JP2000239659A - Method for stabilizing sulfur-base antioxidant - Google Patents

Abstract

PROBLEM TO BE SOLVED: To improve the long-term storage stability of a sulfur-base antioxidant by compounding it with 2,2,6,6-tetramethylpiperidine compound. SOLUTION: At least one 2,2,6,6-tetramethylpiperidine compound selected from among compounds represented by formulas I to VI is compounded in an amount of 1-500 ppm. In the formulas, n is 1-4; R1 is H, methyl, benzyl, acetyl or a group represented by formula VII; when n is 1, R2 is an aliphatic, alicyclic or aromatic monoacyl group; when n is 2, R2 is an aliphatic, alicyclic or aromatic diacyl group; when n is 3, R2 is an aliphatic, alicyclic or aromatic triacyl group; when n is 4, R2 is an aliphatic, alicyclic or aromatic tetraacyl group; R3 is 1-18C alkyl; R4 is a group represented by formula VIII; m is 2-20; Y is morpholino or -NH-R8 (wherein R8 is 1-18C alkyl); p is 1-8; and r is 2-50.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a method for improving the storage stability of a sulfur-based antioxidant.

[0002]

2. Description of the Related Art Organic polymer materials composed of organic compounds such as natural polymers, synthetic polymers, oils and fats, lubricating oils and hydraulic oils are oxidized by heat, light, etc., causing discoloration and reduction in mechanical strength. It is known that the service life is extremely shortened. Many kinds of antioxidants have been developed to prevent the deterioration.

[0003] Among the antioxidants, sulfur-based antioxidants are widely used in combination with phenol-based antioxidants to increase heat resistance. However, sulfur-based antioxidants have an acid value during the storage period after production. Has risen, causing problems of off-flavors and reduced efficacy.

[0004] In order to prevent this, a method of suppressing an increase in the acid value by devising a purification method at the time of production and minimizing the remaining of impurities such as catalyst residues has been used.

In order to enhance the heat resistance and weather resistance of an organic polymer material, a sulfur-based antioxidant, 2,2,6,6
-The use of a combination with a tetramethylpiperidine compound can be easily considered by those skilled in the art.
In particular, it is not common practice to use them together when considering weather resistance.

Japanese Patent Application Laid-Open No. 1-115941 discloses that a sulfur-based antioxidant and a piperidine compound are used in combination as an antioxidant for synthetic polymers.
No. 3134 describes that a sulfur-based antioxidant and a hindered amine-based light stabilizer are used together in a polyolefin resin. Also, JP-A-60-199039 discloses that
It describes that a thioether compound and a hindered amine are used in combination for a polyolefin resin.

[0007] These documents describe the purpose of improving the heat resistance, weather resistance, and coloring resistance of a synthetic polymer or polyolefin resin.
This is different from the long-term stabilization method of a sulfur-based antioxidant containing a small amount of a 2,2,6,6-tetramethylpiperidine compound according to the invention described in the present application.

Although the above publication uses a sulfur-based antioxidant in combination with a 2,2,6,6-tetramethylpiperidine compound, it does not disclose any preferable composition ratio thereof. However, only the following description is given in the examples.

That is, 2,
The content of the 2,6,6-tetramethylpiperidine compound is set to 0.1 in Examples of JP-A-1-115594.
10: 0.10 (same amount) or 2: 1 (about 500,000)
ppm) is 0.30: 0.30 (same amount) or 0.30: 0.30 in Examples of Japanese Patent Publication No. 5-73134.
An example of 0.05 (about 16700 ppm) is disclosed in
Examples of 199039 disclose examples of 0.1: 0.1 (the same amount), respectively.

[0010] In these documents, the content of the 2,2,6,6-tetramethylpiperidine compound with respect to the sulfur-based antioxidant is 2,2,6,6 with respect to the sulfur-based antioxidant according to the invention described in the present application. The case where the content of the 6-tetramethylpiperidine compound is remarkably large as compared with the case of 1 to 500 ppm is described.

