JPH11236475A - Aromatic monovinyl resin composition, its production and prevention of thermal decomposition of the aromatic monovinylic resin - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain an aromatic monovinylic resin composition that is useful for moldings and the like having excellent resistance to thermal decomposition and discoloration by compounding an aromatic monovinylic resin and a specific phosphite ester in a specific proportion. SOLUTION: (A) 100 pts.wt. of an aromatic monovinylic resin as polystyrene or the like are combined with (B) 0.01-5 pts.wt. of a phosphite ester of the formula [R<1> , R<2> , R<4> and R<5> are each H, a 1-8C alkyl, a 5-8C cycloalkyl, phenyl or the like; R<3> is H, a 1-8C alkyl; X is a single bond, S or -CHR<6> - (R<6> is H, a 1-8C alkyl or the like); A is a 2-8C alkylene or the like; one of Y and Z is hydroxyl or a 1-8C alkoxy or the like, while the other is H, a 1-8C alkyl] for example, 2,4,8,10-tetra-t-buty-6-[3-(3-methyl-4-hydroxy-5-t-butylphenyl) propoxy]ciibenzo[d,f] [1,3,2] dioxaphosphepin or the like.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an aromatic monovinyl resin composition, and more particularly, to an aromatic monovinyl resin composition containing a specific amount of a specific phosphite ester in which the thermal decomposition is suppressed. The present invention relates to a monovinyl resin composition.

[0002]

2. Description of the Related Art An aromatic monovinyl resin such as polystyrene is subjected to a high temperature, for example, a polymerization step, a devolatilization step of removing unreacted monomers and / or a solvent from a reaction product after the polymerization reaction. It is known that thermal decomposition is caused in a molding process or the like, resulting in a decrease in molecular weight, a change in physical properties such as impact strength and rigidity, and a decrease in product yield. For this reason, for example, in order to increase the product yield in the molding process, so-called repros such as defective moldings and remnants are mixed with new pellets and recycled. If the physical properties are different between the above, there is a problem that the moldability fluctuates and a good molded product cannot be stably obtained. Further, in the molding step, the low molecular weight component generated by the thermal decomposition lowers the heat resistance of the aromatic monovinyl resin, volatilizes in the mold during injection molding, remains, and is further transferred to the molded article. And the like, there is a problem that the frequency of cleaning the mold is increased, and the productivity is reduced.

On the other hand, as a method for improving the thermal decomposability of an aromatic monovinyl resin, n-octadecyl 3- (3,5-di-t
-Butyl-4-hydroxyphenyl) propionate, 2,
6-di-t-butyl-4-hydroxytoluene, 2-t-butyl-6- (3-t-butyl-2-hydroxy-5-methylbenzyl)-
Resin compositions comprising 4-methylphenyl acrylate and the like have been proposed (JP-A-3-217445, JP-A-3-217445)
5-170825), but it was not always satisfactory. The present invention and the like, as a result of intensive studies to find an aromatic monovinyl resin composition exhibiting better thermal decomposition resistance, a resin composition comprising a specific amount of a specific phosphite, The present inventors have found that they exhibit an excellent effect of preventing thermal decomposition, and have completed the present invention.

[0004]

That is, according to the present invention, there is provided a compound represented by the general formula (I) based on 100 parts by weight of an aromatic monovinyl resin.

[0005]

(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 is a mere bond, a sulfur atom or a —CHR ⁶ — group (R ⁶ is a hydrogen atom,
Represents an alkyl group or a cycloalkyl group having 5 to 8 carbon atoms). A is an alkylene group having 2 to 8 carbon atoms or *-
Represents a COR ⁷ -group (R ⁷ is a mere bond or an alkylene group having 1 to 8 carbon atoms, and * indicates that it is bonded to the oxygen side). One of Y and Z represents a hydroxy group, 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. The present invention provides an aromatic monovinyl resin composition excellent in heat decomposition resistance, characterized by comprising 0.01 to 5 parts by weight of a phosphite represented by the formula (1).

[0007]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail. In the phosphites represented by the formula (I) in 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, 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. R ¹ , R ² and R ⁴ are preferably an alkyl group having 1 to 8 carbon atoms, a cycloalkyl group having 5 to 8 carbon atoms, or an alkylcycloalkyl group having 6 to 12 carbon atoms, and R ⁵ is preferably , Hydrogen atom, carbon atom number 1
It is preferably an alkyl group having 8 or a cycloalkyl group having 5 to 8 carbon atoms. 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. Further, as typical examples of the cycloalkyl group having 5 to 8 carbon atoms, for example, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl and the like are mentioned, and as typical examples of the alkylcycloalkyl group having 6 to 12 carbon atoms, for example, 1-methylcyclopentyl , 1-methylcyclohexyl, 1-methyl-4-i-propylcyclohexyl and the like. 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 and R ⁴ are preferably a t-alkyl group such as t-butyl, t-pentyl and t-octyl, cyclohexyl and 1-methylcyclohexyl group.
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, methyl, t-butyl and t-pentyl are preferred. R ⁵ is a hydrogen atom, methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, sec-butyl, t-
It is preferably an alkyl group having 1 to 5 carbon atoms such as butyl and t-pentyl.

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 methylene group which may be substituted by a mere bond, a sulfur atom or an alkyl having 1 to 8 carbon atoms or a cycloalkyl 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 a mere bond, a methylene group or methyl, ethyl, n-propyl, i-propyl, n-butyl, i-
Preferably, butyl, t-butyl or the like is a substituted methylene group. In particular, it is preferable that it is a simple bond.

The substituent A is an alkylene group having 2 to 8 carbon atoms or a * -COR ⁷ -group (R ⁷ is a mere bond or an alkylene group having 1 to 8 carbon atoms, and * is bonded to the oxygen side. It is especially preferable that it is a C2-C8 alkylene group. Here, carbon number 2-8
Representative examples of the alkylene group include ethylene, propylene, butylene, pentamethylene, hexamethylene, octamethylene, 2,2-dimethyl-1,3-propylene and the like. Propylene is preferably used. * In the * -COR ⁷ -group indicates that carbonyl is bonded to oxygen of the phosphite. In R ⁷ ,
Representative examples of the alkylene group having 1 to 8 carbon atoms include, for example, methylene, ethylene, propylene, butylene, pentamethylene, hexamethylene, octamethylene, 2,2-dimethyl-1,3-propylene and the like. As R ⁷ , a mere bond, ethylene or the like is preferably used.

