JPH10251468A - Nonhalogen flame retardant for styrene resin - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a nonhalogen flame retardant for styrene resins which gives a flame-retardant resin compsn. which does not caused mold deposits even in long-term continuous molding and is excellent in retention of external appearance, impact strength, heat resistance, and fluidity and to provide a resin compsn. contg. the same. SOLUTION: This flame retardant is represented by the formula (a, b, c, d, and e are each 0-3 excluding the case when all of them are O; R<1> to R<5> are each a 1-10C hydrocarbon group; and n is an integer of 1-3) and has a wt. loss of 0-10wt.% at 300 deg.C and a wt. loss of 20-100wt.% at 400 deg.C in a heating test in nitrogen at a temp. rise rate of 40 deg.C/min, an acid value of 0.01-1mgKOH/ g according to JIS K 6751, and a total acid content of 1-10,000KOH.mg in hydrolysis test according to MIL H-19475. A flame-retardant styrenic resin compsn., esp. of a dripping-type, is prepd. by compounding 100 pts.wt. styrenic resin with 1-100 pts.wt. above flame-retardant.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to a styrene resin flame retardant. More specifically, the present invention relates to a non-halogen flame retardant of a styrene-based resin, which has excellent flame retardancy, appearance retention, and does not generate a mold deposit even after long-term continuous molding, and a styrene-based resin composition containing this agent. Things.

[0002]

2. Description of the Related Art Styrene-based resins are excellent in impact resistance in addition to excellent moldability.
Although it is used in various fields such as home electric appliance parts and OA equipment parts, its use is limited due to the flammability of styrene resins.

[0003] As a method of making a styrene resin flame-retardant,
It is known to add halogen-based, phosphorus-based, and inorganic-based flame retardants to styrene-based resins, thereby achieving some degree of flame retardancy. However, when a halogen-based flame retardant is used, there are also environmental problems, such as phosphorus-based flame retardants.
When inorganic flame retardants are used, impact strength, molding fluidity and heat resistance are not always satisfactory, and mold contamination due to volatile organic phosphorus during molding, so-called mold deposit occurs. There is a problem in that productivity is reduced, or mold contaminants are transferred to a molded article to cause stress cracking, and industrial use is narrowed.

As techniques for improving the volatility, flame-retardant resin compositions comprising polyamide, polycarbonate and polyphosphate (Japanese Patent Publication No. 18336/1990), and aromatic compounds such as phenylenebis (2,6-dialkylphosphate) Production method and use of diphosphate (JP-A-5-10
No. 79) is disclosed. Although the flame retardant and the resin composition disclosed in the above publication have excellent volatility resistance, they do not have a specific structure and a specific acid value of the present invention, and thus have poor flame retardancy. Further, in the above publication, when the aromatic phosphate ester condensate having a specific thermal decomposition property has a specific acid value and a specific total acid amount in a hydrolysis test, excellent flame retardancy,
It is not disclosed or even implied that appearance retention is developed.

[0005]

SUMMARY OF THE INVENTION In view of the above situation, the present invention is free from the above-mentioned problems, that is, a styrene-based (low-volatility) styrenic resin which does not generate a mold deposit even after continuous molding for a long period of time. An object of the present invention is to provide a non-halogen flame retardant for a resin and a styrene resin composition using the same.

[0006]

Means for Solving the Problems The present inventors diligently studied a technique for preventing mold deposits, which is one indicator of volatility resistance, and as a result, found that aromatic phosphorus having a specific structure and a specific thermal decomposition property was used. Surprisingly, by using an acid ester condensate, it has been found that it is possible to dramatically improve the flame retardancy and appearance retention of a styrenic resin while suppressing mold deposits. Reached.

That is, the present invention relates to a flame retardant represented by the following formula (1), which is subjected to a heating test in nitrogen (at a heating rate of 40 ° C.).
/ Min), the weight loss at 300 ° C. is 0 to 10% by weight, the weight loss at 400 ° C. is 20 to 100% by weight,
And the acid value specified in JIS-K6751 is 0.01-1.
mgKOH / g, and the total acid amount in the hydrolysis test specified in MIL-H19475 is 1 to 10,000 KO.
An object of the present invention is to provide a non-halogen flame retardant of a styrene-based resin of H · mg and a styrene-based resin composition containing this agent, especially a drip-type flame-retardant styrene-based resin composition.

[0008]

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(Where a, b, c, d, and e are each 0
To 3, where a, b, c, d, and e are not simultaneously 0. R ¹ to R ⁵ are hydrocarbons having 1 to 10 carbon atoms, and n represents an integer of 1 to 3. Hereinafter, the present invention will be described in detail.

