JP2001049107A - Flame-retarded resin composition and molded product comprising the molding product - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain the subject composition having excellent flame retardance, fluidity and wet heat resistance and wet heat resistance and controlled mold adhesion by making the composition include a specific aromatic polycarbonate resin, an aromatic polyester resin and a phosphorus-based flame-retardant in a specific ratio. SOLUTION: This resin composition comprises (A) 40-92 wt.% of an aromatic polycarbonate resin having 130,000-19,500 viscosity average molecular weight (generally obtained by a reaction between a dihydric phenol and a carbonate precursor by an interfacial polymerization method or a melt method), (B) 5-40 wt.% of an aromatic polyester resin (e.g. a polyethylene terephthalate, a polyethylene naphthalate, etc., using ethylene glycol as a diol component), (C) 3-20 wt.% of a phosphorus-based flame-retardant of the formula [R1 to R3 are each a 1-8C alkyl or (alkyl-substituted) 6-20C aryl] (e.g. triphenyl phosphate, etc.). Preferably a resin composition comprises 100 pts.wt. of the composition composed of the components and (D) 0.1-25 pts.wt. of a silicate-based filler.

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 Various researches have been made on resin compositions comprising an aromatic polycarbonate resin and an aromatic polyester resin as materials having excellent chemical resistance and impact resistance, and have been applied to various fields such as automobile field and OA field. Widely used.

In recent years, there has been a strong demand for flame-retardant resin materials mainly for applications such as OA equipment and home electric appliances. To meet these demands, polymer alloys of polycarbonate resin and polyester resin have also been required to be flame-retardant. Many studies have been made on the conversion.

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 alkylene terephthalate resin (Japanese Patent Application Laid-Open No. Sho 64-70555), a phosphate-based condensed phosphate ester A method of blending an oligomer (JP-A-6-192553) has been proposed.

[0005] 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, the use of a monophosphate compound such as triphenyl phosphate as a flame retardant with respect to a polymer alloy comprising a polycarbonate resin and a polyester 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 subject that has been strongly demanded.

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 fiber and a bromine-based flame retardant are mixed with a low-molecular-weight aromatic polycarbonate. However, a low-molecular-weight aromatic polycarbonate resin and an aromatic polyester are proposed. Regarding a blended material with a resin, no specific proposal or usefulness has been recognized.

[0009]

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 an aromatic polyester resin mixed with a monophosphate ester flame retardant. It is an object of the present invention to provide a flame-retardant resin composition which is less likely to vaporize. The present inventors have conducted intensive studies to achieve the above object, and as a result, have found that when an aromatic polycarbonate resin having a specific molecular weight is used, vaporization and adhesion of a mold can be extremely significantly suppressed. The present invention, which is a flame-retardant resin composition having good flowability, good wet heat resistance, and low mold adhesion, has been achieved.

[0010]

Means for Solving the Problems The present invention provides the following component a:
When the sum of the components b and c is 100% by weight, 40 to 92% by weight of an aromatic polycarbonate resin having a viscosity average molecular weight of 13,000 to 19,500 (component a) and 5 to 5 of an aromatic polyester resin (component b) 40% by weight, and phosphorus-based flame retardant (c component) 3 to 3 represented by the following general formula (1)
The present invention relates to a flame-retardant resin composition comprising 20% by weight and a molded product obtained by melt-molding the flame-retardant resin composition.

[0011]

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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 polymerization 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 aromatic polycarbonate resin by reacting the above-mentioned dihydric phenol and the carbonate precursor by an interfacial polymerization method or a melting method, if necessary, a catalyst, a terminal stopper and an antioxidant for the dihydric phenol may be used. Agents and the like may be used. The aromatic 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. Alternatively, a mixture of two or more of the obtained aromatic polycarbonate resins may be used.

The reaction by the interfacial polymerization 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 aromatic polycarbonate resins are not terminated because the ends are blocked by groups based on monofunctional phenols. Excellent in thermal 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.

