JPH0627232B2 - Method for stabilizing styrene resin composition - Google Patents

Description

TECHNICAL FIELD The present invention relates to a heat stabilization method for a styrene-based resin composition containing a halogen-containing compound as a flame retardant, which is difficult for styrene-based resins. It can be widely used in fields where flammability is required.

[Conventional technology]

In general, a method of adding a halogen-containing compound has been conventionally performed to make a styrene resin flame-retardant. However, in general, when the styrene-based resin is made flame-retardant by the above method, there is a drawback that the thermal stability originally possessed by the styrene-based resin is significantly lowered.

Therefore, conventionally, in order to thermally stabilize the styrene-based resin composition containing a halogen-containing compound, as a stabilizer, an organotin compound, various metal soaps, epoxy compounds,
A method of adding a phosphorus compound, an antioxidant, etc., or adding a maleic acid metal salt (Japanese Patent Publication No. 56-54023) is disclosed.

[Problems to be solved by the invention]

Among the above-mentioned stabilization methods, the method of adding an organotin compound is widely used because it suppresses a decrease in thermal stability of a styrene-based resin composition flame-retarded with a halogen-containing compound. Is not yet satisfactory,
Furthermore, the development of a stabilizer having an excellent heat stabilizing effect has been awaited.

[Means for solving problems]

From this point of view, the present applicant proposes that, with respect to a styrene resin composition flame-retarded with a halogen-containing compound, an organic tin maleate compound and a saturated dicarboxylic acid dimetal salt are used as a stabilizer having an excellent heat stabilizing effect. The invention was made in combination (Japanese Patent Application No. 60-146184).

The present inventors have conducted extensive studies on a stabilizer having a further excellent heat stabilizing effect, and as a result, for a styrene resin composition flame-retarded with a halogen-containing compound, (a) An organotin maleate compound, and (b) a general formula (1) MOOC (CH ₂ ) _n COOM '(1) (wherein M and M'represent a monovalent metal atom, which may be the same or different) good .n is a saturated dicarboxylic acid di metal salt represented by an integer of 1~18.), (c) general formula _{(2) N a2 O · Al} 2 O 3 · 2S i O 2 · XH 2 O ( 2) (In the formula, X represents a number of 0 to 6.) These stabilizers are added alone or in combination of two types to the resin composition by adding together with the A-type zeolite represented by The present invention has been completed by discovering that an unexpected summarization effect is exhibited from the thermal stabilization effect in the case of doing so.

The styrene resin used in the present invention is a resin having a structure derived from a styrene skeleton in at least a part thereof and a blend resin thereof, and a styrene compound monomer such as styrene or α-methyl. Α like styrene
-Polymers of substituted styrene and monomers such as vinyl-toluene and nucleus-substituted styrenes such as o-chlorostyrene, and styrene compound monomers and other compound monomers such as vinyl compound monomers and conjugated diene compounds Examples thereof include copolymers with monomers and the like. Examples of vinyl compound monomers include cyan-containing vinyl compounds such as acrylonitrile, vinyl carboxylic acids such as acrylic acid and methacrylic acid, vinyl carboxylic acid esters such as methyl ester and ethyl ester thereof, vinyl pyridine, vinyl carbazole such as vinyl carbazole. Examples thereof include heterocyclic compounds.
Examples of the conjugated diene compound include butadiene, 1-chlorobutadiene, 2-chlorobutadiene, isoprene, ethylene-propylene-diene compound and the like. The styrene resin may be a binary or more multi-component copolymer of a styrene compound monomer and the above compound monomer.

The halogen-containing compound used in the present invention is a halogen-containing resin such as vinyl chloride resin, chlorinated vinyl chloride resin and chlorinated polyethylene; chlorinated paraffin, chlorinated polyphenyl, brominated polyphenyl, berchlorpentacyclodecane, tetrabromide. Butane, hexabromocyclododecane, tetrabromobenzene, vinyl chloroacetate,
Bromstyrene, bromophenyl allyl ether, diallyl chlorendate, hettic acid, hettic anhydride, tetrachlorophthalic anhydride, tetrabromophthalic anhydride, chloropropanediol, tetrabromobisphenol A,
Decabromodiphenyl ether, tris (2,3 dibromopropyl) isocyanurate, a carbonate oligomer of tetrabromobisphenol A, and a halogen compound such as bis (tribromophenoxy) ethane.

