JP2003292793A - Flame-retardant composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To obtain a flame-retardant composition to which preferential flame retardancy, water resistance, and extrusion stability (quality stability) can be imparted. <P>SOLUTION: This flame-retardant composition comprising (A) a polymer and (B) an inorganic function-imparting agent which has an average particle diameter of 1 to 1,000 nm and comprises an inorganic compound whose surface is coated with one or more compounds selected from silicon-containing compounds, aromatic group-having compounds and polymers, is characterized in that the content of at least one metal selected from the group consisting of Ia, IIa, Ib, IIb, and IIIb in the composition is &le;1,000 ppm. <P>COPYRIGHT: (C)2004,JPO

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a flame retardant composition. More specifically, it relates to a flame retardant composition capable of imparting excellent flame retardancy, water resistance, and extrusion stability (quality stability).

[0002]

2. Description of the Related Art Plastics such as a thermoplastic resin or a thermosetting resin, rubber, metal or glass have excellent material properties, and are therefore used as automobile materials, home electric appliances materials, and OA.
It is used in various fields such as equipment materials, packaging materials, and building materials. However, in response to the recent demand for high quality or functionality of users, there are problems such as flame retardancy in the case of polymers such as plastics and rubber, and the development of a resin composition having excellent flame retardancy is required. It has been demanded. For example, as a method for improving flame retardancy, it is known to add an inorganic compound or the like to a resin, and although the properties have been improved to some extent by this, problems such as deterioration of mechanical properties have newly occurred. .

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 size of 1 to 1000 μm, a thermoplastic resin containing silicone and an inorganic substance is used. A flame-retardant resin composition (JP-A-11-140329) to which a mixture of the above is added, and the average particle size of polydiorganosiloxane gum and silica is 1 to 100.
Resin composition of 0 μm 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 size of the inorganic compound used in the above publication is large, the flame retardancy, the functions such as mechanical strength are not sufficient, and a flame retardant composition having excellent performance that can withstand practical use is sought. Has been.

[0004]

In view of the above situation, the present invention can provide the above-mentioned problems, that is, excellent flame retardancy, water resistance and extrusion stability (quality stability). The present invention aims to provide a flame-retardant composition.

[0005]

Means for Solving the Problems As a result of diligent studies of an excellent flame retardant composition, the present inventors have surprisingly found that a specific inorganic compound dramatically improves the flame retardancy,
The present invention has been completed. That is, the present invention comprises (A) a polymer, (B) a silicon-containing compound, a compound containing an aromatic group, and an inorganic compound whose surface is coated with one or more compounds selected from the polymers. Particle size is 1 nm or more 1
A flame-retardant composition comprising an inorganic function-imparting agent having a size of less than 000 nm, wherein Ia, IIa, Ib and I are contained in the composition.
A flame-retardant composition, characterized in that the content of at least one metal selected from the group consisting of Ib and IIIb is 1000 ppm or less.

[0006]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention is described in detail below.
The composition of the present invention comprises (A) a polymer and (B) a specific inorganic function-imparting agent. Here, (B) is an inorganic compound surface-coated with at least one compound selected from the group consisting of a silicon-containing compound, a compound containing an aromatic group, and a polymer. And the average particle diameter of (B) is 1 nm.
It is essential that the thickness is less than 1000 nm, preferably 1 to 900 nm, more preferably 1 to 700 n.
m, most preferably 1 to 500 nm, very preferably 1 to 100 nm. Furthermore, I in the flame retardant composition
The content of the metal selected from a, IIa, Ib, IIb, and IIIb is 1000 ppm or less, preferably 100 ppm or less, more preferably 50 ppm or less, most preferably 10 ppm or less, and most preferably 1 ppm or less. . It has been found that, by satisfying the above requirements, the dispersibility of (B) in (A) is improved, and as a result, flame retardancy, water resistance, extrusion stability, etc. are improved.
The present invention has been completed.

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, or a base material such as a metal or glass. Among them, the polymer is preferable, and the heat is particularly preferable. Most preferred are plastic resins. The most preferable thermoplastic resin of (A) in the present invention is, for example, polyaromatic vinyl-based, polycarbonate-based, polyphenylene ether-based, polyolefin-based, polyvinyl chloride-based, polyamide-based, polyester-based, polyphenylene sulfide-based, polymethacrylate. A single system or a mixture of two or more types can be used. Especially polyaromatic vinyl type, polycarbonate type,
A polymer containing an aromatic group such as a polyphenylene ether-based thermoplastic polymer is preferable. Among them, aromatic vinyl polymer alone, aromatic polycarbonate alone, a resin mainly composed of polyphenylene ether or aromatic polycarbonate is very preferable, for example, a blended product of aromatic polycarbonate and aromatic vinyl polymer, or aromatic polycarbonate, Most preferred is a blended product of an aromatic vinyl polymer and polyphenylene ether.

