JP2003226816A - Flame-retardant fiber-reinforced polymer composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To obtain a flame-retardant fiber-reinforced polymer composition which has excellent mechanical strengths such as excellent impact strength and rigidity and excellent extrusion stability. <P>SOLUTION: This flame-retardant fiber-reinforced polymer composition comprises (A) a polymer, (B) an inorganic compound having an average particle diameter of 1 to 1,000 nm, and (C) fibers each having an average fiber diameter of 0.01 to 1,000 &mu;m and an aspect ratio (length/diameter) of 2 to 10,000. <P>COPYRIGHT: (C)2003,JPO

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION This invention relates to flame retardant fiber reinforced polymer compositions. More specifically, it relates to a flame-retardant fiber-reinforced polymer composition having excellent impact strength, mechanical strength such as rigidity, and extrusion stability.

[0002]

2. Description of the Related Art Polymers such as thermoplastic polymers are not only excellent in moldability but also excellent in impact resistance and flexibility, so that they are mainly used for automobile materials, electric materials and housing materials. It is used in various fields. In recent years, inorganic fillers have been added in order to improve the mechanical strength of materials, especially rigidity in such fields, but in order to impart high mechanical strength, a large amount of inorganic fillers are added. Therefore, there is a problem that the polymer is fragile or the fluidity is lowered.

With respect to this problem, the present inventor has found that by mixing a specific fiber, anisotropy is exhibited and the mechanical strength is remarkably improved. On the other hand, short fiber reinforcement of a thermoplastic elastomer is disclosed in Japan Rubber Association, Vol. 69, No. 9, P. 615 (1996).
However, although the fiber-reinforced elastomer of the above publication has excellent impact strength, it does not have sufficient rigidity and flame retardancy, so that the fiber-reinforced flame retardant polymer composition has excellent flame retardancy, mechanical strength and extrusion stability. Development of goods is required.

To solve this problem, a resin composition (US Pat. No. 5,391,594) containing a silicone polymer powder composed of silica and polydiorganosiloxane and having an average particle diameter of 1 to 1000 μm, a thermoplastic resin containing silicone and an inorganic substance is used. A flame-retardant resin composition to which a mixture of (1) and (2) is added (JP-A-11-140329), and an average particle size of polydiorganosiloxane gum and silica is 1 to 1000 μm.
m resin composition of silicone rubber powder and polyphenylene ether (JP-A-5-230362), flame-retardant polyphenylene ether composition comprising polyphenylene ether, liquid polydiorganosiloxane and filler (JP-A-5-262977). Gazette), a polyphenylene ether, a shape anisotropic filler, a phosphoric acid ester flame retardant, and a thermoplastic resin composition comprising a silicone polymer powder composed of polydiorganosiloxane and silica (JP-A-10-46025). There is. However, since the particle diameter of the inorganic compound used in the above publication is large, flame retardancy and mechanical strength are poor,
There is a need for flame retardant polymer compositions that can withstand practical use.

[0005]

In view of the above situation, the present invention has the above-mentioned problems, that is, excellent mechanical strength, flame retardancy, and extrusion stability (quality stability). It is an object of the present invention to provide a flame-retardant fiber-reinforced polymer composition having the composition.

[0006]

Means for Solving the Problems The inventors of the present invention have made earnest studies on a flame-retardant polymer composition having excellent mechanical strength. The present invention was completed by finding that the dynamic strength and extrusion stability are dramatically improved. That is, the present invention relates to (A) polymer,
(B) an inorganic compound having an average particle diameter of 1 nm or more and less than 1000 nm, and (C) an average fiber diameter of 0.01 to 1
000 μm, and the aspect ratio (length / diameter) is 2 to
A flame-retardant fiber reinforced polymer composition consisting of 10,000 fibers, especially (B) is selected from silicon-containing compounds and compounds or polymers containing aromatic groups.
A flame-retardant fiber reinforced polymer composition characterized by being surface-coated with one or more compounds.

[0007]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention will be described in detail below. The composition of the present invention is a flame-retardant fiber-reinforced polymer composition comprising (A) polymer, (B) specific inorganic compound, and (C) specific fiber. Here, the average particle size of the inorganic compound (B) is defined as the average primary particle size, and can be measured by a usual method. It is essential that the average particle diameter of (B) is 1 or more and less than 1000 nm, preferably 1 to 900 nm, more preferably 1 to 700.
nm, most preferably 1-500 nm, very preferably 1-100 nm. By satisfying the above requirements, the dispersibility of (B) in the polymer (A) is improved. When (B) is surface-coated with one or more compounds selected from a silicon-containing compound, a compound containing an aromatic group, and a polymer, the (B) in (A) It has been found that as a result of the dramatic improvement in dispersibility, mechanical strength, flame retardancy, and extrusion stability are improved.

Next, (C) the average fiber diameter is from 0.01 to
1000 μm, aspect ratio (length / diameter) is 2
The present invention has been completed by finding that the inclusion of a fiber having a content of up to 10,000 improves flame retardancy and mechanical strength, particularly impact strength and rigidity while maintaining extrusion stability.
Each component of the present invention will be described in detail below. The component (A) in the present invention is a polymer such as a rubber-like polymer, a thermoplastic resin, or a thermosetting resin, and among them, the thermoplastic resin is preferable.

