JP2003183491A - Flame retardant thermoplastic resin composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a flame retardant thermoplastic resin composition, especially an aromatic polycarbonate resin composition, excellent in light reflection, and small in environmental load and excellent in heat resistance without compounding a bromine compound. <P>SOLUTION: This flame retardant thermoplastic resin composition comprises 100 pts.wt. at least a thermoplastic resin (component A) selected from the group consisting of an aromatic polycarbonate resin, and a polyallylate resin, 0.1-25 pts.wt. titanium dioxide (component B) containing 90-98 wt.% TiO<SB>2</SB>and 0.5-4.0 wt.% Al<SB>2</SB>O<SB>3</SB>as an inorganic surface treating agent, and 0.001-2 pts.wt. at least a metal salt (component C) selected from the group consisting of an aliphatic organic metal sulfonate (component C-1), an aromatic organic metal sulfonate (component C-2), and a metal silicate (component C-3), and contains substantially no bromine compound. <P>COPYRIGHT: (C)2003,JPO

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention comprises a thermoplastic resin, a specific titanium dioxide, and a specific metal salt, and has excellent light-reflecting properties. Since it does not substantially contain a bromine compound, it has a low environmental load and heat resistance. Also relates to excellent flame-retardant thermoplastic resin compositions, especially aromatic polycarbonate resin compositions.

[0002]

2. Description of the Related Art Aromatic polycarbonate resins and polyarylate resins have excellent mechanical properties, dimensional accuracy, electrical properties, etc.
It is widely used in various fields such as electronic devices, automobiles, and office automation. Among these applications, OA fields and electronic and electrical fields are OA
There is a strong demand for flame-retardant equipment and home appliances.

LCD reflector (backlight reflector), L
Flame retardancy is also required for a polycarbonate resin composition containing titanium dioxide, which is used for applications requiring high light reflectance such as ED reflectors, meter reflectors, reflectors, photoelectric switches, and electric lamp covers. In this case, a flame-retardant aromatic polycarbonate resin composition in which various flame retardants are blended to improve combustibility has been proposed.

However, when a bromine compound is used, a toxic gas such as dioxin may be generated at the time of combustion, and in recent years, a resin material which does not use a bromine compound has been demanded due to the growing concern about environmental problems. A flame-retardant aromatic polycarbonate resin composition using a phosphorus compound has been proposed to meet such demands.

For example, JP-A-9-12853 discloses that an aromatic polycarbonate resin has an interpenetrating network structure so that titanium dioxide, a polyorganosiloxane rubber component and a poly (meth) acrylate rubber component cannot be separated. A flame-retardant aromatic polycarbonate resin containing a composite rubber-based graft polymer, an oligomeric phosphate ester, and polytetrafluoroethylene is described. JP-A-10-1600 discloses a flame-retardant aromatic polycarbonate resin in which titanium dioxide and a halogen-free phosphoric acid ester are mixed with an aromatic polycarbonate resin.

However, even if a phosphorus compound is used, there is some concern that the phosphorus content will elute into the soil at the time of landfilling, and a flame-retardant aromatic polycarbonate resin material using a flame retardant with a smaller environmental load. Is desired. Further, in recent years, thinning and lightening have been progressing in the use, and in order to prevent deformation due to heat of the light source when thinning,
Although heat resistance is essential, a flame-retardant aromatic polycarbonate resin composition flame-retarded by using a phosphorus compound cannot be used because of its low heat resistance.

As described above, in the prior art, a flame-retardant aromatic polycarbonate resin composition which has excellent light-reflecting properties, does not use a bromine compound, has a small environmental load, and has excellent heat resistance has not been sufficiently obtained. Is the current situation. Furthermore, the fact that a flame-retardant resin composition that does not contain a bromine compound or a phosphorus compound is required is the same for polyarylate resins.

[0008]

The object of the present invention is to provide a flame-retardant thermoplastic resin composition which is excellent in light reflectivity, has an extremely small environmental load, and is excellent in heat resistance, particularly without blending a bromine compound, and particularly, An object is to provide an aromatic polycarbonate resin composition.

As a result of intensive studies to solve the above problems, the present inventor has specified a specific titanium dioxide and a specific metal salt in one or more thermoplastic resins selected from aromatic polycarbonate resins and polyarylate resins. By blending in combination in an amount, it is possible to obtain a flame-retardant thermoplastic resin composition having excellent light reflectivity, a small environmental load without adding a bromine compound, and excellent heat resistance, in particular, an aromatic polycarbonate resin composition. The present invention has been achieved and the present invention has been achieved.

[0010]

The present invention is based on 100 parts by weight of one or more thermoplastic resins (component A) selected from aromatic polycarbonate resins and polyarylate resins.
The proportion of TiO ₂ is 90 to 98% by weight, and the proportion of Al ₂ O _{3 as} an inorganic surface treatment agent is 0.5 to 4.0% by weight.
0.1 to 25 parts by weight of titanium dioxide (component B), aliphatic organic sulfonic acid metal salt (C-1 component), aromatic organic sulfonic acid metal salt (C-2 component), silicate metal salt (C- Three
Component) one or more kinds of metal salts (component C) 0.0
The present invention relates to a flame-retardant thermoplastic resin composition containing 0 to 1 part by weight and containing substantially no bromine compound.

The details of the present invention will be described below.
The term "substantially free of bromine compound" used in the present invention
Is a flame retardant containing a bromine compound as a main component, a thermoplastic resin containing bromine in a part of the structural skeleton, and an additive containing a bromine compound as a main component, which is present in the composition. The amount of elemental bromine contained is at least 0.01 part by weight or less, preferably 0.001 or less, and more preferably 0.001 or less.

The component A of the present invention is a resin selected from an aromatic polycarbonate resin and a polyarylate resin, or a mixed resin of two or more kinds.

The aromatic polycarbonate resin (A-1 component) used as the A component of the present invention is obtained by reacting a dihydric phenol with a carbonate precursor. Examples of the reaction method include an interfacial polycondensation method, a melt transesterification method, a solid-state transesterification method of a carbonate prepolymer, and a ring-opening polymerization method of a cyclic carbonate compound.

Typical examples of the dihydric phenol used here include hydroquinone, resorcinol, 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 called 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′-dihydroxydiphenyl sulfone, 4,4′-dihydroxydiphenyl sulfoxide, 4,4′-dihydroxydiphenyl sulfide,
4,4'-dihydroxydiphenyl ketone, 4,4'-
Examples thereof include dihydroxydiphenyl ether and 4,4′-dihydroxydiphenyl ester, which may be used alone or in combination 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
-Hydroxyphenyl) -3,3,5-trimethylcyclohexane and a homopolymer obtained from at least one bisphenol selected from the group consisting of α, α'-bis (4-hydroxyphenyl) -m-diisopropylbenzene or Copolymers are preferred.

Particularly, a homopolymer of bisphenol A is preferably used. Such an aromatic polycarbonate resin is preferable because it has excellent impact resistance.

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

In the production of a polycarbonate resin by reacting the above dihydric phenol with a carbonate precursor by an interfacial polycondensation method or a melt transesterification method, the catalyst, the terminal terminator, and the dihydric phenol are optionally oxidized. You may use antioxidant etc. for preventing that.
The aromatic polycarbonate resin may be a polyester carbonate resin obtained by copolymerizing an aromatic or aliphatic bifunctional carboxylic acid, or a mixture of two or more kinds of the obtained aromatic polycarbonate resins. Good.

Examples of the aliphatic bifunctional carboxylic acid include aliphatic bifunctional carboxylic acids having 8 to 20 carbon atoms, preferably 10 to 12 carbon atoms. The aliphatic difunctional carboxylic acid may be linear, branched or cyclic. Aliphatic difunctional carboxylic acids are α, ω
-Dicarboxylic acids are preferred.

In the polymerization reaction of the aromatic polycarbonate resin, the reaction by the interfacial polycondensation method is usually a reaction between a dihydric phenol and phosgene, which 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, halogenated hydrocarbons such as methylene chloride and chlorobenzene are used. It is also possible to use 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 for accelerating the reaction. it can. At that time, the reaction temperature is usually 0 to 40 ° C., the reaction time is preferably 10 minutes to 5 hours, and the pH during the reaction is preferably 9 or more.

In addition, in such a polymerization reaction, a terminal stopper is usually used. Monofunctional phenols can be used as such an end terminator. Monofunctional phenols are commonly used as molecular terminators for molecular weight control, such monofunctional phenols typically being phenol or lower alkyl substituted phenols,
The monofunctional phenols represented by the following general formula (2) can be shown.

[0022]

[Chemical 1]

(In the formula, A is a hydrogen atom or 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 monofunctional phenols include phenol, p-tert-butylphenol, p-cumylphenol and isooctylphenol.

As other monofunctional phenols,
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 shown. Among these, phenols having a long-chain alkyl group represented by the following general formulas (3) and (4) as a substituent are preferably used.

[0025]

[Chemical 2]

[0026]

[Chemical 3]

(In the formula, X is -R-CO-O- or -R
-O-CO-, where R is a single bond or 1 carbon atom
-10, preferably 1-5 divalent aliphatic hydrocarbon group is shown, and n shows the integer of 10-50. ) N is 1 as the substituted phenols of the general formula (3).
0 to 30, particularly 10 to 26 are preferable, and specific examples thereof include decylphenol, dodecylphenol, tetradecylphenol, hexadecylphenol, octadecylphenol, eicosylphenol,
Examples thereof include docosylphenol and triacontylphenol.

As the substituted phenols of the general formula (4), compounds in which X is —R—CO—O— and R is a single bond are suitable, and n is 10 to 30, particularly 10 to 26.
Are preferred, and specific examples thereof include decyl hydroxybenzoate, dodecyl hydroxybenzoate,
Mention may be made of tetradecyl hydroxybenzoate, hexadecyl hydroxybenzoate, eicosyl hydroxybenzoate, docosyl hydroxybenzoate and triacontyl hydroxybenzoate.

