JPH11228957A - Stabilizer composition, and production and use thereof - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a stabilizer compsn. which is excellent in stabilizing org. materials, such as synthetic resins, rubbers, and coating materials by using a combination of a specific phosphite compd. with a phenolic stabilizer or a hindered amine stabilizer. SOLUTION: This compsn. comprises a phosphite compd. of the formula (wherein R<1> to R<6> are each H or 1-8C alkyl provided they other than R<3> and R<6> may each be 5-8C cycloalkyl, 7-12C aryl or the like; X<1> is an alcohol residue; X<2> is a single bond or 1-8C alkylene; and Y is hydroxyl, 1-8C alkoxy, or the like) and a phenolic or hindered amine stabilizer in a wt. ratio of (10:1)-(1:10). Pref., in the formula, R<1> and R<2> are each t-butyl; one of R<4> and R<5> is t-butyl and the other is methyl or t-butyl ; and R<3> and R<6> are both H or methyl. The phosphite compd. is prepd. by reacting a phenol which constitutes the left side of the formula, a phosphorus trihalide, and an alcohol which constitutes the right side of the formula by using a dehydrohalogenating agent. The stabilizer compsn. effectively stabilizes org. materials against degradation by heat or oxidation.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to a stabilizer composition comprising a novel phosphite and at least one stabilizer selected from a phenol stabilizer and a hindered amine stabilizer. The present invention relates to a product, a production method thereof, and a use thereof.

[0002]

2. Description of the Related Art Organic materials such as thermoplastic resins, thermosetting resins, natural or synthetic rubbers, mineral oils, lubricating oils, adhesives, paints and the like are used during production, processing and further use. Occasionally, it is degraded by the action of heat, oxygen, light, etc., resulting in a decrease in strength physical properties of organic materials due to phenomena such as molecular cutting and molecular cross-linking, a change in flowability, coloring, a decrease in surface physical properties, etc. It is known to be severely impaired. For the purpose of solving such problems as heat and oxidative deterioration, a method of stabilizing an organic material by using a stabilizer such as a phenol-based stabilizer and a hindered amine-based stabilizer together with a phosphorus-based stabilizer has been conventionally used. Are known.

[0003] For example, tris (2,4-di-t-butylphenyl) phosphite has been added to 2,6-di-t-butyl-4-methylphenol, n-octadecyl 3- (3,5-di-t-butyl). -Combination use of phenolic stabilizers such as butyl-4-hydroxyphenyl) propionate and neopentanetetrayltetrakis (3,5-di-t-butyl-4-hydroxydihydrocinnamate) No. 5417, Japanese Patent Publication No. 62-4418) are known. However, the combination method using these known phosphorus-based stabilizers has a problem that the stabilizing effect is insufficient, and development of a more excellent stabilizer composition has been demanded.

The present inventors have produced various phosphorus compounds in order to develop a stabilizer composition exhibiting a more excellent stabilizing effect, and as a result of intensive studies, as a result, as a phosphorus compound, a specific cyclic compound was obtained. The present inventors have found that a stabilizer composition using a phosphite exhibits an excellent stabilizing effect, and completed the present invention.

[0005]

That is, the present invention provides a compound represented by the general formula (I):

[0006]

(Wherein R ¹ , R ² , R ⁴ and R ⁵ are each independently a hydrogen atom, an alkyl group having 1 to 8 carbon atoms,
Represents a cycloalkyl group having 5 to 8 carbon atoms, an alkylcycloalkyl group having 6 to 12 carbon atoms, an aralkyl group or a phenyl group having 7 to 12 carbon atoms, and R ³ and R ⁶ each independently represent a hydrogen atom or a carbon atom number; Represents 1 to 8 alkyl groups. X ₁
Represents a dihydric alcohol residue, and X ₂ represents a mere bond or an alkylene group having 1 to 8 carbon atoms. Y is a hydroxyl group,
Represents an alkoxy group having 1 to 8 carbon atoms or an aralkyloxy group having 7 to 12 carbon atoms. ), A phenolic stabilizer and at least one stabilizer selected from hindered amine stabilizers, a method for producing the same, and a method for using the same. To provide.

[0008]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail. In the phosphites represented by the formula (I) of the present invention, the substituents R ¹ , R ² , R ⁴ and R ⁵ each independently represent a hydrogen atom, an alkyl group having 1 to 8 carbon atoms and ⁵ carbon atoms. Represents a cycloalkyl group having 8 to 8 carbon atoms, an alkylcycloalkyl group having 6 to 12 carbon atoms, an aralkyl group having 7 to 12 carbon atoms, or a phenyl group. Here, typical examples of the alkyl group having 1 to 8 carbon atoms include, for example, methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, sec-butyl, t-
Butyl, t-pentyl, i-octyl, t-octyl, 2-ethylhexyl and the like. Representative examples of the cycloalkyl group having 5 to 8 carbon atoms include, for example, cyclopentyl,
Cyclohexyl, cycloheptyl, cyclooctyl and the like are typical examples of alkylcycloalkyl groups having 6 to 12 carbon atoms, for example, 1-methylcyclopentyl, 1-methylcyclohexyl, 1-methyl-4-i-propylcyclohexyl and the like. Can be Representative examples of the aralkyl group having 7 to 12 carbon atoms include, for example, benzyl, α-methylbenzyl, α,
α-dimethylbenzyl and the like.

In particular, R ¹ is t-butyl, t-pentyl,
It is preferably a t-alkyl group such as t-octyl.
R ² is methyl, ethyl, n-propyl, i-propyl, n-
Butyl, i-butyl, sec-butyl, t-butyl, preferably an alkyl group having 1 to 5 carbon atoms such as t-pentyl,
Particularly, t-butyl is preferable. R ⁴ and R ⁵ are preferably an alkyl group having 1 to 5 carbon atoms and a t-alkyl group as described above, and more preferably,
^One of R ⁴ and R ⁵ is a t-alkyl group, particularly a t-butyl group, and the other is an alkyl group having 1 to 5 carbon atoms, particularly a methyl group or a t-butyl group.

The substituents R ³ and R ⁶ each independently represent a hydrogen atom or an alkyl group having 1 to 8 carbon atoms. Examples of the alkyl group having 1 to 8 carbon atoms include the same alkyl groups as described above. No. It is preferably a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and particularly preferably a hydrogen atom or a methyl group. The substituent X ₁
Represents a dihydric alcohol residue. The dihydric alcohol residue represents a group obtained by removing two OH groups from dihydric alcohols, and typical examples thereof include ethylene glycol and 1,2. -Propanediol, 1,3-propanediol, 1,
2-butanediol, 1,3-butanediol, 1,4-butanediol, 2,3-butanediol, 2-methyl-1,3-propanediol, 1,2-pentanediol, 1,5-pentanediol , 2,4-pentanediol, neopentyl glycol,
1,2-hexanediol, 1,5-hexanediol, 1,6-hexanediol, 2,5-hexanediol, 2-methyl-2,4
-Pentanediol, 2-methyl-1,5-pentanediol, 3,3-dimethylbutanediol, 2,3-dimethyl-2,3-
Butanediol, 2-ethyl-2-methyl-1,3-propanol, 2,2-diethyl-1,3-propanediol, 2,4-dimethyl-2,4-pentanediol, 1,2-octanediol, 1,
8-octanediol, 2,5-dimethyl-2,5-hexanediol, 2-ethyl-1,3-hexanediol, 2,2,4-trimethyl-1,3-pentanediol, 1,9-nonanediol , 2-
Butyl-2-ethyl-1,3-propanediol, 1,2-decanediol, 1,10-decanediol, 1,12-dodecanediol, 1,2-tetradecanediol, 1,14-tetradecanediol, 1, 2-hexadecanediol, a residue of an alkylenediol such as 1,16-hexadecanediol,

2-butene-1,4-diol, 2-methylene-1,3
-Residues of diols having a double bond such as propanediol, 5-hexene-1,2-diol, 7-octene-1,2-diol, 1,2-cyclopentanediol, 1,3-cyclopentanediol , 1,2-cyclohexanediol, 1,3-cyclohexanediol, 1,4-cyclohexanediol, 1,2-
Cyclooctadiol, 1,4-cyclooctanediol,
Cyclic diol residues such as 1,5-cyclooctanediol, p-menthane-3,8-diol, 4,4'-isopropylidenedicyclohexanol, ethylene glycol, diethylene glycol, triethylene glycol, 3,9-bis (1,1-
Dimethyl-2-hydroxyethyl) -2,4,8,10-tetraoxaspiro [5,5] undecane, neopentyl glycol
Examples thereof include diol residues having a hetero atom such as hydroxypivalate, 2,2′-thiodiethanol, 2-methylthio-1,2-propanediol, and diethanolamine.

The substituent X ₂ represents a mere bond or an alkylene group having 1 to 8 carbon atoms. Representative examples of the alkylene group include ethylene, propylene, butylene, pentamethylene, hexamethylene, octamethylene, 2 , 2-
Dimethyl-1,3-propylene and the like.

Y represents a hydroxyl group, an alkoxy group having 1 to 8 carbon atoms or an aralkyloxy group having 7 to 12 carbon atoms, and is preferably a hydroxyl group. here,
Examples of the alkyl group having 1 to 8 carbon atoms include the same alkyl groups as described above. Examples of the alkoxy group having 1 to 8 carbon atoms include, for example, an alkyl group in which the alkyl portion is the same as the alkyl having 1 to 8 carbon atoms. The aralkyloxy group having 7 to 12 carbon atoms includes, for example, an aralkyloxy group having an aralkyl moiety which is the same aralkyl as the aralkyl having 7 to 12 carbon atoms.

The phosphites represented by the formula (I) are, for example, those represented by the general formula (II)

[0015]

(Wherein R ¹ , R ² and R ³ have the same meanings as described above), phosphorus trihalide and a compound of the general formula (III)

[0017]

(Wherein, R ⁴ , R ⁵ , R ⁶ , X ₁ , X ₂ and Y have the same meanings as described above) in the presence of a dehydrohalogenating agent. It can be manufactured by the following. Examples of the phosphorus trihalide used here include phosphorus trichloride, phosphorus tribromide and the like. In particular, phosphorus trichloride is preferably used.

The reaction is promoted by coexisting, for example, an amine compound, a dehydrohalogenating agent such as pyridines, pyrrolidines and amides, and an alkali metal or alkaline earth metal hydroxide. Can also. Here, the amine compound may be any of a primary amine, a secondary amine, and a tertiary amine.
t-butylamine, t-pentylamine, t-hexylamine, t-octylamine, di-t-butylamine, di-t-pentylamine, di-t-hexylamine, di-t-octylamine, trimethylamine, triethylamine, N, N-dimethylaniline, N, N-diethylaniline and the like can be mentioned, with preference given to triethylamine.

