JP5290483B2 - Flame retardant aromatic polycarbonate resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an aromatic polycarbonate resin composition containing an inorganic filler having excellent flame retardancy and mild to the environment. SOLUTION: This flame-retarded aromatic polycarbonate resin composition comprises (A) 95.9-22 wt.% aromatic polycarbonate resin, (B) 3-50 wt.% inorganic filler, (C) 0.1-5 wt.% organic siloxane having an alkoxy group, a vinyl group and a phenyl group, (D) 1-20 wt.% organic phosphorus compound and (E) 0-3 wt.% polytetrafluoroethylene having fibril-forming properties when the total of the components A, B, C, D and E is 100 wt.%.

Description

  The present invention relates to an aromatic polycarbonate resin composition containing an inorganic filler excellent in flame retardancy. More specifically, a resin composition containing a solution-like organosiloxane and an organophosphorus compound having an alkoxy group, a vinyl group, and a phenyl group in a resin composition containing an aromatic polycarbonate resin and an inorganic filler, The present invention relates to an environmentally friendly aromatic polycarbonate resin composition that is excellent in flame retardancy, particularly in a thin portion having a thickness of 1.2 mm or less, has high rigidity and has good impact resistance.

  Aromatic polycarbonate resins are known as engineering plastics that are excellent in mechanical properties such as impact resistance, and are excellent in flame retardancy and heat resistance. However, an aromatic polycarbonate resin reinforced with an inorganic filler has a problem that flame retardancy and impact resistance are significantly inferior to those of a non-reinforced polycarbonate resin composition, although strength and rigidity are improved. Especially in the case of notebook-type personal computer housings, portable computer housings, and molded products for thin-walled housings such as mobile terminal devices, etc., it has sufficient strength and rigidity, and further balance between impact resistance and flame retardancy. There is a strong demand for the appearance of a good and environmentally friendly resin composition.

  Various proposals have been made as methods for improving the flame retardancy of aromatic polycarbonate resins. For example, a method of adding an organic halogen compound or this and antimony trioxide can be mentioned. However, these flame retardant resin compositions have a disadvantage that harmful halogen gases are generated during combustion. Further, a method of blending red phosphorus having a high flame retardant effect (Japanese Patent Laid-Open No. 48-85642) and a method of blending microencapsulated red phosphorus (Japanese Patent Laid-Open No. 6-116473) are disclosed. In a system using red phosphorus or microencapsulated red phosphorus in the resin composition, there is a drawback that harmful phosphine gas is generated during combustion. Furthermore, it is known that a silicone resin is blended as a method for imparting flame retardancy without generating harmful gas during combustion, but the silicone resin alone is used in a polycarbonate resin composition reinforced with an inorganic filler. Cannot obtain high flame retardancy. Therefore, methods using a silicone resin and a metal salt flame retardant in combination (Patent No. 2719486, JP-A-11-217494, JP-A-11-263903) have been disclosed, but these flame-retardant resins are disclosed. When the composition is left in a hot and humid environment for a long time, the metal salt flame retardant has a high hygroscopic property, so that the polycarbonate resin is hydrolyzed and the mechanical strength of the molded product, particularly the impact resistance, is significantly reduced. In addition, high flame resistance required for molded products for thin-walled casings with polycarbonate resin compositions reinforced with inorganic fillers, which are difficult to obtain high flame resistance compared to non-reinforced polycarbonate resin compositions For those who are satisfied, such compositions are not yet satisfactory. Furthermore, a method of using a non-softening silicone resin and an organophosphorus compound in combination (Japanese Patent Laid-Open No. 6-1000078) is disclosed, but a molded article for a thin casing with a polycarbonate resin composition reinforced with an inorganic filler. For those satisfying the high flame retardancy required for the above, such compositions are not yet satisfactory. For this reason, there is a demand for the appearance of an excellent resin composition that has an excellent flame retardant effect with a small amount of a flame retardant and has little generation of harmful gas during combustion in order to have excellent mechanical properties, particularly impact resistance. .

Problems to be solved by the invention

An object of this invention is to provide the aromatic polycarbonate resin composition containing the inorganic filler excellent in the flame retardance with little generation | occurrence | production of a harmful gas at the time of combustion.
As a result of intensive studies to achieve the above object, the present inventor in an aromatic polycarbonate resin composition reinforced with an inorganic filler whose flame retardancy is greatly reduced as compared with a non-reinforced polycarbonate resin composition. Incorporating solution-like organosiloxanes having alkoxy groups, vinyl groups and phenyl groups, the dispersibility of inorganic fillers is greatly improved, thereby improving flame retardancy and mechanical properties, especially impact resistance. The present inventors have found that the thin-walled portion (thickness 1.2 mm or less) is excellent in high flame retardancy and impact resistance, and reached the present invention.

