JP2001164105A - Glass-reinforced flame retarded polycarbonate resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a glass-reinforced flame retarded polycarbonate resin composition having excellent flame retardance and mechanical properties. SOLUTION: This glass-reinforced flame retarded polycarbonate resin composition comprises, based on 100 wt.% of the whole resin, 20-74.85 wt.% of an aromatic polycarbonate resin (component A), 0-40 wt.% of at least one type of thermoplastic resin (component B) selected from the group consisting of a polystyrene resin and an aromatic polyester resin, 0.1-30 wt.% of a flame retardant (component C), 25-45 wt.% of an inorganic filler (component Da) having a glass fiber with a diameter of 5-20 μm (component D-1) and wollastonite fibers (component D-2) with a weighted average fiber length of 5-50 μm and with the number of fibers having a diameter of 0.5-5 μm being >=70% of the whole number of the fibers, at a weight ratio (component D-1/ component D-2) of 25:75 to 75: 25, or 25-45 wt.% of an inorganic filler (component Db) having the component D-1 and talc particles (component D-3) with a particle diameter of 2-15 μm at 50% in area integration, at a weight ratio (component D-1/component D-3) of 25:75 to 75:25, and 0.05-01 wt.% of polytetrafluoroethylene (component E) capable of fibril formation.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

[0001] The present invention relates to a glass-reinforced flame-retardant polycarbonate resin composition. More specifically, a high-rigidity, high-strength, high-dimensional accuracy glass fiber reinforced polycarbonate resin composition containing a polytetrafluoroethylene having a fibril-forming ability together with a flame retardant and a specific inorganic filler to reduce a small amount. The present invention relates to a flame-retardant thermoplastic resin composition which achieves good flame retardancy even with the use of the above flame retardant.

[0002]

2. Description of the Related Art In recent years, the demand for flame retardancy to ensure safety for plastic materials used in the field of electric and electronic equipment has become more severe. Glass fiber reinforced polycarbonate resin compositions are widely used in fields requiring high rigidity and flame retardancy, such as chassis parts of OA equipment, because of their excellent mechanical strength and dimensional stability. However, when higher flame retardancy is required, these requirements are met by further adding various flame retardants, but such measures also require advanced requirements in other required characteristics. Not enough in the field.

[0003] As a method of reducing the addition amount of a flame retardant,
For example, Japanese Patent Application Laid-Open No. 2-199162 discloses a method of adding a filler having an L / D ≦ 10 such as talc or milled fiber and polytetrafluoroethylene having a fibril-forming ability to a flame-retardant polycarbonate resin. I have. However, in this method, although a flame retardant effect is excellent, a filler having a small L / D is used. Therefore, when the inorganic filler is highly filled, mechanical strength such as impact and bending strength is insufficient. is there. Also, JP-A-3-160
No. 052 discloses a method of reducing the flame retardant by combining a glass fiber having a specific fiber length in a composition comprising a polycarbonate resin, a styrene resin, and a flame retardant. However, the method proposed therein is insufficient in the effect of reducing the amount of flame retardant added.

Japanese Patent Application Laid-Open No. 10-219094 describes a method of adding an inorganic filler and polytetrafluoroethylene having fibril performance to a flame retardant polycarbonate resin composition having a specific halogen content. However, when glass fibers having a large L / D and polytetrafluoroethylene are used in combination, there is a problem that, unlike glass short fibers having a small L / D, flame retardancy becomes more difficult as the added amount of the glass fibers increases.

[0005]

SUMMARY OF THE INVENTION An object of the present invention is to solve the above-mentioned problems and to provide a glass-reinforced flame-retardant polycarbonate resin composition having excellent flame retardancy and mechanical properties. The present inventors have conducted intensive studies to achieve the above object, and as a result, in a glass fiber reinforced polycarbonate resin composition, a filler having a specific shape together with a flame retardant and a polytetrafluoroethylene having a fibril forming ability in a specific ratio. Thus, the problem was solved by adding a specific amount.

[0006]

According to the present invention, there is provided an aromatic polycarbonate resin (component A) of 20 to 74.85% by weight, at least one kind of thermoplastic resin (B) selected from a styrene resin and an aromatic polyester resin. Component) 0-40
% By weight, flame retardant (component C) 0.1 to 30% by weight, glass fiber having a fiber diameter of 5 to 20 μm (component D-1), a weighted average fiber length of 5 to 50 μm, and a total fiber number of 100%.
Wollastonite (D) in which the number of
-2 component) and the weight ratio (D-1 component: D-2 component) is 2
5:75 to 75:25 inorganic filler (Da component) 2
5 to 45% by weight, and 0.05 to 1% by weight of polytetrafluoroethylene (component E) having a fibril-forming ability
Or a glass-reinforced flame-retardant polycarbonate resin composition comprising a total of 100% by weight, or 20 to 74.85% by weight of an aromatic polycarbonate resin (A component), at least one selected from a styrene resin and an aromatic polyester resin. 0 to 40% by weight of thermoplastic resin (component B), 0.1 to 30% by weight of flame retardant (component C), fiber diameter of 5 to 20 μm
Weight ratio between glass fiber (D-1 component) and talc (D-3 component) having a particle diameter of 2 to 15 μm at a stacking ratio of 50% (D-
25 to 45% by weight of an inorganic filler (Db component) in which 1 component: D-3 component) is 25:75 to 75:25, and polytetrafluoroethylene (E) having a fibril-forming ability.
The present invention relates to a glass-reinforced flame-retardant polycarbonate resin composition comprising a total of 100% by weight of components (0.05 to 1% by weight).

The aromatic polycarbonate resin (component (A)) used in the present invention is usually a resin obtained by reacting a dihydric phenol with a carbonate precursor by an interfacial polycondensation method or a melt transesterification method. It is obtained by polymerizing a polymer by a solid phase transesterification method or by polymerizing a polymer by a ring opening polymerization method of a cyclic carbonate compound.

[0008] Representative examples of the dihydric phenol used here include hydroquinone, resorcinol, 4,4
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 known 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 (4-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′-dihydroxydiphenylsulfone, 4,4′-dihydroxydiphenylsulfoxide, 4,4′-dihydroxydiphenylsulfide,
4,4'-dihydroxydiphenyl ketone, 4,4'-
Examples thereof include dihydroxydiphenyl ether and 4,4′-dihydroxydiphenyl ester, and these can be used alone or as a mixture 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
A homopolymer obtained from at least one bisphenol selected from the group consisting of -hydroxyphenyl) -3,3,5-trimethylcyclohexane and α, α'-bis (4-hydroxyphenyl) -m-diisopropylbenzene, or Copolymers are preferred. In particular, bisphenol A homopolymer and 1,1-bis (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane and bisphenol A, 2,2-bis {(4-hydroxy- Copolymers with 3-methyl) phenyl} propane or α, α′-bis (4-hydroxyphenyl) -m-diisopropylbenzene are preferably used.

As the carbonate precursor, carbonyl halide, carbonate ester or haloformate is used, and specific examples include phosgene, diphenyl carbonate and dihaloformate of dihydric phenol.

In producing the polycarbonate resin by reacting the above-mentioned dihydric phenol with the carbonate precursor by the interfacial polycondensation method or the melt transesterification method, if necessary, a catalyst, a terminal stopper and an oxidation of the dihydric phenol may be carried out. An inhibitor or the like may be used. Further, the polycarbonate resin may be a branched polycarbonate resin obtained by copolymerizing a trifunctional or higher polyfunctional aromatic compound, or a polyester carbonate resin obtained by copolymerizing an aromatic or aliphatic bifunctional carboxylic acid, Further, a mixture of two or more of the obtained polycarbonate resins may be used.

Examples of the trifunctional or higher polyfunctional aromatic compound include phloroglucin, phloroglucid, and 4,6-
Dimethyl-2,4,6-tris (4-hydroxydiphenyl) heptene-2,2,4,6-trimethyl-2,4
6-tris (4-hydroxyphenyl) heptane, 1,
3,5-tris (4-hydroxyphenyl) benzene,
1,1,1-tris (4-hydroxyphenyl) ethane, 1,1,1-tris (3,5-dimethyl-4-hydroxyphenyl) ethane, 2,6-bis (2-hydroxy-5-methylbenzyl) ) -4-Methylphenol, 4
-{4- [1,1-bis (4-hydroxyphenyl) ethyl] benzene} -α, α-dimethylbenzylphenol and other trisphenols, tetra (4-hydroxyphenyl) methane, bis (2,4-dihydroxyphenyl) )
Examples thereof include ketone, 1,4-bis (4,4-dihydroxytriphenylmethyl) benzene, trimellitic acid, pyromellitic acid, benzophenonetetracarboxylic acid, and acid chlorides thereof, among which 1,1,1-tris (4-hydroxyphenyl) ethane, 1,1,1-
Tris (3,5-dimethyl-4-hydroxyphenyl)
Ethane is preferred, and 1,1,1-tris (4-hydroxyphenyl) ethane is particularly preferred.

