JPH10101686A - Phosphite esters, their production and their use - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtian the subject new compound useful as a deterioration- preventing agent against the thermal deterioration and oxidative deterioration of organic materials, etc., by reacting a bisphenol compound with a phosphorus trihalide and a specific alcohol such as a diol monoester. SOLUTION: A new phosphite ester of formula I [R<1> , R<2> , R<4> , R<5> are each H, a 1-8C alkyl, a 5-8C cycloalkyl, a 6-12C alkylcycloalkyl, a 7-12C aralkyl, phenyl; R<3> is H, a 1-8C alkyl; X is a single bond, S, (substituted)methylene; A is a divalent alcohol residue; B is a single bond, a 1-8C alkylene; either or Y, Z is a 1-8C alkoxy, a 7-12C aralkyloxy, and the other is H, a 1-8C alkyl]. The ester of formula I is useful as a stabilizer for organic materials, etc. The compound is obtained by reacting a bisphenol compound of formula II with an alcohol compound of formula III.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

[0001] The present invention relates to a novel phosphite, a method for producing the same, and a use thereof as a stabilizer for organic materials.

[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, etc. act upon heat, oxygen and the like during production, processing, and further use. Degradation of the organic material due to molecular breakage or molecular crosslinking,
It is known that commercial value is significantly impaired due to coloring, deterioration of surface physical properties, and the like. It has been known to stabilize organic materials by adding various phenolic antioxidants and phosphorus-based antioxidants for the purpose of solving such problems as heat and oxidative deterioration.

For example, tris as a phosphorus-based antioxidant
(2,4-Di-t-butylphenyl) phosphite and the like are used. However, these known phosphorus-based antioxidants have a problem that the stabilizing effect against thermal deterioration and oxidative deterioration is insufficient.

On the other hand, to solve the problems of such phosphorus-based antioxidants, for example, 2,10-dimethyl-4,8-di-t
-Butyl-6- ｛2- [3- (3-t-butyl-4-hydroxy-5-
Methylphenyl) propionyloxy] ethoxy} -12H
-A cyclic phosphite having a phenolic hydroxyl group such as dibenzo [d, g] [1,3,2] dioxaphosphine has been proposed (JP-A-5-86084).

[0005]

DISCLOSURE OF THE INVENTION The present inventors have produced various phosphorus compounds and have conducted intensive studies. As a result, it has been determined that the compounds have an alkoxy group or an aralkyloxy group instead of a phenolic hydroxyl group. The cyclic phosphites of the present invention show not only an excellent discoloration resistance effect, but also a superior phosphite having a phenolic hydroxyl group or an excellent stabilizing effect equal to or more than that of the present invention. completed.

[0006]

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

[0007]

(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,
Cycloalkyl group having 5 to 8 carbon atoms, alkylcycloalkyl group having 6 to 12 carbon atoms, an aralkyl group or a phenyl group having 7 to 12 carbon atoms, R ³ is hydrogen or C 1 -C
To 8 alkyl groups. X represents a mere bond, a sulfur atom or a methylene group which may be substituted by an alkyl having 1 to 8 carbon atoms or a nocycloalkyl having 5 to 8 carbon atoms. A represents a dihydric alcohol residue, and B represents a simple bond or an alkylene group having 1 to 8 carbon atoms. One of Y and Z is an alkoxy group having 1 to 8 carbon atoms or 7 carbon atoms.
To 12 aralkyloxy groups, and the other represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms. The present invention provides a practically excellent phosphite represented by the formula (1), a method for producing the phosphite, and a use thereof.

[0009]

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.

Among them, 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 substituent R ³ is a hydrogen atom or a group having 1 carbon atom.
Represents an alkyl group having 1 to 8 carbon atoms, and examples of the alkyl group having 1 to 8 carbon atoms include the same alkyl groups as described above. 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 represents a mere bond, a sulfur atom or a methylene group which may be substituted by alkyl having 1 to 8 carbon atoms or nocycloalkyl having 5 to 8 carbon atoms. Here, the number of carbon atoms substituted with a methylene group is 1 to 1.
Examples of the alkyl having 8 and the cycloalkyl having 5 to 8 carbon atoms include the same alkyl groups and cycloalkyl groups as described above. X is preferably a mere bond, a methylene group or a methylene group substituted by a methyl group.

The substituent A represents a dihydric alcohol residue, that is, a portion obtained by removing two OHs from a dihydric alcohol. Representative examples thereof include ethylene glycol, 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 B is a mere bond or a group having 1 carbon atom.
Represents an alkylene group of 1 to 8, but typical examples of the alkylene group include methylene, ethylene, propylene, butylene, pentamethylene, hexamethylene, octamethylene, 2,2-dimethyl-1,3-propylene and the like. .

One of Y and Z represents an alkoxy group having 1 to 8 carbon atoms or an aralkyloxy group having 7 to 12 carbon atoms, and the other represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms. Z is preferably an alkoxy group having 1 to 8 carbon atoms or an aralkyloxy group having 7 to 12 carbon atoms.
Here, the alkyl group having 1 to 8 carbon atoms includes, for example, the same alkyl group as described above, and the alkoxy group having 1 to 8 carbon atoms includes, for example, The aralkyloxy group having 7 to 12 carbon atoms includes, for example, an aralkyloxy group having 7 to 12 carbon atoms, for example, an aralkyloxy group having the same aralkyl as the aralkyl having 7 to 12 carbon atoms.

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

[0018]

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

[0020]

(Wherein, R ⁴ , R ⁵ , A, B, Y and Z have the same meanings as described above).