[0011] The claims of Japanese Patent Publication No. 59-47704 disclose a 2,2,6,6-tetramethylpiperidine compound, 2,6-di-tert-butyl-4-methylphenol and / or Alternatively, a composition with a thiodialkanoic acid ester as a sulfur-based antioxidant and having a specific composition ratio is described. In terms of the content of the 2,2,6,6-tetramethylpiperidine compound with respect to the sulfur-based antioxidant, the content of the 2,2,6,6-tetramethylpiperidine compound is the same or the 2,2,6,6-tetramethylpiperidine compound is smaller than the sulfur-based antioxidant. Examples are described in which the amount of piperidine compound is high. In the examples (reference examples) of the publication, the content of the 2,2,6,6-tetramethylpiperidine compound with respect to the sulfur-based antioxidant is 0.30: 0.25 (about 833).
000 ppm) or 0.2: 0.1 (about 500,000)
ppm).

Therefore, 2,2,6,6-tetramethylpiperidine compound is added to the sulfur-based antioxidant in an amount of 1 to 2,
Compositions containing less than 500 ppm were not described in the literature and were not known compositions.

On page 233, "Deterioration and stabilization of polymers" by Yoshiharu Osawa, there is described a case where a 2,2,6,6-tetramethylpiperidine compound and a sulfur-based antioxidant are used in combination with a synthetic polymer. On page 232, it is said that HALS (a hindered amine light stabilizer) and a phenolic antioxidant, particularly a phenolic antioxidant which easily produces stilbene quinone, are described. It has been pointed out that yellowing is promoted when an agent is used in combination.

From these facts, when a 2,2,6,6-tetramethylpiperidine compound, a sulfur-based antioxidant and further a phenol-based antioxidant are used in combination in an organic polymer material, the weather resistance is poor. However, there is a drawback in the coloring resistance, and at present, it is not generally used industrially. In addition, a small amount of 2,2
Compounding 2,6,6-tetramethylpiperidine compound
There is no known example of improving the storage stability of a sulfur-based antioxidant.

[0015]

Conventionally, while maintaining the physical properties of a sulfur-based antioxidant, it suppresses an increase in the acid value during the storage period to prevent the generation of an unpleasant odor, and when added to an organic polymer material, has originally been possessed. There has been a demand for obtaining a sulfur-based antioxidant having excellent long-term stability without impairing the efficacy of the sulfur-based antioxidant.

[0016]

Means for Solving the Problems In view of such circumstances, the present inventors have conducted intensive studies and as a result, have found that 2,2,6,6-tetramethylpiperidine compound is added to the sulfur-based antioxidant by sulfur-based oxidation. The present inventors have found that a sulfur-based antioxidant having excellent long-term storage stability can be obtained by adding 1 to less than 500 ppm to the inhibitor, and have completed the present invention.

That is, the present invention relates to a sulfur-based antioxidant containing a 2,2,6,6-tetramethylpiperidine compound, wherein the content of the 2,2,6,6-tetramethylpiperidine compound is a sulfur-based antioxidant. The object of the present invention has been achieved by providing a sulfur-based antioxidant excellent in long-term storage stability, characterized in that the sulfur-based antioxidant is less than 1 to 500 ppm.

[0018]

DETAILED DESCRIPTION OF THE INVENTION A feature of the present invention is to remarkably improve the storage stability of a sulfur-based antioxidant. In the present invention, the prerequisites for achieving the object are to maintain the initial physical properties of the sulfur-based antioxidant, and when used in an organic polymer material, a mixed product is usually used in combination with a phenol-based material. Does not discolor when heated and melted, does not impair the inherent heat resistance effect of the sulfur-based antioxidant when added to the organic polymer material, and does not discolor the organic polymer material.

Further, 2,2,6 which is a constituent of the present invention
The 6-tetramethylpiperidine compound is any one of the compounds represented by the following general formulas (1) to (6). Further, a composition containing two or more of these may be used.

General formula (1)

[0021]

Embedded image

(Wherein, n represents an integer of 1 to 4, and R ¹ and R ² represent the following groups).