When a polyfunctional compound producing such a branched polycarbonate resin is contained, the proportion is preferably from 0.001 to 1 mol%, more preferably from 0.005 to 0.5 mol%, particularly preferably from the total amount of the aromatic polycarbonate. 0.01
~ 0.3 mol%. In addition, particularly in the case of the melt transesterification method, a branched structure may be generated as a side reaction, and the amount of such a branched structure is also 0.001 to 1 mol%, preferably 0.005 to 5 mol%, of the total amount of the aromatic polycarbonate.
0.5 mol%, particularly preferably 0.01 to 0.3 mol%
Is preferred. The ratio is ¹ H
-It can be calculated by NMR measurement.

The reaction by the interfacial polycondensation method is usually a reaction between dihydric phenol and phosgene, and is carried out 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. Further, for promoting the reaction, for example, 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 terminator is usually used. Monofunctional phenols can be used as such a terminal stopper. Monofunctional phenols are commonly used as molecular terminators for molecular weight control, and the resulting polycarbonate resins are capped by groups based on monofunctional phenols, so that Excellent heat stability. Such a monofunctional phenol is generally a phenol or a lower alkyl-substituted phenol, and may be a monofunctional phenol represented by the following general formula (1).

[0016]

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(Where A is a hydrogen atom or a carbon number of 1 to 9)
Is a linear or branched alkyl group or a phenyl group-substituted alkyl group, and r is an integer of 1 to 5, preferably 1 to 3. )

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

Further, other monofunctional phenols include:
Phenols or benzoic acid chlorides having a long-chain alkyl group or aliphatic polyester group as a substituent, or long-chain alkylcarboxylic acid chlorides can also be used. Among these, phenols having a long-chain alkyl group represented by the following general formulas (2) and (3) as a substituent are preferably used.

[0020]

Embedded image

[0021]

Embedded image

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

As the substituted phenols of the general formula (2), those having n of 10 to 30, especially 10 to 26, are preferred. Octadecyl phenol, eicosyl phenol, docosyl phenol, triacontyl phenol and the like can be mentioned.

As the substituted phenols of the general formula (3), compounds wherein X is -R-CO-O- and R is a single bond are suitable, and n is 10-30, especially 10-26.
Are preferred, and specific examples thereof include, for example, decyl hydroxybenzoate, dodecyl hydroxybenzoate,
Examples include tetradecyl hydroxybenzoate, hexadecyl hydroxybenzoate, eicosyl hydroxybenzoate, docosyl hydroxybenzoate and triacontyl hydroxybenzoate.

The terminal terminator is desirably introduced at least 5 mol%, preferably at least 10 mol%, based on all terminals of the obtained 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 dihydric phenol is more preferably 20 mol% or less, and particularly preferably. This is the case when 90 mol% or more of the terminal terminator is introduced to all the terminals, that is, when the OH group is 10 mol% or less. Further, the terminal stoppers may be used alone or in combination of two or more.

The reaction by the melt transesterification method is usually a transesterification reaction between a dihydric phenol and a carbonate ester, and is produced by mixing the dihydric phenol and the carbonate ester while heating in the presence of an inert gas. It is carried out by a method of distilling alcohol or phenol. The reaction temperature varies depending on the boiling point of the produced alcohol or phenol, but is usually in the range of 120 to 350 ° C. In the late stage of the reaction, the system was adjusted to 1.33 × 10 ³ -1.
The alcohol or phenol produced by reducing the pressure to about 3.3 Pa is easily distilled. Reaction time is usually 1-4
About an hour.

Examples of the carbonate ester include an optionally substituted ester such as an aryl group having 6 to 10 carbon atoms, an aralkyl group or an alkyl group having 1 to 4 carbon atoms. Specifically, diphenyl carbonate, ditolyl carbonate, bis (chlorophenyl) carbonate, m-cresyl carbonate, dinaphthyl carbonate, bis (diphenyl) carbonate, dimethyl carbonate, diethyl carbonate, dibutyl carbonate, etc. Is preferred.

A polymerization catalyst can be used to increase the polymerization rate. Examples of such a polymerization catalyst include sodium hydroxide, potassium hydroxide, alkali metal compounds such as sodium and potassium salts of dihydric phenol, and water. Alkaline earth metal compounds such as calcium oxide, 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 Manganese, organic acid salts of alkali metals and alkaline earth metals, zinc compounds, boron compounds, aluminum compounds, silicon compounds, germanium compounds, organic tin compounds, lead compounds, osmium compounds, antimony compounds Compounds, titanium compounds, usually the esterification reaction, such as zirconium compounds, there can be used a catalyst used in the transesterification reaction. The catalyst may be used alone or in combination of two or more. The amount of the polymerization catalyst used is preferably 1 × 10 ⁻⁸ to 1 ×, based on 1 mol of the dihydric phenol used as the raw material.
It is selected in the range of 10 ⁻³ equivalents, more preferably 1 × 10 ^{−7 to} 5 × 10 ⁻⁴ equivalents.

In such a polymerization reaction, to reduce the number of phenolic terminal groups, for example, bis (chlorophenyl) carbonate, bis (bromophenyl) carbonate, bis (nitrophenyl) carbonate is used later or after completion of the polycondensation reaction. , Bis (phenylphenyl)
Carbonate, chlorophenylphenyl carbonate,
It is preferable to add compounds such as bromophenylphenyl carbonate, nitrophenylphenyl carbonate, phenylphenyl carbonate, methoxycarbonylphenylphenyl carbonate, and ethoxycarbonylphenylphenyl carbonate. Of these, 2-chlorophenylphenyl carbonate, 2-methoxycarbonylphenylphenyl carbonate and 2-ethoxycarbonylphenylphenyl carbonate are preferred, and 2-methoxycarbonylphenylphenyl carbonate is particularly preferred.

Although the molecular weight of the polycarbonate resin is not specified, if the molecular weight is less than 10,000, the high-temperature properties and the like will be reduced, and if it exceeds 50,000, the moldability will be reduced. 10,00
0 to 50,000 are preferred, and 14,000 to 3
Particularly preferred are those having a molecular weight of 0000. Also, two or more polycarbonate resins may be mixed. The viscosity average molecular weight in the present invention is determined by inserting the specific viscosity (η _SP ) obtained from a solution of 0.7 g of a polycarbonate resin dissolved 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

The styrenic resin used in the component B of the present invention is a homopolymer or a copolymer of a styrene derivative such as styrene, α-methylstyrene and p-methylstyrene, and these monomers and acrylonitrile, methyl Copolymers with a vinyl monomer such as methacrylate are exemplified. Furthermore, diene rubbers such as polybutadiene, ethylene
Propylene rubber, acrylic rubber, and composite rubber (hereinafter referred to as IPN type rubber) having a structure in which a polyorganosiloxane rubber component and a polyalkyl (meth) acrylate rubber component are entangled with each other so that they cannot be separated. Styrene and / or a styrene derivative, or a product obtained by graft-polymerizing a styrene and / or a styrene derivative with another vinyl monomer may be used. Examples of such a styrene resin include polystyrene, styrene-butadiene-styrene copolymer (SBS), hydrogenated styrene-butadiene-styrene copolymer (hydrogenated SBS), and hydrogenated styrene-isoprene-styrene copolymer (water SIS), impact polystyrene (HIPS), acrylonitrile / styrene copolymer (AS resin), acrylonitrile / butadiene / styrene copolymer (ABS resin), methyl methacrylate / butadiene / styrene copolymer (MBS resin), methyl Methacrylate / acrylonitrile / butadiene / styrene copolymer (MABS resin), acrylonitrile / acryl rubber / styrene copolymer (AAS resin), acrylonitrile / ethylene propylene rubber
Styrene copolymer (AES resin) and styrene / IPN
Resins such as a mold rubber copolymer, or a mixture thereof.

The styrene-based thermoplastic resin may have a high stereoregularity, such as syndiotactic polystyrene, by using a metallocene catalyst or the like at the time of its production. Further, in some cases, a polymer and a copolymer having a narrow molecular weight distribution obtained by a method such as anionic living polymerization or radical living polymerization, a block copolymer, and a highly stereoregular polymer or copolymer are used. It is also possible. For the purpose of improving the compatibility with the polycarbonate resin, a compound having a functional group such as maleic anhydride or N-substituted maleimide can be copolymerized with the styrene resin.

