JPS63170440A - Stabilization of styrene based resin composition - Google Patents

Abstract

PURPOSE:To thermally stabilize a styrene based resin composition containing a bromine based compound as a flame retardant, by adding zeolite containing a specific metal or preferably further an organotin maleate based compound to the composition. CONSTITUTION:(A) 100pts.wt. resin composition containing a bromine based flame retardant, e.g. tetrabromoethane or tribromophenol, in an amount of 5-35pts.wt. based on 100pts.wt. styren based resin is blended with (B) 0.05-5pts. wt., preferably 0.1-3pts.wt. zeolite containing one or more metals selected from group II and IV metals of the periodic table, preferably Ca, Zn or Ba- substituted zeolite and preferably further (C) 0.05-5pts.wt., preferably 0.1-3pts. wt. organotin maleate based compound, e.g. dimethyltin bis(methyl maleate), so as to provide 9:1-3:7 ratio of the components (B) to (C).

Description

Detailed Description of the Invention [Industrial Application Field] The present invention relates to the thermal stabilization of styrenic resin compositions containing bromine compounds as flame retardants. It can be widely used in fields where

[Conventional technology]

Various flame retardants or flame retardant aids are used to make styrene resins flame retardant, and bromine flame retardants are particularly widely used.

However, in general, when a bromine flame retardant is added to a styrene resin, there is a drawback in that the thermal stability of the resin composition is significantly reduced, and various compounds have been used to suppress this problem. (For example, Tokuko Sho 59-4
No. 1462, No. 56-54023, No. 61-2695
issue).

In addition, type A zeolite has been found to have excellent effects (Japanese Patent Application Laid-open No. 61-II5948).

[Problem that the invention seeks to solve]

However, the thermal stabilizing effect of the A-type zeolite has not yet been satisfactory against the severe thermal history during molding.

[Means for solving problems]

From this point of view, the present inventors conducted research on stabilizers that have an even better thermal stabilizing effect on styrene resin compositions containing bromine flame retardants. It has been found that by adding zeolite containing at least one metal selected from Group II and IV metals of the Periodic Table, the resin composition can have excellent thermal stability. The present invention was completed based on the discovery that a resin composition with even more excellent thermal stability can be obtained by using an organotin maleate compound in combination with this compound.

The styrenic resin used in the present invention is a resin having a structure derived from a styrene skeleton at least in part, and a blend resin thereof, and the styrenic compound I@
body, such as styrene or α-methylstyrene
Polymers of monomers such as l1M-substituted styrene and vinyltoluene, nuclear-substituted styrene such as 0-chlorostyrene, and styrenic compound monomers and other compound monomers, such as vinyl compound monomers, conjugated diene compound monomers Copolymers with etc. can be mentioned. Examples of vinyl compound molecules include cyanide-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, and vinyl carboxylic acid such as vinyl carbazole. Examples include heterocyclic compounds.

Examples of the conjugated diene compound include butadiene, 1-chlorobutadiene, 2-chlorobutadiene, isoprene, and ethylene-propylene-diene compounds. The styrene-based resin may be a multicomponent co-electrical combination of a styrene-based compound Lit form and the above-mentioned compound 'I1 form.

As the bromine-based flame retardant used in the present invention, those commonly used in the field can be used without limitation, such as tetrabromoethane, tetrabromobutane, hexabromocyclododecane, tetrabromobenzene, Bromstyrene, bromphenyl allyl ether, tetrabromo phthalic anhydride, tribromophenol,
Pentabromotoluene, pentabromo phenylpropyl ether, tetrabromo bisphenol A, decabromo diphenyl ether, octabromo diphenyl ether, tris(2,3-dibromopropyl)isoanurate, polydibromo phenyl oxide, carbonate oligomer to tetrabromo bisphenol, tetrabromo bisphenol 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
-dibromopropylbentabromphenyl ether, bis(tribromophenol)ethane, and the like. There is no particular limit to the amount of these bromine-based flame retardants added, but it may be varied as appropriate depending on the degree of flame retardancy required.
Generally styrene fruit trees [5-35 for II00 heavy electric parts
It is preferable to use the heavy bottle portion alone or in combination of two or more types.

As mentioned above, the zeolite used in the present invention is a zeolite containing at least one metal selected from Group II and IV metals of the periodic table (hereinafter referred to as "metal-substituted zeolite I"). , a synthetic zeolite obtained by substituting an alkali metal in a zeolite containing an alkali metal with the metal of Group 1+ and Group IV, or a natural zeolite containing a metal of Group 1! and Group IV. There may be.

