JPH0543747B2 - - Google Patents

Description

[Detailed description of the invention]

(Industrial Application Field) The present invention relates to a flame-retardant resin composition that is flame-retardant and has excellent heat resistance. (Prior art) Generally, styrene resins are used in many fields such as home appliances, automobile parts, buildings, interior decoration, and various other molded products due to their excellent physical properties. It has to be limited. In recent years, due to the need for fire safety, flame retardant regulations such as the U.S. UL (Underwriters Laboratory) standards, especially for home appliances, have become increasingly strict, and as a result, the demand for styrene resins with flame retardant properties has increased. ing. By the way, one way to obtain flame retardancy is to blend a relatively low molecular weight organic flame retardant containing a large amount of halogen, a halogen-containing polymer compound such as vinyl chloride resin, and an inorganic compound such as antimony trioxide. is common. However, in order to make the resin highly flame retardant by adding these flame retardants, a large amount is required, and the final resin composition has a high degree of mechanical strength, rigidity,
Problems arise in that the physical properties of the resin composition deteriorate, such as marked deterioration in moldability and thermal stability. (Problems to be Solved by the Invention) As a result of repeated research in order to develop a resin composition with better flame retardancy, the present inventor discovered that a conventionally used flame retardant containing an imide group in the side chain. By adding ferrocene to a copolymer composition, the synergistic effect of the flame retardant and ferrocene results in excellent flame retardancy, and the amount of flame retardant used can be significantly reduced, resulting in extremely low deterioration of physical properties. We succeeded in finding a flame-retardant resin composition with low heat resistance. (Means for solving the problems) The present invention provides (A) a polymer 10 having an imide group in its side chain.
(C) 5 to 40 parts by weight of a halogen-containing organic compound and (D) antimony and/or zirconium per 100 parts by weight of a thermoplastic resin composition consisting of ~100% by weight and (B) 0 to 90% by weight of a thermoplastic resin. This is a flame-retardant resin composition characterized by containing 1 to 20 parts by weight of oxide of (E) and 0.1 to 10 parts by weight of ferrocene (E). (Action) (A) Component will be explained. In the present invention, as a polymer having an imide group in a side chain, (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; (ii) An aromatic vinyl monomer, an unsaturated dicarboxylic acid anhydride, and a vinyl monomer copolymerizable with these are polymerized in the presence or absence of a rubbery polymer. A polymer obtained by imidizing a copolymer, (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, (iv) a rubbery polymer. 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 polymer, (v) in the presence of a rubbery polymer or a polymer obtained by polymerizing an aromatic vinyl monomer, maleimide and/or N-substituted maleimide in the absence of the polymer, (vi) an aromatic vinyl monomer in the presence or absence of a rubbery polymer,
Examples include polymers obtained by polymerizing maleimide and/or N-substituted maleimide and vinyl monomers copolymerizable with these. Examples of aromatic vinyl monomers include styrene monomers such as styrene, α-methylstyrene, vinyltoluene, and chlorostyrene, and substituted monomers thereof, among which styrene and α-methylstyrene monomers Particularly preferred is the body. As the unsaturated dicarboxylic anhydride, for example, maleic anhydride, chloromaleic anhydride, itaconic anhydride, phenylmaleic anhydride, etc. can be used, and maleic anhydride is particularly preferred. Vinyl monomers that can be copolymerized with these include vinyl cyanide monomers such as acrylonitrile, methacrylonitrile, and α-chloroacrylonitrile; methyl acrylate, ethyl acrylate, butyl acrylate, etc. Acrylic acid ester monomers; Methacrylic acid ester monomers such as methyl methacrylic acid ester and ethyl methacrylic acid ester; Vinyl carboxylic acid monomers such as acrylic acid and methacrylic acid; Other acrylic acid amide, methacrylic acid amide, acenaphthylene, and Among them, monomers such as acrylonitrile, acrylic esters, methacrylic esters, acrylic acid, and methacrylic acid are preferred. Examples of the N-substituted maleimide include N-methylmaleimide, N-butylmaleimide, N-arylmaleimide (aryl group such as phenyl,
4-buphenyl, 1-naphthyl, 2,6-diethylphenyl, 2,3- and 4-chlorophenyl,
4-bromophenyl and other mono- and dihalophenyl isomers, 2,4,6-trichlorophenyl, 2,4,6-tribromophenyl, 4-n-
Butylphenyl, 4-benzylphenyl, 2-,
Examples include 3- and 4-methoxyphenyl. )
etc. can be mentioned. In the polymers (i) to (iv) having an imide group in the side chain given as an example of component (A) in the present invention, methylamine, ethylamine, n-propylamine, Examples include alkyl amines such as iso-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 the imidization reaction is carried out in a solution state or in a suspended state in a non-aqueous medium, it is preferable to use an ordinary reaction vessel such as an autoclave, but when it is carried out in a bulk molten state, an extruder equipped with a devolatilization device is used. May be used. The reaction temperature of imidization is about 80-350℃
It is ℃. Solvents for imidization in a solution state include acetone, methyl ethyl ketone, methyl isobutyl ketone, acetophenone, tetrahydrofuran, dimethylformamide, etc. Among these, methyl ethyl ketone and methyl isobutyl ketone are preferred. When imidizing in a suspended state in a non-aqueous medium, the non-aqueous medium includes heptane, hexane, pentane, octane, 2-methylpentane,
There are aliphatic hydrocarbons such as cyclopentane and cyclohexane. Next, component (B) will be explained. Examples of thermoplastic resins to be added to the polymer (A) having an imide group in the side chain as exemplified in (i) to (vi) above include acrylonitrile-butadiene-styrene and/or
or α-methylstyrene copolymer, methyl methacrylate-butadiene-styrene copolymer, acrylonitrile-ethylene and/or propylene-
Styrene copolymers, acrylonitrile-styrene and/or α-methylstyrene copolymers, rubber-modified styrene polymers, styrene-butadiene block copolymers, aromatic polycarbonates, aromatic polyesters, polyphenylene oxides, and styrene-modified polyphenylene oxides. Examples include thermoplastic resins containing one or more polymers selected from nylene oxide. Next, component (C) will be explained. The halogen-containing organic compound used in the present invention acts as a flame retardant, and includes aromatic compounds, aliphatic compounds, and alicyclic compounds that have halogen atoms such as bromine, chlorine, and fluorine in their molecular structures. It is an organic compound that has a flame retardant effect. Specifically, aromatic halogen compounds include hexabromobenzene, pentabromotoluene, biphenyl bromide, triphenyl chloride, tetrachlorophthalic acid, tetrabromo phthalic anhydride, tribromophenol, polydibromophenylene oxide, and tribromophenol. enyl, tetrabromobisphenol A, decabromodiphenyl ether, octabromodiphenyl ether, pentabromophenol; aliphatic halogen compounds include chlorinated paraffin, chlorinated polyethylene, tetrabromoethane, tetrabromobutane, tris( dibromopropyl) phosphate, tris(chlorobromopropyl)phosphate; examples of alicyclic halogen compounds include monoclopentabromocyclohexane, hexabromocyclododecane, perchloropentacyclodecane, perchlorocyclopentadiene, and the like. Component (D) includes antimony trioxide, antimony tetroxide, antimony pentoxide, zirconium dioxide, etc., and one or more of these may be used. In the composition of the present invention, the blending ratio of component (A), a polymer having an imide group in its side chain, and component (B), a thermoplastic resin, is (A) 10 to 100% by weight and (B) 0 to 100% by weight. It is 90% by weight. On the other hand, the amount of the halogen-containing organic compound that is component (C) is usually 5 to 40 parts by weight, preferably 7 to 40 parts by weight, per 100 parts by weight of the thermoplastic resin composition consisting of components (A) and (B). It is 30 parts by weight. If it is less than 5 parts by weight, the resulting composition will have insufficient flame retardancy.
If the amount is more than 1 part by weight, disadvantages such as deterioration of the physical properties of the composition and increase in corrosivity occur, which is not preferable. Also, the amount of antimony and/or zirconium oxide added as component (D) is 100% of the thermoplastic resin composition.
1 to 20 parts by weight, preferably 2 to 10 parts by weight
