JPS6040466B2 - antioxidant composition - Google Patents

Description

[Detailed description of the invention]

The present invention relates to novel antioxidant compositions for synthetic resins. Specifically, the present invention relates to an antioxidant composition for synthetic resins, characterized in that an alkylmercaptocarboxylic acid monoester of a bisphenol sulfide derivative and a gester compound are used in combination. It is known that synthetic resins such as polyethylene, polypropylene, and polypynyl chloride are susceptible to oxidative deterioration, especially when exposed to air and at high temperatures. It is also known that this deterioration causes synthetic resins to become colored and have a decrease in mechanical strength, making them unusable. For this reason, there is a great need for antioxidants that protect these synthetic resins from acid IG deterioration, and various antioxidants have been added to synthetic resins. However, the stabilizing effect of conventionally used antioxidants is not necessarily sufficient, and many of them volatilize during processing at high temperatures or color the resin.
In addition, some were easily extracted from the resin by water or organic solvents. In order to solve these drawbacks, several types of antioxidants have been used in combination, but the previously proposed combinations have not been able to completely solve the above drawbacks. In view of the current situation, the inventors of the present invention have made extensive studies over many years, and as a result, have discovered an antioxidant composition for synthetic resins that has excellent performance, and have completed the present invention. That is, the present invention provides an antioxidant composition for synthetic resins comprising compounds represented by the following general formulas [1] and [D]. (Here, R represents an alkyl group having 1 to 30 carbon atoms, and R' represents an alkylene group having 1 to 4 carbon atoms. R,, R2 and R3 are each a hydrogen atom, and 1 to 1 carbon atoms.
8 represents an alkyl group, a cycloalkyl group, or an arylalkyl group. Moreover, x represents an integer of 1 to 4. ) Specifically, an alkyl group having 1 to 30 carbon atoms or 1 carbon atom
Specific examples of ~18 alkyl groups include methyl, ethyl,
Propyl, isopropyl, butyl, isobutyl, t-butyl, s-butyl, amyl, isoamyl, neobentyl, hexyl, 2-ethylhexyl, isohexyl, heptyl, octyl, isooctyl, nonyl, decyl, isodecyl, lauryl, tetradecyl, hexadecyl, octadecyl, eicosyl Examples include groups such as , tetracosyl, and octacosyl. Further, the alkylene group preferably has 1 to 4 carbon atoms, and these include groups such as methylene, ethylene, propylene, trimethylene, tetramethylene, and ethylethylene. Examples of cycloalkyl groups include cyclobentyl, cyclohexyl, cyclooctyl, cyclododecyl, 4-methylcyclohexyl and the like. Next, specific examples of compounds represented by the general formula [1] in Table 1 are shown in Table 2, and specific examples of compounds represented by the general formula [1] are shown in Table 2.

Specific examples of the compound represented by [0] are shown below. As shown in Table 1, the antioxidant composition of the present invention comprises an alkylmercaptocarboxylic acid monoester of bisphenol sulfide represented by the above-mentioned one-stage formula [1] and a bisphenol sulfide represented by the above-mentioned one-stage formula [n]. The composition is composed of an alkyl mercaptocarboxylic acid gester, and exhibits excellent antioxidant properties when added to various synthetic resins. For details, see the above-Toshiki [1] and

The antioxidant composition of the present invention comprising the compound represented by [0] preferably has a ratio (weight) of 5 to 95, that is, the compound represented by the general formula [1
] Compound 5 to 95 parts (weight) and general formula