Of these, acrylonitrile / styrene copolymer (AS resin) and acrylonitrile / butadiene / styrene copolymer (ABS resin) are preferred. It is also possible to use a mixture of two or more styrene resins.

The AS resin used in the present invention is a thermoplastic copolymer obtained by copolymerizing a vinyl cyanide compound and an aromatic vinyl compound. Such vinyl cyanide compounds include those described above, and acrylonitrile is particularly preferably used. As the aromatic vinyl compound, those described above can be similarly used, but styrene and α-methylstyrene can be preferably used.
The ratio of each component in the AS resin was 10
When the amount is 0% by weight, the content of the vinyl cyanide compound is 5 to 50%.
%, Preferably 15 to 35% by weight, 95 to 50% by weight of aromatic vinyl compound, preferably 85 to 65% by weight
It is. Further, these vinyl compounds may be used in combination with other copolymerizable vinyl compounds described above, and the content thereof is preferably 15% by weight or less in the AS resin component. An initiator used in the reaction,
As the chain transfer agent and the like, various conventionally known ones can be used as necessary.

The AS resin may be produced by any of bulk polymerization, suspension polymerization and emulsion polymerization, but is preferably produced by bulk polymerization. The method of copolymerization may be either one-stage copolymerization or multi-stage copolymerization. The reduced viscosity of the AS resin is as follows.
0.2 to 1.0 dl / g, preferably 0.3 to 1.0 dl / g.
0.5 dl / g. Reduced viscosity is 0.25 AS resin
g was precisely weighed, and a solution dissolved in 50 ml of dimethylformamide over 2 hours was measured using an Ubbelohde viscometer.
It was measured in an environment of ° C. Note that a viscometer having a solvent flow time of 20 to 100 seconds is used. The reduced viscosity is determined by the following equation from the number of seconds for the solvent to flow (t ₀ ) and the number of seconds for the solution to flow (t). Reduced viscosity (η _sp / C) = {(t / t ₀ ) -1} /0.5 If the reduced viscosity is less than 0.2 dl / g, the impact decreases,
If it exceeds 1.0 dl / g, the fluidity becomes poor.

The ABS resin used in the present invention is a thermoplastic graft copolymer obtained by graft-polymerizing a vinyl cyanide compound and an aromatic vinyl compound on a diene rubber component, and a copolymer of a vinyl cyanide compound and an aromatic vinyl compound. It is a mixture of coalescence. As the diene rubber component forming the ABS resin, for example, a rubber having a glass transition temperature of −30 ° C. or less such as polybutadiene, polyisoprene, and styrene-butadiene copolymer is used, and the ratio is 100% by weight of the ABS resin component. The content is preferably 5 to 80% by weight, more preferably 8 to 50% by weight, and particularly preferably 1 to 50% by weight.
0 to 30% by weight. Examples of the vinyl cyanide compound to be grafted to the diene rubber component include those described above, and acrylonitrile is particularly preferably used. As the aromatic vinyl compound to be grafted to the diene rubber component, those described above can be similarly used, but styrene and α-methylstyrene are particularly preferably used. The ratio of the component grafted to the diene rubber component is 95% in 100% by weight of the ABS resin component.
It is preferably from 20 to 20% by weight, particularly preferably from 50 to 90% by weight. Further, it is preferable that the vinyl cyanide compound is 5 to 50% by weight and the aromatic vinyl compound is 95 to 50% by weight based on 100% by weight of the total amount of the vinyl cyanide compound and the aromatic vinyl compound. Further, methyl (meth) acrylate, ethyl acrylate, maleic anhydride, N-substituted maleimide, and the like can be mixed and used for a part of the components grafted to the diene rubber component. It is preferably 15% by weight or less. Further, conventionally known various initiators, chain transfer agents, emulsifiers, and the like can be used as necessary.

In the ABS resin of the present invention, the rubber particle diameter is preferably 0.1 to 5.0 μm, more preferably 0.2 to 3.0 μm, and particularly preferably 0.3 to 1.5 μm.
m. As the distribution of the rubber particle diameter, either a single distribution or a distribution having a plurality of peaks of two or more peaks can be used, and the rubber particles form a single phase in the morphology. Alternatively, the rubber particles may have a salami structure by containing an occlude phase around the rubber particles.

It is well known that the ABS resin contains a vinyl cyanide compound and an aromatic vinyl compound which are not grafted on the diene rubber component, and the ABS resin of the present invention also undergoes such polymerization during the polymerization. It may contain a free polymer component generated. The reduced viscosity of the copolymer comprising the free vinyl cyanide compound and the aromatic vinyl compound is such that the reduced viscosity (30 ° C.) determined by the method described above is 0.2 to 1.0.
dl / g, more preferably 0.3 to 0.7 dl / g.

The ratio of the grafted vinyl cyanide compound and aromatic vinyl compound to the diene rubber component is preferably from 20 to 200%, more preferably from 20 to 70%, expressed as a graft ratio (% by weight). belongs to.

The ABS resin is used for bulk polymerization, suspension polymerization,
Although it may be manufactured by any method of emulsion polymerization,
In particular, those obtained by bulk polymerization are preferred. The copolymerization may be carried out in one step or in multiple steps. Also, a blend of a vinyl compound polymer obtained by separately copolymerizing an aromatic vinyl compound and a vinyl cyanide component with the ABS resin obtained by such a production method can be preferably used.

The aromatic polyester resin as the component B of the present invention refers to a polymer or copolymer obtained by a condensation reaction containing an aromatic dicarboxylic acid or a reactive derivative thereof and a diol or an ester derivative thereof as main components. It is united.

The aromatic dicarboxylic acids mentioned here include terephthalic acid, isophthalic acid, orthophthalic acid, 1,5-
Naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, 4,4'-biphenyldicarboxylic acid, 4,4'-
Biphenyl ether dicarboxylic acid, 4,4'-biphenylmethane dicarboxylic acid, 4,4'-biphenyl sulfone dicarboxylic acid, 4,4'-biphenyl isopropylidene dicarboxylic acid, 1,2-bis (phenoxy) ethane-
4,4′-dicarboxylic acid, 2,5-anthracenedicarboxylic acid, 2,6-anthracenedicarboxylic acid, 4,4 ′
Aromatic dicarboxylic acids such as -p-terphenylenedicarboxylic acid and 2,5-pyridinedicarboxylic acid are preferably used, and terephthalic acid and 2,6-naphthalenedicarboxylic acid are particularly preferably used.

The aromatic dicarboxylic acids may be used as a mixture of two or more kinds. Incidentally, if the amount is small, it is also possible to use a mixture of one or more aliphatic dicarboxylic acids such as adipic acid, azelaic acid, sebacic acid and dodecane diacid, and alicyclic dicarboxylic acids such as cyclohexane dicarboxylic acid together with the dicarboxylic acid. .

The diol which is a component of the aromatic polyester of the present invention includes ethylene glycol, propylene glycol, butylene glycol, hexylene glycol, neopentyl glycol, pentamethylene glycol, hexamethylene glycol, decamethylene glycol, 2-methyl -1,3-propanediol, aliphatic diols such as diethylene glycol and triethylene glycol, alicyclic diols such as 1,4-cyclohexanedimethanol, and fragrances such as 2,2-bis (β-hydroxyethoxyphenyl) propane Ring-containing diols and the like, and mixtures thereof, and the like. If the amount is further small, one or more kinds of long-chain diols having a molecular weight of 400 to 6,000, that is, polyethylene glycol, poly-1,3-propylene glycol, polytetramethylene glycol or the like may be copolymerized.

The aromatic polyester of the present invention can be branched by introducing a small amount of a branching agent.
The type of the branching agent is not limited, and examples thereof include trimesic acid, trimellitic acid, trimethylolethane, trimethylolpropane, and pentaerythritol.

Specific aromatic polyester resins include polyethylene terephthalate (PET), polypropylene terephthalate, polybutylene terephthalate (PBT), polyhexylene terephthalate, polyethylene naphthalate (PEN), polybutylene naphthalate (PBN), polyethylene In addition to -1,2-bis (phenoxy) ethane-4,4'-dicarboxylate and the like, copolymerized polyesters such as polyethylene isophthalate / terephthalate, polybutylene terephthalate / isophthalate and the like can be mentioned.