The phosphorus trihalide used here includes, for example, phosphorus trichloride, phosphorus tribromide and the like.
In particular, phosphorus trichloride is preferably used.

In the reaction, the reaction is promoted by coexistence of a dehalogenating agent such as amines, pyridines, pyrrolidines and amides, and a hydroxide of an alkali metal or an alkaline earth metal. Can also. Here, the amines include primary amines,
Any of secondary amines and tertiary amines may be used, for example, t-butylamine, t-pentylamine, t-hexylamine, t-octylamine, di-t-butylamine, di-t-pentylamine, di-t-hexylamine , Di-t-octylamine,
Examples thereof include trimethylamine, triethylamine, N, N-dimethylaniline, and N, N-diethylaniline, and preferably triethylamine. As pyridines,
For example, pyridine, picoline and the like can be mentioned, and pyridine is preferable. As pyrrolidines, for example, 1-
Methyl-2-pyrrolidine and the like. Examples of the amide include N, N-dimethylformamide and N, N-dimethylacetamide, and 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,
n-Hexane, n-heptane, diethyl ether, tetrahydrofuran, 1,4-dioxane, chloroform, dichloromethane and the like are preferably used.

As a reaction method, usually, a two-step reaction method is employed in which a bisphenol (II) is reacted with phosphorus trihalide to produce an intermediate, and then an alcohol compound (III) is reacted. . In this case,
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 based on the bisphenols (II). When a dehydrohalogenating agent is used, it is preferably used in an amount of about 2 to 2.4 moles per mol of phosphorus trihalide, more preferably 2 to 2.1 times.
It is about mole times. The reaction between the bisphenols (II) and phosphorus trihalide is usually carried out at about 0 to 200 ° C. This reaction is considered to produce an intermediate halogenophosphite, which may be isolated and then used for the next reaction, but usually, alcohols (I
II).

Then, when reacting the alcohol (III), it is usually used in an amount of about 1 to 1.1 mole times the bisphenol (II). In this reaction,
A dehydrohalogenating agent can be used, and in that case, the amount of the dehydrohalogenating agent is preferably about 1 to 1.2 mole times the alcohol (III). When the dehydrohalogenating agent is used in an excessive amount in the first reaction, the amount of the additional dehydrohalogenating agent is usually calculated including the remaining dehydrohalogenating agent. The reaction is usually at room temperature to 200
It is carried out at a temperature of about ° C. This reaction is preferably performed under reflux.

After the completion of the reaction, when a dehydrohalogenating agent is used, the hydrohalide salt of the dehydrohalogenating agent formed by the reaction is removed, and the solvent is further removed. By performing an appropriate post-treatment such as column chromatography, the phosphites (I) of the present invention can be obtained.

Here, bisphenols (II) as a raw material of the phosphites (I) can be prepared by a known method, for example, JP-A-52-122350, US Pat. No. 2,538,355, It can also be produced by condensing alkylphenols according to the method described in JP-A-47451. Bisphenols (II)
If it is commercially available, it can be used.

As the bisphenols (II), for example,
2,2'-methylenebis (4-methyl-6-t-butylphenol), 2,2'-methylenebis (4-ethyl-6-t-butylphenol), 2,2'-methylenebis (4-n-propyl-6 -t-butylphenol), 2,2'-methylenebis (4-i-propyl
-6-t-butylphenol), 2,2'-methylenebis (4-n-
Butyl-6-t-butylphenol), 2,2'-methylenebis
(4-i-butyl-6-t-butylphenol), 2,2'-methylenebis (4,6-di-t-butylphenol), 2,2'-methylenebis (4-t-pentyl-6-t-butylphenol) ), 2,2 '
-Methylenebis (4-nonyl-6-t-butylphenol),
2,2'-methylenebis (4-t-octyl-6-t-butylphenol), 2,2'-methylenebis (4-methyl-6-t-pentylphenol), 2,2'-methylenebis (4-methyl- 6-cyclohexylphenol), 2,2'-methylenebis [4-methyl-6- (α-methylcyclohexyl) phenol)], 2,2 '
-Methylenebis (4-methyl-6-nonylphenol), 2,
2'-methylenebis (4-methyl-6-t-octylphenol), 2,2'-methylenebis (4,6-di-t-pentylphenol), 2,2'-methylenebis [4-nonyl-6- (α -Methylbenzyl) phenol], 2,2′-methylenebis [4-nonyl-6- (α, α-dimethylbenzyl) phenol],
2'-ethylidenebis (4-methyl-6-butylphenol),

2,2'-ethylidenebis (4-ethyl-6-t-butylphenol), 2,2'-ethylidenebis (4-n-propyl-6-t-butylphenol), 2,2'-ethylidenebis (Four
-i-propyl-6-t-butylphenol), 2,2'-ethylidenebis (4-n-butyl-6-t-butylphenol), 2,2 '
-Ethylidenebis (4-i-butyl-6-t-butylphenol), 2,2'-ethylidenebis (4,6-di-t-butylphenol), 2,2'-ethylidenebis (4-t-pentyl- 6-t-butylphenol), 2,2'-ethylidenebis (4-nonyl-6
-t-butylphenol), 2,2'-ethylidenebis (4-t-
Octyl-6-t-butylphenol), 2,2'-ethylidenebis (4-methyl-6-t-pentylphenol), 2,2'-ethylidenebis (4-methyl-6-cyclohexylphenol), 2,2 '-Ethylidenebis [4-methyl-6- (α-methylcyclohexyl) phenol]], 2,2'-ethylidenebis
(4-methyl-6-nonylphenol), 2,2'-ethylidenebis (4-methyl-6-t-octylphenol), 2,2'-ethylidenebis (4,6-di-t-pentylphenol), 2 , 2 '
-Ethylidenebis [4-nonyl-6- (α-methylbenzyl)
Phenol], 2,2'-ethylidenebis [4-nonyl-6-
(α, α-dimethylbenzyl) phenol], 2,2′-propylidenebis (4-methyl-6-t-butylphenol),
2,2'-propylidenebis (4-ethyl-6-t-butylphenol),

