JP2007045907A - Flame-retardant resin composition and molded article composed of the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a flame-retardant resin composition having extremely excellent compatibility with polycarbonate resin, excellent in flame retardancy, mechanical strength, etc., of the resin composition and capable of imparting light reflectivity to applications requiring light reflectivity. <P>SOLUTION: The flame-retardant resin composition is obtained by formulating a polycarbonate resin with a phosphoric acid amide compound having a specific structure and a fiber-forming type fluorine-containing polymer and further as necessary, a specific rubber-like elastomer, a rubber-reinforced styrene-based resin and a mold-releasing agent or titanium oxide. A molded article or a light-reflecting plate is obtained by molding the resin composition. Since the flame-retardant resin composition does not contain a halogen-based flame retardant composed of a chlorine or bromine compound, etc., the resin composition is excellent in the aspect of environmental protection and further has high flame retardancy, light reflectivity (when titanium oxide is formulated therein), mechanical physical properties, good surface appearance, etc., and can suitably be used as a material for various interior and exterior applications in electrical/electronic applications and OA, and for light-reflecting plates for liquid crystal backlight, etc., when titanium oxide is formulated therein. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

 The present invention includes a polycarbonate resin, a specific phosphoramide compound and a fiber-forming fluorine-containing polymer as an anti-drip agent, and a specific rubber-like elastic body, a rubber-reinforced styrene-based resin, a release agent, or an oxidation agent as necessary. The present invention relates to a flame retardant resin composition containing titanium. Moreover, what mix | blended titanium oxide has high light reflectivity, and can be used conveniently for a light reflection board, especially the light reflection board for liquid crystal backlights.

  Polycarbonate resin is a thermoplastic resin excellent in impact resistance, heat resistance, and the like, and is widely used in fields such as electricity, electronics, OA, machinery, and automobiles. On the other hand, in addition to these excellent performances possessed by the polycarbonate resin, in order to satisfy safety requirements in fields such as electricity, electronics and OA, a material having high flame retardancy is required. Therefore, various methods for blending flame retardants such as organic bromine compounds have been proposed and adopted in order to improve the flame retardancy of polycarbonate resins.

However, when a halogen-based compound such as an organic bromine compound is blended, it is accompanied by generation of a halogen-based gas at the time of combustion. Therefore, in recent years, it has been particularly demanded to improve the flame-retardant performance by using a non-halogen-based flame retardant. ing.

As typical non-halogen flame retardants, phosphate esters such as triphenyl phosphate, condensed phosphate amides (condensates of ammonium phosphate), phenyl phosphate ester monoamides, phenyl phosphate ester monoamides are often used, Compositions containing these have been proposed, but each of these compounds has a tendency to reduce the hydrolysis resistance of the polycarbonate resin, and further has the problem that decomposition occurs during heating and kneading with the polycarbonate resin. there were.

JP-A-53-73248 JP 60-108553 A JP 63-235363 A

  In addition, the situation is the same even in the case of a flame retardant resin composition having light reflectivity used for a light reflector such as a liquid crystal backlight, and the use of a non-halogen flame retardant having higher environmental reliability. Was strongly desired.

Japanese Patent Laid-Open No. 09-012853 JP 2000-053854 A

  In view of such circumstances, the present invention has extremely good compatibility with a polycarbonate resin, and is excellent in flame retardancy, mechanical strength, etc. of the resin composition, and in applications that require light reflectivity. Another object of the present invention is to provide a flame retardant resin composition having light reflectivity.

  As a result of intensive studies to solve the above problems, the present inventor has found that a polycarbonate resin, a phosphoric acid amide compound having a specific structure and a fiber-forming fluorine-containing polymer, and a specific rubber-like elastic body as required, Flame retardant resin composition containing rubber reinforced styrene resin, mold release agent or titanium oxide has surprising flame resistance, light reflectivity (when titanium oxide is added), mechanical strength, moldability, The inventors have found that the surface appearance and the like are shown, and have completed the present invention.

That is, the first form of the present invention is at least one phosphate amide compound (B) selected from the compounds represented by 100 parts by weight of the polycarbonate resin (A) and the following general formulas (1) and (2). A flame retardant comprising 0.5 to 25 parts by weight, 0.01 to 2 parts by weight of a fiber-forming fluoropolymer (C) and 0.1 to 10 parts by weight of a rubbery elastic body (D) The resin composition and a molded product formed by molding the same are provided.
General formula (1)

一般式（２）

General formula (2)

ただし、一般式（１）および（２）において、Ｒ_１及びＲ_２は、同一または異なるものであってもよく、水素原子、アルキル基、シクロヘキシル基、アリル基、フェニル基またはアラルキル基であるか、あるいはＲ_１及びＲ_２が環状となり、窒素原子と共にモルホリノ基を形成する残基を表わす。

However, in the general formulas (1) and (2), R ₁ and R ₂ may be the same or different and are a hydrogen atom, an alkyl group, a cyclohexyl group, an allyl group, a phenyl group, or an aralkyl group. Or R ₁ and R ₂ are cyclic, and represent a residue that forms a morpholino group together with a nitrogen atom.

  In the second embodiment of the present invention, 100 parts by weight of the resin component consisting of 1 to 99% by weight of the polycarbonate resin (A) and 99 to 1% by weight of the rubber-reinforced styrene resin (E), the above general formula (1) And 2 to 25 parts by weight of at least one phosphoramide compound (B) selected from the compounds represented by (2), 0.01 to 2 parts by weight of a fiber-forming fluoropolymer (C) and A flame retardant resin composition comprising 0.01 to 3 parts by weight of a mold agent (F) and 0 to 10 parts by weight of a rubber-like elastic body (D), and a molded product formed by molding the flame retardant resin composition It is to provide.

