JP7409902B2 - Polycarbonate resin composition - Google Patents

Description

The present invention relates to a resin composition comprising an aromatic polycarbonate resin, glass fiber, and a polybutylene terephthalate resin. More specifically, the present invention relates to a polycarbonate resin composition for communication equipment with a built-in antenna that is excellent in radio wave transparency, strength, appearance, and thermal stability.

Resin compositions made of polycarbonate resin and polybutylene terephthalate resin have excellent mechanical properties and chemical resistance, and are therefore widely used in various industrial fields. Against this background, a resin composition consisting of a polycarbonate resin and a polybutylene terephthalate resin reinforced with glass fibers subjected to a specific surface treatment has been proposed in order to further improve mechanical properties (Patent Document 1). Although a high strength improvement effect is seen in a composition system containing a certain amount of polybutylene terephthalate resin, even higher strength is required for thin-walled products such as communication equipment with built-in antennas, and further improvements are required. ing. In addition, a resin composition comprising a polycarbonate resin having a specific structure, a polybutylene terephthalate resin, and a phosphorus stabilizer has been proposed as suitable for the housings of electrical and electronic equipment, their covers, single-layer or multilayer sheets, etc. (Patent Document 2), although it has high surface hardness, it is insufficient in strength and radio wave transparency required for antenna communication equipment. A resin composition consisting of a polycarbonate resin having a specific structure and an inorganic filler has been proposed as suitable for housing members such as those of mobile phones, cameras, and personal computers, and building materials (Patent Document 3). Although it has excellent strength, it is insufficient in higher strength, radio wave transparency, good surface appearance, and thermal stability. As mentioned above, a resin composition for communication equipment with a built-in antenna that is excellent in radio wave transparency, strength, appearance, and thermal stability has not been obtained.

Japanese Patent Application Publication No. 10-273585 Patent No. 5946256 JP2013-253187A

An object of the present invention is to provide a polycarbonate resin composition for communication equipment with a built-in antenna that has excellent radio wave transparency, strength, appearance, and thermal stability.

As a result of intensive studies to solve this problem, the present inventors discovered that by adding glass fiber and polybutylene terephthalate resin to aromatic polycarbonate resin having a specific structure, radio waves that could not be obtained with conventional resin compositions were discovered. The present invention was accomplished by discovering that it is possible to obtain a polycarbonate resin composition for communication equipment with a built-in antenna that has excellent transparency, strength, appearance, and thermal stability.

That is, according to the present invention, (1) 1 to 105 parts by weight of (B) glass fiber (component B) and (C) polybutylene terephthalate resin (component A) to 100 parts by weight of aromatic polycarbonate resin (component A). Component C) A polycarbonate resin composition containing 0.01 to 3.5 parts by weight, in which component A contains a carbonate constitutional unit represented by the following formula (1) in an amount of 20 to 100 mol% of all carbonate constitutional units. Provided is a polycarbonate resin composition for a communication device with a built-in antenna, which is an aromatic polycarbonate resin containing 20 to 100% by weight of an aromatic polycarbonate resin (component A-1).

(In the formula, R ¹ and R ² are each independently an alkyl group having 1 to 6 carbon atoms, an optionally substituted cycloalkyl group having 6 to 15 carbon atoms, and a substituted unsubstituted cycloalkyl group having 6 to 15 carbon atoms. represents a group selected from an optionally substituted aryl group and an optionally substituted aralkyl group having 7 to 15 carbon atoms, and R ³ and R ⁴ each independently represent a hydrogen atom, a halogen atom, and an optionally substituted aralkyl group having 1 to 6 carbon atoms. an alkyl group having 6 to 15 carbon atoms, an optionally substituted cycloalkyl group having 6 to 15 carbon atoms, an optionally substituted aryl group having 6 to 15 carbon atoms, and an optionally substituted cycloalkyl group having 6 to 15 carbon atoms. Aralkyl group, optionally substituted alkenyl group having 2 to 20 carbon atoms, alkoxy group having 1 to 6 carbon atoms, optionally substituted cycloalkoxy group having 6 to 20 carbon atoms, 6 carbon atoms Represents a group selected from an optionally substituted aryloxy group having ~15 carbon atoms, an optionally substituted aralkyloxy group having 7 to 15 carbon atoms, a nitro group, an aldehyde group, a cyano group, and a carboxyl group; If there is more than one, they may be the same or different, a and b are natural numbers from 1 to 3, and W is at least one selected from the group consisting of a single bond or a group represented by the following general formula (2). )

(In the formula, 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, and an alkyl group having 6 to 14 carbon atoms. represents a group selected from the group consisting of an aryl group 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, an alkyl group having 1 to 18 carbon atoms, or a carbon atom. 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, aryl group having 6 to 14 carbon atoms, A group selected from the group consisting of an aryloxy group having 6 to 10 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, an aralkyloxy group having 7 to 20 carbon atoms, a nitro group, an aldehyde group, a cyano group, and a carboxyl group. , and R ²¹ , R ²² , R ²³ , R ²⁴ , R ²⁵ and R ²⁶ are each independently a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, or a substituted or unsubstituted aryl group having 6 to 12 carbon atoms. If there is more than one, they may be the same or different, c is an integer from 1 to 10, d is an integer from 4 to 7, e is a natural number, f is 0 or a natural number, and e+f is is a natural number of 150 or less, and X is a divalent aliphatic group having 2 to 8 carbon atoms.)

One of the more preferred embodiments of the present invention is (2) component B has a number average fiber length of 30 to 5000 μm (B-1) the ratio of the major axis to the minor axis of the cross-sectional shape (major axis/minor axis) is 2. Non-circular cross-section glass fiber (B-1 component) and (B- 2) The above configuration 1 is characterized in that the glass fiber is one or more types of glass fiber selected from the group consisting of circular cross-section glass fibers (component B-2) having an average fiber diameter in the range of 7.0 to 13.0 μm. This is a polycarbonate resin composition.

One of the more preferred embodiments of the present invention is that (3) component B includes 52.0 to 57.0% by weight of SiO ₂ , 13.0 to 17.0% by weight of Al ₂ O ₃ , and 15.0 to 21% by weight of Al 2 O 3 . .5 wt% B ₂ O ₃ , 2.0-6.0 wt % MgO, 2.0-6.0 wt % CaO, 1.0-4.0 wt % TiO ₂ and 1.5 The structure 1 or 2 above is characterized in that the glass fiber contains less than 0.6% by weight of F ₂ and the total amount of Li ₂ O, Na ₂ O and K ₂ O is less than 0.6% by weight. The polycarbonate resin composition described above.

One of the more preferred embodiments of the present invention is (4) any of the above configurations 1 to 3, characterized in that the aromatic polycarbonate resin other than component A-1 has a viscosity average molecular weight of 10,000 to 16,000. This is a polycarbonate resin composition according to claim 1.

One of the more preferred embodiments of the present invention is (5) the composition according to any one of configurations 1 to 4 above, wherein component C is a polybutylene terephthalate resin having a terminal carboxyl group content of 40 μeq/g or more. It is a polycarbonate resin composition.

One of the more preferred embodiments of the present invention is the above configuration 1, characterized in that (6) 0.01 to 1 part by weight of a phosphorus compound (component D) is contained per 100 parts by weight of component A. 5. The polycarbonate resin composition according to any one of 5 to 5.

One of the more preferred embodiments of the present invention is (7) the polycarbonate resin composition according to configuration 6 above, wherein component D is a phosphoric acid ester compound having a number average molecular weight of 50 to 300. be.

The present invention will be explained in detail below.

(Component A: aromatic polycarbonate resin)
The aromatic 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.

The aromatic polycarbonate resin used as component A of the present invention contains 20 to 100% by weight of a modified polycarbonate resin containing a carbonate structural unit represented by the following formula (1) as an essential component. The content is preferably 25 to 100% by weight, more preferably 30 to 100% by weight, even more preferably 35 to 100% by weight. When the content is less than 20% by weight, radio wave transmittance and thermal stability are poor.

(In the formula, R ¹ and R ² are each independently an alkyl group having 1 to 6 carbon atoms, an optionally substituted cycloalkyl group having 6 to 15 carbon atoms, and a substituted unsubstituted cycloalkyl group having 6 to 15 carbon atoms. represents a group selected from an optionally substituted aryl group and an optionally substituted aralkyl group having 7 to 15 carbon atoms, and R ³ and R ⁴ each independently represent a hydrogen atom, a halogen atom, and an optionally substituted aralkyl group having 1 to 6 carbon atoms. an alkyl group having 6 to 15 carbon atoms, an optionally substituted cycloalkyl group having 6 to 15 carbon atoms, an optionally substituted aryl group having 6 to 15 carbon atoms, and an optionally substituted cycloalkyl group having 6 to 15 carbon atoms. Aralkyl group, optionally substituted alkenyl group having 2 to 20 carbon atoms, alkoxy group having 1 to 6 carbon atoms, optionally substituted cycloalkoxy group having 6 to 20 carbon atoms, 6 carbon atoms Represents a group selected from an optionally substituted aryloxy group having ~15 carbon atoms, an optionally substituted aralkyloxy group having 7 to 15 carbon atoms, a nitro group, an aldehyde group, a cyano group, and a carboxyl group; If there is more than one, they may be the same or different, a and b are natural numbers from 1 to 3, and W is at least one selected from the group consisting of a single bond or a group represented by the following general formula (2). )

(In the formula, R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ , R ¹⁶ , R ¹⁷ and R ¹⁸ are each independently a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, or an alkyl group having 3 to 14 carbon atoms. represents a group selected from the group consisting of an aryl group 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, an alkyl group having 1 to 18 carbon atoms, or a carbon atom. 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, aryl group having 6 to 14 carbon atoms, A group selected from the group consisting of an aryloxy group having 6 to 10 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, an aralkyloxy group having 7 to 20 carbon atoms, a nitro group, an aldehyde group, a cyano group, and a carboxyl group. , and R ²¹ , R ²² , R ²³ , R ²⁴ , R ²⁵ and R ²⁶ are each independently a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, or a substituted or unsubstituted aryl group having 6 to 12 carbon atoms. If there is more than one, they may be the same or different, c is an integer from 1 to 10, d is an integer from 4 to 7, e is a natural number, f is 0 or a natural number, and e+f is is a natural number of 150 or less, and X is a divalent aliphatic group having 2 to 8 carbon atoms.)

