JPH0733931A - Stable flame-retardant styrenic resin composition - Google Patents

Abstract

PURPOSE:To obtain a stable flame-retardant styrenic resin compsn. excellent in thermal stability. CONSTITUTION:The compsn. is obtd. by compounding a resin compsn. comprising a styrenic resin and a bromine flame retardant (except a brominated epoxy resin flame retardant) with a zinc-substd. hydrotalcite compd. and at least one compd. selected from the group consisting of zeolite A, a zeolite contg. a metal of Group II or IV, and epoxypropyl isocyanurate.

Description

Detailed Description of the Invention

The present invention is a stabilized styrene-based resin comprising a styrene-based resin and a bromine-based flame retardant (excluding brominated epoxy resin-based flame retardant), which is stabilized by adding a specific additive. The present invention relates to a flame-retardant styrene resin composition.

[0002]

INDUSTRIAL APPLICABILITY The present invention can be widely used in fields where styrene resins are required to have flame retardancy.

[0003]

2. Description of the Related Art Generally, in order to make a styrene resin flame-retardant,
A method of adding a so-called flame retardant or flame retardant aid such as a halogen-based compound, a phosphorus compound, or antimony trioxide has been conventionally performed, and among these flame-retardants, a halogen-based compound, particularly a bromine-based compound is often used. .

However, it is generally known that when a bromine flame retardant is added to a styrene resin, the thermal stability of the flame retarded styrene resin is significantly lowered,
In order to suppress the decrease in its thermal stability, a method of adding A-type zeolite (Japanese Patent Laid-Open No. 61-115948) or at least one metal selected from Group II and Group IV metals of the periodic table is used. Method of adding zeolite containing
-170440) and the like.

Further, as a compound having an excellent effect, at least a compound selected from epoxypropyl isocyanurate, A-type zeolite, zeolite containing a metal of Group II or IV of the periodic table, and hydrotalcite. Method of adding one kind in combination (JP-A-4-332743)
No.) is proposed.

[0006]

However, at least one compound selected from the group consisting of epoxypropyl isocyanurate and A-type zeolite, zeolite containing a metal of Group II or IV of the periodic table, and hydrotalcite is used. The combined addition method is not sufficient for the severe heat history during molding, and the development of an additive having an excellent heat stabilizing effect has been awaited.

[0007]

From the above viewpoints, the present inventors have found that the styrene-based resin and the bromine-based flame retardant (excluding the brominated epoxy resin-based flame retardant) are thermally stable against the flame-retarded styrene-based resin. As a result of earnest studies on additives having excellent deoxidizing effect, zinc-substituted hydrotalcite was added to flame-retardant styrene resin composed of styrene resin and bromine flame retardant (excluding brominated epoxy resin flame retardant). Compound and at least one of A-type zeolite, zeolite containing metal of Group II or IV of the periodic table, and compound selected from epoxypropyl isocyanurate
The inventors have found that the thermal stability of a stabilized flame-retardant styrene resin composition to which a seed is added in combination is remarkably improved, and completed the present invention.

The styrene resin used in the present invention is
Polymer of vinyl aromatic compound monomer, copolymer of vinyl aromatic compound monomer and vinyl chain compound monomer and / or vinyl heterocyclic compound monomer, vinyl aromatic compound monomer Copolymer with conjugated diene compound monomer and / or saturated rubber monomer, and vinyl aromatic compound monomer, conjugated diene compound monomer and vinyl chain compound monomer and / or
Alternatively, a copolymer with a vinyl heterocyclic compound monomer and / or a saturated rubber monomer can be used. Examples of vinyl aromatic compound monomers include styrene, side chain-substituted styrene (eg, α-methylstyrene), and nucleus-substituted styrene (eg:
Vinyltoluene, O-chlorostyrene, etc.)
Examples of vinyl chain compound monomers include acrylonitrile, acrylic acid, methacrylic acid, methyl acrylate, ethyl acrylate, methyl methacrylate and ethyl methacrylate, and examples of vinyl heterocyclic compound monomers , Vinyl pyridine, vinyl carbazole, etc.,
Examples of the conjugated diene compound monomer include butadiene and 1
-Chlorobutadiene, 2-chlorobutadiene, isoprene and the like, and examples of the saturated rubber monomer include ethylene-propylene-diene compound and butyl rubber.
Typical examples of these polymers include polystyrene, acrylonitrile-styrene copolymer, methyl methacrylate-styrene copolymer, styrene-α-methylstyrene copolymer, acrylonitrile-butadiene-styrene copolymer. , Methyl methacrylate-butadiene-styrene copolymer, acrylonitrile-acrylic rubber-styrene copolymer, acrylonitrile-styrene-chlorinated polyethylene copolymer, methyl methacrylate-acrylonitrile-butadiene-styrene copolymer, acrylonitrile-butadiene- Styrene-α-methylstyrene copolymer, methyl methacrylate-butadiene-styrene-α
-Methylstyrene copolymers or blends of these resins can be mentioned.

