JP2742479B2 - Stabilization method of flame retardant resin composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION The present invention relates to a styrenic resin
The present invention relates to a method for stabilizing a flame-retardant resin composition obtained by adding a bromo-based flame retardant to a carbonate resin, and can be widely used in fields where the flame retardancy of the resin composition is required.

[0002]

2. Description of the Related Art Heretofore, in order to make a resin composition comprising a styrene resin and a carbonate resin flame retardant, a method of adding a so-called flame retardant or a flame retardant auxiliary such as a halogen-containing compound, a phosphorus compound and antimony trioxide. Among these flame retardants, halogen-containing compounds, particularly bromo-based flame retardants, are frequently used. However, in general, a flame-retardant resin composition obtained by adding a bromo-based flame retardant to a styrene-based resin and a carbonate resin has a remarkably poor thermal stability at the time of heat processing, and in order to suppress the decrease in the thermal stability. Is a conventional method of adding various organotin compounds (JP-A-62
-290757 and JP-A-62-295961)
And a method of adding epoxypropyl isocyanurate (JP-A-2-279763).

[0003]

However, in these methods, the effect of heat stabilization is not yet sufficient, and in order to keep the commercial value of the molded product from decreasing, development of a stabilizer with less coloring especially at the initial stage of heating has been awaited. I was

[0004]

SUMMARY OF THE INVENTION From the above viewpoint, the inventors of the present invention have proposed a stabilizer having an initial coloring preventing effect on a flame retardant resin composition containing a styrene resin and a carbonate resin containing a bromo flame retardant. As a result of intensive studies, the initial coloring of the resin composition is significantly reduced by adding a phosphate ester metal salt to a flame retardant resin composition comprising a styrene resin and a carbonate resin and a bromo flame retardant. Thus, the first invention was completed.

[0005] Further, by adding a phosphoric acid ester metal salt and epoxypropyl isocyanurate to a flame retardant resin composition comprising a styrene resin, a carbonate resin, and a bromo flame retardant, the initial coloring of the resin composition can be further improved. The inventors have found that the number significantly decreases, and completed the second invention.

The styrenic resin used in the first and second inventions includes a polymer of a vinyl aromatic compound monomer, a vinyl aromatic compound monomer and a vinyl chain compound monomer and / or
Or a copolymer of a vinyl heterocyclic compound monomer, a copolymer of a vinyl aromatic compound monomer and a conjugated diene compound monomer and / or a saturated rubber monomer, and a vinyl aromatic compound monomer And a conjugated diene compound monomer and a vinyl chain compound monomer and / or a vinyl heterocyclic compound monomer and / or a saturated rubber monomer.

Examples of vinyl aromatic compound monomers include:
There are styrene, side chain-substituted styrene (eg, α-methylstyrene), nucleus-substituted styrene (eg, vinyltoluene and O-chlorostyrene, etc.). Examples of vinyl chain compound monomers include acrylonitrile, acrylic acid And methacrylic acid, methyl acrylate, ethyl acrylate, methyl methacrylate and ethyl methacrylate, and the like. Examples of vinyl heterocyclic compound monomers include vinyl pyridine and vinyl carbazole, and conjugated diene compound monomers Examples of butadiene, 1-chlorobutadiene, 2-
Examples include chlorobutadiene and isoprene, and examples of the saturated rubber monomer include an ethylene-propylene-diene compound and butyl rubber.

[0008] Among these, typical examples of the polymer include 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 copolymer, or a blend of these resins.

The carbonate resins used in the first and second inventions include those generally used, for example, those represented by the general formula (I)-[-OR ¹ -OC (= O)- ] _n - (I) (wherein, R ¹ represents an aliphatic group, an aromatic group or aliphatic - aromatic radical, n denotes the polymerization degree.) include carbonate resins represented by.

