JPH11228843A - Liquid flame retardant - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a liquid flame retardant enabling excellent flame retardancy by adding a specific high mol.wt. polyorganosiloxane gum. SOLUTION: This flame retardant contains (A) a high mol.wt. polyorganosiloxane gum, and is liquid at 25 deg.C. The component A preferably has a kinematic viscosity of 3,000,000-100,000,000 CS (25 deg.C) measured by JIS-K 2410. The addition of (B) a liquidizing agent (preferably a liquid phosphorous flame retardant) to the flame retardant in an amount (for example, 0.000001-50 wt.% in the flame retardant) capable of liquidizing the component A improves the dispersibility of the flame retardant. For example, a flame-retardant resin composition comprises 1-99 pts.wt. of a liquid phosphate flame retardant comprising 1-50 wt.% of the component A and 1-50 wt.% of an aromatic phosphate ester as the component B and 99-1 pts.wt. of (C) a rubber-modified styrenic resin, and contains a residual aromatic vinyl monomer and the dimer and trimer of the aromatic vinyl monomer in a total amount of <=1 wt.%. The flame- retardant resin composition has excellent flame retardancy.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to a liquid flame retardant. More specifically, the present invention relates to a liquid flame retardant which is capable of providing excellent flame retardancy because it is liquid, and a resin composition containing the liquid flame retardant.

[0002]

2. Description of the Related Art Thermoplastic or thermosetting resins are lighter in weight and superior in impact resistance than metals or glass, and are used in automobile parts, home electric parts, OA equipment parts, and the like. However, its use is limited due to the flammability of the resin.

As a method of making a resin flame-retardant, it is known to add a halogen-based, phosphorus-based, or inorganic-based flame retardant to the resin, thereby achieving some 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.

As a prior art for solving such a problem, a filler-reinforced polyphenylene ether flame-retardant resin composition containing a high-molecular-weight polyorganosiloxane gum has been disclosed (JP-A-7-268217). .
However, high-viscosity high-molecular-weight polyorganosiloxane gums not only have insufficient flame retardancy due to poor dispersibility in the resin, but also have problems in terms of productivity and quality stability. Therefore, there is a need for a low-viscosity liquid flame retardant that can withstand practical use.

[0005]

DISCLOSURE OF THE INVENTION In view of the above situation, the present invention is free from the above-mentioned problems, that is, a liquid flame retardant capable of achieving excellent flame retardancy, and a resin containing the same. It is intended to provide a composition.

[0006]

Means for Solving the Problems The present inventors have intensively studied flame retardants capable of imparting excellent flame retardancy, and found that a flame retardant containing a specific high molecular weight polyorganosiloxane gum was added to a resin. Surprisingly, it has been found that the flame retardancy is drastically improved by the compounding, and the present invention has been completed.

That is, the present invention relates to a liquid flame retardant containing a high molecular weight polyorganosiloxane gum and being liquid at 25 ° C., and a flame retardant resin composition containing the agent, especially a residual aromatic vinyl monomer. Another object of the present invention is to provide a flame-retardant styrene resin composition having a total content of a dimer and a trimer of an aromatic vinyl monomer of 1% by weight or less.

Hereinafter, the present invention will be described in detail.

The present invention is a liquid flame retardant containing (A) a high molecular weight polyorganosiloxane gum and (B) a liquefying agent.

Here, it is important that (A) is a high molecular weight gum. In the gum state, high viscosity can be maintained even during combustion, and the surface of the molded body can be efficiently heat-insulated. But on the other hand,
Due to the gum state, there is a problem of dispersibility, (B)
By using a liquefying agent in combination, while maintaining flame retardancy,
It has been found that dispersibility is improved. When the liquid flame retardant of the present invention is blended with a styrene resin, the aromatic vinyl monomer remaining in the resin composition and the total amount of the dimer and the trimer of the aromatic vinyl monomer are contained. Preferably, the amount is 1% by weight or less. In particular, it has been found that when the above total exceeds 1% by weight, the compound volatilizes during combustion and acts as a fuel, so that the flame retardancy is reduced, thus completing the present invention.

In the present invention, the high molecular weight polyorganosiloxane gum (A) is not particularly limited as long as it is a polyorganosiloxane in a gum state.
The specified kinematic viscosity (25 ° C) is 3,000,000 to 10
It is preferably 0,000,000 CS. High molecular weight polyorganosiloxane gums useful in the present invention are generally random polymers containing siloxane units substituted with alkyl, vinyl and / or aryl groups and are represented, for example, by the following formula (1). In the formula (1), R _{1 to} R ₄
Is most preferably a methyl group.

[0012]

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(R _{1 to} R ₄ are hydrocarbons having 1 to 10 carbon atoms and may be the same or different. N is an integer of 1 or more, and the kinematic viscosity (25 ° C.) is 3,000,000. -10
It varies in the range of 0,000,000 CS. Here, the liquid flame retardant of the present invention comprises (B) a liquefying agent,
It can be achieved by adding a liquefiable amount of (A). The liquefying agent is not particularly limited, but is a commonly used solvent or additive for polymers, and particularly preferably a liquid phosphorus-based flame retardant such as an organic phosphorus compound. The liquefiable amount of the liquefier is not particularly limited, but is, for example, 0.000001 to 50% by weight, preferably 1 to 40% by weight, more preferably 3 to 30% by weight in the liquid flame retardant. Preferably it is 5 to 20% by weight.