The carbonate structural unit represented by the above general formula (1) is usually derived from a dihydroxy compound and a carbonate precursor.

Examples of the dihydroxy compound inducing the carbonate structural unit represented by the above general formula (1) include 2,2-bis(4-hydroxy-3-methylphenyl)propane, 2,2-bis(3-ethyl-4- hydroxyphenyl)propane, 2,2-bis(4-hydroxy-3-isopropylphenyl)propane, 2,2-bis(4-hydroxy-3-isobutylphenyl)propane, 2,2-bis(3-t-butyl) -4-hydroxyphenyl)propane, 2,2-bis(3,5-dimethyl-4-hydroxyphenyl)propane, 2,2-bis(3-cyclohexyl-4-hydroxyphenyl)propane, 2,2-bis( 4-hydroxy-3-phenylphenyl)propane, 1,1-bis(4-hydroxy-3-methylphenyl)cyclohexane, 1,1-bis(3-ethyl-4-hydroxyphenyl)cyclohexane, 1,1-bis (4-hydroxy-3-isopropylphenyl)cyclohexane, 1,1-bis(4-hydroxy-3-isobutylphenyl)cyclohexane, 1,1-bis(3-t-butyl-4-hydroxyphenyl)cyclohexane, 1, 1-bis(3,5-dimethyl-4-hydroxyphenyl)cyclohexane, 1,1-bis(3-cyclohexyl-4-hydroxyphenyl)cyclohexane, 1,1-bis(4-hydroxy-3-phenylphenyl)cyclohexane , 1,1-bis(4-hydroxy-3-methylphenyl)-3,3,5-trimethylcyclohexane, bis(4-hydroxy-3-methylphenyl)methane, 1,1-bis(4-hydroxy-3 -methylphenyl)ethane, 1,1-bis(4-hydroxy-3-methylphenyl)-1-phenylethane, bis(4-hydroxy-3-methylphenyl)diphenylmethane, 9,9-bis(4-hydroxy- 3-methylphenyl)fluorene, 4,4'-dihydroxy-3,3'-dimethyldiphenyl ether, 4,4'-dihydroxy-3,3'-dimethyldiphenyl sulfoxide, 4,4'-dihydroxy-3, Examples include 3'-dimethyldiphenyl sulfide and a bisphenol compound having a siloxane structure represented by the following general formula (3).

(In the formula, R ¹ and R ² are each independently an alkyl group having 1 to 6 carbon atoms, an optionally substituted cycloalkyl group having 6 to 15 carbon atoms, and a substituted unsubstituted cycloalkyl group having 6 to 15 carbon atoms. represents a group selected from an optionally substituted aryl group and an optionally substituted aralkyl group having 7 to 15 carbon atoms, and R ³ and R ⁴ each independently represent a hydrogen atom, a halogen atom, and an optionally substituted aralkyl group having 1 to 6 carbon atoms. an alkyl group having 6 to 15 carbon atoms, an optionally substituted cycloalkyl group having 6 to 15 carbon atoms, an optionally substituted aryl group having 6 to 15 carbon atoms, and an optionally substituted cycloalkyl group having 6 to 15 carbon atoms. Aralkyl group, optionally substituted alkenyl group having 2 to 20 carbon atoms, alkoxy group having 1 to 6 carbon atoms, optionally substituted cycloalkoxy group having 6 to 20 carbon atoms, 6 carbon atoms Represents a group selected from an optionally substituted aryloxy group having ~15 carbon atoms, an optionally substituted aralkyloxy group having 7 to 15 carbon atoms, a nitro group, an aldehyde group, a cyano group, and a carboxyl group; If there is more than one, they may be the same or different. ^{R 21} , R ²² , R ²³ , R ²⁴ , R ²⁵ and R ²⁶ each independently represent a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, or a C 6 alkyl group. ~12 substituted or unsubstituted aryl groups, a and b are natural numbers of 1 to 3, e is a natural number, f is 0 or a natural number, e+f is a natural number of 150 or less, and X is a natural number of 150 or less. It is a divalent aliphatic group having 2 to 8 carbon atoms.)

Among them, 2,2-bis(4-hydroxy-3-methylphenyl)propane, 2,2-bis(4-hydroxy-3-phenylphenyl)propane, 1,1-bis(4-hydroxy-3-methylphenyl) ) cyclohexane, 1,1-bis(4-hydroxy-3-phenylphenyl)cyclohexane, 1,1-bis(4-hydroxy-3-methylphenyl)-3,3,5-trimethylcyclohexane, 9,9-bis (4-hydroxy-3-methylphenyl)fluorene is preferred, 2,2-bis(4-hydroxy-3-methylphenyl)propane, 1,1-bis(4-hydroxy-3-methylphenyl)cyclohexane, 9, 9-bis(4-hydroxy-3-methylphenyl)fluorene is more preferred, and 2,2-bis(4-hydroxy-3-methylphenyl)propane is most preferred.

The modified polycarbonate resin contained in component A of the present invention may contain carbonate structural units other than the above general formula (1) in addition to the carbonate structural unit represented by the above general formula (1). Bisphenols and aliphatic diols can be mentioned as dihydroxy compounds that induce carbonate structural units represented by formulas other than the above general formula (1).

Examples of bisphenols 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, 1,1-bis(4-hydroxyphenyl)-3,3,5-trimethylcyclohexane, 2,2-bis(4-hydroxy-3,3 '-biphenyl)propane, 2,2-bis(4-hydroxyphenyl)butane, 2,2-bis(4-hydroxyphenyl)octane, 2,2-bis(3-bromo-4-hydroxyphenyl)propane, bis (4-hydroxyphenyl)diphenylmethane, 9,9-bis(4-hydroxyphenyl)fluorene, 1,1-bis(4-hydroxyphenyl)cyclohexane, 1,1-bis(4-hydroxyphenyl)cyclopentane, 4, 4'-dihydroxydiphenyl ether, 4,4'-sulfonyl diphenol, 4,4'-dihydroxydiphenyl sulfoxide, 4,4'-dihydroxydiphenyl sulfide, 2,2'-diphenyl-4,4'-sulfonyl diphenol Phenol, 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-adamantane) Examples include bisphenol compounds having a siloxane structure represented by the following general formula (4), such as diyl)diphenol, 1,3-bis(4-hydroxyphenyl)-5,7-dimethyladamantane, and the like.

(In the formula, R ²⁷ and R ²⁸ are each independently an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, a substituted or unsubstituted aryl group having 6 to 15 carbon atoms, or a carbon number A substituted or unsubstituted aryloxy group having 6 to 15 carbon atoms, a substituted or unsubstituted aralkyl group having 7 to 15 carbon atoms, a substituted or unsubstituted aralkyloxy group having 7 to 15 carbon atoms, and R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ and R ¹⁰ are each independently a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, or a substituted or unsubstituted aryl group having 6 to 12 carbon atoms, and p, q is a natural number of 0 or 1 to 4, g+h is a natural number of 150 or less, and X is a divalent aliphatic group having 2 to 8 carbon atoms.)

Examples of aliphatic diols include 2,2-bis-(4-hydroxycyclohexyl)-propane, 1,14-tetradecanediol, octaethylene glycol, 1,16-hexadecanediol, 4,4'-bis(2- hydroxyethoxy)biphenyl, bis{(2-hydroxyethoxy)phenyl}methane, 1,1-bis{(2-hydroxyethoxy)phenyl}ethane, 1,1-bis{(2-hydroxyethoxy)phenyl}-1- Phenylethane, 2,2-bis{(2-hydroxyethoxy)phenyl}propane, 2,2-bis{(2-hydroxyethoxy)-3-methylphenyl}propane, 1,1-bis{(2-hydroxyethoxy) ) phenyl}-3,3,5-trimethylcyclohexane, 2,2-bis{4-(2-hydroxyethoxy)-3,3'-biphenyl}propane, 2,2-bis{(2-hydroxyethoxy)- 3-isopropylphenyl}propane, 2,2-bis{3-t-butyl-4-(2-hydroxyethoxy)phenyl}propane, 2,2-bis{(2-hydroxyethoxy)phenyl}butane, 2,2 -bis{(2-hydroxyethoxy)phenyl}-4-methylpentane, 2,2-bis{(2-hydroxyethoxy)phenyl}octane, 1,1-bis{(2-hydroxyethoxy)phenyl}decane, 2 ,2-bis{3-bromo-4-(2-hydroxyethoxy)phenyl}propane, 2,2-bis{3,5-dimethyl-4-(2-hydroxyethoxy)phenyl}propane, 2,2-bis {3-cyclohexyl-4-(2-hydroxyethoxy)phenyl}propane, 1,1-bis{3-cyclohexyl-4-(2-hydroxyethoxy)phenyl}cyclohexane, bis{(2-hydroxyethoxy)phenyl}diphenylmethane , 9,9-bis{(2-hydroxyethoxy)phenyl}fluorene, 9,9-bis{4-(2-hydroxyethoxy)-3-methylphenyl}fluorene, 1,1-bis{(2-hydroxyethoxy) ) phenyl}cyclohexane, 1,1-bis{(2-hydroxyethoxy)phenyl}cyclopentane, 4,4'-bis(2-hydroxyethoxy) diphenyl ether, 4,4'-bis(2-hydroxyethoxy) )-3,3'-dimethyldiphenyl ether, 1,3-bis[2-{(2-hydroxyethoxy)phenyl}propyl]benzene, 1,4-bis[2-{(2-hydroxyethoxy)phenyl }propyl]benzene, 1,4-bis{(2-hydroxyethoxy)phenyl}cyclohexane, 1,3-bis{(2-hydroxyethoxy)phenyl}cyclohexane, 4,8-bis{(2-hydroxyethoxy)phenyl }Tricyclo[5.2.1.02,6]decane, 1,3-bis{(2-hydroxyethoxy)phenyl}-5,7-dimethyladamantane, 3,9-bis(2-hydroxy-1,1 -dimethylethyl)-2,4,8,10-tetraoxaspiro(5,5)undecane, 1,4:3,6-dianhydro-D-sorbitol (isosorbide), 1,4:3,6-dianhydro- Examples include D-mannitol (isomannide), 1,4:3,6-dianhydro-L-iditol (isooidide), and the like.

