JP2001247870A - Composite flame retardant - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a composite flame retardant which may impart an excellent flame retardance, flow property, mechanical properties and melt extrusion stability (quality stability), and a composition containing the same. SOLUTION: This composite flame retardant comprises (A) a compound containing a metal element selected from the groups 1A, 2A, 2B, 3B, 3A, 4A, 4B other than carbon, 5A, 6A, 7A, 8 and 1B of the periodic table and (B) an aromatic group-containing phosphazen compound. Especially, the component (A) is a polyorganosiloxane and/or an inorganic compound, and the component (B) is a phenoxyphosphazen. The above composition contains this flame retardant.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to a composite flame retardant. More specifically, the present invention relates to a flame retardant capable of imparting excellent flame retardancy, mechanical properties, and melt extrusion stability (quality stability).

[0002]

2. Description of the Related Art Polymers such as polycarbonates are used in various fields including automobile parts, home electric appliance parts, and OA equipment parts because of their light weight and excellent impact resistance. Its use is limited due to its flammability. As a method of making a polymer flame-retardant, it is known to add a halogen-based, phosphorus-based, or inorganic-based flame retardant to a resin, thereby achieving a certain degree of flame retardancy. However, in recent years, the demand for fire safety has been particularly noticed, and with the development of more advanced flame retardant technology, there is a strong demand for technology development that does not cause environmental problems or decrease in mechanical properties.

On the other hand, flame-retardant resin compositions containing dimethyl silicone as an organosilicon compound have been disclosed (JP-B-63-10184, JP-A-64-4656, US Pat. Nos. 4,497,925 and 4,487,176). And JP-A-2-133364). The silicone disclosed in the above publication has low compatibility with the resin and is phase-separated with the resin, so that the flame retardancy and mechanical properties are not sufficient.
In addition, it cannot withstand practical use due to its volatility.

Further, a flame-retardant resin composition containing a branched or cross-linked methylphenyl silicone (JP-A-10-139)
964, JP-A-11-140294, JP-A-11-217494, JP-A-11-222559, Japanese Patent No. 2719486, and Japanese Patent No. 2746519). Since the silicone resin contains a phenyl group, the compatibility with the resin is improved, but is not sufficient, and further improvement in dispersibility with the resin is required.

A resin composition comprising an aromatic polycarbonate / graft copolymer / phosphazene (EP
0728811A2) and a flame-retardant resin composition comprising a rubber-reinforced styrene resin / polyphenylene ether / phosphazene derivative (JP-A-9-71708). However, although the resin composition disclosed in the above-mentioned publication has excellent flame retardancy, mechanical properties such as impact strength are remarkably reduced, which hinders practical use.

[0006]

SUMMARY OF THE INVENTION In view of such circumstances, the present invention has no such problems, namely, excellent flame retardancy, mechanical properties, and melt extrusion stability (quality stability). It is an object of the present invention to provide a flame retardant that can be given.

[0007]

Means for Solving the Problems The present inventors have conducted extensive studies on a flame retardant for making a polymer flame-retardant. As a result, surprisingly, a flame retardant comprising a specific metal-containing compound and a specific phosphazene has been found. The present inventors have found that the flame retardancy of a polymer, especially a polycarbonate, is dramatically improved, and the present invention has been completed.

That is, the present invention relates to (A) periodic table 1A, 2
A, 2B, 3B, 3A, 4A, 4B, 5A other than carbon,
A composite flame retardant comprising a compound containing a metal element selected from Groups 6A, 7A, 8, and 1B and (B) a phosphazene compound having an aromatic group, in particular, (A) is a polyorganosiloxane and / or an inorganic compound The present invention provides a composite flame retardant wherein (B) is phenoxyphosphazene, and a composition containing the agent.

Hereinafter, the present invention will be described in detail. The present invention relates to a composite flame retardant comprising (A) a specific metal-containing compound and (B) an aromatic group-containing phosphazene. By blending this flame retardant with (C) a polymer, excellent flame retardancy is obtained. , Mechanical properties, and melt extrusion stability (quality stability). Here, it is important that (A) has a specific metal atom. Due to the presence of the specific metal-containing compound and the specific phosphazene compound, a film is formed at the time of combustion, and the flame retardancy is improved. And
In particular, in the case of a metal-containing compound containing an aromatic group, the flame retardancy is further improved.