Parts by weight. If it is less than 1 part by weight, the flame retardance will be insufficient, and if it exceeds 20 parts by weight, the physical properties will deteriorate undesirably. The amount of ferrocene, component (E), is 0.1 to 10 parts by weight, preferably 0.2 to 5 parts by weight, based on 100 parts by weight of the thermoplastic resin composition. If it is less than 0.1 part by weight, the synergistic effect on increasing flame retardance will be small, and if it is more than 10 parts by weight, the resin will be colored and its physical properties will deteriorate, which is not preferable. Other phosphate esters such as triphenyl phosphate, tricresyl phosphate, phosphoric acid (trisisopropylphenyl), tributyl phosphate, etc., as necessary;
Added reinforcing materials such as organic fibers, glass fibers, and carbon fibers, fillers such as calcium carbonate, talc, clay, and aluminum hydroxide, heat stabilizers, ultraviolet absorbers, plasticizers, lubricants, colorants, blowing agents, etc. can do. The resin composition of the present invention includes predetermined components by roll milling,
It can be obtained by mixing by a conventional method such as a Banbury mixer, kneader, Henschel mixer, or extruder. (Example) The flammability in Examples and Comparative Examples was measured by a method based on Subdivision No. 94 established by Underwriters Laboratory in the United States. Parts and percentages are by weight. Experimental example (1) Production of a polymer 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 was placed in an autoclave equipped with a stirrer.
100 parts of methyl isobutyl ketone, 50 parts of methyl isobutyl ketone, and 24 parts of polybutadiene cut into small pieces were charged, and after purging the system with nitrogen gas, the mixture was stirred at room temperature all day and night to dissolve the rubber. After raising the temperature to 83° C., a solution of 67 parts of maleic anhydride, 0.2 parts of benzoyl peroxide, and 0.2 parts of azobisisobutyronitrile dissolved in 400 parts of methyl isobutyl ketone was added over 8 hours. After addition, the mixture was kept at 83°C for an additional 3 hours. A portion of the viscous reaction solution was sampled and the amount of unreacted monomer was determined by gas chromatography. As a result, the polymerization rate was 98%. The copolymer solution obtained here contains an equivalent amount of aniline to maleic anhydride.
Add 63.6 parts and 2 parts of triethylamine and heat at 140°C.
Allowed time to react. The imidized polymer obtained by degassing is referred to as Polymer A. Experimental example (2) Production of a polymer by imidizing a copolymer obtained by polymerizing aromatic vinyl, unsaturated carboxylic acid, and a vinyl monomer copolymerizable with these in the presence of a rubbery polymer Experimental example ( Styrene instead of 100 parts of styrene in 1)
An imidized polymer was obtained by carrying out exactly the same operation as in Experimental Example (1) except that 100 parts of acrylonitrile and 17 parts of acrylonitrile were used, 67 parts of maleic anhydride was changed to 50 parts, and 63.6 parts of aniline was changed to 47.4 parts. This will be referred to as Polymer B. The polymerization rate at this time was 95%. Experimental example (3) Production of a polymer by imidizing a copolymer obtained by polymerizing an aromatic vinyl monomer and an unsaturated dicarboxylic acid anhydride in the absence of a rubbery polymer. An imidized polymer was obtained by carrying out exactly the same operation as in Experimental Example (1) except that azobisisobutyronitrile was not used. This will be referred to as Polymer C. Experimental Example (4) Production of a polymer consisting of an aromatic vinyl monomer, an N-substituted maleimide, and a vinyl monomer copolymerizable with these. In an autoclave equipped with a stirrer, 60 parts of α-methylstyrene and N- 15 parts of phenylmaleimide, 10 parts of acrylonitrile, 12.5 parts of a 20% aqueous solution of sodium dodecylbenzenesulfonate, 0.05 parts of potassium chloride
1 part, 0.4 parts of t-dodecylmercaptan, and 210 parts of water, and the inside of the system was purged with nitrogen gas. Temperature 70℃
After raising the temperature to 10ml of 1% potassium persulfate aqueous solution
was added to start polymerization. Immediately after the start of the polymerization, 15 parts of acrylonitrile was added to the polymerization system over 6 hours. After addition, add 10ml of 1% potassium persulfate aqueous solution.
and continued polymerization for an additional 4 hours. As a result of sampling a portion of the polymerization solution and quantifying the unreacted monomer by gas chromatography, the polymerization rate was
