JPH0848839A - Stabilized flame-resistant styrenic resin composition - Google Patents

Abstract

PURPOSE:To obtain the subject thermally stabilized composition excellent in the coloration-preventing property and useful for pale color molded products, etc., by adding a specific additive to a flame-resistant styrenic resin comprising a styrenic resin and a bromine flame retardant. CONSTITUTION:This composition comprises (A) a flame-resistant styrenic resin comprising a styrenic resin and a bromine flame retardant, (B) at least one of A type zeolite such as a compound of formula I (x is 10-6) and a zeolite preferably containing the group II or IV metal in the periodic table, such as Ca, Zn and Ba and/or at least one of hydrotalcite such as a compound of formula II and a Zn-substituted hydrotalcite compound such as a compound of formula III, and (C) at least one of boric acid (anhydride), the borate of a group II-IV metal in the periodic table, and an aliphatic polyhydric alcohol borate ester (e.g. a compound of formula IV).

Description

Detailed Description of the Invention

The present invention relates to a heat-stabilized flame-retardant styrene resin composition obtained by adding a specific additive to a flame-retardant styrene resin comprising a styrene resin and a bromine flame retardant. It is a thing.

[0002]

INDUSTRIAL APPLICABILITY The present invention can be widely used in a field where a flame retardant styrene resin containing a bromine flame retardant is required to have a high degree of thermal stability.

[0003]

2. Description of the Related Art Generally, in order to make a styrene resin flame-retardant,
Flame retardants such as halogen compounds and phosphorus compounds, and methods of adding flame retardant aids such as antimony trioxide have been conventionally performed, and among these flame retardants, halogen compounds, especially bromine compounds are often used. There is.

However, it is generally known that a flame-retardant styrene-based resin obtained by adding a bromine-based compound as a flame-retardant to a styrene-based resin is remarkably deteriorated in thermal stability. Method of adding A-type zeolite in order to suppress the emission (Japanese Patent Laid-Open No. 61-115948).
No.), a method of adding a zeolite containing at least one metal selected from Group II or Group IV metals of the Periodic Table (JP-A-63-170440), and a method of adding hydrotalcite (JP-A-63-170440). No. 60-1241), a method of adding zinc-substituted hydrotalcite (JP-A-61-1).
74270), boric acid, boric anhydride, boric acid metal salt,
Method of adding fatty acid polyhydric alcohol ester borate (JP-A-4-239059), A-type zeolite and / or zeolite containing at least one metal selected from Group II or Group IV metal of the periodic table, and A method of adding hydrotalcite and / or zinc-substituted hydrotalcite (Japanese Patent Application No. 5-179553) has been proposed.

[0005]

However, even with these methods, the thermal stability of the flame-retardant styrene resin, which is particularly problematic in delicate shades, to light-colored molded products is still unsatisfactory and more effective. Development of a flame-retardant styrene-based resin composition obtained by adding a heat stabilizer is awaited.

[0006]

From the above viewpoints, the inventors of the present invention have made earnest studies on a flame-retardant styrene resin composition having excellent thermal stability, and as a result, a flame retardant composed of a styrene resin and a bromine flame retardant has been obtained. For burned styrene resin,
(A) A-type zeolite and Group II or IV of the periodic table
At least one compound selected from zeolites containing Group 3 metals and / or at least one compound selected from (b) hydrotalcite and zinc-substituted hydrotalcite compounds, and (c) boric acid , Boric anhydride,
Flame-retardant styrene-based resin obtained by adding at least one compound selected from borate of Group II, III or IV of the periodic table and fatty acid polyhydric alcohol ester borate. We have found that the composition has significant thermal stability and completed the present invention.

The flame-retardant styrene resin composition of the present invention comprises
(A) component + (b) component + (c) component, (a) component +
The flame-retardant styrene-based resin composition contains the component (c) and the component (b) + the component (c), respectively, and the thermal stability of each of the components (a), (b) or (c) is independent. Ingredients,
This is significantly superior to the case where the components (a) and (b) are added respectively.

The styrene resin used in the present invention is
Examples thereof include polymers of vinyl aromatic compound monomers, copolymers of vinyl aromatic compound monomers and at least one of other monomers, and blend polymers thereof. Examples of the "mer" include vinyl chain compound monomers, vinyl heterocyclic compound monomers, conjugated diene compound monomers and the like.

The vinyl aromatic compound monomer is a styrene having a vinyl group bonded to a benzene nucleus as a basic skeleton, a nucleus-substituted styrene having a substituent introduced into the benzene nucleus, and a substituent introduced into a side chain vinyl group. The side chain-substituted styrenes and the nucleus / side chain-substituted styrenes may be mentioned. Examples of the nuclear substituent include a lower alkyl group such as methyl, ethyl, propyl and butyl and a vinyl group, and halogen such as chlorine and bromine. Examples of the nucleus-substituted styrene include o-, m- and p-vinyltoluene, o-, m- and p-divinylbenzene, o-chlorostyrene, 2,3-dichlorostyrene, 2,4-dichlorostyrene. , 2,5-dichlorostyrene, 2,6-dichlorostyrene, and the like. Examples of the side chain-substituted styrene include α-methylstyrene, α,
Examples thereof include β-dimethylstyrene and β, β′-dimethylstyrene, and examples of the nucleus / side chain-substituted styrene include o-α-methylvinyltoluene.