2,2'-propylidenebis (4-n-propyl-6
-t-butylphenol), 2,2'-propylidenebis (4-i
-Propyl-6-t-butylphenol), 2,2'-propylidenebis (4-n-butyl-6-t-butylphenol), 2,2 '
-Propylidenebis (4-i-butyl-6-t-butylphenol), 2,2'-propylidenebis (4,6-di-t-butylphenol), 2,2'-propylidenebis (4-t-pentyl-6-t
-Butylphenol), 2,2'-propylidenebis (4-nonyl-6-t-butylphenol), 2,2'-propylidenebis (4-t-octyl-6-t-butylphenol), 2,2'-propylidenebis (4 -Methyl-6-t-pentylphenol), 2,2'-propylidenebis (4-methyl-6-cyclohexylphenol), 2,2'-propylidenebis [4-methyl-6- (α-methylcyclohexyl) phenol) , 2,2 '
-Propylidenebis (4-methyl-6-nonylphenol), 2,2'-propylidenebis (4-methyl-6-t-octylphenol), 2,2'-propylidenebis (4,6-di-t-
Pentylphenol), 2,2′-propylidenebis [4-nonyl-6- (α-methylbenzyl) phenol], 2,2′-propylidenebis [4-nonyl-6- (α, α-dimethylbenzyl) phenol], 2,2'-butylidenebis (4-methyl-6
-t-butylphenol), 2,2'-butylidenebis (4-ethyl-6-t-butylphenol), 2,2'-butylidenebis
(4,6-di-t-butylphenol), 2,2'-butylidenebis (4-methyl-6-cyclohexylphenol),

2,2'-butylidenebis [4-methyl-6- (α-
Methylcyclohexyl) phenol)], 2,2'-butylidenebis (4,6-di-t-pentylphenol), 2,2'-i-butylidenebis (4-methyl-6-t-butylphenol),
2'-i-butylidenebis (4-ethyl-6-t-butylphenol), 2,2'-i-butylidenebis (4,6-di-t-butylphenol), 2,2'-i-butylidenebis (4-methyl -6-cyclohexylphenol), 2,2'-i-butylidenebis [4-
Methyl-6- (α-methylcyclohexyl) phenol)], 2,2′-i-butylidenebis (4,6-di-t-pentylphenol), 2,2′-pentylidenebis (4-methyl-6- t
-Butylphenol), 2,2'-pentylidenebis (4-ethyl-6-t-butylphenol), 2,2'-pentylidenebis (4,6-di-t-butylphenol), 2,2'-pliers Redidenbis (4-methyl-6-cyclohexylphenol), 2,
2′-pentylidenebis [4-methyl-6- (α-methylcyclohexyl) phenol)], 2,2′-pentylidenebis (4,6
-Di-t-pentylphenol), biphenyl-2,2'-diol, 3,3 ', 5,5'-tetra-t-butylbiphenyl-2,2'-diol, 1,1'-binaphthyl-2 , 2'-diol and the like. The other raw material, alcohols (III), is, for example, of the general formula (IV)

[0033]

(In the formula, R ⁴ , R ⁵ , B, Y and Z have the same meaning as described above, and W represents, for example, a lower alkoxy group having about 1 to 4 carbon atoms, a hydroxyl group or a halogen atom.) And HO-A-
It can be produced by reacting a dihydric alcohol represented by OH according to a known method.

For example, W of phenylcarboxylic acids (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,
Sodium-t-butoxide, potassium methoxide, potassium ethoxide, alkali metal alkoxides such as potassium-t-butoxide alkali metal amides such as lithium amide, alkali metal alkylamides such as lithium diisopropylamide, lithium hydride, hydrogenation Sodium, potassium hydride, calcium hydride, sodium oxide, calcium oxide, sodium hydroxide, lithium hydroxide, potassium hydroxide, calcium hydroxide, lithium carbonate, sodium carbonate, potassium carbonate, calcium carbonate,
Alkali metal or alkaline earth metal hydrides such as barium carbonate, oxides, hydroxides, carbonates, alkali metals such as lithium, sodium and potassium, dibutyltin oxide, dialkyltin oxides such as dioctyltin oxide, Dialkyltin alkoxides such as dibutyltin methoxide, dibutyltin acetate, dibutyltin malate, dibutyltin dioctanoate, dialkyltin dicarboxylates such as dibutyltin dilaurate, Formula (V) (R ⁶ O) ₄ M (V) (In the formula, R ⁶ represents an alkyl group having 1 to 18 carbon atoms, a phenyl group, or a benzyl group, and M represents an element of germanium, zirconium, tin, or titanium.) Examples thereof include the above mixtures. 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-2-methoxybenzoate, 3-
2-hydroxyethyl t-butyl-4-methoxybenzoate,
2-hydroxyethyl 3-t-butyl-5-methoxybenzoate, 2-hydroxyethyl 3-t-pentyl-4-methoxybenzoate, 2-hydroxyethyl 3-t-octyl-4-methoxybenzoate, 3- Cyclohexyl-4-methoxybenzoic acid
2-hydroxyethyl, 3- (1-methylcyclohexyl)
2-hydroxyethyl -4-methoxybenzoate, 3-hydroxyethyl 3-tert-butyl-2-methoxy-5-methylbenzoate, 2-hydroxyethyl 3-tert-butyl-4-methoxy-5-methylbenzoate 3-hydroxypropyl, 3-t-butyl-4-methoxy-5-methylbenzoate, 4-hydroxybutyl, 3-t-butyl-4-methoxy-5-methylbenzoate, 5-t-butyl-2-methoxy 3-Hydroxymethyl 3-methylbenzoate, 3-t-pentyl-4-methoxy-5-methylbenzoic acid 2-
Hydroxyethyl, 3-t-octyl-4-methoxy-5-methylbenzoic acid 2-hydroxyethyl, 3-cyclohexyl
2-hydroxyethyl 4-methoxy-5-methylbenzoate, 2-hydroxyethyl 3- (1-methylcyclohexyl) -4-methoxy-5-methylbenzoate, 3-t-butyl-4-
2-hydroxyethyl methoxy-5-ethylbenzoate, 3-
2-hydroxyethyl t-pentyl-4-methoxy-5-ethylbenzoate,