Examples of the pyridines include pyridine and picoline, and pyridine is preferred.
Examples of pyrrolidines include 1-methyl-2-pyrrolidine. As amides, for example, N, N-
Examples thereof include dimethylformamide and N, N-dimethylacetamide. N, N-dimethylformamide is preferably used. Examples of the alkali metal or alkaline earth metal hydroxide include sodium hydroxide and calcium hydroxide, and preferably sodium hydroxide.

The reaction is usually performed in an organic solvent. The organic solvent is not particularly limited as long as it does not inhibit the reaction, and examples thereof include aromatic hydrocarbons, aliphatic hydrocarbons, oxygen-containing hydrocarbons, and halogenated hydrocarbons. As aromatic hydrocarbons, for example, benzene, toluene, xylene, ethylbenzene, etc., as aliphatic hydrocarbons, for example, n-hexane, n-heptane, n-octane, etc., as oxygen-containing hydrocarbons, for example, diethyl Ether, dibutyl ether, tetrahydrofuran, 1,4-
Examples of halogenated hydrocarbons such as dioxane include, for example, chloroform, carbon tetrachloride, monochlorobenzene, dichloromethane, 1,2-dichloroethane, dichlorobenzene, and the like. Among these, toluene, xylene,
Diethyl ether, tetrahydrofuran, 1,4-dioxane, chloroform, dichloromethane and the like are preferably used.

As a reaction method, usually, in the presence of a dehydrohalogenating agent, first, a biphenol (II) is reacted with phosphorus trihalide to produce an intermediate, and then the alcohol compound (III) is reacted. The two-step reaction method of causing the reaction is adopted. In the case of this method, the phosphorus trihalide is preferably used in an amount of about 1 to 1.1 mole times, more preferably about 1 to 1.05 mole times the biphenols (II). The dehydrohalogenating agent is preferably used in an amount of about 2 to 2.4 mol times, more preferably about 2 to 2.1 mol times with respect to phosphorus trihalide. Biphenols (I
The reaction between I) and phosphorus trihalide is usually carried out at about 0 to 150 ° C. This reaction is considered to produce an intermediate halogenophosphite, which may be isolated and then used for the next reaction, but is usually used as it is in the reaction mixture for reaction with alcohols (III). Then, when reacting the alcohol (III), it is usually used in an amount of about 1 to 1.1 moles per mole of the biphenol (II). In this reaction, it is preferable to further add a dehydrohalogenating agent. The amount of the dehydrohalogenating agent to be added is preferably about 1 to 1.2 mol times the alcohol (III). The amount of this additional dehydrohalogenating agent is
When an excessive amount of the dehydrohalogenating agent is used in the first reaction, the calculation is usually performed including the remaining dehydrohalogenating agent. The reaction is usually carried out at a temperature of about 100 to 150 ° C. This reaction is preferably performed under reflux.

After completion of the reaction, the hydrohalide salt of the dehydrohalogenating agent formed by the reaction is removed, and after the solvent is removed, an appropriate post-treatment such as crystallization or column chromatography is performed. Thereby, the phosphites (I) used in the present invention can be obtained.

Here, the biphenols (II), which are the raw materials of the phosphites (I), can be prepared by a known method such as the method described in Japanese Patent Publication No. 2-47451. Can be produced by condensation. As the biphenols (II), any commercially available ones can be used. Representative examples of biphenols (II) include, for example, biphenyl
-2,2'-diol, 3,3 ', 5,5'-tetra-t-butylbiphenyl-2,2'-diol, 3,3', 5,5'-tetra-t-pentylbiphenyl -2,2'-diol, 3,3'-di-t-butyl-5,5'-dimethylbiphenyl-2,2'-diol and the like.

Alcohols (III) as the other raw material
Is, for example, the general formula (IV)

[0026]

(Wherein R ⁴ , R ⁵ , R ⁶ , X ₂ and Y have the same meaning as described above, and Z is, for example, 1 to 4 carbon atoms)
Represents a lower alkoxy group, a hydroxyl group or a halogen atom. ) And HO-X ₁
It can be produced by reacting a dihydric alcohol represented by -OH according to a known method.

For example, Z of phenylcarboxylic acid (IV)
Is a lower alkoxy group, the phenylcarboxylic acid (IV) and an almost equimolar amount of a dihydric alcohol are dissolved by heating, a small amount of a catalyst is added, and the mixture is further heated,
An operation in which the reaction proceeds while distilling off the generated monohydric lower alcohol can be employed. The reaction is usually at room temperature to 20
Proceed at a temperature of about 0 ° C. After completion of the reaction, if necessary, an alcohol (III) can be obtained by diluting with a solvent, washing with water, distilling off the solvent, and purifying the residue by, for example, column chromatography. .

In this reaction, the dihydric alcohol is
The phenylcarboxylic acid (IV) is generally used in a molar amount of 1 or more times, preferably about 1 to 1.2 times by mole. Examples of the catalyst include sodium methoxide, lithium methoxide, sodium methoxide, sodium ethoxide,
Alkali metal alkoxides such as sodium-t-butoxide, potassium methoxide, potassium ethoxide, potassium-t-butoxide, alkali metal amides such as lithium amide, alkali metal alkylamides such as lithium diisopropylamide, lithium hydride, hydrogen Such as sodium chloride, potassium hydride, calcium hydride, sodium oxide, calcium oxide, sodium hydroxide, lithium hydroxide, potassium hydroxide, calcium hydroxide, lithium carbonate, sodium carbonate, potassium carbonate, calcium carbonate, barium carbonate Alkali metal or alkaline earth metal hydrides, oxides, hydroxides, carbonates, alkali metals such as lithium, sodium, potassium,
Dibutyltin oxide,

Dialkyltin oxides such as dioctyltin oxide, dialkyltin alkoxides such as dibutyltin methoxide, dialkyltin dicarboxylates such as dibutyltin acetate, dibutyltin malate, dibutyltin dioctanoate, dibutyltin dilaurate; _{^{(6 O R) 4 M (}} V) ( wherein (V), R ⁶ is an alkyl group having 1 to 18 carbon atoms, a phenyl group, a benzyl group, M represents germanium, zirconium, tin, titanium element. ), And a mixture of two or more thereof. Among them, sodium methoxide, lithium amide, dibutyltin oxide and the like are preferably used. Such a catalyst is generally used in an amount of 0.01 to phenylcarboxylic acid (IV).
About 0.5 mol is used.

As the diluting solvent, aromatic hydrocarbons,
Aliphatic hydrocarbons, alcohols, ethers, and the like are used, but aromatic hydrocarbons are usually preferred, and specific examples include toluene, xylene, and monochlorobenzene.

The alcohols (III) include, for example, 3-t-
2-hydroxyethyl butyl-4-hydroxybenzoate, 3
2-hydroxyethyl 3-t-pentyl-4-hydroxybenzoate, 2-hydroxyethyl 3-t-octyl-4-hydroxybenzoate, 2-hydroxyethyl 3-cyclohexyl-4-hydroxybenzoate, 3- (1- Methylcyclohexyl) -4-hydroxybenzoate 2-hydroxyethyl, 3-
2-hydroxyethyl t-butyl-4-hydroxy-5-methylbenzoate, 3-hydroxypropyl 3-tert-butyl-4-hydroxy-5-methylbenzoate, 3-t-butyl-4-hydroxy-5- 4-hydroxybutyl methylbenzoate, 2-hydroxyethyl 3-tert-pentyl-4-hydroxy-5-methylbenzoate, 2-hydroxyethyl 3-tert-octyl-4-hydroxy-5-methylbenzoate, 3- 2-Hydroxyethyl cyclohexyl-4-hydroxy-5-methylbenzoate, 3- (1
-Methylcyclohexyl) -4-hydroxy-5-methylbenzoic acid 2-hydroxyethyl, 3-t-butyl-4-hydroxy-5-ethylbenzoic acid 2-hydroxyethyl, 3-t-pentyl-4-hydroxy-5 -2-hydroxyethyl ethylbenzoate, 2-hydroxyethyl 3-t-octyl-4-hydroxy-5-ethylbenzoate,

2-hydroxyethyl 3-cyclohexyl-4-hydroxy-5-ethylbenzoate, 2-hydroxyethyl 3- (1-methylcyclohexyl) -4-hydroxy-5-ethylbenzoate, 3,5-di-t -Butyl-4-hydroxybenzoic acid 2-hydroxyethyl, 3,5-di-t-butyl-4-
3-hydroxypropyl hydroxybenzoate, 3,5 di
-t-butyl-4-hydroxybenzoic acid 4-hydroxybutyl, 3-t-pentyl-4-hydroxy-5-t-butylbenzoic acid
2-hydroxyethyl, 3-t-octyl-4-hydroxy-5
2-hydroxyethyl 3-t-butylbenzoate, 3-cyclohexyl-4-hydroxy-5-t-butylbenzoic acid 2-hydroxyethyl 3- (1-methylcyclohexyl) -4-hydroxy-5-t-butylbenzoate 2-Hydroxyethyl acid (3-t-butyl-4-hydroxyphenyl) acetic acid 2-hydroxyethyl, (3-t-butyl-5-hydroxyphenyl) acetic acid 2-hydroxyethyl, (3-t-pentyl-4 -Hydroxyphenyl) acetic acid 2-hydroxyethyl, (3-t-octyl-4-hydroxyphenyl) acetic acid 2-hydroxyethyl, (3-cyclohexyl-4-hydroxyphenyl) acetic acid
2-hydroxyethyl, [3- (1-methylcyclohexyl)
-4-hydroxyphenyl] 2-hydroxyethyl acetate,

