried out for 2 hours at a reduced pressure of 1 Torr, 2.3 parts of 2-methoxycarbonylphenylphenyl carbonate was added as a terminal stopper. Thereafter, a terminal blocking reaction was performed at 270 ° C. and 1 Torr or less for 5 minutes. Next, in the molten state, 0.00023 parts of tetrabutylphosphonium dodecylbenzenesulfonate was added as a catalyst neutralizing agent,
The reaction was continued at 70 ° C. and 10 Torr or less for 10 minutes to obtain a polymer having a viscosity average molecular weight of 15,000. The polymer was sent to the extruder by a gear pump. During the extruder, 0.008% by weight of tris (2,4-di-tert-butylphenyl) phosphite was added to obtain polycarbonate pellets. This was designated as PC-2.

Examples 1 to 10, Comparative Examples 1 to 7
The components shown in Tables 2 and 3 were mixed in the amounts shown in the table with a V-type blender, and then pelletized at a cylinder temperature of 240 ° C. with a vented twin-screw extruder having a diameter of 30 mm [TEX30XSST manufactured by Nippon Steel Works, Ltd.]. It has become. After drying the pellets at 100 ° C. for 5 hours, an injection molding machine [FANU
C-T-150D], and various test pieces were prepared and evaluated. The evaluation results are shown in Tables 1 to 3. Table 1
The symbols indicating the components described in 3 are as follows.

(Component a) PC-1: Polycarbonate resin produced in Reference Example 1 (phosgene method) PC-2: Polycarbonate resin produced in Reference Example 2 (melting method) PC-3: Reference example Polycarbonate resin PC-4 having a viscosity average molecular weight of 14,200 manufactured by the same method using the same raw material as in Example 1, and manufactured by the same method using the same raw material as in Reference Example 1 above. Polycarbonate resin having a viscosity average molecular weight of 16,700 (other than the component a) PC-5: a polycarbonate resin having a viscosity average molecular weight of 20,000, manufactured by the same method using the same raw materials as in the above Reference Example 1 PC-6 : A polycarbonate resin having a viscosity average molecular weight of 25,000 and produced by the same method using the same raw materials as in Reference Example 1 above (component (b)) ABS-1: by bulk polymerization ABS resin [Santak UT-61 manufactured by Mitsui Chemicals, Inc.] ABS-2: ABS resin manufactured by emulsion polymerization [Sebian V680 manufactured by Daicel Chemical Industries, Ltd.] (Component c) FR-1: Tri Phenyl phosphate [Daichi Chemical Co., Ltd.
TPP] FR-2: tricresyl phosphate [Daichi Chemical Co., Ltd.]
PX-130 manufactured by Fuji Electric Co., Ltd. (other than the component c) FR-3: resorcinol polyphosphate [CR-733S by Daihachi Chemical Co., Ltd.] (d component) Talc: talc [HS-T0.8 manufactured by Hayashi Kasei Co., Ltd., average particles Mica: Mica powder [A-41, manufactured by Mika Yamaguchi Kogyosho Co., Ltd.]
Average particle size: about 40 μm] WSN: Wollastonite [Tomo Kogyo Co., Ltd.
N-4, average fiber diameter 1.5 μm, average fiber length 17 μm] (Others) PTFE: polytetrafluoroethylene [F-201L manufactured by Daikin Industries, Ltd.]

[0086]

[Table 1]

[0087]

[Table 2]

[0088]

[Table 3]

As is clear from this table, Examples 1 to 3 were used.
From a comparison with Comparative Examples 1 and 2, it was found that when the specific polycarbonate resin of the present invention was used, the number of shots that caused mold adhesion was significantly increased, and mold contamination was extremely suppressed. Understand. In the case of using a condensed phosphoric ester, other properties are insufficient.
In addition, even when the specific polycarbonate resin of the present invention was used, even when the ABS resin was not blended, deposits were generated on the mold surface with a small number of molding shots at the time of molding and the contamination of the mold was observed. When the content of the ABS resin is too large, the flame retardancy is poor.

[0090]

The flame-retardant resin composition of the present invention has flame-retardant properties,
A resin composition that is excellent in fluidity and moist heat resistance and has improved mold contamination when a monophosphate ester flame retardant is used, and in addition to excellent properties, also has excellent appearance and production efficiency. , CRT housing,
It is extremely useful for various industrial uses such as the OA equipment field represented by the portable information terminal housing and the notebook computer housing and the electric and electronic equipment field.

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI theme coat ゛ (reference) C08L 55/02 C08L 55/02 // (C08L 69/00 25:04) F term (reference) 4F071 AA22 AA22X AA34X AA50 AA77 AA81 AB26 AB30 AC15 AE07 AH12 BB05 4J002 BC022 BC032 BC042 BC062 BN072 BN122 BN152 BN162 CG001 DJ007 DJ017 DJ037 DJ047 DJ057 EW046 FD017 FD136 GQ00

Claims (5)

[Claims] 1. A viscosity average molecular weight of 13,000 to 17,0.
No. 00 aromatic polycarbonate resin (a component) 40 to 9
2% by weight, styrene resin (component (b)) 5 to 40% by weight,
And a flame retardant resin composition comprising a total of 100% by weight of 3 to 20% by weight of a phosphorus-based flame retardant (component (c)) represented by the following general formula (1). Embedded image (Wherein R ₁ , R ₂ and R ₃ independently of one another have 1 carbon atom)
Represents an aryl group which may be substituted by an alkyl group having from 8 to 8 or an alkyl group having from 6 to 20 carbon atoms, and n is 0 or 1) 2. A silicate-based filler (d) is added to 100 parts by weight of the flame-retardant resin composition comprising component (a), component (b) and component (c).
The flame-retardant resin composition according to claim 1, wherein the composition comprises 0.1 to 25 parts by weight of a component. 3. The component b is a thermoplastic graft copolymer obtained by grafting a vinyl cyanide compound and an aromatic vinyl compound onto a diene rubber component, and the thermoplastic graft copolymer is produced by a bulk polymerization method. Claim 1
Or the flame-retardant resin composition according to any one of 2. 4. The flame-retardant resin composition according to claim 1, wherein the component d is at least one filler selected from the group consisting of talc, mica and wollastonite. 5. A molded article obtained by melt-molding the flame-retardant resin composition according to any one of claims 1 to 4.