JPS638977B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to flame retardants for organic polymeric substances. The production and use of organic polymeric substances has made remarkable progress, and they are now used in large quantities in a wide variety of applications, including household and industrial electrical equipment parts, textile products, daily necessities, interior decorations, building materials, and structures. . However, organic polymeric materials are composed of hydrocarbons and have ignition and combustion problems in many application areas, which limits their use. Therefore, in order to solve the problems of ignition and combustion of these organic polymer materials, flame retardants are usually used. These flame retardants include halogen-containing compounds,
Phosphorus-containing compounds, nitrogen-containing compounds, etc. are used,
In many cases, flame retardant aids such as antimony trioxide are used in combination. When these flame retardants are used in organic polymeric substances, (a) they have poor compatibility with the organic polymeric substances, and homogeneous mixing cannot be achieved and the latent flame retardant ability is not exhibited; adversely affects the physical properties of (b) The flame retardant has a high migration property in organic polymer substances. (c) It adversely affects the mechanical properties of processed products and during the molding process of organic polymeric substances. (d) Interfering with the effects of other additives present in organic polymeric substances, such as plasticizers, lubricants, antioxidants, colorants, stabilizers, ultraviolet absorbers, etc. There are many disadvantages such as: In order to overcome the above-mentioned drawbacks, flame retardants with high molecular weights such as low polymers or high polymers have been provided.
For example, JP-A-50-53435, JP-A-54-111546
Poly(halogenated phenylene oxide) is described in No. 54-163943. However, when poly(halogenated phenylene oxide) is used as an organic polymer material, depending on the type of organic polymer material, the organic polymer material may lack flame retardancy, have poor compatibility and heat resistance, or There are drawbacks such as adversely affecting the mechanical properties of the processed product and deteriorating the electrical properties during the molding process. The present inventor has conducted extensive research in order to improve the above-mentioned drawbacks, and as a result has come to provide the present invention. That is, it is a flame retardant for organic polymeric substances consisting of a compound represented by the following general formula. [However, in the formula, X ₁ to _{X 5} represent a halogen atom or a hydrogen atom, and at least one of X ₁ to _{X 5} represents a halogen atom. Y ₁ to _{Y 4} represent a halogen atom or a hydrogen atom, and at least one of Y ₁ to _{Y 4} represents a halogen atom. Z ₁ to _{Z 4} represent a halogen atom or a hydrogen atom, and at least one of Z ₁ to _{Z 4} represents a halogen atom. n represents an integer from 2 to 100. A is an alkyl group, a haloalkyl group, a hydroxyalkyl group, a hydroxyhaloalkyl group, a hydroxyalkyl (polyoxyalkylene) group, an alkenyl group, a haloalkenyl group, an aralkyl group, a haloaralkyl group, an alkylacyl group, a haloalkylacyl group, a benzoyl group, halobenzoyl group,
Represents an acryloyl group, a methacryloyl group, or an epoxyalkyl group. ] Flame retardants represented by the general formula of the present invention include a condensate of halogenated phenols and alkyl halides, haloalkyl halides, hydroxyalkyl halides, hydroxyhaloalkyl halides, alkenyl halides, haloalkenyl halides, aralkyl halides, haloaralkyl halides, one or more selected from the group consisting of alkyl acyl halide, haloalkyl acyl halide, benzoyl halide, halobenzoyl halide, acryloyl halide, methacrylloyl halide, alkylene oxide, and haloalkylene oxide in a solvent in the presence of caustic alkali or the like. Alternatively, compounds obtained by reacting without a solvent, or compounds obtained by halogenating the above-mentioned compounds with a halogen atom, if necessary, may be mentioned. Examples of condensates of these halogenated phenols include one or two kinds of halogenated phenols such as dibromophenol, tribromophenol, tetrabromophenol, pentabromophenol, dichlorophenol, trichlorophenol, tetrachlorophenol, and pentachlorophenol. Examples include those obtained by condensation polymerization of the above mixture in the presence of caustic alkali and Cu, Fe, etc. in a solvent or without a solvent. Next, alkyl halide, haloalkyl halide, hydroxyalkyl halide, hydroxyhaloalkyl halide, alkenyl halide, haloalkenyl halide, alkyl acyl halide,
Examples of haloalkyl acyl halides, benzoyl halides, halobenzoyl halides, acryloyl halides, methacryloyl halides, aralkyl halides, haloaralkyl halides, alkylene oxides, haloalkylene oxides, etc.
For example, compounds having 1 to 20 carbon atoms, such as propyl chloride, butyl chloride, dibromoethylene, (tetrabromomethyl)pentane, ethylene chlorohydrin, ethylene bromohydrin, propylene chlorohydrin, propylene bromhydrin, tribromopentyl Alcohol, allyl chloride, meta-allyl chloride, benzyl chloride, dibromobenzyl chloride, acetyl chloride, isobutyl chloride, chlorpropionyl chloride, benzoyl chloride, monobromobenzoyl chloride, acryloyl chloride, methacryloyl chloride, ethylene oxide, propylene oxide, butylene oxide, epichlorohydrin etc. Next, examples of organic polymeric substances to which the flame retardant represented by the general formula of the present invention can be used include polystyrene resin, polyethylene resin, polypropylene resin, ABS resin, acrylic resin, vinyl chloride resin, and polyphenylene resin. Examples include nylene oxide resins, polycarbonate resins, polyamide resins, saturated or unsaturated polyester resins, melamine resins, epoxy resins, phenolic resins, cellulose-based substances, and the like. The added amount of the flame retardant represented by the general formula of the present invention is:
It is optional and preferably 2 to 50% by weight based on the organic polymer material. The flame retardant represented by the general formula of the present invention can be added at any time such as during polymerization of the organic polymer substance, during molding, or during spinning. The flame retardant represented by the general formula of the present invention is added as is, dissolved in a solvent, or dispersed in water or oil and added in the form of an emulsion. In the present invention, in addition to the flame retardant represented by the general formula of the present invention, other flame retardants and flame retardant aids such as halogen-containing alkyl phosphates and phosphites, metal oxides, metal hydroxides,
Alkyl metal compounds, etc. can be used together, and other additives such as stabilizers, colorants, weathering agents, ultraviolet absorbers, matting agents, antistatic agents, extenders, etc. can also be used together. It is. When the flame retardant represented by the general formula of the present invention is used in an organic polymer material, it has excellent flame retardancy, compatibility, weather resistance, and heat resistance, and has very low migration in the organic polymer material. It exhibits excellent characteristics such as not adversely affecting the mechanical properties of processed products during molding of organic polymer materials, and also not degrading electrical properties. Therefore, the flame-retardant organic polymer material using the flame retardant represented by the general formula of the present invention can be used for resin molded products, films, foams, coating materials such as paints, fibrous materials, laminated materials, and other high-grade materials. It can be used for molecular materials, etc. Examples of the present invention are listed below. In the examples, "parts" and "%" are based on weight. Example 1 A flame retardant represented by the general formula of the present invention was synthesized by the method described above. They are shown in Table 1.