[0010] It is essential that (B) has an aromatic group. Phosphazene is an inorganic polymer and therefore lacks compatibility with organic polymers.However, by having an aromatic group, compatibility with aromatic polymers increases, and mechanical strength such as impact strength increases. The present invention was found to be improved, and the present invention was completed. In the present invention, (A) represents periodic table 1A, 2
A, 2B, 3B, 3A, 4A, 4B, 5A other than carbon,
It is a compound containing a metal element selected from the group 6A, 7A, 8, 1B, among which polyorganosiloxane,
An inorganic compound such as a hydrated metal compound or an organic metal salt compound is preferred.

The above-mentioned polyorganosiloxane is a polyorganosiloxane represented by silicone or organic silicate. Silicone is classified into oil, resin, and rubber based on their properties. The oil is a linear silicone, and the resin is an M unit represented by monofunctional R ₃ SiO _0.5 , a D unit represented by difunctional R ₂ SiO, and a trifunctional R
T unit represented by SiO _1.5 , Q unit represented by tetrafunctional SiO ₂ , R (RO) SiO _2.0 (X unit) containing alkoxy or aryloxy, (RO) ₂ SiO
_{3.0 is} a linear silicone having a branched structure or a silicone resin having a three-dimensional network structure, which can be formed by combining structural units of (Y units), and the rubber is a vulcanization of a high molecular weight type gum-like linear silicone. Body. Other silicones include modified silicones modified with epoxy, amino, mercapto, methacrylic groups, etc., polycarbonate (PC) -silicone copolymers, acrylic rubber-silicone composites and the like.

In the present invention, one preferable linear silicone of the polyorganosiloxane contains a unit represented by the following chemical formula 1. In particular, when the kinematic viscosity at 25 ° C. specified in JIS-K2410 is 10 centistokes or more. It is preferably at least 100 centistokes, more preferably at least 1000 centistokes.

[0013]

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Here, R ^{1 to} R ⁴ are hydrocarbons having 1 to 20 carbon atoms containing an aromatic group and an alkyl group, which may be the same or different, and preferably a phenyl group having 10 to 20 carbon atoms.
-90 mol%, more preferably 40-90 mol%, most preferably 50-90 mol%. Also R
¹ and R ⁴ may form a ring. Then, n is represented by a number average and is 1 or more, preferably 10 or more, and more preferably 100 or more.

In the present invention, another preferred polyorganosiloxane is a linear silicone having a branched structure (branched silicone) or a silicone resin having a three-dimensional network structure (crosslinked silicone resin). Such silicones consist of RSiO _1.5 (T units) and / or RSiO _1.0 (D units) and, if desired,
R ₃ SiO _0.5 (M unit), SiO _2.0 (Q unit), R
(RO) SiO _2.0 (X unit), (RO) ₂ SiO _3.0
(Y unit).

Here, R is a hydrocarbon having 1 to 20 carbon atoms, preferably a methyl group, an ethyl group, a butyl group, a phenyl group, or a benzyl group, particularly preferably a group containing a methyl group and a phenyl group. When the phenyl group is contained in an amount of 10% by weight or more, the water resistance, the thermal stability, and the compatibility with the aromatic resin are improved. The branched silicone or crosslinked silicone resin in the present invention preferably has a weight average molecular weight of 100 to 1,000,000 in terms of polystyrene according to the GPC method,
It is more preferably from 1,000 to 10,000, and is produced, for example, by hydrolysis of a silane compound such as an organohalosilane, and the production method is disclosed in JP-A-10-139964.

In the present invention, still another preferred polyorganosiloxane is -OR (R is a group having 1 to 2 carbon atoms.
0 is a hydrocarbon having the substituent represented by the following formula: for example, orthosilicate and
The hydrolysis condensate, or an organic silicate such as an organoalkoxypolysiloxane or an organoaryloxypolysiloxane, or, for example, a side chain Si—O—R as an essential component with respect to the main chain (Si—O) is required. Accordingly, in a polysiloxane having Si-R '(R and R' are hydrocarbon groups), an organic silicate having a branched or crosslinked structure represented by Si-O-Si or the like, or, for example, It contains an organoalkoxypolysiloxane unit or an organoaryloxypolysiloxane unit containing at least one or more of the units shown.

