JP2007051300A - Flame-retardant resin composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a flame-retardant resin compositions which achieves excellent flame retardancy without including conventional flame retardants, consequently gives very little effect on environment, has excellent wet-heat resistance and is suitable to be recycled. <P>SOLUTION: For 100 pts.wt. of an aromatic polycarbonate resin (component A1), a flame-retardant resin composition (i) contains 0.1-2 pts.wt. of phyllosilicate (component B1), a flame-retardant resin composition (ii) contains 0.05-1 pt.wt. of inosilicate (component B2) and a flame-retardant resin composition (iii) contains 0.004-0.06 pt.wt. of a granular silicate alkali (alkaline earth) metal salt (component B3). <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to a flame retardant resin composition, particularly an aromatic polycarbonate resin composition, which has a low environmental load and is excellent in heat and moisture resistance and is suitable for recycling.

  Aromatic polycarbonate resins, polyphenylene ether resins, and polyarylate resins are excellent in mechanical properties, dimensional accuracy, electrical properties, etc., and are widely used in various fields such as electrical, electronic equipment, automotive, and office automation equipment as engineering plastics. in use. Among these applications, in the OA equipment field and the electronic / electrical equipment field, there is a strong demand for flame resistance of OA equipment and home appliances.

  In order to meet these demands, a flame retardant resin composition containing a halogen compound such as a chlorine compound or a bromine compound or a phosphate ester compound as a flame retardant has been generally proposed. However, when halogen compounds are used, toxic gases such as dioxins may be generated during combustion, and when phosphoric acid ester compounds are used, phosphorus may elute into the soil during landfill disposal. Is concerned. In particular, recently, due to increasing interest in environmental problems, a flame retardant resin material using a flame retardant having a smaller environmental load is desired.

  Recently, in order to reduce the environmental impact of plastic materials, the importance of recycling plastic materials has come to be emphasized. To improve the recycling characteristics, the environment (temperature and humidity) during use has been increased. It is necessary to be excellent in resin deterioration (wet heat resistance) due to.

  In response to such demands, flame retardant polycarbonate resin compositions using silicone compounds and metal salt compounds without using halogen compounds or phosphorus compounds as flame retardants have already been proposed. For example, JP-A-51-45159 describes a flame retardant polycarbonate resin composition comprising an aromatic polycarbonate resin and an organic alkali (earth) metal salt and a fluorinated polyolefin. Japanese Patent Application Laid-Open No. 11-263903 describes a flame retardant polycarbonate resin composition obtained by blending a polycarbonate varnish with a silicone varnish having a specific viscosity and an organic sulfonic acid metal salt. In JP-A-11-217494, a polycarbonate resin is blended with a silicone compound having a branched main chain and an aromatic group, a metal salt of an aromatic sulfur compound, and a fiber-forming fluorine-containing polymer. A flame retardant polycarbonate resin composition is described.

  However, the compositions specifically disclosed in these publications contain a relatively large amount of the organic sulfonic acid metal salt compound. When a large amount of the organic sulfonic acid metal salt is blended, the thermal stability and heat-and-moisture resistance are likely to be lowered, and as a result, the flame retardancy is not improved or the properties may be lowered. In addition, when a large amount of the organic sulfonic acid metal salt is blended, there is a problem that the heat and humidity resistance is lowered, leading to a decrease in mechanical properties and impact resistance during recycling. Therefore, flame retardants other than halogen compounds and phosphate ester compounds are required as flame retardants.

Various resin compositions shown below have been proposed as aromatic polycarbonate resin compositions having improved flame retardancy using compounds other than organic sulfonic acids.
JP-A-53-88856 describes a flame-retardant molding composition comprising an aromatic polycarbonate, an inorganic alkali metal salt, and fibril-forming polytetrafluoroethylene. However, the invention described in this publication did not fully disclose a resin composition having both good heat and moisture resistance and flame retardancy.

  JP-A-63-131348 describes a resin composition comprising an aromatic polycarbonate and a dialkali metal salt of alkylpentafluorosilicic acid. However, in this publication, good flame retardancy satisfying UL standard 94 rank V-0 at a thickness of about 1.6 mm is achieved only in a composition containing a halogen flame retardant. Therefore, the invention described in the publication does not disclose flame retardancy at a specific ratio of the metal silicate salt.

  JP-A-5-262974 describes a resin composition comprising a polycarbonate resin, a very small amount of a carboxylic acid and a salt of a group 2B metal of the periodic table, a fluorine resin, and the like. However, this publication did not fully recognize a flame retardant resin composition using a silicate metal salt.

  On the other hand, JP-A-57-209955 discloses a polycarbonate composition comprising a silicate having an average particle diameter of about 0.05 to about 20 μm in an amount of 0.025 to 5 parts by weight with respect to 100 parts by weight of an aromatic polycarbonate resin. Articles are described, and films formed from such compositions have a low coefficient of static friction and are described as having excellent thermal stability. The silicate is preferably 0.025 to 1 part by weight, and kaolin, bentonite, wollastonite and the like are specifically described as the silicate. However, such a polycarbonate composition is not sufficient in flame retardancy.

  JP-A-54-40852 contains an aromatic polycarbonate, a butadiene-based graft copolymer, a flame retardant, and at least one of alkaline earth metals, zinc, aluminum silicate, borate and carbonate A feature and a flame retardant resin composition are described. However, in this publication, the effect of the silicate and the like is aimed at improving the thermal stability of the resin composition. Furthermore, all of the resin compositions described more specifically in the examples contain brominated polycarbonate oligomers, and do not fully disclose the flame retardancy when not containing such oligomers.

  Similarly, JP-A-54-38347 describes a resin composition comprising an aromatic polycarbonate resin, an AS copolymer, an MBS copolymer, and an alkaline earth metal, zinc, aluminum silicate, and the like. ing. However, even in this publication, any resin composition that achieves good flame retardancy contains a brominated polycarbonate oligomer, and does not fully disclose the flame retardancy when such an oligomer is not contained.

  Further, JP-A-11-256022 comprises a polycarbonate-based resin, a phosphate ester having a specific cyclic structure, a fluororesin, and a small amount of talc. The amount of phosphorus atoms in the phosphate ester and the talc have a specific weight. A flame retardant resin composition satisfying the ratio is disclosed. In this publication, it is disclosed that a small amount of talc greatly improves flame retardancy. However, it is difficult to say that this publication sufficiently discloses that effective flame retardancy can be achieved even when the phosphate ester is not substantially contained.

  As described above, in the prior art, a flame-retardant aromatic polycarbonate resin composition that has a low environmental load and is excellent in moisture and heat resistance and suitable for recycling has not been sufficiently obtained. Furthermore, the demand for flame retardant resin compositions that do not contain halogen compounds and phosphate ester compounds is also the same for polyphenylene ether resins and polyarylate resins.

JP 51-45159 JP-A-11-263903 Japanese Patent Laid-Open No. 11-217494 JP-A-53-88856 JP-A-63-312348 Japanese Patent Laid-Open No. 5-262974 JP-A-57-209955 JP-A-54-40852 JP-A-54-38347 Japanese Patent Application Laid-Open No. 11-256022

  An object of the present invention is to provide a flame retardant resin composition that achieves good flame retardancy without blending a conventional flame retardant and thereby has a very low environmental load, and is particularly resistant to moisture and heat resistance. An object of the present invention is to provide a flame retardant polycarbonate resin composition having excellent recyclability.

  As a result of intensive studies to solve this problem, the present inventor has found that a specific aromatic polycarbonate resin achieves good flame retardancy without containing a dripping inhibitor. That is, the present inventors have found that flame retardancy is exhibited by blending a component that is not normally recognized as a flame retardant and a very small amount of a specific amount. In view of the fact that the metal silicate itself exists in nature, the present invention achieves a flame-retardant resin composition that has an extremely low environmental load.

  The present invention is a flame retardant resin composition comprising 0.1 to 2 parts by weight of a phyllosilicate (B1 component) with respect to 100 parts by weight of an aromatic polycarbonate resin (A1 component). An aromatic polycarbonate resin (A1-2 component) comprising 0.05 to 0.3 mol% of a repeating unit having a branched structure in 100 mol% of the repeating unit or an aromatic having a viscosity average molecular weight of 70,000 to 300,000 Group polycarbonate resin (A1-3-1 component) and a viscosity average molecular weight of 10,000 to 30,000 aromatic polycarbonate resin (A1-3-2 component), and the viscosity average molecular weight is 16,000 to 35, 000 is a flame retardant resin composition which is an aromatic polycarbonate resin (A1-3 component).

  One of the preferred embodiments of the present invention is a flame retardant resin composition in which the B1 component is talc.

  The present invention is a flame retardant resin composition comprising 0.05 to 1 part by weight of inosilicate (B2 component) with respect to 100 parts by weight of an aromatic polycarbonate resin (A1 component). Aromatic polycarbonate resin (A1-2 component) comprising 0.05 to 0.3 mol% of repeating units having a branched structure in 100 mol% of repeating units or aromatic having a viscosity average molecular weight of 70,000 to 300,000 It consists of a polycarbonate resin (A-13-1 component) and an aromatic polycarbonate resin (A1-3-2 component) having a viscosity average molecular weight of 10,000 to 30,000, and its viscosity average molecular weight is 16,000 to 35,000. It is a thing concerning the flame-retardant resin composition which is aromatic polycarbonate resin (A1-3 component) which is.

  One of the preferred embodiments of the present invention is a flame retardant resin composition in which the B2 component is wollastonite.

  The present invention provides a flame retardant resin composition comprising 0.004 to 0.06 parts by weight of a granular alkali silicate (earth) metal salt (B3 component) with respect to 100 parts by weight of an aromatic polycarbonate resin (A1 component). The A1 component is an aromatic polycarbonate resin (A1-2 component) comprising 0.05 to 0.3 mol% of a repeating unit having a branched structure in 100 mol% of the repeating unit, or a viscosity average molecular weight of 70. , 300 to 300,000 aromatic polycarbonate resin (A1-3-1 component) and a viscosity average molecular weight of 10,000 to 30,000 aromatic polycarbonate resin (A1-3-2 component). The present invention relates to a flame retardant resin composition which is an aromatic polycarbonate resin (A1-3 component) having a molecular weight of 16,000 to 35,000.

