JP7219102B2 - Thermoplastic resin composition - Google Patents

Description

The present invention relates to thermoplastic resin compositions. More particularly, the present invention relates to a thermoplastic resin composition improved in heat resistance and low-temperature impact resistance by blending an appropriate amount of a polyarylate resin into a polycarbonate-polydiorganosiloxane copolymer resin.

Polycarbonate resins are used in many applications such as machine parts, automobile parts, electrical/electronic parts, and office equipment parts due to their excellent properties such as mechanical strength, dimensional stability and flame retardancy. However, at a low temperature of -30°C, it is sufficient as a material for outdoor electric/electronic storage boxes such as information communication boxes that require extremely high impact properties and thin flame retardant properties, and junction boxes for solar power generation. performance is not obtained. Polycarbonate-polydiorganosiloxane copolymer resin, which is a polycarbonate-based material, is known as a resin material having high low-temperature impact resistance. Polycarbonate-polydiorganosiloxane copolymer resins are superior to conventional polycarbonate resins in terms of flame retardancy and low-temperature impact resistance, but their poor heat resistance limits their use in regions with extreme temperature differences. On the other hand, in order to obtain high heat resistance, there is a method of blending a polyarylate resin with a polycarbonate resin (Patent Documents 1 and 2). However, these documents do not describe that high heat resistance and low temperature impact resistance can be obtained by blending an appropriate amount of a polyarylate resin with a polycarbonate-polydiorganosiloxane copolymer resin.

JP 2017-125187 A JP 2007-119523 A

An object of the present invention is to provide a thermoplastic resin composition having good low-temperature impact properties and heat resistance.

The inventors of the present invention have made intensive studies to achieve the above object, and found that by blending an appropriate amount of a polyarylate resin in a polycarbonate-polydiorganosiloxane copolymer resin, good low-temperature impact resistance and heat resistance can be obtained. After discovering that a thermoplastic resin composition can be obtained, the present invention was completed through extensive studies.
The present invention will be specifically described below.

<A component: polycarbonate-polydiorganosiloxane copolymer resin>
The resin composition of the present invention contains a polycarbonate-polydiorganosiloxane copolymer resin as component A. If a polycarbonate resin other than the polycarbonate-polydiorganosiloxane copolymer resin is used as component A, satisfactory low-temperature impact resistance cannot be obtained. The polycarbonate-polydiorganosiloxane copolymer resin of the present invention is a copolymer resin comprising a polycarbonate block represented by the following general formula (1) and a polydiorganosiloxane block represented by the following general formula (3).

[In the above general formula (1), R ¹ and R ² are each independently a hydrogen atom, a halogen atom, an alkyl group having 1 to 18 carbon atoms, an alkoxy group having 1 to 18 carbon atoms, cycloalkyl group having 20 carbon atoms, cycloalkoxy group having 6 to 20 carbon atoms, alkenyl group having 2 to 10 carbon atoms, aryl group having 6 to 14 carbon atoms, aryloxy group having 6 to 14 carbon atoms, carbon atom represents a group selected from the group consisting of an aralkyl group having 7 to 20 carbon atoms, an aralkyloxy group having 7 to 20 carbon atoms, a nitro group, an aldehyde group, a cyano group and a carboxyl group; a and b are each an integer of 1 to 4, and W is at least one group selected from the group consisting of a single bond or a group represented by the following general formula (2). ]

(In general formula (2) above, R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ , R ¹⁶ , R ¹⁷ and R ¹⁸ are each independently a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, a carbon represents a group selected from the group consisting of an aryl group having 6 to 14 atoms and an aralkyl group having 7 to 20 carbon atoms; R ¹⁹ and R ²⁰ each independently represents a hydrogen atom, a halogen atom, or a an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, a cycloalkyl group having 6 to 20 carbon atoms, a cycloalkoxy group having 6 to 20 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, and 6 carbon atoms. an aryl group of up to 14, an aryloxy group of 6 to 10 carbon atoms, an aralkyl group of 7 to 20 carbon atoms, an aralkyloxy group of 7 to 20 carbon atoms, a nitro group, an aldehyde group, a cyano group and a carboxyl group represents a group selected from the group consisting of, when there are more than one, they may be the same or different, c is an integer of 1 to 10, and d is an integer of 4 to 7.)]

[In the general formula (3), R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ and R ⁸ are each independently a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, or a substituted group having 6 to 12 carbon atoms. or an unsubstituted aryl group, R ⁹ and R ¹⁰ are each independently a hydrogen atom, a halogen atom, an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, e and f are integers of 1 to 4, p is a natural number, q is 0 or a natural number, and p+q is a natural number of 4 or more and 150 or less. X is a divalent aliphatic group having 2 to 8 carbon atoms. ]

Examples of the dihydric phenol (I) from which the carbonate constitutional unit represented by the general formula (1) is derived include 4,4′-dihydroxybiphenyl, bis(4-hydroxyphenyl)methane, 1,1-bis(4 -hydroxyphenyl)ethane, 1,1-bis(4-hydroxyphenyl)-1-phenylethane, 2,2-bis(4-hydroxyphenyl)propane, 2,2-bis(4-hydroxy-3-methylphenyl ) propane, 1,1-bis(4-hydroxyphenyl)-3,3,5-trimethylcyclohexane, 2,2-bis(4-hydroxy-3,3′-biphenyl)propane, 2,2-bis(4 -hydroxy-3-isopropylphenyl)propane, 2,2-bis(3-t-butyl-4-hydroxyphenyl)propane, 2,2-bis(4-hydroxyphenyl)butane, 2,2-bis(4- hydroxyphenyl)octane, 2,2-bis(3-bromo-4-hydroxyphenyl)propane, 2,2-bis(3,5-dimethyl-4-hydroxyphenyl)propane, 2,2-bis(3-cyclohexyl -4-hydroxyphenyl)propane, 1,1-bis(3-cyclohexyl-4-hydroxyphenyl)cyclohexane, bis(4-hydroxyphenyl)diphenylmethane, 9,9-bis(4-hydroxyphenyl)fluorene, 9,9 -bis(4-hydroxy-3-methylphenyl)fluorene, 1,1-bis(4-hydroxyphenyl)cyclohexane, 1,1-bis(4-hydroxyphenyl)cyclopentane, 4,4'-dihydroxydiphenyl- ter, 4,4'-dihydroxy-3,3'-dimethyldiphenyl ether, 4,4'-sulfonyldiphenol, 4,4'-dihydroxydiphenyl sulfoxide, 4,4'-dihydroxydiphenyl sulfide, 2,2 '-dimethyl-4,4'-sulfonyldiphenol, 4,4'-dihydroxy-3,3'-dimethyldiphenyl sulfoxide, 4,4'-dihydroxy-3,3'-dimethyldiphenyl sulfide, 2,2'- Diphenyl-4,4'-sulfonyldiphenol, 4,4'-dihydroxy-3,3'-diphenyldiphenyl sulfoxide, 4,4'-dihydroxy-3,3'-diphenyldiphenyl sulfide, 1,3-bis{2 -(4-hydroxyphenyl)propyl}benzene, 1,4-bis{2-(4-hydroxyphenyl)propyl}ben Zen, 1,4-bis(4-hydroxyphenyl)cyclohexane, 1,3-bis(4-hydroxyphenyl)cyclohexane, 4,8-bis(4-hydroxyphenyl)tricyclo[5.2.1.02,6 ] decane, 4,4′-(1,3-adamantanediyl)diphenol, 1,3-bis(4-hydroxyphenyl)-5,7-dimethyladamantane and the like.

Among others, 1,1-bis(4-hydroxyphenyl)-1-phenylethane, 2,2-bis(4-hydroxyphenyl)propane, 2,2-bis(4-hydroxy-3-methylphenyl)propane, 1,1-bis(4-hydroxyphenyl)cyclohexane, 1,1-bis(4-hydroxyphenyl)-3,3,5-trimethylcyclohexane, 4,4'-sulfonyldiphenol, 2,2'-dimethyl- 4,4′-sulfonyldiphenol, 9,9-bis(4-hydroxy-3-methylphenyl)fluorene, 1,3-bis{2-(4-hydroxyphenyl)propyl}benzene, 1,4-bis{ 2-(4-Hydroxyphenyl)propyl}benzene is preferred, especially 2,2-bis(4-hydroxyphenyl)propane, 1,1-bis(4-hydroxyphenyl)cyclohexane (BPZ), 4,4′- Sulfonyldiphenol, 9,9-bis(4-hydroxy-3-methylphenyl)fluorene are preferred. Among them, 2,2-bis(4-hydroxyphenyl)propane, which has excellent strength and good durability, is most preferable. Moreover, these may be used alone or in combination of two or more.

In the carbonate structural unit represented by the general formula (3), R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ and R ⁸ are each independently preferably a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. , or a substituted or unsubstituted aryl group having 6 to 12 carbon atoms, preferably a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or a phenyl group. R ⁹ and R ¹⁰ are each independently preferably a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, particularly preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. As the dihydroxyaryl-terminated polydiorganosiloxane (II) from which the carbonate structural unit represented by the general formula (3) is derived, for example, compounds represented by the following general formula (I) are preferably used.

p+q is preferably 4 to 120, more preferably 30 to 120, even more preferably 30 to 100, and most preferably 30 to 60.

Next, a method for producing the above polycarbonate-polydiorganosiloxane copolymer resin will be described below. By reacting dihydric phenol (I) with a chloroformate-forming compound such as phosgene or a chloroformate of dihydric phenol (I) in a mixture of a water-insoluble organic solvent and an alkaline aqueous solution, A mixed solution of chloroformate compounds is prepared comprising a chloroformate of dihydric phenol (I) and/or a carbonate oligomer of dihydric phenol (I) having a terminal chloroformate group. Phosgene is preferred as the chloroformate-forming compound.