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 polyaromatic vinyl polymer as the component (A) in the present invention is at least one 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-polymer). 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), and poly (acrylonitrile-butadiene), and saturated rubbers obtained by hydrogenating the above diene rubbers, isoprene rubbers, chloroprene rubbers, polyacrylics. Acrylic rubbers such as butyl acid and ethylene-propylene-diene monomer terpolymers (EPDM) can be mentioned, and diene rubbers are particularly preferable.

The aromatic vinyl monomer which is an essential component in the graft-polymerizable monomer mixture to be polymerized in the presence of the above 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. Preferably 9
It is in the range of 0 to 50% by weight. Within this range, the balance between impact resistance and rigidity of the desired resin composition is improved. Further, the rubber particle size of the styrene 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 a rubber-modified aromatic vinyl resin, a uniform polymerization stock solution composed of a rubber-like 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. Block copolymer. The aromatic vinyl monomer constituting the block copolymer is, for example, styrene, α-methylstyrene, paramethylstyrene, p-chlorostyrene, p-bromostyrene, 2,4,5-tribromostyrene, or the like. However, styrene is the most preferable, but the above-mentioned other aromatic vinyl monomer may be copolymerized mainly with styrene.

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 an integer of 1 to 3), S (BSB) n, (where n is an integer of 1 to 2)
Or a (SB) nX (where n is an integer of 3 to 6, X is a coupling agent residue such as silicon tetrachloride, tin tetrachloride, and a polyepoxy compound). It is preferably a star block copolymer having the B portion as the bonding center. Among them, SB type 2, SBS type 3, and SBSB type 4 linear-block copolymers are preferable.

In the present invention, one polyphenylene ether as the component (A) is a homopolymer and / or copolymer having an aromatic ring in the main chain, and these are linked by an ether bond, and specifically, , 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 a polyphenylene ether is not particularly limited, and for example, a complex of a cuprous salt and an amine according to the method described in US Pat. No. 3,306,874 is used as a catalyst, and, for example, 2,6-xylenol is used. It can be easily produced by oxidative polymerization of propylene.
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. Reduced viscosity ηs of the polyphenylene ether used in the present invention
p / c (0.5 g / dl, chloroform solution, measured at 30 ° C.) is preferably in the range of 0.20 to 0.70 dl / g, and is in the range of 0.30 to 0.60 dl / g. Is more preferable. Examples of means for satisfying the above requirements regarding the reduced viscosity ηsp / c of the polyphenylene ether include adjustment of the catalyst amount in the production of the polyphenylene ether.

The inorganic compound in the component (B) in the present invention is not particularly limited as long as it satisfies the requirements of the surface coating with the surface treatment agent and the average particle diameter of the requirements of the present invention.
Examples of the inorganic compound (B) include 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, cobalt blue (CoO ・ A
l ₂ O ₃ ) or other metal oxides or Al ₂ O ₃ / MgO or other composite oxides,
Metals such as iron, silicon, tungsten, manganese, nickel and platinum, non-metals such as carbon and graphite, and metal carbides such as silicon carbide, boron carbide and zirconium carbide,
Of these, metal oxides are preferable, and silicon oxide and aluminum oxide are particularly preferable.

The metal oxide preferred in (B) in the present invention is produced by a liquid phase method or a vapor phase method, and the vapor phase method is preferable from the viewpoint of dispersibility, and US Pat. No. 5,460,701 (corresponding Japanese Patent Publication). 2000-24493). 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. Amorphous silica (B) is added to a mixture of water and alkali metal silicate at 60-90.
Produced by adding acid at ° 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.

[0021] As another preferable synthetic silica, there is a hydrophilic or hydrophobic fumed silica called 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. The mixed gas containing a combustible gas and oxygen is preferably one capable of producing water, hydrogen, methane, butane, etc. are suitable as the combustible gas, and oxygen, air, etc. are used as the oxygen-containing gas.

