JP6766709B2 - Polycarbonate resin composition and its molded product - Google Patents

Description

The present invention relates to a polycarbonate resin composition and a molded product thereof. Specifically, the present invention has excellent transparency and flame retardancy without impairing mechanical properties such as excellent impact resistance of the polycarbonate resin, does not cause a problem of white turbidity of the molded product, and has moisture and heat resistance. The present invention relates to a polycarbonate resin composition excellent in the above, and a molded product obtained by molding this polycarbonate resin composition.

Polycarbonate resin is widely used in the fields of various parts of electric / electronic / OA equipment, automobile parts, building materials, medical applications, miscellaneous goods, etc. as a resin having excellent mechanical strength, heat resistance, transparency and the like. In particular, the flame-retardant polycarbonate resin is suitably used in the fields of electrical, electronic, and OA equipment such as computers, electronic books, mobile phones, and printers.

Conventionally, as a flame-retardant polycarbonate resin composition, a composition in which a bromine-based flame retardant or a phosphorus-based flame retardant is blended with a polycarbonate resin is known.
However, the polycarbonate resin composition containing a brominated flame retardant may cause a decrease in thermal stability and may cause corrosion of a screw of a molding machine or a molding die during a molding process. In addition, the polycarbonate resin composition containing a phosphorus-based flame retardant inhibits the high transparency characteristic of the polycarbonate resin and causes deterioration of impact resistance and heat resistance, so that its use may be limited. there were.

In recent years, many metal salt compounds typified by organic alkali metal salt compounds have been studied as useful flame retardants. Conventionally, as an organic metal salt-based flame retardant applied to a polycarbonate resin, an alkali metal salt of perfluoroalkyl sulfonic acid having 4 to 8 carbon atoms (Patent Document 1) and perfluoroalkane sulfonic acid having 1 to 3 carbon atoms have been used. Alkane metal salt compounds of perfluoroalkane sulfonic acid such as the alkali metal salt of (Patent Document 2) are used.

When an organometallic salt compound is used as a flame retardant, the effect of imparting flame retardancy can be obtained with a relatively small amount, and the properties such as impact resistance and other mechanical properties, heat resistance, and electrical properties inherent in the polycarbonate resin are impaired. It is possible to impart flame retardancy without using it. However, among these metal salt compounds, organometallic salt compounds such as perfluorobutane sulfonic acid metal salt, which are known to have a particularly high flame retardancy-imparting effect, are basically hydrophilic and have a phase with a polycarbonate resin. Inferior in solubility. If the compatibility between the flame retardant and the polycarbonate resin is low, the haze becomes large, which limits its use in products that require high transparency.
Further, in the case of the organometallic salt compound, even if the amount of the flame retardant added is increased in order to enhance the flame retardant effect, the haze deteriorates and the amount cannot be increased.
Further, there is also a problem that hydrophilic organometallic salt compounds aggregate and become cloudy in a thick portion that is slowly cooled during injection molding. In addition, these organometallic salt compounds are susceptible to hydrolysis under high temperature and high humidity, and there is also a problem that the moisture and heat resistance of the polycarbonate resin composition is lowered.

In addition, Patent Document 3 contains a specific phosphonium salt and a perfluoroalkyl sulfonate as a polycarbonate resin composition which is excellent in transparency, antistatic property, etc. and can be a molded product exhibiting flame retardancy. However, the polycarbonate resin composition described here has a problem of inhibiting the flame-retardant effect of the perfluoroalkyl sulfonate.

Special Publication No. 47-40445 Special Publication No. 54-32456 Japanese Unexamined Patent Publication No. 2014-156536

The present invention is a polycarbonate having excellent transparency and flame retardancy without impairing mechanical properties such as excellent impact resistance of a polycarbonate resin, having no problem of white turbidity of a molded product, and having excellent moisture and heat resistance. An object of the present invention is to provide a resin composition and a molded product obtained by molding the polycarbonate resin composition.

As a result of repeated studies to solve the above problems, the present inventor has added an organic ammonium salt as a compatibilizer for improving the compatibility of the metal salt flame retardant with the polycarbonate resin, thereby achieving transparency and difficulty. It has been found that a polycarbonate resin composition having excellent flammability, no problem of cloudiness, and excellent moisture and heat resistance can be obtained.

The present invention has been achieved based on such findings, and the gist of the present invention is as follows.

[1] With respect to 100 parts by mass of the polycarbonate resin (A), 0.01 parts by mass or more and 0.2 parts by mass or less of the organic sulfonic acid alkali metal salt (B) and 0.05 parts by mass or more of the organic ammonium salt (C) and 0. A polycarbonate resin composition containing less than 5 parts by mass.

[2] The polycarbonate resin composition according to [1], wherein the organic sulfonic acid alkali metal salt is a perfluoroalkane sulfonic acid alkali metal salt.

[3] The polycarbonate resin composition according to [1] or [2], wherein the organic ammonium salt (C) is a fluorine-containing organic ammonium salt represented by the following formula (1).
[(R ¹ ) ₃ R ² N] ⁺ · (R ³ SO ₂ ) (R ⁴ SO ₂ ) N ⁻ … (1)
(In the formula, R ¹ represents an alkyl group having 1 to 4 carbon atoms, R ² represents an alkyl group having 1 to 20 carbon atoms, and R ³ and R ⁴ independently represent perfluoroalkyl groups having 1 to 4 carbon atoms. Indicates a group.)

[4] In any of [1] to [3], the content mass ratio of the organic ammonium salt (C) to the organic sulfonic acid alkali metal salt (B) (organic ammonium salt (C) / organic sulfonic acid alkali metal salt ( B)) is a polycarbonate resin composition having a value of 0.8 to 8.

[5] A molded product obtained by molding the polycarbonate resin composition according to any one of [1] to [4].

According to the present invention, a polycarbonate resin having excellent flame retardancy without impairing mechanical properties such as excellent impact resistance of the polycarbonate resin, having no problem of white turbidity of a molded product, and having excellent moisture and heat resistance. The composition is provided. The polycarbonate resin composition of the present invention is excellent in the original transparency and mechanical properties of the polycarbonate resin, as well as in flame retardancy and moisture heat resistance, and is excellent in various parts of electric, electronic and OA equipment, especially a cover of a liquid crystal screen. It is useful in a wide range of fields such as covers for electronic circuit boards, automobile parts, building materials, medical applications, and miscellaneous goods.

Embodiments of the present invention will be described in detail below.

[Polycarbonate resin composition]
The polycarbonate resin composition of the present invention contains 0.01 parts by mass or more and 0.2 parts by mass or less of the organic sulfonic acid alkali metal salt (B) and the organic ammonium salt (C) 0. It is characterized by containing 05 parts by mass or more and less than 0.5 parts by mass.

[mechanism]
According to the present invention, by blending the organic ammonium salt (C) together with the organic sulfonic acid alkali metal salt (B), the problems of cloudiness and deterioration of moisture heat resistance due to the organic sulfonic acid alkali metal salt (B) can be alleviated. Can be done. Although the details of this action and effect by the organic ammonium salt (C) are not clear, the organic sulfonic acid alkali metal salt (B) and the organic ammonium salt (C) form a complex in the polycarbonate composition, and the organic sulfonic acid alkali It is considered that this is due to the problem of cloudiness due to the aggregation of the metal salt (B) and the suppression of the hydrolysis of the organic sulfonic acid alkali metal salt (B) under high temperature and humidity.

[Polycarbonate resin (A)]
The type of the polycarbonate resin (A) used in the present invention is not limited, and one type of the polycarbonate resin may be used, or two or more types may be used in any combination and in any ratio.

The polycarbonate resin is a polymer having a basic structure having a carbonic acid bond represented by the formula:-[-O-X-OC (= O)-]-. In the formula, X is generally a hydrocarbon, but X having a heteroatom or a heterobond introduced may be used to impart various properties.

Further, the polycarbonate resin can be classified into an aromatic polycarbonate resin in which the carbon directly bonded to the carbonic acid bond is an aromatic carbon and an aliphatic polycarbonate resin in which the carbon is an aliphatic carbon, and any of them can be used. Of these, aromatic polycarbonate resins are preferable from the viewpoints of heat resistance, mechanical properties, electrical properties, and the like.

