JP2011052166A - Flame-retardant polycarbonate resin composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a polycarbonate resin composition or a polycarbonate resin-molded article each of which is excellent in flame retardancy and ignition resistance. <P>SOLUTION: The flame-retardant polycarbonate resin composition is obtained by blending a phosphate compound shown by general formula (1) (wherein each of symbols is defined specially) as an (A) component and polycarbodiimide as a (B) component in a polycarbonate resin. The polycarbonate resin-molded article is obtained by molding the flame-retardant polycarbonate resin composition. <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

  The present invention relates to a polycarbonate resin composition, and particularly relates to a polycarbonate resin composition having excellent flame retardancy and excellent transparency and ignition resistance.

  Since polycarbonate resin has excellent mechanical and thermal properties, it is widely used industrially including the automobile field, OA equipment field, and electric / electronic field. Polycarbonate resin has characteristics such as polarity, strong intermolecular force, amorphous transparent resin due to its molecular structure, wide elastic region and high Izod impact strength. So it is used in a wide range of applications as an excellent engineering plastic. In particular, it is widely used as a glass substitute in consideration of its high transparency, and its importance is increasing in optical applications such as optical disks.

  On the other hand, in recent years, there has been a strong demand for flame retardants of synthetic resin materials used mainly in applications such as OA equipment and home appliances, and many flame retardants have been developed and studied to meet these demands. Yes.

  Conventionally, halogen-based flame retardants are mainly used to make polycarbonate resins flame retardant, but in many cases, antimony trioxide or the like is further used as a flame retardant aid. When a halogen-based flame retardant is blended with a synthetic resin, the effect of flame retardancy is relatively large, but there is a risk of generating harmful gases during combustion, and may cause environmental pollution during a fire or incineration process. There was a problem. Further, the flame retardancy of the polycarbonate resin has problems such as impairing the mechanical properties inherent to the polycarbonate resin, discoloration during molding, deterioration of physical properties due to long-term heat resistance, and significant coloration.

  In order to solve such a problem, a method of using a phosphate ester flame retardant in combination with an anti-drip agent such as polytetrafluoroethylene has been proposed (Patent Documents 1 to 3). However, when polytetrafluoroethylene is used as an anti-drip agent, there is a problem that transparency is impaired although there is an anti-dripping effect.

  On the other hand, the use of perfluoroalkanesulfonic acid alkali metal salts and the use of aromatic sulfonesulfonic acid alkali metal salts have been proposed as flame retardants (flame retardant aids) that do not impair transparency (Patent Documents 4 to 6). Furthermore, it has also been proposed to use a phosphate ester flame retardant and an aromatic sulfonesulfonic acid alkali metal salt in combination (Patent Document 7). However, in these cases, there is a problem that flame retardancy is insufficient and ignition resistance is also insufficient.

  Moreover, it is proposed to use a carbodiimide compound for a polymer blend of polylactic acid and polycarbonate, and a phosphate ester flame retardant is described as an example of the flame retardant used (Patent Document 8). However, the purpose of this proposal is to improve fluidity and hydrolyzability during molding, and the resin composition itself is originally opaque. Moreover, there is no description or suggestion that it has ignition resistance such that the ignition time is delayed.

JP-A-2-115262 JP-A-5-262940 Japanese Patent Laid-Open No. 7-26129 JP-A-6-306265 Japanese Patent Laid-Open No. 50-98549 JP-A-52-54746 JP-A-8-302178 JP 2007-56246 A

Accordingly, a first object of the present invention is to provide a polycarbonate resin composition excellent in transparency, flame retardancy and ignition resistance.
The second object of the present invention is to provide a molded article excellent in transparency, flame retardancy and ignition resistance.

但し、（１）式中のＲ^１、Ｒ^２、Ｒ^４及びＲ^５は、同一でも異なっていてもよく、炭素原子数１〜１０のアルキル基、又は下記一般式（２）で表される芳香族基を表す。Ｒ^３は下記一般式（３）又は（４）で表される２価の芳香族基を表し、ｎは０〜３０の数である。

但し、上式中のＡ^１及びＡ^２は各々独立に、水素原子、ヒドロキシ基、ハロゲン原子又は炭素原子数１〜１０のアルキル基を表す。
Ａ^３、Ａ^４、Ａ^５、Ａ^６、Ａ^７及びＡ^８は各々独立に、水素原子、炭素原子数１〜４のアルキル基、シクロアルキル基、アリール基、アルコキシ基、ニトロ基、ハロゲン原子又はシアノ基を表す。Ｇは直接結合、２価のイオウ原子、スルホン基又は炭素原子数１〜５のアルキリデン基若しくは炭素原子数１〜５のアルキレン基を表す。
本発明においては、前記（Ａ）成分の配合量が、ポリカーボネート樹脂１００質量部に対して、０．０１〜１５質量部であることが好ましく、前記（Ｂ）成分のポリカルボジイミドの配合量は、ポリカーボネート樹脂１００質量部に対して、０．０１〜１０質量部であることが好ましい。また、前記ポリカーボネート樹脂の分子量は１万〜２０万であることが好ましい。 As a result of intensive studies to achieve the above-mentioned objects, the present inventors have found that a favorable result can be obtained by using a combination of a specific phosphate ester compound and polycarbodiimide as a flame retardant, The present invention has been reached.
That is, the present invention relates to a flame retardant polycarbonate resin composition comprising the following (A) component and polycarbodiimide as the component (B) to a polycarbonate resin, and the flame retardant polycarbonate: It is a transparent molded product formed by molding a resin composition.
(A) component:
A phosphoric acid ester compound represented by the following general formula (1);

However, R ¹ , R ² , R ⁴ and R ⁵ in the formula (1) may be the same or different and are represented by an alkyl group having 1 to 10 carbon atoms or the following general formula (2). Represents an aromatic group. R ³ represents a divalent aromatic group represented by the following general formula (3) or (4), and n is a number from 0 to 30.

