JPS6218573B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a heat-stabilized styrenic resin composition containing a bromine flame retardant. Styrenic resins have excellent physical properties and are therefore used in a variety of applications, such as electrical appliances, interior decorations, and building materials. However, since styrene resins are flammable, flame retardant regulations are imposed depending on their use. In order to make the styrene resin flame retardant, a flame retardant such as a polybrominated organic compound, ammotine trioxide, or a phosphorus compound is added. Among these, bromine-based flame retardants are particularly effective and are often used. However, bromine-based flame retardants are unstable at high temperatures and easily decompose, so styrene-based resins containing them become colored during processing. This phenomenon is particularly noticeable for styrene resins, which have high processing temperatures (over 200°C). Therefore, in order to prevent coloring, various metals (Li, Na, K,
A method of adding a maleate salt and/or a maleic acid monoester salt (Mg, Ca, Zn, Sr, Cd, Ba, Sn, Pb, Sb) (Japanese Patent Application Laid-open No. 54-66956) or dialkyltin maleate polymer. How to add (Tokukosho
No. 47-22090), but none of them have sufficient thermal stability at high temperatures, and there is a need for the development of an excellent stabilizer that can prevent this thermal deterioration. As a result of various studies, the present inventors have found that the combination of aluminum maleate and/or maleic acid monoester salt with dialkyl tin maleate polymer thermally stabilizes styrenic resins containing bromine flame retardants even during high-temperature processing. We have discovered that this is the case, and have arrived at the present invention. That is, in the present invention, when thermally stabilizing a flame-retardant resin consisting of 100 parts by weight of a styrene-based resin and 1 to 50 parts by weight of a bromine-based flame retardant, the styrene-based resin
For 100 parts by weight, (a) 0.1 to 5 parts by weight of dialkyltin maleate polymer and (b) 0.1 to 0.1 to 5 parts by weight of aluminum maleate or/and maleic acid monoester salt.
This is a stabilized flame-retardant styrenic resin composition characterized by adding 10 parts by weight. The dialkyltin malate polymer added in the present invention has the general formula (In the formula, R represents an alkyl group having 1 to 12 carbon atoms, and n represents an integer of 2 to 10.) Examples of the alkyl group include a methyl group, a butyl group, an octyl group, and a dodecyl group. Aluminum maleate salts and/or aluminum salts used in the present invention with dialkyltin malate polymer
Or as a maleic acid monoester salt, for example, aluminum maleate and its polymer,
Aluminum monobutyl maleate salt, monooctyl maleate salt, monoisooctyl maleate salt, molar 2-ethylhexyl maleate salt, monolauryl maleate salt, monostearyl maleate salt, monomyristyl maleate salt, monocetyl maleate salt , monobehenyl maleate, monooleyl maleate, monobenzyl maleate, monocyclohexyl maleate, monomethoxybutyl maleate, and the like. These metal salts can be added singly or in combination of two or more. In the present invention, examples of the bromine-based flame retardants used for flame retardant styrene resins include bromides of aliphatic hydrocarbons such as tetrabromoethane, tetrabromobutane, and tribromopropane, tribromotrichlorocyclohexane, and tetrabromodichloro Bromides of alicyclic hydrocarbons such as cyclohexane, pentabromocyclohexane, tetrabromocyclooctane, hexabromocyclododecane, bis(dibromocyclohexyl)-1,2-dibromoethane, hexabromobenzene, decabromodiphenyl, decabromodif enyl ether,
Hexabromodiphenyl ether, pentabromodiphenyl ether, pentabromotoluene, pentabromoethylbenzene, pentabromophenol, tribromophenol, 1,2-dibromopropyl tribromophenyl ether, tetrabromobisphenol A, tetrabromobisphenol S, tetrabromophthalic anhydride, 1,2-
Examples include aromatic bromides such as bis(pentabromophenoxy)ethane, bis(tribromophenoxy)ethane, and polydibromophenylene oxide, and carbonate oligomers of tetrabromobisphenol A. Examples of the styrenic resin used in the present invention include polystyrene, methylstyrene mainly composed of styrene, copolymers with divinylbenzene, butadiene, and acrylonitrile, acrylonitrile-butadiene-styrene terpolymers, acrylonitrile-butadiene-methyl Examples include a styrene terpolymer, a copolymer of butadiene and styrene or acrylonitrile, and a mixture of a copolymer of styrene and acrylonitrile. With respect to 100 parts by weight of the styrene resin, the amount of dialkyltin maleate polymer added is 0.1 to 5 parts by weight, and the amount of aluminum maleate or/and maleic acid monoester salt is 0.1 to 10 parts by weight. be. If the amount is less than the lower limit, thermal stabilization will be insufficient, and if the amount is more than the upper limit, it will be uneconomical. The composition of the present invention may optionally contain an antioxidant,
UV absorbers, boric acid, boric acid esters, epoxy compounds, flame retardants other than brominated organic compounds (e.g. phosphorus compounds, ammothine trioxide, borates,
Aluminum hydroxide, oxygen-containing compounds, etc.), smoke removers (smokeless agents), pigments, fillers, lubricants, etc. can be added. According to the present invention, a styrenic resin containing a bromine flame retardant can be highly thermally stabilized, and the resin can be easily processed at high temperatures. Such effects cannot be achieved with maleates or maleic acid monoester salts of other metals. Next, the present invention will be explained with reference to examples, where parts in the examples indicate parts by weight. Example 1 Acrylonitrile-butadiene-styrene resin (Saicolaku Ex211, manufactured by Ube Cycon Co., Ltd.) 100
parts, 10 parts of tetrabromobisphenol A, 5 parts of antimony trioxide, dioctyltin malate polymer
0.5 part and 0.5 part of maleate or maleic acid monoester salt of the metals listed in Table 1 below were added, and 150
℃ for 4 minutes using a kneading roll to prepare a sheet with a thickness of 0.5 mm. This sheet was subjected to a thermal stability test in a gear oven maintained at 220°C. The numbers in the table represent the following evaluations. 1: white, 2: light yellow, 3: yellow, 4: light brown, 5: brown, 6: dark brown The results are shown in Table 1.

