WO1997044310A1

WO1997044310A1 - Novel phenol compounds and use thereof

Info

Publication number: WO1997044310A1
Application number: PCT/JP1997/001681
Authority: WO
Inventors: Takeshi Inoue; Shoichi Horie; Akiyoshi Onishi; Machiko Mekada
Original assignee: Yoshitomi Fine Chemicals, Ltd.; Mitsubishi Chemical Corporation
Priority date: 1996-05-22
Filing date: 1997-05-19
Publication date: 1997-11-27

Abstract

Phenol compounds obtained by replacing the hydroxyl group of a phenol compound having in its molecule a group represented by general formula (a) (wherein R represents a hydrogen atom, an alkyl group or the like) or the hydroxyl group of a phenol compound used as an existing antioxidant by a group represented by general formula (b) (wherein R represents a hydrogen atom, an alkyl group or the like). The obtained compounds can be used as a stabilizer for various organic polymers and are effective in preventing oxidative deterioration of the polymers. They are particularly effective in preventing oxidative deterioration of organic polymers to be used in such an environment as will cause contact with water or hot water for a long period of time. The invention also provides a composition comprising the above phenol compound and an organic polymer and another composition comprising the above composition and a sulfur antioxidant. The phenol compounds, when used in combination with a sulfur antioxidant, can offer a better antioxidizing effect.

Description

Specification

Novel phenolic compounds and their uses

Technical field

The present invention relates to a regular phenol compound having a phenyl ester structure, and its use. More specifically, it is useful as a stabilizer (antioxidant) for various organic polymers such as natural rubber, including synthetic polymers such as polyolefin, and has a remarkable effect especially in the environment where water or hot water exists. Phenolic compounds and their uses.

Background art

Synthetic polymers such as polyolefins and various organic polymers such as organic rubbers are oxidized during molding and use, and have a problem of deteriorating quality. For this reason, various antioxidants have been conventionally developed for the purpose of preventing oxidative degradation, and are blended in the polymer.

For example, the hindered phenol compounds described in JP-B-38-17164, JP-B-39-460, JP-B-42-9651, and the like, It is useful for preventing oxidative degradation of synthetic polymers such as polyolefins, and is currently in practical use. However, when a polymer stabilized by various conventional antioxidants is used in an environment where water is present, the effect of preventing oxidation deterioration is significantly reduced. There is still no satisfactory one.

Conventionally, it was thought that the reason was that the antioxidant was extracted with water or extracted after being hydrolyzed. Therefore, materials used in an environment where water is present include, for example, an ester such as a composition described in Japanese Patent Application Laid-Open No. 2-2655939 in order to prevent extraction and hydrolysis by water. It was common to incorporate an antioxidant with no structure, a higher molecular weight, and a rigid structure. Conventional antioxidants have not been sufficiently satisfactory in oxidation resistance. In particular, there has been a need for antioxidants that are effective in preventing oxidative degradation in environments where water or hot water is present.

Also, Japanese Patent Application Laid-Open No. 8-225495 describes a compound having a sustained antioxidant effect even when used in an environment in which water or hot water is used, and is modified. —Tris [2-methyl—41- (3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionyloxy) -1-5-tert-butylphenyl] butane, formula

Compounds such as are described, Disclosure of the invention

The present inventors have been studying the effect deterioration mechanism of the antioxidant incorporated in the organic polymer material used in the presence of water or hot water for many years. However, the present inventors conducted a study based on a conventional antioxidant mechanism in which an antioxidant in an organic polymer material was extracted or hydrolyzed by water. Have found that the action of water promotes oxidative deterioration of the antioxidant itself, resulting in a compound having no antioxidant effect.

In an organic polymer material used in the presence of water, even if the antioxidant is oxidatively altered by the action of water, the compound formed by the oxidative alteration is also oxidized. As a result of intensive studies with the idea of designing a compound having a stopping function, an antioxidant having a remarkable effect on the above-mentioned problems was found.

That is, the phenolic compound of the present invention has an excellent ability to prevent oxidative deterioration of an organic polymer material by its own chemical structure, and is used in an environment where water or hot water is present. Even when a compound is oxidatively modified, the present invention was completed by designing a compound having an oxidative deterioration preventing ability that is satisfactory even for a compound generated by the oxidatively modified substance. Things. The phenolic compound of the present invention has the formula (1)

H-() _b- (L ¹ ) _a- (L) _x- (0) _{p This} compound is represented by Rz. The compound represented by the formula (1) is a novel compound that has not been described in any literature.

Here, L, L ¹ and L ² in the formula (1) may be the same or different, and the formula (2)

(Here, R ′ represents an alkyl group having 1 to 8 carbon atoms, and R ² and R ³ may be the same or different and each represent a hydrogen atom or an alkyl group having 1 to 8 carbon atoms.) L ² — L ′ represents a bond formed between the carbonyl group of L ² and the oxygen atom of the phenoquine group of L ^{1 through} an ester bond, and L ¹ -L is a carbonyl group of L ¹ and a phenoxy group of L L forms a bond by an ester bond, and L represents a bond in which the carbonyl group of L and the oxygen atom form a bond by an ester bond. _C represents 1, and b represents 0 or 1 Indicates the integer of

(2a): n represents 1, X represents 1, p represents 1, R z has 1 to 30 carbon atoms. Represents an alkyl group of; or

(lb): n represents 1, X represents 1, p represents 1, and 1¾2 represents an alkenyl group having 2 to 30 carbon atoms; or

(1c): n represents 1, X represents 1, p represents 1, R z represents an alkynyl group having 2 to 30 carbon atoms; or

(Id): n represents 1, X represents 1, p represents 1, and Rz represents a cycloalkyl group having 3 to 7 carbon atoms which may have a substituent.

(1e): n represents 1, X represents 1, p represents 1, and Rz is the number of carbon atoms which may have a substituent. Represents an aralkyl group having up to 20 or an aryl group having 6 to 20 carbon atoms which may have a substituent; or

(2a): n represents 2, x represents 1, p represents 1, and 1¾2 may have 1-10 sulfur atoms and / or oxygen atoms in the chain. Represents an alkylene group having 1 to 20 carbon atoms; or

(2b): n represents 2, X represents 1, p represents 1, 1 ^ 2 is a alkynylene group having 2 to 12 carbon atoms, an alkynylene group having 2 to 12 carbon atoms, or substituted A cycloalkylene group having 3 to 60 carbon atoms which may have a group; or

(2c): n represents 2, X represents 1, p represents 1, and Rz represents an optionally substituted arylene group having 6 to 60 carbon atoms; or

(2 d): n represents 2, X represents 0, p represents 1, R z is a formula (3)

(In the formula, A ¹ is an alkylene group having 1 to 6 carbon atoms which may have 1 to 3 sulfur atoms and a hetero atom of a hydrogen atom or an oxygen atom in the chain, and 1 to 3 sulfur atoms in the chain. C2-5 alkylidene, oxygen, sulfur, sulfinyl (1-SO-) or sulfonyl (An S0 ₂ -) indicates, R ⁴ and R ⁹ may be the same or different, their respective an alkyl group having 1 to 8 carbon atoms, R ^5, R ^6, R and R ⁸ are the same also May be different and each represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms. ) Represents a group represented by; or

(2e): n indicates 2, x indicates 0, p indicates 1, and Rz is a formula (4)

(In the formula, A ² is a carbon atom which may have 1 to 3 sulfur atoms and a hetero atom of Z or oxygen atom in the chain, an alkylene group having 1 to 6 carbon atoms, and 1 to 3 © in the chain. C 2-5 alkylidene, oxygen, sulfur, sulfinyl (1-SO—) or sulfonyl groups which may be intervened by a sulfur atom and a hetero atom of oxygen or oxygen

(- S0 ₂ -) indicates, R ^lfl and R ¹⁵ may be the same or different, their respective represents an alkyl group having a carbon number〗 ^{^{~ 8, R u, R 12}} , R 1 S and RH are the same Or may be different and each represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms. ) Represents a group represented by; or

(2f): n represents 2, X represents 1, p represents 1, and Rz is a formula (5)

Represents a group represented by; or

(2g): n represents 2, X represents 1, p represents 1, Rz is the formula (6)

Represents a group represented by; or

(2h): n represents 2, X represents 1, p represents 1, R z is a formula (7)

CH ₃ 0 CH ₃

'CH ₂ -C— C— O—— CH ₂ -C—— CH ₂

CH3 CH3

Represents a group represented by; or

(i): n represents 2, X represents 1, p represents 1, and Rz represents the equation (8).

? ^HS H ₂ C— CH ₂ CH ₃

1 no \ /

CH ₂ -C— CH C

I \ /

CH3 H2C—— CH ₂

Represents a group represented by; or

(2 j): n indicates 2, X indicates 1, p indicates 0, and R z is an equation (9)

— 0— (CH ₂ CH ₂ 0) _m1 —

(Wherein, m 1 represents an integer of 1 to 4.) or (2 k): n represents 2, X represents 1, p represents 0, R z is the formula _{(1 0) NH- (CH 2} ) m2 - NH

(Wherein, 2 represents the number of 1 to 6) or (2 1): n represents 2, X represents 1, p represents 0, R z is the formula (11) NH-NH

Represents a group represented by; or

(2 m): n indicates 2, x indicates 1, p indicates 1, and R z is a formula (1 2)

(Wherein, A ³ is an alkylene group having 1 to 6 carbon atoms which may have 1 to 3 sulfur atoms and a hetero atom of Z or oxygen atom in the chain, and 1 to 3 sulfur atoms in the chain Atoms and Beauty or alkylidene group of an oxygen atom good carbon atoms 2 be interposed heteroatoms of 5, an oxygen atom, a sulfur atom, a sulfinyl group (-SO-) or sulfonyl group (-S0 ₂ -) indicates, R ^ie , R ¹⁷ , R ¹ R ¹³ , R ²⁰ and R ²¹ may be the same or different and each represents a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, an aryl group having 6 to 10 carbon atoms, or 3 carbon atoms. And represents 7 to 7 cycloalkyl groups. ) Represents a group represented by

(2 n): n represents 2, x represents 1, p represents 1, R z is a formula (1 3)

(Wherein Α ⁴ is an alkylene group having 1 to 6 carbon atoms which may have 1 to 3 sulfur atoms and / or heteroatoms of oxygen atoms in the chain, and 1 to 3 sulfur atoms in the chain And an alkylidene group having 2 to 5 carbon atoms which may be intervened by a hetero atom of Z or an oxygen atom, an oxygen atom, a sulfur atom, a sulfinyl group (one SO—) or a sulfonyl group

(—S〇 ₂ —), wherein R ²² , R ²³ , R ²⁴ , R ²⁵ , R ²⁶ and R ²⁷ may be the same or different and each represents a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, It represents an aryl group having 6 to 10 carbon atoms or a cycloalkyl group having 3 to 7 carbon atoms. ) Indicates a group represented by:

(3a): n represents 3, x represents 1, p represents 1, Rz represents a linear or branched alkanetriyl group having 2 to 6 carbon atoms; or

(3b): n represents 3, X represents 0, p represents 1, Rz is the formula (14)

(Wherein, A ⁵ represents an isocyanuric group or 1,3,5-trimethylphenyl 2,4,6-tolyl group, R ²⁸ represents an alkyl group having 1 to 8 carbon atoms, R ²⁹ and R ³ May be the same or different, and each represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, and m 3 represents an integer of 1 to 3.) represents a group represented by:

(3c): n represents 3, X represents 0, p represents 1, Rz is a formula (15)

(In the formula, A ⁶ represents an isocyanuric group or 1,3,5-trimethylphenyl 2,4,6-tolyl group, R ³ ′ represents an alkyl group having 1 to 8 carbon atoms, R ³² and R ³² ^{And 33} may be the same or different and each represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, and m 4 represents an integer of 1 to 3).