In producing the chloroformate compound from the dihydric phenol (I), the total amount of the dihydric phenol (I) that induces the carbonate structural unit represented by the general formula (1) may be converted into the chloroformate compound at once. Alternatively, a part thereof may be added as a post-addition monomer to the subsequent interfacial polycondensation reaction as a reaction raw material. The post-addition monomer is added in order to facilitate the subsequent polycondensation reaction, and it is not necessary to add it unless necessary. Although the method of this chloroformate compound-producing reaction is not particularly limited, a method of conducting the reaction in a solvent in the presence of an acid binder is usually preferred. Furthermore, if desired, a small amount of antioxidant such as sodium sulfite and hydrosulfide may be added, preferably. The ratio of the chloroformate-forming compound to be used may be appropriately adjusted in consideration of the stoichiometric ratio (equivalents) of the reaction. When phosgene, which is a suitable chloroformate-forming compound, is used, a method of blowing gasified phosgene into the reaction system can be suitably employed.

Examples of the acid binder include alkali metal hydroxides such as sodium hydroxide and potassium hydroxide, alkali metal carbonates such as sodium carbonate and potassium carbonate, organic bases such as pyridine, and mixtures thereof. is used. The ratio of the acid binder to be used may also be appropriately determined in consideration of the stoichiometric ratio (equivalents) of the reaction in the same manner as described above. Specifically, per 1 mol of dihydric phenol (I) used to form a chloroformate compound of dihydric phenol (I) (usually 1 mol corresponds to 2 equivalents), 2 equivalents or a slightly excessive amount of It is preferred to use an acid binding agent.

As the solvent, solvents inert to various reactions, such as those used in the production of known polycarbonates, may be used singly or as a mixed solvent. Representative examples include hydrocarbon solvents such as xylene, and halogenated hydrocarbon solvents such as methylene chloride and chlorobenzene. Halogenated hydrocarbon solvents such as methylene chloride are particularly preferred.

The pressure in the reaction for producing the chloroformate compound is not particularly limited and may be normal pressure, increased pressure or reduced pressure, but it is usually advantageous to carry out the reaction under normal pressure. The reaction temperature is selected from the range of -20°C to 50°C. In many cases, the reaction generates heat, so cooling with water or ice is desirable. Although the reaction time depends on other conditions and cannot be defined unconditionally, it is usually carried out in 0.2 to 10 hours. Known interfacial reaction conditions can be used for the pH range in the production reaction of the chloroformate compound, and the pH is usually adjusted to 10 or higher.

In the preparation of the polycarbonate-polydiorganosiloxane copolymer resin of the present invention, a chloroformate of dihydric phenol (I) and a chloroformate containing a carbonate oligomer of dihydric phenol (I) having terminal chloroformate groups are thus used. After preparing the mixed solution of the formate compound, while stirring the mixed solution, dihydroxyaryl-terminated polydiorganosiloxane (II) that induces the carbonate structural unit represented by the general formula (3) is charged for preparing the mixed solution. by adding at a rate of 0.01 mol/min or less per 1 mol of the dihydric phenol (I) added, and interfacial polycondensation of the dihydroxyaryl-terminated polydiorganosiloxane (II) and the chloroformate compound , to obtain a polycarbonate-polydiorganosiloxane copolymer resin.

The polycarbonate-polydiorganosiloxane copolymer resin can be made into a branched polycarbonate-polydiorganosiloxane copolymer resin by using a branching agent together with a dihydric phenol compound. Examples of trifunctional or higher polyfunctional aromatic compounds used in such branched polycarbonate resins include phloroglucine, phloroglucide, or 4,6-dimethyl-2,4,6-tris(4-hydroxydiphenyl)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-[ trisphenols such as 1,1-bis(4-hydroxyphenyl)ethyl]benzene}-α,α-dimethylbenzylphenol, tetra(4-hydroxyphenyl)methane, bis(2,4-dihydroxyphenyl)ketone, 1, 4-bis(4,4-dihydroxytriphenylmethyl)benzene, or trimellitic acid, pyromellitic acid, benzophenonetetracarboxylic acid and acid chlorides thereof, among others, 1,1,1-tris(4-hydroxy Phenyl)ethane and 1,1,1-tris(3,5-dimethyl-4-hydroxyphenyl)ethane are preferred, and 1,1,1-tris(4-hydroxyphenyl)ethane is particularly preferred.

Even if the method for producing such a branched polycarbonate-polydiorganosiloxane copolymer resin includes a branching agent in the mixed solution during the production reaction of the chloroformate compound, interfacial polycondensation after the production reaction is completed. A method in which a branching agent is added during the reaction may be used. The ratio of carbonate structural units derived from the branching agent is preferably 0.005 to 1.5 mol%, more preferably 0.01 to 1.2 mol%, in the total amount of carbonate structural units constituting the copolymer resin, Especially preferred is 0.05 to 1.0 mol %. The amount of such branched structures can be calculated by ¹ H-NMR measurement.

The pressure in the system in the polycondensation reaction can be any of reduced pressure, normal pressure, or increased pressure. The reaction temperature is selected from the range of −20 to 50° C. In many cases, heat is generated with polymerization, so water cooling or ice cooling is desirable. The reaction time varies depending on other conditions such as the reaction temperature and cannot be generally defined, but is usually 0.5 to 10 hours. In some cases, the obtained polycarbonate-polydiorganosiloxane copolymer resin is appropriately subjected to physical treatment (mixing, fractionation, etc.) and/or chemical treatment (polymer reaction, cross-linking treatment, partial decomposition treatment, etc.) to achieve the desired reduction. It can also be obtained as a polycarbonate-polydiorganosiloxane copolymer resin with a viscosity of [η _SP /c]. The resulting reaction product (crude product) is subjected to various post-treatments such as known separation and purification methods, and can be recovered as a polycarbonate-polydiorganosiloxane copolymer resin of desired purity (purity).

The content of the polydiorganosiloxane block represented by the following general formula (4) contained in the above general formula (3) is 1.0 to 10.0% by weight based on the total weight of the polycarbonate resin composition. is preferred, and 1.0 to 8.0% by weight is more preferred.

(In general formula (4) above, R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ and R ⁸ are each independently a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, or a substituted group having 6 to 12 carbon atoms. or an unsubstituted aryl group, p is a natural number, q is 0 or a natural number, and p+q is a natural number of 4 or more and 150 or less.)

In producing the thermoplastic resin composition of the present invention, the viscosity average molecular weight (M) of the polycarbonate-polydiorganosiloxane copolymer resin is not particularly limited, but is preferably 1.8×10 ⁴ to 4.0×10 ⁴ . , more preferably 2.0×10 ⁴ to 3.5×10 ⁴ , still more preferably 2.2×10 ⁴ to 3.0×10 ⁴ . A polycarbonate-polydiorganosiloxane copolymer resin having a viscosity-average molecular weight of less than 1.8×10 ⁴ may not provide good mechanical properties. On the other hand, a resin composition obtained from a polycarbonate-polydiorganosiloxane copolymer resin having a viscosity-average molecular weight exceeding 4.0×10 ⁴ is inferior in versatility due to poor fluidity during injection molding.

The viscosity-average molecular weight referred to in the present invention is obtained from a solution of 0.7 g of a polycarbonate-polydiorganosiloxane copolymer resin dissolved in 100 ml of methylene chloride at 20° C. to determine the specific viscosity (η _SP ) calculated by the following formula. using a meter,
Specific viscosity (η _SP ) = (tt ₀ )/t ₀
[t ₀ is the number of seconds the methylene chloride falls, t is the number of seconds the sample solution falls]
The viscosity-average molecular weight M is calculated from the determined specific viscosity (η _SP ) by the following formula.
η _SP /c=[η]+0.45×[η] ² c (where [η] is the intrinsic viscosity)
[η]=1.23×10 ⁻⁴ M ^0.83
c=0.7

<B component: polyarylate resin>
The polyarylate resin used as the B component of the present invention may be obtained by a conventional method from a dihydric phenol or a derivative thereof and an aromatic dicarboxylic acid or a derivative thereof. 2,2-bis(4-hydroxyphenyl)propane, 1,1-bis(4-hydroxyphenyl)-3,3,5-trimethylcyclohexane, 4,4-dihydroxy-biphenyl, bis(4-hydroxyphenyl)methane , 2,2-bis(4-hydroxy-3,5-dimethylphenyl)propane, 2,2-bis(4-hydroxy-3,5-dibromophenyl)propane, 2,2-(4-hydroxy-3 -methylphenyl)propane, 4,4'-dihydroxydiphenyl sulfone, 4,4'-dihydroxydiphenyl ether, 4,4'-dihydroxydiphenyl sulfide and the like, and two or more of them may be used in combination.

Any aromatic dicarboxylic acid may be used as long as it reacts with dihydric phenol to give a satisfactory polymer, and may be used singly or in combination of two or more. Preferred aromatic dicarboxylic acids include terephthalic acid and isophthalic acid, and mixtures thereof are particularly preferred for melt processability and overall performance. The mixing ratio of these mixtures does not need to be particularly limited, but terephthalic acid/isophthalic acid = 9/1 to 1/9 (molar ratio) is preferable, especially 7/3 in terms of balance between melt processability and performance. ~3/7 (molar ratio) is preferred.

The polyarylate resin used as component B in the present invention is preferably a copolymer containing polymerized units represented by any one of the following general formulas (5) to (7). When a polyarylate resin that does not contain this structure is used, the impact resistance may deteriorate.

［上記一般式（５）において、ｌ、ｍおよびｎは、ｌ＋ｍ＋ｎ＝１００、ｌ：ｎ＝５０：５０～７０：３０かつ（ｌ＋ｎ）：ｍ＝７５：２５～４０：６０を満足する正の整数である。］

[In the above general formula (5), l, m and n are l + m + n = 100, l: n = 50: 50 to 70: 30 and (l + n): m = 75: 25 to 40: 60. is an integer. ]

［上記一般式（６）において、ｍおよびｎは正の整数であり、ｍ／ｎ＝８／２～２／８である。］

[In the above general formula (6), m and n are positive integers, and m/n=8/2 to 2/8. ]

［上記一般式（７）において、ｎは正の整数である。］

[In the above general formula (7), n is a positive integer. ]

The content of the polyarylate resin used as the B component of the present invention is 1 to 10 parts by weight, preferably 6 to 10 parts by weight, more preferably 8 parts by weight in 100 parts by weight of the resin component consisting of the A component and the B component. ~10 parts by weight. If the content of component B is less than 1 part by weight, excellent heat resistance and low temperature impact properties cannot be obtained, and if it is more than 10 parts by weight, the low temperature impact properties are degraded.