[Table] Example 2 Styrene resin (Styron 666, manufactured by Asahi Kasei Corporation)
100 parts of hexabromocyclododecane, 1 part of titanium oxide, 1 part of dibutyltin maleate polymer, and 1 part of maleate or maleic acid monoester salt of the metal listed in Table 2 below were added, and the mixture was heated at 135°C for 3 minutes. The mixture was mixed using a kneading roll to form a sheet with a thickness of 0.5 mm. This sheet was subjected to a thermal stability test in a gear oven maintained at 220°C. The numbers in the table represent the following evaluations. 1: White, 2: Light yellow, 3: Yellow, 4: Light brown, 5: Light blackish brown, 6: Blackish brown The results are shown in Table 2.

[Table] Example 3 Acrylonitrile-butadiene-styrene resin (Toughflex 450, manufactured by Mitsubishi Monsanto) 100
parts, antimony trioxide 8 parts, bromine-based flame retardant 15 parts shown in Table 3 below, dialkyltin malate polymer
A sheet was prepared in the same manner as in Example 1 with the addition of 0.3 parts and 0.8 parts of aluminum maleate, and a thermal stability test was conducted. The evaluation of thermal stability test in the table has the same meaning as in Example 1, and the numbers for flame retardant and stabilizer represent parts. The results are shown in Table 3.

【table】

Claims (1)

[Claims] 1 When thermally stabilizing a flame retardant resin consisting of 100 parts by weight of styrene resin and 1 to 50 parts by weight of bromine flame retardant, for 100 parts by weight of styrene resin,
Stabilized flame retardancy characterized by the addition of (a) 0.1 to 5 parts by weight of a dialkyltin maleate polymer and (b) 0.1 to 10 parts by weight of aluminum maleate or/and maleic acid monoester salt Styrenic resin composition.