Means for solving the problem

  In the present invention, aromatic polycarbonate resin (A component) 95.9 to 22% by weight, inorganic filler (B component) when the total of component A, component B, component C, component D and component E is 100% by weight. ) 3-50% by weight, organosiloxane having alkoxy group, vinyl group, and phenyl group (C component) 0.1-5% by weight, organophosphorus compound (D component) 1-20% by weight, having fibril forming ability The present invention relates to a flame-retardant aromatic polycarbonate resin composition and a molded article, which are polytetrafluoroethylene (E component) 0 to 3% by weight.

  The aromatic polycarbonate resin used as the component A in the present invention is usually obtained by reacting a dihydric phenol and a carbonate precursor by an interfacial polycondensation method or a melt transesterification method. It is obtained by polymerizing by an exchange method or polymerized by 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, etc., 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 Preferably, furthermore, a homopolymer of bisphenol A and 1,1-bis (4-hydroxyphenyl) -3,3,5-trimethyl Copolymers of rucyclohexane and bisphenol A, 2,2-bis {(4-hydroxy-3-methyl) phenyl} propane or α, α'-bis (4-hydroxyphenyl) -m-diisopropylbenzene are preferably used. Is done. In particular, a homopolymer of bisphenol A is preferred.

  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.

  In producing aromatic polycarbonate resin by reacting the above dihydric phenol and carbonate precursor by interfacial polycondensation method or melt transesterification method, catalyst, terminal terminator, and oxidation prevention of dihydric phenol as necessary An agent or the like may be used. The aromatic polycarbonate resin may be a branched polycarbonate resin copolymerized with a trifunctional or higher polyfunctional aromatic compound, or a polyester carbonate resin copolymerized with an aromatic or aliphatic difunctional carboxylic acid. Moreover, the mixture which mixed 2 or more types of the obtained aromatic polycarbonate resin may be sufficient.

  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-di Hydroxyphenyl) ketone, 1,4-bis (4,4-dihydroxytriphenylmethyl) benzene, or trimellitic acid, pyromellitic acid, benzophenonetetracarboxylic acid and acid chlorides thereof, among others, 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. preferable.

When a polyfunctional compound that yields such a branched polycarbonate resin is included, the proportion is 0.001 to 1 mol%, preferably 0.005 to 0.5 mol%, particularly preferably 0.01, based on the total amount of the aromatic polycarbonate. -0.3 mol%. In particular, in the case of the melt transesterification method, a branched structure may occur as a side reaction. The amount of the branched structure is also 0.001 to 1 mol%, preferably 0.005 to 0.005% in the total amount of the aromatic polycarbonate. 5 mol%, particularly preferably 0.01 to 0.3 mol% is preferable. Such a ratio can be calculated by ¹ H-NMR measurement.

  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 commonly used as end terminators for molecular weight control, and the resulting aromatic polycarbonate resin is not because the ends are blocked by groups based on monofunctional phenols. Compared to thermal stability. Such monofunctional phenols are generally phenols or lower alkyl-substituted phenols, and can be monofunctional phenols represented by the following general formula (1).

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

  Specific examples of the monofunctional phenols include phenol, p-tert-butylphenol, p-cumylphenol and isooctylphenol.

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

Wherein X is —R—O—, —R—CO—O— or —R—O—CO—, wherein R is a single bond or a carbon number of 1 to 10, preferably 1 to 5; A valent aliphatic hydrocarbon group, and n represents an integer of 10 to 50.)

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

  Further, as the substituted phenols of the general formula (3), those in which X is —R—CO—O— and R is a single bond are suitable, and those in which n is 10 to 30, particularly 10 to 26. Specific examples thereof include decyl hydroxybenzoate, dodecyl hydroxybenzoate, tetradecyl hydroxybenzoate, hexadecyl hydroxybenzoate, eicosyl hydroxybenzoate, docosyl hydroxybenzoate and triacontyl hydroxybenzoate.

  The end terminator is desirably introduced at the end of at least 5 mol%, preferably at least 10 mol%, based on the total end of the obtained aromatic polycarbonate resin. More preferably, the terminal terminator is introduced in an amount of 80 mol% or more with respect to all terminals, that is, the terminal hydroxyl group (OH group) derived from the dihydric phenol is more preferably 20 mol% or less, particularly preferably. This is the case where 90 mol% or more of the terminator is introduced with respect to all terminals, that is, the OH group is 10 mol% or less. Moreover, you may use a terminal terminator individually or in mixture of 2 or more types.

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.

In addition, a polymerization catalyst can be used to increase the polymerization rate. Examples of the polymerization catalyst include sodium hydroxide, potassium hydroxide, sodium salts of binary phenol, alkali metal compounds such as potassium salts, 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 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 , Titanium 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 equivalents, more preferably 1 × 10 ^{−7 to} 5 × 10 ⁻⁴ equivalents, relative to 1 mole of dihydric phenol as a raw material. Selected by range.

  In the polymerization reaction, in order to reduce phenolic end groups, for example, bis (chlorophenyl) carbonate, bis (bromophenyl) carbonate, bis (nitrophenyl) carbonate, bis ( It is preferable to add compounds such as (phenylphenyl) carbonate, chlorophenylphenyl carbonate, bromophenylphenyl carbonate, nitrophenylphenyl carbonate, phenylphenyl carbonate, methoxycarbonylphenylphenyl carbonate and ethoxycarbonylphenylphenyl carbonate. 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.

