JP5242870B2 - Flame retardant resin composition - Google Patents

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 as engineering plastics in various fields such as electrical, electronic equipment, automotive, and OA fields. Has been. Among these applications, in the OA field and the electronic / electric field, there is a strong demand for flame retardancy 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.

  In recent years, in order to reduce the environmental load of plastic materials, the recycling characteristics of plastic materials (characteristics that can withstand repeated recycling) have come to be regarded as important. In order to improve the recycling characteristics, it is an important factor that there is little deterioration in various characteristics due to the environment (temperature and humidity) during use, that is, excellent heat and humidity resistance.

  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 and the mechanical properties and impact resistance are lowered during recycling. Therefore, flame retardants other than halogen compounds and phosphate ester compounds are required as flame retardants.

  As a compound for improving flame retardancy other than organic sulfonic acid, various compositions shown below in an aromatic polycarbonate resin have been proposed.

  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 to achieve UL standard 94 rank V-0 at a thickness of about 1.6 mm is disclosed only when a halogen-based flame retardant is included, and a specific ratio of metal silicate salt It does not disclose the flame retardancy.

  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.

Problems to be solved by the invention

  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 which is excellent or has good cycleability.

As a result of intensive studies to solve such problems, the present inventor has obtained at least one thermoplastic resin selected from an aromatic polycarbonate resin, a polyphenylene ether resin, and a polyarylate resin, a fluororesin having a fibril-forming ability, And a resin composition comprising a metal silicate salt composed of a metal oxide component and a SiO ₂ component, when the proportion of the silicate metal salt is a specific ratio calculated from its pH value, extremely remarkable flame retardancy Found to achieve. That is, it has been found that a component not normally recognized as a flame retardant exhibits extremely remarkable flame retardancy at a specific blending amount. In addition, it is found that the blending amount may be extremely small in some cases, and in view of the fact that the metal silicate itself exists in nature, it can be said that a flame retardant resin composition having an extremely low environmental load has been achieved. It is. As a result of further intensive studies, the present invention has been achieved.

Means for solving the problem

The present invention relates to a fluorine-containing resin (component B) having fibril-forming ability with respect to 100 parts by weight of at least one thermoplastic resin (component A) selected from an aromatic polycarbonate resin, a polyphenylene ether resin, and a polyarylate resin. A resin composition comprising 0.005 to 5 parts by weight and w parts by weight of a metal silicate (component C) comprising at least a metal oxide component and a SiO ₂ component, wherein w is represented by the following formula (1) The present invention relates to a flame retardant resin composition that satisfies the above conditions.
50 ≦ (10 ^(p-7) ) × w ≦ 1000 (1)
(Here, p represents the pH value of the C component determined by the method described in the text.)

Hereinafter, the present invention will be described in detail.
(A component)
The component A of the present invention is a thermoplastic resin comprising at least one selected from aromatic polycarbonate resins, polyphenylene ether resins, and polyarylate resins.

  The aromatic polycarbonate resin (A component (1)) which is the component A 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 (i): Monofunctional phenols can be indicated.

(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. Of these, phenols having a long-chain alkyl group represented by the following general formulas (ii) and (iii) as substituents are preferably used.

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 (ii), those having n of 10 to 30, particularly 10 to 26 are preferable. Specific examples thereof include decylphenol, dodecylphenol, tetradecylphenol, hexadecylphenol, octadecylphenol, Examples include eicosylphenol, docosylphenol, and triacontylphenol.

  Further, as the substituted phenols of the general formula (iii), 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 binary 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 the drop time of methylene chloride, t is the drop time of the sample solution]
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 types having different structures and characteristics such as polycarbonate and polyester 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, as one of the A components, an aromatic polycarbonate resin (A {circle around (1)}) containing 0.05 to 0.3 mol% of a repeating unit having a branched structure in 100 mol% of the A component. (Two components) can also be used (hereinafter sometimes 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. 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.

  Further, the aromatic polycarbonate resin (A (1) 2 component) containing 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 branching. It is also possible to use a mixture of an aromatic polycarbonate resin containing a component and an aromatic polycarbonate resin containing a small amount of branching components or substantially no branching components.

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

  Such an aromatic polycarbonate resin containing a high molecular weight component (A (1), three components) increases the entropy elasticity of the resin due to the presence of the A (1) 3-1 component, draw-down properties in blow molding, etc. Functions such as anti-drip and anti-jetting in injection molding. On the other hand, by containing a low molecular weight component of A (1) 3-2 component, the overall melt viscosity is greatly reduced, and the practicality in various molding methods such as injection molding is sufficiently satisfied. That is, similar to the branched aromatic polycarbonate resin, while achieving a higher degree of flame retardancy, it has the above various functions at the same time.

  In the high molecular weight component-containing aromatic polycarbonate resin (A (1) 3 component), the molecular weight of the A (1) 3-1 component is preferably 70,000 to 200,000, more preferably 80,000 to 200,000, More preferably, it is 100,000-200,000, Most preferably, it is 100,000-160,000. The molecular weight of the A-1-3-2 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. ~ 23,000.

  The high molecular weight component-containing aromatic polycarbonate resin (A (1) 3 component) is a mixture of the above A (1) 3-1 component and A (1) 3-2 component in various proportions and satisfies a predetermined molecular weight range. It can be obtained by adjusting as follows. Preferably, the amount of the A (1) 3-1 component is 2 to 40% by weight, more preferably 3 to 30% by weight of the A (1) 3-1 component in 100% by weight of the A (1) 3 component. More preferably, the A-1 3-1 component is 4 to 20% by weight, and particularly preferably the A1 3-1 component is 5 to 20% by weight.

  In addition, as a method for adjusting the A (1) three components, (1) a method of polymerizing the A (1) 3-1 component and the A (1) 3-2 component independently and mixing them, (2 ) A method for producing an aromatic polycarbonate resin showing a plurality of polymer peaks in a molecular weight distribution chart by GPC method represented by the method disclosed in Japanese Patent Application Laid-Open No. 5-306336 in the same system. And (3) the aromatic polycarbonate resin obtained by the production method (production method (2)), and separately produced A (1) Examples thereof include a method of mixing the 3-1 component and / or the A (1) 3-2 component.

