JPH08311278A - Dripping, self-extinguishing, flame-retardant styrene resin composition - Google Patents

Abstract

PURPOSE: To obtain a styrene resin composition which melts and drips satisfactorily upon firing and is excellent in flame retardancy, heat resistance, impact resistance, and flowability. CONSTITUTION: This composition comprises a rubber-modified styrene resin (A), at least one organophosphorus compound (B), and a silicone (C). It is characterized in that the component (B) comprises 50-100wt.% monomeric organophosphorus compound and an organophosphorus compound condensate.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a dripping self-extinguishing flame-retardant styrene resin composition. More specifically, the present invention relates to a styrene-based resin composition having excellent self-extinguishing property of dropping (ignition melting dropping property), flame retardancy, heat resistance, impact resistance and fluidity.

[0002]

2. Description of the Related Art Styrene resins are used in various fields including automobile parts, home electric appliance parts, and OA equipment parts because they are excellent in impact resistance in addition to excellent moldability. The flammability of styrenic resins limits their use. As a method of making the styrene resin flame-retardant, it is known to add a halogen-based, phosphorus-based, or inorganic flame-retardant agent to the styrene resin, and thereby, the flame-retardant is achieved to some extent. However, in recent years, the demand for fire safety has suddenly been highlighted, and the regulations of the UL (Underwriters Laboratory) flame retardant test for home appliances and office automation equipment have become stricter with the years, and higher flame retardancy has been achieved. Is required. As a more advanced flame retardant technology, a method of increasing the amount of the flame retardant is known, but it is not economical to use a large amount of the flame retardant originally, and the generation of toxic gas and mechanical properties It is not preferable because it promotes the decrease. Therefore, it has been desired to develop a method of making the resin flame-retardant by using a flame-retardant in the smallest amount possible.

Conventionally, as a method for improving the flame retardancy of a styrene resin, for example, a resin composition comprising a styrene resin, a nitrogen compound such as melamine, a polyol and an organic phosphate ester (JP-A-4-117442), There is known a self-extinguishing styrene-based resin composition which is composed of a rubber-modified styrene resin having a specific average rubber particle diameter and a halogen-based flame retardant, and which is self-extinguishing after the ignition is added. However, the resin composition of the above publication is not sufficiently flame-retardant, which limits its industrial use. Further, in the above-mentioned JP-A-4-117442, it is disclosed that the organic phosphate ester is effective as a flame retardant, but the monomer of the organic phosphate ester is used as an essential component, and specified as necessary. The effect of improving flame retardancy by adding an amount of the condensate is not mentioned. In addition, the above-mentioned Japanese Patent Publication No. 6-43542 clearly states that the addition of silicone deteriorates the ignition, melting and dropping property, and does not disclose, or even suggest, the flame retardancy improving effect of the silicone addition of the present invention.

[0004]

In view of the above situation, the present invention does not have the above-mentioned problems, that is, it is excellent in igniting and melting dripping property, flame retardancy, heat resistance, impact resistance and fluidity. The purpose is to provide a styrene resin composition.

[0005]

Means for Solving the Problems As a result of intensive investigations by the present inventors on techniques for improving the flame retardancy of styrene resins, (A) rubber-modified styrene resins, (B) specific organophosphorus compounds and (C) ) It has been found that, by combining silicone, it is possible to surprisingly improve the ignition, melting and dropping properties and the flame retardancy while maintaining heat resistance, impact resistance and fluidity. The invention was reached. That is, the present invention provides a styrene resin composition containing (A) a rubber-modified styrene resin, (B) an organic phosphorus compound, and (C) a silicone, wherein (B) is an organic phosphorus compound monomer and an organic phosphorus compound. A dripping self-extinguishing styrene-based flame-retardant resin composition comprising a compound condensate and containing 50 to 100% by weight of the above monomer in (B) an organophosphorus compound. . Hereinafter, the present invention will be described in detail.

The resin composition of the present invention contains (A) a rubber-modified styrene resin, (B) a specific organic phosphorus compound, and (C) silicone. The above-mentioned component (A) is a main component of the molding resin composition and plays a role of maintaining the strength of the molded product, and the components (B) and (C) are (A).
It is a component for imparting ignition-melting dropping property and flame retardancy to the component. Here, the component (B) contains an organic phosphorus compound monomer as an essential component, and optionally contains an organic phosphorus compound condensate. When the above monomer is 50 in the organophosphorus compound (B),
It is indispensable to contain -100% by weight. If the amount of the above monomer is less than 50% by weight, the plasticization of the rubber-modified styrenic resin is not sufficient, so that not only the ignition-melting and dropping property is deteriorated, but also the flame-retardant auxiliary effect by the PO / radical in the gas phase is reduced. However, the flame retardancy is reduced.

The component (C) is a component for relaxing the orientation of the rubber-modified styrenic resin, and as a result, it has been found that it accelerates the ignition, melting and dropping properties of the resin composition molded body, thus completing the present invention. Came to. The rubber-modified styrenic resin used as the component (A) in the present invention is
It also includes a rubber modified product alone or a resin containing a rubber modified product as a main component and a non-rubber modified styrene resin. The rubber-modified styrenic resin is a polymer in which a rubber-like polymer is dispersed in particles in a matrix made of a vinyl-aromatic polymer, and the aromatic vinyl monomer and the aromatic vinyl monomer are present in the presence of the rubber-like polymer. If necessary, a vinyl monomer copolymerizable therewith may be added, and the monomer mixture may be obtained by 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-acrylic rubber-styrene copolymer), AES resin (acrylonitrile-ethylene). Propylene rubber-styrene copolymer) and the like. Here, the rubber-like polymer needs to have a glass transition temperature (Tg) of -30 ° C or lower, and if it exceeds -30 ° C, the impact resistance decreases.
Examples of such rubbery polymers are polybutadiene,
Diene rubbers such as poly (styrene-butadiene) and poly (acrylonitrile-butadiene), saturated rubbers obtained by hydrogenating the above diene rubbers, isoprene rubbers, chloroprene rubbers, acrylic rubbers such as polybutyl acrylate, and ethylene-propylene-diene monomers. Examples thereof include terpolymer (EPDM), and diene rubber is particularly preferable.