Examples of the above 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 phosphate, 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 which is a liquefying agent, an aromatic phosphate ester monomer of the following formula (2) and an aromatic phosphate ester condensate of the following formula (3) are particularly preferred.

[0016]

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[0017]

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(However, Ar ₁ , Ar ₂ , Ar ₃ , Ar ₄ , A
r _5, Ar _7, Ar ₈ is an aromatic group selected from at least one phenyl group substituted with an unsubstituted or a hydrocarbon group having 1 to 10 carbon atoms independently. Ar ₆ is a divalent aromatic group having 6 to 20 carbon atoms. m represents an integer of 1 or more. Among the above-mentioned aromatic phosphate ester monomers as the liquefying agent, one or more of the hydroxyl group-containing aromatic phosphate ester monomers, for example, tricresyl phosphate and triphenyl phosphate, etc. A phosphate ester monomer containing two or more phenolic hydroxyl groups or an aromatic phosphate ester monomer represented by the following formula (4) is preferred.

[0019]

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(Where a, b, and c are from 1 to 3, R ¹ ,
R ² and R ³ are hydrogen or an alkyl group having 1 to 30 carbon atoms, and the total number of carbon atoms of the substituents R ¹ , R ² and R ³ is 12 to 30 on average as the whole compound. Here, when it comprises a plurality of aromatic phosphates having different substituents, the total number of carbon atoms of the substituents R ¹ , R ² , R ³ of the flame retardant is represented by a number average, It is the sum of the product of the weight fraction of each aromatic phosphate component in the flame retardant and the total number of carbon atoms of the substituent of each component. In the present invention, among the aromatic phosphate ester monomers that are liquefying agents, the number average of the total number of carbon atoms of the substituents R ¹ , R ² , and R ³ is preferably 15 to 30, and more preferably 20 to 30. 30
, And most preferably 25 to 30.

Specific substituents include butyl such as nonyl and t-butyl, t-amyl, hexyl, cyclohexyl, heptyl, octyl, decyl, undecyl, dodecyl and tridecyl. Octadecyl group, tetradecyl group, pentadecyl group, hexadecyl group, heptadecyl group, otadecyl group, nonadecyl group, octadodecyl group and the like.
It can be produced by a known method disclosed in, for example, JP-A-294284. For example, there is a method of reacting an alkylphenol, phosphorus oxychloride, and anhydrous aluminum chloride as a catalyst under heating, or a method of oxidizing a phosphite triester with oxygen to convert it to a corresponding aromatic phosphate.

Among the above-mentioned aromatic phosphate ester condensates of another liquefying agent, bisphenol A bis (diphenyl phosphate), bisphenol A
Bis (dicresyl phosphate) is preferred.

By blending the liquid flame retardant of the present invention with the thermoplastic resin and / or the thermosetting resin (C), excellent flame retardancy can be imparted to (C).

Here, (C) is not particularly limited as long as it is compatible with or homogeneously dispersed with the liquid flame retardant. For example, polystyrene, polyphenylene ether,
Polyolefin type, polyvinyl chloride type, polyamide type,
Polyesters, polyphenylene sulfides, polycarbonates, polymethacrylates and the like can be used alone or in combination of two or more. Particularly, a thermoplastic resin is preferred as (C), and for example, a polyphenylene ether-based, polystyrene-based, or polycarbonate-based thermoplastic resin is most preferred.

One of the styrene resins (C-
1) is a rubber-modified styrenic resin and / or a non-rubber-modified styrenic resin, particularly preferably a rubber-modified styrenic resin alone or a rubber-modified styrenic resin and a rubber-unmodified styrenic resin. There is no particular limitation as long as it is compatible with or homogeneously dispersed. The rubber-modified styrenic resin refers to a polymer in which a rubbery polymer is dispersed in a matrix in a matrix composed of a vinyl aromatic polymer, and an aromatic vinyl monomer is present in the presence of the rubbery polymer. The monomer and, if necessary, a vinyl monomer copolymerizable therewith, are added, and the monomer mixture is obtained by known polymerization methods such as bulk polymerization, emulsion polymerization, and suspension polymerization.

Examples of such resins include impact-resistant polystyrene, ABS resin (acrylonitrile-butadiene-styrene copolymer), AAS resin (acrylonitrile-acryl rubber-styrene copolymer), and AES resin (acrylonitrile-ethylene copolymer). Propylene rubber-styrene copolymer).

Here, the rubbery polymer preferably has a glass transition temperature (Tg) of -30 ° C. or less.
If it exceeds 30 ° 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 above diene rubbers, isoprene rubbers and chloroprene rubbers. , An acrylic rubber such as polybutyl acrylate, and an ethylene-propylene-diene monomer terpolymer (EPDM). A diene rubber is particularly preferred.

The aromatic vinyl monomer as 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. Yes, styrene is most preferred, but other aromatic vinyl monomers described above may be copolymerized mainly with styrene.

If necessary, one or more monomer components copolymerizable with the aromatic vinyl monomer can be introduced as components of the rubber-modified styrenic resin in (C-1). When it is necessary to increase oil resistance, unsaturated nitrile monomers such as acrylonitrile and methacrylonitrile can be used.

When it is necessary to lower the melt viscosity at the time of blending, an acrylate comprising an alkyl group having 1 to 8 carbon atoms can be used. Further, 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 from 0 to 40.
% By weight.