2-Hydroxyethyl (3-t-butyl-4-hydroxy-5-methylphenyl) acetate, (3-t-butyl-4-hydroxy-4-methylphenyl) acetate
3-hydroxypropyl hydroxy-5-methylphenyl) acetate, 4-hydroxybutyl (3-t-butyl-4-hydroxy-5-methylphenyl) acetate, (3-t-pentyl-4-hydroxy-5-methylphenyl) ) 2-Hydroxyethyl acetate, (3-t-octyl-4-hydroxy-5-methylphenyl) acetic acid 2-hydroxyethyl, (3-cyclohexyl-4)
-Hydroxy-5-methylphenyl) acetic acid 2-hydroxyethyl, [3- (1-methylcyclohexyl) -4-hydroxy
-5-methylphenyl] 2-hydroxyethyl acetate, (3-
t-butyl-4-hydroxy-5-ethylphenyl) acetic acid 2-
Hydroxyethyl, (3-t-pentyl-4-hydroxy-5-
Ethylphenyl) acetic acid 2-hydroxyethyl, (3-t-octyl-4-hydroxy-5-ethylphenyl) acetic acid 2-hydroxyethyl, (3-cyclohexyl-4-hydroxy-5
-Ethylphenyl) acetic acid 2-hydroxyethyl, [3- (1-
Methylcyclohexyl) -4-hydroxy-5-ethylphenyl] 2-hydroxyethyl acetate, (3,5-di-t-butyl)
-4-hydroxyphenyl) acetic acid 2-hydroxyethyl,
(3,5-di-t-butyl-4-hydroxyphenyl) acetic acid 3-
Hydroxypropyl, 4-hydroxybutyl (3,5-di-t-butyl-4-hydroxyphenyl) acetate,

2-hydroxyethyl (3-t-pentyl-4-hydroxy-5-t-butylphenyl) acetic acid, 2-hydroxyethyl (3-t-octyl-4-hydroxy-5-t-butylphenyl) acetic acid , (3-cyclohexyl-4-hydroxy-5-t
-Butylphenyl) acetic acid 2-hydroxyethyl, [3- (1-
Methylcyclohexyl) -4-hydroxy-5-t-butylphenyl] 2-hydroxyethyl acetate, 3- (3-t-butyl-4
-Hydroxyphenyl) 2-hydroxyethyl propionate, 2-, (3-t-pentyl-4-hydroxyphenyl)
2-hydroxyethyl propionate, 3- (3-t-octyl)
2-hydroxyethyl 4-hydroxyphenyl) propionate, 2-hydroxyethyl 3- (3-cyclohexyl-4-hydroxyphenyl) propionate, 3- [3- (1-methylcyclohexyl) -4-hydroxyphenyl] propion 2-hydroxyethyl acid, 3- (3-t-butyl-4-hydroxy-5-methylphenyl) propionate 2-hydroxyethyl, 3- (3-t-butyl-4-hydroxy-5-methylphenyl) propionate 3-hydroxybutyl acid, 3- (3-t-butyl-4-hydroxy-5-methylphenyl) propionic acid
4-hydroxybutyl,

3- (3-t-pentyl-4-hydroxy-5-methylphenyl) propionic acid 2-hydroxyethyl, 3- (3
-t-octyl-4-hydroxy-5-methylphenyl) propionic acid 2-hydroxyethyl, 3- (3-cyclohexyl
-4-hydroxy-5-methylphenyl) propionic acid 2-
Hydroxyethyl, 3- [3- (1-methylcyclohexyl) -4
-Hydroxy-5-methylphenyl] 2-hydroxyethyl propionate, 2- (3-t-butyl-4-hydroxy-5-ethylphenyl) propionic acid 2-hydroxyethyl
2-Hydroxyethyl (3-t-pentyl-4-hydroxy-5-ethylphenyl) propionate, 3- (3-t-octyl-4
-Hydroxy-5-ethylphenyl) propionic acid 2-hydroxyethyl, 3- (3-cyclohexyl-4-hydroxy
-5-ethylphenyl) propionic acid 2-hydroxyethyl, 3- [3- (1-methylcyclohexyl) -4-hydroxy-5
-Ethylphenyl] 2-hydroxyethyl propionate, 2-hydroxyethyl 3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate, 3- (3,5-di-t-butyl-4 3-hydroxypropyl) -hydroxyphenyl) propionate, 4-hydroxybutyl 3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate,

2-hydroxyethyl 3- (3-t-pentyl-4-hydroxy-5-t-butylphenyl) propionate,
(3-t-octyl-4-hydroxy-5-t-butylphenyl)
2-hydroxyethyl propionate, 3- (3-cyclohexyl-4-hydroxy-5-t-butylphenyl) propionate, 2-hydroxyethyl propionate, 3- [3- (1-methylcyclohexyl) -4-hydroxy-5- t-butylphenyl] 2-hydroxyethyl propionate, 2-hydroxyethyl 4- (3-tbutyl-4-hydroxyphenyl) butyrate, 4- (3-t-butyl-
2-hydroxyethyl 4-hydroxy-5-methylphenyl) butyrate, 3-hydroxypropyl 4- (3-t-butyl-4-hydroxy-5-methylphenyl) butyrate, 4- (3-t-butyl
4-hydroxybutyl-4-hydroxy-5-methylphenyl) butyrate, 2-hydroxyethyl 4- (3,5-di-t-butyl-4-hydroxyphenyl) butyrate, 4- (3,5-di-t -Butyl
3-hydroxypropyl-4-hydroxyphenyl) butyrate, 4-hydroxybutyl 4- (3,5-di-t-butyl-4-hydroxyphenyl) butyrate and the like.

Thus, the phosphites (I) of the present invention can be obtained. The phosphites (I) of the present invention can contain amines, acid-bonded metal salts and the like. Thereby, the hydrolysis resistance can be improved. Representative examples of such amines include, for example, triethanolamine, tripropanolamine, and triamine.
trialkanolamines such as -i-propanolamine, diethanolamine, dipropanolamine, di-i
-Dialkanolamines such as propanolamine, tetraethanolethylenediamine, tetra-i-propanolethylenediamine, monoalkanolamines such as dibutylethanolamine and dibutyl-i-propanolamine, 1,3,5-trimethyl-2,4, Aromatic amines such as 6-triazine, alkylamines such as dibutylamine, piperidine, 2,2,6,6-tetramethylpiperidine, 4-hydroxy-2,2,6,6-tetramethylpiperidine, hexamethylene Examples thereof include polyalkylene polyamines such as tetramine, triethylenediamine, triethylenetetramine, and tetraethylenepentamine. The usage ratio of amines to phosphites (I) is usually about 0.01 to 25% by weight.

Representative examples of the acid-bonded metal salt include hydrotalcites. Examples of hydrotalcites include a double salt compound represented by the following formula. M ²⁺ _1-x・ M ³⁺ _x・ (OH ⁻ ) ₂・ (A ⁿ⁻ ) _{x / n}・ pH ₂ O (where M ²⁺ is Mg, Ca, Sr, Ba, Zn, Pb , Sn and / or
Or Ni, M ³⁺ represents Al, B or Bi, n
Is a numerical value from 1 to 4, x is a numerical value from 0 to 0.5, and p is a numerical value from 0 to
2 represents a numerical value. A ^n- represents an anion having a valence of n. Here, specific examples of the anion having a valence of ^{n represented} by A ⁿ⁻ include, for example, OH ⁻ , Cl ⁻ , Br ⁻ , I ⁻ , ClO ₄ ⁻ , HC
_{^{O 3 -, C 6 H 5}} COO -, CO 3 2-, SO 2-, - OOCCOO -, (CHO
_{^{HCO0) 2 2-, C 2 H}} 4 (COO) 2 2-, (CH 2 COO) 2 2-, CH 3 CHOHCO
_{^{O -, SiO 3 2-, SiO}} 4 4-, Fe (CN) 6 4-, BO 3-, PO 3 3-, HPO
Among _{the 4} ^2- or the like is represented by the general formula mentioned, those particularly preferred include, for example, hydrotalcites represented by the following formula. Mg _1-x Al _x (OH) ₂ (CO ₃ ) _{x / 2} · pH ₂ O (where x and p represent the same meaning as described above) Even if the hydrotalcites are natural products, It may be a synthetic product, and it can be used irrespective of its crystal structure, crystal particle diameter and the like. Further, ultrafine zinc oxide described in JP-A-6-329830 and inorganic compounds described in JP-A-7-278164 can also be used. The content ratio of the acid-bonded metal salt to the phosphite (I) is usually about 0.01 to 25% by weight.

The stabilizer composition of the present invention comprises the above-mentioned phosphites (I) and at least one stabilizer selected from phenol stabilizers and hindered amine stabilizers. The phenolic antioxidant is characterized by, for example, the following. These may be used in combination of two or more. (1) Examples of alkylated monophenols 2,6-di-t-butyl-4-methylphenol, 2,4,6-tri-t
-Butylphenol, 2,6-di-t-butylphenol, 2-
t-butyl-4,6-dimethylphenol, 2,6-di-t-butyl
-4-ethylphenol, 2,6-di-t-butyl-4-n-butylphenol, 2,6-di-t-butyl-4-isobutylphenol, 2,6-dicyclopentyl-4-methylphenol, 2 -(
α-methylcyclohexyl) -4,6-dimethylphenol,
2,6-dioctadecyl-4-methylphenol, 2,4,6-tricyclohexylphenol, 2,6-di-t-butyl-4-methoxymethylphenol, 2,6-di-nonyl-4-methylphenol, 2,4-dimethyl-6- (1'-methylundecyl-1'-yl) phenol, 2,4-dimethyl-6- (1'-methylheptadecyl-1'-yl) phenol, 2,4- Dimethyl-6- (1′-methyltridecyl-1′-yl) phenol and mixtures thereof.

(2) Examples of alkylthiomethylphenol 2,4-dioctylthiomethyl-6-t-butylphenol,
4-dioctylthiomethyl-6-methylphenol, 2,4-dioctylthiomethyl-6-ethylphenol, 2,6-didodecylthiomethyl-4-nonylphenol and mixtures thereof. (3) Examples of hydroquinone and alkylated hydroquinone 2,6-di-t-butyl-4-methoxyphenol, 2,5-di-t-
Butylhydroquinone, 2,5-di-t-amylhydroquinone,
2,6-diphenyl-4-octadecyloxyphenol, 2,
6-di-t-butylhydroquinone, 2,5-di-t-butyl-4-hydroxyanisole, 3,5-di-t-butyl-4-hydroxyphenyl stearate, bis (3,5-di-t -Butyl-4-
Hydroxyphenyl) adipates and mixtures thereof.

(4) Examples of tocopherol α-tocopherol, β-tocopherol, γ-tocopherol, δ-tocopherol and mixtures thereof. (5) Examples of hydroxylated thiodiphenyl ethers 2,2'-thiobis (6-t-butylphenol), 2,2'-thiobis (4-methyl-6-t-butylphenol), 2,2'-thiobis (4- Octylphenol), 4,4'-thiobis (3-methyl-6-t-butylphenol), 4,4'-thiobis (2-methyl-6-t-butylphenol), 4,4'-thiobis (3,6-
Di-t-amylphenol), 4,4 '-(2,6-dimethyl-4-hydroxyphenyl) disulfide and the like.