The aromatic vinyl monomer as an essential component in the graft-polymerizable monomer mixture which is polymerized in the presence of the above rubbery polymer is, for example, styrene, α-methylstyrene, paramethylstyrene or p-methylstyrene. Chlorostyrene, p-bromostyrene, 2,4,5-tribromostyrene and the like are preferable, and styrene is the most preferable, but styrene may be the main component and other aromatic vinyl monomers may be copolymerized. When α-methylstyrene is used mainly in styrene, the ignition, melting and dropping property is improved. If necessary, one or more monomer components copolymerizable with the aromatic vinyl monomer can be introduced as a component of the rubber-modified styrene resin. When it is necessary to enhance oil resistance, unsaturated nitrile monomers such as acrylonitrile and methacrylonitrile can be used. When it is necessary to reduce the melt viscosity at the time of blending, an acrylate ester composed of an alkyl group having 1 to 8 carbon atoms can be used. When it is necessary to further increase the heat resistance of the resin composition, α-
Monomers such as methylstyrene, acrylic acid, methacrylic acid, 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 rubber-like polymer in the rubber-modified styrenic resin contained in the resin composition of the present invention is preferably 5 to
80% by weight, particularly preferably 10 to 50% by weight, and the graft-polymerizable monomer mixture is preferably 95 to 20% by weight, more preferably 90 to 50% by weight.
Within this range, the balance between impact resistance and rigidity of the desired resin composition is improved. Further, the rubber particle diameter of the styrene polymer is preferably 0.1 to 5.0 μm, and particularly 0.2
~ 3.0 μm is preferable. Within the above range, impact resistance is particularly improved. Reduced viscosity ηsp / which is a measure of the molecular weight of the rubber-modified styrene resin contained in the resin composition of the present invention
c (0.5 g / dl, toluene solution, measured at 30 ° C.) is
It is preferably in the range of 0.40 to 0.60 dl / g, and more preferably in the range of 0.50 to 0.60 dl / g. As means for satisfying the above requirements regarding the reduced viscosity ηsp / c of the rubber-modified styrene-based resin, adjustment of the amount of polymerization initiator, polymerization temperature, amount of chain transfer agent and the like can be mentioned.

The organic phosphorus compound used as the component (B) in the present invention contains an organic phosphorus compound monomer as an essential component and, if necessary, an organic phosphorus compound condensate. The above-mentioned organic phosphorus compound is, for example, phosphine, phosphine oxide, biphosphine, phosphonium salt, phosphinate, phosphoric acid ester, phosphorous acid ester and the like. More specifically, triphenyl phosphate, methyl neopentyl phosphite, pentaerythritol diethyl diphosphite, methyl neopentyl phosphonate, phenyl neopentyl phosphate, pentaerythritol diphenyl diphosphate, dicyclopentyl hypophosphite, diphenyl phosphate. Neopentyl hypophosphite, phenylpyrocatechol phosphite, ethylpyrocatechol phosphate, and dipyrocatechol hypophosphite. Here, in particular, as the organic phosphorus compound, an aromatic phosphate ester monomer represented by the following formula (1) is used as an essential component, and if necessary,
It is preferable to add an aromatic phosphoric acid ester condensate represented by the following formula (2).

[0012]

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[However, in the formulas (1) and (2), Ar ₁ and A
r ₂ , Ar ₃ , Ar ₄ , Ar ₅ and Ar ₆ are aromatic groups selected from a phenyl group, a xylenyl group, an ethylphenyl group, an isopropylphenyl group, a butylphenyl group and a 4,4′-dioxydiarylalkane group. is there. Also, n is 0
Represents an integer of 3 and m represents an integer of 1 or more. From the viewpoint of fluidity, heat resistance, and impact strength, among the above aromatic phosphate ester monomers, a hydroxyl group-containing aromatic phosphate ester monomer is particularly preferable, and for example, in the above formula (1) It is a phosphoric acid ester monomer containing one or more phenolic hydroxyl groups in the tricresyl phosphate, triphenyl phosphate, etc. shown.
Among the hydroxyl group-containing aromatic phosphoric acid esters, diphenylresorcinyl phosphate of the following formula (3) or diphenylhydroquinonyl phosphate of the following formula (4) is particularly preferable, and the production method thereof is, for example, JP-A-1- It is disclosed in Japanese Patent No. 223158 and is obtained by a reaction of phenol, hydroxyphenol, aluminum chloride and phosphorus oxychloride.

[0014]

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Another preferable example of the aromatic phosphate ester monomer from the viewpoint of volatility is a monomer represented by the following general formula (5).

[0016]

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(Where a, b and c are 1 to 3, R ₁ ,
R ₂ and R ₃ are hydrogen or a hydrocarbon having 1 to 15 carbon atoms, and the total number of carbon atoms of the substituents R ₁ , R ₂ and R ₃ is 10 to 20 on average in the entire compound. When the aromatic phosphate ester having a plurality of different substituents is used, the total number of carbon atoms of the substituents R ₁ , R ₂ and R ₃ of the B component is represented by a number average, and It is the product of the weight fraction of each aromatic phosphate ester component and the total carbon number of the substituents of each component. Among the aromatic phosphate ester monomers represented by the above formula (5), those containing a nonylphenyl group and a t-butyl group are preferable, and examples thereof include dinonylphenyl, phenylphosphate, nonylphenyl and t-butyl. Phenyl, phenyl phosphate and the like are preferable.

