JPH0518344B2 - - Google Patents

Description

[Detailed description of the invention]

[Industrial Field of Application] The present invention relates to a one-pack stabilizer that provides excellent heat resistance to halogen-containing resins and has good storage stability. The halogen-containing resin stabilized with the one-pack stabilizer of the present invention is widely used as a variety of molded products by processing methods such as extrusion molding, calendar molding, injection molding, and blow molding. [Prior Art] Many types of stabilizers are known for stabilizing halogen-containing resins, but satisfactory resin molded products are rarely obtained by using one stabilizer alone, and in most cases, two types of stabilizers are used. By using the above stabilizers in combination, desired molded products can be obtained that take advantage of the characteristics of each. In particular, when a high degree of heat resistance is required, two or more liquid alkyltin mercaptide stabilizers are used. However, when two or more of these liquid stabilizers are mixed, cloudiness occurs over time during storage, which reduces the commercial value and affects the performance of the stabilizer, resulting in poor heat resistance to halogen-containing resins. . Therefore, a method has been proposed in which the storage stability and heat resistance of the resin are maintained by adding a small amount of glycol to the above stabilizer mixture (Japanese Patent Application Laid-open No. 59-2011).
-Refer to Publication No. 164352). [Problems to be solved by the invention] However, in the above method of adding glycol,
The heat-resistant coloring property for halogen-containing resins is unsatisfactory, the processability (lubricity) is poor, and there are problems with dynamic stability. It is desired to develop a stabilizer composition that imparts high heat resistance and processability to halogen-containing resins and has good storage stability. [Means for Solving the Problem] As a result of various studies, the present inventors have found that if a small amount of a specific polyoxyethylene ether compound or ester compound is added to two or more liquid alkyltin mercaptide stabilizers, We have discovered that it is possible to make a one-pack stabilizer without the above-mentioned drawbacks, and have arrived at the present invention. That is, in the present invention, the general formula [] or [] RO(CH ₂ CH ₂ O) _o H [] RCOO(CH ₂ CH ₂ O ) _o H [] (In the formula, R is an alkyl group having 7 to 22 carbon atoms,
alkenyl group or alkylaryl group, n is 2
This is a one-pack stabilizer for halogen-containing resins, characterized in that 0.01 to 5 parts by weight of a compound represented by (each representing an integer from 1 to 50,000) is added. Examples of the alkyltin mercaptide stabilizers used in the present invention include dimethyltin bis(2-ethylhexylthioglycolate), dimethyltinbis(isooctylthioglycolate), monomethyltin tris(2-ethylhexylthioglycolate), Monomethyltin tris(isooctylthioglycolate), dibutyltinbis(2-ethylhexylthioglycolate), dibutyltinbis(isooctylthioglycolate), dibutyltinbis(nonylthioglycolate), dibutyltinbis(dodecylthioglycolate) glycolate), dibutyltin bis(methoxybutyl thioglycolate), dibutyltin bis(2-ethylhexylmercaptopropionate), dibutyltin bis(isooctylmercaptopropionate), dibutyltin bis(nonylmercaptopropionate), Dibutyltin bis(dodecylmercaptopropionate), dibutyltin bis(methoxybutylmercaptopropionate), monobutyltin tris(2-ethylhexylthioglycolate), monobutyltin tris(isooctylthioglycolate), monobutyltin tris( Nonylthioglycolate), monobutyltin tris (dodecylthioglycolate), monobutyltin tris (methoxybutylthioglycolate), monobutyltin tris (2-ethylhexylmercaptopropionate), monobutyltin tris (isooctylmercaptopropionate) ), monobutyltin tris (nonylmercaptopropionate), monobutyltin tris (dodecylmercaptopropionate), monobutyltin tris (methoxybutylmercaptopropionate), dioctyltin bis(2
-ethylhexylthioglycolate), dioctyltin bis(isooctylthioglycolate), dioctyltin bis(2-ethylhexylmercaptopropionate), dioctyltin bis(n-octylthioglycolate), dioctyltin bis(n
-octylmercaptopropionate), dioctyltin bis(tetradecylthioglycolate),
Dioctyltin bis(tetradecylmercaptopropionate), monooctyltin tris(2-ethylhexylthioglycolate), monooctyltin tris(2-ethylhexylmercaptopropionate), monooctyltin tris(isooctylthioglycolate) , monooctyltin tris (isooctylmercaptopropionate), monooctyltin tris (n-octylthioglycolate), monooctyltin tris (n-octylmercaptopropionate), monooctyltin tris (tetradecylthioglycolate) monooctyltin tris(tetradecyl mercaptopropionate), didodecyltin bis(2-ethylhexylthioglycolate), didodecyltin bis(isooctylthioglycolate), monododecyltin tris(2-ethylhexylthioglycolate) ), monododecyltin tris(isooctylthioglycolate), dimethyltin dilauryl mercaptide, monomethyltin trilauryl mercaptide, dibutyltin dilauryl mercaptide, monobutyltin trilauryl mercaptide, dioctyltin dilauryl Mercaptide, monooctyltin trilauryl mercaptide, didodecyltin dilauryl mercaptide, monododecyltin trilauryl mercaptide, and the like. The one-pack stabilizer of the present invention can be obtained by adding 0.01 to 5 parts by weight of the compound represented by the above general formula [] or [] to 100 parts by weight of the mixture of two or more alkyltin mercaptide stabilizers. . If the amount added is less than 0.01 parts by weight, a sufficient effect on the storage stability of the one-pack stabilizer will not be obtained, and if the amount added is more than 5 parts by weight, the quality as a stabilizer for halogen-containing resins will deteriorate. In the present invention, the blending ratio of two or more types of alkyltin mercaptide stabilizers is arbitrarily determined depending on the application and is not particularly limited. Other stabilizers known to the one-pack stabilizer for halogen-containing resins of the present invention, such as calcium stearate, zinc stearate, barium stearate, alkyltin malate stabilizers, epoxy compounds, organic phosphites, ultraviolet absorbers, It may be used by adding an antioxidant or the like. Examples of the halogen-containing resin stabilized by the one-pack stabilizer of the present invention include vinyl chloride resin,
Vinyl halide homopolymers such as vinyl bromide resin and vinylidene chloride resin, as well as vinyl halides such as vinyl acetate, ethylene, propylene, styrene, isobutylene, vinylidene chloride, maleic anhydride, butadiene, isoprene, methyl methacrylate, acrylonitrile, dialkyl one or two comonomers such as malate and the like;
Examples include copolymers formed by polymerizing with one or more species, post-chlorinated vinyl chloride resins, and the like. In addition, halogen-containing resins and acrylonitrile/butadiene/styrene resins, methyl methacrylate/butadiene/styrene resins, acrylonitrile/chlorinated polyethylene/styrene copolymer resins, acrylic rubber/acrylonitrile/styrene copolymers, acrylic rubber/methyl methacrylate/acrylonitrile copolymers, etc. polymer resin,
Examples include polymer blend resins with impact-improving resins such as vinyl acetate/ethylene copolymer resins, chlorinated polyethylene, and chlorinated rubber. [Function] According to the present invention, by adding a very small amount of a polyoxyethylene ether compound or ester compound to a mixture of two or more types of alkyltin mercaptide stabilizers, the storage stability of the stabilizer mixture is improved. The thus obtained halogen-containing resin to which the one-pack stabilizer was added showed good results in heat coloring resistance and processability (lubricity). The processed and molded products thus obtained are finished into satisfactory products and can be used for industrial plates, extruded products, pipes, films, bottles, etc. (Synthesis example of stabilizer) Dioctyltin bis(isooctylthioglycolate) 252.8g (0.7mol) of dioctyltin oxide and 286.1g (1.4mol) of isooctylthioglycolic acid were placed in a three-necked flask, and heated and stirred. After the internal temperature reached 90°C, dehydration was performed under reduced pressure.
After the reduced pressure became 30 mmHg or less, the reaction was carried out at an internal temperature of 100°C for 1 hour. After that, dioctyltin bis(isooctylthioglycolate) was obtained. Other alkyltin mercaptide stabilizers were synthesized in the same manner. [Example] Next, the present invention will be explained with reference to Examples, where parts in the Examples indicate parts by weight. The polyoxyethylene ether compound or ester compound used in Examples 1 to 8 had the following compound numbers.