Of these, polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, polybutylene naphthalate and a mixture thereof having a good balance of mechanical properties and the like can be preferably used. In particular, a mixture of polyethylene terephthalate and polybutylene terephthalate Use is preferred because it can achieve a very good balance of impact strength, fatigue strength, and chemical resistance. The use (weight) ratio of polyethylene terephthalate and polybutylene terephthalate is polyethylene terephthalate /
It is preferable that the polybutylene terephthalate is in the range of 40/60 to 95/5, and in particular, 50/50 to 90 /
It is preferably in the range of 10.

The terminal group structure of the obtained aromatic polyester resin is not particularly limited, except that the ratio of the hydroxyl group and the carboxyl group in the terminal group is almost the same, and that one of the terminals is large. You may. Further, the terminal groups may be blocked by reacting a compound having reactivity with such terminal groups.

According to a method for producing such an aromatic polyester resin, a dicarboxylic acid component and the diol component are polymerized while heating in the presence of a polycondensation catalyst containing titanium, germanium, antimony and the like according to a conventional method.
It is performed by discharging water or lower alcohol by-product to the outside of the system. For example, as a germanium-based polymerization catalyst, germanium oxide, hydroxide, halide,
Examples thereof include alcoholates and phenolates, and more specifically, germanium oxide, germanium hydroxide, germanium tetrachloride, tetramethoxygermanium and the like.

In the present invention, compounds such as manganese, zinc, calcium, and magnesium used in a transesterification reaction which is a prior step of a conventionally known polycondensation can be used in combination, and phosphoric acid is added after the transesterification reaction is completed. Alternatively, it is also possible to deactivate such a catalyst with a compound of phosphorous acid or the like for polycondensation.

The molecular weight of the aromatic polyester resin is not particularly limited, but the intrinsic viscosity measured at 25 ° C. using o-chlorophenol as a solvent is 0.4 to 1.
2, preferably 0.65 to 1.15.

The ratio of the component B is from the component A to the component A of the present invention.
Preferably, it is added in an amount of not more than 40% by weight, more preferably not more than 30% by weight, out of a total of 100% by weight of the component E. If the addition amount of the component B is more than 40% by weight, the mechanical strength is reduced, the flame retardancy is difficult, and the effect of the present invention is hardly exerted.

The flame retardant used as the component C in the present invention includes a red phosphorus flame retardant, a halogen flame retardant, an organic phosphorus flame retardant, an inorganic phosphate, a hydrate of an inorganic metal compound, an organic alkali ( Earth) At least one type of flame retardant selected from metal salt-based flame retardants and silicone-based flame retardants.

As the red phosphorus-based flame retardant, red phosphorus in which the surface of red phosphorus is microencapsulated with a thermosetting resin and / or an inorganic material can be used in addition to general red phosphorus. Further, in the use of such microencapsulated red phosphorus, a master pellet is preferably used in order to improve safety and workability. Examples of the inorganic material used for such microencapsulation include magnesium hydroxide, aluminum hydroxide, titanium hydroxide, tin hydroxide, cerium hydroxide, and the like.
Phenol-formalin, urea
Formalin-based resins, melamine-formalin-based resins, and the like are included. Furthermore, on those coated with such inorganic materials,
Red phosphorus or the like, which is formed by forming a coating using a thermosetting resin and is double-coated, can also be preferably used. The red phosphorus to be used can also be used by electroless plating. As the electroless plating film, use a metal plating film selected from nickel, cobalt, copper, iron, manganese, zinc or an alloy thereof. be able to. In addition, red phosphorus coated with the above-mentioned inorganic material and thermosetting resin may be used for the electroless plated red phosphorus. The amount of the inorganic material, the thermosetting resin, and the component used for microencapsulation such as electroless plating is preferably 20% by weight or less, more preferably 5 to 15% by weight in 100% by weight of the red phosphorus-based flame retardant. % By weight. 20% by weight
In the following cases, the workability and the dispersibility in the resin are excellent. The average particle size of the red phosphorus flame retardant is 1 to 100 μm.
m, preferably 1 to 40 μm. Commercial products of such microencapsulated red phosphorus flame retardants include:
Nova Excel 140, Nova Excel F-5 (trade name, manufactured by Rin Kagaku Kogyo Co., Ltd.), Hishigard TP-10 (trade name, manufactured by Nippon Chemical Co., Ltd.), Hostafram RP614
(Manufactured by Clariant Japan Co., Ltd .: trade name).

Examples of the halogen-based flame retardant include aromatic halogen compounds, halogenated epoxy resins, halogenated polycarbonates, halogenated aromatic vinyl polymers,
Halogenated cyanurate resin, halogenated polyphenylene ether and the like, preferably, decabromodiphenyl oxide, tetrabromobisphenol A,
Carbonate oligomer of tetrabromobisphenol A, brominated bisphenol-based epoxy resin, brominated bisphenol-based phenoxy resin, brominated bisphenol-based polycarbonate, brominated polystyrene, brominated cross-linked polystyrene, brominated polyphenylene ether, polydibromophenylene ether, decabromodiphenyl Oxide bisphenol condensates and halogen-containing phosphoric acid esters can be exemplified.

As the organic phosphorus-based flame retardant, an organic phosphate ester-based flame retardant is preferable, and as the organic phosphate ester-based flame retardant, one or two of the following general formula (4) are particularly preferred.
More than one phosphate ester compound can be mentioned.

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(Where X in the above formula is hydroquinone,
Derived from resorcinol, bis (4-hydroxydiphenyl) methane, bisphenol A, dihydroxydiphenyl, dihydroxynaphthalene, bis (4-hydroxyphenyl) sulfone, bis (4-hydroxyphenyl) ketone, bis (4-hydroxyphenyl) sulfide J, k, l, and m are each independently 0 or 1, n is an integer of 0 to 5,
Or 0 in the case of a mixture of n different phosphate esters.
And R ₁ , R ₂ , R ₃ , and R ₄ are each independently phenol, cresol, xylenol, isopropylphenol, butylphenol substituted or unsubstituted with one or more halogen atoms. p-
It is derived from cumylphenol. )

Among them, preferably, X in the above formula includes those derived from hydroquinone, resorcinol and bisphenol A, wherein j, k, l and m are each 1 and n is 0-3. Is an integer or an average value of 0 to 3 in the case of a blend of n different phosphate esters, wherein R ₁ , R ₂ , R ₃ , and R ₄ each independently represent
It is derived from phenol, cresol, or xylenol with or without substitution of at least two halogen atoms.

Furthermore, particularly preferably, X is derived from resorcinol, j, k, l, m are each 1, n is 0 or 1, and R ₁ , R ₂ , R ₃ ,
And R ₄ are each independently derived from phenol or xylenol.

Among such organic phosphate ester-based flame retardants, triphenyl phosphate is used as a monophosphate compound, and resorcinol bis (dixylenyl phosphate) and bisphenol A bis (diphenyl phosphate) are used as condensed phosphate esters. Can be preferably used, for example, because of good flowability during molding.

Examples of the inorganic phosphates include ammonium polyphosphate.

Examples of the hydrate of the inorganic metal compound include aluminum hydroxide, magnesium hydroxide, dolomite, hydrotalcite, calcium hydroxide, barium hydroxide,
Basic magnesium carbonate, zirconium hydroxide, tin oxide hydrate and the like can be used.

Examples of the inorganic or organic alkali (earth) metal salt-based flame retardants include alkali metal or alkaline earth metal salts of organic or inorganic acids, and halogen-containing compounds. Here, preferable examples of the inorganic alkali metal salt include a sodium salt, a potassium salt, a lithium salt, a cesium salt and the like. In addition, examples of the inorganic alkaline earth metal salt include a calcium salt and a magnesium salt. The inorganic acid used for obtaining the inorganic alkali metal salt or the inorganic alkaline earth metal salt includes H ₃ A
_{lF 6, H 3 BF 6,} H 3 SbF 6, H 2 TiF 6, H 2 SiF
₆ , H ₃ PO, H ₂ ZrF ₆ , H ₂ WF ₆ , HBF _{4 and the} like. Preferred inorganic alkali metal salts or inorganic alkaline earth metal salts include Na ₃ AlF ₆ , Ca ₃ (AlF
₆ ) ₂ .

