JP7368253B2 - thermoplastic resin composition - Google Patents

Description

The present invention relates to thermoplastic resin compositions. More specifically, by blending appropriate amounts of a phosphoric acid ester compound, a phenol compound, and a rubbery polymer into a resin component consisting of a polycarbonate resin and a polyarylate resin, resin deterioration during molding retention and in high-temperature, high-humidity environments, The present invention relates to a thermoplastic resin composition with improved heat resistance and impact resistance properties.

Compositions made of polycarbonate resins, polyarylate resins, and rubbery polymers have excellent properties such as heat resistance, mechanical strength, dimensional stability, and flame retardancy, and their molded products are used in electrical and electronic equipment parts, automobile parts, and machinery. It is widely applied in the field of parts and the like (see Patent Documents 1 and 2). However, the above resin composition has a problem in resin deterioration during molding retention and under high temperature and high humidity environments.

Japanese Patent Application Publication No. 4-279654 Japanese Patent Application Publication No. 2007-332316

An object of the present invention is to provide a thermoplastic resin composition that has excellent heat resistance and impact resistance, and suppresses resin deterioration during molding retention and in high temperature and high humidity environments.

As a result of extensive studies in order to achieve the above object, the present inventors have found that appropriate amounts of a phosphoric acid ester compound, a phenol compound, and a rubbery polymer are blended into a resin composition consisting of a polycarbonate resin and a polyarylate resin. It was discovered that a thermoplastic resin composition with improved heat resistance, impact resistance, and resin deterioration during molding retention and in a high temperature and high humidity environment could be obtained, and after further intensive studies, the present invention was completed.

The present invention will be explained in detail below.

<Component A: Polycarbonate resin>
The polycarbonate resin used in the present invention is obtained by reacting a dihydric phenol with a carbonate precursor. Examples of reaction methods include interfacial polymerization, melt transesterification, solid phase transesterification of carbonate prepolymers, and ring-opening polymerization of cyclic carbonate compounds.

Representative examples of dihydric phenols used here include hydroquinone, resorcinol, 4,4'-biphenol, 1,1-bis(4-hydroxyphenyl)ethane, 2,2-bis(4-hydroxyphenyl) ) Propane (commonly known as bisphenol A), 2,2-bis(4-hydroxy-3-methylphenyl)propane, 2,2-bis(4-hydroxyphenyl)butane, 1,1-bis(4-hydroxyphenyl)- 1-phenylethane, 1,1-bis(4-hydroxyphenyl)cyclohexane, 1,1-bis(4-hydroxyphenyl)-3,3,5-trimethylcyclohexane, 2,2-bis(4-hydroxyphenyl) Pentane, 4,4'-(p-phenylene diisopropylidene) diphenol, 4,4'-(m-phenylene diisopropylidene) diphenol, 1,1-bis(4-hydroxyphenyl)-4-isopropylcyclohexane , bis(4-hydroxyphenyl) oxide, bis(4-hydroxyphenyl) sulfide, bis(4-hydroxyphenyl) sulfoxide, bis(4-hydroxyphenyl) sulfone, bis(4-hydroxyphenyl) ketone, bis(4- Examples include hydroxyphenyl) ester, bis(4-hydroxy-3-methylphenyl) sulfide, 9,9-bis(4-hydroxyphenyl)fluorene, and 9,9-bis(4-hydroxy-3-methylphenyl)fluorene. It will be done. Preferred dihydric phenols are bis(4-hydroxyphenyl)alkanes, and among them, bisphenol A is particularly preferred from the viewpoint of impact resistance and is widely used.

In the present invention, in addition to bisphenol A-based polycarbonate resin, which is a general-purpose polycarbonate resin, special polycarbonate resins produced using other dihydric phenols can be used as the A component.

For example, as part or all of the divalent phenol component, 4,4'-(m-phenylenediisopropylidene) diphenol (hereinafter sometimes abbreviated as "BPM"), 1,1-bis(4-hydroxy phenyl)cyclohexane, 1,1-bis(4-hydroxyphenyl)-3,3,5-trimethylcyclohexane (hereinafter sometimes abbreviated as "Bis-TMC"), 9,9-bis(4-hydroxyphenyl) Polycarbonate resin (homopolymer or copolymer) using fluorene and 9,9-bis(4-hydroxy-3-methylphenyl)fluorene (hereinafter sometimes abbreviated as "BCF") It is suitable for applications with particularly strict requirements for dimensional change and morphological stability. It is preferable to use these dihydric phenols other than BPA in an amount of 5 mol % or more, particularly 10 mol % or more of the total dihydric phenol components constituting the polycarbonate resin.

In particular, when high rigidity and better hydrolysis resistance are required, it is particularly preferable that component A constituting the resin composition is a copolymerized polycarbonate resin of the following (1) to (3). It is.
(1) BPM is 20 to 80 mol% (more preferably 40 to 75 mol%, even more preferably 45 to 65 mol%) in 100 mol% of the dihydric phenol component constituting the polycarbonate resin, and A copolycarbonate resin containing BCF of 20 to 80 mol% (more preferably 25 to 60 mol%, even more preferably 35 to 55 mol%).
(2) BPA is 10 to 95 mol% (more preferably 50 to 90 mol%, still more preferably 60 to 85 mol%) in 100 mol% of the dihydric phenol component constituting the polycarbonate resin, and A copolycarbonate resin containing BCF of 5 to 90 mol% (more preferably 10 to 50 mol%, still more preferably 15 to 40 mol%).
(3) BPM is 20 to 80 mol% (more preferably 40 to 75 mol%, even more preferably 45 to 65 mol%) in 100 mol% of the dihydric phenol component constituting the polycarbonate resin, and A copolymerized polycarbonate resin in which Bis-TMC is 20 to 80 mol% (more preferably 25 to 60 mol%, even more preferably 35 to 55 mol%).

These special polycarbonate resins may be used alone or in an appropriate mixture of two or more. Moreover, these can also be used in combination with a commonly used bisphenol A type polycarbonate resin. The manufacturing method and characteristics of these special polycarbonate resins are described in detail in, for example, JP-A-6-172508, JP-A-8-27370, JP-A-2001-55435, and JP-A-2002-117580. has been done.

Among the various polycarbonate resins mentioned above, those whose water absorption and Tg (glass transition temperature) are within the ranges below by adjusting the copolymer composition etc. have good hydrolysis resistance of the polymer itself, Moreover, it is particularly excellent in low warpage after molding, so it is particularly suitable in fields where morphological stability is required.
(i) A polycarbonate resin having a water absorption rate of 0.05 to 0.15%, preferably 0.06 to 0.13%, and a Tg of 120 to 180°C, or (ii) a Tg of 160 to 250°C. , preferably 170 to 230°C, and a water absorption rate of 0.10 to 0.30%, preferably 0.13 to 0.30%, more preferably 0.14 to 0.27%.

Here, the water absorption rate of polycarbonate resin is the value obtained by measuring the moisture content after immersing a disc-shaped test piece with a diameter of 45 mm and a thickness of 3.0 mm in water at 23°C for 24 hours in accordance with ISO62-1980. It is. Moreover, Tg (glass transition temperature) is a value determined by differential scanning calorimeter (DSC) measurement based on JIS K7121.

Carbonyl halides, carbonic acid diesters, haloformates, etc. are used as carbonate precursors, and specific examples include phosgene, diphenyl carbonate, and dihaloformates of dihydric phenols.

When producing polycarbonate resin by interfacial polymerization of the dihydric phenol and carbonate precursor, a catalyst, a terminal stopper, an antioxidant to prevent the dihydric phenol from oxidizing, etc. are added as necessary. May be used. The polycarbonate resin of the present invention is a branched polycarbonate resin copolymerized with a trifunctional or higher polyfunctional aromatic compound, and a polyester carbonate resin copolymerized with an aromatic or aliphatic (including alicyclic) difunctional carboxylic acid. , copolymerized polycarbonate resins in which difunctional alcohols (including alicyclics) are copolymerized, and polyester carbonate resins in which such difunctional carboxylic acids and difunctional alcohols are copolymerized together. Alternatively, it may be a mixture of two or more of the obtained polycarbonate resins.