However, A ¹ and A ² in the above formula each independently represent a hydrogen atom, a hydroxy group, a halogen atom, or an alkyl group having 1 to 10 carbon atoms.
A ³ , A ⁴ , A ⁵ , A ⁶ , A ⁷ and A ⁸ are each independently a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, a cycloalkyl group, an aryl group, an alkoxy group, a nitro group, or a halogen atom. Or represents a cyano group. G represents a direct bond, a divalent sulfur atom, a sulfone group, an alkylidene group having 1 to 5 carbon atoms, or an alkylene group having 1 to 5 carbon atoms.
In the present invention, the blending amount of the component (A) is preferably 0.01 to 15 parts by weight with respect to 100 parts by weight of the polycarbonate resin, and the blending amount of the polycarbodiimide of the component (B) is It is preferable that it is 0.01-10 mass parts with respect to 100 mass parts of polycarbonate resin. The molecular weight of the polycarbonate resin is preferably 10,000 to 200,000.

  According to the present invention, a polycarbonate resin composition excellent in transparency, flame retardancy, and ignition resistance can be obtained. Moreover, the molded product excellent in transparency, a flame retardance, and ignition resistance can be provided by shape | molding the obtained polycarbonate resin composition of this invention.

Hereinafter, the flame-retardant polycarbonate resin composition of the present invention will be described in detail.
The polycarbonate resin used in the present invention is a polymer having a carbonate bond. For example, the polycarbonate resin contains two or more hydroxyl groups, each of which is directly bonded to an aromatic carbon atom, or a single ring or a polycycle. It can be obtained from a ring aromatic compound (hereinafter referred to as “polyvalent hydroxyaromatic compound”) and a carbonate precursor. The polycarbonate resin is not particularly limited in its structure, production method, chain terminator, molecular weight and the like, and may be branched. Moreover, you may use as a 1 type, or 2 or more types of mixture, Furthermore, you may contain the well-known high molecular component used by mixing with polycarbonate, such as polyester, for example.

但し、上記一般式（５）中のＡは、下記一般式（６）又は（７）で表される、重合反応に使用したジヒドロキシ芳香族化合物の残基を表し、ｐは２以上の数を表す。

上記一般式（６）又は（７）における、Ｒ^６、Ｒ^７及びＲ^８は、各々独立に水素原子、ハロゲン原子、アルキル基、アルコキシ基、シクロアルキル基、アリール基、アルキルアリール基又はアリールアルキル基を表し、ｍ、ｍ’及びｍ”は、各々独立に０〜４の整数、ｑは０〜２の整数、Ｘは、アルキレン基、シクロアルキリデン基、単結合、−Ｓ−、−Ｓ−Ｓ−、−Ｏ−、−Ｓ（＝Ｏ）−、−（Ｏ＝）Ｓ（＝Ｏ）−又は−Ｃ（＝Ｏ）−を表す。 As said polycarbonate resin, what is obtained from a bivalent hydroxy aromatic compound and a carbonate precursor is common, and the compound represented by following General formula (5) is preferable.

However, A in the said General formula (5) represents the residue of the dihydroxy aromatic compound used for the polymerization reaction represented by the following general formula (6) or (7), and p is two or more numbers. To express.

In the general formula (6) or (7), R ⁶ , R ⁷ and R ⁸ are each independently a hydrogen atom, halogen atom, alkyl group, alkoxy group, cycloalkyl group, aryl group, alkylaryl group or arylalkyl. M, m ′ and m ″ each independently represents an integer of 0 to 4, q is an integer of 0 to 2, X is an alkylene group, a cycloalkylidene group, a single bond, —S—, —S—. S-, -O-, -S (= O)-,-(O =) S (= O)-or -C (= O)-are represented.

Examples of the halogen atom represented by R ⁶ , R ⁷ and R ⁸ include fluorine, chlorine, bromine and iodine, and examples of the alkyl group include methyl, ethyl, propyl, isopropyl, butyl, sec-butyl, and tertiary. Butyl, isobutyl, amyl, isoamyl, tert-amyl, hexyl, cyclohexyl, heptyl, isoheptyl, tert-heptyl, n-octyl, isooctyl, tert-octyl, 2-ethylhexyl, and the like. Examples of the cycloalkyl group include cyclobutane, cyclopentane, cyclohexane or a substituted product thereof. Examples of the aryl group and the alkylaryl group include phenyl, methylphenyl, dimethylphenyl, ethylphenyl, Octylphenyl, chlorophenyl, Examples include bromophenyl and naphthyl, and arylalkyl groups include benzyl and phenethyl.

  Examples of the alkylene group represented by X include methylene, ethylene, ethane-1,1-diyl, propylene, propane-2,2-diyl, 1-methylethylene, butylene, 1-methylpropylene, and 2-methylpropylene. 2,2-dimethylpropylene, 1,3-dimethylpropylene, butylene, 1-methylbutylene, 2-methylbutylene, 3-methylbutylene, 4-methylbutylene, 2,4-dimethylbutylene, 1,3-dimethylbutylene Pentylene, hexylene, heptylene, octylene, and the like. Examples of the cycloalkylidene group include cyclopentylidene, cyclohexylidene, and substituted products thereof.