One of Y and Z represents a hydroxyl group, 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. Represents Here, as the alkyl group having 1 to 8 carbon atoms, for example, the same alkyl group as described above can be mentioned, and as the alkoxy group having 1 to 8 carbon atoms, for example, the alkyl portion is the same as the alkyl having 1 to 8 carbon atoms. Alkoxy groups which are the same as the above alkyl groups;
Examples of the aralkyloxy group having from 12 to 12 include an aralkyloxy group in which the aralkyl moiety is 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)

[0014]

(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)

[0016]

(Wherein, R ⁴ , R ⁵ , A, 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.

The reaction is promoted by coexistence of a dehydrohalogenating agent such as amines, pyridines, pyrrolidines and amides, and a hydroxide of an alkali metal or an alkaline earth metal. You 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-stage reaction method is employed in which a bisphenol (II) is reacted with phosphorus trihalide to produce an intermediate, and then a hydroxy compound (III) is reacted. . In this method, phosphorus trihalide is added to bisphenols (II) in an amount of 1%.
It is preferably used in an amount of about 1.1 to 1.1 times, more preferably about 1 to 1.05 times. When a dehydrohalogenating agent is used, it is preferably used in an amount of about 0.05 to 2.4 mol times the 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 is usually subjected to the reaction with the hydroxy compound (III) as a reaction mixture.

Next, when reacting the hydroxy compound (III), the bisphenol (II) is reacted with
Usually, it is used in an amount of about 1 to 1.1 mole times. Also in this reaction, a dehydrohalogenating agent can be used, and in that case, the amount of the dehydrohalogenating agent is the amount of the hydroxy compound (III).
The molar ratio is preferably about 0.05 to 1.2 mole times. 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 carried out at a temperature of about 0 to 200 ° C.

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 known methods, 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, 3,3', 5,5 '-Tetra-t-pentylbiphenyl-2,
2'-diol, 3,3'-di-t-butyl-5,5'-dimethylbiphenyl-2,2'-diol, 1,1'-binaphthyl-2,2'-diol and the like.

The other starting material, the hydroxy compound (I
II), when A is alkylene having 2 to 8 carbon atoms, can be produced, for example, by reducing the corresponding phenylcarboxylic acid or its ester, benzaldehyde or the like according to a known method. . Here, as the reducing agent, for example, aluminum lithium hydride, aluminum sodium hydride, lithium borohydride, sodium borohydride, calcium borohydride, aluminum sodium triethoxyhydride, sodium triacetoxyborohydride, tributyltin hydride, 9-BBN-pyridine, Examples thereof include sodium / ammonia in the presence of borohydride, sodium and alcohol, lithium / ammonia in the presence of alcohol, and di-iso-butylaluminum hydride.

When A is alkylene having 2 to 8 carbon atoms, typical examples of the hydroxy compound (III) include:
For example, 2- (3-t-butyl-4-hydroxyphenyl) ethanol, 2- (3-t-pentyl-4-hydroxyphenyl) ethanol, 2- (3-t-octyl-ethanol)
4-hydroxyphenyl) ethanol, 2- (3-cyclohexyl-4-hydroxyphenyl) ethanol, 2
-[3- (1-methylcyclohexyl) -4-hydroxyphenyl] ethanol, 2- (3-t-butyl-4-
(Hydroxy-5-methylphenyl) ethanol, 2-
(3-t-pentyl-4-hydroxy-5-methylphenyl) ethanol, 2- (3-t-octyl-4-hydroxy-5-methylphenyl) ethanol, 2- (3-
Cyclohexyl-4-hydroxy-5-methylphenyl) ethanol, 2- [3- (1-methylcyclohexyl) -4-hydroxy-5-methylphenyl] ethanol, 2- (3-t-butyl-4-hydroxy-5) -Ethylphenyl) ethanol, 2- (3-t-pentyl-4)
-Hydroxy-5-ethylphenyl) ethanol, 2-
(3-t-octyl-4-hydroxy-5-ethylphenyl) ethanol, 2- (3-cyclohexyl-4-hydroxy-5-ethylphenyl) ethanol, 2- [3
-(1-methylcyclohexyl) -4-hydroxy-5
-Ethylphenyl] ethanol,

2- (3,5-di-tert-butyl-4-hydroxyphenyl) ethanol, 2- (3-tert-pentyl-4-hydroxy-5-tert-butylphenyl) ethanol, 2- (3- t-octyl-4-hydroxy-5-t
-Butylphenyl) ethanol, 2- (3-cyclohexyl-4-hydroxy-5-t-butylphenyl) ethanol, 2- [3- (1-methylcyclohexyl) -4
-Hydroxy-5-t-butylphenyl] ethanol,
2- (3-t-butyl-4-methoxyphenyl) ethanol, 2- (3-t-pentyl-4-methoxyphenyl) ethanol, 2- (3-t-octyl-4-methoxyphenyl) ethanol, 2- (3-cyclohexyl-
4-methoxyphenyl) ethanol, 2- [3- (1-
Methylcyclohexyl) -4-methoxyphenyl] ethanol, 2- (3-t-butyl-4-methoxy-5-methylphenyl) ethanol, 2- (3-t-pentyl-
4-methoxy-5-methylphenyl) ethanol, 2-
(3-t-octyl-4-methoxy-5-methylphenyl) ethanol, 2- (3-cyclohexyl-4-methoxy-5-methylphenyl) ethanol, 2- [3-
(1-methylcyclohexyl) -4-methoxy-5-methylphenyl] ethanol, 2- (3-t-butyl-4)
-Methoxy-5-ethylphenyl) ethanol, 2-
(3-t-pentyl-4-methoxy-5-ethylphenyl) ethanol, 2- (3-t-octyl-4-methoxy-5-ethylphenyl) ethanol, 2- (3-cyclohexyl-4-methoxy-5) -Ethylphenyl) ethanol,