The silicone used as the component (C) in the present invention is polydiorganosiloxane, and its viscosity is preferably 10 to 1,000,000 centipoise (25 ° C), more preferably 50 to 1000 centipoise (25 ° C). If necessary, a thermoplastic resin other than the component (A) can be added to the resin composition of the present invention. For example, polystyrene-based, polyolefin-based, polyvinyl chloride-based, polyphenylene ether-based, polyamide-based, polyester-based, polyphenylene sulfide-based, polycarbonate-based, polymethacrylate-based, etc., or a mixture of two or more thereof can be used.

If desired, the resin composition of the present invention may contain a halogen-based flame retardant, red phosphorus, an inorganic phosphate, an inorganic flame retardant or the like as a flame retardant other than the component B. Examples of the halogen-based flame retardants include halogenated bisphenols, aromatic halogen compounds, halogenated polycarbonates, halogenated aromatic vinyl polymers, halogenated cyanurate resins, halogenated polyphenylene ethers, etc., and preferably decabromodiphenyl oxide. , Tetrabromobisphenol A,
Tetrabrom bisphenol A oligomer, brominated bisphenol phenoxy resin, brominated bisphenol polycarbonate, brominated polystyrene, brominated crosslinked polystyrene, brominated polyphenylene oxide, polydibromophenylene oxide, decabrom diphenyl oxide bisphenol condensate, halogen-containing phosphorus Examples thereof include acid esters and fluororesins.

The red phosphorus used as the flame retardant in the present invention is, in addition to general red phosphorus, the surface thereof is a metal hydroxide selected in advance from aluminum hydroxide, magnesium hydroxide, zinc hydroxide and titanium hydroxide. A coated with a film of aluminum hydroxide, magnesium hydroxide, zinc hydroxide, a metal hydroxide selected from titanium hydroxide and a coating of a thermosetting resin, aluminum hydroxide, For example, a coating of a metal hydroxide selected from magnesium hydroxide, zinc hydroxide and titanium hydroxide that is doubly coated with a coating of a thermosetting resin. The inorganic phosphate used as the flame retardant is typically ammonium polyphosphate.

The inorganic flame retardant which can be contained as necessary includes aluminum hydroxide, magnesium hydroxide, dolomite, hydrotalcite, calcium hydroxide, barium hydroxide, basic magnesium carbonate, water. Examples thereof include hydrates of inorganic metal compounds such as zirconium oxide and hydrates of tin oxide, 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, especially magnesium hydroxide, aluminum hydroxide,
A material selected from the group consisting of basic magnesium carbonate and hydrotalcite has a good flame retardant effect and is economically advantageous.

When a higher flame retardancy is required for the resin composition of the present invention, a triazine skeleton-containing compound, a novolac resin, a metal-containing compound, a silicone resin, a silicone oil, silica, or an aramid, if necessary. It may contain one or more flame retardant aids selected from fibers, fluororesins and polyacrylonitrile fibers. The triazine skeleton-containing compound is a component for further improving the flame retardancy as a flame retardant aid for phosphorus-based flame retardants. Specific examples thereof include melamine, melam represented by the following formula (6), melem represented by the following formula (7), melon (a product obtained by deammonification of 3 to 3 molecules of melem at 600 ° C. or higher), the following formula: Melamine cyanurate represented by (8), melamine phosphate represented by the following formula (9), succinoguanamine, adipguanamine, methylglutaloganamin represented by the following formula (10), represented by the following formula (11) Melamine resin, the following formula (12)
The BT resin and the like represented by can be mentioned, but melamine cyanurate is particularly preferable from the viewpoint of volatility resistance.

[0023]

[Chemical 4]

[0024]

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The novolak resin is a flame retardant aid,
When used in combination with a hydroxyl group-containing aromatic phosphoric acid ester, it is also 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, and the production method is "Polymer Experimental Science 5 Polycondensation and Polyaddition". (Kyoritsu Shuppan Sho 55-8-15) p. 43
7-455. An example of production of novolac resin is shown in the following formulas (13) and (14).

[0026]

[Chemical 6]

The phenols constituting the novolac resin are 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-
Hydroxybenzenesulfonic 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 metal-containing compound 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, tin oxide,
It is a simple substance such as antimony oxide, nickel oxide, copper oxide, or tungsten oxide or a composite (alloy) thereof, and the metal powder is aluminum, iron, titanium, manganese, zinc,
Molybdenum, cobalt, bismuth, chromium, nickel,
It is a simple substance of copper, tungsten, tin, antimony, etc. or a composite thereof.

The silicone resin is SiO ₂ , RSi.
It is a silicone resin having a three-dimensional network structure formed by combining structural units of O _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 substituents. Here, a silicone resin containing a vinyl group is particularly preferable. Such a silicone resin can be obtained by cohydrolyzing and polymerizing an organohalosilane corresponding to the above structural unit. The silicone oil is a polydiorganosiloxane having a chemical bond unit represented by the following formula (15).

[0030]

[Chemical 7]

R in the above is a C1-8 alkyl group, C6
To 13 aryl groups and one or more kinds of substituents selected from vinyl-containing groups represented by the following formulas (16) and (17), in which a vinyl group is contained in the molecule.

[0032]

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The viscosity of the silicone oil is 600 to 1
000000 centipoise (25 ° C) is preferable, and 90,000 to 150,000 centipoise (25 ° C) is more preferable. Said silica is amorphous silicon dioxide, particularly preferably a hydrocarbon compound-coated silica whose surface is treated with a hydrocarbon compound-based silane coupling agent, and more preferably a vinyl compound-containing hydrocarbon compound-coated silica. Is preferred.