It consists of 95 to 5 parts (by weight) of the compound [0]. Further, even if these are added separately at the time of resin addition, a sufficient synergistic effect appears. Further, it is preferable to use a bisphenol sulfide derivative in combination with the antioxidant composition of the present invention in order to improve the antioxidant properties. It is preferable that the amount of the compound does not exceed 30% (by weight) of the composition of the present invention; if the amount exceeds this amount, phenomena such as plume may occur, which is not preferable. Preferred examples of the compound include 4,4'-thiobisphenol, 4,4'-thiobis(3-methyl-61t-butylphenol), 2,
2'-thiobis(4-methyl-6-t-butylphenol), 4,4'-thiobis(6-t-butyl-o-cresol), 4,4'-thiobis(2,6-dimethylphenol), 2,2'-thiobis(4 , 6-di-t-butylphenol) and the like. Next, the amount of the antioxidant composition of the present invention to be added is preferably 0.005 to 1 part by weight, particularly 0.01 to 5 parts by weight, per 100 parts by weight of the synthetic resin. Examples of the synthetic resins stabilized by the antioxidant composition of the present invention include Q-olefin polymers such as polyethylene, polypropylene, polybutene, and poly3-methylbutene, ethylene-vinyl acetate copolymers, and ethylene-propylene copolymers. polyolefins such as and their copolymers, polyvinyl chloride, polyvinyl bromide, polyvinyl fluoride, polyvinylidene chloride, chlorinated polyethylene, chlorinated polypropylene, polyvinylidene fluoride, brominated polyethylene, chlorinated rubber, vinyl chloride-acetic acid Vinyl copolymer, vinyl chloride-ethylene chloride copolymer, vinyl chloride-propylene copolymer, vinyl chloride-styrene copolymer, vinyl chloride-isobutylene copolymer, vinyl chloride-vinylidene chloride copolymer, vinyl chloride loose Styrene-maleic anhydride terpolymer, vinyl chloride-styrene-acrylonitrile copolymer, vinyl chloride-ptadiene polymer, vinyl chloride-isoprene copolymer, vinyl chloride-chlorinated propylene copolymer, chloride Vinyl-vinylidene chloride-vinyl acetate terpolymer, vinyl chloride-acrylic acid ester copolymer, vinyl chloride-maleic acid ester copolymer, vinyl chloride-methacrylic acid ester copolymer, vinyl chloride-acrylonitrile copolymer, internal Halogen-containing synthetic resins such as plasticized polyvinyl chloride, polystyrene, polyvinyl acetate, acrylic resins, copolymers of styrene and other monopolymers (e.g. maleic anhydride, putadiene, acrylonitrile, etc.), acrylonitrile-butadiene methacrylate resins such as polymethyl methacrylate, polyvinyl alcohol, polyvinyl formal, polyvinyl petyral, linear chain Examples include polyester, polyamide, polycarbonate, polyacetal, polyurethane, cellulose resin, phenol resin, turia resin, melamine resin, epoxy resin, unsaturated polyester resin, and silicone resin. Further, rubbers such as isoprene rubber, butadiene rubber, acrylonitrile-butadiene copolymer rubber, styrene-butadiene copolymer rubber, and blends of these resins may also be used. Furthermore, the composition of the present invention can be favorably used for crosslinked synthetic resins produced by peroxide or radiation, and foamed resins such as foamed polystyrene. Examples of the crosslinking synthetic resin include polyethylene or ethylene-vinyl acetate, ethylene-ethyl acrylate,
Copolymers such as ethylene-propylene and ethylene-propylene-butadiene can be mentioned. In addition, Tsutomu forehead agents include penzoyl peroxide, di-t-butyl peroxide, dicumyl peroxide, 2,
5-dimethyl-2,5-di(t-butylberoxy)hexane, 2,5-dimethyl-2,5-di(t-butylberoxy)hexine, 1,3-bis(t-butylberoxyisopropyl) ) Organic peroxides such as benzene, t-butyl hydroperoxide, cumene hydroperoxide, polysulfone azide, azide formate, titramethylisophthalyl di-t-butylbisperoxide, tetramethylisophthalyl dicumylpisperoxide, etc. Preferred for use. Other antioxidants can also be used in combination with the antioxidant composition of the present invention. These antioxidants include phenolic antioxidants, phosphite antioxidants, amine antioxidants, and sulfur-containing compounds, and specific examples include Samurai Sekisho 4917 & 692.
It is published in the issue of the publication. Further, by using the antioxidant composition of the present invention in combination with a light stabilizer, the light stability of the organic material can be improved, so these can be used as appropriate. Specific examples of such light stabilizers are disclosed in Tokekki No. 49-78,692. Metal deactivators, nucleating agents, etc. can also be used in combination with the antioxidant composition of the present invention; specific examples of these can be found in Hakama Sekisho 49-178, 692.