(3d): n represents 3, X represents 1, p represents 1, and Rz is a formula (16)

(Wherein, A ⁷ represents an isocyanuric group or a nitrogen atom, and m 5 represents an integer of! To 3.) or a group represented by the following formula:

(4a): n represents 4, x represents 1, p represents 1, Rz represents a linear or branched alkane-tetrayl group having 2 to 6 carbon atoms; or

(5a): n represents 5, x represents 1, p represents 1, R z represents a linear or branched alkane-pentile group having 2 to 6 carbon atoms; or

(6a): n represents 6, x represents 1, p represents 1, and Rz represents a linear or branched alkane-hexayl group having 2 to 6 carbon atoms. The compound of the present invention will be described in more detail.

The present invention provides the following: [门: Formula (1)

H-() _b- (L ¹ ) _a- (L) _x- (0) p Rz

(Wherein the definitions of the symbols are as follows.)

(Hereinafter, referred to as the compound of the present invention). Here, each symbol described in the equation (1) has the following meaning.

L, L ¹ and L ² may be the same or different;

(Wherein, R ¹ represents an alkyl group having 1 to 8 carbon atoms, and R ² and R ³ may be the same or different and each represent a hydrogen atom or an alkyl group having 1 to 8 carbon atoms.) , A represents 1, b represents an integer of 0 or 1,

(la): n represents 1, X represents 1, p represents 1, Rz represents an alkyl group having 1 to 30 carbon atoms, that is, the formula (38)

H— (L ² ) _b — L ¹ — L one 0— Rz

(Wherein, R z is an alkyl group having 1 to 30 carbon atoms, and other symbols are as defined above).

(lb): n represents 1, X represents 1, p represents 1, and 1¾2 represents an alkenyl group having 2 to 30 carbon atoms, that is, the formula (38)

H— (L ² ) _b — L ¹ — L—— O—Rz (Wherein, R z is an alkenyl group having 2 to 30 carbon atoms, and the other symbols are as defined above).

(1c): n represents 1, X represents 1, p represents 1, Rz represents an alkynyl group having 2 to 30 carbon atoms, that is, the formula (38)

H- (L ² ) _b — L ¹ —— L—— 0—— Rz

(Wherein, R z is an alkynyl group having 2 to 30 carbon atoms, and the other symbols are as defined above).

(Id): n represents 1, X represents 1, p represents 1, R z represents a cycloalkyl group having 3 to 7 carbon atoms which may have a substituent, that is, the formula ( 3 8)

H— (L ² ) _b — L ¹ —Shichi O— Rz

(Wherein, R z is a cycloalkyl group having 3 to 7 carbon atoms which may have a substituent, and other symbols are as defined above.).

(1e): n represents 1, X represents 1, p represents 1, Rz is an aralkyl group having 7 to 20 carbon atoms which may have a substituent or has a substituent. Represents an aryl group having 6 to 20 carbon atoms, that is, the formula (38)

H- (L ² ) _b — L ¹ — L—— 0— Rz

(Wherein, R z is an optionally substituted aralkyl group having 7 to 20 carbon atoms or an aryl group having 6 to 20 carbon atoms, and other symbols are as defined above.) Compound: or

(2a): n represents 2, x represents 1, p represents 1, R z represents 1 to 10 sulfur atoms and / or oxygen atom hetero atoms in the chain. Shows a good alkylene group having 1 to 20 carbon atoms, that is, the formula (39)

H- (L ² ) _b — L ¹ — L-0— Rz— 0— L— L ^1- (L ² ) _b -H

1 o (In the formula, R z is an alkylene group having 1 to 20 carbon atoms which may have a hetero atom of 1 to 10 sulfur atoms and / or oxygen atoms in the chain. A compound represented by the formula: or

(2b): n represents 2, X represents 1, p represents 1, Rz is a alkenylene group having 2 to 12 carbon atoms, an alkynylene group having 2 to 12 carbon atoms, or A cycloalkylene group having 3 to 60 carbon atoms which may have a substituent, that is, a compound represented by the formula (39)

H- (L ² ) _b — L ¹ — L-0— Rz— 0— L— L ^1- (L ² ) _b -H

(In the formula, Rz is an alkenylene group having 2 to 12 carbon atoms, an alkynylene group having 2 to 12 carbon atoms, or a cycloalkylene having 3 to 60 carbon atoms which may have a substituent. And the other symbols are as defined above.) Or a compound represented by the formula:

(2c): n represents 2, X represents 1, p represents 1, R z represents an arylene group having 6 to 60 carbon atoms which may have a substituent, that is, the formula ( 3 9)

H- (L ² ) _b — L ¹ — L— 0— Rz— 0— L— L ^1- one (L ² ) _b — H

(Wherein, R z is an arylene group having 6 to 60 carbon atoms, and other symbols are as defined above).

(2 d): n represents 2, X represents 0, p represents 1, R z is a formula (3)

(In the formula, A ¹ is an alkylene group having 1 to 6 carbon atoms which may have 1 to 3 sulfur atoms and / or oxygen atom hetero atoms in the chain, and 1 to 3 carbon atoms in the chain. An alkyl group having 2 to 5 carbon atoms which may be intervened by a sulfur atom and a hetero atom such as a sulfur atom or an oxygen atom Kiriden group, an oxygen atom, a sulfur atom, a sulfinyl group (one so-) or sulfonyl Le group (an S0 ₂ -) indicates, and R ^9, which may be the same or different, 1 to 8 carbon atoms, respectively And R ⁵ , R ^e , R ⁷ and R ⁸ may be the same or different and each represent a hydrogen atom or an alkyl group having 1 to 8 carbon atoms. ) Represents a group represented by the formula, that is, the formula (40)

H-(L ² ) _b -L ¹ — () _b _H

(In the formula, A ¹ is an alkylene group having 1 to 6 carbon atoms which may have 1 to 3 sulfur atoms and a hetero atom of a hydrogen atom or an oxygen atom in the chain, and 1 to 3 carbon atoms in the chain. A sulfur atom and / or a hetero atom of an oxygen atom may be interposed, and an alkylidene group having 2 to 5 carbon atoms, an oxygen atom, a sulfur atom, a sulfinyl group (1-SO—) or a sulfonyl group ( one S_〇 ₂ - shows a), R ⁴ and R ^9, which may be the same or different, each represent an alkyl group having 1 to 8 carbon ^{^{atoms, R 5, R s, R}} 7, and R ^8, Which may be the same or different, each being a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, and the other symbols are as defined above.

(2e): n indicates 2, x indicates 0, p indicates 1, and Rz is a formula (4)

(In the formula, A ² is an alkylene group having 1 to 6 carbon atoms which may have 1 to 3 heteroatoms of sulfur and / or oxygen atoms in the chain, and 1 to 3 carbon atoms in the chain. Sulfur atom And / or it may also be hetero atoms of oxygen atoms intervene Les Al Kiriden group 2-5 carbon atoms, an oxygen atom, a sulfur atom, a sulfinyl group (one SO-) or sulfonyl Le group (an S0 ₂ -), Wherein R ¹⁰ and R ¹⁵ may be the same or different and each represent an alkyl group having 1 to 8 carbon atoms, and the lengths ¹¹ , R ¹² , R ¹³ , and R ¹⁴ are the same or different. And each represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms. ), That is, a group represented by the formula (41)

(In the formula, A ² is an alkylene group having 1 to 6 carbon atoms which may have 1 to 3 sulfur atoms and a hetero atom of a hydrogen atom or an oxygen atom in the chain, and 1 to 3 carbon atoms in the chain. sulfur atom and Z or Al Kiriden group oxygen carbon atoms, which may have intervening heteroatom of atomic 2-5, an oxygen atom, a sulfur atom, a sulfinyl group (-SO-) or sulfonyl Le group (- S0 ₂ -), R ^lfl and R ¹⁵ may be the same or different and each represents an alkyl group having 1 to 8 carbon atoms, and R ^ll , R ¹² , R ¹³ , and R "are the same or different. Or a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, and the other symbols are as defined above.

(2f): n represents 2, X represents 1, p represents 1, and Rz is a formula (5)

Which represents a group represented by the following formula: CH ₃ ,. -CH _{2 /} CH ₂ O CH

H— (L ² ) _b —L ¹ —one 0_CH ₂ — C—C CH—-CH ₂ — O— ^{one-one 1} "(L ² ) _b -H

CH ₃ 0-CH ₂ CH ₂ 0 CH ₃

(Wherein the symbol is as defined above.) Or a compound represented by the formula:

(2 g): n represents 2, X represents 1, p represents 1, and R z is a formula (6)

Which represents a group represented by the following formula:

CH ₃ O CH ₂ , CH ₂ CH ₃

H- (L ² ) _b -L ¹ -L'0-CH ₂ -C-CH,

CH ₃ O CH ₂ CH ₂ — O— LL ^1- (L ² ) _b -H

(The symbols in the formula are as defined above.); Or

(2h): n represents 2, X represents 1, p represents 1, R z is a formula (7)

Which represents a group represented by the formula: (44) H- (L ² ) _b -L ¹ -L-0 -shi ¹ "() _b -H

(The symbols in the formula are as defined above.); Or

(2i): n represents 2, X represents 1, p represents 1, and Rz represents the formula (8).

Which represents a group represented by the following formula:

(The symbols in the formula are as defined above.); Or

(2 j): n indicates 2, X indicates 1, p indicates 0, and R z is an equation (9)

——0— (CH ₂ CH ₂ 0) _m1 —

(In the formula, m 1 represents an integer of〗 to 4.) represents a group represented by the following formula:

H- (L ² ) _b -L ¹ -L-0- (CH ₂ CH ₂ 0) ^-LL ^1- (L ² ) _b -H

(In the formula, m 1 is an integer of 1 to 4, and other symbols are as defined above.);

(2k): n indicates 2, X indicates 1, p indicates 0, and Rz is a formula (10)

NH— (CH ₂ ) _m2 — NH

(Wherein, m 2 represents an integer of 1 to 6.) which represents a group represented by the following formula:

H- (L ² ) _b -L ¹ -L-NH- (CH ₂ ) _m2 -NH-LL ^1- (L ² ) _b -H

(In the formula, m 2 is an integer of 1 to 6, and other symbols are as defined above.);

(2 1): n represents 2, X represents 1, p represents 0, and R z represents the formula (1 1)

NH-I Which represents a group represented by the following formula:

H- (L ² ) _b -L ¹ -L-NH— HLL ^1- (L ² ) _b -H

(The symbols in the formula are as defined above.); Or

(2m): n indicates 2, x indicates 1, p indicates 1, and R z is a formula (1 2)

(In the formula, A ³ is an alkylene group having 1 to 6 carbon atoms which may have 1 to 3 sulfur atoms and a hetero atom of Z or oxygen atom in the chain, and 1 to 3 carbon atoms in the chain. sulfur atom and Roh or aralkyl Kiriden group oxygen atom 2-5 carbon atoms which may be hetero atoms are interposed to the oxygen atom, a sulfur atom, a sulfinyl group (one SO-) or sulfonyl Le group (an S0 ₂ -), And R ′ ⁶ , R ¹⁷ , R ¹⁸ , R ¹⁹ , R ²⁰ and R ²¹ may be the same or different and each represents a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, and 6 carbon atoms. Represents an aryl group having up to 10 or a cycloalkyl group having 3 to 7 carbon atoms.), That is, a group represented by the formula (49)