The silane coupling agent is a vinyl group such as p-styryltrimethoxysilane, vinyltrichlorosilane, vinyltris (βmethoxyethoxy) silane, vinyltriethoxysilane, vinyltrimethoxysilane, γ-methacryloxypropyltrimethoxysilane. Contained silanes, epoxy silanes such as β- (3,4 epoxycyclohexyl) ethyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, and N-β (aminoethyl)
It is an aminosilane such as γ-aminopropyltrimethoxysilane, N-β (aminoethyl) γ-aminopropylmethyldimethoxysilane, γ-aminopropyltriethoxysilane and N-phenyl-γ-aminopropyltrimethoxysilane. Here, a silane coupling agent having a unit having a structure similar to that of the thermoplastic resin is particularly preferable. For example, p-styryltrimethoxysilane is suitable for a styrene resin. The treatment of the silane coupling agent on the silica surface 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, and the dry method is to charge silica into a high-speed stirring device such as a Henschel mixer, and stir it while stirring. Slowly,
This is a method of heat treatment thereafter.

The aramid fiber has an average diameter of 1 to 50.
It is preferable that the average fiber length is 0 μm and the average fiber length is 0.1 to 10 mm. It is produced by dissolving isophthalamide or polyparaphenylene terephthalamide in an amide polar solvent or sulfuric acid, and solution spinning by a wet or dry method. You can The fluororesin is a resin containing a fluorine atom in the resin. Specific examples thereof include polymonofluoroethylene, polydifluoroethylene, polytrifluoroethylene, polytetrafluoroethylene, and tetrafluoroethylene / hexafluoropropylene copolymer. Moreover, you may use together the said fluorine-containing monomer and the monomer which can be copolymerized as needed.

The polyacrylonitrile fiber preferably has an average diameter of 1 to 500 μm and an average fiber length of 0.1 to 10 mm. The polymer is dissolved in a solvent such as dimethylformamide and dried in an air stream at 400 ° C. It is produced by a dry spinning method of spinning or a wet spinning method of dissolving a polymer in a solvent such as nitric acid and wet spinning in water. When molding process fluidity is required, the resin composition of the present invention may optionally contain 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. One or more fluidity improvers selected from higher fatty acid amides, higher aliphatic alcohols, and metal soaps can be contained.

The aromatic vinyl unit of the above copolymer resin is
The aromatic vinyl unit shown in the description of (A),
The acrylic acid ester unit is an acrylic acid ester composed of an alkyl group having 1 to 8 carbon atoms such as methyl acrylate and butyl acrylate. Here, the content of acrylic acid ester units in the copolymer resin is preferably 3 to 40% by weight, and more preferably 5 to 20% by weight. Also, the solution viscosity, which is an index of the molecular weight of the above-mentioned copolymer resin (10% by weight of resin)
Methyl ethyl ketone solution, measurement temperature 25 ℃)
It is preferably 10 cp (centipoise). If the solution viscosity is less than 2 cp, the impact strength will be reduced, while 10 cp
If it exceeds, the effect of improving the fluidity decreases. The aliphatic hydrocarbon processing aid is liquid paraffin, natural paraffin, microwax, polyolefin wax, synthetic paraffin and partial oxides thereof, or fluorides, chlorides and the like.

The higher fatty acids include saturated fatty acids such as caproic acid, hexadecanoic acid, palmitic acid, stearic acid, phenylstearic acid and ferric acid, and ricinoleic acid,
Examples thereof include unsaturated fatty acids such as lysine belaidic acid and 9-oxy-12 octadecenoic acid. The higher fatty acid ester is a monohydric alcohol ester of a fatty acid such as methyl phenylstearate and butyl phenylstearate and a monobasic alcohol ester of a polybasic acid such as a phthalic acid diester of diphenylstearyl phthalate, and sorbitan monolaurate, Sorbitan such as sorbitan monostearate, sorbitan monooleate, sorbitan sesquioleate, sorbitan trioleate, polyoxyethylene sorbitan monolaurate, polyoxyethylene sorbitan monopalmitate, polyoxyethylene sorbitan monostearate, polyoxyethylene sorbitan monooleate Glycerates such as ester, stearic acid monoglyceride, oleic acid monoglyceride, capric acid monoglyceride, behenic acid monoglyceride Fatty acid ester of polyglycerin such as monomeric fatty acid ester, polyglycerin stearic acid ester, polyglycerin oleic acid ester, polyglycerin lauric acid ester, polyoxyethylene monolaurate, polyoxyethylene monostearate, polyoxyethylene monoester Examples thereof include fatty acid esters having a polyalkylene ether unit such as oleate and neopentyl polyol fatty acid esters such as neopentyl polyol distearate.

The higher fatty acid amides are monoamides of saturated fatty acids such as phenylstearic acid amide, methylol stearic acid amide, and methylol behenic acid amide, coconut oil fatty acid diethanolamide, lauric acid diethanolamide and coconut fatty acid diethanolamide, oleic acid diethanolamide. And N, N′-2 substituted monoamides and the like, and methylene bis (12-hydroxyphenyl) stearic acid amide, ethylene bis (12-hydroxyphenyl) stearic acid amide, hexamethylene bis (12- Saturated fatty acid bisamides such as hydroxyphenyl) stearic acid amide and aromatic bisamides such as m-xylylenebis (12-hydroxyphenyl) stearic acid amide.

The higher aliphatic alcohol is a monohydric alcohol such as stearyl alcohol or cetyl alcohol,
Polyhydric alcohols such as sorbitol and mannitol, and polyoxyethylene dodecylamine, polyoxyethylene boctadecylamine, and the like, and allyl ethers and polyoxyethylene lauryl having polyalkylene ether units such as polyoxyethylene allyl ether. Polyoxyethylene alkyl ether such as ether, polyoxyethylene tridodecyl ether, polyoxyethylene cetyl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene octylphenyl ether, polyoxyethylene nonylphenyl ether, etc. Oxyethylene alkyl phenyl ether, poly epichlorohydrin ether, polyoxyethylene bisphenol A ether, poly Carboxymethyl ethylene glycol,
It is a dihydric alcohol having a polyalkylene ether unit such as polyoxypropylene bisphenol A ether and polyoxyethylene polyoxypropylene glycol ether.