(6) Examples of alkylidene bisphenols and derivatives thereof 2,2'-methylenebis (4-methyl-6-t-butylphenol), 2,2'-methylenebis (4-ethyl-6-t-butylphenol), 2 , 2'-methylenebis [4-methyl-6- (α-methylcyclohexyl) phenol)], 2,2'-methylenebis
(4-methyl-6-cyclohexylphenol), 2,2'-methylenebis (4-methyl-6-nonylphenol), 2,2'-
Methylenebis (4,6-di-t-butylphenol), 2,2'-
Ethylidenebis (4,6-di-t-butylphenol), 2,2 '
-Ethylidenebis (4-isobutyl-6-t-butylphenol), 2,2'-methylenebis [6- (α-methylbenzyl) -4-
Nonylphenol], 2,2'-methylenebis [6- (α, α-
Dimethylbenzyl) -4-nonylphenol], 4,4'-methylenebis (6-t-butyl-2-methylphenol), 4,4'-
Methylenebis (2,6-di-t-butylphenol), 4,4'-
Butylidenebis (3-methyl-6-t-butylphenol),
1,1-bis (4-hydroxyphenyl) cyclohexane, 1,
1-bis (5-t-butyl-4-hydroxy-2-methylphenyl) butane, 2,6-bis (3-t-butyl-5-methyl-2-hydroxybenzyl) -4-methylphenol, 1, 1,3-Tris (5
-t-butyl-4-hydroxy-2-methylphenyl) butane, 1,1-bis (5-t-butyl-4-hydroxy-2-methylphenyl) -3-n-dodecylmercaptobutane, ethylene glycol bis [ 3,3-bis-3'-t-butyl-4'-hydroxyphenyl) butyrate], bis (3-t-butyl-4-hydroxy-5-methylphenyl) dicyclopentadiene, bis [2
-(3'-t-butyl-2'-hydroxy-5'-methylbenzyl) -6-
t-butyl-4-methylphenyl] terephthalate, 1,1-bis (3,5-dimethyl-2-hydroxyphenyl) butane, 2,
2-bis (3,5-di-t-butyl-4-hydroxyphenyl) propane, 2,2-bis (5-t-butyl-4-hydroxy-2-methylphenyl) -4-n-dodecylmercaptobutane , 1,1,5,5-
Tetra (5-t-butyl-4-hydroxy-2-methylphenyl) pentane, 2-t-butyl-6- (3'-t-butyl-5'-methyl
-2'-hydroxybenzyl) -4-methylphenyl acrylate, 2,4-di-t-pentyl-6- [1- (2-hydroxy-3,5-
Di-t-pentylphenyl) ethyl] phenyl acrylate and mixtures thereof.

(7) Examples of O-, N- and S-benzyl derivatives 3,5,3 ', 5'-tetra-t-butyl-4,4'-dihydroxydibenzyl ether, octadecyl-4-hydroxy- 3,5-dimethylbenzylmercaptoacetate, tris (3,5-di-t
-Butyl-4-hydroxybenzyl) amine, bis (4-t-
Butyl-3-hydroxy-2,6-dimethylbenzyl) dithioterephthalate, bis (3,5-di-t-butyl-4-hydroxybenzyl) sulfide, isooctyl-3,5-di-t-butyl-4-hydroxy Benzyl mercapto acetate and mixtures thereof. (8) Examples of hydroxybenzylated malonate derivatives dioctadecyl-2,2-bis (3,5-di-t-butyl-2-hydroxybenzyl) malonate, dioctadecyl-2- (3-t-
Butyl-4-hydroxy-5-methylbenzyl) malonate, didodecylmercaptoethyl-2,2-bis (3,5-di-t
-Butyl-4-hydroxybenzyl) malonate, bis [4
-(1,1,3,3-tetramethylbutyl) phenyl] -2,2-bis
(3,5-di-t-butyl-4-hydroxybenzyl) malonate and mixtures thereof. (9) Examples of aromatic hydroxybenzyl derivatives 1,3,5-trimethyl-2,4,6-tris (3,5-di-t-butyl-4
-Hydroxybenzyl) benzene, 1,4-bis (3,5-di-t
-Butyl-4-hydroxybenzyl) -2,3,5,6-tetramethylbenzene, 2,4,6-tris (3,5-t-butyl-4-hydroxybenzyl) phenol and mixtures thereof.

(10) Examples of triazine derivatives 2,4-bis (n-octylthio) -6- (4-hydroxy-3,5-di
-t-butylanilino) -1,3,5-triazine, 2-n-octylthio-4,6-bis (4-hydroxy-3,5-di-t-butylanilino) -1,3,5-triazine, 2 -n-octylthio-4,6-bis
(4-hydroxy-3,5-di-t-butylphenoxy) -1,3,5-
Triazine, 2,4,6-tris (3,5-di-t-butyl-4-phenoxy) -1,3,5-triazine, tris (4-t-butyl-3-hydroxy-2,6-dimethyl Benzyl) isocyanurate,
Tris (3,5-di-t-butyl-4-hydroxybenzyl) isocyanurate, 2,4,6-tris (3,5-di-t-butyl-4-hydroxy-4-)
(Hydroxyphenylethyl) -1,3,5-triazine, 2,4,6-
Tris (3,5-di-t-butyl-4-hydroxyphenylpropyl) -1,3,5-triazine, tris (3,5-dicyclohexyl-4-hydroxybenzyl) isocyanurate, tris
[2- (3 ', 5'-di-t-butyl-4'-hydroxycinnamoyloxy) ethyl] isocyanurate and mixtures thereof.

(11) Examples of benzylphosphonate derivatives: dimethyl-3,5-di-t-butyl-4-hydroxybenzylphosphonate, diethyl-3,5-di-t-butyl-4-hydroxybenzylphosphonate, dioctadecyl- 3,5-di-t-
Calcium salts of butyl-4-hydroxybenzylphosphonate, dioctadecyl-5-t-butyl-4-hydroxy-3-methylbenzylphosphonate, 3,5-di-t-butyl-4-hydroxybenzylphosphonic acid monoester and their salts Mixtures and the like. (12) Examples of acylaminophenol derivatives: 4-hydroxylauric anilide, 4-hydroxystearic anilide, octyl-N- (3,5-di-t-butyl-4-hydroxyphenyl) carbanate and mixtures thereof. (13) β- (3,5-di-t-butyl-4-hydroxyphenyl)
Examples of esters of propionic acid with the following monohydric or polyhydric alcohols: methanol, ethanol, octanol, octadecanol, ethylene glycol, 1,3-propanediol, 1,3
4-butanediol, 1,6-hexanediol, 1,9-nonanediol, neopentyl glycol, diethylene glycol, thioethylene glycol, spiro glycol, triethylene glycol, pentaerythritol, tris (hydroxyethyl) isocyanurate, N, N '-Bis (hydroxyethyl) oxamide, 3-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol, trimethylolpropane, 4-hydroxymethyl-1
-Phospha-2,6,7-trioxabicyclo [2,2,2] octane and mixtures thereof.

(14) β- (5-t-butyl-4-hydroxy-3-
Examples of esters of methylphenyl) propionic acid with the following monohydric or polyhydric alcohols: methanol, ethanol, octanol, octadecanol, ethylene glycol, 1,3-propanediol,
4-butanediol, 1,6-hexanediol, 1,9-nonanediol, neopentyl glycol, diethylene glycol, thioethylene glycol, spiro glycol, triethylene glycol, pentaerythritol, tris (hydroxyethyl) isocyanurate, N, N '-Bis (hydroxyethyl) oxamide, 3-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol, trimethylolpropane, 4-hydroxymethyl-1
-Phospha-2,6,7-trioxabicyclo [2,2,2] octane and mixtures thereof. (15) Examples of esters of β- (3,5-dicyclohexyl-4-hydroxyphenyl) propionic acid with the following monohydric or polyhydric alcohols: methanol, ethanol, octanol, octadecanol, ethylene glycol, 1,3- Propanediol, 1,
4-butanediol, 1,6-hexanediol, 1,9-nonanediol, neopentyl glycol, diethylene glycol, thioethylene glycol, spiro glycol, triethylene glycol, pentaerythritol, tris (hydroxyethyl) isocyanurate, N, N '-Bis (hydroxyethyl) oxamide, 3-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol, trimethylolpropane, 4-hydroxymethyl-1
-Phospha-2,6,7-trioxabicyclo [2,2,2] octane and mixtures thereof.

(16) Examples of esters of 3,5-di-t-butyl-4-hydroxyphenylacetic acid with the following monohydric or polyhydric alcohols: methanol, ethanol, octanol, octadecanol, ethylene glycol, 3-propanediol, 1,
4-butanediol, 1,6-hexanediol, 1,9-nonanediol, neopentyl glycol, diethylene glycol, thioethylene glycol, spiro glycol, triethylene glycol, pentaerythritol, tris (hydroxyethyl) isocyanurate, N, N '-Bis (hydroxyethyl) oxamide, 3-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol, trimethylolpropane, 4-hydroxymethyl-1
-Phospha-2,6,7-trioxabicyclo [2,2,2] octane and mixtures thereof. (17) β- (3,5-di-t-butyl-4-hydroxyphenyl)
Examples of amides of propionic acid N, N'-bis [3- (3 ', 5'-di-t-butyl-4'-hydroxyphenyl) propionyl] hydrazine, N, N'-bis [3- (3' ,
5'-di-t-butyl-4'-hydroxyphenyl) propionyl] hexamethylenediamine, N, N'-bis [3- (3 ', 5'-di
-t-butyl-4'-hydroxyphenyl) propionyl] trimethylenediamine and mixtures thereof.