[0018]

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[0019]

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[0020]

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(However, R ^{1 to} R ⁶ are hydrocarbons having 1 to 20 carbon atoms.) Here, R ^{1 to} R ⁶ are 1 to 20 carbon atoms.
, A methyl group, an ethyl group, a butyl group, a phenyl group, and a benzyl group are preferred, and those containing a methyl group and a phenyl group are particularly preferred. When the phenyl group is contained in an amount of 10% by weight or more, the water resistance, the thermal stability, and the compatibility with the aromatic resin are improved.

In the present invention, as the inorganic compound (A), aluminum hydroxide, magnesium hydroxide, dolomite, hydrotalcite, calcium hydroxide, barium hydroxide, basic magnesium carbonate, zirconium hydroxide, tin oxide Hydrates of inorganic metal compounds such as hydrates, 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, and tungsten oxide; aluminum, iron, titanium, manganese, zinc, molybdenum, cobalt, bismuth, chromium, nickel, copper, tungsten, tin, and antimony Metal powder, and zinc borate, etc.
Examples include zinc metaborate, barium metaborate, zinc carbonate, magnesium carbonate, calcium carbonate, barium carbonate, and silicon oxide. 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 particularly good flame retardant effects and are economically advantageous.

In the present invention, examples of the organic metal salt compound as (A) include organic metal sulfonates such as potassium trichlorobenzenesulfonate, potassium perfluorobutanesulfonate and potassium diphenylsulfon-3-sulfonate; A metal salt of an aromatic sulfonimide, or a styrene-based polymer, a metal salt of a sulfonate, a metal salt of a metal sulfate, a metal salt of a metal phosphate, or a metal salt of boric acid bonded to an aromatic ring of an aromatic group-containing polymer such as a polyphenylene ether; Organic metal salt compounds such as polystyrene sulfonate alkali metal salts. Such an organic metal salt-based compound promotes a decarboxylation reaction during combustion, particularly when polycarbonate is used as a polymer, to improve flame retardancy. Further, in the case of the alkali metal polystyrene sulfonate, the metal sulfonate itself becomes a cross-linking point during combustion and greatly contributes to the formation of a carbonized film.

The (B) in the present invention is not particularly limited as long as it is a compound having an aromatic group and having a structure in which a phosphorus atom and a nitrogen atom are connected by a double bond. For example, cyclic phosphazene or linear phosphazene Is mentioned. Among the phosphazenes, those containing an aromatic group such as a phenyl group, a cresyl group, a xylyl group, and a bisphenyl group as a substituent are preferable from the viewpoint of compatibility with the aromatic polycarbonate. Specifically, phenoxypropoxyphosphazene, phenoxymethoxyphosphazene,
Diphenoxyphosphazene, phenoxyaminophosphazene, phenoxyfluoroalkylphosphazene and the like. These phosphazene compounds are produced by substituting chlorophosphazene with alcohols or phenols.

The amount ratio of (A) to (B) in the composite flame retardant of the present invention is preferably such that (A) is 1 to 99% by weight, more preferably 10 to 90% by weight, most preferably 30 to 70% by weight. % By weight. The polymer used as (C) in the present invention is a rubbery polymer, a thermoplastic resin, a thermosetting resin or the like, and among them, a thermoplastic resin is particularly preferable. One rubber-like polymer of the above polymers preferably has a glass transition temperature (Tg) of −30 ° C. or lower, and −3 ° C.
If it exceeds 0 ° C., the impact resistance tends to decrease.

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 diene rubbers, isoprene rubbers, chloroprene rubbers. Rubber or non-crosslinked rubber such as acrylic rubber such as polybutyl acrylate, ethylene-propylene copolymer rubber, ethylene-propylene-diene monomer terpolymer rubber (EPDM), ethylene-octene copolymer rubber Rubber and a thermoplastic elastomer containing the above rubber component can be exemplified.