The rubbery polymer in the rubber-modified styrenic resin is preferably 5 to 80% by weight, particularly preferably 1 to 80% by weight.
0 to 50% by weight, a graft-polymerizable monomer mixture,
Preferably 95 to 20% by weight, more preferably 90 to 5% by weight.
It is in the range of 0% by weight. Within this range, the balance between impact resistance and rigidity of the target resin composition is improved. Further, the rubber particle diameter of the styrene-based polymer is 0.1 to 5.0.
μm is preferred, and 0.2 to 3.0 μm is particularly preferred. Within the above range, impact resistance is particularly improved.

The reduced viscosity ηsp / c of the resin portion, which is a measure of the molecular weight of the rubber-modified styrenic resin (0.5 g / dl,
30 ° C. measurement: toluene solution when the matrix resin is polystyrene, methyl ethyl ketone when the matrix resin is an unsaturated nitrile-aromatic vinyl copolymer)
It 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 ηsp of rubber-modified styrenic resin
Means for satisfying the above requirement regarding / c include adjustment of the amount of polymerization initiator, polymerization temperature, and amount of chain transfer agent. In the present invention, another polyphenylene ether (C-2) of (C) is a homopolymer and / or a copolymer comprising a bonding unit represented by the following formula (5).

[0034]

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(However, R ¹ , R ² , R ³ , and R ⁴ are each selected from the group consisting of hydrogen, hydrocarbon, and substituted hydrocarbon groups, and may be the same or different. Specific examples of the polyphenylene ether include poly (2,6-dimethyl-1,4-phenylene ether) and a copolymer of 2,6-dimethylphenol and 2,3,6-trimethylphenol. Preferred, especially poly (2,6-dimethyl-1,4-phenylene ether)
Is preferred. The method for producing the polyphenylene ether is not particularly limited. 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 Can be easily produced by oxidative polymerization, and in addition, U.S. Patent No. 3,306,875, U.S. Patent No. 3,257,357, U.S. Patent No. 3,257,358, and 52-1
It can be easily produced by the methods described in JP-A-7880 and JP-A-50-51197. The reduced viscosity ηsp / c of the polyphenylene ether used in the present invention (0.5
g / dl, chloroform solution, measured at 30 ° C) is 0.2
It is preferably in the range of 0 to 0.70 dl / g,
More preferably, it is in the range of 0.30 to 0.60 dl / g. Reduced viscosity ηsp / c of polyphenylene ether
Means for satisfying the above requirements include adjustment of the amount of catalyst in the production of the polyphenylene ether.

In the present invention, the amount occupied by (C-1) in 100 parts by weight of the resin component composed of (C-1) and (C-2) is one of the preferable combinations of thermoplastic resins.
1 to 99% by weight, preferably 1 to 50% by weight, more preferably 3 to 40% by weight, most preferably 5 to 5% by weight.
25% by weight.

The aromatic polycarbonate as one of the thermoplastic resins (C) in the present invention can be selected from aromatic homopolycarbonates and aromatic copolycarbonates. The production method includes a phosgene method in which phosgene is blown into a bifunctional phenolic compound in the presence of a caustic alkali and a solvent, or a transesterification method in which a bifunctional phenolic compound is transesterified with diethyl carbonate in the presence of a catalyst. Can be mentioned. 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, and 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.

In the case of imparting a higher degree of flame retardancy in the present invention, a halogen-based, phosphorus-based or inorganic flame retardant other than the above-mentioned liquid flame retardant can be blended as (D) the flame retardant.

The halogen-based flame retardant (D) is as follows:
Halogenated bisphenols, aromatic halogen compounds, halogenated polycarbonates, halogenated aromatic vinyl polymers, halogenated cyanurate resins, halogenated polyphenylene ethers, and the like, preferably decabromodiphenyl oxide, tetrabromobisphenol A, tetrabromo Oligomer of bisphenol 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),
Other examples include organic phosphorus compounds, red phosphorus, and inorganic phosphates.

Red phosphorus, one of the phosphorus-based flame retardants, is a metal hydroxide selected from aluminum hydroxide, magnesium hydroxide, zinc hydroxide, and titanium hydroxide, in addition to ordinary red phosphorus. Those coated with a coating of aluminum hydroxide, magnesium hydroxide, zinc hydroxide, those coated with a coating made of a metal hydroxide and a thermosetting resin selected from titanium hydroxide, aluminum hydroxide, Examples thereof include those obtained by doubly coating a coating of a metal hydroxide selected from magnesium hydroxide, zinc hydroxide, and titanium hydroxide with a coating of a thermosetting resin.

In the above (D), one of the inorganic phosphates of the phosphorus-based flame retardant is typically ammonium polyphosphate.

The inorganic flame retardant (D) includes aluminum hydroxide, magnesium hydroxide, dolomite, hydrotalcite, calcium hydroxide, barium hydroxide, basic magnesium carbonate, zirconium hydroxide, and tin oxide. And hydrates of inorganic metal compounds such as hydrates of, for example, zinc borate, zinc metaborate, barium metaborate, zinc carbonate, magnesium carbonate, mu calcium, 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 particularly good flame retardant effects and are economically advantageous.

In the present invention, the amount of (D) added is
(C) 1 to 100 parts by weight, preferably 1 to 50 parts by weight, more preferably 3 to 100 parts by weight with respect to 100 parts by weight.
20 parts by weight, most preferably 5 to 15 parts by weight.

In the present invention, in particular, when further improvement in flame retardancy and heat resistance is required, (E) a novolak resin can be blended. When (E) is used in combination with an aromatic phosphate, it is also an agent for improving fluidity and heat resistance, and slightly lowers the compatibility between the resin component and the aromatic phosphate. The resin is a thermoplastic resin obtained by condensing phenols and aldehydes in the presence of an acid catalyst such as sulfuric acid or hydrochloric acid. Polyaddition ”p.437-
455 (Kyoritsu Shuppan Co., Ltd.) ".