  The polyphenylene ether resin (component (A) 2) used in the present invention is a polymer or copolymer of a nucleus-substituted phenol having a phenylene ether structure (hereinafter sometimes simply referred to as a PPE polymer), and as required Accordingly, a styrene polymer and a rubber-modified styrene polymer are included.

  Typical examples of the polymer of the nucleus-substituted phenol having a phenylene ether structure include poly (2,6-dimethyl-1,4-phenylene) ether and poly (2-methyl-6-ethyl-1,4-phenylene) ether. Poly (2,6-diethyl-1,4-phenylene) ether, poly (2-ethyl-6-n-propyl-1,4-phenylene) ether, poly (2,6-di-n-propyl-1) , 4-phenylene) ether, poly (2-methyl-6-n-butyl-1,4-phenylene) ether, poly (2-ethyl-6-isopropyl-1,4-phenylene) ether, poly (2-methyl) -6-hydroxyethyl-1,4-phenylene) ether, poly (2-methyl-6-chloroethyl-1,4-phenylene) ether, and the like. Of these, poly (2,6-dimethyl-1,4-phenylene) ether is particularly preferred.

  Representative examples of the copolymer of a nucleus-substituted phenol having a phenylene ether structure include a copolymer of 2,6-dimethylphenol and 2,3,6-trimethylphenol, 2,6-dimethylphenol and o-cresol, Or a copolymer of 2,6-dimethylphenol with 2,3,6-trimethylphenol and o-cresol.

  The method for producing the above PPE polymer is not particularly limited. For example, according to the method described in US Pat. No. 4,788,277 (Japanese Patent Application No. 62-77570), in the presence of dibutylamine. In addition, 2,6-xylenol can be produced by oxidative coupling polymerization.

  Various molecular weights and molecular weight distributions of polyphenylene ether resins can be used. The molecular weight is 0.5 g / dl chloroform solution, and the reduced viscosity at 30 ° C. is 0.20 to 0.70 dl / g. The range is preferable, and the range of 0.30 to 0.55 dl / g is more preferable.

  In addition, in the polyphenylene ether resin of the present invention, other various phenylene ether units that have been proposed to exist in the polyphenylene ether resin as long as they do not contradict the gist of the present invention are partially structured. It may be included. Examples of those proposed to coexist in a small amount include 2- (dialkylaminomethyl) -6-methylphenylene ether described in Japanese Patent Application Nos. 63-12698 and 63-301222. Unit, 2- (N-alkyl-N-phenylaminomethyl) -6-methylphenylene ether unit, and the like. Also included are those in which a small amount of diphenoquinone or the like is bonded to the main chain of the polyphenylene ether resin.

  As the polyphenylene ether resin of the present invention, those containing a styrene polymer and a rubber-modified styrene polymer can also be used. The ratio of the styrene polymer and / or the rubber-modified styrene polymer (hereinafter sometimes referred to simply as PS polymer) and the PPE polymer is such that the PPE polymer is at least 20 in 100% by weight of the total. It is necessary to be at least wt%. The PPE polymer is more preferably 30% by weight or more. The flame retardancy is more preferable as the proportion of the PPE polymer is increased, but it may be inferior in molding processability. Therefore, the PPE polymer is more preferably in the range of 30 to 80% by weight.

  As the vinyl aromatic compound polymer, in addition to styrene, o-methyl styrene, p-methyl styrene, m-methyl styrene, 2,4-dimethyl styrene, ethyl styrene, p-tert-butyl styrene, and other nuclear alkyl-substituted styrenes , Polymers such as α-alkyl-substituted styrene such as α-methylstyrene and α-methyl-p-methylstyrene, and copolymers of one or more of these with at least one of other vinyl compounds, these two The above copolymer is mentioned.

  Examples of the compound copolymerizable with the vinyl aromatic compound include methacrylic acid esters such as methyl methacrylate and ethyl methacrylate, unsaturated nitrile compounds such as acrylonitrile and methacrylonitrile, and acid anhydrides such as maleic anhydride. . Among these polymers, particularly preferred are polystyrene (including syndiotactic polystyrene) and styrene-acrylonitrile copolymer (AS resin).

  Examples of the rubber used in the rubber-modified vinyl aromatic compound polymer include polybutadiene, styrene-butadiene copolymer, polyisoprene, butadiene-isoprene copolymer, natural rubber, and ethylene-propylene copolymer. . In particular, polybutadiene and styrene-butadiene copolymer are preferable, and rubber-modified aromatic compound polymer is preferably rubber-modified polystyrene (HIPS) and rubber-modified styrene-acrylonitrile copolymer (ABS resin).

  Further, the polyphenylene ether resin as the component (A2) can also include a polyphenylene ether resin modified with an ethylenically unsaturated compound such as the following α, β-unsaturated carboxylic acid or its anhydride. When a polyphenylene ether-based resin modified using these is used, it is possible to provide a molded article having excellent mixing properties with a vinyl compound-based polymer and free from phase separation. Examples of α, β-unsaturated carboxylic acids or anhydrides thereof include maleic anhydride, phthalic acid, itaconic anhydride, and glutaconic anhydride described in JP-B-49-2343 and JP-B-3-52486. Citraconic anhydride, aconitic anhydride, hymic anhydride, 5-norbornene-2-methyl-2-carboxylic acid, or maleic acid, fumaric acid, etc., but are not limited thereto, maleic anhydride Is particularly preferred.

  Reaction of α, β-unsaturated carboxylic acid such as maleic anhydride or its anhydride with polyphenylene ether resin is carried out by mixing both in the presence or absence of organic peroxide, and the glass transition of PPE polymer. It can manufacture by heating to the temperature more than temperature. When producing the flame retardant resin composition of the present invention, a polyphenylene ether-based resin in which an α, β-unsaturated carboxylic acid such as maleic anhydride or an anhydride thereof is bonded in advance may be used. Moreover, when manufacturing a flame-retardant resin composition, the method of making it react with a polyphenylene ether polymer by adding (alpha), (beta)-unsaturated carboxylic acid, such as maleic anhydride, or its anhydride may be sufficient.