  Furthermore, the third form of the present invention is at least one phosphate amide compound (B) selected from the compounds represented by 100 parts by weight of the polycarbonate resin (A) and the general formulas (1) and (2). ) 0.5 to 25 parts by weight, 0.01 to 2 parts by weight of a fiber-forming fluoropolymer (C) and 5 to 30 parts by weight of titanium oxide (G) The present invention provides a resin composition and a light reflecting plate obtained by molding the resin composition, particularly a light reflecting plate for a liquid crystal backlight.

  In addition, the fourth form of the present invention is at least one phosphate amide compound selected from the compounds represented by 100 parts by weight of the polycarbonate resin (A) and the general formulas (1) and (2) ( B) 0.5 to 25 parts by weight, 0.01 to 2 parts by weight of a fiber-forming fluoropolymer (C), 5 to 30 parts by weight of titanium oxide (G), and 0.1 to 0.1% of a rubber-like elastic body (D) The present invention provides a flame retardant resin composition comprising 10 parts by weight, and a light reflecting plate formed by molding the flame retardant resin composition, particularly a light reflecting plate for a liquid crystal backlight.

  Since the flame retardant resin composition of the present invention does not contain a halogen-based flame retardant composed of chlorine, bromine compounds, etc., the flame retardant resin composition has excellent performance in terms of environmental protection, and further has high flame retardancy and light reflectivity. (When titanium oxide is blended), it has mechanical properties, moldability, good surface appearance, etc., and is blended with titanium oxide as a material for various interior and exterior applications in relation to electrical / electronic, OA, etc. Can be suitably used for a light reflector such as a liquid crystal backlight.

  The polycarbonate resin (A) used in the present invention is obtained by a phosgene method in which various dihydroxydiaryl compounds and phosgene are reacted, or a transesterification method in which a dihydroxydiaryl compound and a carbonate such as diphenyl carbonate are reacted. A typical example of the polymer is a polycarbonate resin produced from 2,2-bis (4-hydroxyphenyl) propane (bisphenol A).

Examples of the dihydroxydiaryl compound include bisphenol 4-, bis (4-hydroxyphenyl) methane, 1,1-bis (4-hydroxyphenyl) ethane, 2,2-bis (4-hydroxyphenyl) butane, 2, 2-bis (4-hydroxyphenyl) octane, bis (4-hydroxyphenyl) phenylmethane, 2,2-bis (4-hydroxyphenyl-3-methylphenyl) propane, 1,1-bis (4-hydroxy-3) -Tert-butylphenyl) propane, 2,2-bis (4-hydroxy-3-bromophenyl) propane, 2,2-bis (4-hydroxy-3,5-dibromophenyl) propane, 2,2-bis ( Bis (hydroxyaryl) alkanes such as 4-hydroxy-3,5-dichlorophenyl) propane, 1,1- (4-hydroxyphenyl) cyclopentane, bis (hydroxyaryl) cycloalkanes such as 1,1-bis (4-hydroxyphenyl) cyclohexane, 4,4'-dihydroxydiphenyl ether, 4,4'-dihydroxy-3 Dihydroxy diaryl ethers such as 3,3'-dimethyldiphenyl ether, dihydroxy diaryl sulfides such as 4,4'-dihydroxydiphenyl sulfide, 4,4'-dihydroxydiphenyl sulfoxide, 4,4'-dihydroxy-3,3 ' -Dihydroxy diaryl sulfoxides such as dimethyldiphenyl sulfoxide, dihydroxy diary such as 4,4'-dihydroxydiphenyl sulfone, 4,4'-dihydroxy-3,3'-dimethyldiphenyl sulfone Sulfone, and the like.

These are used singly or as a mixture of two or more. However, it is preferable not to be substituted with a halogen from the viewpoint of preventing discharge of a gas containing halogen, which is a concern during combustion, into the environment. In addition to these, piperazine, dipiperidyl hydroquinone, resorcin, 4,4'-dihydroxydiphenyl, and the like may be mixed and used.

  Furthermore, the above dihydroxyaryl compound and a trivalent or higher phenol compound as shown below may be used in combination. Trihydric or higher phenols include phloroglucin, 4,6-dimethyl-2,4,6-tri- (4-hydroxyphenyl) -heptene, 2,4,6-dimethyl-2,4,6-tri- (4 -Hydroxyphenyl) -heptane, 1,3,5-tri- (4-hydroxyphenyl) -benzol, 1,1,1-tri- (4-hydroxyphenyl) -ethane and 2,2-bis- [4 4- (4,4'-dihydroxydiphenyl) -cyclohexyl] -propane and the like.

  The viscosity average molecular weight of the polycarbonate resin (A) is usually 10,000 to 100,000, preferably 15,000 to 35,000, and more preferably 18000 to 22,000. In producing such an aromatic polycarbonate resin, a molecular weight regulator, a catalyst, and the like can be used as necessary.

The phosphoric acid amide compound (B) used in the present invention is at least one phosphoric acid amide compound selected from the compounds represented by the following general formulas (1) and (2).
General formula (1)

ただし、一般式（１）において、Ｒ_１及びＲ_２は、同一または異なるものであってもよく、水素原子、アルキル基、シクロヘキシル基、アリル基、フェニル基またはアラルキル基であるか、あるいはＲ_１及びＲ_２が環状となり、窒素原子と共にモルホリノ基を形成する残基を表わす。

However, in General formula (1), R < ₁ > and R < ₂ > may be the same or different and are a hydrogen atom, an alkyl group, a cyclohexyl group, an allyl group, a phenyl group, or an aralkyl group, or R < ₁ >. And R ₂ is cyclic, and represents a residue that forms a morpholino group together with a nitrogen atom.