The non-halogen flame retardant (component A) of the styrenic resin of the present invention is an aromatic phosphate ester condensate having a specific structure, and has a specific thermal decomposition property, a specific acid value and a hydrolytic test. Has a specific total acid content of

In the heating test in nitrogen (heating rate of 40 ° C./min), the above-mentioned component A has a weight loss of 0 to 1 at 300 ° C.
0% by weight, and the weight loss at 400 ° C. is 20 to 100.
% By weight, preferably 25 to 100% by weight. That is,
Since the weight loss at 300 ° C. is 10% by weight or less, no mold deposit occurs in the molding of the styrenic resin. Flame retardancy develops. It is important that the aromatic phosphate ester satisfying the above requirements as a flame retardant is not a monomer but a condensate. Since it is a condensate, it is non-volatile at a processing temperature of 300 ° C. or less, and there is no problem of mold deposit during processing. In addition, by having the following specific structure, 400
Decomposes or volatilizes at ℃ to develop excellent flame retardancy. More specifically, the aromatic phosphate ester condensate of the formula (1) is composed of a phosphate ester binding portion with a monofunctional phenol and a binding portion where an aromatic phosphate ester is condensed with a bifunctional phenol. The condensed portion (derived from a bifunctional phenol) of the aromatic phosphate condensate is a substituted or unsubstituted phenylene group. The substitution of two phosphate esters on the benzene ring lowers the binding energy, and easily decomposes at 400 to 450 ° C. to promote flame retardancy. If a diphenyl group or an isopropyldiphenyl group is used instead of phenylene, the bond of the ester portion is strong, so that the decomposability at the time of combustion is poor and the flame retardancy is reduced. The monofunctional phenol is preferably substituted with an alkyl group at the 2,6-position. In general, when the condensed portion is a substituted or unsubstituted phenylene group, the hydrolysis resistance is relatively low, but the hydrolysis resistance is dramatically improved by the substitution of a hydrocarbon group, particularly an alkyl group at the 2,6-position. The inventors have found that the present invention is improved, and have completed the present invention.

The aromatic phosphate condensate constituting the non-halogen flame retardant (component A) of the styrene resin of the present invention is represented by the formula (1).

[0013]

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(Where a, b, c, d, and e are each 0
To 3, where a, b, c, d, and e are not simultaneously 0. R ¹ to R ⁵ are hydrocarbons having 1 to 10 carbon atoms, and n represents an integer of 1 to 3. The aromatic phosphate ester condensate of the present invention is disclosed in
It can be produced by a known method disclosed in, for example, Japanese Patent No. 079. For example, a monofunctional phenol substituted at the 2,6-position is reacted with phosphorus oxyhalide in the presence of a Lewis acid catalyst to obtain a diaryl phosphorohalide, which is then reacted with a bifunctional phenol in the presence of a Lewis acid catalyst. It is a method of reacting. Particularly preferred examples of the aromatic phosphate ester condensate flame retardant of the present invention include 1,3-phenylenebis [di (2,6-dimethylphenyl) phosphate] and 1,4-phenylenebis [di (2,6 -Dimethylphenyl) phosphate].

The non-halogen flame retardant of the styrenic resin of the present invention can impart excellent flame retardancy by being blended with the styrenic resin.

The styrene resin (component B) is a rubber-modified styrene resin and / or a non-rubber-modified styrene resin, and is not particularly limited as long as it is compatible with or homogeneously dispersed with the component A. In particular, as the B component, a rubber-modified styrene-based resin alone or a composition comprising a rubber-modified styrene-based resin and a rubber-unmodified styrene-based resin is preferable. 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. It can be obtained by adding a monomer and, if necessary, a vinyl monomer copolymerizable therewith, and subjecting the monomer mixture to known bulk polymerization, bulk suspension polymerization, solution polymerization or emulsion 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 rubber-like polymer must have a glass transition temperature (Tg) of -30 ° C. or less,
If the temperature exceeds -30 ° C, the impact resistance decreases.

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, 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 styrene resin. When it is necessary to increase oil resistance, unsaturated nitrile monomers such as acrylonitrile and methacrylonitrile can be used.

If it is necessary to lower the melt viscosity during 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 part (0.5 g / dl, which is a measure of the molecular weight of the rubber-modified styrenic resin,
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 thermoplastic resin can be blended mainly with a styrene resin. For example, a polyphenylene ether-based, polyamide-based, polyester-based, polyphenylene sulfide-based, polycarbonate-based, polymethacrylate-based, or a mixture of two or more of them can be used. Here, a polyphenylene ether-based or polycarbonate-based thermoplastic resin is particularly preferable.

In the present invention, one of the thermoplastic resins which can be blended with the styrene resin, polyphenylene ether (component C), is a homopolymer and / or a copolymer comprising a bonding unit represented by the following formula (2). .