2- [3- (1-methylcyclohexyl)
-4-methoxy-5-ethylphenyl] ethanol, 2
-(3,5-di-t-butyl-4-methoxyphenyl)
Ethanol, 2- (3-t-pentyl-4-methoxy-
5-t-butylphenyl) ethanol, 2- (3-t-
Octyl-4-methoxy-5-t-butylphenyl) ethanol, 2- (3-cyclohexyl-4-methoxy-5-t-butylphenyl) ethanol, 2- [3-
(1-methylcyclohexyl) -4-methoxy-5-t
-Butylphenyl] ethanol, 3- (3-t-butyl-2-hydroxyphenyl) propanol, 3- (3-
t-butyl-4-hydroxyphenyl) propanol,
3- (5-tert-butyl-2-hydroxyphenyl) propanol, 3- (3-tert-pentyl-4-hydroxyphenyl) propanol, 3- (3-tert-octyl-4-)
(Hydroxyphenyl) propanol, 3- (3-cyclohexyl-4-hydroxyphenyl) propanol, 3
-[3- (1-methylcyclohexyl) -4-hydroxyphenyl] propanol, 3- (3-t-butyl-2)
-Hydroxy-5-methylphenyl) propanol, 3
-(3-t-butyl-4-hydroxy-5-methylphenyl) propanol, 3- (5-t-butyl-2-hydroxy-3-methylphenyl) propanol, 3- (3
-T-pentyl-4-hydroxy-5-methylphenyl) propanol, 3- (3-t-octyl-4-hydroxy-5-methylphenyl) propanol, 3- (3
-Cyclohexyl-4-hydroxy-5-methylphenyl) propanol, 3- [3- (1-methylcyclohexyl) -4-hydroxy-5-methylphenyl] propanol, 3- (3-t-butyl-4-hydroxy- 5
-Ethylphenyl) propanol,

3- (3-tert-pentyl-4-hydroxy-5-ethylphenyl) propanol, 3- (3-tert-pentyl)
Octyl-4-hydroxy-5-ethylphenyl) propanol, 3- (3-cyclohexyl-4-hydroxy-5-ethylphenyl) propanol, 3- [3- (1
-Methylcyclohexyl) -4-hydroxy-5-ethylphenyl] propanol, 3- (3,5-di-t-butyl-2-hydroxyphenyl) propanol, 3-
(3,5-di-t-butyl-4-hydroxyphenyl)
Propanol, 3- (3-t-pentyl-4-hydroxy-5-t-butylphenyl) propanol, 3- (3
-Tert-octyl-4-hydroxy-5-tert-butylphenyl) propanol, 3- (3-cyclohexyl-4-)
(Hydroxy-5-t-butylphenyl) propanol,
3- [3- (1-methylcyclohexyl) -4-hydroxy-5-t-butylphenyl] propanol, 3-
(3-t-butyl-2-methoxyphenyl) propanol, 3- (3-t-butyl-4-methoxyphenyl) propanol, 3- (3-t-butyl-5-methoxyphenyl) propanol, 3- ( 3-t-pentyl-4-
Methoxyphenyl) propanol, 3- (3-t-octyl-4-methoxyphenyl) propanol, 3- (3
-Cyclohexyl-4-methoxyphenyl) propanol, 3- [3- (1-methylcyclohexyl) -4-methoxyphenyl] propanol,

3- (3-tert-butyl-2-methoxy-5)
-Methylphenyl) propanol, 3- (3-t-butyl-4-methoxy-5-methylphenyl) propanol, 3- (5-t-butyl-2-methoxy-3-methylphenyl) propanol, 3- (3 -T-pentyl-4
-Methoxy-5-methylphenyl) propanol, 3-
(3-t-octyl-4-methoxy-5-methylphenyl) propanol, 3- (3-cyclohexyl-4-methoxy-5-methylphenyl) propanol, 3- [3
-(1-methylcyclohexyl) -4-methoxy-5-
Methylphenyl] propanol, 3- (3-t-butyl-4-methoxy-5-ethylphenyl) propanol,
3- (3-t-pentyl-4-methoxy-5-ethylphenyl) propanol, 3- (3-t-octyl-4-
Methoxy-5-ethylphenyl) propanol, 3-
(3-cyclohexyl-4-methoxy-5-ethylphenyl) propanol, 3- [3- (1-methylcyclohexyl) -4-methoxy-5-ethylphenyl] propanol, 3- (3,5-di-t-) Butyl-2-methoxyphenyl) propanol, 3- (3,5-di-t-butyl-4-methoxyphenyl) propanol, 3- (3-
t-pentyl-4-methoxy-5-t-butylphenyl) propanol, 3- (3-t-octyl-4-methoxy-5-t-butylphenyl) propanol, 3-
(3-cyclohexyl-4-methoxy-5-t-butylphenyl) propanol,

3- [3- (1-methylcyclohexyl)
-4-methoxy-5-tert-butylphenyl] propanol, 3- (3-tert-butyl-2-ethoxyphenyl) propanol, 3- (3-tert-butyl-4-ethoxyphenyl) propanol, 3- (3 -Tert-butyl-4-ethoxy-5-methylphenyl) propanol, 3- (3-
t-butyl-2-ethoxy-5-methylphenyl) propanol, 3- (5-tert-butyl-2-ethoxy-3-)
Methylphenyl) propanol, 3- (3,5-di-t)
-Butyl-4-ethoxyphenyl) propanol, 3-
(3,5-di-tert-butyl-2-ethoxyphenyl) propanol, 4- (3-tert-butyl-2-hydroxyphenyl) butanol, 4- (3-tert-butyl-4-hydroxyphenyl) butanol, 4- (3-t-butyl-
4-hydroxy-5-methylphenyl) butanol,
-(3-t-butyl-2-hydroxy-5-methylphenyl) butanol, 4- (5-t-butyl-2-hydroxy-3-methylphenyl) butanol, 4- (3,5
-Di-tert-butyl-4-hydroxyphenyl) butanol, 4- (3,5-di-tert-butyl-2-hydroxyphenyl) butanol, 4- (3-tert-butyl-2-methoxyphenyl) butanol, 4- (3-t-butyl-4
-Methoxyphenyl) butanol, 4- (3-t-butyl-4-methoxy-5-methylphenyl) butanol,
4- (3-t-butyl-2-methoxy-5-methylphenyl) butanol, 4- (5-t-butyl-2-methoxy-3-methylphenyl) butanol, 4- (3,5-
Di-tert-butyl-4-methoxyphenyl) butanol,
4- (3,5-di-tert-butyl-2-methoxyphenyl) butanol,

