JP2672336B2 - Flame retardant resin composition - Google Patents

Description

TECHNICAL FIELD The present invention relates to a flame-retardant resin composition which is flame-retardant and has excellent heat resistance and weather resistance.

(Prior Art) Generally, styrene-based resins are used in many fields as home electric appliances, automobile parts, buildings, interior decorations, and other various molded products due to their excellent physical properties, but on the other hand, since they are flammable, they are used in various fields. There is no choice but to be limited. Due to the need for fire safety in recent years, especially UL for home appliances
(Underwriters Laboratory) Standards for flame retardancy are becoming more and more stringent, and the demand for styrene-based resins with flame retardancy is increasing accordingly.

By the way, as a method for obtaining flame retardancy, it is general to mix a relatively low molecular weight organic flame retardant containing a large amount of halogen and an inorganic compound such as antimony trioxide.

However, the addition of these flame retardants causes weather resistance, particularly discoloration due to light, and there are significant restrictions on the parts exposed to the light, not only the parts used outdoors but also the parts used indoors.

(Problems to be Solved by the Invention) As a result of repeated studies to develop a resin composition that is flame-retardant, has excellent heat resistance and weather resistance, the present inventor has found that the copolymer containing an imide group in its side chain By incorporating a specific halogenated organic compound as a flame retardant into the coalescence composition, we have succeeded in finding a resin composition that is flame retardant, excellent in heat resistance and weather resistance for the first time.

(Means for Solving the Problems) The present invention relates to (A) a polymer having an imide group in the side chain 10 to
(C) 5 to 40 parts by weight of a halogenated organic compound represented by the following general formula (I) with respect to 100 parts by weight of a thermoplastic resin composition consisting of 0 to 90% by weight of a thermoplastic resin (B). (D) A flame-retardant resin composition comprising 1 to 20 parts by weight of an antimony and / or zirconium oxide.

(However, R in the formula represents a substituted or unsubstituted hydrocarbon having 1 to 10 carbon atoms, and X represents chlorine or bromine.) First, the component (A) will be described.

Examples of the polymer having an imide group in the side chain in the present invention include i) a copolymer obtained by polymerizing an aromatic vinyl monomer and an unsaturated dicarboxylic acid anhydride in the presence or absence of a rubbery polymer. Imidized polymer, ii) copolymerization of aromatic vinyl monomer, unsaturated dicarboxylic acid anhydride and vinyl monomer copolymerizable with them in the presence or absence of rubbery polymer A polymer obtained by imidizing the polymer, iii) a polymer obtained by imidizing a copolymer obtained by polymerizing an olefin and an unsaturated carboxylic acid in the presence or absence of a rubbery polymer, i.
v) a polymer obtained by imidizing a copolymer obtained by polymerizing a monomer copolymerizable with acrylic acid and / or methacrylic acid in the presence or absence of a rubber-like polymer, v) a rubber-like polymer A polymer obtained by polymerizing an aromatic vinyl monomer, a maleimide and / or an N-substituted maleimide in the presence or absence, v
i) A polymer obtained by polymerizing an aromatic vinyl monomer, a maleimide and / or an N-substituted maleimide and a vinyl monomer copolymerizable with these in the presence or absence of a rubbery polymer.

Examples of the aromatic vinyl monomer include styrene and α-
Styrene monomers such as methylstyrene, vinyltoluene, and chlorostyrene and substituted monomers thereof, of which styrene and α-methylstyrene monomers are particularly preferable.

As the unsaturated dicarboxylic acid anhydride, for example, maleic anhydride, chloromaleic anhydride, itaconic anhydride,
Phenyl maleic anhydride or the like can be used, and maleic anhydride is particularly preferable. Further, as these copolymerizable vinyl monomers, vinyl cyanide monomers such as acrylonitrile, methacrylonitrile and α-chloroacrylonitrile; methyl acrylic acid ester, ethyl acrylic acid ester, butyl acrylic acid ester, etc. Acrylic ester monomer; Methyl methacrylate ester,
Methacrylic acid ester monomers such as ethyl methacrylic acid ester; vinyl carboxylic acid monomers such as acrylic acid and methacrylic acid; and other acrylic acid amides, methacrylic acid amides, acenaphthylene and N-vinylcarbazole. Therefore, monomers such as acrylonitrile, acrylic acid ester and methacrylic acid ester, acrylic acid and methacrylic acid are preferable.

Examples of the N-substituted maleimide include N-methylmaleimide, N-butylmaleimide, N-arylmaleimide (aryl groups include, for example, phenyl, 4-diphenyl, 1-naphthyl, 2,6-diethylphenyl, 2,3- and 4 -Chlorophenyl, 4-promophenyl and other mono- and dihalophenyl isomers, 2,4,6-trichlorophenyl, 2,4,6-tribromophenyl, 4-n-butylphenyl, 4-benzylphenyl, 2- , 3- and 4-methoxyphenyl, etc.) and the like.