[0027]

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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), 2,6-dimethylphenol and 2,3,3-dimethylphenol.
A copolymer with 6-trimethylphenol is preferred,
Among them, 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, US Pat. No. 3,306,87
No. 5, U.S. Pat. No. 3,257,357,
U.S. Pat. No. 3,257,358 and JP-B-52
It can be easily produced by the methods described in JP-A-17880 and JP-A-50-51197. Reduced viscosity ηsp / c of the polyphenylene ether used in the present invention
(0.5 g / dl, chloroform solution, measured at 30 ° C.)
Is preferably in the range of 0.20 to 0.70 dl / g, and more preferably in the range of 0.30 to 0.60 dl / g. Reduced viscosity η of polyphenylene ether
Means for satisfying the above requirements regarding sp / c include adjustment of the amount of a catalyst in the production of the polyphenylene ether.

When a resin composition is produced by adding the non-halogen flame retardant of the styrene resin of the present invention,
1 to 1 part by weight of styrene resin
It is preferably contained in an amount of 00 parts by weight, more preferably,
It is 1 to 30 parts by weight, most preferably 5 to 20 parts by weight.

In the present invention, as the resin component mainly composed of a styrene resin, a combination of the component B and the component C is most preferable, and the addition weight ratio of the component B / C in the resin component is (1 to 99), respectively. / (99-1) is preferable, (50-99) / (50-1) is more preferable, (70-97) / (30-3) is most preferable, and (80-95) / (20-5).

The non-halogen flame retardant (component A) of the styrenic resin of the present invention may be optionally used depending on the resin composition.
As the flame retardant other than the component A (component D), an organic phosphorus compound other than the component A, red phosphorus, an inorganic phosphate, an inorganic flame retardant, and the like can be blended.

The amount of the component D is preferably 1 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 the styrene resin.

The phosphorus-based flame retardant as the component D is an organic phosphorus compound, red phosphorus, an inorganic phosphate or the like.

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.

In the component D, one of the phosphorus-based flame retardants, red phosphorus, has its surface previously selected from aluminum hydroxide, magnesium hydroxide, zinc hydroxide, and titanium hydroxide in addition to general red phosphorus. Those coated with a metal hydroxide coating, 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, 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 component D, one inorganic phosphate of the phosphorus-based flame retardant is typically ammonium polyphosphate.

The inorganic flame retardant as the component D includes aluminum hydroxide, magnesium hydroxide, dolomite, hydrotalcite, calcium hydroxide, barium hydroxide, basic magnesium carbonate, zirconium hydroxide, and tin oxide. Hydrates of inorganic metal compounds such as hydrates, zinc borate, zinc metaborate, barium metaborate, zinc carbonate, magnesium carbonate, mu calcium, calcium carbonate, barium carbonate and the like can be mentioned. 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.

The amount of the component D in the present invention is 1 to 100 parts by weight, preferably 1 to 50 parts by weight, more preferably 100 to 100 parts by weight of the styrene resin.
It is 3 to 20 parts by weight, most preferably 5 to 15 parts by weight.

The non-halogen flame retardant (A component) of the styrenic resin of the present invention may be optionally used depending on the resin composition.
One or more release agents (E components) selected from saturated higher aliphatic carboxylic acids or metal salts thereof, carboxylic acid ester waxes, organosiloxane waxes, polyolefin waxes, and polycaprolactone can be blended. it can.

Among the above components E, 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 the component E is preferably 0.01 to 5 parts by weight, more preferably 0.1 to 5 parts by weight, most preferably 0.3 to 5 parts by weight based on 100 parts by weight of the styrene resin.
1 part by weight.

In the present invention, if necessary, one or more flame retardants selected from triazine skeleton-containing compounds, novolak resins, metal-containing compounds, silicone resins, silicone oils, silica, aramid fibers, fluororesins, and polyacrylonitrile fibers. An auxiliary agent (F component) can be blended.

The amount of the F component is preferably 0.001 to 40 parts by weight, more preferably 1 to 20 parts by weight, and most preferably 5 to 1 part by weight based on 100 parts by weight of the styrene resin.
0 parts by weight.

The triazine skeleton-containing compound as the F component is a component for further improving the flame retardancy as a flame retardant aid of the phosphorus-based flame retardant. Specific examples thereof include melamine, melam represented by the following formula (3), melem represented by the following formula (4), melon (a product obtained by deammonating three to three molecules of melem at 600 ° C. or higher), and the following formula: (5)
A melamine phosphate represented by the following formula (6), a succinoguanamine represented by the following formula (7), adipoguanamine, methylglutalogamine, a melamine resin represented by the following formula (8) And BT resin represented by the following formula (9), but melamine cyanurate is particularly preferred from the viewpoint of volatility resistance.