In the present invention, the mixing ratio of the styrene resin and the halogen-containing compound is different in the requirement of flame retardancy depending on the purpose of use of the molded product, and the mixing ratio also varies depending on the purpose, but generally,
The amount of the halogen-containing compound added is 10 to 150 parts by weight with respect to 100 parts by weight of the styrene resin.

Examples of the organotin maleate-based compound used in the present invention include commonly used compounds.
(3) and (4) [In the formulas (3) and (4), R ¹ is an alkyl group, a cycloalkyl group,
Alkenyl group, aralkyl group or alkoxyalkyl group, R ² is alkyl group, A is oxygen or —OOCCH═CHCOO—
, K is 0 or 1, and l is an integer of 1 to 10. ] The compound shown by these is mentioned.

To describe the general formulas (3) and (4) in more detail, R ¹ may be an alkyl group having 1 to 18 carbon atoms, a cycloalkyl group, an alkenyl group, an aralkyl group or an alkoxyalkyl group. , Methyl, ethyl, propyl, isopropyl, butyl, hexyl, octyl, isooctyl, 2-ethylhexyl, decyl, dodecyl,
Tridecyl, octadecyl, oleyl, benzyl, methylbenzyl, isopropylbenzyl, cyclohexyl,
Mention may be made of groups such as methoxyethyl, ethoxyethyl, methoxybutyl, butoxyethyl and the like.

R ² may be an alkyl group having 1 to 12 carbon atoms, and specific examples thereof include groups such as methyl, butyl, octyl and lauryl.

Specific examples of the organotin ester maleate compound represented by the general formula (3) include the following.