The branched polycarbonate resin can impart anti-drip performance and the like to the resin composition of the present invention. Examples of trifunctional or higher polyfunctional aromatic compounds used in such branched polycarbonate resins include phloroglucin, 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-[ Trisphenol such as 1,1-bis(4-hydroxyphenyl)ethyl]benzene}-α,α-dimethylbenzylphenol, tetra(4-hydroxyphenyl)methane, bis(2,4-dihydroxyphenyl)ketone, 1, Examples include 4-bis(4,4-dihydroxytriphenylmethyl)benzene, trimellitic acid, pyromellitic acid, benzophenonetetracarboxylic acid, and their acid chlorides, among which 1,1,1-tris(4-hydroxy Phenyl)ethane, 1,1,1-tris(3,5-dimethyl-4-hydroxyphenyl)ethane are preferred, and 1,1,1-tris(4-hydroxyphenyl)ethane is particularly preferred.

The structural unit derived from a polyfunctional aromatic compound in the branched polycarbonate resin is preferably 100% by mole in total of the structural unit derived from a dihydric phenol and the structural unit derived from such a polyfunctional aromatic compound. is 0.01 to 1 mol%, more preferably 0.05 to 0.9 mol%, even more preferably 0.05 to 0.8 mol%. In addition, particularly in the case of the melt transesterification method, branched structural units may be produced as a side reaction, and the amount of such branched structural units is also preferably within the total 100 mol% of the structural units derived from dihydric phenol. The content is preferably 0.001 to 1 mol%, more preferably 0.005 to 0.9 mol%, and even more preferably 0.01 to 0.8 mol%. Note that the proportion of such a branched structure can be calculated by ¹ H-NMR measurement.

The aliphatic difunctional carboxylic acid is preferably α,ω-dicarboxylic acid. Examples of aliphatic difunctional carboxylic acids include linear saturated aliphatic dicarboxylic acids such as sebacic acid (decanedioic acid), dodecanedioic acid, tetradecanedioic acid, octadecanedioic acid, and icosanedioic acid, as well as cyclohexanedicarboxylic acid. Preferred examples include alicyclic dicarboxylic acids such as. As the difunctional alcohol, alicyclic diols are more suitable, and examples include cyclohexanedimethanol, cyclohexanediol, and tricyclodecane dimethanol.

The reaction formats of the interfacial polymerization method, melt transesterification method, carbonate prepolymer solid-phase transesterification method, and ring-opening polymerization method of cyclic carbonate compounds, which are the methods for producing the polycarbonate resin of the present invention, are described in various literatures and patent publications. This is a well-known method.

In producing the thermoplastic resin composition of the present invention, the viscosity average molecular weight (M) of the polycarbonate resin is not particularly limited, but is preferably 1.8×10 ⁴ to 4.0×10 ⁴ , more preferably It is 2.0×10 ⁴ to 3.5×10 ⁴ , more preferably 2.2×10 ⁴ to 3.0×10 ⁴ . If the polycarbonate resin has a viscosity average molecular weight of less than 1.8×10 ⁴ , good mechanical properties may not be obtained. On the other hand, resin compositions obtained from polycarbonate resins having a viscosity average molecular weight of more than 4.0×10 ⁴ have poor versatility in that they have poor fluidity during injection molding.

In addition, the said polycarbonate resin may be obtained by mixing those whose viscosity average molecular weight is outside the said range. In particular, polycarbonate resins having a viscosity average molecular weight exceeding the above range (5×10 ⁴ ) have improved entropic elasticity. As a result, good molding processability is exhibited in gas-assisted molding and foam molding, which are sometimes used when molding reinforced resin materials into structural members. This improvement in moldability is even better than that of the branched polycarbonate resin. In a more preferred embodiment, component A is a polycarbonate resin A-1-1 component having a viscosity average molecular weight of 7×10 ⁴ to 3×10 ⁵ ), and an aromatic polycarbonate having a viscosity average molecular weight of 1×10 ⁴ to 3×10 ⁴ A polycarbonate resin (A-1 component) consisting of a resin (A-1-2 component) and having a viscosity average molecular weight of 1.6×10 ⁴ to 3.5×10 ⁴ (hereinafter referred to as "polycarbonate resin containing high molecular weight component"). ”) can also be used.

In such a polycarbonate resin containing a high molecular weight component (A-1 component), the molecular weight of the A-1-1 component is preferably 7×10 ⁴ to 2×10 ⁵ , more preferably 8×10 ⁴ to 2×10 ^{5 , and more preferably 8×10 4 to 2×10 5} . It is preferably 1×10 ⁵ to 2×10 ⁵ , particularly preferably 1×10 ⁵ to 1.6×10 ⁵ . The molecular weight of component A-1-1-2 is preferably 1×10 ⁴ to 2.5×10 ⁴ , more preferably 1.1×10 ⁴ to 2.4×10 ⁴ , even more preferably 1.2× 10 ⁴ to 2.4×10 ⁴ , particularly preferably 1.2×10 ⁴ to 2.3×10 ⁴ .

The polycarbonate resin containing a high molecular weight component (A-1 component) can be obtained by mixing the above-mentioned A-1-1 component and A-1-2 component in various ratios and adjusting the mixture to satisfy a predetermined molecular weight range. . Preferably, the A-1-1 component is 2 to 40% by weight out of 100% by weight of the A-1 component, more preferably the A-1-1 component is 3 to 30% by weight, and even more preferably The amount of the A-1-1 component is 4 to 20% by weight, particularly preferably the amount of the A-1-1 component is 5 to 20% by weight.

In addition, methods for preparing component A-1 include (1) a method in which component A-1-1 and component A-1-2 are independently polymerized and then mixed; (2) JP-A-5-306336; Using a method of manufacturing aromatic polycarbonate resins exhibiting multiple polymer peaks in a molecular weight distribution chart determined by GPC method in the same system, as typified by the method shown in the above publication, such aromatic polycarbonate resins can be converted into A- (3) an aromatic polycarbonate resin obtained by such a manufacturing method (the manufacturing method of (2)), and a separately manufactured A-1-1 component and/or Examples include a method of mixing component A-1-2.

The viscosity average molecular weight as used in the present invention is determined by first calculating the specific viscosity (η _SP ) using the following formula from a solution of 0.7 g of polycarbonate resin dissolved in 100 ml of methylene chloride at 20° C. using an Ostwald viscometer.
Specific viscosity (η _SP )=(t−t ₀ )/t ₀
[ _t0 is the number of seconds that methylene chloride falls, t is the number of seconds that the sample solution falls]
The viscosity average molecular weight M is calculated from the determined specific viscosity (η _SP ) using the following formula.
η _SP /c=[η]+0.45×[η] ² c (however, [η] is the limiting viscosity)
[η]=1.23× ^10-4 M ^0.83
c=0.7
Note that the viscosity average molecular weight of the polycarbonate resin in the thermoplastic resin composition of the present invention is calculated in the following manner. That is, the composition is mixed with 20 to 30 times its weight of methylene chloride to dissolve the soluble content in the composition. The soluble content is collected by filtration through Celite. The solvent in the resulting solution is then removed. The solid after the solvent is removed is sufficiently dried to obtain a solid containing components that are soluble in methylene chloride. The specific viscosity at 20°C is determined from a solution of 0.7 g of the solid dissolved in 100 ml of methylene chloride in the same manner as above, and the viscosity average molecular weight M is calculated from the specific viscosity in the same manner as above.

A polycarbonate-polydiorganosiloxane copolymer resin can also be used as the polycarbonate resin of the present invention. The polycarbonate-polydiorganosiloxane copolymer resin must be a copolymer resin containing a dihydric phenol unit represented by the following general formula (1) and a hydroxyaryl-terminated polydiorganosiloxane unit represented by the following general formula (3). is preferred.

[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, or a 6 to 18 carbon atom; 20 cycloalkyl group, 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, and if there is more than one of each, 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 above 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, 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, and R ¹⁹ and R ²⁰ each independently represent a hydrogen atom, a halogen atom, or a C 1 to 18 atom. Alkyl group having 1 to 10 carbon atoms, alkoxy 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, 6 carbon atoms ~14 aryl group, aryloxy group having 6 to 10 carbon atoms, aralkyl group having 7 to 20 carbon atoms, aralkyloxy group having 7 to 20 carbon atoms, nitro group, aldehyde group, cyano group, and carboxyl group (If there are multiple groups, they may be the same or different, c is an integer from 1 to 10, and d is an integer from 4 to 7.)

[In the above 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, or an alkoxy group having 1 to 10 carbon atoms, and e and f are each an integer from 1 to 4, p is a natural number, q is 0 or a natural number, and p+q is a natural number from 4 to 150. X is a divalent aliphatic group having 2 to 8 carbon atoms. ]

Examples of the dihydric phenol (I) for inducing the carbonate structural unit represented by the general formula (1) 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 ether- 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}benzene, 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- Examples include bis(4-hydroxyphenyl)-5,7-dimethyladamantane.