Among these, aromatic bisphenols are preferred, and among them, 1,1-bis(4-hydroxyphenyl)-1-phenylethane, 2,2-bis(4-hydroxyphenyl)propane, and 1,1-bis(4-hydroxyphenyl)propane. -hydroxyphenyl)cyclohexane, 1,1-bis(4-hydroxyphenyl)-3,3,5-trimethylcyclohexane, 1,3-bis{2-(4-hydroxyphenyl)propyl}benzene, and 1,4- Bis{2-(4-hydroxyphenyl)propyl}benzene, a bisphenol compound having a siloxane structure represented by the above general formula (4), is preferred, and particularly 2,2-bis(4-hydroxyphenyl)propane, 1, 1-bis(4-hydroxyphenyl)cyclohexane and a bisphenol compound having a siloxane structure represented by the above general formula (4) 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.

The content of the carbonate structural unit represented by the above general formula (1) is 20 to 100 mol%, preferably 25 to 100 mol%, more preferably It is 30 to 100 mol%, more preferably 40 to 100 mol%. When the carbonate structural unit represented by the above general formula (1) is less than 20 mol% of all carbonate structural units, electromagnetic wave permeability decreases.

The modified polycarbonate resin contained in component A of the present invention may be made into a branched polycarbonate resin by using a branching agent in combination with the above dihydroxy 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.

These modified polycarbonate resins are produced by reaction means known per se for producing ordinary polycarbonate resins, such as a method in which a dihydroxy component is reacted with a carbonate precursor such as phosgene or diester carbonate. The basic means of its manufacturing method will be briefly explained.

In reactions using, for example, phosgene as a carbonate precursor, the reaction is usually carried out in the presence of an acid binder and a solvent. As the acid binder, for example, an alkali metal hydroxide such as sodium hydroxide or potassium hydroxide or an amine compound such as pyridine is used. As the solvent, for example, halogenated hydrocarbons such as methylene chloride and chlorobenzene are used. Further, catalysts such as tertiary amines or quaternary ammonium salts can also be used to promote the reaction. At this time, the reaction temperature is usually 0 to 40°C, and the reaction time is several minutes to 5 hours. The transesterification reaction using a carbonate diester as a carbonate precursor is carried out by heating and stirring a predetermined proportion of an aromatic dihydroxy component with a carbonate diester under an inert gas atmosphere, and distilling off the alcohol or phenol produced. . The reaction temperature varies depending on the boiling point of the alcohol or phenol produced, but is usually in the range of 120 to 300°C. The reaction is completed under reduced pressure from the initial stage to distill out the alcohol or phenol produced. Furthermore, a catalyst commonly used in transesterification reactions can also be used to promote the reaction. Examples of the diester carbonate used in the transesterification reaction include diphenyl carbonate, dinaphthyl carbonate, bis(diphenyl) carbonate, dimethyl carbonate, diethyl carbonate, and dibutyl carbonate. Among these, diphenyl carbonate is particularly preferred.

In the present invention, a terminal capping agent is used in the polymerization reaction. The terminal capping agent is used to control the molecular weight, and the resulting aromatic polycarbonate resin has its terminals blocked, so it has superior thermal stability compared to those that are not terminal-blocked. Such terminal capping agents include monofunctional phenols represented by the following general formulas (5) to (7).

[In the formula, A is an alkyl group having 1 to 10 carbon atoms, a substituted or unsubstituted aryl group having 6 to 15 carbon atoms, a substituted or unsubstituted aralkyl group having 7 to 15 carbon atoms, and r is 0 -5, preferably an integer of 0-1. ]

[In the formula, n is an integer having 1 to 50 carbon atoms. ]

[In the formula, W is -R-O-, -R-CO-O- or -R-O-CO-, where R is a single bond or a carbon number of 1 to 10, preferably 1 to 5. represents a valent aliphatic hydrocarbon group, and n is an integer of 1 to 50. ]

Specific examples of monofunctional phenols represented by the above general formula (5) include phenol, isopropylphenol, p-tert-butylphenol, p-cresol, p-cumylphenol, 2-phenylphenol, and 4-phenylphenol. Examples include phenol and isooctylphenol. In addition, the monofunctional phenols represented by the above general formulas (6) to (7) are phenols having long-chain alkyl groups or aliphatic ester groups as substituents, and these are used to prepare aromatic polycarbonate resins. When the terminals of the resins are blocked, they not only function as end-stoppers or molecular weight regulators, but also improve the melt flowability of the resin, making it easier to mold and process, and also have the effect of lowering the water absorption of the resin. Yes, preferably used. The substituted phenols of the general formula (6) are preferably those in which n is 10 to 30, particularly 10 to 26, and specific examples include decylphenol, dodecylphenol, tetradecylphenol, hexadecylphenol, octadecylphenol, Examples include eicosylphenol, docosylphenol and triacontylphenol. Further, as the substituted phenols of the above general formula (7), compounds in which W is -R-CO-O- and R is a single bond are preferred, and those in which n is 10 to 30, particularly 10 to 26 are preferred. Specific examples thereof include decyl hydroxybenzoate, dodecyl hydroxybenzoate, tetradecyl hydroxybenzoate, hexadecyl hydroxybenzoate, eicosyl hydroxybenzoate, docosyl hydroxybenzoate, and triacontyl hydroxybenzoate. Among these monofunctional phenols, monofunctional phenols represented by the above general formula (5) are preferred, alkyl-substituted or phenylalkyl-substituted phenols are more preferred, and p-tert-butylphenol, p-tert-butylphenol and p-tert-butylphenol are particularly preferred. -cumylphenol or 2-phenylphenol. It is desirable that these monofunctional phenolic end-stoppers be introduced at least 5 mol%, preferably at least 10 mol%, at the ends of the obtained aromatic polycarbonate resin. may be used alone or in combination of two or more.

The modified polycarbonate resin contained in component A of the present invention is a polyester carbonate copolymerized with an aromatic dicarboxylic acid, such as terephthalic acid, isophthalic acid, naphthalene dicarboxylic acid, or a derivative thereof, as long as it does not impair the spirit of the present invention. You can.

The viscosity average molecular weight of the modified polycarbonate resin contained in component A of the present invention is preferably in the range of 12,000 to 50,000, more preferably in the range of 12,000 to 30,000, and more preferably in the range of 12,000 to 25,000. More preferably, the range is from 15,000 to 25,000. If the molecular weight exceeds 50,000, the melt viscosity may become too high, resulting in poor moldability, while if the molecular weight is less than 12,000, problems may arise in mechanical strength. The viscosity average molecular weight of the aromatic polycarbonate resin other than component A-1 is preferably in the range of 10,000 to 16,000, more preferably in the range of 10,500 to 16,000, and more preferably in the range of 11,000 to 15,800. The range is more preferred. If the molecular weight exceeds 16,000, the surface appearance may deteriorate; if the molecular weight is less than 10,000, the strength may decrease. The viscosity average molecular weight in the present invention is determined by first determining the specific viscosity calculated by the following formula from a solution of 0.7 g of aromatic polycarbonate resin dissolved in 100 ml of methylene chloride at 20°C using an Ostwald viscometer. The viscosity average molecular weight M is determined by inserting the specific viscosity obtained using the following formula.

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]
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
The modified polycarbonate resin contained in component A of the present invention preferably has a total Cl (chlorine) content of 0 to 200 ppm, more preferably 0 to 150 ppm. If the total Cl content in the modified polycarbonate resin exceeds 200 ppm, the hue and thermal stability may deteriorate, which is not preferable.

(B component: glass fiber)
The glass fiber preferably used in the present invention has an E glass composition (52.0 to 56.0% by weight of SiO ₂ and 12.0 to 16.0% by weight of Al ₂ O ₃ based on the total amount of glass fiber). , a composition comprising a total of 20.0 to 25.0% by weight of MgO and CaO and 5.0 to 10.0% by weight of B ₂ O ₃ (E glass fiber), NE glass composition ( 52.0-57.0% by weight of SiO ₂ , 13.0-17.0% by weight of Al ₂ O ₃ , 15.0-21.5% by weight of B ₂ O ₃ based on the total amount of glass fibers, 2. 0-6.0 wt.% MgO, 2.0-6.0 wt.% CaO, 1.0-4.0 wt.% _TiO2 and less than 1.5 wt.% _F2 , and In addition to glass fibers (NE glass fibers) having a composition in which the total amount of Li ₂ O, Na ₂ O and K ₂ O is less than 0.6% by weight, glass fibers represented by S glass, D glass, etc. However, NE glass fiber is particularly preferred because it has excellent radio wave transmittance.

Furthermore, if the content of SiO2 is less than 52.0% by weight based on the total amount of glass fibers contained in the polycarbonate resin composition of the present invention, radio wave transmittance will be impaired, water resistance and acid resistance will decrease, and the glass This may cause deterioration of fibers and polycarbonate resin compositions. On the other hand, in the glass fiber, if the content of SiO2 exceeds 57.0% by weight based on the total amount of glass fiber, the viscosity becomes too high during spinning, and fiberization may become difficult.

In the NE glass fiber, the content of SiO ₂ based on the total amount of glass fiber is preferably 52.5 to 56.8% by weight, more preferably 53.0 to 56.6% by weight, and 53.5 to 56.5% by weight. is more preferred, 53.8 to 56.3% by weight is particularly preferred, and 54.0 to 56.2% by weight is most preferred.

In the NE glass fiber, the content of Al ₂ O ₃ based on the total amount of glass fiber is preferably 13.3 to 16.5% by weight, more preferably 13.7 to 16.0% by weight, and 14.0 to 15.5% by weight. % by weight is more preferred, 14.3 to 15.3% by weight is particularly preferred, and 14.5 to 15.1% by weight is most preferred. When the content of Al ₂ O ₃ based on the total amount of glass fibers is less than 15.0% by weight, phase separation tends to occur and water resistance may deteriorate. On the other hand, in NE glass fiber, if the content of Al ₂ O ₃ with respect to the total amount of glass fiber exceeds 17.0% by weight, the liquidus temperature becomes high and the working temperature range becomes narrow, making it difficult to manufacture glass fiber. There are cases.

In the NE glass fiber, the content of B ₂ O ₃ based on the total amount of glass fiber is preferably 15.5 to 21.0% by weight, more preferably 16.0 to 20.5% by weight, and 16.5 to 20.0% by weight. % by weight is more preferred, and 17.5 to 19.4% by weight is particularly preferred. When the content of B ₂ O ₃ is less than 15.0% by weight, radio wave transmittance may be significantly impaired. On the other hand, when the B ₂ O ₃ content exceeds 21.5% by weight, the amount of B ₂ O ₃ volatilized during spinning is high, and the glass fibers are likely to be cut due to B ₂ O ₃ contamination that adheres to the vicinity of the bushing nozzle. This may cause problems in workability and productivity. Furthermore, it may not be possible to obtain a homogeneous glass, and the water resistance may be too poor.