Dimethyltin bis (methyl maleate), dimethyltin bis (ethyl maleate), dimethyltin bis (isopropyl maleate), dimethyltin bis (butyl maleate),
Dimethyltin bis (hexyl maleate), dimethyltin bis (octyl maleate), dimethyltin bis (isooctyl maleate), dimethyltin bis (2-ethylhexyl maleate), dimethyltin bis (decyl maleate), dimethyltin bis ( Dodecyl maleate), dimethyl tin bis (tridecyl maleate), dimethyl tin bis (octadecyl maleate), dimethyl tin bis (oleyl maleate), dimethyl tin bis (benzyl maleate), dimethyl tin bis (methyl benzyl maleate) ),
Dimethyltin bis (cyclohexyl maleate), dimethyltin bis (methoxybutyl maleate), dibutyltin bis (methyl maleate), dibutyltin bis (ethyl maleate), dibutyltin bis (propyl maleate), dibutyltin bis ( Isopropyl maleate), dibutyl tin bis (butyl maleate), dibutyl tin bis (amyl maleate), dibutyl tin bis (hexyl maleate),
Dibutyltin bis (heptyl maleate), dibutyltin bis (octyl maleate), dibutyltin bis (isooctyl maleate), dibutyltin bis (2-ethylhexyl maleate), dibutyltin bis (nonyl maleate), dibutyltin bis ( Decyl maleate), dibutyl tin bis (dodecyl maleate), dibutyl tin bis (tridecyl maleate), dibutyl tin bis (octadecyl maleate), dibutyl tin bis (allyl maleate), dibutyl tin bis (oleyl maleate), dibutyl Tin bis (benzyl maleate), dibutyl tin bis (cyclohexyl maleate), dibutyl tin bis (methoxy butyl maleate), dioctyl tin bis (ethyl maleate),
Dioctyl tin bis (propyl maleate), dioctyl tin bis (isopropyl maleate), dioctyl tin bis (butyl maleate), dioctyl tin bis (hexyl maleate), dioctyl tin bis (octyl maleate), dioctyl tin bis (iso Octyl maleate),
Dioctyltin bis (2-ethylhexyl maleate),
Dioctyl tin bis (decyl maleate), dioctyl tin bis (dodecyl maleate), dioctyl tin bis (tridecyl maleate), dioctyl tin bis (octadecyl maleate), dioctyl tin bis (oleyl maleate), dioctyl tin bis (benzyl male) Ato), dioctyltin bis (cyclohexyl maleate), dioctyltin bis (methoxybutyl maleate), dilauryl tin bis (ethyl maleate), dilauryl tin bis (isopropyl maleate), dilauryl tin bis (butyl maleate), dilauryl Tin bis (hexyl maleate), dilauryl tin bis (octyl maleate), dilauryl tin bis (isooctyl maleate), dilauryl tin bis (2-ethylhexyl maleate), dilauryl tin bis (decyl maleate) Dilauryl tin bis (dodecyl maleate), dilauryl tin bis (tridecyl maleate), dilauryl tin bis (octadecyl maleate),
Dilauryl tin bis (oleyl maleate), dilauryl tin bis (benzyl maleate), dilauryl tin bis (cyclohexyl maleate), dilauryl tin bis (methoxybutyl maleate), bis (dimethyl tin methyl maleate) maleate, bis (dimethyl Tin ethyl maleate) maleate, bis (dimethyltin isopropyl maleate) maleate, bis (dimethyltin butyl maleate) maleate, bis (dimethyltin hexyl maleate) maleate, bis (dimethyltin octyl maleate) maleate, bis (dimethyl) Tin isooctyl maleate) maleate, bis (dimethyltin 2-ethylhexyl maleate) maleate, bis (dimethyltin decyl maleate) maleate, bis (dimethyltin dodecyl maleate) maleate, bis Dimethyltin tridecyl maleate) maleate, bis (dimethyltin octadecyl maleate) maleate, bis (dimethyltin oleyl maleate) maleate, bis (dimethyltin benzyl maleate) maleate, bis (dimethyltin cyclohexyl maleate) maleate, bis (Dimethyltin methoxybutyl maleate) maleate, bis (dimethyltin methyl maleate) maleate, bis (dibutyltin ethyl maleate) maleate, bis (dibutyltin propyl maleate) maleate, bis (dibutyltin isopropyl maleate) maleate, Bis (dibutyltin butyl maleate) maleate, bis (dibutyltin amyl maleate)
Maleate, bis (dibutyltin hexyl maleate) maleate, bis (dibutyltin heptyl maleate) maleate, bis (dibutyltin octyl maleate) maleate, bis (dibutyltin isooctyl maleate) maleate, bis (dibutyltin 2-ethylhexyl) Maleate) Maleate, bis (dibutyltin nonyl maleate)
Maleate, bis (dibutyltin decyl maleate) maleate, bis (dibutyltin dodecyl maleate) maleate, bis (dibutyltin tridecyl maleate) maleate, bis (dibutyltin octadecyl maleate) maleate, bis (dibutyltin allyl maleate) maleate , Bis (dibutyltin oleyl maleate) maleate, bis (dibutyltin benzyl maleate) maleate, bis (dibutyltin cyclohexyl maleate) maleate, bis (dibutyltin methoxybutyl maleate)