The molecular weight of the aromatic polycarbonate resin is not specified, but if the molecular weight is less than 10,000, the high-temperature characteristics and the like are lowered, and if it exceeds 40,000, the molding processability is lowered. Those of 10,000 to 40,000 are preferred, those of 14,000 to 30,000 are more preferred, and those of 14,000 to 23,000 are particularly preferred. Also, two or more aromatic polycarbonate resins may be mixed. The viscosity average molecular weight referred to in the present invention is obtained by inserting the specific viscosity (η _SP ) obtained from a solution obtained by dissolving 0.7 g of an aromatic polycarbonate resin in 100 ml of methylene chloride at 20 ° C. into the following equation.
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

  Here, the proportion of the component A in the resin composition is 95.9 to 22% by weight, where the total of the component A, component B, component C, component D and component E is 100% by weight, preferably Is 80-30% by weight. If it is less than 22% by weight, the flame retardancy is insufficient, and if it is more than 95.9% by weight, the moldability is lowered.

  Next, the inorganic filler used as component B is not particularly limited as long as it is generally used for reinforcing aromatic polycarbonate resins, and mineral fibers such as wollastonite, zonotolite, attapulgite; glass fiber , Milled fiber, glass fiber such as metal coated glass fiber; carbon fiber such as carbon fiber, carbon milled fiber, metal coated carbon fiber; metal fiber such as stainless steel wire, copper wire, aluminum wire, tungsten wire; alumina Fibers such as fibers, ceramic fibers such as zirconia fiber, silicon carbide fiber and boron fiber, various whiskers such as aluminum borate whisker, potassium titanate whisker, basic magnesium sulfate whisker, acicular titanium oxide, acicular calcium carbonate Filler, talc, mica, gala Various kinds of plate fillers such as flakes and graphite flakes, glass beads, glass balloons, ceramic balloons, carbon beads, silica particles, titania particles, alumina particles, kaolin, clay, calcium carbonate, titanium oxide, cerium oxide, zinc oxide, etc. Particulate fillers may be mentioned, and these may be used in combination of two or more.

  Among these, preferred inorganic fillers can include fibrous fillers such as glass fibers, carbon fibers, metal fibers, and ceramic fibers. Among them, the effects of the present invention are remarkable, and glass fibers are preferred. And carbon fibers, with carbon fibers being particularly preferred. This is because carbon fibers can achieve high rigidity and high strength in a small amount, while good impact resistance is difficult to achieve, and particularly when flame retardancy is required, More flame retardants are required, and in this case, the impact resistance is significantly reduced.

  As the carbon fiber in the present invention, any of cellulose-based, polyacrylonitrile-based, pitch-based and the like can be used, and a raw material composition comprising a polymer and a solvent by a methylene bond of aromatic sulfonic acids or their salts is used. What was obtained by the method of performing spinning without passing through the infusibilization process represented by the method of spinning or forming and then carbonizing can also be used. Furthermore, those produced by a production method that does not pass through a spinning process represented by a vapor phase growth method can also be used.

  Furthermore, any of a so-called general-purpose type, a medium elastic modulus type, and a high elastic modulus type can be used, but a polyacrylonitrile-based high elastic modulus type is particularly preferable. The shape is a chopped strand, a roving strand or the like. As for the production method, either melt spinning or solvent spinning can be used, and solvent spinning can be either wet spinning or dry spinning.

  The fiber diameter is preferably 0.5 to 20 μm and particularly preferably 1 to 10 μm. If it is less than 0.5 μm, the fibers tend to get entangled, and the fiber is severely bent in the process of dispersing the fiber in the aromatic polycarbonate, so that the efficiency of improving the rigidity is lowered. Reinforcing efficiency is reduced. These carbon fibers oxidize the surface of carbon fibers by methods such as gas phase oxidation in which the fibers are heated in an oxidizing gas, liquid phase oxidation using a solution of an oxidant, or anodizing the carbon fibers in an electrolytic bath. It is desirable. Carbon fibers are usually cut as a chopped strand by a sizing agent into a unit of several thousand to several tens of thousands as a unit, and these fibers can be used as appropriate.

  The carbon milled fiber is obtained by cutting the carbon fiber and then further pulverizing it with a ball mill or the like to adjust the length to less than a normal chopped strand. Also in this case, as the carbon fiber as a base, those mentioned as the above carbon fiber can be used.

  Here, the ratio of the B component in the resin composition is 3 to 50% by weight when the total of the A component, B component, C component, D component and E component is 100% by weight, preferably 10 to 10% by weight. 30% by weight. If it is less than 3% by weight, the strength is insufficient, and if it is more than 50% by weight, flame retardancy is lowered or molding becomes difficult.

