JPH0816182B2 - Method for stabilizing styrenic resin composition - Google Patents

Description

TECHNICAL FIELD The present invention relates to thermal stabilization of a styrene-based resin composition containing a bromine-based compound as a flame retardant, and is flame-retardant to styrene-based resins. It can be widely used in the fields where is required.

[Conventional technology]

Various flame retardants or flame retardants are used to make the styrene resin flame-retardant, and the bromine flame retardant is particularly widely used.

However, in general, when a bromine flame retardant is added to a styrene resin, there is a disadvantage that the thermal stability of the resin composition is remarkably reduced, and various compounds have been conventionally used for suppression thereof. (For example, Japanese Patent Publication No. 59-4146
No. 2, No. 56-54023, No. 61-2695).

A type zeolite has been found to have excellent effects (Japanese Patent Laid-Open No. 61-115948).

[Problems to be solved by the invention]

However, the heat stabilizing effect of the A-type zeolite has not yet been satisfied with respect to the severe heat history during molding.

[Means for solving problems]

From this point of view, the present inventor has conducted a study on a stabilizer having a further excellent heat stabilizing effect on a styrene resin composition containing a brominated flame retardant, and as a result, the resin composition has a zeolite molecular composition In Periodic Tables II and IV
It was found that the resin composition having extremely excellent thermal stability can be obtained by adding a zeolite containing at least one metal selected from the group metals, and an organotin maleate compound is used in combination therewith. It was found that by doing so, a resin composition having further excellent thermal stability can be obtained, and the present invention was completed.

The styrenic 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 blended resin thereof, and is a styrenic compound monomer such as styrene or α-methylstyrene. Polymers of side chain-substituted styrenes such as styrene and vinyltoluene, monomers of nucleus-substituted styrenes such as O-chlorostyrene, and styrene compound monomers and other compound monomers such as vinyl compound monomers, Examples thereof include copolymers with conjugated diene compound 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.

As the bromine-based flame retardant used in the present invention, those usually used in this field can be used without limitation, for example, tetrabromoethane, tetrabromobutane, hexabromocyclododecane, tetrabromobenzene, bromine. Styrene, bromophenylallyl ether, tetrabromophthalic anhydride, tribromophenol, pentabromotoluene, pentabromophenylpropyl ether, tetrabromobisphenol A, decabromodiphenylether, octabromodiphenylether, tris (2,3-dibromopropyl) isocyanurate , Polydibromophenylene oxide, tetrabromo bisphenol A carbonate oligomer, tetrabromo bisphenol A bis (2-hydroxyethyl ether), tetrabromo Scan phenol A-bis (2,3
Dibromopropyl ether), tetrabromobisphenol A bis (2-bromoethyl ether), tetrabromobisphenol A bis (propyl ether), 2,3-
Examples thereof include dibromopropyl pentabromophenyl ether and bis (tribromophenoxy) ethane. The amount of the brominated flame retardant added is not particularly limited, but may be appropriately varied depending on the degree of flame retardancy required, and generally 5 to 35 parts by weight with respect to 100 parts by weight of the styrene resin, either alone or in two kinds. It is preferable to use them together.

As described above, the zeolite used in the present invention is a zeolite containing at least one metal selected from metals of Group II and Group IV of the Periodic Table (hereinafter, referred to as “metal-substituted zeolite”). , A synthetic zeolite obtained by substituting an alkali metal of an alkali metal-containing zeolite with the Group II or Group IV metal, or the Group II
It may be a natural zeolite containing a Group IV and Group IV metal. The metals of Group II and Group IV of the Periodic Table are not particularly limited, but in terms of effects, toxicity and availability,
Mg, Ca, Zn, Sr, Ba, Zr, Sn and the like are preferable, and particularly preferable metals include Ca, Zn, Ba and the like.

Specific examples of the metal-substituted zeolite used in the present invention include Mg-substituted zeolite, Ca-substituted zeolite, Zn-substituted zeolite, Sr-substituted zeolite, Ba-substituted zeolite, Zr-substituted zeolite and synthetic zeolite such as Sn-substituted zeolite. It is also possible to use a natural zeolite containing the metal.

The synthetic zeolite used in the present invention may be produced by a known method, for example, the production method described in JP-A-57-28145.

Examples of the organotin maleate-based compound used in the present invention include compounds that are commonly used, and examples thereof include the general formula (1) and the general formula (2). [In the formulas (1) and (2), R ¹ is an alkyl group, a cycloalkyl group, an alkenyl group, an aralkyl group, or an alkoxyalkyl group, R ² is an alkyl group, A is oxygen or —OOCCH═CHC.
In the group represented by OO-, k is 0 or 1, and q is an integer of 1-10. ] The compound shown by these is mentioned.

To describe the formulas (1) and (2) in more detail, R ¹ can 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, methoxyethyl, ethoxyethyl, methoxybutyl, A group such as butoxyethyl may be mentioned.

R ² is 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 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 (methylbenzyl 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 (dibutyltin 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, and the like. Specific examples of the organic tin maleate compound represented by the general formula (2) include the following: dimethyl tin maleate, dibutyl tin maleate, dioctyl tin maleate, dilauryl tin maleate and polymers thereof. .

In the present invention, the addition amount of the metal-substituted zeolite can be used without particular limitation based on 100 parts by weight of the styrene resin composition flame-retarded with the bromine flame retardant. However, the effective range is 0.05 to 5.0 parts by weight. 0.0
If it is less than 5 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, and it is preferably 0.1 to 3.0 parts by weight.