Maleate, bis (dioctyltin ethyl maleate) maleate, bis (dioctyltin propyl maleate) maleate, bis (dioctyltin isopropyl maleate) maleate, bis (dioctyltin butyl maleate) maleate, bis (dioctyltin hexyl maleate) Maleate, bis (dioctyltin octyl maleate) maleate, bis (dioctyltin isooctyl maleate) maleate, bis (dioctyltin 2-ethylhexyl maleate) maleate, bis (dioctyltin decyl maleate) maleate, bis (dioctyltin dodecyl maleate) ) Maleate, bis (dioctyltin tridecyl maleate) maleate, bis (dioctyltin octadecyl maleate) maleate, bis (dioctyltin oleyl maleate) Maleate, bis (dioctyltin benzyl maleate) maleate, bis (dioctyltin cyclohexyl maleate) maleate, bis (dioctyltin methoxybutyl maleate) maleate, bis (dilauryltin ethyl maleate) maleate, bis (dilauryltin isopropyl maleate) ) Maleate,
Bis (dilauryl tin butyl maleate) maleate, bis (dilauryl tin hexyl maleate) maleate, bis (dilauryl tin octyl maleate) maleate, bis (dilauryl tin isooctyl maleate) maleate, bis (dilauryl tin 2-ethylhexyl maleate) ) Maleate, bis (dilauryl tin decyl maleate) maleate, bis (dilauryl tin dodecyl maleate) maleate, bis (dilauryl tin tridecyl maleate) maleate, bis (dilauryl tin octadecyl maleate) maleate, bis (dilauryl tin oleyl maleate) Maleate, bis (dilauryl tin benzyl maleate) maleate, bis (dilauryl tin cyclohexyl maleate) maleate, bis (dilauryl tin methoxybutyl maleate) Leate, bis (dimethyltin methyl maleate) oxide, bis (dimethyltin butyl maleate) oxide, bis (dimethyltin isooctyl maleate) oxide, bis (dimethyltin benzyl maleate) oxide, bis (dibutyltin methyl maleate) ) Oxide, bis (dibutyltin butyl maleate) oxide, bis (dibutyltin isooctyl maleate) oxide, bis (dibutyltin benzyl maleate) oxide, bis (dioctyltin butyl maleate) oxide, bis (dioctyltin isooctyl) Maleate) oxide, bis (dioctyltin benzyl maleate) oxide, bis (dilauryl tin butyl maleate) oxide, bis (dilauryl tin isooctyl maleate) oxide, bis (dilauryl) Benzyl maleate) oxide and the like. Preferred examples are dibutyltin bis (methyl maleate), dibutyl tin bis (butyl maleate), dibutyl tin bis (isooctyl maleate), dibutyl tin bis (2-ethylhexyl maleate). ), Dibutyltin bis (tridecyl maleate), dibutyltin bis (octadecyl maleate), dibutyltin bis (oleyl maleate), dibutyltin bis (benzyl maleate), dibutyltin bis (cyclohexyl maleate), dioctyltin Bis (butyl maleate), dioctyl tin bis (isooctyl maleate),
Dioctyltin bis (2-ethylhexyl maleate),
Dioctyl tin bis (tridecyl maleate), dioctyl tin bis (octadecyl maleate), dioctyl tin bis (oleyl maleate), dioctyl tin bis (benzyl maleate), dioctyl tin bis (cyclohexyl maleate), bis (dibutyl tin) Methyl maleate) maleate, bis (dibutyltin butyl maleate) maleate, bis (dibutyltin isooctyl maleate) maleate, bis (dibutyltin 2-ethylhexyl maleate) maleate, bis (dibutyltin tridecyl maleate) maleate, Bis (dibutyltin octadecyl maleate) maleate, bis (dibutyltin oleyl maleate) maleate, bis (dibutyltin benzyl maleate) maleate, bis (dibutyltin cyclohexyl maleate) maleate, Sus (dioctyl tin butyl maleate) maleate, bis (dioctyl tin isooctyl maleate) maleate, bis (dioctyl tin 2-ethylhexyl maleate) maleate, bis (dioctyl tin tridecyl maleate) maleate, bis (dioctyl tin octadecyl maleate) Eth) maleate, bis (dioctyltin oleyl maleate) maleate, bis (dioctyltin benzyl maleate) maleate, bis (dioctyltin cyclohexyl maleate) maleate, bis (dibutyltin methyl maleate) oxide, bis (dibutyltin butyl maleate) Acid), bis (dibutyltin benzyl maleate) oxide, bis (dioctyl tin butyl maleate) oxide, bis (dioctyl tin benzyl maleate) oxide, etc. Rukoto can. Specific examples of the organic tin maleate represented by the general formula (4) include the following. Dimethyl tin maleate, dibutyl tin maleate, dioctyl tin maleate,
Examples include dilauryl tin maleate and polymers thereof. Among the organotin maleate compounds of the general formulas (3) and (4), particularly preferable examples are dibutyltin bis (methyl maleate), dibutyltin maleate polymer, dioctyltin maleate polymer and the like.