Representative compounds represented by the general formula (1) include diphenyl (amide phosphate, diphenyl (methyl amide) phosphate, diphenyl (dimethyl amide) phosphate, diphenyl (ethyl amide) phosphate, diphenyl (diethyl amide) phosphate, diphenyl (propyl amide). ) Phosphate, diphenyl (dipropylamide) phosphate, diphenyl (octylamide) phosphate, diphenyl (undecylamide) phosphate, diphenyl (cyclohexylamide) phosphate, diphenyl (dicyclohexylamide) phosphate, diphenyl (allylamide) phosphate, diphenyl (anilide) Phosphate, diphenyl (monophenyl monomethylamide) phosphate, diphenyl (monophenyl) Cycloalkenyl monoethylamide) phosphate, diphenyl (benzylamide) phosphate, and diphenyl (morpholide) phosphate and the like.

General formula (2)

ただし、一般式（２）において、Ｒ_１及びＲ_２は、同一または異なるものであってもよく、水素原子、アルキル基、シクロヘキシル基、アリル基、フェニル基またはアラルキル基であるか、あるいはＲ_１及びＲ_２が環状となり、窒素原子と共にモルホリノ基を形成する残基を表わす。

However, in General formula (2), R < ₁ > and R < ₂ > may be the same or different and are a hydrogen atom, an alkyl group, a cyclohexyl group, an allyl group, a phenyl group, or an aralkyl group, or R < ₁ >. And R ₂ is cyclic, and represents a residue that forms a morpholino group together with a nitrogen atom.

Representative compounds represented by the above general formula (2) include (diamide) phenyl phosphate, (amido) (methylamido) phenylphosphate, (bismethylamido) phenylphosphate, (amido) (ethylamido) phenylphosphate, (bis (Ethylamido) phenyl phosphate, (amido) (propylamido) phosphate, (bispropylamido) phenylphosphate, (amido) (octylamido) phenylphosphate, (amido) (undecylamido) phenylphosphate, (amido) (cyclohexyl) Amido) phenyl phosphate, (biscyclohexylamide) phenyl phosphate, (bisallylamido) phenyl phosphate, (amido) (anilide) phenyl phosphate, (dianilide) phenyl Sufeto, (Monoanirido) (monomethyl) phenyl phosphate, (mono phenyl amide) (monoethylamide) phosphate, (bis benzylamide) phenyl phosphate, and (Jimoruhorido) phenyl phosphate and the like.

The compounding amount of the phosphoric acid amide compound (B) is:
-In the 1st form of this invention, it is 0.5-25 weight part per 100 weight part of polycarbonate resin (A). If the blending amount is less than 0.5 parts by weight, it is not preferable because flame retardancy is hardly obtained. On the other hand, when the blending amount exceeds 25 parts by weight, the heat resistance (thermal deformability) and impact strength of the composition are remarkably lowered, which is not preferable. More preferably, it is in the range of 5 to 20 parts by weight, more preferably 11 to 15 parts by weight.

In the second embodiment of the present invention, 2 to 25 weights per 100 weight parts of the resin component consisting of 1 to 99 weight% of the polycarbonate resin (A) and 99 to 1 weight% of the rubber-reinforced styrene resin (E). Part. If the blending amount is less than 2 parts by weight, it is difficult to obtain flame retardancy. On the other hand, when the blending amount exceeds 25 parts by weight, the heat resistance (thermal deformability) and impact strength of the composition are remarkably lowered, which is not preferable. More preferably, it is in the range of 5 to 22 parts by weight, more preferably 13 to 17 parts by weight.

-In the 3rd and 4th form of this invention, it is 0.5-25 weight part per 100 weight part of polycarbonate resin (A). If the blending amount is less than 0.5 parts by weight, it is not preferable because flame retardancy is hardly obtained. On the other hand, when the blending amount exceeds 25 parts by weight, the heat resistance (thermal deformability) and impact strength of the composition are remarkably lowered, which is not preferable. More preferably, it is in the range of 5 to 20 parts by weight, more preferably 11 to 15 parts by weight.

  The fiber-forming fluorine-containing polymer (C) used in the present invention is preferably one that forms a fibril-like structure in the resin. For example, polytetrafluoroethylene, a tetrafluoroethylene copolymer (for example, tetra Fluoroethylene / hexafluoropropylene copolymer, etc.), partially fluorinated polymers as shown in US Pat. No. 4,379,910, polycarbonates produced from fluorinated diphenols, and the like. In particular, polytetrafluoroethylene having a molecular weight of 1,000,000 or more and a fibril-forming ability having a secondary particle diameter of 100 μm or more is preferably used. These are commercially available, for example, as NEOFRON FA500 from Daikin Industries, Ltd., and are easily available.

Moreover, in this invention, polytetrafluoroethylene containing mixed powder can be used as a fiber formation type fluoropolymer (C) as needed.

  The polytetrafluoroethylene-containing mixed powder is composed of polytetrafluoroethylene particles having a particle diameter of 10 μm or less and an organic polymer, and the polytetrafluoroethylene has a particle diameter exceeding 10 μm and is not an aggregate. Those are preferably used. Furthermore, from the viewpoint of dispersibility when blended in a resin, in a dispersion obtained by mixing an aqueous dispersion of polytetrafluoroethylene particles having a particle diameter of 0.05 to 1.0 μm and an aqueous dispersion of organic polymer particles, A polymer obtained by polymerizing a vinyl monomer and then pulverizing it by coagulation or spray drying can be used. The polytetrafluoroethylene-containing mixed powder used for obtaining the polytetrafluoroethylene-containing mixed powder according to the present invention is prepared by emulsion polymerization using a fluorine-containing surfactant. Those obtained by polymerizing monomers can be used.

  Fluorine-containing olefins such as hexafluoropropylene, chlorotrifluoroethylene, fluoroalkylethylene, and perfluoroalkyl vinyl ether as copolymerization components in the emulsion polymerization of polytetrafluoroethylene particles as long as the properties of polytetrafluoroethylene are not impaired. Fluorine-containing alkyl (meth) acrylates such as perfluoroalkyl (meth) acrylate can be used. The content of the copolymerization component is preferably 10% by weight or less based on tetrafluoroethylene.