As a method for producing a carbonate resin, for example, a dioxy compound represented by the general formula (II) HO—R ² —OH (II) (wherein R ² represents a group having the same meaning as R ¹ ) and phosgene , Reaction of dioxy compound with bischloroformate of dioxy compound, self-condensation reaction of monochloroformate of dioxy compound, transesterification reaction of dioxy compound with diester carbonate,
Methods include a self-condensation reaction of a dioxy compound with a biscarbonate of a dioxy compound, a self-condensation reaction of a monocarbonate of a dioxy compound, and the like.

The dioxy compound used herein is, for example, bis (4-hydroxyphenyl) methane, 1,1′-bis (4-hydroxyphenyl) ethane, 2,2′-bis (4-hydroxy Phenyl) propane, 2,2′-bis (4-hydroxyphenyl) butane, 2,2′-bis (4-hydroxyphenyl) octane, bis (4-hydroxyphenyl) phenylmethane,
2,2'-bis (4-hydroxy-3-methylphenyl) propane, 1,1'-bis (4-hydroxy-3-
Tert-butylphenyl) propane, 2,2′-bis (4-hydroxy-3-bromophenyl) propane,
2,2'-bis (4-hydroxy-3,5-dibromophenyl) propane, 2,2'-bis (4-hydroxy-
Bis (hydroxyaryl) alkanes such as 3,5-dichlorophenyl) propane, 1,1′-bis (4-
Bis (hydroxyaryl) cycloalkanes such as hydroxyphenyl) cyclopentane and 1,1′-bis (4-hydroxyphenyl) cyclohexane, 4,
Dihydroxydiaryl ethers such as 4'-dihydroxydiphenylether, 4,4'-dihydroxy-3,3'-dimethylphenylether, 4,4'-dihydroxydiphenylsulfide and 4,4'-dihydroxy-3,3'- Dihydroxydiaryl sulfides such as dimethyldiphenyl sulfide, 4,4′-
Dihydroxydiarylsulfoxides such as dihydroxydiphenylsulfoxide and 4,4′-dihydroxy-3,3′-dimethyldiphenylsulfoxide;
4,4′-dihydroxydiphenyl sulfone and 4,
And dihydroxydiarylsulfones such as 4'-dihydroxy-3,3'-dimethyldiphenylsulfone.

Among the carbonate resins using these dioxy compounds, carbonate resins produced from 2,2'-bis (4-hydroxyphenyl) propane (so-called bisphenol A) are widely used.

In the present invention, the amounts of the styrene resin and the carbonate resin are not particularly limited, but are usually 1: 9 to 9: 1 by weight, preferably 3: 7 to 7: 3.

As the bromo flame retardant used in the first and second inventions, those usually used in this field can be used without limitation. Examples thereof include tetrabromoethane, tetrabromobutane, and hexabromoethane. Bromocyclododecane, tetrabromobenzene, hexabromobenzene, bromostyrene, bromophenylallyl ether,
Tetrabromophthalic anhydride, tribromophenol, pentabromotoluene, pentabromophenylpropyl ether, tetrabromobisphenol A, hexabromodiphenylether, decabromodiphenylether,
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 bis (2,3-dibromopropyl ether), tetrabromobisphenol A bis (2-bromoethyl ether), tetrabromobisphenol A bis (propyl ether), 2,3-
Dibromopropyl pentabromophenyl ether, bis (tribromophenoxy) ethane, tetrabromobisphenol A diglycidyl ether and brominated bisphenol adduct epoxy oligomer, tetrabromobisphenol A diglycidyl ether and tribromophenol adduct, tetrabromobisphenol S And tetrabromobisphenol S (2,3-dibromopropyl ether).

There are no particular restrictions on the amount of these brominated flame retardants added, but it may be varied as appropriate depending on the required degree of flame retardancy. Generally, a resin composition comprising a styrene resin and a carbonate resin is used. It is preferable to use 5 to 35 parts by weight alone or in combination of two or more kinds with respect to 100 parts by weight of the product. Also,
Further, when a flame retardant aid such as antimony trioxide is used in combination, the flame retardant effect is more excellent, and the amount of the flame retardant is usually 1 to 100 parts by weight of the resin composition comprising the styrene resin and the carbonate resin. -20 parts by weight are preferred.

