JPS60108466A - Sulfide-resistant and flame-retardant resin composition - Google Patents

Abstract

PURPOSE:To provide the titled composition having excellent sulfide-resistance and flame-retardance, by using an antimony oxide obtained by oxidizing antimony trioxide and treating the product with an alkali. CONSTITUTION:An antimony oxide obtained by oxidizing antimony trioxide (in an aqueous solution of hydrogen peroxide) and treating with an alkali (in an aqueous solution of an alkali metal or alkaline earth metal hydroxide or oxide), is added to a resin. The oxidation treatment is carried out by using 0.8-0.3mol of 33% hydrogen peroxide solution per 1mol of antimony trioxide at 40-80 deg.C for 30-60min, and the alkali treatment is performed by using 0.5-0.1mol of the alkaline compound per 1mol of antimony trioxide and immersing and thoroughly stirring antimony trioxide in the solution at 40-60 deg.C for 5-30min. The antimony trioxide is preferably finer than 350 mesh.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a resin composition in which a flame retardant is contained in a resin such as polyvinyl chloride or polyethylene, especially antimony oxide obtained by oxidizing antimony trioxide and then treating it with an alkali. It relates to a resin composition that is imparted with sulfidation resistance and flame retardancy by containing the above.

Flame retardants have been widely used to make resin molded products flame-retardant for architectural interior materials, automobile interior materials, home appliances, and computer-related products, as well as to make various textiles, mainly general clothing, flame-retardant. It is used.

These flame retardants are divided into inorganic and organic types, and those belonging to the organic type include antimony trioxide, norcon oxide, metaboric acid/kuriram, zinc borate, charcoal/dry calcium, magnesium carbonate, and calcium hydroxide. , magnesium hydroxide, aluminum hydroxide, aluminum oxide, etc. are known, and phosphate esters such as tricresyl phosphate are known as those belonging to organic systems.

Among the flame retardants mentioned above, antimony trioxide is widely used to provide excellent flame retardant effects to resin molded products and resin compositions such as Toi. If molded resin products or fibers are used in an atmosphere containing sulfur-containing compounds such as hydrogen sulfide, antimony sulfide is produced and the product becomes yellow. Therefore, when used in such a sulfide-contaminated atmosphere, carbonates of metals such as calcium, magnesium, and aluminum, which are resistant to sulfide contamination, and water
Although beak compounds and lactic compounds have been used as flame retardants, these compounds have a lower flame retardant effect than antimony trioxide and do not provide sufficient effects.

As a result of various studies in order to solve the disadvantages of antimony trioxide, the inventor of the present invention discovered that antimony trioxide is oxidized and then treated with alkali. When blended with resins and fibers, it not only provides excellent flame retardant effects, but also exhibits remarkable resistance to sulfur contamination. Even if products such as resin molded products, fibers, and molded products containing sulfide are used in a sulfide-contaminated atmosphere, the product's height ratio is guaranteed to be 1.
(We have discovered that this can be prevented, and have come up with the present invention.)

Rejected, the present invention will be described in more detail.

The resin composition of the present invention contains antimony oxide obtained by oxidizing antimony trioxide and then treating it with an alkali. This resin composition has improved twist resistance and sulfurization resistance.

In this case, the antimony oxide of the present invention is produced by first oxidizing antimony trioxide and then treating it with alkali as described above. Inorganic peroxides such as hydrogen peroxide, peroxide, IJium, 9lium peroxide, IJium, and organic peroxides such as peracetic acid and benzoyl peroxide are used. Among these, hydrogen peroxide is particularly preferably used. In addition,
These peroxides can usually be used as an aqueous solution. Further, depending on the case, antimony trioxide may be oxidized using air or oxygen gas.

When carrying out the oxidation treatment of antimony trioxide using peroxide, the treatment method is usually done by immersing it in an aqueous solution, and the amount used varies depending on the type of peroxide.
Although not particularly limited, when hydrogen peroxide is used, the amount is 2 to 0.1 mol, particularly 0.8 to 0.3 mol, of a 935% aqueous hydrogen peroxide solution per 1 mol of antimony trioxide. It is preferable. Further, the treatment time is preferably 30 to 60 minutes, and the treatment temperature is 30 to 110°C, particularly 40 to 80°C.
0°C is preferred. Antimony trioxide particles are usually sufficiently stirred in an aqueous hydrogen peroxide solution to complete the oxidation treatment.

Here, as the antimony trioxide to be oxidized, a commercially available product can be used, and a fine particulate product having a particle size as fine as 100 meters, preferably as fine as 350 meters is preferably used.