The reaction by the melt transesterification method is usually a transesterification reaction between a dihydric phenol and a carbonate ester, which is produced by mixing the dihydric phenol and the carbonate ester while heating in the presence of an inert gas. It is carried out by a method of distilling alcohol or phenol. The reaction temperature varies depending on the boiling point of the alcohol or phenol to be produced, but is usually in the range of 120 to 350 ° C. In the latter stage of the reaction, the system was set at 1.33 × 10 ³ -1.
The alcohol or phenol produced by reducing the pressure to about 3.3 Pa is easily distilled. Reaction time is usually 1 to 4
It's about time.

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. Specific examples include diphenyl carbonate, bis (chlorophenyl) carbonate, dinaphthyl carbonate, bis (diphenyl) carbonate, dimethyl carbonate, diethyl carbonate, dibutyl carbonate and the like, with diphenyl carbonate being preferred.

A polymerization catalyst can be used to accelerate the polymerization rate. Examples of the polymerization catalyst include alkali metal compounds such as sodium hydroxide, potassium hydroxide, sodium salt and potassium salt 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 , Organic acid salts of alkali metals and alkaline earth metals, zinc compounds, boron compounds, aluminum compounds, silicon compounds, germanium compounds, organotin compounds, lead compounds, osmium compounds, antimony compounds manganese 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 kinds. The amount of these polymerization catalysts used is preferably 1 × 10 ⁻⁸ to 1 × with ^respect to 1 mol of the dihydric phenol as a raw material.
It is selected in the range of 10 ⁻³ equivalent, more preferably 1 × 10 ^{−7 to} 5 × 10 ⁻⁴ equivalent.

In the polymerization reaction, in order to reduce the number of phenolic end groups, for example, bis (chlorophenyl) carbonate, bis (bromophenyl) carbonate, bis (nitrophenyl) carbonate is added after or after the polycondensation reaction. Compounds such as carbonate, bis (phenylphenyl) carbonate, chlorophenylphenylcarbonate, bromophenylphenylcarbonate, nitrophenylphenylcarbonate, phenylphenylcarbonate, methoxycarbonylphenylphenylcarbonate and ethoxycarbonylphenylphenylcarbonate can be added. Of these, 2-chlorophenylphenyl carbonate, 2-methoxycarbonylphenylphenyl carbonate and 2-ethoxycarbonylphenylphenyl carbonate are preferable, and 2-methoxycarbonylphenylphenyl carbonate is particularly preferable.

Further, it is preferable to use a deactivator which neutralizes the activity of the catalyst in the polymerization reaction. Specific examples of the quenching agent include benzene sulfonic acid, p-toluene sulfonic acid, methyl benzene sulfonate, ethyl benzene sulfonate, butyl benzene sulfonate, octyl benzene sulfonate, phenyl benzene sulfonate, p-toluene sulfone. Sulfonic acid esters such as methyl acidate, ethyl p-toluenesulfonate, butyl p-toluenesulfonate, octyl p-toluenesulfonate, phenyl p-toluenesulfonate; and further, trifluoromethanesulfonic acid, naphthalenesulfonic acid, sulfonated polystyrene. , Methyl acrylate-sulfonated styrene copolymer, dodecylbenzenesulfonic acid-2-phenyl-2-propyl, dodecylbenzenesulfonic acid-2-
Phenyl-2-butyl, octylsulfonic acid tetrabutylphosphonium salt, decylsulfonic acid tetrabutylphosphonium salt, benzenesulfonic acid tetrabutylphosphonium salt, dodecylbenzenesulfonic acid tetraethylphosphonium salt, dodecylbenzenesulfonic acid tetrabutylphosphonium salt, dodecylbenzenesulfone Acid tetrahexylphosphonium salt, dodecylbenzenesulfonic acid tetraoctylphosphonium salt, decyl ammonium butyl sulfate, decyl ammonium decyl sulfate, dodecyl ammonium methyl sulfate, dodecyl ammonium ethyl sulfate, dodecyl methyl ammonium methyl sulfate, dodecyl dimethyl ammonium tetradecyl sulfate, tetradecyl Dimethyl ammonium Chill sulfate, tetramethylammonium hexyl sulfate, decyltrimethylammonium hexadecyl sulfate, tetrabutylammonium dodecylbenzyl sulfate, tetraethylammonium dodecylbenzyl sulfate, there may be mentioned compounds such as tetramethylammonium dodecylbenzyl sulfate, and the like. Two or more of these compounds may be used in combination.

Among the deactivators, those of phosphonium salt type or ammonium salt type are preferable. The amount of the deactivator is preferably 0.5 to 50 mol based on 1 mol of the remaining catalyst, and 0.01 to 500 ppm based on the polycarbonate resin after polymerization, and more preferably Is used in an amount of 0.01 to 300 ppm, particularly preferably 0.01 to 100 ppm.

The molecular weight of the polycarbonate resin is not specified, but if the molecular weight is less than 10,000, the strength and the like decrease, and if it exceeds 50,000, the molding processability decreases, so it is expressed as a viscosity average molecular weight. 10,000
To 50,000 are preferred, and 14,000 to 3
50,000 is more preferable, and 1 is more preferable.
It is 6,000 to 25,000.

The viscosity average molecular weight as referred to in the present invention is obtained by first using a Ostwald viscometer from a solution of 0.7 g of an aromatic polycarbonate resin dissolved in 100 ml of methylene chloride at 20 ° C. Viscosity (η _SP ) = (t−t ₀ ) / t ₀ [t ₀ is the number of seconds for methylene chloride to fall, t is the number of seconds to drop the sample solution] Molecular weight M
Ask for. η _SP /c=[η]+0.45×[η] ² c (however, [η]
Is the intrinsic viscosity) [η] = 1.23 × 10 ⁻⁴ M ^0.83 c = 0.7

The above-mentioned aromatic polycarbonate resins are those having different dihydric phenols, those with and without end-capping agents, those with linear and branched ones, those with different manufacturing methods, and end-capping agents. Two or more kinds having different structures and characteristics such as different types, polycarbonate and polyester may be mixed. In this case, it is naturally possible to mix with an aromatic polycarbonate resin having a viscosity average molecular weight outside the above range.

In the present invention, a linear aromatic polycarbonate resin (A-1-1 component) can also be used as one of the component A (hereinafter, sometimes referred to as "linear aromatic polycarbonate resin"). ). Such a linear aromatic polycarbonate resin has a viscosity average molecular weight of 10,000
0 to 50,000 is preferable, 14,000 to 3
50,000 is more preferable, and 1 is more preferable.
It is 6,000 to 25,000.

In the present invention, as one of the component A, an aromatic polycarbonate resin (A which contains 0.05 to 0.3 mol% of a repeating unit having a branched structure in 100 mol% of the repeating unit of the A component). (1-2 component) can also be used (hereinafter sometimes referred to as “branched aromatic polycarbonate resin”). By using such a branched aromatic polycarbonate resin, melt dripping (so-called drip) when the resin burns can be suppressed, and a higher flame retardancy can be achieved. In order to produce such a branched aromatic polycarbonate resin, a method of copolymerizing a trifunctional or higher polyfunctional aromatic compound is usually used.

Examples of trifunctional or higher polyfunctional aromatic compounds include phloroglucin, phloroglucide, or 4,6-
Dimethyl-2,4,6-tris (4-hydrodiphenyl) heptene-2,2,4,6-trimethyl-2,4
6-tris (4-hydroxyphenyl) heptane, 1,
3,5-tris (4-hydroxyphenyl) benzene,
1,1,1-tris (4-hydroxyphenyl) ethane, 1,1,1-tris (3,5-dimethyl-4-hydroxyphenyl) ethane, 2,6-bis (2-hydroxy-5-methylbenzyl) ) -4-Methylphenol, 4
-{4- [1,1-bis (4-hydroxyphenyl) ethyl] benzene} -α, α-dimethylbenzylphenol and other trisphenols, tetra (4-hydroxyphenyl) methane, bis (2,4-dihydroxyphenyl) )
Examples thereof include ketones, 1,4-bis (4,4-dihydroxytriphenylmethyl) benzene, trimellitic acid, pyromellitic acid, benzophenonetetracarboxylic acid and acid chlorides thereof, among which 1,1,1-tris. (4-hydroxyphenyl) ethane, 1,1,1-
Tris (3,5-dimethyl-4-hydroxyphenyl)
Ethane is preferable, and 1,1,1-tris (4-hydroxyphenyl) ethane is particularly preferable.

In the branched aromatic polycarbonate resin suitable as the component A, the proportion of the polyfunctional compound is 0.05 to 100% by weight of the repeating unit having a branched structure in 100 mol% of the repeating units in the aromatic polycarbonate resin.
The amount is 0.3 mol%, more preferably 0.05 to 0.2 mol%, still more preferably 0.05 to 0.15 mol%.

In particular, in the case of the melt transesterification method, a branched structure may occur as a side reaction. That is, even when the polyfunctional aromatic compound is not contained, a branched structure is generated by the isomerization reaction of the monomer components during the polymerization reaction. The component A of the present invention also includes such a branched aromatic polycarbonate resin. The ratio can be calculated by ¹ H-NMR measurement.

Further, the repeating unit having the above-mentioned branched structure is A
An aromatic polycarbonate resin (A-1-) containing 0.05 to 0.3 mol% in 100 mol% of the repeating unit of the component.
(2 component) uses a mixture of an aromatic polycarbonate resin containing a higher concentration of the branching component and an aromatic polycarbonate resin having a lower content of the branching component or substantially no branching component. Is also possible.