The metal soap is a metal salt of higher fatty acid such as stearic acid such as barium, calcium, zinc, aluminum or magnesium. If a higher impact strength is required, the resin composition of the present invention may optionally contain a thermoplastic elastomer,
For example, polystyrene-based, polyolefin-based, polyester-based, polyurethane-based, 1,2-polybutadiene-based, polyvinyl chloride-based, and the like, and polystyrene-based thermoplastic elastomer is particularly preferable. The polystyrene-based thermoplastic elastomer is a block copolymer composed of an aromatic vinyl monomer and a conjugated diene monomer, or a block copolymer in which the conjugated diene monomer portion is partially hydrogenated.

The aromatic vinyl monomer constituting the block copolymer consisting of the aromatic vinyl monomer and the conjugated diene monomer is the aromatic vinyl monomer shown in the explanation of (A), and is styrene. Is most preferable, but the above-mentioned other aromatic vinyl monomer may be copolymerized mainly with styrene. Also,
The conjugated diene monomer constituting the block copolymer is
1,3-butadiene, isoprene and the like can be mentioned.

In the block structure of the block copolymer, a polymer block composed of an aromatic vinyl monomer is represented by S, and a polymer block composed of a conjugated diene and / or its partially hydrogenated unit is represented. When displayed in B, 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 and (SB) nX (where n is an integer of 3 to 6; X is silicon tetrachloride, tin tetrachloride, polyepoxy) It is preferably a star block copolymer having a B portion represented by a coupling agent residue such as a compound) as a bond center. Among them, SB type 2, SBS type 3, S
BSB type 4 linear block copolymers are preferred.
The resin composition of the present invention, if required light resistance, ultraviolet absorbers, hindered amine light stabilizers, antioxidants, halogen scavengers, light-shielding agents,
One or more light resistance improvers selected from metal deactivators and quenchers may be contained.

The above-mentioned ultraviolet absorber absorbs light energy and becomes a keto-type molecule due to intramolecular proton transfer (benzophenone, benzotriazole type),
Alternatively, cis-trans is a component for isomerizing (cyanoacrylate type) to release it as heat energy and render it harmless. Specific examples thereof are 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-octoxybenzophenone and 5,5'-methylenebis (2-hydroxy-).
2-methoxybenzophenones such as 4-methoxybenzophenone), 2- (2'-hydroxy-5'-methylphenyl) benzotriazole, 2- (2'-hydroxy-5'-t-octylphenyl) benzotriazole, 2 -(2'-hydroxy-3 ', 5'-di-t-butylphenyl) benzotriazole, 2- (2'-hydroxy-3', 5'-di-t-butylphenyl) -5-
Chlorobenzotriazole, 2- (2'-hydroxy-
3'-t-5'-methylphenyl) -5-chlorobenzotriazole, 2- (2'-hydroxy-3 ', 5'-
2- (2′-hydroxyphenyl) such as dicumylphenyl) benzotriazole and 2,2′-methylenebis (4-t-octyl-6-benzotriazolyl) phenol
Benzotriazoles, phenyl salicylates, resorcinol monobenzoates, 2,4-di-t-butylphenyl-3 ′, 5′-di-t-butyl-4′-hydroxybenzoates, hexadecyl-3,5-di-t- Benzoates such as butyl-4-hydroxybenzoate,
Substituted oxanilides such as 2-ethyl-2′-methoxyoxanilide and 2-ethoxy-4′-dodecyloxanilide, and ethyl-α-cyano-β, β-diphenylacrylate, methyl-2-cyano-3. -Methyl-3- (p
Cyanoacrylates such as -methoxyphenyl) acrylate.

The hindered amine light stabilizer is a component for decomposing hydroperoxide generated by light energy to generate stable N—O. Radicals, N—OR and N—OH for stabilization. Specific examples thereof are 2,2,6,6-tetramethyl-4-piperidyl stearate, 1,2,2,6,6-pentamethyl-4-piperidyl stearate, 2,2,6,6-tetramethyl-
4-piperidyl benzoate, bis (2,2,6,6-
Tetramethyl-4-piperidyl) sebacate, bis (1,2,2,6,6-pentamethyl-4-piperidyl) sebacate, tetrakis (2,2,6,6-tetramethyl-4-piperidyl) 1,2, 3,4-butane tetracarboxylate, tetrakis (1,2,2,6,6
-Pentamethyl-4-piperidyl) -1,2,3,4-
Butane tetracarboxylate, bis (1, 2, 2,
6,6-Pentamethyl-4-piperidyl) .di (tridecyl) -1,2,3,4-butanetetracarboxylate, bis (1,2,2,6,6-pentamethyl-4-piperidyl) -2- Butyl-2- (3 ', 5'-di-t-
Butyl-4-hydroxybenzyl) malonate, 1-
(2-Hydroxyethyl) -2,2,6,6-tetramethyl-4-piperidinol / diethyl succinate polycondensate, 1,6-bis (2,2,6,6-tetramethyl-4)
-Piperidylamino) hexane / dibromoethane polycondensate, 1,6-bis (2,2,6,6-tetramethyl-4)
-Piperidylamino) hexane / 2,4-dichloro-6
-T-octylamino-s-triazine polycondensate, 1,
6-bis (2,2,6,6-tetramethyl-4-hyperidylamino) hexane / 2,4-dichloro-6-morpholino-s-triazine polycondensate and the like.