[0047]

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[0048]

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[0049]

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[0050]

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[0051]

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[0052]

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[0053]

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The novolak resin as the component F is a flame retardant aid and, when used in combination with a hydroxyl group-containing aromatic phosphate, also serves as a fluidity and heat resistance improver. 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 represented by the following formula (1)
0) and (11).

[0056]

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The above 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.

The metal-containing compound as the component F is a metal oxide and / or a 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 as the F component is SiO 2
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 as the component F is a polydiorganosiloxane, particularly preferably a vinyl-containing silicone oil, and comprises a chemical bond unit represented by the following formula (12).

[0063]

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R in the above formula is a C1-8 alkyl group, C
It is one or more substituents selected from 6 to 13 aryl groups and vinyl-containing groups represented by the formulas (13) and (14), and particularly contains a vinyl group in the molecule.

[0065]

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[0066]

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The viscosity of the above 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 the component F is amorphous silicon dioxide, and is preferably a silica coated with a hydrocarbon compound, the surface of which is treated with a hydrocarbon compound silane coupling agent. Hydrocarbon compound-coated silica 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 aramid fiber as the component F preferably has 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. It can be produced by dissolving and solution spinning by a wet or dry method.

The fluorine-based resin as the component F is a flame-retardant aid, and 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 above-mentioned fluorine-containing monomer and a copolymerizable monomer may be used in combination.

The polyacrylonitrile fiber as the component F 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.

In the present invention, if necessary, a copolymer resin comprising an aromatic vinyl unit and an acrylate 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 (component G) selected from soaps can be blended.

The amount of the G component is preferably 0.1 to 20 parts by weight, more preferably 0.5 to 10 parts by weight, and most preferably 1 to 5 parts by weight based on 100 parts by weight of the styrene resin.
Parts by weight.

The aromatic vinyl unit of the copolymer resin as the G component includes, for example, styrene, α-methylstyrene, paramethylstyrene, p-chlorostyrene, p-bromostyrene, 2,4,5-tribromostyrene and the like. Styrene is most preferred, but other aromatic vinyl monomers described above 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 the G component include liquid paraffin, natural paraffin, microwax, polyolefin wax, synthetic paraffin, and partial oxides, fluorides and chlorides thereof.

The higher fatty acid as the component G is a releasing agent (E
And unsaturated fatty acids such as ricinoleic acid, ricinbereidic acid and 9-oxy-12-octadecenoic acid.

The higher fatty acid ester as the G component is a monohydric alcohol ester of a fatty acid such as methyl phenylstearate or butyl phenylstearate, or a monohydric alcohol ester of a polybasic acid such as diester stearate of diphenylstearyl phthalate. Yes, further, 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, stearic acid monoglyceride,
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.

The higher fatty acid amide as the component G includes 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'-2-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 the G component is
Monohydric alcohols such as stearyl alcohol and cetyl alcohol; polyhydric alcohols such as sorbitol and mannitol; and polyoxyethylene dodecylamine and polyoxyethylene bactadecylamine. Allylated ethers having an alkylene ether unit, polyoxyethylene lauryl ether, polyoxyethylene tridodecyl ether, polyoxyethylene cetyl ether, polyoxyethylene stearyl ether, polyoxyethylene alkyl ether such as polyoxyethylene oleyl ether, polyoxyethylene Polyoxyethylene alkyl phenyl ether such as ethylene octyl phenyl ether and 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 the G component 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, if necessary, a thermoplastic elastomer (H component) can be blended, and examples thereof include polystyrene, polyolefin, polyester, polyurethane, 1,2-polybutadiene, and polyvinyl chloride. And a polystyrene-based thermoplastic elastomer is particularly preferable.

The amount of the H component is preferably 0.5 to 20 parts by weight, more preferably 1 to 10 parts by weight, and most preferably 2 to 5 parts by weight based on 100 parts by weight of the styrene resin. .

The above-mentioned 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.

Further, examples of the conjugated diene monomer constituting the 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 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) linear 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, if necessary, 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. One or two or more light resistance improvers (component I) selected from the above agents can be blended.

The amount of the component I is preferably 0.05 to 20 parts by weight, more preferably 0.1 to 10 parts by weight, most preferably 1 to 100 parts by weight based on 100 parts by weight of the styrene resin.
5 parts by weight.

In the present invention, as a method for producing a resin composition using polyphenylene ether (component C), a styrene resin and a component C are first melted,
After adding the components and melt kneading with the same extruder, or after producing a masterbatch containing the styrene resin, the C component, or the A component as necessary, the masterbatch and the remaining styrene resin or There is a method of kneading the remaining A component.