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, which has excellent strength and good durability, is most suitable. Further, these may be used alone or in combination of two or more.

In the carbonate structural unit represented by the above 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 particularly 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, and 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 above general formula (3) is derived, for example, a compound as shown in the following general formula (I) is suitably 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-mentioned preferred polycarbonate-polydiorganosiloxane copolymer resin will be explained below. By reacting dihydric phenol (I) with a chloroformate-forming compound such as phosgene or chloroformate of dihydric phenol (I) in a mixture of an organic solvent insoluble in water and an alkaline aqueous solution in advance, A mixed solution of a chloroformate compound containing a chloroformate of dihydric phenol (I) and/or a carbonate oligomer of dihydric phenol (I) having a terminal chloroformate group is prepared. Phosgene is preferred as the chloroformate-forming compound.

In producing a chloroformate compound from dihydric phenol (I), the entire amount of dihydric phenol (I) that induces the carbonate structural unit represented by the above general formula (1) is converted into a chloroformate compound at once. Alternatively, a part thereof may be added as a post-added monomer to the interfacial polycondensation reaction in the latter stage as a reaction raw material. The post-addition monomer is added to speed up the subsequent polycondensation reaction, and there is no need to intentionally add it if it is not necessary. The method for this reaction for producing a chloroformate compound is not particularly limited, but a method in which it is carried out in a solvent in the presence of an acid binder is usually suitable. Furthermore, if desired, a small amount of antioxidants such as sodium sulfite and hydrosulfide may be added, and it is preferable to add them. The proportion of the chloroformate-forming compound to be used may be appropriately adjusted in consideration of the stoichiometric ratio (equivalent) of the reaction. Furthermore, when using phosgene, which is a suitable chloroformate-forming compound, 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, or mixtures thereof. is used. Similarly to the above, the proportion of the acid binder to be used may be appropriately determined in consideration of the stoichiometric ratio (equivalent) of the reaction. Specifically, per 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 excess amount of Preferably, an acid binder is used.

As the solvent, solvents 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 including methylene chloride and chlorobenzene. In particular, halogenated hydrocarbon solvents such as methylene chloride are preferably used.

The pressure in the reaction for producing a 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 since heat is generated during the reaction in many cases, it is desirable to cool with water or ice. Although the reaction time depends on other conditions and cannot be absolutely defined, it is usually carried out for 0.2 to 10 hours. For the pH range in the reaction for producing a chloroformate compound, known interfacial reaction conditions can be used, and the pH is usually adjusted to 10 or higher.

In the production of the polycarbonate-polydiorganosiloxane copolymer resin of the present invention, in this way, a chloroformate of dihydric phenol (I) and a chloroformate containing a carbonate oligomer of dihydric phenol (I) having a terminal chloroformate group are used. After preparing the mixed solution of the formate compound, while stirring the mixed solution, dihydroxyaryl-terminated polydiorganosiloxane (II) which induces the carbonate structural unit represented by the general formula (3) is added to prepare the mixed solution. By adding the dihydric phenol (I) at a rate of 0.01 mol/min or less per mol of the dihydric phenol (I) and interfacial polycondensation of the dihydroxyaryl-terminated polydiorganosiloxane (II) and the chloroformate compound. , 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 in combination with a dihydric phenol compound. Examples of trifunctional or higher polyfunctional aromatic compounds used in such branched polycarbonate resins include phloroglucin, 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-[ Trisphenol such as 1,1-bis(4-hydroxyphenyl)ethyl]benzene}-α,α-dimethylbenzylphenol, tetra(4-hydroxyphenyl)methane, bis(2,4-dihydroxyphenyl)ketone, 1, Examples include 4-bis(4,4-dihydroxytriphenylmethyl)benzene, trimellitic acid, pyromellitic acid, benzophenonetetracarboxylic acid, and their acid chlorides, among which 1,1,1-tris(4-hydroxy Phenyl)ethane, 1,1,1-tris(3,5-dimethyl-4-hydroxyphenyl)ethane are preferred, and 1,1,1-tris(4-hydroxyphenyl)ethane is particularly preferred.

The method for producing such a branched polycarbonate-polydiorganosiloxane copolymer resin is such that even if a branching agent is included 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 also be used. The proportion 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%, based on the total amount of carbonate structural units constituting the copolymer resin. Particularly preferred is 0.05 to 1.0 mol%. Note that the amount of branched structure can be calculated by ¹ H-NMR measurement.

The pressure within the system in the polycondensation reaction can be reduced, normal pressure, or increased pressure, but usually, the reaction can be suitably carried out at normal pressure or about the autopressure of the reaction system. The reaction temperature is selected from the range of -20 to 50°C, and since heat is generated during polymerization in many cases, it is desirable to cool with water or ice. Since the reaction time varies depending on other conditions such as reaction temperature, it cannot be absolutely specified, but it is usually carried out for 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 achieve the desired reduction. It can also be obtained as a polycarbonate-polydiorganosiloxane copolymer resin having a viscosity of [η _SP /c]. The obtained reaction product (crude product) can be subjected to various post-treatments such as known separation and purification methods, and recovered as a polycarbonate-polydiorganosiloxane copolymer resin with a desired purity (purification degree).

The content of the polydiorganosiloxane block represented by the following general formula (4) included 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 preferably 1.0 to 8.0% by weight, more preferably 1.0 to 5.0% by weight, and most preferably 1.0 to 3.0% by weight.

(In the above 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 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 from 4 to 150.)

<Component B: polyarylate resin>
The polyarylate resin used as 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. , 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-dibromphenyl)propane, 2,2-(4-hydroxy-3- (methylphenyl)propane, 4,4'-dihydroxydiphenyl sulfone, 4,4'-dihydroxydiphenyl ether, 4,4'-dihydroxydiphenyl sulfide, etc., and two or more thereof 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 it may be used alone or in combination of two or more. Preferred aromatic dicarboxylic acids include terephthalic acid and isophthalic acid, and mixtures thereof are particularly preferred in terms of melt processability and overall performance. The mixing ratio of these mixtures does not need to be particularly limited, but preferably terephthalic acid/isophthalic acid = 9/1 to 1/9 (molar ratio), particularly 7/3 from the viewpoint of melt processability and balance of performance. ~3/7 (molar ratio) is preferred.

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

[In the above general formula (5), l, m and n are 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 (6), m and n are positive integers, and m/n=8/2 to 2/8. ]

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

The content of the polyarylate resin used as component B in the present invention is 1 to 99 parts by weight, preferably 10 to 50 parts by weight, more preferably 20 parts by weight, based on 100 parts by weight of the resin component consisting of component A and component B. ~40 parts by weight. If the content of component B exceeds 99 parts by weight, the molecular weight decreases during molding retention, and if it is less than 1 part by weight, excellent heat resistance cannot be obtained, and furthermore, resin deterioration in high temperature and high humidity environments may occur. growing.
Examples of commercially available polyarylate resins include "U-100" (trade name), "M-2040" (trade name), and "M-2040H" (trade name) manufactured by Unitika Co., Ltd.

<Component C: Phosphoric ester compound>
The content of the phosphoric acid ester compound used as component C in the present invention is 0.001 to 2 parts by weight, preferably 0.005 to 0 parts by weight, based on 100 parts by weight of the resin component consisting of components A and B. .5 parts by weight, more preferably 0.01 to 0.1 parts by weight. If the content of component C is less than 0.001 parts by weight, the molecular weight decreases greatly during retention in molding, and when it exceeds 2 parts by weight, the molecular weight decreases during retention in molding increases, making it difficult for the resin to withstand high temperature and high humidity environments. Deterioration also increases. In addition, when a phosphorus-based stabilizer other than a phosphoric acid ester-based compound is used, resin deterioration in a high-temperature, high-humidity environment increases.

The type of phosphoric acid ester compound used as component C of the present invention is not particularly limited, but when a phosphoric acid ester compound with a number average molecular weight of 50 to 300 is used, the molecular weight decreases during molding retention, and under high temperature and high humidity environments. The effect of suppressing resin deterioration in is particularly exhibited.

Specifically, phosphoric acid ester compounds include tributyl phosphate, trimethyl phosphate, tricresyl phosphate, triphenyl phosphate, trichlorophenyl phosphate, triethyl phosphate, diphenyl cresyl phosphate, diphenyl monoorthoxenyl phosphate, and tributoxyethyl phosphate. , dibutyl phosphate, dioctyl phosphate, diisopropyl phosphate, etc., with triphenyl phosphate and trimethyl phosphate being preferred.