H- (L ² ) _b -L-L ^1- () _h —H

(Wherein A ³ is an alkylene group having 1 to 6 carbon atoms which may have 1 to 3 sulfur atoms and a hetero atom of Z or oxygen atom in the chain, and 1 to 3 carbon atoms in the chain. sulfur atom and or aralkyl Kiriden group oxygen carbon atoms, which may have intervening heteroatom of atomic 2-5, an oxygen atom, a sulfur atom, a sulfinyl group (-SO-) or sulfonyl Le group (- S_〇 ₂ —), And R ¹⁶ , R, R ¹⁸ , R ′ ⁹ , R ²⁰ and R ²¹ may be the same or different and each represents a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, A aryl group having 6 to 10 carbon atoms or a cycloalkyl group having 3 to 7 carbon atoms, and other symbols are as defined above. Or a compound represented by the formula:

(2 n): n represents 2, x represents 1, p represents 1, R z is a formula (1 3)

(In the formula, A ⁴ is an alkylene group having 1 to 6 carbon atoms which may have 1 to 3 sulfur atoms and a hetero atom of Z or oxygen atom in the chain, and 1 to 3 carbon atoms in the chain. sulfur atom and or heteroatoms of oxygen atoms in a good number of carbon atoms which may have 2-5 intervening Al Kiriden group, an oxygen atom, a sulfur atom, a sulfinyl group (one SO-) or sulfonyl Le group (- S0 ₂ - And R ²² , R ²³ , R ²⁴ , R ²⁵ , R ²⁶ and R ²⁷ may be the same or different and each represents a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, or a carbon atom having 6 to 1 carbon atoms. Represents an aryl group of 0 or a cycloalkyl group having 3 to 7 carbon atoms.) Represents a group represented by the following formula:

(In the formula, A ⁴ is an alkylene group having 1 to 6 carbon atoms which may have 1 to 3 sulfur atoms and a hetero atom of Z or oxygen atom in the chain, and 1 to 3 carbon atoms in the chain. An alkylidene group having 2 to 5 carbon atoms, an oxygen atom, a sulfur atom, a sulfinyl group (—S〇1) or a sulfonyl group (1 S 〇 ₂ —) and R ²² , R ²³ , R ² \ R ²⁵ , R ^2S and R ²⁷ are the same Or a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, an aryl group having 6 to 10 carbon atoms, or a cycloalkyl group having 3 to 7 carbon atoms. Is synonymous with Or a compound represented by the formula:

(3a): n represents 3, x represents 1, p represents 1, Rz represents a linear or branched alkane-triyl group having 2 to 6 carbon atoms, ie, the formula ( 5 1)

(Wherein, R z is a straight-chain or branched-chain alkyne-triyl having 2 to 6 carbon atoms, and other symbols are as defined above); or

(3b): n represents 3, X represents 0, p represents 1, Rz is a formula (14)

(In the formula, A ⁵ represents an isocyanuric group or a group represented by 1,3,5-trimethylphenyl 2,4,6-triyl group, and R ²⁸ represents an alkyl group having 1 to 8 carbon atoms. And R ²⁹ and R ^3e may be the same or different and each represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, and 113 represents an integer of 1 to 3.) Which represents a group represented by the following formula (5 2)

H 2, _

— (Then _b A 5

(Wherein, A ⁵ is any group represented by an isocyanuric group or 3,5-trimethylphenyl 2,4,6-triyl group, and R ²⁸ is an alkyl group having 1 to 8 carbon atoms. R ²⁹ and R ^3e may be the same or different, each is a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, m 3 is an integer of 1 to 3, and other symbols are It is the same as the above. Or a compound represented by the formula:

(3c): n represents 3, X represents 0, p represents 1, Rz is the formula (15)

(In the formula, A ⁶ represents any group represented by an isocyanuric group or 1,3,5-trimethylphenyl-1,2,4,6-triyl group, and R ³¹ represents an alkyl group having 1 to 8 carbon atoms. And R ³² and R ³³ may be the same or different and each represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, and m 4 represents an integer of 1 to 3. That is, the equation (53)

(Wherein, A ⁶ is an isocyanuric group or any group represented by 1,3,5-trimethylphenyl 2,4,6-triyl group, and R ³¹ is an alkyl having 1 to 8 carbon atoms. R ³² and R ³³ may be the same or different, each is a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, m 4 is an integer of 1 to 3, and the other symbols are A compound represented by the formula: or

(3d): n represents 3, X represents 1, p represents 1, and Rz is a formula (16)

(In the formula, A ⁷ represents a group represented by an isocyanuric group or a nitrogen atom, and m 5 represents an integer of 13.) In other words, a group represented by the following formula:

H- (L ² ) _b -LL-0- (CH ₂ ) _m5-7

Three

(Wherein, A ⁷ is a group represented by an isocyanuric group or a nitrogen atom, m 5 is an integer of 1 to 3, and other symbols are as defined above.);

(4a): n represents 4, x represents 1, p represents 1, Rz represents a straight-chain or branched alkane-tetrayl group having 2 to 6 carbon atoms, that is, the formula: (5 5)

H— (L ² ) _b — — O Rz

Four

(Wherein, R z is a straight-chain or branched-chain alkin-tetrayl group having 2 to 6 carbon atoms, and other symbols are as defined above); or

(5a): n represents 5, x represents 1, p represents 1, Rz represents a straight or branched chain alkane-pentile group having 2 to 6 carbon atoms, that is, the formula ( 5 6)

(Wherein, R z is a straight-chain or branched-chain alpenpentile group having 2 to 6 carbon atoms, and other symbols are as defined above).

(6a): n represents 6, x represents 1, p represents 1, and Rz has 2 to 6 carbon atoms. Represents a straight-chain or branched-chain alkane-hexayl group, that is, the formula (57)

H— () _b — 0 Rz

(Wherein, R z is a straight-chain or branched chain alkane-hexyl group having 2 to 6 carbon atoms, and other symbols are as defined above). The present invention also relates to [2], [3], [4], or [5].

[2]: Among the compounds of the formula (1), R z force (la). (Le), (2a), (2d), (2e), (2f), (2j), (2j) 2k), (21), (3b), (3c), (3d) or (4a).

[3]: Among the compounds of the formula (1), L, L ¹ and L ² are

Equation (1 7)

CH ₃

Or equation (1 8)

Or equation (1 9)

When the phenolic compound is, that is, x = 0, the formula (5 8)

(In the formula, R ^b may be the same or different and each is a hydrogen atom, a methyl group, or a tertiary butyl group, and other symbols are as defined above.) (5 9)

(Wherein, R ^b may be the same or different and are each a hydrogen atom, a methyl group or a tertiary butyl group, and other symbols are as defined above.), A compound represented by the formula: If = 1, the formula (60)

(Wherein, R ^b may be the same or different and each represents a hydrogen atom, a methyl group, Or a tertiary butyl group, and the other symbols are as defined above. Or a compound represented by the formula (61)

CO

CD =

(Wherein, R ^b may be the same or different and each is a hydrogen atom, a methyl group or a tertiary butyl group, and the other symbols are as defined above.).

[4]: In the compound of the formula (1), n is 1 or n is 2 or more and a substituent of the formula (20)

H- (L ² ) _b- (L ¹ ) _a- (L) x

(The symbols in the formula are as defined above.) A phenol compound having the same group represented by

[5]: Among the compounds of the formula (1), a phenol compound wherein b is 0. Furthermore, the present invention relates to [6], [7], [8], [9], [10], [11], [12], and [13].

[6]: n is 2, X is 1, p is 0, and R z is the formula (2 1)

—— 0— (CH ₂ CH ₂ 0) ₃ ——

[1], [2], [3], [4], or [5], which is represented by the following formula: Nol compound, that is, formula (62) or formula (63)

9 Z

I89T0 / ^ 6If / I3d 0U P / L6 OAV (Wherein, R ¹ may be the same or different and each is an alkyl group having 1 to 8 carbon atoms, and R ² and R ³ may be the same or different and each is a hydrogen atom or a carbon atom 1 A compound represented by the formula:

[7]: n is 2, X is 0, p is 1 and R z is the formula (64)

(Where A ⁸ is a sulfur atom or a butylidene group, R ⁶ and R ⁷ are methyl groups, R ⁴ and R ³ are tertiary butyl groups, and R ⁵ and R ⁸ are hydrogen atoms [1], [2], [3], [4], or [5], ie, n is 2, X is 0, p is 1, R z is the formula

(6 5)

(Wherein A ⁸ is a sulfur atom or a butylidene group.) [1], [2], [3], [4], or the phenolic compound according to [5], that is, a compound of the formula (66) Or expression (6 7)

L Z

, = O

l89I0 / I6 <If / IDd otewz.6 OAV (In the formula, A ⁸ is a sulfur atom or a butylidene group, R ¹ is an alkyl group having 1 to 8 carbon atoms, R ² and R ³ may be the same or different, and are each a hydrogen atom or a carbon number. A compound represented by the formula:

[8]: n is 2, X is 0, p is 1 and R z is given by the equation (68)

Wherein A ³ is a methylene group or a butylidene group, R ¹ ′ and R ¹⁴ are a methyl group or an ethyl group, R ^ie and R ¹⁵ are tertiary petit / silyl groups, R ¹² and R ¹³ is a hydrogen atom.) [1], [2], [3], [4], or

[5] The phenol compound according to the above, ie, n is 2, X is 0, p is 1, and R z is a compound of the formula (69)

(Wherein A ³ is a methylene group or a butylidene group, and R ¹ ′ and R ″ are a methyl group or an ethyl group.) [1], [2], [3], [4] Or the phenolic compound according to [5], that is, the formula (70) or the formula (71)

(Where A ⁹ is a methylene group or a butylidene group, R ¹¹ and R ″ are a methyl group or an ethyl group, respectively, R ¹ is an alkyl group having 1 to 8 carbon atoms, R ² and R ² ³ may be the same or different and are each a hydrogen atom or an alkyl group having 1 to 8 carbon atoms.