The specific type of the polycarbonate resin (A) is not limited, and examples thereof include a polycarbonate polymer obtained by reacting a dihydroxy compound with a carbonate precursor. At this time, in addition to the dihydroxy compound and the carbonate precursor, a polyhydroxy compound or the like may be reacted. Further, a method of reacting carbon dioxide with cyclic ether using carbon dioxide as a carbonate precursor may also be used. Further, the polycarbonate polymer may be linear or branched. Further, the polycarbonate polymer may be a copolymer composed of one type of repeating unit or a copolymer having two or more types of repeating units. At this time, as the copolymer, various copolymer forms such as a random copolymer and a block copolymer can be selected. Usually, such a polycarbonate polymer becomes a thermoplastic resin.

Among the monomers used as raw materials for aromatic polycarbonate resins, examples of aromatic dihydroxy compounds include

Dihydroxybenzenes such as 1,2-dihydroxybenzene, 1,3-dihydroxybenzene (ie resorcinol), 1,4-dihydroxybenzene;
Dihydroxybiphenyls such as 2,5-dihydroxybiphenyl, 2,2'-dihydroxybiphenyl, 4,4'-dihydroxybiphenyl;

2,2'-Dihydroxy-1,1'-binaphthyl, 1,2-dihydroxynaphthalene, 1,3-dihydroxynaphthalene, 2,3-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, 1 , 7-Dihydroxynaphthalene, 2,7-dihydroxynaphthalene and other dihydroxynaphthalene;

2,2'-Dihydroxydiphenyl ether, 3,3'-dihydroxydiphenyl ether, 4,4'-dihydroxydiphenyl ether, 4,4'-dihydroxy-3,3'-dimethyldiphenyl ether, 1,4-bis (3-hydroxyphenoxy) Dihydroxydiaryl ethers such as benzene and 1,3-bis (4-hydroxyphenoxy) benzene;

2,2-bis (4-hydroxyphenyl) propane (ie, bisphenol A),
1,1-bis (4-hydroxyphenyl) propane,
2,2-Bis (3-methyl-4-hydroxyphenyl) propane,
2,2-Bis (3-methoxy-4-hydroxyphenyl) propane,
2- (4-Hydroxyphenyl) -2- (3-methoxy-4-hydroxyphenyl) propane,
1,1-bis (3-tert-butyl-4-hydroxyphenyl) propane,
2,2-Bis (3,5-dimethyl-4-hydroxyphenyl) propane,
2,2-Bis (3-cyclohexyl-4-hydroxyphenyl) propane,
2- (4-Hydroxyphenyl) -2- (3-cyclohexyl-4-hydroxyphenyl) propane,
α, α'-bis (4-hydroxyphenyl) -1,4-diisopropylbenzene,
1,3-bis [2- (4-hydroxyphenyl) -2-propyl] benzene,
Bis (4-hydroxyphenyl) methane,
Bis (4-hydroxyphenyl) cyclohexylmethane,
Bis (4-hydroxyphenyl) phenylmethane,
Bis (4-hydroxyphenyl) (4-propenylphenyl) methane,
Bis (4-hydroxyphenyl) diphenylmethane,
Bis (4-hydroxyphenyl) naphthylmethane,
1,1-bis (4-hydroxyphenyl) ethane,
1,1-bis (4-hydroxyphenyl) -1-phenylethane,
1,1-bis (4-hydroxyphenyl) -1-naphthylethane,
1,1-bis (4-hydroxyphenyl) butane,
2,2-bis (4-hydroxyphenyl) butane,
2,2-bis (4-hydroxyphenyl) pentane,
1,1-bis (4-hydroxyphenyl) hexane,
2,2-bis (4-hydroxyphenyl) hexane,
1,1-bis (4-hydroxyphenyl) octane,
2,2-bis (4-hydroxyphenyl) octane,
4,4-Bis (4-hydroxyphenyl) heptane,
2,2-bis (4-hydroxyphenyl) nonane,
1,1-bis (4-hydroxyphenyl) decane,
1,1-bis (4-hydroxyphenyl) dodecane,
Bis (hydroxyaryl) alkanes such as;

1,1-bis (4-hydroxyphenyl) cyclopentane,
1,1-bis (4-hydroxyphenyl) cyclohexane,
1,1-bis (4-hydroxyphenyl) -3,3-dimethylcyclohexane,
1,1-bis (4-hydroxyphenyl) -3,4-dimethylcyclohexane,
1,1-bis (4-hydroxyphenyl) -3,5-dimethylcyclohexane,
1,1-bis (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane,
1,1-bis (4-hydroxy-3,5-dimethylphenyl) -3,3,5-trimethylcyclohexane,
1,1-bis (4-hydroxyphenyl) -3-propyl-5-methylcyclohexane, 1,1-bis (4-hydroxyphenyl) -3-tert-butyl-cyclohexane,
1,1-bis (4-hydroxyphenyl) -4-tert-butyl-cyclohexane,
1,1-bis (4-hydroxyphenyl) -3-phenylcyclohexane,
1,1-bis (4-hydroxyphenyl) -4-phenylcyclohexane,
Bis (hydroxyaryl) cycloalkanes such as;

9,9-bis (4-hydroxyphenyl) fluorene,
Cardo-structure-containing bisphenols such as 9,9-bis (4-hydroxy-3-methylphenyl) fluorene;

4,4'-Dihydroxydiphenylsulfide,
Dihydroxydiarylsulfides such as 4,4'-dihydroxy-3,3'-dimethyldiphenylsulfide;

Dihydroxydiarylsulfoxides such as 4,4'-dihydroxydiphenylsulfoxide, 4,4'-dihydroxy-3,3'-dimethyldiphenylsulfoxide;

4,4'-Dihydroxydiphenyl sulfone,
Dihydroxydiaryl sulfones such as 4,4'-dihydroxy-3,3'-dimethyldiphenyl sulfone;
And so on.

Among these, bis (hydroxyaryl) alkanes are preferable, and bis (4-hydroxyphenyl) alkanes are particularly preferable, and 2,2-bis (4-hydroxyphenyl) propane (particularly from the viewpoint of impact resistance and heat resistance). That is, bisphenol A) is preferable.
As the aromatic dihydroxy compound, one type may be used, or two or more types may be used in any combination and ratio.

Among the monomers used as raw materials for the polycarbonate resin, carbonyl halide, carbonate ester and the like are used as an example of the carbonate precursor. As the carbonate precursor, one kind may be used, or two or more kinds may be used in any combination and ratio.

Specific examples of the carbonyl halide include phosgene; a bischloroformate of a dihydroxy compound, and a haloformate such as a monochloroformate of a dihydroxy compound.

Specific examples of the carbonate ester include diaryl carbonates such as diphenyl carbonate and ditril carbonate; dialkyl carbonates such as dimethyl carbonate and diethyl carbonate; biscarbonate of dihydroxy compound, monocarbonate of dihydroxy compound, and cyclic carbonate. Examples thereof include carbonates of dihydroxy compounds such as.

Method for Producing Polycarbonate Resin The method for producing the polycarbonate resin is not particularly limited, and any method can be adopted. Examples thereof include an interfacial polymerization method, a melting method, a pyridine method, a ring-opening polymerization method of a cyclic carbonate compound, and a solid phase transesterification method of a prepolymer.
Hereinafter, particularly suitable of these methods will be specifically described.

Interfacial polymerization method First, a case where the polycarbonate resin is produced by the interfacial polymerization method will be described.
In the interfacial polymerization method, the pH is usually maintained at 9 or higher in the presence of an organic solvent inert to the reaction and an aqueous alkaline solution, and the dihydroxy compound is reacted with a carbonate precursor (preferably phosgene), and then the polymerization catalyst is used. A polycarbonate resin is obtained by performing interfacial polymerization in the presence. If necessary, a molecular weight modifier (terminal terminator) may be present in the reaction system, or an antioxidant may be present to prevent the oxidation of the dihydroxy compound.

The dihydroxy compound and carbonate precursor are as described above. It is preferable to use phosgene among the carbonate precursors, and the method using phosgene is particularly called a phosgene method.

Examples of the organic solvent inert to the reaction include chlorinated hydrocarbons such as dichloromethane, 1,2-dichloroethane, chloroform, monochlorobenzene and dichlorobenzene; and aromatic hydrocarbons such as benzene, toluene and xylene. Be done. As the organic solvent, one type may be used, or two or more types may be used in any combination and ratio.

Examples of the alkaline compound contained in the alkaline aqueous solution include alkali metal compounds such as sodium hydroxide, potassium hydroxide, lithium hydroxide and sodium hydrogen carbonate, and alkaline earth metal compounds. Among them, sodium hydroxide and water. Potassium oxide is preferred. As the alkaline compound, one type may be used, or two or more types may be used in any combination and ratio.