The polyarylate resin used as component B in the present invention preferably has a viscosity average molecular weight of 5,000 to 100,000, more preferably 10,000 to 50,000. If the viscosity-average molecular weight of the polyarylate resin is less than 5,000, the impact properties may deteriorate. On the other hand, if it is higher than 100,000, the fluidity may decrease. The viscosity average molecular weight of the polyarylate resin is a value measured by the same method as for the polycarbonate-polyorganosiloxane copolymer resin used as the A component of the present invention.
Examples of commercially available polyarylate resins include "U-100" (trade name), "M-2040" (trade name) and "M-2040H" (trade name) available from Unitika Ltd.

(Other additives)
In the thermoplastic resin composition of the present invention, the additives used for these improvements are advantageously used in order to improve the thermal stability and design properties. These additives will be specifically described below.

(I) Thermal Stabilizer The thermoplastic resin composition of the present invention may contain various known stabilizers. Examples of stabilizers include phosphorus stabilizers and hindered phenol antioxidants.

(i) Phosphorus-Based Stabilizer The thermoplastic resin composition of the present invention preferably contains a phosphorus-based stabilizer to the extent that it does not promote hydrolyzability. Such phosphorus-based stabilizers improve thermal stability during production or molding, and improve mechanical properties, color, and molding stability. Phosphorous stabilizers include phosphorous acid, phosphoric acid, phosphonous acid, phosphonic acid and their esters, and tertiary phosphines. Specific examples of phosphite compounds include triphenylphosphite, tris(nonylphenyl)phosphite, tridecylphosphite, trioctylphosphite, trioctadecylphosphite, didecylmonophenylphosphite, dioctylmonophenyl Phosphite, diisopropylmonophenylphosphite, monobutyldiphenylphosphite, monodecyldiphenylphosphite, monooctyldiphenylphosphite, 2,2-methylenebis(4,6-di-tert-butylphenyl)octylphosphite, 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, distearylpentaerythritol diphosphite, bis(2,4-di-tert-butylphenyl)pentaerythritol diphosphite, bis(2,6-di-tert-butyl -4-methylphenyl)pentaerythritol diphosphite, bis(2,6-di-tert-butyl-4-ethylphenyl)pentaerythritol diphosphite, phenylbisphenol A pentaerythritol diphosphite, bis(nonylphenyl)penta Erythritol diphosphite, dicyclohexylpentaerythritol diphosphite and the like. Furthermore, as other phosphite compounds, those having a cyclic structure which react with dihydric phenols can also be used. For example, 2,2′-methylenebis(4,6-di-tert-butylphenyl)(2,4-di-tert-butylphenyl)phosphite, 2,2′-methylenebis(4,6-di-tert- butylphenyl)(2-tert-butyl-4-methylphenyl)phosphite, 2,2′-methylenebis(4-methyl-6-tert-butylphenyl)(2-tert-butyl-4-methylphenyl)phosphite , 2,2′-ethylidenebis(4-methyl-6-tert-butylphenyl)(2-tert-butyl-4-methylphenyl)phosphite. Phosphate compounds include tributyl phosphate, trimethyl phosphate, tricresyl phosphate, triphenyl phosphate, trichlorophenyl phosphate, triethyl phosphate, diphenyl cresyl phosphate, diphenyl monoorthoxenyl phosphate, tributoxyethyl phosphate, dibutyl phosphate, dioctyl phosphate, Diisopropyl phosphate and the like can be mentioned, and triphenyl phosphate and trimethyl phosphate are preferred.

Phosphonite compounds include tetrakis(2,4-di-tert-butylphenyl)-4,4'-biphenylenediphosphonite, tetrakis(2,4-di-tert-butylphenyl)-4,3'-biphenylenedi Phosphonite, Tetrakis(2,4-di-tert-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′-biphenylenediphosphonite, bis (2,4-di-tert-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) -3-phenyl-phenylphosphonite and the like, preferably tetrakis(di-tert-butylphenyl)-biphenylenediphosphonite, bis(di-tert-butylphenyl)-phenyl-phenylphosphonite, tetrakis(2, 4-di-tert-butylphenyl)-biphenylenediphosphonite, bis(2,4-di-tert-butylphenyl)-phenyl-phenylphosphonite are more preferred. Such a phosphonite compound can be used in combination with a phosphite compound having an aryl group substituted with two or more alkyl groups, and is therefore preferable. Phosphonate compounds include dimethyl benzenephosphonate, diethyl benzenephosphonate, dipropyl benzenephosphonate, and the like. Tertiary phosphines include triethylphosphine, tripropylphosphine, tributylphosphine, trioctylphosphine, triamylphosphine, dimethylphenylphosphine, dibutylphenylphosphine, diphenylmethylphosphine, diphenyloctylphosphine, triphenylphosphine, and tri-p-tolyl. Examples include phosphine, trinaphthylphosphine, and diphenylbenzylphosphine. A particularly preferred tertiary phosphine is triphenylphosphine. The phosphorus-based stabilizers can be used singly or in combination of two or more. Among the above phosphorus-based stabilizers, it is preferable to incorporate an alkyl phosphate compound represented by trimethyl phosphate. In addition, the combination use of such an alkyl phosphate compound with a phosphite compound and/or a phosphonite compound is also a preferred embodiment.

The content of the alkyl phosphate compound is preferably 0.01 to 2 parts by weight, more preferably 0.03 to 1 part by weight, per 100 parts by weight of components A and B combined. If the content of the alkyl phosphate compound is less than 0.01 parts by weight, the effect of sufficiently suppressing the decrease in the molecular weight of the resin composition may not be obtained. May have adverse effects.

(ii) Hindered Phenolic Stabilizer The thermoplastic resin composition of the present invention may contain a hindered phenol stabilizer. Such blending exhibits an effect of suppressing deterioration of hue during molding and deterioration of hue during long-term use, for example. Examples of hindered phenol stabilizers include α-tocopherol, butylhydroxytoluene, sinapyl alcohol, vitamin E, n-octadecyl-β-(4′-hydroxy-3′,5′-di-tert-butylfer) propionate, 2-tert-butyl-6-(3′-tert-butyl-5′-methyl-2′-hydroxybenzyl)-4-methylphenyl acrylate, 2,6-di-tert-butyl-4-(N ,N-dimethylaminomethyl)phenol, 3,5-di-tert-butyl-4-hydroxybenzylphosphonate diethyl ester, 2,2′-methylenebis(4-methyl-6-tert-butylphenol), 2,2′- methylenebis(4-ethyl-6-tert-butylphenol), 4,4'-methylenebis(2,6-di-tert-butylphenol), 2,2'-methylenebis(4-methyl-6-cyclohexylphenol), 2, 2′-dimethylene-bis(6-α-methyl-benzyl-p-cresol) 2,2′-ethylidene-bis(4,6-di-tert-butylphenol), 2,2′-butylidene-bis(4- methyl-6-tert-butylphenol), 4,4′-butylidenebis(3-methyl-6-tert-butylphenol), triethylene glycol-N-bis-3-(3-tert-butyl-4-hydroxy-5- methylphenyl)propionate, 1,6-hexanediol bis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], bis[2-tert-butyl-4-methyl 6-(3 -tert-butyl-5-methyl-2-hydroxybenzyl)phenyl]terephthalate, 3,9-bis{2-[3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propionyloxy]-1 ,1,-dimethylethyl}-2,4,8,10-tetraoxaspiro[5,5]undecane, 4,4′-thiobis(6-tert-butyl-m-cresol), 4,4′-thiobis (3-methyl-6-tert-butylphenol), 2,2′-thiobis(4-methyl-6-tert-butylphenol), bis(3,5-di-tert-butyl-4-hydroxybenzyl)sulfide, 4 , 4′-di-thiobis(2,6-di-tert-butylphenol), 4,4′-tri-thiobis(2,6-di-tert-butylphenol mol), 2,2-thiodiethylenebis-[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], 2,4-bis(n-octylthio)-6-(4- Hydroxy-3′,5′-di-tert-butylanilino)-1,3,5-triazine, N,N′-hexamethylenebis-(3,5-di-tert-butyl-4-hydroxyhydrocinnamide) , N,N′-bis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionyl]hydrazine, 1,1,3-tris(2-methyl-4-hydroxy-5-tert- Butylphenyl)butane, 1,3,5-trimethyl-2,4,6-tris(3,5-di-tert-butyl-4-hydroxybenzyl)benzene, tris(3,5-di-tert-butyl- 4-hydroxyphenyl)isocyanurate, tris(3,5-di-tert-butyl-4-hydroxybenzyl)isocyanurate, 1,3,5-tris(4-tert-butyl-3-hydroxy-2,6- dimethylbenzyl)isocyanurate, 1,3,5-tris-2[3(3,5-di-tert-butyl-4-hydroxyphenyl)propionyloxy]ethylisocyanurate, and tetrakis[methylene-3-(3′, 5′-di-tert-butyl-4-hydroxyphenyl)propionate]methane and the like are exemplified. All of these are readily available. The above hindered phenol stabilizers may be used alone or in combination of two or more. The amount of the phosphorus-based stabilizer and the hindered phenol-based stabilizer other than the alkyl phosphate compound is preferably 0.0001 to 1 part by weight, more preferably 0, per 100 parts by weight of the total of components A and B. 0.001 to 0.5 parts by weight, more preferably 0.005 to 0.3 parts by weight.