[9]: n is 3, X is 0, p is 1 and R z is the formula (2 4)

(Wherein, A ¹ is an isocyanuric group.) [1], [2], [3], [4], or the phenolic compound according to [5], that is, a compound represented by the formula (73) Or expression (74)

(Wherein, R ′ is an alkyl group having 1 to 8 carbon atoms, and R ² and R ³ may be the same or different and are each a hydrogen atom or an alkyl group having 1 to 8 carbon atoms.) Compound,

[10]: n is 1, X is 1, p is 1, R z is the formula (25)

(H2) 17 H3

[1], [2], [3], [4], or the phenolic compound according to [5] represented by (n-octyldecyl group), that is, the formula (75) or the formula (76) ) 0 (CH ₂ ), 7-CH ₃ (75)

(Wherein, R ¹ is an alkyl group having 1 to 8 carbon atoms, and R ² and R ³ may be the same or different and are each a hydrogen atom or an alkyl group having 1 to 8 carbon atoms.) Compound,

[1 1]: n is 4, X is 1, p is 1, R z is the formula (2 6)

The phenolic compound according to [门, [2], [3], [4], or [5], which is represented by the formula (77) or (78)

CH

(78)

[1 2] n is 2, X is 1, p is 1, and R z is given by equation (5)

[1], [2], [3], [4], or the phenolic compound according to [5], that is, the formula (79) or the formula (80)

CO

CD:

[13]: triethylene glycol bis (3- (3-tertiary butyl-41- (3- (3,5-di-tertiary butyl-4-hydroxyphenyl) propionyloxy) -5-methylphenyl) (Provionate), that is, the formula (27)

(Hereinafter, sometimes referred to as compound S 1),

Thiobis (2-methyl-4-1- (3- (3,5-di-tert-butyl- 4-hydroxy-pi-xylphenyl) propionyloxy) -1-5-tert-butylbutyl), ie, formula (28)

(Hereinafter, sometimes referred to as compound S 2),

1, 1-bis (2-methyl-4-1- (3- (3,5-di-tert-butyl-4-hydroxyxylphenyl) propionyloxy) -propane-5-tert-butylbutyl) butane, formula (29) )

(Hereinafter, sometimes referred to as compound S 3),

Methylenebis (2- (3- (3,5-di-tert-butyl-l-hydroxyphenyl) propionyloquine) -l3-tert-butyl-5-methylphenyl), ie, formula (30)

(Hereinafter, sometimes referred to as compound S),

Methylenebis (2- (3- (3,5-di-tertiary tertiary petite 4-hydroxyphenyl) propionyloxy) 1-3-tertiary butyl-5-ethylphenyl), ie, formula (31 )

(Hereinafter, sometimes referred to as compound S5),

1,3,5—tris (3—tertiary tert-butyl 4- (3— (3,5 g tertiary butyl 1-4-hydridoxyphenyl) propionyloxy)) — 5-socyanurate, (3 2)

(Hereinafter, sometimes referred to as compound S 6),

n-octyl decyl 3- (3-tertiary tert-butyl 4- (3- (3,5-di-tert-butyl-4-hydroquinphenyl) propionyloquin) -1-methylphenyl) probionet Equation (3 3)

(Hereinafter, sometimes referred to as compound S7),

Tetrakis (methylene-1- (3-tertiary-butyl-4-1- (3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionylloquine) —5-methylphenyl) probionet) methane, That is, equation (3 4)

(Hereinafter, sometimes referred to as compound S8),

3,9-bis [2 -— (3 -— (3-tert-butylbutyl 4- (3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionyloxy)) 15-methylphenyl ) Propionyloxy) 1, 1 dimethylethyl] — 2,4,8,10—te-Traoxaspiro [5.5] pentane, ie formula (35)

(Hereinafter, sometimes referred to as compound S9),

Thiobis (3-tert-butyl-4-1) (3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionyloxy) -6-methylphenyl, ie, formula (36)

(Hereinafter, also referred to as compound S10). [1], [2], [3], [4], [5], [6], [7], [8], [9], [10], [11], [1] 2], and any of those described in [1 3] Is abbreviated as “compound of the present invention” hereinafter.

[14]: a stabilizer for an organic polymer material comprising the compound of the present invention, [15] ·. An organic polymer material containing the compound of the present invention,

[16]: The stabilizer for organic polymer material according to [14], further comprising a sulfur-based antioxidant,

[17]: The sulfur-based antioxidant is

Dilauryl thiodipropionate,

Lauryl stearyl thiodibu mouth pionate,

Jimi ristylthiodiprobionet,

Distearyl thiodipropionate,

Ditridecylthiodipropionate,

Tetrakis [methylene (laurylthiopropionate)] methane,

Tetrakis [methylene (stearylthiopropionate)] methane, or bis [2-methyl-41- (3-n-alkyl (C 12-14) thiopropionyloxy)-5-tertiary butylphenyl] sulfide The stabilizer for organic polymer materials according to [16],

[18]: a method for stabilizing an organic polymer, comprising adding the compound of the present invention to the organic polymer,

[19] The method for stabilizing an organic polymer according to [18], wherein the organic polymer is an olefin resin. [20]: The organic compound according to [18], wherein the compounding amount of the compound of the present invention is selected in the range of 0.01 to 10 parts by weight based on 100 parts by weight of the olefin resin. Polymer stabilization method,

[21] The method for stabilizing an organic polymer according to [18], wherein the olefin resin is selected from α-olefin homopolymer and α-olefin copolymer.

[22]: a composition comprising the compound of the present invention and an organic polymer,

[23]: The composition according to [22], wherein the organic polymer is an olefin resin.

[24]: The composition according to [23], wherein the compounding amount of the compound of the present invention is selected in the range of 0.01 to 10 parts by weight per 100 parts by weight of the olefin resin. object,

[25]: The composition according to [23], wherein the olefin resin is selected from an α-olefin homopolymer and a monoolefin copolymer.

[26] The composition according to [22], further comprising a sulfur-based antioxidant,

[27]: sulfur-based antioxidant

Dilauryl thiodiprobionet,

Lauryl stearyl thiodipropionate,

Jimi ristylthiodipropionate,

Distearyl thiodipropionate,

Ditridecylthiodipropionate,

Tetrakis [methylene (laurylthiopropionate)] methane,

Tetrakis [methylene (stearylthiopropionate)] methane, or 26. The composition according to [26], which is bis [2-methyl-4- (3-n-alkyl (C.sub.12-14) thiopropionyloxy) —5-tert-butylbutyl] sulfide; and

* [2 8]: [2 2], [2 3], [2 4], [2 5], [2 6], or

[27] A stabilizer for an organic polymer material comprising the composition as described above. The feature of the compound of the present invention represented by the formula (1) is that it is a hindered phenol compound having a hindered phenyl ester structure. In other words, in an environment where water is present, when the hindered phenol X exerts an antioxidant effect at the beginning of use and the hindered phenyl ester is transformed by the action of water during use, a new hindered phenol compound is obtained. Is generated and the ability to prevent oxidative deterioration continues to be exhibited, so that a longer-term effect of preventing oxidative deterioration can be exhibited as compared with conventional antioxidants. The compound of the present invention represented by the formula (1) can be used as a stabilizer for various organic polymers, and is effective in preventing oxidative deterioration of organic polymers. This is effective in preventing the oxidative deterioration of a synthetic polymer that is often used. The present inventors have been studying the mechanism of reducing the effect of the antioxidant compounded in the organic polymer used in the environment where water is present. As a result, it cannot be explained by the conventional idea that the antioxidant contained in the organic polymer is extracted or hydrolyzed by water, and the antioxidant is oxidized by the action of water. However, they discovered that the compound did not exhibit antioxidant effects. Therefore, for organic polymers used in an environment where water is present, even if they are oxidatively altered by the action of water, it is important to design a compound that has antioxidant properties even for the compounds produced by the oxidative alteration. I conceived and worked diligently. As a result, the compound represented by the general formula (1) has an excellent antioxidant effect on organic polymers due to its own chemical structure, and furthermore, when used in an environment where water or hot water exists, It has been found that even in the case where a sufficient antioxidant effect is exhibited, the present invention has been completed.

Even if the compound of the present invention is deteriorated by water or hot water, a compound having a new ability to prevent oxidative deterioration is successively formed, so that the effect of maintaining the ability to prevent oxidative deterioration is remarkable. . Equation (2)

For the symbols described in ( _c ), one example is the following _{c. In the} formula (2), R ¹ may be the same or different, and may be any of linear, branched or cyclic. And an alkyl group having 1 to 8 carbon atoms.

For example, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, secondary butyl group, tertiary butyl group, n-pentyl group, isopentyl group, secondary pentyl Group, tertiary pentyl group, 2-methylbutyl group, n-hexyl group, isohexyl group, secondary hexyl group, tertiary hexyl group, cyclohexyl group, heptyl group, n-octyl Group, isooctyl group, secondary octyl group, tertiary octyl group, 2-ethylhexyl group and the like.

Preferably, there may be mentioned 1 to 5 alkyl groups which may be straight-chain or branched. For example, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, secondary butyl, tertiary butyl, n-pentyl, Examples include an isopentyl group, a secondary pentyl group, a tertiary pentyl group, and a 2-methylbutyl group.

More preferred are a tertiary butyl group, a methyl group and an ethyl group, and among them, a tertiary butyl group is particularly preferred. R ² shown in the formula (2) may be the same or different, and includes an alkyl group having 1 to 8 carbon atoms which may be linear, branched or cyclic.

For example, methyl group, ethyl group, n-propyl group, isopropyl group, _n -butyl group, y-butyl group, secondary butyl group, tertiary butyl group, n-pentyl group, isobentyl group, secondary pentyl Group, tertiary pentyl group, 2-methylbutyl group, n-hexyl group, isohexyl group, secondary hexyl group, tertiary hexyl group, cyclohexyl group, heptyl group, n-octyl Group, an isooctyl group, a secondary octyl group, a tertiary octyl group, a 2-ethylhexyl group, or a hydrogen atom.

Preferably, it may be either straight-chain or branched! To 5 alkyl groups. For example, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, secondary butyl, tertiary butyl, n-pentyl, isopentyl, secondary pentyl, Examples include a tertiary pentyl group, a 2-methylbutyl group, and a hydrogen atom.

More preferred are a tertiary butyl group, a methyl group, an ethyl group and a hydrogen atom, and among them, a tertiary butyl group and a methyl group are particularly preferred. R ³ in the formula (2) may be the same or different, and includes an alkyl group having 1 to 8 carbon atoms which may be linear, branched or cyclic. For example, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, secondary butyl, tertiary butyl, n-pentyl, isopentyl, secondary pentyl, Tertiary pentyl group, 2-methylbutyl group, n-hexyl group, isohexyl group, secondary hexyl group, tertiary hexyl group, cyclohexyl group, heptyl group, n-hexyl group, isooctyl group, secondary octyl group, Tertiary octyl group, 2-ethylhexyl group, or hydrogen atom. Preferably, there may be mentioned 1 to 5 alkyl groups which may be either linear or branched. For example, methyl group, ethyl group, n-propyl group, isopropyl group, _n -butyl group, isobutyl group, secondary butyl group, tertiary butyl group, n-pentyl group, isopentyl group, secondary pentyl group And a tertiary pentyl group, a 2-methylbutyl group, and a hydrogen atom.

More preferred are a tertiary butyl group, a methyl group, an ethyl group, and a hydrogen atom, and among them, a methyl group or a hydrogen atom is particularly preferred.

As the alkyl group having 1 to 30 carbon atoms of R z shown in (1a), a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a secondary butyl group , Tertiary butyl, n-pentyl, isopentyl, secondary pentyl, tertiary pentyl, 2-methylbutyl, n-hexyl, isohexyl, secondary hexyl , Tertiary hexyl, heptyl, n-octyl, isooctyl, secondary octyl, tertiary octyl, 2-ethylhexyl, nonyl, decyl, pendecyl, A linear or straight chain having 1 to 30 carbon atoms such as a dodecyl group, a tridecyl group, a tetradecyl group, a pendecyl group, a hexadecyl group, a heptanedecyl group, an octadecyl group, a nonadecyl group, an icon group, and a docosyl group; The alkyl group of the chain It is below.

Preferably, a dodecyl group, a tetradecyl group, a hexadecyl group, an octadecyl group and the like are listed, and among them, an octadecyl group is particularly preferable.

Examples of the alkenyl group having 2 to 30 carbon atoms of RZ shown in (lb) include a vinyl group, a 1-propenyl group, an aryl group, a butenyl group, a pentenyl group, a hexenyl group, an octenyl group, and a nonenyl group. , Decenyl group, didecenyl group, dodecenyl group, tridecenyl group A straight-chain or branched chain having 2 to 30 carbon atoms, such as a benzyl group, a tetradecenyl group, a pentadecenyl group, a hexadecenyl group, a heptane decenyl group, an octadecenyl group, a nonadecenyl group, an icosenyl group, or a docosenyl group. An alkenyl group is mentioned.