  Examples of the polyvalent hydroxyaromatic compound used as a raw material for the polycarbonate resin include those corresponding to the general formula (5). Specifically, resorcin, catechol, hydroquinone, 3-methyl resorcin, 3-ethyl resorcin, 3-propyl resorcin, 3-butyl resorcin, 3-tert-butyl resorcin, 3-phenyl resorcin, 3-cumyl resorcin, 3 -Dihydroxybenzenes such as methylhydroquinone, 3-ethylhydroquinone, 3-propylhydroquinone, 3-butylhydroquinone, 3-tert-butylhydroquinone, 3-phenylhydroquinone, 3-cumylhydroquinone; 4,4'-dihydroxydiphenyl, etc. 1,1-bis (4-hydroxyphenyl) -2,4,4-trimethylcyclopentane, 1,1-bis (4-hydroxyphenyl) cyclohexane, 1,1-bis (4-hydroxy) Phenyl) -3, 3-dimethylcyclohexane, 1,1-bis (4-hydroxyphenyl) cyclohexane, 1,1-bis (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane, 1,1-bis (4-hydroxy-3) , 5-dimethylphenyl) cyclohexane, 1,1-bis (4-hydroxyphenyl) cyclododecane, 1,1-bis (4-hydroxy-3,5-dimethylphenyl) cyclododecane, 1,1-bis (4- Bis (hydroxyaryl) cycloalkanes such as hydroxyphenyl) cyclododecane; bis (hydroxyaryl) such as 1,4-bis (4-hydroxyphenylsulfonyl) benzene and 4,4-bis (4-hydroxyphenylsulfonyl) benzene Aryls; bis (4-hydroxyphenyl) methane, 1,1-bis ( -Hydroxyphenyl) ethane, 1,2-bis (4-hydroxyphenoxy) ethane, 1,4-bis (4-hydroxyphenyl) propane, 2,2-bis (4-hydroxyphenyl) propane, 2,2-bis (3-chloro-4-hydroxyphenyl) propane, 2,2-bis (3,5-dichloro-4-hydroxyphenyl) propane, 2,2-bis (4-hydroxy-3,5-dimethylphenyl) propane, 2,2-bis (4-hydroxy-3,5-dibromophenyl) propane, 2,2-bis (4-hydroxyphenyl-3-methylphenyl) propane, 2,2-bis (4-hydroxyphenyl-3-) Cyclohexylphenyl) propane, 2,2-bis (4-hydroxy-3-tert-butylphenyl) propane, 2,2-bis (4-hydro) Siphenyl-3-methoxyphenyl) propane, 1,1-bis (4-hydroxyphenyl) butane, 1,1-bis (4-hydroxyphenyl) isobutane, 2,2-bis (4-hydroxy) butane, 2,4 Bis (hydroxyaryl) alkanes such as bis (4-hydroxyphenyl 2-methyl) butane; dihydroxyaryl ketones such as bis (4-hydroxyphenyl) ketone and bis (4-hydroxy-3-methylphenyl) ketone; Dihydroxy aryl ethers such as 4,4′-dihydroxydiphenyl ether, 4,4′-dihydroxy-3,3′-dimethylphenyl ether, 4,4′-dihydroxy-2,5-dihydroxydiphenyl ether; 4,4′-thio Diphenol, bis (4-hydroxyphenyl) sulfide, 4,4'- Dihydroxy-3,3′-dimethyldiphenyl sulfide, 4,4′-dihydroxy-3,3′-dimethyldiphenyl sulfoxide, 4,4′-dihydroxy-3,3′-dimethyldiphenyl sulfoxide, 2,2-bis (4 -Hydroxyphenyl) sulfone, 4,4′-dihydroxydiphenylsulfone, 4,4′-dihydroxy-3,3′-dimethyldiphenylsulfone and the like dihydroxyaryl sulfur compounds and phenolphthalein. Examples other than those corresponding to the above general formula (5) include 2,2,2 ′, 2′-tetrahydro-3,3,3 ′, 3′-tetramethyl-1,1′-spirobis (1H -Indene) Those having a condensed ring such as -7,7'-diol. These may be used singly or in combination of two or more, and may further be used by mixing with a trivalent or higher polyvalent hydroxyaromatic compound.

  Moreover, as a carbonate precursor which is a raw material of polycarbonate resin, a carbonyl halide, carbonyl ester, haloformate etc. are mentioned, for example. Preferable specific examples include phosgene, carbonic acid diester, diphenyl carbonate, dihaloformate of dihydric phenol, and mixtures thereof.

  The molecular weight of the polycarbonate resin used in the present invention is preferably 10,000 to 200,000, and more preferably 20,000 to 60,000. If the molecular weight is less than 10,000, the impact resistance of the molded product may be reduced, and if it exceeds 200,000, the fluidity may be reduced and processing may be difficult.

  For the above reasons, a chain terminator may be used to control the molecular weight during the production of the polycarbonate resin. Examples of the chain terminator used in this case include phenol, p-chlorophenol, p-tert-butylphenol, 2,4,6-tribromophenol, 4- (1,3-tetramethylbutyl) phenol, and the like. Long-chain alkylphenols; 3,5-ditert-butylphenol, p-isooctylphenol, p-tert-octylphenol, p-dodecylphenol, 2- (3,5-dimethylheptyl) phenol, 4- (3,5- And phenolic compounds such as dimethylheptyl) phenol. The general use amount of these chain terminators is 0.5 to 10 mol% of diphenol in the polyvalent hydroxyaromatic compound used.