<Component D: Phenol compound>
The content of the phenolic compound used as component D in the present invention is 0.001 to 2 parts by weight, preferably 0.01 to 0.5 parts by weight, based on 100 parts by weight of the resin component consisting of components A and B. Parts by weight, more preferably 0.03 to 0.08 parts by weight. When the content of component D is less than 0.001 parts by weight or more than 2 parts by weight, the molecular weight decreases greatly during molding retention, and resin deterioration in high temperature and high humidity environments also increases.

The type of phenolic compound used as component D of the present invention is not particularly limited, but when a hindered phenolic antioxidant or a phenolic compound with a melting point of 30 to 70°C is used, yellowing during molding retention can be suppressed, It is particularly effective in suppressing resin deterioration in high temperature and high humidity environments. Examples of phenolic antioxidants include α-tocopherol, butylated hydroxytoluene, 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-methylphenylacrylate, 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-methyl phenyl)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), 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]ethyl isocyanurate, and tetrakis[methylene-3-(3',5'-di-tert-butyl-4-hydroxyphenyl)propionate] Examples include methane. All of these are easily available.

<Component E: Rubber polymer>
In the present invention, conventionally known rubbery polymers can be used as component E, and examples of preferably used rubbery polymers include acrylonitrile-butadiene-styrene copolymer resin, butadiene-based core-shell graft copolymer, acrylic At least one rubbery polymer selected from the group consisting of core-shell type graft copolymers and silicone-based core-shell type graft copolymers.

The rubbery polymer contains 40% by weight or more of a rubber component having a glass transition temperature of 10°C or lower, preferably -10°C or lower, more preferably -30°C or lower. For example, a graft in which such a rubber component is copolymerized with one or more monomers selected from aromatic vinyl, vinyl cyanide, acrylic ester, methacrylic ester, and vinyl compounds copolymerizable with these. Copolymers can be mentioned. Rubber components with a glass transition temperature of 10°C or less include butadiene rubber, butadiene-acrylic composite rubber, acrylic rubber, acrylic-silicone composite rubber, isobutylene-silicone composite rubber, isoprene rubber, styrene-butadiene rubber, and chloroprene rubber. , ethylene-propylene rubber, nitrile rubber, ethylene-acrylic rubber, silicone rubber, epichlorohydrin rubber, fluororubber, and those in which hydrogen is added to the unsaturated bond portions thereof.

Among these, core-shul type graft polymers are preferred. The core-shell type graft polymer mentioned here has a rubber component with a glass transition temperature of 10°C or less as a core, and is selected from aromatic vinyl, vinyl cyanide, acrylic ester, methacrylic ester, and a vinyl compound copolymerizable with these. It is a graft copolymer copolymerized using one or more types of monomers as a shell. Rubber components of the core-shell type graft polymer include butadiene rubber, butadiene-acrylic composite rubber, acrylic rubber, acrylic-silicone composite rubber, isobutylene-silicone composite rubber, isoprene rubber, styrene-butadiene rubber, chloroprene rubber, ethylene-propylene rubber, Examples include nitrile rubber, ethylene-acrylic rubber, silicone rubber, epichlorohydrin rubber, fluororubber, and products in which hydrogen is added to the unsaturated bonds of these rubbers, but due to concerns about the generation of harmful substances during combustion, , rubber components that do not contain halogen atoms are preferable in terms of environmental impact. The glass transition temperature of the rubber component is preferably -10°C or lower, more preferably -30°C or lower, and the rubber component is particularly preferably butadiene rubber, butadiene-acrylic composite rubber, acrylic rubber, silicone rubber, or acrylic-silicone composite rubber. preferable. Composite rubber refers to a rubber that is a copolymerization of two rubber components, or a rubber that is polymerized to have an IPN structure in which they are intertwined with each other so that they cannot be separated. In the core-shell type graft polymer, the particle size of the core is preferably 0.05 to 0.8 μm, more preferably 0.1 to 0.6 μm, and even more preferably 0.15 to 0.5 μm in weight average particle size. Better impact resistance is achieved in the range of 0.05 to 0.8 μm.

Examples of the aromatic vinyl in the vinyl compound copolymerized with the rubber component as the shell of the core-shell graft polymer include styrene, α-methylstyrene, p-methylstyrene, alkoxystyrene, and halogenated styrene. Examples of acrylic esters include methyl acrylate, ethyl acrylate, butyl acrylate, cyclohexyl acrylate, and octyl acrylate. Examples of methacrylic esters include methyl methacrylate, ethyl methacrylate, and butyl methacrylate. , cyclohexyl methacrylate, octyl methacrylate, etc., with methyl methacrylate being particularly preferred. Among these, it is particularly preferable to contain a methacrylic acid ester such as methyl methacrylate as an essential component, and from the viewpoint of mechanical properties and thermal stability, it is more preferable not to contain an aromatic vinyl component. This is because the core-shell type graft polymer has excellent affinity with the aromatic polycarbonate resin, so more rubber components are present in the resin, and the good impact resistance of the aromatic polycarbonate resin is further enhanced. This is because the impact resistance is effectively exhibited and, as a result, the impact resistance of the resin composition becomes good. More specifically, the methacrylic acid ester is contained in 100% by weight of the graft component (in 100% by weight of the shell in the case of a core-shell type polymer), preferably 10% by weight or more, more preferably 15% by weight or more. The elastic polymer containing a rubber component with a glass transition temperature of 10°C or less may be produced by any polymerization method including bulk polymerization, solution polymerization, suspension polymerization, and emulsion polymerization, and the copolymerization method may be It may be a single-stage graft or a multi-stage graft. Alternatively, it may be a mixture of only a graft component produced as a by-product during production with a copolymer. Furthermore, examples of the polymerization method include, in addition to the general emulsion polymerization method, a soap-free polymerization method using an initiator such as potassium persulfate, a seed polymerization method, a two-step swelling polymerization method, and the like. In addition, in the suspension polymerization method, the aqueous phase and the monomer phase are held separately and both are accurately supplied to a continuous dispersion machine, and the particle size is controlled by the rotation speed of the dispersion machine. In the method, a method may be used in which the monomer phase is supplied into an aqueous liquid having dispersibility by passing it through a small orifice or porous filter with a diameter of several to several tens of μm to control the particle size. In the case of a core-shell type graft polymer, the reaction may be carried out in one stage or in multiple stages for both the core and shell.

Such polymers are commercially available and can be easily obtained. For example, the rubber component whose main component is butadiene rubber is the Kane Ace M series manufactured by Kaneka Corporation (for example, M-711 whose shell component is mainly methyl methacrylate, and the shell component whose main component is methyl methacrylate/styrene. (M-701, etc.) manufactured by Mitsubishi Rayon Co., Ltd., Metablane C series (for example, C-223A, whose shell components are mainly composed of methyl methacrylate and styrene), and E series (such as C-223A, whose shell components are mainly composed of methyl methacrylate and styrene). DOW Chemical Co., Ltd.'s Paraloid EXL series (for example, EXL-2690, whose shell component is methyl methacrylate as the main component), etc.), and the main component is acrylic rubber or butadiene-acrylic composite rubber. The W series (for example, W-600A whose shell component is mainly composed of methyl methacrylate), the Paraloid EXL series of DOW Chemical Co., Ltd. (for example, EXL-2390 whose shell component is mainly composed of methyl methacrylate), Examples of rubber components whose main component is acrylic-silicone composite rubber include Metablane S-2001 manufactured by Mitsubishi Rayon Co., Ltd. whose shell component is methyl methacrylate, or whose shell component is acrylonitrile/styrene. One example is a product commercially available under the trade name SRK-200, which contains as a main component. Among these, those that do not contain styrene, which is an aromatic vinyl component, are particularly preferred in terms of mechanical properties and chemical resistance.

The content of component E is 1 to 15 parts by weight, preferably 1 to 10 parts by weight, and more preferably 2 to 6 parts by weight, based on a total of 100 parts by weight of components A and B. If the content is less than 1 part by weight, it is insufficient to satisfy the impact resistance properties of the product, and if it exceeds 15 parts by weight, the heat resistance will decrease and the resin will deteriorate during molding retention and in high temperature and high humidity environments. also becomes larger.