Particularly preferred phenolic stabilizers include the following compounds, which may be used in combination of two or more. 2,6-di-t-butyl-4-methylphenol, 2,4,6-tri-t-butylphenol, 2,4-dioctylthiomethyl-6
-Methylphenol, 2,2'-thiobis (6-t-butylphenol), 4,4'-thiobis (3-methyl-6-t-butylphenol), 2,2'-methylenebis (4-methyl-6-t -Butylphenol), 2,2'-methylenebis (4-ethyl-6-t-butylphenol), 2,2'-methylenebis [4-methyl-6-
(α-methylcyclohexyl) phenol)], 2,2′-
Methylenebis (4-methyl-6-cyclohexylphenol), 2,2'-methylenebis (4,6-di-t-butylphenol), 2,2'-ethylidenebis (4,6-di-t-butylphenol), 4 , 4'-methylenebis (6-t-butyl-2-methylphenol), 4,4'-methylenebis (2,6-di-t-butylphenol), 4,4'-butylidenebis (3-methyl-6-t -Butylphenol), 1,1-bis (4-hydroxyphenyl)
Cyclohexane, 1,1-bis (5-t-butyl-4-hydroxy
-2-methylphenyl) butane, 1,1,3-tris (5-t-butyl-4-hydroxy-2-methylphenyl) butane, ethylene glycol bis [3,3-bis-3'-t-butyl- 4'-hydroxyphenyl) butyrate], 2-t-butyl-6- (3'-t-butyl-5'-methyl-2'-hydroxybenzyl) -4-methylphenyl acrylate, 2,4-di-t -Pentyl-6- [1- (2-hydroxy-3,5-di-t-pentylphenyl) ethyl] phenyl acrylate,

2,4,6-tris (3,5-di-t-butyl-4-phenoxy) -1,3,5-triazine, tris (4-t-butyl-3-hydroxy-2,6- Dimethylbenzyl) isocyanurate,
Bis (3,5-di-t-butyl-4-hydroxybenzyl) isocyanurate, tris [2- (3 ′, 5′-di-t-butyl-4′-hydroxycinnamoyloxy) ethyl] isocyanurate, Diethyl-3,5-di-t-butyl-4-hydroxybenzylphosphonate, di-n-octadecyl-3,5-di-t-butyl-4-hydroxybenzylphosphonate, 3,5-di-t-butyl- Calcium salt of 4-hydroxybenzylphosphonic acid monoester, n-octadecyl 3- (3,5-di-t-butyl
-4-hydroxyphenyl) propionate, neopentanetetrayltetrakis (3,5-di-t-butyl-4-hydroxydihydrocinnamate), thiodiethylenebis (3,5
-Di-t-butyl-4-hydroxycinnamate), 1,3,5-
Trimethyl-2,4,6-tris (3,5-di-t-butyl-4-hydroxybenzyl) benzene, 3,6-dioxaoctamethylenebis (3,5-di-t-butyl-4-hydroxy) Cinnamate), hexamethylenebis (3,5-di-t-butyl-4-hydroxycinnamate), triethylene glycol bis
(5-t-tyl-4-hydroxy-3-methylcinnamate),
3,9-bis [2- (3- (3-t-butyl-4-hydroxy-5-methylphenyl) propionyloxy) -1,1-dimethylethyl]-
2,4,8,10-tetraoxaspiro [5.5] undecane, N, N '
-Bis [3- (3 ', 5'-di-t-butyl-4'-hydroxyphenyl) propionyl] hydrazine, N, N'-bis [3- (3', 5'-
Di-t-butyl-4'-hydroxyphenyl) propionyl]
Hexamethylenediamine and the like.

Further, as the hindered amine-based stabilizer,
For example, the following are mentioned. Bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis ((2,
2,6,6-tetramethyl-4-piperidyl) succinate, bis (1,2,2,6,6-pentamethyl-4-piperidyl)
Sebacate, bis (N-octoxy-2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis (N-benzyloxy-2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis (N-cyclohexyloxy-2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis (1,2,2,6,6
-Pentamethyl-4-piperidyl) 2- (3,5-di-t-butyl-
4-hydroxybenzyl) -2-butylmalonate, bis (1-
Acroyl-2,2,6,6-tetramethyl-4-piperidyl)
2,2-bis (3,5-di-t-butyl-4-hydroxybenzyl) -2-butylmalonate, bis (1,2,2,6,6-pentamethyl-4-piperidyl decandioate, 2 , 2,6,6-tetramethyl-4-piperidyl methacrylate, 4- [3- (3,5-
Di-t-butyl-4-hydroxyphenyl) propionyloxy] -1- [2- (3- (3,5-di-t-butyl-4-hydroxyphenyl) propionyloxy) ethyl] -2,2,6 , 6-Tetramethylpiperidine, 2-methyl-2- (2,2,6,6-tetramethyl-4
-Piperidyl) amino-N- (2,2,6,6-tetramethyl-4-piperidyl) propionamide, tetrakis (2,2,6,6-tetramethyl-4-piperidyl) 1,2,3,4 -Butanetetracarboxylate, tetrakis (1,2,2,6,6-pentamethyl
-4-piperidyl) 1,2,3,4-butanetetracarboxylate, 1,2,3,4-butanetetracarboxylic acid and 1,2,2,6,6-pentamethyl-4-piperidinol and 1-tridecanol Mixed esterified with,

Mixed esterified product of 1,2,3,4-butanetetrabonic acid with 2,2,6,6-tetramethyl-4-piperidinol and 1-tridecanol, 1,2,3,4-butanetetra Carboxylic acid and 1,2,2,6,6-pentamethyl-4-piperidinol and
3, 9-bis (2-hydroxy-1,1-dimethylethyl) -2,4,
Mixed esterified product with 8,10-tetraoxaspiro [5.5] undecane, 1,2,3,4-butanetetracarboxylic acid and 2,2,6,
6-tetramethyl-4-piperidinol and 3,9-bis (2-
Mixed esterified product with hydroxy-1,1-dimethylethyl) -2,4,8,10-tetraoxaspiro [5.5] undecane, dimethyl succinate and 1- (2-hydroxyethyl) -4-hydroxy-2 Polycondensation product with 2,6,6-tetramethylpiperidine, poly [(6-morpholino-1,3,5-triazine-2,4-diyl) ((2,2,6,6-tetramethyl- 4-piperidyl) imino)
Hexamethylene ((2,2,6,6-tetramethyl-4-piperidyl) imino)], poly [(6- (1,1,3,3-tetramethylbutyl) imino-1,3,5-triazine -2,4-diyl ((2,2,6,6-
Tetramethyl-4-piperidyl) imino) hexamethylene
((2,2,6,6-tetramethyl-4-piperidyl) imino)],
Polycondensate of N, N'-bis (2,2,6,6-tetramethyl-4-piperidyl) hexamethylenediamine with 1,2-dibromoethane, N, N ', 4,7-tetrakis [4 , 6-Bis (N-butyl-N- (2,
2,6,6-tetramethyl-4-piperidyl) amino) -1,3,5-triazin-2-yl] -4,7-diazadecane-1,10 diamine,
N, N ', 4-Tris [4,6-bis (N-butyl-N- (2,2,6,6-tetramethyl-4-piperidyl) amino) -1,3,5-triazine-2
-Yl] -4,7-diazadecane-1,10-diamine, N, N ', 4,7-
Tetrakis [4,6-bis (N-butyl-N- (1,2,2,6,6-pentamethyl-4-piperidyl) amino) -1,3,5-triazine-2-
Yl] -4,7-diazadecane-1,10-diamine, N, N ', 4-tris [4,6-bis (N-butyl-N- (1,2,2,6,6-pentamethyl
-4-piperidyl) amino) -1,3,5-triazin-2-yl]-
4,7-diazadecane-1,10-diamine and mixtures thereof.

Particularly preferred hindered amine stabilizers include the following, and two or more of these can be used. Bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis (1,2,2,6,6-pentamethyl-4-
Piperidyl) sebacate, bis (N-octoxy-2,2,
6,6-tetramethyl-4-piperidyl) sebacate, bis
(N-benzyloxy-2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis (N-cyclohexyloxy-
2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis (1,2,2,6,6-pentamethyl-4-piperidyl)
2- (3,5-di-t-butyl-4-hydroxybenzyl) -2-butylmalonate, bis (1-acyl-2,2,6,6-tetramethyl-4-piperidyl) 2,2- Bis (3,5-di-t-butyl-4
-Hydroxybenzyl) -2-butylmalonate, bis (2,
2,6,6-tetramethyl-4-piperidyl) succinate, 2,2,6,6-tetramethyl-4-piperidyl methacrylate, 4- [3- (3,5-di-t-butyl-4-hydroxy) Phenyl) propionyloxy] -1- [2- (3- (3,5-di-t-butyl)
-4- -Hydroxyphenyl) propionyloxy) ethyl] -2,2,6,6-tetramethylpiperidine, 2-methyl-2- (2,
2,6,6-tetramethyl-4-piperidyl) amino-N- (2,2,6,
6-tetramethyl-4-piperidyl) propionamide, tetrakis (2,2,6,6-tetramethyl-4-piperidyl) 1,
2,3,4-butanetetracarboxylate,

Tetrakis (1,2,6,6-pentamethyl-4-piperidyl) 1,2,3,4-butanetetracarboxylate,
Mixed esterified product of 1,2,3,4-butanetetracarboxylic acid and 1,2,2,6,6-pentamethyl-4-piperidinol and 1-tridecanol, 1,2,3,4-butanetetracarboxylic acid And two,
Mixed esterified product of 2,6,6-tetramethyl-4-piperidinol and 1-tridecanol, 1,2,3,4-butanetetracarboxylic acid and 1,2,2,6,6-pentamethyl-4-piperidinol And a mixed esterified product with 3,9-bis (2-hydroxy-1,1-dimethylethyl) -2,4,8,10-tetraoxaspiro [5.5] undecane, 1,2,3,4- Butanetetracarboxylic acid and 2,2,6,6-tetramethyl-4-piperidinol and 3,9-
Bis (2-hydroxy-1,1-dimethylethyl) -2,4,8,10-
Mixed esterified product with tetraoxaspiro [5.5] undecane, polycondensate of dimethyl succinate and 1- (2-hydroxyethyl) -4-hydroxy-2,2,6,6-tetramethylpiperidine, poly [ (6-morpholino-1,3,5-triazine-
2,4-diyl) ((2,2,6,6-tetramethyl-4-piperidyl) imino) hexamethylene ((2,2,6,6-tetramethyl-4
-Piperidyl) imino)], poly [(6- (1,1,3,3-tetramethylbutyl) -1,3,5-triazine-2,4-diyl) ((2,2,
6,6-tetramethyl-4-piperidyl) imino) hexamethylene ((2,2,6,6-tetramethyl-4-piperidyl) imino)] and the like.

The stabilizer composition of the present invention comprises the above-mentioned phosphites (I) and at least one stabilizer selected from phenol stabilizers and hindered amine stabilizers. As a characteristic feature, the content ratio is usually 10: 1 to 1:10, preferably 5: 1 to 1: 5, more preferably 3: 1 to 1: 3 by weight. The content ratio of each component with respect to the phosphites (I) is as follows:
Usually, it is about 10: 1 to 1:10, and for a hindered amine-based stabilizer, it is usually about 3: 1 to 1:10, and the total content thereof is usually in the above range.