In the present invention, the thermoplastic resin which is the most preferable polymer in (A) is, for example, a polyaromatic vinyl type, a polycarbonate type, a polyphenylene ether type, a polyolefin type, a polyvinyl chloride type, a polyamide type, Polyester type, polyphenylene sulfide type,
It is possible to use a single polymethacrylate type or a mixture of two or more types. Particularly, polyaromatic vinyl-based, polycarbonate-based, and polyphenylene ether-based thermoplastic polymers are extremely preferable. As the combination of (A), aromatic polycarbonate and aromatic vinyl polymer, or aromatic vinyl polymer and polyphenylene ether, or aromatic polycarbonate, aromatic vinyl polymer, and polyphenylene ether are most preferable.

The aromatic polycarbonate used as the component (A) in the present invention can be selected from aromatic homopolycarbonates and aromatic copolycarbonates.
As a production method, a phosgene method in which phosgene is blown into a bifunctional phenol compound in the presence of a caustic alkali and a solvent, or, for example, a transesterification method in which a bifunctional phenol compound and diethyl carbonate are transesterified in the presence of a catalyst Can be mentioned. The aromatic polycarbonate preferably has a viscosity average molecular weight in the range of 10,000 to 100,000. Here, the bifunctional phenol compound is 2,
2'-bis (4-hydroxyphenyl) propane, 2,
2'-bis (4-hydroxy-3,5-dimethylphenyl) propane, bis (4-hydroxyphenyl) methane, 1,1'-bis (4-hydroxyphenyl) ethane, 2,2'-bis (4- Hydroxyphenyl) butane, 2,2'-bis (4-hydroxy-3,5-diphenyl) butane, 2,2'-bis (4-hydroxy-3,
5-dipropylphenyl) propane, 1,1′-bis (4-hydroxyphenyl) cyclohexane, 1-phenyl-1,1′-bis (4-hydroxyphenyl) ethane and the like, especially 2,2′-bis (4-Hydroxyphenyl) propane [bisphenol A] is preferred. In the present invention, the bifunctional phenol compounds may be used alone or in combination.

The aromatic vinyl polymer as the component (A) in the present invention is one or more selected from rubber-modified aromatic vinyl-based resins, rubber-unmodified aromatic vinyl-based resins, and aromatic vinyl-based thermoplastic elastomers. Is an aromatic vinyl polymer. The rubber-modified aromatic vinyl-based resin comprises a matrix of the aromatic vinyl-based resin and rubber particles dispersed therein, and the aromatic vinyl-based resin is an aromatic vinyl monomer in the presence of a rubber-like polymer. , And, if desired, a vinyl monomer copolymerizable therewith, and the monomer (or mixture thereof) is subjected to a known bulk polymerization method, bulk suspension polymerization method, solution polymerization method, or emulsion polymerization method, It can be obtained by graft polymerization on a rubber-like polymer.

Examples of such polymers include high impact polystyrene, ABS resin (acrylonitrile-butadiene-styrene copolymer), AAS resin (acrylonitrile-acrylic rubber-styrene copolymer), AES resin (acrylonitrile- Ethylene propylene rubber-styrene copolymer) and the like. Here, the rubbery polymer needs to have a glass transition temperature (Tg) of −30 ° C. or lower, and if it exceeds −30 ° C., impact resistance is lowered.

Examples of such rubbery polymers include diene rubbers such as polybutadiene, poly (styrene-butadiene), poly (acrylonitrile-butadiene), and the like.
And saturated rubber obtained by hydrogenating the above diene rubber, isoprene rubber, chloroprene rubber, acrylic rubber such as polybutyl acrylate, and ethylene-propylene-diene monomer terpolymer (EPDM), and the like. A system rubber is preferred.

The aromatic vinyl monomer which is an essential component in the graft-polymerizable monomer mixture to be polymerized in the presence of the rubbery polymer is, for example, styrene, α-methylstyrene, paramethylstyrene or the like. However, styrene is the most preferable, but the above-mentioned other aromatic vinyl monomer may be copolymerized mainly with styrene. If necessary, one or more monomer components copolymerizable with the aromatic vinyl monomer can be introduced as a component of the rubber-modified aromatic vinyl resin in (A). When it is necessary to enhance oil resistance, unsaturated nitrile monomers such as acrylonitrile and methacrylonitrile can be used.

When it is necessary to reduce the melt viscosity at the time of blending, an acrylate ester composed of an alkyl group having 1 to 8 carbon atoms can be used. Furthermore, when it is necessary to further increase the heat resistance of the resin composition, α-methylstyrene, acrylic acid, methacrylic acid,
Monomers such as maleic anhydride and N-substituted maleimide may be copolymerized. The content of the vinyl monomer copolymerizable with the vinyl aromatic monomer in the monomer mixture is 0-40.
% By weight.

The rubber-like polymer in the rubber-modified aromatic vinyl resin is preferably 5 to 80% by weight, particularly preferably 10 to 50% by weight, and the graft-polymerizable monomer mixture is preferably 95 to 20% by weight. %, More preferably 90
Is in the range of 50% by weight. Within this range, the balance between impact resistance and rigidity of the desired resin composition is improved.
Furthermore, the rubber particle size of the styrene-based polymer is 0.1 to
5.0 μm is preferable, and 0.2 to 3.0 μm is particularly preferable. Within the above range, impact resistance is particularly improved.

