JP2024018016A - Thermoplastic resin composition and molded article composed of the same - Google Patents

Abstract

To provide a thermoplastic resin composition that is less prone to discoloration and strength deterioration, exhibits superior recyclability, and offers superior flame retardancy, even under severe processing conditions, and a molded article composed of the same.SOLUTION: A thermoplastic resin composition is provided. Based on 100 pts.wt. of (A) a thermoplastic resin (A component), the thermoplastic resin composition comprises 0.001-1 pt.wt. of (B) phosphonate with an acid value of 0.01-0.30 mgKOH/g (B component) and (C) 0.01-25 pts.wt. of a flame retardant (C component).SELECTED DRAWING: None

Description

The present invention relates to a thermoplastic resin composition that exhibits little discoloration and decrease in strength during molding and has excellent flame retardancy, and a molded article made from the same. More specifically, the present invention relates to a thermoplastic resin composition that exhibits little discoloration and strength loss even under severe processing conditions, has excellent recyclability, and has excellent flame retardancy, and molded articles made from the same.

Thermoplastic resin compositions are used in a wide range of fields, including housings and parts for electrical, electronic, and OA equipment, interior and exterior parts for automobiles, furniture, musical instruments, and miscellaneous goods. Particularly in recent years, high recyclability has been desired for thermoplastic resin compositions in order to realize a sustainable society. On the other hand, it is widely known that a phosphorus compound is used as a heat stabilizer in a thermoplastic resin composition. Patent Document 1 discloses that a specific phosphorus compound is used in a resin consisting of a polycarbonate resin and a polyester resin. Patent Document 2 discloses the combined use of a phosphorus compound. However, with existing methods, thermal stability during molding is still insufficient, and in applications that require thinner walls and lighter weight, molding conditions tend to be high and there are an increasing number of cases where thermal stability is insufficient. There is. Furthermore, there is a high demand for products to be recycled and used again, and we are meeting the demand for thermoplastic resin compositions that have excellent recyclability with minimal discoloration and strength loss even under harsh processing conditions, and excellent flame retardancy. There is an increasing need to propose materials that can be used.

Patent No. 4983427 Patent No. 5640734

An object of the present invention is to provide a thermoplastic resin composition that exhibits minimal discoloration and strength loss even under severe processing conditions, excellent recyclability, and excellent flame retardancy, and a molded article made from the same.

As a result of intensive research aimed at achieving the above object, the present inventors have found that by blending a phosphonic acid ester with a specific acid value and a flame retardant into a thermoplastic resin composition, it can withstand harsh processing conditions. The present inventors have discovered that it is possible to provide a thermoplastic resin composition that exhibits little discoloration and strength loss, excellent recyclability, and excellent flame retardancy, and a molded article made from the same, and has thus arrived at the present invention.
That is, the present invention is as follows.

1. (A) 0.001 to 1 part by weight of a phosphonic acid ester (component B) having an acid value of 0.01 to 0.30 mgKOH/g to 100 parts by weight of the thermoplastic resin (component A) and ( C) A thermoplastic resin composition containing 0.01 to 25 parts by weight of a flame retardant (component C).
2. A component is selected from the group consisting of (A-1) polycarbonate resin (A-1 component), (A-2) ABS resin (A-2 component), and (A-3) polyester resin (A-3 component). The thermoplastic resin composition according to item 1 above, which is at least one thermoplastic resin comprising:
3. The thermoplastic resin composition according to item 1 or 2 above, wherein the content of component A-1 is 40 to 100 parts by weight based on 100 parts by weight of component A.
4. C component is (C-1) halogenated carbonate compound (C-1 component), (C-2) phosphate ester compound (C-2 component), (C-3) phosphazene compound (C-3 component), Any one of items 1 to 3 above, which is at least one flame retardant selected from the group consisting of (C-4) sulfonic acid metal salt (C-4 component) and (C-5) silicone compound (C-5 component) The thermoplastic resin composition described in .
5. The thermoplastic resin composition according to any one of items 1 to 4 above, which contains 0.05 to 3 parts by weight of (D) an anti-drip agent (component D) per 100 parts by weight of component A.
6. 6. The thermoplastic resin composition according to any one of items 1 to 5 above, wherein component B is triethylphosphonoacetate.
7. A molded article made of the thermoplastic resin composition according to any one of items 1 to 6 above.

The details of the present invention will be explained below.

<A component: thermoplastic resin>
Thermoplastic resins used as component A of the present invention include polycarbonate resins, ABS resins, polyester resins, AS resins, PS resins, AAS resins, AES resins, polyamide resins, polyolefin resins, fluorine resins, PPS resins, PEEK resins, These include polyarylate resins, polyacetal resins, etc., and preferably at least one thermoplastic resin selected from the group consisting of polycarbonate resins, ABS resins, and polyester resins. Further, the content of the polycarbonate resin is preferably 40 to 100 parts by weight in 100 parts by weight of component A. The content of the polycarbonate resin is more preferably 60 to 100 parts by weight based on 100 parts by weight of component A.

<A-1 component: polycarbonate resin>
The polycarbonate resin used as component A-1 of the present invention is obtained by reacting 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, it is also possible to use special polycarbonate resins produced using other dihydric phenols as the A-1 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.

In addition, among the various polycarbonate resins mentioned above, those whose water absorption rate and Tg (glass transition temperature) are within the following range 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 properties and the like to the thermoplastic 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 of the polycarbonate resin is preferably 12,500 to 32,000, more preferably 16,000 to 28,000, and even more preferably 18,000 to 32,000. 000 to 26,000. Polycarbonate resins with a viscosity average molecular weight of less than 12,500 may not provide good mechanical properties. On the other hand, resin compositions obtained from polycarbonate resins having a viscosity average molecular weight of more than 32,000 may have poor moldability.

The viscosity average molecular weight 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 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. Polycarbonate-polydiorganosiloxane copolymer resin is a copolymerization resin prepared by copolymerizing a dihydric phenol represented by the following general formula (1) and a hydroxyaryl-terminated polydiorganosiloxane represented by the following general formula (3). Preferably, it is a resin.

[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 carboxy group, and if there are multiple of each, they may be the same or different. e and f are each integers 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 each independently represent 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 carboxy group If there are multiple groups, they may be the same or different, g is an integer of 1 to 10, and h is an integer of 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 p is a natural number. , q is 0 or a natural number, and p+q is a natural number from 10 to 300. X is a divalent aliphatic group having 2 to 8 carbon atoms. ]

Examples of the dihydric phenol (I) represented by 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-isopropyl) phenyl)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-bis(4-hydroxyphenyl) )-5,7-dimethyladamantane and the like.

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.