Preferred organic acids used for obtaining the organic alkali metal salt or the organic alkaline earth metal salt include aliphatic sulfonic acids, aromatic sulfonic acids, aromatic carboxylic acids and aliphatic carboxylic acids. Specific examples include mono- or disulfone such as methyl sulfonic acid, lauryl sulfonic acid, hexadecyl sulfonic acid, polyoxyethylene alkyl ether sulfonic acid, polyoxyethylene alkyl phenyl ether sulfonic acid, ethylene glycol, propylene glycol, and butanediol. Acid, pentaerythritol mono, di, tri or tetrasulfonic acid, stearic acid monoglyceride monosulfonic acid, 1,3-bis (2-ethylhexyl) glycerin ether monosulfonic acid, trifluoromethanesulfonic acid, perfluoroethanesulfonic acid, perfluoroethanesulfonic acid Fluoropropanesulfonic acid, perfluorobutanesulfonic acid, perfluoromethylbutanesulfonic acid, perfluorohexanesulfonic acid, perfluoroheptanesulfonic acid, Fluorooctanesulfonic acid, dodecanesulfonic acid, benzenesulfonic acid, 2,5-dichlorobenzenesulfonic acid, 2,4,6-trichlorobenzenesulfonic acid, 2,4,5-trichlorobenzenesulfonic acid, diphenylsulfone-3- Sulfonic acid, diphenylsulfone-3,3′-disulfonic acid, naphthalenetrisulfonic acid, caprylic acid, lauric acid, benzoic acid, naphtholcarboxylic acid, 2,4,6-tribromobenzoic acid and the like can be mentioned. Preferred organic alkali metal salts or organic alkaline earth metal salts include potassium perfluorobutanesulfonate, calcium perfluorobutanesulfonate,
Cesium perfluorobutanesulfonate, potassium diphenylsulfon-3-sulfonate, and potassium diphenylsulfone-3,3'-disulfonate.

Further, examples of the silicone flame retardant include those having a basic structure represented by the following general formula (5).

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In the general formula (5), R1, R2 and R3 each represent a hydrocarbon group having 1 to 12 carbon atoms.
For example, an alkyl group having 1 to 12 carbon atoms, an alkenyl group having 2 to 12 carbon atoms, an aryl group having 6 to 12 carbon atoms, and 7 carbon atoms
To 12 arylalkyl groups. Specific examples of such an alkyl group include a methyl group, an ethyl group, and n-
Propyl group, n-propyl group, isopropyl group, various butyl groups, various hexyl groups, cyclohexyl groups and the like, specific examples of alkenyl groups, vinyl groups, allyl groups, cyclohexenyl groups and the like, specific examples of aryl groups Is a phenyl group, a naphthyl group, a tolyl group, and the like, and specific examples of the arylalkyl group include a benzyl group, a β-phenethyl group, a 2-phenylpropyl group, and the like.
Of these, phenyl, vinyl, and methyl groups are particularly preferred because they exhibit more effective flame retardancy.

Further, it is also possible to use those in which R1, R2 and R3 are phenolic hydroxyl group-containing monovalent organic groups, and such an organosiloxane compound is copolymerized with a polycarbonate resin. Examples of the phenolic hydroxyl group-containing monovalent organic group include 2- (o-hydroxyphenyl) ethyl, 2- (p-hydroxyphenyl) ethyl, 2- (m-hydroxyphenyl) ethyl, 1-
(O-hydroxyphenyl) ethyl group, 1- (p-hydroxyphenyl) ethyl group, 1- (m-hydroxyphenyl) ethyl group, 3- (o-hydroxyphenyl) propyl group, 3- (p-hydroxyphenyl) Propyl group,
3- (m-hydroxyphenyl) propyl group, 2- (o
-Hydroxyphenyl) propyl group, 2- (p-hydroxyphenyl) propyl group, 2- (m-hydroxyphenyl) propyl group and the like.

A, b, c and d in the general formula (5)
As 0 ≦ a ≦ 0.75, 0 ≦ b ≦ 1, 0 ≦ c ≦
0.5, 0 ≦ d ≦ 0.25 and (a + b + c + d) =
1 is satisfied. Also, c and d are not simultaneously 0. Furthermore, 0 ≦ a ≦ 0.5, 0.25 ≦ b ≦ 0.
9 is preferable.

Further, such an organosiloxane compound has a kinematic viscosity at 25 ° C. of 100 to 100,000.
It is preferably cS (centistokes), more preferably 200 to 10,000 cS.

Among them, at least one selected from red phosphorus flame retardants, organic phosphate ester flame retardants, halogen flame retardants, organic alkali (earth) metal salt flame retardants, and silicone flame retardants. Types of flame retardants are preferred, more preferably at least one flame retardant selected from red phosphorus flame retardants, organic phosphate flame retardants and halogen flame retardants, and particularly preferably organic phosphoric ester flame retardants. It is at least one flame retardant selected from a flame retardant and a halogen-based flame retardant.

The proportion of the flame retardant of component C is preferably from 0.1 to 30% by weight, more preferably from 1 to 20% by weight, based on 100% by weight of the total of components A to E of the present invention. 50% of at least one flame retardant selected from a phosphoric ester flame retardant and a halogen flame retardant
What is contained above is more preferred, and particularly preferred is at least one flame retardant selected from organic phosphoric ester flame retardants and halogen flame retardants. When the addition amount of the component C is less than 0.1% by weight, the flame retardant effect is insufficient,
If it is more than 30% by weight, the mechanical strength is reduced.

The glass fiber used as the component D-1 in the present invention has a fiber diameter of 5 to 20 μm, preferably 8 to 15 μm.
m. The fiber length is preferably 1 to 10 mm, more preferably 1.5 to 6 mm. The glass fiber does not particularly limit the glass composition such as A glass, C glass, and E glass. In some cases, TiO ₂ , SO ₃ , P
_It may contain a component such as ₂ O ₅ . However, E glass (alkali-free glass) is more preferable because it does not adversely affect the aromatic polycarbonate resin.

The glass fiber of the present invention is obtained by quenching molten glass while stretching it by various methods to form a predetermined fiber. The quenching and stretching conditions in such a case are not particularly limited. The cross-sectional shape may be a general circular shape, or a non-circular cross-sectional shape in which true circular fibers are overlapped in parallel. Further, a glass fiber mixed with a perfect circular shape and an irregular cross-sectional shape may be used. The glass fiber can be subjected to a convergence treatment with various compounds such as an epoxy-based, urethane-based, and acrylic-based compound. The amount of the sizing agent is preferably from 0.05 to 10% by weight, more preferably from 0.1 to 5% by weight, based on 100% by weight of the bunched glass fibers. Further, those surface-treated with a silane coupling agent, a titanate coupling agent, an aluminate coupling agent or the like are preferable. When the number average fiber length of these fibers in the molded product is 200 μm or more, the effect of the present invention is sufficiently exhibited.

The wollastonite used as the D-2 component in the present invention is substantially represented by the chemical formula CaSiO ₃ ,
Usually, it contains about 50% by weight or more of SiO ₂ , about 47% by weight of CaO, other Fe ₂ O ₃ , Al ₂ O _3, etc., and is a white needle-like powder obtained by grinding and classifying raw wollastonite. In the present invention, among such wollastonite, the weighted average fiber length is 5 to 50 μm and the total fiber number is 100%.
Wollastonite whose number of 5 μm is 70% or more is used. Preferably, the weighted average fiber length is 20 to 40 µm, and the number of fibers having a fiber diameter of 1 to 5 µm in 100% of the total number is 70.
% Of wollastonite. When the weighted average fiber length is less than 5 μm, the effect on flame retardancy and strength becomes insufficient, and when it exceeds 50 μm, the fiber diameter becomes too large, resulting in insufficient dimensional accuracy of the molded product. On the other hand, if the fiber diameter is not more than 70% in the range of 0.5 to 5 μm, the influence on the properties such as flame retardancy and rigidity becomes insufficient, and it is not preferable in terms of the dimensional accuracy of the molded product.

For the calculation of the weighted average fiber length,
Wollastonite is observed with an optical microscope or an electron microscope or the like at a magnification at which the entire image of wollastonite can be almost completely observed, and such an image is input to an image analyzer. Such an image analysis device is, for example, PIAS-I manufactured by Pierce.
II system and the like. A fiber length of wollastonite is calculated from the input image data by the analyzer, and a weighted average value, that is, a value obtained by dividing a sum of squares of each fiber length by a sum of each fiber length from a total of 1,000 values. Is calculated. Since wollastonite is a filler that is easily crushed, such wollastonite contains many fine powdery components. Therefore, since simply the number average value is strongly affected by those values, the use of the weighted average value makes it possible to further clarify the correlation with characteristics such as flame retardancy.