General formula (2)

[0024]

Embedded image

(Wherein, R ¹ and R ³ represent the following groups).

General formula (3)

[0027]

Embedded image

(Wherein, R ⁴ is a group described below).

General formula (4)

[0030]

Embedded image

(Wherein, R ⁴ is a group described below).

Formula (5)

[0033]

Embedded image

[0034] (wherein, m represents an integer of 2 to 20, R ¹
Represents the following group, and Y also represents the following group. ).

Formula (6)

[0036]

Embedded image

(Where p is an integer of 1 to 8, and r is 2
Represents an integer of 50 to 50. ).

The symbols described in the general formulas (1) to (6) will be described.

R ¹ is a hydrogen atom, a methyl group, a benzyl group,
Acetyl group or formula (7)

General formula (7)

[0041]

Embedded image

And a group containing

R ² represents an aliphatic, alicyclic or aromatic monoacyl group when n is 1, and an aliphatic, alicyclic or aromatic monoacyl group when n is 2.
An alicyclic or aromatic diacyl group, when n is 3, an aliphatic, alicyclic or aromatic triacyl group, and when n is 4, an aliphatic, alicyclic or aromatic tetraacyl group .

R ³ represents an alkyl group having 1 to 18 carbon atoms.

R ⁴ is represented by the general formula (8)

Embedded image (Wherein, R ¹ and R ³ have the same meanings as described above).

In the general formula (5), Y is a morpholino group or a compound represented by the formula (9)

Embedded image

(R ⁸ represents an alkyl group having 1 to 18 carbon atoms).

Specific examples of the 2,2,6,6-tetramethylpiperidine compound in the present invention include, but are not limited to, the following.

2,2,6,6-tetramethyl-4-hydroxypiperidine, 2,2,6,6-tetramethyl-4
-Benzoyloxypiperidine, bis (2,2,6,6
-Tetramethyl-4-piperidyl) sebacate, bis (1,2,2,6,6-pentamethyl-4-piperidinyl) sebacate, bis (1,2,2,6,6-pentamethyl-4-piperidyl) sebacate Lysinyl) -2- (3,5-di-tert-butyl-4-hydroxybenzyl) -2-n-butylmalonate, bis (1-acryloyl-2,2,6,6-tetramethyl-4-pi (Rizil) bis (3,5-di-third)
Tert-butyl-4-hydroxybenzyl) malonate, tetrakis (2,2,6,6-tetramethyl-4-pyridyl) -1,2,3,4-butanetetracarboxylate, poly {[6- (1 , 1,3,3-tetramethylbutyl) amino-1,3,5-triazine-2,4-diyl] [(2,2,6,6-tetramethyl-4-piperidyl) imino] hexamethylene [( 2,2,6,6-tetramethyl-4-pyridyl) imino]}, poly {(6-
Morpholino-1,3,5-triazine-2,4-diyl) [(2,2,6,6-tetramethyl-4-piperidyl) imino] hexamethylene [(2,2,6,6-tetra Methyl-4-piperidyl) imino]}, dimethyl succinate / 1- (2-hydroxyethyl) -4-hydroxy-2,2,6,6-tetramethyl-piperidine polycondensate, cyanuric chloride / tertiary octyl Amine / 1,6-bis (2,2,6,6-tetramethyl-4-piperidylamino) hexane condensate and the like.

The sulfur-based antioxidant which is a component of the present invention is represented by the following general formulas (10) to (12).
Are any one of the compounds shown in Table 1. Alternatively, a composition containing two or more of these may be used.

The general formula (10) is

[0052]

Embedded image

(Wherein R ⁹ represents an alkyl group having 4 to 18 carbon atoms).

General formula (11)

[0055]

Embedded image

(Wherein q represents an integer of 2 to 4, R ⁹ has the same meaning as described above, and Z has the same meaning as described later.)

General formula (12)

[0058]

Embedded image

(Wherein R ⁹ has the same meaning as described above).

