JP2020122073A - Thermoplastic resin composition - Google Patents

Abstract

To provide a thermoplastic resin composition having excellent low temperature impact property and heat resistance.SOLUTION: A thermoplastic resin composition contains (A) a polycarbonate-polydiorganosiloxane copolymer resin (component A) comprising a polycarbonate block shown by following general formula (1), and polydiorganosiloxane block shown by following general formula (3), as much as 90-99 pts.wt. and (B) a polyarylate resin (component B) as much as 1-10 pts.wt.SELECTED DRAWING: None

Description

The present invention relates to a thermoplastic resin composition. More specifically, the present invention relates to a thermoplastic resin composition having improved heat resistance and low-temperature impact properties by blending a polycarbonate-polydiorganosiloxane copolymer resin with an appropriate amount of polyarylate resin.

Polycarbonate resins are used in many applications such as mechanical parts, automobile parts, electric/electronic parts, and office equipment parts because of their excellent properties such as mechanical strength, dimensional stability and flame retardancy. However, it is sufficient as a material for outdoor electric/electronic storage boxes such as information and communication boxes and junction boxes for solar power generation that require very high impact and thin flame retardancy at low temperatures such as -30°C. Performance is not obtained. A polycarbonate-polydiorganosiloxane copolymer resin, which is a polycarbonate material, is known as a resin material having a high-temperature impact resistance property. Polycarbonate-polydiorganosiloxane copolymer resin is superior to conventional polycarbonate resin in flame retardancy and low-temperature impact characteristics, but is inferior in heat resistance, so that it is limited to use in a region where temperature difference is severe. On the other hand, there is a method of blending a polyarylate resin with a polycarbonate resin in order to obtain high heat resistance (Patent Documents 1 and 2). However, these documents do not describe that high heat resistance and low temperature impact properties can be obtained by blending a polycarbonate-polydiorganosiloxane copolymer resin with an appropriate amount of polyarylate 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.

As a result of intensive studies to achieve the above object, the present inventors have obtained good low-temperature impact properties and heat resistance by blending a polycarbonate-polydiorganosiloxane copolymer resin with an appropriate amount of polyarylate resin. It was found that a thermoplastic resin composition can be obtained, and further intensive studies were conducted to complete the present invention.
Hereinafter, the present invention will be specifically described.

<A component: polycarbonate-polydiorganosiloxane copolymer resin>
The resin composition of the present invention contains a polycarbonate-polydiorganosiloxane copolymer resin as component A. When a polycarbonate resin other than the polycarbonate-polydiorganosiloxane copolymer resin is used as the 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 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, or 6 to 6 carbon atoms. 20 cycloalkyl group, C6-20 cycloalkoxy group, C2-10 alkenyl group, C6-14 aryl group, C6-14 aryloxy group, 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, and when there are a plurality of groups, they may be the same or different. A and b are each an integer of 1 to 4, and W is a single bond or at least one group selected from the group consisting of groups represented by the following general formula (2). ]

(In the general formula (2), 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, or a carbon atom. 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, wherein R ¹⁹ and R ²⁰ are each independently a hydrogen atom, a halogen atom, or a carbon atom number of 1 to 18; Alkyl group having 1 to 10 carbon atoms, cycloalkyl group having 6 to 20 carbon atoms, cycloalkoxy group having 6 to 20 carbon atoms, alkenyl group having 2 to 10 carbon atoms, and 6 carbon atoms From an aryl group having 14 to 14 carbon atoms, an aryloxy group having 6 to 10 carbon atoms, 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. Represents a group selected from the group consisting of two or more, and when there are a plurality of groups, 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 substituent 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, and e and f Are integers of 1 to 4, respectively, 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) for deriving the carbonate structural unit represented by the general formula (1) include, for example, 4,4′-dihydroxybiphenyl, bis(4-hydroxyphenyl)methane, and 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'-dihydroxydiphenylene- 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'-diphenyldiphenylsulfoxide, 4,4'-dihydroxy-3,3'-diphenyldiphenylsulfide, 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 can be mentioned.

Among them, 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 and 9,9-bis(4-hydroxy-3-methylphenyl)fluorene are preferred. Among them, 2,2-bis(4-hydroxyphenyl)propane having excellent strength and good durability is most suitable. 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, and a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or a phenyl group is particularly preferable. R ⁹ and R ¹⁰ are each independently preferably a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, and particularly preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. As the dihydroxyaryl-terminated polydiorganosiloxane (II) for deriving the carbonate structural unit represented by the general formula (3), for example, a compound represented by the following general formula (I) is preferably used.

4-120 are preferable, as for p+q, 30-120 are more preferable, 30-100 are more preferable, 30-60 are the most preferable.

Next, a method for producing the above polycarbonate-polydiorganosiloxane copolymer resin will be described below. In advance in a mixed solution of an organic solvent insoluble in water and an aqueous alkaline solution, the reaction of the dihydric phenol (I) with a chloroformate-forming compound such as phosgene or the chloroformate of the dihydric phenol (I), A mixed solution of a chloroformate compound containing a carbonate oligomer of a dihydric phenol (I) and/or a carbonate oligomer of a dihydric phenol (I) having a terminal chloroformate group is prepared. 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 used as the chloroformate compound at once. Alternatively, or a part thereof may be added as a post-added monomer to the subsequent interfacial polycondensation reaction as a reaction raw material. The post-addition monomer is added in order to accelerate the subsequent polycondensation reaction, and it is not necessary to intentionally add it when it is not necessary. The method of this chloroformate compound formation reaction is not particularly limited, but a method in which the reaction is carried out in a solvent in the presence of an acid binder is generally preferred. Further, if desired, a small amount of antioxidants such as sodium sulfite and hydrosulfide may be added, and it is preferable to add them. The use ratio of the chloroformate-forming compound may be appropriately adjusted in consideration of the stoichiometric ratio (equivalent) of the reaction. When using phosgene, which is a suitable chloroformate-forming compound, a method of blowing gasified phosgene into the reaction system can be suitably adopted.

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 a mixture thereof. Is used. The ratio of the acid binder used may be appropriately determined in consideration of the stoichiometric ratio (equivalent amount) of the reaction as in the above. Specifically, per 1 mol of the dihydric phenol (I) used to form the chloroformate compound of the dihydric phenol (I) (usually 1 mol corresponds to 2 equivalents), 2 equivalents or a slight excess thereof. Preference is given to using acid binders.

As the solvent, solvents that are inert to various reactions such as those used in the production of known polycarbonates may be used alone or as a mixed solvent. Representative examples include, for example, hydrocarbon solvents such as xylene, and halogenated hydrocarbon solvents such as methylene chloride and chlorobenzene. Particularly, a halogenated hydrocarbon solvent such as methylene chloride is preferably used.

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 to 50° C., and in many cases, heat is generated with the reaction, so water cooling or ice cooling is desirable. The reaction time depends on other conditions and cannot be specified unconditionally, but is usually 0.2 to 10 hours. For the pH range in the reaction for producing the chloroformate compound, known interfacial reaction conditions can be used, and the pH is usually adjusted to 10 or more.

