JPS62236846A - Method of stabilizing styrene resin composition - Google Patents

Abstract

PURPOSE:To obtain the titled compsn. having excellent thermal stability, by adding an organotin maleate compd., a metal salt of a specified satd. dicarboxylic acid and zeolite A to a styrene resin compsn. contg. a halogen- contg. compd. CONSTITUTION:100pts.wt. flame-retardant styrene resin (A) contg. a halogen compd. obtd. by blending 10-150pts.wt. halogen-contg. compd. (e.g., PVC) with 100pts.wt. styrene resin (e.g., PS) is blended with 0.01-10pts.wt. organotin maleate compd. (B) of formula I or II [wherein R<1> is a (cyclo)alkyl, an alkenyl, an aralkyl or an alkoxyalkyl; R<2> is an alkyl; A is O or a group of formula III; k is 0 or 1; and l is a number of 1-10], 0.01-5.0pts.wt. metal salt of a satd. dicarboxylic acid (C) of formula IV (wherein M and M' are each a monovalent metal atom; and n is a number of 1-18) and 0.01-10pts.wt. zeolite A (D) of formula V (wherein X is a number of 0-6) in a weight ratio of B:C:D of 10-60:80-10:10-30.

Description

Detailed Description of the Invention [Field of Industrial Application] The present invention relates to a method for thermally stabilizing a styrenic resin composition containing a halogen-containing compound as a flame retardant. It can be widely used in fields where flammability is required.

[Conventional technology]

Generally, a method of adding a halogen-containing compound has been conventionally used to make styrenic resins flame-retardant. However, in general, when a styrenic resin is rendered flammable by the above method, the inherent thermal stability of the styrenic resin is significantly reduced.

Therefore, in order to thermally stabilize styrenic resin compositions containing halogen-containing compounds, organic tin compounds, various metal stones, epoxy compounds,
A method of adding a phosphorus compound, an antioxidant, etc. or a maleic acid metal salt (% Publication No. 58-54023) is disclosed.

[Problem that the invention seeks to solve]

Among the above-mentioned stabilization methods, the method of adding an organic tin compound is widely used because it suppresses a decrease in thermal stability of a styrenic resin composition made flame retardant with a halogen-containing compound. The thermal stabilization effect is still not satisfactory, and the development of a stabilizer with even better thermal stabilization effects has been awaited.

[Means to solve the problem]

From this point of view, the present applicant proposed that 21. Invented the use of an organotin maleate compound and a saturated dicarboxylic acid dimetal salt in combination as a stabilizer having an excellent thermal stabilization effect for a styrene resin composition (Japanese Patent Application No. 146184/1984).

The inventors of the present invention have conducted intensive research into a stabilizer that has excellent thermal stabilizing effects.

For styrenic resin compositions made flame retardant with halogen-containing compounds.

(a) With an organic tin maleate compound.

(b) General formula (1) %formula% (In the formula, M and M' represent monovalent metal atoms.

They may be the same or different. n represents an integer of 1 to 18. ) A saturated dicarboxylic acid digold striped salt represented by (0) General formula (2) % formula % (2) (wherein, The present invention has been made based on the discovery that, by adding these safety agents in combination, a mutual effect that could not be expected from the thermal stabilization effect obtained when these safety agents are added alone or in combination to the resin composition has been achieved. completed.

The styrenic resin used in the present invention is a resin having a structure derived from a styrene skeleton at least in part, or a blend resin thereof, which contains a styrene compound monomer 2 such as styrene, α-methyl Polymers of monomers such as α-substituted styrene such as styrene and nuclear substituted styrene such as vinyltoluene and 0-chlorostyrene.

Further, copolymers of styrene compound monomers and other compound monomers 1, such as vinyl compound monomers, conjugated diene compound Ljt bodies, etc., can also be mentioned. Examples of vinyl compound monomers include cyanide-containing vinyl compounds such as acrylonitrile.