The vinyl chain compound monomer, which is the "other monomer", is a nitrile compound having a vinyl group with or without a methyl group, an amide compound thereof, and a lower aliphatic carboxylic acid thereof. And lower aliphatic carboxylic acid lower alkyl esters thereof and the like. Examples thereof include acrylonitrile, methacrylonitrile, acrylamide, methacrylamide, acrylic acid, methacrylic acid, methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, methyl methacrylate, methacrylic acid. Examples thereof include ethyl, propyl methacrylate, butyl methacrylate and 2-ethylhexyl methacrylate.

The vinyl heterocyclic compound monomer is a heterocyclic compound having a vinyl group with or without a methyl group, and the heterocyclic ring is a 5-membered compound containing at least one N, O or S. Examples of the heterocyclic ring to 11-membered ring, for example, furan, γ-pyran, pyrrole, pyridine, piperidine, imidazole, pyrazole, pyridazine, pyrimidine, pyrazine, quinoline, isoquinoline,
Examples thereof include oxazole, isoxazole, thiophene, thiazole, 1,2,3-thiadiazole, carbazole and substituted derivatives thereof. Examples of the vinyl heterocyclic compound monomer include vinyl pyridine, vinyl piperidine and vinyl imidazole. , Vinylpyrazine,
Examples thereof include vinylthiophene, vinylthiazole and vinylcarbazole.

The conjugated diene compound monomer is a monomer in which two or more carbon-carbon double bonds are bonded to each other with a carbon-carbon single bond interposed therebetween, and a chain having 4 or more carbon atoms. Examples of the conjugated diene compound monomer include a halogen atom such as chlorine or bromine as a substituent. Examples of the conjugated diene compound monomer include butadiene, 1-chlorobutadiene, 2-chlorobutadiene and isoprene.

Further, as "other monomers", maleimide, N-methylmaleimide, N-ethylmaleimide, N
-Propylmaleimide, N-butylmaleimide, N-2
Of maleimide compound monomers such as -ethylhexylmaleimide, N-phenylmaleimide and N-cyclohexylmaleimide, maleic acid, fumaric acid, itaconic acid and these organic acids and monovalent saturated aliphatic alcohols having 1 to 8 carbon atoms Examples thereof include esters and maleic anhydride.

Typical of these styrene resins are polystyrene, acrylonitrile-styrene copolymer (hereinafter referred to as "AS resin"), methyl methacrylate-styrene copolymer, and styrene-α-. Methyl styrene copolymer, styrene-maleic anhydride copolymer,
Styrene-maleimide copolymer, styrene-N-substituted maleimide copolymer, acrylonitrile-butadiene-styrene copolymer (hereinafter referred to as "ABS resin"),
Methyl methacrylate-butadiene-styrene copolymer (hereinafter referred to as "MBS resin"), acrylonitrile-acrylic rubber-styrene copolymer (hereinafter referred to as "AAS resin"), acrylonitrile-styrene-chlorinated polyethylene. Copolymer (hereinafter referred to as "ACS resin"), methyl methacrylate-acrylonitrile-butadiene-styrene copolymer, acrylonitrile-butadiene-styrene-α-methylstyrene copolymer, methyl methacrylate-butadiene-styrene-α. -Methylstyrene copolymers or blends thereof can be mentioned.

As the bromine-based flame retardant used in the present invention, any bromine-based flame retardant generally used in this field can be used without limitation. For example, brominated chain aliphatic hydrocarbons and brominated cyclic compounds can be used. Examples thereof include aliphatic hydrocarbons, brominated aromatic hydrocarbons, brominated isocyanates and brominated epoxy resins.

The brominated chain aliphatic hydrocarbons are hydrocarbons having at least one bromine atom bonded to a chain aliphatic hydrocarbon having 2 to 6 carbon atoms, and examples thereof include bromine. Those having two or more atoms are preferable, and examples thereof include dibromoethane, tetrabromoethane, tribromopropane, tetrabromobutane, octabromohexane and the like.

Brominated cycloaliphatic hydrocarbons are hydrocarbons in which at least one bromine atom is bonded to a cycloaliphatic hydrocarbon having 6 to 12 carbon atoms. It is preferably 6 or more, and examples thereof include hexabromocyclohexane and hexabromocyclododecane. Brominated aromatic hydrocarbons are hydrocarbons having at least one bromine atom attached to a benzene ring, the aromatic hydrocarbons including aromatic hydrocarbons and

[0018]

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(R is an alkyl group having 1 to 8 carbon atoms, an alkenyl group, a bromine substitution product thereof and an -OH substitution product thereof, and R ¹ is an alkylene group having 1 to 8 carbon atoms.) Bound aromatic hydrocarbons, examples of which are preferably those having two or more bromine atoms, are tetrabromobenzene, hexabromobenzene, bromostyrene, bromophenylallyl ether, tetrabromophthalic anhydride, and dibromo. Phenol, tribromophenol, pentabromotoluene, tribromophenylmaleimide, pentabromophenylpropyl ether, tetrabromobisphenol A, hexabromodiphenylether, decabromodiphenylether, octabromodiphenylether, ethylenebis (tetrabromophthalimide), brominated Polystyrene, polydibromophenylene oxide, tetrabromobisphenol A carbonate oligomer, tetrabromobisphenol A bis (2-hydroxyethyl ether), tetrabromobisphenol A bis (2,3-dibromopropyl ether), tetrabromobisphenol A bis ( 2-bromoethyl ether), tetrabromobisphenol A bis (propyl ether), 2,3-dibromopropylpentabromophenyl ether, bis (tribromophenoxy) ethane, tetrabromobisphenol S, tetrabromobisphenol S bis (2. 3-dibromopropyl ether) and bis (pentabromophenyl) ethane.