It is desirable that the terminal terminator is introduced at least at 5 mol%, preferably at least 10 mol%, based on all terminals of the obtained aromatic 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. 90 mol% or more of a terminator is introduced to all terminals, that is, O
This is the case when the H 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 to be used is preferably 1 × 10 ⁻⁸ to 1 × 10 ⁸ per 1 mol of the starting dihydric phenol.
^-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 aromatic polycarbonate resin is as follows:
The viscosity average molecular weight (M) is from 13,000 to 19,500, more preferably from 13,000 to 17,000, still more preferably from 14,000 to 17,000, and most preferably from 14,000 to 17,000. 16,000. The viscosity average molecular weight here is 100 methylene chloride.
The specific viscosity (η _SP ) obtained from a solution obtained by dissolving 0.7 g of an aromatic polycarbonate resin in L at 20 ° C. was inserted into the following equation. η _SP /c=[η]+0.45×[η] ² c (where [η]
Is 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 19,500 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 aromatic polycarbonate resin is produced by a conventionally known conventional method (interfacial polymerization method, melt polymerization method, etc.), and then subjected to microfiltration treatment in a solution state, or to granular raw material after granulation (desolvation). It is preferable to remove impurities and foreign substances such as low molecular weight components and unreacted components by washing the mixture with a poor solvent such as acetone under heating conditions. In the extrusion step (pelletization step) for obtaining a pelletized aromatic 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 wet heat resistance of the aromatic polycarbonate resin, and thus are preferably incorporated in the aromatic polycarbonate resin at 0.0001 to 0.1% by weight. , More preferably 0.0005 to 0.05% by weight, particularly preferably 0.05 to 0.05% by weight.
It is the case of 01 to 0.01% by weight. In any case, in order to improve the moist heat resistance, the raw material resin should contain foreign matter, impurities,
It is necessary to keep the content of the solvent and the like as low as possible.

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 aromatic polyester resin used as the component b in the present invention is a polymer obtained by a condensation reaction comprising an aromatic dicarboxylic acid or its reactive inducer and a diol or its ester derivative as main components. Or a copolymer.

The aromatic dicarboxylic acids mentioned here include terephthalic acid, isophthalic acid, orthophthalic acid, 1,5-
Naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, 4,4'-biphenyldicarboxylic acid, 4,4'-
Biphenyl ether dicarboxylic acid, 4,4'-biphenylmethane dicarboxylic acid, 4,4'-biphenyl sulfone dicarboxylic acid, 4,4'-biphenyl isopropylidene dicarboxylic acid, 1,2-bis (phenoxy) ethane-
4,4′-dicarboxylic acid, 2,5-anthracenedicarboxylic acid, 2,6-anthracenedicarboxylic acid, 4,4 ′
Aromatic dicarboxylic acids such as -p-terphenylenedicarboxylic acid and 2,5-pyridinedicarboxylic acid are preferably used, and terephthalic acid and 2,6-naphthalenedicarboxylic acid are particularly preferably used.

The aromatic dicarboxylic acids may be used as a mixture of two or more kinds. In addition, if it is a small amount, it is also possible to use one or more kinds of aliphatic dicarboxylic acids such as adipic acid, azelaic acid, sebacic acid and dodecane diacid, and alicyclic dicarboxylic acids such as cyclohexane dicarboxylic acid together with the dicarboxylic acid. .

The diol which is a component of the aromatic polyester of the present invention includes ethylene glycol, propylene glycol, butylene glycol, hexylene glycol, neopentyl glycol, pentamethylene glycol, hexamethylene glycol, decamethylene glycol, 2-methyl -1,3-propanediol, aliphatic diols such as diethylene glycol and triethylene glycol, alicyclic diols such as 1,4-cyclohexanedimethanol, and fragrances such as 2,2-bis (β-hydroxyethoxyphenyl) propane Ring-containing diols and the like, and mixtures thereof. If it is a small amount,
One or more long-chain diols having a molecular weight of 400 to 6000, that is, polyethylene glycol, poly-1,3-propylene glycol, polytetramethylene glycol or the like may be copolymerized.