Z shown in the general formula (11) represents an ethylene group when t is 2, and when t is 3, the formula (13)

[0061]

Embedded image

Or a group represented by the formula (14)

[0063]

Embedded image

A group represented by the formula: when t is 4,
Equation (15)

[0065]

Embedded image

The group represented by

Specific examples of the sulfur-based antioxidant in the present invention include, but are not limited to, the following. Esters with dilauryl ester, dimyristyl ester, distearyl ester, didocosyl ester and the like, and esters with polyhydric alcohols such as glycerin, trimethylolethane, trimethylolpropane, pentaerythritol and trishydroxyethylisocyanurate.

The organic polymer material stabilized by the compound of the present invention is represented by a polymer itself, a fat or oil, a mineral oil, or the like or a material composed thereof. Among these, the polymer is a polyolefin. , Halogen-containing synthetic resin, petroleum resin, coumarone resin, polystyrene, styrene copolymer, styrene resin, polyvinyl acetate, polyvinyl alcohol, polyvinyl formal, polyvinyl butyral, acrylic resin, methacrylate resin, polyacrylonitrile, linear polyester, Polyphenylene oxide, polyamide, polycarbonate, modified polyphenylene oxide, polyacetal, polyurethane, cellulose resin, unsaturated polyester resin, phenol resin,
Urea resin, melamine resin, epoxy resin, silicone resin, polyethylene terephthalate, reinforced polyethylene terephthalate, polybutylene terephthalate, polysulfone resin, polyether sulfone, polyphenylene sulfide, polyether ketone, polyether imide, polyoxybenzoyl, polyimide, Examples include polymaleimide, polyamideimide, natural rubber, synthetic rubber, and blends thereof.

Examples of the polyolefin include polyethylene (high-density polyethylene, low-density polyethylene, linear low-density polyethylene, linear medium-density polyethylene, etc.), polypropylene, polybutene, polypentene, poly-3-methylbutylene, poly-4-methylpentene. Α-olefin polymers, such as polystyrene, admixtures of polyethylene and polypropylene with other compatible polymers, ethylene-vinyl acetate copolymers, ethylene-propylene copolymers and the like. After the polyolefin is polymerized,
A catalyst that has been subjected to a slight purification treatment with a step of removing catalyst residues, a relatively highly purified one, a highly active catalyst, a catalyst that has not undergone a catalyst removal step, or is obtained in a simplified manner. A crystalline polyolefin obtained using a Ziegler-type catalyst or a chromium-based catalyst using a halogen-containing magnesium compound as a catalyst carrier, and not having undergone a catalyst residue removing step, may be used. Japanese Patent Publication No. 4418, Tokuhei 3-
No. 56245, U.S. Pat. No. 4,115,639). Further, a polyolefin having a very narrow molecular weight distribution obtained by a metallocene-based single-site catalyst may be used [Journal of Polymer Science Polymer Chemistry Edition (Jour)
nal of Polymer Science. Po
(Lymer Chemistry Edition), 23, 2151 (1985)].

Examples of the halogen-containing synthetic resin include polyvinyl chloride, polyvinyl bromide, polyvinyl fluoride, polyvinylidene chloride, polyvinylidene fluoride, chlorinated polyethylene, chlorinated polypropylene, brominated polyethylene, chlorinated rubber, and vinyl chloride-acetic acid. Vinyl 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-maleic anhydride terpolymer,
Vinyl chloride-styrene-acrylonitrile terpolymer, vinyl chloride-butadiene copolymer, vinyl chloride-isobutylene copolymer, vinyl chloride-isoprene copolymer, vinyl chloride-chlorinated propylene copolymer, vinyl chloride-chloride Vinylidene-vinyl acetate terpolymer, vinyl chloride-acrylate copolymer, vinyl chloride-maleate copolymer, vinyl chloride-methacrylate copolymer, vinyl chloride-acrylonitrile copolymer, internal plasticity Polyvinyl chloride and the like.