The brominated flame retardant (excluding brominated epoxy resin-based flame retardant) used in the present invention is usually used in this field (excluding brominated epoxy resin-based flame retardant). Can be used without limitation, for example, excluding brominated epoxy resin flame retardant,
Examples thereof include brominated aliphatic hydrocarbons, brominated cycloaliphatic hydrocarbons, brominated aromatic hydrocarbons and brominated isocyanates. Examples thereof include tetrabromoethane, tetrabromobutane, hexabromocyclododecane, tetrabromobenzene, hexabromobenzene, bromostyrene, bromophenylallyl ether, tetrabromophthalic anhydride, tribromophenol, pentabromotoluene, pentabromophenylpropyrene. Ether, tetrabromobisphenol A, hexabromodiphenyl ether, decabromodiphenyl ether, octabromodiphenyl ether, tris (2,
3-dibromopropyl) isocyanurate, ethylenebis (tetrabromophthalimide), brominated polystyrene, polydibromophenylene oxide, carbonate oligomer of tetrabromobisphenol A, tetrabromobisphenol A bis (2-hydroxyethyl ether), tetrabromobisphenol A screw (2,3-
Dibromopropyl ether), tetrabromobisphenol A bis (2-bromoethyl ether), tetrabromobisphenol A bis (propyl ether), 2,3
-Dibromopropyl pentabromophenyl ether, bis (tribromophenoxy) ethane, tris (tribromophenoxy) isocyanurate, tetrabromobisphenol S, tetrabromobisphenol S bis (2
3-dibromopropyl ether) and bis (pentabromophenyl) ethane.

Examples of the brominated epoxy resin-based flame retardant not used in the present invention 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,
Examples thereof include brominated resorcinol type epoxy resin, brominated hydroquinone type epoxy resin, brominated bisphenol A novolac type epoxy resin, brominated methylresorcin type epoxy resin, and brominated resorcinol novolac type epoxy resin, but usually the average degree of polymerization is A brominated bisphenol type epoxy resin of about -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. Further, the compound for blocking a part or all of the terminal epoxy groups of the brominated epoxy resin is not particularly limited as long as it is a compound capable of ring-opening addition to the epoxy group, for example, carboxylic acids, alcohols,
Examples thereof include amines, isocyanates, and phenols. Among them, brominated phenols are preferable in terms of improving the flame retardant effect, and specific examples thereof include dibromophenol, dibromocresol, tribromophenol, penta. Examples include bromophenol, dibromoethylphenol, dibromopropylphenol and dibromobutylphenol.

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 generally, it is 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.

The zinc-substituted hydrotalcite compound used in the present invention has the general formula (I)

[0013]

[Chemical 1]

A zinc-substituted hydrotalcite compound represented by

In the present invention, in order to improve the compatibility, dispersibility and the like of the zinc-substituted hydrotalcite compound with the styrene resin, the zinc-substituted hydrotalcite compound is surface-treated with a surface treating agent. Can be done.

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.

The type A zeolite used in the present invention has the general formula (II)

[0018]

[Chemical 2]

[In the formula, X represents a number of 0 to 6. ] A type zeolite shown by the above is mentioned, and may be a natural or synthetic product. Examples of the A-type zeolite used include higher fatty acid alkali metal salts such as alkali metal salts of stearic acid and oleic acid, and organic sulfonic acid alkali metal salts such as dodecylbenzene sulfonic acid alkali metal salts. It may be surface-treated.

Further, the zeolite containing Group II or Group IV of the Periodic Table is the same as Na in the A-type zeolite described above.
A zeolite substituted with a Group II or Group IV metal (hereinafter referred to as “metal-substituted zeolite”), and the metal is not particularly limited, but from the viewpoint of effects, toxicity, and availability. , Magnesium, calcium, zinc, strontium, barium, zirconium, tin and the like are preferable, and particularly preferable metals include calcium, zinc and barium.

