JPH04332743A - Stabilization of styrene resin composition - Google Patents

Abstract

PURPOSE:To impart excellent thermal stability to a styrene resin composition by adding epoxypropyl isocyanurate to the resin. CONSTITUTION:The objective composition is produced by compounding (A) 100 pts.wt. of a styrene resin with (B) 5-35 pts.wt. of a bromine-based flame- retardant (e.g. tetrabromoethane), (C) 0.01-5 pts.wt. (preferably 0.1-3 pts.wt.) of epoxypropyl isocyanurate or the component C and (D) 0.01-5 pts.wt. (preferably 0.1-3 pts.wt.) of one or more compounds selected from type A zeolite, zeolite containing group II or group IV metal of the periodic table and hydrotalcite.

Description

[Detailed description of the invention]

The present invention relates to a method for thermally stabilizing a styrenic resin composition containing a bromine compound as a flame retardant.

0002

[Industrial Field of Application] The present invention can be widely used in fields where flame retardancy is required for styrenic resins.

0003

[Prior Art] Generally, to make styrene resin flame retardant,
The conventional method of adding so-called flame retardants or flame retardant aids, such as halogen compounds, phosphorus compounds, and antimony trioxide, has been used, and among these flame retardants, halogen compounds, especially bromine compounds, are frequently used. .

However, it is generally known that when a bromine flame retardant is added to a styrenic resin, the thermal stability of the styrenic resin composition is significantly reduced.
In order to suppress the decrease in thermal stability, there is a conventional method of adding an organic tin compound (Japanese Patent Publication No. 59-41462).
, method of adding maleic acid metal salt (Japanese Patent Publication No. 56-54
023), a method of adding ethylenediaminetetraacetic acid metal salt (Japanese Patent Publication No. 61-2695), etc.

[0005] Also, as having excellent effects, type A zeolite (Japanese Unexamined Patent Publication No. 61-115948) and zeolite containing at least one metal selected from group II and group IV metals of the periodic table (specially Kaisho 63-17044
No. 0) was found.

[0006]

[Problems to be Solved by the Invention] However, the thermal stabilization of the A-type zeolite or zeolite containing at least one metal selected from Group II and IV metals of the Periodic Table in its composition is In terms of effectiveness, it is still not sufficient to withstand the harsh thermal history during molding, and the development of a stabilizer with even better thermal stabilizing effects has been awaited.

[0007]

[Means for Solving the Problems] From this perspective, the present inventors have conducted extensive research into a stabilizer that has an excellent thermal stabilizing effect for styrene resin compositions consisting of a styrene resin and a bromine flame retardant. As a result, they discovered that by adding epoxypropyl isocyanurate to a styrenic resin composition consisting of a styrene resin and a bromine flame retardant, the thermal stability of the styrenic resin composition was significantly improved. Completed invention 1.

Furthermore, for a styrene resin composition comprising a styrene resin and a bromine flame retardant, (a) epoxypropyl isocyanurate and (b) A-type zeolite, a group II or IV group of the periodic table, are added. It was discovered that the thermal stability of the styrenic resin composition was further improved by adding at least one compound selected from metal-containing zeolite and hydrotalcite, and the second invention was completed. .

The styrenic resin used in the first and second inventions is a polymer of vinyl aromatic compound monomer, a vinyl aromatic compound monomer and a vinyl chain compound monomer, and/or a vinyl Copolymers with heterocyclic compound monomers, copolymers with vinyl aromatic compound monomers and conjugated diene compound monomers and/or saturated rubber monomers, and conjugates with vinyl aromatic compound monomers Examples include copolymers of diene compound monomers and vinyl chain compound monomers and/or vinyl heterocyclic compound monomers and/or saturated rubber monomers.

Examples of vinyl aromatic compound monomers include:
Styrene, side chain substituted styrene (e.g. α-methylstyrene), nuclear substituted styrene (e.g. vinyltoluene and O-chlorostyrene, etc.), etc. Examples of vinyl chain compound monomers include acrylonitrile, acrylic acid , methacrylic acid, methyl acrylate, ethyl acrylate, methyl methacrylate, and ethyl methacrylate. Examples of vinyl heterocyclic compound monomers include vinylpyridine and vinylcarbazole. Conjugated diene compound monomers Examples include butadiene, 1-chlorobutadiene,
Examples of saturated rubber monomers include 2-chlorobutadiene and isoprene, and examples of saturated rubber monomers include ethylene-propylene-diene compounds and butyl rubber.