In the present invention, as one of the A components, A
An aromatic polycarbonate resin having a viscosity average molecular weight of 70,000 to 300,000 (component A-1-3-1),
And an aromatic polycarbonate resin (A-1-3-2 component) having a viscosity average molecular weight of 10,000 to 30,000 and a viscosity average molecular weight of 16,000 to 35,000.
An aromatic polycarbonate resin having 0 (component A-1-3) (hereinafter sometimes referred to as "high molecular weight component-containing aromatic polycarbonate resin") can also be used.

The aromatic polycarbonate resin (A-1-3 component) containing the high molecular weight component increases the entropy elasticity of the resin due to the presence of the A-1-3-1 component, and has a drawdown property in blow molding, It exerts functions such as drip prevention during combustion and jetting prevention during injection molding. On the other hand, A-1-3-2
By containing a low molecular weight component, the overall melt viscosity is significantly reduced, and the practicality in various molding methods such as injection molding is sufficiently satisfied. That is, while achieving higher flame retardancy as with the branched aromatic polycarbonate resin, it simultaneously has the above-mentioned various functions.

In the aromatic polycarbonate resin (A-1-3 component) containing a high molecular weight component, the molecular weight of the A-1-3-1 component is preferably 70,000 to 200,000,
It is more preferably 80,000 to 200,000, still more preferably 100,000 to 200,000, and particularly preferably 100,000 to 160,000. Also A-
The molecular weight of the 1-3-2 component is 10,000 to 25,000.
Is preferred, and more preferably 11,000 to 24,000.
0, more preferably 12,000 to 24,000, and particularly preferably 12,000 to 23,000.

The aromatic polycarbonate resin (A-1-3 component) containing a high molecular weight component is the above-mentioned A-1-3-1 component and A-component.
It can be obtained by mixing the -1-3-2 components in various proportions and adjusting them so as to satisfy a predetermined molecular weight range. Preferably, A-1-3-1 in 100% by weight of the A-1-3 component is used.
When the content of the component is 2 to 40% by weight, more preferably A
-1-3-1 component is 3 to 30% by weight, more preferably A-1-3-1 component is 4 to 20% by weight, particularly preferably A-1-3-1 component is 5 to 30% by weight. It is 20% by weight.

As the method for adjusting the A-1-3 component, (1) a method of independently polymerizing the A-1-3-1 component and the A-1-3-2 component and mixing them ,
(2) A method for producing an aromatic polycarbonate resin showing a plurality of polymer peaks in a molecular weight distribution chart by the GPC method in the same system, which is represented by JP-A-5-306336, is used. A method of producing a polycarbonate resin so as to satisfy the condition of the component A-1 of the present invention, and (3) an aromatic polycarbonate resin obtained by the production method (production method of (2)), and A produced separately. Examples include a method of mixing the -1-3-1 component and / or the A-1-3-2 component.

The polyarylate resin (A-2 component) used as the component A of the present invention is obtained from an aromatic dicarboxylic acid or its derivative and a dihydric phenol or its derivative. The aromatic dicarboxylic acid used for preparing the polyarylate may be any one as long as it reacts with the dihydric phenol to give a satisfactory polymer, and one kind or a mixture of two or more kinds is used.

As a preferred aromatic dicarboxylic acid component,
Examples include terephthalic acid and isophthalic acid. It may also be a mixture of these.

Specific examples of the dihydric phenol component include:
2,2-bis (4-hydroxyphenyl) propane,
2,2-bis (4-hydroxy-3,5-dibromophenyl) propane, 2,2-bis (4-hydroxy-3,
5-dichlorophenyl) propane, 4,4'-dihydroxydiphenyl sulfone, 4,4'-dihydroxydiphenyl ether, 4,4'-dihydroxydiphenyl sulfide, 4,4'-dihydroxydiphenyl ketone,
4,4'-dihydroxydiphenylmethane, 2,2'-
Bis (4hydroxy-3,5-dimethylphenyl) propane, 1,1-bis (4-hydroxyphenyl) ethane, 1,1-bis (4-hydroxyphenyl) cyclohexane, 4,4′-dihydroxydiphenyl, hydroquinone, etc. Is mentioned. Although these dihydric phenol components are para-substituted, other isomers may be used, and ethylene glycol, propylene glycol, neopentyl glycol and the like may be used in combination with the dihydric phenol component.

Among the above preferred polyarylate resins, the aromatic dicarboxylic acid component is terephthalic acid and isophthalic acid, and the dihydric phenol component is 2,2-bis (4-hydroxyphenyl) propane (bisphenol A). There are things. The ratio of terephthalic acid and isophthalic acid is preferably terephthalic acid / isophthalic acid = 9/1 to 9/1 (molar ratio), and particularly preferably 7/3 to 3/7 in terms of melt processability and performance balance.

As another typical polyarylate resin, the aromatic dicarboxylic acid component is terephthalic acid,
The dihydric phenol component includes bisphenol A and hydroquinone. The ratio of such bisphenol A and hydroquinone is bisphenol A /
Hydroquinone = 50/50 to 70/30 (molar ratio) is preferable, 55/45 to 70/30 is more preferable, and 6
0/40 to 70/30 is more preferable.

The viscosity average molecular weight of the polyarylate resin in the present invention is preferably in the range of about 7,000 to 100,000 from the viewpoint of physical properties and extrusion processability. For the polyarylate resin, any of the interfacial polycondensation method and the transesterification reaction method can be selected.

The component A used in the present invention may be a mixed resin of two or more kinds selected from the above aromatic polycarbonate resin and polyarylate resin. The mixing ratio is arbitrarily selected. The A component is preferably an aromatic polycarbonate resin simple substance having a remarkable flame retardant effect, or a mixed resin containing an aromatic polycarbonate resin.

(Component B) The titanium dioxide used as the component B of the present invention has a TiO ₂ content of 90 to 98% by weight and an Al ₂ O ₃ content of 0.5 as an inorganic surface treatment agent.
The content of the titanium dioxide component is from about 4.0% by weight (in the present invention, the titanium dioxide component of titanium dioxide is referred to as “TiO ₂ ”, and the entirety including the surface treatment agent is referred to as “titanium dioxide”).

The crystal form of TiO _{2 as the} component B may be either anatase type or rutile type, and they can be used as a mixture if necessary. The rutile type is more preferable in terms of initial mechanical properties and long-term weather resistance.
The rutile type crystal may contain an anatase type crystal. Further, as the TiO ₂ production method, the products produced by the sulfuric acid method, the chlorine method and various other methods can be used, but the chlorine method is more preferable. Further, the titanium dioxide of the present invention is not particularly limited in its shape, but particles are more preferable. The average particle size of titanium dioxide is 0.01
To 0.4 μm is preferable, 0.1 to 0.3 μm is more preferable, and 0.15 to 0.25 μm is further preferable. still,
The average particle diameter refers to D50 (median diameter of particle diameter distribution) measured by an X-ray transmission method which is one of liquid phase sedimentation methods. As a specific example of the apparatus for performing such measurement, Sedigraph 5100 manufactured by Micromeritics, Inc. can be mentioned.

The coating of the Al ₂ O ₃ surface treatment agent on the TiO ₂ surface can be carried out by various methods which are usually used. For example, an untreated TiO ₂ after dry pulverization is made into an aqueous slurry, the slurry is wet pulverized to be atomized, a fine particle slurry is collected, a water-soluble compound of an aluminum salt is added to the fine particle slurry, and neutralized. Coating the TiO ₂ surface with aluminum hydrous oxide,
Examples of the method include removing by-products, adjusting the slurry pH, filtering, and washing with pure water, drying the washed cake, and pulverizing the dried product with a jet mill or the like. In addition to this method, for example, a method of reacting TiO ₂ particles with an active aluminum compound in a gas phase can be mentioned. Further, in coating the TiO ₂ surface with the Al ₂ O ₃ surface treatment agent, it is necessary to perform firing after the surface treatment, perform surface treatment again after the surface treatment, and perform firing again after the surface treatment. Is also possible.

Further, the surface treatment of TiO ₂ can be carried out not only by the oxide of aluminum but also by the oxide of various metals such as silicon, titanium, zirconium, antimony, tin and zinc. Above all, silicon, that is, SiO
Surface treatment with ₂ is preferred. As the surface treatment, either high-density treatment or low-density (porous) treatment can be selected.

Further, the titanium dioxide as the component B may be surface-treated with an organic compound. As such a surface treating agent, various treating agents such as a polyol type, an amine type and a silicon type can be used. Examples of the polyol-based surface treatment agent include pentaerythritol, trimethylolethane, and trimethylolpropane, and examples of the amine-based surface treatment agent include triethanolamine acetate and trimethylolamine acetate. Examples of the silicon-based surface treatment agent include alkylchlorosilane (such as trimethylchlorosilane), alkylalkoxysilane (such as methyltrimethoxysilane), and alkylhydrogenpolysiloxane (such as methylhydrogenpolysiloxane). it can. Among them, those treated with a silicon-based surface treatment agent are preferable because they have excellent flame retardancy (compared to other treatment agents, the heat resistance is high and the TiO ₂ surface is difficult to be exposed when exposed to TiO _{2. (2} ) It is presumed that it is possible to suppress the decrease in flame retardancy due to the decomposition of aromatic polycarbonate resin on the surface.) Appropriate surface treatment of such an organic compound is preferable because it makes it possible to improve dispersibility and efficiently improve hydrolysis resistance. The amount of the organic compound to be surface-treated is B
1% by weight or less is preferable per 100% by weight of the component, 0.6
It is more preferably not more than wt%, more preferably not more than 0.4 wt%. On the other hand, the lower limit is 0.05% by weight or more. The organic compound surface treatment agent is an aspect in which the resin composition of the present invention is separately added when the raw material is mixed by melt-kneading or the like to produce a composition, and as a result, the titanium dioxide surface is treated. May be.

