JP2002060638A - Stabilizer for organic polymer material, and organic polymer material composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a stabilizer composition for an organic polymer material excellent in working stability, and long-time storage stability, and provide an organic polymer material composition excellent in heat resistance. SOLUTION: This stabilizer composition for organic polymer material comprises a spirochroman compound (a), a polyhydric alcohol (b), a phosphorus- based antioxidant (c), and a phenolic antioxidant (d), and it contains 0.5-10 wt.% of component (a)+(b), and 99.5-90 wt.% of component (c)+(d) to the total of component (a), (b), (c), and (d), respectively. The organic polymer material composition is provided by compounding the stabilizer composition to an organic polymer material.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

[0001] The present invention relates to a stabilizer composition for an organic polymer material and a stabilized organic polymer material composition containing the same.

[0002]

2. Description of the Related Art Organic polymer materials composed of organic compounds such as natural polymers, synthetic polymers, fats and oils, lubricating oils, and hydraulic oils are deteriorated by oxidation, heat, light and the like, thereby impairing their usefulness. Various stabilizers, especially antioxidants, have been added to organic polymer materials for the purpose of preventing the occurrence of organic polymer materials to obtain organic polymer material compositions that are hardly deteriorated.

The general formula

Embedded image (In the formula, R ¹ , R ² , R ³ , R ⁴ and R ⁵ each represent the same or different hydrogen atom, hydroxyl group, alkoxy group having 1 to 4 carbon atoms or alkyl group having 1 to 4 carbon atoms.)
The compound represented by is described in JP-B-59-44343 as an antioxidant for organic synthetic polymer materials, fats and oils and petroleums. According to the publication, the antioxidant of the general formula is used in a ratio of 0.001 to 30% by weight based on the material to be stabilized, and may be used in combination with other antioxidants. Has been described. However, in Examples, the amount near the lower limit was not blended with the organic polymer material, nor was any specific example described in combination with other components, nor was there any description or suggestion regarding processing stability. It has not been.

[0004] Polyhydric alcohols are generally added to synthetic resins as lubricants, but it is hardly known that sugar alcohols and sugars are used in organic polymer materials. Phosphonite-based and phosphite-based phosphorus compounds have been researched and developed as antioxidants, and some phosphorus-based antioxidants are particularly widely used. It is also widely known that these compounds and compositions containing these compounds are effective as stabilizers for organic polymer materials.

[0005] Hindered phenol compounds such as n
-Octadecyl 3- (3,5-ditert-butyl-4-hydroxyphenyl) propionate and the like have been studied and developed as antioxidants for a long time, and some phenolic antioxidants are used in a very wide range. ing. Also,
It is also widely practiced to combine and use a plurality of types of antioxidants in order to simultaneously exert different effects or obtain a synergistic effect.

Meanwhile, it has been proposed to use a phenolic antioxidant and a phosphorus antioxidant in combination from the viewpoint that both exhibit different effects, and to use a phosphorus compound at the time of processing a synthetic resin. It is also well known that a hindered phenol compound is used as a secondary antioxidant in combination with a primary antioxidant to improve the coloring of an organic polymer material.

[0007]

In recent years, 3-arylbenzofuranone compounds have been developed as synergists when phosphorous antioxidants and phenolic antioxidants are used in combination. For example, in Example 14 of JP-A-7-233160, 3- (3,4-dimethylphenyl) -5,7-dithiamine which can be used for the same purpose as the present invention is described.
Tert-butyl-3H-benzofuran-2-one (compound 10
3) is described. This compound was also included in a lecture titled "Dramatic Advances in Polymer Stabilization" at the 10th International Conference on Polyolefins held in Houston, Texas, USA, February 23-26, 1997. It is described as a synergistic agent for phenolic antioxidants and phosphorus antioxidants. However, this synergistic effect is not practically satisfactory, and a more effective synergistic agent is required.

Recently, there has been an increasing demand for an antioxidant which is more excellent in heat resistance and processing stability due to a high molding temperature for high speed molding and a high temperature molding by alloying with engineering plastics. However, these known stabilizer compositions cannot sufficiently meet the demand. In addition, there is an increasing demand for an antioxidant that is effective even with a small amount in terms of heat resistance and processing stability. Furthermore, in the case of certain antioxidants, a small amount does not provide processing stability, and if a large amount is added to satisfy the requirement of processing stability, a problem such as a large amount of bleed-out from the resin is caused. There is a need for antioxidant compositions that exhibit sufficient processing stability even in small amounts.

As means for improving the stabilizing effect on organic polymer materials, WO 97/49758 discloses a phenolic antioxidant which contains a phenolic antioxidant, a phosphorus antioxidant and vitamin E (tocopherol). A stabilizer composition wherein the weight ratio of the agent to the phosphorus antioxidant is 2: 1 to 1: 4 and the weight ratio of the phenolic antioxidant to vitamin E is 2: 1 to 10: 1. Have been. This stabilizer composition has a high effect of preventing decomposition or crosslinking of a polymer material due to heat or light, and
It is described that a preferable weight ratio of the phenolic antioxidant to the phosphorus antioxidant is 1: 1 and a weight ratio of the phenolic antioxidant to vitamin E is 5: 1.

[0010] However, vitamin E is susceptible to air oxidation and is markedly colored and is a viscous liquid. Therefore, when added in a large amount, there is a problem that the stability is remarkably reduced. There are drawbacks such as the need for equipment and packaging. In addition, although vitamin E may be used in small amounts as an antioxidant in foods from the viewpoint of safety, very few examples are used for industrial applications as stabilizers for organic polymer materials.