【table】

[Table] Example 2 5 parts of various flame retardants shown in Table 1 and 2 parts of antimony trioxide were added to 100 parts of HI polystyrene resin, and after kneading at 200°C for 6 minutes, a test piece was prepared and the flame retardance was evaluated. and weather resistance were measured. The results are shown in Table 2.

[Table] Example 3 Add 15 of the various flame retardants shown in Table 1 to 100 parts of ABS resin.
1 part and 5 parts of antimony trioxide were added, and the mixture was kneaded at 200°C for 6 minutes, and a test piece was prepared to measure flame retardancy. The results are shown in Table 3.

【table】

[Table] Example 4 10 parts of the various flame retardants shown in Table 1 and 3 parts of antimony trioxide were added to 100 parts of polyethylene resin, and after kneading at 170°C, a test piece was prepared.
Flame retardancy and migration properties were measured. The results are shown in Table 4.

[Table] Example 5 Add 5 parts of barium metasilicate and 9 parts of various flame retardants to 100 parts of polyethylene terephthalate, and add 260 parts of barium metasilicate and 9 parts of various flame retardants.
After kneading at °C, test pieces are made and flame retardant,
Migration properties, tensile strength and bending strength were measured. The results are shown in Table 5.

[Table] Example 6 10 parts of polycarbonate and 9 parts of various flame retardants were added to 90 parts of polyamide resin, and 2 parts of antimony trioxide were added. After kneading at 260°C, a test piece was prepared, and the flame retardance and tensile strength were determined. , bending strength and weather resistance were measured. The results are shown in Table 6.

[Table] Example 7 Commercially available phenolic resin varnish 100 with a solid content of 60%
10 parts of various flame retardants, 3 parts of antimony trioxide, and 30 parts of tricresyl phosphate were added to the mixture, and after mixing, it was impregnated into 0.25 mm thick cotton linter paper to a resin content of 45%, and dried. A resin-impregnated base material was obtained. Next, seven sheets of the resin-impregnated base material were laminated and heated at 160℃.
Pressing was carried out for 50 minutes at 80 kg/cm ² to obtain a laminate with a thickness of 1.6 mm. The flame retardancy, insulation, heat resistance, punching workability, interlayer adhesion, and surface finish of this laminate were measured. The results are shown in Table 7.

[Table] Example 8 40 parts of flame retardant, 10 parts of tricresyl phosphate,
Noigen ET-180 (nonionic surfactant: Daiichi Kogyo Seiyaku Co., Ltd. product name) 5 parts, trimethylolmelamine
20 parts, 2 parts ammonium phosphate and dilution water
Mix 110 parts, emulsify, and add to the resulting emulsion bath.
Test cotton was prepared by impregnating 127.0 g/m ² cotton, squeezing to 80% weight gain, drying at 80°C, and curing for 5 minutes at 140°C, after which flame retardancy and washing loss were measured. The results are shown in Table 8.

【table】

【table】

Claims (1)

[Claims] 1. A flame retardant for organic polymeric substances comprising a compound represented by the following general formula. [However, in the formula, X ₁ to _{X 5} represent a halogen atom or a hydrogen atom, and at least one of X ₁ to _{X 5} represents a halogen atom. Y ₁ to _{Y 4} represent a halogen atom or a hydrogen atom, and at least one of Y ₁ to _{Y 4} represents a halogen atom. Z ₁ to _{Z 4} represent a halogen atom or a hydrogen atom, and at least one of Z ₁ to _{Z 4} represents a halogen atom. n represents an integer from 2 to 100. A is an alkyl group, a haloalkyl group, a hydroxyalkyl group, a hydroxyhaloalkyl group, a hydroxyalkyl (polyoxyalkylene) group, an alkenyl group, a haloalkenyl group, an aralkyl group, a haloaralkyl group, an alkylacyl group, a haloalkylacyl group, a benzoyl group, halobenzoyl group,
Represents an acryloyl group, a methacryloyl group, or an epoxyalkyl group. ]