The molar 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 hydrogen molar equivalents of 1.5-3.
Adjust to the range of 5. Here, the molar equivalents of oxygen and hydrogen refer to stoichiometric equivalents that react with each raw material compound (volatile silicon compound). 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 Nanophase Technology, Inc. manufactured by the above-mentioned vapor phase method. And, one of the preferable synthetic silica is Polyhedral Oligomeric Silsesquioxane (P
OSS) and is manufactured by the organic-inorganic hybrid method. The surface treatment method for the compound (B) is not particularly limited, but it is preferable to use a surface treatment agent having a functional group capable of reacting or interacting with the inorganic compound. For example, (B) is surface-coated with one or more compounds selected from silicon-containing compounds, aromatic group-containing compounds, especially compounds containing an aromatic group and silicon, and polymers.

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 polymer having a functional group bonded to a polymer such as a rubber-like polymer, a thermoplastic resin, or a thermosetting resin described in (A). Although the polymer itself is not particularly limited, for example, a polymer having the same or compatibility or interaction with (A) is preferable. 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. For example, dimethyldichlorosilane treatment, hexamethyldisilazane treatment, octylsilane treatment, methacryloxysilane treatment, aminosilane, hexamethyldisilazane treatment, and dimethylsilicone oil treatment, diphenyldichlorosilane treatment, methylphenyldichlorosilane treatment, hexaphenyldisilazane treatment. Those treated with phenylalkylsilane, phenylmethacryloxysilane, phenylaminosilane, and phenyl group-containing silicone oil can be preferably used.
Among them, diorganosilicone treatment such as dimethylsilicone oil treatment and methylphenylsilicone treatment or dialkyldihalosilane treatment such as dimethyldichlorosilane treatment, aromatic group-containing organosilicone treatment such as diphenylsilicone oil treatment and methylphenylsilicone treatment, or diphenyldiene The aromatic group-containing dihalosilane treatment such as chlorosilane treatment and phenylalkyldichlorosilane silane treatment is most preferable.

The surface treatment is carried out, for example, in 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 the surface treatment with a polymer is performed, a polymerizable monomer such as styrene is heat-treated or irradiated with a radical initiator or a photosensitizer in the presence of silica to coat the silica surface with a polymer such as polystyrene. . The concrete method is Y.Shirai, Journ
al ofPolymer Science: Part A: Polymer Chemistry, vol.
39, 2157-2163 (2001); N. Tsubokawa, ibid., Vol. 30, 2241-22.
46 (1992).

[0027] 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 content of the metal selected from Ia, IIa, Ib, IIb, and IIIb is controlled by the number of washings after the production of (B) or the addition amount of the above-mentioned metal to the final composition, and is controlled by a usual fluorescent X-ray. It can be quantified.
The amount of (B) is 0.00 with respect to 100 parts by weight of (A).
1 to 200 parts by weight, preferably 0.01 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. In the present invention, other flame retardant (C) may be used in combination with (B) of the present invention, if necessary.

The other flame retardant (C) is a sulfur type, phosphorus type, nitrogen type, inorganic type flame retardant, halogen type flame retardant, or fibrous flame retardant. Examples of the sulfur-based flame retardant as (C) above include organic sulfonic acid metal salts such as potassium trichlorobenzene sulfonate, potassium perfluorobutane sulfonate, potassium diphenylsulfone-3-sulfonate, aromatic sulfonimide metal salts, and the like. Or styrene-based polymer, the aromatic ring of the aromatic group-containing polymer such as polyphenylene ether, sulfonic acid metal salt,
It is a sulfur-based flame retardant such as a polystyrene sulfonic acid alkali metal salt to which a metal sulfate, a metal phosphate, a metal borate or an ammonium salt or a phosphonium salt of the above acid 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. Further, in the case of polystyrene sulfonic acid alkali metal salt, the metal sulfonic acid salt itself becomes a cross-linking point during combustion and greatly contributes to the formation of a carbonized film.

Examples of the phosphorus-based flame retardant (C) 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 (C), one of the phosphorus-based flame retardants is red phosphorus, in addition to general red phosphorus, the surface thereof is a metallic water previously selected from aluminum hydroxide, magnesium hydroxide, zinc hydroxide, and titanium hydroxide. Those coated with an oxide film, those coated with a film composed of a metal hydroxide selected from aluminum hydroxide, magnesium hydroxide, zinc hydroxide, titanium hydroxide and a thermosetting resin, and hydroxylated For example, a metal hydroxide selected from aluminum, magnesium hydroxide, zinc hydroxide, and titanium hydroxide may be doubly coated with a thermosetting resin film.