[0011] The present inventors previously used a small amount of a 6-hydroxychroman compound in combination with a general-purpose phenolic antioxidant and a phosphorus-based antioxidant to obtain an organic polymer material having excellent processing stability. (WO 99/18154, WO 00/00540, WO
99/54394). International Publication WO99 / 18154
Contains a 6-hydroxychroman compound, a phenolic antioxidant, and a phosphorus-based antioxidant, and an organic compound containing a 6-hydroxychroman compound in a proportion of 1 to 6.5% by weight based on the total amount of these compounds. The present invention relates to a stabilizer for molecular materials. International Publication WO00 / 00540 also contains vitamin E, a phenolic antioxidant and a phosphorus antioxidant.
The present invention relates to a stabilizer composition for an organic polymer material containing 5.5% by weight. In addition, WO 99/54394 states that
An organic polymer material containing a 6-hydroxychroman compound, a phenolic antioxidant, and a phosphorus-based antioxidant, and containing the 6-hydroxychroman compound in a ratio of 0.5 to 10% by weight based on the total amount thereof. The present invention relates to a stabilizer composition for use.

Further, by using tocopherol in place of the phenolic antioxidant and combining a polyhydric alcohol such as trimethylolpropane, tripentaerythritol and dipentaerythritol and a phosphorus antioxidant, the processing stability can be improved. Being peeled, Po
lymer Dcgradation and Sta
bilety 64 (1999) 145-156,65
(1999) 143-151. In these documents, since tocopherol is used in place of the hindered phenolic antioxidant, even if the amount of tocopherol is as small as about several hundred ppm, which is suppressed to the minimum necessary by adding a polyhydric alcohol, the stabilizer composition The storage stability and powder properties of the resin were poor, and the colorability during processing was not sufficiently improved, and the balance of properties such as heat resistance was not good.

Accordingly, an object of the present invention is to provide a stabilizer composition for an organic polymer material which is excellent in processing stability, long-term storage stability and heat resistance, and an organic polymer material composition containing the same. It is. An economically advantageous stabilizer composition and an organic polymer material composition containing the stabilizer composition that can sufficiently achieve the object even when the amount of the expensive main component added is small in the stabilizer composition. It also aims to provide things.

[0014]

Means for Solving the Problems In order to solve the above-mentioned problems, the present inventors contain a phosphorus-based antioxidant, a phenol-based antioxidant and a spirochroman compound represented by the following general formula (Formula 1). By adding a very small amount of polyhydric alcohols to the stabilizer composition, not only can the total amount of antioxidants added be significantly reduced, but also the amount of expensive spirochroman compounds can be significantly reduced. It has been found that an excellent stabilizer which significantly improves the coloring prevention effect, heat resistance and processing stability of an organic polymer material can be obtained. One aspect of the present invention is (a): the following general formula:

Embedded image (In the formula, R ¹ , R ² , R ³ , R ⁴ and R ⁵ each represent the same or different hydrogen atom, hydroxyl group, alkoxy group having 1 to 4 carbon atoms or alkyl group having 1 to 4 carbon atoms.) (B): polyhydric alcohols, (c): phosphorus antioxidant, (d): phenolic antioxidant, a composition comprising the above four components. The content of component (a) + (b) is 0.5 to 10% by weight, and the content of component (c) + (based on the total weight of components (a), (b), (c) and (d). A stabilizer composition for an organic polymer material, wherein the content of d) is 99.5 to 90% by weight.

A second invention is an organic polymer material composition containing the organic polymer material and the stabilizer composition,
An organic polymer material composition containing 0.005 to 0.500% by weight of the stabilizer composition based on the organic polymer material composition.

A feature of the present invention is that a polyhydric alcohol and a polyhydric alcohol are added to the total amount of a general-purpose phenolic antioxidant, a phosphorus-based antioxidant, a polyhydric alcohol and a compound represented by the general formula (1). The general formula (1) is contained in a proportion of 0.5 to 10% by weight, preferably 1 to 5% by weight, more preferably 1 to 3% by weight. Another feature of the present invention is that the amount of the stabilizer composition in the organic polymer material composition is
0.005 to 0.50 with respect to the organic polymer material composition
% By weight, preferably 0.050 to 0.30% by weight. Addition of a polyhydric alcohol in an amount smaller than the above range and the compound of the general formula (Chemical Formula 1) does not provide a satisfactory synergistic effect on processing stability, but on the other hand, a polyhydric alcohol in an amount larger than the above range When the compound of the general formula (Formula 1) is added, a problem of coloring of the resin is observed, so the above numerical range condition is indispensable.

The organic polymer material in the organic polymer material composition of the present invention is a synthetic resin, and is preferably a polyolefin resin. More preferably, a polyethylene resin, a polypropylene resin, a mixture of a polyethylene resin and a polypropylene resin or a compatible polymer, a compatible polymer containing a polyethylene resin and / or a polypropylene resin, ethylene-vinyl acetate copolymer It is a polymer or an ethylene-propylene copolymer.

[0018]

BEST MODE FOR CARRYING OUT THE INVENTION The components of the stabilizer composition for an organic polymer material of the present invention will be described below. First, regarding the component (a), the substituent in the compound represented by the following general formula (Chemical Formula 1) will be described.

Embedded image Examples of the linear or branched alkyl group having 1 to 4 carbon atoms represented by R ¹ , R ² , R ³ , R ⁴ , and R ⁵ include a methyl group, an ethyl group, a propyl group, an isopropyl group, and a butyl group. Group, isobutyl group, secondary butyl group and tertiary butyl group. The alkoxy group having 1 to 4 carbon atoms represented by R ¹ , R ² , R ³ , R ⁴ , and R ⁵ may be a linear or branched alkoxy group, for example, a methoxy group, an ethoxy group, a propoxy group. Group, isopropoxy group, butoxy group, isobutyloxy group, secondary butoxy group, and tertiary butoxy group. Preferably,
R ¹ , R ² , R ³ , R ⁴ , and R ⁵ each represent the same or different hydrogen atom, hydroxyl group, or linear or branched alkyl group having 1 to 4 carbon atoms. More preferably, R
² is a hydroxyl group or a linear or branched alkyl group having 1 to 4 carbon atoms; R ¹ and R ³ are hydrogen atoms;
⁴ and R ⁵ are a linear or branched alkyl group having 1 to 4 carbon atoms. More preferably, R ¹ and R ³ are hydrogen atoms, R ² is a hydroxyl group or a methyl group, and R ⁴
And R ⁵ is a methyl group.