Among the above thermoplastic elastomers, styrene thermoplastic elastomers are particularly preferable, and a block copolymer comprising an aromatic vinyl unit and a conjugated diene unit,
Or the conjugated diene unit portion is a partially hydrogenated block copolymer, particularly from the viewpoint of thermal stability,
Hydrogenated styrenic thermoplastic elastomers are more preferred. In the present invention, the most preferable thermoplastic resins among the polymers (C) include, for example, polystyrene, polyphenylene ether, polyolefin, polyvinyl chloride, polyamide, polyester, polyphenylene sulfide, polycarbonate, and polymethacrylate. And the like, or a mixture of two or more thereof can be used. In particular, as the thermoplastic polymer, a polyphenylene ether-based, polystyrene-based, or polycarbonate-based thermoplastic resin is preferable.

The aromatic polycarbonate as one of the thermoplastic resins can be selected from an aromatic homopolycarbonate and an aromatic copolycarbonate. As a production method, a phosgene method in which phosgene is blown into a bifunctional phenolic compound in the presence of a caustic alkali and a solvent, or
For example, there can be mentioned a transesterification method in which a bifunctional phenol compound and diethyl carbonate are transesterified in the presence of a catalyst. The aromatic polycarbonate preferably has a viscosity average molecular weight of 10,000 to 100,000. here,
The bifunctional phenolic 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 Etc., especially 2,
2'-bis (4-hydroxyphenyl) propane [bisphenol A] is preferred. In the present invention, the bifunctional phenolic compounds may be used alone or in combination.

The styrene resin as one of the thermoplastic resins in the above (C) is a rubber-modified styrene resin and / or a non-rubber-modified styrene resin, particularly a rubber-modified styrene resin alone or a rubber-modified styrene resin. And a non-rubber-modified styrenic resin, and are not particularly limited as long as they are compatible or uniformly dispersed with the flame retardant of the present invention. The rubber-modified styrene-based polymer refers to a polymer in which a rubber-like polymer is dispersed in a matrix in a matrix composed of a vinyl aromatic-based polymer, and an aromatic vinyl-based polymer is present in the presence of a rubber-like polymer. The monomer and, if necessary, a vinyl monomer copolymerizable therewith are added to obtain a monomer mixture by a known polymerization method such as bulk polymerization, emulsion polymerization and suspension polymerization.

The other polyphenylene ether of the thermoplastic resin in the above (C) is a polymer having an aromatic ring in the main chain and linked by an ether bond, and specifically, a poly (2,6) -Dimethyl-1,4-phenylene ether), and copolymers of 2,6-dimethylphenol and 2,3,6-trimethylphenol, among which poly (2,6-dimethyl-1,4-phenylene ether) Is preferred. In the present invention, the most preferable polymer as (C) is a resin mainly composed of aromatic polycarbonate and blended with a styrene-based resin or a styrene-based thermoplastic elastomer, polyphenylene ether or the like.

The compounding amount of the composite flame retardant of the present invention is (C) 1
The amount is preferably 0.01 to 100 parts by weight, more preferably 0.1 to 50 parts by weight, and most preferably 1 to 20 parts by weight with respect to 00 parts by weight. The composite flame retardant of the present invention is (C)
If necessary, a flame retardant other than (A) and (B) can be blended as (D) a flame retardant auxiliary. For example, one or more selected from halogen-based, phosphorus-based, nitrogen-based, and char-forming agents can be blended.

The halogen-based flame retardant (D) is as follows:
Halogenated bisphenol, aromatic halogen compound, halogenated polycarbonate, halogenated aromatic vinyl polymer, halogenated cyanurate resin, halogenated polyphenylene ether and the like, preferably decabromodiphenyl oxide, tetrabromobisphenol A, Oligomers of tetrabromobisphenol A, brominated bisphenol-based phenoxy resin, brominated bisphenol-based polycarbonate, brominated polystyrene,
Brominated cross-linked polystyrene, brominated polyphenylene oxide, polydibromophenylene oxide, decabromodiphenyl oxide bisphenol condensate, halogen-containing phosphoric acid ester, fluorine resin and the like. As the phosphorus-based flame retardant in the above (D), an organic phosphorus compound,
Red phosphorus, inorganic phosphate and the like can be mentioned.