An example of the production of a novolak resin is shown in the following formulas (6) and (7).

[0047]

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The phenols include phenol, o-cresol, m-cresol, p-cresol, 2,5-
Dimethyl-, 3,5-dimethyl-, 2,3,5-trimethyl-, 3,4,5-trimethyl-, pt-butyl-, pn-octyl-, p-stearyl-, p-phenyl -, P- (2-phenylethyl)-, o-isopropyl-, p-isopropyl-, m-isopropyl-, p
-Methoxy- and p-phenoxyphenol, pyrocatechol, resorcinol, hydroquinone, salicylaldehyde, salicylic acid, p-hydroxybenzoic acid, methyl p-hydroxybenzoate, p-cyano-, and o-cyanophenol, p-hydroxybenzene Sulfonic acid, p-hydroxybenzenesulfonamide, cyclohexyl p-hydroxybenzenesulfonate, 4-
Hydroxyphenylphenylphosphinic acid, methyl 4
-Hydroxyphenylphenylphosphinate, 4-hydroxyphenylphosphonic acid, ethyl 4-hydroxyphenylphosphonate, diphenyl 4-hydroxyphenylphosphonate and the like.

The aldehydes include formaldehyde,
Acetaldehyde, n-propanal, n-butanal, isopropanal, isobutyraldehyde, 3-methyl-n-butanal, benzaldehyde, p-tolylaldehyde, 2-phenylacetaldehyde and the like.

In the present invention, if necessary, one or more compounds selected from saturated higher aliphatic carboxylic acids or metal salts thereof, carboxylic acid ester waxes, organosiloxane waxes, polyolefin waxes, and polycaprolactone. And (F) a release agent.

Among the above (F), one or more compounds selected from saturated higher aliphatic carboxylic acids and metal salts thereof are preferred.

The carboxylic acid of the saturated higher fatty acid is preferably a straight-chain saturated monocarboxylic acid having 12 to 42 carbon atoms. For example, lauric acid, myristic acid, palmitic acid, stearic acid, behenic acid, montanic acid and the like can be mentioned. Examples of the metal of these metal salts include lithium, sodium, potassium, magnesium, calcium, aluminum, zinc and the like, and particularly preferred are zinc stearate, magnesium stearate, calcium stearate, and aluminum stearate.

The amount of (F) is preferably 0.01 to 5 parts by weight, more preferably 100 parts by weight of (C).
0.1 to 5 parts by weight, most preferably 0.3 to 1 part by weight.

In the present invention, if necessary, at least one compound selected from the group consisting of a triazine skeleton-containing compound, a metal-containing compound, a silicone resin, a silicone oil, silica, an organic silicate, an aramid fiber, a polyacrylonitrile fiber, and a fluororesin. A combustion aid (G) can be blended.

The amount of (G) is preferably 0.001 to 40 parts by weight, more preferably 1 to 20 parts by weight, and most preferably 5 to 10 parts by weight based on 100 parts by weight of (C). is there.

The compound having a triazine skeleton as (G) is a component for further improving the flame retardancy as a flame retardant aid of a phosphorus-based flame retardant. Specific examples thereof include melamine, melam of the following formula (8), melem of the following formula (9), melon (product of deammonification of three to three molecules of melem at 600 ° C. or more), and the following formula (10) Melamine cyanurate, melamine phosphate of the following formula (11), succinoguanamine, adipoguanamine, methylglutaloganamine of the following formula (12), melamine resin of the following formula (13), BT resin of the following formula (14) Although melamine cyanurate is particularly preferable from the viewpoint of low volatility.

[0057]

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[0058]

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[0059]

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[0060]

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[0061]

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[0062]

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[0063]

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The metal-containing compound as (G) is a metal oxide and / or metal powder. The metal oxide is aluminum oxide, iron oxide, titanium oxide, manganese oxide, magnesium oxide, zirconium oxide, zinc oxide, molybdenum oxide, cobalt oxide, bismuth oxide, chromium oxide,
It is a simple substance such as tin oxide, antimony oxide, nickel oxide, copper oxide, tungsten oxide, or a composite (alloy) thereof, and the metal powder is aluminum, iron, titanium, manganese, zinc, molybdenum, cobalt, bismuth, It is a simple substance of chromium, nickel, copper, tungsten, tin, antimony or the like, or a composite thereof.

The silicone resin (G) is made of SiO
₂ , a silicone resin having a three-dimensional network structure formed by combining structural units of RSiO _3/2 , R ₂ SiO, and R ₃ SiO _1/2 . Here, R represents an alkyl group such as a methyl group, an ethyl group or a propyl group, an aromatic group such as a phenyl group or a benzyl group, or a substituent containing a vinyl group in the above substituent. Here, a silicone resin containing a vinyl group is particularly preferable.

Such a silicone resin is obtained by co-hydrolyzing and polymerizing an organohalosilane corresponding to the above structural unit.

The silicone oil (G) is a polydiorganosiloxane, particularly preferably a vinyl-containing silicone oil, which comprises a chemical bond unit represented by the following formula (15).

[0068]

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R in the above formula is a C1-8 alkyl group, C
It is one or more substituents selected from aryl groups of 6 to 13 and vinyl-containing groups represented by the following formulas (16) and (17), and particularly contains a vinyl group in the molecule.