In the above (C), one of the phosphorus-based flame retardants is an inorganic phosphorus-based flame retardant, which is ammonium polyphosphate or a composite flame retardant of the same and a nitrogen compound, or a phosphazene-based compound, and particularly has an aromatic group. 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 component (C) is typically a compound containing a triazine skeleton, and is a component for further improving the flame retardancy as a flame retardant aid for phosphorus flame retardants. Specific examples thereof include melamine, melam, melem, melon (a product obtained by deammonification of 3 molecules of melem at 600 ° C. or higher), melamine cyanurate,
Examples thereof include melamine phosphate, succinoguanamine, adipoguanamine, methylglutaloganamin, melamine resin, and BT resin, and melamine cyanurate is particularly preferable from the viewpoint of low volatility.

The inorganic flame retardant as (C) 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, those selected from the group consisting of magnesium hydroxide, aluminum hydroxide, basic magnesium carbonate and hydrotalcite have a good flame retarding effect and are economically advantageous.

In the present invention, the fibrous flame retardant used as (C) is a fiber in a broad sense that also includes a filler having anisotropy including a plate-shaped filler, and is not particularly limited. The average fiber diameter of the fibrous flame retardant is 0.01 to 10
00 μm, preferably 0.1 to 500 μm, more preferably 1 to 100 μm, and most preferably 5 to 50 μm.
m, and the aspect ratio (length / diameter) is 2 to 10
000, preferably 50 to 500, more preferably 50 to 300, and most preferably 100 to 200. Further, specific examples of the fibrous flame retardant, cotton, silk, wool, natural fibers such as hemp, rayon, recycled fibers such as cupra, acetate, semi-synthetic fibers such as Promix, polyester, polyacrylonitrile, polyamide, aramid, Polyolefin, carbon, synthetic fiber such as vinyl, glass, inorganic fiber such as asbestos, fiber such as metal fiber or plate-shaped talc, filler such as kaolin or viscous compound, especially aramid fiber, polyacrylonitrile fiber, glass fiber Is preferred.

In the present invention, (C) is preferably 0.001 to 100 parts by weight with respect to 100 parts by weight of (A),
More preferably 0.1 to 50 parts by weight, most preferably 1
~ 20 parts by weight. In the present invention, if necessary,
One or more release agents selected from aliphatic hydrocarbons, higher fatty acids, higher fatty acid esters, higher fatty acid amides, higher aliphatic alcohols, metal soaps, organosiloxane waxes, polyolefin waxes, polycaprolactones A processing aid as an agent can be blended.

In the present invention, when light resistance is required, an ultraviolet absorber, a hindered amine light stabilizer, an antioxidant, an active species scavenger, a light shielding agent, a metal deactivator, or, if necessary, One or more light resistance improvers selected from quenchers can be blended. In the present invention, the release agent, the processing aid, and the light resistance improver are preferably 0.001 to 100 parts by weight, more preferably 0.1 to 50 parts by weight, relative to 100 parts by weight of (A). Most preferably, it is 1 to 20 parts by weight.

In the present invention, the following may be mentioned as examples of particularly preferable embodiments. (A)
As polymers, bisphenol A type polycarbonate (PC), nylon 6 (PA6), polyethylene terephthalate (PET), polybutylene terephthalate (P
BT), polytetramethylene terephthalate (PT
T), rubber modified polystyrene (HIPS), ABS resin (ABS), styrene-ethylene-butylene-styrene copolymer (SEBS), maleic anhydride modified SEBS
(M-SEBS), styrene-butadiene copolymer (S
B), polyphenylene ether (PPE), polypropylene (PP), ethylene-octene copolymer (EO),
EO-PP crosslinked product [TPV: EO / PP = 50/50
It is a thermoplastic polypropylene dynamically crosslinked by a twin-screw extruder using (by weight) an organic peroxide and triallyl isocyanurate. ], And especially PC, PP
Polymer alloys obtained by E, HIPS alone or a combination thereof are preferable, and P is extremely preferable.
It is a polymer alloy of C alone or PC and other polymers. For example, PC / ABS, PC / HIPS, PC / PBT, PC / TPV, PC
/ SEBS, PC / M-SEBS, PC / PPE, PC / PPE / HIPS. The composition ratio of the polymer alloy is 100 parts by weight of PC,
The other polymer is 0.001 to 10000 parts by weight, preferably 0.1 to 100 parts by weight, and very preferably 1 to 5 parts by weight.
0 parts by weight.