(iii) Thermal Stabilizers Other Than Above The thermoplastic resin composition of the present invention may contain other thermal stabilizers than the phosphorus-based stabilizer and the hindered phenol-based stabilizer. Such other heat stabilizers are preferably lactone-based stabilizers represented by reaction products of 3-hydroxy-5,7-di-tert-butyl-furan-2-one and o-xylene. be done. Details of such stabilizers are described in JP-A-7-233160. Such a compound is available commercially as Irganox HP-136 (trademark, CIBA SPECIALTY CHEMICALS). Further, stabilizers obtained by mixing said compound with various phosphite compounds and hindered phenol compounds are commercially available. For example, Irganox HP-2921 manufactured by the above company is a suitable example. The amount of the lactone stabilizer is preferably 0.0005 to 0.05 parts by weight, more preferably 0.001 to 0.03 parts by weight, based on 100 parts by weight of the total of components A and B. be. Other stabilizers include sulfur-containing stabilizers such as pentaerythritol tetrakis (3-mercaptopropionate), pentaerythritol tetrakis (3-laurylthiopropionate), and glycerol-3-stearylthiopropionate. exemplified. The amount of the sulfur-containing stabilizer to be blended is preferably 0.001 to 0.1 parts by weight, more preferably 0.01 to 0.08 parts by weight, based on 100 parts by weight of components A and B in total. be. The thermoplastic resin composition of the present invention may optionally contain an epoxy compound. Such epoxy compounds are blended for the purpose of suppressing mold corrosion, and basically all those having epoxy functional groups can be applied. Specific examples of preferred epoxy compounds include 3,4-epoxycyclohexylmethyl-3',4'-epoxycyclohexylcarboxylate, 2,2-bis(hydroxymethyl)-1-butanol of 1,2-epoxy-4- (2-oxiranyl)cyclohexane adducts, copolymers of methyl methacrylate and glycidyl methacrylate, copolymers of styrene and glycidyl methacrylate, and the like. The amount of the epoxy compound to be added is preferably 0.003 to 0.2 parts by weight, more preferably 0.004 to 0.15 parts by weight, based on 100 parts by weight of the components A and B in total. , more preferably 0.005 to 0.1 parts by weight.

(II) Flame Retardant The thermoplastic resin composition of the present invention may contain a flame retardant. Incorporation of such compounds provides improved flame retardancy, but also provides, depending on the properties of each compound, improved antistatic properties, fluidity, stiffness, and thermal stability, for example. Examples of such flame retardants include (i) organic metal salt flame retardants (e.g., organic sulfonic acid alkali (earth) metal salts, organic borate metal salt flame retardants, and organic stannate metal salt flame retardants), ( ii) organic phosphorus-based flame retardants (e.g., organic group-containing monophosphate compounds, phosphate oligomeric compounds, phosphonate oligomeric compounds, phosphonitrile oligomeric compounds, phosphonic acid amide compounds, etc.), (iii) silicone-based flame retardants consisting of silicone compounds and (iv) fibrillated PTFE, among which organic metal salt-based flame retardants and organic phosphorus-based flame retardants are preferred. These may be used alone or in combination of two.

(i) Organometallic salt-based flame retardant The organometallic salt compound is an alkali (earth) metal salt of an organic acid having 1 to 50 carbon atoms, preferably 1 to 40 carbon atoms, preferably an alkali (earth) metal organic sulfonate. is preferably The organic sulfonic acid alkali (earth) metal salts include fluorine-substituted alkyl sulfones such as metal salts of perfluoroalkyl sulfonic acids having 1 to 10 carbon atoms, preferably 2 to 8 carbon atoms, with alkali metals or alkaline earth metals. Metal salts of acids and metal salts of aromatic sulfonic acids having 7 to 50 carbon atoms, preferably 7 to 40 carbon atoms, with alkali metals or alkaline earth metals are included. Alkali metals that make up the metal salt include lithium, sodium, potassium, rubidium and cesium, and alkaline earth metals include beryllium, magnesium, calcium, strontium and barium. Alkali metals are more preferred. Among such alkali metals, rubidium and cesium, which have larger ionic radii, are suitable when the demand for transparency is higher. It may be disadvantageous. On the other hand, metals with smaller ionic radii, such as lithium and sodium, may be disadvantageous in terms of flame retardancy. Although the alkali metal in the alkali metal sulfonate can be properly used in consideration of these factors, the potassium sulfonate is most suitable because of its well-balanced properties in all respects. Such potassium salts and alkali metal sulfonate salts of other alkali metals can also be used in combination.

Specific examples of perfluoroalkylsulfonic acid alkali metal salts include potassium trifluoromethanesulfonate, potassium perfluorobutanesulfonate, potassium perfluorohexanesulfonate, potassium perfluorooctane sulfonate, sodium pentafluoroethanesulfonate, perfluoro Sodium butanesulfonate, sodium perfluorooctanesulfonate, lithium trifluoromethanesulfonate, lithium perfluorobutanesulfonate, lithium perfluoroheptanesulfonate, cesium trifluoromethanesulfonate, cesium perfluorobutanesulfonate, perfluorooctanesulfonic acid Cesium, cesium perfluorohexanesulfonate, rubidium perfluorobutanesulfonate, rubidium perfluorohexanesulfonate, and the like can be mentioned, and these can be used alone or in combination of two or more. The perfluoroalkyl group preferably has 1 to 18 carbon atoms, more preferably 1 to 10 carbon atoms, and still more preferably 1 to 8 carbon atoms.

Among these, potassium perfluorobutanesulfonate is particularly preferred. The alkali (earth) metal salt of perfluoroalkylsulfonate, which is an alkali metal, usually contains not a small amount of fluoride ions (F-). Since the presence of such fluoride ions can be a factor in deteriorating flame retardancy, it is preferable to reduce them as much as possible. The proportion of such fluoride ions can be measured by ion chromatography. The content of fluoride ions is preferably 100 ppm or less, more preferably 40 ppm or less, and particularly preferably 10 ppm or less. Moreover, it is preferable that it is 0.2 ppm or more in terms of production efficiency. Such an alkali (earth) metal perfluoroalkylsulfonate having a reduced amount of fluoride ions is produced by a known production method and is contained in raw materials for producing a fluorine-containing organic metal salt. A method of reducing the amount of fluoride ions, a method of removing hydrogen fluoride and the like obtained by the reaction by gas generated during the reaction or by heating, and a purification method such as recrystallization and reprecipitation for the production of fluorine-containing organometallic salts. can be produced by a method of reducing the amount of fluoride ions using In particular, since organometallic salt-based flame retardants are relatively soluble in water, ion-exchanged water, especially water satisfying an electrical resistance value of 18 MΩ·cm or more, that is, an electrical conductivity of about 0.55 μS / cm or less, is used. It is also preferable to manufacture by a step of dissolving at a temperature higher than room temperature, washing, and then cooling to recrystallize.

Specific examples of the alkali (earth) metal aromatic sulfonate include disodium diphenylsulfide-4,4′-disulfonate, dipotassium diphenylsulfide-4,4′-disulfonate, potassium 5-sulfoisophthalate, Sodium 5-sulfoisophthalate, polysodium polyethylene terephthalate polysulfonate, calcium 1-methoxynaphthalene-4-sulfonate, disodium 4-dodecylphenyl ether disulfonate, poly(2,6-dimethylphenylene oxide) polysodium polysulfonate , poly(1,3-phenylene oxide) polysodium polysulfonate, poly(1,4-phenylene oxide) polysodium polysulfonate, poly(2,6-diphenylphenylene oxide) polypotassium polysulfonate, poly(2-fluoro- 6-Butylphenylene oxide) lithium polysulfonate, potassium benzenesulfonate sulfonate, sodium benzenesulfonate, strontium benzenesulfonate, magnesium benzenesulfonate, dipotassium p-benzenedisulfonate, dipotassium p-benzenedisulfonate, dipotassium naphthalene-2,6-disulfonate, biphenyl -3,3'-calcium disulfonate, sodium diphenylsulfone-3-sulfonate, potassium diphenylsulfone-3-sulfonate, dipotassium diphenylsulfone-3,3'-disulfonate, diphenylsulfone-3,4'-disulfonic acid dipotassium, sodium α,α,α-trifluoroacetophenone-4-sulfonate, dipotassium benzophenone-3,3′-disulfonate, disodium thiophene-2,5-disulfonate, dipotassium thiophene-2,5-disulfonate, Calcium thiophene-2,5-disulfonate, sodium benzothiophene sulfonate, potassium diphenyl sulfoxide-4-sulfonate, formalin condensate of sodium naphthalenesulfonate, and formalin condensate of sodium anthracene sulfonate. can. Of these alkali (earth) metal salts of aromatic sulfonates, potassium salts are particularly preferred. Among these alkali (earth) metal salts of aromatic sulfonates, potassium diphenylsulfone-3-sulfonate and dipotassium diphenylsulfone-3,3'-disulfonate are preferred, and mixtures thereof (the former and the latter weight ratio of 15/85 to 30/70).

Preferred examples of organic metal salts other than alkali (earth) metal sulfonates include alkali (earth) metal salts of sulfate esters and alkali (earth) metal salts of aromatic sulfonamides. As alkali (earth) metal salts of sulfate esters, mention may be made in particular of alkali (earth) metal salts of sulfate esters of monohydric and/or polyhydric alcohols, such monohydric and/or polyhydric alcohols Sulfuric acid esters include methyl sulfate, ethyl sulfate, lauryl sulfate, hexadecyl sulfate, polyoxyethylene alkylphenyl ether sulfate, pentaerythritol mono-, di-, tri-, tetra-sulfate, lauric acid monoglyceride sulfate esters, palmitate monoglyceride sulfates, stearate monoglyceride sulfates, and the like. The alkali (earth) metal salts of these sulfate esters are preferably alkali (earth) metal salts of lauryl sulfate. Alkali (earth) metal salts of aromatic sulfonamides include, for example, saccharin, N-(p-tolylsulfonyl)-p-toluenesulfimide, N-(N'-benzylaminocarbonyl)sulfanilimide, and N-( and alkali (earth) metal salts of phenylcarboxyl)sulfanilimide. The content of the organometallic salt-based flame retardant is preferably 0.001 to 1 part by weight, more preferably 0.005 to 0.5 part by weight, and further It is preferably 0.01 to 0.3 parts by weight, particularly preferably 0.03 to 0.15 parts by weight.

(ii) Organic Phosphorus Flame Retardant As the organic phosphorus flame retardant, aryl phosphate compounds and phosphazene compounds are preferably used. Since these organic phosphorus flame retardants have a plasticizing effect, they are advantageous in terms of improving moldability. Various phosphate compounds known as conventional flame retardants can be used as the aryl phosphate compound, and more preferably, one or more phosphate compounds represented by the following general formula (8) can be mentioned.