As the hydroxyaryl-terminated polydiorganosiloxane represented by the above general formula (3), for example, the compounds shown below are preferably used.

The hydroxyaryl-terminated polydiorganosiloxane (II) is a phenol having an olefinic unsaturated carbon-carbon bond, preferably vinylphenol, 2-allylphenol, isopropenylphenol, or 2-methoxy-4-allylphenol. It is easily produced by subjecting the end of a polysiloxane chain having a degree of polymerization of Among these, preferred are (2-allylphenol)-terminated polydiorganosiloxane and (2-methoxy-4-allylphenol)-terminated polydiorganosiloxane, particularly (2-allylphenol)-terminated polydimethylsiloxane and (2-methoxy-4-allylphenol)-terminated polydiorganosiloxane. -allylphenol)-terminated polydimethylsiloxane is preferred. The hydroxyaryl-terminated polydiorganosiloxane (II) preferably has a molecular weight distribution (Mw/Mn) of 3 or less. In order to further exhibit excellent low outgassing properties during high temperature molding and low temperature impact properties, the molecular weight distribution (Mw/Mn) is more preferably 2.5 or less, and even more preferably 2 or less. If the upper limit of this preferred range is exceeded, a large amount of outgas will be generated during high-temperature molding, and low-temperature impact properties may be poor.

Furthermore, in order to achieve high impact resistance, the degree of diorganosiloxane polymerization (p+q) of the hydroxyaryl-terminated polydiorganosiloxane (II) is suitably 10 to 300. The diorganosiloxane polymerization degree (p+q) is preferably 10 to 200, more preferably 12 to 150, even more preferably 14 to 100. Below the lower limit of this preferred range, the impact resistance, which is a characteristic of the polycarbonate-polydiorganosiloxane copolymer, will not be effectively expressed, and if it exceeds the upper limit of this preferred range, poor appearance will appear.

The polydiorganosiloxane content in the total weight of the polycarbonate-polydiorganosiloxane copolymer resin used in component A-1 is preferably 0.1 to 50% by weight. The content of the polydiorganosiloxane component is more preferably 0.5 to 30% by weight, and even more preferably 1 to 20% by weight. When it is above the lower limit of this preferred range, it has excellent impact resistance and flame retardancy, and when it is below the upper limit of this preferred range, it is easy to obtain a stable appearance that is not easily affected by molding conditions. The degree of polymerization of polydiorganosiloxane and the content of polydiorganosiloxane can be calculated by ¹ H-NMR measurement.

In the present invention, only one type of hydroxyaryl-terminated polydiorganosiloxane (II) may be used, or two or more types may be used.

In addition, other comonomers other than the above-mentioned dihydric phenol (I) and hydroxyaryl-terminated polydiorganosiloxane (II) may be contained in an amount of 10% by weight or less based on the total weight of the copolymer, to the extent that it does not interfere with the present invention. They can also be used together.

In the present invention, a mixed solution containing an oligomer having a terminal chloroformate group is prepared in advance by reacting dihydric phenol (I) with a carbonate-forming compound in a mixed solution of a water-insoluble organic solvent and an alkaline aqueous solution. do.

In producing an oligomer of dihydric phenol (I), the entire amount of dihydric phenol (I) used in the method of the present invention may be made into an oligomer at once, or a part thereof may be used as a post-added monomer to form an oligomer at the subsequent interface. It may be added as a reaction raw material to the polycondensation reaction. 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 of this oligomer production reaction is not particularly limited, but it is usually preferable to carry out the reaction in a solvent in the presence of an acid binder.

The proportion of the carbonate ester-forming compound to be used may be appropriately adjusted in consideration of the stoichiometric ratio (equivalent) of the reaction. Furthermore, when using a gaseous carbonate ester-forming compound such as phosgene, a method of blowing it into the reaction system can be suitably employed.

As the acid binder, for example, 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 are 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, it is preferable to use the acid binder in an amount of 2 equivalents or slightly in excess of the number of moles of dihydric phenol (I) used to form the oligomer (usually 1 mole corresponds to 2 equivalents). .

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. Typical examples include hydrocarbon solvents such as xylene, halogenated hydrocarbon solvents such as methylene chloride, and chlorobenzene. In particular, halogenated hydrocarbon solvents such as methylene chloride are preferably used.

The reaction pressure for oligomer production is not particularly limited and may be at 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 polymerization 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. The pH range of the oligomer production reaction is similar to known interfacial reaction conditions, and the pH is always adjusted to 10 or higher.

In this way, the present invention obtains a mixed solution containing an oligomer of dihydric phenol (I) having a terminal chloroformate group, and then, while stirring the mixed solution, the molecular weight distribution (Mw/Mn) is reduced to 3 or less. A highly purified hydroxyaryl-terminated polydiorganosiloxane (II) represented by general formula (3) is added to dihydric phenol (I), and the hydroxyaryl-terminated polydiorganosiloxane (II) and the oligomer are subjected to interfacial polycondensation. A polycarbonate-polydiorganosiloxane copolymer is thereby obtained.

(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 p is a natural number. (where q is 0 or a natural number, and p+q is a natural number from 10 to 300. X is a divalent aliphatic group having 2 to 8 carbon atoms.)

When carrying out the interfacial polycondensation reaction, an acid binder may be added as appropriate in consideration of the stoichiometric ratio (equivalent) of the reaction. As the acid binder, for example, 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 are used. Specifically, when the hydroxyaryl-terminated polydiorganosiloxane (II) used or a part of the dihydric phenol (I) as described above is added to this reaction step as a post-addition monomer, the post-addition amount is It is preferable to use the alkali in an amount of 2 equivalents or in excess of the total number of moles of the hydric phenol (I) and the hydroxyaryl-terminated polydiorganosiloxane (II) (usually 1 mole corresponds to 2 equivalents).

Polycondensation by interfacial polycondensation reaction between the oligomer of dihydric phenol (I) and the hydroxyaryl-terminated polydiorganosiloxane (II) is carried out by vigorously stirring the mixture.

In such polymerization reactions, terminal terminators or molecular weight regulators are usually used. Examples of the terminal capping agent include compounds having a monovalent phenolic hydroxyl group, including ordinary phenol, p-tert-butylphenol, p-cumylphenol, tribromophenol, etc., as well as long-chain alkylphenols and aliphatic carboxylic acids. Examples include chloride, aliphatic carboxylic acid, hydroxybenzoic acid alkyl ester, hydroxyphenylalkyl ester, and alkyl ether phenol. The amount used is in the range of 100 to 0.5 mol, preferably 50 to 2 mol, per 100 mol of all the dihydric phenol compounds used, and it is naturally possible to use two or more types of compounds together. be.