The alkynyl group having 2 to 30 carbon atoms of R z shown in (1c) includes an ethynyl group, a 1-propynyl group, a propargyl group, a butynyl group, a pentynyl group, a hexynyl group, a heptynyl group, and an octynyl group , Noninyl group, decynyl group, pendecinyl group, dodecynyl group, tridecynyl group, tetradecynyl group, pendecinyl group, hexadenyl group, heptanedecinyl group, okdecinyl group, nonadecinyl group, icosinyl group, docosynyl group And a straight or branched alkynyl group having 2 to 30 carbon atoms.

Examples of the cycloalkyl group of the cycloalkyl group having 3 to 7 carbon atoms which may have a substituent represented by R z shown in (1d) include cyclopropyl group, cyclobutyl group, cyclopentyl group, and cyclohexyl. group, _c consequent o alkyl group or other natural or synthetic based terpene having 3 to 7 carbon atoms such as heptyl group cycloheteroalkyl is举down

As the substituent of the cycloalkyl group having 3 to 7 carbon atoms which may have a substituent of R z shown in (1d), a linear or branched chain alkyl group having 1 to 8 carbon atoms (E.g., methyl, ethyl, propyl, isopropyl, butyl, isobutyl, secondary butyl, tertiary butyl, heptyl, octyl, etc.), and phenyl. The cycloalkyl group may have 1 to 3 of these substituents.

As the aralkyl group of the aralkyl group having 7 to 20 carbon atoms which may have a substituent of R z shown in (1e), a benzyl group, a 2-phenylethyl group, a 2-phenylpropyl group, 2-phenylbutyl, 1-naphthylmethyl, 2-naphthylmethyl And a 2- (2-naphthyl) ethyl group.

(1e) The number of carbons which may have a substituent of R z shown in (e)? Examples of the substituent of the aralkyl group having 20 to 20 carbon atoms include a linear or branched alkyl group having 1 to 8 carbon atoms (methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, grade butyl group, tertiary butyl group, a butyl group, etc. Okuchiru group), or a phenyl group, and these substituents may have the Ararukiru groups 1-3 pieces _c

Examples of the aryl group having 6 to 20 carbon atoms which may have a substituent of R Z shown in (1e) include a phenyl group and a naphthyl group.

The substituent of the aryl group having 6 to 20 carbon atoms which may have a substituent of R z shown in (1e) includes a linear or branched alkyl group having 1 to 8 carbon atoms. (Methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, secondary butyl group, tertiary butyl group, heptyl group, octyl group, etc.), or phenyl group. The aryl group may have 1 to 3 groups.

The alkylene group having 1 to 20 carbon atoms which may have〗 to 10 sulfur atoms and / or heteroatoms such as oxygen atoms in the chain of R z shown in (2a) is a methylene group. , Ethylene, trimethylene, α-pyrene (also referred to as methylethylene), tetramethylene, pentamethylene, hexamethylene, heptamethylene, octamethylene, dimethylethylene, getylethylene, dimethyltrimethylene And straight-chain or branched alkylene groups having 1 to 20 carbon atoms such as a group, getyl trimethylene group, dimethyltetramethylene group, getyl tetramethylene group, nonamethylene group, decamethylene group and dodecamethylene group.

Further, some of these carbon atoms is a group that is a sulfur atom or an oxygen atom one CH _₂ - S-CH ₂ one _{_{group, -CH 2 -CH 2 -S-CH}} 2 - CH 2 - group , —0— (CH ₂ —CH ₂ —0) 3 and the like.

Preferably, a _{_{0- (CH 2 - CH 2 -0}} ) 3 one group, one _{_{_{CH 2 -CH 2 - S- CH 2}}} - CH 2 - group, etc. Kisamechiren group to.

The alkenylene group having 2 to 12 carbon atoms of Rz shown in (2b) includes vinylene group, propenylene group, butenylene group, pentenylene group, hexenylene group, octenylene group, and nonene. Examples thereof include a linear or branched alkenylene group having 2 to 12 carbon atoms such as a diene group, a desenylene group, a pendecenylene group, and a dodecenylene group.

The alkynylene group having 2 to 12 carbon atoms of Rz shown in (2b) includes an ethynylene group, a propynylene group, a petynylene group, a pentynylene group, a hexynylene group, a heptinylene group, and an octynylene group. And straight-chain or branched alkynylene groups having 2 to 12 carbon atoms, such as nonylene group, decylene group, pendecylene group, and dodecylene group.

Examples of the cycloalkylene group of the cycloalkylene group having 3 to 60 carbon atoms which may have a substituent of Rz shown in (2b) include a cyclopropylene group, a cyclobutylene group, a cyclopentylene group, and a cyclo π Examples thereof include a cycloalkylene group having 3 to 7 carbon atoms, such as a hexylene group and a cycloheptylene group, or other natural or synthetic terpene-based groups.

As the substituent of the cycloalkylene group having 3 to 60 carbon atoms which may have a substituent of R z shown in (2b), a linear or branched alkyl group having 1 to 8 carbon atoms ( Methyl, ethyl, propyl, isopropyl, butyl, isobutyl, secondary butyl, tertiary butyl, heptyl, octyl, etc.) or phenyl. The cycloalkylene group may have 1 to 3 cycloalkyl groups. As the arylene group having 6 to 60 carbon atoms which may have a substituent of R z shown in (2c), a phenylene group, a biphenylene group or a naphthalene diyl Groups.

As the substituent of the arylene group having 6 to 60 carbon atoms which may have a substituent of R z shown in (2c), a linear or branched alkyl group having 1 to 8 carbon atoms (Methyl, ethyl, propyl, isopropyl, butyl, isobutyl, secondary butyl, tertiary butyl, heptyl, octyl, etc.), or phenyl. The arylene group may have 1 to 3 groups c

Equation (3) shown in (2 d)

An example of the symbols described in is shown below.

In the formula (3) shown in (2d), R ⁴ and R ⁹ can be selected from the same groups as R ¹ in the formula (2), and R ⁵ and R ⁸ are the same as those in the formula (2) R ² can be selected from the same groups as R ^2, and R ^e and R ⁷ can be selected from the same groups as those described for R ³ in formula (2).

In the formula (3) shown in (2d), an alkylene having 1 to 6 carbon atoms which may have 1 to 3 sulfur atoms and / or heteroatoms of oxygen atoms in the chain of A ¹ Examples of the group include a methylene group, an ethylene group, a trimethylene group, a propylene group (also referred to as a methylethylene group), a tetramethylene group, a pentamethylene group, a hexamethylene group, Examples thereof include straight-chain or branched-chain alkylene groups having 1 to 6 carbon atoms, such as dimethylethylene, getylethylene, dimethyltrimethylene, and dimethyltetramethylene.

Preferably, a methylene group, an ethylene group and the like are mentioned.

During (2 d) in the indicated equation (3), Yo be terrorist atom to the 1-3 sulfur atoms Oyo Binomatawa oxygen atom in the chain of A ¹ is interposed Les, carbon atoms 2 The alkylidene groups (1) to (5) include an ethylidene group (also called a methylmethylene group), a propylidene group (also called an ethylmethylene group), an isopropylidene group (also called a dimethylmethylene group), a butylidene group (also called a propylmethylene group), and isopropyl Examples thereof include a linear or branched alkylidene group having 2 to 5 carbon atoms such as a methylene group, a getylmethylene group, and a methylethylmethylene group.

Preferably, an ethylidene group, a propylidene group, a butylidene group and the like are mentioned.

As an example of formula (3) shown in (2d), R ⁴ and R ⁹ are tertiary butyl groups, R ⁶ and R ⁷ are methyl groups, and R ⁵ and R ⁸ are hydrogen atoms. Wherein A ¹ is a butylidene group (8 1)

Or R ⁴ and R ⁹ are tertiary butyl groups, R ^e and R ⁷ are methyl groups, R ⁵ and R ⁸ are hydrogen atoms, and A ¹ is sulfur Formula that is an atom (82)

Or R ⁴ and R ⁹ are tertiary butyl groups, R ⁵ and R ⁸ are methyl groups, R ^e and R ⁷ are hydrogen atoms, and A ^{1 is} CH _₂ - S-CH ₂ formula (8 3) which is an group

And the like represented by

Equation (4) shown in (2 e)

An example of the symbols described in ₍₎ is shown below ₍

In the formula (4) shown in (2e), an alkylene group having from 6 to 6 carbon atoms which may have 1 to 3 sulfur atoms and / or heteroatoms of oxygen atoms in the chain of A ² Can be selected from the same groups as A ′ in formula (3).

In the formula (4) shown in (2 e), 1 to 3 sulfur atoms and / or hetero atoms of an acid atom may be present in the chain of A ^2. The group can be selected from the same groups as A ¹ in formula (3).

In the formula (4) shown in (2 e), R ′ ° and R ¹⁵ can be selected from the same groups as R ¹ in the formula (2), and R ¹¹ and RH are the same as those in the formula (2). R ² can be selected from the same groups as R ^2, and R ¹² and R ¹³ can be selected from the same groups as R ³ in the formula (2).

An example of equation (4) shown in (2 e) is R ¹ . And R ¹⁵ is a tertiary butyl group, R ¹¹ and RH are methyl groups, R ¹² and R ¹³ are hydrogen atoms, and A ² is a sulfur atom.

Or R ^1G and R ¹⁵ are tert-butyl groups, R ¹¹ and R ¹⁴ are methyl groups, R ¹² and R ¹³ are hydrogen atoms, and A ² is methylene Formula (85) C (CH ₃ ) ₃

Or R ^{) e} and R ¹⁵ are tertiary butyl groups, R ¹¹ and R ¹⁴ are methyl groups, R ¹² and R ¹³ are hydrogen atoms, and A ² isー CH ₂ -S-CH ₂ —Formula (8 6)

And the like represented by <

In equation (9) shown in (2 j), m 1 is preferably 3.

M 2 in the formula (10) shown in (2 k) is preferably 6.

Equation (1 2) shown in (2m)

An example of the symbols described in is shown below.

R ¹⁶ , R ′ \ R ′ ⁸ , R ¹³ , R ² ° and R ²¹ shown in the formula (12) may be the same or different, and each may be a hydrogen atom, a linear or Examples thereof include a linear alkyl group having 1 to 8 carbon atoms, an aryl group having 6 to 10 carbon atoms, and a cycloalkyl group having 3 to 3 carbon atoms.

For example, hydrogen atom, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, secondary butyl group, tertiary butyl group, n-pentyl group, isopentyl group, secondary Pentyl group, tertiary pentyl group, 2-methylbutyl group, n-hexyl group, isohexyl group, secondary hexyl group, tertiary hexyl group, heptyl group, n-octyl group, isooctyl group, Examples include a secondary octyl group, a tertiary octyl group, a 2-ethylhexyl group, a phenyl group, and a cyclohexyl group. Preferably, there are 1 to 5 alkyl groups which may be linear or branched. For example, a methyl group, an ethyl group, an n-pi π-pi-gemetic group, an isopropyl group, an n-pepti-gemetic group, an isobutyl group, a secondary butyl group, a tert-butyl group, an n-pentyl group, an isopentyl group, a second Examples include a graded pentyl group, a 3rd pentyl / le group, a 2-methylbutyl group, and a hydrogen atom.

More preferred are a hydrogen atom, a methyl group and a tertiary butyl group, of which a hydrogen atom is particularly preferred.