The styrene-based copolymer is a copolymer of styrene and another monomer, and examples of the other monomer include maleic anhydride, butadiene, acrylonitrile and the like. Examples of the styrene resin include acrylonitrile-butadiene-styrene resin, acrylate-butadiene-styrene resin, and methacrylate-butadiene-styrene resin.

Examples of the methacrylate resin include polymethyl methacrylate. As synthetic rubber,
Isoprene rubber, butadiene rubber, acrylonitrile
Butadiene copolymer rubber.

The sulfur-based antioxidant having a good storage stability according to the present invention is a sulfur-based antioxidant containing 1 to less than 500 ppm of 2,2,6,6-tetramethylpiperidine compound. , 6,6-tetramethylpiperidine compound in an amount of 5 to 300 ppm, more preferably 2,2,
6,6-tetramethylpiperidine compound is added in an amount of 10 to 100.
It is a sulfur-based antioxidant containing ppm.

In preparing the antioxidant composition of the present invention, the sulfur-based antioxidant and the 2,2,6,6-tetramethylpiperidine compound may be mixed as they are, or may be melted and mixed. May be dissolved and mixed in a solvent, or may be used during purification after production of the sulfur-based antioxidant.
It can also be obtained by adding a 6,6-tetramethylpiperidine compound.

When the compound of the present invention is used as a stabilizer for an organic polymer material, it is preferably used in a proportion of 0.01 to 10% by weight, more preferably 0.01 to 5% by weight, based on the organic polymer material. Is good. Furthermore, by combining the stabilizer compound of the present invention with a phenolic antioxidant and a phosphorus-based antioxidant, an organic polymer material having excellent heat stability and processing stability can be obtained.

In the present invention, by combining one or more of these phenolic antioxidants or phosphorus antioxidants,
When used as a stabilizer for organic polymer materials, these antioxidants are preferably added at a ratio of 0.01 to 10% by weight, more preferably 0.01 to 5% by weight, based on the organic polymer material. Is good. When used in combination, they may be added separately or as a premixed compounding agent.

Preferred compounds as phenolic antioxidants are 3,5-di-tert-butyl-4-hydroxyphenylpropionic acid or esters of 3-tert-butyl-4-hydroxy-5-methylphenylpropionic acid. Hexyl alcohol, octyl alcohol, 2-
Ethylhexyl alcohol, nonyl alcohol, decyl alcohol, dodecyl alcohol, tridecyl alcohol, tetradecyl alcohol, hexadecyl alcohol, octadecyl alcohol, eicosyl alcohol,
Monoesters with monohydric alcohols such as docosyl alcohol and tetracosyl alcohol, ethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, neopentyl glycol, 1,6-
Hexanediol, thio-di-ethylene glycol,
3,9-bis (1,1-dimethyl-2-hydroxyethyl) -2,4,8,10-tetraoxyethyl [5
5] Diesters with dihydric alcohols such as undecane and hydrogenated bisphenol A, triesters with trihydric alcohols such as glycerin, trimethylolethane, trimethylolpropane, tris (2-hydroxyethyl) isocyanurate, pentaerythritol, ditri Examples include tetraesters with tetrahydric alcohols such as methylolethane and ditrimethylolpropane. Of these, more preferably, n-octadecyl-3- (4-hydroxy-
3,5-di-tert-butylphenyl) propionate, tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionyloxymethyl] methane,
1,6-hexanediol-bis [3- (3,5-ditert-butyl-4-hydroxyphenyl) propionate], triethylene glycol-bis [3- (3-third
Tert-butyl-4-hydroxy-5-methylphenyl) propionate], 3,9-bis [2- [3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionyloxy] -1,1 -Dimethylethyl] -2,4.
8,10-tetraoxaspiro [5.5] undecane or 3,9-bis [2- [3- (3,5-ditert-butyl-4-hydroxyphenyl) propionyloxy]-
1,1-dimethylethyl] -2,4,8,10-tetraoxaspiro [5.5] undecane.