  Commercially available raw materials for polytetrafluoroethylene particle dispersions include: Fullon AD-1 and AD-936 manufactured by Asahi Glass Fluoropolymer, Polyflon D-1 and D-2 manufactured by Daikin Industries, Ltd., and Teflon manufactured by Mitsui DuPont Fluorochemical Co., Ltd. 30J etc. can be mentioned as a representative example.

  The organic polymer particle aqueous dispersion used for obtaining the polytetrafluoroethylene-containing mixed powder can be obtained by polymerizing a vinyl monomer by a known method such as emulsion polymerization.

  The vinyl monomer used to obtain the organic polymer particle aqueous dispersion, and the polytetrafluoroethylene particle aqueous dispersion having a particle diameter of 0.05 to 1.0 μm and the organic polymer particle aqueous dispersion were mixed. Although it does not restrict | limit especially as a vinyl monomer polymerized in a dispersion liquid, A high affinity with resin can be used conveniently from a dispersible viewpoint at the time of mix | blending with resin.

  Specific examples of these vinyl monomers include styrene, α-methylstyrene, p-methylstyrene, o-methylstyrene, t-butylstyrene, o-ethylstyrene, p-chlorostyrene, o-chlorostyrene, 2, Aromatic vinyl monomers such as 4-dichlorostyrene, p-methoxystyrene, o-methoxystyrene, 2,4-dimethylstyrene; methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, butyl acrylate, Butyl methacrylate, 2-ethylhexyl acrylate, 2-ethylhexyl methacrylate, dodecyl acrylate, dodecyl methacrylate, tridecyl acrylate, tridecyl methacrylate, octadecyl acrylate, octadecyl methacrylate, cyclohexyl acrylate, cyclohexane methacrylate (Meth) acrylic acid ester monomers such as xylyl; vinyl cyanide monomers such as acrylonitrile and methacrylonitrile; α, β-unsaturated carboxylic acids such as maleic anhydride; N-phenylmaleimide, N-methylmaleimide, Maleimide monomers such as N-cyclohexylmaleimide; Epoxy group-containing monomers such as glycidyl methacrylate; Vinyl ether monomers such as vinyl methyl ether and vinyl ethyl ether; Vinyl carboxylates such as vinyl acetate and vinyl butyrate Body; α-olefin monomers such as ethylene, propylene, and isobutylene; and diene monomers such as butadiene, isoprene, and dimethylbutadiene. These monomers can be used alone or in admixture of two or more.

  Among these monomers, 30 or more monomers selected from the group consisting of aromatic vinyl monomers and vinyl cyanide monomers are preferred from the viewpoint of affinity with the resin. Mention may be made of monomers containing at least% by weight. Particularly preferred is a monomer containing 30% by weight or more of one or more monomers selected from the group consisting of styrene and acrylonitrile.

  The content ratio of polytetrafluoroethylene in the polytetrafluoroethylene-containing mixed powder is preferably 0.1 to 90% by weight. If it is less than 0.1% by weight, the effect of improving flame retardancy becomes insufficient, and if it exceeds 90% by weight, the surface appearance may be adversely affected.

  The mixed powder containing polytetrafluoroethylene is poured into hot water in which a metal salt such as calcium chloride or magnesium sulfate is dissolved and dried after salting out, solidifying, or by spray drying. Can be used.

  In contrast to the usual polytetrafluoroethylene fine powder, it is difficult to uniformly disperse in the resin because it becomes an aggregate of 100 μm or more in the step of recovering as a powder from the state of the particle dispersion. The polytetrafluoroethylene-containing mixed powder used in the present invention is extremely excellent in dispersibility with respect to the resin because polytetrafluoroethylene alone does not form a domain having a particle diameter exceeding 10 μm. As a result, in the resin composition of the present invention, polytetrafluoroethylene is efficiently made into fine fibers in the resin, and the flame retardancy is excellent, and the surface properties and impact characteristics are also excellent.

The compounding amount of the fiber-forming fluoropolymer (C) is:
-In the 1st form of this invention, it is 0.01-2 weight part per 100 weight part of polycarbonate resin (A). If the blending amount is less than 0.01 parts by weight, the anti-dripping property is inferior, and if it exceeds 2 parts by weight, the surface appearance and mechanical properties (impact strength) deteriorate, which is not preferable. More preferably, it is in the range of 0.2 to 0.5 parts by weight.

In the second embodiment of the present invention, 0.01 to 99 parts by weight of the resin component consisting of 1 to 99% by weight of the polycarbonate resin (A) and 99 to 1% by weight of the rubber-reinforced styrene resin (E). 2 parts by weight. If the blending amount is less than 0.01 parts by weight, the anti-dripping property is inferior, and if it exceeds 2 parts by weight, the surface appearance and mechanical properties (impact strength) deteriorate, which is not preferable. More preferably, it is in the range of 0.2 to 0.5 parts by weight.

-In the 3rd and 4th form of this invention, it is 0.01-2 weight part per 100 weight part of polycarbonate resin (A). If the blending amount is less than 0.01 parts by weight, the anti-dripping property is inferior, and if it exceeds 2 parts by weight, the surface appearance and mechanical properties (impact strength) deteriorate, which is not preferable. More preferably, it is in the range of 0.2 to 0.5 parts by weight.

  As the rubber-like elastic body (D) used in the present invention, a butadiene rubber-like elastic body having a core-shell structure or a polyorganosiloxane rubber component and a polyalkyl (meth) acrylate rubber component cannot be separated. Examples thereof include a composite rubber graft copolymer obtained by graft-polymerizing one or two or more vinyl monomers to a composite rubber having a structure intertwined with each other.