(C component) The C component of the present invention is an aliphatic organic sulfonic acid metal salt (C-1 component), an aromatic organic sulfonic acid metal salt (C-2 component), a silicate metal salt (C-3 component). ),
It is one or more metal salts selected from For these metal salts, various metal salts that have been conventionally used to make polycarbonate resins flame-retardant can be used, and by using a small amount together, good flame retardancy without deteriorating thermal stability and heat resistance. To be able to obtain. These may be used alone or in combination of two or more. The metal of the metal salt used as the C-1 component and C-2 component of the present invention is preferably an alkali metal or an alkaline earth metal.

The alkali metals used as the C-1 and C-2 components of the present invention include lithium, sodium, potassium, rubidium and cesium, and the alkaline earth metals include beryllium and magnesium.
Examples thereof include calcium, strontium and barium, with sodium, potassium and calcium being particularly preferable.

Preferable examples of the aliphatic organic sulfonic acid metal salt of the present invention include alkali alkane sulfonic acid (earth) metal salts, and a part of the alkyl groups of the alkane sulfonic acid alkali (earth) metal salt is a fluorine atom. Examples thereof include alkali (earth) metal salts of sulfonic acid substituted with and alkali (earth) metal salts of perfluoroalkanesulfonic acid, which can be used alone or in combination of two or more ( Here, the expression of an alkali (earth) metal salt is used to include both an alkali metal salt and an alkaline earth metal salt).

Preferred examples of the alkanesulfonic acid used for the alkali (earth) alkanesulfonic acid metal salt include methanesulfonic acid, ethanesulfonic acid, propanesulfonic acid, butanesulfonic acid, methylbutanesulfonic acid, hexanesulfonic acid, Heptanesulfonic acid, octanesulfonic acid and the like can be mentioned, and these can be used alone or in combination of two or more. Further, a metal salt in which a part of the alkyl group is substituted with a fluorine atom can also be mentioned.

On the other hand, preferable examples of perfluoroalkanesulfonic acid include perfluoromethanesulfonic acid and
Perfluoroethanesulfonic acid, perfluoropropanesulfonic acid, perfluorobutanesulfonic acid, perfluoromethylbutanesulfonic acid, perfluorohexanesulfonic acid, perfluoroheptanesulfonic acid, perfluorooctanesulfonic acid, etc., and especially the number of carbon atoms Is 1
The thing of -8 is preferable. These can be used alone or in combination of two or more.

As the alkali (earth) alkane sulfonic acid metal salt, sodium ethane sulfonate is used as the alkali (earth) perfluoroalkane sulfonate.
Preferred examples of the metal salt include potassium perfluorobutane sulfonate.

Examples of the aromatic organic sulfonic acid used in the alkali (earth) metal salt of aromatic organic sulfonic acid of the present invention include monomeric or polymeric sulfonic acids of aromatic sulfides, sulfonic acids of aromatic carboxylic acids and esters. Acid, monomeric or polymeric aromatic ether sulfonic acid, aromatic sulfonate sulfonic acid, monomeric or polymeric aromatic sulfonic acid, monomeric or polymeric aromatic sulfone sulfonic acid, aromatic ketone sulfone Examples thereof include at least one acid selected from the group consisting of an acid, a heterocyclic sulfonic acid, a sulfonic acid of aromatic sulfoxide, and a condensation product of an aromatic sulfonic acid with a methylene type bond. One or more species can be used in combination.

The sulfonic acid alkali (earth) metal salt of monomeric or polymeric aromatic sulfide is described in JP-A-50-98539.
For example, diphenyl sulfide-4,4'-disodium disulfonate, diphenyl sulfide-4,4 '
And dipotassium disulfonate.

Alkaline (earth) metal sulfonates of aromatic carboxylic acids and esters are described in JP-A-50-9.
It is described in Japanese Patent No. 8540, and examples thereof include potassium 5-sulfoisophthalate, sodium 5-sulfoisophthalate, and polysodium polyethylene terephthalate polysulfonate.

Alkali (earth) metal sulfonates of monomeric or polymeric aromatic ethers are described in JP-A-50-98542, for example, calcium 1-methoxynaphthalene-4-sulfonate. ,
4-sodium dodecylphenyl ether disulfonate, sodium poly (2,6-dimethylphenylene oxide) polysulfonate, sodium poly (1,3-phenylene oxide) polysulfonate, poly (1,
4-phenylene oxide) polysodium polysulfonate, poly (2,6-diphenylphenylene oxide) polypotassium polysulfonate, poly (2-fluoro-6-)
Butylphenylene oxide) lithium polysulfonate and the like.

The alkali (earth) sulfonate metal salt of aromatic sulfonate is described in JP-A-50-98544, and examples thereof include potassium sulfonate of benzene sulfonate.

As the monomeric or polymeric alkaline (earth) aromatic organic sulfonic acid metal salt, there is disclosed in Japanese Patent Laid-Open No.
0-98546, for example, sodium benzenesulfonate, strontium benzenesulfonate, magnesium benzenesulfonate, dipotassium p-benzenedisulfonate, naphthalene-2,6-dipotassium disulfonate, biphenyl-3,3 '. -Calcium disulfonate etc. can be mentioned.

As the monomeric or polymeric aromatic organic sulfonesulfonic acid alkali (earth) metal salt,
It is described in JP-A-52-54746, for example sodium diphenylsulfone-3-sulfonate, potassium diphenylsulfone-3-sulfonate, diphenylsulfone-3,3'-dipotassium disulfonate, diphenylsulfone-3, 4′-dipotassium disulfonate and the like can be mentioned.

Alkali sulfonate (earth) metal salts of aromatic ketones are described in JP-A-50-98547, for example, sodium α, α, α-trifluoroacetophenone-4-sulfonate, Examples thereof include benzophenone-3,3′-dipotassium disulfonate.

The heterocyclic sulfonic acid alkali (earth) metal salt is described in JP-A-50-116542, for example, disodium thiophene-2,5-disulfonate and thiophene-2,5-. Dipotassium disulfonate, calcium thiophene-2,5-disulfonate,
Examples thereof include sodium benzothiophene sulfonate.

The alkali (earth) metal sulfonate of aromatic sulfoxide is described in JP-A-52-54745, and examples thereof include potassium diphenyl sulfoxide-4-sulfonate. .

Examples of the condensate of an aromatic organic sulfonic acid alkali (earth) metal salt with a methylene type bond include sodium naphthalene sulfonate formalin condensate and sodium anthracene sulfonate formalin condensate.

On the other hand, as the alkali (earth) metal salt of sulfuric acid ester, there may be mentioned, in particular, alkali (earth) metal salts of sulfuric acid ester of monohydric and / or polyhydric alcohols. Or, as the sulfuric acid ester of polyhydric alcohols, methyl sulfuric acid ester, ethyl sulfuric acid ester, lauryl sulfuric acid ester, hexadecyl sulfuric acid ester, sulfuric acid ester of polyoxyethylene alkyl phenyl ether, mono of pentaerythritol,
Examples thereof include di-, tri-, tetra-sulfate esters, lauric acid monoglyceride sulfates, palmitic acid monoglyceride sulfates, stearic acid monoglyceride sulfates, and the like. Preferable examples of the alkali (earth) metal salt of these sulfates include alkali (earth) metal salts of lauryl sulfate.

Examples of the aromatic organic alkali (earth) metal salts include alkali (earth) metal salts of aromatic sulfonamides such as saccharin and N- (p-
Tolylsulfonyl) -p-toluenesulfoimide, N-
Examples thereof include (N′-benzylaminocarbonyl) sulfanylimide, and an alkali (earth) metal salt of N- (phenylcarboxyl) sulfanylimide.

Of the above-mentioned aliphatic or aromatic organic alkali (earth) metal salts, more preferable components include alkali (earth) metal salts of aromatic organic sulfonic acids and alkali (earth) salts of perfluoroalkane sulfonic acids. Examples thereof include metal salts.

The silicate metal salt of the C-3 component of the present invention is a silicate metal salt containing at least a metal oxide component and a SiO ₂ component.

The silicate metal salt of the C-3 component may be in any form of orthosilicate, disilicate, cyclic silicate, chain silicate, layered silicate, and tectosilicate as the silicate ion form. Especially in the case of natural minerals, orthosilicate, disilicate,
Cyclic silicates and chain silicates are advantageous. Further, it may be in any of a crystalline state, a glass state, and a mixed state of crystal and glass, and the crystal may be any modification that each metal silicate salt can take. The crystal may have various shapes such as fibrous shape and plate shape, and may be crystalline or amorphous.

The silicate metal salt of the C-3 component may be any compound of a complex oxide, an oxyacid salt (consisting of an ionic lattice) and a solid solution. Further, the complex oxide is a combination of two or more kinds of a single oxide, And any combination of two or more of a single oxide and an oxyacid salt.
It may be either a solid solution of one or more kinds of metal oxides or a solid solution of two or more kinds of oxygenates.

The silicate metal salt of the C-3 component may be a hydrate. Those forms of crystal water in the hydrate is entering as a hydrogen silicate ion as Si-OH, to the metal cation hydroxide ion - to fall ionic as, ^(OH)
And any of those that enter as H ₂ O molecules in the gaps of the structure.

The C-3 component metal silicate may be either a natural product or an artificial synthetic product. As the artificial synthetic product, a metal silicate obtained by various conventionally known methods, for example, various synthetic methods utilizing solid reaction, hydrothermal reaction, ultrahigh pressure reaction and the like can be used.

The C-3 component silicate metal salt preferably has a composition substantially represented by the following formula (1). _{xMO · ySiO 2 · zH 2 O} (1) ( where x and y represents a natural number, z represents an integer of 0 or more, MO represents a metal oxide component, be a plurality of metal oxide components Good.)