In the formula (12) shown in (2m), an alkylene group having 1 to 6 carbon atoms which may have 1 to 3 hetero atoms of sulfur and / or oxygen atoms in the chain of A ³ Can be selected from the same groups as A ¹ in formula (3).

In the formula (1 2) shown in (2m), Arukiride of A ³ of 1 in the chain of three carbon atoms, which may be interposed heteroatoms of sulfur Contact preliminary or an oxygen atom 2-5 down The group can be selected from the same groups as A ¹ in formula (3).

R ^1S, R ¹⁷ of formula (1 2) are shown in ^{(2m), R 18, R} '9, 1¾ 2. Formula (87) in which ¾ 1 ¾ ² ′ is a hydrogen atom and A ³ is a sulfur atom

Group represented by ^{^{or,, R ie, R 17,}} R 18, R 19, R 2. And R ²¹ is a hydrogen atom, and A ³ is a dimethylmethylene group.

Or a group represented by the formula (89), wherein R ¹⁶ , R ^] R ¹⁸ , R ′ \ R ²⁰ and R ²¹ are hydrogen atoms and A ³ is an oxygen atom

And the like represented by <

Equation (1 3) shown in (2 n)

For the symbols described in, one example is shown below. C In the formula (13), as R ²² , R ²³ , R ² \ R ²⁵ , R ²⁶ and R ²⁷ , the formula (1 2) The group can be selected from the same groups as those described in R ¹⁶ , R ¹⁷ , R ′ ⁸ , R ″, R ² ° and R ² ′.

In the formula (1 3) shown in (2 n), A ⁴ of the 1 in the chain 3 sulfur atoms Contact Yobino or oxygen atoms hetero atom may be interposed into the coal稟数1-6 The alkylene group of can be selected from the same groups as A ¹ in the formula (3).

In the formula (1 3) shown in (2 n), of 1 to 3 to縝中of A ⁴ sulfur atoms Contact and / or to the oxygen atom hetero atom and which may number from 2 to 5 carbon intervening The alkylidene group can be selected from the same groups as A 'in formula (3).

In the formula (90), R ²² , R ²³ , R ", R ^2S , R ²⁶ and R ^{27 in} the formula (13) shown in (2 n) are a hydrogen atom, and A ⁴ is a sulfur atom.

Or a group represented by the formula (91), wherein R ²² , R ²³ , R ²⁴ , R ²⁵ , R ²⁶ and R ²⁷ are hydrogen atoms and A ⁴ is a dimethylmethylene group

Or a group represented by the formula (92), wherein R ²² , R ²³ , R ²⁴ , R ²⁵ , R ²⁶ and R ²⁷ are hydrogen atoms and A ⁴ is an oxygen atom

And the like.

As the straight-chain or branched-chain alkanetrityl group having 2 to 6 carbon atoms of Rz shown in (3a), ethanetriyl group, propanetriyl geometry group, butanetriyl group, pentanetriyl group And hexanetriyl groups.

Equation (1 4) shown in (3b)

An example of the symbols described in is shown below.

In the formula (14) shown in (3b), R ²⁸ can be selected from the same groups as R, in the formula (2), and R ²⁹ is the same as R ² in the formula (2). The group can be selected from R ³ . Can be selected from the same groups as R ³ in formula (2). In addition, 3 is preferably 1. In particular, R ²⁸ is a tertiary butyl group, R ²⁹ is a methyl group, R ³ . Is preferably a hydrogen atom, and m 3 is preferably 1.

Equation (15) shown in (3c)

An example of the symbols described in is shown below.

In the formula (15) shown in (3c), R ³¹ can be selected from the same group as R ′ in the formula (2), and R ³² is the same as R ² in the formula (2). R ³³ can be selected from the same groups as R ³ in formula (2). Also, m 4 is preferably 1. In particular, it is preferable that R ³¹ is a tertiary butyl group, R ³² and R ³³ are methyl groups, and m 4 is 1. Equation (16) shown in (3d)

An example of the symbols described in is shown below.

M 5 in the formula (16) shown in (3d) is preferably 2.

Examples of the straight-chain or branched-chain alkyne-tetrayl group having 2 to 6 carbon atoms of Rz shown in (4a) include an ethanetetrayl group, a propanetetrayl group, a butanetetriyl group, and a pentanetetrayl group. And hexantetri groups. Among them, equation (26)

The group represented by is particularly preferred.

As the linear or branched alkane monopentyl group having 2 to 6 carbon atoms of Rz shown in (5a), propane pentile group, butanepentile group, pentanepentile group, hexanepentene tile And the like.

The linear or branched alkenyl hexyl group having 2 to 6 carbon atoms of R z shown in (6a) includes a propanehexyl group, a butanehexyl group, and a pentanehexyl group. And hexane hexyl groups. Therefore, specific examples of the compound of the present invention represented by the formula (1) are shown below, but the present invention is not limited thereto.

As an example of a preferable compound as a raw material of the compound of the present invention, formulas (93) to (123)

0— (CH ₂ ) ₁₇ -CH: (93)

(96)

6 e

6) H OH

l89I0 / .6df / XD ue OAV 0 9

01) OH

01)

I89I0 / i6dI / 13d 0KPf / L6 OAV I 9

I89l0 / i6df / X3d 0 PP / L6 ΟΛλ Z 9

I89l0 / .6df / X3c [Oie 6 OAV 9

CO o

\ mo / L6dr / iDd QIZPVIL6 OAV f 9

I89I0 / i6cIf / XDd 01 Time 6 OAV

(Where R is

One CH ₂ CH ₂ O

Is shown. )

(122)

(one two Three)

(In each formula, R ^b is a methyl group or a tertiary butyl group.), But is not limited thereto. Many of these compounds are used as stabilizers for organic polymer materials. Other compounds can be produced by known methods.

The compound of the present invention includes, for example, a hydroxyl group of the compound represented by the formula (93) to the formula (123).

HO- is calculated, for example, by the equation (1 24)

R ^a

('In the formula, Ra is ^a tertiary butyl group, a methyl group, or a hydrogen atom.) Or Formula (125)

Wherein ^Ra is a tertiary butyl group, a methyl group, or a hydrogen atom, which may be the same or different, and is a compound substituted by a group represented by the following formula: )-Expression (1 5 6)

CH ₂ CH ₂ C0- (CH ₂ ) ₁₇ -CH ₃ (126)

OCH2CH (127)

0CH ₂ CH S (128)

(129)

3) 0 L

CO CO

n

T89l0 / Z, 6df / X3d 01 Hi Wum 6 OAV IL

CO

I89I0 / .6 <If / 13d 0 \ £ PPfL6 OAV

L

lS9lO / L6d £ HDd QUPPIL6 OAV SI

l89I0 / L6df / XDd 9 L

(6H) OH

189 Otori 6di710d QKPP / L6 OAV

O 97/44310

(Where R is

HO OCH ₂ CH ₂

Is shown. )

(155)

C (156)

Wherein R ^a is a tertiary butyl group, a methyl group, or a hydrogen atom, which may be the same or different, and R ^b is a methyl group or a tertiary butyl group. And the compounds of S1 to S10. Equation (1)

H- (L ² ) b- (L ¹ ) _a- (L) _x- (0) P Rz

n

(The symbols in the formula have the same meanings as in formula (1).) First, a method for producing the compound of the present invention when b is 0 will be described.

(Expression U5 7)

(The symbols in the formula are synonymous with formula (1).) A phenol compound represented by formula (1 58)

H- teeth ¹ -丫

(In the formula, Y represents a halogen atom, and other symbols are as defined in the formula (2).)

(In the formula, Y represents a halogen atom, R ¹ represents an alkyl group having 1 to 8 carbon atoms, R ² and R ³ may be the same or different, and each represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms. Is reacted in the presence of a basic substance, usually in an inert solvent such as toluene, to obtain a compound of the formula (159)

H— L ^1- (L) _x- (0) p Rz

(The symbols in the formula are synonymous with formula (1).) The compound of the present invention represented by the formula (1) can be produced. Or the above equation (1 5 7)

(The symbols in the formula are synonymous with formula (1).) A phenol compound represented by formula (16)

H— L ¹ -OH

(Wherein each symbol has the same meaning as in formula (2).)

(Wherein R ′ represents an alkyl group having from 8 to 8 carbon atoms, and R ² and R ³ may be the same or different and each represent a hydrogen atom or an alkyl group having from 1 to 8 carbon atoms.) The reaction can also be carried out in the presence of an acid anhydride such as trifluoroacetic anhydride or acetic anhydride, usually in an inert solvent such as toluene.

H—L ¹ — (L) _x- (〇) _p -Rz

n

(Each symbol in the formula has the same meaning as in formula (1).) The compound of the present invention represented by the formula (1) can be produced. When n is 2 or more, the above equation (1 5 7)

H— (one (O) p Rz

n

(The symbols in the formula are synonymous with formula (1).) And a phenolic compound represented by formula (158) H—L ¹ -Y

In the formula, Y represents a halogen atom, R ¹ represents an alkyl group having 1 to 8 carbon atoms, R ² and R ³ may be the same or different, and are each a hydrogen atom or an alkyl group having 1 to 8 carbon atoms. Is shown. ) In the presence of a basic substance, usually in an inert solvent such as toluene, to obtain the formula (161)

Η 一 I 1

(Wherein, m is an integer of 1 or more and less than n, and each of the other symbols has the same meaning as in formula (1).) A compound represented by the formula (1) is produced.

(Wherein, m is an integer of 1 or more and less than n, and other symbols are as defined in the formula (1)).

H 1— 'Y

(The symbols in the formula are synonymous with formula (1).) The compound of the present invention represented by the formula (1) can be produced.

If n is 2 or more, the formula (1 5 7)

H— L ¹ -OH

(Wherein the symbols have the same meanings as in formula (2).)

(Wherein, R ′ represents an alkyl group having 1 to 8 carbon atoms, and R ² and R ³ may be the same or different and each represent a hydrogen atom or an alkyl group having 1 to 8 carbon atoms.) The reaction is usually carried out in an inert solvent such as toluene in the presence of an acid anhydride such as trifluoroacetic acetic anhydride or acetic anhydride to obtain a compound of the formula (161)

H— L ¹ — (L

(Wherein m is an integer of 1 or more and less than n, and other symbols are as defined in the formula (1).) And a compound represented by the formula (160)

H— L ¹ ~ OH (Wherein the symbols have the same meanings as in formula (2).)

(Wherein, R ¹ represents an alkyl group having 1 to 8 carbon atoms, and R ² and R ³ may be the same or different and each represent a hydrogen atom or an alkyl group having 1 to 8 carbon atoms.) The reaction is usually carried out in an inert solvent such as toluene in the presence of an acid anhydride such as trifluoroacetic anhydride or acetic anhydride to obtain the formula (159)

(The symbols in the formula are synonymous with formula (1).) The compound of the present invention represented by the formula (1) can be produced. Furthermore, when n is 2 or more, the expression (1 57)

H— L ¹ -OH

(Wherein each symbol has the same meaning as in formula (2)), and the compound represented by the formula (2) is usually dissolved in an inert solvent such as toluene in the presence of an acid anhydride such as trifluoroacetic anhydride or acetic anhydride. By reacting, the formula (16 1)

H-1-1 (L

(Wherein m is an integer of 1 or more and less than n, and each of the other symbols is as defined in formula (1)).

And the equation (1 5 8)

H— L ¹ ~ Y

(Wherein Y represents a halogen atom, and other symbols have the same meanings as in formula (2)). A compound represented by the following formula: Equation (1 5 9)

H—L, one (L) _x- (0) _p † ^ ~ Rz

(Wherein each symbol has the same meaning as in formula (1)).