The concentration of the alkaline compound in the alkaline aqueous solution is not limited, but is usually used in an amount of 5 to 10% by mass in order to control the pH of the reaction in the alkaline aqueous solution to 10 to 12. Further, for example, when phosgene is blown, the molar ratio of the bisphenol compound to the alkaline compound is usually 1: 1.9 or more in order to control the pH of the aqueous phase to be 10 to 12, preferably 10 to 11. Above all, it is preferably 1: 2.0 or more, and usually 1: 3.2 or less, and above all, 1: 2.5 or less.

Examples of the polymerization catalyst include aliphatic tertiary amines such as trimethylamine, triethylamine, tributylamine, tripropylamine and trihexylamine; and alicyclic such as N, N'-dimethylcyclohexylamine and N, N'-diethylcyclohexylamine. Formula tertiary amines; aromatic tertiary amines such as N, N'-dimethylaniline, N, N'-diethylaniline; quaternary ammonium salts such as trimethylbenzylammonium chloride, tetramethylammonium chloride, triethylbenzylammonium chloride, etc. ; Ppyridine; guanine; salt of guanidine; and the like. As the polymerization catalyst, one type may be used, or two or more types may be used in any combination and ratio.

Examples of the molecular weight modifier include aromatic phenols having a monovalent phenolic hydroxyl group; fatty alcohols such as methanol and butanol; mercaptan; phthalic acid imide, and the like, among which aromatic phenols are preferable. Specific examples of such aromatic phenols include alkyl groups such as m-methylphenol, p-methylphenol, m-propylphenol, p-propylphenol, p-tert-butylphenol, and p-long chain alkyl-substituted phenol. Substituted phenols; vinyl group-containing phenols such as isopropenylphenol; epoxy group-containing phenols; carboxyl group-containing phenols such as o-hydroxybenzoic acid and 2-methyl-6-hydroxyphenylacetic acid; and the like. As the molecular weight adjusting agent, one type may be used, or two or more types may be used in any combination and ratio.

The amount of the molecular weight modifier used is usually 0.5 mol or more, preferably 1 mol or more, and usually 50 mol or less, preferably 30 mol or less, based on 100 mol of the dihydroxy compound. By setting the amount of the molecular weight adjusting agent used in this range, the thermal stability and hydrolysis resistance of the resin composition can be improved.

At the time of the reaction, the order in which the reaction substrate, reaction medium, catalyst, additives and the like are mixed is arbitrary as long as a desired polycarbonate resin can be obtained, and an appropriate order may be set arbitrarily. For example, when phosgene is used as the carbonate precursor, the molecular weight modifier can be mixed at any time between the time of the reaction (phosgenation) between the dihydroxy compound and phosgene and the start of the polymerization reaction.
The reaction temperature is usually 0 to 40 ° C., and the reaction time is usually several minutes (for example, 10 minutes) to several hours (for example, 6 hours).

Melting Method Next, a case where the polycarbonate resin is produced by the melting method will be described.
The melting method is also referred to as a transesterification method, and for example, a transesterification reaction between a carbonic acid diester and a dihydroxy compound is performed.

The dihydroxy compound is as described above.
On the other hand, examples of the carbonic acid diester include dialkyl carbonate compounds such as dimethyl carbonate, diethyl carbonate and di-tert-butyl carbonate; diphenyl carbonate; and substituted diphenyl carbonate such as ditril carbonate. Of these, diphenyl carbonate and substituted diphenyl carbonate are preferable, and diphenyl carbonate is particularly preferable. In addition, 1 type of carbonic acid diester may be used, and 2 or more types may be used in arbitrary combination and ratio.

The ratio of the dihydroxy compound to the carbonic acid diester is arbitrary as long as a desired polycarbonate resin can be obtained, but it is preferable to use an equimolar amount or more of the carbonic acid diester with respect to 1 mol of the dihydroxy compound, and 1.01 mol or more is particularly used. Is more preferable. The upper limit is usually 1.30 mol or less. By setting the range to such a range, the amount of terminal hydroxyl groups can be adjusted to a suitable range.

In polycarbonate resin, the amount of terminal hydroxyl groups tends to have a great influence on thermal stability, hydrolysis stability, color tone and the like. Therefore, the amount of terminal hydroxyl groups may be adjusted as necessary by any known method. In the transesterification reaction, usually, a polycarbonate resin having an adjusted amount of terminal hydroxyl groups can be obtained by adjusting the mixing ratio of the carbonic acid diester and the aromatic dihydroxy compound; the degree of reduced pressure during the transesterification reaction. By this operation, the molecular weight of the normally obtained polycarbonate resin can also be adjusted.

When the mixing ratio of the carbonic acid diester and the dihydroxy compound is adjusted to adjust the amount of terminal hydroxyl groups, the mixing ratio is as described above.
Further, as a more aggressive adjustment method, a method of separately mixing a terminal terminator at the time of reaction can be mentioned. Examples of the terminal terminator at this time include monohydric phenols, monovalent carboxylic acids, and carbonic acid diesters. In addition, as the terminal terminator, 1 type may be used, and 2 or more types may be used in arbitrary combination and ratio.

When producing a polycarbonate resin by the melting method, a transesterification catalyst is usually used. Any transesterification catalyst can be used. Among them, for example, it is preferable to use an alkali metal compound and / or an alkaline earth metal compound. Alternatively, a basic compound such as a basic boron compound, a basic phosphorus compound, a basic ammonium compound, or an amine compound may be used in combination. As the transesterification catalyst, one type may be used, or two or more types may be used in any combination and ratio.

In the melting method, the reaction temperature is usually 100 to 320 ° C. The pressure during the reaction is usually a reduced pressure condition of 2 mmHg or less. As a specific operation, the melt polycondensation reaction may be carried out under the above conditions while removing by-products such as aromatic hydroxy compounds.

The melt polycondensation reaction can be carried out by either a batch method or a continuous method. In the case of batch method, the order of mixing the reaction substrate, reaction medium, catalyst, additives and the like is arbitrary as long as a desired aromatic polycarbonate resin can be obtained, and an appropriate order may be set arbitrarily. However, above all, considering the stability of the polycarbonate resin and the like, it is preferable to carry out the melt polycondensation reaction in a continuous manner.

In the melting method, a catalytic deactivator may be used if necessary. As the catalyst deactivator, a compound that neutralizes the transesterification catalyst can be arbitrarily used. Examples thereof include sulfur-containing acidic compounds and derivatives thereof. As the catalyst deactivator, one type may be used, or two or more types may be used in combination in any combination and ratio.

The amount of the catalyst deactivator used is usually 0.5 equivalents or more, preferably 1 equivalent or more, and usually 10 equivalents or less, relative to the alkali metal or alkaline earth metal contained in the transesterification catalyst. It is preferably 5 equivalents or less. Further, it is usually 1 ppm or more, and usually 100 ppm or less, preferably 20 ppm or less, with respect to the polycarbonate resin.

In the present invention, the polycarbonate resin (A) is preferably 20 to 100% by mass, more preferably 30 to 100% by mass, further 40 to 100% by mass, and particularly preferably 50 to 100% by mass of the polycarbonate resin (A). However, it is preferable that the polycarbonate resin has a branched structure. Having a polycarbonate resin having a branched structure is preferable because the flame retardancy is further improved. As the polycarbonate resin having a branched structure, the above-mentioned melted polycarbonate resin and / or a polycarbonate resin containing a branching agent is preferable.
The molten polycarbonate resin tends to generate branched structural units as a side reaction.

The polycarbonate resin containing a branching agent can be produced by a method of blending a branching agent when it is produced by the above-mentioned interface method or melting method according to a conventional method. As the branching agent, a trifunctional or higher functional compound is preferably used.

Examples of the trifunctional or higher polyfunctional compound include 1,3,5-trihydroxybenzene, 4,6-dimethyl-2,4,6-tri (4-hydroxyphenyl) heptene-2,4,6-. Dimethyl-2,4,6-tri (4-hydroxyphenyl) heptane, 2,6-dimethyl-2,4,6-tri (4-hydroxyphenyl) heptene-3,1,3,5-tri (4-) Polyhydroxy compounds such as hydroxyphenyl) benzene, 1,1,1-tri (4-hydroxyphenyl) ethane; 3,3-bis (4-hydroxyaryl) oxyindole (ie, isatin bisphenol), Examples thereof include 5-chloroisatin, 5,7-dichloroisatin and 5-bromuisatin. Of these, 1,1,1-tri (4-hydroxyphenyl) ethane is preferable.