Further, in the above formula (1), in the relation of x and y, x: y is preferably 1: 5 to 10: 1, and more preferably 1: 4 to 3: 1.
It is more preferably 1: 3 to 3: 1 and 5: 8 to
2: 1 is particularly preferred. When a plurality of metal oxide components are present, the value of x indicates the total number of them.

Examples of the metal in the metal oxide MO include potassium, sodium, lithium, barium, calcium, zinc, manganese, iron, cobalt, magnesium, zirconium, aluminum and titanium. Here, the interionic bonding force of these metal oxides is determined by the charges of positive and negative ions being e1 and e2, respectively.
And the ion radius of the cation is r, then e1 · e2
It can be approximately calculated by / r2. The order of magnitude of the interionic bond strength is from K ₂ O and Na.
₂ O, Li ₂ O, BaO, CaO, ZnO, MnO, Fe
O, CoO, MgO, Fe ₂ O ₃ , ZrO ₂ , Al ₂ O ₃ ,
TiO ₂ (ion radius is Wyckoff (194
8) Measured value (based on Inorganic Chemistry Handbook published by Gihodo Publishing Co., Ltd.)).

Metal oxide M in the C-3 component of the present invention
In a preferred embodiment of O, the binding force is preferably Al ₂ O ₃ or less, more preferably Fe ₂ O ₃ or less, and even more preferably MgO in the above order of interionic binding force. Further Li ₂
O or higher is more preferable, and CaO or higher is further preferable. K
_Although good flame retardancy is achieved with ₂ O and Na ₂ O, the wet heat resistance may be poor. With the silicate metal salt in the above preferred range, more excellent compatibility between the flame retardancy of the flame-retardant resin composition and the environmental resistance such as wet heat resistance is achieved. The reason why the above range is more preferable is that the lower the interionic bond strength is, the higher the activity in the ionic reaction with other components is, and the higher the activity is, the higher the flame retardancy is achieved, but the wet heat resistance and the like. It is thought that this is because the ionic decomposition reaction of is also facilitated. The term "substantially have" means that when the metal oxide MO contains two or more kinds of metal oxides, the total amount of the metal oxides in the formula (1) is 100 m.
In the ol%, it means that the above-mentioned preferred metal oxide is contained in an amount of 20 mol% or more, more preferably 25 mol% or more, further preferably 40 mol% or more, particularly preferably 50 m.
It means that it is ol% or more.

A more preferable embodiment of the metal oxide MO is that which substantially contains a metal oxide whose interionic bond strength is in the range of CaO to MgO, and in particular from the viewpoint of availability, it is preferable to use CaO or MgO. Those which substantially contain any of them are preferable. More preferred metal oxide M
O is at least 1 selected from CaO and MgO
It is substantially composed of seed components, and particularly preferably composed of MgO.

Specific examples of the silicate metal salt in each metal oxide MO include the following. Here, the notation in parentheses means that the compound in parentheses can be used as a metal salt exemplified by the name of a mineral or the like containing such a silicate metal salt as a main component.

[0092] as including K ₂ O in the component, K ₂
O ・ SiO ₂ , K ₂ O ・ 4SiO ₂ , H ₂ O, K ₂ O ・ Al
₂ O ₃ · ₂ SiO ₂ (calcilite), K ₂ O · Al ₂ O ₃ ·
4SiO ₂ (white ryushu), and K ₂ O ・ Al ₂ O ₃・ 6
SiO ₂ (orthoclase), and the like.

Na₂As containing O as its component
Is Na₂O / SiO₂, And its hydrate, Na₂O
2 SiO₂2Na₂O / SiO₂, Na₂O ・ 4Si
O₂, Na ₂O ・ 3SiO₂・ 3H₂O, Na₂O ・ Al₂O
₃・ 2SiO₂, Na₂O ・ Al₂O₃・ 4SiO₂(Jade
Pyroxene), 2Na₂O / 3CaO / 5SiO₂3Na₂O
・ 2CaO ・ 5SiO₂, And Na₂O ・ Al₂O₃・ 6
SiO₂(Sorbital) and the like.

Li₂As containing O as its component
Is Li₂O / SiO₂2Li₂O / SiO₂, Li₂O
・ SiO₂・ H₂O, 3Li₂O ・ 2SiO₂, Li₂O
Al₂O ₃・ 4SiO₂(Petalite), Li₂O ・ Al₂
O₃・ 2SiO₂(Eucryptite), and Li₂O
・ Al₂O₃・ 4SiO₂(Spojumen) etc.
Be done.

[0095] as comprising BaO as its _{component, BaO · SiO 2, 2BaO ·} SiO 2, BaO · A
l ₂ O ₃ .2SiO ₂ (celsian) and BaO.T
Examples include iO ₂ .3SiO ₂ (ventite).

As CaO as a component, 3CaO.SiO ₂ (cement clinker mineral alite), 2CaO.SiO ₂ (cement clinker mineral belite), 2CaO.MgO.2SiO
₂ (Akermanite), 2CaO ・ Al ₂ O ₃・ SiO ₂
(Gerhenite), solid solution (meryllite) of akermanite and gerhenite, CaO.SiO ₂ (wollastonite (including both α-type and β-type)), CaO
・ MgO ・ 2SiO ₂ (diopside), CaO ・ Mg
O ・ SiO ₂ (ash olivine olivine), 3CaO ・ MgO
・ 2SiO ₂ (Meluwinite), CaO ・ Al ₂ O ₃・
2SiO ₂ (anorthite), 5CaO ・ 6SiO ₂・ 5
H ₂ O (tobermorite, other 5CaO ・ 6SiO ₂・ 9
Tobamovirus Light Group hydrates such H ₂ O, etc.), 2C
Wollastonite group hydrates such as aO ・ SiO ₂・ H ₂ O (Hirebrandite), 6CaO ・ 6SiO ₂・
Zonotolite group hydrate such as H ₂ O (Zonotolite), 2CaO · SiO ₂ · 2H ₂ O (gyrolite)
Gyrolite group hydrate, CaO ・ Al ₂
O ₃・ 2SiO ₂・ H ₂ O (lawsonite), CaO ・ F
eO ・ 2SiO ₂ (Hedenki stone), 3CaO ・ 2SiO ₂
(Chillcorenite) 3CaO ・ Al ₂ O ₃・ 3SiO _{2
(Guroshura), 3CaO · Fe 2 O 3} · 3SiO 2 ( Andhra _{Daito), 6CaO · 4Al 2 O 3} · FeO · Si
O ₂ (pre-cloroite), and clinozoisite,
Examples include phenanthrite, lintite, vesuvite, onoseite, scourtite, and augite.

Further, as a silicate metal salt containing CaO as its component, Portland cement can be mentioned. The type of Portland cement is not particularly limited, and any type such as normal, early strength, ultra-early strength, medium heat, sulfate resistance, and white can be used. Further, various mixed cements such as blast furnace cement, silica cement and fly ash cement can also be used as the C component.

As other silicic acid metal salts containing CaO as a component, blast furnace slag, ferrite and the like can be mentioned.

As a component containing ZnO, Z is
Examples thereof include nO.SiO ₂ , 2ZnO.SiO ₂ (troustite), and 4ZnO.2SiO ₂ .H ₂ O (heteromorphite).

MnO is included in the component as M
nO ・ SiO ₂ , 2MnO ・ SiO ₂ , CaO ・ 4MnO
5 SiO ₂ (Rhodonite) and cordierite are included.

FeO is included in the component as F
eO ・ SiO ₂ (ferrocyllite), 2FeO ・ SiO ₂
(Iron olivine), 3FeO ・ Al ₂ O ₃・ 3SiO
₂ (almandine), and 2CaO / 5FeO / 8S
Examples include iO ₂ · H ₂ O (tetsuactinocene stone).

As a component containing CoO, C
Examples include oO.SiO ₂ and 2CoO.SiO ₂ .

As a component containing MgO, M
gO / SiO₂(Steatite, enstatite), 2
MgO / SiO₂(Forsterite) 3MgO · A
l₂O ₃・ 3 SiO₂(Bi-rope), 2MgO / 2Al₂
O₃・ 5 SiO₂(Cordierite) 2MgO / 3S
iO₂・ 5H₂O, 3MgO ・ 4SiO₂・ H₂O (tal
5) 5MgO / 8SiO₂・ 9H₂O (Atta Pul Jai
G) 4MgO ・ 6SiO₂・ 7H₂O (Sepio Rai
G) 3MgO / 2SiO₂・ 2H₂O (chrysoray
G) 5MgO / 2CaO / 8SiO₂・ H2O
Stone) 5MgO ・ Al₂O ₃・ 3 SiO₂・ 4H₂O (green
Mudstone), K₂O ・ 6MgO ・ Al₂O₃・ 6 SiO₂・ 2H
₂O (frogbite), Na₂O / 3MgO / 3Al₂O₃
・ 8 SiO₂・ H₂O (lansenite) and magnesiu
Tourmaline, anemite, camington stone, vermicula
Ito and smectite.

The composition containing Fe ₂ O ₃ is as follows:
Fe ₂ O ₃ .SiO _{2 and the} like can be mentioned. ZrO ₂ · SiO ₂ (zircon) is included as a component containing ZrO _2.
And AZS refractories.