A catalyst such as a tertiary amine such as triethylamine or a quaternary ammonium salt may be added to accelerate the polycondensation reaction.

The reaction time of this polymerization reaction is preferably 30 minutes or more, more preferably 50 minutes or more. If desired, a small amount of an antioxidant such as sodium sulfite or hydrosulfide may be added.

A branching agent can be used in combination with the dihydric phenol compound described above to form a branched polycarbonate-polydiorganosiloxane. Examples of the trifunctional or higher polyfunctional aromatic compound used in the branched polycarbonate-polydiorganosiloxane copolymer resin 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, Trisphenol such as 4-{4-[1,1-bis(4-hydroxyphenyl)ethyl]benzene}-α,α-dimethylbenzylphenol, tetra(4-hydroxyphenyl)methane, bis(2,4-dihydroxy phenyl)ketone, 1,4-bis(4,4-dihydroxytriphenylmethyl)benzene, or trimellitic acid, pyromellitic acid, benzophenonetetracarboxylic acid, and their acid chlorides, among others, 1,1,1 -Tris(4-hydroxyphenyl)ethane, 1,1,1-tris(3,5-dimethyl-4-hydroxyphenyl)ethane is preferred, and 1,1,1-tris(4-hydroxyphenyl)ethane is particularly preferred . The proportion of the polyfunctional compound in the branched polycarbonate-polydiorganosiloxane copolymer resin is preferably 0.001 to 1 mol%, more preferably 0.005 to 0.9% based on the total amount of the polycarbonate-polydiorganosiloxane copolymer resin. It is mol%, more preferably 0.01 to 0.8 mol%, particularly preferably 0.05 to 0.4 mol%. Note that the amount of branched structure can be calculated by ¹ H-NMR measurement.

The reaction pressure can be any of reduced pressure, normal pressure, and increased pressure, but usually, the reaction can be suitably carried out at normal pressure or about the own pressure 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 average size of the polydiorganosiloxane domains in the polycarbonate-polydiorganosiloxane copolymer resin molded article is preferably in the range of 1 to 40 nm. Such average size is more preferably 1 to 30 nm, even more preferably 5 to 25 nm. If it is less than the lower limit of this preferred range, impact resistance and flame retardancy may not be sufficiently exhibited, and if it exceeds the upper limit of this preferred range, impact resistance may not be stably exhibited.

The average domain size and normalized dispersion of the polydiorganosiloxane domains of the polycarbonate-polydiorganosiloxane copolymer resin molded article in the present invention were evaluated by small angle X-ray scattering (SAXS). The small-angle X-ray scattering method is a method for measuring diffuse scattering and diffraction that occurs in a small-angle region where the scattering angle (2θ) is less than 10°. In this small-angle X-ray scattering method, when there are regions with different electron densities of about 1 to 100 nm in size in a substance, diffuse scattering of X-rays is measured based on the difference in electron density. The particle diameter of the object to be measured is determined based on this scattering angle and scattering intensity. In the case of a polycarbonate-polydiorganosiloxane copolymer resin that has an aggregated structure in which polydiorganosiloxane domains are dispersed in a polycarbonate polymer matrix, diffuse scattering of X-rays occurs due to the difference in electron density between the polycarbonate matrix and the polydiorganosiloxane domains. The scattering intensity I at each scattering angle (2θ) in a range of less than 10° was measured to measure the small-angle X-ray scattering profile, and it was determined that the polydiorganosiloxane domain was a spherical domain and that the particle size distribution was uneven. Assuming that exists, a simulation is performed using commercially available analysis software from the tentative particle size and the tentative particle size distribution model, and the average size and particle size distribution (normalized dispersion) of the polydiorganosiloxane domains are determined. Small-angle X-ray scattering allows the average size and particle size distribution of polydiorganosiloxane domains dispersed in a polycarbonate polymer matrix to be accurately, easily, and reproducibly measured, which cannot be accurately measured using transmission electron microscopy. can be measured. Average domain size means the number average of individual domain sizes. Normalized dispersion means a parameter in which the spread of particle size distribution is normalized by the average size. Specifically, it is a value obtained by normalizing the dispersion of polydiorganosiloxane domain sizes by the average domain size, and is expressed by the following formula (1).

In the above formula (1), δ is the standard deviation of the polydiorganosiloxane domain size, and Dav is the average domain size.

The terms "average domain size" and "normalized dispersion" used in connection with the present invention refer to the measurement of a 1.0 mm thick portion of a three-tiered plate produced by the method described in the example using the small-angle X-ray scattering method. The measured values obtained are shown below. In addition, analysis was performed using an isolated particle model that does not take into account interparticle interactions (interparticle interference).

<A-2 component: ABS resin>
The ABS resin used as the A-2 component of the present invention is a copolymer obtained by graft polymerizing acrylonitrile and styrene onto polybutadiene. As the styrene, styrene and α-methylstyrene can be particularly preferably used. The proportion of the component grafted onto such polybutadiene is preferably 95 to 20% by weight, particularly preferably 90 to 50% by weight, based on 100% by weight of the ABS resin component. Further, it is preferable that the acrylonitrile content is 5 to 50% by weight and the styrene content is 95 to 50% by weight, based on 100% by weight of the total amount of acrylonitrile and styrene. Furthermore, methyl (meth)acrylate, ethyl acrylate, maleic anhydride, N-substituted maleimide, etc. can be mixed and used as a part of the components graft-polymerized to the above polybutadiene, and the content ratio of these is 15% by weight in the ABS resin component. % or less is preferable. Furthermore, various conventionally known initiators, chain transfer agents, emulsifiers, etc. used in the reaction can be used as required. In the ABS resin of the present invention, the particle size of polybutadiene is preferably 0.1 to 5.0 μm, more preferably 0.2 to 3.0 μm, particularly preferably 0.3 to 1.5 μm. The polybutadiene particle size distribution can be either a single distribution or a polybutadiene particle size distribution having two or more peaks, and its morphology is such that the particles form a single phase. However, it may also have a salami structure by containing an occluded phase around the particles. Furthermore, it has been well known that ABS resin contains a copolymer of acrylonitrile and styrene that is not grafted to the diene rubber component, and the ABS resin of the present invention also contains free substances generated during such polymerization. It may contain a polymer component of. The reduced viscosity (at 30° C.) of such a copolymer consisting of free acrylonitrile and styrene is preferably 0.2 to 1.0 dl/g, more preferably 0.3 to 0.7 dl/g. It is something. The proportion of grafted acrylonitrile and styrene relative to polybutadiene is preferably 20 to 200%, more preferably 20 to 70%, expressed as a grafting rate (% by weight). Such ABS resins may be produced by any method such as bulk polymerization, suspension polymerization, or emulsion polymerization, but those produced by bulk polymerization are particularly preferred. In the case of bulk polymerization, since alkali metal salts derived from emulsifiers and the like are not substantially contained, it is possible to maintain better thermal stability of the resin composition. Further, the copolymerization method may be one-stage copolymerization or multi-stage copolymerization. Furthermore, a blend of ABS resin obtained by such a production method with a vinyl compound polymer obtained by separately copolymerizing acrylonitrile and styrene can also be preferably used.