The brominated isocyanates are the above-mentioned brominated chain aliphatic hydrocarbons and isocyanic acid residue --N = C.
Examples thereof include a compound having ═O bound thereto and a compound having the above-mentioned brominated aromatic hydrocarbons bound to an isocyanic acid residue —N═C═O. For example, Tris (2,
3-dibromopropyl) isocyanurate, tris (dibromophenoxy) isocyanurate, tris (dibromoethylphenoxy) isocyanurate, tris (tribromophenoxy) isocyanurate, tris (dibromopropylphenoxy) isocyanurate, etc. Can be done. The brominated epoxy resin is an epoxy resin having at least one bromine atom, and the epoxy resin is an epoxy resin obtained by a reaction of epichlorohydrin with a polyhydric phenol or a polyhydric alcohol, and a peroxyacid of olefin. An epoxy resin and the like obtained by epoxidation with can be mentioned. Examples of the brominated epoxy resins include brominated epoxy resins and compounds having a structure in which a part or all of terminal epoxy groups of the epoxy resin are blocked.
Examples of the brominated epoxy resin include brominated bisphenol type epoxy resin, brominated phenol novolac type epoxy resin, brominated cresol novolac type epoxy resin, brominated resorcinol type epoxy resin, brominated hydroquinone type epoxy resin, brominated bisphenol A. Examples thereof include novolac type epoxy resin, brominated methylresorcin type epoxy resin, and brominated resorcinol novolac type epoxy resin, but usually a brominated bisphenol type epoxy resin having an average degree of polymerization of 0 to 50 is used. Specific examples of the brominated bisphenol constituting the brominated bisphenol type epoxy resin include dibromobisphenol A, tetrabromobisphenol A, dibromobisphenol F, tetrabromobisphenol F, dibromobisphenol S and tetrabromobisphenol S. I can.

In the compound having a structure in which a part or all of the terminal epoxy groups of the brominated epoxy resin are blocked, the compound for blocking a part or all of the terminal epoxy groups is a compound capable of ring-opening addition of an epoxy group. Without limitation, phenols, alcohols, carboxylic acids,
The amines and isocyanates include those containing a bromine atom, and among them, brominated phenols are preferable from the viewpoint of improving the flame retardant effect, and dibromophenol, tribromophenol, pentabromophenol, dibromoethylphenol. , Dibromopropylphenol, dibromobutylphenol, dibromocresol and the like.

As the compound having a structure in which a part or all of the terminal epoxy groups of the brominated epoxy resin are blocked,

[0023]

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And the like.

The addition amount of the bromine flame retardant used in the present invention is not particularly limited, but it may be appropriately changed depending on the required degree of flame retardancy, and is generally 5 per 100 parts by weight of the styrene resin. It is preferable to use ˜35 parts by weight alone or in combination of two or more. Further, when a flame retardant aid such as antimony trioxide is used in combination, the flame retardant effect is more excellent, and the addition amount thereof is preferably 1 to 20 parts by weight with respect to 100 parts by weight of the styrene resin.

[0026] As A-type zeolites used in the present invention have the general formula _{(1) Na 2 O · Al} 2 O 3 · 2SiO in ₂ · xH ₂ O [wherein, X is a number of 0 to 6. ] A type zeolite shown by the above is mentioned, and may be a natural or synthetic product. The A-type zeolite used includes higher fatty acids such as higher fatty acid alkali metal salts such as stearic acid and oleic acid, and organic sulfonic acids such as dodecylbenzene sulfonic acid. It may be surface-treated with such an organic sulfonic acid alkali metal salt.

The zeolite containing a metal of Group II or IV of the periodic table is a zeolite in which Na in the A-type zeolite is replaced with a metal of Group II or IV of the periodic table ( Hereinafter, referred to as "metal-substituted zeolite"), the metal is not particularly limited, magnesium, calcium, zinc, strontium, barium, zirconium and tin, etc. from the viewpoint of effect, toxicity and availability. Among them, preferable metals include calcium, zinc and barium.

It is preferable that the metal substitution rate of the A-type zeolite in the metal substitution zeolite is high, but usually, the substitution rate is about 10 to 70 mol% as an industrially easily obtainable one. Is.

Examples of the metal-substituted zeolite include synthetic zeolites such as magnesium-substituted zeolite, calcium-substituted zeolite, zinc-substituted zeolite, strontium-substituted zeolite, barium-substituted zeolite, zirconium-substituted zeolite and tin-substituted zeolite. A natural zeolite containing a metal can be used, and these A-type zeolite and metal-substituted zeolite can be used alone or in combination of two or more kinds.

Regarding the method for producing the above synthetic zeolite,
A known method may be used, and examples thereof include the method described in JP-A-57-28145.