The reduced viscosity ηsp / c (0.5 g / d) of the resin portion, which is a measure of the molecular weight of the rubber-modified aromatic vinyl resin.
1, 30 ° C measurement: toluene solution when the matrix resin is polystyrene, methyl ethyl ketone when the matrix resin is unsaturated nitrile-aromatic vinyl copolymer)
Is preferably in the range of 0.30 to 0.80 dl / g, and more preferably in the range of 0.40 to 0.60 dl / g. Reduced viscosity η of rubber modified styrene resin
As means for satisfying the above requirements regarding sp / c, adjustment of the amount of polymerization initiator, polymerization temperature, amount of chain transfer agent and the like can be mentioned.

As a method for producing the rubber-modified aromatic vinyl resin, in particular, a homogeneous polymerization stock solution comprising a rubbery polymer, a monomer (or a mixture of monomers) and a polymerization solvent is continuously prepared with a stirrer. A bulk polymerization method in which it is fed to a multistage bulk polymerization reactor and continuously polymerized and devolatilized is preferable. When a rubber-modified styrene polymer is produced by the bulk polymerization method, the reduced viscosity ηs
The p / c can be controlled by the polymerization temperature, the type and amount of the initiator, the solvent, and the amount of the chain transfer agent. When a monomer mixture is used, the copolymer composition can be controlled by adjusting the charged monomer composition. The rubber particle size can be controlled by the number of stirring rotations. That is, the particle size can be reduced by increasing the rotation speed and the particle size can be reduced by decreasing the rotation speed.

The aromatic vinyl type thermoplastic elastomer as (A) used in the present invention is a block copolymer comprising an aromatic vinyl unit and a conjugated diene unit, or the conjugated diene unit portion is partially hydrogenated. Is a block copolymer obtained from the above. The aromatic vinyl monomer constituting the block copolymer is, for example, styrene or α-
Methyl styrene, paramethyl styrene, p-chlorostyrene, p-bromostyrene, 2,4,5-tribromostyrene and the like, and styrene is the most preferable, but styrene is the main component and other aromatic vinyl monomers are added. You may copolymerize.

Examples of the conjugated diene monomer which constitutes the above block copolymer include 1,3-butadiene and isoprene. In the block structure of the block copolymer, a polymer block composed of an aromatic vinyl unit is represented by S, and a polymer block composed of a conjugated diene and / or its partially hydrogenated unit is represented by B. In this case, SB, S (BS) n, (where n is 1 to 3)
, S (BSB) n, (where n is an integer of 1 to 2) linear-block copolymer, or (SB) nX.
(However, n is an integer of 3 to 6. X is a residue of a coupling agent such as silicon tetrachloride, tin tetrachloride, and a polyepoxy compound.)
The star shape with the part B as the bond center
It is preferably a block copolymer. Above all, SB
2 type, SBS type 3 and SBBS type 4 linear-block copolymers are preferred.

In the present invention, one polyphenylene ether as the component (A) is a homopolymer and / or a copolymer having an aromatic ring in the main chain, and these are linked by an ether bond. , Poly (2,6-dimethyl-1,4
-Phenylene ether), a copolymer of 2,6-dimethylphenol and 2,3,6-trimethylphenol, and the like, among which poly (2,6-dimethyl-1,4-phenylene ether) is preferable. The method for producing such polyphenylene ether is not particularly limited, and for example, a complex of a cuprous salt and an amine according to the method described in U.S. Pat. No. 3,306,874 is used as a catalyst, for example, 2, It can be easily produced by oxidative polymerization of 6-xylenol.
06,875, U.S. Pat. No. 3,257,357.
U.S. Pat. No. 3,257,358, Japanese Patent Publication No. 52-17880, and Japanese Patent Laid-Open No. 50-5119.
It can be easily manufactured by the method described in Japanese Patent Publication No.

The polyphenylene ether used in the present invention
The reduced viscosity ηsp / c (0.5 g / dl, chloroform solution, measured at 30 ° C.) of Tell is 0.20 to 0.70 dl /
g is preferably in the range of 0.30 to 0.60d
It is more preferably in the range of 1 / g. Examples of means for satisfying the above requirements regarding the reduced viscosity ηsp / c of polyphenylene ether include adjustment of the catalyst amount in the production of the polyphenylene ether.

The inorganic compound (B) in the present invention is not particularly limited as long as it satisfies the requirement of the average particle diameter of the present invention. For example, silicon oxide, aluminum oxide, iron oxide, cesium oxide, zinc oxide, titanium oxide, yttrium oxide, zirconium oxide, tin oxide, copper oxide, magnesium oxide, manganese oxide, molybdenum oxide, calcium zinc molybdate, zinc molybdate, Zinc phosphate, holmium oxide, metal oxides such as cobalt blue (CoO ・ Al ₂ O ₃ ) or composite oxides such as Al ₂ O ₃ / MgO, metals such as iron, silicon, tungsten, manganese, nickel and platinum, Examples include non-metals such as carbon and graphite, and metal carbides such as silicon carbide, boron carbide and zirconium carbide. Among them, metal oxides are preferable, and silicon oxide and aluminum oxide are particularly preferable.