<A-3 component: polyester resin>
The polyester resin used as component A-3 of the present invention is preferably a polyester resin in which aromatic dicarboxylic acid accounts for 70 mol% or more of 100 mol% of the dicarboxylic acid component among the dicarboxylic acid component and diol component forming the polyester. , more preferably 90 mol % or more, most preferably 99 mol % or more of aromatic dicarboxylic acid.

Examples of this dicarboxylic acid include terephthalic acid, isophthalic acid, 2-chloroterephthalic acid, 2,5-dichloroterephthalic acid, 2-methylterephthalic acid, 4,4-stilbenedicarboxylic acid, 4,4-biphenyldicarboxylic acid, orthophthalic acid. Acid, 2,6-naphthalene dicarboxylic acid, 2,7-naphthalene dicarboxylic acid, bisbenzoic acid, bis(p-carboxyphenyl)methane, anthracene dicarboxylic acid, 4,4-diphenyl ether dicarboxylic acid, 4,4-diphenoxyethane Examples include dicarboxylic acid, 5-Na sulfoisophthalic acid, and ethylene-bis-p-benzoic acid. These dicarboxylic acids can be used alone or in combination of two or more. In addition to the aromatic dicarboxylic acid described above, less than 30 mol % of an aliphatic dicarboxylic acid component can be copolymerized with the polyester resin of the present invention. Specific examples thereof include adipic acid, sebacic acid, azelaic acid, dodecanedioic acid, 1,3-cyclohexanedicarboxylic acid, and 1,4-cyclohexanedicarboxylic acid.

Examples of the diol component of the present invention include ethylene glycol, diethylene glycol, 1,2-propylene glycol, 1,3-propanediol, 2,2-dimethyl-1,3-propanediol, trans- or cis-2,2, 4,4-tetramethyl-1,3-cyclobutanediol, 1,4-butanediol, neopentyl glycol, 1,5-pentanediol, 1,6-hexanediol, 1,4-cyclohexanedimethanol, 1,3 -Cyclohexane dimethanol, decamethylene glycol, cyclohexanediol, p-xylene diol, bisphenol A, tetrabromobisphenol A, tetrabromobisphenol A-bis(2-hydroxyethyl ether), and the like. These can be used alone or in combination of two or more. In addition, it is preferable that the dihydric phenol in the diol component is 30 mol% or less.

Specific polyester resins include polyethylene terephthalate (PET), polypropylene terephthalate, polybutylene terephthalate (PBT), polyhexylene terephthalate, polyethylene naphthalate (PEN), polybutylene naphthalate (PBN), and polyethylene-1,2- In addition to bis(phenoxy)ethane-4,4'-dicarboxylate, copolymerized polyester resins such as polyethylene isophthalate/terephthalate copolymer, polybutylene terephthalate/isophthalate copolymer, and the like can be mentioned.

Further, the terminal group structure of the polyester resin used in the present invention is not particularly limited, and in addition to cases where the proportion of hydroxyl groups and carboxyl groups in the terminal groups is approximately the same, even when the proportion of one is larger. good. Further, the terminal groups may be blocked by reacting a compound having reactivity with such terminal groups.

The method for producing the polyester resin used in the present invention involves polymerizing the dicarboxylic acid component and the diol component while heating in the presence of a polycondensation catalyst containing titanium, germanium, antimony, etc., according to a conventional method. This is done by discharging by-product water or lower alcohol from the system. For example, germanium-based polymerization catalysts include germanium oxides, hydroxides, halides, alcoholates, phenolates, etc. More specifically, germanium oxide, germanium hydroxide, germanium tetrachloride, tetramethoxygermanium, etc. can be exemplified. In addition, in the present invention, compounds such as manganese, zinc, calcium, and magnesium, which are used in the transesterification reaction which is a pre-stage of conventionally known polycondensation, can be used together, and after the completion of the transesterification reaction, phosphoric acid or phosphorous acid can be used. It is also possible to perform polycondensation by deactivating such a catalyst with an acid compound or the like. Furthermore, the method for producing the polyester resin can be either a batch method or a continuous polymerization method.

Further, among the above polyester resins, polyethylene terephthalate is particularly suitable. The polyethylene terephthalate of the present invention is a polymer obtained by a polycondensation reaction of terephthalic acid or its derivative and ethylene glycol or its derivative, but as mentioned above, it also contains other dicarboxylic acid components and other alkylene glycol components. Including polymerized products.

Although the terminal group structure of polyethylene terephthalate is not particularly limited as described above, it is more preferable that the number of terminal carboxy groups is smaller than that of terminal hydroxyl groups. Further, as for the manufacturing method, various methods mentioned above can be used, but a continuous polymerization method is preferable. This is because it has high quality stability and is advantageous in terms of cost. Furthermore, it is preferable to use an organic titanium compound as the polymerization catalyst. This is because it tends to have less influence on transesterification reactions and the like. Preferred specific examples of such organic titanium compounds include titanium tetrabutoxide, titanium isopropoxide, titanium oxalate, titanium acetate, titanium benzoate, titanium trimellitate, and a reaction product of tetrabutyl titanate and trimellitic anhydride. be able to. The amount of the organic titanium compound to be used is preferably such that the titanium atoms are 3 to 12 mg atomic % based on the acid component constituting the polyethylene terephthalate.

The molecular weight of the polyester resin of the present invention is not particularly limited, but the intrinsic viscosity measured at 35°C using o-chlorophenol as a solvent is preferably 0.5 to 1.5, particularly preferably 0.6 to 1. .2.

<Component B: Phosphonate ester>
As the phosphonic acid ester used in the present invention, phosphonic acid monoester, phosphonic acid diester, and phosphonic acid triester can be used, but phosphonic acid triester is preferable. Although various combinations of esters having carbon atoms from 1 to 22 can be used, triethylphosphonoacetate is most preferred. The acid value of the phosphonate ester is 0.01 to 0.30 mgKOH/g, preferably 0.01 to 0.20 mgKOH/g, more preferably 0.05 to 0.15 mgKOH/g. If the acid value is less than 0.01 mgKOH/g, it is not practical for production, and if it is more than 0.30 mgKOH/g, discoloration and decrease in strength during molding cannot be prevented. The acid value was measured using a potentiometric titration device, and the alcohol solution of the phosphonic acid ester was titrated with the KOH alcohol solution.