  One preferred embodiment of the present invention is a flame retardant resin composition in which the B3 component is at least one selected from calcium silicate and magnesium silicate.

  One of the more preferable embodiments of the present invention further comprises 0.0005 to 0.08 parts by weight of an organic alkali metal salt and / or an organic alkaline earth metal salt (component D) with respect to 100 parts by weight of the above component A. It is the said flame retardant resin composition consisting of.

  Furthermore, one of the more preferable embodiments of the present invention is the above-mentioned flame retardant resin composition substantially free from a flame retardant comprising a chlorine compound, a bromine compound, or a phosphate ester compound.

Hereinafter, the present invention will be described in detail.
(A component)
The aromatic polycarbonate resin (A1 component) which is the A component of the present invention is obtained by reacting a dihydric phenol and a carbonate precursor. Examples of the reaction method include an interfacial polycondensation method, a melt transesterification method, a solid phase transesterification method of a carbonate prepolymer, and a ring-opening polymerization method of a cyclic carbonate compound.

  Representative examples of the dihydric phenol used here include hydroquinone, resorcinol, 4,4′-dihydroxydiphenyl, bis (4-hydroxyphenyl) methane, bis {(4-hydroxy-3,5-dimethyl). Phenyl} methane, 1,1-bis (4-hydroxyphenyl) ethane, 1,1-bis (4-hydroxyphenyl) -1-phenylethane, 2,2-bis (4-hydroxyphenyl) propane (commonly referred to as bisphenol A) ), 2,2-bis {(4-hydroxy-3-methyl) phenyl} propane, 2,2-bis {(4-hydroxy-3,5-dimethyl) phenyl} propane, 2,2-bis {(3 -Isopropyl-4-hydroxy) phenyl} propane, 2,2-bis {(4-hydroxy-3-phenyl) phenyl} propane, 2 2-bis (4-hydroxyphenyl) butane, 2,2-bis (4-hydroxyphenyl) -3-methylbutane, 2,2-bis (4-hydroxyphenyl) -3,3-dimethylbutane, 2,4- Bis (4-hydroxyphenyl) -2-methylbutane, 2,2-bis (4-hydroxyphenyl) pentane, 2,2-bis (4-hydroxyphenyl) -4-methylpentane, 1,1-bis (4- Hydroxyphenyl) cyclohexane, 1,1-bis (4-hydroxyphenyl) -4-isopropylcyclohexane, 1,1-bis (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane, 9,9-bis (4 -Hydroxyphenyl) fluorene, 9,9-bis {(4-hydroxy-3-methyl) phenyl} fluorene, α, α'-bis ( -Hydroxyphenyl) -o-diisopropylbenzene, α, α'-bis (4-hydroxyphenyl) -m-diisopropylbenzene, α, α'-bis (4-hydroxyphenyl) -p-diisopropylbenzene, 1,3- Bis (4-hydroxyphenyl) -5,7-dimethyladamantane, 4,4′-dihydroxydiphenyl sulfone, 4,4′-dihydroxydiphenyl sulfoxide, 4,4′-dihydroxydiphenyl sulfide, 4,4′-dihydroxydiphenyl ketone 4,4′-dihydroxydiphenyl ether, 4,4′-dihydroxydiphenyl ester and the like, and these can be used alone or in admixture of two or more.

  Among them, bisphenol A, 2,2-bis {(4-hydroxy-3-methyl) phenyl} propane, 2,2-bis (4-hydroxyphenyl) butane, 2,2-bis (4-hydroxyphenyl) -3 -Methylbutane, 2,2-bis (4-hydroxyphenyl) -3,3-dimethylbutane, 2,2-bis (4-hydroxyphenyl) -4-methylpentane, 1,1-bis (4-hydroxyphenyl) A homopolymer or copolymer obtained from at least one bisphenol selected from the group consisting of 3,3,5-trimethylcyclohexane and α, α′-bis (4-hydroxyphenyl) -m-diisopropylbenzene preferable.

In particular, a homopolymer of bisphenol A is preferably used. Such an aromatic polycarbonate resin is preferable in terms of excellent impact resistance.
As the carbonate precursor, carbonyl halide, carbonate ester, haloformate or the like is used, and specific examples include phosgene, diphenyl carbonate, dihaloformate of dihydric phenol, and the like.

  When the polycarbonate resin is produced by reacting the dihydric phenol and the carbonate precursor by the interfacial polycondensation method or the melt transesterification method, the catalyst, the terminal terminator, and the dihydric phenol are oxidized as necessary. You may use antioxidant etc. for preventing. The aromatic polycarbonate resin may be a polyester carbonate resin copolymerized with an aromatic or aliphatic difunctional carboxylic acid, or a mixture of two or more of the obtained aromatic polycarbonate resins. Also good.

  Examples of the aliphatic bifunctional carboxylic acid include aliphatic bifunctional carboxylic acids having 8 to 20 carbon atoms, preferably 10 to 12 carbon atoms. Such aliphatic difunctional carboxylic acid may be linear, branched or cyclic. The aliphatic bifunctional carboxylic acid is preferably α, ω-dicarboxylic acid.

  In the polymerization reaction of the aromatic polycarbonate resin, the reaction by the interfacial polycondensation method is usually a reaction between a dihydric phenol and phosgene, and is reacted in the presence of an acid binder and an organic 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 organic 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 such as triethylamine, tetra-n-butylammonium bromide or tetra-n-butylphosphonium bromide, a quaternary ammonium compound or a quaternary phosphonium compound may be used. it can. At that time, the reaction temperature is usually 0 to 40 ° C., the reaction time is preferably about 10 minutes to 5 hours, and the pH during the reaction is preferably maintained at 9 or more.

  In such a polymerization reaction, a terminal stopper is usually used. Monofunctional phenols can be used as such end terminators. Monofunctional phenols are generally used as end terminators for molecular weight control. Such monofunctional phenols are generally phenols or lower alkyl-substituted phenols represented by the following general formula (1). Monofunctional phenols can be indicated.

（式中、Ａは水素原子または炭素数１〜９の直鎖または分岐のアルキル基あるいはフェニル基置換アルキル基であり、ｒは１〜５、好ましくは１〜３の整数である。）

(In the formula, A is a hydrogen atom, a linear or branched alkyl group having 1 to 9 carbon atoms or a phenyl group-substituted alkyl group, and r is an integer of 1 to 5, preferably 1 to 3.)

Specific examples of the monofunctional phenols include phenol, p-tert-butylphenol, p-cumylphenol and isooctylphenol.
In addition, as other monofunctional phenols, phenols or benzoic acid chlorides having a long chain alkyl group or an aliphatic polyester group as a substituent, or long chain alkyl carboxylic acid chlorides can also be shown. Among these, phenols having a long-chain alkyl group represented by the following general formulas (2) and (3) as a substituent are preferably used.

（式中、Ｘは−Ｒ−ＣＯ−Ｏ−または−Ｒ−Ｏ−ＣＯ−である、ここでＲは単結合または炭素数１〜１０、好ましくは１〜５の二価の脂肪族炭化水素基を示し、ｎは１０〜５０の整数を示す。）

Wherein X is —R—CO—O— or —R—O—CO—, wherein R is a single bond or a divalent aliphatic hydrocarbon having 1 to 10 carbon atoms, preferably 1 to 5 carbon atoms. And n represents an integer of 10 to 50.)

  As the substituted phenols of the general formula (2), those having n of 10 to 30, particularly 10 to 26 are preferable, and specific examples thereof include decylphenol, dodecylphenol, tetradecylphenol, hexadecylphenol, octadecylphenol, Examples include eicosylphenol, docosylphenol, and triacontylphenol.

  Further, as the substituted phenols of the general formula (3), those in which X is —R—CO—O— and R is a single bond are suitable, and those in which 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.

The reaction by the melt transesterification method is usually a transesterification reaction between a dihydric phenol and a carbonate ester, and the alcohol or phenol produced by mixing the dihydric phenol and the carbonate ester with heating in the presence of an inert gas. Is carried out by distilling the water. The reaction temperature varies depending on the boiling point of the alcohol or phenol produced, but is usually in the range of 120 to 350 ° C. In the latter stage of the reaction, the system is evacuated to about 1.33 × 10 ^{3 to} 13.3 Pa to facilitate the distillation of the alcohol or phenol produced. The reaction time is usually about 1 to 4 hours.

  Examples of the carbonate ester include esters such as an optionally substituted aryl group having 6 to 10 carbon atoms, an aralkyl group, or an alkyl group having 1 to 4 carbon atoms. Specific examples include diphenyl carbonate, bis (chlorophenyl) carbonate, dinaphthyl carbonate, bis (diphenyl) carbonate, dimethyl carbonate, diethyl carbonate, and dibutyl carbonate. Among them, diphenyl carbonate is preferable.

A polymerization catalyst can be used to increase the polymerization rate. Examples of such polymerization catalyst include sodium hydroxide, potassium hydroxide, sodium salt of dihydric phenol, alkali metal compounds such as potassium salt, calcium hydroxide, Alkaline earth metal compounds such as barium hydroxide and magnesium hydroxide, nitrogen-containing basic compounds such as tetramethylammonium hydroxide, tetraethylammonium hydroxide, trimethylamine and triethylamine, alkoxides of alkali metals and alkaline earth metals, alkali metals And organic earth salts of alkaline earth metals, zinc compounds, boron compounds, aluminum compounds, silicon compounds, germanium compounds, organotin compounds, lead compounds, osmium compounds, antimony compounds manganese compounds, H Emission compounds, usually the esterification reaction, such as zirconium compounds, there can be used a catalyst used in the transesterification reaction. A catalyst may be used independently and may be used in combination of 2 or more type. The amount of these polymerization catalysts used is preferably 1 × 10 ⁻⁸ to 1 × 10 ⁻³ equivalent, more preferably 1 × 10 ^{−7 to} 5 × 10 ⁻⁴ equivalent, relative to 1 mol of dihydric phenol as a raw material. Selected by range.

