JP2018080300A - Flame-retardant polycarbonate resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a flame-retardant polycarbonate resin composition having good flame retardancy and surface hardness, and a good appearance.SOLUTION: A flame-retardant polycarbonate resin composition contains (A) polycarbonate resin (component A) 100 pts.wt., and (B) specific phosphorous flame retardant (component B) 1-20 pts.wt. The component A, polycarbonate resin, contains a specific polycarbonate constitutional unit.SELECTED DRAWING: None

Description

  The present invention relates to a flame retardant polycarbonate resin composition. More specifically, the present invention relates to a flame retardant polycarbonate resin composition that includes a polycarbonate resin component containing a specific carbonate structural unit and is excellent in surface hardness and appearance.

  Polycarbonate resin is excellent in transparency, impact resistance, heat resistance, and dimensional stability, so as an engineering plastic, it can be used as an electrical / electronic / OA equipment casing and parts, automotive interior / exterior parts, furniture, and musical instruments. It is used in a wide range of fields such as miscellaneous goods. Polycarbonate resin, on the other hand, is a paint general test method described in JIS K5600-5-4-Part 5: Mechanical properties of coating film-Section 4: Pencil hardness measured in accordance with scratch hardness (pencil method) is 2B The surface is soft and easily damaged. In particular, it is represented by casings, interior panels, door handles, steering, car audio / car navigation frames, and shift knobs of electric / electronic / OA devices such as mobile phones, LCD TVs, speakers, portable game machines, and notebook computers. Automotive exterior parts such as automobile interiors, roof spoilers, and window garnishes, furniture, and musical instruments are required to have a high-quality lacquer-like texture and depth to create a high-class feel. Scratches can cause a fatal appearance defect. In addition, due to the recent increase in safety awareness, flame retardant properties are being demanded for applications other than electrical, electronic, and OA applications. Materials that combine high appearance, high coloration, scratch resistance, and flame resistance are strong. It is getting demanded.

  As a method for improving the scratch resistance of polycarbonate resin, generally, a method of coating on the resin surface or laminating an acrylic resin film or sheet on the surface is known. There exists a subject that it becomes difficult to provide a flame retardance. As a method for improving the scratch resistance and flame retardancy of a polycarbonate resin, Patent Document 1 reports an aromatic polycarbonate resin composition comprising an aromatic polycarbonate resin, titanium oxide, a metal salt compound, a fluoropolymer, and a specific silicone resin. Has been. However, titanium oxide is an essential component, and there is a problem in colorability. In Patent Document 2, an aromatic polycarbonate resin composition comprising an aromatic polycarbonate resin, a specific reinforcing filler, and a flame retardant is reported. In Patent Document 3, a polycarbonate resin, a polymethyl methacrylate resin, a phosphorus-based difficult resin is reported. A polycarbonate resin composition comprising a flame retardant, a fluoropolymer and a plate-like silicate compound has been reported. Patent Document 4 reports a polycarbonate resin composition comprising a polycarbonate resin, a polymethyl methacrylate resin, a phosphorus flame retardant, a fluoropolymer, a plate-like silicate compound, and a specific graft copolymer. However, these cannot obtain a high appearance because they contain a reinforcing filler. In Patent Document 5, a hard material obtained by graft polymerization of at least one selected from the group consisting of an aromatic polycarbonate resin, an aromatic vinyl monomer, a vinyl cyanide monomer, and an alkyl (meth) acrylate monomer. A graft-modified polymer, a rubber-modified polymer obtained by polymerizing at least one selected from the group consisting of an aromatic vinyl monomer, a vinyl cyanide monomer, and an alkyl (meth) acrylate monomer on a rubber component; and A polycarbonate resin composition comprising an acrylic surface hardness modifier having a specific configuration has been reported. However, when repeatedly contacting and rubbing, there is a problem that the resin may be deformed / welded and the range of use is limited. Moreover, the resin composition is opaque and is inferior to coloring with design properties such as jetness. As examples of modifying the polycarbonate resin itself, Patent Documents 6 to 10 report a polycarbonate resin composition containing a specific polycarbonate resin and a flame retardant. However, when repeatedly contacting and rubbing, there is a problem that the resin may be deformed / welded and the range of use is limited.

JP 2010-59340 A JP 2011-16901 A JP 2013-213154 A Japanese Patent Laying-Open No. 2015-4044 JP 2012-207164 A JP 2011-256368 A JP 2013-14728 A JP 2013-64046 A JP 2013-64047 A JP2013-82887A

  An object of the present invention is to provide a flame retardant polycarbonate resin composition having a good surface hardness, excellent appearance, and capable of being used without any problem even in applications such as repeated contact and friction.

  As a result of intensive research aimed at achieving the above object, the present inventors have found that a polycarbonate resin composition containing a specific carbonate constituent unit and a polycarbonate resin composition containing a specific phosphorus flame retardant have surface hardness and appearance. It has been found that it is good and also excellent in flame retardancy, and has reached the present invention.

  That is, according to the present invention, (B) the compound represented by the following general formula [1] and the following general formula [2] are represented by (B) 100 parts by weight of the (A) polycarbonate resin (component A). A flame retardant polycarbonate resin composition containing 1 to 20 parts by weight of at least one phosphorus-based flame retardant selected from the group consisting of the following compounds, wherein the component A polycarbonate resin is represented by the following general formula [3]: A flame retardant characterized by being a polycarbonate resin (A-1 component) comprising a carbonate structural unit or a blend of the polycarbonate resin (A-1 component) and another polycarbonate resin (A-2 component) A polycarbonate resin composition is provided.

[In the above formula [1], M represents a divalent organic group derived from a dihydric phenol, and R ¹¹ , R ¹² , R ¹³ , and R ¹⁴ each independently has 1 to 10 carbon atoms. A group selected from the group consisting of an alkyl group, a cycloalkyl group having 6 to 20 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, and an aralkyl group having 7 to 20 carbon atoms D, e, f and g are each independently 0 or 1, n is an integer of 0 to 5, and in the case of a mixture of phosphate esters having different degrees of polymerization, n is an average value thereof. Represents a value between 0 and 5. ]

[In the above formula [2], R ¹⁵ and R ¹⁶ are each independently an alkoxy group having 1 to 10 carbon atoms, a cycloalkoxy group having 6 to 20 carbon atoms, or an alkenyloxy group having 2 to 10 carbon atoms. Represents a group selected from the group consisting of an aryloxy group having 6 to 10 carbon atoms and an aralkyloxy group having 7 to 20 carbon atoms, and h is an integer of 3 to 10].

[In the above formula [3], W is an alkylene group having 1 to 4 carbon atoms, and R ¹ and R ² are each independently an alkyl group having 1 to 10 carbon atoms and a cyclohexane having 6 to 20 carbon atoms. Represents a group selected from the group consisting of an alkyl group, an alkenyl group having 2 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, and an aralkyl group having 7 to 20 carbon atoms, and R ³ and R ⁴ are each independently A hydrogen atom, a halogen atom, an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, a cycloalkyl group having 6 to 20 carbon atoms, a cycloalkoxy group having 6 to 20 carbon atoms, An alkenyl group having 2 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, an aryloxy group having 6 to 10 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, and an aralkyloxy group having 7 to 20 carbon atoms. Represents a group selected from the group consisting of a group, a nitro group, an aldehyde group, a cyano group and a carboxyl group, and when there are plural groups, they may be the same or different, a is 0 or 1, and b and c are Each independently represents an integer of 1 to 4. ]

One of the more preferable embodiments of the present invention is (2) a polycarbonate resin in which the component A is a proportion of 5 to 70 mol% of the carbonate structural unit represented by the above formula [3] in all carbonate structural units. It is a flame-retardant polycarbonate resin composition as described in said structure (1) characterized by the above-mentioned.
One of the more preferred embodiments of the present invention is (3) (C) (c-1) aromatic (meth) acrylate monomer (c-1 component), (c- 2) A copolymer (component C) consisting of an alkyl (meth) acrylate monomer (component c-2) and (c-3) a modified aromatic vinyl monomer (component c-3) is added in an amount of 5 to 100. It is a flame retardant polycarbonate resin composition according to the above constitution (1) or (2), characterized in that it contains parts by weight.
One of the more preferable embodiments of the present invention is (4) a carbonate structure in which the carbonate structural unit represented by the above formula [3] is derived from 9,9-bis (4-hydroxy-3-methylphenyl) fluorene. It is a flame retardant polycarbonate resin composition as described in any one of said structure (1)-(3) characterized by being a unit.
One of the more preferable embodiments of the present invention is (5) a molded article comprising the flame-retardant polycarbonate resin composition according to any one of the above-described configurations (1) to (4).

Hereinafter, the details of the present invention will be described.
<Component A: Polycarbonate resin>
As described above, the polycarbonate resin used as the component A of the present invention is a polycarbonate resin (component A-1) comprising a carbonate constituent unit represented by the following general formula [3] or the polycarbonate resin (A-1). Component) and other polycarbonate resin (component A-2). When the A component does not contain the A-1 component, the surface hardness, wear resistance, and flame retardancy are reduced.

In the above formula [3], W is an alkylene group having 1 to 4 carbon atoms, more preferably an alkylene group having 2 to 3 carbon atoms. R ¹ and R ² are each independently an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 6 to 20 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, or an aryl group having 6 to 10 carbon atoms. , A group selected from the group consisting of aralkyl groups having 7 to 20 carbon atoms, an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 6 to 20 carbon atoms, and an aralkyl group having 7 to 20 carbon atoms. Is more preferable. R ³ and R ⁴ are each independently a hydrogen atom, a halogen atom, an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, a cycloalkyl group having 6 to 20 carbon atoms, or the number of carbon atoms 6 to 20 cycloalkoxy group, alkenyl group having 2 to 10 carbon atoms, aryl group having 6 to 10 carbon atoms, aryloxy group having 6 to 10 carbon atoms, aralkyl group having 7 to 20 carbon atoms, carbon A group selected from the group consisting of an aralkyloxy group having 7 to 20 atoms, a nitro group, an aldehyde group, a cyano group, and a carboxyl group, a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, and a group having 1 to 10 carbon atoms. An alkoxy group, a cycloalkyl group having 6 to 20 carbon atoms, a cycloalkoxy group having 6 to 20 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, and an aryl group having 6 to 10 carbon atoms. Group, an aryloxy group having 6 to 10 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, and an aralkyloxy group having 7 to 20 carbon atoms, preferably a hydrogen atom, an alkyl group having 1 to 10 carbon atoms. Is more preferable.

  Examples of the carbonate structural unit represented by the above formula [3] include 9,9-bis (4-hydroxyphenyl) fluorene, 9,9-bis (4- (2-hydroxyethoxy) phenyl) fluorene, 9,9- Examples thereof include bis (3-methyl-4-hydroxyphenyl) fluorene and carbonate structural units derived from 9,9-bis (3-ethyl-4-hydroxyphenyl) fluorene, and in particular 9,9-bis (4- A carbonate structural unit derived from hydroxy-3-methylphenyl) fluorene (hereinafter sometimes abbreviated as “biscresol fluorene”) is preferably used.