Vinyl carbon PR such as acrylic acid and methacrylic acid
, vinylcarboxylic acid esters such as sonomethyl ester and ethyl ester, and vinyl heterocyclic compounds such as vinylpyridine and vinylcarbazole. Examples of the conjugated diene compound include butadiene, 1-chlorobutadiene, 2-chlorobutadiene, isoprene, and ethylene-propylene-diene compounds. The styrenic resin may be a multicomponent copolymer of two or more styrene compound monomers and the above compound monomers.

The halogen-containing compounds used in the present invention include halogen-containing resins such as vinyl chloride resin, salt-accumulated vinyl chloride resin, and chlorinated polyethylene; Flotican, tetrabromobutane, hexabromocyclododecane.

Tetrabromobenzene, vinyl chloroacetate, fromstyrene, bromphenyl allyl ether, diallyl chlorendoate, het acid.

Het's acid anhydride, tetrachlorophthalic anhydride, tetrabromo phthalic anhydride, chloropropanediol, tetrabromo bisphenol A, decabrom diphenyl ether,
tris(2,3 dibromopropyl) isocyanurate,
Carbonate oligomer of tetrabromobisphenol A.

These include halogen compounds such as bis(tribromphenoxy)ethane.

In the present invention, the mixing ratio of the styrene resin and the halogen-containing compound has different flammability requirements depending on the intended use of the molded product, and the mixing ratio also varies depending on the purpose, but in general,
The amount of the halogen-containing compound added to 100 parts by weight of the styrene resin is 10 to 150 parts by weight.

The organotin maleate compounds used in the present invention can include commonly used compounds (1), for example, those represented by the general formulas (3) and (4) [2f31, (in 41, R+ is an alkyl group, Cycloalkyl group, alkenyl group, aralkyl group or alkoxyalkyl group, R2 is an alkyl group, A is oxygen or -
The group represented by oocaH=cuaoo- is 0 or 1. l! is an integer from 1 to 10! Indicates l. ).

General formulas (3) and (4) will be described in more detail.

R1 can include an alkyl group, a cycloalkyl group, an alkenyl group, an aralkyl group, and an alkoxyalkyl group having 1 to 18 carbon atoms; specific examples include methyl, ethyl, propyl, isoglobil, butyl, hexyl, octyl, inoctyl, 2-ethylhexyl, decyl, dodecyl, )! Examples include groups such as J7'yl, octadecyl, oleyl, benzyl, methylbenzyl, isopropylbenzyl, cyclohexyl, methoxyethyl, ethoxyethyl, methoxybutyl, butoxyethyl.

R2 is an alkyl group having 1 to 12 carbon atoms, and specific examples thereof include methyl, butyl, octyl, lauryl, and the like.

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

Dimethyltin bis(methyl maleate), dimethyltin bis(ethyl maleate), dimethyltin bis(inclovir maleate), dimethyltin bis(butyl maleate),
Dimethyltin bis(hexyl maleate), dimethyltin bis(octyl maleate), dimethyltin bis(in octyl maleate), dimethyltin bis(2-ethylhexyl maleate), dimethyltin hiss(decyl maleate)
, dimethyltin bis(dotesyl maleate), dimethyltin bis(tridecyl maleate), dimethyltin bis(octadecyl maleate), dimethyltin bis(oleyl maleate) & dimethyltin bis(benzyl maleyate)), dimethyl Tin bis(methylbenzyl maleate), dimethyltin bis(cyclohexyl maleate), dimethyltin bis(methoxyethylma V:X, -)) * dibutyltin bis(
Methyl maleyate)), dibutyltin bis(ethyl maleate).

Dibutyltin bis(propyl maleate)% dibutyltin bis(inclobyl maleate), dibutyltin bis(butyl maleate), dibutyltin bis(amyl maleate)
, dibutyltin bis(hexyl maleate), dibutyltin hiss(heptyl maleate), dibutyltin bis(octyl maleate), dibutyltin bis(isooctyl maleate), dibutyltin bis(2-ethylhexyl maleate) h dibutyl tin bis(nyl maleate), dibutyltin bis(decyl maleate), dibutyltin hiss(dodecyl maleate), dibutyltin hiss(tridecyl maleate) h dibutyltin bis(octadecyl maleate).