  In order to obtain a composite rubber-based graft copolymer, first, various cyclic organosiloxanes having three or more members, such as hexamethylcyclotrisiloxane, octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, and the like, a crosslinking agent and / or A latex of polyorganosiloxane rubber is prepared by emulsion polymerization using a grafting agent, and then the polyorganosiloxane rubber latex is impregnated with an alkyl (meth) acrylate monomer, a crosslinking agent and a grafting agent, and then polymerized. It is obtained by doing. Examples of the alkyl (meth) acrylate monomer used herein include alkyl acrylates such as methyl acrylate, ethyl acrylate, n-propyl acrylate, n-butyl acrylate, and 2-ethylhexyl acrylate, and alkyls such as hexyl methacrylate and 2-ethylhexyl methacrylate. Although methacrylate is mentioned, it is particularly preferable to use n-butyl acrylate. Examples of vinyl monomers to be graft polymerized to the composite rubber include aromatic vinyl compounds such as styrene and α-methylstyrene, vinyl cyanide compounds such as acrylonitrile and methacrylonitrile, and methacrylic compounds such as methyl methacrylate and 2-ethylhexyl methacrylate. Examples thereof include acrylic acid esters such as acid ester, methyl acrylate, ethyl acrylate, and butyl acrylate, and these are used alone or in combination of two or more. The average particle size of the composite rubber is preferably 0.08 to 0.6 μm. When the average particle size of the composite rubber is less than 0.08 μm, the impact resistance of the resulting resin composition is lowered, and when the average particle size exceeds 0.6 μm, the surface appearance of the molded product of the resulting resin composition is deteriorated. . Particularly preferred is a product marketed under the trade name of METABRENE S-2001 manufactured by Mitsubishi Rayon Co., Ltd.

The compounding amount of the rubber-like elastic body (D) is:
-In the 1st form of this invention, it is 0.1-10 weight part per 100 weight part of polycarbonate resin (A). If it is less than 0.1 parts by weight, the degree of improvement in impact strength is insufficient, which is not preferable. On the other hand, when the amount exceeds 10 parts by weight, the flame retardancy is lowered, which is not preferable. More preferably, it is in the range of 2 to 8 parts by weight, and more preferably 3 to 5 parts by weight.

In the second embodiment of the present invention, 0 to 10% by weight with respect to 100 parts by weight of the resin component consisting of 1 to 99% by weight of the polycarbonate resin (A) and 99 to 1% by weight of the rubber-reinforced styrene resin (E). Part. Exceeding 10 parts by weight is not preferable because the flame retardancy decreases. More preferably, it is 1-8 weight part, More preferably, it is the range of 2-4 weight part.

-In the 4th form of this invention, it is 0.1-10 weight part per 100 weight part of polycarbonate resin (A). If it is less than 0.1 parts by weight, the degree of improvement in impact strength is insufficient, which is not preferable. On the other hand, when the amount exceeds 10 parts by weight, the flame retardancy is lowered, which is not preferable. More preferably, it is in the range of 2 to 8 parts by weight, and more preferably 3 to 5 parts by weight.

  The rubber-reinforced styrenic resin (E) used in the present invention includes (a) an aromatic vinyl monomer component, (b) a vinyl cyanide monomer component, and (c) a rubbery polymer. It is composed of (E-1) copolymer containing as a constituent component of the coalescence and (E-2) copolymer containing (a) and (b) as constituent components of the copolymer. Resin. Examples of the preferred rubber-reinforced styrene resin (E) include those containing (c) a graft copolymer obtained by graft copolymerization of components (a) and (b) in the presence of a rubbery polymer, Preferably, ABS resin (acrylonitrile-butadiene-styrene copolymer) produced by bulk polymerization is used.

(A) Examples of the aromatic vinyl monomer component include styrene, α-methylstyrene, o-, m-, p-methylstyrene, vinylxylene, ethylstyrene, vinylnaphthalene, and the like. More than seeds can be used. Of these components, styrene is preferably used.

(B) As a vinyl cyanide monomer component, acrylonitrile, methacrylonitrile, etc. are mentioned, for example, These can be used 1 type, or 2 or more types. Of these components, acrylonitrile is preferably used.

(C) Examples of the rubbery polymer include polybutadiene, styrene-butadiene random copolymer or block copolymer, hydrogenated product of the block copolymer, acrylonitrile-butadiene copolymer, isoprene-butadiene copolymer, etc. Diene rubber, ethylene-propylene random copolymer or block copolymer, polyisoprene, ethylene and α-olefin copolymer, ethylene-unsaturated such as ethylene-methacrylate, ethylene-butyl acrylate Copolymers with carboxylates, acrylic ester-butadiene copolymers, acrylic elastic polymers such as butyl acrylate-butadiene copolymers, copolymers of ethylene and fatty acid vinyl such as ethylene-vinyl acetate , Ethylene-propylene-hexadiene copolymer, etc. Len - propylene nonconjugated Jienta - polymer -, butylene - Isoburen copolymers, chlorinated polyethylene and the like, may be to use them in one or two or more thereof. Preferred rubbery polymers are diene rubber, ethylene-propylene non-conjugated diene polymer, and acrylic elastic polymer, and polybutadiene and styrene-butadiene copolymers are preferably used.

There is no restriction | limiting in particular in the composition ratio of each component of said (a), (b), (c), It can adjust according to a use. In addition to the above components (a), (b), and (c), the monomer that can be copolymerized with these components does not impair the purpose of the present invention. Can be used in a range.

Examples of such copolymerizable monomers include α, β-unsaturated carboxylic acids such as acrylic acid and methacrylic acid, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl ( Α, β-unsaturated carboxylic acid esters such as (meth) acrylate, 2-ethyl (meth) acrylate, 2-ethylhexyl methacrylate; α, β-unsaturated dicarboxylic acid anhydrides such as maleic anhydride and itaconic anhydride; Monomers of α, β-unsaturated dicarboxylic acids such as maleimide, N-methylmaleimide, N-ethylmaleimide, N-phenylmaleimide, and N-o-chlorophenylmaleimide; Can be used alone or in combination of two or more.