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

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 for the branched polycarbonate resin include phloroglucin, phlorogluside, 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)ketone, 1, Examples thereof include 4-bis(4,4-dihydroxytriphenylmethyl)benzene, trimellitic acid, pyromellitic acid, benzophenonetetracarboxylic acid and acid chlorides thereof, and among them, 1,1,1-tris(4-hydroxy) Phenyl)ethane and 1,1,1-tris(3,5-dimethyl-4-hydroxyphenyl)ethane are preferable, and 1,1,1-tris(4-hydroxyphenyl)ethane is particularly preferable.

Even if the method for producing the branched polycarbonate-polydiorganosiloxane copolymer resin is a method in which a branching agent is contained in the mixed solution during the formation reaction of the chloroformate compound, the interfacial polycondensation after the formation reaction is completed. A method in which a branching agent is added during the reaction may be used. The proportion of the carbonate constitutional unit 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 the carbonate constitutional units constituting the copolymer resin. It is particularly preferably 0.05 to 1.0 mol %. The amount of the branched structure can be calculated by ¹ H-NMR measurement.

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

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. It is preferable, and 1.0 to 8.0% by weight is more preferable.

(In the general formula (4), 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 substituent having 6 to 12 carbon atoms. Alternatively, it is 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. Is more preferable, 2.0×10 ^{4 to} 3.5×10 ⁴ is more preferable, and 2.2×10 ^{4 to} 3.0×10 ⁴ is more preferable. With a polycarbonate-polydiorganosiloxane copolymer resin having a viscosity average molecular weight of less than 1.8×10 ⁴ , good mechanical properties may not be obtained in some cases. On the other hand, a resin composition obtained from a polycarbonate-polydiorganosiloxane copolymer resin having a viscosity average molecular weight of more than 4.0×10 ⁴ is inferior in versatility because it is inferior in fluidity during injection molding.

The viscosity average molecular weight as used in the present invention is the Ostwald viscosity from a solution in which 0.7 g of a polycarbonate-polydiorganosiloxane copolymer resin is dissolved in 100 ml of methylene chloride at a specific viscosity (η _SP ) calculated by the following formula. Using a total,
Specific viscosity (η _SP )=(t−t ₀ )/t ₀
[T ₀ is the number of seconds of methylene chloride drop, t is the number of seconds of drop of the sample solution]
The viscosity average molecular weight M is calculated from the determined specific viscosity (η _SP ) by the following mathematical 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 component B of the present invention may be obtained by a conventional method from a dihydric phenol or its derivative and an aromatic dicarboxylic acid or its derivative. Examples of the dihydric phenol used here include: 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'-dihydroxydiphenylsulfone, 4,4'-dihydroxydiphenylether, 4,4'-dihydroxydiphenylsulfide and the like, and two or more kinds may be used in combination.

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

The polyarylate resin used as the component B of the present invention is preferably a copolymer containing a polymerized unit 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 positive numbers satisfying l+m+n=100, l:n=50:50 to 70:30 and (l+n):m=75:25 to 40:60. It 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 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 component B of the present invention is 1 to 10 parts by weight, preferably 6 to 10 parts by weight, more preferably 8 parts by weight, based on 100 parts by weight of the resin component consisting of the components A and B. 10 to 10 parts by weight. When the content of the component B is less than 1 part by weight, excellent heat resistance and low temperature impact properties cannot be obtained, and when it is more than 10 parts by weight, the low temperature impact properties are deteriorated.

The polyarylate resin used as the component B of the present invention preferably has a viscosity average molecular weight of 5,000 to 100,000, more preferably 10,000 to 50,000. When the viscosity average molecular weight of the polyarylate resin is less than 5,000, impact properties may be deteriorated. 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 the polycarbonate-polyorganosiloxane copolymer resin used as the component A of the present invention.
Examples of commercially available products of polyarylate resin include “U-100” (trade name), “M-2040” (trade name), “M-2040H” (trade name) and the like manufactured by Unitika Ltd.

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

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

(I) Phosphorus-Based Stabilizer The thermoplastic resin composition of the present invention preferably contains a phosphorus-based stabilizer to the extent that hydrolysis is not promoted. Such a phosphorus-based stabilizer improves thermal stability during manufacturing or molding, and improves mechanical properties, hue, and molding stability. Examples of the phosphorus-based stabilizer include phosphorous acid, phosphoric acid, phosphonous acid, phosphonic acid and their esters, and tertiary phosphine. Specific examples of the phosphite compound include triphenyl phosphite, tris(nonylphenyl)phosphite, tridecyl phosphite, trioctyl phosphite, trioctadecyl phosphite, didecyl monophenyl phosphite, dioctyl monophenyl. 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(2,2 6-di-tert-butylphenyl)phosphite, distearyl pentaerythritol 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 Examples thereof include erythritol diphosphite and dicyclohexyl pentaerythritol diphosphite. Further, as another phosphite compound, one having a cyclic structure which reacts with a dihydric phenol can 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′-ethylidene bis(4-methyl-6-tert-butylphenyl)(2-tert-butyl-4-methylphenyl)phosphite and the like. Examples of the phosphate compound 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 preferable.

Examples of the phosphonite compound include tetrakis(2,4-di-tert-butylphenyl)-4,4′-biphenylenediphosphonite and tetrakis(2,4-di-tert-butylphenyl)-4,3′-biphenylenediene. 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 can be mentioned, and tetrakis(di-tert-butylphenyl)-biphenylene diphosphonite and bis(di-tert-butylphenyl)-phenyl-phenylphosphonite are preferable, and tetrakis(2,2 4-di-tert-butylphenyl)-biphenylenediphosphonite and bis(2,4-di-tert-butylphenyl)-phenyl-phenylphosphonite are more preferred. Such a phosphonite compound is preferable because it can be used in combination with a phosphite compound having an aryl group in which two or more alkyl groups are substituted. Examples of the phosphonate compound include dimethyl benzenephosphonate, diethyl benzenephosphonate, and dipropyl benzenephosphonate. Examples of the tertiary phosphine include triethylphosphine, tripropylphosphine, tributylphosphine, trioctylphosphine, triamylphosphine, dimethylphenylphosphine, dibutylphenylphosphine, diphenylmethylphosphine, diphenyloctylphosphine, triphenylphosphine, tri-p-tolyl. Examples include phosphine, trinaphthylphosphine, and diphenylbenzylphosphine. A particularly preferred tertiary phosphine is triphenylphosphine. The above phosphorus-based stabilizers may be used alone or in combination of two or more. Among the above phosphorus-based stabilizers, it is preferable to add an alkyl phosphate compound typified by trimethyl phosphate. A combined use of such an alkyl phosphate compound and a phosphite compound and/or phosphonite compound is also a preferred embodiment.