  The organosiloxane having an alkoxy group, a vinyl group, and a phenyl group used as the C component in the present invention is in the form of a solution at room temperature, and the silicon at the terminal of the main chain or side chain of the siloxane bond is a methoxy group, an ethoxy group, or a propoxy group. In addition to having an alkoxy group having 1 to 5 carbon atoms such as a vinyl group at an arbitrary silicon position of a siloxane bond, two bonds of silicon in the molecule are substituted with a phenyl group at an arbitrary ratio. Is. Only one type of organic siloxane may be used, or a plurality of types may be used. Here, the ratio of the C component in the resin composition is 0.1 to 5% by weight, where the total of the A component, B component, C component, D component and E component is 100% by weight, preferably 0.3 to 3% by weight. If it is less than 0.1% by weight, the flame retardancy is insufficient, and if it is more than 5% by weight, the appearance is deteriorated and the mechanical properties are deteriorated.

  Although it does not specifically limit as an organic phosphorus compound (D component) of this invention, As an organic phosphorus compound, a phosphine, a phosphine oxide, a biphosphine, a phosphonium salt, a phosphinic acid salt, phosphate ester, phosphite ester, etc. Can be mentioned. More specifically, triphenyl phosphate, methyl neopentyl phosphite, pentaerythritol diethyl diphosphite, methyl neopentyl phosphate, phenyl neopentyl phosphate, pentaerythritol diphenyl diphosphate, dicyclopentyl high positive phosphate, dineopentyl hypo Examples thereof include phosphite, phenyl pyrocatechol phosphite, ethyl pyrocatechol phosphate, and dipyrrocatechol high-positive phosphate.

  Here, in particular, one or more phosphate ester compounds represented by the following general formula (4) may be mentioned.

(However, X in the above formula is hydroquinone, resorcinol, bis (4-hydroxydiphenyl) methane, bisphenol A, dihydroxydiphenyl, dihydroxynaphthalene, bis (4-hydroxyphenyl) sulfone, bis (4-hydroxyphenyl) ketone, bis And those derived from (4-hydroxyphenyl) sulfide, wherein j, k, l and m are each independently 0 or 1, n is an integer of 0 to 5, or n different phosphorus In the case of a mixture of acid esters, the average value is from 0 to 5, and R ₁ , R ₂ , R ₃ , and R ₄ are each independently a phenol or cresol substituted with or without one or more halogen atoms. Derived from xylenol, isopropylphenol, butylphenol, p-cumylphenol Is intended.)

Among these, preferably, X in the above formula includes those derived from hydroquinone, resorcinol and bisphenol A, j, k, l and m are each 1, and n is an integer of 0 to 3. Or an average value of 0 to 3 in the case of blends of phosphoric acid esters having different numbers of n, and R ₁ , R ₂ , R ₃ , and R ₄ are each independently substituted with one or more halogen atoms, or It is derived from unsubstituted phenol, cresol, xylenol.

  Among such phosphate ester flame retardants, triphenyl phosphate is a monophosphate compound, and resorcinol bis (dixylenyl phosphate) and bisphenol A bis (diphenyl phosphate) are good flame retardants. And it can be most preferably used for reasons such as good fluidity during molding.

  Furthermore, phosphazene compounds represented by phenoxyphosphazene oligomers and cyclic phenoxyphosphazene oligomers can also be used.

  Here, the ratio of the D component in the resin composition is 1 to 20% by weight, preferably 1 when the total of the A component, B component, C component, D component and E component is 100% by weight. ~ 15% by weight. If it is less than 1% by weight, the flame retardancy is insufficient, and if it is more than 20% by weight, the mechanical properties are lowered.

  In the composition of the present invention, polytetrafluoroethylene having fibril-forming ability can be blended as the E component in order to further improve the flame retardancy. Polytetrafluoroethylene having fibril-forming ability is classified as type 3 in the ASTM standard. Further, the polytetrafluoroethylene having such fibril forming ability preferably has a primary particle diameter in the range of 0.05 to 10 μm, and preferably has a secondary particle diameter of 50 to 700 μm. Such polytetrafluoroethylene has a melting and dripping prevention performance during the combustion test of a test piece in a UL vertical combustion test, and such polytetrafluoroethylene having such fibril forming ability is, for example, Mitsui DuPont Fluorochemical Co., Ltd. It is more commercially available as Teflon 6J or as Polyflon from Daikin Chemical Industries.

  Such polytetrafluoroethylene (hereinafter sometimes simply referred to as “PTFE”) can be used in the form of an aqueous dispersion in addition to the usual solid form. In addition, PTFE having such fibril-forming ability can improve the dispersibility in the resin, and in order to obtain better flame retardancy and mechanical properties, it is also possible to use a PTFE mixture of the following form.

  First, a co-aggregated mixture of a PTFE dispersion and a vinyl polymer dispersion may be mentioned. Specifically, in JP-A-60-258263, a PTFE dispersion having an average particle size of 0.05 to 5 μm and a vinyl polymer dispersion are mixed, and PTFE particles larger than 30 μm are solidified without being purified, A method for obtaining a PTFE mixture by drying such a coagulum is described, and such a mixture can be used.