Other phenolic antioxidants include 2,6-di-tert-butyl-4-methylphenol,
4-hydroxymethyl-2,6-di-tert-butylphenol, 2,6-di-tert-butyl-4-ethylphenol, butylated hydroxyanisole, distearyl.
(4-hydroxy-3-methyl-5-tert-butyl) benzylmalonate, propyl gallate, octyl gallate, dodecyl gallate, tocopherol, 2,2'-methylenebis (4-methyl-6-tertiary Butylphenol), 2,2'-methylenebis (4-ethyl-6-third
Grade butylphenol), 4,4'-methylenebis (2,
6-di-tert-butylphenol), 4,4′-butylidenebis (6-tert-butyl-m-cresol), 4,
4′-thiobis (6-tert-butyl-m-cresol), styrenated phenol, N, N′-hexamethylenebis (3,5-ditert-butyl-4-hydroxyhydrocinnamide), bis ( 3,5-di-tert-butyl-4-
Hydroxybenzylphosphonic acid ethyl ester) calcium, 1,1,3-tris (2-methyl-4-hydroxy-5-tert-butylphenyl) butane, 1,3,5-
Trimethyl-2,4,6-tris (3,5-ditert-butyl-4-hydroxybenzyl) benzene, 2,2′-
Methylenebis (4-methyl-6-cyclohexylphenol), 2,2′-methylenebis [6- (1-methylcyclohexyl) -p-cresol], 1,3,5-tris (4-tert-butyl-3- Hydroxy-2,6-dimethylbenzyl) isocyanuric acid, 1,3,5-tris (3,5-di-tert-butyl-4-hydroxybenzyl)
Isocyanuric acid, 2,2'-oxamidobis [ethyl
3- (3,5-ditert-butyl-4-hydroxyphenyl) propionate], 6- (4-hydroxy-3,5
-Di-tert-butylanilino) -2,4-dioctylthio-1,3,5-triazine or bis [2-tert-butyl-4-methyl-6- (2-hydroxy-3-tert-butyl- 5-methylbenzyl) phenyl] terephthalate and the like, but are not limited thereto.

Examples of the phosphorus antioxidant include tetrakis (2,4-di-tert-butylphenyl) -4,4′-biphenylenediphosphonite, tris (2,4-di-tert-butylphenyl) phosphite, Bis (2,4-di-tert-butylphenyl) biphenylene monophosphonite, tetrakis (2,4-di-tert-butyl-5-methylphenyl) -4,4′-biphenylenediphosphonite, tris (2 4-di-tert-butyl-5-methylphenyl) phosphite, bis (2,4-di-tert-butyl-5-methylphenyl) biphenylenemonophosphonite, bis (2
4-di-tert-butylphenyl) pentaerythritol diphosphite, bis (2,6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphite,
Examples include, but are not limited to, 2,2'-methylenebis (4,6-di-tert-butylphenyl) -2-ethylhexyl phosphite or a mixture thereof.

An ultraviolet absorber may be used together with the stabilizer compound of the present invention to further improve the weather resistance of the organic polymer material.