The hydrotalcite used in the present invention is a compound composed of magnesium and aluminum. For example, the general formula (2) Mg _1-x Al _x (OH) ₂ (A) _{x / 2} · aH _{2 is used.} Examples thereof include compounds represented by O (2), and the zinc-substituted hydrotalcite compound is, for example, a compound in which a part of Mg in the general formula (2) is replaced with Zn, and the compound represented by the general formula ( 3) A compound of [Mg _y1 Zn _y2 ] _1-x Al _x (OH) ₂ (A) _{x / 2} · aH ₂ O (3) can be given. The substitution rate of Zn is 1 mol% to 50 mol% and preferably 15 mol% to 30 mol% with respect to Mg.

[In the formulas (2) and (3), A is CO ₃ or ClO ₄ , and x, y1, y2 and a each represent a positive number satisfying the following conditions.

O <x ≦ 0.5, y1 + y2 = 1-x, y
1> y2,0 ≦ a <2] Typical examples of the general formula (2) include the following. No. 1; Mg _0.750 Al _0.250 (OH) ₂ (CO ₃ )
_0.125・ 0.3 H ₂ O No. 2; Mg _0.692 Al _0.308 (OH) ₂ (CO ₃ )
_0.154・ 0.5 H ₂ O No. 3; Mg _0.667 Al _0.333 (OH) ₂ (CO ₃ )
_0.167・ 0.54H ₂ O No. 4; Mg _0.750 Al _0.250 (OH) ₂ (ClO ₄ )
_0.125 No. 5; Mg _0.692 Al _0.308 (OH) ₂ (ClO ₄ )
_0.154・ 0.5 H ₂ O No. 6; Mg _0.667 Al _0.333 (OH) ₂ (ClO ₄ )
_0.167 · 0.54H ₂ O and the like.

The following are typical examples of the general formula (3). No. 7; Mg _0.625 Zn _0.125 Al _0.250 (OH) ₂
(CO ₃ ) _0.125・ 0.45H ₂ O No. 8; Mg _0.538 Zn _0.154 Al _0.308 (OH) ₂
(CO ₃ ) _0.154 No. 9; Mg _0.500 Zn _0.167 Al _0.333 (OH) ₂
(CO ₃ ) _0.167・ 0.54H ₂ O No. 10; Mg _0.625 Zn _0.125 Al _0.250 (OH) ₂
(ClO ₄ ) _0.125・ 0.3 H ₂ O No. 11; Mg _0.538 Zn _0.154 Al _0.308 (OH) ₂
(ClO ₄ ) _0.154・ 0.5 H ₂ O No. 12; Mg _0.500 Zn _0.167 Al _0.333 (OH) ₂
(CO ₃ ) _0.167 · 0.1 H ₂ O and the like.

In the present invention, in order to improve the compatibility, dispersibility, etc. of the hydrotalcite and zinc-substituted hydrotalcite compounds with the flame-retardant styrene resin, the hydrotalcite and the zinc-substituted hydrotalcite are used. The compound can be surface-treated with a surface-treating agent.

Examples of such surface treatment agents include those generally used in this field,
For example, higher fatty acids, anionic surfactants, silane coupling agents, titanate coupling agents, esters of glycerin and fatty acids, and the like can be mentioned, and specific examples thereof include stearin. Acids, higher fatty acids such as oleic acid and lauric acid, anionic surfactants such as sodium stearate, sodium oleate and sodium laurylbenzene sulfonate, vinyltriethoxysilane, γ-methacryloxypropyltriethoxysilane, isopropyl Examples thereof include silane-based or titanate-based coupling agents such as triisostearoyl titanate and isopropyl tridecylbenzenesulfonyl titanate, and glycerin fatty acid esters such as glycerin monostearate and glycerin monooleate.

Examples of the boric acid used in the present invention include orthoboric acid (H ₃ BO ₃ ), metaboric acid (HBO ₂ ), tetraboric acid (H ₂ B ₄ O ₇ ), and the like. , Generally refers to diboron trioxide (B ₂ O ₃ ), but includes diboron dioxide (B ₂ O ₂ ), tetraboron trioxide (B ₄ O ₃ .2H _2).
O) and tetraboron pentoxide (B ₄ O ₅ ) are also present, so these may be used. Further, boric acid and boric anhydride may be used in combination.

Periodic Table Group II, II used in the present invention
The metal of the boric acid metal salt containing a Group I or Group IV metal is magnesium, in terms of its effect, toxicity and availability.
Examples thereof include calcium, zinc, strontium, barium, aluminum, zirconium and tin.
Preferred metals include calcium, zinc, barium and aluminum.

Examples of the metal borate include magnesium borate (3MgO.B ₂ O ₃ , 2MgO.B ₂ O ₃ , M
gO ・ B ₂ O ₃ ), calcium borate (CaO ・ B ₂ O)
₃ , CaO ・ 2B ₂ O ₃ ), zinc borate (ZnO ・ B ₂ O)
₃ , 2ZnO.3B ₂ O ₃ ), strontium borate (S
_{rO · B 2 O 3, SrO} · 2B 2 O 3), barium borate _{(BaO · 2B 2 O 3 ·} 2H 2 O, BaO · B 2 O
₃ ), aluminum borate (Al ₂ O ₃ · B ₂ O ₃ , Al
₂ O ₃ · 2B ₂ O ₃ ), zirconium borate (ZrO ₂ ·
B ₂ O ₃ , ZrO ₂ .2B ₂ O ₃ ) and tin borate (Sn
O ₂ · B ₂ O ₃ , SnO ₂ · 2B ₂ O ₃ ) and the like can be mentioned, and they can be used alone or in combination of two or more.