The metal oxides preferred in (B) are produced by a liquid phase method or a vapor phase method, but the vapor phase method is preferable in terms of dispersibility, and US Pat. No. 5,460,701 (corresponding Japanese Patent Publication No. 2000-24493) is used. Japanese Patent Publication). Such metal oxides are sold, for example, by Nanophase Technology Inc. in the US as ultrafine particle nanotechs. Further, a metal molybdate of Sherwin-Williams, USA can also be preferably used.

Among the compounds of (B), silicon oxide is extremely preferable. Silicon oxide is also referred to as synthetic silica, and when roughly classified, there are two synthetic methods, a wet method and a dry method. The former is
There are those synthesized by the reaction of sodium silicate and mineral acid, those by hydrolysis of alkoxysilane, and the like. The latter includes those synthesized by high temperature hydrolysis of silicon halide in an oxyhydrogen flame. Such synthetic silica is preferably amorphous.

The amorphous silica (B) is produced by adding an acid to a mixture of water and an alkali metal silicate at 60 to 90 ° C. Water and / or silicate may be heated separately or may be mixed and heated at the same time.
The alkali metal silicate is, for example, an alkali metal or alkaline earth metal salt of meta or disilicate, and is not particularly limited. Further, it is preferable to use an electrolyte such as sodium sulfate as a reaction medium.

As another preferable synthetic silica, there is a hydrophilic or hydrophobic fumed silica referred to as fumed silica, and hydrophobic fumed silica is particularly preferable. Such fumed silica is disclosed in
It is manufactured by the method described in JP-A-000-86227, and can be manufactured by a dry method in which silicon tetrachloride and hydrogen, oxygen, and water are used for high-temperature hydrolysis. For example, it is obtained by using a volatile silicon compound as a raw material, and heating and decomposing it in a flame burned by supplying it to a burner together with a mixed gas containing a combustible gas and oxygen at a high temperature of 1000 to 2100 ° C. As the volatile silicon compound as a raw material, for example, a volatile silicon halide compound is preferable,
_{SiH 4, SiCl 4, CH 3} SiCl 3, CH 3 SiHCl 2, HSiCl 3, (CH 3) 2 SiCl 2,
(CH ₃ ) ₃ SiCl, (CH ₃ ) ₂ SiH ₂ , (CH ₃ ) ₃ SiH, alkoxysilanes and the like can be mentioned. The mixed gas containing a combustible gas and oxygen is preferably one that can generate water, hydrogen, methane, butane, etc. are suitable as the combustible gas, and oxygen, air, etc. are used as the oxygen-containing gas.

The amount ratio of the volatile silicon compound to the mixed gas is such that the molar equivalent of the volatile silicon compound is 1 molar equivalent and the molar equivalent of oxygen in the mixed gas containing oxygen and hydrogen which is a flammable gas is 2.5 to. 3.5, and the molar equivalent of hydrogen is 1.5 to
Adjust to a range of 3.5. The molar equivalents of oxygen and hydrogen are the raw material compounds (volatile silicon compounds).
Refers to the stoichiometric equivalent that reacts with. When a hydrocarbon fuel such as methane is used, it means a molar equivalent in terms of hydrogen. To reduce the average particle size of silica, hydrogen and oxygen are used in excess with respect to 1 mol of the volatile silicon compound, so that the solid (silica) / gas (oxygen, hydrogen) ratio in the reaction mixture is reduced. However, this can be achieved by reducing collisions between solid particles and suppressing particle growth due to melting.

Yet another preferred synthetic silica is the synthetic silica manufactured by the above-mentioned vapor phase process manufactured by Nanophase Technology, Inc. of the United States. And, one of the preferable synthetic silica is Polyhedral Oligomeric Silsesquioxane (P
OSS) and is manufactured by the organic-inorganic hybrid method. The method of surface-treating the compound (B) is not particularly limited, but it is preferable to use a surface-treating agent having a functional group capable of reacting or interacting with the inorganic compound. For example, (B) is surface-coated with a silicon-containing compound and an aromatic group-containing compound or polymer, particularly one or more compounds selected from a compound or polymer containing an aromatic group and silicon.

For example, in the case of the most preferred synthetic silica as (B), a method of forming a bond by surface-treating the silica with a polymer having a functional group capable of reacting with the silanol group of silica, a silane coupling agent, or the like is given. be able to. The polymer having a functional group capable of reacting with the silanol group of silica is a rubber-like polymer defined as (A),
It is a polymer in which a functional group is bonded to a polymer such as a thermoplastic resin or a thermosetting resin, and the polymer itself is not particularly limited, but is, for example, the same as, or compatible with, or interacting with (A). Coalescence is preferred. Examples of functional groups capable of reacting with silanol groups include epoxy groups, hydroxyl groups, isocyanate groups, ester groups such as maleic acid esters, amino groups, carboxylic acid groups, and maleic acid groups. When a styrene polymer is used as (A), one of the preferable surface treatment agents is an epoxy-modified styrene polymer.