In the NE glass fiber, the content of MgO based on the total amount of glass fiber is preferably 2.5 to 5.9% by weight, more preferably 2.9 to 5.8% by weight, and 3.3 to 5.7% by weight. More preferably, 3.6 to 5.3% by weight is particularly preferred, and most preferably 4.0 to 4.8% by weight. If the content of MgO based on the total amount of glass fibers is less than 2.0% by weight, striae may increase and the amount of B ₂ O ₃ volatilized may increase. On the other hand, if the MgO content exceeds 6.0% by weight, phase separation becomes strong, water resistance decreases, and radio wave transmittance may be significantly impaired.

In the NE glass fiber, the content of CaO based on the total amount of glass fiber is preferably 2.6 to 5.5% by weight, more preferably 3.2 to 5.0% by weight, and 3.7 to 4.7% by weight. More preferably, 3.9 to 4.5% by weight is particularly preferred, and most preferably 4.0 to 4.4% by weight. If the content of CaO based on the total amount of glass fibers is less than 2.0% by weight, the meltability may deteriorate and the water resistance may become too poor. On the other hand, if the CaO content exceeds 6.0 parts by weight, radio wave transmittance may be significantly impaired.

In the NE glass fiber, the content of TiO ₂ based on the total amount of glass fiber is 1.3 to 3.
0% by weight is preferred, 1.5 to 2.5% by weight is more preferred, 1.6 to 2.3% by weight is even more preferred, 1.7 to 2.1% by weight is particularly preferred, 1.8 to 2% by weight. .0% by weight is most preferred. When the content of TiO ₂ is less than 1.0% by weight based on the total amount of glass fibers, the effect is to lower the dielectric loss tangent, lower the viscosity, suppress melt separation during initial melting, and reduce scum generated on the furnace surface. may become smaller. On the other hand, if the content of TiO ₂ exceeds 4.0% by weight, phase separation tends to occur and chemical durability may deteriorate.

In the NE glass fiber, the content of F ₂ based on the total amount of glass fiber is preferably 0.1 to 1.4% by weight, more preferably 0.3 to 1.3% by weight, and 0.4 to 1.2% by weight. is more preferred, 0.5 to 1.1% by weight is particularly preferred, and 0.6 to 1.0% by weight is most preferred. When the content of F ₂ is 1.5% by weight or more based on the total amount of glass fibers, the glass tends to undergo phase separation, and the heat resistance of the glass may deteriorate. On the other hand, the inclusion of _F2 in the glass fiber not only reduces the viscosity of the glass and makes it easier to melt, but also may improve the radio wave transmittance of the glass.

In the NE glass fiber, the total content of Li ₂ O, Na ₂ O and K ₂ O based on the total amount of glass fiber is preferably 0.02 to 0.50% by weight, and 0.03 to 0.40% by weight. The content is more preferably 0.04 to 0.30% by weight, even more preferably 0.05 to 0.25% by weight. If the total amount of Li ₂ O, Na ₂ O and K ₂ O based on the total amount of glass fibers is 0.6% by weight or more, the radio wave transmittance may become too low and the water resistance may also deteriorate. On the other hand, the inclusion of Li ₂ O, Na ₂ O, and K ₂ O may reduce the viscosity of the glass, making it easier to melt the glass.

Further, the NE glass fibers contained in the polycarbonate resin composition of the present invention may contain impurities other than the above-mentioned components in a range of less than 0.4% by weight based on the total amount of glass fibers. Examples of impurities that the glass fiber may contain include Fe ₂ O ₃ , Cr ₂ O ₃ , ZrO ₂ , MoO ₃ , SO ₃ , and Cl ₂ . Among these, the content of Fe ₂ O ₃ based on the total amount of glass fibers is preferably in the range of 0.05 to 0.15% by weight since it affects the absorption of radiant heat in the molten glass and the coloring of the glass fibers.

In addition, in the NE glass fibers contained in the polycarbonate resin composition of the present invention, the content of each component mentioned above was measured using an ICP emission spectrometer for Li, which is a light element, and using a wavelength dispersion spectrometer for other elements. This can be carried out using a type fluorescent X-ray analyzer.

As a measuring method, first, a polycarbonate resin composition is heated, for example, in a muffle furnace at 300 to 650° C. for about 0.5 to 24 hours to decompose organic substances. Next, the remaining glass fibers are placed in a platinum crucible, held at a temperature of 1550° C. for 6 hours in an electric furnace, and melted with stirring to obtain homogeneous molten glass. Next, the obtained molten glass is poured onto a carbon plate to produce a glass cullet, which is then crushed and powdered. Regarding Li, which is a light element, glass powder is decomposed by alkali and acid melting, and then quantitatively analyzed using an ICP emission spectrometer. Other elements are quantitatively analyzed using a wavelength dispersive X-ray fluorescence analyzer after forming glass powder into a disk shape using a press. The content and total amount of each component can be calculated by converting these quantitative analysis results into oxides, and the content rate of each component described above can be determined from these values.

In the present invention, the glass fibers contained in the polycarbonate resin composition preferably have a number average fiber length of 30 to 5000 μm. If the number average fiber length of the glass fibers is less than 30 μm, sufficient tensile strength and impact strength may not be obtained in the polycarbonate resin molded product. Furthermore, since breakage of glass fibers occurs during the manufacturing process of the polycarbonate resin composition, it is difficult to make the number average fiber length of the glass fibers more than 5000 μm.

In the glass fibers, the number average fiber length is more preferably in the range of 100 to 3000 μm, even more preferably in the range of 150 to 2000 μm, particularly preferably in the range of 200 to 1000 μm, and particularly preferably in the range of 300 to 500 μm. A range of 315 to 450 μm is particularly preferred, and a range of 315 to 450 μm is most preferred.

In addition, as a method for measuring the number average fiber length of the glass fibers in the polycarbonate resin composition of the present invention, first, the polycarbonate resin composition is heated, for example, in a muffle at 300 to 650°C for about 0.5 to 24 hours. Decompose organic matter by heating, etc. Next, the remaining glass fibers are transferred to a glass Petri dish and dispersed on the surface of the Petri dish using acetone. Next, the fiber length of 500 or more glass fibers dispersed on the surface is measured using a stereomicroscope, and the number average fiber length is calculated.

In the present invention, the glass fibers contained in the polycarbonate resin composition have a cross-sectional shape whose ratio of the major axis to the minor axis (major axis/minor axis) is in the range of 2.0 to 10.0, and the cross-sectional area is converted into a perfect circle. It is preferable to have a non-circular cross section with a fiber diameter (hereinafter also referred to as equivalent fiber diameter) in the range of 3.0 to 35.0 μm. When the glass fibers contained in the polycarbonate resin composition have such a cross section, the tensile strength of the polycarbonate resin composition using the glass fibers under the same conditions except for the composition is lower than when the glass fibers have a circular cross section. The improvement rate of tensile strength and notched Charpy impact strength based on the notched Charpy impact strength and notched Charpy impact strength may be extremely high.

In the glass fiber, the ratio of the major axis to the minor axis of the cross-sectional shape (major axis/minor axis) is determined to achieve both the high tensile strength and notched Charpy impact strength of the glass fiber reinforced resin molded product and the ease of manufacturing of the glass fiber. From this point of view, the range is more preferably from 2.2 to 6.0, and even more preferably from 3.2 to 4.5. In addition, when a glass fiber is formed by converging a plurality of glass filaments, the cross-sectional shape of the glass fiber means the cross-sectional shape of the glass filament forming the glass fiber.

In addition, in the glass fibers, the converted fiber diameter is determined from the viewpoint of achieving both the high tensile strength and notched Charpy impact strength of the polycarbonate resin composition and the ease of manufacturing when manufacturing glass fibers or glass fiber reinforced resin molded products. Therefore, the range is more preferably from 6.0 to 20.0 μm, and more preferably from 6.5 to 16.0 μm. In addition, when a glass fiber is formed by converging a plurality of glass filaments, the fiber diameter of the glass fiber means the fiber diameter of the glass filament forming the glass fiber.

In addition, the non-circular shape of the glass fibers may be a cocoon shape, an ellipse shape, or an oval shape (a rectangle with semicircular shapes at both ends) because of its excellent fluidity when producing a polycarbonate resin composition. or a similar shape) is preferable, and an oval shape is more preferable.

Note that the polycarbonate resin composition of the present invention can include both the glass fibers having the non-circular cross section and the glass fibers having the circular cross section. In the case of including both the glass fiber with a non-circular cross section and the glass fiber with a circular cross section, for example, the content ratio (wt%) of the circular cross-section glass fiber with respect to the content ratio (wt%) of the non-circular cross-section glass fiber. The ratio (glass fibers with circular cross-section (% by weight)/glass fibers with non-circular cross-section (% by weight)) can range from 0.1 to 1.0.

Further, in the present invention, the glass fibers with a circular cross section contained in the polycarbonate resin composition preferably have a circular cross section with a fiber diameter in the range of 7.0 to 13.0 μm. If the fiber diameter is less than 7.0 μm, the strength may not be sufficient, and if it exceeds 13.0 μm, the processability of the glass fiber may be poor.

In the present invention, the NE glass fiber has a ratio of B ₂ O ₃ content (weight %) to TiO ₂ content (weight %) (B ₂ O ₃ (weight %)/TiO ₂ (weight %)). Preferably, the composition has a composition ranging from 9.6 to 11.4.

In the NE glass fiber, the ratio of the B ₂ O ₃ content (wt%) to the TiO ₂ content (wt%) is more preferably in the range of 9.8 to 10.8, and more preferably in the range of 10.0 to 10.8. More preferably, the range is 10.4. By including glass fibers with a ratio of B ₂ O ₃ content (weight %) to TiO ₂ content (weight %) within the above range, productivity can be maintained at high levels during glass melting and spinning. In some cases, it can also have high radio wave transparency.