(However, M in the above formula represents a divalent organic group derived from a dihydric phenol, and Ar ¹ , Ar ² , Ar ³ and Ar ⁴ are monovalent organic groups derived from a monohydric phenol, respectively. a, b, c and d are each independently 0 or 1, m is an integer of 0 to 5, and in the case of a mixture of phosphate esters with different polymerization degrees m, m is the average value and values from 0 to 5.)

The phosphate compound of the above formula may be a mixture of compounds having different m numbers, and in such mixtures the average m number is preferably between 0.5 and 1.5, more preferably between 0.8 and 1.5. 2, more preferably 0.95 to 1.15, particularly preferably 1 to 1.14.

Suitable specific examples of dihydric phenols from which M is derived include hydroquinone, resorcinol, bis(4-hydroxydiphenyl)methane, bisphenol A, dihydroxydiphenyl, dihydroxynaphthalene, bis(4-hydroxyphenyl)sulfone, bis(4 -hydroxyphenyl)ketone, and bis(4-hydroxyphenyl)sulfide, among which resorcinol, bisphenol A, and dihydroxydiphenyl are preferred.

Preferable specific examples of monohydric phenols from which Ar ¹ , Ar ² , Ar ³ and Ar ⁴ are derived include phenol, cresol, xylenol, isopropylphenol, butylphenol and p-cumylphenol. is phenol, and 2,6-dimethylphenol.

Such monohydric phenol may be substituted with a halogen atom, and specific examples of phosphate compounds having a group derived from the monohydric phenol include tris(2,4,6-tribromophenyl)phosphate and tris(2,4,6-tribromophenyl)phosphate. Examples include (2,4-dibromophenyl)phosphate, tris(4-bromophenyl)phosphate and the like.

On the other hand, specific examples of phosphate compounds not substituted with halogen atoms include monophosphate compounds such as triphenyl phosphate and tri(2,6-xylyl)phosphate, and resorcinol bisdi(2,6-xylyl)phosphate). Preferred are phosphate oligomers based on 4,4-dihydroxydiphenyl bis(diphenyl phosphate), and phosphate ester oligomers based on bisphenol A bis(diphenyl phosphate). indicates that a small amount of other components with different polymerization degrees may be included, more preferably the component of m = 1 in the above formula [8] is 80% by weight or more, more preferably 85% by weight or more, and still more preferably 90% by weight or more).

Various phosphazene compounds known as conventional flame retardants can be used as the phosphazene compound, but phosphazene compounds represented by the following general formulas (9) and (10) are preferable.

（式中、Ｘ^１、Ｘ^２、Ｘ^３、Ｘ^４は、水素、水酸基、アミノ基、またはハロゲン原子を含まない有機基を表す。また、ｒは３～１０の整数を表す。）

(Wherein, X ¹ , X ² , X ³ and X ⁴ represent hydrogen, hydroxyl group, amino group, or an organic group containing no halogen atom, and r represents an integer of 3 to 10.)

Examples of the halogen-free organic groups represented by X ¹ , X ² , X ³ and X ⁴ in the formulas (9) and (10) include an alkoxy group, a phenyl group, an amino group and an allyl group. is mentioned. Among them, a cyclic phosphazene compound represented by the above formula (9) is preferable, and a cyclic phenoxyphosphazene in which X ¹ and X ² in the above formula (9) are phenoxy groups is particularly preferable.

The content of the organic phosphorus-based flame retardant is preferably 1 to 50 parts by weight, more preferably 2 to 30 parts by weight, and 5 to 20 parts by weight with respect to a total of 100 parts by weight of the components A and B. is more preferred. When the amount of the organic phosphorus flame retardant is less than 1 part by weight, it is difficult to obtain the flame retardant effect. may occur.

(iii) Silicone Flame Retardant A silicone compound used as a silicone flame retardant improves flame retardancy through a chemical reaction during combustion. As the compound, various compounds that have been proposed as flame retardants for aromatic polycarbonate resins can be used. When the silicone compound is burned, it combines with itself or with a component derived from the resin to form a structure, or through a reduction reaction during the formation of the structure. considered to be effective.

Therefore, it preferably contains a group that is highly active in such reactions, and more specifically, it preferably contains a predetermined amount of at least one group selected from alkoxy groups and hydrogen (that is, Si—H groups). preferable. The content ratio of such groups (alkoxy group, Si—H group) is preferably in the range of 0.1 to 1.2 mol/100 g, more preferably in the range of 0.12 to 1 mol/100 g, and more preferably 0.15 to 0.15 mol/100 g. A range of 6 mol/100 g is more preferred. Such a ratio can be obtained by measuring the amount of hydrogen or alcohol generated per unit weight of the silicone compound by the alkaline decomposition method. As the alkoxy group, an alkoxy group having 1 to 4 carbon atoms is preferable, and a methoxy group is particularly preferable.

Generally, the structure of a silicone compound is constructed by arbitrarily combining the four types of siloxane units shown below. That is, M units: ( _CH3 )3SiO1/2, H( _CH3 )2SiO1 _{/2 ,} H2( _CH3 ) _{SiO1 /2 ,} ( _CH3 ) ₂ ( _{CH2 =} CH) _{SiO1 /2} , ( _CH3 ) ₂ ( _C6H5 ) _SiO1 / ₂ , ( _CH3 )( _C6H5 )( _CH2 =CH) _{SiO1/2 ,} and other monofunctional siloxane units, D units: ₂ such as ( _CH3 )2SiO, H( _CH3 )SiO, _H2SiO , H _{( C6H5} )SiO, ( _CH3 )( _{CH2 =} CH)SiO, ( _C6H5 ) _2SiO ; Functional siloxane units, T units: ( _CH3 )SiO3/ ₂ , ( _C3H7 )SiO3/ ₂ , HSiO3 _/2 , ( _CH2 =CH)SiO3 _{/ 2} , _{( C6H5} ) Trifunctional siloxane units such as SiO _3/2 , and Q units: tetrafunctional siloxane units represented by SiO ₂ .

Specifically, the structures of silicone compounds used in silicone-based flame retardants include Dn, Tp, MmDn, MmTp, MmQq, MmDnTp, MmDnQq, MmTpQq, MmDnTpQq, DnTp, DnQq, and DnTpQq. Among these, preferred structures of the silicone compounds are MmDn, MmTp, MmDnTp and MmDnQq, and more preferred structures are MmDn or MmDnTp.

Here, the coefficients m, n, p, and q in the formula are integers of 1 or more representing the degree of polymerization of each siloxane unit, and the sum of the coefficients in each formula is the average degree of polymerization of the silicone compound. . The average degree of polymerization is preferably in the range of 3-150, more preferably in the range of 3-80, still more preferably in the range of 3-60, and most preferably in the range of 4-40. It comes to be excellent in flame retardance, so that it is such a suitable range. Furthermore, as described later, silicone compounds containing a predetermined amount of aromatic groups are excellent in transparency and hue. As a result, good reflected light can be obtained. When any of m, n, p, and q is a numerical value of 2 or more, the siloxane unit with that coefficient can be two or more siloxane units having different bonding hydrogen atoms and organic residues. .

The silicone compound may be linear or branched. Also, the organic residue that bonds to the silicon atom preferably has 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms. Specific examples of such organic residues include alkyl groups such as methyl group, ethyl group, propyl group, butyl group, hexyl group and decyl group, cycloalkyl groups such as cyclohexyl group, aryl groups such as phenyl group, and aralkyl groups such as tolyl groups. More preferably, it is an alkyl group, alkenyl group or aryl group having 1 to 8 carbon atoms. As the alkyl group, an alkyl group having 1 to 4 carbon atoms such as methyl group, ethyl group and propyl group is particularly preferred. Furthermore, the silicone compound used as the silicone-based flame retardant preferably contains an aryl group. On the other hand, silane compounds and siloxane compounds used as organic surface treatment agents for titanium dioxide pigments are clearly distinguished from silicone-based flame retardants in their preferred aspects in that they exhibit favorable effects when they do not contain aryl groups. . Silicone compounds used as silicone flame retardants may contain reactive groups other than the Si—H groups and alkoxy groups. Examples of such reactive groups include amino groups, carboxyl groups, epoxy groups, vinyl groups, mercapto groups, and methacryloxy groups.

The content of the silicone-based flame retardant is preferably 0.01 to 20 parts by weight, more preferably 0.5 to 10 parts by weight, and still more preferably 1 to 5 parts by weight with respect to 100 parts by weight of components A and B in total. weight part.

(iv) polytetrafluoroethylene (fibrillated PTFE) having fibril-forming ability
The fibrillated PTFE may be fibrillated PTFE alone or mixed fibrillated PTFE, that is, a polytetrafluoroethylene-based mixture comprising fibrillated PTFE particles and an organic polymer. Fibrillated PTFE has a very high molecular weight and tends to bind PTFE together by an external action such as a shearing force to form a fibrous form. Its number average molecular weight ranges from 1.5 million to tens of millions. Such a lower limit is more preferably 3 million. Such number-average molecular weight is calculated based on the melt viscosity of polytetrafluoroethylene at 380° C., as disclosed in JP-A-6-145520, for example. That is, the fibrillated PTFE has a melt viscosity of 10 ⁷ to 10 ¹³ poise, preferably 10 ⁸ to 10 ¹² poise at 380° C. measured by the method described in the publication. Such PTFE can be used not only in a solid form but also in an aqueous dispersion form. In addition, such fibrillated PTFE improves its dispersibility in resins, and it is also possible to use PTFE mixtures in the form of mixtures with other resins in order to obtain better flame retardancy and mechanical properties.

Further, as disclosed in JP-A-6-145520, those having such a fibrillated PTFE as a core and a low-molecular-weight polytetrafluoroethylene as a shell are also preferably used.
Commercially available products of such fibrillated PTFE include, for example, Teflon (registered trademark) 6J manufactured by Mitsui-DuPont Fluorochemical Co., Ltd., Polyflon MPA FA500 and F-201L manufactured by Daikin Chemical Industries, Ltd., and the like.