  Secondly, there can be mentioned a mixture in which PTFE dispersion and dried polymer particles are mixed, and various kinds of such polymer particles can be used. More preferably, polycarbonate resin powder or ABS resin powder is used. is there. Regarding such a mixture, JP-A-4-272957 describes a mixture of PTFE dispersion and ABS resin powder, and such a method can be used.

  Thirdly, the PTFE mixture obtained by simultaneously removing each medium from the mixture of the PTFE dispersion and the thermoplastic resin solution can be mentioned, and specifically, the mixture from which the medium is removed by using a spray dryer. Such a mixture is described in JP-A-08-188653.

  Fourthly, a PTFE mixture obtained by polymerizing another vinyl monomer in the PTFE dispersion can be mentioned. Regarding such a mixture, JP-A-9-95583 discloses styrene and PTFE latex in the PTFE latex. A method for obtaining a PTFE mixture by supplying acrylonitrile is specifically described, and such a mixture can be used.

  Fifth, after mixing the PTFE dispersion and the polymer particle dispersion, a method of polymerizing an ethylenically unsaturated monomer in the mixed dispersion can be mentioned. It can be mentioned as a preferred PTFE mixture in terms of achieving both finer dispersion. The details of such a mixture are described in JP-A No. 11-29679, that is, in a dispersion obtained by mixing a PTFE dispersion having a particle diameter of 0.05 to 1.0 μm and a polymer particle dispersion, an ethylenic non-polymer is used. A preferable example is a PTFE mixture obtained by emulsion polymerization of a monomer having a saturated bond and then pulverized by coagulation or spray drying.

  Here, as the polymer particles, polypropylene, polyethylene, polystyrene, HIPS, AS resin, ABS resin, MBS resin, MABS resin, ASA resin, polyalkyl (meth) acrylate, block copolymer composed of styrene and butadiene, and hydrogenation thereof. Copolymer, block copolymer of styrene and isoprene, and hydrogenated copolymer thereof, acrylonitrile-butadiene copolymer, ethylene-propylene random copolymer and block copolymer, ethylene-butene random copolymer Copolymers and block copolymers, copolymers of ethylene and α-olefin, copolymers of ethylene-unsaturated carboxylic acid esters such as ethylene-butyl acrylate, acrylate-butadiene copolymers, polyorganosiloxanes and polymers. Examples include composite rubbers containing alkyl (meth) acrylates, and copolymers obtained by grafting vinyl monomers such as styrene, acrylonitrile, and polyalkyl methacrylates to such composite rubbers. Among them, polyalkyl (meth) Acrylate, polystyrene, AS resin, ABS resin and ASA resin are preferred.

  On the other hand, ethylenically unsaturated monomers include styrene, p-methylstyrene, o-methylstyrene, p-methoxystyrene, o-methoxystyrene, 2,4-dimethylstyrene, α-methylstyrene and the like. Body: Methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, butyl acrylate, butyl methacrylate, 2-ethylhexyl acrylate, 2-ethylhexyl methacrylate, dodecyl acrylate, dodecyl methacrylate, acrylic acid Acrylic ester monomers such as cyclohexyl and cyclohexyl methacrylate; Vinyl cyanide monomers such as acrylonitrile and methacrylonitrile; Vinyl ether monomers such as vinyl methyl ether and vinyl ethyl ether; Vinyl acetate and vinyl butyrate Cal of etc Nsan vinyl monomer, ethylene, propylene, olefin monomers such as isobutylene; butadiene, may be selected isoprene, from such diene monomer dimethyl butadiene. These monomers can be used alone or in admixture of two or more.

  As the PTFE mixture of the fifth form, metablene “A3000” (trade name) is commercially available from Mitsubishi Rayon Co., Ltd., and is easily available and can be preferably used in the present invention.

  Here, the proportion of the E component in the resin composition is preferably 3% by weight or less, more preferably, when the total of the A component, B component, C component, D component and E component is 100% by weight. Is 0.05 to 1.5% by weight, particularly preferably 0.1 to 1.0% by weight. In the range of 3% by weight, sufficient melt dripping prevention performance can be obtained.

  The lubricant in the lubricant having at least one functional group selected from the carboxyl group, carboxylic anhydride group, epoxy group, and oxazoline group used as the F component of the present invention includes mineral oil, synthetic oil, higher fatty acid Examples thereof include fluorine oils such as esters, higher fatty acid amides, paraffin waxes, polyolefin waxes, polyalkylene glycols, fluorinated fatty acid esters, trifluorochloroethylene, and polyhexafluoropropylene glycol.

  Examples of the higher fatty acid ester include glycerin fatty acid ester, sorbitan fatty acid ester, polyglycerin fatty acid ester, propylene glycol fatty acid ester, ethylene glycol fatty acid ester, and polyoxyethylene fatty acid ester.