The content of component B is 1 to 105 parts by weight, preferably 5 to 100 parts by weight, and more preferably 10 to 90 parts by weight, based on 100 parts by weight of component A. If the content of component B is less than 1 part by weight, sufficient strength cannot be obtained, and if it exceeds 105 parts by weight, electromagnetic wave permeability may be impaired, and strand breakage or surging may occur during kneading and extrusion, resulting in decreased productivity. The problem arises.

(Component C: polybutylene terephthalate resin)
The polybutylene terephthalate resin suitably used in the present invention is preferably an aromatic polyester resin in which 70 mol% or more of the dicarboxylic acid component of the dicarboxylic acid component and diol component forming the polyester is an aromatic dicarboxylic acid. The aromatic polyester resin is 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, adipic acid, 2-chloroterephthalic acid, 2,5-dichloroterephthalic acid, 2-methylterephthalic acid, 4,4-stilbenedicarboxylic acid, 4,4-biphenyldicarboxylic acid. Acid, orthophthalic 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- Examples include diphenoxyethanedicarboxylic 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 aromatic 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.

The method for producing the polybutylene terephthalate 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 draining the by-product water or lower alcohol out of 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 polybutylene terephthalate resin can be either a batch method or a continuous polymerization method.

The molecular weight of the polybutylene terephthalate resin of the present invention is not particularly limited, but the intrinsic viscosity measured at 25°C using o-chlorophenol as a solvent is preferably 0.4 to 1.5, particularly preferably 0.5. ~1.2.

Further, the amount of terminal carboxyl groups in the aromatic polybutylene terephthalate resin used in the present invention is preferably 40 eq/g or more, more preferably 40 to 75 eq/ton, even more preferably 40 to 70 eq/ton, particularly preferably It is 42 to 65 eq/ton. If the amount of terminal carboxyl groups is less than 40 eq/ton, the thermal stability may be poor, and if it exceeds 75 eq/ton, the strength may decrease.

The content of component C is 0.01 to 3.5 parts by weight, preferably 0.1 to 3.3 parts by weight, and more preferably 0.3 to 3.0 parts by weight, based on 100 parts by weight of component A. . When the content of component B is less than 0.01 parts by weight, sufficient strength and electromagnetic wave permeability cannot be obtained, and when it exceeds 3.5 parts by weight, thermal stability and surface appearance are poor.

(Component D: phosphorus compound)
As the phosphorus compound used in the present invention, any of phosphite compounds, phosphonite compounds, and phosphate compounds can be used, but it is particularly preferable to use phosphate compounds with a number average molecular weight of 50 to 300 because the appearance is particularly excellent.

Various phosphite compounds can be used. Specific examples include a phosphite compound represented by the following general formula (8), a phosphite compound represented by the following general formula (9), and a phosphite compound represented by the following general formula (10).

[In the formula, R ³¹ is a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group or alkaryl group having 6 to 20 carbon atoms, an aralkyl group having 7 to 30 carbon atoms, or a halo, alkylthio (alkyl group) thereof; represents a carbon number of 1 to 30) or a hydroxy substituent, and the three R ^31s can be selected to be the same or different from each other, and a cyclic structure can also be selected by being derived from a dihydric phenol. ]

[In the formula, R ³² and R ³³ are each a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group or alkylaryl group having 6 to 20 carbon atoms, an aralkyl group having 7 to 30 carbon atoms, or an aralkyl group having 4 to 20 carbon atoms. Indicates a cycloalkyl group and a 2-(4-oxyphenyl)propyl-substituted aryl group having 15 to 25 carbon atoms. Note that the cycloalkyl group and the aryl group can be selected from those that are not substituted with an alkyl group or those that are substituted with an alkyl group. ]

[In the formula, R ³⁴ and R ³⁵ are alkyl groups having 12 to 15 carbon atoms. Note that R ³⁴ and R ³⁵ can be selected to be the same or different. ]
Examples of the phosphonite compound include a phosphonite compound represented by the following general formula (11) and a phosphonite compound represented by the following general formula (12).

[In the formula, Ar ¹ and Ar ² represent an aryl group or alkylaryl group having 6 to 20 carbon atoms, or a 2-(4-oxyphenyl)propyl-substituted aryl group having 15 to 25 carbon atoms, and the four Ar ¹ are Either the same or different can be selected. Alternatively, the two Ar ² 's can be selected to be the same or different from each other. ]

Preferred specific examples of the phosphite compound represented by the above general formula (8) include diphenyl isooctyl phosphite, 2,2'-methylenebis(4,6-di-tert-butylphenyl)octyl phosphite, diphenyl mono (tridecyl) phosphite, phenyl diisodecyl phosphite, and phenyl di(tridecyl) phosphite.

Preferred specific examples of the phosphite compound represented by the general formula (9) include distearyl pentaerythritol diphosphite, bis(2,4-di-tert-butylphenyl) pentaerythritol diphosphite, bis(2 , 6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphite, phenylbisphenol A pentaerythritol diphosphite, dicyclohexyl pentaerythritol diphosphite, and preferably distearyl pentaerythritol diphosphite, Bis(2,4-di-tert-butylphenyl)pentaerythritol diphosphite and bis(2,6-di-tert-butyl-4-methylphenyl)pentaerythritol diphosphite can be mentioned. Such phosphite compounds can be used alone or in combination of two or more.

A preferred specific example of the phosphite compound represented by the above general formula (10) is 4,4'-isopropylidenediphenol tetratridecyl phosphite.

Preferred specific examples of the phosphonite compound represented by the above general formula (11) include tetrakis(2,4-di-iso-propylphenyl)-4,4'-biphenylene diphosphonite, tetrakis(2,4-di-iso-propylphenyl)-4,4'-biphenylene diphosphonite, -n-butylphenyl)-4,4'-biphenylene diphosphonite, tetrakis(2,4-di-tert-butylphenyl)-4,4'-biphenylene diphosphonite, tetrakis(2,4-di-tert -butylphenyl)-4,3'-biphenylene diphosphonite, tetrakis(2,4-di-tert-butylphenyl)-3,3'-biphenylene diphosphonite, tetrakis(2,6-di-iso-propyl) phenyl)-4,4'-biphenylene diphosphonite, tetrakis(2,6-di-n-butylphenyl)-4,4'-biphenylene diphosphonite, tetrakis(2,6-di-tert-butylphenyl) -4,4'-biphenylene diphosphonite, tetrakis(2,6-di-tert-butylphenyl)-4,3'-biphenylene diphosphonite, tetrakis(2,6-di-tert-butylphenyl)-3 , 3'-biphenylene diphosphonite, etc., tetrakis(di-tert-butylphenyl)-biphenylene diphosphonite is preferred, and tetrakis(2,4-di-tert-butylphenyl)-biphenylene diphosphonite is more preferred. preferable. This tetrakis(2,4-di-tert-butylphenyl)-biphenylene diphosphonite is preferably a mixture of two or more types, specifically, tetrakis(2,4-di-tert-butylphenyl)-4,4 '-biphenylene diphosphonite, tetrakis(2,4-di-tert-butylphenyl)-4,3'-biphenylene diphosphonite and tetrakis(2,4-di-tert-butylphenyl)-3,3' -Biphenylene diphosphonites can be used alone or in combination of two or more, but a mixture of three of these is preferred.

Preferred specific examples of the phosphonite compound represented by the above general formula (12) include bis(2,4-di-iso-propylphenyl)-4-phenyl-phenylphosphonite, bis(2,4-di-n -butylphenyl)-3-phenyl-phenylphosphonite, bis(2,4-di-tert-butylphenyl)-4-phenyl-phenylphosphonite, bis(2,4-di-tert-butylphenyl)-3 -Phenyl-phenylphosphonite bis(2,6-di-iso-propylphenyl)-4-phenyl-phenylphosphonite, bis(2,6-di-n-butylphenyl)-3-phenyl-phenylphosphonite, Examples include bis(2,6-di-tert-butylphenyl)-4-phenyl-phenylphosphonite, bis(2,6-di-tert-butylphenyl)-3-phenyl-phenylphosphonite, and bis( Di-tert-butylphenyl)-phenyl-phenylphosphonite is preferred, and bis(2,4-di-tert-butylphenyl)-phenyl-phenylphosphonite is more preferred. This bis(2,4-di-tert-butylphenyl)-phenyl-phenylphosphonite is preferably a mixture of two or more types, specifically, bis(2,4-di-tert-butylphenyl)-4- One or two types of phenyl-phenylphosphonite and bis(2,4-di-tert-butylphenyl)-3-phenyl-phenylphosphonite can be used in combination, but preferably these two types It is a mixture. Further, in the case of a mixture of two types, the mixing ratio is preferably in the range of 5:1 to 4, more preferably 5:2 to 3 in terms of weight ratio.

On the other hand, phosphate compounds include tributyl phosphate, trimethyl phosphate, tricresyl phosphate, triphenyl phosphate, trichlorophenyl phosphate, triethyl phosphate, diphenyl cresyl phosphate, diphenyl monoorthoxenyl phosphate, tributoxyethyl phosphate, dibutyl phosphate, and dioctyl phosphate. Examples include phosphate, diisopropyl phosphate, etc., and trimethyl phosphate is preferred.

Among the above-mentioned phosphorus compounds, more preferable compounds include compounds represented by the following general formulas (13) and (14).

[In the formula, R ³⁶ and R ³⁷ each independently represent an alkyl group, a cycloalkyl group, an aryl group, or an aralkyl group having 1 to 12 carbon atoms. ]

[In the formula, R ⁴¹ , R ⁴² , R ⁴³ , R ⁴⁴ , R ⁴⁷ , R ⁴⁸ and R ⁴⁹ are each independently a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group, an aryl group, or an aralkyl group. R ⁴⁵ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and R ⁴⁶ represents a hydrogen atom or a methyl group. ]
In formula (13), R ³⁶ and R ³⁷ are preferably an alkyl group having 1 to 12 carbon atoms, more preferably an alkyl group having 1 to 8 carbon atoms. Specifically, the compound represented by formula (13) includes tris(dimethylphenyl)phosphite, tris(diethylphenyl)phosphite, tris(di-iso-propylphenyl)phosphite, tris(di-n-butyl) phenyl) phosphite, tris(2,4-di-tert-butylphenyl) phosphite, tris(2,6-di-tert-butylphenyl) phosphite, tris(2,6-di-tert-butylphenyl) Examples include phosphite, and tris(2,6-di-tert-butylphenyl) phosphite is particularly preferred.