The content of the alkyl phosphate compound is preferably 0.01 to 2 parts by weight, and more preferably 0.03 to 1 part by weight, based on 100 parts by weight of the total of the components A and B. 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, and if it is more than 2 parts by weight, the heat resistance of the obtained composition may be poor. May have an adverse effect.

(Ii) Hindered Phenol Stabilizer The thermoplastic resin composition of the present invention may contain a hindered phenol stabilizer. Such a compound exhibits an effect of suppressing deterioration of hue during molding or deterioration of hue during long-term use. Examples of hindered phenol stabilizers include α-tocopherol, butylhydroxytoluene, sinapyl alcohol, vitamin E, n-octadecyl-β-(4′-hydroxy-3′,5′-di-tert-butylfel). 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), triethyleneglycol-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-butylpheno) 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-tris2[3(3,5-di-tert-butyl-4-hydroxyphenyl)propionyloxy]ethyl isocyanurate, and tetrakis[methylene-3-(3', 5′-di-tert-butyl-4-hydroxyphenyl)propionate]methane and the like are exemplified. All of these are easily available. The 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, relative to 100 parts by weight of the total of the component A and the component B, respectively. 0.001 to 0.5 parts by weight, and more preferably 0.005 to 0.3 parts by weight.

(Iii) Heat Stabilizer Other Than Above The heat stabilizers other than the phosphorus-based stabilizer and the hindered phenol-based stabilizer may be added to the thermoplastic resin composition of the present invention. Suitable examples of such other heat stabilizers include lactone-based stabilizers typified by the reaction product of 3-hydroxy-5,7-di-tert-butyl-furan-2-one and o-xylene. To be done. Details of such stabilizers are described in JP-A-7-233160. Such a compound is commercially available as Irganox HP-136 (trademark, manufactured by CIBA SPECIALTY CHEMICALS), and the compound can be used. Further, stabilizers obtained by mixing the compound with various phosphite compounds and hindered phenol compounds are commercially available. For example, Irganox HP-2921 manufactured by the above company is preferably exemplified. The compounding amount of the lactone-based stabilizer is preferably 0.0005 to 0.05 part by weight, more preferably 0.001 to 0.03 part by weight, based on 100 parts by weight of the total of the component A and the component B. is there. Other stabilizers include sulfur-containing stabilizers such as pentaerythritol tetrakis (3-mercaptopropionate), pentaerythritol tetrakis (3-laurylthiopropionate), and glycerol-3-stearylthiopropionate. It is illustrated. The amount of the sulfur-containing stabilizer blended is preferably 0.001 to 0.1 part by weight, more preferably 0.01 to 0.08 part by weight, based on 100 parts by weight of the total of the components A and B. is there. An epoxy compound may be added to the thermoplastic resin composition of the present invention as needed. Such an epoxy compound is compounded for the purpose of suppressing mold corrosion, and basically any compound having an epoxy functional group can be applied. Specific examples of preferred epoxy compounds include 3,4-epoxycyclohexylmethyl-3′,4′-epoxycyclohexylcarboxylate and 2,2-bis(hydroxymethyl)-1-butanol 1,2-epoxy-4-. Examples thereof include (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 added is preferably 0.003 to 0.2 part by weight, more preferably 0.004 to 0.15 part by weight, based on 100 parts by weight of the total of the components A and B. , And more preferably 0.005 to 0.1 part by weight.

(II) Flame Retardant A flame retardant can be added to the thermoplastic resin composition of the present invention. The compounding of such a compound brings about an improvement in flame retardancy, but also brings about an improvement in antistatic property, fluidity, rigidity, and thermal stability in addition to the above, based on the properties of each compound. Examples of such flame retardants include (i) organic metal salt-based flame retardants (for example, alkali sulfonate (earth) metal salts of organic sulfonates, organic borate metal salt-based flame retardants, and organic stannic acid metal salt-based flame retardants), ( ii) Organophosphorus flame retardants (for example, organic group-containing monophosphate compounds, phosphate oligomer compounds, phosphonate oligomer compounds, phosphonitrile oligomer compounds, and phosphonic acid amide compounds), (iii) silicone compound-based flame retardants , (Iv) fibrillated PTFE, of which organometallic salt flame retardants and organic phosphorus flame retardants are preferred. You may use these in combination of 1 type or 2 types.

(I) Organic Metal Salt-Based Flame Retardant The organic metal 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 organic sulfonate alkali (earth) metal salt. Is preferred. The organic (salt) alkali metal sulfonate includes a fluorine-substituted alkyl sulfone such as a metal salt of a perfluoroalkyl sulfonic acid having 1 to 10 carbon atoms, preferably 2 to 8 carbon atoms and an alkali metal or an alkaline earth metal. Included are metal salts of acids, as well as 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. Examples of the alkali metal constituting the metal salt include lithium, sodium, potassium, rubidium and cesium, and examples of the alkaline earth metal include beryllium, magnesium, calcium, strontium and barium. More preferably, it is an alkali metal. Among such alkali metals, rubidium and cesium having a larger ionic radius are preferable when the requirement for transparency is higher, while they are not versatile and difficult to purify, resulting in cost. May be disadvantageous. On the other hand, metals having smaller ionic radii such as lithium and sodium may be disadvantageous in terms of flame retardancy. Taking these into consideration, the alkali metal in the sulfonic acid alkali metal salt can be used properly, but potassium sulfonate having an excellent balance of properties is most preferable in any respect. It is also possible to use the potassium salt and an alkali metal sulfonate of another alkali metal together.

Specific examples of the alkali metal salt of perfluoroalkyl sulfonic acid include potassium trifluoromethane sulfonate, potassium perfluorobutane sulfonate, potassium perfluorohexane sulfonate, potassium perfluorooctane sulfonate, sodium pentafluoroethane sulfonate, and perfluoro. Sodium butanesulfonate, sodium perfluorooctanesulfonate, lithium trifluoromethanesulfonate, lithium perfluorobutanesulfonate, lithium perfluoroheptanesulfonate, cesium trifluoromethanesulfonate, cesium perfluorobutanesulfonate, perfluorooctanesulfonate Examples thereof include cesium, cesium perfluorohexane sulfonate, rubidium perfluorobutane sulfonate, and rubidium perfluorohexane sulfonate, and these can be used alone or in combination of two or more. Here, the carbon number of the perfluoroalkyl group is preferably in the range of 1 to 18, more preferably in the range of 1 to 10, and further preferably in the range of 1 to 8.