Typical examples of these polymers include polystyrene, acrylonitrile-styrene copolymer, methyl methacrylate-styrene copolymer, and styrene-styrene copolymer.
α-methylstyrene copolymer, acrylonitrile-butadiene-styrene copolymer, methyl methacrylate-butadiene-styrene copolymer, acrylonitrile-acrylic rubber-styrene copolymer, acrylonitrile-styrene-chlorinated polyethylene copolymer, methacryl methyl acid-acrylonitrile-butadiene-styrene copolymer,
Acrylonitrile-butadiene-styrene-α-methylstyrene copolymer, methyl methacrylate-butadiene-
Examples include styrene-α-methylstyrene copolymer and blends of these resins.

[0012] As the bromine-based flame retardant used in the first and second inventions, those normally used in this field can be used without limitation, but for example, tetrabromoethane, tetrabromobutane, hexabromobutane, etc. Bromocyclododecane, tetrabromobenzene, hexabromobenzene, bromustyrene, bromophenyl allyl ether, tetrabromophthalic anhydride, tribromophenol,
Pentabromo toluene, pentabromo phenylpropyl ether, tetrabromo bisphenol A, hexabromo diphenyl ether, decabromo diphenyl ether, octabromo diphenyl ether, tris(2,3-
dibromopropyl) isocyanurate, ethylene bis(
tetrabromophthalimide), brominated polystyrene,
Polydibromophenylene oxide, carbonate oligomer of tetrabromobisphenol A, tetrabromobisphenol 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-dibromopropylpentabromphenyl ether, bis(
tribromophenoxy)ethane, tetrabromobisphenol A diglycidyl ether and brominated bisphenol adduct epoxy oligomer, tetrabromobisphenol A diglycidyl ether and tribromophenol adduct, tetrabromobisphenol S, tetrabromobisphenol S (2,3- dibromopropyl ether)
etc. can be mentioned.

There is no particular limit to the amount of these bromine flame retardants added, but it may be varied as appropriate depending on the degree of flame retardancy required, and generally 5 parts by weight of the styrene resin.
It is preferable to use up to 35 parts by weight alone or in combination of two or more. Furthermore, if a flame retardant aid such as antimony trioxide is used in combination, the flame retardant effect will be even better, and the amount added is usually preferably 1 to 20 parts by weight per 100 parts by weight of the styrene resin.

[0014] The epoxypropyl isocyanurate used in the first and second inventions includes mono(epoxypropyl)isocyanurate, bis(epoxypropyl)isocyanurate, tris(epoxypropyl)isocyanurate, etc., preferably. Examples include tris(epoxypropyl)isocyanurate.

The A-type zeolite used in the second invention has the general formula (I) Na2O.Al2O3.2SiO2.XH2O
(I) [Wherein, X represents a number from 0 to 6. ] A-type zeolite shown by these can be mentioned, and may be a natural or synthetic product. The A-type zeolite used is, for example, a higher fatty acid alkali metal salt such as an alkali metal salt of stearic acid or oleic acid, or an organic sulfonic acid alkali metal salt such as an alkali metal salt of dodecylbenzenesulfonic acid. It may be surface treated.

[0016] In addition, zeolites containing metals of Group II or IV of the periodic table may contain Na in the A-type zeolite.
This is a zeolite in which the metal is substituted with a metal from Group II or Group IV of the Periodic Table (hereinafter referred to as "metal-substituted zeolite"), and the metal is not particularly limited, but has certain characteristics such as effectiveness, toxicity, and easy availability. In terms of strength, magnesium, calcium,
Zinc, strontium, barium, zirconium, tin, etc. are preferred, and particularly preferred metals include calcium, zinc, barium, etc.

The metal-substituted zeolite is, for example, a synthetic zeolite obtained by substituting part or all of the alkali metal and the above-mentioned metal in a zeolite containing an alkali metal, and the metal substitution rate is high. However, those with a substitution rate of about 10 to 70% are usually easily obtained industrially.

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; Natural zeolites containing metals can also be used, and these A-type zeolites and metal-substituted zeolites can be used alone or in combination of two or more.

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

[0020] The hydrotalcite used in the second invention, for example, has the general formula (II) Mg1-a Ala(OH)2 (CO3)a/2
・yH2O (II) [In the formula, a is 0<a≦0. Indicates the number 5, and y is 0~
Shows the number 5. ] Examples include hydrotalcites shown in the following, and they may be natural or synthetic. Further, the hydrotalcite used may be, for example, a higher fatty acid alkali metal salt such as an alkali metal salt of stearic acid or oleic acid, or an organic sulfonic acid alkali metal salt such as an alkali metal salt of dodecylbenzenesulfonic acid. It may be surface treated.

[0021] When the hydrotalcite is a synthetic product, any known method may be used, such as the method described in Japanese Patent Publication No. 51-29129.