The boric acid metal salt used in the present invention is obtained by, for example, melting a predetermined amount (mole number) of metal oxide and boric acid or boric anhydride, or reacting a metal chloride with boric acid in an alkaline aqueous solution. Obtained by

The fatty acid polyhydric alcohol ester borate used in the present invention was then esterified with at least one polyhydric alcohol esterified with at least one fatty acid and at least one boric acid. It is a boric acid ester and is represented by the general formulas (4) to (12).

[0042]

[Chemical 3]

[R ² = C ₂ -C ₂₈ monovalent saturated fatty acid and unsaturated fatty acid except the -COO- group.

R ³ = C ₂ -C having ₂ to 6 OH groups
A residue obtained by removing two OH groups from ₃₀ aliphatic alcohols.

R ⁴ , R ⁵ , R ⁸ = R ² CO-OR ^3-
Group, H, a residue obtained by removing one OH group from a C _{1 to} C ₃₀ aliphatic alcohol having ₁ to 6 OH groups.

R ⁶ = R ² CO-OR ⁷ -group, R ³ . R ⁷ = a residue obtained by removing 3 OH groups from a C _{2 to} C ₃₀ aliphatic alcohol having 3 to 6 OH groups.

R ⁹ = C ₂ -C having 4 to 6 OH groups
Residues obtained by removing 4 OH groups from ₃₀ aliphatic alcohols. Examples of the C _{2 to} C ₂₈ monovalent saturated fatty acids and unsaturated fatty acids include acetic acid, propionic acid, caproic acid, enanthic acid, caprylic acid, 2-ethylhexylic acid, pelargonic acid, capric acid, undecyl acid, Saturated fatty acids such as lauric acid, tridecyl acid, myristic acid, pentadecyl acid, palmitic acid, heptadecyl acid, stearic acid, isostearic acid, hydroxystearic acid, nonadecanoic acid, arachidic acid, behenic acid, lignoceric acid and montanic acid, and acrylic acid. , Crotonic acid, undecylenic acid, oleic acid, erucic acid, sorbic acid, linoleic acid,
Examples thereof include unsaturated fatty acids such as linolenic acid, preferably lauric acid, myristic acid, palmitic acid, stearic acid, isostearic acid, hydroxystearic acid, behenic acid, oleic acid, and linoleic acid, and particularly preferably stearic acid. And oleic acid and the like.

C _{1 to} C having the above 1 to 6 OH groups
Examples of ₃₀ aliphatic alcohols include methanol, ethanol, n-propanol, iso-propanol, n-propanol.
Butanol, sec-butanol, tert-butanol, n-pentanol, n-hexanol, n-heptanol, n-octanol, isooctanol, 2-ethylhexanol, n-nonanol, n-decanol,
n-undecanol, n-dodecanol, n-tridecanol, n-tetradecanol, n-pentadecanol, n-hexadecanol, n-heptadecanol, n
-Octadecanol, n-nonadecanol, n-eicosanol, ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol, propylene glycol, dipropylene glycol,
Polypropylene glycol, butylene glycol, hexylene glycol, neopentyl glycol, hexamethylene glycol, tetramethylene glycol, 1,6
-Hexanediol, methylpropylpropanediol, octanediol, 2,2,4-trimethylpentanediol, 1,4-butanediol, 1,3-butanediol, glycerin, polyglycerin, trimethylolmethane, trimethylolethane, tri Methylolpropane, trimethylolbutane, erythritol, pentaerythritol, diventaerythritol, sorbitol and mannitol, and other aliphatic alcohols, and the like, preferably ethylene glycol, 1,4-butanediol, glycerin, pentaerythritol, and the like, Particularly preferred are 1,4-butanediol and glycerin.

C ₂ -C having ₂ to 6 OH groups as described above
Examples of ₃₀ aliphatic alcohols include ethylene glycol, diethylene glycol, triethylene glycol,
Polyethylene glycol, propylene glycol, dipropylene glycol, polypropylene glycol, butylene glycol, hexylene glycol, neopentyl glycol, hexamethylene glycol, tetramethylene glycol, 1,6-hexanediol, methylpropylpropanediol, octanediol, 2,2 , 4
-Trimethylpentanediol, 1,4-butanediol, 1,3-butanediol, glycerin, polyglycerin, trimethylolmethane, trimethylolethane,
Trimethylolpropane, trimethylolbutane, erythritol, pentaerythritol, diventaerythritol, aliphatic alcohols such as sorbitol and mannitol, and the like, preferably ethylene glycol,
1,4-butanediol, glycerin, pentaerythritol and the like can be mentioned, and particularly preferably 1,4-butanediol and glycerin and the like can be mentioned.

C ₂ -C having the above 3 to 6 OH groups
Examples of ₃₀ aliphatic alcohols include aliphatic alcohols such as glycerin, trimethylolmethane, trimethylolethane, trimethylolpropane and trimethylolbutane. Examples of the C _{2 to} C ₃₀ aliphatic alcohol having 4 to 6 OH groups are:
Examples thereof include aliphatic alcohols such as polyglycerin, erythritol, pentaerythritol, dipentaerythritol, sorbitol and mannitol.