Examples of the metal-substituted zeolite include synthetic zeolite obtained by substituting a part or all of the alkali metal of the alkali metal-containing zeolite with the metal, and the metal substitution ratio is high. It is preferable that the substitution ratio is 10 to 70 mol%, which is usually industrially easily obtained.

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.

Further, examples of the epoxypropyl isocyanurate used in the present invention include mono (epoxypropyl) isocyanurate, bis (epoxypropyl) isocyanurate, tris (epoxypropyl) isocyanurate and the like, preferably tris ( Epoxypropyl) isocyanurate.

Among the (a) zinc-substituted hydrotalcite compounds used in the present invention and (b) A-type zeolite, zeolite containing a metal of Group II or IV of the periodic table, and epoxypropyl isocyanurate There is no particular limitation on the amount of the compound selected from the above to be added in combination, but the effective range is 0.01 to 5.0 parts by weight with respect to 100 parts by weight of the styrene resin. . If the addition amount is less than 0.01 parts by weight, the heat stabilizing effect is not significantly seen, and if it exceeds 5.0 parts by weight, the expected heat stabilizing effect is not seen, and preferably 0.1 to 0.1 parts by weight. 3.0
Parts by weight. In addition, there is no particular limitation on the combined use, and any combination ratio may be used as long as it is within the range of the addition amount.

The method of adding the specific additive used in the present invention to the flame-retardant styrene-based resin comprising the styrene-based resin and the bromine-based 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.

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

[0029]

The present invention will be specifically described below with reference to examples, but the present invention is not limited thereto. In these examples, parts mean parts by weight.

[Zinc-substituted hydrotalcite compounds used in the present invention]

[0031]

[Chemical 3]

[A-type zeolite used in the present invention]

[0033]

[Chemical 4]

[Metal-Substituted Zeolite Used in the Present Invention] C-1: Magnesium-Substituted Zeolite C-2: Calcium-Substituted Zeolite C-3: Zinc-Substituted Zeolite C-4: Barium-Substituted Zeolite (of C-1 to C-4) The metal substitution rate is 70 mol% for each) [Epoxypropyl isocyanurate used in the present invention] D-1: Bis (epoxypropyl) isocyanurate D-2: Tris (epoxypropyl) isocyanurate [Additives other than the present invention]

[0035]

[Chemical 5]

E-4: Dibutyltin maleate E-5: Dibutyltin thiodipropionate E-6: Epoxidized soybean oil [Sanso Sizer E-2000 manufactured by Shin Nippon Rika Co., Ltd.].

[Example 1] 90 parts of ABS resin [JSR # 15NP manufactured by Nippon Synthetic Rubber Co., Ltd.], 10 parts of MBS resin [Kane Ace B-12 manufactured by Kanegafuchi Chemical Industry Co., Ltd.], chlorinated polyethylene [Showa Denko] Eraslen 30 manufactured by Co., Ltd.
3B] 3 parts, tetrabromobisphenol A carbonate oligomer [manufactured by Teijin Kasei Co., Ltd. Fireguard 7
500] 20 parts, 5 parts of antimony trioxide, and a mixture obtained by adding the additives shown in Tables 1 and 2 were kneaded with an 8-inch test roll adjusted to 165 ° C. for 3 minutes to form a sheet having a thickness of 0.5 mm. It was made. The obtained sheets are cut into 8 layers and 2
The sample was pressed at 70 ° C. and 5 kg / cm ² , and the deterioration time (minutes) until the sample turned blackish brown was measured. The results are shown in Tables 1 and 2.

[0038]

[Table 1]

[0039]

[Table 2]

Sample Nos. 1 to 7 are examples and the same Nos. 8 to 22
Is a comparative example. As is clear from the comparison of the results in Table 1 and Table 2, it is understood that the stabilized flame-retardant styrene resin composition of the present invention has extremely excellent thermal stability.
Incidentally, when the additive of the present invention is added alone as in Sample Nos. 8 to 10, when additives other than the present invention are used in combination as in No. 11 to 17 or as in No. 18 to 21 of the same. ,
Sufficient thermal stability cannot be obtained in the case where the additives other than the present invention are added alone, or in the case where the additives are not added as in the case of No. 22 above.