  Further, in this polymerization reaction, in order to reduce the phenolic end groups, for example, bis (chlorophenyl) carbonate, bis (bromophenyl) carbonate, bis (nitrophenyl) carbonate, bis Compounds such as (phenylphenyl) carbonate, chlorophenylphenyl carbonate, bromophenylphenyl carbonate, nitrophenylphenyl carbonate, phenylphenyl carbonate, methoxycarbonylphenylphenyl carbonate and ethoxycarbonylphenylphenyl carbonate can be added. Of these, 2-chlorophenyl phenyl carbonate, 2-methoxycarbonylphenyl phenyl carbonate and 2-ethoxycarbonylphenyl phenyl carbonate are preferable, and 2-methoxycarbonylphenyl phenyl carbonate is particularly preferably used.

  Furthermore, it is preferable to use a deactivator that neutralizes the activity of the catalyst in such a polymerization reaction. Specific examples of the deactivator include, for example, benzene sulfonic acid, p-toluene sulfonic acid, methyl benzene sulfonate, ethyl benzene sulfonate, butyl benzene sulfonate, octyl benzene sulfonate, phenyl benzene sulfonate, p-toluene sulfone. Sulfonic acid esters such as methyl acid, ethyl p-toluenesulfonate, butyl p-toluenesulfonate, octyl p-toluenesulfonate, phenyl p-toluenesulfonate; trifluoromethanesulfonic acid, naphthalenesulfonic acid, sulfonated polystyrene , Methyl acrylate-sulfonated styrene copolymer, dodecylbenzenesulfonate-2-phenyl-2-propyl, dodecylbenzenesulfonate-2-phenyl-2-butyl, octylsulfonate tetrabutylphospho Salts, tetrabutylphosphonium decylsulfonate, tetrabutylphosphonium benzenesulfonate, tetraethylphosphonium dodecylbenzenesulfonate, tetrabutylphosphonium dodecylbenzenesulfonate, tetrahexylphosphonium dodecylbenzenesulfonate, tetradecylbenzenesulfonate tetra Octyl phosphonium salt, decyl ammonium butyl sulfate, decyl ammonium decyl sulfate, dodecyl ammonium methyl sulfate, dodecyl ammonium ethyl sulfate, dodecyl methyl ammonium methyl sulfate, dodecyl dimethyl ammonium tetradecyl sulfate, tetradecyl dimethyl ammonium methyl sulfate, tetramethyl ammonium hexyl sulfate Over DOO, decyl trimethyl ammonium hexadecyl sulfate, tetrabutylammonium dodecylbenzyl sulfate, tetraethylammonium dodecylbenzyl sulfate, there may be mentioned compounds such as tetramethylammonium dodecylbenzyl sulfate, and the like. Two or more of these compounds can be used in combination.

  Among the quenching agents, those of phosphonium salt or ammonium salt type are preferred. The amount of the deactivator is preferably 0.5 to 50 mol with respect to 1 mol of the remaining catalyst, and more preferably 0.01 to 500 ppm with respect to the polycarbonate resin after polymerization. Is used in a proportion of 0.01 to 300 ppm, particularly preferably 0.01 to 100 ppm.

  The molecular weight of the polycarbonate resin is not specified, but if the molecular weight is less than 10,000, the strength and the like are lowered, and if it exceeds 50,000, the moldability is lowered. Therefore, the viscosity average molecular weight is 10,000. ˜50,000 is preferable, 14,000 to 30,000 is more preferable, and 16,000 to 25,000 is more preferable.

The viscosity average molecular weight referred to in the present invention is obtained by first using a Ostwald viscometer from a solution in which 0.7 g of an aromatic polycarbonate resin is dissolved in 100 ml of methylene chloride at 20 ° C., as calculated 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]
The obtained specific viscosity is inserted by the following equation to determine the viscosity average molecular weight M.
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

  The above aromatic polycarbonate resins are different in dihydric phenol, those with and without end terminator, linear and branched, different manufacturing methods, and different end terminators Two or more kinds having different structures and characteristics such as polycarbonate and polyester carbonate may be mixed. In this case, it is naturally possible to mix with an aromatic polycarbonate resin having a viscosity average molecular weight outside the above range.

  In the present invention, an aromatic polycarbonate resin (A1-2 component) comprising 0.05 to 0.3 mol% of a repeating unit having a branched structure in 100 mol% of the repeating unit as one of the A components. (Hereinafter also referred to as “branched aromatic polycarbonate resin”). By using such a branched aromatic polycarbonate resin, it is possible to suppress melt dripping (so-called drip) when the resin burns, and to achieve higher flame retardancy. The branched aromatic polycarbonate resin achieves sufficient flame retardancy without using an anti-dripping agent. In order to produce such a branched aromatic polycarbonate resin, a method of copolymerizing a trifunctional or higher polyfunctional aromatic compound is usually used.

  Examples of the trifunctional or higher polyfunctional aromatic compound include phloroglucin, phloroglucid, 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-dihi And droxyphenyl) ketone, 1,4-bis (4,4-dihydroxytriphenylmethyl) benzene, trimellitic acid, pyromellitic acid, benzophenonetetracarboxylic acid, and acid chlorides thereof. Among these, 1,1 1,1-tris (4-hydroxyphenyl) ethane and 1,1,1-tris (3,5-dimethyl-4-hydroxyphenyl) ethane are preferable, and 1,1,1-tris (4-hydroxyphenyl) ethane is particularly preferable. Is preferred.

  In the branched aromatic polycarbonate resin suitable as the component A, the ratio of the polyfunctional compound is 0.05 to 0.3 mol% of repeating units having a branched structure in 100 mol% of repeating units in the aromatic polycarbonate resin. More preferably, it is 0.05-0.2 mol%, More preferably, it is 0.05-0.15 mol%.

In particular, in the case of the melt transesterification method, a branched structure may occur as a side reaction. That is, even when the polyfunctional aromatic compound is not contained, a branched structure is generated by an isomerization reaction of the monomer component during the polymerization reaction. The component A of the present invention includes such a branched aromatic polycarbonate resin. Such a ratio can be calculated by ¹ H-NMR measurement.

  Furthermore, the aromatic polycarbonate resin (A1-2 component) comprising 0.05 to 0.3 mol% of the repeating unit having the above branched structure in 100 mol% of the repeating unit of the A component has a higher concentration of the branched component. It is also possible to use a mixture of the aromatic polycarbonate resin contained and an aromatic polycarbonate resin containing a small amount of branching components or substantially free of branching components.

  In the present invention, as one of the A1 components, an A1 component is an aromatic polycarbonate resin having a viscosity average molecular weight of 70,000 to 300,000 (A1-3-1 component), and a viscosity average molecular weight of 10,000 to 30,000. Aromatic polycarbonate resin (A1-3 component) (hereinafter referred to as “high molecular weight component-containing aromatic”) having a viscosity average molecular weight of 16,000 to 35,000. Polycarbonate resin ”(sometimes referred to as“ polycarbonate resin ”) can also be used.

  Such an aromatic polycarbonate resin containing a high molecular weight component (A1-3 component) increases the entropy elasticity of the resin due to the presence of the A1-3-1 component, draw-down property in blow molding, etc., drip prevention property during combustion, It also exhibits functions such as jetting prevention in injection molding. On the other hand, by containing a low molecular weight component of the A1-3-2 component, the overall melt viscosity is greatly reduced, and the practicality in various molding methods such as injection molding is sufficiently satisfied. The high molecular weight component-containing aromatic polycarbonate resin achieves high flame retardancy higher than that of the branched aromatic polycarbonate resin, and at the same time has the above-mentioned various functions.

  In the high molecular weight component-containing aromatic polycarbonate resin (A1-3 component), the molecular weight of the A-13-1 component is preferably 70,000 to 200,000, more preferably 80,000 to 200,000, still more preferably 100. 1,000 to 200,000, particularly preferably 100,000 to 160,000. The molecular weight of the A1-3-2 component is preferably 10,000 to 25,000, more preferably 11,000 to 24,000, still more preferably 12,000 to 24,000, and particularly preferably 12,000 to 23. , 000.

  The high molecular weight component-containing aromatic polycarbonate resin (A1-3 component) is obtained by mixing the above A1-3-1 component and A1-3-2 component in various proportions and adjusting to satisfy a predetermined molecular weight range. Can do. Preferably, it is a case where the A1-3-1 component is 2 to 40% by weight in 100% by weight of the A1-3 component, more preferably the A1-3-1 component is 3 to 30% by weight, and still more preferably. The A1-3-1 component is 4 to 20% by weight, and particularly preferably the A1-3-1 component is 5 to 20% by weight.

  As the method for adjusting the A1-3 component, (1) a method in which the A1-3-1 component and the A1-3-2 component are independently polymerized and mixed, and (2) JP-A-5-306336. The method of producing an aromatic polycarbonate resin showing a plurality of polymer peaks in a molecular weight distribution chart by GPC method, represented by the method shown in Japanese Patent Publication No. Gazette, in the same system, the aromatic polycarbonate resin of the present invention A- A method for producing the composition so as to satisfy the conditions of one component, and (3) an aromatic polycarbonate resin obtained by the production method (the production method of (2)), a separately produced A1-3-1 component and / or The method etc. which mix A1-3-2 component can be mentioned.

(B1 component-B3 component)
In the present invention, a resin composition containing phyllosilicate (B1 component), a resin composition containing inosilicate (B2 component), or a granular alkali silicate (earth) metal salt ( (B3 component) (hereinafter, the B1 component to B3 component may be collectively referred to as “B component”).
The B component silicate metal salt represents a silicate metal salt composed of at least a metal oxide component and a SiO ₂ component.

  The B component silicate metal salt may be a compound oxide, an oxyacid salt (consisting of an ionic lattice), or a solid solution, and the compound oxide may be a combination of two or more of a single oxide, and a single oxide. And any combination of two or more of oxyacid salts, and also in solid solution, any of solid solutions of two or more metal oxides and solid solutions of two or more oxyacid salts may be used. .

Hydrate may be sufficient as B component silicic acid metal salt. The form of crystal water in the hydrate is one that enters as hydrogen silicate ion as Si—OH, one that enters ionically as a hydroxide ion (OH ⁻ ) with respect to the metal cation, and H ₂ O molecules in the gaps in the structure. Any form of entry may be used.