Of these, potassium perfluorobutane sulfonate is particularly preferable. Fluoride ions (F-) are usually mixed in the alkali (earth) metal salt of perfluoroalkyl sulfonic acid composed of an alkali metal. Since the presence of such fluoride ions can be a factor of reducing the flame retardancy, it is preferable to reduce it as much as possible. The ratio of such fluoride ions can be measured by an ion chromatography method. The fluoride ion content is preferably 100 ppm or less, more preferably 40 ppm or less, and particularly preferably 10 ppm or less. Further, it is preferable that the production efficiency is 0.2 ppm or more. Such a perfluoroalkylsulfonic acid alkali (earth) metal salt having a reduced amount of fluoride ions is produced by using a known production method and is contained in a raw material for producing a fluorine-containing organic metal salt. Method for reducing the amount of fluoride ions, method for removing hydrogen fluoride obtained by the reaction by gas generated during the reaction and heating, and purification method for producing fluorine-containing organometallic salt by recrystallization and reprecipitation Can be used to reduce the amount of fluoride ions. In particular, the organic metal salt flame retardant is relatively soluble in water, and therefore ion-exchanged water, particularly water having an electric resistance value of 18 MΩ·cm or more, that is, an electric conductivity of about 0.55 μS/cm or less is used. Moreover, it is preferable to manufacture by a step of melting and washing at a temperature higher than room temperature, followed by cooling and recrystallization.

Specific examples of the alkaline (earth) aromatic sulfonic acid metal salt include, for example, diphenyl sulfide-4,4′-disodium disulfonate, diphenyl sulfide-4,4′-dipotassium disulfonate, potassium 5-sulfoisophthalate, and the like. Sodium 5-sulfoisophthalate, Polysodium polyethylene terephthalate, Polysodium polysulfonate, Calcium 1-methoxynaphthalene-4-sulfonate, Disodium 4-dodecylphenyl ether disulfonate, Polysodium poly(2,6-dimethylphenylene oxide) 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 sulfonate of benzenesulfonate, sodium benzenesulfonate, strontium benzenesulfonate, magnesium benzenesulfonate, 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, Examples thereof include calcium thiophene-2,5-disulfonate, sodium benzothiophene sulfonate, potassium diphenyl sulfoxide-4-sulfonate, formalin condensate of sodium naphthalene sulfonate, and formalin condensate of sodium anthracene sulfonate. it can. Of these aromatic (earth) aromatic sulfonic acid metal salts, potassium salts are particularly preferable. Among these aromatic (earth) aromatic sulfonic acid metal salts, potassium diphenylsulfone-3-sulfonate and diphenylsulfone-3,3′-dipotassium disulfonate are preferable, and particularly a mixture thereof (the former and the latter). Is preferably 15/85 to 30/70).

Preferable examples of the organic metal salt other than the alkali (earth) metal sulfonate include alkali (earth) metal salts of sulfuric acid ester and alkali (earth) metal salts of aromatic sulfonamide. Examples of alkali (earth) metal salts of sulfuric acid esters include alkali (earth) metal salts of sulfuric acid esters of monohydric and/or polyhydric alcohols, and such monohydric and/or polyhydric alcohols can be mentioned. As the sulfuric acid ester of, methyl sulfuric acid ester, ethyl sulfuric acid ester, lauryl sulfuric acid ester, hexadecyl sulfuric acid ester, sulfuric acid ester of polyoxyethylene alkyl phenyl ether, pentaerythritol mono-, di-, tri-, tetra-sulfuric acid ester, sulfuric acid of lauric acid monoglyceride Examples thereof include esters, sulfuric acid esters of palmitic acid monoglyceride, and sulfuric acid esters of stearic acid monoglyceride. Preferable examples of the alkali (earth) metal salt of these sulfates include alkali (earth) metal salts of lauryl sulfate. Examples of the alkaline (earth) metal salt of aromatic sulfonamide include saccharin, N-(p-tolylsulfonyl)-p-toluenesulfoimide, N-(N'-benzylaminocarbonyl)sulfanylimide, and N-( Examples thereof include an alkali (earth) metal salt of phenylcarboxylic)sulfanylimide. The content of the organic metal salt-based flame retardant is preferably 0.001 to 1 part by weight, more preferably 0.005 to 0.5 part by weight, and more preferably 100 to 1 part by weight with respect to the total of 100 parts by weight of the component A and the component B. It is preferably 0.01 to 0.3 part by weight, and particularly preferably 0.03 to 0.15 part by weight.

(Ii) Organic Phosphorus Flame Retardant An aryl phosphate compound or a phosphazene compound is preferably used as the organic phosphorus flame retardant. Since these organic phosphorus flame retardants have a plasticizing effect, they are advantageous in that molding processability can be improved. As the aryl phosphate compound, various phosphate compounds conventionally known as flame retardants can be used, but 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 divalent phenol, and Ar ¹ , Ar ² , Ar ³ and Ar ⁴ are each a monovalent organic group derived from a monovalent phenol. 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 phosphoric acid esters having different degrees of polymerization m, m is the average value thereof. It is a value of 0-5.

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

Specific examples of suitable dihydric phenols for inducing M include hydroquinone, resorcinol, bis(4-hydroxydiphenyl)methane, bisphenol A, dihydroxydiphenyl, dihydroxynaphthalene, bis(4-hydroxyphenyl)sulfone, bis(4 -Hydroxyphenyl)ketone and bis(4-hydroxyphenyl)sulfide are exemplified, and among them, resorcinol, bisphenol A, and dihydroxydiphenyl are preferable.

Preferable specific examples of the monohydric phenol for inducing Ar ¹ , Ar ² , Ar ³ and Ar ⁴ include phenol, cresol, xylenol, isopropylphenol, butylphenol, and p-cumylphenol, among which preferred. Are phenol and 2,6-dimethylphenol.

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

On the other hand, specific examples of the phosphate compound not substituted by a halogen atom include monophosphate compounds such as triphenyl phosphate and tri(2,6-xylyl)phosphate, and resorcinol bisdi(2,6-xylyl)phosphate). Phosphate oligomers having a main component, phosphate oligomers having 4,4-dihydroxydiphenylbis(diphenylphosphate) as a main component, and phosphoric acid ester oligomers having a bisphenol A bis(diphenylphosphate) as a main component are preferable. Indicates that a small amount of another component having a different polymerization degree may be contained, 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 further preferably 90% by weight or more).

As the phosphazene compound, various phosphazene compounds conventionally known as flame retardants can be used, 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。）

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

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

The content of the organophosphorus 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 based on 100 parts by weight of the total of the components A and B. Is more preferable. If the compounding amount of the organic phosphorus flame retardant is less than 1 part by weight, the flame retarding effect may not be obtained, and if it exceeds 50 parts by weight, strand breakage or surging may occur during kneading and extrusion, resulting in a decrease in productivity. It may occur.

(Iii) Silicone-based flame retardant The silicone compound used as the silicone-based flame retardant improves flame retardancy by a chemical reaction during combustion. As the compound, various compounds conventionally proposed as flame retardants for aromatic polycarbonate resins can be used. The silicone compound is highly flame-retardant, especially when a polycarbonate resin is used, by forming a structure by combining itself with a component derived from a resin or by combining with a component derived from a resin during its combustion. It is believed to give an effect.