Dibutyltin hiss (allyl maleate), dibutyltin bis (oleyl maleate), dibutyltin bis (benzyl maleate), dibutyltin hiss (cyclohexyl maleate), dibutyltin hiss (methoxybutyl maleate),
Dioctyltin bis(ethyl maleate), dioctyltin bis(propyl maleate), dioctyltin bis(impropyl maleate), dioctyltin bis(butyl maleate), dioctyltin bis(hexyl maleyate),
Dioctyltin bis(octyl maleate) & dioctyltin bis(in-octyl maleate), dioctyltin bis(2-ethylhexyl maleate), dioctyltin bis(decyl maleate), dioctyltin bis(dodecyl maleate)% dioctyltin bis( tridecyl maleate), dioctyltin bis(octadecyl maleate), dioctyltin bis(oleyl maleate), dioctyltin bis(benzyl maleate), dioctyltin hiss(cyclohexyl maleate), dioctyltin bis(methoxybutyl maleate) ), Ji? 'l) Ryltin bis(ethyl maleate), dilauryltin bis(isopropyl maleate), dilauryltin bis(butyl maleate), dilauryltin bis(hexyl maleate), dilauryltin bis(octyl maleate) h dilauryltin Dilauryltin bis(inoctyl maleate), dilauryltin bis(2-ethylhexyl maley 1-), dilauryltin bis(decyl maleate), dilauryltin bis(dodecyl maleate), dilauryltin bis(lJfsilmaleate), dilauryltin bis() octadecyl maleate), dilauryltin bis(oleyl maleate), dilauryltin bis(benzyl maleate), dilauryltin bis(cyclohexyl maleate), dilauryltin bis(methoxybutyl maleate) h bis[dimethyltin methyl maleate] Maleate.

Bis(dimethyltin ethyl maleate) maleate, His(dimethyltin isopropyl maleate) maleate, His(dimethyltin butyl maleate) maleate, Bis(
dimethyltin hexyl maleate) maleate, bis(dimethyltin octyl maleate) maleate, bis(dimethyltin octyl maleate) maleate, bis(dimethyltin 2-ethylhexyl maleate) maleate,
Bis(dimethyltin dodecyl maleate) maleate, bis(dimethyltin dodecyl maleate) maleate, bis(
dimethyltin tridecyl maleate) maleate, bis(
dimethyltin octadecyl maleate) maleate, bis(dimethyltin oleyl maleate) maleate, bis(
dibutyltin benzyl maleate) maleate, bis(dimethyltin cyclohexyl maleate) maleate, bis(dimethyltin methoxybutyl maleate) maleate,
Bis(dibutyltin butyl maleate) maleate, bis(dibutyltin ethyl maleate) maleate.

Bi, t (dibutyltin furobyl maleate) maleate,
Bis(dimethyltin isopropyl maleate) maleate, bis(dibutyltin butyl maleate) maleate, bis(diptyltin amyl maleate) maleate, bis(
Dibutyltin hexyl maleate) maleate, bis(dibutyltin hexyl maleate) maleate, bis(dimethyltin octyl maleate) maleate, bis(dimethyltin octyl maleate) maleate, bis(dibutyltin 2-ethylhexyl maleate) maleate , bis(diptytin nonyl maleate) maleate, bis(
cyphtyltin decyl maleate) maleate, bis(diptyltin P-decyl maleate) maleate, bis(dimethyltin tridecyl maleate) maleate, his(diptyltin octadecyl maleate) maleate, his(cyphtyltin adilemaleate) maleate, bis(dibutyltin tridecyl maleate) maleate Bis(dibutyltin benzyl maleate) maleate, Bis(dibutyltin cyclohexyl maleate) maleate.

Bis(dibutyltin methoxybutyl maleate) maleate, bis(dioctyltin ethyl maleate) maleyate,
bis(dioctyltin isopropyl maleate) maleate, bis(dioctyltin isopropyl maleate) maleate, bis(dioctyltin butyl maleate) maleate.