Mixed forms of fibrillated PTFE include (1) a method of mixing an aqueous dispersion of fibrillated PTFE and an aqueous dispersion or solution of an organic polymer to co-precipitate to obtain a co-aggregated mixture (JP-A-60-258263; (2) A method of mixing an aqueous dispersion of fibrillated PTFE and dried organic polymer particles (described in JP-A-4-272957). (3) A method in which an aqueous dispersion of fibrillated PTFE and a solution of organic polymer particles are uniformly mixed, and the respective media are simultaneously removed from the mixture (JP-A-06-220210, JP-A-06-220210; 08-188653, etc.), (4) a method of polymerizing a monomer that forms an organic polymer in an aqueous dispersion of fibrillated PTFE (described in JP-A-9-95583, method), and (5) a method of uniformly mixing an aqueous PTFE dispersion and an organic polymer dispersion, further polymerizing a vinyl monomer in the mixed dispersion, and then obtaining a mixture (JP-A-11- 29679) can be used.

Commercial products of fibrillated PTFE in a mixed form include METABLEN typified by "METABLEN A3000" (trade name), "METABLEN A3700" (trade name), and "METABLEN A3800" (trade name) manufactured by Mitsubishi Rayon Co., Ltd. A series, Shine Polymer's SN3300B7 (trade name), and GE Specialty Chemicals' "BLENDEX B449" (trade name) are exemplified.

The ratio of fibrillated PTFE in the mixed form is preferably 1% to 95% by weight, more preferably 10% to 90% by weight, and 20% by weight, based on 100% by weight of the mixture. Weight percent to 80 weight percent is most preferred.
Good dispersibility of the fibrillated PTFE can be achieved when the proportion of the fibrillated PTFE in the mixed form is in this range. The content of the fibrillated PTFE is preferably 0.001 to 0.5 parts by weight, more preferably 0.01 to 0.5 parts by weight, per 100 parts by weight of the total resin component of components A and B. , 0.1 to 0.5 parts by weight are more preferable.

(III) Dyes and Pigments The thermoplastic resin composition of the present invention further contains various dyes and pigments to provide molded articles exhibiting various design properties. The dyes and pigments used in the present invention include perylene dyes, coumarin dyes, thioindigo dyes, anthraquinone dyes, thioxanthone dyes, ferrocyanides such as Prussian blue, perinone dyes, quinoline dyes, quinacridone dyes, Examples include dioxazine dyes, isoindolinone dyes, and phthalocyanine dyes. Furthermore, the thermoplastic resin composition of the present invention can be blended with a metallic pigment to obtain a better metallic color. Aluminum powder is suitable as the metallic pigment. Further, by blending a fluorescent brightening agent or other fluorescent dye that emits light, it is possible to impart a better design effect by making use of the luminescent color.

(IV) Fluorescent brightener In the thermoplastic resin composition of the present invention, the fluorescent brightener is not particularly limited as long as it is used to improve the color tone of the resin or the like to white or bluish white. , benzimidazole-based, benzoxazole-based, naphthalimide-based, rhodamine-based, coumarin-based, and oxazine-based compounds. Specific examples include CI Fluorescent Brightener 219:1, EASTOBRITE OB-1 manufactured by Eastman Chemical Co., Ltd., and "Hakkor PSR" manufactured by Showa Chemical Co., Ltd., and the like. Here, the fluorescent whitening agent has the function of absorbing energy in the ultraviolet region of light and emitting this energy in the visible region. The content of the fluorescent whitening agent is preferably 0.001 to 0.1 parts by weight, more preferably 0.001 to 0.05 parts by weight, per 100 parts by weight of the total of the A component and the B component. Even if it exceeds 0.1 part by weight, the effect of improving the color tone of the composition is small.

(V) Compound Having Ability to Absorb Heat Rays The thermoplastic resin composition of the present invention can contain a compound having ability to absorb heat rays. Examples of such compounds include phthalocyanine near-infrared absorbers, metal oxide near-infrared absorbers such as ATO, ITO, iridium oxide and ruthenium oxide, imonium oxide and titanium oxide, lanthanum boride, cerium boride and tungsten boride. Preferable examples include various metal compounds having excellent near-infrared absorptivity, such as metal boride-based and tungsten oxide-based near-infrared absorbers, and carbon fillers. As such a phthalocyanine-based near-infrared absorber, for example, MIR-362 manufactured by Mitsui Chemicals, Inc. is commercially available and readily available. Examples of carbon fillers include carbon black, graphite (both natural and artificial) and fullerenes, preferably carbon black and graphite. These can be used singly or in combination of two or more. The content of the phthalocyanine-based near-infrared absorbent is preferably 0.0005 to 0.2 parts by weight, more preferably 0.0008 to 0.1 parts by weight, with respect to the total of 100 parts by weight of the components A and B. , 0.001 to 0.07 parts by weight are more preferable. The content of the metal oxide near-infrared absorber, the metal boride near-infrared absorber and the carbon filler is preferably in the range of 0.1 to 200 ppm (weight ratio) in the thermoplastic resin composition of the present invention. A range of 0.5 to 100 ppm is more preferred.

(VI) Light diffusing agent The thermoplastic resin composition of the present invention may be blended with a light diffusing agent to impart a light diffusing effect. Examples of such light diffusing agents include polymeric fine particles, inorganic fine particles with a low refractive index such as calcium carbonate, and composites thereof. Such polymer microparticles are already known microparticles as light diffusing agents for polycarbonate resins. More preferably, acrylic crosslinked particles having a particle size of several μm and silicone crosslinked particles represented by polyorganosilsesquioxane are exemplified. The shape of the light diffusing agent is exemplified by a spherical shape, a discoidal shape, a columnar shape, and an amorphous shape. Such spheres do not have to be perfect spheres, but include deformed ones, and such cylinders include cubes. A preferred light diffusing agent is spherical, and the more uniform the particle size, the better. The content of the light diffusing agent is preferably 0.005 to 20 parts by weight, more preferably 0.01 to 10 parts by weight, and still more preferably 0.01 parts by weight with respect to the total 100 parts by weight of the components A and B. ~3 parts by weight. Two or more light diffusing agents can be used in combination.

(VII) High Light Reflection White Pigment The thermoplastic resin composition of the present invention may be blended with a high light reflection white pigment to impart a light reflection effect. Titanium dioxide (particularly titanium dioxide treated with an organic surface treatment agent such as silicone) is particularly preferred as such a white pigment. The content of the white pigment for high light reflection is preferably 3 to 30 parts by weight, more preferably 8 to 25 parts by weight, based on 100 parts by weight of the components A and B combined. Two or more kinds of the high light reflection white pigment can be used in combination.

(VIII) Ultraviolet absorber The thermoplastic resin composition of the present invention may be blended with an ultraviolet absorber to impart weather resistance. Specific examples of such UV absorbers include benzophenones such as 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-octoxybenzophenone, 2-hydroxy-4-benzene oxybenzophenone, 2-hydroxy-4-methoxy-5-sulfoxybenzophenone, 2,2'-dihydroxy-4-methoxybenzophenone, 2,2',4,4'-tetrahydroxybenzophenone, 2,2'-dihydroxy- 4,4'-dimethoxybenzophenone, 2,2'-dihydroxy-4,4'-dimethoxy-5-sodium sulfoxybenzophenone, bis(5-benzoyl-4-hydroxy-2-methoxyphenyl)methane, 2-hydroxy -4-n-dodecyloxybenzophenone, 2-hydroxy-4-methoxy-2'-carboxybenzophenone, and the like. Specific examples of benzotriazole-based UV absorbers include 2-(2-hydroxy-5-methylphenyl)benzotriazole and 2-(2-hydroxy-5-tert-octylphenyl)benzotriazole. , 2-(2-hydroxy-3,5-dicumylphenyl)phenylbenzotriazole, 2-(2-hydroxy-3-tert-butyl-5-methylphenyl)-5-chlorobenzotriazole, 2,2′- methylenebis[4-(1,1,3,3-tetramethylbutyl)-6-(2H-benzotriazol-2-yl)phenol], 2-(2-hydroxy-3,5-di-tert-butylphenyl ) benzotriazole, 2-(2-hydroxy-3,5-di-tert-butylphenyl)-5-chlorobenzotriazole, 2-(2-hydroxy-3,5-di-tert-amylphenyl)benzotriazole- 2-(2-hydroxy-5-tert-octylphenyl)benzotriazole, 2-(2-hydroxy-5-tert-butylphenyl)benzotriazole, 2-(2-hydroxy-4-octoxyphenyl ) benzotriazole, 2,2′-methylenebis(4-cumyl-6-benzotriazolephenyl), 2,2′-p-phenylenebis(1,3-benzoxazin-4-one), and 2-[2 -hydroxy-3-(3,4,5,6-tetrahydrophthalimidomethyl)-5-methylphenyl]benzotriazole, and 2-(2′-hydroxy-5-methacryloxyethylphenyl)-2H-benzotriazole, and a copolymer of said monomer and a vinyl-based monomer copolymerizable with said monomer, or a copolymer of 2-(2'-hydroxy-5-acryloxyethylphenyl)-2H-benzotriazole and said monomer and a vinyl-based monomer copolymerizable with said monomer; Examples thereof include polymers having a 2-hydroxyphenyl-2H-benzotriazole skeleton, such as polymers. Specifically, the ultraviolet absorber is hydroxyphenyltriazine-based, for example, 2-(4,6-diphenyl-1,3,5-triazin-2-yl)-5-hexyloxyphenol, 2-(4, 6-diphenyl-1,3,5-triazin-2-yl)-5-methyloxyphenol, 2-(4,6-diphenyl-1,3,5-triazin-2-yl)-5-ethyloxyphenol , 2-(4,6-diphenyl-1,3,5-triazin-2-yl)-5-propyloxyphenol, and 2-(4,6-diphenyl-1,3,5-triazin-2-yl )-5-butyloxyphenol and the like. Furthermore, 2-(4,6-bis(2,4-dimethylphenyl)-1,3,5-triazin-2-yl)-5-hexyloxyphenol, etc., in which the phenyl group of the above-exemplified compounds is 2,4-dimethylphenyl A compound having a phenyl group is exemplified. Specifically, cyclic iminoester-based UV absorbers include, for example, 2,2′-p-phenylenebis(3,1-benzoxazin-4-one), 2,2′-m-phenylenebis(3,1 -benzoxazin-4-one), and 2,2′-p,p′-diphenylenebis(3,1-benzoxazin-4-one). Further, as the ultraviolet absorber, specifically in the cyanoacrylate type, for example, 1,3-bis-[(2′-cyano-3′,3′-diphenylacryloyl)oxy]-2,2-bis[(2- Examples include cyano-3,3-diphenylacryloyl)oxy]methyl)propane and 1,3-bis-[(2-cyano-3,3-diphenylacryloyl)oxy]benzene. Furthermore, the above-mentioned ultraviolet absorber has a structure of a monomer compound capable of radical polymerization, so that the ultraviolet-absorbing monomer and/or photostable monomer and a monomer such as alkyl (meth)acrylate It may be a polymer-type UV absorber obtained by copolymerizing with a body. Preferred examples of the UV-absorbing monomer include compounds containing a benzotriazole skeleton, a benzophenone skeleton, a triazine skeleton, a cyclic iminoester skeleton, and a cyanoacrylate skeleton in the ester substituent of the (meth)acrylic acid ester. be. Among them, benzotriazole and hydroxyphenyltriazine are preferable in terms of ultraviolet absorption ability, and cyclic iminoester and cyanoacrylate are preferable in terms of heat resistance and hue. Specific examples thereof include "Chemisorb 79" manufactured by Chemipro Kasei Co., Ltd., "TINUVIN 234" manufactured by BASF Japan Ltd., and the like. The ultraviolet absorbers may be used singly or as a mixture of two or more.