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

(I) Heat stabilizer (i) Heat stabilizer other than the above The thermoplastic resin composition of the present invention may contain a heat stabilizer other than the above-mentioned phosphate stabilizer and hindered phenol stabilizer. You can also do that. Suitable examples of such other heat stabilizers include lactone stabilizers represented by the reaction product 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 commercially available as Irganox HP-136 (trademark, manufactured by CIBA SPECIALTY CHEMICALS), and this compound can be used. Furthermore, stabilizers prepared by mixing this 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 content 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 a total of 100 parts by weight 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. Illustrated. The content of the sulfur-containing stabilizer is preferably 0.001 to 0.1 part by weight, more preferably 0.01 to 0.08 part by weight, based on a total of 100 parts by weight of components A and B. be. An epoxy compound can be added to the thermoplastic resin composition of the present invention, if necessary. Such epoxy compounds are blended for the purpose of suppressing mold corrosion, and basically any compound having an epoxy functional group can be used. Specific examples of preferred epoxy compounds include 3,4-epoxycyclohexylmethyl-3',4'-epoxycyclohexylcarboxylate, 1,2-epoxy-4- of 2,2-bis(hydroxymethyl)-1-butanol; Examples include (2-oxiranyl)cyclohexane adducts, copolymers of methyl methacrylate and glycidyl methacrylate, and copolymers of styrene and glycidyl methacrylate. The content of such an epoxy compound is preferably 0.003 to 0.2 parts by weight, more preferably 0.004 to 0.15 parts by weight, based on the total of 100 parts by weight of components A and B. More preferably, the amount is 0.005 to 0.1 part by weight.

(II) Flame retardant A flame retardant can be blended into the thermoplastic resin composition of the present invention. Incorporation of such compounds provides improved flame retardancy, but also provides other benefits, such as improved antistatic properties, fluidity, stiffness, and thermal stability, depending on the properties of each compound. Such flame retardants include (i) organometallic salt flame retardants (for example, organic sulfonic acid alkali (earth) metal salts, organic borate metal salt flame retardants, and organic stannate metal salt flame retardants); ii) an organophosphorus flame retardant (for example, an organic group-containing monophosphate compound, a phosphate oligomer compound, a phosphonate oligomer compound, a phosphonitrile oligomer compound, a phosphonic acid amide compound, etc.), (iii) a silicone flame retardant consisting of a silicone compound , (iv) fibrillated PTFE, among which organic metal salt flame retardants and organic phosphorus flame retardants are preferred. These may be used alone or in combination.

(i) Organic metal salt 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 alkali (earth) metal salt of an organic sulfonic acid. It is preferable that 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, and alkali metals or alkaline earth metals. Included are metal salts of acids and metal salts of aromatic sulfonic acids having from 7 to 50 carbon atoms, preferably from 7 to 40 carbon atoms, with alkali metals or alkaline earth metals. Alkali metals constituting the metal salt include lithium, sodium, potassium, rubidium, and cesium, and alkaline earth metals include beryllium, magnesium, calcium, strontium, and barium. More preferred are alkali metals. Among such alkali metals, rubidium and cesium, which have larger ionic radii, are preferred when transparency is required, but they are not widely used and are difficult to purify, resulting in lower costs. 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. The alkali metal in the alkali metal sulfonate can be selected depending on these considerations, but potassium sulfonate is the most suitable because it has excellent balance of properties in all respects. Such a potassium salt and an alkali metal sulfonic acid salt consisting of another alkali metal can also be used in combination.

Specific examples of alkali metal perfluoroalkylsulfonates include potassium trifluoromethanesulfonate, potassium perfluorobutanesulfonate, potassium perfluorohexanesulfonate, potassium perfluorooctanesulfonate, sodium pentafluoroethanesulfonate, and perfluorobutanesulfonate. Sodium butanesulfonate, sodium perfluorooctanesulfonate, lithium trifluoromethanesulfonate, lithium perfluorobutanesulfonate, lithium perfluoroheptanesulfonate, cesium trifluoromethanesulfonate, cesium perfluorobutanesulfonate, perfluorooctanesulfonic acid Examples include cesium, cesium perfluorohexanesulfonate, rubidium perfluorobutanesulfonate, and rubidium perfluorohexanesulfonate, and these can be used alone or in combination of two or more. The number of carbon atoms in the perfluoroalkyl group is preferably in the range of 1 to 18, more preferably in the range of 1 to 10, even more preferably in the range of 1 to 8.

Among these, potassium perfluorobutanesulfonate is particularly preferred. A considerable amount of fluoride ion (F-) is usually mixed into the alkali (earth) metal salt of perfluoroalkylsulfonic acid made of an alkali metal. Since the presence of such fluoride ions can be a factor in reducing 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, particularly preferably 10 ppm or less. Further, in terms of manufacturing efficiency, it is preferable that the content is 0.2 ppm or more. Such an alkali (earth) metal salt of perfluoroalkylsulfonic acid with a reduced amount of fluoride ions can be produced by using a known production method and contained in the raw materials for producing the fluorine-containing organic metal salt. Methods for reducing the amount of fluoride ions, methods for removing hydrogen fluoride etc. obtained by the reaction by using gas generated during the reaction or heating, and purification methods such as recrystallization and reprecipitation for producing fluorine-containing organometallic salts. It can be manufactured by a method of reducing the amount of fluoride ions using fluoride ions. In particular, organic metal salt flame retardants are relatively easily soluble in water, so use ion-exchanged water, especially water that satisfies an electrical resistance value of 18 MΩ·cm or more, that is, an electrical conductivity of about 0.55 μS/cm or less. , and is preferably manufactured by a process of dissolving and washing at a temperature higher than room temperature, and then cooling and recrystallizing.

Specific examples of aromatic sulfonic acid alkali (earth) metal salts include, for example, 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-dodecyl phenyl ether disulfonate, polysodium poly(2,6-dimethylphenylene oxide) polysulfonate , polysodium poly(1,3-phenylene oxide) polysulfonate, polysodium poly(1,4-phenylene oxide) polysulfonate, polypotassium poly(2,6-diphenylphenylene oxide) polysulfonate, poly(2-fluoro- 6-Butylphenylene oxide) lithium polysulfonate, potassium benzenesulfonate sulfonate, 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, α,α,α-sodium trifluoroacetophenone-4-sulfonate, dipotassium benzophenone-3,3'-disulfonate, disodium thiophene-2,5-disulfonate, dipotassium thiophene-2,5-disulfonate, Examples include calcium thiophene-2,5-disulfonate, sodium benzothiophenesulfonate, potassium diphenylsulfoxide-4-sulfonate, formalin condensate of sodium naphthalenesulfonate, and formalin condensate of sodium anthracene sulfonate. can. Among these alkali (earth) metal salts of aromatic sulfonic acids, 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 in particular mixtures thereof (the former and the latter) are preferred. The weight ratio of 15/85 to 30/70) is suitable.

Preferred examples of organic metal salts other than alkali (earth) metal sulfonates include alkali (earth) metal salts of sulfuric esters and alkali (earth) metal salts of aromatic sulfonamides. As alkali (earth) metal salts of sulfuric esters, mention may be made in particular of alkali (earth) metal salts of sulfuric esters of monohydric and/or polyhydric alcohols; Examples of sulfuric esters include methyl sulfate, ethyl sulfate, lauryl sulfate, hexadecyl sulfate, polyoxyethylene alkyl phenyl ether sulfate, pentaerythritol mono-, di-, tri-, and tetra-sulfate ester, and lauric acid monoglyceride sulfate. Examples include esters, sulfuric esters of palmitic acid monoglyceride, and sulfuric esters of stearic acid monoglyceride. Preferred examples of the alkali (earth) metal salts of these sulfuric esters include 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)sulfanylimide, and N-( Examples include alkali (earth) metal salts of phenylcarboxyl) sulfanylimide. The content of the organic metal salt flame retardant is preferably 0.001 to 1 part by weight, more preferably 0.005 to 0.5 part by weight, and more preferably The amount 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 that they can improve moldability. 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 dihydric phenol, and Ar ¹ , Ar ² , Ar ³ , and Ar ⁴ are each a monovalent organic group derived from a monohydric phenol. a, b, c and d are each independently 0 or 1, m is an integer from 0 to 5, and in the case of a mixture of phosphoric esters with different degrees of polymerization m, m is the average value. (value from 0 to 5)
The phosphate compound of the above formula may be a mixture of compounds having different m numbers; in the case of such mixtures, the average m number is preferably from 0.5 to 1.5, more preferably from 0.8 to 1. 2, more preferably 0.95 to 1.15, particularly preferably 1 to 1.14.