These ultraviolet absorbers include phenyl salicylate, p-tertiary butyl phenyl salicylate,
p-octylphenyl salicylate, 2,4-dihydroxybenzophenone, 2-hydroxy-4-acetoxyethoxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2,2′-dihydroxy-4,4 ′
-Dimethoxybenzophenone, 2-hydroxy-4-n
-Octyloxybenzophenone, 2-hydroxy-4
-Isooctyloxybenzophenone, 2-hydroxy-4-dodecyloxybenzophenone, 2-hydroxy-4-octadecyloxybenzophenone, 2,2'-
Dihydroxy-4,4'-dimethoxy-5,5'-disulfobenzophenone disodium, 2-hydroxy-
4- (2-hydroxy-3-methacryloxy) propoxybenzophenone, 2- (2-hydroxy-5-methylphenyl) benzotriazole, 2- (2-hydroxy-3,5-ditert-butylphenyl) benzotriazole , 2- (2-hydroxy-3-tert-butyl-5-
Methylphenyl) -5-chlorobenzotriazole, 2
-(2-hydroxy-3,5-di-tert-butylphenyl) -5-chlorobenzotriazole, 2- (2-hydroxy-3,5-di-tert-butylphenyl) benzotriazole, 2- [2- Hydroxy-5- (1,1,3,
3-tetramethylbutyl) phenyl] benzotriazole, n-hexadecyl-3,5-ditertiarybutyl-4-
Hydroxybenzoate, 2,4-di-tert-butylphenyl / 3,5-di-tert-butyl-4-hydroxybenzoate, ethyl-2-cyano-3,3-diphenylacrylate, {2,2′-thiobis [ 4- (1,1,3,
3-tetramethylbutyl) phenolate]}-n-butylamine nickel, {2,2′-thiobis [4-
(1,1,3,3-tetramethylbutyl) phenolate]｝ nickel, bis (3,5-ditert-butyl-4-)
Examples thereof include, but are not limited to, salicylic acid, benzophenone, benzotriazole, cyanoacrylate, and nickel compound compounds typified by nickel (ethyl hydroxybenzylphosphonate) and the like.

In the present invention, a phenolic antioxidant,
When a stabilizer such as an ultraviolet absorber or a phosphorus-based antioxidant is used as a stabilizer for an organic polymer material by combining at least one or more thereof, these stabilizers are preferably used in an amount of 0.01 to 10 based on the organic polymer material. % By weight, more preferably 0.01 to 5% by weight.

Thus, one or two of the compounds of the present invention
Kind Code: A1 An organic polymer material stabilizer comprising at least one species and at least one selected from a phenolic antioxidant, an ultraviolet absorber and a phosphorus antioxidant is provided. In addition, an organic polymer material containing the stabilizer is also provided.

One or more of the compounds of the present invention, or a combination of the compounds of the present invention with one or more other stabilizers such as antioxidants or ultraviolet absorbers, may be incorporated into an organic polymer material. Can be mixed, then kneaded, and extruded.

The compound of the present invention may further comprise a metal soap such as calcium stearate, a heavy metal deactivator such as a hydrazine compound, a nucleating agent such as bis (p-tert-butylbenzoic acid) aluminum hydroxide, a monoalkyl Organic tin stabilizers such as tin tris (octyl thioglycolate), dialkyl tin bis (octyl thioglycolate), monoalkyl tin tris (monoalkyl maleate) or dialkyl tin bis (monoalkyl maleate), Plasticizers such as di-2-ethylhexyl phthalate or di-2-ethylhexyl adipate; epoxy compounds such as epoxidized soybean oil or epoxy octyl stearate; various organic pigments; fillers such as aluminum oxide; sodium bicarbonate or azodicarbonate Amide Any foaming agents, antistatic agents such as cationic or anionic surfactants, flame retardants such as phosphate esters, lubricants such as lower alcohol esters of aliphatic amides or fatty acids, acrylic polymer processing aids, etc. You can also.

[0086]

EXAMPLES The present invention will be described below in more detail with reference to Examples and Experimental Examples, but the present invention is not limited thereto.

Example 1 In a 20 ml ampoule, dilauryl thiodipropionate and various additives described in Table 1 were mixed in the indicated amounts, and the mixture was placed in a gear oven kept at 75 ° C. in an open state (air contact possible).
Hold for 0 days. The acid value before and after the heat treatment was measured to confirm the off-odor. The results are shown in Table 1.

The acid value was measured by neutralization titration of the number of mg of potassium hydroxide required to neutralize the free fatty acid contained in 1 g of fat and oil. The smaller this value is, the less decomposition is occurring.

In the off-flavor evaluation, the presence or absence of off-flavor was determined by five panelists.