The content of component B is 0.001 to 1 part by weight, preferably 0.01 to 0.1 part by weight, and more preferably 0.01 to 0.07 part by weight based on 100 parts by weight of component A. be. When the content of component B is less than 0.001 part by weight, and when it exceeds 1 part by weight, discoloration and decrease in strength during molding cannot be prevented.

<Component C: Flame retardant>
The flame retardant of component C may include various compounds known as flame retardants for polycarbonate resins, among which (C-1) halogenated carbonate compound (C-1 component), (C-2) phosphoric acid Ester compound (C-2 component), (C-3) phosphazene compound (C-3 component), (C-4) sulfonic acid metal salt (C-4 component) and (C-5) silicone compound (C-5) It is preferable that the flame retardant is at least one kind of flame retardant selected from the group consisting of 5 components).

The content of component C is 0.01 to 25 parts by weight, preferably 0.015 to 22 parts by weight, and more preferably 0.02 to 20 parts by weight, based on 100 parts by weight of component A. If the content of component C is less than 0.01 parts by weight, sufficient flame retardancy cannot be obtained, and if it exceeds 25 parts by weight, discoloration and decrease in strength during molding cannot be prevented.

<C-1 component: halogenated carbonate compound>
The halogenated carbonate compound used in the present invention is a halogenated carbonate in which the structural unit represented by the following general formula (4) accounts for at least 60 mol% of the total structural units and has a specific viscosity of 0.015 to 0.1. Compounds are preferably used.

[In the general formula (4), X is a halogen atom, R is an alkylene group having 1 to 4 carbon atoms, an alkylidene group having 1 to 4 carbon atoms, or -SO ₂ -. ]
In the formula (4), R preferably represents a methylene group, an ethylene group, an isopropylidene group, -SO ₂ -, and particularly preferably an isopropylidene group. Further, X is preferably a bromine atom.

The halogenated carbonate compound preferably has a small amount of residual chloroformate group terminals, and the terminal chlorine content is preferably 0.3 ppm or less, more preferably 0.2 ppm or less. The amount of terminal chlorine can be determined by dissolving the sample in methylene chloride, adding 4-(p-nitrobenzyl)pyridine to react with terminal chlorine (terminal chloroformate), and measuring this with an ultraviolet-visible spectrophotometer (U -3200). When the amount of terminal chlorine is 0.3 ppm or less, the thermal stability of the polycarbonate resin composition becomes better, and molding at a higher temperature becomes possible, and as a result, a resin composition with better molding processability may be provided. be.

Further, it is preferable that the halogenated carbonate compound has a small amount of residual hydroxyl group terminals. More specifically, the amount of terminal hydroxyl groups is preferably at most 0.0005 mol, more preferably at most 0.0003 mol, per mol of the structural unit of the halogenated carbonate compound. The amount of terminal hydroxyl groups can be determined by dissolving a sample in deuterated chloroform and measuring by ¹ H-NMR method. Such an amount of terminal hydroxyl groups may further improve the thermal stability of the polycarbonate resin composition.

The specific viscosity of the halogenated carbonate compound is preferably in the range of 0.015 to 0.1, more preferably in the range of 0.015 to 0.08. The specific viscosity of the halogenated carbonate compound was calculated according to the formula used to calculate the viscosity average molecular weight of the polycarbonate resin, which is component A-1 of the present invention described above.

Further, such halogenated carbonate compounds are commercially available, such as tetrabromobisphenol A carbonate oligomers (trade names FG-7000 and FG-8500) manufactured by Teijin Ltd., which can be used in the present invention. can.

<C-2 component: phosphoric acid ester compound>
As the phosphoric acid ester compound used in the present invention, phosphate compounds, particularly aryl phosphate compounds are suitable.

The phosphate compound preferably has a molecular weight of 300 or more. If the molecular weight is less than 300, the difference between the boiling point of the phosphate compound and the combustion temperature of the resin composition becomes large, and the phosphate compound may volatilize more during combustion, which may reduce its effectiveness as a flame retardant. be.

As such a 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 (5) can be mentioned.

(In general formula (5), A dihydric phenol residue derived from a dihydroxy compound selected from the group consisting of bis(4-hydroxyphenyl) sulfide, where n is an integer from 0 to 5, or a mixture of phosphoric esters with different n numbers. is their average value, and R ¹ , R ² , R ³ , and R ⁴ are each independently derived from an aryl group selected from the group consisting of phenol, cresol, xylenol, isopropylphenol, butylphenol, and p-cumylphenol. (It is a monohydric phenol residue.)

The phosphate compound of the above general formula may be a mixture of compounds having different n numbers; in the case of such mixtures, the average n 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 X in the above general formula (5) are resorcinol, bisphenol A, and dihydroxydiphenyl, and among them, resorcinol and bisphenol A are preferred.

Preferred specific examples of the monohydric phenol for inducing R ¹ , R ² , R ³ , and R ⁴ in the above general formula (5) include phenol, cresol, xylenol, and 2,6-dimethylphenol, and among them, preferred are phenol, cresol, xylenol, and 2,6-dimethylphenol. are phenol and 2,6-dimethylphenol.

Specific examples of the phosphate compound represented by the above general formula (5) include monophosphate compounds such as triphenyl phosphate and tri(2,6-xylyl) phosphate, and resorcinol bis di(2,6-xylyl) phosphate). Phosphate oligomers mainly composed of 4,4-dihydroxydiphenylbis (diphenyl phosphate), and phosphate ester oligomers mainly composed of bisphenol A bis(diphenyl phosphate) are suitable, and among them, resorcinol bis(diphenyl phosphate) is preferred. Phosphate oligomers mainly composed of 2,6-xylyl)phosphate), phosphate oligomers mainly composed of 4,4-dihydroxydiphenylbis(diphenylphosphate), and phosphate ester oligomers mainly composed of bisphenol A bis(diphenylphosphate). preferable.

<C-3 component: phosphazene compound>
The phosphazene compound used in the present invention is not particularly limited as long as it does not contain a halogen atom and has a phosphazene structure in its molecule. The phosphazene structure herein refers to a structure represented by the formula: -P(R2)=N- [wherein R2 is an organic group]. Phosphazene is represented by general formulas (6) and (7).

(In the general formulas (6) and (7), 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, n is 3 to 10 ).

In the above general formulas (6) and (7), examples of the halogen-free organic group represented by X ₁ , X ₂ , X ₃ , and X ₄ include an alkoxy group, a phenyl group, an amino group, and an allyl group. Examples include. Among these, cyclic phenoxyphosphazene represented by the following general formula (8) is preferred.