2-hydroxyethyl 3-t-octyl-4-methoxy-5-ethylbenzoate, 2-hydroxyethyl 3-cyclohexyl-4-methoxy-5-ethylbenzoate, 3- (1
-Methylcyclohexyl) -4-methoxy-5-ethylbenzoic acid 2-hydroxyethyl, 3,5-di-t-butyl-2-methoxybenzoic acid 2-hydroxyethyl, 3,5-di-t-butyl-4 -2-hydroxyethyl methoxybenzoate, 3,5-t-
3-hydroxypropyl butyl-4-methoxybenzoate,
4-hydroxybutyl 3,5-di-t-butyl-4-methoxybenzoate, 2-hydroxyethyl 3-t-pentyl-4-methoxy-5-t-butylbenzoate, 3-t-octyl-4- Methoxy-5
2-Hydroxyethyl -t-butylbenzoate, 3-cyclohexyl-4-methoxy-5-t-hydroxyethyl 2-tert-butylbenzoate, 3- (3- (1-methylcyclohexyl) -4-methoxy-5-t -2-hydroxyethyl butylbenzoate, 3-t-
2-hydroxyethyl butyl-2-ethoxybenzoate, 3-
t-butyl-4-ethoxybenzoic acid 2-hydroxyethyl,
2-hydroxyethyl 3-t-butyl-4-ethoxy-5-methylbenzoate, 3-hydroxypropyl 3-t-butyl-4-ethoxy-5-methylbenzoate, 3-t-butyl-4-ethoxy- Five
-4-hydroxybutyl methylbenzoate, 3-t-butyl-2-
2-hydroxyethyl ethoxy-5-methylbenzoate, 5
-t-butyl-2-ethoxy-3-methylbenzoic acid 2-hydroxyethyl,

3,5-di-t-butyl-4-ethoxybenzoic acid 2
-Hydroxyethyl, 2-hydroxyethyl 3,5-di-t-butyl-2-ethoxybenzoate, 2-hydroxyethyl (3-t-butyl-4-methoxyphenyl) acetate, (3-t-butyl
-5-methoxyphenyl) acetic acid 2-hydroxyethyl,
2-hydroxyethyl (3-t-pentyl-4-methoxyphenyl) acetic acid, 2-hydroxyethyl (3-t-octyl-4-methoxyphenyl) acetic acid, 2-hydroxyethyl (3-cyclohexyl-4-methoxyphenyl) acetic acid Ethyl, 2-hydroxyethyl [3- (1-methylcyclohexyl) -4-methoxyphenyl] acetate, 2-hydroxyethyl (3-t-butyl-2-methoxy-5-methylphenyl) acetate, (3-t- Butyl-4
-Methoxy-5-methylphenyl) acetic acid 2-hydroxyethyl, (3-t-butyl-4-methoxy-5-methylphenyl)
3-hydroxypropyl acetate, (3-t-butyl-4-methoxy-5-methylphenyl) acetic acid 4-hydroxybutyl, (5
-t-butyl-2-methoxy-3-methylphenyl) acetic acid 2-
Hydroxyethyl, (3-t-pentyl-4-methoxy-5-methylphenyl) acetic acid 2-hydroxyethyl, (3-t-octyl-4-methoxy-5-methylphenyl) acetic acid 2-hydroxyethyl, (3- 2-Hydroxyethyl cyclohexyl-4-methoxy-5-methylphenyl) acetate, 2-hydroxyethyl [3- (1-methylcyclohexyl) -4-methoxy-5-methylphenyl] acetate, (3-t-butyl-4) -Methoxy-5
-Ethylphenyl) 2-hydroxyethyl acetate,