As another surface treating agent capable of reacting with the silanol group of silica, a silane coupling agent and the like can be mentioned. Treatment using it, for example, dimethyldichlorosilane treatment, hexamethyldisilazane treatment, octylsilane treatment, methacryloxysilane treatment, aminosilane, hexamethyldisilazane treatment, and dimethylsilicone oil treatment, diphenyldichlorosilane treatment, methylphenyldisilane Those treated with chlorosilane, hexaphenyldisilazane, phenylalkylsilane, phenylmethacryloxysilane, phenylaminosilane, and phenyl group-containing silicone oil can be preferably used. Among them, dimethyl silicone oil treatment, diorganosilicone treatment such as methylphenyl silicone treatment, or dialkyldihalosilane treatment such as dimethyldichlorosilane treatment, diphenyl silicone oil treatment, aromatic group-containing organosilicone treatment such as methylphenyl silicone treatment, or The aromatic group-containing dihalosilane treatment such as diphenyldichlorosilane treatment and phenylalkyldichlorosilanesilane treatment is most preferable.

The surface treatment is carried out, for example, by Japanese Patent Laid-Open No. 9-3100.
No. 27, No. 9-59533, No. 6-87609, the silica is put in a container equipped with a stirrer such as a Henschel mixer, and various surface treatment agents are added while stirring, preferably. It can be performed by spraying and uniformly mixing. When performing surface treatment with a polymer, a polymerizable monomer such as styrene in the presence of silica is treated with a radical initiator or a photosensitizer, and the silica surface is coated with a polymer such as polystyrene by heat treatment or light irradiation. To do. The concrete method is Y. Shirai, Jou
rnal of Polymer Science: Part A: Polymer Chemistry, v
ol.39,2157-2163 (2001); N.Tsubokawa, ibid., vol.30,2241.
-2246 (1992).

The POSS manufactured by Hybrid Plastics, Inc. of the United States contains synthetic silica surface-coated with a low-molecular compound or a polymer, for example, alcohol, phenol, amine, chlorosilane, epoxy, ester,
It is surface-coated with various polymers such as fluoroalkyl, halide, isocyanate, methacrylate, acrylate, silicone, nitrile, norborenyl, olefin, phosphine, silane, thiol, and polystyrene.

The amount of (B) is 0.001 to 200 parts by weight, and preferably 0.001 to 100 parts by weight of (A).
01 to 100 parts by weight, more preferably 0.1 to 50 parts by weight, still more preferably 0.1 to 20 parts by weight, and most preferably 1 to 10 parts by weight. The fiber used as (C) in the present invention is a fiber in a broad sense including a filler having anisotropy including a plate-like filler, and is not particularly limited. The average fiber diameter of (C) is 0.01 to 1000 μm, preferably 0.1 to 500 μm, more preferably 1 to 100 μm, and most preferably 5 to 50 μm.
The aspect ratio (length / diameter) is 2 to 10,000, preferably 50 to 500, and more preferably 50 to 500.
300, most preferably 100-200.

If the average fiber diameter is less than 0.01 μm, the reinforcing effect is small and the mechanical strength is poor.
When it exceeds m, the dispersibility is lowered, and similarly the mechanical strength is lowered. If the aspect ratio (length / diameter) is less than 2, the anisotropy is insufficient and the flame retardancy improving effect and the reinforcing effect are small, while if it exceeds 10,000, the reinforcing effect is lost due to cutting during kneading. . The above (C) includes natural fibers such as cotton, silk, wool and hemp, regenerated fibers such as rayon and cupra, semi-synthetic fibers such as acetate and promix, polyester,
It is a synthetic fiber such as polyacrylonitrile, polyamide, aramid, polyolefin, carbon or vinyl, an inorganic fiber such as glass or asbestos, a fiber such as a metal fiber, or a filler such as a plate-shaped talc, kaolin or a viscous compound.

In the present invention, as (C), aramid fiber, polyacrylonitrile fiber and glass fiber are particularly preferable. The aramid fiber can be produced by dissolving isophthalamide or polyparaphenylene terephthalamide in an amide-based polar solvent or sulfuric acid and solution spinning by a wet or dry method. The polyacrylonitrile fiber is prepared by dissolving the polymer in a solvent such as dimethylformamide and dry-spinning it in a stream of air at 400 ° C, or wet spinning in which the polymer is dissolved in a solvent such as nitric acid and wet-spun in water. Manufactured by the method.

The fiber reinforcing effect is further promoted by subjecting (C) to a surface treatment with maleic anhydride, a silane coupling agent or the like. The amount of (C) is
It is 0.1 to 200 parts by weight, preferably 1 to 150 parts by weight, and more preferably 1 to 100 parts by weight of (A).
The amount is 0 to 100 parts by weight, more preferably 20 to 100 parts by weight, and most preferably 30 to 70 parts by weight. In the present invention, a flame retardant (D) other than (B) can be blended if necessary, and it is a sulfur-based, phosphorus-based, nitrogen-based, inorganic flame-retardant or halogen-based flame retardant.

The sulfur-based flame retardant as (D) is, for example, an organic sulfonic acid metal salt such as potassium trichlorobenzenesulfonate, potassium perfluorobutanesulfonate, potassium diphenylsulfone-3-sulfonate, or an aromatic sulfonimide. Metal salts, or styrene polymers, aromatic rings of aromatic group-containing polymers such as polyphenylene ether, sulfonic acid metal salts, metal sulfate salts, metal phosphate salts, metal borate salts, or ammonium salts of the above acids, It is a sulfur-based flame retardant such as polystyrene sulfonate alkali metal salt to which a phosphonium salt or the like is bound. Such a sulfur-based flame retardant promotes a decarboxylation reaction at the time of combustion to improve flame retardancy, particularly when polycarbonate is used as a polymer. Furthermore, in the case of polystyrene sulfonic acid alkali metal salt, the metal sulfonic acid salt itself becomes a cross-linking point at the time of combustion and greatly contributes to the formation of a carbonized film.