5- (3-tert-butyl-2-hydroxyphenyl) pentanol, 5- (3-tert-butyl-4-hydroxyphenyl) pentanol, 5- (3-tert-butyl-4-hydroxy-pentanol) 5- (5-methylphenyl) pentanol, 5- (3-t-butyl-2-hydroxy-5-methylphenyl) pentanol, 5- (5-t-butyl-2)
-Hydroxy-3-methylphenyl) pentanol, 5
-(3,5-di-t-butyl-4-hydroxyphenyl) pentanol, 6- (3,5-di-t-butyl-2)
-Hydroxyphenyl) hexanol, 6- (3-t-
Butyl-2-hydroxyphenyl) hexanol, 6-
(3-t-butyl-4-hydroxyphenyl) hexanol, 6- (3-t-butyl-4-hydroxy-5-methylphenyl) hexanol, 6- (3-t-butyl-
2-hydroxy-5-methylphenyl) hexanol,
6- (5-tert-butyl-2-hydroxy-3-methylphenyl) hexanol, 6- (3,5-di-tert-butyl-4-hydroxyphenyl) hexanol, 6- (3
5-di-t-butyl-2-hydroxyphenyl) hexanol and the like.

In the hydroxy compound (III), A is represented by *
When it is a —COR ⁷ — group, it can be produced, for example, according to the following known method. When R ⁷ is a mere bond, the compound is produced, for example, by subjecting the corresponding hydroxybenzoic acid, alkoxybenzoic acid, aralkyloxybenzoic acid or the like to a Friedel-Crafts reaction using a catalyst such as aluminum chloride or zinc chloride. And when Z is a hydroxy group, an alkoxy group, or an aralkyloxy group, use a corresponding phenol, sodium hydroxide, an alkali metal hydroxide such as potassium hydroxide and carbon dioxide,
It can be produced by a Kolbe-Schmidt reaction according to the methods described in JP-A-62-61949 and JP-A-63-165341. When R ⁷ is an alkylene having 1 to 8 carbon atoms, the corresponding phenol is converted to a compound such as aluminum chloride or zinc chloride in accordance with the method described in Rubber Chemistry and Technology 46 , 96 (1973). After acylation using a Friedel-Crafts catalyst and a carboalkoxyalkanoyl halogenoid, the carbonyl group at the benzyl position is reduced to an alkylene with a hydrogenation catalyst such as palladium charcoal or platinum charcoal, and then the ester is acidified or alkalinized. It can be produced by hydrolysis. A typical example of the hydroxy compound (III) when A is a * -COR ⁷ -group is, for example, 3
-Tert-butyl-2-hydroxybenzoic acid, 3-tert-butyl-4-hydroxybenzoic acid, 5-tert-butyl-2-hydroxybenzoic acid, 3-tert-pentyl-4-hydroxybenzoic acid, 3-t -Octyl-4-hydroxybenzoic acid, 3-cyclohexyl-4-hydroxybenzoic acid, 3
-(1-methylcyclohexyl) -4-hydroxybenzoic acid, 3-t-butyl-2-hydroxy-5-methylbenzoic acid, 3-t-butyl-4-hydroxy-5-methylbenzoic acid, 5-t- Butyl-2-hydroxy-3-methylbenzoic acid, 3-t-pentyl-4-hydroxy-5
Methylbenzoic acid, 3-t-octyl-4-hydroxy-
5-methylbenzoic acid, 3-cyclohexyl-4-hydroxy-5-methylbenzoic acid, 3- (1-methylcyclohexyl) -4-hydroxy-5-methylbenzoic acid, 3-
t-butyl-4-hydroxy-5-ethylbenzoic acid, 3
-T-pentyl-4-hydroxy-5-ethylbenzoic acid, 3-t-octyl-4-hydroxy-5-ethylbenzoic acid, 3-cyclohexyl-4-hydroxy-5-ethylbenzoic acid,

3- (1-methylcyclohexyl) -4-
Hydroxy-5-ethylbenzoic acid, 3,5-di-t-butyl-2-hydroxybenzoic acid, 3,5-di-t-butyl-4-hydroxybenzoic acid, 3-t-pentyl-4-
Hydroxy-5-t-butylbenzoic acid, 3-t-octyl-4-hydroxy-5-t-butylbenzoic acid, 3-
Cyclohexyl-4-hydroxy-5-t-butylbenzoic acid, 3- (1-methylcyclohexyl) -4-hydroxy-5-t-butylbenzoic acid, 3-t-butyl-2-
Methoxybenzoic acid, 3-tert-butyl-4-methoxybenzoic acid, 3-tert-butyl-5-methoxybenzoic acid, 3-
t-pentyl-4-methoxybenzoic acid, 3-t-octyl-4-methoxybenzoic acid, 3-cyclohexyl-4-
Methoxybenzoic acid, 3- (1-methylcyclohexyl)
-4-methoxybenzoic acid, 3-tert-butyl-2-methoxy-5-methylbenzoic acid, 3-tert-butyl-4-methoxy-5-methylbenzoic acid, 5-tert-butyl-2-methoxy-3 -Methylbenzoic acid, 3-t-pentyl-4-methoxy-5-methylbenzoic acid, 3-t-octyl-4-methoxy-5-methylbenzoic acid, 3-cyclohexyl-
4-methoxy-5-methylbenzoic acid, 3- (1-methylcyclohexyl) -4-methoxy-5-methylbenzoic acid, 3-t-butyl-4-methoxy-5-ethylbenzoic acid, 3-t-pentyl -4-methoxy-5-ethylbenzoic acid, 3-t-octyl-4-methoxy-5-ethylbenzoic acid, 3-cyclohexyl-4-methoxy-5-ethylbenzoic acid,