The antimony trioxide thus oxidized is then treated with an alkali, and a method of immersing it in an alkaline solution is preferably employed as the alkali treatment method. Here, examples of the alkaline compound used for preparing the alkaline solution include oxides of alkali metals and alkaline earth metals, and (5) hydroxides, and specifically, lithium hydroxide, sodium hydroxide, etc. , potassium hydroxide, magnesium hydroxide, calcium hydroxide, barium hydroxide, strontium hydroxide, magnesium oxide, calcium oxide,
One or more types of barium oxide, strontium oxide, etc. are used.

In this case, the amount of alkaline compound used is 11.0 to 0.01 mol per 1 mol of anticeph trioxide, and the percentage is 0.5 to 0.01 mol.
0.1 mol is preferred. In the alkali treatment method, oxidized antimony trioxide particles are immersed in an alkaline aqueous solution and sufficiently stirred to complete the reaction. In this case, conditions are suitably employed in which the treatment time is 5 to 30 minutes and the treatment temperature is 40 to 60°C.

After antimony trioxide is subjected to oxidation treatment and alkali treatment, the obtained antimony oxide particles are filtered, dried, and pulverized to obtain the flame retardant of the present invention.

The resin composition of the present invention is one in which the antimony oxide obtained by the method described above is blended into the resin and/or surface treated. (6) polyvinylidene chloride, chlorinated polyethylene, chlorinated polypropylene, polyvinylidene fluoride, brominated polyethylene, chlorinated rubber, vinyl chloride-vinyl acetate copolymer,
Vinyl chloride-ethylene copolymer, vinyl chloride-propylene copolymer, vinyl chloride-styrene copolymer, vinyl chloride-isobutylene copolymer, vinyl chloride-vinylidene chloride copolymer, vinyl chloride-styrene-trimaleic anhydride Original copolymer, vinyl chloride-styrene-acrylonitrile copolymer, vinyl chloride-butadiene copolymer, vinyl chloride-isoprene copolymer, vinyl chloride-chlorinated propylene copolymer, vinyl chloride-vinylidene chloride-vinyl acetate ternary copolymers, vinyl chloride-acrylic ester copolymers, vinyl chloride-maleic ester copolymers, vinyl chloride-methacrylic ester copolymers, vinyl chloride-acrylonitrile copolymers, internally plasticized polyvinyl chloride, etc. Halon-containing synthetic resins, polyethylene, polyethylene-chlorinated polyethylene copolymers, polyzolopyrene, polybutene, α-olefin polymers such as poly-3-'methylbutene, ethylene-vinyl acetate copolymers, ethylene-
Polyolefins such as propylene copolymers and their copolymers, polystyrene, polyvinyl acetate, acrylic resins, copolymers of styrene and other monomers (e.g. maleic anhydride, butadiene, acrylonitrile, etc.),
Acrylonitrile-butadiene-styrene copolymer, acrylic ester-butadiene-styrene copolymer, methacrylic ester-butadiene-styrene copolymer,
Methacrylate resin such as polymethyl methacrylate, polyvinyl alcohol, polyvinyl formal, polyvinyl butyral, linear polyester, polyamide, polycarbonate, polyacetal, polyurethane, cellulose resin, or phenolic resin, urea resin, melamine resin, epoxy resin, unsaturated Examples include one or a blend of two resins such as polyester resin and silicone resin. Further, as a rubber, one or a blend of two or more of the following rubbers can be blended: rubber, natural rubber, isogrene rubber, butadiene rubber, acrylonitrile-butadiene copolymer rubber, and styrene-butadiene copolymer rubber.

The amount of antimony oxide used in the present invention varies depending on the type of resin, but is preferably 1 to 15 parts by weight, particularly 3 to 8 parts by weight, per 100 parts by weight of resin.

The resin composition of the present invention contains plasticizers such as dioctyl phthalate, dibutyl phthalate, dioctyl adipate, and tricresyl phosphate, fillers such as calcium carbonate, kaolin clay, talc, silica, and mica, lead,
Inorganic metal salts of heavy metals such as cadmium, zinc, and barium, higher fatty acid salts such as stearates, organometallic stabilizers such as heptads, cadmium yellow, chrome yellow, phthalocyanine blue, titanium oxide, etc. coloring agents, benzenesulfohydrazine-based, azonitrile compound-based, diazoacetamide-based, nitroso compound-based foaming agents, etc., ultraviolet absorbers such as 2-hydroxybenzophenone, to'X 2.6-di-tert-butyl-para-cresol , antioxidants such as 4-methyl-6-tert-butylphenol, quaternary ammonium salts, betaine type amphoteric surfactants, antistatic agents such as glycerin fatty acid esters, lubricants, casitas, fungicides, preservatives, etc. It may also contain known additives.