Preferred compounds of the component (a) are (1) 6,6'-dihydroxy-4,4,4 ', 4',
7,7'-hexamethyl-2,2'-spiro-bis-chroman (2) 6,6'-dihydroxy-4,4,4 ', 4'-
Tetramethyl-7,7'-diethyl-2,2'-spiro-bis-chroman (3) 6,6'-dihydroxy-4,4,4 ', 4'-
Tetramethyl-7,7'-dipropyl-2,2'-spiro-bis-chroman (4) 6,6'-dihydroxy-4,4,4 ', 4'-
Tetramethyl-7,7'-dibutyl-2,2'-spiro-bis-chroman (5) 4,4,4 ', 4'-tetramethyl-2,2'-
Spiro-bis-chroman-6,6 ′, 7,7′-tetraol, but is not limited thereto. More preferred are the compounds (1), (2) and (3).

Specific examples of the polyhydric alcohol as the component (b) include trimethylolpropane, tripentaerythritol, dipentaerythritol, pentaerythritol, trimethylolpropane ethoxylate,
Ethylene glycol, diethylene glycol, glycerin, sorbitol, xylitol, xylose, erythritol, mannitol, arabitol, ribose, glucose, galactose, maltose, fructose, saccharose, lactose, cellulose, α, β, γ-cyclodextrin, methylcellulose and the like. . Among them, preferred polyhydric alcohols include trimethylolpropane, ethylene glycol, diethylene glycol, sorbitol, xylitol, xylose, pentaerythritol, erythritol, mannitol, arabitol, ribose, lactose, cellulose, α, β,
γ-cyclodextrin, methylcellulose and the like. These polyhydric alcohols may be used alone or in combination of two or more.

Examples of the phosphorus-based antioxidant as the component (c) include the following. Tetrakis (2,4-di-tert-butylphenyl) -4,4'- described in JP-B-50-35096
4,4'-biphenylenediphosphonite compound represented by biphenylenediphosphonite Tetrakis (2,4-di-tert-butylphenyl) -4,4'- described in JP-A-1-254744.
Composition containing biphenylenediphosphonite and corresponding biphenylene monophosphonite Tetrakis (2,4-di-tert-butyl-6-methylphenyl) described in JP-A-2-270892
Composition comprising -4,4'-biphenylenediphosphonite and the like Tetrakis (2,4-ditert-butylphenyl) -4,4'- described in JP-A-5-202078.
Composition comprising biphenylenediphosphonate and the like Tetrakis (2,4-di-tert-butyl-5-methylphenyl) described in JP-A-5-178870
4,4'-biphenylenediphosphonite compounds represented by -4,4'-biphenylenediphosphonite 2,4 described in JP-A-8-231568
-Di-tert-butylphenylbis [4'-bis (2,4-
Di-tert-butylphenoxy) phosphanylbiphenyl-
4-yl] phosphinite} or (2,4-di-tert-butylphenoxy) bis [4 '-[bis (2,4-di-tert-butylphenoxy) phosphino] biphenyl-4-
Yl], 2,4-di-tert-butylphenyl [4'-bis (2,4-di-tert-butylphenoxy) phosphanylbiphenyl-4-yl]
[4′-bis (2,4-di-tert-butylphenoxy) phosphorylbiphenyl-4-yl] phosphinite, 2,
4-di-tert-butylphenylbis [4'-bis (2,
4-di-tert-butylphenoxy) phosphanylbiphenyl-4-yl] phosphinate, 2,4-di-tert-butylphenyl [4'-bis (2,4-di-tert-butylphenoxy) phosphanylbiphenyl- 4-yl] [4 '
-Bis (2,4-di-tert-butylphenoxy) phosphorylbiphenyl-4-yl] phosphinate, 2,4-di-tert-butylphenyl bis [4'-bis (2,4-di-tert-butylphenoxy) ) Phosphorylbiphenyl-4-
Yl] phosphinite, 2,4-di-tert-butylphenyl bis [4'-bis (2,4-di-tert-butylphenoxy) phosphorylbiphenyl-4-yl] phosphinate, 2,4-di-tert-butyl -5-methylphenyl bis [4'-bis (2,4-ditert-butyl-5-methylphenoxy) phosphanylbiphenyl-4-yl] phosphinite} or (2,4-tert-butyl-5- Methylphenoxy) bis [4 '-[bis (2,4-di-tert-butyl-5-methylphenoxy) phosphino] biphenyl-4-yl] phosphine {, 2,4-di-tert-butyl-5 -Methylphenyl [4'-bis (2,4-ditert-butyl-5-methylphenoxy) phosphanylbiphenyl-4-yl] [4'-bis (2
4-di-tert-butyl-5-methylphenoxy) phosphorylbiphenyl-4-yl] phosphinite, 2,4-di-tert-butyl-5-methylphenylbis [4'-bis (2,4-ditert. Tert-butyl-5-methylphenoxy) phosphanylbiphenyl-4-yl] phosphinate,
2,4-ditert-butyl-5-methylphenyl [4 ′
-Bis (2,4-di-tert-butyl-5-methylphenoxy) phosphanylbiphenyl-4-yl] [4'-bis (2,4-di-tert-butyl-5-methylphenoxy) phosphorylbiphenyl- 4-yl] phosphinate, 2,
4-ditert-butyl-5-methylphenylbis [4 '
-Bis (2,4-di-tert-butyl-5-methylphenoxy) phosphorylbiphenyl-4-yl] phosphinite, 2,4-di-tert-butyl-5-methylphenyl bis [4'-bis (2 4-di-tert-butyl-5-methylphenoxy) phosphorylbiphenyl-4-yl] phosphinate, 2,4-di-tert-butylphenyl (biphenyl-4-yl) [4'-bis (2,4-di Tertiary butylphenoxy) phosphanylbiphenyl-4-yl] phosphinite, 2,4-ditertiarybutyl-5-methylphenyl (biphenyl-4-yl) [4'-bis (2,4-
Di-tert-butyl-5-methylphenoxy) phosphanylbiphenyl-4-yl] phosphinite, 2,4-di-tert-butyl-6-methylphenyl (biphenyl-4-yl) [4'-bis (2, 4-ditertiarybutyl-6-methylphenoxy) phosphanylbiphenyl-4-yl] phosphinite, 2,4-ditertiarybutylphenyl (biphenyl-4-yl) [4'-bis (2,4- Di-tert-butylphenoxy) phosphorylbiphenyl-4-yl] phosphinite, 2,4-di-tert-butylphenyl (biphenyl-4-yl) [4′-bis (2,4-di-tert-butylphenoxy) Phosphanylbiphenyl-4-yl]
Phosphinate, 2,4-di-tert-butylphenyl (biphenyl-4-yl) [4'-bis (2,4-di-tert-butylphenoxy) phosphorylbiphenyl-4-yl]
Mixtures with other phosphorus-based antioxidants containing phosphinate, tetrakis (2,4-di-tert-butylphenyl) -4,4′-biphenylenediphosphonite in an amount of 50% by weight or more, preferably 60% by weight or more. The mixture further comprises (2,4-di-tert-butylphenoxy) bis [4 '-[bis (2,4-di-tert-butylphenoxy) phosphino] biphenyl-4-yl] phosphine in addition to the phosphonite. , [(2,4-di-tert-butylphenoxy) phosphino] biphenyl, tris (2,4-di-tert-butylphenyl) phosphite and the like.と, another phosphorus-based antioxidant containing 50% by weight or more, preferably 60% by weight or more of tetrakis (2,4-ditert-butyl-5-methylphenyl) -4,4′-biphenylenediphosphonite; {Circle around (2)} The mixture further comprises (2,4-ditert-butyl-5-methylphenoxy) bis [4 ′-[bis (2,4
-Di-tert-butyl-5-methylphenoxy) phosphino] biphenyl-4-yl] phosphine, [(2,4-
Ditertiary butyl-5-methylphenoxy) phosphino]
It may contain biphenyl, tris (2,4-ditert-butyl-5-methylphenyl) phosphite and the like. ｝, Tris (2,4-ditert-butylphenyl) phosphite, bis- [2-methyl-4,6-bis (1,
1-dimethylethyl) phenyl] ethyl phosphite,
Triphenyl phosphite, diphenylalkyl phosphite, phenyl dialkyl phosphite, tris (nonylphenyl) phosphite, trilauryl phosphite, trioctadecyl phosphite, bis (2,4-di-tert-butyl-6-methylphenyl) ) Methyl phosphite, hexatridecyl 1,1,3-tris (2-methyl-4-hydroxy-5-tert-butylphenyl) butanetriphosphite bis (2,4-di-tert-butylphenyl) pentaerythritol Diphosphite, bis (2,6-ditert-butyl-4-methylphenyl) pentaerythritol diphosphite, distearylpentaerythritol diphosphite, bis [2,4-bis (α, α-dimethylbenzyl) Phenyl] pentaerythritol diphosphite (2,4,6-tri-tert-butylphenyl) -2-butyl-2-ethyl-1,3-propanediol phosphite, bisisodecylpentaerythritol diphosphite bis (2,4,6-tri-tert-butylphenyl) Tertiary butylphenyl) pentaerythritol diphosphite 2,2'-methylenebis (4,6-ditertiarybutylphenyl) -2-ethylhexyl phosphite, 2,
2 ′, 2 ″ -nitrilo [triethyltris (3,3 ′,
5,5'-tetra-tert-butyl-1,1'-biphenyl-2,2'-diyl) phosphite], 2,2-ethylidene-bis (4,6-di-tert-butylphenyl) fluoro Phosphonite, 2,10-dimethyl-4,8-ditertiarybutyl-6- {2- [3- (3-tertiarybutyl-4)
-Hydroxy-5-methylphenyl) propionyloxy] ethoxy} -12H-dibenzo [d, g] [1,
3,2] dioxaphosphosine, 6- [3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propoxy] -2,4,8,10-tetratert-butyldibenzo [d , F] [1,3,2] dioxaphosphepin.