In the present invention, regarding the twin-screw extruder used for the production of the flame-retardant resin composition, especially when polyphenylene ether is contained, the ratio L / D of the screw length L to the cylinder inner diameter D is 20/20. To 50, and has two or more supply openings of a main feed opening and a side feed opening having different distances from the tip of the twin-screw extruder. It is preferable that a kneading portion is provided between the opening portions and between the distal end portion and the supply opening portion located at a short distance from the distal end portion, and the length of the kneading portion is 3D to 10D, respectively.

In the present invention, in particular, UL-94 regulated V
Preferred examples of the drop-type flame-retardant resin composition corresponding to the -2 ranking include the following.

The reduced viscosity ηsp / C of the resin portion is 0.4 to
80-95% by weight of a styrene-based resin composed of a rubber-modified styrene-based resin and a rubber non-modified styrene-based resin of 0.6,
Thermoplastic resin 1 containing 20 to 5% by weight of polyphenylene ether having a reduced viscosity ηsp / C of 0.3 to 0.6
5 parts by weight of the flame retardant represented by the formula (1)
0 parts by weight, one or more compounds selected from saturated higher aliphatic carboxylic acids and metal salts thereof 0.01
~ 5 parts by weight.

By satisfying the above-mentioned combination and the requirement of the reduced viscosity, the balance between the flame retardancy of dropping fire and the impact strength is improved.

In the case of the above composition, the balance between flame retardancy, especially drop-type flame retardancy, appearance retention, mold release, continuous moldability, moldability (flowability), impact resistance and heat resistance. Excellent characteristics.

The composition thus obtained is, for example,
It is possible to perform continuous molding for a long time using an injection molding machine or an extrusion molding machine, and the obtained molded product has flame retardancy (drop type flame retardancy), appearance retention, heat resistance and impact resistance. Are better.

[0099]

The present invention will be described in more detail with reference to the following examples and comparative examples, but the present invention is not limited thereto.

In Examples and Comparative Examples, various measurements were performed using the following measuring methods or measuring machines.

(1) Analysis of Flame Retardant and Resin Composition A) 5 g of the resin composition is dissolved in 100 ml of methyl ethyl ketone and separated using an ultracentrifuge. (2000
0 rpm, 1 hour) Then, twice the amount of methanol was added to the supernatant obtained by separation to precipitate a resin component,
The solution part and the resin part were separated using an ultracentrifuge.
For the solution part, GPC (gel permeation chromatography) [manufactured by Tosoh Corporation, Japan; HLC-8020 main unit (with a RI refractive index detector); Column: Tosoh Corp., two G1000HXL; mobile phase
Tetrahydrofuran; flow rate 0.8 ml / min; pressure 6
0 kgf / cm ² ; temperature INLET 35 ° C, OVE
N 40 ° C, RI 35 ° C; sample loop 100m
l; injection sample amount: 0.08 g / 20 ml], and assuming the area ratio of each component on the chromatogram to be the weight fraction of each component, the amount of phosphate ester was determined from the area ratio.
On the other hand, for the above resin part, the ratio of integral values of aromatic protons or aliphatic protons was determined using a Fourier transform nuclear magnetic resonance apparatus (proton-FT-NMR), and the rubber-modified styrene resin and aromatic polycarbonate were determined. And the amount of a thermoplastic resin such as polyphenylene ether.

B) Volatility of flame retardant (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 weight loss at 300 ° C. or 400 ° C. was taken as a measure of volatility. .

C) Acid value Measured according to JIS-K6751.

(2) 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 give a solution having a concentration of 0.5 g / dl. 10 ml of this solution is placed in a Canon-Fenske viscometer, 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, regarding 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.

(3) Izod Impact Strength Measured at 23 ° C. by a method according to ASTM-D256.

(V Notch, 1/8 inch Test Specimen) (4) Vicat Softening Temperature Measured by a method in accordance with ASTM-D1525 and used as a measure of heat resistance.

(5) Melt flow rate (MFR) The melt flow rate was measured by a method in accordance with ASTM-D1238 as an index of melt fluidity. It was determined from the extruded amount per 10 minutes (g / 10 minutes) under the conditions of a load of 5 kg and a melting temperature of 200 ° C.

(6) Flame retardancy VB (Vertical Bur) conforming to UL-94
ning) method. (1/8 inch test piece) (7) Hydrolysis test MIL standard (Millitary Specifica)
tions) Measured by a method according to H-19475. That is, 75 g of a flame retardant and 25 g of distilled water were added to the sample bottle, and the sample bottle was sealed and kept in a thermostat at 93 ± 0.2 ° C. for 48 hours while rotating the sample bottle. Thereafter, the aqueous phase and the organic phase were separated, and the acid value of each phase was titrated with potassium hydroxide (KOH) using the indicator phenolphthalein to determine the total amount of total acid (KOH · mg).