The inorganic compound as (B) is preferably silicon dioxide SiO ₂ having a primary particle size of 10 to 100 nm, especially 10 to 50 nm, and its surface contains a silicon-containing compound, a compound containing an aromatic group, It is coated with one or more compounds selected from polymers. At that time, it is preferable that the coating is not performed by physical adsorption but by a strong bond such as a covalent bond. Specific examples of the surface coating include styrene-based polymer treatment containing active halogen or epoxy group, dimethyldichlorosilane treatment, hexamethyldisilazane treatment, octylsilane treatment, methacryloxysilane treatment, aminosilane, hexamethyldisilazane treatment. Those treated with dimethyl silicone oil, diphenyldichlorosilane, methylphenyldichlorosilane, hexaphenyldisilazane, phenylalkylsilane, phenylmethacryloxysilane, phenylaminosilane, and phenyl group-containing silicone oil are preferred. Can be used for.
Among them, dimethyl silicone oil treatment, methylphenyl silicone treatment, dimethyldichlorosilane treatment, diphenylsilicone oil treatment, methylphenylsilicone treatment, diphenyldichlorosilane treatment, phenylalkyldichlorosilanesilane treatment, among others, styrene containing active halogen or epoxy group Polymer treatment,
Dimethyldichlorosilane treatment, hexamethyldisilazane treatment, dimethyl silicone oil treatment, and methylphenyldichlorosilane treatment are particularly preferable. The treatment amount is 0.0001 to 10,000 with respect to 100 parts by weight of silicon oxide.
Parts by weight, more preferably 0.01 to 1000 parts by weight, most preferably 0.1 to 100 parts by weight. As the inorganic compound other than silicon oxide as (B), Al ₂ O ₃ , CeO ₂ , TiO
₂ , Y ₂ O ₃ , ZnO, ZrO ₂ , SnO ₂ , CuO, Fe ₂ O ₃ , MgO, Mn ₃ O ₄ , Ho ₂ O ₃ , Al _{2
O 3 / MgO, ZnMoO 4,} MgO 4 SiO 2, CaMoO 4, CaCO 3, Zn 3 (PO 4) 2 and the like, it is preferred to surface-coated with the same surface treatment agent.

When higher flame retardancy is required, it can be achieved by using the following flame retardant in combination. For example, in the case of PC alone or a polymer alloy mainly containing PC as the polymer, SF alone or the following SF,
By using PTFE together, extremely excellent flame retardancy is exhibited. The amount of SF and / or PTFE added is preferably 0.001 to 10 with respect to 100 parts by weight of the polymer.
It is 0 part by weight, more preferably 0.01 to 10 parts by weight, and most preferably 0.01 to 1 part by weight.

(1) Metal salt of organic sulfonic acid, manufactured by Dainippon Ink and Chemicals, Inc., potassium perfluorobutane sulfonate (referred to as SF) (2) Bisphenol A bis (diphenyl phosphate), manufactured by Daihachi Chemical Co., Ltd. , [Trade name CR741 (referred to as P1)] (3) 1,3-phenylene bis (diphenyl phosphate) manufactured by Daihachi Chemical Industry Co., Ltd., aromatic condensed phosphate ester derived from resorcin [trade 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) manufactured by Akarin Phosphorus Chemical Industry Co., Ltd. Name Nova Excel (P4
Called))]

(6) Ammonium polyphosphate manufactured by Chisso Co., Ltd., [trade name: Terrage (referred to as P5)] (7) Phenoxyphosphazene (P6) (8) Magnesium hydroxide manufactured by Kyowa Chemical Industry Co., Ltd., product Name Kisuma (referred to as MOH) (9) Melamine Cyanurate Nissan Chemical Co., Ltd. [trade name MC610 (referred to as M1)] (10) Polytetrafluoroethylene Daikin Industries Co., Ltd. (referred to as PTFE) The most preferable combination of the present invention is a combination of the most preferable components of each component, but extremely excellent properties are exhibited even when at least the most preferable components are contained.