Preferred examples of the above-mentioned phosphorus antioxidants are as follows. Tris (2,4-ditert-butylphenyl) phosphite, tetrakis (2,4-ditert-butyl)
Butylphenyl) -4,4'-biphenylenediphosphonite, tetrakis (2,4-ditertiarybutyl-5-methylphenyl) -4,4'-biphenylenediphosphonite, bis (2,4-diphenyl Tertiary butylphenyl) pentaerythritol diphosphite, bis (2,6-ditertiarybutyl-4-methylphenyl) pentaerythritol diphosphite, 2,2′-methylenebis (4,6-ditertiary) Butylphenyl) -2-ethylhexyl phosphite, bis- [2-methyl-4,6-bis (1,1-dimethylethyl) phenyl] ethyl phosphite, 2,
2 ′, 2 ″ -nitrilo [triethyltris (3,3 ′,
5,5'-tetra-tert-butyl-1,1'-biphenyl-2,2'-diyl) phosphite], 2,2-ethylidene-bis (4,6-di-tert-butylphenyl) fluoro Phosphonite, 2,10-dimethyl-4,8-ditertiarybutyl-6- {2- [3- (3-tertiarybutyl-4)
-Hydroxy-5-methylphenyl) propionyloxy] ethoxy} -12H-dibenzo [d, g] [1,
3,2] dioxaphosphin, bis [2,4-bis (α, α-dimethylbenzyl) phenyl] pentaerythritol diphosphite, (2,4,6-tritert-butylphenyl) -2-butyl -2-ethyl-1,3-propanediol phosphite, 6- [3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propoxy] -2,4,8,10-tetratert. Tert-butyldibenzo [d, f] [1,3,2] dioxaphosphepin. Particularly preferred are tris (2,4-di-tert-butylphenyl) phosphite, tetrakis (2,4-di-tert-butylphenyl) -4,4′-biphenylenediphosphonite, tetrakis (2,4 -Di-tert-butyl-5-methylphenyl) -4,4'-biphenylenediphosphonite. Of course, these phosphorus-based antioxidants can be used alone or in combination of two or more.