In the polymers i) to iv) having an imide group in the side chain as an example of the component (A) in the present invention, methylamine, ethylamine, n-propylamine, iso-, as a primary amine for the imidization reaction. Examples thereof include alkylamines such as propylamine, butylamine, pentylamine and cyclohexylamine; aromatic amines such as aniline and naphthylamine, and halogen-substituted aromatic amines such as chloro- or bromo-substituted aniline.

When carrying out the imidization reaction in a solution state or in a suspension state in a non-aqueous medium, it is preferable to use an ordinary reaction vessel, for example, an autoclave, but when carrying out in a bulk molten state, an extruder equipped with a devolatilization device is used. You may use. The reaction temperature for imidization is about 80-350 ° C. Solvents for imidization in a solution state include acetone, methyl ethyl ketone, methyl isobutyl ketone, acetophenone, tetrahydrofuran, dimethylformamide, etc. Among them, methyl ethyl ketone and methyl isobutyl ketone are preferred. The non-aqueous medium used for imidization in suspension in the non-aqueous medium includes aliphatic hydrocarbons such as heptane, hexane, pentane, octane, 2-methylpentane, cyclopentane and cyclohexane.

 Next, the component (B) will be described.

The thermoplastic resin to be added to the polymer (A) having an imide group in the side chain as exemplified in i) to iv) is acrylonitrile-butadiene-styrene and / or α-methylstyrene copolymer, methylmethacrylate- Butadiene-styrene copolymer, acrylonitrile-ethylene and / or propylene-styrene copolymer, acrylonitrile-styrene and / or α-methylstyrene copolymer, rubber modified styrene polymer, styrene-butadiene block copolymer, aromatic Examples of the thermoplastic resin include one or more polymers selected from polycarbonate, aromatic polyester, nylon, polyphenylene oxide, and styrene-modified polyphenylene oxide.

 Next, the component (C) will be described.

The halogenated organic compound used in the present invention is represented by the following general formula.

(However, R in the formula represents a substituted or unsubstituted hydrocarbon having 1 to 10 carbon atoms, and X represents chlorine or bromine.) Specifically, methylene bis (tetrabromophthalimide), ethylene bis (tetrabromophthal) Acid imide),
Propylene bis (tetrabromophthalimide), butylene bis (tetrabromophthalimide), benzidine bis (tetrabromophthalimide), methylenebis (tetrachlorophthalimide), ethylenebis (tetrachlorophthalimide), propylenebis (Tetrachlorophthalic acid imide), butylene bis (tetrachlorophthalic acid imide), and the like. Among these, ethylene bis (tetrabromophthalic acid imide) is particularly preferable.

Examples of the component (D) include antimony trioxide, antimony tetroxide, antimony pentoxide, zirconium dioxide and the like, and at least one of them is used.

In the composition of the present invention, the compounding ratio of the polymer having a side chain imide group as the component (A) and the thermoplastic resin as the component (B) is 10 to 100% by weight of (A) and 0 to (B). 90% by weight
It is. On the other hand, the addition amount of the halogenated organic compound as the component (C) is usually 5 to 40 parts by weight, preferably 7 parts by weight with respect to 100 parts by weight of the thermoplastic resin composition comprising the components (A) and (B). ~ 30 parts by weight. If it is less than 5 parts by weight, the flame retardancy of the resulting composition is insufficient, and if it exceeds 40 parts by weight, disadvantages such as deterioration of physical properties of the composition and increase of corrosiveness occur.

The amount of the antimony and / or zirconium oxide as the component (D) added is 1 to 20 parts by weight, preferably 2 to 10 parts by weight, based on 100 parts by weight of the thermoplastic resin composition.
If it is less than 1 part by weight, the flame retardance is insufficient, and if it exceeds 20 parts by weight, the deterioration of physical properties is unfavorably increased.

Other phosphoric acid esters such as triphenyl phosphate, tricresyl phosphate, phosphoric acid (trisisopropylphenyl), tributyl phosphate, etc., reinforcing materials such as organic fibers, glass fibers, carbon fibers, calcium carbonate, talc, etc.
Fillers such as clay and aluminum hydroxide, heat stabilizers, ultraviolet absorbers, plasticizers, lubricants, colorants, foaming agents and the like can be added.

The resin composition of the present invention can be obtained by mixing the predetermined components by a usual method such as a roll mill, a Banbury mixer, a kneader, a Henschel mixer and an extruder.

(Examples) Parts and% in Examples and Comparative Examples are based on weight.

Experimental Example (1) Manufacture of a polymer obtained by imidizing a copolymer obtained by polymerizing an aromatic vinyl monomer and an unsaturated dicarboxylic acid anhydride in the presence of a rubbery polymer, styrene in an autoclave equipped with a stirrer. 100 copies,
Then, 50 parts of methyl isobutyl ketone and 24 parts of polybutadiene cut into small pieces were charged, the system was replaced with nitrogen gas, and the mixture was stirred overnight at room temperature to dissolve the rubber. Temperature up to 83 ℃
After the temperature was raised, 67 parts of maleic anhydride, 0.2 part of benzoyl peroxide and 0.2 part of azobisisobutyronitrile were dissolved in 400 parts of methyl isobutyl ketone, and the solution was added over 8 hours. After the addition, the temperature was kept at 83 ° C. for 3 hours. As a result of sampling a part of the viscous reaction liquid and quantifying the unreacted monomer by gas chromatography, the polymerization rate was 98%. 63.6 parts of aniline and 2 parts of triethylamine, which are equivalent to maleic anhydride, were added to the obtained copolymer solution.
The reaction was carried out at 140 ° C for 7 hours. The imidized polymer obtained by the degassing treatment is referred to as polymer A.