[0090]

[Table 1]

The symbols in the table have the following meanings. S-1: bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate S-2: tetrakis (2,2,6,6-tetramethyl-
4-pyridyl) -1,2,3,4-butanetetracarboxylate S-3: poly {[6- (1,1,3,3-tetramethylbutyl) amino-1,3,5-triazine -2,4-diyl] [(2,2,6,6-tetramethyl-4-piperidyl) imino] hexamethylene [(2,2,6,6-tetramethyl-4-piperidyl) imino]} C-1: Octadecyl-3- (3,5-ditertiarybutyl-4-hydroxyphenyl) propionate C-2: Triisopropanolamine C-3: Lauryl alcohol C-4: Glycerin C-5: Elka Acid amide C-6: No additive x: Paneler had off-flavor. ：: Panelers have no odor.

As shown in Table 1, it was confirmed that the examples exhibited extremely excellent storage stability as compared with the comparative examples.

Example 2 In a 100 ml bottle, dilauryl thiodipropionate and bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate (hereinafter sometimes also referred to as S-1) are shown in Table 2.
Add the amount described in the above, and in the opened state (air contact possible)
It was kept in a gear oven kept at 5 ° C. for 30 days.
The acid value before and after the heat treatment was measured to confirm the off-odor. The results are shown in Table 2.

[0094]

[Table 2]

As shown in Table 2, the effect of S-1 mixed with dilauryl thiodipropionate was recognized at an addition amount of 1 ppm or more, and a remarkable effect was observed at an addition amount of 30 ppm or more.

Example 3 In order to examine the discoloration when the composition of the present invention is used in combination with a phenolic antioxidant in an organic polymer material, the composition of Example 2 and 2,2-methylenebis (4-methyl- 6
-Tertiary butyl phenol) at a ratio of 1: 1 was maintained at 150 ° C. for 2 hours, and the degree of coloring (yellowness YI value) after the heat treatment was measured with a color meter. Table 3 shows the results.

[0097]

[Table 3]

As shown in Table 3, S-1 was 500 ppm
The dilauryl thiodipropionate contained above was not practical because the coloring was confirmed when used in combination with a phenolic compound.
When the content was 00 ppm, it was recognized that coloring was not so much observed and that it was practical. Also, when the results of Example 2 and Example 3 were comprehensively determined, 1 ppm to 500 pp
m, preferably in the range of 5 to 300 ppm, has been found to be suitable as an antioxidant for organic polymeric materials.

Example 4 Additives described in Table 4 were blended with an additive-free polypropylene (homopolymer) resin, and the total amount was 400 g.
And It was mixed for 5 minutes using a tumbler mixer, and using a 20 mm diameter extruder, the die temperature was 260 ° C.
Under the conditions described above, pellets were produced by a strand method.
A 1 mm thick test piece was prepared from the pellets using a vertical screw-type injection molding machine having a heating cylinder temperature of 200 ° C. The prepared test piece was left hanging under gears in a gear oven adjusted to 150 ° C., and the state of deterioration was visually observed to determine the time until embrittlement. The longer the time, the better the heat resistance effect. Table 4 shows the measured results.

[0100]

[Table 4]

The symbols described in Table 4 are as follows. PP resin: Polypropylene (homopolymer) additive-free product Additive DLTP-A: Dilaurylthiodipropionate containing 50 ppm of bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate Addition of DLTP-B : Dilauryl thiodipropionate containing 300 ppm of bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate DLTP: dilauryl thiodipropionate BHT: 2,6-di-tert-butyl -4-methylphenol Ca-St: calcium stearate

As shown in Table 4, it was confirmed that the polypropylene resin containing the composition of the present invention exhibited heat resistance equivalent to or slightly better than that of the sulfur-based antioxidant alone, and showed no adverse effect on heat resistance.

[0103]

It is understood that the composition of the present invention is a sulfur-based antioxidant which is extremely industrially effective and has excellent long-term storage properties.

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Claims (2)

[Claims] 1. A sulfur-based antioxidant containing a 2,2,6,6-tetramethylpiperidine compound, wherein the content thereof is less than 1 to 500 ppm based on the sulfur-based antioxidant. Sulfur-based antioxidants. 2. An organic polymer material composition comprising the sulfur-based antioxidant according to claim 1.