  The polyarylate resin (component A3) of the present invention is obtained from an aromatic dicarboxylic acid or a derivative thereof and a binary phenol or a derivative thereof. The aromatic dicarboxylic acid used for the preparation of the polyarylate may be any one as long as it reacts with a dihydric phenol to give a satisfactory polymer, and one or a mixture of two or more are used.

  Preferred aromatic dicarboxylic acid components include terephthalic acid and isophthalic acid. A mixture thereof may also be used.

  Specific examples of the dihydric phenol component include 2,2-bis (4-hydroxyphenyl) propane, 4,4′-dihydroxydiphenyl sulfone, 4,4′-dihydroxydiphenyl ether, 4,4′-dihydroxydiphenyl sulfide, 4 , 4′-dihydroxydiphenyl ketone, 4,4′-dihydroxydiphenylmethane, 2,2′-bis (4hydroxy-3,5-dimethylphenyl) propane, 1,1-bis (4-hydroxyphenyl) ethane, 1, Examples include 1-bis (4-hydroxyphenyl) cyclohexane, 4,4′-dihydroxydiphenyl, hydroquinone, and the like. These dihydric phenol components are para-substituted products, but other isomers may be used, and ethylene glycol, propylene glycol, neopentyl glycol and the like may be used in combination with the dihydric phenol component.

  Among these, preferred polyarylate resins include those in which the aromatic dicarboxylic acid component is composed of terephthalic acid and isophthalic acid, and the divalent phenol component is composed of 2,2-bis (4-hydroxyphenyl) propane (bisphenol A). It is done. The ratio of terephthalic acid to isophthalic acid is preferably terephthalic acid / isophthalic acid = 9/1 to 9/1 (molar ratio), particularly preferably 7/3 to 3/7 in terms of melt processability and performance balance.

  Other typical polyarylate resins include those in which the aromatic dicarboxylic acid component is composed of terephthalic acid and the dihydric phenol component is composed of bisphenol A and hydroquinone. The ratio of bisphenol A and hydroquinone is preferably bisphenol A / hydroquinone = 50/50 to 70/30 (molar ratio), more preferably 55/45 to 70/30, and still more preferably 60/40 to 70/30. .

  The viscosity average molecular weight of the polyarylate resin in the present invention is preferably in the range of about 7,000 to 100,000 in view of physical properties and extrusion processability. The polyarylate resin can be selected from any polymerization method of interfacial polycondensation and transesterification.

  The component A used in the present invention may be a mixed resin of two or more selected from the above aromatic polycarbonate resins, polyphenylene ether resins, and polyarylate resins. The mixing ratio is arbitrarily selected. The component A is preferably an aromatic polycarbonate resin having a remarkable flame retardant effect, or a resin comprising an aromatic polycarbonate resin and a polyphenylene ether resin and / or a polyarylate resin. In the latter, the aromatic polycarbonate resin is preferably 50% by weight or more, more preferably 60% by weight or more per 100% by weight of the component A.

(B component)
Examples of the fluorinated polymer having the ability to form fibrils used as the component B of the present invention include polytetrafluoroethylene, tetrafluoroethylene copolymers (for example, tetrafluoroethylene / hexafluoropropylene copolymers, etc.), US patents Examples thereof include partially fluorinated polymers as disclosed in Japanese Patent No. 4379910, polycarbonate resins produced from fluorinated diphenols, and the like, and polytetrafluoroethylene (hereinafter sometimes referred to as PTFE) is preferable.

  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 6J from Mitsui DuPont Fluorochemical Co., Ltd., Polyflon MPA FA500 and F-201L from Daikin Chemical Industries, Ltd. 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 30J manufactured by Chemical Corporation.

  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 then a vinyl monomer is further polymerized in the mixed dispersion, and then a mixture is obtained (described in JP-A-11-29679, etc.). Those obtained by (Method) can be used. Commercially available products of PTFE in these mixed forms 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, 1 to 60% by weight of PTFE is preferable in 100% by weight of the PTFE mixture, and more preferably 5 to 55% by weight. When the ratio of PTFE is within such a range, good dispersibility of PTFE can be achieved.

(C component)
The present invention is a component that is not recognized as a conventional flame retardant when the ratio w part by weight of C component to 100 parts by weight of component A satisfies the following formula (1) in relation to its pH value p. High flame retardancy is obtained.
50 ≦ (10 ^(p-7) ) × w ≦ 1000 (1)
(Here, p represents the pH value of the C component determined by the method described in the text.)

  The lower limit of the formula (1) is preferably 100, more preferably 150, still more preferably 200, and particularly preferably 250. On the other hand, the upper limit of the formula (1) is preferably 700, more preferably 650, still more preferably 600, and particularly preferably 550.

That is, the ratio w part by weight of the C component to 100 parts by weight of the A component is most preferably in a range satisfying the following formula (3) in relation to the pH value p.
250 ≦ (10 ^(p-7) ) × w ≦ 550 (3)
(Here, p represents the pH value of the C component determined by the method described in the text.)

  Here, p is preferably 8 to 12, more preferably 9 to 12, and further preferably 10 to 11.5. The higher the pH value p, the better the flame retardancy can be achieved with a smaller blending amount. On the other hand, when the pH value p is too high, it is disadvantageous in terms of moisture and heat resistance. On the other hand, when the pH value is low, a substantial amount of metal silicate is required, and adverse effects on other characteristics are likely to increase.

  In addition, said pH value p is calculated | required with the following method. That is, the pH value is 1 g of the C component and 99 g of water having an electric resistance value of 18 MΩ · cm or more (that is, electric conductivity of about 0.55 μS / cm or less) mixed at 23 ° C. to obtain a suspension (or solution ), Shake for 10 minutes in a sealed state, and then measure at 23 ° C. with a pH meter.

  Due to the relationship between the preferable range of the above formula (1) and the preferable range of p, the amount w of the C component satisfies the above formula (1) and is in the range of 0.005 to 1.5 parts by weight. More preferably, what satisfies the above formula (1) and is 0.01 to 1 part by weight is more preferable.