Examples of the above-mentioned organic phosphorus compounds include phosphine, phosphine oxide, biphosphine, phosphonium salt, phosphinate, phosphate, phosphite and the like. More specifically, triphenyl phosphate, methyl neopentyl phosphite, pentaerythritol diethyl diphosphite, methyl neopentyl phosphonate, phenyl neopentyl phosphate, pentaerythritol diphenyl diphosphate, dicyclopentyl hypophosphate , Dineopentyl hypophosphite, phenylpyrocatechol phosphite, ethyl pyrocatechol phosphate and dipyrocatechol hypopositive phosphate. Here, as the organic phosphorus compound, an aromatic phosphate ester monomer and an aromatic phosphate ester condensate are particularly preferred.

In the above (D), one of the phosphorus-based flame retardants, red phosphorus, is not limited to ordinary red phosphorus, and its surface is previously selected from aluminum hydroxide, magnesium hydroxide, zinc hydroxide and titanium hydroxide. Coated with a metal hydroxide coating, coated with a coating composed of a metal hydroxide selected from aluminum hydroxide, magnesium hydroxide, zinc hydroxide, and titanium hydroxide, and a thermosetting resin , Aluminum hydroxide, magnesium hydroxide,
Examples thereof include those obtained by double-coating a thermosetting resin film on a metal hydroxide film selected from zinc hydroxide and titanium hydroxide.

In the above (D), one of the inorganic phosphates of the phosphorus-based flame retardant is typically ammonium polyphosphate. Typical examples of the nitrogen-based flame retardant (D) include triazine-based, phosphazene, diazo-based, triazole-based, and tetrazole-based compounds. Specific examples of the triazine-based compound include melamine, melam, melem, melon (a product of deammonification of three to three molecules of melem at 600 ° C. or higher), melamine cyanurate.
G, melamine phosphate, succinoguanamine, adipoguanamine, methylglutalogamine, melamine resin, B
T resin can be used, but melamine cyanurate is particularly preferable from the viewpoint of low volatility.

Tetrazole compounds as nitrogen-based flame retardants include 5-phenyltetrazole, 5,5'-bistetrazole diammonium salt, 5,5'-bistetrazole diaminoguanidine salt, and 5,5'-bistetrazole piperazine Salt, azobistetrazole 2-guanidine salt,
Azobistetrazole 2-aminoguanidine salt and the like.
The fibrous flame retardant as (D) is a flame retardant used for preventing dripping of fire, and becomes fibrous at the time of addition or processing. Specific examples thereof include aramid fiber, polyacrylonitrile fiber, and fluororesin.

The aramid fiber has an average diameter of 1 to 50.
It is preferable that the average fiber length is 0 to 10 mm and the average fiber length is 0.1 to 10 mm. It is produced by dissolving isophthalamide or polyparaphenylene terephthalamide in an amide polar solvent or sulfuric acid and spinning the solution by a wet or dry method. Can be. The polyacrylonitrile fiber as the fibrous flame retardant preferably has an average diameter of 1 to 500 μm and an average fiber length of 0.1 to 10 mm, and is prepared by dissolving a polymer in a solvent such as dimethylformamide.
Dry spinning in which the polymer is dissolved in a solvent such as nitric acid or the like, or wet spinning in water.

The fluororesin as the fibrous flame retardant is a resin containing a fluorine atom in the resin. Specific examples thereof include polymonofluoroethylene, polydifluoroethylene, polytrifluoroethylene, polytetrafluoroethylene, and a tetrafluoroethylene / hexafluoropropylene copolymer. If necessary, the fluorine-containing monomer may be used in combination with a copolymerizable monomer. The novolak resin as a char-forming agent as (D) is a phenol novolak resin obtained by condensing phenol and an aldehyde in the presence of an acid catalyst such as sulfuric acid or hydrochloric acid.