Bis(dioctyltinhexyl maleate) maleate,
Bis(dioctyltin octyl maleate) maleite,
Bis(dioctyltin octyl maleate) maleate, bis(dioctyltin 2-ethylhexyl maleate) maleate, bis(dioctyltin tesyl maleate)
His(dioctyltin dodecyl maleate) maleate, Bis(dioctyltin tridecyl maleate) maleate, Bis(dioctyltin octadecyl maleate) maleate, Bis(dioctyltin oleyl maleate) maleate, Bis(dioctyltin benzyl maleate) ate) maleate, bis(dioctyltin cyclohexyl maleate) maleate, bis(dio, ctyltin methoxybutyl maleate) maleate, bis(dilauryltin ethyl maleate) maleate, His(dioctyltin cyclohexyl maleate) maleate, bis( dilauryltin butyl maleate) maleate, bis(dilauryltin hexyl maleate) maleate, bis(dilauryltin octyl maleate) maleate, bis(dilauryltin octyl maleate) maleate, bis(dilauryltin 2-ethylhexyl maleate) maleate, bis(dilauryltin tesyl maleate) maleate,
bis(dilauryltin dodecyl maleate) maleate,
His(dilauryltin tridecyl maleate) maleate, Bis(dilauryltin octadecyl maleate) maleate, Bis(dilauryltin oleyl maleate) maleate, Bis(dilauryltin benzyl maleate) maleate, Bis(dilauryltin cyclohexyl maleate)
Maleate, bis(dilauryltin methoxybutyl maleate) maleate, bis(dimethyltin methoxybutyl maleate).

tilmaleate) oxide, bis(dimethyltinbutylmaleate)oxide, bis(dimethyltinisooctylmaleate)oxide.

Bis(dibutyltin benzyl maleate) oxide, bis(dibutyltin methyl maleate) oxide, bis(
dimethyltin butyl maleate) oxide, bis(dibutyltin octyl maleate) oxide, bis(dibutyltin benzyl maleate) oxide, bis(dioctyltin butyl maleate) oxide, bis(dioctyltin isooctyl maleate) oxide, Bis(dioctyltin benzyl maleate) oxide, bis(dilauryltin butyl maleate) oxide, bis(dilauryltin isooctyl maleate) oxide, bis(
dilauryltin benzyl maleate) oxide, and preferred examples include dibutyltin bis(methyl maleate), dibutyltin bis(butyl maleate), dibutyltin bis(isooctyl maleate), and dibutyltin bis(isooctyl maleate).
2-ethylhexyl maleate), dibutyltin bis(tridecyl maleate), dibutyltin bis(octadecyl maleate), dibutyltin bis(oleyl male x-))
, dibutyltin bis(benzyl maleate), dibutyltin bis(cyclohexyl maleate), dioctyltin bis(butyl maleate).

Dioctyltin bis(in-octyl maleate).

Dioctyltin bis(2-ethylhexyl maleate),
Dioctyltin bis(tridecyl maleate), dioctyltin bis(octadecyl maleate), dioctyltin bis(oleyl maleate), dioctyltin bis(benzyl maleyate) L Dioctyltin bis(cyclohexyl maleate), bis(dibutyltin) Methyl maleate, bis(diptytintinphthyl YL/ate)
Maleate, bis(dibutyltin isooctyl maleate) maleate, bis(diptyltin 2-ethylhexyl maleate) maleate.

bis(dibutyltintritesyl maleate) maleate,
Bis(dibutyltin octadecyl maleate) maleate, bis(dibutyltin oleyl maleate) maleate,
Bis(dibutyltin benzyl maleate) maleate, bis(diptytin cyclohexyl maleate) maleate.

Bis(dioctyltin butyl maleate) maleate, bis(dioctyltin octyl maleate) maleate, bis(dioctyltin 2-ethylhexyl maleate)
Maleate, bis(dioctyltin tridecyl maleate) maleate, bis(dioctyltin occudecyl maleate) maleate, bis(dioctyltin oleyl maleate) maleate, bis(dioctyltin benzyl maleate) maleate, bis(dioctyltin occudecyl maleate) ate) maleate, bis(dibutyltin methyl maleate) oxide, bis(dimethyltin butyl maleate) oxide, bis(diptyltin benzyl maleate) oxide, bis(dioctyltin butyl maleate)
Oxide, bis(dioctyltin benzyl maleate)
You can enjoy oxide etc. Specific examples of the organotin maleate compound represented by the general formula (4) include the following. These include dimethyltin maleate, dibutyltin maleate, dioctyltin maleate, dilauryltin maleate, and polymers thereof. General formula (8
) and (4), particularly preferred examples include dibutyltin bis(methyl maleate), dibutyltin maleate polymer, dioctyltin maleate polymer, and the like.