  The dihydroxy compound for deriving the carbonate constituent unit other than the above formula [3] may be any compound that is usually used as a dihydroxy component of an aromatic polycarbonate. For example, 4,4′-dihydroxybiphenyl, bis (4-hydroxy Phenyl) methane, 1,1-bis (4-hydroxyphenyl) ethane, 1,1-bis (4-hydroxyphenyl) decane, 1,1-bis (4-hydroxyphenyl) -1-phenylethane, 2,2 -Bis (4-hydroxyphenyl) propane, 2,2-bis (4-hydroxy-3-methylphenyl) propane, 1,1-bis (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane, 2, 2-bis (4-hydroxy-3,3′-biphenyl) propane, 2,2-bis (4-hydroxy-) -Isopropylphenyl) propane, 2,2-bis (3-tert-butyl-4-hydroxyphenyl) propane, 2,2-bis (4-hydroxyphenyl) butane, 2,2-bis (4-hydroxyphenyl) octane 2,2-bis (3-bromo-4-hydroxyphenyl) propane, 2,2-bis (3,5-dimethyl-4-hydroxyphenyl) propane, 2,2-bis (3-cyclohexyl-4-hydroxy) Phenyl) propane, 1,1-bis (3-cyclohexyl-4-hydroxyphenyl) cyclohexane, bis (4-hydroxyphenyl) diphenylmethane, 1,1-bis (4-hydroxyphenyl) cyclohexane, 1,1-bis (4 -Hydroxyphenyl) cyclopentane, 4,4'-dihydroxydiphenyl ether, 4,4 -Dihydroxy-3,3'-dimethyldiphenyl ether, 4,4'-sulfonyldiphenol, 4,4'-dihydroxydiphenyl sulfoxide, 4,4'-dihydroxydiphenyl sulfide, 2,2'-dimethyl-4, 4′-sulfonyldiphenol, 4,4′-dihydroxy-3,3′-dimethyldiphenyl sulfoxide, 4,4′-dihydroxy-3,3′-dimethyldiphenyl sulfide, 2,2′-diphenyl-4,4 ′ -Sulfonyldiphenol, 4,4'-dihydroxy-3,3'-diphenyldiphenyl sulfoxide, 4,4'-dihydroxy-3,3'-diphenyldiphenyl sulfide, 1,3-bis {2- (4-hydroxyphenyl) ) Propyl} benzene, 1,4-bis {2- (4-hydroxyphenyl) propi L} benzene, 1,4-bis (4-hydroxyphenyl) cyclohexane, 1,3-bis (4-hydroxyphenyl) cyclohexane, 4,8-bis (4-hydroxyphenyl) tricyclo [5.2.1.02 , 6] decane, 4,4 ′-(1,3-adamantanediyl) diphenol, 1,3-bis (4-hydroxyphenyl) -5,7-dimethyladamantane and the following general formula [4] Examples thereof include bisphenol compounds having a siloxane structure.

[Wherein R ²¹ , R ²² , R ²³ , R ²⁴ , R ²⁵ and R ²⁶ are each independently a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, or a substituted or unsubstituted aryl having 6 to 12 carbon atoms. R ⁸ and R ⁹ are each independently a hydrogen atom, a halogen atom, an alkyl group having 1 to 10 carbon atoms, or an alkoxy group having 1 to 10 carbon atoms, and p and q are each 1 to 4 E is a natural number, f is 0 or a natural number, and e + f is a natural number less than 100. X is a divalent aliphatic group having 2 to 8 carbon atoms. ]

  Among them, 1,1-bis (4-hydroxyphenyl) -1-phenylethane, 2,2-bis (4-hydroxyphenyl) propane, 1,1-bis (4-hydroxyphenyl) decane, 2,2-bis (4-hydroxy-3-methylphenyl) propane, 1,1-bis (4-hydroxyphenyl) cyclohexane, 1,1-bis (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane, 4,4 ′ -Sulfonyldiphenol, 2,2'-dimethyl-4,4'-sulfonyldiphenol, 1,3-bis {2- (4-hydroxyphenyl) propyl} benzene, and 1,4-bis {2- (4 -Hydroxyphenyl) propyl} benzene, the bisphenol compound represented by the above general formula [4] is preferred, especially 2,2-bis (4-hydroxy Enyl) propane, 2,2-bis (4-hydroxy-3-methylphenyl) propane, 1,1-bis (4-hydroxyphenyl) decane, 1,1-bis (4-hydroxyphenyl) cyclohexane, the above general formula The bisphenol compound represented by [4] is more preferred, among which 2,2-bis (4-hydroxyphenyl) propane having excellent strength and good durability is most preferred. Moreover, you may use these individually or in combination of 2 or more types.

  The polycarbonate resin (A-1 component) containing the carbonate structural unit represented by the above formula [3] can be made into a branched polycarbonate resin by using a branching agent in combination with the dihydroxy compound. Examples of the branching agent used in the branched polycarbonate resin include phloroglucin, phloroglucide, or 4,6-dimethyl-2,4,6-tris (4-hydroxydiphenyl) heptene-2, 2,4,6-trimethyl. -2,4,6-tris (4-hydroxyphenyl) heptane, 1,3,5-tris (4-hydroxyphenyl) benzene, 1,1,1-tris (4-hydroxyphenyl) ethane, 1,1, 1-tris (3,5-dimethyl-4-hydroxyphenyl) ethane, 2,6-bis (2-hydroxy-5-methylbenzyl) -4-methylphenol, 4- {4- [1,1-bis ( 4-hydroxyphenyl) ethyl] benzene} -α, α-dimethylbenzylphenol and other trisphenols, tetra (4-hydroxyphenyl) methane Bis (2,4-dihydroxyphenyl) ketone, 1,4-bis (4,4-dihydroxytriphenylmethyl) benzene, or trimellitic acid, pyromellitic acid, benzophenonetetracarboxylic acid and acid chlorides thereof More than functional polyfunctional aromatic compounds are mentioned, among which 1,1,1-tris (4-hydroxyphenyl) ethane and 1,1,1-tris (3,5-dimethyl-4-hydroxyphenyl) ethane 1,1,1-tris (4-hydroxyphenyl) ethane is particularly preferable. The proportion of the carbonate constituent unit derived from the branching agent is preferably 0.005 to 1.5 mol%, more preferably 0.01 to 1.2 mol% in the total amount of carbonate constituent units constituting the copolymer. Especially preferably, it is 0.05-1.0 mol%.

In the polycarbonate resin used as the A-1 component of the present invention, the carbonate constituent unit represented by the above formula [3] is preferably in a proportion of 5 to 70 mol% in all carbonate constituent units, and 10 to 70 mol. % Is more preferable, and a ratio of 10 to 50 mol% is still more preferable. When the carbonate structural unit represented by the above formula [3] is less than 5 mol%, the surface hardness and flame retardancy may be lowered. Moreover, when the carbonate structural unit represented by said Formula [3] exceeds 70 mol%, the fall of fluidity | liquidity and the fall of a mechanical physical property may become remarkable.
As the dihydroxy compound for inducing the carbonate structural unit constituting the other polycarbonate resin (component A-2), a dihydroxy compound for inducing a carbonate structural unit other than the above-mentioned formula [3] is used. You may use these individually or in combination of 2 or more types.

  Other polycarbonate resins (component A-2) can be made into branched polycarbonate resins by using a branching agent in combination with the dihydroxy compound. Examples of the branching agent used in the branched polycarbonate resin include phloroglucin, phloroglucide, or 4,6-dimethyl-2,4,6-tris (4-hydroxydiphenyl) heptene-2, 2,4,6-trimethyl. -2,4,6-tris (4-hydroxyphenyl) heptane, 1,3,5-tris (4-hydroxyphenyl) benzene, 1,1,1-tris (4-hydroxyphenyl) ethane, 1,1, 1-tris (3,5-dimethyl-4-hydroxyphenyl) ethane, 2,6-bis (2-hydroxy-5-methylbenzyl) -4-methylphenol, 4- {4- [1,1-bis ( 4-hydroxyphenyl) ethyl] benzene} -α, α-dimethylbenzylphenol and other trisphenols, tetra (4-hydroxyphenyl) methane Bis (2,4-dihydroxyphenyl) ketone, 1,4-bis (4,4-dihydroxytriphenylmethyl) benzene, or trimellitic acid, pyromellitic acid, benzophenonetetracarboxylic acid and acid chlorides thereof More than functional polyfunctional aromatic compounds are mentioned, among which 1,1,1-tris (4-hydroxyphenyl) ethane and 1,1,1-tris (3,5-dimethyl-4-hydroxyphenyl) ethane 1,1,1-tris (4-hydroxyphenyl) ethane is particularly preferable. The proportion of the carbonate constituent unit derived from the branching agent is preferably 0.005 to 1.5 mol%, more preferably 0.01 to 1.2 mol% in the total amount of carbonate constituent units constituting the copolymer. Especially preferably, it is 0.05-1.0 mol%.

The weight ratio of the A-1 component and the A-2 component in the blend (A-1 component / A-2 component) is preferably 95/5 to 5/95, more preferably 90/10 to 10/90, and 70 / 30-30 / 70 is particularly preferred. When the weight ratio of the A-1 component and the A-2 component (A-1 component / A-2 component) exceeds 95/5, there may be a significant decrease in fluidity and mechanical properties. If it is less than 95, surface hardness, abrasion resistance and flame retardancy may be reduced.
These polycarbonate resins are produced by a reaction means known per se for producing ordinary aromatic polycarbonate resins, for example, a method of reacting an aromatic dihydroxy component with a carbonate precursor such as phosgene or carbonic acid diester. The basic means of the manufacturing method will be briefly described.

  In a reaction using, for example, phosgene as a carbonate precursor, the reaction is usually performed in the presence of an acid binder and a solvent. As the acid binder, for example, an alkali metal hydroxide such as sodium hydroxide or potassium hydroxide or an amine compound such as pyridine is used. As the solvent, for example, halogenated hydrocarbons such as methylene chloride and chlorobenzene are used. In order to accelerate the reaction, a catalyst such as a tertiary amine or a quaternary ammonium salt can also be used. In that case, reaction temperature is 0-40 degreeC normally, and reaction time is several minutes-5 hours. The transesterification reaction using a carbonic acid diester as a carbonate precursor is performed by a method in which an aromatic dihydroxy component in a predetermined ratio is stirred with a carbonic acid diester while heating with an inert gas atmosphere to distill the generated alcohol or phenols. . The reaction temperature varies depending on the boiling point of the alcohol or phenol produced, but is usually in the range of 120 to 300 ° C. The reaction is completed while distilling off the alcohol or phenol produced under reduced pressure from the beginning. Moreover, in order to accelerate | stimulate reaction, the catalyst normally used for transesterification can also be used. Examples of the carbonic acid diester used in the transesterification include diphenyl carbonate, dinaphthyl carbonate, bis (diphenyl) carbonate, dimethyl carbonate, diethyl carbonate, and dibutyl carbonate. Of these, diphenyl carbonate is particularly preferred.

  In the present invention, a terminal terminator is used in the polymerization reaction. The end terminator is used for molecular weight control, and the obtained polycarbonate resin is excellent in thermal stability as compared with the other one because the end is blocked. Examples of the terminal terminator include monofunctional phenols represented by the following general formulas [5] to [7].

  [In the formula [5], A is a hydrogen atom, an alkyl group having 1 to 9 carbon atoms, an alkylphenyl group (the alkyl portion has 1 to 9 carbon atoms), a phenyl group, or a phenylalkyl group (the alkyl portion having 1 carbon atom). To 9) and r is an integer from 1 to 5, preferably from 1 to 3].