Specific examples of the phenolic antioxidant which is the component (d) are shown below. n-octadecyl-3-
(3,5-di-tert-butyl-4-hydroxyphenyl)
Propionate, tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionyloxymethyl] methane, 1,3,5-tris (3,5-di-tert.
Tert-butyl-4-hydroxybenzyl) isocyanurate, 1,3,5-trimethyl-2,4,6-tris (3,5-ditert-butyl-4-hydroxybenzyl)
Benzene, 1,1,3-tris [2-methyl-4- [3
-(3,5-Ditert-butyl-4-hydroxyphenyl) propionyloxy] -5-tert-butylphenyl] butane, bis (3-tert-butyl-4-hydroxy-5-methylphenyl) di Cyclopentadiene, 1,
3,5-tris (4-tert-butyl-3-hydroxy-
2,6-dimethylbenzyl) isocyanuric acid, 3,9-
Bis [2- [3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionyloxy] -1,1
-Dimethylethyl] -2,4,8,10-tetraoxaspiro [5.5] undecane, 2,6-ditertiarybutyl-4-methylphenol, 2,4-dimethyl-6-tertiary
Tert-butylphenol, 2,6-di-tert-butyl-4-hydroxymethylphenol, 2,6-di-tert-butyl
4-ethylphenol, 2,4,6-tritertiary butylphenol, butylated hydroxyanisole, isooctyl-3- (4-hydroxy-3,5-ditertiarybutylphenyl) propionate, distearyl. (Hydroxy-3-methyl-5-tert-butyl) benzylmalonate, 2,2′-methylenebis (4-methyl-6-tert-butylphenol), 2,2′-methylenebis (4
-Ethyl-6-tertiary butylphenol), 4,4'-
Methylene bis (2,6-ditertiary butylphenol),
2,2′-butylidenebis (4-ethyl-6-tert-butylphenol), 4,4′-butylidenebis (3-methyl-6-tert-butylphenol), 2,2′-thiobis (4-methyl-6 -Tertiary butyl phenol),
4,4′-thiobis (3-methyl-6-tert-butylphenol), styrenated phenol, N, N′-hexamethylenebis (3,5-ditert-butyl-4-hydroxyhydrocinnamide), Bis (3,5-ditert-butyl-4-hydroxybenzylphosphonate ethyl) calcium, 1,1,3-tris (2-methyl-4-hydroxy-5-tert-butylphenyl) butane, 1, 6-hexanediol-bis [3- (3,5-ditert-butyl-4)
-Hydroxyphenyl) propionate], 2,2'-
Methylenebis (4-methyl-6-cyclohexylphenol), 2,2′-methylenebis [6- (1-methylcyclohexyl) -4-methylphenol], triethylene glycol-bis [3- (3-tert-butyl- 4-hydroxy-5-methylphenyl) propionate], ethylene glycol-bis (3,3-bis (3-tert-butyl-4-hydroxyphenyl) butyrate), 2-tert-butyl-6- (3- Tertiary butyl-5-methyl-2
-Hydroxybenzyl) -4-methylphenyl acrylate, 2,2'-oxamido-bis [ethyl-3-
(3,5-di-tert-butyl-4-hydroxyphenyl)
Propionate], 6- (4-hydroxy-3,5-di-tert-butylanilino) -2,4-dioctylthio-
1,3,5-triazine, bis [2-tertiary butyl-4
-Methyl-6- (2-hydroxy-3-tert-butyl-
5-methylbenzyl) phenyl] terephthalate, 3,
9-bis [2- [3- (3,5-ditert-butyl-4-)
[Hydroxyphenyl) propionyloxy] -1,1-
Dimethylethyl] -2,4,8,10-tetraoxaspiro [5.5] undecane, 1,3,5-tris [3-
(3,5-di-tert-butyl-4-hydroxyphenyl)
Propionyloxy] ethyl isocyanate, 2,2-
Thiodiethylene-bis [3- (3,5-ditert-butyl-4-hydroxyphenyl) propionate], 2-
[1- (2-hydroxy-3,5-di-tert-pentylphenyl) ethyl] -4,6-di-tert-pentylphenyl acrylate, 2,4-bis [(octylthio) methyl] -o-cresol, Propyl gallate, octyl gallate, dodecyl gallate.

Examples of more preferred phenolic antioxidants include n-octadecyl 3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate and tetrakis [3- (3,5-di-tertiary). Butyl-4-hydroxyphenyl) propionyloxymethyl] methane, 1,3,
5-tris (3,5-ditert-butyl-4-hydroxybenzyl) isocyanurate, 1,3,5-trimethyl-2,4,6-tris (3,5-ditert-butyl-4-
(Hydroxybenzyl) benzene, and these phenolic antioxidants can be used alone or in combination.

An organic polymer material composition containing the stabilizer composition as another aspect of the present invention will be described below. The organic polymer material stabilized by the stabilizer composition of the present invention is a synthetic or natural organic polymer material, but a synthetic resin such as a thermoplastic resin and a thermosetting resin is preferable. As the thermoplastic resin, for example, polyolefin resin, halogen-containing polymer, styrene resin, acrylic resin, thermoplastic polyester resin, polyamide resin, aromatic polycarbonate resin, polyacetal resin, polyethylene oxide resin, polyphenylene ether resin, polysulfone Resin, polyurethane resin, petroleum resin, polyvinyl acetate resin, vinyl acetal resin, cellulose (cellulose) resin, polyether sulfone resin,
Polyphenylene sulfide resin, polyether ketone resin, polyether imide resin, polyoxybenzoyl resin, polyimide resin, polymaleimide resin, polyamide imide resin, polyarylate resin, fluororesin, ionomer, thermoplastic elastomer, etc., alone or in combination Can be used.