Experimental Example (2) Production of a polymer obtained by imidizing a copolymer obtained by polymerizing an aromatic vinyl monomer and an unsaturated dicarboxylic acid anhydride in the absence of a rubber-like polymer, the polybutadiene of Experimental Example (1) and Except for not using azobisisobutyronitrile, the same operation as in Experimental Example (1) was performed to obtain an imidized polymer. This is referred to as polymer B.

Experimental Example (3) Production of acrylonitrile-butadiene-styrene copolymer Polybutadiene latex 80 parts (solid content 50%, average particle size 0.35μ, gel content 88%), sodium stearate 1 part,
Sodium formaldehyde sulfoxylate 0.1 part, tetrasodium ethylenediamine tetraacetic acid 0.03 part, ferrous sulfate 0.003 part and water 200 parts are heated to 65 ° C., and a single amount consisting of 30% acrylonitrile and 70% styrene. 60 parts body mixture, t-dodecyl mercaptan 0.3
Parts and cumene hydroperoxide (0.2 parts) were continuously added over 4 hours, and after the addition was completed, polymerization was carried out at 65 ° C. for 2 hours.
The conversion was 97%. After adding an antioxidant to the obtained latex, it was coagulated with calcium chloride, washed with water and dried to obtain a white powdery polymer. This is indicated as ABS.

Example 1 55 parts of Polymer A obtained in Experimental Example (1), Experimental Example (3)
45 parts of ABS resin and 18 parts of ethylene bis (tetrabromophthalimide) as a flame retardant, 9 parts of antimony trioxide as a flame retardant aid, otakudecyl 3- (3,5- 0.5 parts of ditertiarybutyl-4-hydroxyphenyl) -propionate, 2- (5
-Methyl-2-hydroxyphenyl) benzotriazole 0.3 part, tetrakis (2,2,6,6-tetramethyl-4-piperidyl) 1,2,3,4-butanetetracarboxylate 0.3
The parts were blended, and the mixture was extruded at 260 ° C. by an extruder with a vent to form pellets, and injection-molded at 260 ° C. to prepare predetermined test pieces, and the physical properties were measured.

 The measurement results of the examples are shown in Table 1 below.

Example 2 Instead of polymer A, polymer B obtained in experimental example (2)
The same procedure as in Example 1 was performed except that was used.

Comparative Example 1 Example 1 was repeated except that decabromodiphenyl ether was used instead of ethylene bis (tetrabromophthalimide) in Example 1.

 The measurement results of the comparative examples are shown in Table 1 below.

Example 3 45 parts of polymer B obtained in Experimental Example (2), Experimental Example (3)
40 parts of ABS resin, 15 parts of acrylonitrile styrene (AS) resin (AS-H manufactured by Denka Kagaku Co., Ltd.) and prolenbis (tetrabromophthalimide) 20 as flame retardant
Parts, 8 parts of antimony trioxide as a flame retardant aid, 0.5 parts of octadecyl 3- (3,5-ditertiarybutyl-4-hydroxyphenyl) -propionate as a stabilizer and an ultraviolet absorber, 2- (5-methyl-2) -Hydroxyphenyl) benzotriazole 0.3 part, tetrakis (2,2,6,6-
Tetramethyl-4-piperidyl) 1,2,3,4-butane tetracarboxylate 0.3 parts was blended and the mixture was mixed with 2 parts.
The mixture was extruded with a vented twin-screw extruder with a vent at 60 ° C., pelletized, and injection-molded at 250 ° C. to prepare predetermined test pieces, and the physical properties were measured.

Comparative Example 2 Example 3 was repeated except that octabromodiphenyl ether was used instead of propylene bis (tetrabromophthalimide).

(Effect of the invention) The present invention makes a resin composition having a imide group in a side chain flame retardant by using a specific halogenated organic compound as a flame retardant, and a resin composition excellent in heat resistance and weather resistance. It is a thing.

Claims (1)

(57) [Claims] 1. A polymer having an imide group in the side chain (A) 10 to
(C) 5 to 40 parts by weight of a halogenated organic compound represented by the following general formula (I) with respect to 100 parts by weight of a thermoplastic resin composition comprising 100% by weight and (B) a thermoplastic resin of 0 to 90% by weight. , (D) 1 to 20 parts by weight of an oxide of antimony and / or zirconium, which is a flame-retardant resin composition. (However, R in the formula represents a substituted or unsubstituted hydrocarbon having 1 to 10 carbon atoms, and X represents chlorine or bromine.)