3- (1-methylcyclohexyl) -4-
Methoxy-5-ethylbenzoic acid, 3,5-di-t-butyl-2-methoxybenzoic acid, 3,5-di-t-butyl-
4-methoxybenzoic acid, 3-tert-pentyl-4-methoxy-5-tert-butylbenzoic acid, 3-tert-octyl-4-
Methoxy-5-t-butylbenzoic acid, 3-cyclohexyl-4-methoxy-5-t-butylbenzoic acid, 3-
(3- (1-methylcyclohexyl) -4-methoxy-
5-tert-butylbenzoic acid, 3-tert-butyl-2-ethoxybenzoic acid, 3-tert-butyl-4-ethoxybenzoic acid,
3-tert-butyl-4-ethoxy-5-methylbenzoic acid,
3-tert-butyl-2-ethoxy-5-methylbenzoic acid,
5-tert-butyl-2-ethoxy-3-methylbenzoic acid,
3,5-di-t-butyl-4-ethoxybenzoic acid, 3,
5-di-t-butyl-2-ethoxybenzoic acid, (3-t
-Butyl-2-hydroxyphenyl) acetic acid, (3-t-
(Butyl-4-hydroxyphenyl) acetic acid, (5-t-butyl-2-hydroxyphenyl) acetic acid, (3-t-pentyl-4-hydroxyphenyl) acetic acid, (3-t-octyl-4-hydroxyphenyl) acetic acid , (3-cyclohexyl-4-hydroxyphenyl) acetic acid, [3- (1-
Methylcyclohexyl) -4-hydroxyphenyl] acetic acid, (3-t-butyl-2-hydroxy-5-methylphenyl) acetic acid, (3-t-butyl-4-hydroxy-5)
-Methylphenyl) acetic acid,

(5-t-butyl-2-hydroxy-3-
(Methylphenyl) acetic acid, (3-t-pentyl-4-hydroxy-5-methylphenyl) acetic acid, (3-t-octyl-4-hydroxy-5-methylphenyl) acetic acid, (3
-Cyclohexyl-4-hydroxy-5-methylphenyl) acetic acid, [3- (1-methylcyclohexyl) -4-
[Hydroxy-5-methylphenyl] acetic acid, (3-t-butyl-4-hydroxy-5-ethylphenyl) acetic acid,
(3-t-pentyl-4-hydroxy-5-ethylphenyl) acetic acid, (3-t-octyl-4-hydroxy-5)
-Ethylphenyl) acetic acid, (3-cyclohexyl-4-
Hydroxy-5-ethylphenyl) acetic acid, [3- (1-
Methylcyclohexyl) -4-hydroxy-5-ethylphenyl] acetic acid, (3,5-di-t-butyl-2-hydroxyphenyl) acetic acid, (3,5-di-t-butyl-4)
-Hydroxyphenyl) acetic acid, (3-t-pentyl-4)
-Hydroxy-5-t-butylphenyl) acetic acid, (3-
t-octyl-4-hydroxy-5-t-butylphenyl) acetic acid, (3-cyclohexyl-4-hydroxy-5)
-T-butylphenyl) acetic acid,

[3- (1-methylcyclohexyl) -4
-Hydroxy-5-t-butylphenyl] acetic acid, (3-
t-butyl-2-methoxyphenyl) acetic acid, (3-t-
(Butyl-4-methoxyphenyl) acetic acid, (3-t-butyl-5-methoxyphenyl) acetic acid, (3-t-pentyl-4-methoxyphenyl) acetic acid, (3-t-octyl-4-methoxyphenyl) Acetic acid, (3-cyclohexyl-4-methoxyphenyl) acetic acid, [3- (1-methylcyclohexyl) -4-methoxyphenyl] acetic acid, (3-
t-butyl-2-methoxy-5-methylphenyl) acetic acid, (3-t-butyl-4-methoxy-5-methylphenyl) acetic acid, (5-t-butyl-2-methoxy-3-methylphenyl) acetic acid , (3-t-pentyl-4-methoxy-5-methylphenyl) acetic acid, (3-t-octyl-
4-methoxy-5-methylphenyl) acetic acid, (3-cyclohexyl-4-methoxy-5-methylphenyl) acetic acid, [3- (1-methylcyclohexyl) -4-methoxy-5-methylphenyl] acetic acid, (3 -T-butyl-4
-Methoxy-5-ethylphenyl) acetic acid, (3-t-pentyl-4-methoxy-5-ethylphenyl) acetic acid,
(3-t-octyl-4-methoxy-5-ethylphenyl) acetic acid, (3-cyclohexyl-4-methoxy-5-
Ethylphenyl) acetic acid, [3- (1-methylcyclohexyl) -4-methoxy-5-ethylphenyl] acetic acid,
(3,5-di-t-butyl-2-methoxyphenyl) acetic acid,

(3,5-di-tert-butyl-4-methoxyphenyl) acetic acid, (3-tert-pentyl-4-methoxy-)
5-t-butylphenyl) acetic acid, (3-t-octyl-
4-methoxy-5-t-butylphenyl) acetic acid, (3-
Cyclohexyl-4-methoxy-5-t-butylphenyl) acetic acid, [3- (1-methylcyclohexyl) -4-
[Methoxy-5-t-butylphenyl] acetic acid, (3-t-
Butyl-2-ethoxyphenyl) acetic acid, (3-t-butyl-4-ethoxyphenyl) acetic acid, (3-t-butyl-acetic acid)
4-ethoxy-5-methylphenyl) acetic acid, (3-t-
Butyl-2-ethoxy-5-methylphenyl) acetic acid,
(5-tert-butyl-2-ethoxy-3-methylphenyl) acetic acid, (3,5-di-tert-butyl-4-ethoxyphenyl) acetic acid, (3,5-di-tert-butyl-2-ethoxy) Phenyl) acetic acid, 3- (3-t-butyl-2-hydroxyphenyl) propionic acid, 3- (3-t-butyl-
4-hydroxyphenyl) propionic acid, 3- (5-t
-Butyl-2-hydroxyphenyl) propionic acid, 3
-(3-t-pentyl-4-hydroxyphenyl) propionic acid, 3- (3-t-octyl-4-hydroxyphenyl) propionic acid, 3- (3-cyclohexyl-4)
-Hydroxyphenyl) propionic acid, 3- [3- (1
-Methylcyclohexyl) -4-hydroxyphenyl]
Propionic acid, 3- (3-t-butyl-2-hydroxy-5-methylphenyl) propionic acid, 3- (3-t-
Butyl-4-hydroxy-5-methylphenyl) propionic acid, 3- (5-tert-butyl-2-hydroxy-3-
Methylphenyl) propionic acid,