Particularly preferred are polyolefin resins,
Among them, α-olefin homopolymer or α-olefin copolymer. Examples of the polyolefin resin, low-density polyethylene, linear low-density polyethylene,
Medium-density polyethylene, high-density polyethylene, ultra-high-molecular-weight polyethylene, polypropylene, polybutene-1, polypentene, poly-2-methylbutylene, etc.
Α-olefin homopolymer of No. 8; α such as ethylene / propylene random copolymer, ethylene / propylene block copolymer, ethylene / butene-1 random copolymer, propylene / ethylene / butene-1 random copolymer
-Olefin copolymers; copolymers of α-olefins and other monomers such as maleic anhydride-modified polypropylene and ethylene / vinyl acetate copolymer. These can be used alone or in the form of a mixture of two or more thereof or another compatible polymer. However, the most preferred resin is polypropylene or polyethylene. After polymerization, these polyolefin-based resins have been subjected to a slight purification treatment including a step of removing catalyst residues, and those having a relatively high degree of purification, in addition to using a highly active catalyst and not undergoing a catalyst removal step. Or a polyolefin-based resin containing a catalyst residue obtained by simplification,
In particular, a crystalline polyolefin-based resin obtained by using a Ziegler-type catalyst or a chromium-based catalyst using a halogen-containing magnesium compound as a catalyst carrier and not yet subjected to a catalyst residue removal step may be used (Japanese Patent Publication No. 62-4418). Gazette, Japanese Patent Publication No. 3-56245, U.S. Pat.
No. 39). Further, a polyolefin resin having a very narrow molecular weight distribution obtained by a metallocene single-site catalyst may be used (Journal of
Polymer Science. Polymer Chemistry Edition, Vol. 23, p. 2151 (1985)).

Examples of the halogen-containing polymer include polyvinyl chloride, polyvinylidene chloride, polyvinyl fluoride, polyvinylidene fluoride, vinyl chloride / alkyl acrylate copolymer, and chlorinated polyethylene. As the styrene resin, for example,
Polystyrene, high impact polystyrene, styrene / acrylonitrile copolymer, styrene / MMA copolymer, A
BS resin, AES resin, ACS resin, AAS resin, EE
S resins and the like, and mixtures thereof.
Examples of the acrylic resin include polyacrylate and polymethacrylate. Examples of the thermoplastic polyester resin include polyethylene terephthalate and polybutylene terephthalate. Examples of the polyamide resin include nylon 4, nylon 6, nylon 4.6, nylon 6.6,
Nylon 6, 10, Nylon 7, Nylon 8, Nylon 12, Nylon 6, 12, Nylon 11, 12, Aramid, and the like, and mixtures thereof.

Examples of the thermosetting resin include unsaturated polyester resin, phenol resin, urea resin, melamine resin, epoxy resin, polyimide resin, silicone resin, diallyl phthalate resin, polyurethane resin, furan resin and the like.

When the stabilizer composition of the present invention is blended with such an organic polymer material, an excellent antioxidant effect is exhibited, but by further blending a sulfur-based antioxidant,
An organic polymer material having better stability can be obtained. As the sulfur-based antioxidant, preferably, dilaurylthiodipropionate, laurylstearylthiodipropionate, dimyristylthiodipropionate, distearylthiodipropionate, ditridecylthiodipropionate, tetrakis [(3- Laurylthiopropionyloxy) methyl] methane, tetrakis [(3-stearylthiopropionyloxy) methyl] methane, bis [2-methyl-4- (3-n-alkyl (C ₁₂ -C
₁₄ ) Thiopropionyloxy) -5-tertiary butylphenyl] sulfide and the like. These may be used alone or in combination. The sulfur-based antioxidant can be added at a ratio of 0.005 to 5% by weight, preferably 0.01 to 1% by weight, based on the organic polymer material composition.

The organic polymer material composition of the present invention is further blended with an ultraviolet absorber or a light stabilizer,
An organic polymer material having better stability can be obtained. Examples of the ultraviolet absorber or light stabilizer include salicylic acid compounds, benzophenone compounds, benzotriazole compounds, benzoate compounds, cyanoacrylate compounds, nickel compounds, and piperidine compounds. The ultraviolet absorber or the light stabilizer can be added at a ratio of 0.005 to 5% by weight, preferably 0.01 to 1% by weight, based on the organic polymer material composition.

The components of the stabilizer composition of the present invention are represented by the general formula (Chemical Formula 1) (Component a), a polyhydric alcohol antioxidant (Component b), a phosphorus antioxidant (Component c) and a phenolic antioxidant. In addition to the antioxidant (component d), if necessary, a sulfur-based antioxidant, an ultraviolet absorber, and a light stabilizer are added to the organic polymer material to further stabilize the composition of the organic polymer material. You can get things.

If necessary, other additives, for example, metal soaps such as hydrotalcites and calcium stearate, and heavy metals such as hydrazine-based compounds, as long as the performance of the organic polymer material composition of the present invention is not significantly impaired. Deactivator, monoalkyl tin tris (octyl thioglycolate), dialkyl tin tris (octyl thioglycolate), monoalkyl tin tris (monoalkyl maleate) or dialkyl tin tris (monoalkyl maleate) Such as organotin stabilizers, epoxy compounds such as epoxidized soybean oil or epoxy octyl stearate, various organic pigments, flame retardants such as phosphate esters, antistatic agents such as cationic or anionic surfactants, and aliphatics Lower alcohols of amides or fatty acids Lubricants such as toluene, acrylic polymer processing aids, plasticizers such as di-2-ethylhexyl phthalate or di-2-ethylhexyl adipate, fillers such as aluminum oxide, foaming agents such as sodium bicarbonate or azodicarbonamide. Etc. can also be used. If necessary, a nucleating agent, a clarifying agent, and the like can be added.