2-hydroxyethyl (3-t-pentyl-4-methoxy-5-ethylphenyl) acetate, (3-t-octyl-4)
-Methoxy-5-ethylphenyl) acetic acid 2-hydroxyethyl, (3-cyclohexyl-4-methoxy-5-ethylphenyl) acetic acid 2-hydroxyethyl, [3- (1-methylcyclohexyl) -4-methoxy-5- Ethylphenyl] acetic acid 2-
Hydroxyethyl, 2-hydroxyethyl (3,5-di-t-butyl-2-methoxyphenyl) acetate, 2-hydroxyethyl (3,5-di-t-butyl-4-methoxyphenyl) acetate,
3-hydroxypropyl (3,5-di-t-butyl-4-methoxyphenyl) acetate, 4-hydroxybutyl (3,5-di-t-butyl-4-methoxyphenyl) acetate, (3-t-pentyl) -Four
-Methoxy-5-t-butylphenyl) acetic acid 2-hydroxyethyl, (3-t-octyl-4-methoxy-5-t-butylphenyl) acetic acid 2-hydroxyethyl, (3-cyclohexyl-4)
-Methoxy-5-t-butylphenyl) acetic acid 2-hydroxyethyl, [3- (1-methylcyclohexyl) -4-methoxy-5
-t-butylphenyl] 2-hydroxyethyl acetate, (3-t
-Butyl-2-ethoxyphenyl) acetic acid 2-hydroxyethyl, (3-t-butyl-4-ethoxyphenyl) acetic acid 2-hydroxyethyl, (3-t-butyl-4-ethoxy-5-methylphenyl) acetic acid 2 -Hydroxyethyl, (3-t-butyl-4-
3-hydroxypropyl ethoxy-5-methylphenyl) acetate, 4-hydroxybutyl (3-t-butyl-4-ethoxy-5-methylphenyl) acetate,

2-hydroxyethyl (3-t-butyl-2-ethoxy-5-methylphenyl) acetate, 2-hydroxyethyl (3-t-butyl-2-ethoxy-5-methylphenyl) acetate, 2-hydroxyethyl t-butyl-2-ethoxy-3-methylphenyl) acetate, 2-hydroxyethyl (3,5-di-t-butyl-4-ethoxyphenyl) acetate, (3,5-di-t
3-hydroxypropyl (3-butyl-4-ethoxyphenyl) acetate, 4-hydroxybutyl (3,5-di-t-butyl-4-ethoxyphenyl) acetate, (3,5-di-t-butyl-2-ethoxy) 2-hydroxyethyl phenyl) acetate, 2-hydroxyethyl 3- (3-t-butyl-2-methoxyphenyl) propionate, 2-hydroxyethyl 3- (3-t-butyl-4-methoxyphenyl) propionate, 2-hydroxyethyl 3- (3-t-butyl-5-methoxyphenyl) propionate,
2-hydroxyethyl 2-, (3-t-pentyl-4-methoxyphenyl) propionate, 2-hydroxyethyl 3- (3-t-octyl-4-methoxyphenyl) propionate, 3- (3
-Cyclohexyl-4-methoxyphenyl) propionic acid
2-hydroxyethyl, 3- [3- (1-methylcyclohexyl) -4-methoxyphenyl] propionic acid 2-hydroxyethyl, 3- (3-t-butyl-2-methoxy-5-methylphenyl) propionic acid 2 -Hydroxyethyl,

2-hydroxyethyl 3- (3-t-butyl-4-methoxy-5-methylphenyl) propionate, 3- (3-t-
Butyl-4-methoxy-5-methylphenyl) propionic acid
3-hydroxybutyl, 3- (3-t-butyl-4-methoxy-5
-Methylphenyl) 4-hydroxybutyl propionate, 3- (5-t-butyl-2-methoxy-3-methylphenyl)
2-hydroxyethyl propionate, 3- (3-t-pentyl)
2-hydroxyethyl-4-methoxy-5-methylphenyl) propionate, 2-hydroxyethyl 3- (3-t-octyl-4-methoxy-5-methylphenyl) propionate
(3-cyclohexyl-4-methoxy-5-methylphenyl)
2-hydroxyethyl propionate, 3- [3- (1-methylcyclohexyl) -4-methoxy-5-methylphenyl] 2-hydroxyethyl propionate, 3- (3-t-butyl-4-methoxy-5- 2-hydroxyethyl ethylphenyl) propionate, 2-hydroxyethyl 3- (3-t-pentyl-4-methoxy-5-ethylphenyl) propionate, 3- (3-t-
2-hydroxyethyl octyl-4-methoxy-5-ethylphenyl) propionate, 2-hydroxyethyl 3- (3-cyclohexyl-4-methoxy-5-ethylphenyl) propionate, 3- [3- (1-methyl Cyclohexyl) -4-methoxy-5-ethylphenyl] 2-hydroxyethyl propionate, 2- (hydroxyethyl) 3- (3,5-di-t-butyl-2-methoxyphenyl) propionate,

2-hydroxyethyl 3- (3,5-di-t-butyl-4-methoxyphenyl) propionate, 3- (3,5-di-t
-3-Hydroxypropyl butyl-4-methoxyphenyl) propionate, 4-Hydroxybutyl 3- (3,5-di-t-butyl-4-methoxyphenyl) propionate, 3- (3-t-
2-hydroxyethyl pentyl-4-methoxy-5-t-butylphenyl) propionate, 2-hydroxyethyl 3- (3-t-octyl-4-methoxy-5-t-butylphenyl) propionate, 3- ( 3-cyclohexyl-4-methoxy-5-t-butylphenyl) propionic acid 2-hydroxyethyl,
[3- (1-Methylcyclohexyl) -4-methoxy-5-t-butylphenyl] 2-hydroxyethyl propionate, 3- (3
2-hydroxyethyl 3-t-butyl-2-ethoxyphenyl) propionate, 2-hydroxyethyl 3- (3-t-butyl-4-ethoxyphenyl) propionate, 3- (3-t-butyl-4-ethoxy) -5-methylphenyl) propionic acid 2-
Hydroxyethyl, 3- (3-t-butyl-4-ethoxy-5-methylphenyl) propionate 3-hydroxypropyl,
4-hydroxybutyl 3- (3-t-butyl-2-ethoxy-5-methylphenyl) propionate, 2-hydroxyethyl 3- (5-t-butyl-2-ethoxy-3-methylphenyl) propionate, 2-hydroxyethyl 3- (3,5-di-t-butyl-4-ethoxyphenyl) propionate,

