JP2840009B2 - Flame retardant styrene resin composition - Google Patents

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-based flame retardant as a flame retardant. .

[0002]

The present invention can be widely used in fields where styrene resin is required to have flame retardancy.

[0003]

2. Description of the Related Art Generally, in order to make styrene resin flame-retardant,
A method of adding a so-called flame retardant or a flame retardant auxiliary such as a halogen compound, a phosphorus compound, and antimony trioxide has been conventionally performed, and among these flame retardants, a halogen flame retardant is frequently used. Halogenated epoxy resin flame retardants have come to be used to improve not only the flame resistance 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-based resin, the thermal stability of the flame-retarded styrene-based resin is significantly reduced. For the purpose of suppressing, at least one compound selected from epoxypropyl isocyanurate and zeolite A, zeolite containing a metal of Group II or Group IV of the periodic table and hydrotalcite is used.
A method of adding species 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, zeolite A, zeolite containing a metal of Group II or IV of the periodic table and hydrotalcite is used. The method of simultaneous addition is not sufficient for severe heat history during molding, and development of an additive having further excellent heat stabilizing effect has been awaited.

[0006]

SUMMARY OF THE INVENTION From the above viewpoints, the present inventors have eagerly sought an additive having an excellent heat stabilizing effect on a flame retardant styrene resin composed of a styrene resin and a halogenated epoxy resin flame retardant. As a result of repeated studies, a zinc-substituted hydrotalcite compound and a zeolite A, a zeolite A, a group II or group IV of the periodic table were applied to a flame-retardant styrene resin composed of a styrene resin and a halogenated epoxy resin flame retardant. It has been found that the thermal stability of a flame-retarded styrenic resin composition to which at least one compound selected from the group consisting of zeolite containing group III metal and epoxypropyl isocyanurate is added in combination is remarkably improved. completed.

The styrenic resin used in the present invention is:
A polymer of a vinyl aromatic compound monomer, a copolymer of a vinyl aromatic compound monomer and a vinyl chain compound monomer and / or a vinyl heterocyclic compound monomer, and a vinyl aromatic compound monomer A copolymer of a conjugated diene compound monomer and / or a saturated rubber monomer, and a vinyl aromatic compound monomer, a conjugated diene compound monomer and a vinyl chain compound monomer and / or
Or a copolymer of a vinyl heterocyclic compound monomer and / or a saturated rubber monomer. Examples of the vinyl aromatic compound monomer include styrene, side-chain-substituted styrene (eg, α-methylstyrene), and nucleus-substituted styrene (eg,
Vinyl toluene and 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 and vinyl carbazole, etc.,
Examples of the conjugated diene compound monomer include butadiene, 1
-Chlorobutadiene, 2-chlorobutadiene, isoprene and the like, and examples of the saturated rubber monomer include an ethylene-propylene-diene compound and butyl rubber.
Examples of typical polymers among these are polystyrene, acrylonitrile-styrene copolymer, methyl methacrylate-styrene copolymer, styrene-α-methylstyrene copolymer, acrylonitrile-butadiene-styrene copolymer Methyl methacrylate-butadiene-styrene copolymer, acrylonitrile-acryl 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.

As the halogenated epoxy resin-based flame retardant used in the present invention, those usually used in this field can be used without limitation. Examples thereof include halogenated epoxy resins and terminal epoxy groups of the epoxy resins. And a compound having a structure in which a part or all of is blocked.

Examples of the halogenated epoxy resin include a halogenated bisphenol type epoxy resin, a halogenated phenol novolak type epoxy resin, a halogenated cresol novolak type epoxy resin, a halogenated resorcinol type epoxy resin, a halogenated hydroquinone type epoxy resin, and a halogenated epoxy resin. Examples thereof include bisphenol A novolak type epoxy resin, halogenated methyl resorcinol type epoxy resin, and halogenated resorcinol novolak type epoxy resin. Usually, a halogenated bisphenol type epoxy resin having an average degree of polymerization of about 0 to 50 is used. Specific examples of the halogenated bisphenol constituting the 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 which blocks part or all of the terminal epoxy group 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, and trichlorophenol. Phenol, pentachlorophenol,
Examples thereof include dibromoethylphenol, dibromopropylphenol, and dibromobutylphenol.

[0011] Such a halogenated epoxy resin-based flame retardant can be produced by various methods. For example, a method of producing by a condensation reaction of halogenated bisphenol A and epichlorohydrin, a method of producing by reacting diglycidyl ether of halogenated bisphenol A with halogenated bisphenol A, and the above-mentioned halogenated bisphenol having an epoxy group at the terminal A method in which an A-type epoxy resin is heated to react with a halogenated phenol such as tribromophenol, pentabromophenol, trichlorophenol, dibromocresol, and dichlorocresol in the presence of a basic catalyst, etc.