The stabilizer composition of the present invention may further contain, if necessary, further additives such as a sulfur-based stabilizer, a phosphorus-based stabilizer, an ultraviolet absorber, a non-hindered amine-based light stabilizer, and a peroxide scavenger. , Polyamide stabilizer, hydroxylamine, lubricant, plasticizer, flame retardant, nucleating agent, metal deactivator, antistatic agent, pigment, filler, pigment, antiblocking agent, surfactant, processing aid, foaming Agents, emulsifiers, brighteners, neutralizing agents such as calcium stearate, hydrotalcite, and 9,10-dihydro-9-oxa-10-
Coloring improvers such as phosphophenanthrene-10-oxide,
U.S. Pat.Nos. 4,325,853, 4,338,244, 5,175,312,
5,216,053, 5,252,643, DE-A-4,316,611, 4,316,622, 4,316,876, EP-A-589,839,
Co-stabilizers such as benzofurans and indolines described in the specifications of CA-2,132,132 of 591,102 and the like can also be contained.

Here, examples of the sulfur-based antioxidant include the following. These may be used in combination of two or more. Dilauryl 3,3'-thiodipropionate, tridecyl 3,3'-thiodipropionate, dimyristyl 3,3'-thiodipropionate, distearyl 3,3'-thiodipropionate, lauryl stearyl 3,3 '-Thiodipropionate, neopentanetetrayltetrakis (3-laurylthiopropionate) and the like. Further, examples of the phosphorus-based antioxidant include the following. Triphenyl phosphite,
Tris (nonylphenyl) phosphite, tris (2,4-
Di-t-butylphenyl) phosphite, trilauryl phosphite, trioctadecyl phosphite, distearyl pentaerythritol diphosphite, diisodecyl pentaerythritol diphosphite, bis
(2,4-di-t-butylphenyl) pentaerythritol
Diphosphite, bis (2,4-di-t-butyl-6-methylphenyl) pentaerythritol diphosphite, bis
(2,6-di-t-butyl-4-methylphenyl) pentaerythritol diphosphite, bis (2,4,6-tri-t-butylphenyl) pentaerythritol diphosphite,
Tristearylsorbitol triphosphite, tetrakis (2,4-di-t-butylphenyl) -4,4′-diphenylenediphosphonite, 2,2′-methylenebis (4,6-di-t-butylphenyl) 2 -Ethylhexyl phosphite, 2,2 '
-Ethylidenebis (4,6-di-t-butylphenyl) fluorophosphite, bis (2,4-di-t-butyl-6-methylphenyl) ethyl phosphite, bis (2,4-di-t
-Butyl-6-methylphenyl) methyl phosphite, 2- (2,4,6-tri-t-butylphenyl) -5-ethyl-5-
Butyl-1,3,2-oxaphosphorinane, 2,2 ', 2''-nitrilo [triethyl-tris (3,3', 5,5'-tetra-t-butyl
-1,1'-biphenyl-2,2'-diyl) phosphite and mixtures thereof.

Particularly preferred phosphorus-based antioxidants include the following, and two or more of these can be used. Tris (nonylphenyl) phosphite, tris
(2,4-di-t-butylphenyl) phosphite, distearyl pentaerythritol diphosphite, bis
(2,4-di-t-butylphenyl) pentaerythritol
Diphosphite, bis (2,4-di-t-butyl-6-methylphenyl) pentaerythritol diphosphite, bis
(2,6-di-t-butyl-4-methylphenyl) pentaerythritol diphosphite, tetrakis (2,4-di-t-butylphenyl) -4,4′-diphenylenediphosphonite,
2'-methylenebis (4,6-di-t-butylphenyl) 2-ethylhexyl phosphite, 2,2'-ethylidenebis
(4,6-di-t-butylphenyl) fluorophosphite, bis (2,4-di-t-butyl-6-methylphenyl) ethyl phosphite, 2- (2,4,6-tri-t- (Butylphenyl) -5-ethyl-5-butyl-1,3,2-oxaphosphorinane,
2,2 ', 2''-nitrilo [triethyl-tris (3,3', 5,5'-
Tetra-t-butyl-1,1'-biphenyl-2,2'-diyl) phosphite and the like.

Examples of the ultraviolet absorber include the following. (1) Examples of salicylate derivatives phenyl salicylate, 4-t-butylphenyl salicylate, 2,4-di-t-butylphenyl 3 ′, 5′-di-t-butyl-4′-hydroxybenzoate, 4-t- Octylphenyl salicylate, bis (4-t-butylbenzoyl) resorcinol, benzoylresorcinol, hesisadecyl
3 ', 5'-di-t-butyl-4'-hydroxybenzoate,
Octadecyl 3 ', 5'-di-t-butyl-4'-hydroxybenzoate, 2-methyl-4,6-di-t-butylphenyl 3',
5'-di-t-butyl-4'-hydroxybenzoate and mixtures thereof. (2) Examples of 2-hydroxybenzophenone derivatives 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-octoxybenzophenone, 2,2′-dihydroxy-4-methoxybenzophenone, bis ( 5-benzoyl-4-hydroxy-2-methoxyphenyl) methane, 2,2 ', 4,4'-tetrahydroxybenzophenone and mixtures thereof.

(3) Examples of 2- (2′-hydroxyphenyl) benzotriazole 2- (2-hydroxy-5-methylphenyl) benzotriazole, 2- (3 ′, 5′-di-t-butyl-2) '-Hydroxyphenyl) benzotriazole, 2- (5'-t-butyl-2'-hydroxyphenyl) benzotriazole, 2- (2'-hydroxy-
5'-t-octylphenyl) benzotriazole, 2- (3-t-
Butyl-2-hydroxy-5-methylphenyl) -5-chlorobenzotriazole, 2- (3'-s-butyl-2'-hydroxy-
5'-t-butylphenyl) benzotriazole, 2- (2'-hydroxy-4'-octyloxyphenyl) benzotriazole, 2- (3 ', 5'-di-t-amyl-2'-hydroxyphenyl) Benzotriazole, 2- [2'-hydroxy-3 ', 5'-bis (α, α-dimethylbenzyl) phenyl] -2H-benzotriazole, 2-[(3'-t-butyl-2'-hydroxyphenyl ) -5 '-(2-Octyloxycarbonylethyl) phenyl] -5-chlorobenzotriazole, 2- [3'-t-butyl-5'-
[2- (2-ethylhexyloxy) carbonylethyl] -2'-
Hydroxyphenyl] -5-chlorobenzotriazole, 2-
[3'-t-butyl-2'-hydroxy-5 '-(2-methoxycarbonylethyl) phenyl] -5-chlorobenzotriazole, 2-
[3'-t-butyl-2'-hydroxy-5 '-(2-methoxycarbonylethyl) phenyl] benzotriazole, 2- [3'-t-butyl-2'-hydroxy-5- (2-octyloxy Carbonylethyl) phenyl] benzotriazole, 2- [3'-t-butyl
-2'-Hydroxy-5 '-[2- (2-ethylhexyloxy) carbonylethyl] phenyl] benzotriazole, 2- [2-
Hydroxy-3- (3,4,5,6-tetrahydrophthalimidomethyl) -5-methylphenyl] benzotriazole, 2- (3,5-
Di-t-butyl-2-hydroxyphenyl) -5-chlorobenzotriazole, 2- (3'-dodecyl-2'-hydroxy-5'-methylphenyl) benzotriazole and 2- [3'-t-butyl
-2'-Hydroxy-5 '-(2-isooctyloxycarbonylethyl) phenyl] benzotriazole mixture, 2,2'
-Methylenebis [6- (2H-benzotriazol-2-yl)-
4- (1,1,3,3-tetramethylbutyl) phenol, 2,2'-
Methylenebis [4-t-butyl-6- (2H-benzotriazole
2-yl) phenol], poly (3-11) (ethylene glycol) and 2- [3'-t-butyl-2'-hydroxy-5 '-(2-methoxycarbonylethyl) phenyl] benzotriazole Condensate, poly (3-11) (ethylene glycol) with methyl 3- [3- (2H-benzotriazol-2-yl) -5-t-butyl-4-hydroxyphenyl] propionate, 2- Ethylhexyl 3- [3-t-butyl-5- (5-chloro-2
H-benzotriazol-2-yl) -4-hydroxyphenyl] propionate, octyl 3- [3-t-butyl-5- (5-
Chloro-2H-benzotriazol-2-yl) -4-hydroxyphenyl] propionate, methyl 3- [3-t-butyl-5
-(5-chloro-2H-benzotriazol-2-yl) -4-hydroxyphenyl] propionate, 3- [3-t-butyl-5- (5-
Chloro-2H-benzotriazol-2-yl) -4-hydroxyphenyl] propionic acid and mixtures thereof.

Particularly preferred UV absorbers include:
The following are mentioned, and these can be used in combination of two or more.
Phenyl salicylate, 4-t-butylphenyl salicylate, 2,4-di-t-butylphenyl 3 ', 5'-di-t-butyl-4'-hydroxybenzoate, 4-t-octylphenyl salicylate, 2,4 -Dihydroxybenzophenone, 2-
Hydroxy-4-methoxybenzophenone, 2-hydroxy-
4-octoxybenzophenone, 2,2'-dihydroxy-4-
Methoxybenzophenone, bis (5-benzoyl-4-hydroxy-2-methoxyphenyl) methane, 2,2 ', 4,4'-tetrahydroxybenzophenone, 2- (2-hydroxy-5-methylphenyl) benzotriazole, 2 -(3 ', 5'- di-t-
Butyl-2'-hydroxyphenyl) benzotriazole,
2- (5'-t-butyl-2'-hydroxyphenyl) benzotriazole, 2- (2'-hydroxy-5'-t-octylphenyl) benzotriazole, 2- (3-t-butyl-2-hydroxy -Five-
Methylphenyl) -5-chlorobenzotriazole, 2- (3'-
s-butyl-2'-hydroxy-5'-t-butylphenyl) benzotriazole, 2- (2'-hydroxy-4'-octyloxyphenyl) benzotriazole, 2- (3 ', 5'-di-t -Amyl-2'-hydroxyphenyl) benzotriazole, 2-
[2'-hydroxy-3 ', 5'-bis (α, α-dimethylbenzyl) phenyl] -2H-benzotriazole and the like.

Examples of the light stabilizer other than the hindered amine-based light stabilizer include the following. (1) Examples of acrylate light stabilizers Ethyl α-cyano-β, β-diphenyl acrylate, isooctyl α-cyano-β, β-diphenyl acrylate, methyl α-carbomethoxycinnamate, methyl α-cyano-β-methyl -P-methoxycinnamate, butyl α-cyano-β-methyl-p-methoxycinnamate, methyl α-carbomethoxy-p-
Methoxycinnamate and N- (β-carbomethoxy-
β-cyanovinyl) -2-methylindoline and mixtures thereof. (2) Examples of nickel-based light stabilizers Nickel complexes of 2,2'-thiobis- [4- (1,1,3,3-tetramethylbutyl) phenol], nickel dibutyldithiocarbamate, nickel salts of monoalkyl esters , Nickel complexes of ketoxime and mixtures thereof.