On the other hand, as for the fiber diameter, a total of 100 randomly extracted from images observed with an electron microscope photograph or the like was used.
It is possible to calculate such a distribution by measuring the fiber diameter of zero fibers.

The talc used as the D-3 component in the present invention is a flaky particle having a layered structure, is a hydrous magnesium silicate in chemical composition, and generally has a chemical formula of 4SiO ₂ .3MgO. 2H ₂ O, usually SiO ₂
56-65% by weight, MgO 28-35% by weight, H ₂
O is about 5% by weight. 0.03 to 1.2% by weight of Fe ₂ O ₃ as other minor components, Al ₂ O ₃
Is 0.05 to 1.5% by weight, and CaO is 0.05 to 1.2% by weight.
% By weight, K ₂ O is 0.2% by weight or less, Na ₂ O is 0.2% by weight or less, and the specific gravity is about 2.7.
The particle size of the talc of the present invention is a particle size at a stacking rate of 50% obtained from a particle size distribution measured by the Andreazen pipette method measured according to JIS M8016. Its particle size is 2 to 15 μm, preferably 5 to 10 μm.
Outside this range, the flame retardancy is undesirably reduced.

The ratio of D-1 to D-2 in the Da component is 25:75 to 75:25 by weight, preferably 75:25 to 50:50. 25: 75-75:
Outside the range of 25, the flame retardancy is undesirably reduced. In the Db component, the ratio between D-1 and D-3 is 25:75 to 75:25 by weight, and more preferably 75:25 to 50:50. When the proportion of the D-1 component in the Da component or the Db component exceeds 75% by weight, the flame retardancy is reduced, and when it is less than 25% by weight, the flexural modulus is particularly low. It will not be suitable for chassis parts etc. Further, A of the present invention
In the total 100% by weight of the components E to E, the Da component or D
When the proportion of the component b is less than 25% by weight, rigidity is low and
There is not much difference in the flame retardant effect by the combination of the fillers. On the other hand, if the content exceeds 45% by weight, the moldability is deteriorated, and the shape retention during combustion by the filler is strong, and there is no influence on the flame retardancy due to the presence or absence of polytetrafluoroethylene having fibril forming ability. On the contrary, the effect of reducing the amount of addition decreases.

The polytetrafluoroethylene having a fibril-forming ability used as the component E used in the present invention is classified into type 3 in the ASTM standard. Further, polytetrafluoroethylene having such a fibril-forming ability has a primary particle diameter of 0.05 to 10 μm.
Are preferable, and the secondary particle diameter is 50 to 700 μm.
m is preferred. Such a polytetrafluoroethylene has a drip-preventing performance at the time of a combustion test of a test piece in a vertical combustion test of UL standard, and such a polytetrafluoroethylene having a fibril-forming ability is, for example, Mitsui-Dupont Fluorochemical Co., Ltd. It is commercially available as Teflon 6J or as Polyflon from Daikin Chemical Industries, Ltd. and can be easily obtained.

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

First, a coagulated mixture of a PTFE dispersion and a dispersion of a vinyl polymer can be mentioned. Specifically, JP-A-60-258263 discloses an average particle size of 0.0
A method of mixing a PTFE dispersion of 5 to 5 μm and a dispersion of a vinyl polymer, coagulating PTFE particles larger than 30 μm without purification, and drying the coagulated product to obtain a PTFE mixture is described. The use of such mixtures is possible.

Secondly, there can be mentioned a mixture obtained by mixing a PTFE dispersion and dried polymer particles. As such polymer particles, various types can be used, and more preferably, polycarbonate resin powder or ABS resin powder is used. It was done. For such a mixture, JP-A-4-272957 discloses a PTFE dispersion and ABS.
A mixture with a resin powder is described, and such a method can be used.

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

Fourthly, a PTFE mixture obtained by polymerizing another vinyl monomer in a PTFE dispersion can be mentioned.
No. 5583 specifically describes a method of obtaining a PTFE mixture by supplying styrene and acrylonitrile into a PTFE latex, and such a mixture can be used.

Fifth, a method of mixing the PTFE dispersion and the polymer particle dispersion and then polymerizing the ethylenically unsaturated monomer in the mixed dispersion can be mentioned. And a fine PTFE mixture in terms of achieving both fine dispersion of PTFE. Details of such a mixture are described in JP-A-11-29679, that is, a particle diameter of 0.05.
PTFE mixture pulverized by coagulation or spray-drying after emulsion polymerization of a monomer having an ethylenically unsaturated bond in a dispersion obtained by mixing a PTFE dispersion of about 1.0 μm and a polymer particle dispersion. Are preferred.

Here, the polymer particles include a block copolymer composed of polypropylene, polyethylene, polystyrene, HIPS, AS resin, ABS resin, MBS resin, MABS resin, ASA resin, polyalkyl (meth) acrylate, styrene and butadiene. The hydrogenated copolymer, a block copolymer composed of styrene and isoprene, and the hydrogenated copolymer, an acrylonitrile-butadiene copolymer, a random copolymer and a block copolymer of ethylene-propylene, and a copolymer of ethylene-butene Random copolymer and block copolymer, copolymer of ethylene and α-olefin, copolymer of ethylene-unsaturated carboxylic acid ester such as ethylene-butyl acrylate, acrylate-butadiene copolymer, polyorgano Shiroki Rubber and a copolymer obtained by grafting a vinyl-based monomer such as styrene, acrylonitrile, or polyalkyl methacrylate onto such a composite rubber. (Meth) acrylate, polystyrene, AS resin, ABS resin and ASA resin are preferred.

On the other hand, the ethylenically unsaturated monomers include styrene, p-methylstyrene, o-methylstyrene and p-methylstyrene.
-Methoxystyrene, o-methoxystyrene, 2,4-
Styrene-based monomers such as dimethylstyrene and α-methylstyrene; methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, butyl acrylate, butyl methacrylate, 2-ethylhexyl acrylate, methacrylic acid-2 Acrylate monomers such as ethylhexyl, dodecyl acrylate, dodecyl methacrylate, cyclohexyl acrylate and cyclohexyl methacrylate; vinyl cyanide monomers such as acrylonitrile and methacrylonitrile; vinyl methyl ether and vinyl ethyl ether Vinyl ether monomers such as vinyl acetate and vinyl butyrate; olefin monomers such as ethylene, propylene and isobutylene; diene monomers such as butadiene, isoprene and dimethylbutadiene. It can be selected from among. These monomers can be used alone or in combination of two or more.

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

On the other hand, in the present invention, a mixture having a high bulk specific gravity obtained by mixing the component E with the component D-2 or the component D-3 and compressing the mixture can be used. Such E component and D
Japanese Patent Application Laid-Open No. 11-1
No. 72119 describes the details.

The compounding amount of polytetrafluoroethylene having a fibril-forming ability is 0.05 to 1% by weight based on 100% by weight of the total of the components A to E of the present invention. 0.05
When the content is in the range of 1 to 1% by weight, it is possible to obtain sufficient molten dropping prevention performance.

Further, the glass-reinforced flame-retardant polycarbonate resin composition of the present invention may contain a small amount of other various inorganic fillers. Here, the small amount refers to an amount of 10% by weight or less based on 100% by weight of the D component of the present invention.

Other inorganic fillers include fibrous fillers such as carbon fiber, metal fiber, zonotolite, potassium titanate whisker, aluminum borate whisker, basic magnesium sulfate whisker, mica, glass flake, graphite flake and the like. Plate filler, short glass fiber (milled fiber), short carbon fiber, glass beads,
Various particulate fillers such as glass balloons, ceramic balloons, carbon beads, silica particles, titania particles, alumina particles, kaolin, clay, calcium carbonate, titanium oxide, cesium oxide, zinc oxide, red phosphorus, and the above various inorganic fillers Various metals represented by gold, silver, nickel, copper, chromium, aluminum, etc., titanium oxide, iron oxide, tin oxide, zirconium oxide, cesium oxide, etc. Inorganic filler coated with a metal oxide or the like.

The glass-reinforced flame-retardant polycarbonate resin composition of the present invention further comprises a heat-resistant organic filler, a phosphorus-based heat stabilizer, an antioxidant, an ultraviolet absorber, a release agent, an antistatic agent, and a foaming agent. And dyes and pigments.

The heat-resistant organic fillers are those which do not melt at the molding and processing temperature of the aromatic polycarbonate resin which is the component A of the present invention. Examples of such fillers include fibrous fillers such as aramid fibers and polyarylate fibers. , Aramid powder, polytetrafluoroethylene powder, phenol resin particles, crosslinked styrene particles, crosslinked acryl particles, and other particulate fillers.