The fatty acid polyhydric alcohol ester borate used in the present invention may be further reacted with boric acid after producing a partially esterified product from a fatty acid and a polyhydric alcohol, or if necessary, further added with boric acid. Obtained by reacting with a polyhydric and / or polyhydric alcohol. The following may be mentioned as specific examples of the fatty acid polyhydric alcohol ester borate.

[0052]

[Chemical 4]

[0053]

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[0054]

[Chemical 6]

[0055]

[Chemical 7]

[0056]

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[0057]

[Chemical 9]

At least one compound selected from the group consisting of (a) type A zeolite used in the present invention, zeolite containing a metal of Group II or Group IV of the periodic table, and / or (b) hydrotal. At least one compound selected from the group consisting of sites and zinc-substituted hydrotalcite compounds, and (c) boric acid, boric anhydride, a borate of a metal of Group II, Group III or Group IV of the periodic table, There is no particular restriction on the amount of the fatty acid polyhydric alcohol ester / borate and at least one compound selected from the compounds to be added in combination, but the effective range is styrene resin 100.
It is 0.01 to 5.0 parts by weight with respect to parts by weight.

If the addition amount is less than 0.01 parts by weight, the heat stabilizing effect is not noticeable, and if it exceeds 5.0 parts by weight, the expected heat stabilizing effect is not observed. .1
To 3.0 parts by weight. Also, in the case of combined use, there is no particular limitation on the combined ratio of the components (a) and / or (b) and (c), but as the effective combined ratio, the components (a) and / or ( b) vs. (c) is 98: 2
50 to 50% by weight, preferably 95 to 5 to 6
0 to 40% by weight. When the combined use ratio of the component (c) is less than 2% by weight, the effect of preventing coloration is not remarkable, and when it exceeds 50% by weight, the thermal stability decreases.

The method of adding the specific additive used in the present invention to the flame-retardant styrene resin composed of the styrene resin and the bromine flame retardant may be carried out by a conventionally known technique.
For example, the flame-retardant styrene resin and the additive may be mixed with a Henschel mixer, a ribbon blender, a Banbury mixer, or the additive may be pre-packed in one package. You may mix with resin with the above-mentioned mixer.

Further, known stabilizers for these additives, for example, metal soaps, organophosphorus compounds, antioxidants,
An ultraviolet absorber and an organic tin compound can be used together.

Further, if necessary, a plasticizer, a lubricant, a pigment,
Fillers, processing aids, chlorinated flame retardants, flame retardant aids, etc. can be added.

[0063]

EXAMPLES The present invention will be specifically described below with reference to examples.
However, the invention is not limited to these.
Absent. In these examples, parts means parts by weight.
It (A) component [A-type zeolite used in the present invention] A-1: Na₂ O ・ Al₂ O₃ ・ 2SiO₂ ・ 4.5H
₂ OA-2: Na₂ O ・ Al₂ O₃ ・ 2SiO₂ [Metal-Substituted Zeolites Used in the Present Invention] B-1: Magnesium-Substituted Zeolites B-2: Calcium-Substituted Zeolites B-3: Zinc-Substituted Zeolites B-4: Barium-Substituted Zeolites (Metal Substitution Rates of B-1 to B-4) Each is 70 mol%)(B) component [Hydrotalcite used in the present invention] C-1: Hydrotalcite represented by the formula No. 1 in the specification
Lucite C-2: Hydrosa represented by the formula No. 3 in the specification
Lucite C-3: Hydrosa represented by Formula No. 5 in the specification
Lucite [Zinc-substituted hydrotalcite used in the present invention
Compound] D-1: Zinc Substituted Ha Represented by Formula No. 7 in the Description
Irodrosalsite D-2: Zinc-substituted Ha represented by Formula No. 8 in the specification
Irodrosalsite D-3: Zinc substitution represented by formula No. 10 in the description
Hydrosalcite (C) component [Boric Acid / Boric Anhydride Used in the Present Invention] E-1: Orthoboric Acid E-2: Metaboric Acid E-3: Tetraboric Acid E-4: Tetraboron Trioxide [Boric Acid Metal Salt Used in the Present Invention] F-1 : Calcium borate (CaO / 2B₂ O₃ ) F-2: Zinc borate (ZnO.B)₂ O₃ ) F-3: Aluminum borate (Al₂ O₃ ・ B₂ O₃ ) F-4: Magnesium borate (MgO.B)₂ O₃ ) F-5: Barium borate (BaO.2B)₂ O₃ ・ 2H₂ 
O) [Fatty acid polyhydric alcohol ester used in the present invention
Borate] G-1: Boron compound represented by the formula No. 14 in the specification
Product G-2: Boron compound represented by the formula No. 21 in the specification
Product G-3: Boron compound represented by formula No. 23 in the specification
Product G-4: Boron compound represented by formula No. 26 in the specification
Product G-5: Boron compound represented by the formula No. 29 in the specification
Product G-6: Boron compound represented by the formula No. 30 in the specification
Product G-7: Boron compound represented by the formula No. 32 in the specification
Product G-8: Boron compound represented by the formula No. 35 in the specification
Product G-9: Boron compound represented by the formula No. 39 in the specification
Product G-10: Boron compound represented by formula No. 41 in the specification
Product G-11: Boron compound represented by formula No. 43 in the specification
Product G-12: Boron compound represented by the formula No. 45 in the specification
Examples [Example 1] ABS resin [Tufref manufactured by Mitsubishi Kasei Co., Ltd.
Box 410CB] 85 parts, MBS resin [Kureha Chemical Industry
Kureha BTA-751] 15 parts, chlorinated poly
Ethylene [Showa Denko KK Erasulene 303B] 3
Part, tetrabromobisphenol A carbonate oligo
Mar [Teijin Kasei Co., Ltd. Fireguard 7500]
18 parts, 5 parts antimony trioxide, shown in Tables 1 to 3
8 inches adjusted to 165 ° C with additive formulation
Knead with a test roll for 3 minutes to make a 0.5 mm thick sheet.
Made. The obtained sheets are cut and stacked on eight sheets, 260 ° C,
5 kg / cm² Press to check the coloring of the press plate visually.
Judged. The results are shown in Tables 1 to 3.