For the production of the composition obtained by adding the function-imparting agent of the present invention, a Banbury mixer, a kneader, a single-screw extruder, a twin-screw extruder used for the production of ordinary resin compositions and rubber compositions are used. Although a general method such as a machine can be adopted, a twin-screw extruder is preferably used. In the twin-screw extruder, (A) and (B), and optionally (C) are uniformly and finely dispersed, and other components are added to continuously add the composition of the present invention. To manufacture,
More suitable.

The composition of the present invention may be prepared by first preparing (B) dispersed in (A) in an average particle size of the requirements of the present application in advance, and then melt-extruding it using it (or While simultaneously melt-extruding A) and (B),
(B) may be produced by simultaneously reaching the average particle of the requirements of the present application, and the production method is not particularly limited. A particularly preferable melt extrusion method has a length L in the die direction with the raw material addition section as a base point, and L / D is 5 to 100.
(Where D is the barrel diameter) when a twin-screw extruder is used. The twin-screw extruder has a plurality of supply parts of a main feed part and a side feed part which are different in distance from the tip part, and between the plurality of supply parts and between the tip part and the tip part. It is preferable that the kneading portion has a kneading portion between the feeding portion and the feeding portion at a short distance from and the length of the kneading portion is 3D to 10D, respectively. The composition thus obtained can be used to produce various molded products by any molding method. Injection molding, extrusion molding, compression molding, blow molding,
Calender molding and foam molding are preferably used.

[0044]

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 particle size of inorganic function-imparting agent The particle size of the inorganic function-imparting agent is calculated by calculating the respective particles of 500 inorganic function-imparting agents in a transmission electron micrograph dispersed in water by the following method. can get. That is, for the particle diameter of each particle, the area S of each particle is obtained, and S is used to calculate (4S
/ π) ^0.5 is set as the particle size of each particle, and the average particle size is calculated by number average. (2) Ia, IIa, Ib, IIb, and IIIb,
The content of the metal selected from was determined by the usual fluorescent X-ray method.

(3) Flame retardant VB (Vertical Bur) compliant with UL-94
self-extinguishing property is evaluated by the Ning method. (1
/ 8 inch thickness test piece) ◎: Self-extinguishing property in less than 20 seconds ○: Self-extinguishing property in 20 or more and less than 40 seconds △: Self-extinguishing property in 40 seconds or more ×: Complete firing (4) Extrusion stability (quality stability) Using a melt extruder, the resin composition is continuously melt-extruded for 10 hours, the Izod impact strength of the composition obtained is measured every hour, and the continuous productivity (quality Stability). However, the Izod impact strength is measured by a method according to ASTM-D256. (23 ° C, 1/8 inch thickness test piece with V notch)

(5) To 100 parts by weight of the water-resistant aromatic polycarbonate, 5 parts by weight of the inorganic compound of the present invention was added and melt-mixed.
Form a 1/8 "thick molded body.
Of gloss (G1) after soaking in water at 00 ° C for 10 hours,
The rate of change (%) with respect to the gloss (G0) before immersion is used as an index of water resistance. Gloss change rate (%) = [(absolute value of difference between G1 and G0) /
G0] × 100 The following components are used in each of the examples and comparative examples. (B) Functionality-imparting agent 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 average particle size is controlled by changing the molar equivalent ratio of oxygen and hydrogen to 1.0 molar equivalent of silicon tetrachloride. Metal oxides other than silica are produced by the vapor phase method disclosed in US Pat. No. 5,460,701 (corresponding Japanese Patent Publication No. 2000-24493).

Then, the surface was coated with various surface treatment agents. The surface treatment method is, for example, JP-A-9-310027,
The method described in JP-A-9-59533 and JP-A-6-87609 is used. 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 silica while stirring. 20 parts by weight is spray mixed. Then, continue heating and stirring at 250 ° C for 30 minutes,
Cool to room temperature to produce surface treated silica. When the surface is coated with dimethyl silicone, polyether-modified dimethyl silicone (Shin-Etsu Chemical Co., Ltd., trade name: KF
618) is used. Similarly, dimethyldichlorosilane treatment, hexamethyldisilazane treatment, methacryloxysilane treatment, diphenyldichlorosilane treatment, and methylphenyldichlorosilane treatment are performed. When the surface is coated with a polymer, the polymerizable monomer is added to Y. Shirai, Journal of Po
lymer Science: Part A: Polymer Chemistry, vol.39, 2157
-2163 (2001); N. Tsubokawa, ibid., Vol. 30, 2241-2246 (199
Graft polymerization is carried out by the method disclosed in 2). For other surface coatings, see Hybrid P
Polyhedral Oligomeric Silse manufactured by lastics
Use squioxane (POSS). Various inorganic compounds described above are shown in Tables 1 to 3.