The silicate metal salt of component C of the present invention will be further described. The C component is a metal silicate composed of at least a metal oxide component and a SiO ₂ component. The silicate metal salt of component C may be any form of orthosilicate, disilicate, cyclic silicate, chain silicate, layered silicate, and tectosilicate. However, as described above, a relatively high pH value p is advantageous in the present invention because the ratio is small, and particularly when the component C is a natural mineral, orthosilicate, disilicate, cyclic silicate, and chain The silicate silicate is advantageous. This is presumably because, in the case of natural minerals, the SiO ₂ chain is extremely large, and in a structure like a layered silicate, the incorporated metal ion component is difficult to get out of the system.

  The silicate metal salt of component C 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. . Moreover, the shape of a crystal | crystallization can take various shapes, such as fiber shape and plate shape. Further, the silicic acid metal salt of component C may be crystalline or amorphous.

  The silicate metal salt of component C may be a compound oxide, oxyacid salt (consisting of an ionic lattice), or a solid solution compound, and the compound oxide is 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 the silicic acid metal salt of C component. The form of crystal water in the hydrate is entered as hydrogen silicate ion as Si—OH, entered ionically as hydroxide ion (OH ⁻ ) with respect to the metal cation, and as H ₂ O molecules in the structure gap. Any form of entry may be used.

  Either a natural product or an artificially synthesized product can be used as the C component silicate metal salt. 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.

The component C silicate metal salt preferably has a composition substantially represented by the following formula (2).
_{xMO · ySiO 2 · zH 2 O} (2)
(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.)

  Furthermore, in the above formula (2), in the relationship between x and y, x: y is preferably 1: 5 to 10: 1, more preferably 1: 4 to 3: 1, and 1: 3 3: 1 is more preferable, and 5: 8 to 2: 1 is particularly preferable. Note that the value of x indicates the total number of metal oxide components when a plurality of metal oxide components are present.

Examples of the metal in the metal oxide MO include potassium, sodium, lithium, barium, calcium, zinc, manganese, iron, cobalt, magnesium, zirconium, aluminum, and titanium. Here, the ion-to-ion bonding force of these metal oxides is approximately determined by e1 · e2 / r ² , where c 1 and e 2 are the charges of the cation and anion, respectively, and r is the ion radius of the cation. Can do. The order of the magnitude of the interionic bond strength is K ₂ O, Na ₂ O, Li ₂ O, BaO, CaO, ZnO, MnO, FeO, CoO, MgO · Fe ₂ O ₃ , ZrO ₂ , Al ₂ from the lowest order. O ₃ and TiO ₂ (the ionic radius is based on the measured value of Wyckoff (1948) (published in Inorganic Chemistry Handbook, published by Gihodo Publishing Co., Ltd.)).

In a preferred embodiment of the metal oxide MO in the component C of the present invention, the bonding strength is preferably Al ₂ O ₃ or less, more preferably Fe ₂ O ₃ or less, and even more preferably MgO or less in the order of the interionic bonding strength. . Further, Li ₂ O or more is more preferable, and CaO or more is more preferable. While K ₂ O and Na ₂ O achieve good flame retardancy, they may be inferior in moist heat resistance. In the silicate metal salt in the above preferred range, it is possible to achieve further excellent compatibility between the flame retardancy of the flame retardant resin composition and the environmental resistance such as moist heat resistance. The reason why the above range is more preferable is that the lower the interionic bond strength, the richer the activity in the ionic reaction with other components. This is thought to be due to the fact that the ionic decomposition reaction of is facilitated. In addition, the following “substantially includes” means that when two or more kinds of metal oxides are included in the metal oxide MO, the above-mentioned preferred metals in the total 100 mol% of the metal oxides in the formula (2) This refers to the case where the oxide is contained in an amount of 20 mol% or more, more preferably 25 mol% or more, still more preferably 40 mol% or more, and particularly preferably 50 mol% or more.

  In the metal oxide MO, a more preferable embodiment is that the metal oxide substantially includes a metal oxide whose interionic bond strength is in the range of CaO to MgO. In particular, from the viewpoint of availability, either CaO or MgO is preferable. Those containing substantially these are preferred. Further preferred is the case where the metal oxide MO consists essentially of at least one component selected from CaO and MgO, and particularly preferred is the case consisting essentially of MgO.

  Specific examples of the silicate metal salt in each metal oxide MO include the following. Here, the description in parentheses is the name of a mineral or the like whose main component is such a silicate metal salt, and means that the compound in parentheses can be used as the exemplified metal salt.

As those containing K ₂ O in the _{component, K 2 O · SiO 2,} K 2 O · 4SiO 2 · H 2 O, K 2 O · Al 2 O 3 · 2SiO 2 ( Karushiraito), K ₂ O · Al ₂ O ₃ · 4SiO ₂ (leucite), and _{K 2 O · Al 2 O 3} · 6SiO 2 ( orthoclase), and the like.

As comprising Na ₂ O in the component, Na ₂ O · SiO _2, and its _{hydrates, Na 2 O · 2SiO 2,} 2Na 2 O · SiO 2, Na 2 O · 4SiO 2, Na 2 O · 3SiO _{2 · 3H 2 O, Na 2} O · Al 2 O 3 · 2SiO 2, Na 2 O · Al 2 O 3 · 4SiO 2 ( _{jadeite), 2Na 2 O · 3CaO ·} 5SiO 2, 3Na 2 O · 2CaO · 5SiO _2, and _{Na 2 O · Al 2 O 3} · 6SiO 2 ( albite), and the like.

Li ₂ O and as including the components _{thereof, Li 2 O · SiO 2,} 2Li 2 O · SiO 2 · Li 2 O · SiO 2 · H 2 O, 3Li 2 O · 2SiO 2, Li 2 O · Al 2 Examples thereof include O ₃ .4SiO ₂ (petalite), Li ₂ O.Al ₂ O ₃ .2SiO ₂ (eucryptite), and Li ₂ O.Al ₂ O ₃ .4SiO ₂ (spodumene).

As those containing BaO into its _components, and the like BaO · SiO 2, 2BaO · SiO 2, BaO · Al 2 O 3 · 2SiO 2 ( celsian), and BaO · TiO ₂ · 3SiO ₂ (Bentoaito).