The colorability of the press plate was evaluated according to the following criteria.

1: White, 2: Light yellow, 3: Yellow, 4: Yellow brown, 5: Brown

[0066]

[Table 1]

[0067]

[Table 2]

[0068]

[Table 3]

Sample Nos. 1 to 13 are examples and the same No. 14 to
34 is a comparative example. As is clear from the comparison of the results in Tables 1 to 3, it is understood that the stabilized flame-retardant styrenic resin composition of the present invention is extremely excellent in anti-coloring property. Incidentally, as in the case of Sample Nos. 14 to 33, when the components (a) and / or (b) and (c) of the present invention are not used in combination, or when no additive is added as in the case of No. 34, both are used. Sufficient anti-coloring property cannot be obtained.

[Example 2] Styrene resin [Asahi Kasei Co., Ltd.
Styron 492] 100 parts, ethylene bis (tetrabromophthalimide) [Ethyl Corporation Saytex BT-93W] 17 parts, and antimony trioxide 3 parts, a mixture prepared by adding the additives shown in Table 4 to Table 5 to 140 ° C. The mixture was kneaded for 3 minutes with the 8-inch test roll adjusted to the above to prepare a sheet having a thickness of 0.6 mm. The obtained sheet was cut into eight sheets, which were pressed at 275 ° C. and 5 kg / cm ² , and the colorability of the pressed plate was visually determined. The results are shown in Tables 4 to 5. The colorability of the press plate was evaluated according to the following criteria.

1: White, 2: Light gray, 3: Gray, 4: Grayish brown

[0072]

[Table 4]

[0073]

[Table 5]

Sample Nos. 1 to 11 are Examples and the same No. 12 to
24 is a comparative example. As is clear from the results of Tables 4 to 5, it is understood that the stabilized flame-retardant styrene resin composition of the present invention is extremely excellent in anti-coloring property. still,
As in Sample Nos. 12 to 22, the component (a) of the present invention and / or
Alternatively, in the case where (b) and (c) are not added together, or as in the case of the same number 23, the combined ratio of the component (c) is obtained even if the components (a) and / or (b) and (c) are added together. Is more than 50% by weight, or no additive is added as in the case of No. 24, no sufficient coloring preventing property can be obtained.

[Example 3] 90 parts of ABS resin [JSR ABS # 15NP manufactured by Japan Synthetic Rubber Co., Ltd.], AAS
Resin [Mitsubishi Rayon Co., Ltd. dialac A S61
0] 10 parts, brominated epoxy oligomer [Prasarm EP-16 manufactured by Dainippon Ink and Chemicals, Inc.] 20
Parts and 5 parts of antimony trioxide were kneaded for 3 minutes with an 8-inch test roll adjusted to 155 ° C. for 3 minutes to prepare a sheet having a thickness of 0.7 mm. The obtained sheets are cut and stacked on 8 sheets, 270 ° C, 5 kg
Pressing was performed at / cm ² , and the colorability of the pressed plate was visually determined. The results are shown in Tables 6 to 8.

The colorability of the press plate was evaluated according to the same criteria as in Example 1.

[0077]

[Table 6]

[0078]

[Table 7]

[0079]

[Table 8]

Sample Nos. 1 to 11 are Examples and the same No. 12 to
27 is a comparative example. As is clear from the comparison of the results in Tables 6 to 8, it is understood that the stabilized flame-retardant styrene resin composition of the present invention is extremely excellent in the coloration preventing effect. In addition, as in the case of Sample Nos. 12 to 26, when the components (a) and / or (b) and (c) of the present invention are not used in combination, or when the additive is not added, as in the case of No. 27, both are used. Sufficient anti-coloring property cannot be obtained.

Example 4 To 100 parts of ABS resin [JSR ABS # 15NP manufactured by Nippon Synthetic Rubber Co., Ltd.] and 20 parts of brominated epoxy oligomer [Prasam EC-20 manufactured by Dainippon Ink and Chemicals, Inc.], Compounds containing the additives shown in Tables 9 to 11 were kneaded with an 8-inch test roll adjusted to 160 ° C. for 3 minutes to give a thickness of 0.7 mm.
The sheet of was produced. The obtained sheet was cut, eight sheets were stacked and pressed at 265 ° C. and 5 kg / cm ² , and the colorability of the pressed plate was visually determined. The results are shown in Tables 9 to 11.