The metals of Group II and IV of the periodic table are not particularly limited, but Mg
, Ca, Zn, 5r1Ba1Zr, Sn etc. are preferable,
Particularly preferred metals include Ca, Zn, and Ba.

Specific examples of the metal-substituted zeolite used in the present invention include Mgl-substituted zeolite, Ca-substituted zeolite, 7.
Synthetic zeolites such as n-substituted zeolite, Sr-substituted zeolite, Ra11-substituted zeolite, Zr1W-substituted zeolite and Sn-substituted zeolite can be mentioned, and natural zeolites containing the metal can also be used.

Regarding the method for producing the synthetic zeolite used in the present invention,
Any known method may be used, such as the method described in JP-A-57-28145.

The organotin maleate compounds used in the present invention include commonly used compounds, examples of which include general formulas (1) and (2) [in formulas (1) and (2), R'
is an alkyl group, a cycloalkyl group, an alkenyl group, an aralkyl group, or an alkoxyalkyl group, R'' is an alkyl group, A is oxygen or a group represented by -00CCH=CHCOO-, k is O or I, and Q is 1 to 1O ]
Examples include compounds represented by:

To explain general formula (1) Shibibi (2) 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, and specific examples include methyl, ethyl, propyl, isopropyl, butyl, hexyl, octyl, Mention may be made of groups such as isooctyl, 2-ethylhexyl, decyl, dodecyl, tridecyl, octadecyl, oleyl, benzyl, methylbenzyl, isopropylbenzyl, nclohexyl, methoxybutyl, ethoxyethyl, methoxybutyl, butoxyethyl.