In the first and second inventions, the amount of epoxypropyl isocyanurate used in the first invention and (a) epoxypropyl isocyanurate used in the second invention, and (b) type A There is no particular limit to the amount of at least one compound selected from zeolite, zeolite containing metals from Group II or IV of the periodic table, and hydrotalcite, but as an effective range. is 0.0% per 100 parts by weight of styrene resin. 01-5. It is 0 parts by weight. In addition, if the amount added is 0. If the amount is less than 0.01 part by weight, no significant thermal stabilizing effect is observed. If the amount exceeds 0 parts by weight, the expected thermal stabilizing effect will not be observed, and preferably 0. 1-3.
It is 0 parts by weight.

In addition, (a) epoxypropyl isocyanurate used in the second invention, and (b) type A zeolite, a zeolite and hydrotalcite containing a metal of group II or group IV of the periodic table. There is no particular restriction on the proportion of at least one compound selected from the following, and any proportion may be used as long as it is within the range of the above-mentioned addition amount.

Epoxypropyl isocyanurate used in the first invention and (a) used in the second invention
Epoxypropyl isocyanurate and (b) at least one compound selected from A-type zeolite, zeolite containing a metal of Group II or Group IV of the periodic table, and hydrotalcite, and a styrenic resin and a bromine-based zeolite. The method for adding the stabilizer to the styrenic resin composition consisting of a fuel agent may be carried out by conventionally known techniques, for example, the resin composition and the stabilizer may be mixed using a Henschel mixer, a ribbon blender, a Banbury mixer, etc. Alternatively, the stabilizer may be packed in advance and mixed with the styrenic resin composition using the above-mentioned mixer.

In addition to these stabilizers, known stabilizers such as metal soaps, organic phosphorus compounds, antioxidants,
Ultraviolet absorbers, organic tin compounds, etc. can be used in combination.

[0026] Furthermore, if necessary, plasticizers, lubricants, pigments,
Fillers, processing aids, chlorine flame retardants, phosphorus flame retardants, flame retardant aids, etc. can be added.

[0027]

EXAMPLES The first and second inventions will be specifically explained below with reference to examples, but the invention is not limited by these. In these examples, parts mean parts by weight. In addition, “
A-1 to A-2", "B-1 to B-2", "C-1 to C
-7'', ``D-1 to D-3'', and ``E-1 to E-17'' represent the following compounds. Note that the * mark in the table is a comparative example, and the blank mark is an example.

A-1 Bis(epoxypropyl)isocyanurate A-2 Tris(epoxypropyl)isocyanurate B-1 Na2O.Al2O3.2SiO2
・4.5 H2 OB-2 Na2 O・Al2O3
・2SiO2C-1 Magnesium-substituted zeolite C-2 Calcium-substituted zeolite C-3 Zinc-substituted zeolite C-4 Strontium-substituted zeolite C-5 Barium-substituted zeolite C-6 Zirconium-substituted zeolite C-7 Tin-substituted zeolite (C-1 to C- The metal substitution rate of 7 is 70%)D-1
Mg0.7 Al0.3(OH)2 (CO3)0
．． 15・0.54H2 O D-2 Mg0.67Al0.33 (OH)2 (
CO3 )0.165 ・0.3 H2 O D-3 Mg0.75Al0.25 (OH)2 (
CO3 )0.125E-1 Dibutyltin maleate E-2 Dibutyltin thiodipropionate E-3
Dioctyltin bis(benzyl maleate) E-4 Dibutyltin 3-mercaptopropionate E-5 Dioctyltin distearate E-6
Calcium silicate E-7 Calcium carbonate E-8 Barium maleate E-9 Trisnonylphenyl phosphite E-10
Ethylenediaminetetraacetate disodium/calcium E-11 Epoxidized soybean oil [manufactured by Shin Nippon Chemical Co., Ltd.]
Sansocizer E-2000] E-12 Bisphenol A type epoxy resin [Epicoat 828 manufactured by Yuka Shell Epoxy Co., Ltd.] E-13 Bisphenol A type epoxy resin [Epicoat 1010 manufactured by Yuka Shell Epoxy Co., Ltd.] E-14
Phenol novolac type epoxy resin [EPPN-201 manufactured by Nippon Kayaku Co., Ltd.] E-15 Glycidyl ester type epoxy resin [Epicote 871 manufactured by Yuka Shell Epoxy Co., Ltd.] E-16
Isocyanuric acid E-17 Cyanuric acid.