As including CaO its components, 3CaO · SiO ₂ (cement clinker minerals of alite), 2CaO · SiO ₂ (cement clinker minerals of _{belite), 2CaO · MgO · 2SiO 2} ( O Keruma night), 2CaO · Al ₂ O ₃ · SiO ₂ (Gerlenite), solid solution of akermanite and gehlenite (Merilite), CaO · SiO ₂ (Wollastonite (including both α-type and β-type)), CaO · MgO · 2SiO _{2 (Jiopusaido), CaO · MgO · SiO 2} ( ash magnesia _{olivine), 3CaO · MgO · 2SiO 2} ( _{Meruuinaito), CaO · Al 2 O 3} · 2SiO 2 ( anorthite), 5CaO · 6SiO ₂ · 5H ₂ O (tobermorite, other 5CaO · 6SiO ₂ · 9H ₂ O, etc.) Tobamoraitogu such as -Loop hydrate, Zono Toraito group hydrate, such as _{2CaO · SiO 2 · H 2 O} ( fin Blanc Daito) wollastonite group hydrate, such _{as, 6CaO · 6SiO 2 · H 2} O ( xonotlite), 2CaO · Gyrolite group hydrates such as SiO ₂ · 2H ₂ O (gyrolite), CaO · Al ₂ O ₃ · 2SiO ₂ · H ₂ O (lawsonite), CaO · FeO · 2SiO ₂ (headenite), 3CaO · 2SiO _{2 (Chirukoanaito), 3CaO · Al 2 O 3} · 3SiO 2 ( _{Guroshura), 3CaO · Fe 2 O 3} · 3SiO 2 ( Andhra _{Daito), 6CaO · 4Al 2 O 3} · FeO · SiO 2 ( pleo black Ait), and Examples include clinozoite, olivine, olivine, vesuvite, onolite, scootite, and augite.

  Furthermore, Portland cement can be mentioned as a silicate metal salt containing CaO as its component. The type of Portland cement is not particularly limited, and any of normal, early strength, ultra-early strength, moderate heat, sulfate resistance, white, and the like can be used. Further, various mixed cements such as blast furnace cement, silica cement, fly ash cement and the like can be used as the C component.

  Moreover, blast furnace slag, a ferrite, etc. can be mentioned as a silicate metal salt which contains other CaO in the component.

Examples of those containing ZnO as the component include ZnO.SiO ₂ , 2ZnO.SiO ₂ (trothite), and 4ZnO.2SiO ₂ .H ₂ O (heteropolar ore).

As including MnO into its _components, such as _{MnO · SiO 2, 2MnO · SiO} 2, CaO · 4MnO · 5SiO 2 ( rhodonite) and Coe write the like.

As the component containing FeO, FeO · SiO ₂ (ferrosilite), 2FeO · SiO ₂ (iron olivine), 3FeO · Al ₂ O ₃ · 3SiO ₂ (almandin), and 2CaO · 5FeO · 8SiO ₂ · H ₂ O (Tetsuakuchinosenite) and the like can be mentioned.

Examples of the component containing CoO include CoO.SiO ₂ and 2CoO.SiO ₂ .

MgO · SiO ₂ (steatite, enstatite), 2MgO · SiO ₂ (forsterite), 3MgO · Al ₂ O ₃ · 3SiO ₂ (birop), 2MgO · 2Al ₂ O ₃・ 5SiO ₂ (cordierite), 2MgO.3SiO ₂ .5H ₂ O, 3MgO.4SiO ₂ .H ₂ O (talc), 5MgO.8SiO ₂ .9H ₂ O (attapulgite), 4MgO.6SiO ₂ .7H ₂ O (Sepiolite), 3MgO · 2SiO ₂ · 2H ₂ O (Chrysolite), 5MgO · 2CaO · 8SiO ₂ · H ₂ O (Translucentite), 5MgO · Al ₂ O ₃ · 3SiO ₂ · 4H ₂ O (Chlorite) _{, K 2 O · 6MgO · Al} 2 O 3 · 6SiO 2 · 2H 2 O ( _{phlogopite), Na 2 O · 3MgO ·} 3Al 2 O 3 · 8SiO 2 · H 2 O (Lanthanite), magnesium tourmaline, orthoxenite, camingtonite, vermiculite, smectite and the like.

As containing Fe ₂ O ₃ on the component, and a Fe ₂ O ₃ · SiO _2.

As those containing ZrO ₂ into its _components, ZrO 2 · SiO ₂ (zircon) and AZS refractory and the like.

As containing Al ₂ O ₃ on the _{component, Al 2 O 3 · SiO 2} ( silicon Ma night under-leucite, _{kyanite), 2Al 2 O 3 · SiO} 2, Al 2 O 3 · 3SiO 2, 3Al 2 O 3 · 2SiO ₂ (mullite), Al ₂ O ₃ .2SiO ₂ .2H ₂ O (kaolinite), Al ₂ O ₃ .4SiO ₂ .H ₂ O (pyrophyllite), Al ₂ O ₃ .4SiO ₂ .H ₂ O _{(bentonite), K 2 O · 3Na 2} O · 4Al 2 O 3 · 8SiO 2 ( _{nepheline), K 2 O · 3Al 2} O 3 · 6SiO 2 · 2H 2 O ( muscovite, sericite), K ₂ O -6MgO.Al ₂ O ₃ .6SiO ₂ .2H ₂ O (phlogobite), various zeolites, fluorine phlogopite, biotite, etc. can be mentioned.

  As said silicate metal salt, the thing of arbitrary shapes (granular, fibrous form, needle shape, plate shape, etc.) can be used. Any average particle size can be used, but the smaller the average particle size, the better. The average particle size is preferably 20 μm or less, more preferably 5 μm or less, and particularly preferably 2 μm or less. is there. On the other hand, a lower limit of 0.03 μm or more is appropriate, and a lower limit is relatively rare. The reason why the lower average particle diameter is more preferable is that the C component exhibits a flame retardant effect especially on the particle surface, and the smaller the average particle diameter, the larger the surface area per weight. The average particle diameter refers to D50 (median diameter of particle diameter distribution) measured by an X-ray transmission method that 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.

(D component)
In addition, the flame retardant resin composition of the present invention may contain an organic siloxane having an aromatic group as a D component for the purpose of further improving flame retardancy. Further, by including the D component, it is possible to achieve more stable 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. As a result, a high level of flame retardancy can be achieved without impairing properties such as thermal stability.