Such a polyfunctional compound may be used as a part of the dihydroxy compound, and the amount used thereof is preferably 0.01 to 5 mol%, more preferably 0.1 to 2 mol% with respect to the hydroxy compound. %, More preferably 0.1 to 1 mol%.
As the polyfunctional compound, one type may be used, or two or more types may be used in any combination and ratio.

As the polycarbonate resin having a branched structure, the ratio (mol%) of the total number of moles of the branched structural units to 1 mol of the structural units represented by the following formula (I) exceeds 0.3 mol% and 0.95 mol% or less. It is preferably within the range of. Within such a range, flame retardancy can be further improved. If the relationship between Mw / Mn and Mv / Mn'and the degree of branching is smaller than the above range, the melting tension cannot be obtained, the target branched aromatic polycarbonate having excellent melting characteristics cannot be produced, and the branching aromatic polycarbonate cannot be produced. If it is larger than the above range, the melt tension is too large, the fluidity is inferior, and it tends to be impossible to produce the target branched aromatic polycarbonate having excellent melt characteristics.

In the formula (I), X is synonymous with X of the above-mentioned basic structure of the polycarbonate resin:-[-O-X-OC (= O)-]-.

The branched structural unit is typically a structural unit represented by the following equation.

The molecular weight of the polycarbonate resin (A) may be appropriately selected and determined, but the viscosity average molecular weight [Mv] converted from the solution viscosity is preferably 5,000 or more, more preferably 10,000 or more, still more preferably 10,000 or more. It is 15,000 or more, preferably 70,000 or less, more preferably 40,000 or less, still more preferably 35,000 or less, and particularly preferably 31,000 or less. By setting the viscosity average molecular weight to be equal to or higher than the lower limit of the above range, the mechanical strength of the polycarbonate resin composition of the present invention can be further improved, which is more preferable when used in applications with high mechanical strength requirements. On the other hand, by setting the viscosity average molecular weight to less than the upper limit of the above range, it is possible to suppress and improve the decrease in fluidity of the polycarbonate resin composition of the present invention, improve the molding processability, and facilitate the molding process.

As the polycarbonate resin (A), two or more types of polycarbonate resins having different viscosity average molecular weights may be mixed and used. Further, when adjusting the viscosity average molecular weight of the polycarbonate resin (A) to the above-mentioned preferable range, it is also preferable to mix and adjust the polycarbonate resin whose Mv is outside the above-mentioned preferable range.

In the present invention, the viscosity average molecular weight [Mv] of the polycarbonate resin is the ultimate viscosity [η] (unit: dl / g) at a temperature of 20 ° C. using methylene chloride as a solvent and using an Ubbelohde viscometer. In formula (i) (in the formula, ηsp is the specific viscosity of the methylene chloride solution of the polycarbonate resin measured at 20 ° C., and C is the concentration of the methylene chloride solution. The methylene chloride solution has a concentration of 0.6 g / dl of the polycarbonate resin. Use the one.)
_{η sp /C=[η]×(1+0.28η sp) ... (i} )
It is a value calculated from the viscosity formula of Schnell of the following formula (ii).
η = 1.23 × 10 ^-4 Mv ^0.83 … (ii)

The polycarbonate resin (A) is a mixture of a polycarbonate resin (a1) having a viscosity average molecular weight of 3,000 to 40,000 and a polycarbonate resin (a2) having a viscosity average molecular weight of 50,000 to 95,000. In this case, the ratio of (a1) and (a2) is preferably 50 to 99% by mass for (a1) and 1 to 50% by mass for (a2) based on a total of 100% by mass of both.

The viscosity average molecular weight of the polycarbonate resin (a1) is more preferably 4,000 or more, still more preferably 5,000 or more, particularly preferably 10,000 or more, most preferably 15,000 or more, and more preferably. It is 37,000 or less, more preferably 35,000 or less, particularly preferably 33,000 or less, and particularly preferably 31,000 or less.
The viscosity average molecular weight of the polycarbonate resin (a2) is more preferably 55,000 or more, further preferably 60,000 or more, still more preferably 85,000 or less, still more preferably 80,000 or less. In particular, 70,000 or less is preferable.

The difference in viscosity average molecular weight between the polycarbonate resin (a1) and the polycarbonate resin (a2) is preferably 30,000 or more, more preferably 35,000 or more, still more preferably 40,000 or more, particularly 45, It is preferably 000 or more. Such a difference in viscosity average molecular weight is preferable because the fluidity of the resin composition can be increased and a large molded product can be molded without difficulty.

The ratio of the polycarbonate resin (a1) and the polycarbonate resin (a2) is based on a total of 100% by mass of the polycarbonate resin (a1) and (a2), and the polycarbonate resin (a2) is more preferably 20 to 50% by mass, and further. It is preferably 25 to 50% by mass, and particularly preferably 30 to 45% by mass.

The terminal hydroxyl group concentration of the polycarbonate resin is arbitrary and may be appropriately selected and determined, but is usually 1000 ppm or less, preferably 800 ppm or less, and more preferably 600 ppm or less. Thereby, the retention heat stability and the color tone of the polycarbonate resin can be further improved. Further, the lower limit thereof is usually 10 ppm or more, preferably 30 ppm or more, and more preferably 40 ppm or more, particularly for a polycarbonate resin produced by a melting method. As a result, it is possible to suppress a decrease in molecular weight and further improve the mechanical properties of the resin composition.

The unit of the terminal hydroxyl group concentration is the mass of the terminal hydroxyl group expressed in ppm with respect to the mass of the polycarbonate resin. The measuring method is colorimetric quantification by the titanium tetrachloride / acetic acid method (the method described in Macromol. Chem. 88 215 (1965)).

The polycarbonate resin (A) is not limited to a mode containing only one type of polycarbonate resin, and includes, for example, a mode containing a plurality of types of polycarbonate resins having different monomer compositions and molecular weights. It may be used in a sense (), or it may be used in combination with an alloy (mixture) of a polycarbonate resin and another thermoplastic resin. Further, for example, a polycarbonate resin is a copolymer of an oligomer or a polymer having a siloxane structure for the purpose of further improving flame retardancy and impact resistance; a phosphorus atom for the purpose of further improving thermal oxidation stability and flame retardancy. Copolymer with a monomer, oligomer or polymer having a dihydroxyanthraquinone structure; a copolymer with a monomer, oligomer or polymer having a dihydroxyanthraquinone structure for the purpose of improving thermal oxidation stability; polystyrene or the like to improve the optical properties. Even if it is configured as a copolymer mainly composed of a polycarbonate resin, such as a copolymer with an oligomer or a polymer having an olefin structure; a copolymer with a polyester resin oligomer or a polymer for the purpose of improving chemical resistance; Good.

Further, in order to improve the appearance and fluidity of the molded product, the polycarbonate resin (A) may contain a polycarbonate oligomer. The viscosity average molecular weight [Mv] of this polycarbonate oligomer is usually 1,500 or more, preferably 2,000 or more, and usually 9,500 or less, preferably 9,000 or less. Further, the contained polycarbonate ligomer is preferably 30% by mass or less of the polycarbonate resin (including the polycarbonate oligomer).

Further, the polycarbonate resin may be not only a virgin raw material but also a polycarbonate resin recycled from a used product (so-called material recycled polycarbonate resin).
However, the regenerated polycarbonate resin is preferably 80% by mass or less, and more preferably 50% by mass or less of the polycarbonate resin. Since the regenerated polycarbonate resin is likely to be deteriorated by heat deterioration, aging deterioration, etc., if such a polycarbonate resin is used in a larger amount than the above range, the hue and mechanical properties can be deteriorated. Because there is sex.

<Organic sulfonic acid alkali metal salt (B)>
In the present invention, the organic sulfonic acid alkali metal salt (B) is used as the flame retardant.

The metal salt is effective in improving the flame retardancy of the polycarbonate resin composition, but among the metal salts, the organic metal salt is particularly preferable in terms of dispersibility in the aromatic polycarbonate resin, and among the organic metal salts, the organic metal salt is preferable. The organic sulfonic acid alkali metal salt (B) is most preferable in that it is excellent in thermal stability when blended with the polycarbonate resin (A).