In the present invention, the amount of (D) added is
(C) 0.001 to 10 with respect to 100 parts by weight of the polymer.
0 parts by weight is preferable, and 1 to 50 parts by weight is more preferable.
Most preferably, 3 to 20 parts by weight, very preferably,
5 to 15 parts by weight. The polymer composition containing the composite flame retardant of the present invention can be obtained, for example, by melt-kneading the above components with a commercially available single-screw extruder or twin-screw extruder. Other than the above, a heat stabilizer, a lubricant, a filler, a reinforcing agent such as a glass fiber, a coloring agent such as a dye or a pigment, and the like can be added. The composition thus obtained is excellent in balance properties of flame retardancy, mechanical properties, and melt extrusion stability (quality stability).

[0040]

The present invention will be described in more detail with reference to the following Examples, which should not be construed as limiting the invention. In addition, the measurement in an Example and a comparative example was performed using the following method or a measuring device. (1) Flame retardancy VB (Vertical Bur) conforming to UL-94
The self-extinguishing property was evaluated by the ning method. (1
/ 16 inch thickness test piece) (2) Izod impact strength Measured by a method according to TM-D256 described in AS.
(1/8 inch thickness test piece with V notch at 23 ° C .: J / m) (3) Extrusion stability (quality stability) Using a melt extruder, the resin composition was continuously melt-extruded for 10 hours. The Izod impact strength of the composition obtained every hour was measured, and the continuous productivity (quality stability) was evaluated from the rate of change (%) with respect to the average strength.

The following components were used in Examples and Comparative Examples. (A) Metal-containing compound (1) Polyorganosiloxane According to a known technique, for example, Chapter 17 of the "Silicone Handbook" [edited by Kunio Ito (Nikkan Kogyo Shimbun) (1990)], different JIS-K2410 according to the silicone production method.
Different phenyl-substituted silicones of different structure, mol%, having a defined kinematic viscosity (25 ° C.) were obtained. (2) Magnesium hydroxide (MOH) manufactured by Kyowa Chemical Industry Co., Ltd., trade name Kisuma (referred to as MOH)

(3) Metal salt of organic sulfonic acid (KSS) Potassium diphenylsulfon-3-sulfonate (KSS) manufactured by UCB Japan Ltd. (4) Metal salt of organic sulfonic acid (FS) Dainippon Ink and Chemicals, Inc. Co., Ltd., potassium perfluorobutanesulfonate (referred to as FS) (b) Phosphazene compound (referred to as FZ) Known production method (described in JP-A-11-181429)
According to the above, various phosphazenes were produced.

(C) Polymer (1) Aromatic Polycarbonate manufactured by Sumitomo Dow Co., Ltd. [Bisphenol A type trade name Caliber 13 (referred to as PC)] (2) Rubber-modified polystyrene (HIPS) manufactured by Asahi Chemical Industry Co., Ltd. Polybutadiene / polystyrene (10/90: weight ratio) Trade name Stylon (HIPS
(3) ABS resin (ABS) Asahi Kasei Kogyo Co., Ltd. [acrylonitrile / polybutadiene / styrene (24/20/56: weight ratio) trade name Stylac ABS (referred to as ABS)]

(4) Styrene-ethylene butylene-styrene copolymer (SEBS) manufactured by Asahi Kasei Corporation (trade name: Tuftec (referred to as SEBS)) (5) Maleic anhydride-modified styrene-ethylene butylene-styrene copolymer Polymer (m-SEBS) manufactured by Asahi Kasei Kogyo Co., Ltd. [Product name ToughTech (m-SEB)
S)] (6) Styrene butadiene copolymer (SB) manufactured by Asahi Kasei Kogyo Co., Ltd. [Tafprene (SB)] (7) Epoxy-modified styrene butadiene copolymer (E
SB) Daicel Chemical Industries, Ltd. [brand name Epo Friend (E
SB))]

(8) Polyphenylene ether (PPE) manufactured by Asahi Chemical Industry Co., Ltd. (trade name: Zylon (referred to as PPE)) (9) Polypropylene (PP) manufactured by Nippon Polychem Co., Ltd. (referred to as PP) (10) Ethylene Octene copolymer (EO) Dupont Dow elastomer [trade name Engage (E
(11) EO-PP crosslinked product (TPV) Heat dynamically crosslinked with a twin screw extruder using EO / PP = 50/50 (weight ratio) using an organic peroxide and divinylbenzene. Plastic polypropylene was used. (Referred to as TPV)