As the B component silicate metal salt, either a natural product or an artificial synthetic product can be used. As the artificial compound, a metal silicate obtained from various conventionally known methods, for example, various synthesis methods using a solid reaction, a hydrothermal reaction, an ultrahigh pressure reaction, and the like can be used. In addition, examples of the SiO ₂ source in the composite include quartz, diatomaceous earth, white carbon, silica gel, colloidal silica, and tetramethylsilane. In addition to alkali metal silicates, alkali silicate metals such as sodium silicate and potassium silicate are used. Salt can be used.

The phyllosilicate (B1 component) of the present invention has a layered crystal structure in which SiO ₂ tetrahedra are two-dimensionally connected infinitely. Examples of the B1 component include talc, mica, smectite, vermiculite, and the like, and talc is particularly preferable. The B1 component is cleaved from the crystal structure at the layered interface and generally has a plate shape. A preferred B1 component has a plate shape. The average particle size of the B1 component is preferably in the range of 0.05 to 20 μm, more preferably in the range of 0.05 to 5 μm, and still more preferably in the range of 0.05 to 3 μm. The measurement of the average particle diameter refers to D50 (median diameter of particle diameter distribution) measured by an X-ray transmission method which is one of liquid phase precipitation methods. As a specific example of an apparatus for performing such a measurement, Sedigraph 5100 manufactured by Micromeritics Inc. can be cited.

The inosilicate (B2 component) of the present invention is one in which SiO ₂ tetrahedrons are infinitely connected one-dimensionally and have a chain or band-like crystal structure. Preferred examples of the B2 component include wollastonite, sepiolite, attapulgite, and zonotolite, and wollastonite is particularly preferable. The B2 component is cleaved from the crystal structure at the layered interface and generally has a needle-like or fibrous shape. A preferred B2 component has a needle-like or fibrous shape. The average fiber diameter of the B2 component is preferably in the range of 0.05 to 20 μm, more preferably in the range of 0.05 to 5 μm, and still more preferably in the range of 0.05 to 3 μm. The average fiber diameter refers to a number average value measured by randomly extracting 500 or more from electron microscope observation.

  The granular alkali silicate (earth) metal salt (component B3) of the present invention refers to particles other than the above-mentioned components B1 and B2, particularly irregularly shaped alkali silicate (earth) metal salts. As described above, the B1 component and the B2 component generally exhibit a cleavage property from the crystal structure thereof, the B1 component mainly has a plate-like form, and the B2 component mainly has a needle-like or fibrous form. Therefore, it is clearly distinguished from the B3 component.

  The silicate metal salt of the B3 component may be any form of orthosilicate, disilicate, and cyclic silicate as the form of the silicate ion. Further, the B3 component silicate metal salt may be in any of a crystalline state, a glass state, and a mixed state of crystal and glass, and the crystal may be any transformation that each silicate metal salt can take. Good. The B3 component is particularly preferably a synthetic product. The particle size of the B3 component is preferably 0.05 to 20 μm, more preferably 0.05 to 5 μm, still more preferably 0.05 to 3 μm.

Furthermore, B3 component says that the total of an alkali metal oxide and an alkaline-earth metal oxide is 50 mol% or more in MO, when the composition is represented by the following general formula (1).
xMO.ySiO ₂ .zH ₂ O (1)
(Here, x and y represent natural numbers, z represents an integer of 0 or more, MO represents a metal oxide component, and may be a plurality of metal oxide components.)

Examples of the B3 component include lithium silicate (Li ₂ O · SiO ₂ , 2Li ₂ O · SiO ₂ , Li ₂ O · 2SiO _{2 and the} like), sodium silicate (Na ₂ O · SiO ₂ , 2Na ₂ O · SiO ₂ , Na ₂ O · 2SiO ₂ ), potassium silicate (K ₂ O · SiO ₂ , K ₂ O · 4SiO ₂ · H ₂ O etc.), beryllium silicate (2BeO · SiO ₂ etc.), magnesium silicate (2MgO · SiO ₂ , MgO-SiO _2, and the like 2MgO · 3SiO ₂ · zH ₂ O, such as _{2MgO · 3SiO 2 · 5H 2 O} ), magnesium silicate, calcium _{(CaO · MgO · SiO 2,} CaO · MgO · 2SiO 2, 3CaO · MgO · 2SiO _2, etc.), etc. calcium silicate _{(3CaO · SiO 2, 2CaO ·} SiO 2), silicates Cal Sodium um _{(Na 2 O · 3CaO · 3SiO} 2 · H 2 O , etc.), _(such as BaO · SiO 2, 2BaO · SiO 2) barium silicate, sodium aluminum silicate _(such as _{Al 2 O 3 · Na 2 O} · SiO 2) , Aluminum potassium silicate (Al ₂ O ₃ · K ₂ O · 6SiO ₂ etc.), aluminum beryllium silicate (3BeO · Al ₂ O ₃ · 6SiO ₂ etc.), and aluminum calcium silicate (Al ₂ O ₃ · CaO · SiO ₂ etc.) ) And the like.

  Among the above B3 components, those in which the alkaline earth metal oxide is 50 mol% or more are particularly preferable in MO, and those in which MO is all alkaline earth metal oxide are more preferable. Further, the B3 component is more preferably one in which the metal oxide is CaO or MgO, that is, calcium silicate or magnesium silicate is particularly suitable. Alkaline earth metal oxides have both good flame retardancy and hydrolysis resistance.

(C component)
The flame retardant resin composition of the present invention may further contain a fluorine-containing anti-dripping agent as the C component. Representative examples of the fluorine-containing anti-drip agent used as the C component of the present invention include various fluorine-based polymers having fibril-forming ability. Such fluoropolymers include polytetrafluoroethylene, tetrafluoroethylene copolymers (for example, tetrafluoroethylene / hexafluoropropylene copolymers, etc.), partially fluorinated polymers as shown in US Pat. No. 4,379,910. Polycarbonate resin produced from fluorinated diphenol can be mentioned, and polytetrafluoroethylene (hereinafter sometimes referred to as PTFE) is preferred.

  PTFE having a fibril forming ability has a very high molecular weight, and tends to be bonded to each other by an external action such as shearing force to form a fiber. The molecular weight is 1 million to 10 million, more preferably 2 million to 9 million in the number average molecular weight determined from the standard specific gravity. Such PTFE can be used in solid form or in the form of an aqueous dispersion. In addition, PTFE having such fibril-forming ability can improve the dispersibility in the resin, and it is also possible to use a PTFE mixture in a mixed form with other resins in order to obtain better flame retardancy and mechanical properties. is there.

  Examples of commercially available PTFE having such fibril-forming ability include Teflon (registered trademark) 6J from Mitsui DuPont Fluorochemical Co., Ltd., Polyflon MPA FA500, F-201L from Daikin Chemical Industries, Ltd., and the like. Commercially available aqueous dispersions of PTFE include: Fullon AD-1, AD-936 manufactured by Asahi IC Fluoropolymers Co., Ltd. Fullon D-1, D-2 manufactured by Daikin Industries, Ltd., Mitsui DuPont Fluoro A typical example is Teflon (registered trademark) 30J manufactured by Chemical Co., Ltd.

  As a mixed form of PTFE, (1) a method in which an aqueous dispersion of PTFE and an aqueous dispersion or solution of an organic polymer are mixed and co-precipitated to obtain a co-aggregated mixture (Japanese Patent Application Laid-Open No. 60-258263; (Method described in JP-A-63-154744), (2) A method of mixing an aqueous dispersion of PTFE and dried organic polymer particles (method described in JP-A-4-272957), (3) A method in which an aqueous dispersion of PTFE and an organic polymer particle solution are uniformly mixed, and each medium is simultaneously removed from the mixture (described in JP-A-06-220210, JP-A-08-188653, etc.) And (4) a method of polymerizing monomers forming an organic polymer in an aqueous dispersion of PTFE (a method described in JP-A-9-95583), and (5) A method in which an aqueous dispersion of TFE and an organic polymer dispersion are uniformly mixed, and a vinyl monomer is further polymerized in the mixture dispersion, and then a mixture is obtained (described in JP-A-11-29679, etc.). Those obtained by (Method) can be used. Examples of commercially available PTFE in a mixed form include “Metablene A3000” (trade name) manufactured by Mitsubishi Rayon Co., Ltd. and “BLENDEX B449” (trade name) manufactured by GE Specialty Chemicals.

  As a ratio of PTFE in the mixed form, PTFE is preferably 1 to 60% by weight, more preferably 5 to 55% by weight in 100% by weight of the PTFE mixture. When the ratio of PTFE is in such a range, good dispersibility of PTFE can be achieved.

(D component)
The flame retardant resin composition of the present invention may contain an organic alkali metal salt and / or an organic alkaline earth metal salt as component D for the purpose of further improving flame retardancy.
As the organic alkali metal salt and organic alkaline earth metal salt used as the component D of the present invention, various metal salts conventionally used for flame-retarding polycarbonate resins can be used. Mention may be made, for example, of metal salts of sulfonic acids or of metal sulfates. Organic alkali metal salts and organic alkaline earth metal salts can be used together in a small amount to obtain better flame retardancy without deteriorating thermal stability and moist heat resistance. These may be used alone or in combination of two or more. The alkali metal of the present invention includes lithium, sodium, potassium, rubidium and cesium, and the alkaline earth metal includes beryllium, magnesium, calcium, strontium and barium, particularly preferably lithium, sodium, Potassium.

  Examples of the metal salt of the organic sulfonic acid of the present invention include an alkali metal salt of an aliphatic sulfonic acid, an alkaline earth metal salt of an aliphatic sulfonic acid, an alkali metal salt of an aromatic sulfonic acid, and an alkaline earth metal of an aromatic sulfonic acid. Examples include salts. Preferred examples of such aliphatic sulfonic acid metal salts include alkali (earth) alkane sulfonates and alkali sulfonates in which part of the alkyl group of the alkali (earth) alkane sulfonate is substituted with a fluorine atom. (Earth) metal salts and alkali (earth) metal salts of perfluoroalkanesulfonic acid can be mentioned, and these can be used alone or in combination of two or more (where alkali (earth) Class) The term “metal salt” is used to include both alkali metal salts and alkaline earth metal salts).

