JPH0733930A - Flame-retardant styrene resin composition - Google Patents

Abstract

PURPOSE:To obtain the title compsn. excellent in thermal stability. CONSTITUTION:The compsn. is obtd. by compounding a resin compsn. comprising a styrene resin and a halogenated 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 relates to a flame-retardant styrene resin composition obtained by adding a specific additive to a flame-retardant styrene resin containing a halogenated epoxy resin flame retardant as a flame retardant. .

[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,
Halogen compounds, phosphorus compounds, a method of adding a so-called flame retardant or flame retardant aid such as antimony trioxide has been conventionally performed, and among these flame retardants, halogen flame retardants are often used, but in recent years, Halogenated epoxy resin-based flame retardants have come to be used as a material that can improve not only the flame retardancy of styrene resins but also the weather resistance.

However, it is known that when a halogenated epoxy resin-based flame retardant is added to a styrene resin, the thermal stability of the flame-retarded styrene resin is remarkably reduced. For the purpose of suppressing, at least one compound selected from epoxypropyl isocyanurate, a type A zeolite, a zeolite containing a metal of Group II or IV of the periodic table, and hydrotalcite is used.
A method in which seeds are added in combination (Japanese Patent Laid-Open No. 4-332743) has been proposed.

[0005]

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.

[0006]

From such a viewpoint, the inventors of the present invention have been keen on an additive having an excellent heat stabilizing effect with respect to a flame-retardant styrene resin composed of a styrene resin and a halogenated epoxy resin flame retardant. As a result of repeated research, zinc-substituted hydrotalcite compounds and A-type zeolites, Group II or Group IV of the Periodic Table are used for flame-retardant styrene resins composed of styrene-based resins and halogenated epoxy resin-based flame retardants. It has been found that the thermal stability of a flame-retardant styrene resin composition to which a zeolite containing a group III metal and at least one compound selected from epoxypropyl isocyanurate is added in combination is remarkably improved, and the present invention is achieved. completed.

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.
Examples of typical polymers among these 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.

As the halogenated epoxy resin type flame retardant used in the present invention, those generally used in this field can be used without limitation. For example, a halogenated epoxy resin and a terminal epoxy group of the epoxy resin can be used. Examples thereof include compounds having a structure in which some or all of the above are blocked.

Examples of the halogenated epoxy resin include halogenated bisphenol type epoxy resin, halogenated phenol novolac type epoxy resin, halogenated cresol novolac type epoxy resin, halogenated resorcinol type epoxy resin, halogenated hydroquinone type epoxy resin, halogenated epoxy resin. Examples thereof include bisphenol A novolac type epoxy resin, halogenated methylresorcinol type epoxy resin, halogenated resorcinol novolac type epoxy resin and the like, but normally halogenated bisphenol type epoxy resin having an average degree of polymerization of 0 to 50 is used. Specific examples of the halogenated bisphenol constituting this halogenated bisphenol type epoxy resin include dibromobisphenol A, tetrabromobisphenol A, dichlorobisphenol A, tetrachlorobisphenol A, dibromobisphenol F, tetrabromobisphenol F, dichlorobisphenol F, Examples thereof include tetrachlorobisphenol F, dibromobisphenol S, tetrabromobisphenol S, dichlorobisphenol S and tetrachlorobisphenol S.

The compound for blocking a part or all of the terminal epoxy groups of the halogenated epoxy resin can be used without any particular limitation as long as it is a compound capable of ring-opening addition to the epoxy group. Examples thereof include acids, alcohols, amines, isocyanates and phenols. Among them, halogenated phenols can be used in terms of improving the flame retardant effect, and specific examples thereof include dibromophenol, dibromocresol, tribromophenol, pentabromophenol, dichlorophenol, dichlorocresol, trichloro. Phenol, pentachlorophenol,
Examples include dibromoethylphenol, dibromopropylphenol, dibromobutylphenol, and the like.

Such a halogenated epoxy resin flame retardant can be produced by various methods. For example, a method for producing by condensation reaction of halogenated bisphenol A and epichlorohydrin, a method for producing by reaction of diglycidyl ether of halogenated bisphenol A and halogenated bisphenol A, and the above halogenated bisphenol having an epoxy group at the terminal Examples thereof include a method in which an A-type epoxy resin and a halogenated phenol such as tribromophenol, pentabromophenol, trichlorophenol, dibromocresol and dichlorocresol are heated and reacted in the presence of a basic catalyst.

Commercially available products of the halogenated epoxy resin-based flame retardant used in the present invention are, for example, Platherm EP-16 and EP-10 manufactured by Dainippon Ink and Chemicals, Inc.
0, EP-500, EC-14, EC-20, EC-30 and the like. There is no particular limitation on the amount of the halogenated epoxy resin-based flame retardant added, but the amount may be appropriately changed depending on the required performance, and generally 5 to 35 parts by weight with respect to 100 parts by weight of the styrene resin alone or 2 It is preferable to use one or more kinds in combination. Further, when a flame retardant aid such as antimony trioxide is further used together, 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)

[0014]

[Chemical 1]

A zinc-substituted hydrotalcite compound represented by

In the present invention, in order to improve the compatibility, dispersibility, etc. 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 A-type zeolite used in the present invention has the general formula (II)

[0019]

[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. 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.

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 and tris (epoxypropyl) isocyanurate, and 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.

When the styrene resin, the halogenated epoxy resin flame retardant and the specific additive used in the present invention are mixed, the respective components may be mixed in any combination and in any order. It may be appropriately selected according to the purpose.