As a component containing Al ₂ O ₃ ,
Al ₂ O ₃ · SiO ₂ (sillimanite, under-leucite, kyanite), 2Al ₂ O ₃ · SiO ₂ , Al ₂ O ₃
・ 3SiO ₂ , 3Al ₂ O ₃・ 2SiO ₂ (mullite), A
l ₂ O ₃ · 2SiO ₂ · 2H ₂ O (kaolinite), Al _{2
O 3 · 4SiO 2 · H 2} O ( pyrophyllite), Al ₂ O
_{3 · 4SiO 2 · H 2 O} ( bentonite), K ₂ O · 3Na
₂ O ・ 4Al ₂ O ₃・ 8SiO ₂ (kasumi stone), K ₂ O ・ 3
Al ₂ O ₃ · 6SiO ₂ · 2H ₂ O (mascobite, sericite), K ₂ O · 6MgO · Al ₂ O ₃ · 6SiO ₂ · 2H
Examples include ₂ O (phlogovite), various zeolites, fluorophlogopite and biotite.

The silicate metal salt may have any shape (granular, fibrous, needle-like, plate-like, etc.). The average particle diameter may be arbitrary, but the smaller the average particle diameter, the more preferable. Among them, the average particle diameter is preferably 20 μm or less, more preferably 5 μm or less, and particularly preferably 2 μm or less. is there. On the other hand, a lower limit of 0.03 μm or more is suitable, and a lower limit is relatively rare. It is considered that the reason why the lower average particle diameter is preferable is that the C component exhibits a flame retardant effect particularly on the surface of the particles, and the smaller the average particle diameter, the larger the surface area per weight. The average particle diameter is D measured by an X-ray transmission method which is one of liquid phase sedimentation methods.
50 (median diameter of particle size distribution). As a specific example of the apparatus for performing such measurement, Sedigraph 5100 manufactured by Micromeritics, Inc. can be mentioned.

(Blending Amount) Ingredient A and B in the present invention
The composition ratios of the component and the C component are as follows. 0.1 to 25 parts by weight of B component, relative to 100 parts by weight of A component,
And C component 0.001 to 2 parts by weight, and component B 2
20 parts by weight and 0.005 to 1.5 parts by weight of C component are preferable, 3 to 15 parts by weight of B component, and 0.0 of C component.
It is more preferably 1 to 1 part by weight. Within the above range, it is possible to achieve both flame retardancy and heat resistance.

(Characteristics) The flame-retardant resin composition of the present invention has L
When used in applications requiring high light reflectance such as CD reflectors (backlight reflectors), LED reflectors, meter reflectors, reflectors, photoelectric switches, electric lamp covers, etc., the heat resistance is insufficient. When thinned, there is a risk of deformation due to the heat of the light source, so ISO75-1 or ISO
According to the 75-2 standard, the deflection temperature under load measured with a load of 1.80 MPa is preferably 115 ° C. or higher, and 12
0 ° C or higher is more preferable, and 124 ° C or higher is further preferable.

(Component D) The flame-retardant thermoplastic resin composition of the present invention prevents melting and dripping at the time of combustion and further improves flame retardancy. The agent (D component) is preferably contained in an amount of 0.01 to 1 part by weight, more preferably 0.05 to 0.6 part by weight. As the fluorine-containing anti-dripping agent, a fluorine-containing anti-dripping agent having fibril forming ability is particularly preferable.

Examples of the fluorine-containing anti-dripping agent having a fibril forming ability used as the component D of the present invention include polytetrafluoroethylene and tetrafluoroethylene copolymers (for example, tetrafluoroethylene / hexafluoropropylene copolymer and the like). ), A partially fluorinated polymer as shown in U.S. Pat. No. 4,379,910, a polycarbonate resin produced from fluorinated diphenol, and the like, but preferably polytetrafluoroethylene (hereinafter sometimes referred to as PTFE). ).

The PTFE having fibril-forming ability has an extremely high molecular weight, and tends to be fibrous by binding PTFE with each other by an external action such as shearing force. Its molecular weight is 1,000,000 to 10,000,000, more preferably 2,000,000 to 9,000,000 in terms of number average molecular weight determined from standard specific gravity. In addition to the solid form, such PTFE may be in the form of an aqueous dispersion. In addition, PTFE having such a fibril-forming ability improves the dispersibility in the resin, and it is also possible to use a PTFE mixture in a mixed form with other resins in order to obtain better flame retardancy and mechanical properties. is there.

PTFE having the ability to form fibrils
Examples of commercially available products include Teflon 6J manufactured by Mitsui DuPont Fluorochemical Co., Ltd., Polyflon MPA FA500 manufactured by Daikin Chemical Co., Ltd., and F-201L. Commercially available aqueous dispersions of PTFE include Fluon AD-1, AD-936 manufactured by Asahi IC Polymers Co., Ltd., Fluon D-1, D-2 manufactured by Daikin Industries, Ltd., Mitsui DuPont Fluoro. Representative examples thereof include Teflon 30J manufactured by Chemical Co., Ltd.

The mixed form of PTFE includes (1) PT
A method in which an aqueous dispersion of FE and an aqueous dispersion or solution of an organic polymer are mixed and co-precipitated to obtain a co-aggregated mixture (JP-A-60-258263 and JP-A-63-15474).
No. 4, etc.), (2) a method of mixing an aqueous dispersion of PTFE with dried organic polymer particles (the method described in JP-A-4-272957),
(3) A method in which an aqueous dispersion of PTFE and an organic polymer particle solution are uniformly mixed, and respective media are simultaneously removed from the mixture (described in JP-A 06-220210 and JP-A 08-188653). Method),
(4) A method of polymerizing a monomer forming an organic polymer in an aqueous dispersion of PTFE (a method described in JP-A-9-95583), and (5) an aqueous dispersion of PTFE and an organic polymer. Those obtained by a method of uniformly mixing the combined dispersion, further polymerizing a vinyl-based monomer in the mixed dispersion, and then obtaining a mixture (method described in JP-A No. 11-29679, etc.). Can be used. P of these mixed forms
Commercially available products of TFE include "METABLEN A3000" (trade name) manufactured by Mitsubishi Rayon Co., Ltd. and "BLENDEX B449" manufactured by GE Specialty Chemicals.
(Product name) etc. can be mentioned.

The proportion of PTFE in the mixed form is as follows: PTFE is 1 to 6 in 100% by weight of the PTFE mixture.
0% by weight is preferable, and more preferably 5 to 55% by weight. If the ratio of PTFE is in the range, PT
Good dispersibility of FE can be achieved.

(Other Components) The flame-retardant thermoplastic resin composition of the present invention may contain various additives as long as the effects of the present invention are not impaired. Heat stabilizers, UV absorbers, light stabilizers, release agents, lubricants, sliding agents, colorants (dyes and pigments such as carbon black), crosslinked polymer particles, fluorescent whitening agents, phosphorescent pigments, fluorescent dyes, electrification Examples thereof include inhibitors, flow modifiers, crystal nucleating agents, inorganic and organic antibacterial agents, photocatalytic antifouling agents (fine particle titanium oxide, fine particle zinc oxide, etc.), infrared absorbers, photochromic agents and the like. In order to prevent deterioration of the resin composition, it is preferable that a heat stabilizer, an ultraviolet absorber, a light stabilizer and the like be contained in the resin composition. In particular, it is preferable to include a heat stabilizer.

The heat stabilizer of the flame-retardant thermoplastic resin composition of the present invention preferably contains a phosphorus-based stabilizer. As the phosphorus-based stabilizer, any of phosphite-based, phosphonite-based, and phosphate-based stabilizers can be used.

Preferred examples of the phosphite stabilizer include phosphite compounds having an aryl group in which two or more alkyl groups are substituted. For example, tris (diethylphenyl) phosphite, tris (di-iso-propylphenyl) phosphite, tris (di-n-butylphenyl) phosphite, tris (2,4-di-tert).
-Butylphenyl) phosphite, tris (2,6-di-tert-butylphenyl) phosphite, tris (2,6-di-tert-butylphenyl) phosphite and the like, particularly tris (2,4- The-tert
-Butylphenyl) phosphite is preferred.

Further, a phosphite compound having an aryl group in which a part of the aryl group has a cyclic structure can also be used. For example, 2,2'-methylenebis (4,6-di-te
rt-Butylphenyl) (2,4-di-tert-butylphenyl) phosphite, 2,2′-methylenebis (4,6-di-tert-butylphenyl) (2-te
rt-butyl-4-methylphenyl) phosphite,
2,2'-methylenebis (4-methyl-6-tert-
Butylphenyl) (2-tert-butyl-4-methylphenyl) phosphite, 2,2′-ethylidene bis
(4-methyl-6-tert-butylphenyl) (2-
Examples include tert-butyl-4-methylphenyl) phosphite.

Other phosphorus-based heat stabilizers other than those mentioned above may be mentioned below. Examples of the phosphite compound include distearyl pentaerythritol diphosphite, bis (2,4-di-tert-butylphenyl) pentaerythritol diphosphite, and bis (2,6-di-tert-butyl-4-methylphenyl). Pentaerythritol diphosphite, phenylbisphenol A
Pentaerythritol diphosphite, dicyclohexyl pentaerythritol diphosphite and the like can be mentioned, preferably distearyl pentaerythritol diphosphite, bis (2,4-di-tert-butylphenyl) pentaerythritol diphosphite, bis (2,2 6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphite, 4,4′-
Mention may be made of isopropylidene diphenol ditridecyl phosphite.

Examples of the phosphate compound include tributyl phosphate, trimethyl phosphate, tricresyl phosphate, triphenyl phosphate, trichlorophenyl phosphate, triethyl phosphate, diphenyl cresyl phosphate, diphenyl mono-orthoxenyl phosphate, tributoxyethyl phosphate, dibutyl phosphate, Dioctyl phosphate,
Examples include diisopropyl phosphate,
Preferred are triphenyl phosphate and trimethyl phosphate.