【table】

[Table] Examples 1 to 4 and Comparative Examples 1 to 4 Two or more alkyltin mercaptide stabilizers listed in Table 1 and the respective parts of the polyoxyethylene ether compound or ester compound were placed in a 500 cc three-necked flask. The mixture was mixed and stirred at 70°C to obtain a one-pack stabilizer. Further, only two or more types of alkyltin mercaptide stabilizers listed in Table 1 were mixed and stirred in the same manner as above to obtain a one-pack stabilizer. (Storage Stability Test) The one-pack stabilizers obtained in Examples 1 to 4 and Comparative Examples 1 to 4 were placed in a 100 cc glass bottle, sealed, and the state of cloudiness was observed at room temperature for 90 days. The symbols in the table represent the following evaluations. ○: No turbidity ×: Slight turbidity XX: Much turbidity The results are shown in Table 1.

[Table] Examples 5 to 8 and Comparative Example 5 In a 500 cc three-necked flask, the following compounds were added to the alkyltin mercaptide stabilizer weight ratio: dioctyltin bis(isooctylthioglycolate) 70 dimethyltinbis(isooctylthioglycolate) 25 Add 99 parts of a stabilizer mixture consisting of monomethyltin tris(isooctylthioglycolate) 5 and 1 part of the polyoxyethylene ether compound or ester compound shown in Table 2, mix and stir at 70°C to stabilize the mixture in one package. obtained the drug. A one-pack stabilizer was also obtained in the same manner using 1 part of ethylene glycol instead of 1 part of the ether compound or ester compound of polyoxyethylene. (Heat coloring resistance test) 100 parts of vinyl chloride resin (Kane Vinyl S-1008, manufactured by Kanebuchi Chemical Co., Ltd.), 5 parts of methyl methacrylate-butadiene-styrene resin (Kane Ace B-11A, manufactured by Kanebuchi Chemical Co., Ltd.), Example 5 ~8 or 2 parts of the one-pack stabilizer obtained in Comparative Example 5 and a lubricant (Wax
0.4 part of OP (manufactured by Hoechst) was kneaded with a mixing roll at 180°C, and the heat coloring resistance and adhesion (decomposition) time were observed. The numbers in the table represent the following evaluations. 1...Colorless, 2...Slight yellow, 3...Pale yellow, 4
...Yellow The results are shown in Table 2.

【table】

Claims (1)

[Claims] 1. General formula [] or [] RO(CH ₂ CH ₂ O) _o H [] RCOO(CH ₂ CH ₂ O) _o H [] (In the formula, R is an alkyl group having 7 to 22 carbon atoms,
alkenyl group or alkylaryl group, n is 2
A one-pack stabilizer for halogen-containing resins, characterized in that 0.01 to 5 parts by weight of a compound represented by (each representing an integer from 1 to 50,000) is added.