The stabilizer composition of the present invention comprises the component (a),
(B), (c), (d) and, if necessary, a predetermined amount of each of the sulfur-based antioxidant, ultraviolet absorber, light stabilizer, and other additives is weighed and mixed by a conventional means. Can be prepared. The mixed stabilizer composition is
There is no change in appearance or stickiness after long-term storage, and no change is observed in powder characteristics. The compounding of the stabilizer composition into the organic polymer material is performed by a conventional compounding method, that is, a series of steps such as mixing, kneading, and extruding the organic polymer material and the stabilizer composition. As a mixer for organic polymer materials,
Ball mills, pebble mills, tumble mixers, change can mixers, super mixers (Henschel mixers), etc. can be used. Mixing rolls, Banbury mixers, vane type mixers, high-speed twin-screw continuous mixers, extruder type A kneader or the like can be used.

The organic polymer material composition according to the present invention has applications as various molded articles by injection molding, extrusion molding, calender molding, blow molding, compression molding and the like. For example, electrical product parts, electronic product parts, agricultural machine parts, agricultural products, fishery machine parts, fishery products, automobile parts, daily necessities, and miscellaneous goods.

[0035]

EXAMPLES The present invention will be described in more detail with reference to the following Examples, which are based on the following melt index and yellowness as a measure of the effects of the present invention. The melt index (MI), which indicates the moldability of synthetic resins, is JI
It is measured according to SK7210. MI is a numerical value expressing the flow rate for 10 minutes by weight (g) when extruding an organic polymer material melted at a constant temperature from a circular die having a prescribed length and diameter with a constant load, and is used as an index of melt viscosity. ing. In the case of polypropylene among the high molecular weight polymers, it is considered that the smaller the numerical value is, the better the processing stability is, and the larger the numerical value is, the worse the processing stability is. In the case of polyethylene, under normal processing conditions, a crosslinking phenomenon occurs at an early stage of deterioration, and numerically, it is known that the MI value tends to decrease.Unlike polypropylene, which causes only molecular breakage, It is considered that the smaller the value, the worse the processing stability. In any case, by repeatedly measuring, it is said that those with little change in the numerical value have a large MI holding effect and are excellent in processing stability. As another method known as an index of stability during processing of polyethylene, there is an evaluation method using a Labo Plastomill to track a change in torque during kneading. For materials such as polyethylene that undergo both molecular cross-linking and molecular breakage due to thermal history and undergo deterioration, not only evaluation of MI alone, but also evaluation method to track torque change during kneading by Labo Plastomill It is being done at the same time. In this case, a time until the torque starts to increase (hereinafter, referred to as a heat stabilization time) is obtained,
It is said that the larger the value, the better the thermal stability.

The degree of yellowness (YI) indicating the degree of discoloration when the additive is kneaded into an organic polymer material is JIS K 7103.
It is measured according to. YI is measured by a color meter. The larger the numerical value, the greater the degree of discoloration or coloring, and the smaller the value, the less coloring during processing and the better.

An example of the synthesis of a spirochroman compound used in this example is shown below. To a 5-liter three-necked flask equipped with a stirrer and a reflux condenser, 620 g (5.0 mol) of methylhydroquinone, 1500 ml of glacial acetic acid, 580 g (10.0 mol) of acetone, and 850 ml of concentrated hydrochloric acid were sequentially added while stirring. The mixture slightly generated heat and gradually dissolved homogeneously to form a light brown liquid. Next, the reaction mixture was heated and refluxed for 7 to 9 hours while being stirred on an oil bath, and then left at room temperature for several days. Thereafter, a deposited black precipitate was collected by filtration. When 60 ml of acetone was added to the black reaction mother liquor and left at room temperature, 6,6′-dihydroxy-4,4,4 ′, 4 ′, 7,7′-hexamethyl-2,
50 g of white crystals of 2'-spiro-bis-chroman were obtained. 201-207 ° C. Elemental analysis found: C, 75.05%, H, 7.5.
7%, theory: C 75.00%, H 7.61%.

Example 1 Dry mixing for 5 minutes using a tumbler mixer Table 1
A strand was extruded using an extruder having a diameter of 20 mm (die setting temperature: 280 ° C.), cooled with water, and then cut to obtain a pellet using the compound described in the above. This was repeated four times. In order to check the processing stability, the MI of the pellets extruded each time was measured at a temperature and a load condition of 230 ° C. and 2.16 kgf. Every time,
The yellowness (YI) of the extruded pellets was also measured.

[Table 1]

The formulations and symbols described in Table 1 are as follows. PP: polypropylene homopolymer Ca-St: calcium stearate c-1: tetrakis (2,4-ditert-butyl-5-methylphenyl) -4,4′-biphenylenediphosphonite (manufactured by Yoshitomi Fine Chemical Co., Ltd.) Name: "GS
Y-P01 ") c-2: Tetrakis (2,4-ditert-butyl-phenyl) -4,4'-biphenylenediphosphonite (manufactured by Clariant Co., Ltd., trade name:" Sandstab-PE ")
PQ ") d-1: tetrakis [3- (3,5-di-tert-butyl-
4-hydroxyphenyl) propionyloxymethyl]
Methane (product name: manufactured by Yoshitomi Fine Chemical Co., Ltd.)
"Tominox TT") d-3: 1,3,5-tris- (3,5-ditert-butyl-4-hydroxybenzyl) isocyanurate (trade name: Yoshinox 314, manufactured by Yoshitomi Fine Chemical Co., Ltd.) a-1: 4,4,4 ', 4', 7,7'-Hexamethyl-2,2'-spiro-bis-chroman (compound according to the above synthesis example) b-1: Trimethylolpropane (Wako Pure Chemical Industries, Ltd.) B-2: Pentaerythritol (reagent manufactured by Wako Pure Chemical Industries, Ltd.) MI1: MI value of pellet obtained at the first time MI4: MI value of pellet obtained at the fourth time YI1: Obtained at the first time YI value of pellet YI4: YI value of pellet obtained at the fourth time From Table 1, it can be seen that the formulation by mixing the four components shows processing stability (M
It can be seen that the coloration (YI) of the kneaded resin is improved while maintaining I), and the amount of the synergist added can be significantly reduced. In addition, it can be seen that the formulas 13, 14, 15, and 16 have a poor MI and YI balance and are inferior to all the formulas in Example 1.