The phosphate metal salts used in the first and second inventions are, for example, the following general formulas (III) and (IV)
The compound shown by these can be mentioned.

[(R ³ O) ₂ (O =) PO—] _m M (III)

[0018]

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Wherein R ³ is an alkyl group, a hydroxyalkyl group, an alkenyl group, an aryl group and a cycloalkyl group, and M is a group 1, 2, 12, 12 or 13 of the periodic table. And m represents the valence of M.) When R ³ in the formula is an alkyl group, it includes a straight-chain alkyl group and a branched-chain alkyl group. Examples of the alkyl group include methyl, ethyl, propyl, butyl, hexyl, heptyl, octyl, 2-ethylhexyl, isooctyl, decyl, isodecyl, undecyl, dodecyl, tridecyl, heptadecyl, octadecyl, eicosyl. And docosyl.

When R ³ is a hydroxyalkyl group, examples thereof include a hydroxyalkyl group having 1 to 22 carbon atoms. Specific examples include 3-hydroxypropyl, 2-hydroxyoctyl, and 12-hydroxy Groups such as octadecyl and 18-hydroxydokosyl can be mentioned.

When R ³ is an alkenyl group, examples thereof include alkenyl groups having 2 to 22 carbon atoms. Specific examples include vinyl, propenyl, butenyl, pentenyl, heptynyl, decenyl, dodecenyl, pentadecenyl, Groups such as heptadecenyl, octadecenyl, nonadecenyl and docosenyl can be mentioned.

When R ³ is an aryl group, examples thereof include aryl groups having 6 to 18 carbon atoms. Specific examples include phenyl, tolyl, xylyl, butylphenyl, nonylphenyl and tertiarybutylphenyl. , Tris (tert-butyl) phenyl, methoxyphenyl, ethoxyphenyl and butoxyphenyl.

When R ³ is a cycloalkyl group, examples thereof include a cycloalkyl group having 6 to 18 carbon atoms. Specific examples include cyclohexyl, methylcyclohexyl, ethylcyclohexyl, butylcyclohexyl, nonylcyclohexyl and Groups such as tris (tert-butyl) cyclohexyl can be mentioned.

M represents a metal belonging to Groups 1, 2, 12 and 13 of the periodic table, and specific examples thereof include lithium, sodium, potassium, magnesium, calcium, strontium, barium, zinc, Metals such as boron, aluminum and the like, preferably sodium,
Magnesium, calcium, zinc and aluminum.

Specific examples of the phosphoric acid ester metal salt represented by the general formula (III) include, but are not limited to, the following.

(1) [(H ₃ CO) ₂ (O =) PO—] ₂ Ca (2) {[H ₃ C (H ₂ C) ₂ O] ₂ (O =) PO—} ₂ Zn (3) _{{[H 3 C (H 2 C)} 3 O ] _{2 (O =) P-O-} } 2 Ba (4) { _{[H 3 C (H 2 C)} 5 O ] ₂ (O = ) PO-｝ ₂ Mg (5) ｛[H ₃ C (H ₂ C) ₇ O] ₂ (O =) PO-｝ ₂ Sr (6) [H ₃ C (H ₂ C) ₉ O ] _{2 (O =) P-O} -Na (7) { _{[H 3 C (H 2 C)} 12 O ] _{2 (O =) P-O-} } 2 Mg (8) { [H ₃ C (H ₂ C) ₁₇ O] ₂ (O =) PO-｝ ₂ Ca (9) [H ₃ C (H ₂ C) ₁₉ O] ₂ (O =) PO-Li (10) ｛[H ₃ C (H ₂ C) ₂₁ O] ₂ (O =) PO-｝ ₂ Zn (11) ｛[HO (H ₂ C) ₃ O] ₂ (O =) PO-｝ ₂ Ba (12) [ H ₃ C (H ₂ C) ₅ (HO) HCH ₂ CO] ₂ (O =) PO—K (13) [(H ₂ C = CHCH ₂ O) ₂ (O =) PO—] ₂ Ca (14) ｛[H ₂ C = CH (CH ₂ ) ₃ O] ₂ (O =) PO-｝ ₂ Zn (15) ｛[H ₂ C ＝ CH (CH ₂ ) ₅ O] ₂ (O =) PO-｝ ₃ B (16 ) ｛[H ₂ C ＝ CH (CH ₂ ) ₈ O] ₂ (O =) PO—｝ ₂ Mg (17) ｛[H ₂ C ＝ CH (CH ₂ ) ₁₀ O] ₂ (O =) P -O-｝ ₃ Al (18) [H ₂ C ＝ CH (CH ₂ ) ₁₃ O] ₂ (O =) PO-Na (19) ｛[H ₃ C (H ₂ C) ₇ HC = CH ( CH _{2) 8} O] _{2 (O =) P -O-}} 2 Ca (20) { _{[H 2 C = CH (CH 2} ) 20 O ] _{2 (O =) P-O-} } 2 Ba