3- (3-t-pentyl-4-hydroxy-5-methylphenyl) propionic acid;
Octyl-4-hydroxy-5-methylphenyl) propionic acid, 3- (3-cyclohexyl-4-hydroxy-5-methylphenyl) propionic acid, 3- [3- (1
-Methylcyclohexyl) -4-hydroxy-5-methylphenyl] propionic acid, 3- (3-tert-butyl-
4-hydroxy-5-ethylphenyl) propionic acid,
3- (3-t-pentyl-4-hydroxy-5-ethylphenyl) propionic acid, 3- (3-t-octyl-4
-Hydroxy-5-ethylphenyl) propionic acid, 3
-(3-cyclohexyl-4-hydroxy-5-ethylphenyl) propionic acid, 3- [3- (1-methylcyclohexyl) -4-hydroxy-5-ethylphenyl]
Propionic acid, 3- (3,5-di-t-butyl-2-hydroxyphenyl) propionic acid, 3- (3,5-di-
t-butyl-4-hydroxyphenyl) propionic acid,
3- (3-t-pentyl-4-hydroxy-5-t-butylphenyl) propionic acid, 3- (3-t-octyl-4-hydroxy-5-t-butylphenyl) propionic acid, 3- (3 -Cyclohexyl-4-hydroxy-5
-T-butylphenyl) propionic acid, 3- [3- (1
-Methylcyclohexyl) -4-hydroxy-5-t-
Butylphenyl] propionic acid, 3- (3-t-butyl-2-methoxyphenyl) propionic acid,

3- (3-tert-butyl-4-methoxyphenyl) propionic acid, 3- (3-tert-butyl-5-methoxyphenyl) propionic acid, 3- (3-tert-pentyl-4-methoxyphenyl) ) Propionic acid, 3- (3-t
-Octyl-4-methoxyphenyl) propionic acid, 3
-(3-cyclohexyl-4-methoxyphenyl) propionic acid, 3- [3- (1-methylcyclohexyl)-
4-methoxyphenyl] propionic acid, 3- (3-t-
Butyl-2-methoxy-5-methylphenyl) propionic acid, 3- (3-t-butyl-4-methoxy-5-methylphenyl) propionic acid, 3- (5-t-butyl-2)
-Methoxy-3-methylphenyl) propionic acid, 3-
(3-t-pentyl-4-methoxy-5-methylphenyl) propionic acid, 3- (3-t-octyl-4-methoxy-5-methylphenyl) propionic acid, 3- (3-
Cyclohexyl-4-methoxy-5-methylphenyl)
Propionic acid, 3- [3- (1-methylcyclohexyl) -4-methoxy-5-methylphenyl] propionic acid, 3- (3-t-butyl-4-methoxy-5-ethylphenyl) propionic acid, 3- (3-t-pentyl-4
-Methoxy-5-ethylphenyl) propionic acid, 3-
(3-t-octyl-4-methoxy-5-ethylphenyl) propionic acid, 3- (3-cyclohexyl-4-methoxy-5-ethylphenyl) propionic acid, 3- [3
-(1-methylcyclohexyl) -4-methoxy-5-
Ethylphenyl] propionic acid,

3- (3,5-di-tert-butyl-2-methoxyphenyl) propionic acid, 3- (3,5-di-tert-propionic acid)
Butyl-4-methoxyphenyl) propionic acid, 3-
(3-t-pentyl-4-methoxy-5-t-butylphenyl) propionic acid, 3- (3-t-octyl-4-)
Methoxy-5-t-butylphenyl) propionic acid, 3
-(3-cyclohexyl-4-methoxy-5-t-butylphenyl) propionic acid, 3- [3- (1-methylcyclohexyl) -4-methoxy-5-t-butylphenyl] propionic acid, 3- (3 -Tert-butyl-2-ethoxyphenyl) propionic acid, 3- (3-tert-butyl-4)
-Ethoxyphenyl) propionic acid, 3- (3-t-butyl-4-ethoxy-5-methylphenyl) propionic acid, 3- (3-t-butyl-2-ethoxy-5-methylphenyl) propionic acid, 3 -(5-t-butyl-2-
Ethoxy-3-methylphenyl) propionic acid, 3-
(3,5-di-t-butyl-4-ethoxyphenyl) propionic acid, 3- (3,5-di-t-butyl-2-ethoxyphenyl) propionic acid, 3- (3-t-butyl-
2-hydroxyphenyl) butanoic acid, 3-
(3-t-butyl-4-hydroxyphenyl) butanoic acid, 3- (3-t-butyl-4-hydroxy-5-methylphenyl) butanoic acid, 3-
(3-t-butyl-2-hydroxy-5-methylphenyl) butanoic acid,

3- (5-tert-butyl-2-hydroxy-
3-methylphenyl) butanoic acid, 3-
(3,5-di-t-butyl-4-hydroxyphenyl)
Butanoic acid, 3- (3,5-di-t-butyl-2-hydroxyphenyl) butanoic acid, 3
-(3-t-butyl-2-methoxyphenyl) butanoic acid, 3- (3-t-butyl-4-methoxyphenyl) butanoic acid, 3- (3-t-butyl-4-methoxy-) 5- (methylphenyl) butanoic acid, 3- (3-t-butyl-2-methoxy-5-methylphenyl) butanoic acid, 3- (5-t-acid)
Butyl-2-methoxy-3-methylphenyl) butanoic acid, 3- (3,5-di-t-butyl-4-methoxyphenyl) butanoic acid, 3- (3,5
-Di-t-butyl-2-methoxyphenyl) butanoic acid;

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, and hindered amine light stabilizers described below. Furthermore, 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 stabilizer, JP-A-7-27
Organic amines described in JP-A-8164 can also be used. 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 phosphites (I) in the present invention
Is 0.01 to 100 parts by weight of the aromatic monovinyl resin.
~ 5 parts by weight are used. Preferably, about 0.03 to 3 parts by weight, more preferably about 0.05 to 1 part by weight is blended. 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.