(E-2) The copolymer is composed of the above-mentioned (a) aromatic vinyl monomer component and (b) vinyl cyanide monomer component, preferably SAN resin (styrene-acrylonitrile copolymer). Is used. (E-2) A copolymer contributes to the improvement of the moldability (fluidity) of the obtained flame-retardant thermoplastic resin composition.

There is no restriction | limiting in particular in the composition ratio of each component of said (a), (b), Although it can adjust according to a use, Preferably, it is based on (E-2) copolymer, (a) component Is 95 to 50% by weight, component (b) is 5 to 50% by weight, more preferably (a) is 90 to 65% by weight, and (b) is 10 to 35% by weight. In addition to the above components (a) and (b), a monomer that can be copolymerized with these components is used in the (E-2) copolymer as long as the object of the present invention is not impaired. be able to.

Examples of such copolymerizable monomers include α, β-unsaturated carboxylic acids such as acrylic acid and methacrylic acid, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl ( Α, β-unsaturated carboxylic acid esters such as (meth) acrylate, 2-ethyl (meth) acrylate, 2-ethylhexyl methacrylate; α, β-unsaturated dicarboxylic acid anhydrides such as maleic anhydride and itaconic anhydride; And imide compounds of α, β-unsaturated dicarboxylic acids such as maleimide, N-methylmaleimide, N-ethylmaleimide, N-phenylmaleimide, N-o-chlorophenylmaleimide, and the like. Can be used alone or in combination of two or more.

  The blending ratio of the rubber-reinforced styrene resin (E) in the second embodiment of the present invention is 99 to 1% by weight based on the mixture of the polycarbonate resin (A) and the rubber-reinforced styrene resin (E). When the blending ratio is less than 1% by weight, the fluidity is poor, which is not preferable. On the other hand, if it exceeds 99% by weight, the flame retardancy and impact strength are inferior. More preferably, it is 50 to 5 weight%, More preferably, it is the range of 30 to 10 weight%.

  The release agent (F) used in the present invention is not particularly limited as long as it is incorporated into the polycarbonate resin (A) and exhibits a release effect, but is not limited to polyolefin wax, glycerol monostearate, glycerol trioxide. It is preferable to use one or more compounds selected from stearate, pentaerythritol tetrastearate, beeswax, montanic acid ester wax, and carboxylic acid ester (eg, stearyl stearate).

  The compounding quantity of the mold release agent (F) in the 2nd form of this invention is 0.01-3 weight with respect to 100 weight part of resin components which consist of polycarbonate resin (A) and rubber-reinforced styrene resin (E). Part. If the blending amount is less than 0.01 parts by weight, the releasability is not sufficient. Conversely, if the blending amount exceeds 3 parts by weight, the polycarbonate resin (A) is decomposed by the release agent, and bleeding occurs during molding. May cause problems such as mold contamination. Preferably, it is 0.05-2 weight part, More preferably, it is the range of 0.2-1 weight part.

  The titanium oxide (G) used in the present invention may be one produced by the chlorine method or the sulfuric acid method, and the crystal form may be either a rutile type or an anatase type. Further, the particle size of titanium oxide (G) is not particularly limited, but a particle size of about 0.1 to 0.5 μm can be suitably used.

  The compounding quantity of the titanium oxide (G) in the 3rd and 4th form of this invention is 5-30 weight part per 100 weight part of polycarbonate resin (A). If the blending amount is less than 5 parts by weight, the light reflectivity is inferior, and if it exceeds 30 parts by weight, the surface appearance, impact strength, flame retardancy and the like are deteriorated, which is not preferable. More preferably, it is 8-20 weight part, More preferably, it is 10-16 weight part.

  Furthermore, various heat stabilizers, antioxidants, polyorganohydrogensiloxanes, fluorescent whitening agents, pigments / dyes, fillers, mold release agents are added to the flame-retardant resin composition of the present invention within the range not impairing the effects of the present invention. An additive such as an agent, a softening material, an antistatic agent, a spreading agent (liquid paraffin, epoxy soybean oil, etc.), an organic metal salt, and other polymers may be blended.

  Examples of the filler include glass fiber, glass beads, glass flakes, talc powder, clay powder, mica, aluminum borate whisker, potassium titanate whisker, wollastonite powder, silica powder, and alumina powder.

  Examples of the organic metal salt compound include aromatic sulfonic acid metal salts and perfluoroalkanesulfonic acid metal salts. Examples of the metal include alkali metals and alkaline earth metals. Preferably, potassium salt of 4-methyl-N- (4-methylphenyl) sulfonyl-benzenesulfonamide, potassium diphenylsulfone-3-sulfonate, potassium diphenylsulfone-3-3'-disulfonate, paratoluenesulfonic acid Sodium, perfluorobutanesulfonic acid potassium salt and the like can be used.

EXAMPLES The present invention will be specifically described below with reference to examples, but the present invention is not limited to these examples. “Parts” and “%” are based on weight unless otherwise specified.
The materials used are as follows.