The content of the ultraviolet absorber is preferably 0.01 to 3 parts by weight, more preferably 0.01 to 1 part by weight, and still more preferably 0.05 parts by weight with respect to the total 100 parts by weight of the components A and B. to 1 part by weight, particularly preferably 0.05 to 0.5 part by weight.

(IX) Antistatic Agent The thermoplastic resin composition of the present invention may be required to have antistatic performance, and in such cases, it preferably contains an antistatic agent. Examples of such antistatic agents include (1) arylsulfonic acid phosphonium salts typified by dodecylbenzenesulfonic acid phosphonium salts, organic sulfonic acid phosphonium salts such as alkylsulfonic acid phosphonium salts, and tetrafluoroborate phosphonium salts. Phosphonium borate salts are mentioned. The content of the phosphonium salt is appropriately 5 parts by weight or less, preferably 0.05 to 5 parts by weight, more preferably 1 to 3.5 parts by weight, per 100 parts by weight of the component A and B. parts, more preferably 1.5 to 3 parts by weight. Examples of antistatic agents include (2) organic lithium sulfonate, organic sodium sulfonate, organic potassium sulfonate, organic cesium sulfonate, organic rubidium sulfonate, organic calcium sulfonate, organic magnesium sulfonate, and organic barium sulfonate. organic sulfonic acid alkali (earth) metal salts such as Such metal salts are also used as flame retardants, as described above. More specific examples of such metal salts include metal salts of dodecylbenzenesulfonic acid and metal salts of perfluoroalkanesulfonic acid. The content of the organic alkali (earth) metal sulfonate is appropriately 0.5 parts by weight or less, preferably 0.001 to 0.3 parts by weight, per 100 parts by weight of the component A and B. parts, more preferably 0.005 to 0.2 parts by weight. Especially preferred are alkali metal salts such as potassium, cesium and rubidium.

Examples of antistatic agents include (3) organic sulfonate ammonium salts such as alkylsulfonate ammonium salts and arylsulfonate ammonium salts. The amount of the ammonium salt is appropriately 0.05 parts by weight or less per 100 parts by weight of the component A and B. The antistatic agent includes, for example, (4) a polymer containing a poly(oxyalkylene) glycol component such as polyetheresteramide as its constituent component. The amount of the polymer is suitably 5 parts by weight or less per 100 parts by weight in total of the A component and the B component.

(X) Filler The thermoplastic resin composition of the present invention may contain various fillers known as reinforcing fillers other than fibrous fillers. Various plate-like fillers and granular fillers can be used as such fillers. Here, the plate-like filler is a filler having a plate-like shape (including those having irregularities on the surface and those having curved plates). Particulate fillers are fillers of shapes other than these, including irregularly shaped fillers.

Plate-shaped fillers include glass flakes, talc, mica, kaolin, metal flakes, carbon flakes, and graphite, and plate-shaped fillers in which these fillers are surface-coated with different materials such as metals and metal oxides. Materials and the like are preferably exemplified. Its particle size is preferably in the range of 0.1 to 300 μm. Such a particle size refers to the median diameter (D50) of the particle size distribution measured by the X-ray transmission method, which is one of the liquid phase sedimentation methods, in the region up to about 10 μm, and laser diffraction in the region of 10 to 50 μm.・It refers to the median diameter (D50) of the particle size distribution measured by the scattering method, and in the range of 50 to 300 μm, it is the value obtained by the vibratory sieving method. Such particle size is the particle size in the resin composition. The plate-like fillers may be surface-treated with various silane-based, titanate-based, aluminate-based, and zirconate-based coupling agents. , epoxy resins, urethane resins, and other resins, higher fatty acid esters, and the like, or may be granules subjected to compression.

(XI) Other Resins and Elastomers In the thermoplastic resin composition of the present invention, other resins and elastomers can be used in place of a part of the resin component to exhibit the effects of the present invention within a range that does not impair the effects of the present invention. It can also be used in a small proportion within the range. The amount of other resins and elastomers to be blended is preferably 20 parts by weight or less, more preferably 10 parts by weight or less, still more preferably 5 parts by weight or less, and most preferably 100 parts by weight of the resin component consisting of components A and B. is 3 parts by weight or less. Examples of such other resins include polyester resins such as polyethylene terephthalate and polybutylene terephthalate, polyamide resins, polyimide resins, polyetherimide resins, polyurethane resins, silicone resins, polyphenylene ether resins, polyphenylene sulfide resins, polysulfone resins, and polymethacrylate resins. , phenolic resins, and epoxy resins. Examples of elastomers include isobutylene/isoprene rubber, styrene/butadiene rubber, ethylene/propylene rubber, acrylic elastomers, polyester elastomers, polyamide elastomers, and MBS (methyl methacrylate/sterene/butadiene), which is a core-shell type elastomer. rubber, MB (methyl methacrylate/butadiene) rubber, MAS (methyl methacrylate/acrylonitrile/styrene) rubber, and the like.

(XII) Other Additives The thermoplastic resin composition of the present invention may contain other flow modifiers, antibacterial agents, dispersants such as liquid paraffin, photocatalytic antifouling agents, photochromic agents, and the like. .

<Regarding the production of the resin composition>
The thermoplastic resin composition of the present invention can be pelletized by melt-kneading using an extruder such as a single-screw extruder or a twin-screw extruder. In preparing such pellets, the above various reinforcing fillers and additives can be blended.

<About manufacturing molded products>
The thermoplastic resin composition of the present invention can be used to produce various products by injection molding the pellets produced as described above. Further, it is also possible to directly form a sheet, film, profile extrusion molded product, direct blow molded product, and injection molded product from the melt-kneaded resin in an extruder without going through pellets. In such injection molding, not only ordinary molding methods but also injection compression molding, injection press molding, gas-assisted injection molding, foam molding (including injection of supercritical fluid), insert molding, Molded articles can be obtained using injection molding methods such as in-mold coating molding, adiabatic molding, rapid heat and cool molding, two-color molding, sandwich molding, and ultra-high speed injection molding. The advantages of these various molding methods are already widely known. For molding, either cold runner method or hot runner method can be selected. Also, the resin composition of the present invention can be used in the form of various profile extrudates, sheets, films, and the like by extrusion molding. In addition, the inflation method, calender method, casting method, and the like can be used for forming sheets and films. Furthermore, it is also possible to mold it as a heat-shrinkable tube by subjecting it to a specific stretching operation. The resin composition of the present invention can also be molded by rotational molding, blow molding, or the like.

Since the thermoplastic resin composition of the present invention is excellent in heat resistance and low-temperature impact properties, it is useful for various applications such as electrical and electronic parts, home appliances, automobile-related parts, infrastructure-related parts, and housing-related parts. The industrial effect it produces is exceptional.

The mode for carrying out the present invention summarizes the preferable range of each of the above requirements, and for example, the representative examples are described in the following examples. Of course, the present invention is not limited to these forms.

The present invention will be further described with reference to the following examples. In addition, unless otherwise specified, parts in the examples are parts by weight, and %s are % by weight. In addition, evaluation was implemented by the following method.

(Evaluation of thermoplastic resin composition)
(i) Amount of change in viscosity-average molecular weight The amount of decrease in the viscosity-average molecular weight between the test piece obtained by molding after staying in the cylinder for 10 minutes under the same conditions as the following method and the pellet used for molding ( ΔMv) was calculated based on the following formula.
Amount of decrease in viscosity-average molecular weight (ΔMv) = (viscosity-average molecular weight of pellet) - (viscosity-average molecular weight of molded product after residence for 10 minutes)
(ii) fluidity (MFR)
The MFR was measured at a temperature of 280° C. and a load of 2.16 kg according to JIS K-6719.
(iii) Charpy impact strength Notched Charpy impact strength at 23°C and -30°C was measured according to ISO179 using an ISO bending test piece obtained by the following method. The resin composition of the present invention should have a Charpy impact strength (23°C) of 56 or more and a Charpy impact strength (-30°C) of 30 or more.
(iv) Deflection temperature under load Using an ISO bending test piece obtained by the following method, the deflection temperature under load (0.45 MPa load) was measured according to ISO75-1 and ISO75-2. The resin composition of the present invention should have a deflection temperature under load of 130° C. or higher.