In the general formula fil used in the present invention, M and M' represent monovalent metal atoms, preferably Li, Na, or the like, and specific examples thereof include the following.

Dilithium propane diate, di-sodium propane,
Dipotassium propanedioate, dilithium butanedioate, disodium butanedioate, dipotassium butanedioate, dilithium pentanedioate.

Pentani nk disodium, dipotassium pentaniate, sodium/potassium pentaninate.

Dilithium hexane diate, disodium hexane diide,
Potassium hexanoate, dilithium heptane, disodium heptane, dipotassium heptane, dilithium octane.

Disodium octanoate, dipotassium octanoate,
Dilithium nonannic acid, disodium nonannic acid, dilithium nonannic acid, dilithium diannic acid, disodium diannic acid, dipotassium diannic acid, dilithium unannic acid.

Disodium undecanoate, dipotassium undecanoate, dilithium dodecanoate, disodium dodecanoate, dipotassium dodecanoate.

Tridecani diritinium, tridecani dihydritinium, tridecani dipotassium, tridecani dipotassium, tetradecani dilithium, tetradecani difertate disodium, tetradecani dipotassium.

Dilithium pentadecanoate, sodium pentadecanidioate, dipotassium pentadecanoate.

Dilithium hexadecanoate, disodium hexadecanoate, dipotassium hexadecanoate.

Dilithium heptadecanate, disodium heptadecanide, dipotassium heptadecanide, dilithium octadecanoate, disodium octadecanoate, dipotassium octadecanoate.

Dilithium nonadecanedioate, dinatrichum nonadecanedioate, dipotassium nonadecanedioate, dilithium icosanidioate, dinatonium icosanidioate, dipotassium icosanidioate, lithium/sodium butanedioate, sodium/potassium butanedioate, sodium/potassium hexanedioate, lithium/potassium hexanedioate, hexanidioate Particularly preferable examples include dilithium hexane diate, disodium hexane diate, dipotassium hexane diate, lithium sodium hexane diate, and sodium hexane diate.
Examples include potassium, lithium potassium hexane diate, and the like.

Type A zeolites represented by the general formula (21) used in the present invention include natural and synthetic ha zeolites. The surface may be treated with an alkali metal salt of a higher fatty acid or an alkali metal salt of an organic sulfonic acid such as an alkali metal salt of dodecylbenzenesulfonic acid.

In the present invention, the amount of the organotin maleate compound added to 100 parts by weight of the styrene resin composition flame-retardant with a halogen-containing compound is not particularly limited, but is usually 17, for example, 0.01 part by weight. 10 parts by weight, preferably 0
05 to 6.0 parts by weight. If it is less than 0.001 parts by weight, the thermal stabilizing effect will be small, and if it exceeds 10 parts by weight, the expected thermal stabilizing effect will not be obtained. Further, the amount of the saturated dicarboxylic acid dimetal salt represented by the general formula (1) is not particularly limited, but is usually 1 to 5.0 parts by weight, preferably 1105 parts by weight. Part weight: 0 parts. If it is less than a01, the thermal stabilizing effect will be reduced. Further, the amount of the type A zeolite represented by the general formula (2) is not particularly limited, but is usually 5, for example, 0.01 parts by weight to 10 parts by weight, preferably 0.05 parts by weight to 5 parts by weight.
It is 0 parts by weight. If it is less than 0.01 parts by weight, the thermal stabilizing effect will be small, and if it exceeds 10 parts by weight, the expected thermal stabilizing effect will not be obtained.

Organotin maleate compound, dicarboxylic acid dimetal salt, and A
There is no particular limitation on the ratio of the combined use with type zeolite, but 2 parts by weight of organic tin maleate compound dicarboxylic acid digold maple salt and type A zeolite = 10-60:80-10:1
0-30 is preferable and 1% is preferably 20-50:6
0-20: 20-30. It is not preferable to deviate from this combination ratio because there will be poor synergistic effects.