Examples of the phosphorus-based flame retardant (D) include organic phosphorus-based, red phosphorus-based, and inorganic phosphorus-based flame retardants. Examples of the organic phosphorus flame retardant include phosphine, phosphine oxide, biphosphine, phosphonium salt, phosphinate, phosphate ester, and phosphite ester. More specifically, triphenyl phosphate, methyl neopentyl phosphite, hentaerythritol diethyl diphosphite, methyl neopentyl phosphate, phenyl neopentyl phosphate,
Pentaerythritol diphenyl diphosphate, dicyclopentyl hypophosphite, dineopentyl hypophosphite, phenylpyrocatechol phosphite, ethylpyrocatechol phosphate, dipyrocatechol hypophosphite.

Here, as the organic phosphorus compound, an aromatic phosphoric acid ester monomer and an aromatic phosphoric acid ester condensate are particularly preferable. In the above (D), one of the phosphorus-based flame retardants is red phosphorus, which is a metal selected from aluminum hydroxide, magnesium hydroxide, zinc hydroxide, and titanium hydroxide, in addition to general red phosphorus. Those coated with a hydroxide film, aluminum hydroxide,
From a metal hydroxide selected from magnesium hydroxide, zinc hydroxide, and titanium hydroxide, and a coating treatment with a film made of a thermosetting resin, aluminum hydroxide, magnesium hydroxide, zinc hydroxide, titanium hydroxide For example, the metal hydroxide film selected may be double-coated with a thermosetting resin film.

In the above (D), one inorganic phosphorus flame retardant which is a phosphorus flame retardant is ammonium polyphosphate or a composite flame retardant of it and a nitrogen compound, or a phosphazene compound, which has an aromatic group in particular. A compound having a structure in which a phosphorus atom and a nitrogen atom are bonded by a double bond is preferable, and examples thereof include cyclic phosphazene and linear phosphazene. Among phosphazenes, from the viewpoint of compatibility with aromatic polycarbonate, it contains an aromatic group such as a phenyl group, a cresyl group, a xylyl group, and a bisphenyl group as a substituent. Specifically, phenoxypropoxyphosphazene, diphenoxyphosphazene, phenoxyaminophosphazene,
Such as phenoxyfluoroalkylphosphazene,
These phosphazene compounds are produced by substituting chlorophosphazenes with alcohols or phenols.

The nitrogen-based flame retardant as the above-mentioned (D) is typically a triazine skeleton-containing compound, and is a component for further improving the flame retardancy as a flame retardant aid for phosphorus-based flame retardants. Specific examples thereof include melamine, melam, melem, melon (product of deammonification of 3 to 3 molecules of melem at 600 ° C. or higher), melamine cyanuree.
, Melamine phosphate, succinoguanamine, adipoguanamine, methylglutaloganamin, melamine resin, B
Although T resin can be mentioned, melamine cyanurate is particularly preferable from the viewpoint of low volatility.

The inorganic flame retardant as (D) is silica, aluminum hydroxide, magnesium hydroxide, dolomite, hydrotalcite, calcium hydroxide, barium hydroxide, basic magnesium carbonate, zirconium hydroxide, Hydrate of inorganic metal compound such as hydrate of tin oxide, aluminum oxide, iron oxide, titanium oxide, manganese oxide, magnesium oxide, zirconium oxide, zinc oxide, molybdenum oxide, cobalt oxide, bismuth oxide,
Metal oxides such as chromium oxide, tin oxide, antimony oxide, nickel oxide, copper oxide, tungsten oxide, aluminum, iron, titanium, manganese, zinc, molybdenum, cobalt, bismuth, chromium, nickel, copper, tungsten, tin, antimony. Metal powder, such as zinc borate,
Examples thereof include zinc metaborate, barium metaborate, zinc carbonate, magnesium carbonate, calcium carbonate and barium carbonate. These may be used alone or in combination of two or more. Among them, especially those selected from the group consisting of magnesium hydroxide, aluminum hydroxide, basic magnesium carbonate, and hydrotalcite have a good flame retardant effect,
It is economically advantageous.

In the present invention, (D) is preferably 0.001 to 100 parts by weight, based on 100 parts by weight of (A),
More preferably 0.1 to 50 parts by weight, most preferably 1
Used at ~ 20 parts by weight. In the present invention, one selected from aliphatic hydrocarbon, higher fatty acid, higher fatty acid ester, higher fatty acid amide, higher aliphatic alcohol, metal soap, organosiloxane wax, polyolefin wax, and polycaprolactone, if necessary. Alternatively, two or more releasing agents or processing aids as a fluidity improver can be blended.

The amount of the processing aid is preferably 0.01 to 20 parts by weight, more preferably 0.5 to 10 parts by weight, and most preferably 1 to 5 parts by weight with respect to 100 parts by weight of (A).
Parts by weight. In the present invention, when light resistance is required, if necessary, an ultraviolet absorber, a hindered amine light stabilizer, an antioxidant, an active species scavenger, a light shielding agent, a metal deactivator, or a quencher. One or more light resistance improvers selected from the agents can be blended.