The aromatic monovinyl resin in the present invention is produced by subjecting an aromatic vinyl monomer to a bulk polymerization method, a suspension polymerization method, or a multistage polymerization method such as a bulk-suspension polymerization method. Are used. Specific examples of the aromatic monovinyl monomer used as a raw material include not only styrene alone but also a mixture of styrene with another vinyl monomer copolymerizable with styrene.

Here, other vinyl monomers copolymerizable with styrene include, for example, methyl methacrylate, methyl acrylate, ethyl methacrylate, acrylonitrile, methacrylonitrile, halogen-containing vinyl monomers, α-methylstyrene, o-methylstyrene, Methylstyrene, m-
Methyl styrene, p-methyl styrene and the like can be mentioned.
These vinyl monomers copolymerizable with styrene are generally used in a proportion of 30 parts by weight or less, preferably 10 parts by weight or less of all monomers.

The aromatic monovinyl resin used in the present invention may be one produced by appropriately adding a polymerization initiator, a chain transfer agent and a solvent. As the polymerization initiator,
Organic peroxides such as 2,2-bis (t-butylperoxy) butane 2,2-bis (t-butylperoxy) octane, 1,1-bis (t-butylperoxy) -3,
3,5-trimethylcyclohexane, 1,1-bis (t
-Butylperoxy) cyclohexane, n-butyl-
Peroxyketals such as 4,4-bis (t-butylperoxy) valerate, di-t-butyl peroxide, t-butylcumyl peroxide, dicumyl peroxide, α, α′-bis (t-butylperoxyisopropyl) benzene , 2,5-dimethyl-2,5-di (t-
Butylperoxy) hexane, 2,5-dimethyl-2,
Dialkyl peroxides such as 5-di (t-butylperoxy) hexine-3, acetyl peroxide, isobutyryl peroxide, octanoyl peroxide, decanoyl peroxide, lauroyl peroxide, 3,
Diacyl peroxides such as 5,5-trimethylhexanoyl peroxide, benzoyl peroxide, 2,4-dichlorobenzoyl peroxide, m-trioil peroxide, diisopropylperoxydicarbonate, di-2-ethylhexylperoxydicarbonate, di-n-propyl Peroxydicarbonate, dimyristyl peroxydicarbonate, di-n-ethoxyethyl peroxydicarbonate, dimethoxyisopropylperoxydicarbonate, di (3-methyl-3
-Methoxybutyl) peroxydicarbonates such as peroxydicarbonate, t-butylperoxyacetate, t-butylperoxyisobutyrate, t-butylperoxypivalate, t-butylperoxyneodecanoate, cumylperoxyneodecaine Noate, t
-Butylperoxy-2-ethylhexanoate, t-
Butylperoxy-3,3,5-trimethylhexanoate, t-butylheroxylaurate, t-butylperoxybenzoate, di-t-butylperoxyisophthalate, 2,5-dimethyl-2,5-di (benzoyl Peroxy esters such as peroxy) hexane, t-butylperoxyisopropyl carbonate, acetylacetone peroxide, methyl ethyl ketone peroxide, cyclohexanone peroxide, 3,3,5-
Ketone peroxides such as trimethylcyclohexanone peroxide and methylcyclohexanone peroxide, t-butyl hydroperoxide, cumene hydroperoxide, diisopropylbenzene hydroperoxide, p-menthane hydroperoxide, 2,5-dimethylhexane-2,5-dihydroperoxide, , 1,
Hydroperoxides such as 3,3-tetramethylbutyl hydroperoxide and the like can be mentioned. These organic peroxides may be used alone or in combination of two or more.

Examples of the solvent used as required include aromatic hydrocarbons, for example, toluene, xylene, ethylbenzene, etc., which may be used alone or in combination of two or more. It may be. Further, other solvents such as aliphatic hydrocarbons and dialkyl ketones may be mixed with aromatic hydrocarbons as long as the solubility of the polymerization product is not reduced. This solvent is preferably used in an amount usually not exceeding 25% by weight based on the monomer. When the amount of the solvent exceeds 25% by weight, the polymerization rate is significantly reduced, and the impact strength of the obtained resin is greatly reduced. Further, a large amount of energy is required for the recovery of the solvent, so that the economy is poor. The solvent may be added after the polymerization has progressed to a relatively high viscosity, or may be added before the polymerization,
It is preferable to add 5 to 15% by weight before polymerization in order to make the quality uniform and to control the polymerization temperature.

When the phosphites (I) are blended with the aromatic monovinyl resin, other additives such as a phenolic antioxidant may be added, if necessary.
Sulfur-based antioxidants, other phosphorus-based antioxidants, ultraviolet absorbers, light stabilizers, lubricants such as hydroxylamine and higher aliphatic amides, plasticizers such as mineral oil and silicone oil, flame retardants, higher fatty acids, etc. A release agent, an antistatic agent, a pigment, a dye, a filler, a foaming agent, and the like can be added. U.S. Pat.Nos. 4,325,853, 4,338,244, 5,17
5,312, 5,216,053, 5,252,643, DE-A-
4,316,611, 4,316,622, 4,316,876, EP-
Benzofuranones, indolines and the like described in A-589,839, 591,102, CA-2,132,132 and the like can also be added. 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.

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
-Lauryl thiopropionate). 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-butyl) 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-butyl) Phenyl) 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) 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 and 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.

As the hydroxyamine, for example, N,
N-dibenzylhydroxyamine, N, N-diethylhydroxyamine, N, N-dioctylhydroxyamine, N, N-dilaurylhydroxyamine, N, N-ditetradecylhydroxyamine, N, N-dihexadecylhydroxy Amine, N, N-
Dioctadecylhydroxyamine, N-hexadecyl-N-
Examples include octadecylhydroxyamine, N-heptadecyl-N-octadecylhydroxyamine, and mixtures thereof. As the filler, for example, glass fiber,
Carbon fiber, alumina fiber, carbon black, graphite, titanium dioxide, silica, talc, sheet, calcium carbonate, calcium sulfate, barium carbonate, oxysulfate, tin oxide, alumina, kaolin, silicon carbide,
Examples thereof include metal powder and a mixture thereof.

Of these additives, those preferably used are phenolic antioxidants, phosphorus antioxidants,
It is an ultraviolet absorber and a hindered amine light stabilizer. 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
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-methylphenol) 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-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.