但し、（１）式中のＲ^１、Ｒ^２、Ｒ^４及びＲ^５は、同一でも異なっていてもよく、炭素原子数１〜１０のアルキル基、又は下記一般式（２）で表される芳香族基を表す。Ｒ^３は下記一般式（３）又は（４）で表される２価の芳香族基を表し、ｎは０〜３０の数を表す。

但し、上式中のＡ^１及びＡ^２は各々独立に、水素原子、ヒドロキシ基、ハロゲン原子又は炭素原子数１〜１０のアルキル基を表す。Ａ^３、Ａ^４、Ａ^５、Ａ^６、Ａ^７及びＡ^８は各々独立に、水素原子、炭素原子数１〜４のアルキル基、シクロアルキル基、アリール基、アルコキシ基、ニトロ基、ハロゲン原子又はシアノ基を表す。Ｇは直接結合、２価のイオウ原子、スルホン基又は炭素原子数１〜５のアルキリデン基若しくは炭素原子数１〜５のアルキレン基を表す。 Next, the phosphoric acid ester compound (A) used in the present invention will be described.
The phosphoric acid ester compound of the component (A) used in the present invention is represented by the following general formula (1).

However, R ¹ , R ² , R ⁴ and R ⁵ in the formula (1) may be the same or different and are represented by an alkyl group having 1 to 10 carbon atoms or the following general formula (2). Represents an aromatic group. R ³ represents a divalent aromatic group represented by the following general formula (3) or (4), and n represents a number of 0 to 30.

However, A ¹ and A ² in the above formula each independently represent a hydrogen atom, a hydroxy group, a halogen atom, or an alkyl group having 1 to 10 carbon atoms. A ³ , A ⁴ , A ⁵ , A ⁶ , A ⁷ and A ⁸ are each independently a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, a cycloalkyl group, an aryl group, an alkoxy group, a nitro group, or a halogen atom. Or represents a cyano group. G represents a direct bond, a divalent sulfur atom, a sulfone group, an alkylidene group having 1 to 5 carbon atoms, or an alkylene group having 1 to 5 carbon atoms.

Specific examples of the alkyl group having 1 to 10 carbon atoms represented by R ¹ , R ² , R ⁴ , R ⁵ , A ¹ and A ² in the general formulas (1) to (4) include methyl, Examples include ethyl, propyl, isopropyl, butyl, isobutyl, secondary butyl, tertiary butyl, amyl, tertiary amyl, hexyl, 2-ethylhexyl, n-octyl, nonyl, decyl and the like. Specific examples of the alkyl group having 1 to 4 carbon atoms represented by A ³ , A ⁴ , A ⁵ , A ⁶ , A ⁷ and A ⁸ include methyl, ethyl, propyl, butyl, isobutyl, sec-butyl, Tertiary butyl and the like can be mentioned, and examples of the cycloalkyl group include cyclohexyl and the like. Examples of the aryl group include phenyl, cresyl, xylyl, 2,6-xylyl, 2,4,6-trimethylphenyl, butylphenyl, nonylphenyl and the like. Examples of the alkoxy group include methoxy, ethoxy, propoxy, butoxy and the like. Examples of the halogen atom include a fluorine atom, a chlorine atom, and a bromine atom. Examples of the aromatic group represented by the general formula (2) include phenyl, cresyl, xylyl, 2,6-xylyl, butylphenyl, nonylphenyl, and the like. Examples of the alkylidene group having 1 to 5 carbon atoms represented by G include ethylidene and isopropylidene, and examples of the alkylene group having 1 to 5 carbon atoms include methylene, ethylene, trimethylene and tetramethylene. .
Moreover, n in the said General formula (1) showing the phosphate ester compound which is (A) component is a number of 0-30, Preferably it is a number of 1-10.

  Specific examples of the phosphoric ester compound used as the component (A) in the polycarbonate resin composition of the present invention include the following compound No. The compound of 1-6 is mentioned. From the viewpoint of transparency, flame retardancy, and ignition resistance, Compound No. 2 and Compound No. The compound of No. 5 is preferable, and especially compound No. 5 is used. The compound of 5 is most preferred.

  These phosphate ester compounds may be used alone or in combination of two or more. The blending amount of the component (A) in the flame-retardant polycarbonate resin composition of the present invention is preferably 0.01 to 15 parts by mass, more preferably 0.1 to 10 parts by mass with respect to 100 parts by mass of the polycarbonate resin. is there. If it is less than 0.01 part by mass, sufficient flame retardancy may not be obtained, and if it is 15 parts by mass or more, it may be economically disadvantageous.

Next, the polycarbodiimide as the component (B) used in the present invention will be described.
The polycarbodiimide as the component (B) is a (co) polymer using at least one selected from polyvalent isocyanate compounds. Specific examples of the polyvalent isocyanate compound include, for example, hexamethylene diisocyanate, xylene diisocyanate, cyclohexane diisocyanate, pyridine diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 4,4-diphenylmethane diisocyanate, p- Examples include phenylene diisocyanate, m-phenylene diisocyanate, and 1,5-naphthylene diisocyanate.

  Specific examples of the polycarbodiimide of the component (B) include Carbodilite HMV-8CA (trade name, manufactured by Nisshinbo Chemical Co., Ltd.), Carbodilite LA-1 (trade name, manufactured by Nisshinbo Chemical Co., Ltd.), and Starvacol I (Rhein Chemie). Brand name manufactured by the company), Starbuxol P (trade name manufactured by Rhein Chemie), Starbaxol P100 (trade name manufactured by Rhein Chemie), Eutab HS-700 (trade name manufactured by Eutec Chemical), etc. Among these, carbodilite HMV-8CA and carbodilite LA-1 are preferable from the viewpoints of transparency, flame retardancy, and ignition resistance.

  The blending amount of the polycarbodiimide as the component (B) is preferably 0.01 to 10 parts by mass, more preferably 0, from the viewpoint of transparency, flame retardancy and ignition resistance with respect to 100 parts by mass of the polycarbonate resin. .1 to 5 parts by mass. If it is less than 0.01 parts by mass, the flame retardancy and the ignition resistance may not be sufficient, and if it exceeds 10 parts by mass, the transparency may be lowered.