  Of the lubricants listed above, polyolefin waxes are preferred. As the polyolefin wax, it is particularly preferable to use a polyethylene wax and / or a 1-alkene polymer. As the polyethylene wax, those generally known at present can be used, and those obtained by polymerizing ethylene under high temperature and high pressure, those obtained by thermally decomposing polyethylene, those obtained by separating and purifying low molecular weight components from the polyethylene polymer, and the like. The molecular weight, the degree of branching, etc. are not particularly limited, but the molecular weight is preferably a number average molecular weight of 500 to 20,000, more preferably 1,000 to 15,000.

  As the functional group, at least one functional group selected from a carboxyl group, a carboxylic anhydride group, and an epoxy group is more preferable, and in particular, at least one functional group selected from a carboxyl group and a carboxylic anhydride group. Groups are preferred.

  As a method for bonding these lubricants to at least one functional group selected from a carboxyl group, a carboxylic acid anhydride group, an epoxy group, and an oxazoline group, the lubricant is reactive with the specific functional group and the lubricant described above. Examples include a method of reacting a compound having a certain functional group, a method of copolymerizing the above compound having a specific functional group during the synthesis of a lubricant, a method of mixing a lubricant, a compound having a functional group and a radical generator under heating. Either method can be used.

  Particularly preferred as the F component in the present invention is a polyolefin wax having at least one functional group selected from a carboxyl group and a carboxylic anhydride group. Various methods can be appropriately employed as a method for incorporating such a carboxyl group or carboxylic acid anhydride group into the polyolefin wax. For example, maleic acid or maleic anhydride and polyethylene, a polymer of 1-alkene, 1- Examples include a method in which an alkene and a polymer such as an ethylene copolymer are mixed with heating in the presence or absence of a radical generator, and the main chain, side chain, or bond atom is cleaved. Functional groups can be introduced. An even more preferable method is a method of introducing a functional group by copolymerizing maleic acid, preferably maleic anhydride, when polymerizing or copolymerizing ethylene, propylene, 1-alkene having 4 or more carbon atoms or the like. is there. Such a method is a more preferable method in that there is no unnecessary heat load and the amount of the functional group is easily controlled. The amount of such functional groups is preferably in the range of 0.1 to 6 meq / g per gram of polyolefin wax.

  Here, the proportion of the F component in the resin composition is preferably 0.05 to 5 parts by weight, more preferably 100 parts by weight in total of the A component, B component, C component, D component and E component. Is 0.05 to 3 parts by weight.

  Furthermore, in the present invention, for the purpose of improving impact resistance as a G component, a composite rubber having a structure in which a polyorganosiloxane rubber component and a polyalkyl (meth) acrylate rubber component are intertwined so that they cannot be separated. It is also possible to add a composite rubber-based graft polymer obtained by graft-polymerizing one or two or more vinyl monomers to the resin, and better impact resistance can be obtained and preferably used. In order to obtain the composite rubber-based graft copolymer used in the present invention, first, various cyclic organosiloxanes having three or more members, such as hexamethylcyclotrisiloxane, octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, etc. And a latex of the polyorganosiloxane rubber by emulsion polymerization using a crosslinking agent and / or a grafting agent, and then the alkyl (meth) acrylate monomer, the crosslinking agent and the grafting agent are added to the polyorganosiloxane rubber. It is obtained by impregnating latex and then polymerizing. Examples of the alkyl (meth) acrylate monomer used herein include alkyl acrylates such as methyl acrylate, ethyl acrylate, n-propyl acrylate, n-butyl acrylate, and 2-ethylhexyl acrylate, and alkyls such as hexyl methacrylate and 2-ethylhexyl methacrylate. Although methacrylate is mentioned, it is particularly preferable to use n-butyl acrylate.

  Examples of the vinyl monomer to be graft-polymerized on the composite rubber include aromatic vinyl compounds such as styrene and α-methylstyrene, vinyl cyanide compounds such as acrylonitrile and methacrylonitrile, and methacrylic compounds such as methyl methacrylate and 2-ethylhexyl methacrylate. Examples thereof include acrylic acid esters such as acid ester, methyl acrylate, ethyl acrylate, and butyl acrylate, and these are used alone or in combination of two or more. Among such composite rubber-based graft copolymers, particularly preferred are those commercially available from Mitsubishi Rayon Co., Ltd. under the trade name Methbrene S-2001 or SRK-200.

  Here, as a ratio in the resin composition of G component, 1-20 weight part is preferable with respect to a total of 100 weight part of A component, B component, C component, D component, and E component, More preferably, 1 ~ 15 parts by weight.

  Furthermore, at least one metal salt selected from alkali metal salts and alkaline earth metal salts can be used as the H component of the present invention. As the H component, various metal salts conventionally used for flame-retarding a polycarbonate resin can be used. Particularly, a metal salt of an organic sulfonic acid or a metal salt of a sulfate ester can be mentioned. . 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.

  As the metal salt of organic sulfonic acid of the present invention, alkali metal salt of aliphatic sulfonic acid, alkaline earth metal salt of aliphatic sulfonic acid, alkali metal salt of aromatic sulfonic acid, alkaline earth metal salt of aromatic sulfonic acid Etc. 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).