3-hydroxypropyl 3- (3,5-di-t-butyl-4-ethoxyphenyl) propionate
4-Hydroxybutyl-t-butyl-4-ethoxyphenyl) propionate, 2-Hydroxyethyl 3- (3,5-di-t-butyl-2-ethoxyphenyl) propionate, 4- (3-t-
2-hydroxyethyl butyl-2-methoxyphenyl) butyrate, 2-hydroxyethyl 4- (3t-butyl-4-methoxyphenyl) butyrate, 2- (4-t-butyl-4-methoxy-5-methylphenyl) butyrate 2 -Hydroxyethyl, 4- (3-t-butyl-
3-hydroxypropyl 4-methoxy-5-methylphenyl) butyrate, 4-hydroxybutyl 4- (3-t-butyl-4-methoxy-5-methylphenyl) butyrate, 4- (3-t-butyl-2-
2-hydroxyethyl methoxy-5-methylphenyl) butyrate, 4- (5-t-butyl-2-methoxy-3-methylphenyl)
2-hydroxyethyl butyrate, 4- (3,5-di-t-butyl-4-)
2-hydroxyethyl methoxyphenyl) butyrate, 4- (3,
3-hydroxypropyl 5-di-t-butyl-4-methoxyphenyl) butyrate, 4-hydroxybutyl 4- (3,5-di-t-butyl-4-methoxyphenyl) butyrate, 4- (3,5- 2-hydroxyethyl di-t-butyl-2-methoxyphenyl) butyrate,

2-hydroxyethyl 4- (3-t-butyl-4-ethoxy-5-methylphenyl) butyrate, 4- (3-t-butyl-4)
3-Ethoxy-5-methylphenyl) butyrate 3-hydroxypropyl, 4- (3-t-butyl-4-ethoxy-5-methylphenyl) butyrate 4-hydroxybutyl, 4- (3,5-di-t-butyl)
-4-ethoxyphenyl) butyric acid 2-hydroxyethyl, 4-
3-hydroxypropyl (3,5-di-t-butyl-4-ethoxyphenyl) butyrate, 4-hydroxybutyl 4- (3,5-di-t-butyl-4-ethoxyphenyl) butyrate and the like.

Thus, the phosphites (I) of the present invention can be obtained, and the phosphites (I) of the present invention can be prepared by adding amines, acid-bonded metal salts, etc. Degradability can be improved. Representative examples of such amines include, for example, trialkanolamines such as triethanolamine, tripropanolamine, and tri-i-propanolamine, diethanolamine, dipropanolamine, di-i-propanolamine, tetraethanolethylenediamine, and tetra-ethanolamine. i-
Dialkanolamines such as propanolethylenediamine, monoalkanolamines such as dibutylethanolamine and dibutyl-i-propanolamine, aromatic amines such as 1,3,5-trimethyl-2,4,6-triazine, dibutylamine , Piperidine, alkylamines such as 2,2,6,6-tetramethylpiperidine, 4-hydroxy-2,2,6,6-tetramethylpiperidine, hexamethylenetetramine, triethylenediamine, triethylenetetramine, tetraethylenepentamine Polyalkylene polyamines such as min,
The following hindered amine light stabilizers are mentioned.
Further, long-chain aliphatic amines described in JP-A-61-63686, compounds containing a sterically hindered amine group described in JP-A-6-329830, hindered amines described in JP-A-7-90270 are disclosed. Peridinyl-based light stabilizers, organic amines described in JP-A-7-278164, and the like can also be used. The use ratio of amines to phosphites (I) is usually 0.01 to 25% by weight.
It is about.

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 ratio of the acid-bonded metal salt to the phosphite (I) is usually about 0.01 to 25% by weight.

The phosphites (I) of the present invention are effective for stabilizing organic materials against thermal deterioration and oxidative 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) Polysulfone, polyetheretherketone, polyethersulfone, (24) Thermoplastic resin such as 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 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 phosphites (I) of the present invention are added to stabilize an organic material, the phosphites (I) are usually added in an amount of 0.0
About 1 to 5 parts by weight, preferably about 0.03 to 3 parts by weight, more preferably about 0.05 to 1 part by weight. If the amount used is less than 0.01 part 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 incorporating the phosphites (I) of the present invention into an organic material, other additives such as phenol-based antioxidants, sulfur-based antioxidants, and phosphorus-based antioxidants may be used, if necessary. Agent, ultraviolet absorber, light stabilizer, peroxide scavenger, polyamide stabilizer, hydroxylamine, lubricant, plasticizer, flame retardant, nucleating agent, metal deactivator, antistatic agent, pigment, filler, pigment , Antiblocking agents, surfactants, processing aids, foaming agents, emulsifiers, brighteners, calcium stearate, neutralizing agents such as hydrotalcite, and even 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, 4,316,611, DE
-A-4,316,622, 4,316,876, EP-A-589,839,
Co-stabilizers such as benzofurans and indolines described in JP-A-591,102 and the like can also be contained. Of course, these additives can be blended simultaneously with the phosphites (I), or can be blended at a different stage from the phosphites (I).

Here, examples of the phenolic antioxidant include the following. (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.

Further, examples of the sulfur-based antioxidant include the following. 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-triphenyl
-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 -Oxaphospholinane, 2,2 ', 2''
-Nitrilo [triethyl-tris (3,3 ', 5,5'-tetra-t
-Butyl-1,1'-biphenyl-2,2'-diyl) phosphites and mixtures thereof.