Examples of the alkali metal of the organic sulfonic acid alkali metal salt (B) include lithium (Li), sodium (Na), potassium (K), rubidium (Rb), and cesium (Cs). Among them, in particular, the formation of a carbide layer during combustion of the polycarbonate resin composition of the present invention can be promoted, the flame retardancy can be further enhanced, and the mechanical properties such as impact resistance and heat resistance of the polycarbonate resin (A) can be improved. Sodium, potassium, and cesium are preferable because they can maintain good properties such as physical properties and electrical properties. That is, examples of the organic sulfonic acid alkali metal salt (B) include an organic sulfonic acid lithium (Li) salt, an organic sulfonic acid sodium (Na) salt, an organic sulfonic acid potassium (K) salt, and an organic sulfonic acid rubidium (Rb) salt. Examples thereof include cesium (Cs) organic sulfonate, and among these, sodium (Na) organic sulfonate, potassium (K) organic sulfonate, and cesium (Cs) organic sulfonate are particularly preferable.

Among the organic sulfonic acid alkali metal salts (B), examples of preferable ones include perfluoroalkane sulfonic acid alkali metal salts. The perfluoroalkanesulfonic acid alkali metal salt preferably has 1 to 8 carbon atoms of alkane, particularly 1 to 4, and specifically, perfluoro (nonafluoro) potassium butanesulfonate and perfluoro (nonafluoro). Lithium butane sulfonate, sodium perfluoro (nonafluoro) butane sulfonate, cesium perfluoro (nonafluoro) butane sulfonate, potassium perfluoro (pentafluoro) ethane sulfonate, lithium perfluoro (pentafluoro) ethane sulfonate, perfluoro ( Sodium pentafluoro) ethanesulfonate, cesium perfluoro (pentafluoro) ethanesulfonate, potassium perfluoro (trifluoro) methanesulfonate, lithium perfluoro (trifluoro) methanesulfonate, perfluoro (trifluoro) methanesulfonic acid Examples thereof include sodium and cesium perfluoro (trifluoro) methanesulfonate.

Among the above-mentioned examples, potassium perfluorobutanesulfonate, potassium perfluoromethanesulfonate and the like are preferable.

As the organic sulfonic acid alkali metal salt (B), only one type may be used, or two or more types may be mixed and used.

The content of the organic sulfonic acid alkali metal salt (B) in the polycarbonate resin composition of the present invention is 0.01 part by mass or more and 0.2 part by mass or less, preferably 0, with respect to 100 parts by mass of the polycarbonate resin (A). .05 to 0.15 parts by mass, more preferably 0.05 to 0.1 parts by mass. If the content of the organic sulfonic acid alkali metal salt (B) is less than the above lower limit, the effect of improving flame retardancy cannot be sufficiently obtained, and if it exceeds the above upper limit, the transparency is lowered, which is not preferable.

<Organic ammonium salt (C)>
As the organic ammonium salt (C) used in the present invention, a fluorine-containing organic ammonium salt represented by the following formula (1) is particularly preferable.

[(R ¹ ) ₃ R ² N] ⁺ · (R ³ SO ₂ ) (R ⁴ SO ₂ ) N ⁻ … (1)
(In the formula, R ¹ represents an alkyl group having 1 to 4 carbon atoms, R ² represents an alkyl group having 1 to 20 carbon atoms, and R ³ and R ⁴ independently represent perfluoroalkyl groups having 1 to 4 carbon atoms. Indicates a group.)

Among the fluorine-containing organic ammonium salts represented by the above formula (1), the bis (perfluoromethanesulfonylimide) methyltributylammonium salt (1,1,1-tributyl-1-methyl) represented by the following formula (1A) is particularly effective. Ammonium = bis (trifluoromethanesulfonyl) imide) can be preferably used.

As the organic ammonium salt (C), only one kind may be used, or two or more kinds may be mixed and used.

The content of the organic ammonium salt (C) in the polycarbonate resin composition of the present invention is 0.05 or more and less than 0.5 parts by mass, preferably 0.05 to 0 parts by mass with respect to 100 parts by mass of the polycarbonate resin (A). It is 45 parts by mass, more preferably 0.08 to 0.4 parts by mass, further preferably 0.12 to 0.35 parts by mass, and particularly preferably 0.2 to 0.35 parts by mass. If the content of the organic ammonium salt (C) is less than the above lower limit, the effect of preventing white turbidity and the effect of improving the moist heat resistance cannot be sufficiently obtained, and if it exceeds the above upper limit, the flame retardancy is lowered, which is not preferable.

<Mass ratio of organic sulfonic acid alkali metal salt (B) and organic ammonium salt (C)>
The polycarbonate resin composition of the present invention does not impair the flame retardancy improving effect of the organic sulfonic acid alkali metal salt (B), and causes cloudiness and moisture resistance of the molded product due to the organic sulfonic acid alkali metal salt (B). From the viewpoint of effectively preventing the problem of heat deterioration in the formulation of the organic ammonium salt (C), the mass ratio of the organic ammonium salt (C) to the organic sulfonic acid alkali metal salt (B) in the polycarbonate resin composition (organic ammonium). The salt (C) / organic sulfonic acid alkali metal salt (B)) is preferably 0.8 to 8, more preferably 1 to 7, still more preferably 1.5 to 6, and particularly preferably 2 to 5. Is preferably blended with an organic sulfonic acid alkali metal salt (B) and an organic ammonium salt (C).
If the amount of the organic ammonium salt (C) blended is less than the lower limit of the mass ratio, the effect of preventing white turbidity and the effect of improving the heat resistance to moisture and heat by the organic ammonium salt (C) may not be sufficiently obtained. On the other hand, even if the amount is larger than the upper limit of the mass ratio, the improvement of the above effect by the organic ammonium salt (C) tends not to be observed.

<Ultraviolet absorber (D)>
The polycarbonate resin composition of the present invention preferably contains an ultraviolet absorber (D). By containing the ultraviolet absorber (D), the weather resistance of the polycarbonate resin composition of the present invention can be improved.

Examples of the ultraviolet absorber (D) include inorganic ultraviolet absorbers such as cerium oxide and zinc oxide; benzotriazole compounds, benzophenone compounds, salicylate compounds, cyanoacrylate compounds, triazine compounds, ogizanylide compounds, malonic acid ester compounds, and hindered amine compounds. Examples include organic ultraviolet absorbers such as. Among these, an organic ultraviolet absorber is preferable, and a benzotriazole compound is more preferable. By selecting the organic ultraviolet absorber, the transparency and mechanical properties of the polycarbonate resin composition of the present invention become good.

Specific examples of the benzotriazole compound include 2- (2'-hydroxy-5'-methylphenyl) benzotriazole, 2- [2'-hydroxy-3', 5'-bis (α, α-dimethylbenzyl). ) Phenyl] -benzotriazole, 2- (2'-hydroxy-3', 5'-di-tert-butyl-phenyl) -benzotriazole, 2- (2'-hydroxy-3'-tert-butyl-5' -Methylphenyl) -5-chlorobenzotriazole, 2- (2'-hydroxy-3', 5'-di-tert-butyl-phenyl) -5-chlorobenzotriazole), 2- (2'-hydroxy-3) ', 5'-di-tert-amyl) -benzotriazole, 2- (2'-hydroxy-5'-tert-octylphenyl) benzotriazole, 2,2'-methylenebis [4- (1,1,3,3) 3-Tetramethylbutyl) -6- (2N-benzotriazole-2-yl) phenol] and the like, among which 2- (2'-hydroxy-5'-tert-octylphenyl) benzotriazole, 2,2 '-Methylenebis [4- (1,1,3,3-tetramethylbutyl) -6- (2N-benzotriazole-2-yl) phenol] is preferred, especially 2- (2'-hydroxy-5'-tert -Octylphenyl) Benzotriazole is preferred. Specific examples of such a benzotriazole compound include "Seasorb 701", "Seasorb 705", "Seasorb 703", "Seasorb 702", "Seasorb 704", and "Seasorb 709" manufactured by Cytec Chemical Industries, Ltd. "Biosorb 520", "Biosorb 582", "Biosorb 580", "Biosorb 583" manufactured by Yakuhin Co., Ltd., "Chemisorb 71", "Chemisorb 72" manufactured by Chemipro Kasei, "Siasorb UV5411" manufactured by Cytec Industries, "Siasorb UV5411" manufactured by Cytec Industries, Ltd. LA-32 ”,“ LA-38 ”,“ LA-36 ”,“ LA-34 ”,“ LA-31 ”,“ Chinubin P ”,“ Chinubin 234 ”,“ Chinubin 326 ”, manufactured by Ciba Specialty Chemicals, Inc. Examples thereof include "Chinubin 327" and "Chinubin 328".