・ Polycarbonate resin:
(1) Sumitomo Dow Caliber 200-20
Viscosity average molecular weight 19,000. (Hereafter, abbreviated as “PC-1”.)
(2) Caliber 200-13 manufactured by Sumitomo Dow
Viscosity average molecular weight 21,000. (Hereafter, abbreviated as “PC-2”.)
・ Rubber reinforced styrene resin:
Santac AT07 made by Japan A & L
ABS resin by bulk polymerization. (Hereafter abbreviated as “ABS”.)
・ Phosphate amide compounds:
SP-670 manufactured by Shikoku Kasei Co., Ltd.
Diphenyl phenylaminophosphinate (hereinafter abbreviated as “AP”)
・ Rubber elastic body:
(1) Rohm and Haas Paraloid EXL2602
(Hereafter, abbreviated as “E-1”.)
(2) Metablene S-2001 manufactured by Mitsubishi Rayon Co., Ltd.
(Hereafter, abbreviated as “E-2”.)
・ Fiber-forming fluorine-containing polymer:
(1) Polytetrafluoroethylene
NEOFRON FA500 manufactured by Daikin Industries
(Hereafter, abbreviated as “PTFE”.)
(2) Mixed powder containing polytetrafluoroethylene
Metablene A3800 manufactured by Mitsubishi Rayon Co., Ltd.
Polytetrafluoroethylene content: 50%
(Hereafter, abbreviated as “PTFE-MB”.)
·Release agent:
Montanic acid ester wax Rico Wax E (hereinafter abbreviated as “MR”) manufactured by Clariant Japan
・ Titanium oxide:
2230 made by Kronos International
(Hereafter, abbreviated as “TiO2”.)

  As a blending method, the above-mentioned various raw materials are collectively put into a tumbler at the blending ratios shown in Tables 2 to 7, mixed dry for 10 minutes, and then melted using a twin-screw extruder (Kobe Steel KTX37). Melt-kneading was performed at a temperature of 250 ° C. to obtain a flame-retardant resin composition pellet.

  From the obtained pellets, a test piece for mechanical property evaluation according to ASTM specifications and a test piece for UL94 flammability evaluation under conditions of a melting temperature of 260 to 300 ° C. using an injection molding machine (J100E-C5 manufactured by Nippon Steel) 0.8 mm thickness).

The evaluation methods are as follows.
(Impact strength)
1/8 inch thick notched Izod impact strength at 23 ° C. Measured according to ASTM D256.

(Combustion quality)
The test piece is left for 48 hours in a constant temperature room with a temperature of 23 ° C and humidity of 50%. Evaluation was performed. UL94V is a method of evaluating flame retardance from the afterflame time and drip properties after indirect flames of a burner for 10 seconds on a test piece of a predetermined size held vertically, and is divided into the following classes: .

上に示す残炎時間とは、着火源を遠ざけた後の試験片が有炎燃焼を続ける時間の長さであり、ドリップによる綿の着火とは、試験片の下端から約３００ｍｍ下にある標識用の綿が、試験片からの滴下（ドリップ）物によって着火されるかどうかによって決定される。

The after-flame time shown above is the length of time that the specimen keeps flaming combustion after moving the ignition source away, and the ignition of cotton by drip is about 300 mm below the lower end of the specimen. It is determined by whether the marking cotton is ignited by a drip from the specimen.

(Load deflection temperature)
Using an HDT tester (Toyo Seiki Co., Ltd., HD & VST PTTER), measurement was performed under the conditions of a test piece thickness of 6.4 mm and a fiber stress of 18.6 kg / cm2. A test piece without annealing was used.

(Surface appearance)
The surface appearance of ASTM No. 1 dumbbell (mainly presence or absence of occurrence of silver streak) was visually confirmed. Very good (◎) and good (○) were accepted and bad (x) were rejected.

(Releasability)
A box-shaped test piece of 70 mm (vertical) × 150 mm (horizontal) × 40 mm (height) was injection-molded, and the releasability at the time of mold release was confirmed visually and auditorily (size of squeak noise). Very good (◎) and good (○) were accepted and bad (x) were rejected.

(Light reflectivity)
A three-stage plate (thickness 3, 2, 1 mm) test piece having a length of 90 mm and a width of 40 mm was prepared. 35SP). A sample having a Y value (light reflectance) of 93% or more was regarded as acceptable.

  Examples and comparative examples in the first embodiment of the present invention are shown in Tables 2 and 3.

注：難燃性がＮＲとは、どのクラスにも属さないことをあらわす。

Note: NR means that it does not belong to any class.

As shown in Examples 1 to 5, all the performances such as flame retardancy, Izod impact strength, deflection temperature under load are good for those satisfying the specified value range of the essential components of the present invention and the blending amounts of each blending component. Met.
On the other hand, as shown in Comparative Examples 1 to 6, those in which the blending amount of the essential components of the present invention did not satisfy the specified value range had drawbacks.
Comparative example 1: Since the compounding quantity of the phosphoric acid amide compound was further less than the minimum of a regulation range, it was inferior to the flame retardance.
Comparative Example 2: Since the blending amount of the phosphoric acid amide compound exceeded the upper limit of the specified range, the impact strength and the weighted deflection temperature were lowered.
Comparative Example 3: Since the blending amount of the fiber-forming fluoropolymer was less than the lower limit of the specified range, the flame retardancy was poor.
Comparative Example 4: Since the blending amount of the fiber-forming fluoropolymer exceeded the upper limit of the specified range, the surface appearance and impact strength were inferior.
Comparative Example 5: The impact strength was inferior because the blending amount of the rubber-like elastic material was smaller than the lower limit of the specified range.
Comparative Example 6: Since the blending amount of the rubbery elastic body exceeded the upper limit of the specified range, the flame retardancy was inferior.

  Examples and comparative examples in the second embodiment of the present invention are shown in Tables 4 and 5.

注：難燃性がＮＲとは、どのクラスにも属さないことをあらわす。

Note: NR means that it does not belong to any class.

As shown in Examples 11 to 18, flame retardant, Izod impact strength, load deflection temperature surface appearance, releasability for those satisfying the specified value range of the essential component of the present invention and the blending amount of each blending component The results were good for all the performances.
On the other hand, as shown in Comparative Examples 11 to 16, those in which the blending amount of the essential components of the present invention did not satisfy the specified value range had drawbacks.
Comparative example 11: Since the compounding quantity of the phosphoric acid amide compound was further less than the minimum of a regulation range, the flame retardance was inferior.
Comparative Example 12: Since the blending amount of the phosphoramide compound exceeded the upper limit of the specified range, the impact strength and the weighted deflection temperature were lowered.
Comparative Example 13: Since the blending amount of the fluoropolymer exceeded the upper limit of the specified range, the surface appearance and impact strength were inferior.
Comparative Example 14: Since the blending amount of the rubber-like elastic body was larger than the upper limit of the specified range, the flame retardancy was inferior.
Comparative Example 15: Since the compounding amount of the release agent was less than the lower limit of the specified range, the release property was inferior.
Comparative Example 16: Since the blending amount of the release agent exceeded the upper limit of the specified range, the flame retardancy was inferior.