Specifically, the compound represented by formula (14) is a phosphite derived from 2,2'-methylenebis(4,6-di-tert-butylphenol) and 2,6-di-tert-butylphenol; , 2'-methylenebis(4,6-di-tert-butylphenol) and phenol, particularly phosphites derived from 2,2'-methylenebis(4,6-di-tert-butylphenol) and phenol. Preferred are derived phosphites.

The content of the phosphorus compound is preferably 0.01 to 1.0 parts by weight, more preferably 0.01 to 0.9 parts by weight, and still more preferably 0.02 to 0.0 parts by weight, based on 100 parts by weight of component A. It is 8 parts by weight. If the content of the phosphorus compound is less than 0.01 parts by weight, mechanical properties may not be sufficiently developed, and even if it exceeds 1.0 parts by weight, mechanical properties may not be sufficiently developed.

(Other ingredients)
A flame retardant can be added to the polycarbonate 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 easy to dissolve 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 even more preferably 0.01 to 1 part by weight, per 100 parts by weight of component A. The amount is 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 (15) 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 Ar1, Ar2, Ar3, and Ar4 include phenol, cresol, xylenol, isopropylphenol, butylphenol, and p-cumylphenol, and among them, 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 m=1 in the formula (15) 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 (16) and (17) 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 (16) and (17), the organic groups not containing a halogen atom represented by X ¹ , X ² , X ³ , and X ⁴ include, for example, an alkoxy group, a phenyl group, an amino group, an allyl group, etc. can be mentioned. Among these, a cyclic phosphazene compound represented by the above formula (16) is preferred, and a cyclic phenoxyphosphazene in which X ¹ and X ² in the above formula (17) 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 even more preferably 5 to 20 parts by weight, based on 100 parts by weight of component A. 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, and still more preferably 1 to 5 parts by weight, based on 100 parts by weight of component A.

(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 at 380°C of 107 to 1013 poise, preferably 108 to 1012 poise, 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 more preferably 0.1 to 0.5 parts by weight, based on 100 parts by weight of component A. More preferably 5 parts by weight.

Various additives can be added to the polycarbonate resin composition of the present invention as long as they do not impair the effects of the present invention. Examples of such additives include phenolic heat stabilizers, sulfur-containing antioxidants, mold release agents, ultraviolet absorbers, hindered amine light stabilizers, compatibilizers, dyes and pigments, and the like. These additives will be specifically explained below.

(phenolic heat stabilizer)
The phenolic stabilizers used in the present invention generally include hindered phenol, semi-hindered phenol, and unhindered phenol compounds, but from the viewpoint of applying heat-stabilizing formulations to polypropylene resins, Hindered phenol compounds are more preferably used. Specific examples of such hindered phenol compounds include 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-methylphenyl)propionate, 1,6- Hexanediol bis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate, bis[2-tert-butyl-4-methyl 6-(3-tert-butyl-5-methyl-2 -hydroxybenzyl)phenyl]terephthalate, 3,9-bis{2-[3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propionyloxy]-1,1,-dimethylethyl}-2, 4,8,10-tetraoxaspiro[5,5]undecane, 4,4'-thiobis(6-tert-butyl-m-cresol), 4,4'-thiobis(3-methyl-6-tert-butylphenol) ), 2,2'-thiobis(4-methyl-6-tert-butylphenol), bis(3,5-di-tert-butyl-4-hydroxybenzyl) sulfide, 4,4'-di-thiobis(2, 6-di-tert-butylphenol), 4,4'-tri-thiobis(2,6-di-tert-butylphenol), 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, tetrakis[methylene-3-(3',5'-di-tert -butyl-4-hydroxyphenyl)propionate]methane, etc., which can be preferably used.

More preferably, n-octadecyl-β-(4'-hydroxy-3',5'-di-tert-butylfer) propionate, 2-tert-butyl-6-(3'-tert-butyl-5'-methyl -2'-hydroxybenzyl)-4-methylphenylacrylate, 3,9-bis{2-[3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propionyloxy]-1,1,- dimethylethyl}-2,4,8,10-tetraoxaspiro[5,5]undecane, and tetrakis[methylene-3-(3',5'-di-tert-butyl-4-hydroxyphenyl)propionate]methane and n-octadecyl-β-(4'-hydroxy-3',5'-di-tert-butylfer) propionate is more preferred.

(Sulfur-containing antioxidant)
A sulfur-containing antioxidant can also be used as an antioxidant in the polycarbonate resin composition of the present invention. It is particularly suitable when the resin composition is used for rotational molding or compression molding. Specific examples of such sulfur-containing antioxidants include dilauryl-3,3'-thiodipropionic acid ester, ditridecyl-3,3'-thiodipropionic acid ester, and dimyristyl-3,3'-thiodipropionic acid ester. , distearyl-3,3'-thiodipropionate, laurylstearyl-3,3'-thiodipropionate, pentaerythritol tetra(β-laurylthiopropionate) ester, bis[2-methyl-4 -(3-laurylthiopropionyloxy)-5-tert-butylphenyl] sulfide, octadecyl disulfide, mercaptobenzimidazole, 2-mercapto-6-methylbenzimidazole, 1,1'-thiobis(2-naphthol), etc. be able to. More preferred is pentaerythritol tetra(β-laurylthiopropionate) ester.

The above-mentioned phosphorus stabilizers, phenol stabilizers, and sulfur-containing antioxidants can be used alone or in combination of two or more. The content of the phenolic stabilizer and the sulfur-containing antioxidant is preferably 0.0001 to 1 part by weight per 100 parts by weight of component A. The amount is more preferably 0.0005 to 0.5 parts by weight, and even more preferably 0.001 to 0.2 parts by weight.

(Ultraviolet absorber)
The polycarbonate resin composition of the present invention can contain an ultraviolet absorber. Examples of benzophenones include 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-octoxybenzophenone, 2-hydroxy-4-benzyloxybenzophenone, and 2-hydroxy-4-methoxybenzophenone. 5-Sulfoxybenzophenone, 2-hydroxy-4-methoxy-5-sulfoxytrihydride dolate benzophenone, 2,2'-dihydroxy-4-methoxybenzophenone, 2,2',4,4'-tetrahydroxybenzophenone, 2 , 2'-dihydroxy-4,4'-dimethoxybenzophenone, 2,2'-dihydroxy-4,4'-dimethoxy-5-sodium sulfoxybenzophenone, bis(5-benzoyl-4-hydroxy-2-methoxyphenyl) ) methane, 2-hydroxy-4-n-dodecyloxybenzophenone, and 2-hydroxy-4-methoxy-2'-carboxybenzophenone.

Examples of benzotriazole-based compounds include 2-(2-hydroxy-5-methylphenyl)benzotriazole, 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 and a vinyl monomer copolymerizable with the monomer. 2-hydroxyphenyl-2H, such as a copolymer with 2-(2'-hydroxy-5-acryloxyethylphenyl)-2H-benzotriazole and a vinyl monomer copolymerizable with the monomer. - Polymers having a benzotriazole skeleton are exemplified.

Hydroxyphenyltriazine-based compounds include, 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. Illustrated. 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.

Examples of cyclic iminoesters include 2,2'-p-phenylenebis(3,1-benzoxazin-4-one), 2,2'-(4,4'-diphenylene)bis(3,1-benzoxazine) -4-one), and 2,2'-(2,6-naphthalene)bis(3,1-benzoxazin-4-one).

For cyanoacrylates, for example, 1,3-bis-[(2'-cyano-3',3'-diphenylacryloyl)oxy]-2,2-bis[(2-cyano-3,3-diphenylacryloyl)oxy ] methyl)propane, and 1,3-bis-[(2-cyano-3,3-diphenylacryloyl)oxy]benzene.

Furthermore, the above-mentioned ultraviolet absorber takes the structure of a monomer compound capable of radical polymerization, thereby combining such an ultraviolet absorbing monomer and/or a photostable monomer having a hindered amine structure with an alkyl (meth)acrylate. It may also be a polymer-type ultraviolet absorber copolymerized with monomers such as. 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 absorption ability, and cyclic iminoester-based and cyanoacrylate-based are preferred in terms of heat resistance and hue (transparency). The above 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 2 parts by weight, more preferably 0.02 to 2 parts by weight, even more preferably 0.03 to 1 part by weight, based on 100 parts by weight of component A. Preferably it is 0.05 to 0.5 part by weight.