The aromatic polyester of the present invention can be branched by introducing a small amount of a branching agent.
The type of the branching agent is not limited, and examples thereof include trimesic acid, trimellitic acid, trimethylolethane, trimethylolpropane, and pentaerythritol.

Specific aromatic polyester resins include polyethylene terephthalate (PET), polypropylene terephthalate, polybutylene terephthalate (PBT), polyhexylene terephthalate, polyethylene naphthalate (PEN), polybutylene naphthalate (PBN), polyethylene -1,2-bis (phenoxy) ethane-4,4′-dicarboxylate, and the like,
Copolyesters such as polyethylene isophthalate / terephthalate, polybutylene terephthalate / isophthalate, and the like, and mixtures thereof can be preferably used. Among them, as the diol component, polyethylene terephthalate and polyethylene naphthalate using ethylene glycol are preferable because thermal properties and mechanical properties are balanced.
A polyethylene terephthalate and polyethylene naphthalate content of 00% by weight or more is preferably 50% by weight or more, particularly preferably a polyethylene terephthalate content of 50% by weight or more. Polybutylene terephthalate and polybutylene naphthalate using butylene glycol as the diol component are also preferably balanced in terms of moldability, mechanical properties, and the like. Furthermore, the weight ratio of polybutylene terephthalate / polyethylene terephthalate is preferably in the range of 2 to 10. preferable.

The structure of the terminal group of the obtained aromatic polyester resin is not particularly limited, except that the ratio of the hydroxyl group and the carboxyl group in the terminal group is almost the same, and that one of the ratios is large. You may. Further, the terminal groups may be blocked by reacting a compound having reactivity with such terminal groups.

According to a method for producing such an aromatic polyester resin, the dicarboxylic acid component and the diol component are polymerized while heating in the presence of a polycondensation catalyst containing titanium, germanium, antimony, etc.
It is performed by discharging water or lower alcohol by-product to the outside of the system. For example, as a germanium-based polymerization catalyst, germanium oxide, hydroxide, halide,
Examples thereof include alcoholates and phenolates, and more specifically, germanium oxide, germanium hydroxide, germanium tetrachloride, tetramethoxygermanium and the like.

In the present invention, compounds such as manganese, zinc, calcium, and magnesium used in a transesterification reaction which is a former stage of a conventionally known polycondensation can be used together, and phosphoric acid is added after the transesterification reaction is completed. Alternatively, it is possible to deactivate such a catalyst with a phosphorous acid compound or the like to perform polycondensation.

The molecular weight of the aromatic polyester resin is not particularly limited, but the intrinsic viscosity measured at 25 ° C. using o-chlorophenol as a solvent is 0.4 to 1.
2, preferably 0.65 to 1.15.

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

[0048]

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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 having 6 to 20 carbon atoms which may be alkyl-substituted;
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 35% due to its chemical composition.
Inorganic filler containing at least 40% by weight, preferably 40% by weight
It refers to the inorganic filler contained above. 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 hydrolysis by finely dispersing such a filler, and that the reinforcing effect on the resin is also important from the viewpoint of imparting flame retardancy. 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 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 the mica thickness, 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 diameter 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 and the like, but it is more preferable that 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.

[0058] 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 further 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
When the content of the component is less than 5% by weight, the chemical resistance is reduced and the fluidity is reduced, and the molding temperature is increased accordingly. Defects and productivity will decrease. 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, block copolymer composed of polymethyl (meth) acrylate, styrene and butadiene and its hydrogenated copolymer, block copolymer composed of styrene and isoprene, and its hydrogenated copolymer, acrylonitrile
Butadiene copolymer, random copolymer and block copolymer of ethylene-propylene, random copolymer and block copolymer of ethylene-butene, copolymer of ethylene and α-olefin, ethylene such as ethylene-butyl acrylate -Copolymer with unsaturated carboxylic acid ester, acrylate such as butyl acrylate-butadiene-butadiene copolymer, polyalkyl (meth)
Rubbery polymers such as acrylates, composite rubbers containing polyorganosiloxanes and polyalkyl (meth) acrylates, and copolymers obtained by grafting vinyl monomers such as styrene, acrylonitrile and polyalkyl methacrylate onto such composite rubbers. Can be mentioned.