Therefore, it is preferable to contain a group having a high activity in such a reaction, and more specifically, it is preferable to contain a predetermined amount of at least one group selected from an alkoxy group and a hydrogen (that is, Si—H group). preferable. The content ratio of such a group (alkoxy group, Si—H group) is preferably 0.1 to 1.2 mol/100 g, more preferably 0.12 to 1 mol/100 g, and 0.15 to 0. The range of 6 mol/100 g is more preferable. Such a ratio can be determined by measuring the amount of hydrogen or alcohol generated per unit weight of the silicone compound by the alkali decomposition method. The alkoxy group is preferably an alkoxy group having 1 to 4 carbon atoms, and particularly preferably a methoxy group.

Generally, the structure of a silicone compound is formed by arbitrarily combining the following four types of siloxane units. That, M _{units: (CH 3) 3 SiO 1/2} , H (CH 3) 2 SiO 1/2, H 2 (CH 3) SiO 1/2, (CH 3) 2 (CH 2 = CH) SiO 1 _1/2 , (CH ₃ ) ₂ (C ₆ H ₅ )SiO _1/2 , (CH ₃ )(C ₆ H ₅ )(CH ₂ ═CH)SiO _1/2, etc., a monofunctional siloxane unit, D unit: _{(CH 3) 2 SiO, H} (CH 3) SiO, H 2 SiO, H (C 6 H 5) SiO, (CH 3) (CH 2 = CH) SiO, (C 6 H 5) 2 2 such as SiO functional siloxane units, T _{units: (CH 3) SiO 3/2,} (C 3 H 7) SiO 3/2, HSiO 3/2, (CH 2 = CH) SiO 3/2, (C 6 H 5) A trifunctional siloxane unit such as SiO _3/2 , and a Q unit: a tetrafunctional siloxane unit represented by SiO ₂ .

Specific examples of the structure of the silicone compound used for the silicone-based flame retardant include Dn, Tp, MmDn, MmTp, MmQq, MmDnTp, MmDnQq, MmTpQq, MmDnTpQq, DnTp, DnQq and DnTpQq. Of these, preferred structures of the silicone compound are MmDn, MmTp, MmDnTp, and MmDnQq, and more preferred structures are MmDn or MmDnTp.

Here, the coefficients m, n, p, and q in the rational formula are integers of 1 or more representing the degree of polymerization of each siloxane unit, and the sum of the coefficients in each rational formula is the average degree of polymerization of the silicone compound. .. This average degree of polymerization is preferably in the range of 3 to 150, more preferably in the range of 3 to 80, further preferably in the range of 3 to 60, and particularly preferably in the range of 4 to 40. The more preferable the range is, the more excellent the flame retardancy becomes. Further, as will be described later, a silicone compound containing a predetermined amount of an aromatic group is also excellent in transparency and hue. As a result, good reflected light can be obtained. When any of m, n, p, and q has a numerical value of 2 or more, the siloxane unit having the coefficient can be two or more kinds of siloxane units having different hydrogen atoms or organic residues bonded. ..

The silicone compound may be linear or may have a branched structure. The organic residue bonded to the silicon atom is preferably an organic residue having 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms. Specific examples of the organic residue include an alkyl group such as a methyl group, an ethyl group, a propyl group, a butyl group, a hexyl group, and a decyl group, a cycloalkyl group such as a cyclohexyl group, an aryl group such as a phenyl group, Also mentioned are aralkyl groups such as tolyl groups. More preferably, they are a C1-C8 alkyl group, an alkenyl group, or an aryl group. As the alkyl group, an alkyl group having 1 to 4 carbon atoms such as a methyl group, an ethyl group, and a propyl group is particularly preferable. Further, the silicone compound used as the silicone-based flame retardant preferably contains an aryl group. On the other hand, the silane compound and the siloxane compound as the organic surface treatment agent for the titanium dioxide pigment are clearly distinguished from the silicone-based flame retardant in that they are preferable in that they do not contain an aryl group. .. The silicone compound used as the silicone-based flame retardant may contain a reactive group other than the Si-H group and the alkoxy group, and examples of the reactive group include an amino group, a carboxyl group, an epoxy group, and a vinyl group. Examples thereof include a group, a mercapto group, and a methacryloxy group.

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 further preferably 1 to 5 with respect to 100 parts by weight of the total of the components A and B. Parts by weight.

(Iv) Polytetrafluoroethylene having fibril forming ability (fibrillated PTFE)
The fibrillated PTFE may be fibrillated PTFE alone or a mixed form of fibrillated PTFE, that is, a polytetrafluoroethylene-based mixture of fibrillated PTFE particles and an organic polymer. The fibrillated PTFE has an extremely high molecular weight, and tends to be bonded to each other to form a fibrous state by an external action such as a shearing force. Its number average molecular weight is in the range of 1.5 million to tens of millions. The lower limit is more preferably 3 million. The number average molecular weight is calculated based on the melt viscosity of polytetrafluoroethylene at 380° C., for example, as disclosed in JP-A-6-145520. That is, the fibrillated PTFE has a melt viscosity at 380° C. measured by the method described in the publication of 10 ⁷ to 10 ¹³ poise, and preferably 10 ⁸ to 10 ¹² poise. In addition to the solid form, such PTFE may be used in the form of an aqueous dispersion. It is also possible to use a PTFE mixture in the form of a mixture with other resins in order to improve the dispersibility of the fibrillated PTFE in the resin and to obtain better flame retardancy and mechanical properties.

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

As the fibrillated PTFE in a mixed form, (1) a method in which an aqueous dispersion of fibrillated PTFE 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). JP-A No. 63-154744), and (2) a method of mixing an aqueous dispersion of fibrillated PTFE with dried organic polymer particles (JP-A-4-272957). Described method), (3) a method of uniformly mixing an aqueous dispersion of fibrillated PTFE and a solution of organic polymer particles, and simultaneously removing respective media from the mixture (Japanese Patent Laid-Open No. 06-220210, Japanese Patent Laid-Open No. 06-220210). 08-188653) and (4) a method of polymerizing a monomer forming an organic polymer in an aqueous dispersion of fibrillated PTFE (described in JP-A-9-95583). Method), and (5) a method in which an aqueous dispersion of PTFE and an organic polymer dispersion are uniformly mixed, and then vinyl monomers are further polymerized in the mixed dispersion, and then a mixture is obtained (JP-A-11- Those obtained by the method described in Japanese Patent Publication No. 29679) can be used.

Examples of commercially available fibrillated PTFE in the mixed form include METAVEBLEN A3000 (trade name), METAVEBLEN A3700 (trade name), and METABrene A3800 (trade name) manufactured by Mitsubishi Rayon Co., Ltd. Examples include the A series, SN3300B7 (trade name) manufactured by Shine Polymer, and “BLENDEX B449” (trade name) manufactured by GE Specialty Chemicals.

The proportion of fibrillated PTFE in the mixed form is preferably 1% by weight to 95% by weight, more preferably 10% by weight to 90% by weight, and more preferably 20% by weight, in 100% by weight of the mixture. Most preferred is between 80% and 80% by weight.
When the proportion of fibrillated PTFE in the mixed form is in such a range, good dispersibility of fibrillated PTFE can be achieved. The content of fibrillated PTFE is preferably 0.001 to 0.5 parts by weight, more preferably 0.01 to 0.5 parts by weight, based on 100 parts by weight of the total resin components of the A component and the B component. 0.1 to 0.5 parts by weight is more preferable.