The combination ratio of the metal-substituted zeolite and the organotin maleate-based compound is not particularly limited, and the combination can be used at any ratio. However, if the ratio of the metal-substituted zeolite and the organotin maleate compound is used in the range of 9: 1 to 3: 7, a preferable effect is obtained, and the total amount thereof can be used without limitation to the resin composition. . However, the effective range is 0.05 to 5.0 parts by weight. If it is less than 0.05 parts by weight, the heat stabilizing effect is not remarkable, and if it exceeds 5.0 parts by weight, the expected heat stabilizing effect is not observed, and it is preferably 0.1 to 3.0 parts by weight.

The method of adding the stabilizer used in the present invention to a styrene resin composition flame-retarded with a bromine flame retardant may be carried out by a conventionally known technique, for example, the resin composition and the stabilizer. May be mixed with a Henschel mixer, a ribbon blender, a Banbury mixer, or the like, or a metal-substituted zeolite and an organotin maleate-based compound previously packed in one pack may be mixed with the resin composition by the above-mentioned mixer. .

Further, known stabilizers such as various metal soaps, organic phosphorus compounds, and organic tin-containing sulfur 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.

〔Example〕

Hereinafter, the present invention will be described in detail with reference to Examples.
The present invention is not limited to these. In the examples, parts means parts by weight.

Example 1 100 parts of acrylonitrile / butadiene / styrene copolymer [JSR ABS # 1ONP manufactured by Nippon Synthetic Rubber Co., Ltd.] and 25 parts of tetrabromobisphenol A [Fireguard 2000 manufactured by Teijin Chemicals Co., Ltd.] [Table-1 ] Stabilized formulation as shown in 5] on an 8-inch test roll adjusted to 130 ° C
After kneading for a minute, a sample having a thickness of 0.5 mm was prepared. After cutting the obtained sheet, 8 sheets were stacked and pressed at 240 ° C. and 10 kg / cm ² , and the test piece after the pressing was taken out, and the degree of coloring was visually judged, and the deterioration time (minute) until it became blackish brown It was judged.

 The results are shown in [Table-1].

Example 2 100 parts of acrylonitrile-butadiene-styrene copolymer [JSR ABS # 10NP, manufactured by Nippon Synthetic Rubber Co., Ltd.], 20 parts of tetrabromobisphenol A [Teijin Kasei Co., Ltd. Fireguard 2000], 3.0 parts of antimony trioxide. [Table-
The compound containing the stabilizer shown in 2] was kneaded with an 8-inch test roll adjusted to 130 ° C. for 5 minutes, and then a sample having a thickness of 0.5 mm was prepared.

After cutting the obtained sheets, 8 sheets were piled up, 240 ℃, 10kg / cm ²
After pressing, the test piece is taken out and the degree of coloring is judged with the naked eye, and the deterioration time (minutes) until it becomes blackish brown
It was judged by.

 The results are shown in [Table-2].

Example 3 Styrene resin [Styron 492, manufactured by Asahi Kasei Corporation] 100
Part, hexabromocyclododecane [Daiichi Kogyo Seiyaku Co., Ltd.
Pyrogard SR-103] (10 parts), di-n-lauryl tin maleate (0.3 parts) and the stabilizers shown in [Table-3] were mixed for 5 minutes with an 8-inch test roll adjusted to 120 ° C to obtain a thick mixture. I made a 0.8mm thick sheet.

After cutting the obtained sheets, 8 sheets were piled up, 220 ℃, 10kg / cm ²
After pressing with, the sample was taken out, and the degree of coloring was visually judged, and the deterioration time (minutes) until it became grayish brown was judged.

 The results are shown in [Table-3].

(Effect of the invention) In stabilizing the styrene resin composition containing a bromine flame retardant, by adding a zeolite containing at least one metal selected from the metals of Group II and Group IV of the periodic table, Excellent heat stability can be imparted.

Furthermore, by further adding together a zeolite containing at least one metal selected from Group II and Group IV metals of the Periodic Table and an organotin maleate compound, it is possible to impart further excellent thermal stability. You can

Front page continuation (51) Int.Cl. ⁶ Identification code Office reference number FI Technical indication location C08L 55/02 LMC (72) Inventor Hisashi Ihara 788 Hisaji, Takatsu-ku, Kawasaki-shi, Kanagawa Sankyo Organic Synthesis Co., Ltd. (72) Inventor Yoshimura Adult, Sanyo Organic Synthesis Co., Ltd., 788 Hisaji, Takatsu-ku, Kawasaki City, Kanagawa Prefecture (72) Inventor Satoshi Imai 788, Hisaji, Takatsu-ku, Kawasaki City, Kanagawa Sankyo Organic Synthesis Co., Ltd. (56) Kai 61-115948 (JP, A) JP 61-118450 (JP, A) JP 62-236846 (JP, A) JP 61-17767 (JP, B2) JP 58-20974 (JP JP, B2) Japanese Patent Publication 5-46863 (JP, B2)

Claims (2)

[Claims] 1. When stabilizing a styrene resin composition containing a bromine flame retardant, a zeolite containing at least one metal selected from metals of groups II and IV of the periodic table is added. And a method for stabilizing the resin composition. 2. A zeolite containing at least one metal selected from metals of groups II and IV of the periodic table and an organotin maleate compound for stabilizing a styrene resin composition containing a bromine flame retardant. A method for stabilizing the resin composition, characterized in that and are added together.