  Preferable examples of alkane sulfonic acid used for alkane sulfonic acid alkali (earth) metal salt include methane sulfonic acid, ethane sulfonic acid, propane sulfonic acid, butane sulfonic acid, methylbutane sulfonic acid, hexane sulfonic acid, heptane sulfone. Examples thereof include acids and octanesulfonic acid, and these can be used alone or in combination of two or more. In addition, a metal salt in which a part of the alkyl group is substituted with a fluorine atom can also be mentioned.

  On the other hand, preferred examples of perfluoroalkanesulfonic acid include perfluoromethanesulfonic acid, perfluoroethanesulfonic acid, perfluoropropanesulfonic acid, perfluorobutanesulfonic acid, perfluoromethylbutanesulfonic acid, perfluorohexanesulfonic acid, Examples thereof include perfluoroheptanesulfonic acid and perfluorooctanesulfonic acid, and those having 1 to 8 carbon atoms are particularly preferable. These can be used alone or in combination of two or more.

  Preferred examples of the alkali (earth) metal salt of alkanesulfonic acid include sodium ethanesulfonate, and preferred examples of the alkali (earth) metal salt of perfluoroalkanesulfonic acid include potassium perfluorobutanesulfonic acid.

  The aromatic sulfonic acid used in the aromatic (earth) metal salt of aromatic sulfonate includes monomeric or polymeric aromatic sulfide sulfonic acid, aromatic carboxylic acid and ester sulfonic acid, monomeric or polymeric sulfonic acid. Aromatic ether sulfonic acid, aromatic sulfonate sulfonic acid, monomeric or polymeric aromatic sulfonic acid, monomeric or polymeric aromatic sulfonic acid, aromatic ketone sulfonic acid, heterocyclic sulfonic acid, Examples include at least one acid selected from the group consisting of sulfonic acids of aromatic sulfoxides and condensates of methylene type bonds of aromatic sulfonic acids, and these are used alone or in combination of two or more. be able to.

  Monomer or polymer aromatic sulfite alkali (earth) metal salts of aromatic sulfides are described in JP-A-50-98539, for example, disodium diphenyl sulfide-4,4′-disulfonate. And dipotassium diphenyl sulfide-4,4′-disulfonate.

  Examples of sulfonic acid alkali (earth) metal salts of aromatic carboxylic acids and esters are described in JP-A No. 50-98540, for example, potassium 5-sulfoisophthalate, sodium 5-sulfoisophthalate, polyethylene terephthalate. And polysodium acid polysulfonate.

  Monomeric or polymeric aromatic ether sulfonate alkali (earth) metal salts are described in JP-A-50-98542, for example, 1-methoxynaphthalene-4-sulfonate calcium, 4- Disodium dodecylphenyl ether disulfonate, polysodium poly (2,6-dimethylphenylene oxide) polysulfonate, polysodium poly (1,3-phenylene oxide) polysulfonate, polysodium poly (1,4-phenylene oxide) polysulfonate And poly (2,6-diphenylphenylene oxide) polypotassium polysulfonate, poly (2-fluoro-6-butylphenylene oxide) lithium polysulfonate, and the like.

  Examples of alkali (earth) metal sulfonates of aromatic sulfonates are described in JP-A No. 50-98544, and examples thereof include potassium sulfonate of benzene sulfonate.

  Monomeric or polymeric aromatic (earth) metal sulfonates are described in JP-A No. 50-98546, for example, sodium benzenesulfonate, strontium benzenesulfonate, magnesium benzenesulfonate, Examples include dipotassium p-benzenedisulfonate, dipotassium naphthalene-2,6-disulfonate, and calcium biphenyl-3,3′-disulfonate.

  Monomeric or polymeric aromatic sulfonesulfonic acid alkali (earth) metal salts are described in JP-A-52-54746, for example, sodium diphenylsulfone-3-sulfonate, diphenylsulfone-3- Examples include potassium sulfonate, dipotassium diphenyl-3,3′-disulfonate, dipotassium diphenylsulfone-3,4′-disulfonate, and the like.

  Examples of alkali sulfonate alkali (earth) metal salts of aromatic ketones are described in JP-A No. 50-98547, for example, α, α, α-trifluoroacetophenone-4-sulfonic acid sodium salt, benzophenone-3 , 3'-disulfonic acid dipotassium.

  Heterocyclic sulfonic acid alkali (earth) metal salts are described in JP-A-50-116542, for example, disodium thiophene-2,5-disulfonate, dipotassium thiophene-2,5-disulfonate. Thiophene-2,5-disulfonate calcium, sodium benzothiophenesulfonate, and the like.

  Examples of the alkali (earth) metal sulfonate of aromatic sulfoxide are described in JP-A-52-54745, and examples thereof include potassium diphenyl sulfoxide-4-sulfonate.

  As a condensate by the methylene type bond of an alkali (earth) metal salt of an aromatic sulfonate, for example, it is described in JP-A No. 2001-270984, a formalin condensate of sodium naphthalene sulfonate, an anthracene sulfonate sodium Formalin condensates can be mentioned.

  On the other hand, the alkali (earth) metal salt of sulfate ester may include, in particular, the alkali (earth) metal salt of sulfate ester of monovalent and / or polyhydric alcohols. Alcohol sulfates include methyl sulfate, ethyl sulfate, lauryl sulfate, hexadecyl sulfate, polyoxyethylene alkylphenyl ether sulfate, pentaerythritol mono, di, tri, tetrasulfate, and lauric acid monoglyceride. And sulfuric acid ester of palmitic acid monoglyceride, stearic acid monoglyceride sulfate and the like. The alkali (earth) metal salts of these sulfates are preferably alkali (earth) metal salts of lauryl sulfate.

  Examples of other organic alkali (earth) metal salts include alkali (earth) metal salts of aromatic sulfonamides such as saccharin, N- (p-tolylsulfonyl) -p-toluenesulfonimide, Examples thereof include N- (N′-benzylaminocarbonyl) sulfanilimide and alkali (earth) metal salts of N- (phenylcarboxyl) sulfanilimide.

  Among the organic alkali (earth) metal salts listed above, more preferable components include alkali (earth) metal salts of aromatic sulfonic acid and alkali (earth) metal salts of perfluoroalkanesulfonic acid. . Of these, potassium salts are particularly preferred.

(Composition ratio)
The composition ratio in the flame-retardant resin composition containing a phyllosilicate (B1 component) is 0.1 to 2 parts by weight of the B1 component with respect to 100 parts by weight of the A component. The lower limit of the composition ratio of the component B1 is preferably 0.2 parts by weight, more preferably 0.35 parts by weight, and still more preferably 0.5 parts by weight. The upper limit of the composition ratio of the component B1 is preferably 1.4 parts by weight, more preferably 1.3 parts by weight, still more preferably 1.2 parts by weight, and particularly preferably 1.1 parts by weight.

  The composition ratio in the flame-retardant resin composition containing inosilicate (B2 component) is 0.05 to 1 part by weight for the B2 component with respect to 100 parts by weight of the A component. The lower limit of the composition ratio of the B2 component is preferably 0.1 parts by weight, more preferably 0.2 parts by weight, and still more preferably 0.3 parts by weight. The upper limit of the composition ratio of the component B2 is preferably 0.7 parts by weight, more preferably 0.65 parts by weight, still more preferably 0.6 parts by weight, and particularly preferably 0.55 parts by weight.

  The composition ratio in the flame-retardant resin composition containing the granular alkali silicate (earth) metal salt (B3 component) is 0.004 to 0.06 parts by weight with respect to 100 parts by weight of the A component. The lower limit of the composition ratio of the B3 component is preferably 0.007 parts by weight, more preferably 0.013 parts by weight, and still more preferably 0.019 parts by weight. The upper limit of the composition ratio of the component B3 is preferably 0.045 parts by weight, more preferably 0.04 parts by weight, and still more preferably 0.035 parts by weight.

  Although the details of the flame retardant mechanism of the B component have not been clarified, the silicate site on the particle surface promotes carbonization due to decomposition of a resin having relatively excellent char-forming properties such as an aromatic polycarbonate resin, It is presumed that flame retardancy is improved by making it easy to form a carbonized film that blocks oxygen. Furthermore, the decomposition effect is considered to achieve a specific blending amount, that is, a very small amount of effective flame retardancy. Here, there is an optimum range for the amount of component B added depending on the type of silicate. If the resin is excessively decomposed, the melt viscosity of the resin is lowered before the formation of the carbonized film. It is presumed that the formation of the carbonized film does not proceed due to the exposure of the new resin surface accompanying the deformation. And it is thought that their actions differ depending on the type of silicate.

  Furthermore, when it contains C component, 0.01-1 weight part is preferable with respect to 100 weight part of A component, 0.03-1 weight part is more preferable, The composition ratio is 0.1-0.5. Part by weight is more preferred. If the C component is less than 0.01 part by weight with respect to 100 parts by weight of the A component, the drip prevention effect may be insufficient, and if it exceeds 1 part by weight, the mechanical strength is lowered and molding processability is disadvantageous. There is a case.

  Furthermore, when it contains D component, it is preferable that the composition ratio is 0.0005-0.08 weight part with respect to 100 weight part of A component. The lower limit of the composition ratio is more preferably 0.001 part by weight with respect to 100 parts by weight of component A, still more preferably 0.002 part by weight, and particularly preferably 0.003 part by weight. On the other hand, the upper limit of the composition ratio is more preferably 0.07 parts by weight with respect to 100 parts by weight of component A, still more preferably 0.05 parts by weight, and particularly preferably 0.02 parts by weight. When D component is 0.08 weight part or less, heat resistance and heat-and-moisture resistance are favorable.

(E component)
Furthermore, the present invention may contain an elastic polymer (E component) for the purpose of improving impact resistance. Here, the elastic polymer means a rubber component having a glass transition temperature of 10 ° C. or lower, preferably −10 ° C. or lower, more preferably −30 ° C. or lower, and a monomer component copolymerizable with the rubber component. It refers to a copolymerized polymer. Examples of rubber components include polybutadiene, polyisoprene, and diene copolymers (for example, random and block copolymers of styrene / butadiene, acrylonitrile / butadiene copolymers, and acrylic / butadiene rubbers (alkyl acrylate esters or Copolymers of ethylene and α-olefins (eg, ethylene / propylene random copolymers and block copolymers, ethylene / butene random copolymers and blocks). Copolymers), copolymers of ethylene and unsaturated carboxylic acid esters (for example, ethylene / methacrylate copolymers, ethylene / butyl acrylate copolymers, etc.), copolymers of ethylene and aliphatic vinyl (for example, ,ethylene· Acid vinyl copolymers, etc., ethylene, propylene and non-conjugated diene terpolymers (eg, ethylene / propylene / hexadiene copolymers), acrylic rubber (eg, polybutyl acrylate, poly (2-ethylhexyl acrylate), and butyl) Acrylate and 2-ethylhexyl acrylate copolymer, etc.), and silicone rubber (eg, polyorganosiloxane rubber, IPN type rubber comprising a polyorganosiloxane rubber component and a polyalkyl (meth) acrylate rubber component; And rubber having a structure in which the rubber components are entangled with each other so that the rubber components cannot be separated, and an IPN type rubber composed of a polyorganosiloxane rubber component and a polyisobutylene rubber component. Still other rubber components include urethane rubber, amide rubber, phosphazene rubber, and fluorine rubber.

  Preferred examples of the monomer component copolymerized with the rubber component include aromatic vinyl compounds, vinyl cyanide compounds, (meth) acrylic acid ester compounds, and (meth) acrylic acid compounds. Other monomer components include epoxy group-containing methacrylates such as glycidyl methacrylate, maleimide monomers such as maleimide, N-methylmaleimide, N-phenylmaleimide, acrylic acid, methacrylic acid, maleic acid, maleic anhydride Examples include α, β-unsaturated carboxylic acids such as acid, phthalic acid, and itaconic acid, and anhydrides thereof.

  More specifically, SB (styrene-butadiene) polymer, ABS (acrylonitrile-butadiene-styrene) polymer, MBS (methyl methacrylate-butadiene-styrene) polymer, MABS (methyl methacrylate-acrylonitrile-butadiene-styrene) heavy Polymer, MB (methyl methacrylate-butadiene) polymer, ASA (acrylonitrile-styrene-acrylic rubber) polymer, AES (acrylonitrile-ethylenepropylene rubber-styrene) polymer, MA (methyl methacrylate-acrylic rubber) polymer, MAS ( Methyl methacrylate-acrylic rubber-styrene) polymer, methyl methacrylate-acrylic butadiene rubber copolymer, methyl methacrylate-acrylic butadiene rubber-styrene copolymer, methylmeta Relate - and the like (acrylic silicone IPN rubber) polymer. The structure of the elastic polymer is not particularly limited, but a graft polymer and a block polymer are generally used, and a graft polymer is more preferable.

  Other examples of the elastic polymer include thermoplastic elastomers typified by polyester elastomers, polyurethane elastomers, and polyamide elastomers. Still other impact modifying polymers include polyethylene, polyorganosiloxane, and copolymers of olefins and unsaturated carboxylic acid esters.

  Examples of the aromatic vinyl compound include styrene, α-methylstyrene, o-methylstyrene, p-methylstyrene, vinylxylene, ethylstyrene, dimethylstyrene, p-tert-butylstyrene, vinylnaphthalene, and methoxystyrene. In particular, styrene is preferred. These may be used alone or in combination of two or more.

  Examples of the vinyl cyanide compound include acrylonitrile and methacrylonitrile, with acrylonitrile being particularly preferred. These may be used alone or in combination of two or more.

  Specific examples of the (meth) acrylic acid ester compound include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate, butyl (meth) acrylate, and amyl (meth) acrylate. , Hexyl (meth) acrylate, octyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, cyclohexyl (meth) acrylate, dodecyl (meth) acrylate, octadecyl (meth) acrylate, phenyl (meth) acrylate, benzyl (meth) acrylate And so on. The notation of (meth) acrylate indicates that both methacrylate and acrylate are included, and the notation of (meth) acrylic acid ester indicates that both methacrylic acid ester and acrylic acid ester are included.

When the component E is included, the composition ratio is 0.1 with respect to 100 parts by weight of the component A.
-20 parts by weight, preferably 0.5-10 parts by weight, more preferably 0.5-8 parts by weight with respect to 100 parts by weight of component A.

(Other flame retardant components)
In addition, the flame retardant resin composition of the present invention may contain an organic siloxane having an aromatic group for the purpose of improving flame retardancy. When such an organosiloxane is included, the composition ratio is preferably 0.1 to 5 parts by weight, more preferably 0.3 to 3 parts by weight per 100 parts by weight of component A.

  The organic siloxane is an organic siloxane having a phenyl group, a biphenyl group, a naphthalene group, or a derivative thereof as an aromatic group, and among them, an organic siloxane having a phenyl group is preferable. The content of the aromatic group is preferably 10 mol% or more, more preferably 20 mol% or more and 95 mol% or less of the organic functional group. A methyl group is preferable as the organic group other than the aromatic group. Further, the organosiloxane may be substituted with a functional group such as an epoxy group, a carboxyl group, or a vinyl group. Such organic siloxane may be used alone or in combination.

  Further, the organosiloxane preferably has a weight average molecular weight of 300 to 10,000 measured by GPC (gel permeation chromatography) shown below, more preferably a weight average molecular weight of 400 to 5,000, still more preferably. Is 400 to 1,000. The GPC method used for the measurement of the D component of the present invention is as follows: apparatus: Gulliver series (manufactured by JASCO), column: MIXED-C (manufactured by PL), mobile phase: chloroform, standard substance: easy cal (PS -2) Detector: Using a differential refractometer, 100 μl of a sample having a concentration of 1 mg / ml was injected at a flow rate of 1 ml / min and measured at a column temperature of 35 ° C.

(Other ingredients)
The flame retardant resin composition of the present invention can contain other thermoplastic resins and various additives as long as the effects of the present invention are not impaired. Various additives include heat stabilizers, UV absorbers, light stabilizers, release agents, lubricants, sliding agents, colorants (pigments such as carbon black and titanium oxide, dyes), polymer cross-linked particles, and fluorescent enhancement agents. Whitening agent, phosphorescent pigment, fluorescent dye, antistatic agent, flow modifier, crystal nucleating agent, inorganic and organic antibacterial agent, photocatalytic antifouling agent (fine particle titanium oxide, fine particle zinc oxide, etc.), infrared absorber, photochromic An agent etc. can be mentioned. In order to prevent deterioration of the resin composition, it is preferable that a heat stabilizer, an ultraviolet absorber, a light stabilizer and the like are contained in the resin composition. In particular, a heat stabilizer is preferably included.

  The heat stabilizer of the flame retardant resin composition of the present invention preferably contains a phosphorus stabilizer. As the phosphorus stabilizer, any of phosphite, phosphonite, and phosphate can be used.

  Preferred examples of the phosphite stabilizer include phosphite compounds having an aryl group substituted with 2 or more alkyl groups. For example, tris (diethylphenyl) phosphite, tris (di-iso-propylphenyl) phosphite, tris (di-n-butylphenyl) phosphite, tris (2,4-di-tert-butylphenyl) phosphite, Examples include tris (2,6-di-tert-butylphenyl) phosphite, tris (2,6-di-tert-butylphenyl) phosphite, and particularly tris (2,4-di-tert-butylphenyl) phosphite. Phosphites are preferred.

  Furthermore, a phosphite compound having an aryl group in which a part of the aryl group has a cyclic structure can also 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-butyl) Phenyl) (2-tert-butyl-4-methylphenyl) phosphite, 2,2′-methylenebis (4-methyl-6-tert-butylphenyl) (2-tert-butyl-4-methylphenyl) phosphite, Examples include 2,2′-ethylidenebis (4-methyl-6-tert-butylphenyl) (2-tert-butyl-4-methylphenyl) phosphite.

  Examples of phosphorus heat stabilizers other than those described above can further include the following. Examples of the phosphite compound include distearyl pentaerythritol diphosphite, bis (2,4-di-tert-butylphenyl) pentaerythritol diphosphite, bis (2,6-di-tert-butyl-4-methylphenyl). Pentaerythritol diphosphite, phenylbisphenol A pentaerythritol diphosphite, dicyclohexyl pentaerythritol diphosphite, etc. are preferable, preferably distearyl pentaerythritol diphosphite, bis (2,4-di-tert-butylphenyl) penta Erythritol diphosphite, bis (2,6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphite, 4,4′-isopropylidenediphenol ditridecyl phosphite It can be mentioned.

  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)- 4-phenyl-phenylphosphonite, bis (2,6-di-tert-butylphenyl) -3-phenyl-phenylphosphonite, and the like, 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.

  The flame retardant resin composition of the present invention can contain various stabilizers. Examples of the antioxidant include phenolic antioxidants and sulfur antioxidants. Various phenolic antioxidants can be used.

  Specific examples of the phenolic antioxidant include, for example, n-octadecyl-β- (4′-hydroxy-3 ′, 5′-di-tert-butylphenyl) propionate, 2-tert-butyl-6- (3 ′ -Tert-butyl-5'-methyl-2'-hydroxybenzyl) -4-methylphenyl acrylate, 3,9-bis {2- [3- (3-tert-butyl-4-hydroxy-5-methylphenyl) Propionyloxy] -1,1, -dimethylethyl} -2,4,8,10-tetraoxaspiro [5,5] undecane and tetrakis [methylene-3- (3 ′, 5′-di-tert-butyl) -4-Hydroxyphenyl) propionate] methane etc. can be mentioned preferably, n-octadecyl-β- (4′-hydroxy-3 ′, 5′-di- More preferred is tert-butylphenyl) propionate.

  Specific examples of the sulfur-based antioxidant of the present invention include dilauryl-3,3′-thiodipropionate, ditridecyl-3,3′-thiodipropionate, dimyristyl-3,3′-thiodipropion. Acid ester, distearyl-3,3′-thiodipropionate, laurylstearyl-3,3′-thiodipropionate, pentaerythritol tetra (β-laurylthiopropionate) ester, bis [2-methyl -4- (3-laurylthiopropionyloxy) -5-tert-butylphenyl] sulfide, octadecyl disulfide, mercaptobenzimidazole, 2-mercapto-6-methylbenzimidazole, 1,1′-thiobis (2-naphthol), etc. Can be mentioned. More preferably, a pentaerythritol tetra ((beta) -lauryl thiopropionate) ester can be mentioned.