[0027]

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Specific examples of the phosphoric acid ester metal salt represented by the general formula (IV) include, but are not limited to, the following.

[0029]

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[0030]

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[0031]

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[0032]

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The epoxypropyl isocyanurate used in the second invention may be mono (epoxypropyl)
Examples include isocyanurate, bis (epoxypropyl) isocyanurate, and tris (epoxypropyl) isocyanurate, and preferably, tris (epoxypropyl) isocyanurate.

The amount of the phosphate metal salt used in the first invention and the amount of the phosphate metal salt used in combination with the epoxypropyl isocyanurate used in the second invention are particularly limited. There is no, but as the effective range, 0.01 to 100 parts by weight of the resin composition composed of a styrene resin and a carbonate resin,
5.0 parts by weight. If the addition amount is less than 0.01 part by weight, the effect of preventing initial coloring is small, and if it exceeds 5.0 parts by weight, the effect is not as expected.
２．０2.0 parts by weight.

There is no particular limitation on the ratio of the phosphate metal salt and the epoxypropyl isocyanurate used in the second invention, but the ratio is 90:10 to 1: 1.
0:90 is preferred.

The method of adding the stabilizer used in the first and second inventions to a flame retardant resin composition comprising a styrene resin, a carbonate resin and a bromo flame retardant is as follows.
Conventionally known techniques may be used.For example, the resin composition and the stabilizer may be mixed with a Hensiel mixer, a ribbon blender, a Banbury mixer, or the like, or one obtained by pre-packing the stabilizer. The resin composition may be mixed with the aforementioned mixer.

Further, known stabilizers such as organotin compounds, metal soaps, organophosphorus compounds, antioxidants and ultraviolet absorbers can be used in combination with these stabilizers. Further, if necessary, a plasticizer, a lubricant, a pigment, a filler, a processing aid, a chlorinated flame retardant, a phosphorus-based flame retardant, and a flame retardant auxiliary can be added.

[0038]

EXAMPLES Hereinafter, the first and second inventions will be specifically described with reference to examples, but the invention is not limited thereto. In these examples, "parts" means parts by weight, "*" in the sample number indicates a comparative example, and no mark indicates an example. In addition, “A-
1 to A-14 "," B-1 to B-3 "," C-1 to C- "
The symbol “3” indicates the following compound.

A-1 Metal phosphate salt represented by formula (6) in the specification A-2 Metal phosphate salt represented by formula (8) in the specification A-3 Formula (3) 12) A phosphate metal salt represented by the formula (20) in the specification A-4 A-5 A phosphate metal salt represented by the formula (25) in the description A-5 6 Phosphate metal salt represented by formula (28) in the specification A-7 Phosphate metal salt represented by formula (36) in the description A-8 Formula (39) shown in the specification Phosphate ester metal salt A-9 Phosphate ester metal salt represented by formula (43) in the specification A-10 Phosphate ester metal salt represented by formula (48) in the specification A-11 Phosphoric acid ester metal salt represented by formula (50) A-12 Formula (57) in the specification A-13 phosphate metal salt represented by the formula (59) in the specification A-13 Phosphate metal salt represented by the formula (63) in the specification A-14 B-1 mono ( Epoxypropyl) isocyanurate B-2 bis (epoxypropyl) isocyanurate B-3 tris (epoxypropyl) isocyanurate C-1 dibutyltin maleate C-2 triphenylphosphite C-3 epoxidized soybean oil.