The above-mentioned antioxidant is a component for stabilizing peroxide radicals such as hydroperoxy radicals produced or for decomposing peroxides such as hydroperoxide produced by thermoforming or by exposure to light. is there. Specific examples thereof are hindered phenolic antioxidants and / or peroxide decomposers. The former serves as a radical chain inhibitor and the latter serves to prevent autoxidation by decomposing the peroxide generated in the system into more stable alcohols. The hindered phenolic antioxidant as the antioxidant,
2,6-ditertiarybutyl-4-methylphenol,
Styrenated phenol, n-octadecyl 3-
(3,5-ditert-butyl-4-hydroxyphenyl) propionate, 2,2'-methylenebis (4-methyl-6-tert-butylphenol), 2-tert-butyl-6- (3-tert-butyl-2) -Hydroxy-5-methylbenzyl) -4-methylphenyl acrylate, 2- [1- (2-hydroxy-3,5-ditertiary pentylphenyl) ethyl] -4,6-ditertiary pentylphenyl acrylate, 4,4 '-Butylidene bis (3-methyl-6-tert-butylphenol), 4,4'-thiobis (3-methyl-6-tert-butylphenol), alkylated bisphenol, tetrakis [methylene 3- (3,5-ditertiary] Butyl-4-hydroxyphenyl) propionate]
Methane, 3,9-bis {2- [3- (3-tert-butyl-4-hydroxy-5-methylphenyl) -propionyloxy] -1,1-dimethylethyl} -2,4
8,10-tetraoxaspiro [5.5] undecane and the like.

Further, the peroxide decomposer as the antioxidant is an organic phosphorus peroxide decomposer such as trisnonylphenyl phosphite, triphenyl phosphite and tris (2,4-ditertiary butylphenyl) phosphite. Or dilauryl 3,3′-thiodipropionate, dimyristyl 3,3′-thiodipropionate, distearyl 3,3′-thiodipropionate, pentaerythrityl tetrakis (3-laurylthiopropionate),
It is an organic sulfur-based peroxide decomposer such as ditridecyl 3,3′-thiodipropionate and 2-mercaptobenzimidazole. The halogen scavenger is a component for capturing free halogen generated during thermoforming or light exposure. Specific examples thereof include basic metal salts such as hydrotalcite, zeolite, magnesium oxide, calcium stearate and zinc stearate, organic tin compounds or organic epoxy compounds.

The above-mentioned hydrotalcite as a halogen scavenger does not contain a water-containing basic carbonate such as magnesium, calcium, zinc, aluminum, bismuth or its crystal water, and includes natural products and synthetic products. Examples of natural products include those having a structure of Mg ₆ Al ₂ (OH) ₁₆ CO ₃ .4H ₂ O. As a synthetic product, Mg _0.7 A
l _0.3 (OH) ₂ (CO ₃ ) _0.15・ 0.54H ₂ O, Mg
_4.5 Al ₂ (OH) ₁₃ CO ₃ · 3.5H ₂ O, Mg _4.2 Al _{2
(OH) 12.4 CO 3, Zn} 6 Al 2 (OH) 16 CO 3 · 4H
₂ O, Ca ₆ Al ₂ (OH) ₁₆ CO ₃ .4H ₂ O, Mg ₁₄ B
_{i 2 (OH) 29.6 · 4.2H} 2 O , and the like. The zeolite is an A-type zeolite represented by Na ₂ O · Al ₂ O ₃ · 2SiO ₂ · XH ₂ O, or Group II and Group II of the periodic table.
It is a metal-substituted zeolite containing at least one metal selected from Group IV metals. The substitution metal is Mg, Ca, Zn, Sr, Ba, Zr, Sn or the like, and Ca, Zn and Ba are particularly preferable.

The organic epoxy compound as the halogen scavenger is epoxidized soybean oil, tris (epoxypropyl) isocyanurate, hydroquinone diglycidyl ether, terephthalic acid diglycidyl ester, 4,4 '.
-Sulfobisphenol / polyglycidyl ether, N
-Glycidyl phthalimide, hydrogenated bisphenol A glycidyl ether, 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, 2- (3,4-epoxycyclohexylspiro [5,5] -3,4-epoxy ) Cyclohexane-m-
Dioxane, bis (3,4-epoxycyclohexylmethyl) adipate, vinylcyclohexene dioxide, 4-vinylepoxycyclohexane, bis (3,4
-Epoxy-6-methylcyclohexylmethyl) adipate, 3,4-epoxy-6-methylcyclohexyl-
3,4-epoxy-6-methylcyclohexanecarboxylate, methylenebis (3,4-epoxycyclohexane), dicyclopentadienebepoxide, di (3,4-epoxycyclohexylmethyl) ether of ethylene glycol, ethylenebis (3,3) 4-epoxycyclohexanecarboxylate), dioctyl epoxyhexahydrophthalate, di-hexahexahydrophthalate
Examples thereof include alicyclic epoxy compounds such as 2-ethylhexyl.

The light-shielding agent is a component for preventing light from reaching the bulk of the polymer. Specific examples thereof include rutile type titanium oxide (TiO ₂ ), zinc oxide (ZnO), chromium oxide (Cr ₂ O ₃ ), cerium oxide (CeO ₂ ), and the like. The metal deactivator is a component for deactivating heavy metal ions in the resin with a chelate compound. Specific examples thereof include acid amine derivatives, benzotriazole and its derivatives. The quencher is a component for deactivating photoexcited functional groups such as hydroperoxide and carbonyl groups in a polymer by energy transfer, and organic nickel and the like are known.

If necessary, a lubricant, a filler, a reinforcing agent such as glass fiber, a coloring agent such as a dye or a pigment, and the like can be added to the resin composition of the present invention as components other than those described above.
In the resin composition of the present invention, (A) the rubber-modified styrene resin is 70 to 98.9% by weight, and (B) the organic phosphorus compound is 29 to
It is preferable that 1% by weight and (C) silicone contain 0.1 to 10% by weight, more preferably (A) rubber-modified styrene resin is 87 to 96% by weight, and (B) organophosphorus compound is 10 to 10% by weight. 3% by weight and 1 to (C) silicone
Contains 3% by weight. Here, in the above-mentioned range, the balance characteristics of the ignition melting drop property, the flame retardancy, the molding process fluidity, the impact strength and the heat resistance are excellent. A molded product obtained by using the composition thus obtained by using, for example, an injection molding machine or an extrusion molding machine has excellent flame retardancy, impact strength and heat resistance.