Examples of the phosphonite compound include tetrakis (2,4-di-tert-butylphenyl) -4,4 '.
-Biphenylene diphosphonite, tetrakis (2,4-
Di-tert-butylphenyl) -4,3′-biphenylenediphosphonite, tetrakis (2,4-di-ter
t-butylphenyl) -3,3'-biphenylenediphosphonite, tetrakis (2,6-di-tert-butylphenyl) -4,4'-biphenylenediphosphonite,
Tetrakis (2,6-di-tert-butylphenyl)
-4,3'-biphenylenediphosphonite, tetrakis (2,6-di-tert-butylphenyl) -3,3 '
-Biphenylene diphosphonite, bis (2,4-di-t
ert-butylphenyl) -4-phenyl-phenylphosphonite, bis (2,4-di-tert-butylphenyl) -3-phenyl-phenylphosphonite, bis (2,6-di-n-butylphenyl)- 3-phenyl-
Phenylphosphonite, bis (2,6-di-tert-
Butylphenyl) -4-phenyl-phenylphosphonite, bis (2,6-di-tert-butylphenyl)-
Examples thereof include 3-phenyl-phenylphosphonite, and tetrakis (di-tert-butylphenyl) -biphenylene diphosphonite and bis (di-tert-butylphenyl) -phenyl-phenylphosphonite are preferable,
Tetrakis (2,4-di-tert-butylphenyl)
-Biphenylene diphosphonite, bis (2,4-di-t
More preferred is ert-butylphenyl) -phenyl-phenylphosphonite. Such a phosphonite compound is preferable because it can be used in combination with the phosphite compound having an aryl group in which two or more alkyl groups are substituted.

The flame-retardant thermoplastic resin composition of the present invention can contain various stabilizers. Examples of the antioxidants include phenolic antioxidants and sulfur antioxidants. Various types of phenolic antioxidants can be used.

Specific examples of the phenolic antioxidant include, for example, n-octadecyl-β- (4'-hydroxy-3 ', 5'-di-tert-butylphenyl) propionate, 2-tert-butyl-6-. (3'-ter
t-Butyl-5'-methyl-2'-hydroxybenzyl) -4-methylphenyl acrylate, 3,9-bis {2- [3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionyl Oxy] -1,
1, -Dimethylethyl} -2,4,8,10-tetraoxaspiro [5,5] undecane, and tetrakis [methylene-3- (3 ', 5'-di-tert-butyl-4-hydroxyphenyl) Propionate] methane and the like can be preferably mentioned, and n-octadecyl-β
More preferred is-(4'-hydroxy-3 ', 5'-di-tert-butylphenyl) propionate.

Specific examples of the sulfur antioxidant of the present invention include dilauryl-3,3'-thiodipropionic acid ester, ditridecyl-3,3'-thiodipropionic acid ester, dimyristyl-3,3'-. Thiodipropionate, distearyl-3,3′-thiodipropionate, laurylstearyl-3,3′-thiodipropionate, pentaerythritol tetra (β
-Lauryl thiopropionate) ester, bis [2-
Methyl-4- (3-laurylthiopropionyloxy)
-5-tert-butylphenyl] sulfide, octadecyl disulfide, mercaptobenzimidazole,
2-mercapto-6-methylbenzimidazole, 1,
1'-thiobis (2-naphthol) and the like can be mentioned. More preferably, a pentaerythritol tetra ((beta) -lauryl thiopropionate) ester can be mentioned.

The flame-retardant thermoplastic resin composition of the present invention may contain an ultraviolet absorber. As an ultraviolet absorber,
For example, benzophenone typified by 2-hydroxy-4-n-dodecyloxybenzophenone, 2,2'-dihydroxy-4,4'-dimethoxybenzophenone, bis (5-benzoyl-4-hydroxy-2-methoxyphenyl) methane and the like. Examples thereof include ultraviolet absorbers.

Examples of the ultraviolet absorber include 2-
(2'-hydroxy-5'-methylphenyl) benzotriazole, 2- (2'-hydroxy-3 ', 5'-di-tert-amylphenyl) benzotriazole, 2
-(2'-hydroxy-3 ', 5'-bis (α, α'-
Dimethylbenzyl) phenylbenzotriazole, 2,
2'methylenebis [4- (1,1,3,3-tetramethylbutyl) -6- (2H-benzotriazol-2-yl) phenol], methyl-3- [3-tert-butyl-5- (2H -Benzotriazol-2-yl) -4
-A benzotriazole-based ultraviolet absorber represented by a condensate of -hydroxyphenyl propionate-polyethylene glycol can be mentioned.

Further, as the ultraviolet absorber, for example, 2-
(4,6-diphenyl-1,3,5-triazine-2-
Yl) -5-hexyloxyphenol, 2- (4,6
Examples thereof include hydroxyphenyltriazine compounds such as -bis (2,4-dimethylphenyl) -1,3,5-triazin-2-yl) -5-hexyloxyphenol.

Bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis (1,2,2,2)
6,6-pentamethyl-4-piperidyl) sebacate,
Tetrakis (2,2,6,6-tetramethyl-4-piperidyl) -1,2,3,4-butanetetracarboxylate, tetrakis (1,2,2,6,6-pentamethyl-4-piperidyl)- 1,2,3,4-butanetetracarboxylate, poly {[6- (1,1,3,3-tetramethylbutyl) amino-1,3,5-triazine-
2,4-Diyl] [(2,2,6,6-tetramethylpiperidyl) imino] hexamethylene [(2,2,6,6
-Tetramethylpiperidyl) imino]}, polymethylpropyl 3-oxy- [4- (2,2,6,6-tetramethyl) piperidinyl] siloxane, and other hindered amine-based light stabilizers may also be included. When such a light stabilizer is used in combination with the above-mentioned ultraviolet absorber and various antioxidants, it exhibits better performance in terms of weather resistance and the like.

The above-mentioned phosphorus-based stabilizer, phenol-based antioxidant, and sulfur-based antioxidant can be used alone or in combination of two or more kinds.

The ratio of these stabilizers in the composition is as follows.
In 100% by weight of the flame-retardant thermoplastic resin composition of the present invention, the phosphorus-based stabilizer, the phenol-based antioxidant, or the sulfur-based antioxidant is preferably 0.0001 to 1% by weight, respectively. More preferably, it is 0.0005 to 0.5 wt% in 100 wt% of the flame-retardant thermoplastic resin composition.
More preferably, it is 0.001 to 0.2% by weight.

The ratio of the ultraviolet absorber and the light stabilizer is 0.0 in 100% by weight of the flame-retardant thermoplastic resin composition of the present invention.
It is 1 to 5% by weight, and more preferably 0.02 to 1% by weight.

The flame-retardant thermoplastic resin composition of the present invention may contain a release agent. As such a release agent, known release agents can be used. For example, saturated fatty acid ester, unsaturated fatty acid ester, polyolefin wax (polyethylene wax, 1-alkene polymer, etc., those modified with a functional group-containing compound such as acid modification can also be used), fluorine compound (polyfluoroalkyl) Fluorine oil typified by ether), paraffin wax,
Beeswax etc. can be mentioned.

Preferred releasing agents include saturated fatty acid esters. In the case of such a release agent, good transparency can be maintained. For example, glycerin fatty acid esters such as stearic acid monoglyceride, diglyceride, and triglyceride, polyglycerin fatty acid esters such as decaglycerin decasterate and decaglycerin tetrastearate, lower fatty acid esters such as stearic acid stearate, sebacic acid behenate, etc. And higher erythritol esters such as pentaerythritol tetrastearate. The release agent is a flame-retardant thermoplastic resin composition 10
It is preferably 0.01 to 2% by weight in 0% by weight.

The flame-retardant thermoplastic resin composition of the present invention may contain a bluing agent for canceling the yellow tint due to an ultraviolet absorber or the like. Specific examples of bluing agents include Macrolex Blue RR, Macrolex Violet B, and Terrazol Blue RLS.

Further, a fluorescent whitening agent can be added to the flame-retardant thermoplastic resin composition of the present invention. Specific fluorescent whitening agents include, for example, coumarin derivatives, bisbenzoxazolyl stilbene derivatives, bisbenzoxazolylnaphthalene derivatives, bisbenzoxazolylthiophene derivatives and the like.

(Manufacturing Method) In order to manufacture the flame-retardant thermoplastic resin composition of the present invention, any method is adopted. For example, A component to C component, optionally D component and other additives, V
After thoroughly mixing using a pre-mixing means such as a mold blender, a Henschel mixer, a mechanochemical device, and an extrusion mixer, granulation may be performed by an extrusion granulator or a briquetting machine, if necessary, and then a vented twin-screw Examples thereof include a method of melt-kneading with a melt-kneader represented by a ruder and pelletizing with a device such as a pelletizer.

In addition, a method of supplying each component independently to a melt-kneader represented by a vent type twin-screw ruder,
A method of pre-mixing a part of each component and then supplying the mixture to the melt-kneader independently of the remaining components may be used. As a premixing method, for example, when a powder having a form of A is included as a component A, a method of blending a part of the powder with an additive to be blended to form a masterbatch of the additive diluted with the powder is used. Can be mentioned.

More specifically, for example, when a solid fibril-forming PTFE is used as the D component and a filler such as talc or wollastonite is used as the C component, both are mixed with a high-speed stirring mixer such as a Henschel mixer. The method of premixing can be mentioned. Further, in such a case, a method of using a dispersion type as the component D to make the dispersed state finer, a method of further mixing a part of the powder of the component A, and the like can be mentioned.

Further, a method of independently supplying one component from the middle of the melt extruder may be mentioned. When the components to be blended are liquid, a so-called liquid injection device or liquid addition device can be used for supplying to the melt extruder.

The flame-retardant thermoplastic resin composition of the present invention can be manufactured into various products by injection molding such pellets to obtain molded products. In such injection molding, not only the usual cold runner molding method, but also in the injection molding, not only the usual molding method but also gas assisted injection molding, injection compression molding, injection press molding, insert molding, in-mold molding. Local high temperature mold molding (including heat insulation mold molding), two-color molding, sandwich molding, ultra-high speed injection molding and the like can be used.