The colorability of the press plate was evaluated according to the same criteria as in Example 1.

[0083]

[Table 9]

[0084]

[Table 10]

[0085]

[Table 11]

Sample Nos. 1 to 18 are examples and the same No. 19 to
26 is a comparative example. As is clear from the comparison of the results in Tables 9 to 11, the stabilized flame-retardant styrenic resin composition of the present invention is extremely excellent in anti-coloring property. In addition, as in the case of Sample Nos. 19 to 25, when the components (a) and / or (b) and (c) of the present invention are not added together, or when no additive is added as in the case of No. 26, both Sufficient anti-coloring property cannot be obtained.

[Example 5] ACS resin [Showa Denko KK]
NF-960, 100 parts, decabrom diphenyl ether [Mitsui Toatsu Chemicals, Inc., Planeteron DB-1
00] 20 parts and 3 parts of antimony trioxide were kneaded with a mixture prepared by adding the additives shown in Tables 12 to 14 for 3 minutes with an 8-inch test roll adjusted to 150 ° C. to give a sheet of 0.6 mm in thickness. It was made. Cut the obtained sheets and stack 8 sheets,
Pressing was performed at 250 ° C. and 5 kg / cm ² , and the colorability of the pressed plate was visually determined. The results are shown in Tables 12 to 14.

The colorability of the press plate was evaluated according to the same criteria as in Example 1.

[0089]

[Table 12]

[0090]

[Table 13]

[0091]

[Table 14]

Sample Nos. 1 to 19 are examples and the same No. 20 to
30 is a comparative example. As is clear from the comparison of the results in Tables 12 to 14, it is understood that the stabilized flame-retardant styrene resin composition of the present invention is extremely excellent in anti-coloring property. It is to be noted that when the components (a) and / or (b) and (c) of the present invention are not used in combination as in Sample Nos. 20 to 29, or when no additive is added as in No. 30 in any case Sufficient anti-coloring property cannot be obtained.

[0093]

The flame-retardant styrene resin composition of the present invention has an excellent anti-coloring property.

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[Procedure amendment]

[Submission date] June 20, 1995

[Procedure Amendment 1]

[Document name to be amended] Statement

[Correction target item name] 0010

[Correction method] Change

[Correction content]

The vinyl chain compound monomer, which is the "other monomer", is a nitrile compound having a vinyl group with or without a methyl group, an amide compound thereof, a lower aliphatic carboxylic acid thereof and The same lower aliphatic carboxylic acid lower alkyl ester can be used. Examples thereof include acrylonitrile, methacrylonitrile, acrylamide, methacrylamide, acrylic acid, methacrylic acid, methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, methyl methacrylate, methacrylic acid. Examples thereof include ethyl, propyl methacrylate, butyl methacrylate and 2-ethylhexyl methacrylate.

[Procedure Amendment 2]

[Document name to be amended] Statement

[Correction target item name] 0011

[Correction method] Change

[Correction content]

The vinyl heterocyclic compound monomer is a heterocyclic compound having a vinyl group with or without a methyl group, and the heterocyclic ring is a five-membered ring containing at least one N, O or S. To 13-membered heterocycles, for example, furan, γ-pyran, pyrrole, pyridine, piperidine, imidazole, pyrazole, pyridazine, pyrimidine, pyrazine, quinoline, isoquinoline,
Examples thereof include oxazole, isoxazole, thiophene, thiazole, 1,2,3-thiadiazole, carbazole and substituted derivatives thereof. Examples of the vinyl heterocyclic compound monomer include vinyl pyridine, vinyl piperidine and vinyl imidazole. , Vinylpyrazine,
Examples thereof include vinylthiophene, vinylthiazole and vinylcarbazole.

[Procedure 3]

[Document name to be amended] Statement

[Correction target item name] 0026

[Correction method] Change

[Correction content]

[0026] As A-type zeolites used in the present invention have the general formula _{(1) Na 2 O · Al} 2 O 3 · 2SiO 2 · xH 2 O (1) wherein, x is a number from 0 to 6 Show. ] A type zeolite shown by the above is mentioned, and may be a natural or synthetic product. The A-type zeolite used includes higher fatty acids such as higher fatty acid alkali metal salts such as stearic acid and oleic acid, and organic sulfonic acids such as dodecylbenzene sulfonic acid. It may be surface-treated with such an organic sulfonic acid alkali metal salt.

─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. ⁶ Identification number Internal reference number FI Technical indication location C08K 5/103 KFY (72) Inventor Michihiro Kubo 788 Hisaji, Takatsu-ku, Kawasaki-shi, Kanagawa Sankyo Organic Synthesis Stock In the company

Claims (1)

[Claims] 1. A flame-retardant styrene resin comprising a styrene resin and a bromine flame retardant, and (a) A-type zeolite and Group II or IV of the periodic table.
At least one compound selected from zeolites containing Group 3 metals and / or at least one compound selected from (b) hydrotalcite and zinc-substituted hydrotalcite compounds, and (c) boric acid , Boric anhydride,
Stabilized flame-retardant obtained by adding at least one compound selected from borate of Group II, III or IV of the periodic table and fatty acid polyhydric alcohol ester borate. Styrene resin composition.