  [In the formulas [6] and [7], Y is —R—O—, —R—CO—O— or —R—O—CO—, wherein R is a single bond or a carbon number of 1 to 10, preferably Represents a divalent aliphatic hydrocarbon group of 1 to 5, and n represents an integer of 10 to 50. ]

  Specific examples of the monofunctional phenols represented by the general formula [5] include, for example, phenol, isopropylphenol, p-tert-butylphenol, p-cresol, p-cumylphenol, 2-phenylphenol, 4-phenyl. Phenol, isooctylphenol, etc. are mentioned. The monofunctional phenols represented by the general formulas [6] to [7] are phenols having a long-chain alkyl group or an aliphatic ester group as a substituent, and using these, the terminal of the polycarbonate resin is used. These not only function as a terminal terminator or molecular weight regulator, but also improve the melt fluidity of the resin and facilitate molding, as well as reducing the water absorption rate of the resin. used. The substituted phenols represented by the general formula [6] preferably have n of 10 to 30, particularly 10 to 26. Specific examples thereof include decylphenol, dodecylphenol, tetradecylphenol, hexadecylphenol, octadecylphenol, Examples include eicosylphenol, docosylphenol, and triacontylphenol. Further, as the substituted phenols represented by the general formula [7], compounds in which X is —R—CO—O— and R is a single bond are suitable, and n is 10 to 30, particularly 10 to 26. Specific examples thereof include decyl hydroxybenzoate, dodecyl hydroxybenzoate, tetradecyl hydroxybenzoate, hexadecyl hydroxybenzoate, eicosyl hydroxybenzoate, docosyl hydroxybenzoate and triacontyl hydroxybenzoate. Among these monofunctional phenols, monofunctional phenols represented by the above general formula [5] are preferable, more preferably alkyl-substituted or phenylalkyl-substituted phenols, and particularly preferably p-tert-butylphenol, p -Cumylphenol or 2-phenylphenol. These monofunctional phenolic terminal terminators are desirably introduced at the terminal at least 5 mol%, preferably at least 10 mol%, based on all the terminals of the obtained polycarbonate resin. Or a mixture of two or more thereof.

The viscosity average molecular weight of the polycarbonate resin used as the component A of the present invention is preferably in the range of 12,500 to 50,000, more preferably 15,500 to 30,000, and in the range of 18,000 to 28,000. Even more preferred is the range of 19,000 to 26,000. If the molecular weight exceeds 50,000, the melt viscosity becomes too high and the moldability may be inferior, and if the molecular weight is less than 12,500, there may be a problem in mechanical strength. In addition, the viscosity average molecular weight as used in the field of this invention was calculated | required and calculated | required first using the Ostwald viscometer from the solution which melt | dissolved the polycarbonate resin 0.7g in 20 ml of methylene chloride in the specific viscosity computed by following Formula. The viscosity average molecular weight M is determined by inserting the specific viscosity by the following formula.
Specific viscosity (η _SP ) = (t−t ₀ ) / t ₀
[T ₀ is methylene chloride falling seconds, t is sample solution falling seconds]
η _SP /c=[η]+0.45×[η] ² c (where [η] is the intrinsic viscosity)
[Η] = 1.23 × 10 ⁻⁴ M ^0.83
c = 0.7

<B component: phosphorus flame retardant>
The phosphorus-based flame retardant used as the component B of the present invention is at least one phosphorus-based flame retardant selected from the group consisting of a compound represented by the following general formula [1] and a compound represented by the following general formula [2]. It is a flame retardant. When B component is not the said compound, surface hardness and an abrasion-resistant characteristic will fall.

  In the above formula [1], M represents a divalent organic group derived from a dihydric phenol. Examples of dihydric phenols include 1,2-dihydroxybenzene (catechol), 1,3-dihydroxybenzene (resorcinol), 1,4-dihydroxybenzene (hydroquinone), 4,4′-dihydroxybiphenyl, and 2,2′-dihydroxy. Biphenyl, bis (4-hydroxyphenyl) methane, 1,1-bis (4-hydroxyphenyl) ethane, 1,1-bis (4-hydroxyphenyl) decane, 1,1-bis (4-hydroxyphenyl) -1 -Phenylethane, 2,2-bis (4-hydroxyphenyl) propane, 2,2-bis (4-hydroxy-3-methylphenyl) propane, 1,1-bis (4-hydroxyphenyl) -3,3 5-trimethylcyclohexane, 2,2-bis (4-hydroxy-3,3′-biphenyl) propa 2,2-bis (4-hydroxy-3-isopropylphenyl) propane, 2,2-bis (3-tert-butyl-4-hydroxyphenyl) propane, 2,2-bis (4-hydroxyphenyl) butane, 2,2-bis (4-hydroxyphenyl) octane, 2,2-bis (3-bromo-4-hydroxyphenyl) propane, 2,2-bis (3,5-dimethyl-4-hydroxyphenyl) propane, 2 , 2-bis (3-cyclohexyl-4-hydroxyphenyl) propane, 1,1-bis (3-cyclohexyl-4-hydroxyphenyl) cyclohexane, bis (4-hydroxyphenyl) diphenylmethane, 1,1-bis (4- Hydroxyphenyl) cyclohexane, 1,1-bis (4-hydroxyphenyl) cyclopentane, 4,4′-dihy Roxydiphenyl ether, 4,4′-dihydroxy-3,3′-dimethyldiphenyl ether, 4,4′-sulfonyldiphenol, 4,4′-dihydroxydiphenyl sulfoxide, 4,4′-dihydroxydiphenyl sulfide 2,2′-dimethyl-4,4′-sulfonyldiphenol, 4,4′-dihydroxy-3,3′-dimethyldiphenyl sulfoxide, 4,4′-dihydroxy-3,3′-dimethyldiphenyl sulfide, 2, 2,4′-diphenyl-4,4′-sulfonyldiphenol, 4,4′-dihydroxy-3,3′-diphenyldiphenyl sulfoxide, 4,4′-dihydroxy-3,3′-diphenyldiphenyl sulfide, 1,3 -Bis {2- (4-hydroxyphenyl) propyl} benzene, 1,4-bis {2 -(4-hydroxyphenyl) propyl} benzene, 1,4-bis (4-hydroxyphenyl) cyclohexane, 1,3-bis (4-hydroxyphenyl) cyclohexane, 4,8-bis (4-hydroxyphenyl) tricyclo [ 5.2.1.02,6] decane, 4,4 ′-(1,3-adamantanediyl) diphenol, 1,3-bis (4-hydroxyphenyl) -5,7-dimethyladamantane and the like. Among them, 1,2-dihydroxybenzene (catechol), 1,3-dihydroxybenzene (resorcinol), 1,4-dihydroxybenzene (hydroquinone), 4,4′-dihydroxybiphenyl, 2,2′-dihydroxybiphenyl, bis ( 4-hydroxyphenyl) methane, 1,1-bis (4-hydroxyphenyl) ethane , 2,2-bis (4-hydroxyphenyl) propane is preferable.

R ¹¹ , R ¹² , R ¹³ , and R ¹⁴ are each independently an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 6 to 20 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, or a carbon atom. A group selected from the group consisting of an aryl group having 6 to 10 carbon atoms and an aralkyl group having 7 to 20 carbon atoms, and an aryl group having 6 to 10 carbon atoms is particularly preferable. Preferable specific examples of the monohydric phenol for deriving R ¹¹ , R ¹² , R ¹³ , and R ¹⁴ include phenol, cresol, xylenol, isopropylphenol, butylphenol, and p-cumylphenol. Phenol and 2,6-dimethylphenol. E, f and g are each independently 0 or 1, n is an integer of 0 to 5, and in the case of a mixture of phosphate esters having different polymerization degrees n, n represents an average value thereof; A value of ~ 5.

In the above formula [2], R ¹⁵ and R ¹⁶ are each independently an alkoxy group having 1 to 10 carbon atoms, a cycloalkoxy group having 6 to 20 carbon atoms, an alkenyloxy group having 2 to 10 carbon atoms, It is a group selected from the group consisting of an aryloxy group having 6 to 10 carbon atoms and an aralkyloxy group having 7 to 20 carbon atoms, and among them, an aryloxy group having 6 to 10 carbon atoms is preferable. Moreover, h is an integer of 3-10, 4-8 are preferable and 5-7 are more preferable.
Content of B component is 1-20 weight part with respect to 100 weight part of A component, Preferably it is 2-15 weight part, More preferably, it is 2-10 weight part. When the content of the B component is more than 20 parts by weight, problems occur in the surface hardness, friction resistance and flame retardancy, and when it is less than 1 part by weight, flame retardancy cannot be obtained.

<C component: copolymer>
The copolymer used as the C component of the present invention includes an aromatic (meth) acrylate monomer (component c-1), an alkyl (meth) acrylate monomer (component c-2), and a modified aromatic vinyl. It is a copolymer composed of a monomer (component c-3). In addition, the copolymer of this invention has the effect | action which further improves surface hardness, without impairing the transparency of a resin composition.
An aromatic (meth) acrylate monomer includes a methacrylate having an aromatic group in the ester portion, an acrylate having an aromatic group in the ester portion, or both. Specifically, phenyl methacrylate, benzyl methacrylate. , Phenyl acrylate, and benzyl acrylate. This may be used alone or in combination of two or more. Among these, phenyl methacrylate and benzyl methacrylate are preferable, and phenyl methacrylate is more preferable.

Specific examples of the alkyl (meth) acrylate monomer include methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, and 2-ethylhexyl methacrylate. Among these, methyl (meth) acrylate Ethyl (meth) acrylate is preferred, and methyl (meth) acrylate is more preferred.
Specific examples of the modified aromatic vinyl monomer include α-methylstyrene, o-methylstyrene, p-methylstyrene and the like, and α-methylstyrene is particularly preferable.

  Regarding the ratio of each component used in the copolymer, the aromatic (meth) acrylate monomer (component c-1) is preferably 10 to 59 wt. %, More preferably 12 to 50% by weight, still more preferably 15 to 40% by weight, and the alkyl (meth) acrylate monomer (component c-2) is preferably 40 to 89% by weight, more preferably 45 to 85% by weight. %, More preferably 50 to 80% by weight, and the modified aromatic vinyl monomer (component c-3) is preferably 1 to 30% by weight, more preferably 1 to 20% by weight, still more preferably 3 to 18%. % By weight. When each component constituting the copolymer is not within the above range, the compatibility between the copolymer and the polycarbonate resin as the component A may be deteriorated, and the surface hardness and appearance may be lowered.

  The copolymer used as the component C of the present invention has a weight average molecular weight of preferably 5,000 to 30,000, more preferably 7,000 to 28,000, and further preferably 8,000 to 25,000. . When the weight average molecular weight deviates from the range of 5,000 to 30,000, the compatibility with the polycarbonate resin as the component A is deteriorated, and the surface hardness and the appearance may be deteriorated. Such weight average molecular weight is calculated by GPC measurement (gel permeation chromatography measurement). The weight average molecular weight shown here is calculated as a value in terms of polystyrene by GPC measurement using a calibration straight line by standard polystyrene resin.

Examples of the polymerization method of the copolymer used as the component C of the present invention include a known emulsion polymerization method, suspension polymerization method, bulk polymerization method, solution polymerization method and the like. Among these, the emulsion polymerization method is preferable because the polymerizability of the modified aromatic vinyl becomes good. As the emulsifier used in the emulsion polymerization method, known emulsifiers such as sodium alkyldiphenyl ether disulfonate, sodium polyoxyethylene lauryl ether sulfate, sodium dodecylbenzene sulfonate and the like can be used. As the polymerization initiator used in the emulsion polymerization, known polymerization initiators such as t-butyl hydroperoxide and potassium persulfate can be used.
The content of component C is preferably 5 to 100 parts by weight, more preferably 5 to 80 parts by weight, and still more preferably 10 to 80 parts by weight with respect to 100 parts by weight of component A. When the content of component C is less than 5 parts by weight, the effect of further improving the surface hardness may not be seen, and when it exceeds 100 parts by weight, flame retardancy may be reduced.