R1 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 (1) 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), dimethyltin bis(tridecyl maleate),
Dimethyltin bis(octadecyl maleate), dimethyltin bis(oleyl maleate), dimethyltin bis(benzyl maleate), dimethyltin bis(methylbennormaleate), dimethyltin bis(ncrohexyl maleate), dimethyltin bis (methoxybutyl maleate), dibutyltin bis(methyl maleate), dibutyltin bis(ethyl maleate), dibutyltin bis(propyl maleate), dibutyltin bis(isopropyl maleate), dibutyltin bis(butyl maleate) ), dibutyltin bis(amyl maleate), dibutyltin bis(hexyl maleate), dibutyltin bis(heptyl maleate), dibutyltin bis(octyl maleate), dibutyltin bis(isooctyl maleate), dibutyltin bis( 2-ethylhexyl maleate), dibutyltin bis(nonylmazibutyltin bis(dodecyl maleate),
Dibutyltin bis (tridecyl maleate), dibutyltin bis (octadecyl maleate), dibutyltin bis (
allyl maleate), dibutyltin bis(oleyl maleate), dibutyltin bis(benzyl maleate), dibutyltin bis(sochlorhexyl maleate), dibutyltin bis(methoxybutyl maleate), dioctyltin bis(ethyl maleate) , dioctyltin bis(propyl maleate), dioctyltin bis(isopropyl maleate), dioctyltin bis(butyl maleate), dioctyltin bis(hexyl maleate), dioctyl knitted bis(octyl maleate), dioctyltin bis( isooctyl maleate), dioctyltin bis(2-ethylhexyl maleate), dioctyltin bis(decyl maleate), dioctyltin bis(dodecyl maleate)
, dioctyl tin bis (tridecyl maleate), dioctyl tin bis (octadecyl maleate), dioctyl tin bis (oleyl maleate), dioctyl tin bis (1 paste 17 squares -L N; j + h, f-
C 1) f・-/y-hexyl maleate), dioctyltin bis(methoxybutyl maleate), dilauryltin bis(ethyl maleate), dilauryltin bis(isopropyl maleate), dilauryltin bis(butyl maleate) ), dilauryltin 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 knitted bis (benzyl maleate), dilauryl tin bis (cyclohexyl maleate), dilauryl tin bis (methoxy) butyl maleate), bis(trimethyltin methyl maleate) maleate, bis(trimethyltin ethyl maleate) maleate, bis(dimethyltin isopropyl maleate) maleate, bis(trimethyltin butyl maleate) maleate, bis(dimethyltin to ethyl maleate) maleate xyl maleate) maleate, bis(trimethyltin octyl maleate) maleate, bis(dimethyltin isooctyl maleate) maleate, bis(dimethyltin 2-ethylhexyl maleate) maleate, bis(trimethyltin decyl maleate) maleate, bis(dimethyltin octyl maleate) maleate dodecyl maleate) maleate, bis(dimethyltin tridecyl maleate) maleate, bis(trimethyltin octadecyl maleate) maleate, bis(trimethyltin oleyl maleate) maleate, his(dimethyltin benzyl maleate) maleate, bis(dimethyl Tin cyclohexyl maleate) maleate, bis(dimethyltin methoxybutyl maleate) maleate, bis(dibutyltin methyl maleate) maleate, bis(dibutyltin ethyl maleate) maleate, bis(nobdeltin propyl maleate) maleate, bis (dibutyltin isopropyl maleate) maleate, bis(dibutyltin butyl maleate) maleate, bis(dibutyltin amyl maleate)
maleate, bis(dibutyltin hexyl maleate) maleate, his(dibutyltin heptyl maleate) maleate, bis(dibutyltin octyl maleate) maleate, bis(dibutyltin isooctyl maleate) maleate, bis(dibutyltin heptyl maleate) xyl maleate) maleate, bis(dibutyltin nonyl maleate) maleate, bis(dibutyltin decyl maleate) maleate, bis(dibutyltin dodecyl maleate) maleate, bis(butyl 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, His()ocdyltin propyl maleate) maleate, Bis(dioctyltin isopropyl maleate) ate) maleate, bis(dioctyltin butyl maleate) maleate, bis(dioctyltin hexyl maleate) male J6-to, his(dioctyltin octyl maleate)
Male', -t, bis(dioctyltin isooctyl maleate) maleate, bis(dioctyltin 2-edylhexyl maleate) maleate, bis(dioctyltin denulmaleate) maleate, bis(dioctyltin dodecyl maleate) maleate, bis( Dioctyltin tridecyl maleate) maleate, bis(dimethyltin tridecyl maleate) maleate, bis(dibutyltin 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(
dilauryltin butyl maleate) maleate, bis(dilauryltin hexyl maleate) maleate, bis(dilauryltin octyl maleate) maleate, bis(dilauryltin isooctyl maleate) maleate, bis(dilauryltin 2-ethylhexyl maleate) maleate, Bis(nolauryltin decyl maleate) maleate, His(nolauryltin dodecyl maleate) maleate, Bis(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 methquin butyl maleate) maleate, bis(dilauryltin cyclohexyl maleate) maleate, bis(dilauryltin cyclohexyl maleate) maleate, 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 nooctyl maleate) oxide, bis(dibutyl 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 pennormaleate) oxide, etc. Preferred examples include dibutyltin bis(methyl maleate) and dibutyltin bis(methyl maleate).
(butyl maleate), dibutyltin bis(isooctyl maleate), dibutyltin 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), dioctyltin bis(isooctyl maleate),
Dioctyltin bis(2-ethylhexyl maleate),
Dioctyltin bis(tridecyl maleate), dioctyl knitted bis(octadecyl maleate), dioctyltin bis(oleyl maleate), dioctyltin bis(benzyl maleate), dioctyltin bis(cyclohexyl maleate), bis( dibutyltin methyl maleate)
Maleate, bis(dibutyltin butyl maleate) maleate, bis(dibutyltin octyl maleate)
Maleate, bis(dibutyltin 2-ethylhexyl maleate) maleate, bis(dibutyl tridecyl maleate) maleate, bis(dibutyl octadecyl maleate) maleate, bis(butyltin oleyl maleate) maleate, bis(dibutyltin beno normal maleate) maleate, bis(dibutyltin cyclohexyl maleate) maleate, bis(dioctyltin butyl maleate) maleate, bis(dioctyl tin isooctyl maleate) maleate, bis(dioctyltin 2-ethylhexyl maleate) maleate, bis (dioctyltin tridecyl maleate) maleate, bis(dioctyltin octadecyl maleate) maleate, bis(dioctyltin oleyl maleate) maleate, bis(dioctyltin benzyl maleate) maleate, bis(
Dioctyltin cyclohexol maleate) maleate,
Bis(dibutyltin methyl maleate) oxide, bis(dibutyltin butyl maleate) oxide, bis(dibutyl benzyl maleate) oxide, bis(dioctyltin butyl maleate) oxide, bis(nooctyltin benzyl maleate) oxide, etc. Specific examples of the organotin maleate compound represented by the general formula (2) include the following.

These include dimethyltin maleate, dibutyltin maleate, dioctyltin maleate, dilauryltin maleate, and polymers thereof.

In the present invention, the amount of metal-substituted zeolite added to 100 parts by weight of the styrene-based resin composition flame-retardant with a bromine-based flame retardant can be used without any particular limitation. However, the effective range is 0.05 to 5.0 parts by weight. If the amount is less than 0.05 parts by weight, no significant thermal stabilizing effect will be observed, and if it exceeds 5.0 parts by weight, the expected thermal stabilizing effect will not be observed. Oii amount part place part ru.