The method for adding the stabilizer used in the present invention to a styrenic resin composition that has been flame-retardated with a halogen-containing compound is as follows:
Conventionally known techniques may be used.2For example, the resin composition and the stabilizer may be mixed in a Henschel mixer, a ribbon printer,
It may be mixed with a Banbury mixer or the like, or
An organotin maleate compound, a saturated dicarboxylic acid digold paulownia salt represented by the general formula (1), and an A-type theolite represented by the general formula (2) are mixed together in advance, and then the resin composition is mixed with the above-mentioned mixer. You can mix it with

Further, in addition to these stabilizers, known stabilizers 5 such as various metal soaps, organic phosphorus compounds, etc. can be used in combination.

Furthermore, if necessary, plasticizers, lubricants, antioxidants, pigments, fillers, processing aids, etc. can be added.

[Examples and effects]

EXAMPLES The present invention will be specifically explained below with reference to Examples, but the present invention is not limited thereto. In the examples, 1 part means part by weight.

Example 1 Acrylonitrile-butadiene-styrene copolymer [Mitsubishi Monsanto Chemical Co., Ltd. M-Tuflex TF'X-41
0) 50 parts, vinyl chloride resin [Ge manufactured by Nippon Zeon Co., Ltd.
on 103 EF-8) A mixture of 50 parts and the stabilizer shown in [Table 1] was kneaded for 5 minutes using an 8-inch test roll adjusted to 155°C to produce a sheet with a thickness of 0.5 wn. did.

After cutting the obtained sheets, 8 sheets were stacked and heated at 210°C.

20] Pressing was carried out for 90 minutes at $'d, and the test pieces after pressing were taken out and the degree of coloration was visually evaluated. [Table-
1], it can be seen that the combined use of the organotin maleate compound of the present invention, disodium hexane diate, and mu-type zeolite improves the thermal stabilization effect.

Example 2 Acrylonitrile, butadiene, styrene copolymer [manufactured by Japan Synthetic Rubber Co., Ltd., JSRABS'IGNP]>
OP part, tetrabromobisphenol A [Fire Card 2000 manufactured by Teijin Kasei Ltd.] to 25 parts [Table-2]
A compound containing the stabilizer shown in was kneaded for 5 minutes using an 8-inch test roll adjusted to 130°C to a thickness of 0.5 mm.
A sheet was prepared. After cutting the obtained sheets, 8 sheets were stacked and heated at 240°C.

Pressing was performed for 60 minutes at IQ kg/7, and the test piece after pressing was taken out and its degree of coloration was visually determined. [Table-2
] As can be seen, the mutual effect of the stabilizer according to the present invention is extremely excellent (jO).
ootL hexap U muciclododetsun [Daiichi Kogyo Seiyaku (
The stabilizer shown in [Table 3] was added to 0.2 part of Pyroguard 5R-1031siL di-n-butyltin maleate polymer.

The blend was kneaded for 5 minutes on an 8-inch test roll adjusted to 120°C to form a sheet with a thickness of 0.7wn.

After cutting the obtained sheets, 8 sheets were stacked and heated at 250℃10 for 9 minutes.
Pressing was performed with cIl, and the time until the test piece deteriorated (blackened) was measured.

As can be seen from [Table 3], the additive effect of the leg softening agent according to the present invention is extremely excellent.

Sample numbers 10 to 24 are comparative examples.

Claims (1)

[Claims] 1. When stabilizing a styrenic resin composition made flame retardant with a halogen-containing compound, (a) an organotin maleate compound; (b) general formula (1) MOOC(CH_2 )_nCOOM'(1) (where M
, M' represent monovalent metal atoms and may be the same or different. n represents an integer of 1 to 18. ) A saturated dicarboxylic acid dimetal salt represented by (c) General formula (2) Na_2O・Al_2O_3・2SiO_2・XH_2
A method for stabilizing the resin composition, which comprises adding a type A zeolite represented by O(2) (in the formula, X represents a number from 0 to 6) in combination.