<Other ingredients>
(Other additives)
In the flame-retardant polycarbonate resin composition of the present invention, the additives used for these improvements are advantageously used for improving the thermal stability, mold release, design and functionality. Hereinafter, these additives will be specifically described.

(I) Thermal stabilizer Various well-known stabilizers can be mix | blended with the flame-retardant polycarbonate resin composition of this invention. Examples of the stabilizer include phosphorus stabilizers and hindered phenol antioxidants.

(I) Phosphorus stabilizer It is preferable that the resin composition of the present invention contains a phosphorus stabilizer to the extent that it does not promote hydrolyzability. Such phosphorus stabilizers improve thermal stability during production or molding, and improve mechanical properties, hue, and molding stability. Examples of phosphorus stabilizers include phosphorous acid, phosphoric acid, phosphonous acid, phosphonic acid and esters thereof, and tertiary phosphine. Specifically, as the phosphite compound, for example, triphenyl phosphite, tris (nonylphenyl) phosphite, tridecyl phosphite, trioctyl phosphite, trioctadecyl phosphite, didecyl monophenyl phosphite, dioctyl monophenyl Phosphite, diisopropyl monophenyl phosphite, monobutyl diphenyl phosphite, monodecyl diphenyl phosphite, monooctyl diphenyl phosphite, 2,2-methylenebis (4,6-di-tert-butylphenyl) octyl phosphite, tris ( Diethylphenyl) phosphite, tris (di-iso-propylphenyl) phosphite, tris (di-n-butylphenyl) phosphite, tris (2,4-di-tert-butylpheny) ) Phosphite, tris (2,6-di-tert-butylphenyl) phosphite, distearyl pentaerythritol diphosphite, bis (2,4-di-tert-butylphenyl) pentaerythritol diphosphite, bis (2 , 6-Di-tert-butyl-4-methylphenyl) pentaerythritol diphosphite, bis (2,6-di-tert-butyl-4-ethylphenyl) pentaerythritol diphosphite, phenylbisphenol A pentaerythritol diphosphite Phyto, bis (nonylphenyl) pentaerythritol diphosphite, dicyclohexyl pentaerythritol diphosphite, and the like. Further, as other phosphite compounds, those which react with dihydric phenols and have a cyclic structure can be used. For example, 2,2′-methylenebis (4,6-di-tert-butylphenyl) (2,4-di-tert-butylphenyl) phosphite, 2,2′-methylenebis (4,6-di-tert- Butylphenyl) (2-tert-butyl-4-methylphenyl) phosphite, 2,2′-methylenebis (4-methyl-6-tert-butylphenyl) (2-tert-butyl-4-methylphenyl) phosphite 2,2′-ethylidenebis (4-methyl-6-tert-butylphenyl) (2-tert-butyl-4-methylphenyl) phosphite. Examples of the phosphate compound include tributyl phosphate, trimethyl phosphate, tricresyl phosphate, triphenyl phosphate, trichlorophenyl phosphate, triethyl phosphate, diphenyl cresyl phosphate, diphenyl monoorxenyl phosphate, tributoxyethyl phosphate, dibutyl phosphate, dioctyl phosphate, Examples thereof include diisopropyl phosphate, and triphenyl phosphate and trimethyl phosphate are preferable.

  Examples of the phosphonite compound include tetrakis (2,4-di-tert-butylphenyl) -4,4′-biphenylenediphosphonite, tetrakis (2,4-di-tert-butylphenyl) -4,3′-biphenylenedi. Phosphonite, tetrakis (2,4-di-tert-butylphenyl) -3,3′-biphenylenediphosphonite, tetrakis (2,6-di-tert-butylphenyl) -4,4′-biphenylenediphosphonite Tetrakis (2,6-di-tert-butylphenyl) -4,3′-biphenylene diphosphonite, tetrakis (2,6-di-tert-butylphenyl) -3,3′-biphenylene diphosphonite, bis (2,4-di-tert-butylphenyl) -4-phenyl-phenylphosphonite, bis (2,4-di tert-butylphenyl) -3-phenyl-phenylphosphonite, bis (2,6-di-n-butylphenyl) -3-phenyl-phenylphosphonite, bis (2,6-di-tert-butylphenyl)- Examples include 4-phenyl-phenylphosphonite, bis (2,6-di-tert-butylphenyl) -3-phenyl-phenylphosphonite, and tetrakis (di-tert-butylphenyl) -biphenylenediphosphonite, bis. (Di-tert-butylphenyl) -phenyl-phenylphosphonite is preferred, tetrakis (2,4-di-tert-butylphenyl) -biphenylenediphosphonite, bis (2,4-di-tert-butylphenyl)- More preferred is phenyl-phenylphosphonite. Such a phosphonite compound is preferable because it can be used in combination with a phosphite compound having an aryl group in which two or more alkyl groups are substituted. Examples of the phosphonate compound include dimethyl benzenephosphonate, diethyl benzenephosphonate, and dipropyl benzenephosphonate. Tertiary phosphine includes triethylphosphine, tripropylphosphine, tributylphosphine, trioctylphosphine, triamylphosphine, dimethylphenylphosphine, dibutylphenylphosphine, diphenylmethylphosphine, diphenyloctylphosphine, triphenylphosphine, tri-p-tolyl. Examples include phosphine, trinaphthylphosphine, and diphenylbenzylphosphine. A particularly preferred tertiary phosphine is triphenylphosphine. The phosphorus stabilizers can be used alone or in combination of two or more. Among the phosphorus stabilizers, an alkyl phosphate compound typified by trimethyl phosphate is preferably blended. A combination of such an alkyl phosphate compound and a phosphite compound and / or phosphonite compound is also a preferred embodiment.

(Ii) Hindered phenol stabilizer A hindered phenol stabilizer can be further blended in the resin composition of the present invention. Such blending exhibits an effect of suppressing, for example, hue deterioration during molding and hue deterioration during long-term use. Examples of the hindered phenol-based stabilizer include α-tocopherol, butylhydroxytoluene, sinapir alcohol, vitamin E, n-octadecyl-β- (4′-hydroxy-3 ′, 5′-di-tert-butylfel). Propionate, 2-tert-butyl-6- (3′-tert-butyl-5′-methyl-2′-hydroxybenzyl) -4-methylphenyl acrylate, 2,6-di-tert-butyl-4- (N , N-dimethylaminomethyl) phenol, 3,5-di-tert-butyl-4-hydroxybenzylphosphonate diethyl ester, 2,2′-methylenebis (4-methyl-6-tert-butylphenol), 2,2′- Methylene bis (4-ethyl-6-tert-butylphenol), 4,4′-methylene bis (2,6- Di-tert-butylphenol), 2,2′-methylenebis (4-methyl-6-cyclohexylphenol), 2,2′-dimethylene-bis (6-α-methyl-benzyl-p-cresol) 2,2′- Ethylidene-bis (4,6-di-tert-butylphenol), 2,2'-butylidene-bis (4-methyl-6-tert-butylphenol), 4,4'-butylidenebis (3-methyl-6-tert- Butylphenol), triethylene glycol-N-bis-3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionate, 1,6-hexanediol bis [3- (3,5-di-tert -Butyl-4-hydroxyphenyl) propionate], bis [2-tert-butyl-4-methyl 6- (3-tert-butyl) -5-methyl-2-hydroxybenzyl) phenyl] terephthalate, 3,9-bis {2- [3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionyloxy] -1,1,- Dimethylethyl} -2,4,8,10-tetraoxaspiro [5,5] undecane, 4,4′-thiobis (6-tert-butyl-m-cresol), 4,4′-thiobis (3-methyl) -6-tert-butylphenol), 2,2'-thiobis (4-methyl-6-tert-butylphenol), bis (3,5-di-tert-butyl-4-hydroxybenzyl) sulfide, 4,4'- Di-thiobis (2,6-di-tert-butylphenol), 4,4′-tri-thiobis (2,6-di-tert-butylphenol), 2,2-thiodiethyl Nbis- [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], 2,4-bis (n-octylthio) -6- (4-hydroxy-3 ′, 5′-di- tert-butylanilino) -1,3,5-triazine, N, N′-hexamethylenebis- (3,5-di-tert-butyl-4-hydroxyhydrocinnamide), N, N′-bis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionyl] hydrazine, 1,1,3-tris (2-methyl-4-hydroxy-5-tert-butylphenyl) butane, 1,3,5 -Trimethyl-2,4,6-tris (3,5-di-tert-butyl-4-hydroxybenzyl) benzene, tris (3,5-di-tert-butyl-4-hydroxyphenyl) iso Anurate, tris (3,5-di-tert-butyl-4-hydroxybenzyl) isocyanurate, 1,3,5-tris (4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl) isocyanurate, 1,3,5-tris 2 [3 (3,5-di-tert-butyl-4-hydroxyphenyl) propionyloxy] ethyl isocyanurate and tetrakis [methylene-3- (3 ′, 5′-di-tert -Butyl-4-hydroxyphenyl) propionate] methane and the like. All of these are readily available. The said hindered phenol type stabilizer can be used individually or in combination of 2 or more types. The amount of the phosphorus stabilizer and the hindered phenol stabilizer is preferably 0.0001 to 1 part by weight, more preferably 0.001 to 0.5 part by weight, and still more preferably 100 parts by weight of component A. Is 0.005 to 0.3 parts by weight.

(Iii) Heat stabilizer other than the above The flame retardant polycarbonate resin composition of the present invention may contain other heat stabilizers other than the phosphorus stabilizer and the hindered phenol stabilizer. Preferable examples of such other heat stabilizers include lactone stabilizers represented by a reaction product of 3-hydroxy-5,7-di-tert-butyl-furan-2-one and o-xylene. Is done. Details of such a stabilizer are described in JP-A-7-233160. Such a compound is commercially available as Irganox HP-136 (trademark, manufactured by CIBA SPECIALTY CHEMICALS) and can be used. Furthermore, a stabilizer obtained by mixing the compound with various phosphite compounds and hindered phenol compounds is commercially available. For example, Irganox HP-2921 manufactured by the above company is preferably exemplified. The blending amount of the lactone stabilizer is preferably 0.0005 to 0.05 parts by weight, more preferably 0.001 to 0.03 parts by weight with respect to 100 parts by weight of the component A. Other stabilizers include sulfur-containing stabilizers such as pentaerythritol tetrakis (3-mercaptopropionate), pentaerythritol tetrakis (3-laurylthiopropionate), and glycerol-3-stearylthiopropionate. Illustrated. The amount of the sulfur-containing stabilizer is preferably 0.001 to 0.1 parts by weight, more preferably 0.01 to 0.08 parts by weight, based on 100 parts by weight of component A. An epoxy compound can be mix | blended with the resin composition of this invention as needed. Such an epoxy compound is blended for the purpose of suppressing mold corrosion, and basically any compound having an epoxy functional group can be applied. Specific examples of preferable epoxy compounds include 3,4-epoxycyclohexylmethyl-3 ′, 4′-epoxycyclohexylcarboxylate, 1,2-epoxy-4-butane of 2,2-bis (hydroxymethyl) -1-butanol. Examples include (2-oxiranyl) cyclosexane adduct, a copolymer of methyl methacrylate and glycidyl methacrylate, and a copolymer of styrene and glycidyl methacrylate. The amount of the epoxy compound added is preferably 0.003 to 0.2 parts by weight, more preferably 0.004 to 0.15 parts by weight, and still more preferably 0.005 to 100 parts by weight of component A. -0.1 parts by weight.