  The organic siloxane having an aromatic group (component D) used in the present invention is an organic siloxane having a phenyl group, a biphenyl group, a naphthalene group, or a derivative thereof as an aromatic group. preferable. The content of the aromatic group is preferably 10 mol% or more, more preferably 20 mol% or more and 95 mol% or less, among the organic functional groups contained in the component D. A methyl group is preferable as the organic group other than the aromatic group. Furthermore, the organosiloxane that is the component D of the present invention may be one having a functional group such as an epoxy group, a carboxyl group, or a vinyl group substituted. Such organic siloxane may be used alone or in combination.

  Furthermore, as D component of this invention, the thing of the weight average molecular weights measured by GPC (gel permeation chromatography) method shown below of 300-10,000 is preferable, More preferably, the weight average molecular weight is 400-5, 000, more preferably 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 0.1 w / vol% was injected at a flow rate of 1 ml / min and measured at a column temperature of 35 ° C.

  As a preferable aspect as said D component, the at least 1 sort (s) of compound chosen from the compound shown, for example in general formula (iv) and general formula (v) is mention | raise | lifted.

(In the formula, β ¹ represents a vinyl group, an alkyl group having 1 to 6 carbon atoms, a cycloalkyl group having 3 to 6 carbon atoms, and an aryl group or aralkyl group having 6 to 12 carbon atoms. Γ ¹ , γ ² , γ ³ , γ ⁴ , γ ⁵ , and γ ⁶ represent an alkyl group and a cycloalkyl group having 1 to ⁶ carbon atoms, and an aryl group and an aralkyl group having 6 to 12 carbon atoms, and at least one group is an aryl group or an aralkyl group. Δ ¹ , δ ² , and δ ³ are each an alkoxy group having 1 to 4 carbon atoms.)

(Wherein β ² and β ³ represent a vinyl group, an alkyl group having 1 to 6 carbon atoms, a cycloalkyl group having 3 to 6 carbon atoms, and an aryl group and an aralkyl group having 6 to 12 carbon atoms, γ ⁷ , γ ⁸ , γ ⁹ , γ ¹⁰ , γ ¹¹ , γ ¹² , γ ^13, and γ ¹⁴ are each an alkyl group having 1 to 6 carbon atoms, a cycloalkyl group having 3 to 6 carbon atoms, and an aryl group having 6 to 12 carbon atoms. And at least one group is an aryl group or aralkyl, and δ ⁴ , δ ⁵ , δ ⁶ , and δ ⁷ represent an alkoxy group having 1 to 4 carbon atoms.)
(E component)
As the organic alkali metal salt and organic alkaline earth metal salt used as the E component 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 in combination with a very small amount to obtain better flame retardancy without deteriorating thermal stability and heat-and-moisture 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 alkali (earth) metal salt of alkane sulfonate include methane sulfonic acid, ethane sulfonic acid, propane sulfonic acid, butane sulfonic acid, methyl butane sulfonic acid, hexane sulfonic acid, heptane sulfonic acid. , Octanesulfonic acid and the like, 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 thereof include potassium sulfonate, dipotassium sulfone-3,3′-disulfonate, and dipotassium disulfone-3,4′-disulfonate.

  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.

  Examples of the condensate obtained by methylene bond of alkali (earth) metal salt of aromatic sulfonate include formalin condensate of sodium naphthalene sulfonate and formalin condensate of sodium anthracene sulfonate.

  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. .

(Composition ratio)
The composition ratio of each component is 0.005 to 5 parts by weight of the B component and w parts by weight of the C component with respect to 100 parts by weight of the A component, and the w of the above formula (1) with respect to the pH value p. It satisfies the range. B component is preferably 0.01 to 3 parts by weight, more preferably 0.05 to 1 part by weight, and still more preferably 0.1 to 0.5 part by weight with respect to 100 parts by weight of component A. Even when the component B is in the form of a mixture with an aqueous dispersion or other resin, it refers to the net amount of PTFE.

  On the other hand, w which is the weight ratio of the component C more preferably satisfies the above formula (1) and is 0.005 to 1.5 parts by weight, and more preferably satisfies the above formula (1) and 0.01. -1 part by weight.

  When the B component is less than 0.005 parts by weight with respect to 100 parts of the A component, the drip prevention effect may be insufficient, and when it exceeds 5 parts by weight, the mechanical strength is reduced and molding processability is disadvantageous. There is. In addition, when the C component is out of the range of w, a sufficient flame retardant effect is not exhibited.

  Although the details of the flame retardant mechanism of the C component have not been clarified, the silicate site on the particle surface promotes carbonization by 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 attributed to the basicity of the metal silicate salt, and it is considered that effective flame retardancy is achieved at the specific ratio. Here, there is an optimum range for the amount of component C added. If the resin is excessively decomposed, the melt viscosity of the resin is lowered before the formation of the carbonized film, and a new resin accompanying deformation is formed. It is estimated that this is because the formation of the carbonized film does not proceed due to the exposure of the surface.

  Furthermore, when it contains D component, it is preferable that the composition ratio is 0.1-5 weight part with respect to 100 weight part of A component, 0.5-4 weight part is more preferable, 1-3 weight Part is more preferred.

  Furthermore, when it contains E component, it is preferable that the composition ratio is 0.0005-0.2 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 0.004 part by weight. On the other hand, the upper limit of the composition ratio is more preferably 0.1 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 E component exceeds 0.2 weight part, in heat resistance and heat-and-moisture resistance, it may be inferior.

  Furthermore, this invention can be made into the flame-retardant resin composition which contains an elastic polymer (F component), and this resin composition is suitable when impact resistance etc. are calculated | required further.