Specific examples of the benzophenone compound include 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-methoxybenzophenone-5-sulfonic acid, and 2-hydroxy-4-n-octoxy. Benzophenone, 2-hydroxy-n-dodecyloxybenzophenone, bis (5-benzoyl-4-hydroxy-2-methoxyphenyl) methane, 2,2'-dihydroxy-4-methoxybenzophenone, 2,2'-dihydroxy-4 , 4'-Dimethoxybenzophenone and the like. Specific examples of such a benzophenone compound include "Seasorb 100", "Seasorb 101", "Seasorb 101S", "Seasorb 102" and "Seasorb 102" manufactured by Cipro Chemical Co., Ltd. Sea Sorb 103, Kyodo Yakuhin Co., Ltd. "Bio Sorb 100", "Bio Sorb 110", "Bio Sorb 130", ChemiPro Kasei Co., Ltd. "Chemi Sorb 10", "Chemi Sorb 11", "Chemi Sorb 11S", "Chemi Sorb 12", "Chemi Sorb 13" , "Chemisorb 111", BASF "Ubinul 400", BASF "Ubinul M-40", BASF "Ubinul MS-40", Cytec Industries "Siasorb UV9", "Siasorb UV284", " Examples thereof include "Siasorb UV531", "Siasorb UV24", "Adecastab 1413" manufactured by Adeca, and "Adecastab LA-51".

Specific examples of the salicylate compound include phenyl salicylate, 4-tert-butylphenyl salicylate, and the like. Specific examples of such salicylate compounds include "Seasorb 201" and "Seasorb" manufactured by Cipro Kasei Co., Ltd. 202 ”,“ Chemisorb 21 ”manufactured by Chemipro Kasei Co., Ltd.,“ Chemisorb 22 ”and the like.

Specific examples of the cyanoacrylate compound include ethyl-2-cyano-3,3-diphenylacrylate, 2-ethylhexyl-2-cyano-3,3-diphenylacrylate, and the like, and examples of such a cyanoacrylate compound include ethyl-2-cyano-3,3-diphenylacrylate. Specifically, for example, "Sea Sorb 501" manufactured by Cipro Kasei Co., Ltd., "Biosorb 910" manufactured by Kyodo Yakuhin Co., Ltd., "Ubisolator 300" manufactured by Daiichi Kasei Co., Ltd. 539 ”and the like.

Specific examples of the oxalinide compound include 2-ethoxy-2'-ethyl oxalinic acid bisarinide, and specific examples of such oxalinide compounds include "Sanduboa" manufactured by Clariant AG. "VSU" and the like.

As the malonic acid ester compound, 2- (alkylidene) malonic acid esters are preferable, and 2- (1-arylalkylidene) malonic acid esters are more preferable. Specific examples of such a malonic acid ester compound include "PR-25" manufactured by Clariant Japan, "B-CAP" manufactured by Ciba Specialty Chemicals, and the like.

When the polycarbonate resin composition of the present invention contains the ultraviolet absorber (D), the content thereof is usually 0.001 part by mass or more, preferably 0.01 with respect to 100 parts by mass of the polycarbonate resin (A). By mass or more, more preferably 0.1 parts by mass or more, and usually 3 parts by mass or less, preferably 1 part by mass or less, more preferably 0.5 parts by mass or less, still more preferably 0.4 parts by mass or less. Is. When the content of the ultraviolet absorber (D) is not more than the lower limit of the above range, the effect of improving the weather resistance may be insufficient, and the content of the ultraviolet absorber (D) is the upper limit of the above range. If it exceeds the above value, mold ultraviolet rays and the like may occur, which may cause mold contamination.
The ultraviolet absorber (D) may contain one type or two or more types in any combination and ratio.

<Phosphorus heat stabilizer (E)>
The polycarbonate resin composition of the present invention preferably has a phosphorus-based heat stabilizer (E).
The phosphorus-based heat stabilizer (E) is generally effective in improving the retention stability at high temperatures and the heat resistance stability when using a resin molded product when the resin component is melt-kneaded.

Examples of the phosphorus-based heat stabilizer (E) used in the present invention include phosphorous acid, phosphoric acid, phosphorous acid ester, and phosphoric acid ester. Among them, trivalent phosphorus is contained and a discoloration suppressing effect is likely to be exhibited. In that respect, phosphite esters such as phosphite and phosphonite are preferable.

Examples of phosphite include triphenyl phosphite, tris (nonylphenyl) phosphite, dilaurylhydrogen phosphite, triethyl phosphite, tridecylphosphite, tris (2-ethylhexyl) phosphite, and tris (tridecyl) phos. Fight, tristearyl phosphite, diphenylmonodecylphosphite, monophenyldidecylphosphite, diphenylmono (tridecyl) phosphite, tetraphenyldipropylene glycol diphosphite, tetraphenyltetra (tridecyl) pentaerythritol tetraphosphite, water Additive bisphenol A phenol phosphite polymer, diphenylhydrogen phosphite, 4,4'-butylidene-bis (3-methyl-6-tert-butylphenyldi (tridecyl) phosphite) tetra (tridecyl) 4,4'-isopropi Redendiphenyl diphosphite, bis (tridecyl) pentaerythritol diphosphite, bis (nonylphenyl) pentaerythritol diphosphite, dilauryl pentaerythritol diphosphite, distearyl pentaerythritol diphosphite, tris (4-tert-butyl) Phenyl) phosphite, tris (2,4-di-tert-butylphenyl) phosphite, hydrogenated bisphenol A pentaerythritol phosphite polymer, bis (2,4-di-tert-butylphenyl) pentaerythritol diphosphite, Bis (2,6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphite, 2,2'-methylenebis (4,6-di-tert-butylphenyl) octylphosphite, bis (2,4) − Dicumylphenyl) Pentaerythritol diphosphite and the like.

As phosphonite, tetrakis (2,4-di-iso-propylphenyl) -4,4'-biphenylenediphosphonite and tetrakis (2,4-di-n-butylphenyl) -4,4'-bipheni Range phosphonite, tetrakis (2,4-di-tert-butylphenyl) -4,4'-biphenylenediphosphonite, tetrakis (2,4-di-tert-butylphenyl) -4,3'-biphenylenediphospho Nite, tetrakis (2,4-di-tert-butylphenyl) -3,3'-biphenylenediphosphonite, tetrakis (2,6-di-iso-propylphenyl) -4,4'-biphenylenediphosphonite, Tetrax (2,6-di-n-butylphenyl) -4,4'-biphenylenediphosphonite, tetrakis (2,6-di-tert-butylphenyl) -4,4'-biphenylenediphosphonite, tetrakis (2,6-di-n-butylphenyl) Examples thereof include 2,6-di-tert-butylphenyl) -4,3'-biphenylenediphosphonite and tetrakis (2,6-di-tert-butylphenyl) -3,3'-biphenylenediphosphonite.

Examples of acid phosphates include methyl acid phosphate, ethyl acid phosphate, propyl acid phosphate, isopropyl acid phosphate, butyl acid phosphate, butoxyethyl acid phosphate, octyl acid phosphate, 2-ethylhexyl acid phosphate, decyl acid phosphate, and lauryl acid. Phenyl acid phosphate, stearyl acid phosphate, oleyl acid phosphate, behenyl acid phosphate, phenyl acid phosphate, nonyl phenyl acid phosphate, cyclohexyl acid phosphate, phenoxyethyl acid phosphate, alkoxypolyethylene glycol acid phosphate, bisphenol A acid phosphate, dimethyl acid phosphate, diethyl acid phosphate. , Dipropyl acid phosphate, diisopropyl acid phosphate, dibutyl acid phosphate, dioctyl acid phosphate, di-2-ethylhexyl acid phosphate, dioctyl acid phosphate, dilauryl acid phosphate, distearyl acid phosphate, diphenyl acid phosphate, bisnonylphenyl acid phosphate, etc. Can be mentioned.

Among the phosphites, distearylpentaerythritol diphosphite, tris (2,4-di-tert-butylphenyl) phosphite, bis (2,6-di-tert-butyl-4-methylphenyl) penta Ellisritol diphosphite, 2,2'-methylenebis (4,6-di-tert-butylphenyl) octylphosphite, bis (2,4-dicumylphenyl) pentaerythritol diphosphite are preferred and have good heat resistance. Tris (2,4-di-tert-butylphenyl) phosphite is particularly preferred because of its presence and resistance to hydrolysis.