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 adjust such an agglomerated mixture, the average particle size 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.

Various forms of a coagulated mixture of an emulsion of polytetrafluoroethylene having a fibril-forming ability and an emulsion of a vinyl polymer can be used. 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 contain a rubbery polymer for the purpose of improving impact strength. Examples of such rubbery polymers include acrylate-based core-shell graft copolymers, polyurethane-based elastomers, polyester-based elastomers, and the like.

Examples of the acrylate-based core-shell graft copolymer include a copolymer or a mixture of a rubbery alkyl (meth) acrylate polymer having 2 to 8 alkyl groups and a diene rubbery polymer. A core-shell type polymer having a shell formed by polymerizing an alkyl (meth) acrylate and optionally a copolymerizable vinyl monomer on the core, or a multi-stage core-shell type polymer similarly used can also be used. is there. Also, a core composed solely of a diene rubbery polymer can be used. As such an acrylate core-shell graft polymer, "HIA-15" (trade name) from Kureha Chemical Industry Co., Ltd.
A resin commercially available as "HIA-28" can be mentioned, and as a core consisting solely of a diene-based rubber-like polymer, commercially available from Kureha Chemical Industry Co., Ltd. under the trade name "PARALOID EXL-2602" Resins that have been used.

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 that they cannot be separated 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 kinds of currently known thermoplastic polyurethane elastomers can be used. Such a thermoplastic polyurethane elastomer is easily available, for example, “Kuramilon U” (trade name) manufactured by Kuraray Co., Ltd.

The thermoplastic polyester elastomer which can be used 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 Nauter 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 objects of the present invention are not impaired, stabilizers (for example, phosphoric acid esters, phosphites, etc.), antioxidants (for example, hindered phenol compounds, etc.), light stabilizers (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 conventionally known heat stabilizers for aromatic polycarbonates such as phosphorous acid, phosphoric acid, phosphonous acid, phosphonic acid and esters thereof. Specific examples thereof include trisnonylphenyl Phosphite, tetrakis (4,4'-biphenylenediphosphosphinate) (2,4-di-tert-butylphenyl), trimethyl phosphate, tris (2,4-di-tert-
Butylphenyl) phosphite and dimethyl benzenephosphonate are preferred. These heat stabilizers may be used alone or in combination of two or more.

As the heat stabilizer of the present invention, a hindered phenol compound or a sulfur compound, which is generally known as an antioxidant, is preferably blended in addition to the above. 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.
Also, it can be applied to blow molding, vacuum molding and the like. Especially UL
It is most suitable as a material for electrical and electronic parts that require 94V-0 and exterior use of OA.

[0082]

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: Approximately 50 g of pellets were treated with an environmental tester (Platinous Subzero Lucifer manufactured by Tabai Espec Corp.) at 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 insolubles were 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 aromatic polycarbonate resin described in the text, and the same calculation was performed. The value of the apparent viscosity average molecular weight was calculated using the equation. (2) Moisture / heat resistance-2: A bending test was performed in accordance with ASTM D790, and a change in strength before and after the wet heat treatment was observed. That is, the test piece was placed in an environment of 23 ° C. and 50% RH after molding, and a bending test was performed 24 hours later. The value was set to the value before the wet heat treatment, left for 24 hours under the same conditions, and then the same as (1) above A bending test was performed after treating the device under the conditions of 65 ° C. and 85% RH for 500 hours, and this was defined as a value after the treatment.