Commercially available halogenated epoxy resin flame retardants used in the present invention include, for example, Pratherm EP-16 and EP-10 manufactured by Dainippon Ink and Chemicals, Inc.
0, the same EP-500, the same EC-14, the same EC-20, and the same EC-30. The amount of the halogenated epoxy resin flame retardant to be added is not particularly limited, but may be appropriately varied depending on the required performance. Generally, 5 to 35 parts by weight of 100 parts by weight of the styrene resin alone or 2 parts by weight is used. It is preferable to use two or more kinds in combination. Further, when a flame retardant auxiliary such as antimony trioxide is further used in combination, the flame retardant effect is more excellent, and the addition amount is usually preferably 1 to 20 parts by weight based on 100 parts by weight of the styrene resin.

The zinc-substituted hydrotalcite compound of the component (a) used in the present invention is represented by the general formula (I):

[0014]

Embedded image 0 <b ≦ 0.5, 0.5 ≦ x + y <1, a positive number satisfying 0 ≦ m <2]

[0015] Zinc-substituted hydrotalcite compounds represented by the following formula:

In the present invention, in order to improve the compatibility and dispersibility of the zinc-substituted hydrotalcite compound and the styrene resin, the zinc-substituted hydrotalcite compound is subjected to a surface treatment 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-based coupling agents, titanate-based coupling agents, esters of glycerin and a fatty acid, and the like, and specific examples thereof include, for example, stearin Acids, oleic acid, higher fatty acids such as lauric acid, anionic surfactants such as sodium stearate, sodium oleate, sodium laurylbenzenesulfonate, vinyltriethoxysilane, γ-methacryloxypropyltriethoxysilane, isopropyl Examples thereof include silane-based or titanate-based coupling agents such as triisostearoyl titanate and isopropyltridecylbenzenesulfonyl titanate, and glycerin fatty acid esters such as glycerin monostearate and glycerin monooleate.

One of the components (b) used in the present invention
The zeolite A has the general formula (II)

[0019]

Embedded image

Wherein X represents a number from 0 to 6. A type zeolite represented by the formula [I], and may be a natural or synthetic product. The type A zeolite used is, for example, a higher fatty acid alkali metal salt such as stearic acid or oleic acid alkali metal salt, or an organic sulfonic acid alkali metal salt such as dodecylbenzenesulfonic acid alkali metal salt. Surface treatment may be performed.

Further , one of the components (b) used in the present invention
The zeolite containing a group II or IV of the periodic table as a species is a zeolite obtained by replacing Na in the A-type zeolite with a metal of the group II or IV of the periodic table (hereinafter, referred to as a zeolite).
It is called "metal-substituted zeolite". ), The metal is not particularly limited, but magnesium, calcium, zinc, strontium, barium, zirconium, tin and the like are preferable from the viewpoints of effect, toxicity, and availability, and particularly preferable metals are calcium, Zinc and barium.

Examples of the metal-substituted zeolite include synthetic zeolites obtained by substituting some or all of the above metals with the alkali metal of the zeolite containing an alkali metal. It is preferable that the substitution ratio is usually about 10 to 70 mol% as an industrially easily obtained one.

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 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 above-mentioned synthetic zeolite,
A known method may be used, for example, a production method described in JP-A-57-28145.

Further, one of the components (b) used in the present invention
As a seed, epoxypropyl isocyanurate,
Mono (epoxypropyl) isocyanurate, bis (epoxypropyl) isocyanurate, tris (epoxypropyl) isocyanurate and the like are preferable, and tris (epoxypropyl) isocyanurate is preferable.

Among the (a) zinc-substituted hydrotalcite compounds used in the present invention and (b) zeolite A, zeolites containing a Group II or IV metal of the periodic table and epoxypropyl isocyanurate. Compounds selected from
Although there is no particular limitation on the total amount of addition of at least one of the above, the effective range is 0.01 to 5.0 parts by weight based on 100 parts by weight of the styrene resin. If the addition amount is less than 0.01 part by weight, the heat stabilizing effect is not remarkably observed, 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. Also, there is no particular limitation on the case of using together, and any combination ratio may be used as long as it is within the range of the addition amount.

In mixing the styrene resin, the halogenated epoxy resin flame retardant and the specific additives used in the present invention, the respective components may be mixed in any combination and in any order, and the mixing machine used is also What is necessary is just to select suitably according to the objective.

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

Further, known additives such as metal soap, an organic phosphorus compound, an antioxidant,
An ultraviolet absorber, an organic tin compound or the like can be used in combination.