Further, 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, 2,2'-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 -Oxaphospholinane, 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.

Particularly preferred light 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-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-diperidyl)
-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 incorporating the phosphites (I) or other additives used as necessary into the organic material, any known method and apparatus for obtaining a homogeneous mixture may be used. it can. Also, for example, when added to the polymerization step, during the polymerization or
The phosphites (I) or other additives can be added to the polymer solution immediately after polymerization in the form of a solution or a dispersant, or can be directly added in a molten state. In the case of blending in the heating step after devolatilization, the phosphites (I) or other additives are mixed directly with the aromatic monovinyl resin by dry blending or using a mixer such as a Henschel mixer. can do. Further, the phosphites (I) or other additives can be mixed with the aromatic monovinyl resin in the form of a master batch.

[0079]

As described above, the aromatic monovinyl resin composition of the present invention is excellent in thermal decomposition resistance. For example, the aromatic monovinyl resin composition can be thermally decomposed in a step exposed to heat such as a polymer polymerization step, a devolatilization step, a granulation step and a molding step. Can be prevented.

[0080]

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.

Reference Example 1: 2,4,8,10-tetra-t-butyl-6
-[3- (3-Methyl-4-hydroxy-5-t-butylphenyl)
Preparation of propoxy] dibenzo [d, f] [1,3,2] dioxaphosphepin (compound 1) , 5'-Tetra-t-butylbiphenyl-2,
After adding 12 g of 2'-diol and 200 ml of toluene, 4 g of phosphorus trichloride was added with stirring, and then triethylamine was added.
6.5 g was added and the mixture was kept at 80 ° C. for 4 hours. After cooling to room temperature, 50 ml of toluene and 3- (3-t-butyl-4-hydroxy-5
6.5 g of (methylphenyl) propanol was added, followed by 3.3 g of triethylamine, and the mixture was kept at 80 ° C. for 4 hours.
Then, after cooling to room temperature, the generated triethylamine hydrochloride was filtered and washed. After concentrating the filtrate, the residue was purified by silica gel chromatography to obtain white crystals. Mass spectrometry value (FD-MS): m / z 660

¹ H-NMR (CDCl ₃ ) 1.34 (s, 18H), 1.37 (s, 9H), 1.49 (s, 18H), 1.84 (m, 2H),
2,18 (s, 3H), 2.51 (t, 2H), 3.81 (dt, 2H), 4.59 (s, 1H),
6.76 (s, 1H), 6.89 (S, 1H), 7.16 (d, 2H), 7.42 (d, 2H) 31 P-NMR (CDCl 3) 136.4ppm

Example 1: Heat resistance test of polystyrene [Compound] Polystyrene 100 parts by weight Test stabilizer Stabilized parts by weight described in the table Chemical Formula 1: Compound 1 (produced in Reference Example 1) -(3,5-di-t-butyl-4-hydroxyphenyl) propionate P-1: tetrakis (2,4-di-t-butylphenyl) -2,
4'-Diphenylenediphosphonite P-2: 2,4,8,10-tetra-t-butyl-6- ｛2- [3- (3,
5-t-butyl-4-hydroxyphenyl) propionyloxy] ethoxydibenzo [d, f] [1,3,2] dioxaphosphepin

Using a 30 mmΦ single screw extruder, the above-mentioned compound was melt-kneaded at 240 ° C. and pelletized. The color of the pellet obtained by repeating the same operation four times is shown in Table 1, and the obtained pellet was subjected to MFR (230 ° C., 5 kg load, 5 minute residence time) using a melt indexer. (g / 10min) was measured and the results are shown in Table 1. ○ is white, Δ is pale yellow, and the smaller the MFR,
It means that it has excellent thermal decomposition resistance.

[0085]

TABLE 1 implementation example comparisons Example 1 2 1 2 3 4 5 Test compounds of -1 0.3 0.15 - - - - - AO-1 - 0.15 - 0.3 0.15 - 0.15 P-1 - - - - 0.15 - - P-2-----0.3 0.15 Thermal stability 8.1 9.2 17.7 15.5 14.0 12.6 13.2 Discoloration resistance ○ ○ △ △ △ △ △

Claims (5)

[Claims] 1. A compound of the formula (I) based on 100 parts by weight of an aromatic monovinyl resin. (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 -CH
R ^{6 represents a} group (R ⁶ represents a hydrogen atom, an alkyl group having 1 to 8 carbon atoms or a cycloalkyl group having 5 to 8 carbon atoms).
A represents an alkylene group having 2 to 8 carbon atoms or a * -COR ⁷ -group (R ⁷ represents a mere bond or an alkylene group having 1 to 8 carbon atoms, and * represents an oxygen-bonded group). .
One of Y and Z is a hydroxyl group and has 1 to 1 carbon atoms.
8 represents an alkoxy group 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. The phosphites represented by
An aromatic monovinyl resin composition characterized by being mixed in an amount of from 01 to 5 parts by weight. (2) R ¹ and R ⁴ in the phosphites are
a t-alkyl group, a cyclohexyl or 1-methylcyclohexyl group, R ² is an alkyl group having 1 to 5 carbon atoms, R ⁵ is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and R ³ is a hydrogen atom or 1 carbon atom. The resin composition according to claim 1, wherein X is a mere bond, and A is an alkylene group having 2 to 8 carbon atoms. 3. A phosphite represented by the above general formula (I) is added to 100 parts by weight of an aromatic monovinyl resin.
A method for producing an aromatic monovinyl resin composition, comprising 0.01 to 5 parts by weight. 4. A phosphorous ester represented by the above general formula (I) is added to 100 parts by weight of an aromatic monovinyl resin.
A method for preventing thermal decomposition of an aromatic monovinyl-based resin, which is added in an amount of 0.01 to 5 parts by weight. Wherein R ¹ in phosphites, R ⁴ is
t-alkyl group, cyclohexyl or 1-methylcyclohexyl group, R ² is an alkyl group having 1 to 5 carbon atoms, R ⁵ is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, R ³ is a hydrogen atom or 1 carbon atom The method according to claim 3, wherein X is a mere bond, and A is an alkylene group having 2 to 8 carbon atoms.