[In general formula (8), m represents an integer of 3 to 25. Ph represents a phenyl group. ]

Commercially available phosphazene compounds include SPS-100, SPR-100, SA-100, SPB-100, SPB-100L (manufactured by Otsuka Chemical Co., Ltd.), FP-100, and FP-110 (manufactured by Fushimi Pharmaceutical Co., Ltd.). (manufactured by Tosho).

<C-4 component: sulfonic acid metal salt>
The metal used in the sulfonic acid metal salt used in the present invention is preferably an alkali metal or an alkaline earth metal, and more preferably an alkali metal. Examples of alkali metals include lithium, sodium, potassium, rubidium, and cesium, and examples of alkaline earth metals include beryllium, magnesium, calcium, strontium, and barium, with lithium, sodium, and potassium being particularly preferred.

The sulfonic acid used in the sulfonic acid metal salt used in the present invention is preferably an organic sulfonic acid, more preferably an aliphatic sulfonic acid or an aromatic sulfonic acid.

The aliphatic sulfonic acid is preferably an alkyl sulfonic acid, more preferably a fluoroalkylsulfonic acid in which some or all of the alkyl groups are substituted with fluorine atoms, and a perfluoroalkylsulfonic acid in which all or all of the alkyl groups are substituted with fluorine atoms. Most preferably it is an acid. Preferred examples of perfluoroalkyl sulfonic acids include perfluoromethanesulfonic acid, perfluoroethanesulfonic acid, perfluoropropanesulfonic acid, perfluorobutanesulfonate, perfluoromethylbutanesulfonic acid, perfluorohexanesulfonic acid, and perfluorobutanesulfonic acid. Examples include fluoroheptanesulfonic acid and perfluorooctanesulfonic acid, with those having 1 to 8 carbon atoms being particularly preferred. These can be used alone or in combination of two or more.

Aromatic sulfonic acids include sulfonic acids of monomeric or polymeric aromatic sulfides, sulfonic acids of aromatic carboxylic acids and esters, sulfonic acids of monomeric or polymeric aromatic ethers, sulfonic acids of aromatic sulfonates, sulfonic acids of aromatic sulfonates, monomeric or by polymeric aromatic sulfonic acids, monomeric or polymeric aromatic sulfone sulfonic acids, sulfonic acids of aromatic ketones, heterocyclic sulfonic acids, sulfonic acids of aromatic sulfoxides, methylene-type bonds of aromatic sulfonic acids. At least one type of acid selected from the group consisting of condensates can be mentioned, and these can be used alone or in combination of two or more types.

<C-5 component: silicone compound>
The silicone compound used in the present invention preferably has a highly active group, and preferred examples thereof include an alkoxy group or a Si-H group. The content ratio of such groups is preferably in the range of 0.1 to 1.2 mol/100g, more preferably in the range of 0.12 to 1 mol/100g, even more preferably in the range of 0.15 to 0.6 mol/100g. 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, particularly preferably a methoxy group.

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. . A more preferred silicone flame retardant is a silicone compound containing an aromatic group (amount of aromatic groups) of 10 to 70% by weight (more preferably 15 to 60% by weight).

<Component D: Anti-drip agent>
Examples of the anti-drip agent used as component D in the present invention include fluorine-containing polymers having fibril-forming ability, such as polytetrafluoroethylene and tetrafluoroethylene copolymers (e.g., tetrafluoroethylene copolymers). /hexafluoropropylene copolymer, etc.), partially fluorinated polymers as shown in US Pat. No. 4,379,910, and polycarbonate resins produced from fluorinated diphenols. Among these, polytetrafluoroethylene (hereinafter sometimes referred to as PTFE) is preferred.

PTFE having fibril-forming ability has an extremely high molecular weight, and exhibits a tendency to bond together and become fibrous due to external action such as shearing force. Its molecular weight is 1 million to 10 million, more preferably 2 million to 9 million, in terms of number average molecular weight determined from standard specific gravity. Such PTFE can be used not only in solid form but also in aqueous dispersion form. In addition, PTFE having such fibril-forming ability improves its dispersibility in resin, and it is also possible to use a PTFE mixture in a mixed form with other resins to obtain better flame retardance and mechanical properties. be.

Examples of commercially available PTFE products having such fibril-forming ability include Teflon (registered trademark) 6-J from Mitsui Chemours Fluoro Products Co., Ltd. and Polyflon MPA FA500H and F-201 from Daikin Industries, Ltd. can. Representative examples of commercially available aqueous PTFE dispersions include Fluon D series manufactured by Daikin Industries, Ltd. and Teflon (registered trademark) 31-JR manufactured by Mitsui Chemours Fluoro Products Co., Ltd.

The mixed form of PTFE can be obtained by (1) a method of mixing an aqueous dispersion of PTFE and an aqueous dispersion or solution of an organic polymer and co-precipitating to obtain a co-agglomerated mixture (Japanese Unexamined Patent Publication No. 60-258263; (2) method of mixing an aqueous PTFE dispersion and dried organic polymer particles (method described in JP-A-4-272957); (3) A method of uniformly mixing an aqueous PTFE dispersion and an organic polymer particle solution and simultaneously removing each medium from the mixture (described in JP-A-06-220210, JP-A-08-188653, etc.) (4) method of polymerizing monomers forming an organic polymer in an aqueous dispersion of PTFE (method described in JP-A-9-95583), and (5) aqueous dispersion of PTFE After uniformly mixing the dispersion liquid and the organic polymer dispersion liquid, a vinyl monomer is further polymerized in the mixed dispersion liquid, and then a mixture is obtained by a method (method described in JP-A No. 11-29679 etc.). You can use what you get. Commercially available products of these mixed forms of PTFE include "Metablen A3800" (trade name) and "Metablen A3750" manufactured by Mitsubishi Chemical Corporation.

The proportion of PTFE in the mixed form is preferably 1 to 60% by weight, more preferably 5 to 55% by weight based on 100% by weight of the PTFE mixture. If the proportion of PTFE is within this range, good dispersibility of PTFE may be achieved.

The styrene monomer used as the organic polymer used in the polytetrafluoroethylene mixture is selected from the group consisting of an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, and a halogen. Styrene optionally substituted with one or more groups, such as ortho-methylstyrene, meta-methylstyrene, para-methylstyrene, dimethylstyrene, ethyl-styrene, para-tert-butylstyrene, methoxystyrene, fluorostyrene, Examples include, but are not limited to, monobromostyrene, dibromostyrene, tribromostyrene, vinylxylene, and vinylnaphthalene. The styrenic monomers can be used alone or in combination of two or more types.