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

[0031]

EXAMPLES The present invention will now be described specifically with reference to examples, but the present invention is not limited to these examples. In these examples, parts means parts by weight.

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

[0033]

Embedded image

[Type A zeolite used in the present invention]

[0035]

Embedded image

[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 (C-1 to C-4) [Epoxypropyl isocyanurate used in the present invention] D-1: bis (epoxypropyl) isocyanurate D-2: tris (epoxypropyl) isocyanurate [additives other than the present invention]

[0037]

Embedded image

E-4: dibutyltin maleate E-5: dibutyltin thiodipropionate E-6: epoxidized soybean oil [Sansoizer E-2000 manufactured by Shin Nippon Rika Co., Ltd.]

Example 1 85 parts of ABS resin [JSR ABS # 15NP manufactured by Nippon Synthetic Rubber Co., Ltd.], AAS
Resin [Diarack A S61 manufactured by Mitsubishi Rayon Co., Ltd.]
0] 15 parts, brominated epoxy oligomer [Platherm EP-16] 20 manufactured by Dainippon Ink and Chemicals, Inc.
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 resulting sheet is cut and stacked eight times, 280 ° C, 5 kg
/ Cm ² , and the deterioration time (min) until the sample turned black-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 Sample Nos. 10 to 2
2 is a comparative example. As is clear from comparison of the results in Tables 1 and 2, it can be seen that the flame-retarded styrene-based resin composition of the present invention has extremely excellent thermal stability. In addition, as in Sample Nos. 10 to 18, when an additive other than the present invention is used in combination, as in Sample Nos. 19 to 21, when an additive other than the present invention is added alone, and as in Sample No. 22, When no additive is added, no sufficient thermal stability can be obtained.

Example 2 Styrene resin [Asahi Kasei Corporation
100 parts of Stylon 492, 15 parts of brominated epoxy oligomer [Platherm EC-14, manufactured by Dainippon Ink and Chemicals, Inc.] and 3 parts of antimony trioxide in Table 3.
And a mixture containing the additives shown in Table 4 was kneaded for 3 minutes with an 8-inch test roll adjusted to 140 ° C.
mm sheets were prepared. The obtained sheets were cut, eight sheets were stacked, and pressed at 260 ° C. and 5 kg / cm ² , and the deterioration time (minute) until the sample became gray-brown was measured. Table 3 shows the results
And Table 4 below.

[0044]

[Table 3]

[0045]

[Table 4]

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

[Example 3] ABS resin [Taflex 410C manufactured by Mitsubishi Kasei Co., Ltd.]
B] 100 parts of a brominated epoxy oligomer [Prasam EC-20 manufactured by Dainippon Ink and Chemicals, Inc.] and 20 parts of a blend obtained by adding the additives shown in Tables 5 and 6 to 16 parts
The mixture was kneaded with an 8-inch test roll adjusted to 0 ° C. for 3 minutes to prepare a sheet having a thickness of 0.7 mm. The obtained sheets were cut, eight sheets were stacked, and pressed at 280 ° C. and 5 kg / cm ² , and the deterioration time (minute) until the sample became dark 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 Sample Nos. 11 to
23 is a comparative example. As is clear from comparison of the results in Tables 5 and 6, it can be seen that the flame-retarded 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, when additives other than the present invention are used in combination as in Nos. 13 to 22, and in No. 23 As described above, when no additive is added, no sufficient thermal stability can be obtained.

[0051]

The flame-retarded styrenic resin composition of the present invention has excellent thermal stability.

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁶ Identification symbol FI C08K 3:34) (C08K 13/02 3:26 5: 3492) (C08L 25/04 63:00) (72) Inventor Akitsu Masaharu Katsuchi, Kuzuchi-ku, Kawasaki-shi, Kanagawa Prefecture, Japan (72) Inside the shared machine synthesis company (72) Inventor Yoshimura, Adult: 788-3 Kuji, Kachi, Takatsu-ku, Kawasaki city, Kanagawa prefecture Inside the shared machine synthesis company (72) Inventor Yuuki Kunitake Chiba (72) The inventor Yuji Sato 2-17-4 Eharadai, Sakura-shi, Chiba (56) References JP-A-7-33931 (JP, A) JP-A-6-61 107885 (JP, A) JP-A-4-332743 (JP, A) JP-A-3-153747 (JP, A) JP-A-4-239044 (JP, A) JP-A-61-115948 (JP, A) (58) Field surveyed (Int. Cl. ⁶ , DB name) C08L 25/00-25/18 C08L 51/0 0-51/10 C08L 55/02 C08L 63/00-63/10 C08K 3/26 C08K 3/34 C08K 5/3477-5/3492

Claims (1)

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