For example, a styrene resin and a halogenated epoxy resin flame retardant are mixed in advance, and this is mixed with a specific additive, or a halogenated epoxy resin flame retardant and a specific additive are mixed in advance. However, this can be mixed with a styrene resin, or the styrene resin and a specific additive can be mixed in advance and this can be mixed with a halogenated epoxy resin flame retardant. It is also possible to mix a halogenated epoxy resin-based flame retardant and / or a specific additive with an appropriate amount of a styrene-based resin to prepare a master batch and the styrene-based resin. For mixing, a method of dry blending with a Henschel mixer, a ribbon blender, a tumbler mixer, or the like, a method of heating and melting with a Banbury mixer, an extruder, or the like, and the like are used.

Further, known stabilizers for these additives are, for example, metal soaps, organic phosphorus compounds, antioxidants,
An ultraviolet absorber and an organic tin compound can be used together.

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

[0031]

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]

[0033]

[Chemical 3]

[A-type zeolite used in the present invention]

[0035]

[Chemical 4]

[Metal-Substituted Zeolites Used in the Present Invention] C-1: Magnesium-Substituted Zeolites C-2: Calcium-Substituted Zeolites C-3: Zinc-Substituted Zeolites C-4: Barium-Substituted Zeolites (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]

[0037]

[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] 85 parts of ABS resin [JSR ABS # 15NP manufactured by Japan Synthetic Rubber Co., Ltd.], AAS
Resin [Mitsubishi Rayon Co., Ltd. dialac A S61
0] 15 parts, brominated epoxy-based oligomer [Prasam EP-16 manufactured by Dainippon Ink and Chemicals, Inc.] 20
Parts and 5 parts of antimony trioxide were kneaded for 3 minutes with an 8-inch test roll adjusted to 155 ° C. for 3 minutes to prepare a sheet having a thickness of 0.7 mm. The obtained sheets are cut and stacked on 8 sheets, 280 ° C, 5 kg
The sample was pressed at / cm ² and the deterioration time (minutes) until the sample turned blackish brown was measured. The results are shown in Tables 1 and 2.

[0040]

[Table 1]

[0041]

[Table 2]

Sample Nos. 1 to 9 are examples, and Nos. 10 to 2 are the same.
2 is a comparative example. As is clear from the comparison of the results in Tables 1 and 2, it can be seen that the flame-retardant styrene-based resin composition of the present invention has extremely excellent thermal stability. It should be noted that when using an additive other than the present invention as in Sample Nos. 10-18, when adding an additive other than the present invention alone as in No. 19-21, and as in No. 22 If no additive is added, sufficient thermal stability cannot be obtained in any case.

[Example 2] Styrene resin [Asahi Kasei Co., Ltd.
Styron 492] 100 parts, brominated epoxy oligomer [Prasam EC-14 manufactured by Dainippon Ink and Chemicals, Inc.] 15 parts, antimony trioxide 3 parts, and Table 3
And the compound containing the additives shown in Table 4 was kneaded with an 8-inch test roll adjusted to 140 ° C. for 3 minutes to give a thickness of 0.7.
mm sheets were made. The obtained sheet was cut into eight sheets, which were pressed at 260 ° C. and 5 kg / cm ² to measure the deterioration time (minutes) until the sample became grayish brown. The results are shown in Table 3.
And shown in Table 4.

[0044]

[Table 3]

[0045]

[Table 4]

Sample Nos. 1 to 11 are examples and the same No. 12 to
23 is a comparative example. As is clear from the comparison of the results in Tables 3 and 4, it can be seen that the flame-retardant styrenic resin composition of the present invention has extremely excellent thermal stability. In addition, in the case where additives other than the present invention are used in combination as in Sample Nos. 12 to 22 or when the additive is not added as in Sample No. 23, sufficient thermal stability cannot be obtained in any case.

[Example 3] ABS resin [Mitsubishi Kasei Co., Ltd.
Toflex 410CB] 100 parts by weight, brominated epoxy oligomer [manufactured by Dainippon Ink and Chemicals, Inc.]
20 parts of Pratherm EC-20 was blended with the additives shown in Tables 5 and 6 for 3 minutes with an 8-inch test roll adjusted to 160 ° C. to prepare a sheet having a thickness of 0.7 mm. The obtained sheets are cut into 8 sheets and stacked at 280 ° C.
The sample was pressed at 5 kg / cm ² and the deterioration time (minutes) until the sample turned blackish brown was measured. The results are shown in Tables 5 and 6.

[0048]

[Table 5]

[0049]

[Table 6]

Sample Nos. 1 to 10 are Examples, and Nos. 11 to 11 are the same.
23 is a comparative example. As is clear from the comparison of the results in Tables 5 and 6, it can be seen that the flame-retardant styrene-based resin composition of the present invention has extremely excellent thermal stability. In addition, when the additive of (a) of the present invention is added alone as in Sample Nos. 11 to 12 or when additives other than the present invention are used in combination as in Nos. 13 to 22 and No. 23 of the same. As described above, when no additive is added, sufficient thermal stability cannot be obtained in any case.

[0051]

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

 ─────────────────────────────────────────────────── ─── Continued front page (72) Inventor Masaharu Akitsu 788 Hisachi, Takatsu-ku, Kawasaki-shi, Kanagawa Sankyo Organic Synthesis Co., Ltd. (72) Adult Yoshimura 788 Hisachi, Takatsu-ku, Kawasaki, Kanagawa Sankyo Organic Synthesis Co., Ltd. (72) Inventor Kunitake Yuzuru 1-15-401 Chigusadai, Inage-ku, Chiba City, Chiba Prefecture (72) Yuji Sato 2-17-4 Eharadai, Sakura City, Chiba Prefecture

Claims (1)

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