(B) Polymer Abbreviated in parentheses as follows. Bisphenol A type polycarbonate (PC), nylon 6 (PA6), polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polytetramethylene terephthalate (PTT), rubber modified polystyrene (HIPS),
ABS resin (ABS), styrene-ethylene-butylene-styrene copolymer (SEBS), styrene-butadiene copolymer (SB), polyphenylene ether (PP
E), polypropylene (PP), ethylene-octene copolymer (EO), EO-PP cross-linked 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.

(C) Other function-imparting agents (flame retardants) (1) Organic sulfonic acid metal salt manufactured by Dainippon Ink and Chemicals, Inc., potassium perfluorobutane sulfonate (referred to as SF) (2) polytetrafluoro Ethylene Daikin Industries, Ltd. (referred to as PTFE)

Examples 1 to 20 and Comparative Examples 1 to 3 In a Henschel mixer, the compositions shown in Tables 1 to 3 were mixed, and subsequently, a twin-screw extruder having an injection port at the center of the barrel (40 mmφ, L / Using D = 47), continuous melt extrusion is carried out at a temperature of 250 ° C. for 10 hours. As the screw, a double thread screw having a kneading section before and after the injection port is used. A molded body is produced from the composition thus obtained by injection molding at a cylinder temperature of 250 ° C. and a mold temperature of 60 ° C., and evaluation is performed. The results are shown in Tables 1 to 3.

[0051]

[Table 1]

[0052]

[Table 2]

[0053]

[Table 3]

[0054]

The flame-retardant composition of the present invention has excellent flame retardancy, water resistance, and extrusion stability (quality stability). The flame-retardant composition of the present invention is a home electric appliance housing for VTRs, distribution boards, televisions, audio players, capacitors, household outlets, radio-cassettes, video cassettes, video disc players, air conditioners, humidifiers, electric warm air machines, Chassis or parts, CD-RO
M mainframe (mechanical chassis), printer, fax, PPC, CRT, word processor copier, electronic cash register, office computer system, floppy disk drive, keyboard, type, ECR, calculator, toner cartridge, OA such as telephone
Equipment housing, chassis or parts, connector, coil bobbin, switch, relay, relay socket, LE
D, variable condenser, AC adaptor, FBT high pressure bobbin,
Electronic and electrical materials such as FBT case, IFT coil bobbin, jack, volume shaft, motor parts, instrument panel, radiator grill, cluster, speaker grill, louver, console box, defroster garnish, ornament, fuse box, relay case It is suitable for automobile materials such as connector shift tapes, and plays a large role in these industries.

   ─────────────────────────────────────────────────── ─── Continued front page    F-term (reference) 4H028 AA05 AA12 AA25 AA42 AA43                       AB02 BA06                 4J002 BN061 BN121 BN141 BN151                       BP011 CG011 CH071 DA026                       DA086 DA116 DE076 DE096                       DE106 DE116 DE136 DE146                       DE186 DH046 DJ006 DJ016                       DK006 FB096 FB116 FB146                       FB266 FD136 GN00 GQ00

Claims (6)

[Claims] 1. An (A) polymer, and (B) a silicon-containing compound, a compound containing an aromatic group, and an inorganic compound surface-coated with at least one compound selected from the polymers, and having an average value. An inorganic function-imparting agent having a particle size of 1 nm or more and less than 1000 nm, which is Ia, IIa, Ib, IIb, or III in the composition.
The flame-retardant composition, wherein the content of at least one metal selected from the group consisting of b) is 1000 ppm or less. 2. The flame-retardant composition according to claim 1, wherein (A) is an aromatic thermoplastic polymer. 3. The flame-retardant composition according to claim 2, wherein (A) is an aromatic polycarbonate. 4. The flame-retardant composition according to claim 1, wherein (B) is an inorganic compound whose surface is coated with polyorganosiloxane. 5. The flame retardant composition according to any one of claims 1 to 4, wherein the inorganic compound (B) is a metal oxide. 6. The inorganic compound (B) is at least one selected from the group consisting of silicon oxide and aluminum oxide.
The flame-retardant composition according to claim 1, wherein the flame-retardant composition is a seed.