These phosphorus-based heat stabilizers (E) may be used alone or in combination of two or more.

When the polycarbonate resin composition of the present invention contains a phosphorus-based heat stabilizer (E), the content thereof is usually 0.001 part by mass or more, preferably 0.% by mass, based on 100 parts by mass of the polycarbonate resin (A). It is 003 parts by mass or more, more preferably 0.005 parts by mass or more, usually 0.1 parts by mass or less, preferably 0.08 parts by mass or less, and more preferably 0.06 parts by mass or less. If the content of the phosphorus-based heat stabilizer (E) is less than the lower limit of the above range, the heat stabilizing effect may be insufficient, and the content of the phosphorus-based heat stabilizer (E) is within the above range. If it exceeds the upper limit, the effect may reach a plateau and become uneconomical.

[Release agent (F)]
The polycarbonate resin composition of the present invention may contain a release agent (F), and as the release agent (F), a full esterified product of an aliphatic alcohol and an aliphatic carboxylic acid is preferably used. ..

Examples of the aliphatic carboxylic acid constituting the fully esterified product include saturated or unsaturated aliphatic monocarboxylic acids, dicarboxylic acids and tricarboxylic acids. Here, the aliphatic carboxylic acid also includes an alicyclic carboxylic acid. Of these, the preferred aliphatic carboxylic acid is a mono or dicarboxylic acid having 6 to 36 carbon atoms, and an aliphatic saturated monocarboxylic acid having 6 to 36 carbon atoms is more preferable. Specific examples of such aliphatic carboxylic acids include palmitic acid, stearic acid, valeric acid, caproic acid, capric acid, lauric acid, araquinic acid, behenic acid, lignoceric acid, cerotic acid, melissic acid, and tetratria-montanic acid. , Montanic acid, glutaric acid, adipic acid, azelaic acid and the like.

On the other hand, examples of the fatty alcohol component constituting the fully esterified product include saturated or unsaturated monohydric alcohols, saturated or unsaturated polyhydric alcohols, and the like. These alcohols may have a substituent such as a fluorine atom or an aryl group. Among these alcohols, monohydric or polyhydric saturated alcohols having 30 or less carbon atoms are preferable, and aliphatic saturated monohydric alcohols or polyhydric alcohols having 30 or less carbon atoms are preferable. Here, the aliphatic alcohol also includes an alicyclic alcohol.

Specific examples of these alcohols include octanol, decanol, dodecanol, stearyl alcohol, behenyl alcohol, ethylene glycol, diethylene glycol, glycerin, pentaerythritol, 2,2-dihydroxyperfluoropropanol, neopentylene glycol, ditrimethylolpropane, and dipentaerythritol. And so on.

The esterification rate of the full esterified product of the aliphatic alcohol and the aliphatic carboxylic acid does not necessarily have to be 100%, but may be 80% or more. The esterification rate of the full esterified product according to the present invention is preferably 85% or more, and particularly preferably 90% or more.

The full esterified product of the aliphatic alcohol and the aliphatic carboxylic acid used in the present invention is particularly one or more of the full esterified products of the monoaliphatic alcohol and the monoaliphatic carboxylic acid, and the polyvalent aliphatic alcohol. It is preferable to contain one or more of a full esterified product of and a monoaliphatic carboxylic acid, a full esterified product of a monoaliphatic alcohol and a monoaliphatic carboxylic acid, and a polyvalent aliphatic alcohol and a mono. When used in combination with a full esterified product of an aliphatic carboxylic acid, the effect of improving the mold release effect, suppressing the generation of gas during melt-kneading, and reducing the mold deposit can be obtained.

As the full esterified product of monoaliphatic alcohol and monoaliphatic carboxylic acid, a full esterified product of stearyl alcohol and stearic acid (stearyl stearate) and a full esterified product of behenyl alcohol and behenic acid (behenyl behenate) are preferable. As a full esterified product of polyvalent aliphatic alcohol and monoaliphatic carboxylic acid, a full esterified product of glycerin serine and stearic acid (glycerin tristearylate) and a full esterified product of pentaerythritol and stearic acid (pentaerythritol tetra). Stearate) is preferable, and pentaerythritol tetrastearilate is particularly preferable.

The full esterified product of the aliphatic alcohol and the aliphatic carboxylic acid may contain the aliphatic carboxylic acid and / or the alcohol as an impurity, or may be a mixture of a plurality of compounds.

When the polycarbonate resin composition of the present invention contains a mold release agent (F) such as a full esterified product of an aliphatic alcohol and an aliphatic carboxylic acid, the content thereof is 100 parts by mass of the polycarbonate resin (A). On the other hand, it is usually 2 parts by mass or less, preferably 1 part by mass or less. If the content of the release agent (F) is too large, there are problems such as deterioration of hydrolysis resistance and mold contamination during injection molding.

When a full esterified product of a monofatty alcohol and a monoaliphatic carboxylic acid and a full esterified product of a polyhydric fatty alcohol and a monoaliphatic carboxylic acid are used in combination as the release agent (F), these are used. The ratio (mass ratio) may be a full esterified product of a monofatty alcohol and a monoaliphatic carboxylic acid: a full esterified product of a polyhydric aliphatic alcohol and a monoaliphatic carboxylic acid = 1: 1-10. It is preferable to use these in combination to ensure that the above effects are obtained.

<Antioxidant (G)>
The polycarbonate resin composition of the present invention preferably contains an antioxidant (G), if desired. By containing the antioxidant (G), deterioration of hue and deterioration of mechanical properties during heat retention can be suppressed.

Examples of the antioxidant (G) include a hindered phenolic antioxidant. Specific examples thereof include pentaerythritol tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate] and octadecyl-3- (3,5-di-tert-butyl-4-hydroxyphenyl). ) Propionate, thiodiethylenebis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], N, N'-hexane-1,6-diylbis [3- (3,5-di-) tert-Butyl-4-hydroxyphenylpropionamide), 2,4-dimethyl-6- (1-methylpentadecyl) phenol, diethyl [[3,5-bis (1,1-dimethylethyl) -4-hydroxyphenyl) ] Methyl] Phosphoate, 3,3', 3'', 5,5', 5''-Hexa-tert-butyl-a, a', a''-(mesitylen-2,4,6-triyl) tri -P-cresol, 4,6-bis (octylthiomethyl) -o-cresol, ethylenebis (oxyethylene) bis [3- (5-tert-butyl-4-hydroxy-m-tolyl) propionate], hexamethylene Bis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], 1,3,5-tris (3,5-di-tert-butyl-4-hydroxybenzyl) -1,3 , 5-Triazine-2,4,6 (1H, 3H, 5H) -trione, 2,6-di-tert-butyl-4- (4,6-bis (octylthio) -1,3,5-triazine- 2-Ilamino) phenol and the like can be mentioned.

Among them, pentaerythritol tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate] and octadecyl-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate are preferable. Examples of commercially available products of such phenolic antioxidants include "Irganox 1010" and "Irganox 1076" manufactured by Ciba, "Adeka Stub AO-50" and "Adeka Stub AO-60" manufactured by Adeka Corporation. Be done.

The antioxidant (G) may contain one type or two or more types in any combination and ratio.

When the polycarbonate resin composition of the present invention contains an antioxidant (G), the content thereof is usually 0.0001 parts by mass or more, preferably 0.001 parts by mass, based on 100 parts by mass of the polycarbonate resin (A). By mass or more, more preferably 0.01 parts by mass or more, and usually 3 parts by mass or less, preferably 1 part by mass or less, more preferably 0.5 parts by mass or less, still more preferably 0.3 parts by mass or less. Is. If the content of the antioxidant (G) is less than the lower limit of the above range, the effect as an antioxidant may be insufficient, and the content of the antioxidant (G) is the upper limit of the above range. If it exceeds the value, the effect may reach a plateau and become uneconomical.

<Other ingredients>
The polycarbonate resin composition of the present invention further contains a fluorescent whitening agent, a dyeing pigment, an impact resistance improving agent, a lubricant, a plasticizer, a compatibilizer, a filler and the like as optional components as long as the object of the present invention is not impaired. It may be blended.