In the general formula (1) used in the present invention, M, M 'represents a monovalent metal atom, preferably L _i, N a, _K, include the following specific examples thereof.

Dilithium propanedioate, disodium propanedioate,
Dipotassium propanedioate, dilithium butanedioate, disodium butanedioate, dipotassium butanedioate, dilithium pentanedioate, disodium pentanedioate, dipotassium pentanedioate, sodium potassium pentanedioate,
Dilithium hexanedioate, disodium hexanedioate,
Dipotassium hexanedioate, dilithium heptanedioate, disodium heptanedioate, dipotassium heptanedioate, dilithium octanedioate, disodium octanedioate, dipotassium octanedioate, dilithium nonanedioate, disodium nonanedioate, nonanedioate Dipotassium acid, dilithium decanedioate, disodium decanedioate, dipotassium decanedioate, dilithium undecanedioate, disodium undecanedioate, dipotassium undecanedioate, dilithium dodecanedioate, disodium dodecanedioate, dipotassium dodecanedioate , Dilithium tridecanedioate, disodium tridecanedioate, dipotassium tridecanedioate, dilithium tetradecanedioate, disodium tetradecanedioate,
Tetradecanedioate dipotassium, pentadecanedioate dilithium, pentadecanedioate disodium, pentadecanedioate dipotassium, hexadecanedioate dilithium, hexadecanedioate disodium, hexadecanedioate dipotassium,
Dilithium heptadecanedioate, disodium heptadecanedioate, dipotassium heptadecanedioate, dilithium octadecanedioate, disodium octadecanedioate, dipotassium octadecanedioate, dilithium nonadecanedioate, disodium nonadecanedioate, dipotassium nonadecanedioate, aicosan di Dilithium acid, disodium eicosane diate, dipotassium eicosane diate, lithium / sodium butanedioate, sodium / potassium butanedioate, sodium / potassium hexanedioate, lithium / potassium hexanedioate, lithium / sodium hexanedioate, etc. Among them, particularly preferred examples are dilithium hexanedioate, disodium hexanedioate, dipotassium hexanedioate, lithium sodium hexanedioate,
Examples thereof include sodium / potassium hexanedioate and lithium / potassium hexanedioate.

Examples of the A-type zeolite represented by the general formula (2) used in the present invention include natural and synthetic A-type zeolite. The type A zeolite used is surface-treated with a higher fatty acid alkali metal salt such as stearic acid or oleic acid alkali metal salt, or an organic sulfonic acid alkali metal salt such as dodecylbenzene sulfonic acid alkali metal salt. May be.

In the present invention, the addition amount of the organotin maleate compound is not particularly limited with respect to 100 parts by weight of the styrene resin composition flame-retarded with the halogen-containing compound, but usually 0.01 part by weight to 10 parts by weight, for example. Part, preferably 0.05-
It is 6.0 parts by weight. If it is less than 0.01 parts by weight, the heat stabilizing effect is small, and if it exceeds 10 parts by weight, the expected heat stabilizing effect cannot be obtained. The addition amount of the saturated dicarboxylic acid dimetal salt represented by the general formula (1) is not particularly limited, but is usually 0.01 parts by weight to 5.0 parts by weight, preferably 0.05 parts by weight to 2.0 parts by weight. . If it is less than 0.01 parts by weight, the effect of phase retention is not remarkable, and if it exceeds 5.0 parts by weight, the heat stabilizing effect is rather lowered. Furthermore, A represented by the general formula (2)
The addition amount of the type zeolite is not particularly limited, but is usually 0.01 parts by weight to 10 parts by weight, preferably 0.05 parts by weight to 5.0 parts by weight. If it is less than 0.01 parts by weight, the heat stabilizing effect is small, and if it exceeds 10 parts by weight, the expected heat stabilizing effect cannot be obtained.

Organotin maleate compound, dicarboxylic acid dimetal salt and A
The combination ratio with the type zeolite is not particularly limited, but in wt%, organotin maleate compound: dicarboxylic acid dimetal salt: A type zeolite = 10 to 60:80 to 10:
10 to 30 is preferable, and particularly preferable is 20 to 50:
60-20: 20-30. If it is out of this combination ratio, the replenishment effect is poor, which is not preferable.

The method of adding the stabilizer used in the present invention to a styrene resin composition flame-retarded with a halogen-containing compound is
It may be carried out by a conventionally known technique. For example, the resin composition and the stabilizer are mixed with a Henschel mixer, a ribbon blender,
It may be mixed with a Banbury mixer, or
An organotin maleate-based compound, a saturated dicarboxylic acid dimetal salt represented by the general formula (1) and an A-type zeolite represented by the general formula (2), which were previously packed, were mixed with the resin composition by the above-mentioned mixer. You may.

Further, known stabilizers such as various metal soaps and organic phosphorus compounds can be used in combination with these stabilizers.

Further, if necessary, a plasticizer, a lubricant, an antioxidant, a pigment, a filler, a processing aid and the like can be added.

[Examples and effects]

Hereinafter, the present invention will be specifically described with reference to Examples, but the present invention is not limited thereto. In the examples, parts means parts by weight.

Example 1. Acrylonitrile / Butadiene / Styrene Copolymer [Mitsubishi Flex Inc. TFX-410]
50 parts, vinyl chloride resin [Geon 10 manufactured by Nippon Zeon Co., Ltd.
3EP-8] A compound prepared by adding the stabilizer shown in [Table 1] to 50 parts was used with an 8-inch test roll adjusted to 155 ° C.
Kneading was carried out for a minute to prepare a sheet having a thickness of 0.5 mm.

After cutting the obtained sheets, 8 sheets are piled up, 210 ℃, 20kg / c
Pressing was carried out for 90 minutes at m ² , the test piece after pressing was taken out, and the degree of coloring was visually judged. As can be seen from Table 1, the combined use of the organotin maleate compound of the present invention, disodium hexanedioate, and A-type zeolite improves the heat stabilizing effect.

Example 2 100 parts of acrylonitrile-butadiene-styrene copolymer [Nippon Synthetic Rubber Co., Ltd., JSR ABS ^# 10NP] 100 parts, Tetrabrom bisphenol A [Teijin Kasei Co., Ltd. Fireguard 2000] 25 parts [Table-2 ] The stabilizer-added composition shown in the above] was kneaded with an 8-inch test roll adjusted to 130 ° C. for 5 minutes to prepare a sheet having a thickness of 0.5 mm. After cutting the obtained sheet, 8 sheets were piled up and 6 at 240 ° C. and 10 kg / cm ²
Pressing was performed for 0 minutes, the test piece after pressing was taken out, and the degree of coloring was visually judged. As can be seen from [Table-2], the additive effect of the stabilizer according to the present invention is remarkably excellent.

Example 3. Styrene resin [Styron 492 manufactured by Asahi Kasei Corporation] 1
00 parts, 15 parts of hexabromocyclododecane [Piroguard SR-103 manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd.], 0.2 parts of di-n-butyltin maleate polymer, and a stabilizer compound shown in [Table 3] The material was kneaded with an 8-inch test roll adjusted to 120 ° C. for 5 minutes to prepare a sheet having a thickness of 0.7 mm.

After cutting the obtained sheets, 8 sheets are piled up at 250 ° C, 10 kg / c
By pressing at m ² , the time (minutes) until the test piece deteriorates (blackens) was measured.

As can be seen from [Table 3], the stabilizing effect of the stabilizer according to the present invention is remarkably excellent.

Front page continuation (51) Int.Cl. ⁵ Identification code Office reference number FI Technical display location C08L 25/00 LEE 9166-4J 55/02 LME 7142-4J // (C08L 25/00 27:06) (C08L 25/00 85:00) (C08L 55/02 23:28) (56) Reference JP 62-199654 (JP, A) JP 61-118450 (JP, A) JP 62-7751 ( JP, A) JP 61-115948 (JP, A)

Claims (1)

[Claims] 1. When stabilizing a styrene resin composition flame-retarded with a halogen-containing compound, (a) an organotin maleate compound, and (b) a general formula (1) MOOC (CH ₂ ) _n Saturated dicarboxylic acid dimetal represented by COOM '(1) (wherein M and M'represent monovalent metal atoms, which may be the same or different; n is an integer of 1 to 18) Salt and (c) A type represented by the general formula (2) N _a2 O · Al ₂ O ₃ · 2S _i O ₂ · XH ₂ O (2) (wherein X represents a number of 0 to 6) A method for stabilizing a resin composition, which comprises adding zeolite together.