It is disclosed in the publication. Others as necessary, such as epoxy stabilizers, organic chelators, pigments, fillers, antistatic agents, antifogging agents, plate-out inhibitors, surface treatment agents, lubricants, flame retardants, metal soaps, glazing agents, Preventive agents, bactericidal agents, photodegradants, non-metallic stabilizers, epoxy resins, enoic acid esters, thiourea derivatives, processing aids, nada type agents, and the like can be included. The effects of the antioxidant according to the present invention will be specifically explained with reference to the following examples. However, these Examples are merely illustrative of the present invention, and the present invention is not limited in any way by these Examples. Example 1 In order to see the excellent stabilizing effect of the antioxidant of the present invention on organic materials, 10 parts by weight of the stabilized polypropylene resin and the sample compounds (Table 3) were mixed together for 10 minutes using a paddle. did. This blended mixture was kneaded with a mixing roll for 6 minutes at a temperature of 18,000°C, and then kneaded for 200k9 at a temperature of 18,000°C.
A sheet with a thickness of 1.0 sail was produced by compression molding for 5 minutes under the conditions of 1.0 mm. The obtained sheets were cut into pieces measuring 40 x 15 mm and hung in separate cylinders to measure the time at which oxidative deterioration began. The results are shown in Table 3. The inside of the siliwader is set at a temperature of 1 atm and 161.0 pm in an oxygen atmosphere. In addition, the oxidative deterioration start time was read from the recorder at the time when the pressure inside the cylinder began to decrease rapidly. Part 3 Table of Contents *1 Example of 1CI phenolic antioxidant 2 Unstabilized polypropylene resin (profax6501,
Hercules) and 10 parts by weight of the sample compound (4th part)
Table 1) was boiled and mixed in a machine for 10 minutes. Next, a sheet having a thickness of 1.0 was prepared under the conditions described in Example 1. This sheet was used as a 10×2 test piece and was placed on aluminum foil at a temperature of 150 oo in an air atmosphere to perform a heating test. In addition, using female test pieces No. 1 for the same sample, the time when 5 or more pieces faded and became brittle was defined as the deterioration start time. Table 4 Example 3 10 parts by weight of stabilized polyethylene resin (Hyzex 510 Mitsui Petrochemical Co., Ltd. product, Japan) and sample compound (No. 5
Table) was kneaded with a mixing roll for 5 minutes at a temperature of 150 qo, and then compression molded for 5 minutes at a temperature of 150 qo and a condition of 180 k9/m, to create a sheet with a thickness of 1.2. This sheet was used as a 10 x 2 board test piece on aluminum foil.
A gear oven heating deterioration test in air at 149.5°C was conducted. In addition, using lq father's mystery pieces for the same sample, the time when 5 or more pieces changed color and became waxy was defined as the deterioration time. The results are shown in Table 5. Notes to Table 5 *1 Example of phenolic antioxidant manufactured by Ciba-Geigy Co., Ltd. 4 10 parts by weight of Blendexllll, 0.5 parts by weight of zinc stearate, 5 parts by weight of titanium dioxide. The weir crown and the sample compounds (Table 6) were dried, strained, and dry blended in a machine for 1 minute. This mixture was extruded at a temperature of 240° C. using a three-side extruder (rotation speed: 3 pm) to prepare a compound. This compound was heated to 200k9/kg at a temperature of 180°C.
Compression molding was performed for 5 minutes under the same conditions to create a sheet with a thickness of 0.5 ribs. The test method was the same as in Example 1, except that the measurement temperature was 1°C. The results are shown in Table 6. Table 6 Example 5 Polyvinyl chloride resin (BOONl03EP, Nippon Zeon Co., Ltd. product, Japan) 10 foundations, 42 dioctyl phthalate,
After kneading 3 parts of epoxidized soybean oil, part of zinc stearate OS, 0.5 part of barium stearate, 0.3 part of stearic acid and the sample compound (Table 7) for 5 minutes at a temperature of 17yo on a mixing roll, 175q0 of A transparent sheet was created by compression molding at high temperature. Next, a thermal deterioration test was conducted in an air atmosphere in a gear oven at a temperature of 19 pi. The deterioration time was determined based on the degree of coloration. The results are shown in Table 7. Table 7 Example 6 To examine the effect of the stabilizer of the present invention on polyptene resin, the following formulation was mixed for 5 minutes at a temperature of 14 pi. The mixture was kneaded in a roller, and compression molded for 5 minutes at a pressure of 16 pi and 200 k9 to form a sheet with a thickness of one square. The obtained sheets were cut into pieces measuring 40 x 15 yards and hung in separate cylinders to measure the time at which acid C deterioration began. The results are shown in Table 8. Note that the temperature inside the cylinder is set at 1 atm and 160° C. in an oxidizing atmosphere. The time at which oxidation deterioration started was determined by reading the time when the pressure inside the cylinder began to decrease rapidly using a recorder. (Formulation) Stabilized polyptene resin 10 parts by weight Calcium stiarate 1.0 Sample compound