(The symbols in the formula are synonymous with formula (1).) A phenolic compound represented by formula (15) H—L ¹ —Y

(Wherein, Y represents a halogen atom, and other symbols have the same meanings as in formula (2).) The compound represented by the formula (I) is reacted in the presence of a basic substance, usually in an inert solvent such as toluene. By letting

Equation (1 6 1)

HL ^1- (L) _x- (0) _p -Rz- (0) _p- (L) _X -H

n-m m

(Wherein, m is an integer of 1 or more and less than n, and each of the other symbols has the same meaning as in formula (1)).

H- / X (〇) P Rz- nm (0) _p — (L) _x -H m

And the equation (1 6 0)

H— L ^{1 —} OH (Wherein each symbol has the same meaning as in formula (2)), and the compound represented by the formula (2) is usually dissolved in an inert solvent such as toluene in the presence of an acid anhydride such as trifluoroacetic anhydride or acetic anhydride. By reacting, the formula (15 9)

HL ^1- (L) _x- (0), p Rz

n

(Wherein each symbol has the same meaning as in formula (1)). The compound of the present invention represented by the formula (1) can also be produced. Next, a method for producing the compound of the present invention in the case of our own will be described.

The manufacturing method is shown above, Equation (15 9)

(The symbols in the formula are synonymous with formula (1).) And a phenolic compound represented by formula (158)

H Y

(In the formula, Y represents a halogen atom, R ¹ represents an alkyl group having 1 to 8 carbon atoms, R ² and R ³ may be the same or different, and each represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms. Is reacted in the presence of a basic substance, usually in an inert solvent such as toluene, to obtain a compound of the formula (162)

Η— L ² — L ¹ (L) _x (〇) 'P ■ Rz

n (The symbols in the formula are synonymous with formula (1).) The compound of the present invention represented by the formula (1) can be produced. Also, the equation (1 5 9)

(The symbols in the formula have the same meanings as in formula (1).)

(1 60)

H _ | 1- OH

(The symbol in the formula is the same as in formula (2).) The compound represented by the formula is usually reacted in the presence of an acid anhydride such as trifluoroacetic anhydride or acetic anhydride in an inert solvent such as toluene. Equation (1 62)

H- L ² - tooth ¹ one _{(L) x - (0)} p ■ Rz

n

Can be produced.

When n is 2 or more, the expression (163) is the same as described in the case where b is 0.

H —- IL 2_. 1— (L) _x- (0) p Rz- (O)

nm p one cog ¹ - H m

(The symbols in the formula are synonymous with formula (I61).) The compound of the present invention can also be produced via a compound represented by formula (I61). Is not limited to this for the above process, in _c here shows one example of the formula (1) method for producing some of the compounds selected from the compound of the present invention represented by the more specific An example is shown below. Other compounds can be produced in a similar manner. In addition, the method for producing the compounds shown below is not limited thereto. Equation (1 6 4)

(In the formula, n represents an integer of 1 to 6, R c represents a group selected from R z shown in the formula (1), R ′ represents an alkyl group having 1 to 8 carbon atoms, and R ^{2 represents} And R ³ may be the same or different and each represent a hydrogen atom or an alkyl group having 1 to 8 carbon atoms.) And the formula (165)

(In the formula, A ′ is an alkylene group having 1 to 6 carbon atoms which may have 1 to 3 sulfur atoms and a hetero atom of a hydrogen atom or an oxygen atom in the chain, 1 to 3 sulfur atoms and Or a heteroatom of oxygen or oxygen, and may be an alkylidene group having 2 to 5 carbon atoms, an oxygen atom, a sulfur atom, a sulfinyl group (—SO—) or a sulfonyl group.

(- S0 ₂ -) indicates, R ⁴ and R ⁹ may be the same or different, their respective an alkyl group having 1 to 8 carbon ^{^{atoms, R 5, R 6, R}} 7 and R ⁸ are the same Or may be different and each represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms. ), Formula (1 6 6)

(In the formula, A ² is an alkylene group having 1 to 6 carbon atoms which may have 1 to 3 sulfur atoms and a hetero atom of a hydrogen atom or an oxygen atom in the chain, 1 to 3 sulfur atoms and A C 2-5 alkylidene group, oxygen atom, sulfur atom, sulfinyl group (one SO—) or sulfonyl group which may have a hetero atom Z or oxygen atom

(An S0 ₂ -) indicates, R ^ie and R ¹⁵ may be the same or different, their respective an alkyl group having 1 to 8 carbon ^{^{atoms, R 11 R '2, R}} ' 3 and R ¹⁴ They may be the same or different and each represent a hydrogen atom or an alkyl group having 1 to 8 carbon atoms. ) Or formula (1 67)

(Wherein, A ⁵ represents an isocyanuric group or 1,3,5-trinotylphenyl 2,4,6-tolyl group, R ²⁸ represents an alkyl group having 1 to 8 carbon atoms, R ^2S and R ³ May be the same or different, each represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, and m 3 represents an integer of 1 to 3.) and a compound represented by the formula:

(Wherein, Y represents a halogen atom such as chlorine, bromine or iodine, R ^la represents an alkyl group having 1 to 8 carbon atoms, and R ^3a may be the same or different. An alkyl group of 1 to 8) is reacted with a compound represented by the formula (1669) in the presence of a basic substance, usually in an inert solvent such as toluene.

(The symbols in the formula are equivalent to formula (164) or formula (168).), Formula (170)

(The symbols in the formula are synonymous with formula (165) or formula (168).), Formula (177)

(The symbols in the formula are synonymous with formula (166) or formula (168).)

(1 72)

(The symbols in the formula have the same meanings as in formula (167) or formula (168).) The compound of the present invention represented by the formula can be produced. Equation (1 68)

('The symbols in the formula are the same as in formula (168).) Instead of reacting the compound represented by formula (16) in the presence of a basic substance, usually in an inert solvent such as toluene, 3)

(Wherein the symbols have the same meanings as in formula (168).) The compound represented by the formula (1) is usually prepared in the presence of an anhydride such as trifluoroacetic anhydride or acetic anhydride in an inert solvent such as toluene. It can also be produced by reacting. If n is 2 or more,

(Wherein, n represents an integer of 2 to 6, R c represents a group selected from R z as shown in Equation (1), R ¹ represents an alkyl group having 1 to 8 carbon atoms, R ² And R ³ may be the same or different and each represent a hydrogen atom or an alkyl group having 1 to 8 carbon atoms.) And the formula (165)

(In the formula, A ¹ is an alkylene group having 1 to 6 carbon atoms which may have 1 to 3 sulfur atoms and a hetero atom of Z or oxygen atom in the chain, 1 to 3 sulfur atoms and A C 2 -C 5 alkylidene group, oxygen atom, sulfur atom, sulfinyl group (— SO—) or sulfonyl group which may have a hetero atom or a hetero atom of an oxygen atom

(An S0 ₂ -) indicates, R ⁴ and R ⁹ may be the same or different, their respective an alkyl group having 1 to 8 carbon ^{^{atoms, R 5, R 6, R}} 7 and R ⁸ are the same Or may be different and each represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms. ), Formula (1 6 6)

(In the formula, A ² is an alkylene group having 1 to 6 carbon atoms which may have 1 to 3 sulfur atoms and a hetero atom of Z or oxygen atom in the chain, 1 to 3 sulfur atoms and Z or an alkylene group having 2 to 5 carbon atoms which may have a hetero atom of oxygen or oxygen atom, oxygen atom, sulfur atom, sulfinyl group (—SO—) or sulfonyl group

(An S0 ₂ ^-)! Indicates, and R ¹⁵ may be the same or different, their respective an alkyl group having 1 to 8 carbon ^{^{atoms, R '1 R 12, R}} 3 and R ¹⁴ are the same also May be different and each represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms. ) Or formula (1 67)

(Wherein, A ⁵ represents an isocyanuric group or 1,3,5-trimethylphenyl 2,4,6-tolyl group, R ²⁸ represents an alkyl group having 1 to 8 carbon atoms, R ²⁹ and R ³ May be the same or different, each represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, and m 3 represents an integer of 1 to 3.) and a compound represented by the formula (1688)

(Wherein, Y represents a halogen atom such as chlorine, bromine, iodine, etc., R ^la represents an alkyl group having 1 to 8 carbon atoms, and R ^2a and R ^3a may be the same or different, and are each a hydrogen atom or a carbon atom. The compound represented by the formula (174) is reacted with a compound represented by the formula (1) in the presence of a basic substance, usually in an inert solvent such as toluene.

HO

(In the formula, n represents an integer of 2 to 6, m represents an integer of 1 or more and less than n, Rc represents a group selected from Rz shown in formula (1), and each other symbol is Synonymous with equation (1), equation (164), or equation (168).), Equation (175)

(The symbols in the formula are equivalent to formula (1), formula (165), or formula (168).) Formula (Ί76)

(The symbol in the formula is synonymous with formula (1), formula (166), or formula (168).) Or formula (177)

(Wherein P represents 1 or 2, and the other symbols have the same meanings as in formula (1), formula (167), or formula (168).) And a compound represented by the above formula (174), formula (175), formula (176) or formula (177), and a compound represented by formula (168)

(Wherein, Y represents a halogen atom such as chlorine, bromine or iodine, R ^LA represents an alkyl group having 18 carbon atoms, and R ^2A and R ^3A may be the same or different. Each represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms. ) Is reacted with a compound represented by the formula (169) in the presence of a basic substance, usually in an inert solvent such as toluene.

(In the formula, n represents an integer of 2 to 6, R c represents a group selected from R z shown in the formula (1), and each other symbol represents a formula (1) or a formula (164) , Or synonymous with equation (1 68)) equation (1 70)

(The symbols in the formula are synonymous with formula (1), formula (165), or formula (168).), Formula (17 1)

(The symbols in the formula are equivalent to formula (1), formula (166), or formula (168).) Or formula (172)

(The symbols in the formula are synonymous with formula (1), formula (167), or formula (168).) This invention compound represented by this can be manufactured. As shown above, the equation (1 6 8)

(The symbols in the formula have the same meanings as in formula (168).) Instead of reacting the compound represented by the formula (167) in the presence of a basic substance, usually in an inert solvent such as toluene,

(The symbols in the formula are the same as defined in formula (168).) The compound represented by the formula (1) is usually prepared in the presence of an acid anhydride such as trifluoroacetic anhydride or acetic anhydride in an inert solvent such as toluene. It can also be produced by reacting.

The compound in which b is 1 can be produced by the same method. Further, the present invention provides an organic polymer material containing the compound represented by the formula (1) and an organic polymer.

Examples of the organic polymer include a synthetic organic polymer and a natural organic polymer.

Examples of the synthetic organic polymer include a thermoplastic resin and a thermosetting resin. The following are examples of the thermoplastic resin.