(III) Dye/pigment The thermoplastic resin composition of the present invention can further contain various dyes/pigments to provide molded articles exhibiting various design properties. The dyes and pigments used in the present invention, perylene dyes, coumarin dyes, thioindigo dyes, anthraquinone dyes, thioxanthone dyes, ferrocyanides such as dark blue, perinone dyes, quinoline dyes, quinacridone dyes, Examples thereof include dioxazine dyes, isoindolinone dyes, and phthalocyanine dyes. Further, 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 adding a fluorescent whitening agent or a fluorescent dye which emits light other than the fluorescent whitening agent, it is possible to impart a more excellent design effect by utilizing the emission color.

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

(V) Compound Having Heat Ray Absorption Ability The thermoplastic resin composition of the present invention may contain a compound having heat ray absorption ability. Examples of such compounds include phthalocyanine-based near-infrared absorbers, metal oxide-based near-infrared absorbers such as ATO, ITO, iridium oxide and ruthenium oxide, immonium oxide and titanium oxide, lanthanum boride, cerium boride and tungsten boride. Suitable examples are various metal compounds having excellent near-infrared absorbing ability such as metal boride-based or 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 easily available. Examples of the carbon filler include carbon black, graphite (including both natural and artificial) and fullerene, and carbon black and graphite are preferable. These can be used alone or in combination of two or more. The content of the phthalocyanine near-infrared absorber is preferably 0.0005 to 0.2 parts by weight, more preferably 0.0008 to 0.1 parts by weight, based on 100 parts by weight of the total of the components A and B. , 0.001 to 0.07 parts by weight are more preferable. The content of the metal oxide-based near-infrared absorber, the metal boride-based 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, 0 The range of 0.5 to 100 ppm is more preferable.

(VI) Light Diffusing Agent A light diffusing agent can be added to the thermoplastic resin composition of the present invention to impart a light diffusing effect. Examples of such a light diffusing agent include polymer fine particles, low refractive index inorganic fine particles such as calcium carbonate, and composites thereof. Such polymer fine particles are fine particles already known as a light diffusing agent for polycarbonate resins. More preferred are acrylic crosslinked particles having a particle size of several μm and silicone crosslinked particles represented by polyorganosilsesquioxane. Examples of the shape of the light diffusing agent include a spherical shape, a disk shape, a pillar shape, and an amorphous shape. Such spheres include deformed shapes that need not be perfect spheres, and such columnar shapes include cubes. The preferred light diffusing agent is spherical, and it is more preferable that the particle size is uniform. 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 further preferably 0.01 with respect to 100 parts by weight of the total of the components A and B. ~ 3 parts by weight. Two or more light diffusing agents can be used in combination.

(VII) White pigment for high light reflection The thermoplastic resin composition of the present invention may be blended with a white pigment for high light reflection to impart a light reflection effect. As such a white pigment, a titanium dioxide (particularly titanium dioxide treated with an organic surface treating agent such as silicone) pigment is particularly preferable. 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 total of the components A and B. Two or more kinds of white pigments for high light reflection can be used in combination.

(VIII) Ultraviolet absorber An ultraviolet absorber can be blended with the thermoplastic resin composition of the present invention to impart weather resistance thereto. Specific examples of such an ultraviolet absorber include benzophenone-based compounds such as 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-octoxybenzophenone, and 2-hydroxy-4-benzdiene. Roxybenzophenone, 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 Examples include -4-n-dodecyloxybenzophenone and 2-hydroxy-4-methoxy-2'-carboxybenzophenone. Specific examples of the ultraviolet absorber include 2-(2-hydroxy-5-methylphenyl)benzotriazole and 2-(2-hydroxy-5-tert-octylphenyl)benzotriazole in the benzotriazole type. , 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)benzotriazo- 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 A copolymer of a vinyl monomer copolymerizable with the monomer or a copolymer of 2-(2'-hydroxy-5-acryloxyethylphenyl)-2H-benzotriazole with a vinyl monomer copolymerizable with the monomer. Examples thereof include polymers having a 2-hydroxyphenyl-2H-benzotriazole skeleton such as polymers. Specific examples of the ultraviolet absorber include 2-(4,6-diphenyl-1,3,5-triazin-2-yl)-5-hexyloxyphenol and 2-(4, in the hydroxyphenyltriazine type. 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 are exemplified. Furthermore, the phenyl group of the above exemplified compounds such as 2-(4,6-bis(2,4-dimethylphenyl)-1,3,5-triazin-2-yl)-5-hexyloxyphenol is 2,4-dimethyl. A compound having a phenyl group is exemplified. Specific examples of the ultraviolet absorber include, for example, 2,2′-p-phenylene bis(3,1-benzoxazin-4-one) and 2,2′-m-phenylene bis(3,1) in the cyclic imino ester type. -Benzoxazin-4-one), 2,2'-p,p'-diphenylenebis(3,1-benzoxazin-4-one), and the like. As the ultraviolet absorber, specifically, in the case of a cyanoacrylate type, for example, 1,3-bis-[(2′-cyano-3′,3′-diphenylacryloyl)oxy]-2,2-bis[(2- Examples are cyano-3,3-diphenylacryloyl)oxy]methyl)propane, 1,3-bis-[(2-cyano-3,3-diphenylacryloyl)oxy]benzene, and the like. Further, the ultraviolet absorber has a structure of a monomer compound capable of radical polymerization, so that the ultraviolet absorber and/or the photostable monomer are combined with a monomer such as an alkyl (meth)acrylate. It may be a polymer type ultraviolet absorber obtained by copolymerizing with the body. Preferred examples of the ultraviolet absorbing monomer include compounds having a benzotriazole skeleton, a benzophenone skeleton, a triazine skeleton, a cyclic iminoester skeleton, and a cyanoacrylate skeleton in the ester substituent of a (meth)acrylic acid ester. It Among the above, a benzotriazole type and a hydroxyphenyl triazine type are preferable from the viewpoint of ultraviolet absorbing ability, and a cyclic iminoester type and a cyanoacrylate type are preferable from the viewpoint of heat resistance and hue. Specific examples thereof include “Chemisorb 79” from Chemipro Kasei Co., Ltd. and “Tinubin 234” from BASF Japan Ltd. The UV absorbers may be used alone or as a mixture of two or more kinds.