(Table 8) Table 8 Example 7 Ten parts by weight of nylon 66 matted by adding 0.05 parts by weight of titanium dioxide were dissolved in 90 parts by weight of 90% formic acid, and the sample compound (No. 9 Table) and mix thoroughly. This solution was poured uniformly onto a glass plate and dried for 1 minute in a heated air oven at 105°C to form a film. Table 9 shows the degree of discoloration of the film when this film was heated in a hot air oven for 30 minutes at a high temperature. Table 9 Example 8 10 parts by weight of polycarbonate resin powder was added to the sample compound (
(Table 10) and pressed at 260oo to create the first sheet. The degree of discoloration of the sheet when this sheet was heated at 225° C. for 30 minutes in a heated air oven is shown in Table 1. 10th
Table Example 9 Unstabilized polyethylene (low density polyethylene for crosslinking M1
2.0) 100 parts by weight, sample compound (Table 11) 0.4
Parts by weight were drained, strained and mixed in a machine for 10 minutes. This mixture was mixed with a mixing roll for 10 minutes at 110°C, and then mixed with dicumyl peroxide [Percyl D,
Manufactured by Nihon Yushi ■ 2. 2 parts by weight were added and further heated at the same temperature.
I practiced fishing for a minute. This rolled sheet was compression molded for 5 minutes at a temperature of 110 pm and 100 k9/ground, then the temperature was immediately raised to 180 k9,
A sheet with a thickness of 1 cape was created by molding for 18 minutes while maintaining the compression pressure. The resulting sheet is 40x15
& A heat aging test was carried out at 160° C. in an air atmosphere by cutting the pieces into pig size pieces and hanging them in a gar oven. The deterioration start time was visually determined as the time when 50% or more of the wood pieces became colored or deformed. The results are shown in Table 11. Table 11 Example 10 Unstabilized polyethylene (skin 3.7, density 0.0) 100
Parts by weight of azodicarponamide were added to the sample compound (No. 12 barley), and the mixture was mixed for 1 minute using a mustard sieve machine. This mixture was kneaded with a mixing roll at 120° C. for 7 minutes, and then the rolled sheet was compression molded at a temperature of 130°C and 100k9/base for 5 minutes to produce a sheet with a thickness of 0.1 mm. This sheet was exposed to ad radiation at 40° C. using a Cock-Crot-Walton accelerator.
This sheet was cut into a size of 100 x 253 ribs, and the pieces were hung in a 230° C. gear oven for 7 minutes to foam. The density of the obtained foam is approximately 0.03P
The sheet, whose crosslinking was inhibited, dripped during the foaming process in the oven, and no test piece could be obtained. This sample piece that dripped down was determined to be defective in crosslinking. The obtained foam specimen is 1
A heat aging test was conducted at 85°C for 12 days using a No. 1 dumbbell puzzle piece. Thereafter, the elongation after aging was measured in accordance with JISK676 Shukugakuho, and the ratio to the original, that is, the retention rate was determined. The results will be shown to the 12th year old. Table 12 Example 11 In order to examine the effect of the antioxidant according to the present invention on ethylene vinyl acetate copolymer, samples were prepared with the following formulation.
Thermal stability and initial coloration in a 5qo gear oven were measured. Regarding initial coloration, yellowness was determined using a Hunter colorimeter. The results are shown in Table 1. (Blend) Ethylene-vinyl acetate copolymer resin 10 parts by weight Montanic acid thickener 0.3 Sample compound
(Table 1) Table 13 Example 12 Holybutylene terephthalate A compound consisting of 10 parts by weight of sample compound (Table 14) was injection processed at 27,000 to prepare test pieces. Using this test piece, the residual tensile strength after heat aging at 150° C. for 240 hours was measured. The results obtained are shown in Table 14. Table 14

Claims (1)

[Scope of Claims] 1. An antioxidant for synthetic resins comprising at least one compound selected from the following general formula [I] and at least one compound selected from the following general formula [II]. Composition. ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (Here, R represents an alkyl group having 1 to 30 carbon atoms, and R' represents an alkylene group having 1 to 4 carbon atoms. R_1, R_2, and R_3 are each It represents a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, a cycloalkyl group, or an arylalkyl group. Also, x represents an integer of 1 to 4.)