The resin composition of the present invention is used as a desired product, such as a resin molded product, a fiber, or a molded product thereof.The resin composition of the present invention is used after antimony trioxide is oxidized and then treated with an alkali. Because it contains antimony oxide obtained by It is something.

EXAMPLES Hereinafter, the present invention will be specifically explained with reference to Examples, but the present invention is not limited to these Examples.

〔Example〕

Antimony trioxide treatment method Weigh out 100 g of water and 100 g of antimony trioxide (10) into a beaker to make a slurry. Next, hydrogen peroxide solution (
After stirring and heating to 10 o'C, various hydroxides were added and stirring was continued for 30 minutes. After the reaction is completed, it is dried and pulverized to obtain the antimony oxide of the present invention. The amounts of hydrogen peroxide and various hydroxides are shown in Table 1.

Table 1 Next, the following sulfidation resistance test (sulfide contamination test) and flame retardant test were conducted using the antimony oxide described above.

[Sulfide contamination test 1] Take 10 mg of a saturated hydrogen sulfide aqueous solution in a test tube, add g to the anti-9 volumes obtained in No. 1 Omoteya 1 to A7, stir, and visually judge the degree of discoloration. did.

[Sulfur contamination test 2] A resin composition having the ingredients shown in Table 2 was kneaded for 10 minutes with a 6-inch roll at 150°C, then heated and foamed in an oven at 210°C for 90 minutes, and then shaped into a sheet and kneaded. A test piece with a sheet size of 12.76 n×1.27 crn was prepared. These test pieces were placed in saturated hydrogen sulfide gas at room temperature for 3 hours.
After being left for 0 minutes, the degree of discoloration of the test piece was visually determined.

Table 2 Vinyl chloride resin 100 parts by weight Dioctyl phthalate 6o Calcium carbonate 4o Titanium oxide 10// Azoshika? Namide 4 [Sulfur contamination test 3] A composition consisting of the ingredients shown in Table 3 was kneaded for 5 minutes with a 6-inch roll at 150°C j) 12.7crnX1
．． Test pieces of 27 m in length were prepared, and after leaving these test pieces in saturated hydrogen sulfide gas at room temperature for 30 minutes, the degree of discoloration of the test pieces was visually determined.

(13) Table 3 Polyethylene 100 parts by weight Chlorinated polyethylene 15 Tecafrom diphenyl ether 20 Dibutyltin malate 1 Stearic acid 1 The above results are shown in Table 4. The criteria for judgment are as follows.

Judgment criteria ◎: Very good ○: Good △: Slightly good ×: Poor (14) Table 4 From the results in Table 4, antimony oxide obtained by treatment with hydrogen peroxide solution and then treatment with alkaline water bath solution. It has been found that resins containing the following are extremely excellent in sulfidation resistance.

[Flame retardancy test]

The flame release effect of antimony trioxide treated with oxidation and alkaline aqueous solution on resin was tested.

In this case, the test method described in UL-94 [Flammation test for grading materials] of Underwriters Uga Radleys Inc. was adopted, and the test piece was sulfide contamination test 2. 5 test pieces each prepared
A total of 70 sheets (5 x 7 = 35 sheets) and 5 test pieces each prepared in sulfur contamination test 3, 35 sheets in total, were used.

As a result, all test pieces were rated UL-94V-0, and therefore, antimony trioxide treated with oxidation treatment and alkaline aqueous solution and untreated antimony trioxide have good flame resistance, and both of them have good flame resistance. It was found that there was no difference in flame retardant effect.

Applicant: Nissan Chemical Industries, Ltd. Representative Patent Attorney Takashi Kojima

Claims (1)

[Scope of Claims] l. A sulfide-resistant flame-retardant resin composition comprising an antimony oxide obtained by oxidizing antimony trioxide and treating it with an alkali. 2. The sulfide-resistant flame-retardant resin composition according to claim 1, wherein the oxidation treatment of antimony trioxide is carried out in an aqueous hydrogen peroxide solution. 3. The sulfide-resistant flame-retardant resin composition according to claim 1 or 2, wherein the alkali treatment is performed with an aqueous solution of an alkali metal or alkaline earth metal hydroxide or oxide.