The ratio of the metal-substituted zeolite and the organotin maleate compound is not particularly limited, and they can be used together in any ratio. However, if the ratio of the metal-substituted zeolite to the organotin maleate compound is within the range of 9=1 to 3, a preferable effect can be obtained, and the total amount of the compound can be used without any restriction in the resin composition. However, the effective range is 0.05 to 5.0 times. If the amount is less than 0.05 parts by weight, no significant thermal stabilizing effect will be observed, and if it exceeds 5.0 parts by weight, the expected thermal stabilizing effect will not be observed. Department.

The stabilizer used in the present invention may be added to the styrenic resin composition flame-retardant with a bromine-based flame retardant by a conventionally known technique. may be mixed using a Henschel mixer, a ribbon blender, a Banbury mixer, etc., or a prepacked package of metal-substituted zeolite and organotin maleate compound may be mixed with the resin composition using the above-mentioned mixer. .

Further, in addition to these stabilizers, known stabilizers such as various metal soaps, organic phosphorus compounds, a-tin sulfur-containing compounds, etc. can be used in combination.

Plasticizers, lubricants, antioxidants, pigments,
Fillers, processing aids, etc. can be added.

〔Example〕

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

Example 1 Acrylonitrile-butadiene-styrene Jl: Polymer [manufactured by Japan Synthetic Rubber Co., Ltd., JSRABS#1oNp) I
o01! , Tetrabromobisphenol A [Ondai Kasei (
Fire Guard Co., Ltd. 2000) 25th round [Table = 1]
A formulation containing the stabilizer shown in 8 was adjusted to 130°C.
After kneading for 5 minutes with an inch test roll, the thickness is 0.5 mm.
A sample was prepared.

After cutting the obtained sheets, 8 sheets were stacked and heated at 240℃, 10K.
After pressing, the test piece was taken out and the degree of coloration was determined visually, and the deterioration time (minutes) until it became blackish brown was determined.

[Table-1] Sample numbers 7 to 15 are comparative examples.

Example 2 Acrylonitrile-butadiene-styrene polymer (manufactured by Japan Synthetic Rubber Co., Ltd., JSRABS#1ONP) 100
II1 (, Tetrabromobisphenol A [Ondai Kasei (
A mixture of 20 parts of Fire Guard Co., Ltd. 2000), 3.0 parts of E antimony oxide, and the stabilizer shown in Table 2 was kneaded for 5 minutes using an 8-inch test roll adjusted to 130°C. A 0.5-1 sample was prepared.

After cutting the obtained sheets, 8 sheets were stacked and heated at 240℃, 10K.
Pressing was carried out at a pressure of 100 g/cs+'', and the test piece after pressing was taken out and its degree of coloration was determined with the naked eye, and the deterioration time (minutes) until it turned blackish brown was determined.

C table-2] Material numbers 8 to 13 are comparative examples.

Example 3 Styrene resin (manufactured by Asahi Kasei Corporation, Styron 492) 1
00 parts, hexabromunclododecane [Daiichi Kogyo Seiyaku (
A mixture of 100 parts of Pyroguard 5R-1033 manufactured by Co., Ltd., 0.3 parts of G-n-lauryltin maleate, and the stabilizer shown in [Table 3] was kneaded for 5 minutes using an 8-inch test roll adjusted to 120°C. A sheet with a thickness of 0.8 m was prepared.

After cutting the obtained sheets, stack 8 sheets and heat at 220℃, 10K.
After pressing at g/cm', the sample was taken out and its degree of coloration was determined visually, and the deterioration time (minutes) until it turned grayish brown was determined.

Sample numbers 7 to +4 are comparative examples.

〔Effect of the invention〕

When stabilizing a styrenic resin composition containing a bromine-based pheasant retardant, excellent thermal stability can be achieved by adding zeolite containing at least one metal selected from Group II and Group IV metals of the periodic table. can be granted.

Furthermore, further superior thermal stability is imparted by adding together a zeolite containing at least one metal selected from Group I and Group IV metals of the periodic table and an organotin maleate compound. be able to.

Claims (1)

[Claims] 1. When stabilizing a styrenic resin composition containing a bromine flame retardant, a zeolite containing at least one metal selected from Group II and IV metals of the Periodic Table is added. A method for stabilizing a resin composition, characterized in that: 2. When stabilizing a styrene resin composition containing a bromine flame retardant, a zeolite containing at least one metal selected from Group II and IV metals of the periodic table and an organotin maleate compound are used in combination. A method for stabilizing the resin composition, which comprises adding the following: