JPS60139744A - Flame-retarding resin composition - Google Patents

Abstract

PURPOSE:A flame-retarding resin composition of excellent heat resistance, prepared by mixing a specified thermoplastic resin composition with a halogen- containing organic compound and Sb and/or Zr oxides. CONSTITUTION:A polymer having an imide group as a side chain is obtained by reacting a copolymer prepared by copolymerizing an aromatic vinyl monomer (e.g., styrene) with an unsaturated dicarboxylic acid (e.g., maleic anhydide) and, optionally, a vinyl monomer copolymerizable therewith (e.g., acrylonitirle) with a prim. amine (e.g., aniline) at 80-350 deg.C. 100pts.wt. thermoplastic resin composition 10-100wt% above-produced polymer and 0-90wt% thermoplastic resin (e.g., polyacrylonitrile) is mixed with 5-40pts.wt. halogen-containing organic compound (e.g., hexabromobenzene) and 1-20pts.wt. Sb and/or Zr oxides.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a flame-retardant resin composition that is flame-retardant and has excellent heat resistance.

In general, styrene resins have limited applications in home appliances, automobile parts, buildings, and other fields due to their excellent physical properties. In recent years, due to the need for fire safety, U.S. UL+ Underwriters Laboratories, especially for home appliances, has been
) standards and other flame retardant standards are becoming increasingly strict, and as a result, the demand for styrenic resins with flame retardancy is increasing. 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, or an inorganic compound such as antimony trioxide. Common. However, although the desired flame retardancy can be achieved by adding these flame retardants, 1. It tends to have an adverse effect on other physical properties, and in particular, when a low molecular weight flame retardant is added in its entirety, problems such as a decrease in heat distortion temperature and a decrease in the physical properties of the resin composition occur.

As a result of repeated research in order to develop a resin composition with superior flame retardancy, the present inventor blended a conventionally used flame retardant into a copolymer composition containing all imide groups in the side chain. As a result, we succeeded in finding a highly heat-resistant flame-retardant resin composition that has excellent flame retardancy and exhibits extremely little deterioration in physical properties due to the addition of flame retardants. That is, the present invention comprises (10 to 100% by weight of a polymer having an imide group on the Al side chain) and (
Bl thermoplastic resin 0 to 90% by weight, based on 100 parts by weight of the thermoplastic resin composition, (0 halogen-containing organic compound 5 to 40 parts by weight and (Dl oxide of antimony and/or zirconium 1 to 20 parts by weight of a flame-retardant resin composition.

(A) Component will be explained.

In the present invention, as a polymer having an imide group in a side chain, 1) 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, 11) A copolymer obtained by polymerizing an aromatic vinyl monomer, an unsaturated dicarboxylic acid anhydride, and a vinyl monomer copolymerizable with these in the presence or absence of a rubbery polymer. Imidization of coalescence (1, polymer, l11)
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, acrylic acid and/or in the presence or absence of an IVI rubbery polymer polymer. A polymer obtained by imidizing a copolymer obtained by polymerizing a monomer copolymerizable with methacrylic acid, ■) an aromatic vinyl monomer, maleimide and/or in the presence or absence of a rubbery polymer. A polymer obtained by polymerizing N-substituted maleimide, an aromatic vinyl monomer in the presence or absence of a V++ rubbery polymer, maleimide and/or N-substituted maleimide, and a vinyl monomer copolymerizable with these. There are polymers made by polymerizing .

Examples of aromatic vinyl monomers include styrene monomers such as styrene, α-methylstyrene, vinyltoluene, and chlorostyrene, and substituted monomers thereof; among these, styrene and α-methylstyrene monomers is particularly preferred.

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; acrylic monomers such as methyl acrylate, ethyl acrylate, and butyl acrylate; Acid ester monomers: Methacrylic acid ester monomers such as methyl methacrylic acid ester and ethyl methacrylic acid ester Vinyl carboxylic acid monomers such as nialic acid and methacrylic acid: Others Acrylic acid amide, methacrylic acid amide, acenaphthylene and N- Among them, monomers such as acrylonitrile, acrylic esters, methacrylic esters, acrylic acid, and methacrylic acid are preferred.

Examples of N-substituted maleimide include N-methylmaleimide, N
-butylmaleimide, N-arylmaleimide (aryl groups include phenyl, 4-diphenyl 1.i-
Naphthyl, 2,6-dinitylphenyl, 2,3- and 4
-Chlorophenyl, 4-bromophenyl and other heptano and dihalophenyl isomers, 2゜4.6-dolichlorophenyl, 2.4.6-dolifuromophenyl, 4-n-butylphenyl, 4-benzylphenyl , 2-. 3- and 4-methoxyphenyl, etc.).

In the polymers 1) to +V+ having imide groups in the side chains given as examples of component (A) in the present invention, primary amines used in the imidization reaction include methylamine, ethylamine, n-propylamine, 1so-propyl Alkylamines such as amine, butylamine, pentylamine, and cyclohexylamine; aromatic amines such as aniline and naphthylamine; and halogen-substituted aromatic amines such as chloro- or bromine-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 for imidization is about 80 to 350°C. Examples of solvents for imidization in a solution state include acetone, methyl ethyl ketone, methyl isobutyl ketone, acetophenone, tetrahydrofuran, and dimethylformamide, and among these, methyl ethyl ketone and methyl isobutyl ketone are preferred. Non-aqueous media used for imidization in suspension in non-aqueous media include aliphatic hydrocarbons such as hebutane, hexane, pentane, octane, 2-methylpentane, cyclopentane, and cyclohexane.

Next, component (B) will be explained.

Polymers having imide groups in their side chains as exemplified in 1) to Vj) above (thermoplastic resins to be blended with Al include acrylonitrile-butadiene-styrene and/or α-methylstyrene copolymers, methyl methacrylate-butadiene) -Styrene co-electrolyte, acrylonitrile-ethylene and/or propylene-styrene copolymer, acrylonitrile-styrene and/or α-methylstyrene copolymer, rubber-modified styrene polymer, styrene-butadiene block copolymer, aromatic Examples include thermoplastic resins containing one or more polymers selected from group polycarbonates, aromatic polyesters, polyphenylene oxides, and styrene-modified polyphenylene oxides.

Next, the C1 component will be explained.

The halokene-containing organic compound used in the present invention acts as a flame retardant, and is a flame retardant for aromatic compounds, aliphatic compounds, alicyclic compounds, etc. that have halogen atoms such as bromine, chlorine, and fluorine in their molecular structure. It is an organic compound that has an effect. Specifically, aromatic halogen compounds include hexabromobenzene, pentabromotoluene, biphenyl bromide, triphenyl chloride, tetrachlorophthalic acid, tetrabromophthalic anhydride, tribromophenol, triflomophenyl, and tetrabromobenzene. and suphenol A
, decabromodiphenyl ether, pentabromophenol; aliphatic halogen compounds include chlorinated paraffin, chlorinated polyethylene, tetrabromoethane, tetrabromobutane, tris (dibromopropyl) post-7ate, tris (chlorobromopropyl) phosphate; Examples of the cyclic halogen compounds include monochloropentabromocyclohexane, hexabromocyclododecane, perchloropentacyclodecane, and perchlorocyclopentadiene.

Examples of the component (I) include 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 the polymer having an imide group in the side chain (A) and the thermoplastic resin (BI component) is (A) 10 to 100% by weight and (BI 0 to 9
It is 0% by weight. On the other hand, the amount of the halogen-containing organic compound (which is the Cl component) is usually 5 to 4 parts by weight (C) per 100 parts by weight of the thermoplastic resin composition consisting of the Al and (B) components.
0 parts by weight, preferably 7 to 30 parts by weight. If it is less than 5 parts by weight, the resulting composition will have insufficient flame retardancy, and if it is more than 40 parts by weight, problems such as deterioration of the physical properties of the composition and increase in corrosivity will occur, which is not preferred.

In addition, the amount of antimony and/or zirconium oxide added as the DIl component is 1 to 20 parts by weight, preferably 2 to 10 parts by weight, per 100 parts by weight of the thermoplastic resin composition. Triphenyl acid, tricresyl phosphate, phosphoric acid (tri-propylphenyl trichloride)
, phosphate esters such as tributyl phosphate, reinforcing agents such as organic fibers, glass fibers, and carbon fibers, fillers and heat stabilizers such as calcium carbonate, Merck, clay, and aluminum hydroxide, ultraviolet absorbers, plasticizers, A lubricant, a coloring agent, a blowing agent, etc. can be added.

The resin composition of the present invention can be obtained by mixing predetermined components using a conventional method such as a roll mill, Banbury mixer, Nigu, Henschel mixer, or extruder.

The present invention will be explained in more detail with reference to Examples below. The flammability in Examples and Comparative Examples was measured by a method based on Subject No. 94 established by Underwriters Laboratory of the United States.

Parts and parts are based on weight.

100 parts of styrene in an autoclave equipped with a stirrer,
50 parts of methyl isobutyl lactone and 24 parts of polybutadiene cut into small pieces were charged, and the system was purged with gold nitrogen gas, and then stirred at room temperature all day and night to dissolve the rubber. After raising the temperature to 83°C, 67 parts of maleic anhydride, 0.2 parts of benzoyl peroxide, and 0.2 parts of azobisisobutyronitrile were added.
A solution of 2 parts dissolved in 400 parts of methyl isobutyl lactone was added over 8 hours. After the addition, the temperature was maintained 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%.