  The flame retardant resin composition of the present invention can contain an ultraviolet absorber. Examples of the ultraviolet absorber include 2-hydroxy-4-n-dodecyloxybenzophenone, 2,2′-dihydroxy-4,4′-dimethoxybenzophenone, and bis (5-benzoyl-4-hydroxy-2-methoxyphenyl) methane. Benzophenone-based ultraviolet absorbers represented by

  Examples of the ultraviolet absorber include 2- (2′-hydroxy-5′-methylphenyl) benzotriazole, 2- (2′-hydroxy-3 ′, 5′-di-tert-amylphenyl) benzotriazole, 2- (2′-hydroxy-3 ′, 5′-bis (α, α′-dimethylbenzyl) phenylbenzotriazole, 2,2′methylenebis [4- (1,1,3,3-tetramethylbutyl) -6- (2H-benzotriazol-2-yl) phenol], condensate with methyl-3- [3-tert-butyl-5- (2H-benzotriazol-2-yl) -4-hydroxyphenylpropionate-polyethylene glycol The benzotriazole type ultraviolet absorber represented by can be mentioned.

  Further, examples of the ultraviolet absorber include 2- (4,6-diphenyl-1,3,5-triazin-2-yl) -5-hexyloxyphenol and 2- (4,6-bis (2,4-dimethyl). And hydroxyphenyltriazine compounds such as phenyl) -1,3,5-triazin-2-yl) -5-hexyloxyphenol.

  Also, bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis (1,2,2,6,6-pentamethyl-4-piperidyl) sebacate, tetrakis (2,2,6,6- Tetramethyl-4-piperidyl) -1,2,3,4-butanetetracarboxylate, tetrakis (1,2,2,6,6-pentamethyl-4-piperidyl) -1,2,3,4-butanetetra Carboxylate, poly {[6- (1,1,3,3-tetramethylbutyl) amino-1,3,5-triazine-2,4-diyl] [(2,2,6,6-tetramethylpiperidyl ) Imino] hexamethylene [(2,2,6,6-tetramethylpiperidyl) imino]}, polymethylpropyl 3-oxy- [4- (2,2,6,6-tetramethyl) piperidinyl] siloxane. It can also include hindered amine light stabilizers represented by, such light stabilizers in combination with the ultraviolet absorber and various antioxidants, exhibit better performance in terms of weather resistance.

The phosphorus-based stabilizer, phenol-based antioxidant, and sulfur-based antioxidant listed above can be used alone or in combination of two or more.
The proportion of these stabilizers in the composition is 0.0001 to 1 for 100% by weight of the flame retardant resin composition of the present invention, each of phosphorus stabilizer, phenol antioxidant, or sulfur antioxidant. It is preferable that it is weight%. More preferably, it is 0.0005 to 0.5% by weight in 100% by weight of the flame retardant resin composition. More preferably, it is 0.001 to 0.2 weight%.
Moreover, the ratio of a ultraviolet absorber and a light stabilizer is 0.01-5 weight% in 100 weight% of flame-retardant resin compositions of this invention, More preferably, it is 0.02-1 weight%.

  The flame retardant resin composition of the present invention can contain a release agent. Known release agents can be used. For example, saturated fatty acid ester, unsaturated fatty acid ester, polyolefin wax (polyethylene wax, 1-alkene polymer, etc., which may be modified with a functional group-containing compound such as acid modification), fluorine compound (polyfluoroalkyl) And fluorine oil represented by ether), paraffin wax, beeswax and the like.

  Saturated fatty acid ester is mentioned as a preferable mold release agent. In the case of such a release agent, good transparency can be maintained. For example, glycerin fatty acid esters such as monoglyceride, diglyceride and triglyceride of stearic acid, polyglycerin fatty acid esters such as decaglycerin decastate and decaglycerin tetrastearate, lower fatty acid esters such as stearic acid stearate, sebacic acid behenate, etc. Higher fatty acid esters and erythritol esters such as pentaerythritol tetrastearate are used. The release agent is preferably 0.01 to 2% by weight in 100% by weight of the flame retardant resin composition.

  In addition, the flame retardant resin composition of the present invention can be blended with a bluing agent in order to counteract the yellowishness based on an ultraviolet absorber or the like. Specific examples of the bluing agent include Macrolex Blue RR, Macrolex Violet B, and Terazole Blue RLS.

(Production method)
Arbitrary methods are employ | adopted in order to manufacture the flame-retardant resin composition of this invention. For example, component A and component B, and optionally other additives, are thoroughly mixed using premixing means such as a V-type blender, Henschel mixer, mechanochemical apparatus, extrusion mixer, etc., and optionally an extrusion granulator And granulating with a briquetting machine or the like, and then melt-kneading with a melt-kneader represented by a vent type twin-screw extruder and pelletizing with a device such as a pelletizer.

  In addition, a method of supplying each component independently to a melt kneader represented by a vent type twin screw extruder, or a part of each component is premixed and then supplied to the melt kneader independently of the remaining components. The method of doing is also mentioned. As a method of premixing, for example, when a component having a powder form is included as the component A, a method of blending a part of the powder and an additive to be blended to form a master batch of the additive diluted with powder Can be mentioned.

  More specifically, for example, when PTFE having solid fibril forming ability is used as the C component, a method of premixing the A component and the C component of the powder with a stirring mixer may be used. Furthermore, in such a case, a method of using a dispersion type as the C component and making the dispersion state finer, a method of mixing a part of the powder of the B component, and the like are also included.

  Furthermore, the method etc. which supply one component independently from the middle of a melt extruder are 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 extruder.

  The flame-retardant resin composition of the present invention can usually be produced in various products by injection molding such pellets to obtain molded products. In such injection molding, not only a normal cold runner molding method but also a hot runner molding method can be performed. In injection molding, not only ordinary molding methods but also gas-assisted injection molding, injection compression molding, injection press molding, insert molding, in-mold molding, local high-temperature mold molding (including heat-insulating mold molding), two-color molding Sandwich molding, ultra-high speed injection molding, foam molding (including those by supercritical fluid injection), and the like can be used.

  The flame-retardant resin composition of the present invention can also be used in the form of various shaped extrusions, sheets, films, etc. by extrusion molding. For forming sheets and films, an inflation method, a calendar method, a casting method, or the like can also be used. It is also possible to form a heat-shrinkable tube by applying a specific stretching operation. The flame-retardant resin composition of the present invention can be made into a hollow molded product by rotational molding, blow molding or the like. Since the resin composition of the present invention has sufficient melt elasticity both when it contains a fluorine-containing anti-dripping agent and when it does not contain a fluorine-containing anti-drop agent using a specific polycarbonate resin, And has properties suitable for blow molding.

  The flame retardant resin composition of the present invention thus obtained achieves excellent flame retardancy without substantially containing a chlorine compound, a bromine compound, or a phosphate ester compound as a flame retardant. “Substantially not containing” means that the flame-retardant resin composition of the present invention is produced without blending a flame retardant comprising these compounds, and more preferably a chlorine atom, a bromine atom, and a phosphorus atom. Is 0.1% by weight or less, more preferably 0.05% by weight or less in 100% by weight of the composition.

  From the above, the flame retardant resin composition of the present invention achieves both a low environmental load and excellent flame retardancy. Furthermore, it is excellent also in heat-and-moisture resistance. Therefore, according to the present invention, it contains 60% by weight or more of an aromatic polycarbonate resin, has a flame retardancy of V-0 at a thickness of 2.0 mm or less in the UL94 standard, and has a temperature of 120 ° C. and a humidity of 100%. The flame-retardant polycarbonate resin composition in which the molecular weight reduction rate of the aromatic polycarbonate resin after treatment for 48 hours under the conditions is 10% or less is achieved. More preferably, a resin composition having flame retardancy of V-0 at a thickness of 1.8 mm or less, and more preferably having flame retardancy of V-0 at a thickness of 1.5 mm or less is provided. By having the above-mentioned heat and humidity resistance, the flame-retardant resin composition of the present invention has good resistance to environmental degradation and excellent recycling characteristics.

  The flame-retardant resin composition of the present invention is suitable for OA equipment and home appliances having high demands on recycling characteristics, and the like. Specific examples of such applications include, for example, interior and exterior of personal computers, exterior of notebook computers, CRT displays, printers, mobile terminals, mobile phones, copiers, fax machines, recording media (CD, DVD, PD, FDD, etc.) drives, parabolic antennas, etc. , Power tools, VTRs, TVs, irons, hair dryers, rice cookers, microwave ovens, audio equipment, audio equipment such as audio / laser discs / compact discs, lighting equipment, refrigerators, air conditioners, typewriters, word processors, etc. it can. In addition, vehicle parts such as a lamp socket, a lamp reflector, a lamp housing, an instrument panel, a center console panel, a deflector part, a car navigation part, and a car stereo part can be listed. It is also useful for various applications such as machine parts, agricultural materials, fishery materials, transport containers, packaging containers, and miscellaneous goods.

  As is clear from the above examples, the flame-retardant resin composition of the present invention has a very remarkable flame retardancy by blending a specific amount of a specific silicate with a specific aromatic polycarbonate resin. To achieve. In other words, by blending a specific amount of a component that is not normally recognized as a flame retardant, extremely remarkable flame retardancy is exhibited, and this also provides a good effect on mechanical properties and wet heat resistance. Is.

  The flame retardant aromatic polycarbonate resin composition of the present invention does not need to contain a conventional halogen flame retardant and a phosphate ester flame retardant, but the flame retardant itself exists in a very small amount and naturally. The environmental load is small, and the heat and moisture resistance is excellent. Therefore, it is suitable for recycling, and is suitable for internal parts and housings of OA equipment and home appliances. Such applications include, for example, personal computer interior / exterior, notebook computer exterior, CRT display, printer, portable terminal, mobile phone, copy machine, fax, recording medium (CD, DVD, PD, FDD, etc.) drive, parabolic antenna, electric tool, Examples include VTR, TV, iron, hair dryer, rice cooker, microwave oven, audio equipment, audio equipment such as audio / laser disc / compact disc, lighting equipment, refrigerator, air conditioner, typewriter, and word processor. In addition, vehicle parts such as a lamp socket, a lamp reflector, a lamp housing, an instrument panel, a center console panel, a deflector part, a car navigation part, and a car stereo part can be listed. It is also useful for various uses such as machine parts and miscellaneous goods. Therefore, the industrial effect that it plays is exceptional.