Examples of the phosphorus-based heat stabilizer include phosphorous acid, phosphoric acid, phosphonous acid, phosphonic acid and esters thereof, and specific examples thereof include triphenyl phosphite, trisnonylphenyl phosphite, and tris phosphite. (2,
4-di-tert-butylphenyl) phosphite, tridecyl phosphite, trioctyl phosphite, trioctadecyl phosphite, didecyl monophenyl phosphite, dioctyl monophenyl phosphite, diisopropyl monophenyl phosphite, monobutyl diphenyl phosphite Phyte, monodecyldiphenylphosphite, monooctyldiphenylphosphite, bis (2,6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphite, 2,2-methylenebis (4,6-di-tert -Butylphenyl)
Octyl phosphite, bis (nonylphenyl) pentaerythritol diphosphite, bis (2,4-di-t
phosphite compounds such as tert-butylphenyl) pentaerythritol diphosphite, tributyl phosphate, trimethyl phosphate, tricresyl phosphate, triphenyl phosphate, trichlorophenyl phosphate, triethyl phosphate, diphenylcresyl phosphate, diphenyl monoorthoxenyl Phosphate compounds such as phosphate, tributoxyethyl phosphate, dibutyl phosphate, dioctyl phosphate, diisopropyl phosphate, and tetrakis (2,4-
Di-tert-butylphenyl) -4,4'-biphenylenediphosphonite, tetrakis (2,4-di-ter
t-butylphenyl) -4,3′-biphenylenediphosphonite, tetrakis (2,4-di-tert-butylphenyl) -3,3′-biphenylenediphosphonite,
Bis (2,4-di-tert-butylphenyl) -4-
Examples thereof include phosphonite compounds such as biphenylenephosphonite. Of these, trisnonylphenyl phosphite, distearylpentaerythritol diphosphite, bis (2,4-di-tert)
-Butylphenyl) pentaerythritol diphosphite, tris (2,4-di-tert-butylphenyl)
Phosphite, triphenyl phosphate, trimethyl phosphate, tetrakis (2,4-di-tert-butylphenyl) -4,4′-biphenylenediphosphonite, bis (2,4-di-tert-butylphenyl)-
4-Biphenylenephosphonite is preferred. These heat stabilizers may be used alone or in combination of two or more. The amount of the heat stabilizer is preferably 0.0001 to 1 part by weight, more preferably 0.0005 to 0.5 part by weight, based on 100 parts by weight of the total of the component A and the component B.
0.002 to 0.3 parts by weight is more preferred.

Examples of the antioxidant include pentaerythritol tetrakis (3-mercaptopropionate), pentaerythritol tetrakis (3-laurylthiopropionate), glycerol-3-stearylthiopropionate, and triethylene glycol-bis. [3- (3-tert-butyl-5-methyl-4-hydroxyphenyl) propionate], 1,6-hexanediol-bis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate ], Pentaerythritol-tetrakis [3- (3,5-di-tert-butyl-4-)
Hydroxyphenyl) propionate], octadecyl-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate, 1,3,5-trimethyl-2,
4,6-tris (3,5-di-t-butyl-4-hydroxybenzyl) benzene, N, N-hexamethylenebis (3,5-di-t-butyl-4-hydroxy-hydrocinnamide), 3,5-di-t-butyl-4-hydroxy-benzylphosphonate-diethyl ester, tris (3,5-di-t-butyl-4-hydroxybenzyl)
Isocyanurate, tetrakis (4,4′-biphenylenediphosphosphinate) (2,4-di-t-butylphenyl), 3,9-bis {1,1-dimethyl-2- [β-
(3-t-butyl-4-hydroxy-5-methylphenyl) propionyloxy] ethyl {-2,4,8,10
-Tetraoxaspiro (5,5) undecane and the like. The amount of these antioxidants is 0.0001 to 0.05 based on 100 parts by weight of the total of the component A and the component B.
Parts by weight are preferred.

As the ultraviolet absorber, for example, 2,2'-
A benzophenone-based ultraviolet absorber represented by dihydroxy-4-methoxybenzophenone;
(3-tert-butyl-5-methyl-2-hydroxyphenyl) -5-chlorobenzotriazole, 2-
(3,5-di-tert-butyl-2-hydroxyphenyl) -5-chlorobenzotriazole, 2,2′-methylenebis [4- (1,1,3,3-tetramethylbutyl) -6- (2H -Benzotriazol-2-yl) phenol], 2- [2-hydroxy-3,5-bis (α, α-dimethylbenzyl) phenyl] -2H-benzotriazole and 2- (3,5-di-tert- Examples thereof include benzotriazole-based ultraviolet absorbers represented by (amyl-2-hydroxyphenyl) benzotriazole. Further, bis (2,2,6,6-tetramethyl-4-
Piperidyl) sebacate, bis (1,2,2,6,6-
It is also possible to use hindered amine light stabilizers represented by (pentamethyl-4-piperidyl) sebacate and the like. The amount of the ultraviolet absorber and the light stabilizer is
0.0 to 100 parts by weight of the total of the component A and the component B
1 to 5 parts by weight is preferred.

As the release agent, olefin wax,
Examples include silicone oil, organopolysiloxane, higher fatty acid ester of monohydric or polyhydric alcohol, paraffin wax, beeswax and the like. The amount of the release agent is based on 100 parts by weight of the total of the A component and the B component.
0.01 to 2 parts by weight is preferred.

Examples of the antistatic agent include polyetheresteramide, glycerin monostearate, ammonium dodecylbenzenesulfonate, phosphonium dodecylbenzenesulfonate, monoglyceride maleic anhydride, diglyceride maleic anhydride and the like. The compounding amount of the antistatic agent is preferably 0.5 to 20 parts by weight based on 100 parts by weight of the total of the component A and the component B.

The thermoplastic resin composition of the present invention is obtained by mixing the above components simultaneously or in an arbitrary order by using a mixer such as a tumbler, a V-type blender, a Nauter mixer, a Banbury mixer, a kneading roll, and an extruder. Can be manufactured. Preferably, melt-kneading by a twin-screw extruder is preferable, and in this case, it is preferable that the component D is supplied from a second feed port or the like into the other components melt-mixed by a side feeder or the like.

The composition thus obtained can be easily molded by a known method such as injection molding, extrusion molding, compression molding or rotational molding. In particular, a high-precision chassis such as precision equipment is molded by injection molding. It is possible to At that time, it is possible to combine injection compression molding, molding with a heat insulating mold and the like in order to achieve higher precision, and it is also possible to combine gas assist molding and the like for weight reduction.

[0104]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be further described below with reference to examples.

Examples 1 to 11 and Comparative Examples 1 to 16 Of the components A to E shown in Tables 1, 2, 3 and 4, the components D-1 to D-3 (D Component), and a component excluding the inorganic filler other than the component D, and a total of 100 parts by weight of the components A to E (including components other than the component D),
0.1 part by weight of trimethyl phosphate, 0.3 part by weight of stearyl stearate, and 0.3 part by weight of carbon black # 970 (manufactured by Mitsubishi Chemical Corporation) are mixed in a V-type blender, and then a 30 mmφ vent Using a twin-screw extruder [Nippon Steel Works TEX-30XSST]
The mixture was added to the last part of the first charging port (however, the components C of Examples 5 and 11 were heated to 80 ° C., and a predetermined ratio was blended in an extruder by a fixed-quantity liquid transfer device). Filler glass fiber, wollastonite, talc-
1, talc-2 and MF, mica, and GFL, inorganic fillers other than the D component used in the comparative example, were charged from a second charging port in the middle of the cylinder to a predetermined ratio using a measuring instrument. The glass fiber and wollastonite or talc were separately charged using different measuring instruments. Under such conditions, the mixture was melt-extruded at a cylinder temperature of 260 to 270 ° C. under a vacuum of 0.5 kPa using a vacuum pump to form pellets (comparative examples 15 and 16 have a cylinder temperature of 300 ° C.). The obtained pellets were heated at 110 ° C. for 5 hours,
It is dried by a hot air circulation type dryer, and the cylinder temperature is 260 ° C. by an injection molding machine [FANUC T-150D].
A test piece for evaluation was prepared at a mold temperature of 70 ° C. (Comparative Example 1)
5 and 16: cylinder temperature 310 ° C, mold temperature 100 ° C
), And evaluated by the following evaluation methods.