[0052]

EXAMPLES The present invention will be described in more detail with reference to examples below, but the present invention is not limited thereto. The measurements in Examples and Comparative Examples were performed using the following methods or measuring machines. (1) Weight average particle diameter of rubber The weight average particle diameter of the rubber-modified aromatic vinyl resin is obtained by determining the particle diameter of the butadiene-based polymer in the transmission electron microscope photograph taken by the ultrathin section method of the resin composition, and using the following formula. calculate. Weight average particle diameter = ΣNi · Di ⁴ / ΣNi · Di ³ (where Ni is the number of butadiene-based polymer particles whose particles are Di) (2) Reduced viscosity ηsp / c 1 g of rubber-modified styrene-based resin and methyl ethyl ketone 18
Add a mixed solvent of 2 ml of methanol and 2 ml of methanol, and add 2 ml at 25 ° C.
Shake for time and centrifuge at 18000 rpm for 30 minutes at 5 ° C. The supernatant was taken out, the resin component was precipitated with methanol, and then dried.

0.1 g of the resin thus obtained was dissolved in toluene to give a solution having a concentration of 0.5 g / dl, and 10 ml of this solution was placed in a Canon-Fenske viscometer.
At 30 ° C., the number of seconds t _{1 during} which the solution flowed was measured. On the other hand, the flowing down time t ₀ of pure toluene was separately measured with the same viscometer and calculated by the following mathematical formula. ηsp / c = (t ₁ / t ₀ −1) / C (C: polymer concentration g / dl) (3) Izod impact strength Measured at 23 ° C. by a method according to ASTM-D256 (V notch, 1 / 8 inch test piece) (4) Vicat softening temperature It was measured by a method according to ASTM-D1525 and used as a scale of heat resistance.

(5) Melt flow rate (MFR) The melt flow rate was measured by a method according to ASTM-D1238 as an index of fluidity. 10 at a load of 5 kg and a melting temperature of 200 ° C
It was determined from the extrusion rate per minute (g / 10 minutes).

(6) Flame retardance VB (Vertical Bur) compliant with UL-94
(1/8 inch test piece) (7) Heat shrinkage rate of molded resin composition molded article 1 of resin composition obtained by compression molding method, injection molding method
/ 8 inch thick molded product with a hot air dryer at 170 ℃ 1
After left for 5 minutes, the heat shrinkage S (%) was calculated from the dimensional change of the molded body according to the following formula. S = (L ₀ −L) × 100 / L ₀ (where L ₀ is the dimension before heating and L is the dimension after heating) The following components were used in the examples and comparative examples. .

(A) Rubber-modified styrene resin A) Rubber-modified styrene resin (HIPS) Polybutadiene {(cis 1,4 bond / trans 1,4 bond / vinyl 1,2 bond weight ratio = 95/2/3) (Nippon Zeon Co., Ltd., trade name Nipol 1220SL)}
Was dissolved in the following mixed solution to form a uniform solution. Polybutadiene 10.5% by weight Styrene 74.2% by weight Ethylbenzene 15.0% by weight α-Methylstyrene dimer (chain transfer agent) 0.27% by weight 1,1-bis (t-butylperoxy) -3, 3,5-Trimethylcyclohexane (polymerization initiator) 0.03% by weight Then, the above mixture was continuously fed to a series four-stage reactor equipped with a stirrer, and the first stage was stirred at 190 rpm, 126 rpm.
℃, the second stage is 50 rpm, 133 ℃, the third stage is 20 rp
m, 140 ° C., and the fourth stage was 20 rpm and 155 ° C. for polymerization. Subsequently, the polymerization liquid having a solid content of 73% was introduced into a devolatilization device 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.

(B) Organic phosphorus compound Hydroxyl group-containing aromatic phosphate ester (FR-
Preparation of 1) Phenol 122.7 parts by weight (molar ratio 2.0) and aluminum chloride 0.87 parts by weight (molar ratio 0.01) were placed in a flask and phosphorus oxychloride 100 parts by weight (molar ratio 1. 0) was added dropwise over 1 hour. 71.7 parts by weight of resorcin (molar ratio 1.0) was added to the produced intermediate, and further reacted. In order to complete the reaction, the temperature was gradually raised, and finally the temperature was raised to 180 ° C. to complete the esterification. Then, the reaction product was cooled and washed with water to remove the catalyst and the chlorine content to obtain a phosphoric acid ester mixture (hereinafter referred to as FR-1). This mixture was mixed with GPC (gel permeation chromatography Tosoh Corp., HLC-80).
20 mobile phase tetrahydrofuran), diphenylresorcinyl phosphate of the following formula (18) (hereinafter referred to as TPP-OH), triphenyl phosphate (hereinafter referred to as TPP), and the following formula (19)
Of aromatic condensed phosphoric acid ester (hereinafter referred to as TPP dimer), and the weight ratio is 54.2 / 18.3, respectively.
It was /27.5. The phosphorus content is 9.4% by weight.
Met.

[0058]

[Chemical 9]

Production of Hydroxyl Group-Containing Aromatic Phosphate Ester (FR-2) In the production of FR-1, the same experiment was conducted except that equimolar bisphenol A was used instead of resorcin. The phosphoric acid ester mixture thus obtained was treated with F
It is called R-6. When this mixture was analyzed by GPC, diphenylbisphenyl A phosphate (TPP
-A-OH), triphenyl phosphate (T
PP), an aromatic condensed phosphoric ester represented by the following formula (20) [referred to as TPP-A-dimer], an aromatic condensed phosphoric ester [referred to as TPP-A-oligomer] and bisphenol A, and a weight ratio thereof. Are 37.
It was 7 / 11.5 / 32.2 / 12/2 / 6.4.
The phosphorus content was 7.2% by weight.