  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.

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

  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.

  Among the H components listed above, more preferable alkali (earth) metal salts include alkali (earth) metal salts of aromatic sulfonic acid and alkali (earth) metal salts of perfluoroalkanesulfonic acid. it can.

  About the quantity of H component, 0.0001-0.05 weight part is preferable with respect to 100 weight part of resin compositions which consist of A component, B component, C component, D component, and E component, More preferably, it is 0.00. 0001 to 0.01 part by weight.

  In the present invention, a char-forming resin can be added for the purpose of further improving the flame retardancy. Examples of the char-forming resin include novolak-type phenol resin, cresol-modified phenol resin, poly (2,6-dimethyl-1,4-phenylene ether), allylated poly (2,6-dimethyl-1,4-phenylene ether), 2,6-diphenylpolyphenylene ether, polyphenyl, polyethersulfone, polyarylate, polyphenylene sulfide, polysulfone, polyethersulfone, etc. may be mentioned, and one or more selected from these may be used in combination Can do. Among these, particularly preferred char-forming resins include novolac-type phenol resins, poly (2,6-dimethyl-1,4-phenylene ether), and polyphenylene sulfide.

  The flame retardant polycarbonate resin composition of the present invention is a flame retardant polycarbonate resin composition composed of components A to E, optionally F to H, and is substantially different from the flame retardant polycarbonate resin composition of the present invention. As long as equivalent characteristics can be maintained, a mixture of other thermoplastic resins such as ABS resin, polyethylene terephthalate, polybutylene terephthalate, polyamide, acrylic resin, and polyarylate can be used. Furthermore, as long as the object of the present invention is not impaired, a nucleating agent (for example, sodium stearate, an ethylene-sodium acrylate copolymer), a phosphorus-based stabilizer, an antioxidant (for example, a hindered phenol), In general, a trace amount of a light stabilizer, a colorant, a foaming agent, an antistatic agent and the like can be blended.

  In the flame-retardant aromatic polycarbonate resin composition of the present invention, the above-mentioned components are mixed at the same time or in any order by a mixer such as a tumbler, V-type blender, nauter mixer, Banbury mixer, kneading roll, or extruder. Can be manufactured. Preferably, melt kneading with a twin-screw extruder is preferred, and at that time, the B component is preferably fed into the other melt-mixed component from the second feed port by a side feeder or the like.

  The resin composition thus obtained can be easily molded by methods such as extrusion molding, injection molding and compression molding, and can also be applied to blow molding and vacuum molding. In particular, in injection molding and blow molding, those manufactured by using a mold having a heat insulating layer or a mold in which only the surface of the mold cavity is locally high in advance are preferable. Molded articles obtained by the above-described various production methods are excellent in both rigidity and impact resistance, and are optimal for fields such as thin-walled casings. Specific examples include portable communication devices, notebook computers, automobile internal parts, especially electric vehicle parts. It is particularly suitable as a material for fields that require high flame resistance.

  Hereinafter, the present invention will be described in detail with reference to examples. The present invention is not limited to this.

[Examples 1-11, Comparative Examples 1-10]
A component obtained by removing the B component and the component corresponding to the component H from the A component described in Table 1 and Table 2, and 0.1% by weight of trimethyl phosphate (hereinafter sometimes abbreviated as TMP), And 0.3% by weight of carbon black # 970 (Mitsubishi Chemical Co., Ltd .: hereinafter may be abbreviated as CB) in a V-type blender, and 30 mm diameter vent type twin screw extruder [ (Nippon Steel Works TEX-30XSST), the mixture is fed from the first inlet at the end, and the fibrous filler is fed from the second inlet in the middle of the cylinder to a predetermined ratio using a measuring instrument. Then, it was charged using a side feeder. Under such conditions, the mixture was melt-extruded at a cylinder temperature of 290 ° C. and pelletized under a vacuum of 0.5 kPa using a vacuum pump. However, in the following FR-2, it was heated to 80 ° C., and a predetermined ratio was blended in the extruder with a metered liquid transfer device. The obtained pellets were dried with a hot air circulation dryer at 100 ° C. for 5 hours, and impacted by an injection molding machine (SG-150U, manufactured by Sumitomo Heavy Industries, Ltd.) at a cylinder temperature of 290 ° C. and a mold temperature of 80 ° C. A specimen was obtained. The evaluation results are shown in Tables 1 and 2.
(A) Impact value with notch: Measured by ASTM D-256 (with Izod notch, thickness 3.2 mm).
(B) Flexural modulus: measured by ASTM D-790.
(C) Flame retardancy: A combustion test was performed at a thickness of 1.2 mm in accordance with UL standard 94V. However, only Example 11 was tested with a thickness of 1.0 mm.