The acrylic monomer used as the organic polymer used in the polytetrafluoroethylene mixture contains an optionally substituted (meth)acrylate derivative. Specifically, the acrylic monomer is substituted with one or more groups selected from the group consisting of an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 8 carbon atoms, an aryl group, and a glycidyl group. (meth)acrylate derivatives that may be used, such as (meth)acrylonitrile, methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, butyl (meth)acrylate, amyl (meth)acrylate, hexyl ( meth)acrylate, 2-ethylhexyl(meth)acrylate, cyclohexyl(meth)acrylate, octyl(meth)acrylate, dodecyl(meth)acrylate, phenyl(meth)acrylate, benzyl(meth)acrylate and glycidyl(meth)acrylate Examples include acrylates, maleimides which may be substituted with an alkyl group having 1 to 6 carbon atoms, or an aryl group, such as maleimide, N-methyl-maleimide and N-phenyl-maleimide, maleic acid, phthalic acid and itaconic acid. but is not limited to these. The acrylic monomers may be used alone or in combination of two or more types. Among these, (meth)acrylonitrile is preferred.

Also, coated branched PTFE can be used as an anti-drip agent in the present invention. The coated branched PTFE is a polytetrafluoroethylene mixture consisting of branched polytetrafluoroethylene particles and an organic polymer, and an organic polymer, preferably derived from a styrene monomer, is added to the outside of the branched polytetrafluoroethylene. It has a coating layer made of a polymer containing units and/or units derived from acrylic monomers. The coating layer is formed on the surface of branched polytetrafluoroethylene. Further, it is preferable that the coating layer contains a copolymer of a styrene monomer and an acrylic monomer.

The polytetrafluoroethylene contained in the coated branched PTFE is branched polytetrafluoroethylene. If the polytetrafluoroethylene contained is not branched polytetrafluoroethylene, the dripping prevention effect will be insufficient when a small amount of polytetrafluoroethylene is added. The branched polytetrafluoroethylene is in the form of particles, preferably having a particle size of 0.1 to 0.6 μm, more preferably 0.3 to 0.5 μm, even more preferably 0.3 to 0.4 μm. When the particle size is smaller than 0.1 μm, the surface appearance of the molded product is excellent, but it is difficult to commercially obtain polytetrafluoroethylene having a particle size smaller than 0.1 μm. Furthermore, if the particle size is larger than 0.6 μm, the surface appearance of the molded product may deteriorate. The number average molecular weight of the polytetrafluoroethylene used in the present invention is preferably 1×10 ⁴ to 1×10 ⁷ , more preferably 2×10 ⁶ to 9×10 ⁶ , and generally has a high molecular weight polytetrafluoroethylene. Fluoroethylene is more preferred in terms of stability. Either powder or dispersion form can be used.

The content of branched polytetrafluoroethylene in the coated branched PTFE is preferably 20 to 60 parts by weight, more preferably 40 to 55 parts by weight, even more preferably 47 to 55 parts by weight, based on 100 parts by weight of the total weight of the coated branched PTFE. 53 parts by weight, particularly preferably 48 to 52 parts by weight, most preferably 49 to 51 parts by weight. When the proportion of branched polytetrafluoroethylene is within this range, it may be possible to achieve good dispersibility of branched polytetrafluoroethylene.

The content of component D is preferably 0.05 to 3 parts by weight, more preferably 0.1 to 2 parts by weight, and even more preferably 0.2 to 1.5 parts by weight per 100 parts by weight of component A. . If it is larger than this range, not only will the cost increase, but also the extrusion processability may become insufficient. On the other hand, if it is smaller than this range, flame retardation will be insufficient and tensile strength may also decrease. Note that the ratio of the component D indicates the net amount of anti-drip agent, and in the case of mixed PTFE, indicates the net amount of PTFE.

<Other ingredients>
The thermoplastic resin composition of the present invention may contain various fillers and other additives within a range that does not impair the object of the present invention.

<Manufacture of thermoplastic resin composition>
Any method can be used to produce the thermoplastic resin composition of the present invention. For example, components A, B, C, and optionally other components are thoroughly mixed using a premixing means such as a V-type blender, Henschel mixer, mechanochemical device, or extrusion mixer, and then extruded as necessary. Examples include a method in which the premix is granulated using a granulator or briquetting machine, then melt-kneaded using a melt-kneader typified by a vented twin-screw extruder, and then pelletized using a pelletizer.

Other methods include feeding each component independently to a melt-kneading machine, such as a vented twin-screw extruder, or premixing a portion of each component and then feeding it to a melt-kneading machine independently from the remaining components. There are also methods to do so. Examples of a method for premixing a portion of each component include a method in which components other than component A are premixed in advance and then mixed with the thermoplastic resin of component A or directly supplied to an extruder.

For example, when the A component contains a powder form, a premixing method includes blending a part of the powder with the additives to be mixed to produce a masterbatch of the additives diluted with the powder. One method is to use a masterbatch. Furthermore, a method of supplying one component independently from the middle of the melt extruder may also be mentioned. In addition, when the components to be blended are liquid, a so-called liquid injection device or liquid addition device can be used to supply the components to the melt extruder.

As the extruder, one having a vent capable of degassing moisture in the raw materials and volatile gas generated from the melt-kneaded resin can be preferably used. A vacuum pump is preferably installed from the vent to efficiently discharge generated moisture and volatile gas to the outside of the extruder. It is also possible to install a screen in front of the die section of the extruder to remove foreign matter from the resin composition by installing a screen to remove foreign matter mixed into the extrusion raw material. Such screens may include wire mesh, screen changers, sintered metal plates (disc filters, etc.), and the like.

Examples of the melt kneading machine include a twin-screw extruder, a Banbury mixer, a kneading roll, a single-screw extruder, and a multi-screw extruder having three or more screws.

The resin extruded as described above is either directly cut into pellets or formed into strands and then cut with a pelletizer to become pellets. If it is necessary to reduce the influence of external dust during pelletization, it is preferable to clean the atmosphere around the extruder. Furthermore, in the production of such pellets, various methods that have already been proposed for polycarbonate resin for optical discs are used to narrow the shape distribution of the pellets, reduce miscuts, and reduce fine powder generated during shipping or transportation. , as well as the reduction of air bubbles (vacuum bubbles) generated inside the strands and pellets. These formulations can increase the molding cycle and reduce the incidence of defects such as silver. Further, the shape of the pellet can be a general shape such as a cylinder, a prism, or a sphere, but a cylinder is more preferable. The diameter of such a cylinder is preferably 1 to 5 mm, more preferably 1.5 to 4 mm, even more preferably 2 to 3.3 mm. On the other hand, the length of the cylinder is preferably 1 to 30 mm, more preferably 2 to 5 mm, and still more preferably 2.5 to 3.5 mm.