  The flame retardant polycarbonate resin composition of the present invention may contain other optional components together with the (A) component and the (B) component, which are essential components, with respect to the polycarbonate resin. There are no particular restrictions on the timing at which the component (A), the component (B), and other optional components are added to the polycarbonate resin. For example, two or more kinds selected in advance from among the blending components may be made into one pack and blended with the polycarbonate resin, or each component may be blended sequentially with respect to the polycarbonate resin. In the case of making one pack, each component may be pulverized and mixed, or mixed and then pulverized.

Moreover, you may mix | blend organic sulfonic acid metal salt with the flame-retardant polycarbonate resin composition of this invention in the range which does not impair the effect of this invention.
The organic sulfonic acid metal salts which can be used are preferably alkali metal salts or alkaline earth metal salts, in particular sodium or potassium salts. Specifically, sodium 3,4-dichlorobenzenesulfonate, sodium 2,4,5-trichlorobenzenesulfonate, sodium benzenesulfonate, disodium naphthalene-2,6-disulfonate, sodium p-iodobenzenesulfonate Sodium 4,4′-dibromodiphenyl-3-sulfonate, sodium 2,3,4,5,6-pentachloro-β-styrenesulfonate, sodium 4,4′-dichlorodiphenylsulfide-3-sulfonate, tetra Disodium chlorodiphenyl ether disulfonate, disodium 4,4′-dichlorobenzophenone-3,3′-disulfonate, sodium 2,5-dichlorothiophene-3-sulfonate, potassium diphenylsulfone-3-sulfonate, 2,4 , 6-Trichloro-5-sulfur Sodium salt of dimethyl isophthalate, potassium salt of sulfonic acid dichlorophenyl 2,4,5-trichlorobenzenesulfonate, 4 ′-[1,4,5,6,7,7′-hexachlorobicyclo- [2,2, 1] -Hept-5-en-endo-yl] sodium benzenesulfonate and potassium perfluorobutanesulfonate. Particularly preferred are sodium 3,4-dichlorobenzenesulfonate, sodium 2,4,5-trichlorobenzenesulfonate, sodium benzenesulfonate, potassium diphenylsulfone-3-sulfonate, and potassium perfluorobutanesulfonate. These metal salts may be used alone or in combination of two or more.

  In addition, the flame retardant polycarbonate resin composition of the present invention may further include a phenolic antioxidant, a phosphorus antioxidant, a thioether antioxidant, an ultraviolet absorber, a hindered amine light stabilizer, etc. as necessary. It is preferable to add to stabilize the resin composition.

  Examples of the phenol-based antioxidant include 2,6-ditert-butyl-p-cresol, 2,6-diphenyl-4-octadecyloxyphenol, distearyl (3,5-ditert-butyl- 4-hydroxybenzyl) phosphonate, 1,6-hexamethylenebis [(3,5-ditert-butyl-4-hydroxyphenyl) propionic acid amide], 4,4′-thiobis (6-tert-butyl-m-) Cresol), 2,2'-methylenebis (4-methyl-6-tert-butylphenol), 2,2'-methylenebis (4-ethyl-6-tert-butylphenol), 4,4'-butylidenebis (6-tertiary) Butyl-m-cresol), 2,2′-ethylidenebis (4,6-ditert-butylphenol), 2,2′-ethylidenebis (4-secondarybutyl-6-tert-butylphenol) ), 1,1,3-tris (2-methyl-4-hydroxy-5-tert-butylphenyl) butane, 1,3,5-tris (2,6-dimethyl-3-hydroxy-4-tert-butyl) Benzyl) isocyanurate, 1,3,5-tris (3,5-ditert-butyl-4-hydroxybenzyl) isocyanurate, 1,3,5-tris (3,5-ditert-butyl-4-hydroxy) Benzyl) -2,4,6-trimethylbenzene, 2-tert-butyl-4-methyl-6- (2-acryloyloxy-3-tert-butyl-5-methylbenzyl) phenol, stearyl (3,5-di-) Tert-butyl-4-hydroxyphenyl) propionate, tetrakis [methyl 3- (3,5-ditert-butyl-4-hydroxyphenyl) propionate] methane, thiodiethylene glycol bis (3,5-ditert-butyl-4-hydroxyphenyl) propionate], 1,6-hexamethylenebis [(3,5-ditert-butyl-4-hydroxyphenyl) propionate], bis [3,3- Bis (4-hydroxy-3-tert-butylphenyl) butyric acid] glycol ester, bis [2-tert-butyl-4-methyl-6- (2-hydroxy-3-tert-butyl-5-methylbenzyl) Phenyl] terephthalate, 1,3,5-tris [(3,5-ditert-butyl-4-hydroxyphenyl) propionyloxyethyl] isocyanurate, 3,9-bis [1,1-dimethyl-2-{( 3-tert-butyl-4-hydroxy-5-methylphenyl) propionyloxy} ethyl] -2,4,8,10-tetraoxaspiro [5,5] undeca And triethylene glycol bis [(3-tert-butyl-4-hydroxy-5-methylphenyl) propionate]. The amount of these phenolic antioxidants used is preferably 0.001 to 10 parts by mass and more preferably 0.05 to 5 parts by mass with respect to 100 parts by mass of the polycarbonate resin.