(8) Appearance Retention The molded article was immersed in a constant temperature bath at 80 ° C. for 10 hours, and the surface gloss of the molded article before and after immersion was measured at an incident angle of 60 ° based on ASTM-D523-62T. Next, the surface gloss before and after immersion was defined as G ₀ and G ₁ , respectively, and the difference ΔG was used as an index of appearance retention. The smaller ΔG, the better the appearance retention.

The following components were used in Examples and Comparative Examples.

(A) Styrene resin Rubber-modified styrene resin (HIPS) polybutadiene (weight ratio of cis 1,4 bond / trans 1,4 bond / 1 vinyl 1,2 bond = 95/2/3) (Nippon Zeon ( Co., Ltd., brand name Nipol 122 OSL)｝
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 liquid 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. As a result of analyzing the obtained rubber-modified aromatic vinyl resin (referred to as HIPS-1), the rubber content was 12.1% by weight, and the weight average particle diameter of the rubber was 1.5 μm.
m, and the reduced viscosity ηsp / c was 0.53 dl / g.

Further, rubber-modified styrene resins having different reduced viscosities ηsp / c were produced by adjusting the amount of the polymerization initiator, the polymerization temperature and the amount of the chain transfer agent. The results are shown in Table 2.

In the examples and comparative examples, the following HIPS
Was used. (Tables 2, 3) HIPS-1: polybutadiene rubber, rubber content is 12.
The weight average particle diameter of the rubber was 1.5 μm, and the reduced viscosity ηsp / c was 0.53 dl / g.

HIPS-2: polybutadiene rubber, rubber content 12.1% by weight, rubber weight average particle size 1.5
μm, reduced viscosity ηsp / c is 0.79 dl / g.

HIPS-3: polybutadiene rubber, rubber content 12.1% by weight, rubber weight average particle size 1.5
μm, and reduced viscosity ηsp / c is 0.60 dl / g.

HIPS-4: polybutadiene rubber, rubber content 12.1% by weight, rubber weight average particle size 1.5
μm, reduced viscosity ηsp / c is 0.58 dl / g.

HIPS-5: polybutadiene rubber, rubber content 12.1% by weight, rubber weight average particle size 1.5
μm, reduced viscosity ηsp / c is 0.40 dl / g.

HIPS-6: rubber content: 12.1% by weight, rubber weight average particle size: 1.5 μm, reduced viscosity ηs
p / c is 0.35 dl / g.

Rubber-unmodified styrene resin (GPPS) Polystyrene having a weight average molecular weight of 200,000 (produced by Asahi Kasei Kogyo Co., Ltd.) was used (referred to as GPPS).

(B) Production of thermoplastic resin, 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 stirring blades inside was sufficiently replaced with nitrogen, , Cupric bromide 54.8 g, 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. The polymer was sufficiently washed with methanol and then dried to obtain a powdery polyphenylene ether (referred to as PPE-1). The reduced viscosity ηsp / C was 0.41 dl / g.

Further, polyphenylene ethers having different reduced viscosities ηsp / c were produced by adjusting the amount of catalyst or controlling the polymerization time in the production of polyphenylene ether. Table 3 shows the results.

Aromatic Polycarbonate (PC) A commercially available bisphenol A type polycarbonate was used.

ABS Resin (ABS) A commercially available ABS resin (acrylonitrile / butadiene / styrene = 26/14/60 (weight ratio)) was used.

Polyethylene (PE) Commercially available low density polyethylene was used.

Polypropylene (PP) A commercially available unmodified polypropylene was used.

Polyamide (PA) A commercially available polyamide 6 was used.

Polyethylene Terephthalate (PET) Commercially available polyethylene terephthalate was used.

(C) Phosphorus-based flame retardant triphenyl phosphate (TPP) A commercially available aromatic phosphate ester monomer [trade name: TPP (trade name: TPP) manufactured by Daihachi Chemical Industry Co., Ltd.] was used.
The phosphorus content is 9.5% by weight.

Preparation of aromatic phosphate condensate of the present invention: 1,3-phenylenebis [di (2,6-dimethylphenyl) phosphate)] (FR-1) 244 parts by weight of 2,6-xylenol, xylene 20 parts by weight and 1.5 parts by weight of magnesium chloride are added to the reactor,
Heat and mix. When the temperature of the reaction solution reached 120 ° C, 153 parts by weight of phosphorus oxychloride was added dropwise over 2 hours. The hydrochloric acid gas generated at this time was led to a water scrubber. After the addition of phosphorus oxychloride is completed, the temperature of the reaction solution is gradually increased to 180 ° C.
The reaction was completed by raising it over 2 hours. The yield of the obtained intermediate di (2,6-xylenyl) phosphorochloride was 99.7%. Next, 45 parts by weight of the obtained intermediate, 55 parts by weight of resorcinol, and 1.5 parts by weight of aluminum chloride are added to a reactor, and heated and mixed, and the temperature of the reaction solution is gradually raised to 180 ° C. over 2 hours. Then, a dehydrochlorination reaction was performed. And after aging at the same temperature for 2 hours,
Aging was further performed for 2 hours under reduced pressure of 200 mmHg to complete the reaction. To the reaction solution thus obtained, 500 parts by weight of xylene and 200 parts by weight of 10% hydrochloric acid were added to remove the remaining catalyst and the like, and washing with water was repeated. The purified reaction solution was cooled to room temperature with stirring to crystallize, washed with methanol, dried at 100 ° C. under reduced pressure, and treated with 1,3-phenylenebis (2,6) represented by the following formula (15).
-Dimethylphenyl) phosphate)｝ (designated FR-1). The acid value of FR-1 was controlled by changing the number of purifications. Table 1 shows FR-1 with different purity.
It described in.