Preferred specific examples of the dihydric phenol inducing the above M include hydroquinone, resorcinol, bis(4-hydroxydiphenyl)methane, bisphenol A, dihydroxydiphenyl, dihydroxynaphthalene, bis(4-hydroxyphenyl)sulfone, bis(4-hydroxydiphenyl)methane, -hydroxyphenyl)ketone, and bis(4-hydroxyphenyl)sulfide, among which resorcinol, bisphenol A, and dihydroxydiphenyl are preferred.

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

The monohydric phenol may be substituted with a halogen atom, and specific examples of phosphate compounds having groups 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 and tris(4-bromophenyl) phosphate.

On the other hand, specific examples of phosphate compounds that are not substituted with halogen atoms include monophosphate compounds such as triphenyl phosphate and tri(2,6-xylyl) phosphate, and resorcinol bis di(2,6-xylyl) phosphate). Preferred are phosphate oligomers mainly composed of 4,4-dihydroxydiphenyl bis(diphenyl phosphate), and phosphate ester oligomers mainly composed of bisphenol A bis(diphenyl phosphate). indicates that it may contain a small amount of other components having different degrees of polymerization, and more preferably the component where m=1 in the formula [8] is 80% by weight or more, more preferably 85% by weight or more, even more preferably (Indicates that the content is 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.

(In the formula, X ¹ , X ² , X ³ , and X ⁴ represent hydrogen, a hydroxyl group, an amino group, or an organic group not containing a halogen atom. Also, r represents an integer from 3 to 10.)
In the above formulas (9) and (10), examples of the organic group not containing a halogen atom represented by X ¹ , X ² , X ³ , and X ⁴ include an alkoxy group, a phenyl group, an amino group, an allyl group, etc. can be mentioned. Among them, a cyclic phosphazene compound represented by the above formula (9) is preferred, and a cyclic phenoxyphosphazene in which X ¹ and X ² in the above formula (9) are phenoxy groups is particularly preferred.

The content of the organic phosphorus 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 a total of 100 parts by weight of components A and B. is even more preferable. If the content of the organic phosphorus flame retardant is less than 1 part by weight, it is difficult to obtain a flame retardant effect, and if it exceeds 50 parts by weight, problems such as strand breakage and surging may occur during kneading and extrusion, resulting in reduced productivity. may occur.

(iii) Silicone flame retardant Silicone compounds used as silicone flame retardants improve flame retardancy through chemical reactions during combustion. As the compound, various compounds conventionally proposed as flame retardants for aromatic polycarbonate resins can be used. Silicone compounds have high flame retardancy, especially when polycarbonate resin is used, by bonding themselves or with resin-derived components to form a structure during combustion, or by a reduction reaction during the formation of the structure. It is thought that it gives an effect.

Therefore, it is preferable to contain a group having 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 (i.e., Si-H group). 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 in the range of 0.15 to 0. A range of 6 mol/100 g is more preferable. This ratio can be determined by measuring the amount of hydrogen or alcohol generated per unit weight of the silicone compound using an alkaline decomposition method. The alkoxy group is preferably an alkoxy group having 1 to 4 carbon atoms, and a methoxy group is particularly preferred.

Generally, the structure of a silicone compound is constructed by arbitrarily combining 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 , monofunctional siloxane unit, D unit: 2 such as ( _CH3 ) _2SiO , H( _{CH3 )} SiO, _H2SiO , _H ( _C6H5 )SiO, ( _CH3 )( _CH2 =CH)SiO, ( _C6H5 ) _2SiO , etc. Functional siloxane unit, T unit: ( _CH3 )SiO3 _/2 , ( _C3H7 )SiO3 _{/ 2} , HSiO3 _/2 , ( _CH2 =CH)SiO3 _{/2 ,} ( _C6H5 ) A trifunctional siloxane unit such as SiO _3/2 , and a tetrafunctional siloxane unit represented by Q unit: SiO ₂ .

Specifically, the structure of the silicone compound used in the silicone flame retardant includes the following specific formulas: Dn, Tp, MmDn, MmTp, MmQq, MmDnTp, MmDnQq, MmTpQq, MmDnTpQq, DnTp, DnQq, and DnTpQq. Among these, preferred structures of the silicone compound are MmDn, MmTp, MmDnTp, and MmDnQq, and a more preferred structure is MmDn or MmDnTp.

Here, the coefficients m, n, p, and q in the above 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. . This average degree of polymerization is preferably in the range of 3 to 150, more preferably in the range of 3 to 80, even more preferably in the range of 3 to 60, particularly preferably in the range of 4 to 40. The more suitable the range, the better the flame retardancy. Furthermore, as will be described later, silicone compounds containing a predetermined amount of aromatic groups have excellent transparency and hue. As a result, good reflected light can be obtained. In addition, 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 types of siloxane units with different bonding hydrogen atoms or organic residues. .

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. Specifically, such organic residues include alkyl groups such as methyl, ethyl, propyl, butyl, hexyl, and decyl groups, cycloalkyl groups such as cyclohexyl, aryl groups such as phenyl, Also included are aralkyl groups such as tolyl. More preferably, it is an alkyl group, alkenyl group or aryl group having 1 to 8 carbon atoms. As the alkyl group, particularly preferred are alkyl groups having 1 to 4 carbon atoms such as methyl group, ethyl group, and propyl group. Furthermore, the silicone compound used as the silicone 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 flame retardants in their preferred embodiments, in that preferable effects can be obtained when they do not contain aryl groups. . The silicone compound used as a silicone flame retardant may contain a reactive group in addition to the Si--H group and alkoxy group, and such reactive groups include, for example, an amino group, a carboxyl group, an epoxy group, and a vinyl group. Examples include a group, a mercapto group, and a methacryloxy group.

The content of the silicone flame retardant is preferably 0.01 to 20 parts by weight, more preferably 0.5 to 10 parts by weight, even more preferably 1 to 5 parts by weight, based on a total of 100 parts by weight of components A and B. Parts by weight.

(iv) Polytetrafluoroethylene (fibrillated PTFE) with fibril-forming ability
The fibrillated PTFE may be fibrillated PTFE alone or may be a mixed form of fibrillated PTFE, that is, a polytetrafluoroethylene mixture consisting of fibrillated PTFE particles and an organic polymer. Fibrillated PTFE has an extremely high molecular weight and exhibits a tendency for PTFE to bond together and become fibrous due to external effects such as shearing force. Its number average molecular weight ranges from 1.5 million to tens of millions. The 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, for example, JP-A-6-145520. 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., as measured by the method described in this publication. Such PTFE can be used not only in solid form but also in aqueous dispersion form. Such fibrillated PTFE also improves its dispersibility in resins, and it is also possible to use PTFE mixtures in mixed form with other resins in order to obtain even better flame retardancy and mechanical properties.

Furthermore, as disclosed in JP-A-6-145520, a material having a structure in which the fibrillated PTFE is used as a core and a low molecular weight polytetrafluoroethylene is used as a shell is also preferably used.

Commercially available products of such fibrillated PTFE include, for example, Teflon (registered trademark) 6J from DuPont Mitsui Fluorochemical Co., Ltd. and Polyflon MPA FA500 and F-201L from Daikin Chemical Industries, Ltd.

As for the mixed form of fibrillated PTFE, (1) a method of mixing an aqueous dispersion of fibrillated PTFE and an aqueous dispersion or solution of an organic polymer and co-precipitating to obtain a co-agglomerated mixture (JP-A-60-258263; (2) method of mixing an aqueous dispersion of fibrillated PTFE with dried organic polymer particles (method described in Japanese Patent Application Laid-Open No. 4-272957). (3) A method in which an aqueous dispersion of fibrillated PTFE and a solution of organic polymer particles are uniformly mixed, and each medium is simultaneously removed from the mixture (JP-A-06-220210, JP-A No. 08-188653), (4) a method of polymerizing monomers forming an organic polymer in an aqueous dispersion of fibrillated PTFE (method described in JP-A-9-95583), method), and (5) a method of uniformly mixing an aqueous PTFE dispersion and an organic polymer dispersion, then polymerizing a vinyl monomer in the mixed dispersion, and then obtaining a mixture (JP-A-11-1999) Those obtained by the method described in Japanese Patent No. 29679 and the like can be used.

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

The proportion of fibrillated PTFE in the mixed form is preferably 1% to 95% by weight, more preferably 10% to 90% by weight, and more preferably 10% to 90% by weight, based on 100% by weight of the mixture. % to 80% by weight is most preferred.

When the proportion of fibrillated PTFE in the mixed form is within this 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, and .1 to 0.5 part by weight is more preferred.