Example 1 ABS resin [manufactured by Toray Industries, Inc.]
50 parts of Toyolac 100], 50 parts of carbonate resin [Panlite L1250 manufactured by Teijin Chemicals Ltd.], 20 parts of epoxy oligomer of adduct of tetrabromobisphenol A diglycidyl ether and brominated bisphenol [EBR-700 manufactured by Manac Corporation], 20 parts, A mixture of 3 parts of antimony trioxide and a stabilizer shown in Table 1 was heated at 185 ° C.
The mixture was kneaded with an 8 inch test roll adjusted for 5 minutes to prepare a sheet having a thickness of 0.5 mm. The obtained sheets were cut and stacked eight times, and pressed at 265 ° C. and 5 kg / cm ² ,
The time (minute) (initial thermal stability) until the sample turned pale yellow was measured. Table 1 shows the results.

[0041]

[Table 1]

As is clear from comparison between Sample Nos. 1 to 18 and Sample Nos. 19 to 24, the method of the present invention shows that the initial thermal stability is extremely excellent.

Example 2 50 parts of ABS resin [JSR ABS # 10NP manufactured by Nippon Synthetic Rubber Co., Ltd.], carbonate resin [NOVAREX 70 manufactured by Mitsubishi Kasei Kogyo Co., Ltd.]
25A], a mixture of 50 parts of tetrabromobisphenol A carbonate oligomer [Fireguard 7500, manufactured by Teijin Chemicals Ltd.] and 3 parts of antimony trioxide to which a stabilizer shown in Table 2 was added was adjusted to 185 ° C. The mixture was kneaded with an inch test roll for 5 minutes to prepare a sheet having a thickness of 0.5 mm. The resulting sheet was cut and stacked eight times,
Pressing was performed at 0 ° C. and 5 kg / cm ² , and the initial thermal stability was measured in the same manner as in Example 1. Table 2 shows the results.

[0044]

[Table 2]

As is clear from a comparison between Sample Nos. 1 to 15 and Sample Nos. 16 to 20, it is understood that the initial thermal stability is extremely excellent according to the method of the present invention.

Example 3 35 parts of ABS resin [Taflex 41 OCB manufactured by Mitsubishi Monsanto Kasei Co., Ltd.], MB
S resin [Kane Ace B-12 manufactured by Kanebuchi Chemical Industry Co., Ltd.]
15 parts, 50 parts of carbonate resin [NOVAREX 7025A manufactured by Mitsubishi Kasei Kogyo Co., Ltd.], tetrabrombisphenol A [Fire Guard 200 manufactured by Teijin Chemicals Ltd.]
0] to 17 parts of a formulation obtained by adding a stabilizer shown in Table 3 to 1 part
Knead with an 8-inch test roll adjusted to 85 ° C for 5 minutes,
A sheet having a thickness of 0.5 mm was prepared. The obtained sheets were cut, eight sheets were stacked, and pressed at 240 ° C. and 5 kg / cm ² , and the initial thermal stability was measured as in Example 1. Table 3 shows the results.

[0047]

[Table 3]

As is clear from comparison of Sample Nos. 1 to 10 with Sample Nos. 11 to 13, it is understood that the initial thermal stability is extremely excellent according to the method of the present invention.

[0049]

According to the method of the present invention, the initial coloring of a flame-retardant resin composition comprising a styrene-based resin, a carbonate resin and a bromo-based flame retardant during heating can be extremely reduced.

Claims (2)

(57) [Claims] 1. A method for stabilizing a resin composition comprising a flame retardant resin composition comprising a styrene resin, a carbonate resin, and a bromo flame retardant, the method comprising adding a phosphate metal salt. 2. A flame-retardant resin composition comprising a styrene-based resin, a carbonate resin and a bromo-based flame retardant, wherein a phosphoric acid ester metal salt and epoxypropyl isocyanurate are added in combination. Stabilization method.