  Here, the elastic polymer refers to a polymer obtained by copolymerization with a rubber component having a glass transition temperature of 10 ° C. or lower, preferably −10 ° C. or lower, more preferably −30 ° C. or lower. Examples of the rubber component include polybutadiene, polyisoprene, diene copolymers (for example, random copolymers and block copolymers of styrene / butadiene, acrylonitrile / butadiene copolymers, and acrylic acid alkyl esters or methacrylic acid alkyl esters and Butadiene copolymers), ethylene and α-olefin copolymers (eg, ethylene / propylene random copolymers and block copolymers, ethylene / butene random copolymers and block copolymers, etc.), Copolymers of ethylene and unsaturated carboxylic acid esters (for example, ethylene / methacrylate copolymers and ethylene / butyl acrylate copolymers), copolymers of ethylene and aliphatic vinyl (for example, ethylene / vinyl acetate copolymer) Polymer) Lene, propylene, and non-conjugated diene terpolymers (eg, ethylene / propylene / hexadiene copolymers), acrylic rubbers (eg, polybutyl acrylate, poly (2-ethylhexyl acrylate), and butyl acrylate and 2-ethylhexyl acrylate As well as silicone rubber (for example, polyorganosiloxane rubber, IPN type rubber comprising a polyorganosiloxane rubber component and a polyalkyl (meth) acrylate rubber component), that is, the two rubber components cannot be separated. And rubbers having a structure intertwined with each other, and an IPN type rubber composed of a polyorganosiloxane rubber component and a polyisobutylene rubber component.

  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, 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 / silicone IPN rubber) polymer and the like.

  Other examples of the elastic polymer include various thermoplastic elastomers such as a styrene thermoplastic elastomer, an olefin thermoplastic elastomer, a polyurethane thermoplastic elastomer, a polyester thermoplastic elastomer, and a polyamide thermoplastic elastomer.

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

(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.

  Examples of other thermoplastic resins include polyethylene resin, polypropylene resin, polystyrene resin, HIPS resin, MS resin, ABS resin, AS resin, AES resin, ASA resin, SMA resin, poly-4-methylpentyne-1, and phenoxy resin. , Acrylic resin, polyacetal resin, aromatic polyester resin, aliphatic polyester resin, polyamide resin, cyclic polyolefin resin, hydrogenated polystyrene resin, liquid crystal polymer, polyetheretherketone, polyetherimide, polysulfone, polyethersulfone, polyphenylene (Wherein MS resin is a copolymer mainly composed of methyl methacrylate and styrene, AES resin is composed of acrylonitrile, ethylene-propylene rubber, and styrene. The ASA resin is a copolymer mainly composed of acrylonitrile, styrene and acrylic rubber, the MAS resin is a copolymer mainly composed of methyl methacrylate, acrylic rubber and styrene, and the SMA resin is styrene and maleic anhydride ( MA)).

  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, 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). Examples include pentaerythritol diphosphite, phenylbisphenol A pentaerythritol diphosphite, and dicyclohexylpentaerythritol diphosphite, 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 to component C 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 typified by a vent-type biaxial ruder 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 vented biaxial rudder, or a part of each component is premixed and then supplied to the melt-kneader independently of the remaining components. Examples include methods. 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 a solid fibril forming ability is used as the B component and a filler such as talc or wollastonite is used as the C component, both are premixed by a high-speed stirring mixer such as a Henschel mixer. The method of doing is mentioned. Further, in such a case, a dispersion type is used as the B component and the dispersion state is further refined, and a method of mixing a part of the powder of the A component is also included. Moreover, the method etc. which supply one component independently from the middle of a melt extruder are also mentioned. In addition, when there exists a liquid thing in the component to mix | blend, what is called a liquid injection apparatus or a liquid addition apparatus can be used for supply to a melt 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 ordinary cold runner molding methods but also hot runner molding methods are possible, not only ordinary injection molding methods but also gas assist injection molding, injection compression molding, injection press molding, inserts Molding, in-mold molding, local high-temperature mold molding (including heat-insulating mold molding), two-color molding, sandwich molding, ultra-high speed injection molding, 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.

  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. Therefore, 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 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 V-0 flame retardancy at a thickness of 1.8 mm or less, and more preferably V-0 flame retardancy 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.

  Therefore, the flame retardant resin composition of the present invention is suitable for internal parts and housings in OA equipment and home appliances that have high demands on recycling characteristics. 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 uses such as machine parts and miscellaneous goods.

  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 1-35 and Comparative Examples 1-9)
The raw materials listed in Tables 1 to 5 were blended uniformly in a polyethylene bag with B component, C component, and other components, each part of A component (amount that each component would be 10% by weight). Then, after the amount shown in the table was added to the tumbler, the mixture was rotated and mixed uniformly for about 15 minutes. The following was performed with a twin screw extruder with a screw diameter of 30 mm [manufactured by Nippon Steel Works, TEX-30α]. The strand was extruded at a cylinder temperature, a vent suction of 3000 Pa, and a screw rotation speed of 180 rpm. The strand was cooled with water and then cut with a pelletizer to obtain a pellet. The obtained pellets were dried with a hot air circulation dryer at 110 ° C. for 5 hours, and test pieces were molded under the following temperature conditions with an injection molding machine [FANUC T-150D].

(i) For samples using PC-1 to PC-4 as the component A, the cylinder temperature during extrusion was 280 ° C, the cylinder temperature during molding was 300 ° C, and the mold temperature was 70 ° C.
(ii) For samples using PAR as the A component, the cylinder temperature during extrusion is 350 ° C., and the cylinder temperature during molding is 380 ° C. and the mold temperature is 100 ° C. (iii) For samples using PPE as the A component, Cylinder temperature 250 ° C during extrusion and cylinder temperatures 270 ° C and 60 ° C during molding
(iv) For samples using a mixture of PC-1 and PAr as the A component, the cylinder temperature during extrusion was 310 ° C., the cylinder temperature during molding was 330 ° C., and the mold temperature was 90 ° C.
(v) For samples using a mixture of PC-1 and PPE as component A, the cylinder temperature during extrusion was 270 ° C., the cylinder temperature during molding was 290 ° C., and the mold temperature was 70 ° C.

  The pH value of the silicic acid metal salt of C component (or other than some C components) was measured as follows. 1000 mg of component C was weighed into a Pyrex glass flask using an electronic balance. Furthermore, 99000 mg of 23 ° C. water having an electric resistance value of 18 MΩ · cm or more (that is, an electric conductivity of about 0.55 μS / cm or less) obtained through an auto pure WQ500 type manufactured by Yamato Scientific Co., Ltd. in the flask. Measured. The mixture of water and component C was shaken for 10 minutes with a shaker (MK200D type manufactured by Yamato Scientific Co., Ltd.) in a sealed state. After completion of shaking, the mixture was allowed to stand for 1 minute, and immediately after standing, the pH value was measured at 23 ° C. with a pH meter (pH meter D-24 manufactured by Horiba, Ltd.).