  Examples of the phosphorus-based antioxidant include trisnonylphenyl phosphite and tris [2-tert-butyl-4- (3-tert-butyl-4-hydroxy-5-methylphenylthio) -5-methylphenyl. Phosphite, tridecyl phosphite, octyl diphenyl phosphite, di (decyl) monophenyl phosphite, di (tridecyl) pentaerythritol diphosphite, di (nonylphenyl) pentaerythritol diphosphite, bis (2,4- Ditertiarybutylphenyl) pentaerythritol diphosphite, bis (2,6-ditertiarybutyl-4-methylphenyl) pentaerythritol diphosphite, bis (2,4,6-tritertiarybutylphenyl) pentaerythritol Diphosphite, bis (2,4-dicumylphenyl) Intererythritol diphosphite, tetra (tridecyl) isopropylidene diphenol diphosphite, tetra (tridecyl) -4,4'-n-butylidenebis (2-tert-butyl-5-methylphenol) diphosphite, hexa (tridecyl)- 1,1,3-tris (2-methyl-4-hydroxy-5-tert-butylphenyl) butane triphosphite, tetrakis (2,4-ditert-butylphenyl) biphenylene diphosphonite, 9,10-dihydro- 9-oxa-10-phosphaphenanthrene-10-oxide, 2,2′-methylenebis (4,6-tert-butylphenyl) -2-ethylhexyl phosphite, 2,2′-methylenebis (4,6- Tert-butylphenyl) -octadecyl phosphite, 2,2′-ethylidenebis (4 -Di-tert-butylphenyl) fluorophosphite, tris (2-[(2,4,8,10-tetrakis tert-butyldibenzo [d, f] [1,3,2] dioxaphosphine-6- Yl) oxy] ethyl) amine, phosphite of 2-ethyl-2-butylpropylene glycol and 2,4,6-tritert-butylphenol, and the like. The amount of these phosphorus-based antioxidants used is preferably 0.001 to 10 parts by mass, and more preferably 0.05 to 5 parts by mass with respect to 100 parts by mass of the polycarbonate resin.

  Examples of the thioether-based antioxidant include dialkylthiodipropionates such as dilauryl thiodipropionate, dimyristyl thiodipropionate, distearyl thiodipropionate, and pentaerythritol tetra (β-alkylmercaptopropionic acid). The amount of these thioether-based antioxidants used is preferably 0.001 to 10 parts by mass, and 0.05 to 5 parts by mass with respect to 100 parts by mass of the polycarbonate resin. More preferred.

  Examples of the ultraviolet absorber include 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-octoxybenzophenone, 5,5′-methylenebis (2-hydroxy-4-methoxy). 2-hydroxybenzophenones such as benzophenone); 2- (2′-hydroxy-5′-methylphenyl) benzotriazole, 2- (2′-hydroxy-3 ′, 5′-ditert-butylphenyl) -5- Chlorobenzotriazole, 2- (2'-hydroxy-3'-tert-butyl-5'-methylphenyl) -5-chlorobenzotriazole, 2- (2'-hydroxy-5'- Trioctylphenyl) benzotriazole, 2- (2′-hydroxy-3 ′, 5′-dicumylphenyl) benzotriazole, 2,2′-methylenebi 2- (2′-hydroxy) such as (4-tert-octyl-6- (benzotriazolyl) phenol), 2- (2′-hydroxy-3′-tert-butyl-5′-carboxyphenyl) benzotriazole Phenyl) benzotriazoles; phenyl salicylate, resorcinol monobenzoate, 2,4-ditert-butylphenyl-3,5-ditert-butyl-4-hydroxybenzoate, 2,4-ditert-amylphenyl-3,5 -Benzoates such as di-tert-butyl-4-hydroxybenzoate and hexadecyl-3,5-di-tert-butyl-4-hydroxybenzoate; 2-ethyl-2'-ethoxyoxanilide, 2-ethoxy-4'- Substituted oxanilides such as dodecyl oxanilide; ethyl-α-cyano-β, β-diphenyl acrylate, methyl-2-cyano Cyanoacrylates such as 3-methyl-3- (p-methoxyphenyl) acrylate; 2- (2-hydroxy-4-octoxyphenyl) -4,6-bis (2,4-ditert-butylphenyl)- s-triazine, 2- (2-hydroxy-4-methoxyphenyl) -4,6-diphenyl-s-triazine, 2- (2-hydroxy-4-propoxy-5-methylphenyl) -4,6-bis ( And triaryltriazines such as 2,4-ditertiarybutylphenyl) -s-triazine. The amount of the ultraviolet absorber used is preferably 0.001 to 30 parts by mass, more preferably 0.05 to 10 parts by mass with respect to 100 parts by mass of the polycarbonate resin.

  Examples of the hindered amine light stabilizer include 2,2,6,6-tetramethyl-4-piperidyl stearate, 1,2,2,6,6-pentamethyl-4-piperidyl stearate, 2,2 , 6,6-tetramethyl-4-piperidylbenzoate, bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis (1,2,2,6,6-tetramethyl-4-piperidyl ) Sebacate, bis (1-octoxy-2,2,6,6-tetramethyl-4-piperidyl) sebacate, 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, bis (2, 2,6,6-tetramethyl-4-piperidyl) di (tridecyl) -1,2,3,4-butanetetracarboxylate, bis (1,2,2,6,6-pentamethyl-4-piperidyl) Di (tridecyl) -1,2,3,4-butanetetracarboxylate, bis (1,2,2,4,4-pentamethyl-4-piperidyl) -2-butyl-2- (3,5-di Tert-butyl-4-hydroxybenzyl) malonate, 1- (2-hydroxyethyl) -2,2,6,6-tetramethyl-4-piperidinol / diethyl succinate polycondensate, 1,6-bis ( 2,2,6,6-tetramethyl-4-piperidylamino) hexane / 2,4-dichloro-6-morpholino-s-triazine polycondensate, 1,6-bis (2,2,6,6-tetra Methyl-4-piperidylamino Hexane / 2,4-dichloro-6-tert-octylamino-s-triazine polycondensate, 1,5,8,12-tetrakis [2,4-bis (N-butyl-N- (2,2,6 , 6-tetramethyl-4-piperidyl) amino) -s-triazin-6-yl] -1,5,8,12-tetraazadodecane, 1,5,8,12-tetrakis [2,4-bis ( N-butyl-N- (1,2,2,6,6-pentamethyl-4-piperidyl) amino) -s-triazin-6-yl] -1,5,8-12-tetraazadodecane, 1,6 , 11-tris [2,4-bis (N-butyl-N- (2,2,6,6-tetramethyl-4-piperidyl) amino) -s-triazin-6-yl] aminoundecane, 1,6 , 11-tris [2,4-bis (N-butyl-N- (1,2,2 6,6-pentamethyl-4-piperidyl) amino) -s-triazin-6-yl] hindered amine compounds such as aminoundecanoic the like. The amount of these hindered amine light stabilizers used is preferably 0.001 to 30 parts by mass and more preferably 0.05 to 10 parts by mass with respect to 100 parts by mass of the polycarbonate resin.