In addition, the symbol which shows each component of Table 1 and Table 2 is as follows.
(Component A) PC-1: Aromatic polycarbonate resin
(L-1225 manufactured by Teijin Chemicals Ltd., viscosity average molecular weight 22,500)
(Component B) CF-1: Carbon fiber
(Beast Fight HTA-C6-N manufactured by Toho Rayon Co., Ltd.)
CF-2: Carbon fiber
(Beast Fight HTA-C6-U manufactured by Toho Rayon Co., Ltd.)
GF: Glass fiber
(ECS-03T-511 manufactured by Nippon Electric Glass Co., Ltd.)
(C component) C-1: Organosiloxane (organosiloxane having alkoxy group (methoxy group), vinyl group and phenyl group)
(X40-9243 manufactured by Shin-Etsu Chemical Co., Ltd.)
C-2: Organosiloxane (organosiloxane having alkoxy group (methoxy group), vinyl group and phenyl group)
(X40-9228 manufactured by Shin-Etsu Chemical Co., Ltd.)
(Other than C component) C-3: Organosiloxane (dimethylsiloxane)
(SH200 manufactured by Toray Dow Corning Silicone Co., Ltd.)
C-4: Organosiloxane (silicon powder)
(X40-2135 manufactured by Shin-Etsu Chemical Co., Ltd.)
(Component D) FR-1: condensed phosphate ester flame retardant
(Adeka Stub FP-500 manufactured by Asahi Denka Kogyo Co., Ltd.)
FR-2: condensed phosphate ester flame retardant
(CR-741 manufactured by Daihachi Chemical Co., Ltd.)
FR-3: Monophosphate ester flame retardant (triphenyl phosphate) (TPP manufactured by Daihachi Chemical Co., Ltd.)
(E component) E-1; PTFE
Polytetrafluoroethylene having fibril-forming ability
(Daikin Industries Co., Ltd. Polyflon FA-500)
(F component) F-1: Carboxyl group-modified olefin wax
(Diakaruna-30 manufactured by Mitsubishi Kasei)
(G component) G-1: Composite rubber graft copolymer
(Mettablen S-2001 manufactured by Mitsubishi Rayon Co., Ltd.)
(H component) SALT: Alkali (earth) metal salt of perfluoroalkanesulfonic acid
C ₄ F ₉ SO ₃ K
(Dai Nippon Ink Chemical Co., Ltd. MegaFuck F114)

  As is clear from these tables, from the comparison between Example 1 and Comparative Example 1, high flame retardancy is achieved without the B component, but the flexural modulus is inferior. From the comparison between Example 1 and Comparative Examples 2 and 3, high flame retardancy cannot be achieved without the C component. From Comparative Example 4, high flame retardancy cannot be achieved without the D component. From Comparative Examples 5 and 6, even when silicon other than the C component is contained, high flame retardancy cannot be achieved. Furthermore, the impact resistance is greatly reduced. From Comparative Example 9, even if a large amount of metal salt is used in combination, high flame retardancy cannot be achieved, and impact resistance also decreases.

Effect of the invention

  Since the composition of the present invention is excellent in flame retardancy at a thin-walled portion, and further excellent in impact resistance and rigidity, the obtained flame-retardant resin composition is used in a wide range of industrial fields including housings of electronic devices. The industrial effect exhibited by the resin composition obtained according to the present invention is exceptional.

Claims (6)

When the total of component A, component B, component C, component D and component E is 100% by weight, aromatic polycarbonate resin (component A) 95.9-22% by weight, inorganic filler (component B) 3-50 % By weight, organosiloxane having alkoxy group, vinyl group and phenyl group (C component) 0.1-5% by weight, organophosphorus compound (D component) 1-20% by weight, polytetrafluoroethylene having fibril-forming ability (E component) 0 to 3% by weight, and perfluoroalkanesulfonic acid alkali metal salt (H component) with respect to 100 parts by weight of resin composition comprising A component , B component, C component, D component and E component A flame retardant aromatic polycarbonate resin composition comprising 0 to 0.008 parts by weight.
The aromatic polycarbonate resin composition according to claim 1, wherein the inorganic filler of component B is glass fiber.
The aromatic polycarbonate resin composition according to claim 1, wherein the inorganic filler of component B is carbon fiber.
Furthermore, a resin composition 100 comprising a polyolefin wax (F component) having at least one functional group selected from a carboxyl group and / or a carboxylic acid anhydride group, which comprises an A component, a B component, a C component, a D component, and an E component. The aromatic polycarbonate resin composition according to claim 1, comprising 0.05 to 5 parts by weight with respect to parts by weight.
Further, a composite in which one or more vinyl monomers are graft-polymerized on a composite rubber having a structure in which the polyorganosiloxane rubber component and the polyalkyl (meth) acrylate rubber component are intertwined so that they cannot be separated. The rubber-based graft polymer (G component) comprises 1 to 20 parts by weight with respect to 100 parts by weight of the resin composition comprising the A component, B component, C component, D component and E component. The aromatic polycarbonate resin composition according to claim 1.
  The molded article formed from the flame-retardant aromatic polycarbonate resin composition described in any one of Claims 1-5.