(3) Flame retardancy: A flame test was conducted at a thickness of 1.6 mm according to UL standard 94V. (4) Chemical resistance: A test specimen having a thickness of 1/8 ″ prepared according to ASTM standard D-638 was given a strain of 0.4%, and was coated with grease (Multemp SRL manufactured by Kyodo Yushi Co., Ltd.). After treatment at 48 ° C. for 48 hours, the appearance of the molded product was visually observed for the occurrence of cracks, and the chemical resistance was judged according to the following criteria: ○: no cracks generated Δ: crazes generated ×: cracks (5) Mold contamination: Injection molding machine [T by FANUC Co., Ltd.
-150D] (box size; 1)
00mm (length) x 150mm (width) x 15mm (height)
× a box-shaped molded product which is a portable terminal device housing having a product thickness of 1.5 mm) and a cylinder temperature and a mold temperature 70 at which an approximately good molded product can be obtained at an injection pressure of 800 kg / cm ² .
Continuous molding was performed at a temperature of 100 ° C., and the presence or absence of a deposit on the mold surface was checked every 100 shots, and the number of molding shots in which the deposit 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 polycarbonate solution was dropped into warm water in the provided kneader, and the polycarbonate resin was flaked while distilling off methylene chloride. Next, the liquid-containing polycarbonate resin was pulverized and dried 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
After mixing the components shown in Tables 2 and 3 in the amounts shown in the table with a V-type blender, the mixture was pelletized at a cylinder temperature of 260 ° C. using a vented twin-screw extruder having a diameter of 30 mm [TEX30XSST manufactured by Japan 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: Aromatic polycarbonate resin produced in Reference Example 1 (phosgene method) PC-2: Aromatic polycarbonate resin PC-3 produced in Reference Example 2 (melting method) : Aromatic polycarbonate resin having a viscosity average molecular weight of 14,200 and produced by the same method using the same raw material as in the above-mentioned Reference Example 1 PC-4: Using the same raw material as in the above-mentioned Reference Example 1, and using the same raw material Aromatic polycarbonate resin having a viscosity average molecular weight of 16,700 produced by the above method (other than the component a) PC-5: a viscosity average molecular weight of 20 produced by the same method using the same raw materials as in Reference Example 1 above. 6,000 aromatic polycarbonate resin PC-6: an aromatic polycarbonate resin having a viscosity average molecular weight of 25,000, produced by the same method using the same raw materials as in Reference Example 1 above. (B component) PBT: polybutylene terephthalate resin having an intrinsic viscosity of 0.87 [TRB-J manufactured by Teijin Limited] PET: polyethylene terephthalate resin having an intrinsic viscosity of 0.71 [TR-4550 manufactured by Teijin Limited] (component c) ) FR-1: triphenyl 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.]

[0089]

[Table 1]

[0090]

[Table 2]

[0091]

[Table 3]

As is clear from this table, Examples 1 to 3 are shown.
From the comparison with Comparative Examples 1 and 2, when the specific aromatic 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. You can see that. In the case of using a condensed phosphoric ester, other properties are insufficient. It can be seen that when a filler such as talc is blended, the wet heat resistance is improved, but the mold contamination is not improved. In addition, even when the specific aromatic polycarbonate resin of the present invention is used, even if the polyester resin is not blended, the deposits are generated on the mold surface with a small number of molding shots during the molding process, even if the specific aromatic polycarbonate resin of the invention is used. It can be seen that when the contamination is high and the amount of the polyester resin is too large, the flame retardancy is poor.

[0093]

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 a copier housing and the like and the electric and electronic equipment field.

Claims (4)

[Claims] When the total of the following components a, b and c is 100% by weight, the viscosity average molecular weight is 13,000.
40 to 92% by weight of an aromatic polycarbonate resin (component (a)), 5 to 40% by weight of an aromatic polyester resin (component (b)), and a phosphorus-based flame retardant represented by the following general formula (1) (component (c)) ) A flame-retardant resin composition comprising 3 to 20% by weight. Embedded image (Wherein R ₁ , R ₂ and R ₃ independently of one another have 1 carbon atom)
Represents an alkyl group having 8 to 8 carbon atoms or an aryl group having 6 to 20 carbon atoms which may be alkyl-substituted;
Is) 2. 100 parts by weight of a flame-retardant resin composition comprising a component, b component and c component and a silicate filler (d
The flame-retardant resin composition according to claim 1, comprising 0.1 to 25 parts by weight of a component). 3. 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. 4. A molded article obtained by melt-molding the flame-retardant resin composition according to claim 1.