  In the flame-retardant polycarbonate resin composition of the present invention, an antistatic agent, a crystal nucleating agent (nucleating agent), a plasticizer, a lubricant, a metal soap, a hydrostatic soap and a hydrophobic agent are added to the flame retardant polycarbonate resin composition of the present invention as necessary. Talsite, triazine ring-containing compound, metal hydroxide, inorganic phosphorus flame retardant, silicon flame retardant, other inorganic flame retardant auxiliary, other organic flame retardant, anti-drip agent, filler, pigment, foam An agent or the like may be added.

  Examples of the triazine ring-containing compound include melamine, ammelin, benzguanamine, acetoguanamine, phthalodiguanamine, melamine cyanurate, melamine pyrophosphate, butylenediguanamine, norbornene diguanamine, methylene diguanamine, ethylene dimelamine, trimethylene Dimelamine, tetramethylene dimelamine, hexamethylene dimelamine, 1,3-hexylene dimelamine and the like can be mentioned.

  Examples of the metal hydroxide include magnesium hydroxide, aluminum hydroxide, calcium hydroxide, barium hydroxide, zinc hydroxide, Kismer 5A (magnesium hydroxide: trade name manufactured by Kyowa Chemical Industry Co., Ltd.) and the like. .

  Examples of the other inorganic flame retardant aids include inorganic compounds such as zinc oxide, titanium oxide, aluminum oxide, magnesium oxide, hydrotalcite, and surface-treated products thereof. In the present invention, for example, TIPAQUE R-680 (titanium oxide: trade name made by Ishihara Sangyo Co., Ltd.), Kyowa Mag 150 (magnesium oxide: trade name made by Kyowa Chemical Industry Co., Ltd.), DHT-4A (hydrotal) Various commercial products such as “Site: trade name manufactured by Kyowa Chemical Industry Co., Ltd.”, Alkamizer 4 (Zinc-modified hydrotalcite: “trade name” manufactured by Kyowa Chemical Industry Co., Ltd.) can be used.

  Examples of the anti-drip agent include fluorine resins such as polytetrafluoroethylene, polyvinylidene fluoride, and polyhexafluoropropylene, and silicon rubbers, saponite, montmorillonite, hectorite, beidellite, stevensite, nontronite, and other smectites. Examples include clay minerals and layered silicates such as talc, vermiculite, halloysite, and swellable mica.

  Examples of the other organic flame retardant aids include pentaerythritol.

  In the flame-retardant polycarbonate resin composition of the present invention, if necessary, additives usually used for synthetic resins, such as a crosslinking agent, an antistatic agent, an antifogging agent, a plate-out preventing agent, and a surface treatment agent , Plasticizers, lubricants, reinforcing materials, flame retardants, fluorescent agents, antifungal agents, bactericides, foaming agents, metal deactivators, release agents, pigments, processing aids, antioxidants, light stabilizers, silicone oils A silane coupling agent or the like can be blended within a range that does not impair the effects of the present invention.

  The flame-retardant polycarbonate resin molding of the present invention can be obtained by molding the flame-retardant polycarbonate resin composition of the present invention by a known method. The molding method is not particularly limited, and examples thereof include extrusion molding, calendering molding, injection molding, roll molding, compression molding, and blow molding. By these molding methods, molded products of various shapes such as resin plates, sheets, films, and deformed products can be manufactured.

In addition, the flame-retardant polycarbonate resin composition of the present invention and the molded product thereof are preferably used particularly for transparent products, and include electricity, electronics, communications, agriculture, forestry and fisheries, mining, construction, food, textiles, clothing, medical care, coal, It can be used in a wide range of industrial fields such as petroleum, rubber, leather, automobiles, precision equipment, wood, building materials, civil engineering, furniture, printing, and musical instruments. More specifically, printers, personal computers, word processors, keyboards, PDAs (small information terminals), telephones, copiers, facsimiles, ECRs (electronic cash registers), calculators, electronic notebooks, cards, holders, stationery, etc. office OA equipment, washing machines, refrigerators, vacuum cleaners, microwave ovens, lighting equipment, game machines, irons, kotatsu, etc. appliances, TV, VTR, video cameras, radio cassette recorders, tape recorders, mini-disc, CD player, speakers, Electric and electronic parts such as AV equipment such as liquid crystal displays, connectors, relays, capacitors, switches, printed boards, coil bobbins, semiconductor sealing materials, LED sealing materials, electric wires, cables, transformers, deflection yokes, distribution boards, watches, etc. It is used for applications such as communication equipment.

  It can also be used for optical material applications such as optical discs, CD discs, DVD discs, and lenses, and for glass replacement.