  Tables 6 and 7 show examples and comparative examples in the third and fourth aspects of the present invention.

注１．難燃性がＮＲ：どのクラスにも属さないことを表す。

Note 1. Flame retardancy is NR: represents that it does not belong to any class.

As shown in Examples 21 to 26, all the performances such as flame retardancy, reflectance, deflection temperature under load, and overview are obtained for the essential components of the present invention and those satisfying the specified range of the blending amount of each blending component. It was good.
On the other hand, as shown in Comparative Examples 21 to 25, those in which the blending amount of the essential components of the present invention did not satisfy the specified value range had drawbacks.
Comparative Example 21: Since the blending amount of the phosphoramide compound was less than the specified range, the flame retardancy was inferior.
Comparative Example 22: Since the blending amount of the phosphoric acid amide compound exceeded the upper limit of the specified range, the deflection temperature under load and the impact strength were reduced.
Comparative Example 23: Since the amount of titanium oxide exceeds the upper limit of the specified range, the surface appearance, flame retardancy, and impact strength were inferior.
Comparative Example 24: Since the blending amount of the rubbery elastic body exceeded the upper limit of the specified range, the flame retardancy was inferior.
Comparative Example 25: Since the blending amount of titanium oxide was less than the lower limit of the specified range, the reflectance was inferior.

Claims (11)

100 parts by weight of polycarbonate resin (A), 0.5 to 25 parts by weight of at least one phosphoramide compound (B) selected from the compounds represented by the following general formulas (1) and (2), fiber formation A flame-retardant resin composition comprising 0.01 to 2 parts by weight of a fluorine-containing polymer (C) of a mold and 0.1 to 10 parts by weight of a rubber-like elastic body (D).
General formula (1)

General formula (2)

However, in the general formulas (1) and (2), R ₁ and R ₂ may be the same or different and are a hydrogen atom, an alkyl group, a cyclohexyl group, an allyl group, a phenyl group, or an aralkyl group. Or R ₁ and R ₂ are cyclic, and represent a residue that forms a morpholino group together with a nitrogen atom. Compounds represented by the following general formulas (1) and (2) with respect to 100 parts by weight of a resin component comprising 1 to 99% by weight of a polycarbonate resin (A) and 99 to 1% by weight of a rubber-reinforced styrene resin (E) 2 to 25 parts by weight of at least one phosphoramide compound (B), 0.01 to 2 parts by weight of a fiber-forming fluoropolymer (C), and 0.01 to 2 parting agent (F) A flame retardant resin composition comprising 3 parts by weight and 0 to 10 parts by weight of a rubber-like elastic body (D).
General formula (1)

General formula (2)

However, in the general formulas (1) and (2), R ₁ and R ₂ may be the same or different and are a hydrogen atom, an alkyl group, a cyclohexyl group, an allyl group, a phenyl group, or an aralkyl group. Or R ₁ and R ₂ are cyclic, and represent a residue that forms a morpholino group together with a nitrogen atom. 100 parts by weight of polycarbonate resin (A), 0.5 to 25 parts by weight of at least one phosphoramide compound (B) selected from the compounds represented by the following general formulas (1) and (2), fiber formation A flame retardant resin composition comprising 0.01 to 2 parts by weight of a fluorine-containing polymer (C) and 5 to 30 parts by weight of titanium oxide (G).
General formula (1)

General formula (2)

However, in the general formulas (1) and (2), R ₁ and R ₂ may be the same or different and are a hydrogen atom, an alkyl group, a cyclohexyl group, an allyl group, a phenyl group, or an aralkyl group. Or R ₁ and R ₂ are cyclic, and represent a residue that forms a morpholino group together with a nitrogen atom. A flame retardant resin composition comprising 0.1 to 10 parts by weight of a rubber-like elastic body (D) (per 100 parts by weight of a polycarbonate resin (A)) in addition to the flame retardant resin composition according to claim 3. object. The flame retardant according to any one of claims 1 to 3, wherein the fiber-forming fluoropolymer (C) is polytetrafluoroethylene and / or polytetrafluoroethylene-containing mixed powder. Resin composition. Rubber-like elastic body (D) has a structure in which a butadiene-based rubber-like elastic body having a core / shell structure and / or a polyorganosiloxane rubber component and a polyalkyl (meth) acrylate rubber component are intertwined with each other so that they cannot be separated. The composite rubber-based graft copolymer obtained by graft-polymerizing one or two or more kinds of vinyl-based monomers to the composite rubber possessed, according to claim 1, claim 2, or claim 4. The flame-retardant resin composition as described. The flame-retardant resin composition according to claim 2, wherein the rubber-reinforced styrene-based resin (E) is an acrylonitrile-butadiene-styrene copolymer (ABS resin) produced by a bulk polymerization method. The release agent (F) is one or more compounds selected from glycerol monostearate, pentaerythritol tetrastearate, glycerol tristearate, polyolefin wax, beeswax, montanate wax, carboxylic acid ester The flame-retardant resin composition according to claim 2, wherein the flame-retardant resin composition is present. A molded product obtained by molding the flame retardant resin composition according to claim 1. The light reflection board formed by shape | molding the flame-retardant resin composition of Claim 3 or Claim 4. A light reflecting plate for a liquid crystal backlight formed by molding the flame retardant resin composition according to claim 3.