(Hindered amine light stabilizer)
The polycarbonate resin composition of the present invention may contain a hindered amine light stabilizer. Hindered amine light stabilizers are generally called HALS (Hindered Amine Light Stabilizer) and are compounds having a 2,2,6,6-tetramethylpiperidine skeleton in their structure, such as 4-acetoxy-2,2,6 , 6-tetramethylpiperidine, 4-stearoyloxy-2,2,6,6-tetramethylpiperidine, 4-acryloyloxy-2,2,6,6-tetramethylpiperidine, 4-(phenylacetoxy)-2, 2,6,6-tetramethylpiperidine, 4-benzoyloxy-2,2,6,6-tetramethylpiperidine, 4-methoxy-2,2,6,6-tetramethylpiperidine, 4-stearyloxy-2, 2,6,6-tetramethylpiperidine, 4-cyclohexyloxy-2,2,6,6-tetramethylpiperidine, 4-benzyloxy-2,2,6,6-tetramethylpiperidine, 4-phenoxy-2, 2,6,6-tetramethylpiperidine, 4-(ethylcarbamoyloxy)-2,2,6,6-tetramethylpiperidine, 4-(cyclohexylcarbamoyloxy)-2,2,6,6-tetramethylpiperidine, 4-(phenylcarbamoyloxy)-2,2,6,6-tetramethylpiperidine, bis(2,2,6,6-tetramethyl-4-piperidyl)carbonate, bis(2,2,6,6-tetra Methyl-4-piperidyl)oxalate, bis(2,2,6,6-tetramethyl-4-piperidyl)malonate, bis(2,2,6,6-tetramethyl-4-piperidyl)sebacate, bis(2, 2,6,6-tetramethyl-4-piperidyl)adipate, bis(2,2,6,6-tetramethyl-4-piperidyl)terephthalate, bis(1,2,2,6,6-pentamethyl-4- bis(1,2,2,6,6-pentamethyl-4-piperidyl)oxalate, bis(1,2,2,6,6-pentamethyl-4-piperidyl)malonate, bis(1,2, 2,6,6-pentamethyl-4-piperidyl) sebacate, bis(1,2,2,6,6-pentamethyl-4-piperidyl)adipate, bis(1,2,2,6,6-pentamethyl-4- piperidyl) terephthalate, N,N'-bis-2,2,6,6-tetramethyl-4-piperidinyl-1,3-benzenedicarboxamide, 1,2-bis(2,2,6,6-tetra Methyl-4-piperidyloxy)ethane, α,α'-bis(2,2,6,6-tetramethyl-4-piperidyloxy)-p-xylene, bis(2,2,6,6-tetramethyl- 4-piperidyltrilene-2,4-dicarbamate, bis(2,2,6,6-tetramethyl-4-piperidyl)-hexamethylene-1,6-dicarbamate, tris(2,2,6,6 -tetramethyl-4-piperidyl)-benzene-1,3,5-tricarboxylate, N,N',N'',N'''-tetrakis-(4,6-bis-(butyl-(N- Methyl-2,2,6,6-tetramethylpiperidin-4-yl)amino)-triazin-2-yl)-4,7-diazadecane-1,10-diamine, dibutylamine/1,3,5-triazine・N,N'-bis(2,2,6,6-tetramethyl-4-piperidyl)-1,6-hexamethylenediamine and N-(2,2,6,6-tetramethyl-4-piperidyl) Butylamine polycondensate, poly[{6-(1,1,3,3-tetramethylbutyl)amino-1,3,5-triazine-2,4-diyl}{(2,2,6,6- tetramethyl-4-piperidyl)imino}hexamethylene{(2,2,6,6-tetramethyl-4-piperidyl)imino}], tetrakis(2,2,6,6-tetramethyl-4-piperidyl)- 1,2,3,4-butanetetracarboxylate, tetrakis(1,2,2,6,6-pentamethyl-4-piperidyl)-1,2,3,4-butanetetracarboxylate, tris(2,2 ,6,6-tetramethyl-4-piperidyl)-benzene-1,3,4-tricarboxylate, 1-[2-{3-(3,5-di-t-butyl-4-hydroxyphenyl)propionyl oxy}butyl]-4-[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionyloxy]2,2,6,6-tetramethylpiperidine, and 1,2,3,4- Butanetetracarboxylic acid and 1,2,2,6,6-pentamethyl-4-piperidinol and β,β,β',β'-tetramethyl-3,9-[2,4,8,10-tetraoxaspiro (5,5)undecane] and condensates with diethanol.

Hindered amine light stabilizers can be broadly divided into NH type (hydrogen is bonded to the nitrogen atom), NR type (alkyl group (R) is bonded to the nitrogen atom), and NH type (hydrogen is bonded to the nitrogen atom). There are three types: N-OR type (an alkoxy group (OR) is bonded to the nitrogen atom), but from the viewpoint of basicity of hindered amine light stabilizers when applied to polycarbonate resin, N-R type, which has low basicity, It is more preferable to use the N-OR type. The above hindered amine light stabilizers can be used alone or in combination of two or more.

The content of the hindered amine light stabilizer is preferably 0 to 1 part by weight, more preferably 0.05 to 1 part by weight, and still more preferably 0.08 to 0.7 parts by weight, based on 100 parts by weight of component A. Parts by weight, particularly preferably 0.1 to 0.5 parts by weight. If the content of the hindered amine light stabilizer is more than 1 part by weight, it is not preferable because it may cause poor appearance due to gas generation or deterioration of physical properties due to decomposition of the polycarbonate resin. Moreover, if it is less than 0.05 part by weight, sufficient light resistance may not be exhibited.

(dye and pigment)
The polycarbonate resin composition of the present invention further contains various dyes and pigments to provide molded articles exhibiting a variety of designs. By incorporating a fluorescent whitening agent or other fluorescent dyes that emit light, it is possible to provide even better design effects that take advantage of the emitted light color. Furthermore, it is also possible to provide a polycarbonate resin composition that is colored with a trace amount of dye and pigment and has vivid coloring properties.

Examples of the fluorescent dyes (including fluorescent brighteners) used in the present invention include coumarin-based fluorescent dyes, benzopyran-based fluorescent dyes, perylene-based fluorescent dyes, anthraquinone-based fluorescent dyes, thioindigo-based fluorescent dyes, and xanthene-based fluorescent dyes. , xanthone fluorescent dyes, thioxanthene fluorescent dyes, thioxanthone fluorescent dyes, thiazine fluorescent dyes, and diaminostilbene fluorescent dyes. Among these, preferred are coumarin-based fluorescent dyes, benzopyran-based fluorescent dyes, and perylene-based fluorescent dyes, which have good heat resistance and are less likely to deteriorate during molding of polycarbonate resin.

Dyes other than the above bluing agents and fluorescent dyes include perylene dyes, coumarin dyes, thioindigo dyes, anthraquinone dyes, thioxanthone dyes, ferrocyanides such as deep blue, perinone dyes, quinoline dyes, and quinacridones. Examples include dyes based on dyes such as dioxazine dyes, isoindolinone dyes, and phthalocyanine dyes. Furthermore, the resin composition of the present invention can also be blended with a metallic pigment to obtain a better metallic color. As the metallic pigment, those having a metal coating or a metal oxide coating on various plate-shaped fillers are suitable.

The content of the above dye and pigment is preferably 0.00001 to 1 part by weight, more preferably 0.00005 to 0.5 part by weight, per 100 parts by weight of component A.

(other resins)
In the polycarbonate resin composition of the present invention, other resins may be used in small proportions within the range that exhibits the effects of the present invention.

Examples of such other resins include polyamide resins, polyimide resins, polyetherimide resins, polyurethane resins, silicone resins, polyphenylene ether resins, polyphenylene sulfide resins, polysulfone resins, polyolefin resins, polymethacrylate resins, phenol resins, and epoxy resins. The following resins are mentioned.

(Other fillers)
In the polycarbonate resin composition of the present invention, other fillers may be used in small proportions within the range that exhibits the effects of the present invention.

Such other fillers include carbon fibers, potash titanate whiskers, zinc oxide whiskers, alumina fibers, silicon carbide fibers, ceramic fibers, asbestos fibers, gypsum fibers, fibrous fillers such as metal fibers, wollastonite, and sericite. , kaolin, mica, clay, bentonite, asbestos, talc, silicates such as alumina silicate, swellable layered silicates such as montmorillonite, synthetic mica, alumina, silicon oxide, magnesium oxide, zirconium oxide, titanium oxide, iron oxide, etc. metal compounds, carbonates such as calcium carbonate, magnesium carbonate, dolomite, sulfates such as calcium sulfate, barium sulfate, glass beads, carbon black, ceramic beads, boron nitride, silicon carbide, calcium phosphate and silica. Non-fibrous fillers may be mentioned.

(Other additives)
The polycarbonate resin composition of the present invention may contain a small proportion of known additives in order to impart various functions to the molded article or improve its properties. These additives may be added in usual amounts as long as they do not impair the purpose of the present invention. Such additives include sliding agents (e.g. PTFE particles), fluorescent dyes, inorganic phosphors (e.g. phosphors with aluminate as a host crystal), antistatic agents, crystal nucleating agents, inorganic and organic antibacterial agents. , photocatalytic antifouling agents (for example, particulate titanium oxide, particulate zinc oxide), radical generators, infrared absorbers (heat ray absorbers), mechanochromic agents, and photochromic agents.

(Method for producing polycarbonate resin composition)
There are no particular limitations on the method for producing the resin composition of the present invention, and well-known methods can be used. For example, component A, component B, component C, and optionally other additives are thoroughly mixed using a premixing means such as a V-type blender, Henschel mixer, mechanochemical device, extrusion mixer, etc., and then, if necessary, Examples include a method in which the premix is granulated using an extrusion granulator or briquetting machine, then melt-kneaded using a melt-kneader typified by a vented twin-screw extruder, and then pelletized using a pelletizer.

In addition, there are methods to feed each component independently to a melt kneader such as a vented twin-screw extruder, a method to feed to a melt kneader using supercritical fluid, and a method to prepare a portion of each component. After mixing, there is also a method in which the mixture is supplied to a melt kneader independently from the remaining components. 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 component A or directly fed 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 polycarbonate resin composition of the present invention can be generally manufactured into various products by injection molding the pellets produced as described above to obtain molded articles. Such injection molding includes not only normal molding methods, but also injection compression molding, injection press molding, gas-assisted injection molding, foam molding (including methods of injecting supercritical fluid), insert molding, in-mold coating molding, and heat insulation molding. Examples include mold molding, rapid heating and cooling mold molding, two-color molding, sandwich molding, and ultra-high speed injection molding. Further, for molding, either a cold runner method or a hot runner method can be selected.

The glass fiber reinforced polycarbonate resin composition of the present invention can also be used in the form of various 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 polycarbonate resin composition of the present invention can be made into a molded article by rotational molding, blow molding, or the like.

The polycarbonate resin composition of the present invention has excellent radio wave transmittance, strength, appearance, and thermal stability, and therefore can be suitably used as a resin composition for various antenna-equipped communication devices. For example, communication devices with built-in antennas include communication devices having monopole antennas, dipole antennas, whip antennas, loop antennas, slot antennas, etc., and are particularly useful for communication devices that receive high frequencies of 5 GHz or higher. .

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.

Next, Examples and Comparative Examples of the present invention will be described in detail, but the present invention is not limited thereto. In addition, each measurement item in the example was measured by the following method.
1. Evaluation of aromatic polycarbonate resin (i) Viscosity average molecular weight (Mv)
The specific viscosity (η _SP ) calculated by the following formula was determined using an Ostwald viscometer from a solution of aromatic polycarbonate resin 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]
The viscosity average molecular weight Mv 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 Mv ^0.83
c=0.7

2. Evaluation of resin composition (i) Tensile properties (tensile breaking strength)
Measurement was performed at a test speed of 50 mm/min in accordance with ISO527. The test piece used was a dumbbell-shaped test piece obtained by the method described below, and the shape of the parallel part was 80 mm in length x 10 mm in width x 4 mm in thickness.
(ii) Rigidity (flexural modulus)
Using a test piece of length 80 mm x width 10 mm x thickness 4 mm obtained by the method described below, measurement was performed at a test speed of 2 mm/min in accordance with ISO178.
(iii) Impact properties (Charpy impact value) (with notch)
Measurement was carried out in accordance with ISO 179 (measurement conditions: 23° C.) using a test piece of length 80 mm x width 10 mm x thickness 4 mm obtained by the method below.
(iv) Electromagnetic wave transmittance Radio wave transmittance at 28 GHz was measured using a test piece measuring 150 mm in length x 150 mm in width x 3 mm in thickness obtained by the method described below. A digital micrometer (manufactured by Shinwa) and a network analyzer E8361A (manufactured by Keysight) were used as electromagnetic wave transmittance measuring devices.
(v) Surface appearance
Observing the surface appearance of the molding material obtained by the method below, no lumps of fibrous material or bubbles with a diameter of 3 mm or more were found on the surface due to insufficient adhesion between the glass fiber and polycarbonate. The test results were rated as ○ (good), those in which no lumps of fibrous material were observed but bubbles were confirmed were rated as △ (slightly good), and those in which lumps of fibrous material were confirmed were marked as × (poor).
(vi) Thermal stability When the polycarbonate resin composition obtained by the following method was put into an injection molding machine whose cylinder temperature was set to 330°C and allowed to stay for 10 minutes, the amount of resin that naturally fell from the tip of the injection nozzle was measured. .