Example 2 Strands were extruded with a 20 mm diameter extruder (die set temperature: 230 ° C.) using the blends shown in Table 1 which had been dry-mixed for 5 minutes using a tumbler mixer, cooled with water, and cut to obtain pellets. This was repeated five times. The MI of the extruded pellet was measured each time to check the processing stability. The measurement conditions were 190 ° C. and 2.16 kgf. Further, the yellowness (YI) of the extruded pellet was measured every time. Table 2 shows the measurement results.

[Table 2] The formulation and the symbols described in Table 2 will be described.
LLDPE: linear low-density polyethylene Zn-St: zinc stearate d-2: n-octadecyl 3- (3,5-ditertiary butyl-4) -Hydroxyphenyl) propionate (trade name: "Tominox SS", manufactured by Yoshitomi Fine Chemical Co., Ltd.) b-3: D (-)-mannitol (reagent manufactured by Wako Pure Chemical Industries, Ltd.) It is confirmed that the coloring (YI) of the kneaded resin is improved while maintaining the MI), and the amount of the synergist added can be significantly reduced. Formulations 10, 11, 12, and 13 of Comparative Example 2 were different from those of Example 2 in terms of MI. It can be seen that the balance of YI is poor and inferior.

[0041]

The stabilizer composition of the present invention not only has excellent processing stability and storage stability when added to an organic polymer material, but also has an excellent heat resistance. Is excellent. Moreover, this stabilizer composition is economical because the amount of expensive antioxidant components can be greatly reduced.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) C08L 23/02 C08L 23/02 C09K 15/06 C09K 15/06 15/08 15/08 15/32 15 / 32C (72) Inventor Mamoru Suga 2-4-9, Hirano-cho, Chuo-ku, Osaka-shi F-term in Yoshitomi Fine Chemical Co., Ltd. (Reference) 4H025 AA12 AA13 AA16 AA17 AA63 AA65 AA95 AC05 AC07 4J002 AA001 BB001 BB031 BB061 BB1210 BB151 EC EJ019 EJ049 EL126 EW018 EW068 EW128 FD010 FD020 FD036 FD037 FD076 FD078 FD079 FD090 FD100 FD130 FD170 FD177 FD200 FD310

Claims (10)

[Claims] (1) (a): The following general formula: (Wherein, R ¹ , R ² , R ³ , R ⁴ and R ⁵ each represent the same or different hydrogen atom, hydroxyl group, alkoxy group having 1 to 4 carbon atoms or alkyl group having 1 to 4 carbon atoms). (B): polyhydric alcohols, (c): phosphorus antioxidant, (d): phenolic antioxidant, a composition comprising the above four components. The content of component (a) + (b) is 0.5 to 10% by weight, and the content of component (c) + (based on the total weight of components (a), (b), (c) and (d). A stabilizer composition for an organic polymer material, wherein the content of d) is 99.5 to 90% by weight. 2. The composition ratio of component (a) to component (b) is 1: 9.
The stabilizer composition according to claim 1, wherein the ratio is in the range of 9 to 1. 3. Component (a) is 6,6'-dihydroxy-
4,4,4 ', 4', 7,7'-hexamethyl-2,
2′-spiro-bis-chroman, 6,6′-dihydroxy-4,4,4 ′, 4′-tetramethyl-7,7′-diethyl-2,2′-spiro-bis-chroman and
6'-dihydroxy-4,4,4 ', 4'-tetramethyl-7,7'-dipropyl-2,2'-spiro-bis-
3. The stabilizer composition according to claim 1, which is a compound selected from chroman. 4. Component (b) is trimethylolpropane,
Tripentaerythritol, dipentaerythritol,
At least one selected from the group consisting of pentaerythritol, trimethylolpropane ethoxylate, ethylene glycol, diethylene glycol, glycerin, sorbitol, xylitol, xylose, erythritol, mannitol, arabitol, ribose, sugars, cycloamyloses, and methylcellulose. Item 1
Or the stabilizer composition according to 2. 5. Component (c) is tetrakis (2,4-di-tert-butylphenyl) -4,4'-biphenylenediphosphonite, tetrakis (2,4-di-tert-butyl-5-
Methylphenyl) -4,4'-biphenylenediphosphonite, tris (2,4-di-tert-butylphenyl) phosphite, bis (2,4-di-tert-butylphenyl) pentaerythritol diphosphite, bis (2,6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphite, distearylpentaerythritol diphosphite, 2,2-methylenebis (4,6-di-tert-butylphenyl) -2- Ethylhexyl phosphite, 6- [3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propoxy] -2,4,8,1
0-tetra-tert-butyldibenzo [d, f] [1,3
2] The stabilizer composition according to claim 1, which is at least one member selected from the group consisting of dioxaphosphepins. 6. Component (d) is tetrakis [3- (3,5)
-Di-tert-butyl-4-hydroxyphenyl) propionyloxymethyl] methane, n-octadecyl3-
(3,5-di-tert-butyl-4-hydroxyphenyl)
Propionate, 1,3,5-tris (3,5-dithird
Butyl-4-hydroxybenzyl) isocyanurate and 1,3,5-trimethyl-2,4,6-tris (3,5-ditert-butyl-4-hydroxybenzyl) benzene. The stabilizer composition according to claim 1, which is at least one kind. 7. An organic polymer material composition comprising an organic polymer material and the stabilizer composition according to claim 1, wherein the stabilizer composition is added to 100 parts by weight of the organic polymer material composition. On the other hand, an organic polymer material composition containing 0.005 parts by weight to 0.500 parts by weight. 8. The organic polymer material composition according to claim 7, wherein the organic polymer material is a synthetic resin. 9. The organic polymer material composition according to claim 8, wherein the synthetic resin is a polyolefin resin. 10. The polyolefin resin is a polyethylene resin, a polypropylene resin, a mixture of a polyethylene resin and a polypropylene resin or a compatible polymer,
The organic polymer material composition according to claim 9, which is a compatible polymer containing a polyethylene resin and / or a polypropylene resin, an ethylene-vinyl acetate copolymer, or an ethylene-propylene copolymer.