(III) Dyes and Pigments The thermoplastic resin composition of the present invention further contains various dyes and pigments, and can provide molded articles exhibiting various designs. The dyes and pigments used in the present invention include perylene dyes, coumarin dyes, thioindigo dyes, anthraquinone dyes, thioxanthone dyes, ferrocyanides such as navy 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 also 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 whitening agent or other fluorescent dyes that emit light, it is possible to provide an even better design effect that takes advantage of the emitted color.

(IV) Fluorescent brightener In the thermoplastic resin composition of the present invention, the optical brightener is not particularly limited as long as it is used to improve the color tone of the resin, etc. to white or bluish-white, such as stilbene-based , benzimidazole-based, benzoxazole-based, naphthalimide-based, rhodamine-based, coumarin-based, and oxazine-based compounds. Specifically, for example, CI Fluorescent Brightener 219:1, EASTOBRITE OB-1 manufactured by Eastman Chemical Co., Ltd., and "Hakkor PSR" manufactured by Showa Kagaku Co., Ltd. can be mentioned. The fluorescent whitening agent has the function of absorbing energy in the ultraviolet region of light and emitting this energy to the visible region. The content of the optical brightener is preferably 0.001 to 0.1 part by weight, more preferably 0.001 to 0.05 part by weight, based on the total of 100 parts by weight of 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 absorbing ability The thermoplastic resin composition of the present invention can contain a compound having heat ray absorbing ability. Such compounds include phthalocyanine near-infrared absorbers, ATO, ITO, metal oxide near-infrared absorbers such as iridium oxide and ruthenium oxide, immonium oxide, and titanium oxide, lanthanum boride, cerium boride, and tungsten boride. Suitable examples include various metal compounds with excellent near-infrared absorbing ability, 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 easily available. Examples of the carbon filler include carbon black, graphite (both natural and artificial), and fullerene, with carbon black and graphite being preferred. 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 the total of 100 parts by weight of components A and B. , 0.001 to 0.07 parts by weight are more preferred. The content of the metal oxide near-infrared absorber, metal boride near-infrared absorber, and carbon filler is preferably in the range of 0.1 to 200 ppm (weight ratio) in the thermoplastic resin composition of the present invention, and The range of .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 light diffusing agents include polymer fine particles, low refractive index inorganic fine particles such as calcium carbonate, and composites thereof. Such polymer fine particles are already known as light diffusing agents for polycarbonate resins. More preferred examples include crosslinked acrylic particles with a particle size of several μm and crosslinked silicone particles typified by polyorganosilsesquioxane. Examples of the shape of the light diffusing agent include a spherical shape, a disk shape, a columnar shape, and an amorphous shape. Such a spherical shape does not necessarily have to be a perfect sphere, but includes a deformed one, and such a cylindrical shape includes a cube. A preferable light diffusing agent is spherical, and the more uniform the particle size is, the more preferable it is. 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 even more preferably 0.01 parts by weight, based on the total of 100 parts by weight of components A and B. ~3 parts by weight. In addition, two or more types of light diffusing agents can be used in combination.

(VII) White pigment for high light reflection The thermoplastic resin composition of the present invention can be blended with a white pigment for high light reflection to impart a light reflection effect. As such a white pigment, titanium dioxide (particularly titanium dioxide treated with an organic surface treatment agent such as silicone) pigment is particularly preferred. 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 the total of 100 parts by weight of components A and B. Note that two or more types of white pigments for high light reflection can be used in combination.

(VIII) Ultraviolet absorber The thermoplastic resin composition of the present invention can be blended with an ultraviolet absorber to impart weather resistance. Specific examples of such ultraviolet absorbers include benzophenone, such as 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-octoxybenzophenone, and 2-hydroxy-4-benzophenone. 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-sodiumsulfoxybenzophenone, 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 benzotriazole-based agents such as 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-benzotriazolphenyl), 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 and a vinyl monomer copolymerizable with the monomer. Examples include polymers having a 2-hydroxyphenyl-2H-benzotriazole skeleton, such as polymers. Specifically, the ultraviolet absorber is hydroxyphenyltriazine type, 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, the phenyl group of the above-mentioned exemplified compounds is 2,4-dimethyl, such as 2-(4,6-bis(2,4-dimethylphenyl)-1,3,5-triazin-2-yl)-5-hexyloxyphenol. Examples include compounds that have a phenyl group. Specifically, the ultraviolet absorber is a cyclic imino ester type, 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). In addition, as the ultraviolet absorber, specifically 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 it can combine such ultraviolet absorbing monomer and/or photostable monomer with a monomer such as alkyl (meth)acrylate. It may also be a polymer-type ultraviolet absorber copolymerized with the UV absorber. Preferred examples of the ultraviolet 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 a (meth)acrylic acid ester. Ru. Among the above, benzotriazole-based and hydroxyphenyltriazine-based are preferred in terms of ultraviolet absorbing ability, and cyclic iminoester-based and cyanoacrylate-based are preferred in terms of heat resistance and hue. Specific examples include Chemipro Kasei Co., Ltd.'s "Chemisorb 79" and BASF Japan Co., Ltd.'s "Tinuvin 234". The above-mentioned ultraviolet absorbers may be used alone or in 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 even more preferably 0.05 parts by weight, based on the total of 100 parts by weight of components A and B. ~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 is preferable to include an antistatic agent. Examples of such antistatic agents include (1) arylsulfonic acid phosphonium salts represented by dodecylbenzenesulfonic acid phosphonium salts, organic sulfonic acid phosphonium salts such as alkylsulfonic acid phosphonium salts, and phosphonium tetrafluoroborate salts. Examples include phosphonium boric acid salts. The content of the phosphonium salt is suitably 5 parts by weight or less, preferably 0.05 to 5 parts by weight, more preferably 1 to 3.5 parts by weight, based on 100 parts by weight of components A and B. parts, more preferably in the range of 1.5 to 3 parts by weight. Examples of the antistatic agent include (2) lithium organic sulfonate, sodium organic sulfonate, potassium organic sulfonate, cesium organic sulfonate, rubidium organic sulfonate, calcium organic sulfonate, magnesium organic sulfonate, and barium organic sulfonate. and organic sulfonic acid alkali (earth) metal salts. Such metal salts are also used as flame retardants, as mentioned 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 sulfonic acid alkali (earth) metal salt is suitably 0.5 parts by weight or less, preferably 0.001 to 0.3 parts by weight, based on 100 parts by weight of components A and B. parts, more preferably 0.005 to 0.2 parts by weight. Particularly suitable are alkali metal salts such as potassium, cesium, and rubidium.

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

(X) Other resins In the thermoplastic resin composition of the present invention, a small amount of other resin may be added in place of a part of the resin component to the extent that the effects of the present invention are exerted. Proportions can also be used. The blending amount of the other resin 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 3 parts by weight or less, based on 100 parts by weight of the resin component consisting of component A and component B. 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. Examples include resins such as , phenol resin, and epoxy resin.

(XI) 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. .

<About 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 various reinforcing fillers and additives described above can also 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. Furthermore, it is also possible to directly make a sheet, a film, a profile extrusion molded product, a direct blow molded product, and an injection molded product from the resin melt-kneaded 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 molding of supercritical fluid), insert molding, Molded articles can be obtained using injection molding methods such as in-mold coating molding, adiabatic molding, rapid heating and cooling molding, two-color molding, sandwich molding, and ultrahigh-speed injection molding. The advantages of these various molding methods are already widely known. Further, for molding, either a cold runner method or a hot runner method can be selected. Furthermore, the resin composition of the present invention can also be used in the form of various irregular extrusion molded products, sheets, films, etc. by extrusion molding. In addition, an inflation method, a calendar method, a casting method, etc. can also be used for forming sheets and films. Furthermore, by applying a specific stretching operation, it is also possible to form a heat-shrinkable tube. Further, the resin composition of the present invention can be made into a molded article by rotational molding, blow molding, or the like.

The thermoplastic resin composition of the present invention has excellent heat resistance and impact resistance properties, and suppresses resin deterioration during molding retention and in high temperature and high humidity environments, so it can be used for electrical/electronic parts, home appliances, and automobile-related parts. It is useful for various applications such as infrastructure-related parts, housing-related parts, medical instruments and equipment, and its industrial effects are exceptional.

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

The present invention will be further explained below with reference to Examples. In addition, unless otherwise specified, parts in the examples are parts by weight, and % is weight %. Note that the evaluation was carried out by the following method.