Mechanical properties of glass-reinforced flame-retardant polycarbonate resin composition Rigidity: Flexural modulus was measured according to ASTM D-790. Impact resistance: Izod notched impact was measured according to ASTM D-256 (Method A). Heat resistance: 1.82 according to ASTM D-648
The deflection temperature under load was measured under a load of MPa. Flammability: A flammability test was performed according to UL Standard 94V.

The symbols indicating the components shown in Tables 1 to 4 are as follows. (A component) PC: polycarbonate resin [viscosity average molecular weight of 2,2.5 prepared from bisphenol A and phosgene by an ordinary method]
No. 00 polycarbonate resin powder, “Panlite L-1225WP” manufactured by Teijin Chemicals Ltd.]

(Component B) ABS: ABS resin ["Santac" manufactured by Mitsui Chemicals, Inc.
UT-61 "] AS-1: AS resin [Mitsui Chemicals Co., Ltd." Lightac A "
980 PCU "] AS-2: AS resin [Asahi Kasei Corporation" Stylac AS "
767 "]

(Component C) Flame retardant-1: Phosphorus-based flame retardant [triphenyl phosphate, "TPP" manufactured by Daihachi Chemical Industry Co., Ltd.] Flame retardant-2: Phosphorus-based flame retardant [resorcinol bis (dixylenyl phosphate) ), Asahi Denka Kogyo Co., Ltd. “FP-
500 "] Flame Retardant-3: Phosphorus Flame Retardant [Bisphenol A Polyphosphate]" CR-741 "manufactured by Daihachi Chemical Industry Co., Ltd.] Flame Retardant-4: Halogen Flame Retardant [Tetrabromobisphenol A carbonate] Oligomers, "Fireguard FG-7000" manufactured by Teijin Chemicals Ltd.] Flame retardant-5: Red phosphorus-based flame retardant [Nova Excel 140 (manufactured by Rin Kagaku Kogyo KK) polycarbonate resin master pellets, Nova Excel 140: above L-1225WP
Weight ratio of 15:85]

(D component) (D-1 component) GF: 0.8% of glass fiber (γ-aminopropyltriethoxysilane treatment, and mixed sizing agent of bisphenol A-epichlorohydrin type epoxy resin / urethane resin)
% Glass fiber with a fiber diameter of 13 μm and a fiber cut length of 3 mm)

(Component D-2) WSN: Wollastonite (weighted average fiber length is 27 μm, the ratio of the number of fibers having a diameter of 0.5 to 5 μm is 85%, and the number of fibers having a diameter of 1 to 5 μm is Wollastonite having a number-average fiber diameter of 2.7 μm and a ratio of 69%, which was obtained by crushing and classifying a rough produced from Virboro, New York, USA by a jet mill crushing method. )

(D-3 component) Talc-1: Stacking ratio 50% The particle diameter is 2.4 μm,
A talc having a Hunter whiteness of 97.7 and a pH of 9.8, measured according to JIS M8016. The talc had a stacking rate of 2 μm in the particle size distribution measured by the Andreazen pipette method according to JIS M8016.
Less than: 41.6%, less than 3 μm: 59.5%, less than 5 μm: 84.6%, less than 7 μm 94.7%, less than 10 μm: 99.2%, less than 15 μm: 99.9%. Talc-2: a stacking ratio of 50%, the particle diameter is 7.3 μm,
Talc having a Hunter whiteness of 94.5 and a pH of 9.7 measured according to JIS M8016. The talc had a stacking rate of 2 μm in the particle size distribution measured by the Andreazen pipette method according to JIS M8016.
Less than 12.2%, less than 3 μm: 20.4%, less than 5 μm: 34.7%, less than 7 μm 48.0%, less than 10 μm: 62.9%, less than 15 μm: 78.2%. (Inorganic filler other than component D) Mica: Mica having an average particle diameter of 20 μm and an average thickness of 0.5 μm MF: Short glass fiber having a fiber diameter of 9 μm and a number average fiber length of 30 μm GFL: Glass having an average particle diameter of 600 μm and an average thickness of 5 μm flake

(E component) PTFE: Polytetrafluoroethylene having fibril-forming ability [Polyflon FA5 manufactured by Daikin Industries, Ltd.]
00 "]

[0114]

[Table 1]

[0115]

[Table 2]

[0116]

[Table 3]

[0117]

[Table 4]

[0118]

Industrial Applicability The glass-reinforced flame-retardant polycarbonate thermoplastic resin composition of the present invention can be used for any material that requires flame retardancy, mechanical properties such as impact strength, and flame retardancy. In particular, the present invention is effective for OA equipment such as a printer chassis and an optical chassis, and electric and electronic fields, and its industrial effects are particularly remarkable.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) C08K 3/40 C08K 3/40 5/521 5/521 C08L 25/04 C08L 25/04 25/12 25 / 12 51/04 51/04 67/00 67/00 F term (reference) 4F072 AA02 AA05 AA08 AB04 AB08 AB09 AB14 AB15 AD05 AD37 AD41 AD52 AE06 AE07 AF02 AF05 AF06 AF19 AF20 AF21 4J002 BC03X BC04X BC06X BC08X BC09X BC114 BD153 BN07XBN12X BN15X BN16X BP01X CD124 CF04X CF05X CF06X CF07X CF08X CF09X CF10X CF13X CG01W CG02W CG034 CH064 CH074 CM024 CP034 CP064 CP134 CP17X DA056 DD006 DE066 DE076 DE086 DE096 DE146 DE266 DE286 DH046 DH0 046 046046 FD017 FD018 FD050 FD060 FD070 FD100 FD133 FD134 FD136 FD160 GM00

Claims (8)

[Claims] 1. An aromatic polycarbonate resin (A component)
20 to 74.85% by weight, 0 to 40% by weight of at least one kind of thermoplastic resin selected from styrene resin and aromatic polyester resin (component B), flame retardant (component C)
0.1 to 30% by weight, glass fiber (D-1 component) having a fiber diameter of 5 to 20 μm, weighted average fiber length of 5 to 50 μm, and 100% of the total number. Weight ratio with certain wollastonite (D-2 component) (D
-1 component: D-2 component) 25:75 to 75:25, an inorganic filler (Da component) of 25 to 45% by weight, and polytetrafluoroethylene (E component) having a fibril-forming ability of 0.05 to 45% by weight. A glass-reinforced flame-retardant polycarbonate resin composition comprising a total of 100% by weight of 1% by weight. 2. The glass-reinforced flame-retardant polycarbonate resin composition according to claim 1, wherein the styrene-based thermoplastic resin as the component B is an acrylonitrile-styrene copolymer and / or an acrylonitrile-butadiene-styrene copolymer. 3. The D-2 component has a weighted average fiber length of 20 to
2. Wollastonite having a fiber diameter of 40 [mu] m and having a fiber diameter of 1 to 5 [mu] m in a total number of 100% of 70% or more.
The glass-reinforced flame-retardant polycarbonate resin composition according to any one of claims 1 to 3. 4. An aromatic polycarbonate resin (A component)
20 to 74.85% by weight, 0 to 40% by weight of at least one kind of thermoplastic resin selected from styrene resin and aromatic polyester resin (component B), flame retardant (component C)
0.1 to 30% by weight, glass fiber (D-1 component) having a fiber diameter of 5 to 20 μm and a particle diameter of 2 to 15 μm at a stacking ratio of 50%
Weight ratio to talc (D-3 component) (D-1 component: D-
(3 components) 25:75 to 75:25, an inorganic filler (Db component) in an amount of 25 to 45% by weight, and polytetrafluoroethylene (E component) having fibril-forming ability.
A glass-reinforced flame-retardant polycarbonate resin composition consisting of a total of 100% by weight of 0.05 to 1% by weight. 5. The glass-reinforced flame-retardant polycarbonate resin composition according to claim 4, wherein the styrene-based thermoplastic resin as the component B is an acrylonitrile-styrene copolymer or an acrylonitrile-butadiene-styrene copolymer. 6. The composition according to claim 1, wherein the C component is a red phosphorus flame retardant, a halogen flame retardant, an organic phosphate ester flame retardant, an inorganic phosphate,
6. A flame retardant selected from the group consisting of a hydrate of an inorganic metal compound, an inorganic or organic alkali (earth) metal salt flame retardant and a silicone flame retardant.
The glass-reinforced flame-retardant polycarbonate resin composition according to any one of the above. 7. The glass-reinforced flame-retardant polycarbonate resin composition according to claim 4, wherein the particle size of the talc D-3 component at a stacking rate of 50% is 5 to 10 μm. 8. A molded article formed from the glass-reinforced flame-retardant polycarbonate resin composition according to any one of claims 1 to 7.