The thermoplastic resin composition of the present invention is a thermoplastic resin composition that exhibits little discoloration and strength loss even under severe processing conditions, has excellent recyclability, and has excellent flame retardancy, so it can be molded under high temperature conditions. It is useful for applications that require thinner walls and lighter weight, and when products are recycled and used again, and the industrial effect it brings is extremely large.

The mode of the present invention that the present inventors consider to be the best at present is a combination of the 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, but the present invention is not limited thereto.
The evaluation was conducted on the following items.
(i) Discoloration during retention The pellets obtained from each composition of the examples were dried in a hot air dryer at 100°C for 5 hours, and then used in an injection molding machine [Sumitomo Heavy Industries, Ltd. SG150U SM IV]. 100 shots of a 150 mm x 150 mm x 2 mmt square plate were continuously molded at the temperature shown in the table. Thereafter, operation of the molding machine was interrupted and the resin was allowed to remain in the cylinder. After 15 minutes, a square plate was formed again, and the hue of the square plate before and after residence was measured using Tokyo Denshoku Color Analyzer TC-1800MKII, and the color difference (ΔE) before and after residence was calculated.

(ii) Strength retention rate during retention The square plate used in "(i) Discoloration during retention" was used to conduct a high-speed surface impact test, and the fracture energy of the square plate before and after retention was measured. The strength retention rate before and after was calculated. The measurements were conducted using Hydroshot HTM-1 manufactured by Shimadzu Corporation under conditions of 23° C. and a test speed of 7 m/s.
Strength retention rate (%) = [fracture energy after retention/fracture energy before retention] x 100

(iii) Recyclability The square plate used in "(i) Discoloration during retention" before retention was left horizontally outdoors in Midori Ward, Chiba City for one year, and then crushed and re-formed into a square plate. The hue and fracture energy of the square plate before storage and the remolded square plate were measured in the same manner as "(i) Discoloration during retention" and "(ii) Strength retention rate during retention", and the color difference between the two ( ΔE) and strength retention were measured.

(iv) Flame retardancy The pellets obtained from each composition of Examples were dried in a hot air dryer at 100°C for 5 hours, and then molded using an injection molding machine [Sumitomo Heavy Industries, Ltd. SG150U SM IV]. , UL test pieces were continuously molded at the temperatures shown in the table, and a V test (vertical combustion test) at a thickness of 1.5 mm was conducted in accordance with UL94.

[Examples 1 to 13, Comparative Examples 1 to 5]
A resin composition having the blending ratios shown in Table 1 was prepared in the following manner. The explanation will be given according to the symbols in the table below. Each component in the proportions shown in the table was weighed and mixed uniformly using a tumbler, and the mixture was put into an extruder to prepare a resin composition. The extruder used was a vented twin-screw extruder manufactured by Japan Steel Works, Ltd.: TEX-30XSST (fully meshing, co-rotating, double threaded screw). The extrusion conditions were a discharge rate of 20 kg/h, a screw rotation speed of 150 rpm, and a vent vacuum degree of 3 kPa, and the extrusion temperature was as shown in the table. Using the obtained pellets, test pieces for evaluation were molded using an injection molding machine in the manner described above. The results of each evaluation are shown in Table 1. In addition, each component indicated by a symbol in Table 1 is as follows.

(Component A: thermoplastic resin)
A-1: Aromatic polycarbonate resin (polycarbonate resin powder with a viscosity average molecular weight of 20,700 made from bisphenol A and phosgene by a conventional method, Panlite L-1225WS (product name) manufactured by Teijin Ltd.)
A-2: ABS resin (Suntac AT-07 (trade name) manufactured by Japan A&L Co., Ltd., butadiene rubber component approximately 17.5% by weight, weight average rubber particle size 1.2 μm, manufactured by bulk polymerization)
A-3: Polyethylene terephthalate (TRN-8550FF (product name) manufactured by Teijin Ltd.)

(Component B: phosphonic acid ester)
B-1: Triethylphosphonoacetate (Johoku Kagaku Kogyo Co., Ltd. JC-224 (trade name) acid value 0.08 mgKOH/g)
B-2 (comparative example): Triethylphosphonoacetate (manufactured by Solvay, acid value 0.39 mgKOH/g)
B-3: Triethylphosphonoacetate (mixture of B-1 and B-2 (weight ratio 1:1) acid value 0.23 mgKOH/g)

(Component C: flame retardant)
C-1: Tetrabromobisphenol A carbonate oligomer (FG-7000 (product name) manufactured by Teijin Ltd.)
C-2: Phosphate ester containing resolnol [di(2,6-dimethylphenyl)phosphate] as the main component (PX-200 (product name) manufactured by Daihachi Chemical Co., Ltd.)
C-3: Cyclic phenoxyphosphazene (FP-110 (product name) manufactured by Fushimi Pharmaceutical Co., Ltd.)
C-4: Perfluorobutanesulfonic acid potassium salt (F-TOP KSBF (product name) manufactured by Mitsubishi Materials Corporation)
C-5: Organosiloxane flame retardant containing Si-H group, methyl group and phenyl group (X-40-2600J (trade name) manufactured by Shin-Etsu Chemical Co., Ltd.)

(Component D: anti-drip agent)
D-1: Polytetrafluoroethylene (Polyflon MPFA500B (product name) manufactured by Daikin Industries, Ltd.)

Claims (7)

(A) 0.001 to 1 part by weight of a phosphonic acid ester (component B) having an acid value of 0.01 to 0.30 mgKOH/g to 100 parts by weight of the thermoplastic resin (component A) and ( C) A thermoplastic resin composition containing 0.01 to 25 parts by weight of a flame retardant (component C). A component is selected from the group consisting of (A-1) polycarbonate resin (A-1 component), (A-2) ABS resin (A-2 component), and (A-3) polyester resin (A-3 component). The thermoplastic resin composition according to claim 1, which is at least one thermoplastic resin comprising: The thermoplastic resin composition according to claim 1 or 2, wherein the content of component A-1 is 40 to 100 parts by weight based on 100 parts by weight of component A. C component is (C-1) halogenated carbonate compound (C-1 component), (C-2) phosphate ester compound (C-2 component), (C-3) phosphazene compound (C-3 component), (C-4) At least one flame retardant selected from the group consisting of a sulfonic acid metal salt (C-4 component) and (C-5) a silicone compound (C-5 component). thermoplastic resin composition. The thermoplastic resin composition according to claim 1 or 2, containing 0.05 to 3 parts by weight of (D) an anti-drip agent (component D) per 100 parts by weight of component A. 3. The thermoplastic resin composition according to claim 1, wherein component B is triethylphosphonoacetate. A molded article made of the thermoplastic resin composition according to claim 1 or 2.