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.

Examples of the light stabilizer include the following. (1) Examples of hindered amine light stabilizers 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-acryloyl-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 -
Mixed esterified product with tridecanol,

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.

(2) 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. (3) 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.

(4) 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. (5) 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.

As the peroxide scavenger, for example, esters of β-thiodipropionic acid, mercaptobenzimidazole, zinc salt of 2-mercaptobenzimidazole, zinc salt of dibutyldithiocarbamic acid, dioctadecyl disulfide, 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), melamine, amine, polyamide, polyurethane, and mixtures thereof. Can be Examples of the lubricant include aliphatic hydrocarbons such as paraffin and wax, higher aliphatic acids having 8 to 22 carbon atoms, and higher aliphatic acid metals having 8 to 22 carbon atoms (Al, Ca, M
g, Zn) salt, aliphatic alcohol having 8 to 22 carbon atoms, polyglycol, higher fatty acid having 4 to 22 carbon atoms and 4 to 18 carbon atoms
Esters with aliphatic monohydric alcohols, higher aliphatic amides having 8 to 22 carbon atoms, silicone oils, rosin derivatives and the like.

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 mixtures thereof.

Of these additives, those preferably used are phenolic antioxidants, phosphorus antioxidants,
UV absorbers, hindered amine light stabilizers, peroxide scavengers and neutralizers. Particularly preferred phenolic antioxidants 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,
Tris (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-hydroxycinnamate), 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-dioxaoctamethylene Screw
(3,5-di-t-butyl-4-hydroxycinnamate), 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.

Particularly preferred phosphorus 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.

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.

Further, particularly preferred light stabilizers include the following, and these may be used in combination of two or more. Screw
(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-Acroyl-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-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 (1,2,6,6-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.

In blending the phosphites (I) or other additives used as necessary with the organic material, any known method and apparatus for obtaining a homogeneous mixture may be used. it can. For example, when the organic material is a solid polymer, the phosphites (I) or other additives can be directly dry-blended with the solid polymer, or the phosphite compound or another Additives can also be incorporated into the solid polymer in the form of a masterbatch. If the organic material is a liquid polymer,
The phosphites (I) or other additives may be added to the polymer solution during or immediately after the polymerization in the form of a solution or dispersion. On the other hand, when the organic material is a liquid such as oil, phosphites (I) or other additives can be directly added and dissolved, or phosphites (I) or Further, other additives may be added in a state of being dissolved or suspended in a liquid medium.

[0084]

The phosphites (I) of the present invention are:
It has excellent performance as a stabilizer for various organic materials such as thermoplastic resins such as polyolefins. Stable and high quality products.

[0085]

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.

Example 1 2,4,8,10-tetra-t-butyl
-6- {2- [3- (3-t-butyl-4-methoxy-5-methylphenyl) propionyloxy] ethoxy-12-methyl-12H-dibenzo [d, g] [1,3,2] di Preparation of Oxaphosphine (Compound 1) In a flask equipped with a thermometer, a stirrer and a condenser, 21.9 g of 2,2′-ethylidenebis (4,6-di-t-butylphenol) and 100 ml of toluene were placed under a nitrogen stream. 6.9 g of phosphorus trichloride was added under stirring, and then triethylamine 12.1 g was added.
g was added and the mixture was kept at 80 ° C. for 9 hours. After cooling to room temperature, 50 ml of toluene and 14.7 g of 2-hydroxyethyl 3- (3-t-butyl-4-methoxy-5-methylphenyl) propionate were added, followed by 6.1 g of triethylamine, and the mixture was kept at 80 ° C. for 6 hours. . Next, after cooling to room temperature, the formed triethylamine hydrochloride was filtered. After concentrating the filtrate,
The residue was crystallized from a mixed solvent of ethyl acetate-n-hexane to give 20 g of white crystals. Mass spectrum (FD-MS): m / z 760, melting point: 151 ° C.

¹ H-NMR (CDCl ₃ ) 1.30 (s, 18H), 1.38 (s, 9H), 1.42 (s, 18H), 1.61 (d, 3H),
2.30 (s, 3H), 2.69 (t, 2H), 2.92 (t, 2H), 3.75 (s, 3H), 4.48
(m, 2H), 4.60 (t, 2H), 4.89 (q, 1H) 6.90 (d, 1H), 7.00 (d, 1
H), 7.20 (d, 2H ), 7.40 (d, 2H) 31 P-NMR (CDCl 3) 127.4 ppm

Example 2: 2,4,8,10-tetra-t-butyl
-6- {2- [3- (3-t-butyl-4-methoxy-5-methylphenyl) propionyloxy] ethoxy-dibenzo [d, f] [1,
Preparation of 3,2] dioxaphosphepin (Compound 2) In Example 1, 2,2′-ethylidenebis (4,6-di-t-
Butylphenol) is replaced by 3,3'-5,5'-tetra-t-
Except that 20.5 g of butylbiphenyl-2,2′-diol was used, the procedure was carried out according to Example 1 to obtain 25.3 g of white crystals.
g. Mass spectrum (FD-MS): m / z 732, melting point: 133 ° C

¹ H-NMR (CDCl ₃ ) 1.35 (s, 18H), 1.37 (s, 9H), 1.48 (s, 18H), 2.29 (s, 3H),
2.60 (t, 2H), 2.84 (t, 2H), 3.75 (s, 3H), 3.94 (m, 2H), 4.14
(t, 2H), 6.86 (d, 1H), 6.95 (d, 1H), 7.16 (d, 2H), 7.42 (d, 2H) ³¹ P-NMR (CDCl ₃ ) 127.4 ppm