<Manufacturing method of polycarbonate resin composition>
The method for producing the polycarbonate resin composition of the present invention is not particularly limited, and for example, a method in which each component is collectively or dividedly blended and melt-kneaded at an arbitrary stage until the final molded product is molded. Can be mentioned. Examples of the blending method of each component include a method using a tumbler, a Henschel mixer and the like, a method of quantitatively supplying to the extruder hopper by a feeder and mixing. Examples of the melt-kneading method include a method using a single-screw kneading extruder, a twin-screw kneading extruder, a kneader, a Banbury mixer, and the like.

[Molding]
The molded product of the present invention is obtained by molding the above-mentioned polycarbonate resin composition of the present invention.

The method for molding the polycarbonate resin composition of the present invention is not particularly limited, and examples thereof include an injection molding method, a compression molding method, and an injection compression molding method, and an injection molding method is preferable.

In addition, in order to suppress thermal deterioration of the resin during molding and obtain a resin having an excellent initial hue, the polycarbonate resin composition of the present invention is molded in an atmosphere of an inert gas such as nitrogen. Is preferable.

The molded product of the present invention is preferably used as a component such as a housing of an electric / electronic device because of its excellent flame retardancy and moisture heat resistance. More specifically, it can be preferably used as a housing for electrical and electronic devices such as relays, switches, connectors, terminal switches, sensors, actuators, microswitches, microsensors and microactuators. For example, personal computers, pachinko machines, game machines, televisions, display devices such as electronic paper, printers, copiers, scanners, fax machines, electronic organizers and PDAs, electronic desk computers, electronic dictionaries, cameras, video cameras, mobile phones, batteries. Examples include packs, recording medium drives and readers, mice, ten keys, CD players, MD players, portable radio / audio players, and the like. Further, it is used as a housing for amusement, for example, a housing for pachinko, pachislot, and arcade game machines, a protective cover for their internal circuit boards, a cover for a liquid crystal screen, and the like.

Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited to the following examples as long as the gist of the present invention is not exceeded.

The materials used in the examples and comparative examples are as follows.

<Polycarbonate resin (A)>
The aromatic polycarbonate resins (A1) to (A5) shown in Table 1 below were used.

<Organic sulfonic acid alkali metal salt (B)>
LANXESS "Bayowet C4" (potassium perfluorobutane sulfonate)

<Organic ammonium salt (C)>
3M "FC4400" (bis (perfluoroalkylsulfonylimide) methyltributylammonium salt)

<Other salts (X)>
Koei Chemical's "IL-AP3" (bis (perfluoromethanesulfonylimide) tributyldodecylphosphonium salt)

<Ultraviolet absorber (D)>
"Seasorb 709" manufactured by Cipro Kasei Co., Ltd. (2- (2-Hydroxy-5- (1,1,3,3-tetramethylbutyl) phenyl) benzotriazole)

<Phosphorus stabilizer (E)>
ADEKA "ADEKA STUB 2112" (Tris (2,4-di-tert-butylphenyl) phosphite)

<Release agent (F)>
F1: "VPG861" manufactured by Emery Oreo Chemical (pentaerythritol tetrastearate)
F2: NOF Corporation "Unistar M-9676" (stearyl stearate)

[Examples 1 to 6 and Comparative Examples 1 to 7]
<Manufacturing of polycarbonate resin composition>
The components shown in Table 2 were blended in the proportions shown in Table 2 and mixed uniformly with a tumbler mixer to obtain a mixture. This mixture was supplied to a twin-screw extruder (“TEM26SX” manufactured by Toshiba Machine Co., Ltd.), kneaded under the conditions of a screw rotation speed of 100 rpm, a discharge rate of 25 kg / hour, and a barrel temperature of 280 ° C., and extruded into a strand shape from the tip of the extrusion nozzle. .. The extruded product was rapidly cooled in a water tank, cut using a pelletizer and pelletized to obtain pellets of a polycarbonate resin composition.

The following evaluations were performed using the pellets of the obtained resin composition, and the results are shown in Table 2.

<Haze (3, 5, 12 mmt)>
HAZE was measured for the molded product of each thickness using a turbidity meter (“NDH-2000 type” manufactured by Nippon Denshoku Kogyo Co., Ltd.).
For a thickness of 3 mm (3 mmt), pellets of various resin sets are dried at 120 ° C. for 4 hours, and then an injection molding machine (“SE-50DUZ” manufactured by Sumitomo Heavy Industries, Ltd.) is used to set the cylinder temperature to 300 ° C. and the mold temperature to 80. A two-stage plate of 111 mm × 36 mm × thickness 2 mm and 3 mm was formed at ° C., and a 3 mm thick portion of the two-stage plate was measured. For 5 mm thickness (5 mmt) and 12 mm thickness (12 mmt), use an injection molding machine (“Si-80-6” manufactured by Toyo Machinery Metals Co., Ltd.) at a cylinder temperature of 300 ° C and a mold temperature of 80 ° C, 65 mm × 45 mm × thickness. Thick plates having a size of 5 mm and a thickness of 50 mm × 50 mm × 12 mm were formed, and these 5 mm thick portions and 12 mm thick portions were measured.
The smaller the value of HAZE, the higher the transparency, which is preferable. Specifically, in a thickness of 12 mm, 5 or less is preferable, 3 or less is more preferable, and 2 or less is particularly preferable.

<Moist heat (3 mmt)>
Using the two-stage plate used for haze measurement, a high-acceleration life test device (HIRAYAMA "HASTEST MODEL PC-R8D") is used in a high-temperature and humidity-humidity tank under an atmosphere of temperature 110 ° C and humidity 100% RH. After exposure for 100 hours, the haze of the 3 mm thick portion of the two-stage plate after exposure was measured.

<Flame-retardant UL-94 (1.5 mmt)>
After the pellets of various resin sets are dried at 120 ° C. for 4 hours, the cylinder temperature is 260 ° C. and the mold temperature is 80 ° C., 125 mm × 13 mm × thickness 1 by an injection molding machine (“NS-40” manufactured by Nippon Jushi Kogyo Co., Ltd.). A .5 mm combustion test test piece was molded.
The obtained test piece for combustion test was subjected to a vertical combustion test in accordance with UL94V. The flammability test results were classified as V-0, V-1, V-2, and HB in order of goodness, and nonstandard ones were classified as NG.

From Table 2, it can be seen that the polycarbonate resin composition of the present invention is excellent in flame retardancy, transparency, and moisture and heat resistance.

On the other hand, in Comparative Example 1 in which the amount of the organic ammonium salt (C) is too large, the flame retardancy is lowered. Even in Comparative Example 2 in which the amount of the organic sulfonic acid alkali metal salt (B) is too small, the flame retardancy is poor. On the contrary, in Comparative Example 3 in which the amount of the organic sulfonic acid alkali metal salt (B) is too large, the transparency is remarkably lowered. In Comparative Examples 4 to 6 in which a salt other than the organic ammonium salt (C) was used, the effect of improving the flame retardancy of the organic sulfonic acid alkali metal salt (B) was impaired, the transparency was lowered, and the transparency was also lowered. In particular, in Comparative Example 6 in which the blending amount was increased, the moisture and heat resistance also deteriorated. In Comparative Example 7 in which the organic ammonium salt (C) is not blended, the transparency is remarkably lowered and the moisture and heat resistance is also poor.

Claims (5)

For 100 parts by mass of polycarbonate resin (A)
Polycarbonate containing 0.01 part by mass or more and 0.2 part by mass or less of the organic sulfonic acid alkali metal salt (B) and 0.05 part by mass or more and less than 0.5 part by mass of the organic ammonium salt (C). Resin composition. The polycarbonate resin composition according to claim 1, wherein the organic sulfonic acid alkali metal salt is a perfluoroalkane sulfonic acid alkali metal salt. The polycarbonate resin composition according to claim 1 or 2, wherein the organic ammonium salt (C) is a fluorine-containing organic ammonium salt represented by the following formula (1).
[(R ¹ ) ₃ R ² N] ⁺ · (R ³ SO ₂ ) (R ⁴ SO ₂ ) N ⁻ … (1)
(In the formula, R ¹ represents an alkyl group having 1 to 4 carbon atoms, R ² represents an alkyl group having 1 to 20 carbon atoms, and R ³ and R ⁴ independently represent perfluoroalkyl groups having 1 to 4 carbon atoms. Indicates a group.) In any one of claims 1 to 3, the content mass ratio of the organic ammonium salt (C) to the organic sulfonic acid alkali metal salt (B) (organic ammonium salt (C) / organic sulfonic acid alkali metal salt (B)). A polycarbonate resin composition having a value of 0.8 to 8. A molded product obtained by molding the polycarbonate resin composition according to any one of claims 1 to 4.