Example 1 100 parts of ABS resin (Tufflex 41OCB manufactured by Mitsubishi Monsanto Chemical Co., Ltd.), tetrabromobisphenol A diglycidyl ether and brominated bisphenol adduct epoxy oligomer (EBR manufactured by Manac Co., Ltd.)
700] 20 parts, antimony trioxide5. A mixture of 0 part and the stabilizer shown in Table 1 was kneaded for 5 minutes using an 8-inch test roll adjusted to 165°C to give a thickness of 0. A 5 mm sheet was produced. Cut the obtained sheet and stack 8 sheets, 2
Pressing was performed at 70° C. and 5 kg/cm 2 , and the deterioration time (minutes) until the sample turned blackish brown was measured. Table 1 shows the results.
Shown below.

[0030]

[Table 1]

As is clear from a comparison of Sample Nos. 1 to 12 and Samples Nos. 13 to 21, it can be seen that the styrenic resin compositions of the first and second inventions have extremely excellent thermal stability.

Example 2 ABS resin [JSR AB manufactured by Japan Synthetic Rubber Co., Ltd.
S#10NP] 90 parts, MBS resin [Kaneace B-12 manufactured by Kanebuchi Kagaku Kogyo Co., Ltd.] 10 parts, chlorinated polyethylene [Erasuren 303B manufactured by Showa Denko K.K.] 2 parts, tetrabromo bisphenol A carbonate oligomer [Teijin Kasei Co., Ltd. Fire Guard 7500]
A mixture of 20 parts of antimony trioxide, 3 parts of antimony trioxide, and the stabilizers shown in Tables 2 and 3 was kneaded for 5 minutes using an 8-inch test roll adjusted to 160°C to obtain a thickness of 0. A 5 mm sheet was produced. The obtained sheets were cut into 8 sheets and stacked at 260℃, 5 kg/
cm2, and the deterioration time (minutes) until the sample turned blackish brown was measured. The results are shown in Tables 2 and 3.

[0033]

[Table 2]

[0034]

[Table 3]

As is clear from a comparison of Sample Nos. 1 to 12 and Samples Nos. 13 to 30, it can be seen that the styrenic resin compositions of the first and second inventions have extremely excellent thermal stability.

Example 3 Styrene resin [Styron 492 manufactured by Asahi Kasei Corporation] 10
0 parts, tetrabromo bisphenol A carbonate oligomer [Fire Guard 750 manufactured by Teijin Kasei Ltd.
0] A mixture of 20 parts and the stabilizer shown in Table 4 was added to 14 parts.
The mixture was kneaded for 5 minutes using an 8-inch test roll adjusted to 0°C until the thickness was 0. A 7 mm sheet was produced. Eight of the obtained sheets were stacked and pressed at 240° C. and 5 kg/cm 2 , and the deterioration time (minutes) until the sample turned grayish brown was measured. The results are shown in Table 4.

[0037]

[Table 4]

As is clear from a comparison of Sample Nos. 1 to 14 and Samples Nos. 15 to 19, it can be seen that the styrenic resin compositions of the first and second inventions have extremely excellent thermal stability.

Example 4 ABS resin [JSR AB manufactured by Japan Synthetic Rubber Co., Ltd.
S#10NP] 85 parts, AAS resin [Mitsubishi Rayon Co., Ltd. Dialac A S610] 15 parts, tetrabromobisphenol A diglycidyl ether and brominated bisphenol adduct epoxy oligomer [Manac Co., Ltd.]
EBR700] 17 parts, antimony trioxide 5. 0
A mixture containing the stabilizer shown in Table 5 was kneaded for 5 minutes using an 8-inch test roll adjusted to 160°C to give a thickness of 0.
A 5 mm sheet was produced. Cut the obtained sheet 8
Stack the sheets and press at 270℃ and 5kg/cm2.
The deterioration time (minutes) until the sample turned blackish brown was measured. The results are shown in Table 5.

[0040]

[Table 5]

As is clear from a comparison of sample numbers 1 to 4 and samples 5 to 11, it can be seen that the styrenic resin compositions of the first and second inventions have extremely excellent thermal stability.

[0042]

According to the present invention, excellent thermal stability can be imparted to a styrenic resin composition comprising a styrene resin and a bromine flame retardant.

Claims (2)

[Claims] 1. A method for stabilizing a styrenic resin composition, which comprises adding epoxypropyl isocyanurate to a styrenic resin composition comprising a styrene resin and a bromine flame retardant. Claim 2: A styrenic resin composition comprising a styrene resin and a bromine flame retardant, and (a) epoxypropylisocyanurate and (
b) The styrenic resin composition characterized in that at least one compound selected from A-type zeolite, zeolite containing a metal of Group II or IV of the periodic table, and hydrotalcite is added in combination. Stabilization method.