Example 3: Thermal stabilization test of polypropylene [Compound] Polypropylene (block) 100 parts by weight Calcium stearate 0.05 part by weight Test compound 0.05 part by weight Chemical-1: Compound 1 (produced in Example 1) 1: Compound 2 (prepared in Example 2) P-1: 2,10-dimethyl-4,8-di-t-butyl-6- {2-}
[3- (3-t-butyl-4-hydroxy-5-methylphenyl)
Propionyloxy] ethoxy｝ -12H-dibenzo [d, g]
[1,3,2] dioxaphosphosine

Using a 30 mmφ single screw extruder, the above composition was melt-kneaded at 250 ° C. and pelletized. The obtained pellets were melted at 250 ° C. under a load of 2160 using a melt indexer.
g, and MFR (g / min) were measured at a residence time of 5 minutes, and the results are shown in Table 1. The smaller the MFR, the better the processing stability.

[0092]

TABLE 1 implementation example comparisons Example 1 2 1 2 test compound of -1 of -2 - P-1 processing stability 20.6 19.5 29.4 22.0

Example 4: Thermal stabilization test of linear low-density polyethylene [Compound] Unstabilized linear low-density polyethylene 100 parts by weight Hydrotalcite 0.1 part by weight Test compound 0.05 part by weight Chemical-1: Compound 1 (Manufactured in Example 1) Compound-1: Compound 2 (manufactured in Example 2) P-1: 2,10-dimethyl-4,8-di-t-butyl-6- {2-}
[3- (3-t-butyl-4-hydroxy-5-methylphenyl)
Propionyloxy] ethoxy｝ -12H-dibenzo [d, g]
[1,3,2] dioxaphosphosine

Using a 30 mmφ single screw extruder, the above compound was melt-kneaded at 250 ° C. and pelletized. Using a melt indexer, the obtained pellets were heated at 250 ° C and a load of 5k.
g, MFR (g / min) was measured at a residence time of 5 minutes, and the results are shown in Table 2. The higher the MFR, the better the processing stability. The obtained pellets were kneaded using a Labo Plastomill at 230 ° C., 10 rpm for 5 minutes.
Table 2 shows the results of measuring the YI value of the sheet formed by pressing at 250 ° C. The evaluation criteria are as follows. ○: YI = 0 to 5 △: YI = 5 to 10 ×: YI> 10

[0095]

TABLE 2 implementation example comparisons Example 1 2 1 Test compounds of -1 of -2 P-1 processing stability 12.7 12.8 12.3 color phase ○ ○ △

Example 5: Thermal stability test of nylon [Compound] Unstabilized nylon 6 100 parts by weight Test stabilizer 0.5 part by weight 2 (produced in Example 2) P-1: 2,10-dimethyl-4,8-di-t-butyl-6- {2-}
[3- (3-t-butyl-4-hydroxy-5-methylphenyl)
Propionyloxy] ethoxy｝ -12H-dibenzo [d, g]
[1,3,2] dioxaphosphosine

After kneading the above components by dry blending, the mixture was kneaded at 80 ° C. and 300 ° C. for 5 minutes using a Labo Plastomill, and the torque value after 5 minutes is shown in Table 3. Nylon 6 is decomposed due to deterioration and the torque value is reduced.
The higher the torque value after minutes, the better the processing stability.

[0098]

[Table 3]

 ────────────────────────────────────────────────── ─── Continued on the front page (72) Inventor Takashi Sanada 5-1 Anesaki Beach, Ichihara-shi, Chiba Sumitomo Chemical Co., Ltd.

Claims (11)

[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 represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms. X is a mere bond, a sulfur atom or carbon number 1 to
Represents a methylene group which may be substituted by alkyl of 8 or cycloalkyl having from 5 to 8 carbon atoms. A represents a dihydric alcohol residue, and B represents a mere bond or 1 to 1 carbon atoms.
And 8 represents an alkylene group. One of Y and Z represents an alkoxy group having 1 to 8 carbon atoms or an aralkyloxy group having 7 to 12 carbon atoms, and the other represents a hydrogen atom or 1 carbon atom.
To 8 alkyl groups. ) Phosphites represented by). 2. A compound of the general formula (II) (Wherein R ¹ , R ² , R ³ and X have the same meaning as in claim 1), a phosphorus trihalide and a compound represented by the general formula (III) (Wherein R ⁴ , R ⁵ , A, B, Y and Z have the same meanings as defined in claim 1), and are reacted with an alcohol represented by the formula (1). Manufacturing methods. 3. A stabilizer for an organic material comprising the phosphite according to claim 1 as an active ingredient. 4. The method according to claim 3, wherein the organic material is a thermoplastic resin.
The stabilizer as described. 5. The stabilizer according to claim 4, wherein the thermoplastic resin is a polyolefin or an engineering resin. 6. A method for stabilizing an organic material, comprising adding the phosphite according to claim 1 to the organic material. 7. The method according to claim 6, wherein the organic material is a thermoplastic resin.
Stabilization method as described. 8. The method according to claim 7, wherein the thermoplastic resin is a polyolefin or an engineering resin. 9. A stabilized organic material composition comprising the phosphite according to claim 1 in an organic material. 10. The composition according to claim 9, wherein the organic material is a thermoplastic resin. 11. The composition according to claim 10, wherein the thermoplastic resin is a polyolefin or an engineering resin.