(II) Ultraviolet Absorber The flame retardant polycarbonate resin composition of the present invention can contain an ultraviolet absorber as a stabilizer against ultraviolet rays. Specific examples of the ultraviolet absorber include benzophenone-based compounds such as 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-octoxybenzophenone, and 2-hydroxy-4-benzyloxy. Benzophenone, 2-hydroxy-4-methoxy-5-sulfoxybenzophenone, 2,2'-dihydroxy-4-methoxybenzophenone, 2,2 ', 4,4'-tetrahydroxybenzophenone, 2,2'-dihydroxy-4 , 4′-dimethoxybenzophenone, 2,2′-dihydroxy-4,4′-dimethoxy-5-sodiumsulfoxybenzophenone, bis (5-benzoyl-4-hydroxy-2-methoxyphenyl) methane, 2-hydroxy- 4-n-dodecyloxybenzophenone, and 2- Examples thereof include hydroxy-4-methoxy-2′-carboxybenzophenone. Specific examples of the ultraviolet absorber include, for example, 2- (2-hydroxy-5-methylphenyl) benzotriazole and 2- (2-hydroxy-5-tert-octylphenyl) benzotriazole in the benzotriazole series. 2- (2-hydroxy-3,5-dicumylphenyl) phenylbenzotriazole, 2- (2-hydroxy-3-tert-butyl-5-methylphenyl) -5-chlorobenzotriazole, 2,2′- Methylenebis [4- (1,1,3,3-tetramethylbutyl) -6- (2H-benzotriazol-2-yl) phenol], 2- (2-hydroxy-3,5-di-tert-butylphenyl) ) Benzotriazole, 2- (2-hydroxy-3,5-di-tert-butylphenyl) -5-chlorobenzotriazole 2- (2-hydroxy-3,5-di-tert-amylphenyl) benzotriazole, 2- (2-hydroxy-5-tert-octylphenyl) benzotriazole, 2- (2-hydroxy-5- tert-butylphenyl) benzotriazole, 2- (2-hydroxy-4-octoxyphenyl) benzotriazole, 2,2'-methylenebis (4-cumyl-6-benzotriazolephenyl), 2,2'-p -Phenylenebis (1,3-benzoxazin-4-one), and 2- [2-hydroxy-3- (3,4,5,6-tetrahydrophthalimidomethyl) -5-methylphenyl] benzotriazole, and Copolymerizable with 2- (2′-hydroxy-5-methacryloxyethylphenyl) -2H-benzotriazole and the monomer 2-hydroxy such as copolymers with vinyl monomers and copolymers of 2- (2′-hydroxy-5-acryloxyethylphenyl) -2H-benzotriazole and vinyl monomers copolymerizable with the monomers Examples thereof include a polymer having a phenyl-2H-benzotriazole skeleton. Specifically, the ultraviolet absorber is, for example, 2- (4,6-diphenyl-1,3,5-triazin-2-yl) -5-hexyloxyphenol, 2- (4, 4-hydroxyphenyltriazine). 6-diphenyl-1,3,5-triazin-2-yl) -5-methyloxyphenol, 2- (4,6-diphenyl-1,3,5-triazin-2-yl) -5-ethyloxyphenol 2- (4,6-diphenyl-1,3,5-triazin-2-yl) -5-propyloxyphenol, and 2- (4,6-diphenyl-1,3,5-triazin-2-yl) ) -5-butyloxyphenol and the like. Furthermore, the phenyl group of the above exemplary compounds such as 2- (4,6-bis (2,4-dimethylphenyl) -1,3,5-triazin-2-yl) -5-hexyloxyphenol is 2,4-dimethyl. Examples of the compound are phenyl groups. Specifically, in the case of the cyclic imino ester, the ultraviolet absorber is, for example, 2,2′-p-phenylenebis (3,1-benzoxazin-4-one), 2,2′-m-phenylenebis (3,1). -Benzoxazin-4-one), 2,2'-p, p'-diphenylenebis (3,1-benzoxazin-4-one) and the like. Further, as the ultraviolet absorber, specifically, for cyanoacrylate, for example, 1,3-bis-[(2′-cyano-3 ′, 3′-diphenylacryloyl) oxy] -2,2-bis [(2- Examples include cyano-3,3-diphenylacryloyl) oxy] methyl) propane and 1,3-bis-[(2-cyano-3,3-diphenylacryloyl) oxy] benzene. Furthermore, the ultraviolet absorber has a structure of a monomer compound capable of radical polymerization, so that the ultraviolet absorbent monomer and / or the light stable monomer and a single amount of alkyl (meth) acrylate or the like can be obtained. It may be a polymer type ultraviolet absorber copolymerized with a body. Preferred examples of the ultraviolet absorbing monomer include compounds containing a benzotriazole skeleton, a benzophenone skeleton, a triazine skeleton, a cyclic imino ester skeleton, and a cyanoacrylate skeleton in the ester substituent of (meth) acrylic acid ester. The Among them, benzotriazole and hydroxyphenyltriazine are preferable in terms of ultraviolet absorption ability, and cyclic imino ester and cyanoacrylate are preferable in terms of heat resistance and hue. Specifically, for example, Chemipro Kasei Co., Ltd. “Chemisorb 79”, BASF Japan Co., Ltd. “Tinubin 234” and the like can be mentioned. You may use the said ultraviolet absorber individually or in mixture of 2 or more types.
The content of the ultraviolet absorber is preferably 0.01 to 3 parts by weight, more preferably 0.01 to 1 part by weight, still more preferably 0.05 to 1 part by weight, particularly 100 parts by weight of the component A. Preferably it is 0.05-0.5 weight part.

(III) Dye / pigment Various dyes / pigments can be blended in the flame-retardant polycarbonate resin composition of the present invention in order to improve various design properties. Examples of dyes include perylene dyes, coumarin dyes, thioindigo dyes, anthraquinone dyes, thioxanthone dyes, ferrocyanides such as bitumen, perinone dyes, quinoline dyes, quinacridone dyes, dioxazine dyes, Indolinone dyes, phthalocyanine dyes and the like can be mentioned. Furthermore, the flame retardant polycarbonate resin composition of the present invention can be blended with a metallic pigment to obtain a better metallic color. As the metallic pigment, aluminum powder is suitable. In addition, by blending a fluorescent brightening agent or other fluorescent dyes that emit light, a better design effect utilizing the luminescent color can be imparted.

Flame retardancy (IV) Fluorescent brightener In the flame retardant polycarbonate resin composition of the present invention, the fluorescent brightener is not particularly limited as long as it is used for improving the color tone of the resin to white or bluish white. Examples thereof include stilbene-based, benzimidazole-based, benzoxazole-based, naphthalimide-based, rhodamine-based, coumarin-based, and oxazine-based compounds. Specifically, for example, CI Fluorescent Brightener 219: 1, Eastman Chemical OB-1 manufactured by Eastman Chemical Co., Ltd., “Hackol PSR” manufactured by Showa Chemical Co., Ltd., and the like can be mentioned. Here, the fluorescent whitening agent has an action of absorbing energy in the ultraviolet part of the light and radiating this energy to the visible part. The content of the fluorescent brightening agent is preferably 0.001 to 0.1 parts by weight, more preferably 0.001 to 0.05 parts by weight with respect to 100 parts by weight of the component A. Even if it exceeds 0.1 parts by weight, the effect of improving the color tone of the composition is small.

(V) Compound having heat ray absorbing ability The flame retardant polycarbonate resin composition of the present invention may contain a compound having heat ray absorbing ability. Such compounds include phthalocyanine-based near infrared absorbers, metal oxide-based near infrared absorbers such as ATO, ITO, iridium oxide and ruthenium oxide, imonium oxide, and titanium oxide, lanthanum boride, cerium boride, and tungsten boride. Preferable examples include various metal compounds having excellent near-infrared absorptivity such as metal borides and tungsten oxide-based near-infrared absorbers, and carbon fillers. As such a phthalocyanine-based near infrared absorber, for example, MIR-362 manufactured by Mitsui Chemicals, Inc. is commercially available and easily available. Examples of the carbon filler include carbon black, graphite (including both natural and artificial) and fullerene, and carbon black and graphite are preferable. These can be used alone or in combination of two or more. 0.0005-0.2 weight part is preferable with respect to 100 weight part of A component, as for content of a phthalocyanine type near-infrared absorber, 0.0008-0.1 weight part is more preferable, and 0.001-0. More preferred is 07 parts by weight. The content of the metal oxide-based near infrared absorber, the metal boride-based near infrared absorber and the carbon filler is preferably in the range of 0.1 to 200 ppm (weight ratio) in the polycarbonate resin composition, and is 0.5 to 100 ppm. The range of is more preferable.

(VI) Light Diffusing Agent The flame retardant polycarbonate resin composition of the present invention can be provided with a light diffusing effect by blending a light diffusing agent. Examples of such light diffusing agents include polymer fine particles, inorganic fine particles having a low refractive index such as calcium carbonate, and composites thereof. Such polymer fine particles are fine particles that are already known as light diffusing agents for polycarbonate resins. More preferably, acrylic crosslinked particles having a particle size of several μm, silicone crosslinked particles represented by polyorganosilsesquioxane, and the like are exemplified. Examples of the shape of the light diffusing agent include a spherical shape, a disk shape, a column shape, and an indefinite shape. Such spheres need not be perfect spheres, but include deformed ones, and such columnar shapes include cubes. A preferred light diffusing agent is spherical, and the more uniform the particle size is. The content of the light diffusing agent is preferably 0.005 to 20 parts by weight, more preferably 0.01 to 10 parts by weight, and still more preferably 0.01 to 3 parts by weight with respect to 100 parts by weight of the component A. Two or more light diffusing agents can be used in combination.

(VII) White pigment for high light reflection The flame retardant polycarbonate resin composition of the present invention can be provided with a light reflection effect by blending a white pigment for high light reflection. As such a white pigment, a titanium dioxide (particularly titanium dioxide treated with an organic surface treating agent such as silicone) pigment is particularly preferred. The content of the white pigment for high light reflection is preferably 3 to 30 parts by weight, more preferably 8 to 25 parts by weight with respect to 100 parts by weight of the component A. Two or more kinds of white pigments for high light reflection can be used in combination.

(VIII) Release agent A release agent can be mix | blended with the flame-retardant polycarbonate resin composition of this invention as needed. As such a release agent, those known per se can be used. For example, saturated fatty acid ester, unsaturated fatty acid ester, polyolefin wax (polyethylene wax or 1-alkene polymer may be used. These may be modified with a functional group-containing compound such as acid modification), silicone compounds (For example, linear or cyclic polydimethylsiloxane oil or polymethylphenyl silicone oil). These may be modified with a functional group-containing compound such as acid modification), fluorine compounds (fluorine oil represented by polyfluoroalkyl ether, etc.), paraffin wax, beeswax and the like. Among these, saturated fatty acid esters, linear or cyclic polydimethylsiloxane oil, polymethylphenyl silicone oil, and fluorine oil can be mentioned. Preferable mold release agents include saturated fatty acid esters. For example, monoglycerides such as stearic acid monoglyceride, polyglycerin fatty acid esters such as decaglycerin decastate and decaglycerin tetrastearate, and lower fatty acid esters such as stearic acid stearate. , Higher fatty acid esters such as sebacic acid behenate, and erythritol esters such as pentaerythritol tetrastearate are used. The content of the release agent is preferably 0.01 to 1 part by weight and more preferably 0.01 to 0.5 part by weight with respect to 100 parts by weight of component A. Two or more release agents can be used in combination.