[0060]

[Chemical 10]

(However, n = 1: TPP-A = dimer n ≧ 2: referred to as TPP-A-oligomer) Hydroxyl group-free aromatic phosphate ester [triphenyl phosphate (TPP)] Commercially available aromatic phosphorus Acid ester [manufactured by Daihachi Chemical Industry Co., Ltd.,
Trade name TPP (referred to as TPP)] was used. The phosphorus content was 9.5% by weight.

Aromatic phosphoric acid ester containing no hydroxyl group [dinonylphenyl phenyl phosphate (F
Production of R-3)] Nonylphenol 287.3 parts by weight (molar ratio 2.0),
0.87 parts by weight of aluminum chloride (molar ratio 0.01) was placed in a flask, and 100 parts by weight of phosphorus oxychloride (molar ratio 1.0) was added dropwise at 90 ° C. over 1 hour. To the resulting intermediate, 61.4 parts by weight of phenol (molar ratio 1.0) was added and further reacted. In order to complete the reaction, the temperature was gradually raised and finally raised to 180 ° C. to complete the esterification. Then, the reaction product is cooled and washed with water to remove the catalyst and the chlorine content, and a phosphoric acid ester mixture (hereinafter referred to as F
R-3) was obtained. This mixture was mixed with GPC (gel permeation chromatography Tosoh Corp., H
LC-8020) mobile phase tetrahydrofuran analysis showed dinonylphenyl phenyl phosphate (hereinafter referred to as DNP) and trinonylphenyl.
Phosphate (hereinafter referred to as TNPP), nonylphenyldiphenyl phosphate (hereinafter referred to as NDP) and nonylphenol were used, and their weight ratios were 77.8 / 11.3 / 8.4 / 2.5, respectively. The average of the total carbon number of the substituents is 17.9 (1
8 x 0.778 + 27 x 0.113 + 9 x 0.084 =
17.9) And phosphorus content was 5.5 weight%.

Hydroxyl group-free aromatic phosphate ester (FR-5) Commercially available aromatic condensed phosphate ester derived from bisphenol A {manufactured by Daihachi Chemical Industry Co., Ltd., trade name CR741 (FR-
5)) was used. According to GPC analysis, the aromatic condensed phosphoric acid ester is composed of TPP-A-dimer represented by the formula (20), TPP-A-oligomer and triphenyl phosphate (TPP) at a weight ratio of 84. It was 0.7 / 13.0 / 2.3.
The phosphorus content was 9.4% by weight. (C) Silicone A commercially available silicone oil (polydimethylsiloxane viscosity 100 cp) was used (referred to as SI).

Examples 1 and 2, Comparative Examples 1 to 7 Resin compositions shown in Table 1 were produced. That is, a twin-screw extruder (Werner P consisting of 8 zones capable of side feed)
fleiderer ZSK-40mmφL / D = 4
6), HIPS / SI in the previous stage (zones 1 to 3)
Was melt-kneaded at 220 ° C., an organic phosphorus compound was fed in the latter stage, and melt-kneaded at 220 ° C. to produce a resin composition (screw rotation speed 295 rpm, discharge rate 82 kg / h.
r). Then, the obtained composition was injected into an injection molding machine (resin temperature 2
A test piece was prepared at 00 ° C.) and evaluated for flame retardancy, MFR, Izod impact strength and Vicat softening temperature.
The results are shown in Table 1 and FIG. According to Table 1 and FIG. 1, the flame-retardant property is improved by silicone because the ignition-melting dropping property is increased, and the stable flame-retardant property is obtained by using 50 wt% or more of an aromatic phosphate ester monomer as a flame-retardant. It can be seen that the sex is maintained.

Reference Examples 1 to 9 The resin compositions shown in Table 2 were melt-kneaded in the same manner as in Example 1 to obtain resin compositions. Then, the obtained composition was subjected to injection molding machine or compression molding machine to prepare test pieces having various orientations, and the relationship between the added amount of silicone, the heat shrinkage rate and the flame retardancy was determined. The results are shown in Table 2 and FIG. From Table 2 and FIG. 2, it can be seen that the larger the heat shrinkage, the greater the effect of addition on the flame retardancy of silicone. This fact suggests that silicone promotes orientation relaxation.

[0066]

[Table 1]

[0067]

[Table 2]

[0068]

EFFECTS OF THE INVENTION The present invention provides a styrenic resin composition which is excellent in igniting, melting and dropping properties, flame retardancy, heat resistance, impact resistance and fluidity. This composition is suitable for home electric appliance parts, office automation equipment parts and the like, and plays a large role in these industries.

[Brief description of drawings]

FIG. 1 is a diagram showing the relationship between the flame retardancy and the types of aromatic phosphate ester monomers and / or condensates of Examples and Comparative Examples shown in Table 1. The vertical axis is the average flame-extinguishing time (seconds), and the horizontal axis is the phosphorus atom weight part in the phosphoric acid ester added to 100 weight part of the resin. In the figure, Δ indicates that the aromatic phosphate ester monomer is 5 in the organic phosphorus compound.
Examples containing 0% by weight or more are shown, and ● indicates the above monomer /
A comparative example in which a condensate is used together is shown, and a star indicates a comparative example in which the above condensate is the main component.

FIG. 2 is a diagram showing the effect of silicone addition from the relationship between heat shrinkage and flame retardancy of a resin composition molded article. The vertical axis represents the average flame-extinguishing time (seconds), and the horizontal axis represents the heat shrinkage ratio (%) of the resin composition molded body obtained under different molding conditions. The numbers in the figure indicate the parts by weight of silicone added to 100 parts by weight of resin.

Claims (1)

[Claims] 1. A rubber-modified styrene resin, (B)
In a styrene-based resin composition containing an organic phosphorus compound and (C) silicone, the above (B) comprises an organic phosphorus compound monomer and an organic phosphorus compound condensate, and the above monomer is the (B) organic phosphorus compound. 50 to 100% by weight of a dripping self-extinguishing styrene-based flame-retardant resin composition.