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 further preferably 0.05 with respect to 100 parts by weight of the total 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 a case, it is preferable to include an antistatic agent. Examples of such antistatic agents include (1) phosphonium salts of aryl sulfonic acids represented by phosphonium salts of dodecylbenzene sulfonic acid, phosphonium salts of alkyl sulfonic acids such as phosphonium salts, and phosphonium salts of tetrafluoroboric acid. Examples include phosphonium borate salts. The content of the phosphonium salt is appropriately 5 parts by weight or less, preferably 0.05 to 5 parts by weight, and more preferably 1 to 3.5 parts by weight, relative to 100 parts by weight of the components consisting of the components A and B. Parts, more preferably 1.5 to 3 parts by weight. Examples of the antistatic agent include (2) lithium organic sulfonate, organic sodium sulfonate, potassium organic sulfonate, cesium organic sulfonate, rubidium organic sulfonate, calcium organic sulfonate, magnesium organic sulfonate, and barium organic sulfonate. Examples thereof include alkali (earth) metal salts of organic sulfonates such as. As described above, such metal salt is also used as a flame retardant. More specific examples of such metal salts include metal salts of dodecylbenzenesulfonic acid and metal salts of perfluoroalkanesulfonic acid. The content of the alkali (earth) metal salt of organic sulfonic acid is appropriately 0.5 parts by weight or less, preferably 0.001 to 0.3 parts by weight, relative to 100 parts by weight of the components A and B. Parts, and more preferably 0.005 to 0.2 parts by weight. Alkali metal salts such as potassium, cesium, and rubidium are particularly preferable.

Examples of the antistatic agent include (3) ammonium salt of alkyl sulfonic acid, and ammonium salt of organic sulfonic acid such as ammonium salt of aryl sulfonic acid. The appropriate amount of the ammonium salt is 0.05 parts by weight or less based on 100 parts by weight of the component A and the component B. Examples of the antistatic agent include polymers containing (4) a poly(oxyalkylene) glycol component such as a polyether ester amide as its constituent component. The amount of the polymer is suitably 5 parts by weight or less based on 100 parts by weight of the total of the components A and B.

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

Plate-like fillers include glass flakes, talc, mica, kaolin, metal flakes, carbon flakes, and graphite, and plate-like fillers obtained by coating these fillers with different materials such as metals and metal oxides. Materials and the like are preferably exemplified. The particle size is preferably in the range of 0.1 to 300 μm. Such a particle size refers to a value by 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 area up to about 10 μm, and the laser diffraction in the area of 10 to 50 μm. -It means the value by the median diameter (D50) of the particle size distribution measured by the scattering method, and the value by the vibration sieving method in the region of 50 to 300 m. The particle size is the particle size in the resin composition. The plate-like filler may be surface-treated with a coupling agent such as various silane-based, titanate-based, aluminate-based, and zirconate-based fillers, and olefin-based resins, styrene-based resins, acrylic-based resins, polyester-based resins. Granules that have been subjected to a focusing treatment or a compression treatment with various resins such as epoxy resin, urethane resin and higher fatty acid ester may be used.

(XI) Other Resins and Elastomers In the thermoplastic resin composition of the present invention, other resins or elastomers exhibit the effects of the present invention in place of some of the resin components, as long as the effects of the present invention are not impaired. A small proportion can be used within the range. The amount of the other resin or elastomer compounded 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, most preferably 100 parts by weight of the resin component consisting of the 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, polymethacrylate resins. Resins such as phenol resin and epoxy resin can be used. Examples of the elastomer include isobutylene/isoprene rubber, styrene/butadiene rubber, ethylene/propylene rubber, acrylic elastomer, polyester elastomer, polyamide elastomer, and core-shell type MBS (methyl methacrylate/sterene/butadiene). Examples thereof include rubber, MB (methyl methacrylate/butadiene) rubber, and MAS (methyl methacrylate/acrylonitrile/styrene) rubber.

(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 and photochromic agents. ..

<Production of 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 producing such pellets, the above-mentioned various reinforcing fillers and additives can be blended.

<Production of molded products>
The thermoplastic resin composition of the present invention can be manufactured into various products by injection-molding the pellets usually manufactured as described above. Further, the resin melt-kneaded by an extruder can be directly made into a sheet, a film, a profile extrusion molded product, a direct blow molded product, and an injection molded product without passing through pellets. In such injection molding, not only ordinary molding methods but also injection compression molding, injection press molding, gas assist injection molding, foam molding (including injection by supercritical fluid), insert molding, according to the purpose as appropriate. Molded articles can be obtained using injection molding methods such as in-mold coating molding, heat insulation mold molding, rapid heating and cooling mold molding, two-color molding, sandwich molding, and ultra-high speed injection molding. The advantages of these various molding methods are already widely known. Further, either cold runner method or hot runner method can be selected for molding. The resin composition of the present invention can also be used in the form of various shaped extrusion molded articles, sheets, films and the like by extrusion molding. 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 resin composition of the present invention can be formed into a molded product by rotational molding or blow molding.

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

A mode for carrying out the present invention is a compilation of preferable ranges of the above-mentioned requirements, and representative examples thereof will be described in the following examples. Of course, the present invention is not limited to these forms.

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

(Evaluation of thermoplastic resin composition)
(I) Amount of change in viscosity average molecular weight Amount of decrease in viscosity average molecular weight between a test piece obtained by molding after holding for 10 minutes in a cylinder under the same conditions as in the following method and pellets 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 article after 10 minutes retention)
(Ii) Liquidity (MFR)
The MFR at a temperature of 280° C. and a load of 2.16 kg was measured according to JIS K-6719.
(Iii) Charpy impact strength Using an ISO bending test piece obtained by the following method, the Charpy impact strength with notch at 23°C and -30°C was measured according to ISO179. The resin composition of the present invention needs to 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 The deflection temperature under load (load 0.45 MPa) was measured according to ISO75-1 and ISO75-2 using the ISO bending test piece obtained by the following method. The resin composition of the present invention needs to have a deflection temperature under load of 130°C or higher.