  Furthermore, the flame-retardant polycarbonate resin composition and molded product thereof according to the present invention include a seat (filling, outer material, etc.), belt, ceiling, compatible top, armrest, door trim, rear package tray, carpet, mat, sun visor, foil. Cover, mattress cover, airbag, insulation material, suspension hand, suspension belt, electric wire coating material, electrical insulation material, paint, coating material, upholstery material, flooring material, partition wall, carpet, wallpaper, wall covering material, exterior material , Interior materials, roofing materials, deck materials, wall materials, pillar materials, floorboards, eaves materials, frames and repetitive shapes, windows and door shapes, slabs, siding, terraces, balconies, soundproofing plates, heat insulating plates, windows Materials such as automobiles, vehicles, ships, aircraft, buildings, housing and construction materials, civil engineering materials, clothing, curtains, sheets, plywood, synthetic fiber boards, carpets, doormats, sheets, buckets, ho Vinegar, container, glasses, bags, cases, goggles, skis, rackets, tents, household goods of the musical instrument or the like, and is used in sporting goods, various applications and the like.

  EXAMPLES Hereinafter, although an Example demonstrates this invention further in detail, this invention is not restrict | limited at all by these. In addition, all the mixing | blending shown in Tables 1-3 is a mass part reference | standard.

[Examples 1 to 9]
The following test compounds-1 to 3 were used as the phosphoric acid ester compound of component (A), and a flame retardant polycarbonate resin composition was blended according to the blending described in Table 1.

  Next, it was extruded under processing conditions of 270 ° C. to produce pellets, which were used for injection molding at 290 ° C., 127 mm × 12.7 mm × 1.6 mm flame retardant test specimens, and 100 mm × 100 mm × A 3 mm transparency test specimen and an ignition resistance test specimen were obtained. Table 1 shows the results of evaluating each of the obtained test pieces by conducting a transparency test, a flame retardancy test, and an ignition resistance test under the following conditions.

<Transparency test>
About the test piece for transparency testing (100 mm × 100 mm × 3 mm) obtained above, the Haze value was measured using Haze Gard Plus (manufactured by Toyo Seiki Seisakusho).

<Flame retardance test (UL-94V)>
The flame retardant test specimen (127 mm x 12.7 mm x 1.6 mm) obtained above is kept vertical, the burner is fired indirectly for 10 seconds at the lower end, the flame is removed, and the specimen is ignited. The time until the fire was extinguished was measured. Next, at the same time that the fire was extinguished, the second flame contact was performed for 10 seconds, and the time until the fire that ignited extinguished was measured as in the first time. In addition, it was also evaluated whether or not the cotton placed under the test piece was ignited by the falling fire type.
The combustion rank was given according to UL-94V standard from the 1st and 2nd combustion time, the presence or absence of cotton ignition, and the like. Evaluation was performed 10 times, and the number of V-0 cases was evaluated as a percentage (%).

<Ignition resistance test>
The ignition resistance test piece (100 mm × 100 mm × 3 mm) obtained above was ignited using a cone calorimeter (manufactured by Toyo Seiki Seisakusho Co., Ltd .: trade name CONEIII) under the condition that the radiant heat was 50 kW / m ^2. The ignition time was evaluated by taking the time until the heat generation rate increased as the ignition time. The longer the ignition time, the better the ignition resistance.

[Comparative Examples 1 to 13]
The test piece of the comparative example was also tested in the same manner as in the above example. However, in Comparative Examples 10 to 13, the following Comparative Compound-1 was used. The results are as shown in Table 2.

  As is clear from the results in Tables 1 and 2, the molded product of the present invention using both the (A) component and the (B) component is more transparent, flame retardant and ignition resistant than the molded product of the comparative decree. It was confirmed that both were excellent.

The present invention includes electricity, electronics, communications, agriculture, forestry and fisheries, mining, construction, food, textiles, clothing, medical care, coal, petroleum, rubber, leather, automobiles, precision equipment, wood, building materials, civil engineering, furniture, printing, musical instruments, etc. The present invention can be applied to a wide range of industrial fields, and in particular, can be preferably used for transparent products.

Claims (6)

A flame retardant polycarbonate resin composition comprising polycarbodiimide as the following component (A) and component (B) with respect to the polycarbonate resin;
(A) component:
A phosphoric acid ester compound represented by the following general formula (1);

However, R ¹ , R ² , R ⁴ and R ⁵ in the formula (1) may be the same or different and are represented by an alkyl group having 1 to 10 carbon atoms or the following general formula (2). Represents an aromatic group. R ³ represents a divalent aromatic group represented by the following general formula (3) or (4), and n is a number from 0 to 30;

However, A ¹ and A ² in the above formula each independently represent a hydrogen atom, a hydroxy group, a halogen atom, or an alkyl group having 1 to 10 carbon atoms. A ³ , A ⁴ , A ⁵ , A ⁶ , A ⁷ and A ⁸ are each independently a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, a cycloalkyl group, an aryl group, an alkoxy group, a nitro group, or a halogen atom. Or represents a cyano group. G represents a direct bond, a divalent sulfur atom, a sulfone group, an alkylidene group having 1 to 5 carbon atoms, or an alkylene group having 1 to 5 carbon atoms.   The flame-retardant polycarbonate resin composition according to claim 1, wherein a blending amount of the component (A) is 0.01 to 15 parts by mass with respect to 100 parts by mass of the polycarbonate resin.   The flame-retardant polycarbonate resin composition according to claim 1 or 2, wherein a blending amount of the polycarbodiimide as the component (B) is 0.01 to 10 parts by mass with respect to 100 parts by mass of the polycarbonate resin.   The flame-retardant polycarbonate resin composition according to claim 1, wherein the polycarbonate resin has a molecular weight of 10,000 to 200,000. The flame retardant polycarbonate resin composition according to any one of claims 1 to 4, wherein the component (A) is at least one selected from compounds represented by the following compounds No. 1 to No. 6. .

  A transparent molded article obtained by molding the flame retardant polycarbonate resin composition according to any one of claims 1 to 5.