[0070]

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[0071]

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The viscosity of the vinyl-containing silicone oil is 600 to 1,000,000 centistokes (25%).
C.), more preferably 90000 to 150 ° C.
000 centistokes (25 ° C.).

The silica as (G) is an amorphous silicon dioxide, particularly preferably a silica coated with a hydrocarbon compound, the surface of which is treated with a hydrocarbon compound silane coupling agent. The hydrocarbon compound-coated silica contained is preferred.

The silane coupling agent may be a vinyl such as p-styryltrimethoxysilane, vinyltrichlorosilane, vinyltris (β-methoxyethoxy) silane, vinyltriethoxysilane, vinyltrimethoxysilane, or γ-methacryloxypropyltrimethoxysilane. Group-containing silane, epoxy silane such as β- (3,4 epoxycyclohexyl) ethyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, and N-β (aminoethyl) γ-aminopropyltrimethoxysilane, N-β
(Aminoethyl) γ-aminopropylmethyldimethoxysilane, γ-aminopropyltriethoxysilane, N
Aminosilane such as -phenyl-γ-aminopropyltrimethoxysilane. Here, a silane coupling agent having a unit similar in structure to the thermoplastic resin is particularly preferable. For example, p-styryltrimethoxysilane is preferable for a styrene-based resin.

The treatment of the silica surface with the silane coupling agent is roughly classified into a wet method and a dry method. The wet method is a method in which silica is treated in a silane coupling agent solution and then dried.The dry method is a method in which silica is charged into a high-speed stirring device such as a Henschel mixer and stirred. This is a method in which a silane coupling agent solution is slowly dropped while performing a heat treatment.

The organic silicate (G) is an orthosilicate ester (n = 1) represented by the following formula (18) and a hydrolytic condensate thereof.

[0077]

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Here, R _{1 to} R ₄ are hydrocarbons having 1 to 10 carbon atoms, particularly preferably a methyl group, an ethyl group, a butyl group and a phenyl group. R _{1 to} R ₄ may be the same or different.

Next, n in the formula (18) is an integer of 1 or more, preferably 2 or more, more preferably 2 to 100, most preferably 10 to 30 from the viewpoint of hydrolysis resistance.

The silicate of the formula (1) is produced by partial hydrolysis of tetraalkoxysilane, and n can be controlled by the hydrolysis rate.

The aramid fibers as (G) preferably have an average diameter of 1 to 500 μm and an average fiber length of 0.1 to 10 mm. Isophthalamide or polyparaphenylene terephthalamide is converted to an amide polar solvent or sulfuric acid. And solution spinning by a wet or dry method.

The polyacrylonitrile fiber (G) has an average diameter of 1 to 500 μm and an average fiber length of 0.1 to 500 μm.
The thickness is preferably 10 mm, and the polymer is dissolved in a solvent such as dimethylformamide and the like, and dry spinning is performed by dry spinning in an air stream at 400 ° C., or the polymer is dissolved in a solvent such as nitric acid and wet spinning is performed in water. It is manufactured by a spinning method.

The fluorine resin (G) is a resin containing a fluorine atom in the resin. As a specific example,
Polymonofluoroethylene, polydifluoroethylene,
Examples thereof include polytrifluoroethylene, polytetrafluoroethylene, and tetrafluoroethylene / hexafluoropropylene copolymer. If necessary, the above-mentioned fluorine-containing monomer and a copolymerizable monomer may be used in combination.

The method for producing these fluororesins is described in US Pat. No. 2,393,697 and US Pat.
No. 534,058, for example, using tetrafluoroethylene in an aqueous medium with a radical initiator such as ammonium persulfate and potassium persulfate in an amount of 7 to 70 kg.
The polymerization is carried out at a temperature of from 0 to 200 ° C. under a pressure of / cm ² and then a polytetrafluoroethylene powder is obtained by coagulation from a suspension, dispersion or emulsion or by precipitation.

The method of blending the fluororesin is to melt-knead the fluororesin, the thermoplastic resin and, if necessary, the dispersant to prepare a master batch, and then melt-knead the thermoplastic resin and the flame retardant. Using a two-stage extruder, or a two-stage extruder capable of side-feeding, melt-kneading the thermoplastic resin and fluorine-based resin and, if necessary, the first stage, and lowering the melting temperature in the second stage to reduce the flame retardant Or a single-stage process of feeding and melt-kneading, or a single-stage process of feeding all components including the fluororesin to the main feeder and melting and kneading. Here, a two-stage process for producing a master batch is preferable from the viewpoint of flame retardancy.

In the present invention, if necessary, a copolymer resin comprising an aromatic vinyl unit and an acrylic ester unit, an aliphatic hydrocarbon, a higher fatty acid, a higher fatty acid ester, a higher fatty acid amide, a higher fatty alcohol, or a metal One or two or more fluidity improvers (H) selected from soaps can be blended.

The amount of (H) is preferably 0.1 to 20 parts by weight, more preferably 100 parts by weight of (C).
0.5 to 10 parts by weight, most preferably 1 to 5 parts by weight.

The aromatic vinyl unit of the copolymer resin as (H) is, for example, styrene, α-methylstyrene, p-methylstyrene, p-chlorostyrene, p-bromostyrene, 2,4,5-tribromostyrene And the like, and styrene is most preferred, but the above-mentioned other aromatic vinyl monomer may be copolymerized mainly with styrene. The acrylate unit is an acrylate ester having an alkyl group having 1 to 8 carbon atoms, such as methyl acrylate and butyl acrylate.