(A component)
[Production of Polycarbonate-Polyorganosiloxane Copolymer Resin (A-1)]
A reactor equipped with a thermometer, a stirrer and a reflux condenser was charged with 21591 parts of ion-exchanged water and 3674 parts of a 48.5% sodium hydroxide aqueous solution, and 3880 parts of 2,2-bis(4-hydroxyphenyl)propane (bisphenol A). , And 7.6 parts of hydrosulfite were dissolved, 14565 parts of methylene chloride (14 mols relative to 1 mol of dihydroxy compound (I)) was added, and 1900 parts of phosgene was added for 60 minutes at 22 to 30° C. under stirring. I blown in. Next, a solution prepared by dissolving 1131 parts of a 48.5% sodium hydroxide aqueous solution and 105 parts of p-tert-butylphenol in 800 parts of methylene chloride was added, and the polydiorganosiloxane compound 430 represented by the following formula (11) was stirred while stirring. A solution of 1 part of methylene chloride in 1600 parts of methylene chloride was added at a rate such that the dihydroxyaryl-terminated polydiorganosiloxane was 0.0008 mol/min per 1 mol of the dihydric phenol (I) to give an emulsified state, and then again vigorously. It was stirred. Under such stirring, 4.3 parts of triethylamine was added while the reaction liquid was at 26° C., and stirring was continued at a temperature of 26 to 31° C. for 45 minutes to complete the reaction. After the reaction was completed, the organic phase was separated, diluted with methylene chloride, washed with water, acidified with hydrochloric acid and washed with water. Then, methylene chloride was evaporated with stirring to obtain a powder of polycarbonate-polydiorganosiloxane copolymer resin. After dehydration, it was dried at 120° C. for 12 hours by a hot air circulation dryer to obtain a polycarbonate-polydiorganosiloxane copolymer resin powder. (Polydiorganosiloxane component content 8.2%, average size of polydiorganosiloxane domain 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, as dihydric phenol residue, 8.2 kg (36 mol) of 2,2-bis(4-hydroxyphenyl)propane, 1,1-bis(4-hydroxyphenyl)-3 ,3,5-Trimethylcyclohexane 11.1 kg (36 mol), 4,4-dihydroxy-biphenyl 3.4 kg (18 mol), p-tert-butylphenol as a molecular weight modifier (hereinafter, may be abbreviated as PTBP) 670 g (4.4 mol) of PTBP manufactured by DIC, 8.6 kg (213 mol) of sodium hydroxide (manufactured by Tosoh Corporation) as an alkali, and benzyl-tri-n-butylammonium chloride (hereinafter abbreviated as BTBAC) as a polymerization catalyst. 373 g (Lion Akzo Co., Ltd. BTBAC-50), 107 g of sodium hydrosulfaphyto (hereinafter sometimes abbreviated as SHS) (BASF Co.), and 400 L of water is further injected into the reaction vessel. It was then dissolved and used as the aqueous phase.

Furthermore, in another reaction vessel, 240 L of dichloromethylene (methylene chloride manufactured by Tokuyama Corp.) was mixed with phthalic acid chloride (MPC manufactured by Ihara Nikkei Chemical Co., Ltd.; terephthalic acid/isophthalic acid=50/50 (mass %)). 6 kg (91 mol) was dissolved to give an organic phase. This organic phase was added to the already stirred aqueous phase under strong stirring, and the temperature was kept at 15° C. to carry out a polymerization reaction for 2 hours. After this, stirring was stopped and the aqueous phase and the organic phase were separated by decantation. To the organic phase from which the aqueous phase was removed, 400 L of pure water and 100 mL of acetic acid were added to stop the reaction, and the mixture was further stirred at 15°C for 30 minutes. This organic phase was washed 5 times with pure water, and the organic phase was added to 400 L of hexane to precipitate a polymer. The precipitated polymer was separated from the organic phase and then dried to obtain a polyarylate resin (B-1). When the composition of the obtained polyarylate resin (B-1) was analyzed using ¹ H-NMR (ECA500 NMR manufactured by JEOL Ltd.), the polymerization ratio of the dihydric phenol residue and the phthalic acid residue was 1: It was confirmed that it was 1, which was the same as the mixing ratio of the dihydric phenol residue and the phthalic acid residue. The viscosity average molecular weight of the obtained polyarylate resin was 19,300. The results are shown in Table 1.

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

The components represented by symbols in Table 1 are 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 1-5, Comparative Examples 1-3)
The mixture having the composition shown in Table 2 was fed from the first feed port of the extruder. Such a mixture was obtained by mixing with a V-type blender. The twin-screw extruder has a diameter of 30 mmφ and is equipped with one vent having a total of 10 barrel configurations (from the upstream side, referred to as C1-C10 cylinders) having a supply port at C1 at the most upstream side and C5 at the downstream side. A "TEX30αIII" meshing type co-rotating twin-screw extruder manufactured by Steel Works was used. The extrusion conditions were temperature C1:300° C., C2-10:310° C., screw rotation speed 200 rpm, discharge amount 25 kg/h, vent vacuum 3 kPa, and melt kneading to obtain pellets.
A part of the obtained pellets was dried at 120° C. for 6 hours with a hot air circulation dryer, and then an ISO bending test piece for evaluation was used with an injection molding machine at a cylinder temperature of 310° C. and a mold temperature of 90° C. (ISO 179 and ISO 75-1, 75-2 conformity) was shape|molded and each evaluation was implemented. The evaluation results are shown in Table 2.

The components represented by symbols in Table 2 are as follows.
(A component)
A-1: Resin (component B) synthesized in [Production of polycarbonate-polyorganosiloxane copolymer resin (A-1)]
B-1: Resin produced by [Production of polyarylate resin (B-1)] B-2: Resin produced by [Production of polyarylate resin (B-2)] B-3: [Polyarylate resin] Manufacturing of (B-3)] (C component)
C-1: Aromatic polycarbonate resin (polycarbonate resin powder made from bisphenol A and phosgene with a viscosity average molecular weight of 19,700 by a conventional method, Panlite L-1225WX (product name) manufactured by Teijin Ltd.)
(Other ingredients)
STB-3: Phosphorus heat stabilizer (trimethyl phosphate, manufactured by Daihachi Chemical Industry Co., Ltd. TMP)

Claims (5)

(A) 90-99 parts by weight of a polycarbonate-polydiorganosiloxane copolymer resin (A component) 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).

(In the 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, and 6 to 6 carbon atoms. 20 cycloalkyl group, C6-20 cycloalkoxy group, C2-10 alkenyl group, C6-14 aryl group, C6-14 aryloxy group, 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, and when there are a plurality of groups, they may be the same or different. A and b are each an integer of 1 to 4, and W is a single bond or at least one group selected from the group consisting of groups represented by the following general formula (2).)

(In the general formula (2), 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, or a carbon atom. 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, wherein R ¹⁹ and R ²⁰ are each independently a hydrogen atom, a halogen atom, or a carbon atom number of 1 to 18; Alkyl group having 1 to 10 carbon atoms, cycloalkyl group having 6 to 20 carbon atoms, cycloalkoxy group having 6 to 20 carbon atoms, alkenyl group having 2 to 10 carbon atoms, and 6 carbon atoms From an aryl group having 14 to 14 carbon atoms, an aryloxy group having 6 to 10 carbon atoms, 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. Represents a group selected from the group consisting of two or more, and when there are a plurality of groups, 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 carbons or a substituent having 6 to 12 carbons. 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, and e and f Are integers of 1 to 4, p is a natural number, q is 0 or a natural number, p+q is a natural number of 4 or more and 150 or less, and X is a divalent aliphatic group having 2 to 8 carbon atoms. .) The thermoplastic resin composition according to claim 1, wherein the component B is a polyarylate resin containing a polymerized unit represented by any one of the following general formulas (4) to (6).

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

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

(In the general formula (6), n is a positive integer.) The thermoplastic resin composition according to claim 1 or 2, wherein the component B has a viscosity average molecular weight of 10,000 to 50,000. 4. The composition according to claim 1, wherein the component (C) is contained in an amount of 0.01 to 2 parts by weight based on 100 parts by weight of the total of the components A and B. Thermoplastic resin composition. A molded product obtained by molding the thermoplastic resin composition according to claim 1.