(12) Polybutylene terephthalate (P
(BT) Toray Industries, Inc. (referred to as PBT) (13) Epoxy resin (EP) Asahi Chiba Corporation thermoplastic non-halogen resin grade (E
(14) Polyamide 6 (PA6) manufactured by Toray Industries, Inc. (named PA6) (d) Flame retardant aid (1) Polytetrafluoroethylene (PTFE) manufactured by Daikin Industries, Ltd. (referred to as PTFE) )

Examples 1-38, Comparative Examples 1-6 Tables 1-4 ((A), (B),
The amount of (D) is parts by weight. A) mixing the described composition;
Subsequently, continuous melt extrusion was performed for 10 hours at a temperature of 250 ° C. using a twin-screw extruder (40 mmφ, L / D = 47). Two screws were used as the screws. Here, a phosphazene compound containing a unit represented by the following formula (5) was used as the component (B). However, R1,
R2 is a substituent in the table, and n represents a number average polymerization degree.

[0048]

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A molded article was prepared from the composition thus obtained by injection molding at a cylinder setting temperature of 250 ° C. and a mold temperature of 60 ° C. under the following conditions, and was evaluated. The results are shown in Tables 1 to 4. According to Tables 1 to 4, the use of the composite flame retardant composed of (A) and (B) has excellent melt extrusion stability (quality stability) as well as flame retardancy and mechanical properties. I understand. Further, among (A), silicone oil of D unit than branched or crosslinked silicone resin having D unit / T unit, especially linear silicone containing aromatic group, has excellent flame retardancy, mechanical strength and extrusion stability. It can be seen that the property (quality stability) is imparted.

[0050]

[Table 1]

[0051]

[Table 2]

[0052]

[Table 3]

[0053]

[Table 4]

[0054]

The present invention relates to a composite flame retardant capable of imparting excellent flame retardancy, fluidity, mechanical properties, and melt extrusion stability (quality stability). Flame-retardant materials obtained using the composite flame retardant of the present invention include VTRs, distribution boards, televisions, audio players, capacitors, household outlets, radio cassettes, video cassettes, video disc players, air conditioners, and the like. Home appliances housings, chassis or parts such as shockers, humidifiers, electric hot air machines, C
D-ROM main frame (mechanical chassis), printer, fax, PPC, CRT, word processor,
Electronic cash register, office computer system,
Floppy disk drive, keyboard, type, E
OA equipment housing such as CR, calculator, toner cartridge, telephone, chassis or parts, connector, coil bobbin, switch, relay, relay socket, LED, variable condenser, AC adaptor, FBT high voltage bobbin, FBT cable Electronic and electrical materials such as coils, IFT coil bobbins, jacks, volume shafts, motor parts, instrument panels, radiator grills, clusters, speaker grills, louvers, Console box, defroster garnish, ornament, hue
It is suitable for automobile materials such as box boxes, relay cases, and connector shift tapes, and plays a large role in these industries.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) C08L 83/04 C08L 83/04 101/00 101/00 C09K 21/06 C09K 21/06 21/12 21 / 12 F term (reference) 4H028 AA10 AA23 AA38 AA42 AA48 AA49 AB04 BA06 4J002 AC032 AC062 AC082 AC092 AC112 BB052 BB152 BB172 BD032 BG042 BG052 BN142 BP012 CF002 CG012 CH072 CL002 CN012 CP021 CP031

Claims (5)

[Claims] (A) Periodic table 1A, 2A, 2B, 3
B, 3A, 4A, 4B other than carbon, 5A, 6A, 7A,
8, a compound containing a metal element selected from the group 1B,
(B) A composite flame retardant comprising an aromatic group-containing phosphazene compound. 2. The method according to claim 1, wherein (A) is a polyorganosiloxane and / or
2. The composite flame retardant according to claim 1, which is an inorganic compound. 3. The composite flame retardant according to claim 1, wherein (B) is phenoxyphosphazene. 4. A flame-retardant polymer composition comprising a polymer and the flame retardant according to claim 1. 5. The flame-retardant resin composition according to claim 4, wherein the polymer is an aromatic polycarbonate or a resin mainly composed of an aromatic polycarbonate.