Here, the content of the acrylate unit in the copolymer resin is preferably 3 to 40% by weight.
5-20% by weight is preferred. Also, the solution viscosity (MEK of 10% by weight of resin) which is an index of the molecular weight of the copolymer resin is used.
(Solution, measurement temperature 25 ° C.) is preferably 2 to 10 cP (centipoise). If the solution viscosity is less than 2 cP, the impact strength decreases, while if it exceeds 10 cP, the effect of improving the fluidity decreases.

The aliphatic hydrocarbon-based processing aids as (H) include liquid paraffin, natural paraffin, microwax, polyolefin wax, synthetic paraffin, and partial oxides thereof, or fluorides and chlorides.

The higher fatty acids as (H) include saturated fatty acids other than those described in the section of (F) mold release agent, and unsaturated fatty acids such as ricinoleic acid, ricinberidic acid and 9-oxy-12-octadecenoic acid. It is.

The higher fatty acid esters as (H) include monohydric alcohol esters of fatty acids such as methyl phenylstearate and butyl phenylstearate, and monohydric alcohol esters of polybasic acids such as diester stearate of diphenylstearyl phthalate. And sorbitan monolaurate, sorbitan monostearate, sorbitan monooleate, sorbitan sesquiolate, sorbitan triolate, polyoxyethylene sorbitan monolaurate, polyoxyethylene sorbitan monopalmitate, polyoxyethylene sorbitan monostearate , Sorbitan esters such as polyoxyethylene sorbitan monooleate, monoglyceride stearate,
Fatty acid esters of glycerin monomers such as oleic acid monoglyceride, capric acid monoglyceride, behenic acid monoglyceride, polyglycerin fatty acid esters such as polyglycerin stearate, polyglycerin oleate, polyglycerin laurate, and polyoxyethylene mono Fatty acid esters having a polyalkylene ether unit such as laurate, polyoxyethylene monostearate and polyoxyethylene monooleate; and neopentyl polyol fatty acid esters such as neopentyl polyol distearate.

Higher fatty acid amides as (H) include monoamides of saturated fatty acids such as phenylstearic acid amide, methylolstearic acid amide, methylolbehenic acid amide, coconut oil fatty acid diethanolamide, lauric acid diethanolamide, and coconut oil fatty acid diethanolamide. And N, N′-substituted monoamides such as oleic acid diethanolamide and the like.
Saturated fatty acid bisamides such as (hydroxyphenyl) stearamide, ethylenebis (stearic acid amide), ethylenebis (12-hydroxyphenyl) stearic acid amide, hexamethylenebis (12-hydroxyphenyl) stearic acid amide, and m-xylylenebis (12
-Hydroxyphenyl) stearic acid amide and the like.

The higher aliphatic alcohol as (H) is
Monohydric alcohols such as stearyl alcohol and cetyl alcohol; polyhydric alcohols such as sorbitol and mannitol; and polyoxyethylene dodecylamine and polyoxyethylene octadecylamine; and polyalkylene ethers such as polyoxyethylene allylated ether. Allylated ether having a unit, polyoxyethylene lauryl ether, polyoxyethylene tridodecyl ether, polyoxyethylene cetyl ether, polyoxyethylene stearyl ether, polyoxyethylene alkyl ether such as polyoxyethylene oleyl ether, polyoxyethylene octyl Phenyl ether, polyoxyethylene alkyl phenyl ether such as polyoxyethylene nonyl phenyl ether,
Polyepichlorohydrin ether, polyoxyethylene bisphenol A ether, polyoxyethylene ethylene glycol, polyoxypropylene bisphenol A
It is a dihydric alcohol having a polyalkylene ether unit such as ether or polyoxyethylene polyoxypropylene glycol ether.

The metal soap as (H) is a metal salt of a higher fatty acid such as stearic acid described above, such as barium, calcium, zinc, aluminum or magnesium.

In the present invention, a thermoplastic elastomer (I) can be blended, if necessary, such as a polystyrene-based, polyolefin-based, polyester-based, polyurethane-based, 1,2-polybutadiene-based, or polyvinyl chloride-based. And the like, and a polystyrene-based thermoplastic elastomer is particularly preferable.

The amount of (I) is preferably 0.5 to 20 parts by weight, more preferably 100 parts by weight of (C).
It is 1 to 10 parts by weight, most preferably 2 to 5 parts by weight.

The polystyrene-based thermoplastic elastomer is a block copolymer comprising an aromatic vinyl unit and a conjugated diene unit, or a block copolymer in which the conjugated diene unit is partially hydrogenated.

The aromatic vinyl monomer constituting the block copolymer is, for example, styrene, α-methylstyrene, paramethylstyrene, p-chlorostyrene, p-bromostyrene, 2,4,5-tribromobenzene. Styrene is the most preferable, and styrene is most preferable. However, other aromatic vinyl monomers described above may be copolymerized mainly with styrene.

The conjugated diene monomer constituting the block copolymer includes 1,3-butadiene, isoprene and the like.

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 a partially hydrogenated unit thereof is represented by B. When displaying with,
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
A block copolymer or (SB) nX (where n is 3 to 6)
Integer. X is a residue of a coupling agent such as silicon tetrachloride, tin tetrachloride, and a polyepoxy compound. It is preferable to use a star-shaped (star) block copolymer having a B-part as a bonding center. Above all, SB type 2 and SBS 3
And SBSB type 4 linear block copolymers are preferred.