[Example 2] Styrene resin [Asahi Kasei Co., Ltd.
Stylon 492] 100 parts, ethylene bis (tetrabromophthalimide) [Eyt Saytex
BT-93W] 15 parts, antimony trioxide 5 parts, Table 3
The composition containing the additives shown in 1 was adjusted to 140 ° C. 8
The sheet was kneaded with an inch test roll for 3 minutes to prepare a sheet having a thickness of 0.7 mm. The obtained sheets are cut into 8 layers, 27
Pressing was performed at 0 ° C. and 5 kg / cm ² , and the deterioration time (minutes) until the sample became grayish brown was measured. The results are shown in Table 3.

[0042]

[Table 3]

Sample Nos. 1 to 6 are Examples and the same Nos. 7 to 12
Is a comparative example. As is clear from the comparison of the results in Table 3, the thermal stability of Sample Nos. 1 to 6 in which the zinc-substituted hydrotalcite compound is used in combination is the same as that in the sample in which the conventional non-zinc-substituted hydrotalcite compound is used. It can be seen that it is extremely superior to the thermal stability of Nos. 7 to 12.

[Example 3] 100 parts of ABS resin [JSR # 15NP manufactured by Japan Synthetic Rubber Co., Ltd.], 20 parts of decabromodiphenyl ether [Planeron DB-100 manufactured by Mitsui Toatsu Chemicals, Inc.], 3 parts of antimony trioxide Table 4
And the composition containing the additives shown in Table 5 was kneaded with an 8-inch test roll adjusted to 160 ° C. for 3 minutes to give a thickness of 0.5.
mm sheets were made. The obtained sheet was cut into eight layers, and the sheets were pressed at 250 ° C. and 5 kg / cm ² to measure the deterioration time (minutes) until the sample turned blackish brown. The results are shown in Tables 4 and 5.

[0045]

[Table 4]

[0046]

[Table 5]

Sample Nos. 1 to 7 are Examples and the same Nos. 8 to 18
Is a comparative example. As is clear from the comparison of the results in Tables 4 and 5, it is understood that the stabilized flame-retardant styrenic resin composition of the present invention has extremely excellent thermal stability.
In addition, when the additive of the present invention is added alone as in Sample Nos. 8 to 10, when an additive other than the present invention is used in combination as in No. 11 to 17, or as in No. 18 is added. If no agent is added, sufficient thermal stability cannot be obtained in any case.

[Example 4] ABS resin [Mitsubishi Kasei Co., Ltd.]
8 inch test in which a mixture prepared by adding the additives shown in Tables 6 and 7 to 100 parts of Taflex 410CB manufactured by Teflex 410CB and 20 parts of tetrabrom bisphenol A [Fireguard 2000 manufactured by Teijin Chemicals Ltd.] was adjusted to 140 ° C. The roll was kneaded for 3 minutes to prepare a sheet having a thickness of 0.6 mm. The obtained sheets are cut and stacked on 8 sheets, 240 ° C, 5 kg / cm ²
The sample was pressed and the deterioration time (minute) until the sample turned blackish brown was measured. The results are shown in Tables 6 and 7.

[0049]

[Table 6]

[0050]

[Table 7]

Sample Nos. 1 to 6 are Examples and the same Nos. 7 to 15
Is a comparative example. As is clear from the comparison of the results in Tables 6 and 7, it is understood that the stabilized flame-retardant styrene resin composition of the present invention has extremely excellent thermal stability.
In addition, when the additive of the present invention is added alone as in Sample Nos. 7 to 8, when an additive other than the present invention is used in combination as in No. 9 to 14, and as in No. 15 is added. If no agent is added, sufficient thermal stability cannot be obtained in any case.
It can be seen that the stabilized flame-retardant styrene-based resin composition of the present invention has extremely excellent thermal stability.

[0052]

The stabilized flame-retardant styrene resin composition of the present invention has excellent thermal stability.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Adult Yoshimura Sanyo Organic Synthesis Co., Ltd. 788, Hisachi, Takatsu-ku, Kawasaki-shi, Kanagawa

Claims (1)

[Claims] 1. A flame-retardant styrene resin comprising a styrene resin and a bromine flame retardant (excluding brominated epoxy resin flame retardant), (a) zinc-substituted hydrotalcite compound, and (b) A type. Stabilized flame-retardant styrenic resin composition obtained by adding at least one compound selected from the group consisting of zeolite, zeolite containing Group II or Group IV metal of the periodic table, and epoxypropyl isocyanurate object.