(3) Examples of oxamide light stabilizers 4,4'-dioctyloxyoxanilide, 2,2'-diethoxyoxanilide, 2,2'-dioctyloxy-5,5'-di- t-
Butylanilide, 2,2'-didodecyloxy-5,5'-di-t-
Butylanilide, 2-ethoxy-2'-ethyloxanilide,
N, N'-bis (3-dimethylaminopropyl) oxamide, 2
-Ethoxy-5-t-butyl-2'-ethoxyanilide, 2-ethoxy-5,4'-di-t-butyl-2'-ethyloxanilide and mixtures thereof. (4) Examples of 2- (2-hydroxyphenyl) -1,3,5-triazine light stabilizers 2,4,6-tris (2-hydroxy-4-octyloxyphenyl) -1,3,5- Triazine, 2- (2-hydroxy-4-octyloxyphenyl) -4,6-bis (2,4-dimethylphenyl) -1,
3,5-triazine, 2- [2,4-dihydroxyphenyl-4,6-
Bis (2,4-dimethylphenyl) -1,3,5-triazine, 2,4-
Bis (2-hydroxy-4-propyloxyphenyl) -6-
(2,4-dimethylphenyl) -1,3,5-triazine, 2- (2-hydroxy-4-octyloxyphenyl) -4,6-bis (4-methylphenyl) -1,3,5-triazine , 2- (2-hydroxy-4
-Dodecyloxyphenyl) -4,6-bis (2,4-dimethylphenyl) -1,3,5-triazine, 2- [2-hydroxy-4- (2-hydroxy-3-butyloxypropoxy) phenyl] -4,6-
Bis (2,4-dimethylphenyl) -1,3,5-triazine, 2- [2
-Hydroxy-4- (2-hydroxy-3-octyloxypropoxy) phenyl] -4,6-bis (2,4-dimethylphenyl)-
1,3,5-triazine and mixtures thereof.

Examples of the metal deactivator include the following. N, N'-diphenyloxamide, N-salicyral-N'-salicyloylhydrazine, N, N'-
Bis (salicyloyl) hydrazine, N, N'-bis (3,5-di
-t-butyl-4-hydroxyphenylpropionyl) hydrazine, 3-salicyloylamino-1,2,4-triazole,
Bis (benzylidene) oxalyl dihydrazide, oxanilide, isophthaloyl dihydrazide, sebacoyl bisphenyl hydrazide, N, N'-bis (salicyloyl) oxalyl dihydrazide, N, N'-bis (salicyloyl) thiopropionyl dihydrazide and mixtures thereof.

Examples of peroxide scavengers include esters of β-thiodipropionic acid, mercaptobenzimidazole, zinc salts of 2-mercaptobenzimidazole, zinc salts of dibutyldithiocarbamic acid, dioctadecyl disulfide, and pentaerythritol tetrakis (β -Dodecylmercapto) propionate and mixtures thereof. Examples of the polyamide stabilizer include copper or divalent manganese salts of iodides or phosphorus compounds, and mixtures thereof. Examples of the hydroxyamine include, for example, N, N-dibenzylhydroxyamine, N, N-diethylhydroxyamine, N, N-
Dioctylhydroxyamine, N, N-dilaurylhydroxyamine, N, N-ditetradecylhydroxyamine, N, N-
Examples include dihexadecylhydroxyamine, N, N-dioctadecylhydroxyamine, N-hexadecyl-N-octadecylhydroxyamine, N-heptadecyl-N-octadecylhydroxyamine, and mixtures thereof. Examples of the neutralizing agent include calcium stearate, zinc stearate, magnesium stearate, hydrotalcite (basic magnesium aluminum hydroxy carbonate hydrate), calcium oxide, melamine, amine, polyamide, polyurethane and mixtures thereof. And the like. Examples of the lubricant include aliphatic hydrocarbons such as paraffin and wax, and C8
To 22 higher aliphatic acids, higher aliphatic metal salts (Al, Ca, Mg, Zn) having 8 to 22 carbon atoms, aliphatic alcohols having 8 to 22 carbon atoms, polyglycols, higher 4 to 22 carbon atoms Esters of fatty acids and aliphatic monohydric alcohols having 4 to 18 carbon atoms, higher aliphatic amides having 8 to 22 carbon atoms, silicone oils, rosin derivatives and the like can be mentioned.

Examples of the nucleating agent include the following. Sodium 2,2'-methylenebis
(4,6-di-t-butylphenyl) phosphate, [phosphoric acid
-2,2'-Methylenebis (4,6-di-t-butylphenyl)]
Dihydroxyaluminum, bis [2,2'-methylenebis (4,6-di-t-butylphenyl) phosphate] hydroxyaluminum, tris [-2,2'-methylenebisphosphate
(4,6-di-t-butylphenyl)] aluminum, metal salts of benzoic acid such as sodium bis (4-t-butylphenyl) phosphate and sodium benzoate, aluminum p-t-butylbenzoate, 1,3: 2,4-bis (O-benzylidene) sorbitol, 1,3: 2,4-bis (O-methylbenzylidene) sorbitol, 1,3: 2,4-bis (O-ethylbenzylidene) sorbitol, 1,3- O-3,4-dimethylbenzylidene-
2,4-O-benzylidene sorbitol, 1,3-O-benzylidene-2,4-O-3,4-dimethylbenzylidene sorbitol, 1,
3: 2,4-bis (O-3,4-dimethylbenzylidene) sorbitol, 1,3-Op-chlorobenzylidene-2,4-O-3,4-dimethylbenzylidenesorbitol, 1,3-O-3, 4-dimethylbenzylidene-2,4-Op-chlorobenzylidene sorbitol, 1,
3: 2,4-bis (Op-chlorobenzylidene) sorbitol and mixtures thereof. Examples of the filler include calcium carbonate, silicate, glass fiber, asbestos, talc, kaolin, mica, barium sulfate, carbon black, carbon fiber, zeolite, and a mixture thereof. Of these additives, those preferably used are ultraviolet absorbers, peroxide scavengers and neutralizers.

The stabilizer composition of the present invention comprises a phosphite (I), at least one stabilizer selected from a phenol stabilizer and a hindered amine stabilizer, and other additives used as necessary. Can be produced by blending additives and the like. In the compounding, any known method and apparatus for obtaining a homogeneous mixture can be used.

The stabilizer composition of the present invention is effective for stabilizing an organic material against heat, oxidation and light deterioration. Examples of the organic materials that can be stabilized by the present invention include the following, each of which can stabilize a single material or a mixture of two or more, but is limited to these organic materials. It is not something to be done.

(1) Polyethylene, for example, high density polyethylene (HD-PE), low density polyethylene (LD-P)
E), linear low density polyethylene (LLDPE), (2)
Polypropylene, (3) methylpentene polymer, (4) E
EA (ethylene / ethyl acrylate copolymer) resin, (5)
Ethylene / vinyl acetate copolymer resin, (6) polystyrenes, for example, polystyrene, poly (p-methylstyrene), poly (α-methylstyrene), (7) AS (acrylonitrile / styrene copolymer) resin, (8) ABS (Acrylonitrile / butadiene / styrene copolymer) resin,
(9) AAS (special acrylic rubber / acrylonitrile / styrene copolymer) resin, (10) ACS (acrylonitrile / chlorinated polyethylene / styrene copolymer) resin,

(11) chlorinated polyethylene, polychloroprene, chlorinated rubber, (12) polyvinyl chloride, polyvinylidene chloride, (13) methacrylic resin, (14) ethylene / vinyl alcohol copolymer resin, (15) fluororesin , (16) polyacetal, (17) grafted polyphenylene ether resin and polyphenylene sulfide resin, (18) polyurethane, (19) polyamide, (20) polyester resin, such as polyethylene terephthalate, polybutylene terephthalate,

(21) polycarbonate, (22) polyacrylate, (23) thermoplastic resin such as polysulfone, polyetheretherketone, polyethersulfone, (24) aromatic polyester resin, (25) epoxy resin, (26) Diallyl phthalate prepolymer, (27) silicone resin, (28) unsaturated polyester resin, (29) acryl-modified benzoguanamine resin, (30) benzoguanamine / melamine resin, (31) thermosetting resin such as urea resin,

(32) polybutadiene, (33) 1,2-polybutadiene, (34) polyisoprene, (35) styrene / butadiene copolymer, (36) butadiene / acrylonitrile copolymer, (37) ethylene / propylene copolymer Polymer, (3
8) Silicone rubber, (39) Epichlorohydrin rubber, (4
0) acrylic rubber, (41) natural rubber,

(42) Chlorine rubber paint, (43) Polyester resin paint, (44) Urethane resin paint, (45) Epoxy resin paint, (46) Acrylic resin paint, (47) Vinyl resin paint,
(48) amino alkyd resin paint, (49) alkyd resin paint, (50) nitrocellulose resin paint, (51) oil-based paint,
(52) Wax, (53) Lubricating oil, etc.

Among them, thermoplastic resins, especially polyethylene, for example, polyolefins such as HD-PE, LD-PE, LLDPE and polypropylene, and engineering resins such as polyamide, polyethylene terephthalate, polybutylene terephthalate and polycarbonate are preferably used. These polyolefins are not particularly limited, and may be, for example, those obtained by radical polymerization or those produced by polymerization using a catalyst containing a metal belonging to Group IVb, Vb, VIb or VIII of the periodic table. The metal-containing catalyst may be a metal complex having one or more ligands, for example, oxides, halogen compounds, alcoholates, esters, aryls, etc., which are coordinated by π or σ bonds. Magnesium chloride, titanium chloride,
It may be supported on a substrate such as alumina or silicon oxide. As the polyolefin, those produced using, for example, a Ziegler-Natta catalyst, a TNZ catalyst, a metallocene catalyst, a Phillips catalyst or the like are preferably used. The engineering resin is not particularly limited. For example, a polyamide resin having an amide bond in a polymer chain and capable of being heated and melted may be used. For example, those produced by any method such as condensation reaction of diamines and dicarboxylic acids, condensation reaction of aminocarboxylic acids, ring-opening polymerization of lactams, and the like, typical examples of which are nylon 66, nylon 69, nylon 610,
Nylon 612, poly-bis- (p-aminocyclohexyl) methandodecamide, nylon 46, nylon 6,
Nylon 12, nylon 66/6, which is a copolymer of nylon 66 and nylon 6, and copolymers such as nylon 6/12. As the polyester resin, any resin having an ester bond in the polymer chain and capable of being heated and melted may be used, and examples thereof include polyesters obtained by polycondensation of dicarboxylic acids and dihydroxy compounds, and the like. Homopolyesters, copolyesters Any of these may be used. Further, as the polycarbonate resin, any resin having a carbonate bond in the polymer chain and any material that can be heated and melted may be used.
A polycarbonate obtained by reacting an aromatic hydroxy compound or a small amount of a polyhydroxy compound with a carbonate precursor such as phosgene or diphenyl carbonate in the presence of an acid acceptor and a molecular weight modifier is exemplified. The polycarbonate resin may be linear or branched, and may be a copolymer.