In the present invention, when light resistance is required, an ultraviolet absorber, a hindered amine light stabilizer, an antioxidant, a halogen scavenger, a light shielding agent, a metal deactivator, or a quencher may be used, if necessary. One or more lightfastness improvers (J) selected from agents can be blended.

The amount of (J) 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 based on 100 parts by weight of (C). Department.

Examples of preferred compositions of the liquid flame retardant of the present invention and the resin composition containing the same include the following. Liquid phosphorus-based flame retardant 1-99 comprising (A) 1-50% by weight of high molecular weight polyorganosiloxane gum and (B) 1-50% by weight of aromatic phosphate ester
Parts by weight, (C) 1 to 99 parts by weight of the rubber-modified styrene resin, and the total content of the remaining aromatic vinyl monomer and the dimer and trimer of the aromatic vinyl monomer is 1
% By weight or less.

The above composition has excellent flame retardancy.

[0106]

The present invention will be described in more detail with reference to the following Examples, which should not be construed as limiting the invention.

The measurements in the examples and comparative examples were performed using the following methods or measuring instruments.

(1) Reduced viscosity of rubber-modified styrene resin and polyphenylene ether ηsp / C A mixed solvent of 18 ml of methyl ethyl ketone and 2 ml of methanol was added to 1 g of rubber-modified styrene resin, and shaken at 25 ° C. for 2 hours.
Centrifuge at 18000 rpm for 30 minutes. The supernatant was taken out and the resin component was precipitated with methanol and then dried.

0.1 g of the resin thus obtained was
In the case of rubber-modified polystyrene, it is dissolved in toluene, and in the case of rubber-modified acrylonitrile-styrene copolymer resin, it is dissolved in methyl ethyl ketone to obtain a solution having a concentration of 0.5 g / dl. The solution falling time T ₁ (second) was measured at 30 ° C. On the other hand, the falling time T ₀ (second) of pure toluene or pure methyl ethyl ketone was measured separately using the same viscometer, and calculated by the following formula.

Ηsp / C = (T ₁ / T ₀ −1) / C C: polymer concentration (g / dl) On the other hand, for the reduced viscosity ηsp / C of polyphenylene ether, 0.1 g was dissolved in chloroform, 0.
A solution of 5 g / dl was prepared and measured in the same manner as above.

(2) Analysis of Composition 5 g of the resin composition was dissolved in 100 ml of methyl ethyl ketone and separated using an ultracentrifuge (20,000 rpm).
m, 1 hour). Then, the supernatant obtained by separation was added with 2
A double amount of methanol was added to precipitate a resin component, and the solution portion and the resin portion were separated using an ultracentrifuge. For the solution part, use GPC (gel permeation chromatography) [manufactured by Tosoh Corporation, Japan;
HLC-8020; column, manufactured by Tosoh Corporation, two G1000HXL; mobile phase, tetrahydrofuran; flow rate, 0.8 ml / min; pressure, 60 kg
f / cm ² ; temperature INLET 35 ° C, OVEN 4
0 ° C., RI 35 ° C .; sample loop 100 ml; injected sample amount 0.08 g / 20 ml], and the area ratio of each component on the chromatogram is assumed to be the weight fraction of each component, and the phosphate ratio is determined from the area ratio. And residual aromatic vinyl monomer and dimer and 3 of aromatic vinyl monomer
The composition and amount of the monomer were determined. On the other hand, regarding the above resin portion, a Fourier transform nuclear magnetic resonance apparatus (proton-FT-
NMR), the ratio of the integral value of the aromatic proton or the aliphatic proton was determined, and the amounts of the rubber-modified styrene resin and the thermoplastic resin such as polyphenylene ether were determined.

(3) Char generation amount (thermogravimetric balance test: T
GA method) Using a Shimadzu thermal analyzer DT-40 manufactured by Shimadzu Corporation of Japan, the temperature was raised at a rate of 40 ° C./min under a nitrogen stream, and the remaining amount (%) at 500 ° C. did.

(4) Flame retardancy VB (Vertical Bur) conforming to UL-94
The self-extinguishing property was evaluated by the ning method. (1
/ 8 inch thickness test piece) The following components were used in the examples and comparative examples.

(A) High molecular weight polyorganosiloxane gum Polydimethylsiloxane gum manufactured by Shin-Etsu Chemical Co., Ltd. (trade name: Shin-Etsu Silicone Gum X-21-7501)
G) was used (referred to as ME-GUM).

(B) Silicone Polydimethylsiloxane manufactured by Shin-Etsu Chemical Co., Ltd. (trade name: Shin-Etsu Silicone KF96 Series, kinematic viscosity 100C)
S) was used (referred to as ME-silicone).

(C) Rubber-modified styrenic resin (HIP
S) Polybutadiene {(cis 1,4 bond / trans 1,4 bond / vinyl 1,2 bond weight ratio = 95/2/3) (Nipol 122 OSL, manufactured by Zeon Corporation)}
Was dissolved in the following mixture to give a uniform solution.

Polybutadiene 10.5% by weight Styrene 74.2% by weight Ethylbenzene 15.0% by weight α-methylstyrene dimer 0.27% by weight t-butylperoxyisopropyl carbonate 0.03% by weight Is continuously supplied to a series four-stage reactor equipped with a stirrer, and the first stage has a stirring speed of 190 rpm and 126 rpm.
° C, the second stage is 50 rpm, 133 ° C, the third stage is 20 rpm
m, 140 ° C., and polymerization was performed at 20 rpm and 155 ° C. in the fourth stage. Subsequently, the polymerization solution having a solid content of 73% was led to a devolatilizer to remove unreacted monomers and a solvent to obtain a rubber-modified aromatic vinyl resin (referred to as HIPS). As a result of analyzing the obtained rubber-modified aromatic vinyl resin, the rubber content was 1
The weight average particle diameter of the rubber was 2.1 μm, the reduced viscosity ηsp / c was 0.53 dl / g.