[0133]

Embedded image

Production of aromatic phosphate condensate of the present invention: 1,4-phenylenebis (2,6-dixylenyl phosphate) (FR-2) In the production of FR-1, hydroquinone was used instead of resorcinol. The same experiment was repeated except for using 1,4-phenylenebis [di (2,6-dimethylphenyl) phosphate)] (FR represented by the following formula (16).
-2).

[0135]

Embedded image

Aromatic phosphate condensate: bisphenol A bis (diphenyl phosphate) (fr-
1) Commercially available aromatic condensed phosphate ester derived from bisphenol A (trade name: CR741 (f) manufactured by Daihachi Chemical Industry Co., Ltd.)
(referred to as r-1)} was used. According to GPC analysis, the aromatic condensed phosphate was found to have the following formula (17)
TPP-A-dimer (n = 1) and TPP
-A-oligomer (n ≧ 2) and triphenyl phosphate (TPP), each having a weight ratio of 84.7 / 1
3.0 / 2.3.

[0137]

Embedded image

Aromatic phosphate ester condensate: 1,3-
Phenylene bis (diphenyl phosphate) (fr-
2) Commercially available resorcinol-derived aromatic condensed phosphate ester (trade name: CR733S (fr) manufactured by Daihachi Chemical Industry Co., Ltd.)
称 す る) was used. According to GPC analysis, the aromatic condensed phosphoric acid ester is composed of a TPP dimer (n = 1) and a TPP oligomer (n ≧ 2) represented by the following formula (18), and each has a weight ratio of 65/35.
Met.

[0139]

Embedded image

Examples 1 to 5 and Comparative Examples 1 to 5 Various aromatic phosphate esters shown in Table 1 were measured by the method described in the column of the measurement method, and the results were shown in the column of flame retardant evaluation in Table 1 and FIG. .

Next, HIPS-1 / GPPS (70 /
30) with respect to 100 parts by weight of the styrene resin,
9 parts by weight of the aromatic phosphate ester described in Table 1 were mechanically mixed, and using a lab plast mill manufactured by Toyo Seiki Seisaku-sho, Ltd.,
Melting was performed at a melting temperature of 220 ° C. and a rotation speed of 50 rpm for 5 minutes. From the resin composition thus obtained, a test piece having a thickness of 1/8 inch was prepared by a compression molding method, and the flame retardancy and the appearance retention were evaluated. The results are shown in Table 1.

According to Table 1 and FIG. 1, the aromatic phosphate ester satisfying the requirements of the present invention has an extremely small weight loss at 300 ° C., and thus has excellent volatility during molding. On the other hand, the aromatic phosphate of the present invention,
The weight loss at 400 ° C. is as large as 20% or more, and it is excellent in flame retardancy because it volatilizes or decomposes efficiently during combustion.
In addition, it can be seen that the balance characteristic of flame retardancy and appearance retention is exhibited by having a specific amount of acid value and the total acid amount in the hydrolysis test.

[0143]

[Table 1]

Examples 6 to 11 A composition obtained by mixing 9 parts by weight of FR-1 shown in Table 2 with 100 parts by weight of HIPS having a reduced viscosity ηsp / C shown in Table 2 was used in the same manner as in Example 1. To make a test piece,
The MFR, Izod impact strength, Vicat softening temperature, and flame retardancy were evaluated. Table 2 shows the results.

According to Table 2, the smaller the reduced viscosity ηsp / C, which is the index of the molecular weight of HIPS, is, the more excellent the flame retardancy of the dropping type is, but especially the ηsp / C is in the range of 0.4 to 0.6. , It can be understood that the balance characteristics of fluidity, impact strength and flame retardancy are excellent.