When the stabilizer composition of the present invention is added to stabilize an organic material, the stabilizer composition of the present invention is converted to phosphite (I) based on 100 parts by weight of the organic material. , Usually about 0.005 to 5 parts by weight, preferably 0.03 to
About 3 parts by weight, more preferably about 0.05 to 1 part by weight is blended. If the amount used is less than 0.005 parts by weight, the stabilizing effect is not always sufficient, and if it exceeds 5 parts by weight, the effect corresponding to the improvement cannot be obtained, which is economically disadvantageous.

In stabilizing the organic material, the stabilizer composition of the present invention may be directly blended with the organic material, or the phosphites (components of the stabilizer composition of the present invention) may be used. I) or at least one stabilizer selected from phenolic stabilizers and hindered amine stabilizers;
Other additives and the like used as needed may be blended simultaneously or separately. In the compounding, any known method and apparatus for obtaining a homogeneous mixture can be used. For example, when the stabilizer composition of the present invention is blended with a solid organic material, it can be directly dry-blended with the solid material, or the stabilizer composition of the present invention can be used in the form of a master batch to prepare Can also be blended. In the case of a liquid polymer, it can be mixed with a polymer solution during or immediately after polymerization in the form of a solution or dispersion of the stabilizer composition of the present invention. On the other hand, when the organic material is a liquid such as oil, the stabilizer composition of the present invention can be directly added and blended, or the stabilizer composition of the present invention can be dissolved or suspended in a liquid medium. It can also be added in a hot state.

[0077]

The stabilizer composition of the present invention has excellent performance in stabilizing various organic materials such as thermoplastic resins such as polyolefin, and the organic material containing this stabilizer composition is Heat during production, processing, and even use,
It is stable against deterioration due to oxidation, light and the like, and becomes a high quality product.

[0078]

EXAMPLES The present invention will be described in more detail with reference to the following Examples, but it should not be construed that the invention is limited thereto.

<Test Stabilizer> Compound-1: 2,4,8,10-tetra-t-butyl-6- {2- [3- (3,
5-di-t-butyl-4-hydroxyphenyl) propionyloxy] ethoxydibenzo [d, f] [1,3,2] dioxaphosphepin (compound 1) P-1: tris (2,4- Di-t-butylphenyl) phosphite AO-1: n-octadecyl 3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate AO-2: neopentanetetrayltetrakis (3,5-diphenyl)
-t-butyl-4-hydroxydihydrocinnamate) S-1: neopentanetetrayltetrakis (3-laurylthiopropionate) HA-1: poly [(6- (1,1,3,3-tetramethyl) Butyl) -1,
3,5-triazine-2,4-diyl) ((2,2,6,6-tetramethyl
-4- piperidyl) imino) hexamethylene ((2,2,6,6-
Tetramethyl-4-piperidyl) imino)]

Reference Example 1: 2,4,8,10-tetra-t-butyl-6
-｛2- [3- (3,5-di-t-butyl-4-hydroxyphenyl)
Propionyloxy] ethoxydibenzo [d, f] [1,3,
2] Production of dioxaphosphepin (compound 1) In a 500 ml four-necked flask equipped with a thermometer, a stirrer, and a condenser, 120 ml of anhydrous toluene, 3,3 ', 5,5'-tetra-t
-After charging 20.5 g of butyl biphenyl-2,2'-diol and 12.1 g of triethylamine and replacing the inside of the container with nitrogen,
While stirring, 6.9 g of phosphorus trichloride was added dropwise. After completion of the dropwise addition, the mixture was kept at 80 ° C. for 3 hours, then cooled to room temperature, and then 3- (3,5-di-t-butyl-4-hydroxyphenyl) propionic acid 2-solvent dissolved in 6.1 g of triethylamine and 120 ml of anhydrous toluene. 16.1 g of hydroxyethyl was charged and kept under reflux for 6 hours. Next, after cooling to room temperature, the formed triethylamine hydrochloride was filtered. After concentrating the filtrate, the residue was purified by silica gel column chromatography to obtain 26.7 g of white crystals. Mass spectrometry value (FD-MS): m / z 761 Melting point: 100 ° C

¹ H-NMR (CDCl ₃ ) 1.34 (s, 18H), 1.42 (s, 18H), 1.48 (s, 18H), 2.60 (t, 2H),
2.85 (t, 2H), 3.94 (m, 2H), 4.14 (m, 2H), 5.07 (s, 1H), 6.
99 (s, 2H), 7.16 (d, 2H), 7.42 (d, 2H) ³¹ P-NMR (CDCl ₃ ) 134.2 ppm

Example 1 Processing stability test of high-density polyethylene [Compound] 100 parts by weight of high-density polyethylene Test stabilizer Stabilizers described in Table 1

Using a Labo Plastomill under a nitrogen atmosphere,
Time when the above compound is kneaded at 220 ° C and 100 rpm and the torque value due to cross-linking is maximum (gel build-up time (min))
Was measured, and the results are shown in Table 1. The longer the gel build-up time, the more the crosslinking at the time of kneading is suppressed, which means that the processing stability is excellent.

[0084]

TABLE 1 implementation example comparisons Example 1 1 2 test stabilizers of -1 0.1 - - AO-1 0.1 - 0.1 P-1 - - 0.1 processing stability> 60 3 3.5

Example 2: Processing stability test of polyethylene (LLDPE) [Compound] 100 parts by weight of polyethylene (LLDPE) Test stabilizer 0.1 parts by weight of hydrotalcite shown in Table 2

Using a Labo Plastomill under a nitrogen atmosphere,
Time when the above compound is kneaded at 260 ° C and 100 rpm and the torque value due to cross-linking is maximum (gel build-up time (min))
Was measured, and the results are shown in Table 2. The longer the gel build-up time, the more the crosslinking at the time of kneading is suppressed, which means that the processing stability is excellent.

[0087]

TABLE 2 implementation example comparisons Example 1 1 2 test stabilizers of -1 0.1 0.13 - AO-1 0.03 - 0.13 processing stability 32 18 9

Example 3: Weather resistance test [Compound] 100 parts by weight of polypropylene (block) 0.05 parts by weight of calcium stearate Test stabilizer Stabilizers described in Table 3

Using an extruder, the above compound was granulated at 230 ° C., and a 1 mm thick sheet was prepared using an injection molding machine at 240 ° C. This was irradiated with light by a sunshine weather o-meter (black panel temperature: 83 ° C, no rain), and the hue after irradiation for 180 hours (ΔE: hue difference from standard white plate, L, a, b value of white plate was 96.1) , -0.1, 1.9). The results are shown in Table 4.

[0090]

TABLE 3 implementation example comparisons Example 1 2 1 test stabilizers of -1 0.1 0.05 - HA-1 0.1 0.1 0.1 AO-1 0.05 0.05 - hue (ΔE) 17.3 17.6 18.0

Continued on the front page (51) Int.Cl. ⁶ Identification symbol FI C09K 15/30 C09K 15/30 // C07F 9/6574 C07F 9/6574 Z

Claims (12)

[Claims] 1. The compound of the general formula (I) (Wherein R ¹ , R ² , R ⁴ and R ⁵ are each independently a hydrogen atom, an alkyl group having 1 to 8 carbon atoms,
Represents an alkylcycloalkyl group having 6 to 12 carbon atoms, an aralkyl group having 7 to 12 carbon atoms or a phenyl group, and R ³ and R ⁶ each independently represent a hydrogen atom or an alkyl having 1 to 8 carbon atoms. Represents a group. X ₁ represents a divalent alcohol residue, and X ₂ represents a simple bond or an alkylene group having 1 to 8 carbon atoms. Y is a hydroxyl group, having 1 to 8 carbon atoms
Or an aralkyloxy group having 7 to 12 carbon atoms. A) a phosphite, and at least one stabilizer selected from a phenolic stabilizer and a hindered amine stabilizer. 2. The content ratio of the phosphites (I) to at least one stabilizer selected from the group consisting of phenol stabilizers and hindered amine stabilizers is from 10: 1 to 10% by weight.
2. The stabilizer composition according to claim 1, wherein the ratio is 1:10. 3. A stabilizer comprising the phosphite (I) according to claim 1 and at least one stabilizer selected from the group consisting of phenol stabilizers and hindered amine stabilizers. A method for producing the composition. 4. The compounding ratio of the phosphites (I) and at least one stabilizer selected from phenol-based stabilizers and hindered amine-based stabilizers in a weight ratio of 10: 1 to 1: 1.
The method according to claim 3, wherein the ratio is 1:10. 5. An organic material comprising the phosphite (I) according to claim 1 and at least one stabilizer selected from the group consisting of phenol stabilizers and hindered amine stabilizers. How to stabilize organic materials. 6. The content ratio of the phosphites (I) to at least one stabilizer selected from phenol-based stabilizers and hindered amine-based stabilizers is 10: 1 to 10% by weight.
The stabilization method according to claim 5, wherein the ratio is 1:10. 7. The method according to claim 5, wherein the organic material is a thermoplastic resin.
7. The stabilizing method according to 6. 8. The method according to claim 7, wherein the thermoplastic resin is a polyolefin or an engineering resin. 9. A stabilized organic material comprising an organic material containing the phosphites (I) according to claim 1 and at least one stabilizer selected from a phenolic stabilizer and a hindered amine stabilizer. Material composition. 10. The content ratio of the phosphites (I) to at least one stabilizer selected from phenol stabilizers and hindered amine stabilizers is 10: 1 by weight.
10. The composition of claim 9, wherein the composition is ~ 1: 10. 11. The organic material is a thermoplastic resin.
11. The composition according to item 10. 12. The composition according to claim 11, wherein the thermoplastic resin is a polyolefin or an engineering resin.