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. In addition, the total number of seconds burned for the five specimens was recorded. In addition, about Examples 1-3 and Comparative Examples 2-4, the addition amount dependence of the C component with respect to the total combustion seconds of UL94 standard V test (thickness 1.6mm) was shown in FIG.
(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 for 48 hours was carried out, and the difference in viscosity average molecular weight (ΔMy) and the molecular weight reduction rate (100 × ΔMy / viscosity average molecular weight before the treatment) before and after the wet heat treatment were calculated. Only those using aromatic polycarbonate resin as the component A were evaluated.)

The raw materials used in Tables 1 to 5 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 PAR having an average molecular weight of 23,700 and 80 parts by weight, and 10 parts by weight of 120,000 having a viscosity average molecular weight of 29,500 are melt-mixed. (U polymer U-100)
PPE: Polyphenylene ether resin (Asahi Kasei Co., Ltd. Zylon 300H)

(B 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)

(C component)
TALC: Talc (manufactured by Hayashi Kasei Kogyo Co., Ltd. HS-T0.8, pH = 9.8)
WSN: Wollastonite (Nyco Minerals NYGLOS4, pH = 10.0)
Mg silicate: hydrous magnesium silicate reagent (composition formula: 2MgO.3SiO ₂ .5H ₂ O, Wako Pure Chemical Industries, Ltd., pH = 11.2)
Silicate Ca: Calcium silicate reagent (Composition formula: CaO · SiO ₂ , Wako Pure Chemical Industries, Ltd., pH = 11.2)
Silicate Na: Sodium Silicate Reagent (Composition Formula: Na ₂ O.3SiO ₂ .3H ₂ O, Wako Pure Chemical Industries, Ltd., pH = 11.3)
Silicate Al: Aluminum silicate reagent (Composition formula: Al ₂ O ₃ .3SiO ₂ , Wako Pure Chemical Industries, Ltd., pH = 7.5)

(D component)
SI: It is substantially represented by the above formula (iv) (partially there is a reaction between methoxy groups), and the ratio (molar ratio) of vinyl group: methoxy group: phenyl group: methyl group is about 2: 5: 7. : 6, an organosiloxane having a weight average molecular weight of about 630 measured by the GPC method defined in the text (“X-40-9243” manufactured by Shin-Etsu Chemical Co., Ltd.)

(E 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)
CAO: calcium oxide (CaO) (manufactured by Wako Pure Chemical Industries, Ltd., pH = 12.1)
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 5, the flame retardant resin composition of the present invention is blended with a very small amount of a silicate metal salt having a low environmental load, which is naturally present, without blending a conventional flame retardant. It can be seen that good flame retardancy is achieved. Therefore, according to the present invention, a flame retardant resin composition having an extremely low environmental load is provided. 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.

Effect of the invention

As is clear from the above examples, the flame-retardant resin composition of the present invention comprises at least one thermoplastic resin selected from aromatic polycarbonate resins, polyphenylene ether resins, and polyarylate resins, and By blending a silicate metal salt composed of a metal oxide component and a SiO ₂ component with a specific ratio in which the ratio of the silicate metal salt is calculated from the pH value p with respect to the fluororesin having a fibril-forming ability. It achieves extremely remarkable flame retardancy. That is, a component that is not normally recognized as a flame retardant exhibits extremely remarkable flame retardancy at a specific blending amount. In addition, it is clear that the blending amount may be very small in some cases, and this can provide a good effect on the mechanical properties and heat and humidity resistance.

  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, while the flame retardant itself is a very small amount and exists in nature. The environmental impact is small. In addition, it is suitable for recycling because of its excellent resistance to moist heat, and therefore the industrial effect it produces is exceptional.

  It is a graph which shows the addition amount dependence of C component with respect to the total combustion seconds of UL94 standard V test (thickness 1.6mm) in Examples 1-3 and Comparative Examples 2-4, and 100 parts by weight of A component on the horizontal axis The addition amount (parts by weight) of the C component with respect to, and the total combustion seconds of the five samples of the UL test are plotted on the vertical axis, and the seconds of each example and the like are plotted. The solid line shows the approximate outline of such behavior.

Claims (7)

Fluorine-containing resin (B component) having a fibril-forming ability (0.005) with respect to 100 parts by weight of at least one thermoplastic resin (component A) selected from aromatic polycarbonate resin, polyphenylene ether resin, and polyarylate resin 5 parts by weight, and a flame retardant, excluding at least a metal oxide include components and metal silicate component (C) consisting of a SiO ₂ component w parts by weight, and metal silicate comprising at least a metal oxide component and SiO ₂ component A flame retardant resin composition, wherein w satisfies the condition of the following formula (1).
50 ≦ (10 ^(p−7) ) × w ≦ 1000 (1)
(Here, p represents the pH value of the C component determined by the method described in the text.)
The flame retardant resin composition according to claim 1, wherein p of the C component is 8 to 12.
The flame-retardant resin composition according to claim 1, wherein the amount w of the C component is 0.005 to 1.5 parts by weight.
The flame retardant resin composition according to any one of claims 1 to 3, wherein the component C silicic acid metal salt is represented by the following formula (2).
xMO.ySiO ₂ .zH ₂ O (2)
(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.)
The metal oxide MO, at rank least ionic binding force between the flame retardant resin composition of claim 4 in which the coupling force, comprising an ingredient in the range of K ₂ O~Al ₂ O ₃ object.
The flame retardant resin composition according to claim 4, wherein the metal oxide MO includes at least one component selected from CaO and MgO.
  Contains 60% by weight or more of an aromatic polycarbonate resin, has a flame retardancy of V-0 with a thickness of 2.0 mm or less according to the UL94 standard, and is treated for 48 hours under conditions of a temperature of 120 ° C. and a humidity of 100%. The flame-retardant polycarbonate resin composition according to claim 1, wherein the aromatic polycarbonate resin has a molecular weight reduction rate of 10% or less.

Images