(IX) Polytetrafluoroethylene having fibril-forming ability The flame-retardant polycarbonate resin composition of the present invention can be blended with polytetrafluoroethylene having fibril-forming ability, if necessary. Polytetrafluoroethylene (fibrillated PTFE) having a fibril-forming ability may be a fibrillated PTFE mixed with fibrillated PTFE particles, ie, fibrillated PTFE particles and an organic polymer, even if fibrillated PTFE is used alone. It may be a body. Fibrilized PTFE has an extremely high molecular weight and tends to be bonded to each other by an external action such as shearing force to form a fiber. Its number average molecular weight ranges from 1.5 million to tens of millions. The lower limit is more preferably 3 million. The number average molecular weight is calculated based on the melt viscosity of polytetrafluoroethylene at 380 ° C. as disclosed in JP-A-6-145520. That is, the fibrillated PTFE has a melt viscosity at 380 ° C. measured by the method described in this publication in the range of 10 ⁷ to 10 ¹³ poise, preferably in the range of 10 ⁸ to 10 ¹² poise. Such PTFE can be used in solid form or in the form of an aqueous dispersion. Such fibrillated PTFE can also be used in the form of a PTFE mixture with other resins in order to improve dispersibility in the resin and to obtain better flame retardancy and mechanical properties. Further, as disclosed in JP-A-6-145520, those having a structure having such a fibrillated PTFE as a core and a low molecular weight polytetrafluoroethylene as a shell are also preferably used. Examples of such commercially available fibrillated PTFE include Teflon (registered trademark) 6J from Mitsui DuPont Fluorochemical Co., Ltd., Polyflon MPA FA500, F-201L from Daikin Chemical Industries, Ltd., and the like. As a mixed form of fibrillated PTFE, (1) a method in which an aqueous dispersion of fibrillated PTFE and an aqueous dispersion or solution of an organic polymer are mixed and co-precipitated to obtain a co-agglomerated mixture (JP-A-60-258263). (2) A method of mixing an aqueous dispersion of fibrillated PTFE and dried organic polymer particles (Japanese Patent Laid-Open No. 4-272957). Described method), (3) A method in which an aqueous dispersion of fibrillated PTFE and an organic polymer particle solution are uniformly mixed, and the respective media are simultaneously removed from the mixture (Japanese Patent Laid-Open Nos. 06-220210, (Method described in Japanese Patent Application Laid-Open No. 08-188653), (4) A method of polymerizing monomers forming an organic polymer in an aqueous dispersion of fibrillated PTFE (Method described in JP-A-9-95583), and (5) an aqueous dispersion of PTFE and an organic polymer dispersion are uniformly mixed, and then a vinyl monomer is further polymerized in the mixed dispersion. Thereafter, those obtained by a method for obtaining a mixture (a method described in JP-A-11-29679, etc.) can be used. The proportion of fibrillated PTFE in the mixed form is preferably 1% by weight to 95% by weight, more preferably 10% by weight to 90% by weight, and more preferably 20% by weight in 100% by weight of the mixture. Most preferred is from 80% to 80% by weight. When the ratio of fibrillated PTFE in the mixed form is within such a range, good dispersibility of the fibrillated PTFE can be achieved. Commercial products of these mixed forms of fibrillated PTFE include methabrene represented by Mitsubishi Rayon Co., Ltd.'s "methabrene A3000" (trade name), "methabrene A3700" (trade name), and "methabrene A3800" (trade name). Examples include A series, SN3705 (trade name) manufactured by Shine Polymer, and “BLENDEX B449” (trade name) manufactured by GE Specialty Chemicals.

The fibrillated PTFE is preferably branched polytetrafluoroethylene. When the polytetrafluoroethylene contained is a branched polytetrafluoroethylene, a sufficient anti-dripping effect can be obtained even if the addition of polytetrafluoroethylene is reduced. Examples of commercially available polytetrafluoroethylene having a fibril-forming ability using branched polytetrafluoroethylene include “SN3306” (trade name) and “SN3300B7” (trade name) manufactured by Shine Polymer.
The content of fibrillated PTFE is preferably 0.01 to 1 part by weight, more preferably 0.1 to 0.8 part by weight, and further 0.1 to 0.4 part by weight with respect to 100 parts by weight of component A. More preferred is 0.1 to 0.18 parts by weight. In addition, content of fibrillated PTFE shows the amount of net PTFE, and shows the amount of net PTFE even in the case of mixed form PTFE.

(X) Organometallic salt compound An organometallic salt compound can be blended in the flame-retardant polycarbonate resin composition of the present invention as required. The organic metal salt compound is preferably an alkali (earth) metal salt of an organic acid having 1 to 50 carbon atoms, preferably 1 to 40 carbon atoms, preferably an alkali (earth) metal salt of an organic sulfonate. The alkali (earth) metal salt of the organic sulfonate includes a fluorine-substituted alkyl sulfone such as a metal salt of a perfluoroalkyl sulfonic acid having 1 to 10, preferably 2 to 8 carbon atoms and an alkali metal or an alkaline earth metal. Metal salts of acids and metal salts of aromatic sulfonic acids having 7 to 50 carbon atoms, preferably 7 to 40 carbon atoms, and alkali metals or alkaline earth metals are included. Examples of the alkali metal constituting the metal salt include lithium, sodium, potassium, rubidium and cesium, and examples of the alkaline earth metal include beryllium, magnesium, calcium, strontium and barium. More preferred is an alkali metal. Among such alkali metals, rubidium and cesium having larger ionic radii are suitable when the requirement for transparency is higher, but these are not general-purpose and difficult to purify, resulting in cost. It may be disadvantageous. On the other hand, metals with smaller ionic radii such as lithium and sodium may be disadvantageous in terms of flame retardancy. Considering these, the alkali metal in the sulfonic acid alkali metal salt can be properly used. In any respect, the sulfonic acid potassium salt having an excellent balance of properties is most preferable. Such potassium salts and sulfonic acid alkali metal salts comprising other alkali metals can be used in combination.

Specific examples of alkali metal perfluoroalkyl sulfonates include potassium trifluoromethane sulfonate, potassium perfluorobutane sulfonate, potassium perfluorohexane sulfonate, potassium perfluorooctane sulfonate, sodium pentafluoroethane sulfonate, perfluoro Sodium butanesulfonate, sodium perfluorooctanesulfonate, lithium trifluoromethanesulfonate, lithium perfluorobutanesulfonate, lithium perfluoroheptanesulfonate, cesium trifluoromethanesulfonate, cesium perfluorobutanesulfonate, perfluorooctanesulfonate Cesium, cesium perfluorohexane sulfonate, rubidium perfluorobutane sulfonate, and perf Oro hexane sulfonate rubidium, and these may be used in combination of at least one or two. Here, the carbon number of the perfluoroalkyl group is preferably in the range of 1-18, more preferably in the range of 1-10, and still more preferably in the range of 1-8. Of these, potassium perfluorobutanesulfonate is particularly preferred. The alkali (earth) metal salt of perfluoroalkylsulfonic acid composed of an alkali metal is usually mixed with not less than fluoride ions (F ⁻ ). The presence of such fluoride ions can be a factor that lowers the flame retardancy, so it is preferably reduced as much as possible. The ratio of such fluoride ions can be measured by ion chromatography. The content of fluoride ions is preferably 100 ppm or less, more preferably 40 ppm or less, and particularly preferably 10 ppm or less. Moreover, it is suitable that it is 0.2 ppm or more in terms of production efficiency. Such alkali (earth) metal salt of perfluoroalkylsulfonic acid having a reduced amount of fluoride ion is contained in a raw material when producing a fluorine-containing organometallic salt using a known production method. A method for reducing the amount of fluoride ions, a method for removing hydrogen fluoride and the like obtained by the reaction by a gas generated during the reaction or heating, and a purification method such as recrystallization and reprecipitation for producing a fluorine-containing organometallic salt Can be produced by a method of reducing the amount of fluoride ions using, for example. In particular, organic metal salt flame retardants are relatively soluble in water, and therefore ion-exchanged water, especially water that has an electric resistance of 18 MΩ · cm or more, that is, an electric conductivity of about 0.55 μS / cm or less is used. In addition, it is preferable to produce by a process of dissolving at a temperature higher than room temperature and washing, then cooling and recrystallization. Specific examples of the aromatic (earth) metal salt of an aromatic sulfonate include, for example, disodium diphenyl sulfide-4,4′-disulfonate, dipotassium diphenyl sulfide-4,4′-disulfonate, potassium 5-sulfoisophthalate, Sodium 5-sulfoisophthalate, polysodium polyethylene terephthalate polysulfonate, calcium 1-methoxynaphthalene-4-sulfonate, disodium 4-dodecylphenyl ether disulfonate, polysodium poly (2,6-dimethylphenylene oxide) polysulfonate Poly (1,3-phenylene oxide) polysulfonic acid polysodium, poly (1,4-phenylene oxide) polysulfonic acid polysodium, poly (2,6-diphenylphenylene oxide) polysulfonic acid polycarbonate , Lithium poly (2-fluoro-6-butylphenylene oxide) polysulfonate, potassium sulfonate benzenesulfonate, sodium benzenesulfonate, strontium benzenesulfonate, magnesium benzenesulfonate, dipotassium p-benzenedisulfonate, naphthalene-2 , 6-disulfonic acid dipotassium, biphenyl-3,3'-disulfonic acid calcium, diphenylsulfone-3-sulfonic acid sodium, diphenylsulfone-3-sulfonic acid potassium, diphenylsulfone-3,3'-disulfonic acid dipotassium, diphenylsulfone -Potassium 3,4'-disulfonate, sodium α, α, α-trifluoroacetophenone-4-sulfonate, dipotassium benzophenone-3,3'-disulfonate, thiophene-2 Formalin of disodium 5-disulfonate, dipotassium thiophene-2,5-disulfonate, calcium thiophene-2,5-disulfonate, sodium benzothiophenesulfonate, potassium diphenylsulfoxide-4-sulfonate, sodium naphthalenesulfonate Examples thereof include condensates and formalin condensates of sodium anthracene sulfonate. Among these aromatic sulfonate alkali (earth) metal salts, potassium salts are particularly preferable. Among these aromatic sulfonate alkali (earth) metal salts, potassium diphenylsulfone-3-sulfonate and dipotassium diphenylsulfone-3,3′-disulfonate are preferable, and particularly a mixture thereof (the former and the latter). Is preferably 15/85 to 30/70).