[0146]

[Table 2]

Examples 12 to 21 HIPS-1 / GPPS / FR-1 / PPE described in Table 3
Are mixed in the weight ratios shown in Table 3 and a side-feedable twin-screw extruder (Werner Pfleiderer) is used.
The melt extrusion was performed using a ZSK-40 mmφ manufactured by the company. That is, PPE / GPPS is set to 320 at the front stage of the extruder.
° C, and the remaining resin component and FR-1 were side-fed in the subsequent stage at a rotation speed of 295 rpm and a discharge amount of 80 kg /.
for 2 hours at 240 ° C.

A test piece was prepared from the pellet thus obtained using an injection molding machine (Model IS80A, manufactured by Toshiba Machine Co., Ltd.) under the conditions of a cylinder temperature of 230 ° C. and a mold temperature of 60 ° C., and the MFR and the Izod impact strength were measured. The Vicat softening temperature and flame retardancy were evaluated. Table 3 shows the results.

[0149]

[Table 3]

According to Table 3, the presence of PPE improves the heat resistance. In particular, rubber-modified styrenic resin and PPE
When the thermoplastic resin comprises 3 to 10% by weight of PPE and the reduced viscosity ηsp / C is 0.3 to 0.6, fluidity, heat resistance, rigidity, impact strength and flame retardancy It can be seen that the balance characteristic of the above is remarkably improved.

Examples 22 to 25, Comparative Examples 6 to 9 Using the FR-1 used in Examples 6 to 21, a resin composition was prepared from the thermoplastic resins shown in Tables 4 and 5 by the method of Example 14.
And fire retardancy was evaluated. Tables 4 and 5 show the results.

[0152]

[Table 4]

[0153]

[Table 5]

According to Tables 4 and 5, the flame retardant of the present invention is HI
Provides excellent flame retardancy to PS, ABS, PPE, and PC, but has no effect of imparting flame retardancy to PE, PP, PA, and PET, and is specifically effective for styrene resins. It turns out that it is.

[0155]

The non-halogen flame retardant of the styrenic resin of the present invention is added to the styrenic resin so that the mold deposit is significantly reduced even when continuous molding is performed for a long period of time, and the flame retardancy, appearance retention and resistance to flame resistance are maintained. A resin composition having excellent impact resistance, heat resistance, and fluidity can be obtained.

The resin composition obtained by using the styrene resin non-halogen flame retardant includes VTRs, distribution boards, televisions, audio players, capacitors, household outlets, radio cassettes, video cassettes, video disc players, air conditioners. , Humidifiers, home appliances such as electric hot air machines, chassis or parts, CD-RO
OA of 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, telephone, etc. Equipment housing, chassis or parts, connector, coil bobbin, switch, relay, relay socket, LED, variable condenser,
AC adapter, FBT high pressure bobbin, FBT case,
IFT coil bobbin, jack, volume shaft,
Suitable for electronic and electrical materials such as motor parts, 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.

[Brief description of the drawings]

FIG. 1 shows the results of measuring the weight loss of various aromatic phosphates by a thermobalance test (TGA method).

Claims (5)

[Claims] 1. A flame retardant represented by the following formula (1), wherein a weight loss at 300 ° C. is 0 to 10% by weight in a heating test in nitrogen (heating rate: 40 ° C./min): 400
The weight loss at 20 ° C is 20 to 100% by weight, and JIS-
The acid value specified in K6751 is 0.01 to 1 mgKOH /
g of a styrene-based resin having a total acid content of 1 to 10,000 KOH · mg in a hydrolysis test specified in MIL-H19475. Embedded image (Where a, b, c, d, and e are each 0 to 3, provided that a, b, c, d, and e are not simultaneously 0. R
¹ to R ⁵ are a hydrocarbon having 1 to 10 carbon atoms, and n represents an integer of 1 to 3. ) 2. In formula (1), a is 0, and b, c, d,
2. The non-halogen flame retardant for a styrenic resin according to claim 1, wherein e is 2 and R ^{2 to} R ⁵ are substituted at the 2,6-position. 3. The compound of the formula (1) wherein 1,3-phenylenebis [di (2,6-dimethylphenyl) phosphate) and / or 1,4-phenylenebis [di (2,6-dimethylphenyl) phospho] Non-halogen flame retardant for styrenic resin according to claim 1). 4. A styrenic resin composition containing 1 to 100 parts by weight of the flame retardant of claim 1 based on 100 parts by weight of the styrenic resin. 5. The resin part has a reduced viscosity ηsp / C of 0.4.
Resin component 1 consisting of 1 to 99% by weight of a rubber-modified styrene resin having a reduced viscosity of ０．６0.6 and 99-1% by weight of a polyphenylene ether having a reduced viscosity ηsp / C of 0.3 to 0.6.
The dripping flame-retardant styrenic resin composition according to claim 4, comprising 1 to 100 parts by weight of the flame retardant of any one of claims 1 to 3 with respect to 00 parts by weight.