To the copolymer solution obtained here were added 63.6 parts of aniline and 2 parts of triethylamine in equivalent amounts to maleic anhydride, and the mixture was reacted at 140° C. for 7 hours. The imidized polymer obtained by degassing is referred to as Polymer A.

1 part of styrene instead of 100 parts of styrene in Experimental Example (1)
00 parts and 10 parts of acrylonitrile, 67 parts of maleic anhydride was made 50 parts, and 63.6 parts of aniline was made 47.4 parts.
An imidized polymer was obtained by carrying out exactly the same operation as in Experimental Example (1), except that the same amount was used. This will be referred to as Polymer B. Note that the polymerization rate at this time was 95%.

An imidized polymer was obtained by carrying out exactly the same operation as in Experimental Example (1) except that the polybutadiene and azobisisobutyronitrile of Experimental Example (]) were not used. This is polymer C
shall be.

Preparation In an autoclave equipped with a stirrer, 60 parts of α-methylstyrene, 15 parts of N-7 engineered nylmaleimide, 10 parts of acrylonitrile, and 20 parts of sodium dodecylbenzenesulfonate were added.
% aqueous solution, 0.05 part of potassium chloride, 0.4 part of t-dodecylmercaptan, and 210 parts of water, and the inside of the system was purged with nitrogen gas. After raising the temperature to a total of 70°C, 10 mA'e of a 1% potassium persulfate aqueous solution was added to initiate polymerization. Immediately after the start of the polymerization, 15 parts of acrylonitrile was added to the polymerization system for 6 hours. After the addition was completed, 10 g of a 1% aqueous solution of potassium persulfate was added, and the polymerization was continued for an additional 4 hours. A portion of the polymerization solution was sampled and the amount of unreacted monomer was determined by gas chromatography. As a result, the polymerization rate was 97%. The polymer emulsion thus obtained was coagulated with calcium chloride, dehydrated and dried to obtain a white powdery polymer. This is called a polymer.

80 parts of polybutadiene latex (solid content 50 inches, average particle size 0.35μ, gel content 90 inches), 1 part sodium stearate, 0 indium formaldehyde sulfoxylate
．． 1 part of tetrasodium ethylene diamine tetraacetic acid 0.0' 3 parts, 0.003 parts of ferrous sulfate and 200 parts of water were heated to 65°C, and to this was added 30% acrylonitrile and 70% styrene. 60 parts of the monomer mixture, 0.3 parts of L-dodecyl mercaptan, and 0.2 parts of gymene hydrobarogide were continuously added over a period of 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 Experimental example (70 parts of polymer A obtained in ll, Experimental example (5)
30 parts of the ABS obtained above, 10 parts of decabromodiphenyl ether as a flame retardant, and 5 parts of antimony trioxide as a flame retardant were blended, and this mixture was extruded at 260°C using a vented extruder to form pellets, and then injection molded at 260°C. Specified test pieces were prepared and their physical properties were measured. Measurement results first
Shown in the table.

Examples 2 to 4 The same procedure as in Example 1 was conducted using the polymers BD obtained in Experimental Examples (2) to (4).

Comparative Example 1 The same procedure as in Example 1 was carried out except that decabromodiphenyl ether and antimony trioxide were not used in Example 1.

Comparative Example 2 The same procedure as in Example 1 was carried out except that the styrene-maleic anhydride copolymer obtained in Experimental Example (n) was not imidized.

Examples 5 to 7 The same procedures as in Example 1 were conducted except that the amounts of decabromodiphenyl ether and antimony trioxide were changed.

Examples 8 to 9 The same procedures as in Example were carried out except that etetrabromobisphenol A and hegisabromobenzene were used instead of decabromodiphenyl ether.

Example 10 Same as Example 1 except that antimony trioxide/dinoconium dioxide mixture (50/so, Fire DTA: Kigenso Kagaku Kogyo Co., Ltd.) was used instead of antimony trioxide. I did it.

Example 11 Polymer A] 00 parts, decabromodiphenyl ether 10
The same procedure as in Example 1 was carried out by adding 5 parts of antimony trioxide and 5 parts of antimony trioxide.

Examples 12-1 Polymer A and ABS obtained in Experimental Example (5), acrylonitrile-styrene copolymer (As), rubber-modified styrene polymer (HIPS), polycarbonate (PC)
A composition was prepared by mixing decabromodiphenyl ether and antimony trioxide with a thermoplastic resin composition containing each of the above. The physical properties of each were measured and shown in Table 1.

Claims (1)

[Claims] (10 to 100 polymers with imide groups in the Al side chain 4
(C) 5 to 40 parts by weight of a 0-logen-containing organic compound and (Di antimony and/or zirconium oxide A flame-retardant resin composition containing 1 to 20 parts by weight.