It was 97%. The polymer emulsion thus obtained was coagulated with calcium chloride, dehydrated and dried to obtain a white powdery polymer. This will be referred to as Polymer D. Experimental example (5) Production of acrylonitrile-butadiene-styrene copolymer 80 parts of polybutadiene latex (solid content 50%,
Average particle size 0.35μ, gel content 90%), 1 part sodium stearate, 0.1 part sodium formaldehyde sulfoxylate, 0.03 part tetrasodium ethylenediamine tetraacetate acid, ferrous sulfate
0.003 parts and 200 parts of water were heated to 65°C, and to this was added 60 parts of a monomer mixture consisting of 30% acrylonitrile and 70% styrene, 0.3 parts of t-dodecylmercaptan,
0.2 part of kyumene hydroperoxide was continuously added over 4 hours, and after the addition was completed, polymerization was further carried out at 65°C for 2 hours. The polymerization rate was 96%. 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 60 parts of the polymer A obtained in Experimental Example (1), 40 parts of ABS resin obtained in Experimental Example (5), 12 parts of decabromodiphenyl ether as a flame retardant, and antimony trioxide as a flame retardant aid. 6 parts of ferrocene and 1 part of ferrocene were blended, and this mixture was extruded into pellets at 260°C using a vented extruder, and then injection molded at 260°C to prepare specified test pieces and their physical properties were measured. The measurement results of the Examples are shown in Table 1 below. Examples 2 to 4 The same procedure as in Example 1 was conducted except that polymers B to D obtained in Experimental Examples (2) to (4) were used instead of polymer A. Comparative Example 1 The same procedure as in Example 1 was carried out except that decabromodiphenyl ether, Sb ₂ O ₃ and ferrocene were not used in Example 1. The measurement results of the comparative example are shown in Table 2 below. Comparative Example 2 The same procedure as in Example 1 was carried out except that ferrocene was not used in Example 1. Examples 5-6 Example 1 except that the amounts of decabromodiphenyl ether, Sb ₂ O ₃ and ferrocene were changed.
The same procedure as in Example 1 was carried out. Examples 7-8 Example 1 except that polydibromophenyl oxide and hexabromobenzene were used instead of decabromodiphenyl ether in Example 1.
I did the same thing. Example 9 The same procedure as in Example 1 was conducted except that Sb ₂ O ₄ was used instead of Sb ₂ O ₃ in Example 1. Comparative Example 3 The same procedure as in Example 1 was conducted except that ferrocene was not used and the amounts of decabromodiphenyl ether and Sb ₂ O ₃ were changed so that the flammability was VO. Example 10 The same procedure as in Example 1 was carried out except that 100 parts of polymer A, 12 parts of decabromodiphenyl ether, 6 parts of Sb ₂ O ₃ and 1 part of ferrocene were blended. Examples 11-12 Decabromodif was added to a thermoplastic resin containing Polymer A, the ABS resin obtained in Experimental Example (5), an acrylonitrile-styrene copolymer (AS), and a rubber-modified styrene polymer (HIPS), respectively. A composition was prepared by mixing enyl ether, Sb ₂ O ₃ and ferrocene. The physical properties of each are shown in Table 1. Comparative Example 4 The same procedure as in Example 1 was carried out, except that the styrene-maleic anhydride copolymer obtained in Experimental Example (1) was used without imidization, and ferrocene was not used. Comparative Example 5 The same procedure as Comparative Example 5 was carried out except that ferrocene was mixed in Comparative Example 4.

【table】

[Table] The physical properties shown in the table were measured using the following methods. (1) Softening temperature: Load 5Kg ASTM D
-1525 (2) Izod impact strength: Notched ASTM D-256
Compliant with (3) Flammability: Compliant with UL Standard No. 94 (Sample thickness:
1/16'') (Effect of the invention) The present invention uses a flame retardant and ferrocene together in a resin composition having an imide group in the side chain, thereby improving flame retardance due to a synergistic effect. It is a flame-retardant resin composition that has excellent moldability and moldability, and has almost no deterioration in mechanical strength, rigidity, and thermal stability.

Claims (1)

[Claims] 1 (C) halogen-containing organic compound based on 100 parts by weight of a thermoplastic resin composition consisting of (A) 10 to 100% by weight of a polymer having an imide group in its side chain and (B) 0 to 90% by weight of a thermoplastic resin. 5 to 40 parts by weight and (D) 1 to 20 parts by weight of antimony and/or zirconium oxide;
(E) A flame-retardant resin composition comprising 0.1 to 10 parts by weight of ferrocene.