  The form of the invention that the present inventor considers to be the best is an aggregation 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.

  EXAMPLES Examples and comparative examples are given below to specifically describe the effects of the present invention, but the present invention is not limited to them.

(Examples 1-20 and Comparative Examples 1-7)
After the raw materials listed in Tables 1 to 3 are blended uniformly in a polyethylene bag with B component and C component, respectively, a part of another A component (amount that B component and C component are 10% by weight), After adding the amount shown in the table to the tumbler, rotate it for about 15 minutes to mix uniformly, and in a twin screw extruder with a screw diameter of 30 mm [manufactured by Nippon Steel Works, TEX-30α], the following cylinder temperature The strand was extruded at a vent suction of 3000 Pa and a screw rotation speed of 180 rpm, and the strand was cooled with water and then cut with a pelletizer to obtain a pellet. The obtained pellets were dried in a hot air circulating dryer at 110 ° C. for 5 hours, and the cylinder temperature during extrusion was 280 ° C. and the cylinder temperature during molding was 300 ° C. by an injection molding machine [FANUC T-150D]. And the test piece was shape | molded on the temperature conditions of the mold temperature of 70 degreeC.

The sample characteristics were evaluated for the following items.
1) Flame retardancy A vertical combustion test (V test) was performed using 1.6 mm and 1.2 mm thick test pieces prepared according to the UL94 standard. Based on the results of the test, the grade was evaluated as any of UL-94V-0, V-1, V-2 and non-standard Not-V.
2) Moisture and heat resistance Evaluation of the moisture and heat resistance was carried out by an accelerated test according to the following procedure. Using a super accelerated life test apparatus (model PC-305III / V) manufactured by Hirayama Mfg. Co., Ltd., a molded product for evaluation of combustibility obtained by the above method under the conditions of a temperature of 120 ° C. and a humidity of 100% RH The wet heat treatment was performed for 48 hours, and the difference in viscosity average molecular weight (ΔMv) before and after the wet heat treatment (ΔMv) and the molecular weight reduction rate (100 × ΔMv / viscosity average molecular weight before the treatment) were calculated. Only those using aromatic polycarbonate resin as the component A were evaluated.)

The raw materials used in Tables 1 to 3 are as follows.
(A component)
PC-1: Linear aromatic polycarbonate resin powder having a viscosity average molecular weight of 19,700 (Panlite L-1225WX manufactured by Teijin Chemicals Ltd.)
PC-2: Polycarbonate resin pellets obtained by a melt transesterification reaction of bisphenol A and diphenyl carbonate and having a branched bond component of about 0.1 mol% in all repeating units (viscosity average molecular weight 19,700, such branched bonds) The ratio of the component was calculated from the measurement of ¹ H-NMR, and was 0 mol% (no corresponding peak) in the PC-1 polycarbonate resin measured in the same manner)
PC-3: Branched aromatic polycarbonate resin pellet (Teflon IB2500 manufactured by Idemitsu Petrochemical Co., Ltd.)
PC-4: a linear aromatic polycarbonate resin synthesized from bisphenol A and p-tert-butylphenol as a terminal terminator and phosgene by an interfacial polycondensation method, having a viscosity average molecular weight of 15,200, 10 parts by weight, viscosity Aromatic polycarbonate resin pellets having an average molecular weight of 23,700, 80 parts by weight, and 120,000 having an average molecular weight of 29 parts are melt-mixed.

(B component)
Mg silicate: hydrous magnesium silicate reagent (composition formula: 2MgO · 3SiO ₂ · 5H ₂ O, manufactured by Wako Pure Chemical Industries, Ltd.)
Silicate Ca: Calcium Silicate Reagent (Compositional formula: CaO · SiO ₂ , Wako Pure Chemical Industries, Ltd.)
TALC: Talc (HS-T0.8, Hayashi Kasei Kogyo Co., Ltd.)
WSN: Wollastonite (NYGLOS4 manufactured by Niko Minerals)

(C component)
PTFE: Polytetrafluoroethylene having a fibril forming ability (Polyflon MPA FA500, manufactured by Daikin Industries, Ltd.)
B449: A mixture of polytetrafluoroethylene particles having fibril-forming ability and styrene-acrylonitrile copolymer particles (polytetrafluoroethylene content 50% by weight) (BLENDEX B449 manufactured by GE Specialty Chemicals)

(D component)
F114: Perfluorobutanesulfonic acid potassium salt (“Megafac F-114P” manufactured by Dainippon Ink and Chemicals, Inc.)

(F component)
IM-1: butadiene rubber reinforced-ethyl acrylate-methyl methacrylate copolymer [Kureha Chemical Industry Co., Ltd. EXL2602]
IM-2: a copolymer obtained by copolymerizing methyl methacrylate with a composite rubber polymer having a structure in which a polyorganosiloxane rubber and an acrylate rubber are intertwined with each other [METABrene S-2001 manufactured by Mitsubishi Rayon Co., Ltd.]
IM-3: Butadiene-2-ethylhexyl acrylate copolymer rubber reinforced-styrene-methyl methacrylate copolymer (HIA15 manufactured by Kureha Chemical Industry Co., Ltd.)
IM-4: 2-ethylhexyl acrylate-n-butyl acrylate rubber reinforced-methyl methacrylate copolymer [Metblene W-450A manufactured by Mitsubishi Rayon Co., Ltd.]

(Ingredient for comparative example)
FP: Phosphate ester flame retardant (resorcinol bis (dixylenyl phosphate), Adekastab FP-500 manufactured by Asahi Denka Kogyo Co., Ltd.)
FG: Halogen flame retardant (polycarbonate oligomer from tetrabromobisphenol A, Fireguard FG-7000 manufactured by Teijin Chemicals Ltd.)
(Other ingredients)
Antioxidant: Phosphorous antioxidant (Irgafos 168, manufactured by Ciba Geigy Japan)
Release agent: Saturated fatty acid ester release agent (RIKENAL SL900 manufactured by Riken Vitamin Co., Ltd.)

  From Table 1 to Table 3, the flame retardant resin composition of the present invention achieves good flame retardancy by blending a specific amount of a specific silicate without blending a conventional flame retardant. It turns out that it is a thing. Furthermore, it is excellent in heat-and-moisture resistance, and therefore recyclability is also good. Compared to the case where a conventional halogen flame retardant, phosphate ester flame retardant or the like is blended, the flame retardant resin composition of the present invention has equivalent flame retardancy and good heat and humidity resistance. I understand.

  Also, a notebook PC housing (display device side cover) molded product shown in FIG. 1 which is almost transparent from the composition of Example 1 and slightly opaque from the composition of Example 15 is molded to obtain a good molded product. It was.

It is a front side perspective schematic diagram of the housing molded product of the notebook computer used in the examples (length 178 mm × width 245 mm × edge height 10 mm).

Explanation of symbols

1 Notebook PC housing body 2 Matte surface 3 Mirror surface

Claims (8)

  A flame retardant resin composition comprising 0.1 to 2 parts by weight of a phyllosilicate (B1 component) with respect to 100 parts by weight of an aromatic polycarbonate resin (A1 component), wherein the A1 component has 100 repeating units. An aromatic polycarbonate resin (A1-2 component) or an aromatic polycarbonate resin having a viscosity average molecular weight of 70,000 to 300,000 containing 0.05 to 0.3 mol% of a repeating unit having a branched structure in mol% ( A1-3-1 component) and an aromatic polycarbonate resin having a viscosity average molecular weight of 10,000 to 30,000 (A1-3-2 component), and having a viscosity average molecular weight of 16,000 to 35,000 Flame retardant resin composition which is a group polycarbonate resin (A1-3 component).   The flame retardant resin composition according to claim 1, wherein the B1 component is talc.   A flame-retardant resin composition comprising 0.05 to 1 part by weight of an inosilicate (B2 component) with respect to 100 parts by weight of an aromatic polycarbonate resin (A1 component), wherein the A1 component comprises 100 repeating units. An aromatic polycarbonate resin (A1-2 component) or an aromatic polycarbonate resin having a viscosity average molecular weight of 70,000 to 300,000 containing 0.05 to 0.3 mol% of a repeating unit having a branched structure in mol% ( A1-3-1 component) and an aromatic polycarbonate resin having a viscosity average molecular weight of 10,000 to 30,000 (A1-3-2 component), and having a viscosity average molecular weight of 16,000 to 35,000 Flame retardant resin composition which is a group polycarbonate resin (A1-3 component).   The flame retardant resin composition according to claim 3, wherein the B2 component is wollastonite.   A flame-retardant resin composition comprising 0.004 to 0.06 parts by weight of a granular alkali silicate (earth) metal salt (B3 component) with respect to 100 parts by weight of an aromatic polycarbonate resin (A1 component), The component A1 is an aromatic polycarbonate resin comprising 0.05 to 0.3 mol% of repeating units having a branched structure in 100 mol% of the repeating units, or a viscosity average molecular weight of 70,000 to 300. , 000 aromatic polycarbonate resin (A1-3-1 component) and a viscosity average molecular weight of 10,000 to 30,000 aromatic polycarbonate resin (A1-3-2 component), and the viscosity average molecular weight is 16, A flame retardant resin composition which is an aromatic polycarbonate resin (A1-3 component) of 000 to 35,000.   The flame retardant resin composition according to claim 5, wherein the component B3 is at least one selected from calcium silicate and magnesium silicate.   The organic alkali metal salt and / or the organic alkaline earth metal salt (component D) 0.0005 to 0.08 parts by weight are further added to 100 parts by weight of the component A. The flame-retardant resin composition described in 1.   The flame-retardant resin composition according to any one of claims 1 to 7, which does not substantially contain a flame retardant comprising a chlorine compound, a bromine compound, or a phosphate ester compound.

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