(A component)
[Production of polycarbonate-polyorganosiloxane copolymer resin (A-1)]
21591 parts of ion-exchanged water and 3674 parts of 48.5% aqueous sodium hydroxide solution are placed in a reactor equipped with a thermometer, a stirrer and a reflux condenser, and 3880 parts of 2,2-bis(4-hydroxyphenyl)propane (bisphenol A). , and 7.6 parts of hydrosulfite are dissolved, 14565 parts of methylene chloride (14 mols per 1 mol of the dihydroxy compound (I)) are added, and 1900 parts of phosgene are added at 22 to 30°C with stirring for 60 minutes. I blew it in. Next, a solution of 1131 parts of a 48.5% aqueous sodium hydroxide solution and 105 parts of p-tert-butylphenol dissolved in 800 parts of methylene chloride was added, and the polydiorganosiloxane compound 430 represented by the following formula (11) was added with stirring. part dissolved in 1,600 parts of methylene chloride is added at a rate of 0.0008 mol/min for dihydroxyaryl-terminated polydiorganosiloxane per 1 mol of dihydric phenol (I) to emulsify, and then vigorously again. Stirred. Under such stirring, 4.3 parts of triethylamine was added while the reaction solution was at 26° C., and stirring was continued for 45 minutes at a temperature of 26 to 31° C. to complete the reaction. After completion of the reaction, the organic phase was separated, diluted with methylene chloride and washed with water, then acidified with hydrochloric acid and washed with water. Then, the methylene chloride was evaporated with stirring to obtain a polycarbonate-polydiorganosiloxane copolymer resin powder. After dehydration, it was dried at 120° C. for 12 hours in a hot air circulating dryer to obtain a polycarbonate-polydiorganosiloxane copolymer resin powder. (Polydiorganosiloxane component content 8.2%, average polydiorganosiloxane domain size 9 nm, viscosity average molecular weight 19,400)

(B component)
[Production of polyarylate resin (B-1)]
In a reaction vessel equipped with a stirring vessel, 8.2 kg (36 mol) of 2,2-bis(4-hydroxyphenyl)propane and 1,1-bis(4-hydroxyphenyl)-3 were added as dihydric phenol residues. , 3,5-trimethylcyclohexane 11.1 kg (36 mol), 4,4-dihydroxy-biphenyl 3.4 kg (18 mol), p-tert-butylphenol (hereinafter sometimes abbreviated as PTBP) as a molecular weight modifier. (PTBP manufactured by DIC Corporation) 670 g (4.4 mol), sodium hydroxide (manufactured by Tosoh Corporation) 8.6 kg (213 mol) as an alkali, benzyl-tri-n-butylammonium chloride (hereinafter abbreviated as BTBAC) as a polymerization catalyst 373 g of BTBAC-50 manufactured by Lion Akzo Co., Ltd., 107 g of sodium hydrosulfite (hereinafter sometimes abbreviated as SHS) (manufactured by BASF), and 400 L of water are added into the reaction vessel. and dissolved to form an aqueous phase.

18. Mixed phthaloyl chloride (MPC manufactured by Iharanikkei Chemical Industry Co., Ltd.; terephthalic acid/isophthalic acid = 50/50 (mass%)) was added to 240 L of dichloromethylene (methylene chloride manufactured by Tokuyama Corporation) in another reaction vessel. 6 kg (91 mol) were dissolved to form the organic phase. This organic phase was added to the already stirred aqueous phase under strong stirring, and the temperature was maintained at 15° C. to carry out a polymerization reaction for 2 hours. After that, the stirring was stopped and the aqueous phase and the organic phase were separated by decantation. 400 L of pure water and 100 mL of acetic acid were added to the organic phase from which the aqueous phase was removed to stop the reaction, and the mixture was further stirred at 15° C. for 30 minutes. This organic phase was washed with pure water five times, and the organic phase was added to 400 L of hexane to precipitate the polymer. The precipitated polymer was separated from the organic phase and then dried to obtain polyarylate resin (B-1). Composition analysis of the obtained polyarylate resin (B-1) using ¹ H-NMR (ECA500 NMR manufactured by JEOL Ltd.) revealed that the polymerization ratio of the dihydric phenol residue and the phthalic acid residue was 1:1. 1, which is the same as the mixing ratio of the dihydric phenol residue and the phthalic acid residue. Moreover, the viscosity average molecular weight of the obtained polyarylate resin was 19,300. Table 1 shows the results.

[Production of polyarylate resins (B-2, B-3)]
[Production of polyarylate resin (B-1)] in the same manner as in [Preparation of polyarylate resin (B-1)] except that the amounts of dihydric phenol and aromatic dicarboxylic acid are shown in Table 1, [Polyarylate resin (B-2)] and [Polyarylate resin (B-3)] was obtained. The viscosity average molecular weights of the resulting polyarylate resins were 21,800 and 60,000, respectively. Table 1 shows the results.

In addition, each component of symbol notation in Table 1 is as follows.
(aromatic dicarboxylic acid)
TP: terephthalic acid IP: isophthalic acid (dihydric phenol)
BPA: bisphenol A [2,2-bis(4-hydroxyphenyl)propane]
BPTMC: bisphenol TMC [bisphenol 3,3,5-trimethylcyclohexane]
BP: biphenol [4,4-dihydroxy-biphenyl]

(Examples 1 to 5, Comparative Examples 1 to 3)
A mixture having the composition shown in Table 2 was fed through the first feed port of the extruder. Such a mixture was obtained by mixing in a V-blender. The twin-screw extruder has a diameter of 30 mmφ, and has a total of 10 barrels (referred to as C1 to C10 cylinders from the upstream) having a supply port at C1 at the most upstream part and C5 at the downstream thereof. A "TEX30αIII" intermeshing co-rotating twin-screw extruder manufactured by Steel Works was used. Extrusion conditions were temperature C1: 300° C., C2-10: 310° C., screw rotation speed 200 rpm, discharge rate 25 kg/h, vent vacuum degree 3 kPa, and pellets were obtained by melt-kneading.
A part of the obtained pellets was dried at 120°C for 6 hours in a hot air circulation dryer, and then an ISO bending test piece for evaluation was made at a cylinder temperature of 310°C and a mold temperature of 90°C using an injection molding machine. (ISO 179 and ISO 75-1, 75-2 compliant) were molded and each evaluation was performed. Table 2 shows the evaluation results.

In addition, each component of symbol notation in Table 2 is as follows.
(A component)
A-1: Resin synthesized in [Production of polycarbonate-polyorganosiloxane copolymer resin (A-1)] (Component B)
B-1: Resin synthesized in [Production of polyarylate resin (B-1)] B-2: Resin synthesized in [Production of polyarylate resin (B-2)] B-3: [Polyarylate resin Production of (B-3)] Synthesized resin (component C)
C-1: Aromatic polycarbonate resin (polycarbonate resin powder with a viscosity average molecular weight of 19,700 made from bisphenol A and phosgene by a conventional method, Panlite L-1225WX (product name) manufactured by Teijin Limited)
(other ingredients)
STB-3: Phosphorus-based heat stabilizer (trimethyl phosphate, TMP manufactured by Daihachi Chemical Industry Co., Ltd.)

Claims (4)

(A) 90 to 99 parts by weight of a polycarbonate-polydiorganosiloxane copolymer resin (Component A) comprising a polycarbonate block represented by the following general formula (1) and a polydiorganosiloxane block represented by the following general formula (3) and (B) a thermoplastic resin composition containing 1 to 10 parts by weight of a polyarylate resin (component B) containing a polymerized unit represented by any one of the following general formulas (4) to (6) .

(In general formula (1) above, R ¹ and R ² each independently represent a hydrogen atom, a halogen atom, an alkyl group having 1 to 18 carbon atoms, an alkoxy group having 1 to 18 carbon atoms, or cycloalkyl group having 20 carbon atoms, cycloalkoxy group having 6 to 20 carbon atoms, alkenyl group having 2 to 10 carbon atoms, aryl group having 6 to 14 carbon atoms, aryloxy group having 6 to 14 carbon atoms, carbon atom represents a group selected from the group consisting of an aralkyl group having 7 to 20 carbon atoms, an aralkyloxy group having 7 to 20 carbon atoms, a nitro group, an aldehyde group, a cyano group and a carboxyl group; a and b are each an integer of 1 to 4, and W is at least one group selected from the group consisting of a single bond or a group represented by the following general formula (2).)

(In general formula (2) above, R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ , R ¹⁶ , R ¹⁷ and R ¹⁸ are each independently a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, a carbon represents a group selected from the group consisting of an aryl group having 6 to 14 atoms and an aralkyl group having 7 to 20 carbon atoms; R ¹⁹ and R ²⁰ each independently represents a hydrogen atom, a halogen atom, or a an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, a cycloalkyl group having 6 to 20 carbon atoms, a cycloalkoxy group having 6 to 20 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, and 6 carbon atoms. an aryl group of up to 14, an aryloxy group of 6 to 10 carbon atoms, an aralkyl group of 7 to 20 carbon atoms, an aralkyloxy group of 7 to 20 carbon atoms, a nitro group, an aldehyde group, a cyano group and a carboxyl group represents a group selected from the group consisting of, when there are more than one, they may be the same or different, c is an integer of 1 to 10, and d is an integer of 4 to 7.)

(In general formula (3) above, R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ and R ⁸ are each independently a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, or a substituted group having 6 to 12 carbon atoms. or an unsubstituted aryl group, R ⁹ and R ¹⁰ are each independently a hydrogen atom, a halogen atom, an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, e and f are each an integer of 1 to 4, p is a natural number, q is 0 or a natural number, p + q is a natural number of 4 to 150. X is a divalent aliphatic group having 2 to 8 carbon atoms .)

(In the above general formula (4), l, m and n are positive positive values satisfying l + m + n = 100, l: n = 50: 50 to 70: 30 and (l + n): m = 75: 25 to 40: 60 is an integer.)

(In the above general formula (5), m and n are positive integers, m/n=8/2 to 2/8.)

(In the above general formula (6), n is a positive integer.) 2. The thermoplastic resin composition according to claim 1, wherein component B has a viscosity average molecular weight of 10,000 to 50,000. The thermoplastic resin according to claim 1 or 2 , characterized by containing 0.01 to 2 parts by weight of (C) an alkyl phosphate compound (component C) with respect to a total of 100 parts by weight of components A and B. Composition. A molded article obtained by molding the thermoplastic resin composition according to any one of claims 1 to 3 .