Preferable examples of the organic metal salt other than the alkali (earth) metal sulfonate include an alkali (earth) metal salt of a sulfate ester and an alkali (earth) metal salt of an aromatic sulfonamide. Examples of alkali (earth) metal salts of sulfates include alkali (earth) metal salts of sulfates of monovalent and / or polyhydric alcohols, and such monovalent and / or polyhydric alcohols. Examples of sulfuric acid esters include methyl sulfate, ethyl sulfate, lauryl sulfate, hexadecyl sulfate, polyoxyethylene alkylphenyl ether sulfate, pentaerythritol mono-, di-, tri-, tetra-sulfate, and lauric acid monoglyceride sulfate. Examples include esters, sulfates of palmitic acid monoglyceride, and sulfates of stearic acid monoglyceride. The alkali (earth) metal salts of these sulfates are preferably alkali (earth) metal salts of lauryl sulfate. Alkali (earth) metal salts of aromatic sulfonamides include, for example, saccharin, N- (p-tolylsulfonyl) -p-toluenesulfonimide, N- (N′-benzylaminocarbonyl) sulfanilimide, and N- ( And an alkali (earth) metal salt of phenylcarboxyl) sulfanilimide.
The content of the organometallic salt compound is preferably 0.01 to 1.0 part by weight, more preferably 0.01 to 0.5 part by weight, and still more preferably 0.01 to 1.0 part by weight with respect to 100 parts by weight of the component A. 0.3 part by weight, particularly preferably 0.03 to 0.15 part by weight.

(XI) Filler In the flame-retardant polycarbonate resin composition of the present invention, various known fillers can be blended as reinforcing fillers. As such a filler, various fibrous fillers, plate-like fillers, and granular fillers can be used. Here, the fibrous filler has a fibrous shape (including a rod shape, a needle shape, or a shape whose axis extends in a plurality of directions), and the plate-like filler has a plate shape (surface) (Including those having irregularities and those having a curved plate). The granular filler is a filler having a shape other than these including an indefinite shape. The fiber-like and plate-like shapes are often clear from the observation of the shape of the filler. For example, a difference from a so-called indeterminate shape can be said to be a fiber-like or plate-like one having an aspect ratio of 3 or more.

  As plate-like fillers, glass-flake, talc, mica, kaolin, metal flakes, carbon flakes, and graphite, and these fillers are coated with different materials such as metals and metal oxides. A material etc. are illustrated preferably. The particle size is preferably in the range of 0.1 to 300 μm. The particle size is about 10 μm in terms of the median diameter (D50) of the particle size distribution measured by the X-ray transmission method, which is one of the liquid phase precipitation methods. In the region of 10-50 μm, laser diffraction is performed. -The value by the median diameter (D50) of the particle size distribution measured by the scattering method is referred to, and in the region of 50 to 300 μm, the value is by the vibration sieving method. Such a particle size is a particle size in the resin composition. The plate-like filler may be surface-treated with various coupling agents such as silane, titanate, aluminate, and zirconate, and olefin resin, styrene resin, acrylic resin, polyester resin. It may be a granulated product that has been subjected to a bundling treatment or compression treatment with various resins such as epoxy resins and urethane resins, higher fatty acid esters, and the like.

  The fiber diameter of the fibrous filler is preferably in the range of 0.1 to 20 μm. The upper limit of the fiber diameter is more preferably 13 μm, further preferably 10 μm. On the other hand, the lower limit of the fiber diameter is preferably 1 μm. The fiber diameter here refers to the number average fiber diameter. The number average fiber diameter is obtained by scanning the residue collected after dissolving the molded product in a solvent, or decomposing the resin with a basic compound, and the ash residue collected after ashing with a crucible. It is a value calculated from an image observed with an electron microscope. Examples of the fibrous filler include glass fiber, flat cross-section glass fiber, glass milled fiber, carbon fiber, carbon milled fiber, metal fiber, asbestos, rock wool, ceramic fiber, slag fiber, potassium titanate whisker, and boron whisker. , Aluminum inorganic whisker, calcium carbonate whisker, titanium oxide whisker, wollastonite, zonotolite, palygorskite (attapulgite), and fibrous inorganic fillers such as sepiolite, heat-resistant organic fibers such as aramid fiber, polyimide fiber and polybenzthiazole fiber And heat-resistant organic fillers represented by the above, as well as fibrous fillers whose surfaces are coated with different materials such as metals and metal oxides. It is exemplified. Examples of the filler whose surface is coated with a different material include metal-coated glass fibers, metal-coated glass flakes, titanium oxide-coated glass flakes, and metal-coated carbon fibers. The surface coating method of different materials is not particularly limited. For example, various known plating methods (for example, electrolytic plating, electroless plating, hot-dip plating, etc.), vacuum deposition methods, ion plating methods, CVD methods ( For example, thermal CVD, MOCVD, plasma CVD, etc.), PVD method, sputtering method, etc. can be mentioned. Here, the fibrous filler means a fibrous filler having an aspect ratio of 3 or more, preferably 5 or more, more preferably 10 or more. The upper limit of the aspect ratio is about 10,000, preferably 200. The aspect ratio of such a filler is a value in the resin composition. The flat cross-section glass fiber has an average value of the major axis of the fiber cross section of 10 to 50 μm, preferably 15 to 40 μm, more preferably 20 to 35 μm, and an average value of the ratio of major axis to minor axis (major axis / minor axis) of 1. .5-8, preferably 2-6, more preferably 2.5-5 glass fiber. The fibrous filler may be surface-treated with various coupling agents in the same manner as the plate-like filler, may be converged with various resins, and may be granulated by compression. The content of the filler is preferably 200 parts by weight or less, more preferably 100 parts by weight or less, still more preferably 50 parts by weight or less, and particularly preferably 30 parts by weight or less with respect to 100 parts by weight of the component A.

(XII) Other Resins and Elastomers The flame retardant polycarbonate resin composition of the present invention contains a small amount of other resins and elastomers in the range where the effects of the present invention are exhibited, instead of a part of the polycarbonate resin of component A. Percentage can also be used. The blending amount of other resins and elastomers is preferably 20% by weight or less, more preferably 10% by weight or less, and still more preferably 5% by weight or less in a total of 100% by weight with the component A. Examples of such other resins include polyester resins such as polyethylene terephthalate and polybutylene terephthalate, polyamide resins, polyimide resins, polyetherimide resins, polyurethane resins, silicone resins, polyphenylene ether resins, polyphenylene sulfide resins, polysulfone resins, and polymethacrylate resins. And resins such as phenol resins and epoxy resins. As the elastomer, for example, isobutylene / isoprene rubber, styrene / butadiene rubber, ethylene / propylene rubber, acrylic elastomer, polyester elastomer, polyamide elastomer, MBS (methyl methacrylate / sterene / butadiene) which is a core-shell type elastomer. Examples thereof include rubber, MB (methyl methacrylate / butadiene) rubber, MAS (methyl methacrylate / acrylonitrile / styrene) rubber, and the like.

(XIII) Other Additives The flame retardant polycarbonate resin composition of the present invention contains other flow modifiers, antibacterial agents, dispersants such as liquid paraffin, photocatalytic antifouling agents, and photochromic agents. Can do.

<About production of resin composition>
Arbitrary methods are employ | adopted in order to manufacture the resin composition of this invention. For example, component A, component B and optionally other components are mixed thoroughly using premixing means such as a V-type blender, Henschel mixer, mechanochemical apparatus, extrusion mixer, etc., and then an extrusion granulator as necessary. And granulating with a briquetting machine or the like, and then melt-kneading with a melt-kneader typified by a vent-type biaxial ruder and pelletizing with a device such as a pelletizer. Alternatively, the A component, the B component and optionally other components are each independently fed to a melt kneader represented by a vented twin-screw rudder, and after pre-mixing part of the A component and other components , A method of supplying to the melt kneader independently of the remaining components, the component B is diluted and mixed with water or an organic solvent, and then supplied to the melt kneader, or the diluted mixture is premixed with other components and then melt kneaded. The method of supplying to a machine is also mentioned. In addition, when there exists a liquid thing in the component to mix | blend, what is called a liquid injection apparatus or a liquid addition apparatus can be used for supply to a melt kneader.

<Manufacture of molded products>
The resin composition of this invention can manufacture various products by usually injection-molding this pellet and obtaining a molded article. In such injection molding, not only a normal cold runner type molding method but also a hot runner that enables runnerlessness can be used. Also in injection molding, not only ordinary molding methods, but also gas-assisted injection molding, injection compression molding, ultra-high speed injection molding, injection press molding, two-color molding, sandwich molding, in-mold coating molding, insert molding, foam molding (ultra-molding) Including those using critical fluids), rapid heating / cooling mold forming, heat insulating mold forming and in-mold remelt molding, and combinations of these, etc. can be used. Furthermore, various surface treatments can be performed on the molded product formed from the resin composition. Surface treatment includes decorative coating, hard coat, water / oil repellent coat, hydrophilic coat, UV absorbing coat, infrared absorbing coat, electromagnetic wave absorbing coat, heat generating coat, antistatic coat, antistatic coating, conductive coating, and meta coating. Various surface treatments such as rising (plating, chemical vapor deposition (CVD), physical vapor deposition (PVD), thermal spraying, etc.) can be performed. In particular, a transparent sheet coated with a transparent conductive layer is preferred.

  The aromatic polycarbonate resin composition of the present invention has a high surface hardness by using an unprecedented combination in a resin composition in which a specific phosphorus flame retardant is blended with a polycarbonate resin containing a specific carbonate structural unit. It has excellent appearance and flame retardancy while being maintained, and these technologies are not present in conventional flame retarding technologies. The flame retardant polycarbonate resin composition of the present invention can impart high flame retardancy without using a brominated flame retardant, which is said to have a high environmental load, and further has a high surface hardness, repeated contact and Even in applications that rub, since deformation and fusion of molded products are not observed, it is extremely useful in various industrial applications such as the OA equipment field and the electrical and electronic equipment field, and the industrial effects that it exhibits are extremely large. is there.

  The form of the present invention considered to be the best by the present inventors is a collection of the preferable ranges of the above requirements. For example, typical examples are described in the following examples. Of course, the present invention is not limited to these forms.

The present invention will be further described below with reference to examples, but the present invention is not limited thereto.
The following items were evaluated.

(I) Surface appearance The pellets obtained from each composition of the examples were dried at 120 ° C. for 5 hours with a hot air dryer, and by an injection molding machine [Sumitomo Heavy Industries, Ltd. SG150U · SM IV], A plate having a cylinder temperature of 300 ° C., a mold temperature of 90 ° C., a length of 150 mm × width of 150 mm, a thickness of 2.0 mm, and Ra of 0.03 μm was molded. The molded product was visually confirmed, and the case where the surface was smooth and no spots or white streaks were observed was rated as “◯”, and the case where spots or white streaks were confirmed in a part of the molded product was marked as “X”.

(Ii) Surface Hardness The pellets obtained from each composition of the examples were dried at 120 ° C. for 5 hours with a hot air dryer, and by an injection molding machine [Sumitomo Heavy Industries, Ltd. SG150U / SMIV] A plate having a cylinder temperature of 300 ° C., a mold temperature of 90 ° C., a length of 150 mm × width of 150 mm, a thickness of 2.0 mm, and a Ra of 0.03 μm was molded, and pencil hardness was measured according to JIS K5600. In addition, when shaving occurred even when the pencil of 2B was used, it was described as “> 2B”.