The amount of the light resistance improving agent is preferably 0.05 to 20 parts by weight, more preferably 0.1 to 10 parts by weight, and most preferably 1 to 5 parts by weight with respect to 100 parts by weight of (A).
Parts by weight. The suitable polymer composition thus obtained can be manufactured into various molded articles by any molding method. Injection molding, extrusion molding, compression molding, blow molding, calender molding, foam molding and the like are preferably used.

Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples, but the present invention is not limited thereto. In addition, in these Examples and Comparative Examples, the test methods used for evaluation of various physical properties are as follows. (1) Average Diameter of Fiber, Aspect Ratio The number average particle diameter of the fiber was determined by an electron microscope, while the average length of the fiber was determined by an optical microscope, and the aspect ratio was calculated from the length / diameter ratio. That is, assuming that the cross section of each fiber is a circle, the arithmetic mean of the major axis and the minor axis is the average diameter of each particle. Then, the number average particle diameter was obtained by arithmetically averaging the average diameters of 100 particles. The average length of the above fibers was similarly determined as the number average fiber length.

(2) Flame retardant VB (Vertical Bur) compliant with UL-94
The self-extinguishing property was evaluated according to the following criteria. (1/8 inch thickness test piece) ◎ Self-extinguishing within 20 seconds ○ Self-extinguishing within 20-40 seconds △ Self-extinguishing over 40 seconds × burned down

(3) Izod impact strength The Izod impact strength was measured by the method according to ASTM-D256. (23
(° C, 1/4 inch thickness test piece with V notch) (4) Extrusion stability (stability of quality) The resin composition was continuously melt-extruded for 10 hours using a melt extruder, and obtained every hour. The Izod impact strength of the composition was measured, and the continuous productivity (quality stability) was evaluated from the rate of change (%) with respect to the average strength.

(5) Flexural Modulus Measured at 23 ° C. by a method according to JIS K6758. The following components were used as the components used in Examples and Comparative Examples. (A) Polymer Abbreviated in parentheses as follows. Bisphenol A type polycarbonate (PC), nylon 6 (PA6), polyethylene terephthalate (PET), polybutylene terephthalate (PBT), rubber modified polystyrene (HIP)
S), ABS resin (ABS), styrene-ethylene-butylene-styrene copolymer (SEBS), styrene-butadiene copolymer (SB), polyphenylene ether (PPE), polypropylene (PP), ethylene-octene copolymer (EO), EO-PP crosslinked product (TPV) where TPV is EO / PP = 50/50 (weight ratio)
It is a thermoplastic polypropylene dynamically cross-linked in a twin-screw extruder using organic peroxide and triallyl isocyanurate.

(B) Inorganic compound By the method described in JP-A-2000-86227,
It was synthesized by high-temperature hydrolysis of silicon tetrachloride in an oxyhydrogen flame to produce silica having different average particle sizes. Specifically, 1.0 molar equivalent of silicon tetrachloride is supplied to a burner together with a mixed gas of oxygen and hydrogen preheated to 60 ° C. (oxygen 2.69 molar equivalent, hydrogen 1.60 molar equivalent) to burn ( 1
(600 ° C.) to produce fine particle silica. The control of the average particle diameter was performed by changing the molar equivalent ratio of oxygen and hydrogen to 1.0 molar equivalent of silicon tetrachloride.

Metal oxides other than silica are described in US Pat. No. 5,460,701 (corresponding Japanese Patent Publication No. 2000-2449).
It was manufactured by the gas phase method disclosed in Japanese Patent No. 3).
Then, the surface was coated with various surface treatment agents. The surface treatment method is described, for example, in JP-A-9-310027 and 9-595.
33, 6-87609, for example, after putting the silica in a closed Henschel mixer and replacing the inside of the container with nitrogen gas, various treating agents are added to 100 parts by weight of silica while stirring. 20 parts by weight was spray mixed. After that, heating and stirring were continued at 250 ° C. for 30 minutes and then cooled to room temperature to produce surface-treated silica. When the surface is coated with dimethyl silicone, polyether-modified dimethyl silicone (manufactured by Shin-Etsu Chemical Co., Ltd., trade name:
KF618) was used. Similarly, dimethyldichlorosilane treatment, hexamethyldisilazane treatment, methacryloxysilane treatment, diphenyldichlorosilane treatment, and methylphenyldichlorosilane treatment were performed. When the surface is coated with a polymer, the polymerizable monomer is added to Y. Shirai, Journal of
Polymer Science: Part A: Polymer Chemistry, vol.39,21
57-2163 (2001); N. Tsubokawa, ibid., Vol. 30, 2241-2246 (19
It was carried out by carrying out graft polymerization by the method disclosed in 92). For other surface coatings, Hybrid
Polyhedral Oligomeric Sil manufactured by Plastics
sesquioxane (POSS) was used. The various inorganic compounds described above are shown in Tables 1 to 8.