(Evaluation of thermoplastic resin composition)
(i) ΔMw-1 (change amount of viscosity average molecular weight before and after molding retention)
A sample board with a side of 50 mm and a thickness of 3 mm was molded continuously from the 1st shot to the 15th shot using the method described below, and after stopping molding for 20 minutes, the 16th shot and the 17th shot were molded continuously, and ΔMw -1 was calculated by the following formula.
ΔMw-1=Mw ₁ -Mw ₂
Mw ₁ : Viscosity average molecular weight of the molded product of the 8th shot Mw ₂ : Viscosity average molecular weight of the molded product of the 17th shot The viscosity average molecular weight (Mw) is first calculated by the specific viscosity (η _SP ) was determined using an Ostwald viscometer from a solution of 0.7 g of the sample plate obtained by the following method dissolved in 100 ml of methylene chloride at 20°C.
Specific viscosity (η _SP )=(t−t ₀ )/t ₀
[ _t0 is the number of seconds that methylene chloride falls, t is the number of seconds that the sample solution falls]
It was calculated from the determined specific viscosity (η _SP ) using the following formula.
η _SP /c=[η]+0.45×[η] ² c (however, [η] is the limiting viscosity)
[η]=1.23× ^10-4 Mw ^0.83
c=0.7

(ii) Charpy impact value Notched Charpy impact strength was measured at 23°C and -30°C in accordance with ISO179 using the ISO bending test piece obtained by the method below. The resin composition of the present invention must have a Charpy impact value of 53 kJ/m ² or more at 23°C and 15 kJ/m ² or more at -30°C.

(iii) Deflection temperature under load Using the ISO bending test piece obtained by the method below, the deflection temperature under load (load 0.45 MPa) was measured in accordance with ISO75-1 and ISO75-2. The resin composition of the present invention needs to have a deflection temperature under load of 144°C or higher.

(iv) ΔMw-2 (change in viscosity average molecular weight before and after high temperature and high humidity environment test)
Using the sample plate obtained by the method described below, ΔMw-2 was calculated using the following formula.
ΔMw-2=Mw ₃ -Mw ₄
Mw ₃ : Viscosity average molecular weight before the test Mw ₄ : Viscosity average molecular weight after a 20-hour test in an environment of 130°C/100% using a highly accelerated life tester (ESPEC EHS-412MD)

(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. , 11.1 kg (36 mol) of 3,5-trimethylcyclohexane, 3.4 kg (18 mol) of 4,4-dihydroxy-biphenyl, and p-tert-butylphenol (hereinafter sometimes abbreviated as PTBP) as a molecular weight regulator. (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. Inject 373 g of BTBAC-50 (manufactured by Lion Akzo), 107 g of sodium hydrosalafite (hereinafter sometimes abbreviated as SHS) (manufactured by BASF), and further inject 400 L of water into the reaction vessel. The mixture was dissolved to form an aqueous phase.

Furthermore, in another reaction vessel, 18.0 L of mixed phthalic acid chloride (MPC, manufactured by Ihara Nikkei Chemical Industry Co., Ltd.; terephthalic acid/isophthalic acid = 50/50 (mass %)) was added to 240 L of dichloromethylene (methylene chloride manufactured by Tokuyama Corporation). 6 kg (91 mol) was dissolved to form an organic phase. This organic phase was added to the already stirred aqueous phase under strong stirring, and the polymerization reaction was carried out for 2 hours while maintaining the temperature at 15°C. After this, stirring was stopped and the aqueous phase and organic phase were separated by decantation. The reaction was stopped by adding 400 L of pure water and 100 mL of acetic acid to the organic phase from which the aqueous phase had been removed, and the mixture was further stirred at 15° C. for 30 minutes. This organic phase was washed five times with pure water, 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). A compositional analysis of the obtained polyarylate resin (B-1) using ¹ H-NMR (ECA500 NMR manufactured by JEOL Ltd.) revealed that the polymerization ratio of dihydric phenol residues and phthalic acid residues was 1: 1, which was confirmed to be the same as the mixing ratio of dihydric phenol residues and phthalic acid residues. Moreover, 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-3)] was obtained. The viscosity average molecular weights of the obtained polyarylate resins were 21,800 and 60,000, respectively. The results are shown in Table 1.

In addition, each component indicated by the symbol 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 14, Comparative Examples 1 to 12)
A mixture having the composition shown in Tables 2 and 3 was supplied from the first supply port of the extruder. Such a mixture was obtained by mixing in a V-type blender. The twin-screw extruder has a diameter of 30 mm and has a total of 10 barrels (referred to as cylinders C1 to C10 from upstream) with supply ports at C1 at the most upstream section and C5 at the downstream thereof. A "TEX30αIII" intermeshing type co-rotating twin screw extruder manufactured by Steel Works Co., Ltd. was used. The 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 melt-kneaded to obtain pellets.

A portion of the obtained pellets was dried in a hot air circulation dryer at 120°C for 6 hours, and then molded using an injection molding machine with a cylinder temperature of 320°C and a mold temperature of 90°C, each side of 50 mm for evaluation. Sample plates with a thickness of 3 mm and ISO bending test pieces (compliant with ISO 75-1, 75-2 and ISO 179) were molded and various evaluations were performed. The evaluation results are shown in Tables 2 and 3.

The components indicated by symbols in Tables 2 and 3 are as follows.
(A component)
A-1: Aromatic polycarbonate resin [polycarbonate resin powder with a viscosity average molecular weight of 22,400 made from bisphenol A and phosgene by a conventional method, manufactured by Teijin Ltd., Panlite L-1225WP (product name)]
(B component)
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 (B-3) Production] Resin synthesized in (C component)
C-1: Trimethyl phosphate (TMP manufactured by Daihachi Chemical Industry Co., Ltd.)
C-2: 3,9-bis(2,6-di-tert-butyl-4-methylphenoxy)-2,4,8,10-tetraoxa 3,9-diphosphaspiro[5,5]undecane (PEP36 manufactured by ADEKA) )
C-3: Tris(2,4-di-tert-butylphenyl) phosphite (2112 manufactured by ADEKA)
(D component)
D-1: Octadecyl-3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate (AO-50 manufactured by Adeka)
D-2: 3,9-bis{2-[3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propionyloxy]-1,1,-dimethylethyl}-2,4,8, 10-Tetraoxaspiro[5,5]undecane (AO-80 manufactured by Adeka)
(E component)
E-1: Butadiene-based core-shell type graft copolymer (graft copolymer having a core-shell structure in which the core is mainly composed of butadiene rubber at 70 wt% and the shell is mainly composed of methyl methacrylate and styrene at 30 wt%, manufactured by Co., Ltd.) Kaneka Kane Ace M-701 (product name))
E-2: Acrylic core-shell type graft copolymer (graft copolymer having a core-shell structure in which the core is 60 wt% mainly composed of butadiene-acrylic composite rubber and butyl acrylate, and the shell is 40 wt% mainly composed of methyl methacrylate) , Metablen W-600A (product name) manufactured by Mitsubishi Rayon Co., Ltd.)
E-3: Silicone-based core-shell type graft copolymer (graft copolymer with a core-shell structure in which the core is 70 wt% based on acrylic-silicone composite rubber and the shell is 30 wt% based on methyl methacrylate, Mitsubishi Rayon) Metablen S-2001 (product name)) manufactured by Co., Ltd.
E-4: Acrylonitrile-butadiene-styrene copolymer resin (SXH-330 (product name) manufactured by Japan A&L Co., Ltd.)

Claims (6)

(C) phosphate ester compound (C component) 0.001 to 2 parts by weight, (D) hindered phenolic antioxidant (D component) 0.001 to 2 parts by weight, and (E) rubbery polymer (E component) 1 to 15 parts by weight. A thermoplastic resin composition characterized by: The thermoplastic resin composition according to claim 1, wherein component B is a polyarylate resin containing a polymerized unit represented by any of the following general formulas (1) to (3).
(In the above general formula (1), l, m, and n are positive values 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 above general formula (2), m and n are positive integers, and m/n = 8/2 to 2/8.)
(In the above general formula (3), n is a positive integer.) 3. The thermoplastic resin composition according to claim 1, wherein component D has a melting point of 30 to 70°C. 4. The thermoplastic resin composition according to claim 1 , wherein component C has a number average molecular weight of 50 to 300. Component E is at least one rubber selected from the group consisting of acrylonitrile-butadiene-styrene copolymer resin, butadiene core-shell graft copolymer, acrylic core-shell graft copolymer, and silicone core-shell graft copolymer. The thermoplastic resin composition according to any one of claims 1 to 4 , which is a polymer. A molded article obtained by molding the thermoplastic resin composition according to any one of claims 1 to 5 .