(Iii) Repeated friction resistance The pellets obtained from each composition of the examples were dried with a hot air dryer at 120 ° C. for 5 hours, and injection molding machine [Sumitomo Heavy Industries, Ltd. SG150U · SM IV]. Three-stage plate with a cylinder temperature of 300 ° C, a mold temperature of 90 ° C, a width of 50 mm, a length of 90 mm, and a thickness of 3 mm (length 20 mm), 2 mm (length 45 mm), and 1 mm (length 25 mm) from the gate side Was prepared by injection molding under the above conditions. A reciprocating friction and wear tester AFT-15M manufactured by Orientec Co., Ltd. was used as an evaluation device. A pin-shaped test piece (material: steel) having a spherical surface at the tip, in which a hemisphere with a diameter of 3 mmφ and a cylinder with a diameter of 5 mmφ and a length of 30 mmφ were combined at a circular cross section, was mounted on a fixed-side test piece holder. On the other hand, the molded plate is fixed on a reciprocating pedestal, and the tip spherical surface portion of the pin-shaped test piece is placed on the plane portion of the test piece. It was made to contact in the state where the load of 4.9N was applied in the state where the line direction became parallel. In such a contact state, a distance of 20 mm one way was reciprocated 500 times on a straight line in a plane at a rate of 1 reciprocation 1 second in an atmosphere of 23 ° C. and relative humidity 50% RH, and visually judged according to the following criteria. .
○: The molded product cannot be scraped. Δ: The molded product is slightly scraped, but the scraped powder can be removed by wiping.
X: The molded product is scraped and the scraped powder is fused to the molded product.

(Iv) Flame retardancy The pellets obtained from each composition of the examples were dried at 120 ° C. for 5 hours in a hot air circulating dryer, and the cylinder temperature was 300 using an injection molding machine [Toshiba Machine Co., Ltd. IS150EN-5Y]. A test piece for flame retardancy evaluation was molded at 0 ° C. and a mold temperature of 90 ° C. The vertical combustion test of UL standard 94 was performed at thicknesses of 1.8 mm, 1.5 mm, and 1.2 mm, and the grade was evaluated. When the determination fails to satisfy any of the criteria of V-0, V-1, and V-2, “notV” is indicated.

[Examples 1 to 15 and Comparative Examples 1 to 6]
The resin composition which consists of a mixture ratio of Table 1 and Table 2 was created in the following ways. Each component of the ratio of Table 1 and Table 2 was measured, it mixed uniformly using the tumbler, and this mixture was thrown into the extruder and preparation of the resin composition was performed. As the extruder, a vent type twin screw extruder (Kobe Steel Works KTX-30) having a diameter of 30 mmφ was used. The screw configuration is the first stage kneading zone (consisting of 2 feed kneading discs, 1 feed rotor, 1 return rotor and 1 return kneading disc) before the vent position. Thereafter, a second-stage kneading zone (consisting of a feed rotor × 1 and a return rotor × 1) was provided. The strand was extruded under the conditions of cylinder temperature and die temperature of 290 ° C. and vent suction of 3000 Pa, cooled in a water bath, then strand-cut with a pelletizer and pelletized. Using the above-described method, the obtained pellets were molded into test pieces for various evaluations and evaluated. The evaluation results are shown in Tables 1 and 2. The raw materials used in Tables 1 and 2 are as follows.

(A component)
(A-1 component)
PC-1: 9,9-bis (4-hydroxy-3-methylphenyl) fluorene (hereinafter sometimes abbreviated as “biscresol fluorene”) and 2,2-bis (4-hydroxyphenyl) propane (hereinafter “ Polycarbonate resin in which the ratio of bisphenol A "(sometimes abbreviated as" bisphenol A ") is 50:50 in molar ratio (PC-1 production method)
A reactor equipped with a thermometer, a stirrer and a reflux condenser was charged with 23030 parts of ion exchange water and 3957 parts of 48.5% aqueous sodium hydroxide solution, and 3026 parts of biscresol fluorene, 1826 parts of bisphenol A and 10 parts of hydrosulfite were dissolved. Thereafter, 17183 parts of methylene chloride was added, and 1900 parts of phosgene was blown in for 60 minutes at 15 to 25 ° C. with stirring. After completion of the phosgene blowing, a solution obtained by dissolving 96 parts of p-tert-butylphenol in 1300 parts of methylene chloride and 660 parts of a 48.5% aqueous sodium hydroxide solution were added and emulsified. The reaction was terminated by stirring at 33 ° C. for 1 hour. After completion of the reaction, the product is diluted with methylene chloride, washed with water, acidified with hydrochloric acid, washed with water, and when the conductivity of the aqueous phase is almost the same as that of ion-exchanged water, the methylene chloride phase is concentrated and dehydrated to remove polycarbonate. A solution with a concentration of 20% was obtained. The polycarbonate obtained by removing the solvent from this solution had a molar ratio of biscresol fluorene to bisphenol A of 50:50 (polymer yield 97%).

PC-2: Polycarbonate resin having a molar ratio of biscresol fluorene to bisphenol A of 10:90 (PC-2 production method)
Except for using 605 parts of biscresol fluorene and 3286 parts of bisphenol A, the ratio of the constituent units of biscresol fluorene and bisphenol A is 10 in terms of molar ratio, in the same manner as in PC-1. : A polycarbonate of 90 was obtained (polymer yield 98%)

PC-3: Polycarbonate resin in which the ratio of biscresol fluorene to bisphenol A is 70:30 in molar ratio (PC-3 production method)
The ratio of the structural units of biscresol fluorene and bisphenol A was 70 in terms of molar ratio in the same manner as in PC-1, except that the amount of biscresol fluorene used was 4236 parts and the amount of bisphenol A used was 1095 parts. : 30 was obtained (polymer yield 96%)

(A-2 component)
PC-4: Polycarbonate resin made of bisphenol A.
(Manufacturing method of PC-4)
A reactor equipped with a thermometer, a stirrer, and a reflux condenser was charged with 18024 parts of ion exchange water and 3441 parts of 48.5% aqueous sodium hydroxide solution, dissolved 3810 parts of bisphenol A and 8 parts of hydrosulfite, and then 17931 parts of methylene chloride. And 1900 parts of phosgene was blown in for 60 minutes at 15 to 25 ° C. with stirring. After completion of the phosgene blowing, a solution obtained by dissolving 87.6 parts of p-tert-butylphenol in 1200 parts of methylene chloride and 688 parts of 48.5% aqueous sodium hydroxide solution were added and emulsified, and then 5.8 parts of triethylamine was added. The reaction was terminated by stirring at 28 to 33 ° C. for 1 hour. After completion of the reaction, the product is diluted with methylene chloride, washed with water, acidified with hydrochloric acid, washed with water, and when the conductivity of the aqueous phase is almost the same as that of ion-exchanged water, the methylene chloride phase is concentrated and dehydrated to remove polycarbonate. A solution with a concentration of 20% was obtained. The solvent was removed from this solution to obtain a polycarbonate composed of bisphenol A (polymer yield 97%).

PC-5: A polycarbonate resin composed of 2,2-bis (4-hydroxy-3-methylphenyl) propane (hereinafter sometimes abbreviated as “bisphenol C”).
(Manufacturing method of PC-5)
A polycarbonate made of bisphenol C was obtained in the same manner as in the production method of PC-4 except that 4278 parts of bisphenol C was used instead of 3810 parts of bisphenol A (polymer yield: 95%).

(B component)
B-1: Phosphate ester mainly composed of bisphenol A bis (diphenyl phosphate) (manufactured by Daihachi Chemical Industry Co., Ltd .: “CR-741 (trade name)”)
B-2: Phosphate ester mainly composed of resorcinol bis (dixylenyl phosphate) (manufactured by Daihachi Chemical Industry Co., Ltd .: “PX-200 (trade name)”)
B-3: Cyclic phenoxyphosphazene (Fushimi Pharmaceutical Co., Ltd .: FP-110T (trade name))
(Phosphorus flame retardants other than component B)
B-4: Triphenyl phosphate (manufactured by Daihachi Chemical Industry Co., Ltd .: “TPP (trade name)”)
(C component)
C-1: a copolymer having a weight average molecular weight of 16,700 phenyl methacrylate / methyl methacrylate / α-methylstyrene in a weight ratio of 30: 62: 8 (manufactured by Mitsubishi Rayon Co., Ltd .: H-880 (trade name)) )
(Other ingredients)
SN-1: A mixture comprising polytetrafluoroethylene particles and a styrene-acrylic copolymer (manufactured by Shine Polymer: SN3307 (trade name))
SN-2: A mixture comprising branched polytetrafluoroethylene particles and a styrene-acrylic copolymer (manufactured by Shine Polymer: SN3300B7 (trade name))
TALC: Talc (manufactured by Katsumiyama Mining Co., Ltd .; Victorite TK-RC (trade name))

Claims (5)

(A) With respect to 100 parts by weight of the polycarbonate resin (component A), (B) at least one selected from the group consisting of a compound represented by the following general formula [1] and a compound represented by the following general formula [2] A flame retardant polycarbonate resin composition containing 1 to 20 parts by weight of a phosphorus-based flame retardant, wherein the polycarbonate resin of component A comprises a carbonate constituent unit represented by the following general formula [3] ( A flame retardant polycarbonate resin composition, which is a blend of (A-1 component) or the polycarbonate resin (A-1 component) and another polycarbonate resin (A-2 component).

[In the above formula [1], M represents a divalent organic group derived from a dihydric phenol, and R ¹¹ , R ¹² , R ¹³ , and R ¹⁴ each independently has 1 to 10 carbon atoms. A group selected from the group consisting of an alkyl group, a cycloalkyl group having 6 to 20 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, and an aralkyl group having 7 to 20 carbon atoms D, e, f and g are each independently 0 or 1, n is an integer of 0 to 5, and in the case of a mixture of phosphate esters having different degrees of polymerization, n is an average value thereof. Represents a value between 0 and 5. ]

[In the above formula [2], R ¹⁵ and R ¹⁶ are each independently an alkoxy group having 1 to 10 carbon atoms, a cycloalkoxy group having 6 to 20 carbon atoms, or an alkenyloxy group having 2 to 10 carbon atoms. Represents a group selected from the group consisting of an aryloxy group having 6 to 10 carbon atoms and an aralkyloxy group having 7 to 20 carbon atoms, and h is an integer of 3 to 10].

[In the above formula [3], W is an alkylene group having 1 to 4 carbon atoms, and R ¹ and R ² are each independently an alkyl group having 1 to 10 carbon atoms and a cyclohexane having 6 to 20 carbon atoms. Represents a group selected from the group consisting of an alkyl group, an alkenyl group having 2 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, and an aralkyl group having 7 to 20 carbon atoms, and R ³ and R ⁴ are each independently A hydrogen atom, a halogen atom, an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, a cycloalkyl group having 6 to 20 carbon atoms, a cycloalkoxy group having 6 to 20 carbon atoms, An alkenyl group having 2 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, an aryloxy group having 6 to 10 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, and an aralkyloxy group having 7 to 20 carbon atoms. Represents a group selected from the group consisting of a group, a nitro group, an aldehyde group, a cyano group and a carboxyl group, and when there are plural groups, they may be the same or different, a is 0 or 1, and b and c are Each independently represents an integer of 1 to 4. ]   The flame retardant polycarbonate according to claim 1, wherein the component A is a polycarbonate resin in which the carbonate structural unit represented by the formula [3] is a proportion of 5 to 70 mol% in all carbonate structural units. Resin composition.   (C) (c-1) aromatic (meth) acrylate monomer (c-1 component), (c-2) alkyl (meth) acrylate monomer (c-2 component) with respect to 100 parts by weight of component A And (c-3) a copolymer (component C) comprising a modified aromatic vinyl monomer (component c-3) is contained in an amount of 5 to 100 parts by weight. The flame-retardant polycarbonate resin composition as described.   The carbonate constituent unit represented by the formula [3] is a carbonate constituent unit derived from 9,9-bis (4-hydroxy-3-methylphenyl) fluorene. The flame-retardant polycarbonate resin composition according to claim 1.   The molded article which consists of a flame-retardant polycarbonate resin composition as described in any one of Claims 1-4.