(C) Fiber (1) Glass fiber (GF) When silica glass is produced by melt spinning, the average fiber diameter is controlled by the size of the spinneret, and the aspect ratio (length / diameter) is cut. Controlled by speed. (2) Carbon fiber (CF) When melt-spun polyacrylonitrile, the average fiber diameter was controlled by the size of the spinneret, and the aspect ratio (length / diameter) was controlled by the cutting speed.

(D) Flame retardant (1) Organic sulfonic acid metal salt manufactured by Dainippon Ink and Chemicals, Inc., potassium perfluorobutane sulfonate (SF) (2) Bisphenol A bis (diphenyl phosphate) Daihachi Chemical Industrial Co., Ltd. [Product name CR741 (referred to as P1)] (3) 1,3-phenylene bis (diphenyl phosphate) Daihachi Chemical Industry Co., Ltd., resorcin-derived aromatic condensed phosphate ester [Product name] CR733S (referred to as P2)] (4) 1,3-phenylene bis (dixylyl phosphate) manufactured by Daihachi Chemical Industry Co., Ltd., [trade name PX200 (referred to as P3)] (5) Akarin Phosphorus Chemical Co., Ltd. ), [Product name: Nova Excel (P4
(6) Ammonium polyphosphate manufactured by Chisso Co., Ltd., [trade name: Terrage (referred to as P5)] (7) Phenoxyphosphazene (referred to as P6) (8) Magnesium hydroxide Kyowa Chemical Industry Co., Ltd. Product name: Kisuma (referred to as MOH) (9) Melamine cyanurate Nissan Chemical Co., Ltd. [Product name: MC610 (referred to as M1)] (10) Polytetrafluoroethylene Daikin Industries Co., Ltd. (PTFE) Called)

[0055]

Examples 1 to 82 and Comparative Examples 1 to 8 In a Henschel mixer, the compositions shown in Tables 1 to 8 were mixed, and then a twin-screw extruder (40 mm) having an injection port at the center of the barrel was used.
φ, L / D = 47), and under the temperature condition of 240 ° C, 1
Continuous melt extrusion was performed for 0 hours. As the screw, a double thread screw having a kneading section before and after the injection port was used. From the composition thus obtained, the cylinder set temperature 2
A molded body was produced by injection molding at 50 ° C. and a mold temperature of 80 ° C. and evaluated. The results are shown in Tables 1-8.

[0056]

[Table 1]

[0057]

[Table 2]

[0058]

[Table 3]

[0059]

[Table 4]

[0060]

[Table 5]

[0061]

[Table 6]

[0062]

[Table 7]

[0063]

[Table 8]

[0064]

The flame-retardant fiber-reinforced polymer composition of the present invention is excellent in mechanical strength such as impact strength and rigidity and extrusion stability. The composition of the present invention comprises a VTR, a distribution board,
Home appliances housings such as TVs, audio players, condensers, household outlets, radio-cassettes, video cassettes, video disc players, air conditioners, humidifiers, electric warm air machines, chassis or parts, CD-
ROM main frame (mechanical chassis), printer, fax, PPC, CRT, word processor copying machine, electronic cash register, office computer system, floppy disk drive, key Board,
OA equipment housings such as type, ECR, calculator, toner cartridge, telephone, chassis or parts, connector,
Coil bobbin, switch, relay, relay socket, L
ED, variable condenser, AC adapter, FBT high pressure bobbin,
Electronic and electrical materials such as FBT cases, IFT coil bobbins, jacks, volume shafts and motor parts, and instrument panels, radiator grills, clusters, speaker grills, louvers. -, Suitable for automotive materials such as console boxes, defroster garnishes, ornaments, fuse boxes, relay cases, connector shift tapes, etc., and play a major role in these industries. .

Continued front page    F term (reference) 4J002 AB022 BB011 BB012 BC031                       BD031 BG051 BG102 BN061                       BN121 BN151 CF001 CF032                       CG011 CH061 CL001 CL012                       CL032 CL062 CN021 DA017                       DA026 DA036 DA086 DE076                       DE096 DE106 DE116 DE136                       DE146 DE186 DJ016 DJ046                       DL007 DM006 DM007 FA042                       FA047 FB096 FD012 FD016                       FD017

Claims (7)

[Claims] 1. An (A) polymer and (B) an average particle size of 1 n.
an inorganic compound of m or more and less than 1000 nm, and (C) an average fiber diameter of 0.01 to 1000 μm,
A flame-retardant fiber-reinforced polymer composition comprising a fiber having an aspect ratio (length / diameter) of 2 to 10,000. 2. The method according to claim 1, wherein (B) is surface-coated with one or more compounds selected from silicon-containing compounds and aromatic group-containing compounds or polymers. Flame retardant fiber reinforced polymer composition. 3. The flame-retardant fiber-reinforced polymer composition according to claim 1, wherein (A) is an aromatic thermoplastic polymer. 4. The flame-retardant fiber-reinforced polymer composition according to claim 3, wherein (A) is an aromatic polycarbonate. 5. The flame-retardant fiber-reinforced polymer composition according to any one of claims 1 to 4, wherein (B) is surface-coated with a polyorganosiloxane. 6. The flame-retardant fiber-reinforced polymer composition according to any one of claims 1 to 5, wherein (B) is a metal oxide. 7. The flame-retardant fiber-reinforced polymer composition according to any one of claims 1 to 6, wherein (B) is silicon oxide and / or aluminum oxide.