[Examples 1 to 13, Comparative Examples 1 to 7]
Aromatic polycarbonate resin, polybutylene terephthalate resin, glass fiber, and various additives are mixed in a blender in the amounts listed in Tables 2 and 3, and then melt-kneaded using a vented twin-screw extruder to form pellets. Obtained. A preliminary mixture of the various additives used with the aromatic polycarbonate resin was prepared in advance at a concentration of 10 to 100 times the blended amount, and then the entire mixture was mixed using a blender. For extrusion, a vented twin-screw extruder with a diameter of 30 mmφ (Japan Steel Works, Ltd. TEX30α-38.5BW-3V) was used, with a screw rotation speed of 230 rpm, a discharge rate of 25 kg/h, a vent vacuum level of 3 kPa, and an extrusion temperature of The temperature was 300°C from the first supply port to the second supply port, and 310°C from the second supply port to the die portion, and the mixture was melt-kneaded to obtain pellets. The reinforcing filler was supplied from the second supply port using the side feeder of the extruder, and the remaining polycarbonate resin and additives were supplied to the extruder from the first supply port. The first supply port here is the supply port furthest from the die, and the second supply port is the supply port located between the die of the extruder and the first supply port. The obtained pellets were dried at 120°C for 5 hours in a hot air circulation dryer, and then molded using an injection molding machine (SG-150U manufactured by Sumitomo Heavy Industries, Ltd.) at a cylinder temperature of 300°C and a mold temperature of 80°C. Test pieces for evaluation were molded under the molding conditions. 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 prepared under the following conditions A reactor equipped with a thermometer, a stirrer, and a reflux condenser was charged with 3,844 parts of a 48% aqueous sodium hydroxide solution and 22,380 parts of ion-exchanged water. After dissolving 3,984 parts of 2,2-bis(4-hydroxy-3-methylphenyl)propane (Bis-C, manufactured by Honshu Chemical) and 7.53 parts of hydrosulfite (manufactured by Wako Pure Chemical Industries), chlorination 13,210 parts of methylene was added, and 2,000 parts of phosgene was blown into the mixture at 15 to 25° C. over about 60 minutes while stirring. After blowing phosgene, 640 parts of a 48% aqueous sodium hydroxide solution and 93.2 parts of p-tert-butylphenol were added, stirring was resumed, and after emulsification, 3.24 parts of triethylamine was added, and the mixture was further stirred at 28 to 33°C for 1 hour. The reaction was terminated. After the reaction, the product is diluted with methylene chloride and washed with water, acidified with hydrochloric acid and washed with water, and the water washing is repeated until the conductivity of the aqueous phase becomes almost the same as that of ion-exchanged water. A solution was obtained. Next, this solution was passed through a filter with an opening of 0.3 μm, and further added dropwise to warm water in a kneader with an isolation chamber having a foreign matter outlet in the bearing part, and the aromatic polycarbonate resin was turned into flakes while methylene chloride was distilled off. Subsequently, the liquid-containing flakes were crushed and dried to obtain an aromatic polycarbonate resin powder.
A-2: Aromatic polycarbonate resin prepared under the following conditions The monomer used was 1,992 parts (7 Same as A-1 except that 1,773 parts (7.8 mol) of 2,2-bis(4-hydroxyphenyl)propane (Bis-A, manufactured by Nippon Steel Chemical Co., Ltd.) were used. An aromatic polycarbonate resin powder was obtained by the method.
A-3: Aromatic polycarbonate resin prepared under the following conditions The monomers used were 766 parts (3.0 mol) of 2,2-bis(4-hydroxy-3-methylphenyl)propane, 2,2-bis(4 An aromatic polycarbonate resin powder was obtained in the same manner as in A-1 except that 2,728 parts (12.0 mol) of -hydroxyphenyl)propane was used.
A-4: Aromatic polycarbonate resin prepared under the following conditions The monomers used were 511 parts (2.0 mol) of 2,2-bis(4-hydroxy-3-methylphenyl)propane, 2,2-bis(4 An aromatic polycarbonate resin powder was obtained in the same manner as in A-1 except that 3,182 parts (14.0 mol) of -hydroxyphenyl)propane was used.
A-5: Aromatic polycarbonate resin (polycarbonate resin powder with a viscosity average molecular weight of 15,500 made from bisphenol A and phosgene by a conventional method, Panlite CM-1000 (product name) manufactured by Teijin Ltd.)
A-6: Aromatic polycarbonate resin (polycarbonate resin powder with a viscosity average molecular weight of 19,700 made from bisphenol A and phosgene by a conventional method, manufactured by Teijin Ltd., Panlite L-1225WX (product name))
(B component)
Glass fibers B-1 to B-4 consisting of the components listed in Table 1 were used. Composition 1 corresponds to the NE glass composition, and composition 2 corresponds to the E glass composition.

B-1: Circular cross-section glass fiber consisting of composition 1 (fiber diameter 11 μm, cut length 3 mm, length/breadth ratio = 1.0)
B-2: Non-circular cross-section glass fiber consisting of composition 1 (fiber diameter 15 μm, cut length 3 mm, major axis 28 μm, minor axis 7 μm)
B-3: Circular cross-section glass fiber consisting of composition 2 (fiber diameter 11 μm, cut length 3 mm, length/breadth ratio = 1.0)
B-4: Non-circular cross-section glass fiber consisting of composition 2 (fiber diameter 15 μm, cut length 3 mm, major axis 28 μm, minor axis 7 μm)
Note that the fiber diameter of a glass fiber having a non-circular cross-sectional shape means the fiber diameter when the cross-sectional area is converted to a perfect circle (converted fiber diameter).

(C component)
C-1: Polybutylene terephthalate (manufactured by Polyplastics Co., Ltd.: DURANEX 500FP EF202X, IV value: 0.85, terminal carboxyl group: 55 eq/ton)
C-2: Polybutylene terephthalate (manufactured by Polyplastics Co., Ltd.: DURANEX 500FP EF202R, IV value: 0.875, terminal carboxyl group: 10 eq/ton)
(D component)
D-1: Trimethyl phosphate (TMP manufactured by Daihachi Chemical Industry Co., Ltd.)
D-2: Tris(2,4-di-tert-butylphenyl) phosphite (2112 manufactured by ADEKA)
(Other ingredients)
UV: Benzotriazole ultraviolet absorber (manufactured by Ciba Specialty Chemicals: Tinuvin234)
L: Low molecular weight polyethylene (Highwax HW405MP (trade name) manufactured by Mitsui Chemicals, Inc.)
CB: Carbon black (RB-90003S manufactured by Koshigaya Kasei Kogyo Co., Ltd.)

It can be seen from Tables 2 and 3 that by the blending of the present invention, a polycarbonate resin composition excellent in electromagnetic wave permeability, strength, appearance, and thermal stability can be obtained.

Claims (7)

(A) 100 parts by weight of aromatic polycarbonate resin (component A), (B) 1 to 105 parts by weight of glass fiber (component B) and (C) 0.01 to 3.5 parts by weight of polybutylene terephthalate resin (component C) A polycarbonate resin composition containing parts by weight of carbonate structural units derived from 2,2-bis(4-hydroxy-3-methylphenyl)propane in a proportion of 20 to 100 mol% of the total carbonate structural units. A polycarbonate resin composition for communication equipment with a built-in antenna, which is an aromatic polycarbonate resin containing 20 to 100% by weight of an aromatic polycarbonate resin (component A-1) . The B component has a number average fiber length of 30 to 5000 μm (B-1) The ratio of the major axis to the minor axis of the cross-sectional shape (major axis/minor axis) is in the range of 2.0 to 10.0, and the cross-sectional area is Non-circular cross-section glass fibers (B-1 component) with a fiber diameter in the range of 3.0 to 35.0 μm when converted to a perfect circle, and (B-2) glass fibers with an average fiber diameter of 7.0 to 13.0 μm. The polycarbonate resin composition according to claim 1, characterized in that the polycarbonate resin composition is one or more glass fibers selected from the group consisting of circular cross-section glass fibers (component B-2) within the following range. The B component is 52.0 to 57.0% by weight of SiO ₂ , 13.0 to 17.0% by weight of Al ₂ O ₃ , 15.0 to 21.5% by weight of B ₂ O ₃ , 2.0 to 2.0% by weight 6.0 wt% MgO, 2.0-6.0 wt% CaO, 1.0-4.0 wt% _TiO2 and less than 1.5 wt% _F2 , and _Li2 The polycarbonate resin composition according to claim 1 or 2, characterized in that the polycarbonate resin composition is glass fiber in which the total amount of O, Na ₂ O and K ₂ O is less than 0.6% by weight. The polycarbonate resin composition according to any one of claims 1 to 3, wherein the aromatic polycarbonate resin other than component A-1 has a viscosity average molecular weight of 10,000 to 16,000. The polycarbonate resin composition according to any one of claims 1 to 4, wherein component C is a polybutylene terephthalate resin having a terminal carboxyl group content of 40 eq/g or more. The polycarbonate resin composition according to any one of claims 1 to 5, containing 0.01 to 1 part by weight of (D) a phosphorus compound (component D) per 100 parts by weight of component A. 7. The polycarbonate resin composition according to claim 6, wherein component D is a phosphoric acid ester compound having a number average molecular weight of 50 to 300.