By changing the polymerization temperature and the amount of the chain transfer agent, polystyrene containing a large amount of residual styrene monomer and oligomer (styrene dimer and trimer) was produced, and the above HIPS was purified. By blending with rubber-modified polystyrene, rubber-modified polystyrene having different residual styrene monomer and oligomer amounts was produced.

(D) Polyphenylene ether (PPE) After the inside of a stainless steel reactor having an oxygen inlet at the bottom of the reactor and having a cooling coil and a stirring blade inside is sufficiently replaced with nitrogen, the second bromide is removed. 54.8 g of copper, di-n-
1110 g of butylamine and 20 liters of toluene,
8.75 kg of 2,6-xylenol was dissolved in a mixed solvent of 16 liters of n-butanol and 4 liters of methanol and charged into the reactor. Oxygen was continuously blown into the reactor while stirring, and polymerization was performed for 90 minutes while controlling the internal temperature to 30 ° C. After completion of the polymerization, the precipitated polymer was separated by filtration. A mixed solution of methanol / hydrochloric acid was added thereto to decompose the remaining catalyst in the polymer, further sufficiently washed with methanol, and dried to obtain a powdered polyphenylene ether (referred to as PPE). The reduced viscosity ηsp / C is 0.4
It was 1 dl / g.

(E) Flame retardant: 1,3-phenylene bis (diphenyl phosphate) (FR) Commercially available aromatic condensed phosphoric acid ester derived from resorcinol (trade name: CR733S, manufactured by Daihachi Chemical Industry Co., Ltd.) ｝ Was used. Further, the aromatic condensed phosphoric acid ester is GP
According to C analysis, it was composed of a TPP dimer (n = 1) and a TPP oligomer (n ≧ 2) represented by the following formula (19), and the weight ratio was 65/35, respectively.

[0121]

Embedded image

[0122]

Examples 1-4, Comparative Examples 1-8 A twin-screw extruder (W
ZSK-40 manufactured by erner Pfleiderer
mmΦ), melt extrusion was performed. That is, when using a liquid flame retardant to melt the above mixed composition with an extruder, components other than the liquid flame retardant are added to the hopper, only the liquid flame retardant is added by side feed, and the number of rotations is 2
Melt extrusion was performed under the conditions of 95 rpm, a discharge rate of 80 kg / h, and 300 ° C. On the other hand, when ME-GUM without a liquefying agent was used, all components were added to a hopper, and melt extrusion was performed in the same manner as described above.

A test piece was prepared from the pellet thus obtained using an injection molding machine (Model IS80A, manufactured by Toshiba Machine Co., Ltd.) under conditions of a cylinder temperature of 250 ° C. and a mold temperature of 60 ° C. The production amount was evaluated. Table 1 shows the results. In addition, styrene resin compositions having different styrene monomer and oligomer contents were also evaluated for flame retardancy. Table 2 shows the results.

[0124]

[Table 1]

[0125]

[Table 2]

According to Table 1, among the same polydimethylsiloxanes, the amount of char formation of the resin composition using the ME-GUM-containing liquid flame retardant is a value calculated based on the additivity of the TGA measurement data of each component. Higher, it is observed that there is an interaction between each component.

On the other hand, when ME-GUM without a liquefying agent was used (Comparative Example 8), ME-GUM and P
It can be seen that the dispersibility of ME-GUM is poor and the flame retardancy is poor because FR is side-fed after PE is melted.

Further, Table 2 shows that in the styrenic resin composition, the flame retardancy is significantly improved by reducing the residual styrene monomer and oligomer in the composition to 1% by weight or less.

[0129]

Industrial Applicability The present invention relates to a liquid flame retardant capable of achieving excellent flame retardancy, and a resin composition containing the liquid flame retardant.

The composition obtained according to the present invention has a VT
R, distribution board, television, audio player, condenser, household outlet, boombox, video cassette, video disk player, air conditioner, humidifier, electric home appliance housing such as electric hot air machine, chassis or parts, CD-ROM main Frame (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 equipment housing such as telephone, Chassis or parts, connector, coil bobbin, switch, relay, relay socket, LED, variable condenser, AC adapter, FBT high-voltage bobbin, FBT case, IFT coil bobbin, jack, volume shaft, motor Suitable for electronic and electrical materials such as electrical components, and automotive materials such as instrument panels, radiator grills, clusters, speaker grills, louvers, console boxes, defroster garnishes, ornaments, fuse boxes, relay cases, connector shift tapes, etc. And play a large role in these industries.

──────────────────────────────────────────────────の Continued on front page (51) Int.Cl. ⁶ Identification code FI C09K 21/14 C09K 21/14

Claims (4)

[Claims] 1. A liquid flame retardant which is liquid at 25 ° C., comprising a high molecular weight polyorganosiloxane gum. 2. The liquid flame retardant according to claim 1, further comprising a liquid phosphorus-based flame retardant. 3. A flame-retardant resin composition containing the liquid flame retardant according to claim 1. 4. The residual aromatic vinyl monomer and the total content of dimers and trimers of the aromatic vinyl monomer are 1
The flame-retardant styrenic resin composition according to claim 3, which is less than or equal to% by weight.