The flame-retardant resin composition of the present invention can also be used by extrusion molding in the form of various shaped extrusion molded products, sheets, films and the like. Further, an inflation method, a calendar method, a casting method or the like can be used for forming a sheet or a film. It is also possible to form a heat-shrinkable tube by applying a specific stretching operation. Further, the flame-retardant thermoplastic resin composition of the present invention can be formed into a hollow molded product by rotational molding, blow molding or the like.

[0142]

BEST MODE FOR CARRYING OUT THE INVENTION The effects of the present invention will be specifically described below with reference to Examples and Comparative Examples, but the present invention is not limited thereto. The evaluation items and the symbols of each component in the composition mean the following contents.

[Examples 1 to 17 and Comparative Examples 1 to 8]
In the raw materials listed in Tables 1 to 3, C component or D component is a part of another A component (C component or D component is 10% by weight).
The amount of the mixture is uniformly blended in a polyethylene bag, and then the mixture is put into a tumbler in the amount shown in the table and then rotated for about 15 minutes to uniformly mix, and a twin screw extruder with a vent having a screw diameter of 30 mm [Japan Co., Ltd.] Steelworks, TEX-30α], the following cylinder temperature, vent suction degree 3000P
A strand was extruded at a and a screw rotation speed of 180 rpm, the strand was cooled with water, and then cut with a pelletizer to obtain pellets. The resulting pellets are 120
It was dried at a temperature of 6 ° C. for 6 hours by a hot air circulation dryer, and a test piece was molded under the following temperature conditions by an injection molding machine [FANUC T-150D]. (I) For the sample using PC as the A component, the cylinder temperature during extrusion is 260 ° C., and the cylinder temperature during molding is 280 ° C. and the mold temperature is 80 ° C. (ii) For the sample using PAR as the A component, Cylinder temperature during extrusion 350 ° C, cylinder temperature during molding 380 ° C and mold temperature 100 ° C

The symbols showing the evaluation items of the material properties and the components of the compositions shown in Tables 1 to 3 are as follows.

(Evaluation Item) A vertical combustion test (V test) was performed using a test piece having a thickness of 1.6 mmt, which was prepared according to the flame retardant UL94 standard. Based on the result of the test, UL-94V-0, V-1, V-2 and non-standard Not-V were evaluated. The deflection temperature under load was measured according to heat resistance ISO 75-1 or 75-2. The measurement load was 1.80 MPa. Light reflectance A light reflectance at a wavelength of 550 nm was measured using a sample plate having a thickness of 2 mm with a color eye MS2020PLUS manufactured by Macbeth. Measurement of TiO ₂ content Based on JIS K 5116, TiO ₂ in the titanium dioxide pigment used in the metal aluminum reduction method
The content was measured.

(Component A) PC-1: Aromatic polycarbonate resin (polycarbonate resin powder having a viscosity average molecular weight of 19,700 made from bisphenol A and phosgene by a conventional method, manufactured by Teijin Kasei Co., Ltd., "Panlite L-1225WX" )) PC-2: Bisphenol A and p as a terminator
A linear aromatic polycarbonate resin synthesized from -tert-butylphenol and phosgene by an interfacial polycondensation method has a viscosity average molecular weight of 15,200 of 10
Aromatic polycarbonate resin pellets (component A) having a viscosity average molecular weight of 29,500 obtained by melting and mixing 80 parts by weight of a resin having a viscosity average molecular weight of 23,700 and 10 parts by weight of a resin having a viscosity average molecular weight of 120,000. ) PAR: Polyarylate resin (manufactured by Unitika Ltd., “U”)
Polymer U-100 ") manufactured by component (B) TiO ₂ -1 titanium dioxide (Ishihara Sangyo Kaisha Ltd." TIPAQUE PC-3 ", average particle diameter: 0.22 [mu] m, Al ₂
O ₃ amount: 2.0% by weight, TiO ₂ amount: 91% by weight, silicon-based surface treatment agent) TiO ₂ -2: titanium dioxide (“R” manufactured by Tioxide Co., Ltd.
-TC30 ", average particle size: 0.18 μm, Al ₂ O
₃ amount: 3.5% by weight, TiO ₂ amount: 93% by weight, amine-based surface treatment agent) (C component) F114: Perfluorobutanesulfonic acid potassium salt (manufactured by Dainippon Ink and Chemicals, Inc., "Megafuck F-" 114
P ") KSS: potassium salt of diphenylsulfone sulfonic acid (" KSS "manufactured by UCB Japan Co., Ltd.) TALC: talc (" HS-T "manufactured by Hayashi Chemical Industry Co., Ltd.)
0.8 ") WSN: Wollastonite (Nyco Minerals Co., Ltd.)
"NYGLOS4)) Mg silicate: hydrous magnesium silicate reagent (compositional formula: 2Mg
O.3SiO ₂ .5H ₂ O, manufactured by Wako Pure Chemical Industries, Ltd. Ca silicate: calcium silicate reagent (compositional formula: CaO ・ Si
O ₂ , manufactured by Wako Pure Chemical Industries, Ltd. (D component) PTFE: Polytetrafluoroethylene ("Polyflon MP FA500" manufactured by Daikin Industries, Ltd.)

(Components for Comparative Examples) TiO ₂ -3: Titanium dioxide (“R” manufactured by Tioxide Corporation)
-TC90 ", average particle size: 0.22 μm, Al ₂ O
₃ amount: 4.1% by weight, TiO ₂ amount: 94% by weight) TiO ₂ -4: titanium dioxide ("Taipec R-780" manufactured by Ishihara Sangyo Co., Ltd., average particle diameter: 0.24 µm, Al
₂ O ₃ amount: 2.2 wt%, TiO ₂ amount: 88 wt%) Phosphate ester: Phosphate ester containing bisphenol A bis (diphenyl phosphate) as a main component (manufactured by Daihachi Chemical Industry Co., Ltd., “CR- 741 ") (Other components) Impact modifier: Composite rubber core-shell graft polymer (" Metabrene S-2001 "manufactured by Mitsubishi Rayon Co., Ltd .; dimethylsiloxane polymer and n-butyl acrylate polymer were intertwined with each other. 80% by weight of a composite rubber having a structure and containing methyl methacrylate) KS-N: optical brightener ("Hostacruz KS-N" manufactured by Hoechst Co., Ltd.) Antioxidant: phosphorus-based antioxidant (Nihon Ciba Geigy Co., Ltd.) "Irgafos 168" manufactured by RIKEN Release Agent: Saturated fatty acid ester-based release agent ("Rikemar SL900" manufactured by Riken Vitamin Co., Ltd.)

[0148]

[Table 1]

[0149]

[Table 2]

[0150]

[Table 3]

From Tables 1 to 3, the flame-retardant thermoplastic resin composition of the present invention is prepared by combining a specific titanium oxide and a specific metal salt without adding a conventional bromine compound. It can be seen from the above that it has high flame retardancy and is excellent in heat resistance as compared with the case where a phosphate ester flame retardant or the like is blended.

[0152]

The flame-retardant thermoplastic resin composition of the present invention comprises
It has excellent light reflectivity, has a small environmental load without the addition of bromine compounds, and has excellent heat resistance. LCD reflectors (backlight reflectors), LED reflectors, meter reflectors, illuminated push switches. It is suitable for applications requiring high light reflectance, such as photoelectric switches, electric parts, lamp reflectors, lamp holders, and electric lamp covers.

   ─────────────────────────────────────────────────── ─── Continued front page    F term (reference) 4J002 CF161 CG011 DE136 DJ007                       EV237 FB076 FB116 FB126                       GQ00

Claims (6)

[Claims] 1. A ratio of TiO ₂ is 90 to 98 relative to 100 parts by weight of one or more thermoplastic resins (component A) selected from aromatic polycarbonate resins and polyarylate resins.
0.1 to 25 parts by weight of titanium dioxide (component B) having an Al ₂ O ₃ content of 0.5 to 4.0% by weight, which is an inorganic surface treatment agent, and an aliphatic organic sulfonate metal Salt (C-1 component), aromatic organic sulfonic acid metal salt (C-2
Component), 0.001 to 2 parts by weight of one or more metal salts (component C) selected from silicate metal salts (component C-3), and substantially flame-retardant thermoplastic containing no bromine compound. Resin composition. 2. The flame-retardant thermoplastic resin composition according to claim 1, which further comprises 0.01 to 1 part by weight of a fluorine-containing anti-dripping agent (component D) with respect to 100 parts by weight of component A. . 3. The flame-retardant thermoplastic according to claim 1, which has a deflection temperature under load measured by a load of 1.80 MPa of 115 ° C. or higher in accordance with ISO75-1 or ISO75-2 standard. Resin composition. 4. The flame-retardant thermoplastic resin composition according to claim 1, wherein the component B is treated with a silicon-based surface treatment agent. 5. The C component is an alkali metal salt of aromatic organic sulfonic acid, an alkaline earth metal salt of aromatic organic sulfonic acid, an alkali metal salt of perfluoroalkanesulfonic acid, an alkaline earth metal of perfluoroalkanesulfonic acid. 1. One or more metal salts selected from metal salts.
The flame-retardant thermoplastic resin composition according to any one of 4 above. 6. The flame-retardant thermoplastic resin according to any one of claims 1 to 4, wherein the C-3 component is a metal silicate whose composition formula is substantially represented by the following formula (1). Composition. _{xMO · ySiO 2 · zH 2 O} (1) ( where x and y represents a natural number, z represents an integer of 0 or more, MO represents a metal oxide component, be a plurality of metal oxide components Good.)