Low density polyethylene, linear 状 high density polyethylene, medium density polyethylene, high density Polyolefins such as polyethylene, ultra-high molecular weight polyethylene, polypropylene, polybutene-1, polylipene, poly-3-methylbutylene, and other homopolymers of haloolefins having 2 to 8 carbon atoms;

Poly-α-olefin copolymers such as ethylene 'propylene random copolymer, ethylene' propylene block copolymer, ethylene-butene-11 random copolymer, and propylene 'ethylene.butene-1 random copolymer;

Polyolefins such as copolymers of polyolefins such as maleic anhydride-modified boropropylene and other monomers;

Halogen-containing polymers such as polyvinyl chloride, polyvinylidene chloride, polyvinyl fluoride, polyvinylidene fluoride, vinyl chloride alkyl acrylate copolymer, and chlorinated polyethylene;

Polystyrene, high-impact polystyrene, styrene-acrylonitrile copolymer, styrene-copolymer, ABS resin, AES resin, ACS resin, AAS resin,

Styrenic resins such as EES resins and mixtures thereof;

Acryl-based resins such as polyacrylate and polymethacrylate;

Thermoplastic polyesters such as polyethylene terephthalate and polybutylene terephthalate;

Nylon 4, Nylon 6, Nylon 4,6, Nylon 6,6, Nylon 6,10, Nylon 7, Nylon 8, Nylon 12, Nylon 6,12, Nylon 11,12, Alamide, and these Polyamides such as mixtures of:

Aromatic polycarbonate; Polyamide oxide: Polyethylene oxide; Polyphenylene ether; Polysulfone; Polyurethane; Petroleum resin: Polyvinyl acetate; Polyvinyl acetal: Cellulosic resin; Polyethersulfone: Polyphenylene sulfite; Ether ketone; polyetherimide; boroxybenzoyl; polyimid; bolimaleimide; boramidoimid; polyarylate; fluororesin ionomer; thermoplastic elastomer; and mixtures thereof may be used. it can.

Unsaturated polyester resin; phenol resin; urea resin Melamine resin; Epoxy resin: Polyimide resin; Silicone resin; Diaryl phthalate resin; Polyurethane resin; Furan resin.

Examples of the polyolefin include polystyrene, a mixture of polyethylene and polypropylene with another compatible polymer, an ethylene-vinyl acetate copolymer, an ethylene-propylene copolymer, and the like. After the polymerization, is the polyolefin subjected to a slight purification treatment including a step of removing the catalyst residue after polymerization, or a relatively highly purified one, as well as a catalyst that has undergone a catalyst removal step using a highly active catalyst? Or a polyolefin containing a catalyst residue obtained by simplification, in particular, a Ziegler-type catalyst or a chromium-based catalyst using a halogen-containing magnesium compound as a catalyst carrier, and has not yet undergone a catalyst residue removal step. It may be a crystalline polyolefin (see Japanese Patent Publication No. 62-4418, Japanese Patent Publication No. 3-56245, and US Pat. No. 4,115,639). Further, it may be a polyolefin having a very narrow molecular weight distribution obtained by a meta-mouthed single-site catalyst [Journab of Volima. Science "Bolimar" Chemistry "Edition (Journa 1 of Polymer Sci en c e. Polymer Chemistry Edition), Vol. 23, pp. 2151 (1985)]. Particularly when it is blended with an olefin resin, especially an α-olefin homopolymer or a cr-one-year olefin copolymer, it exhibits an excellent effect of preventing oxidative deterioration. Examples of the natural organic polymer include natural rubber, proteins, derivatives such as cellulose, mineral oil, animal and vegetable oils, waxes, oils and fats, and the like. Further, the compound of the present invention exhibits more excellent effects, particularly when used in combination with a sulfur-based antioxidant. That is, when the compound of the present invention and the sulfur-based antioxidant are used as stabilizers and contained in an organic polymer material, a composition containing an organic polymer material having more excellent stability can be obtained. The sulfur-based antioxidant is not particularly limited, but is preferably dilaurylthiodipropionate,

Lauryl stearyl thiodipropionate,

Jimi ristylthiodipropionate,

Distearyl thiodipropionate,

Ditridecylthiodipropionate,

Tetrakis [methylene (laurylthiopropionate)] methane,

Tetrakis [methylene (stearylthiopropionate)] methane, bis [2-methyl-4- (3-n-alkyl (C12-C14) thiopropionyloxy) -5-tert-butylphenyl] sulfide

And the like. One or more of these can be used. When the compound of the present invention is used as a stabilizer for an organic polymer, the compound of the present invention is preferably used in an amount of 0.01 to 10 parts by weight, more preferably 0.01 to 5 parts by weight, based on 100 parts by weight of the organic polymer. It is preferable to mix them in parts by weight. The proportion of the compound of the present invention is the same whether the compound of the present invention is used alone or in the case of using the compound of the present invention and a sulfur-based antioxidant in combination. Further, the sulfur-based antioxidant is preferably added in a proportion of 0.01 to 10 parts by weight, more preferably 0.01 to 5 parts by weight, based on 100 parts by weight of the organic polymer material. Is good. Further, by combining the stabilizer compound of the present invention with a phenol-based antioxidant, an organic material having excellent thermal stability can be obtained. As a phenolic antioxidant, 2,6-Gee tertiary butyl-4-methylphenol,

2, 4-monodimethyl 6-tertiary butyl phenol,

2,6-di-tertiary butyl-1-4-hydroxymethyl-phenol,

2, 6-G tertiary butyl 4-ethyl phenol,

2, 4, 6—tri-tertiary butyl phenol,

Butylated hydroxya tool,

n-octane decyl '3- (4-hydroxy 3,5-di-tert-butylphenyl) propionate,

Isooctyl · 3— (3,5-di-tert-butyl-4-hydroxyphenyl) propionate,

Distearyl-(4-hydroxy-1-3-methyl-5-tert-butyl) benzyl malonate,

Propyl gallate,

Octyl gallate,

Dodecyl gallate,

Tocopherol (vitamin E),

2,2'-Methylenebis (4-methyl-1-6-tert-butylphenol), 2,2'-Methylenebis (4-ethyl-6-tert-butylphenol), 4,4'-Methylenebis (2,6-di- Tertiary butyl phenol),

2, 2'butylidenebis (4-methyl-6-tert-butylphenol), 4,4'butylidenebis (3-methyl-6-tert-butylphenol), 2,2'-thiobis (4-methyl-1-6) —Tertiary butyl phenol),

4, 4'-thiobis (3-methyl-6-tertiary butyl phenol),

Styrenated phenol,

N, N * —Hexamethylenebis (3,5-di—tertiary butyl-4—hydroxy hydrocinamide),

Bis (3,5-di-tert-butyl-1-ethyl 4-hydroxybenzylphosphonate) calcium,

1,1,3-tris (2-methyl-4-hydroxy-5-tert-butylphenyl) butane,

1,3,5-trimethyl-2,4,6-tris (3,5-di-tert-butyl-4-hydroxybenzyl) benzene,

Tetrakis [3- (3,5-di-tert-butyl-4-hydroxy phenyl) pulpionyloxymethyl] methane,

1, 6-hexanediol-bis [3- (3,5-di-tertiary butyl-4-hydroxydiphenyl) propionate],

2, 2'-methylenebis (4-methyl-6-cyclohexylphenol),

2, 2'-methylenebis [6- (1-methylcyclohexyl) -14-methylphenol],

1,3,5-tris (4-I-tert-butyl-3, hydroxy-2,6-dimethylbenzyl) isocyanuric acid,

1,3,5-tris (3,5-di-tert-butyl-4-hydroxybenzyl) isocyanuric acid,

Triethylene glycol monobis [3- (3-tertiary butyl-4-hydroxy-1-5-methylphenyl) propionate],

Ethylene glycol-bis (3,3-bis (3-tertiary 1-4-hydroxyphenyl) butylate),

2—Tertiary butyl— 6— (3—Tertiary butyl—5—Methyl—2-Hydroxybenzyl 4-Methylphenylacrylate,

2, 2'-oxamidobis [ethyl 3- (3,5-di-tert-butyl-4 -hydroxyphenyl) propionate],

6— (4-Hydroxy 3,5-di-tertiary butyl tertiary butyl) 1,2,4—Dioctylthio-1,3,5—triazine,

Bis [2-tert-butyl-4-methyl-6- (2-hydroxy-3-tert-butyl) Chill-5-methylbenzyl) phenyl] terephthalate,

3,9-bis [2- [3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionyloxy] 1,1,1-dimethylethyl] 1,2,4,8,10-tetraoxaspiro [5.5] Pendecane,

3,9-bis [2-[3- (3,5-di-tert-butyl-3-4-hydroxyphenyl) propionyloxy] -1-1,1-dimethylethyl] -1,2,4,8,10-tetraoxaspiro [5.5] Pendecane,

1,3,5—tris [3— (3,5-G tertiary butyl-4—hydroxyphenyl) propionyloxy] ethyl isocyanate,

2,2-thioethylene-bis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate],

2— [1— (2-Hydroxy 3,5-di-tert-pentylphenyl) ethyl] —4,6-di-tert-pentylphenyl atalylate,

2,4-dioctylthiomethyl-1-6-methylphenol

And the like, but are not limited to these. Preferred phenolic antioxidants include

2, 6-di-tertiary tert-butyl 4-methylphenol,

2, 6-G Tertiary butyl-4-ethyl phenol,

n-octadecyl 3- (4-hydroxy-3,5-di-tert-butylphenyl) propionate,

2,2'-methylenebis (4-methyl-6-tert-butylphenol), 2.2,1-methylenebis (4-ethyl-6-tert-butylphenol),

4, 4'-butylidenebis (3-methyl-6-tert-butylphenol), 4,4'-thiobis (3-methyl-6-tert-butylphenol),

1,1,3-tris (2-methyl-4-hydroxy-5-tert-butylphenyl) 1,3,5-trimethyl-2,4,6-tris (3,5-di-tert-butyl-

4-hydroxybenzyl) benzene,

Tetrakis [3- (3,5-di-tertiary butyl-4-hydroquinphenyl) butane pionyloxymethyl] methane,

1,3,5-tris (3,5-di-tert-butyl-4-hydroxybenzyl) isocyanuric acid,

Triethylene glycol monobis [3- (3-tertiary tert-butyl 4-hydroxy)

5-methylphenyl) propionate],

3,9-bis [2- [3- (3-tert-butyl-4-hydroxy-1-5-methylphenyl) propionyloxy]-—1-dimethylethyl] -1,2,4,8,10-tetraoxaspiro [ 5.5) Pendecane,

2,2-thioethylenebis [3- (3,5-di-tert-butyl-1-4-hydroxyphenyl) propionate,

2— [1- (2-Hydroxy-3,5-di-tert-pentylphenyl) ethyl]-4,6-di-tert-pentylphenyl acrylate

2, 4-dioctylthiomethyl-6-methyl-phenol

And so on. In the present invention, when one or more of these phenolic antioxidants are combined and used as a stabilizer for organic materials, the antioxidants are preferably used in an amount of 0.01 to 10 wt. Parts, more preferably 0.01 to 5 parts by weight. When used in combination, they may be added separately or as premixed ingredients. The compounding ratio is preferably in the range of 0.1 to 10 times the amount of the compound of the present invention. Further, the compounding amount of the sulfur-based antioxidant is preferably in the range of 0.1 to 10 parts by weight for 1 part by weight of the compound of the present invention. Further, in order to further improve the weather resistance of the organic polymer, an ultraviolet absorber, a light stabilizer and the like can be used together with the stabilizer compound of the present invention.

As these ultraviolet absorbers and light stabilizers,

X X

P—tertiary butyl phenol salicylate,

P—octylphenyl salicylate,

Salicylic acid compounds such as;

2,4-dihydroxybenzophenone,

2-hydroxy-1 4-methoxybenzophenone,

2,2'dihydroxy-1,4'-dimethoxybenzophenone,

2—Hydroxy 4-n-octyloxybenzophenone,

2—Hydroxy 4—Isooctyloxybenzophenone,

2—hydroxy 4—dodecylquinenzophenone,

2—Hydroxy-1 41-year-old Kutadecyloxybenzophenone,

2-Hydroxy 4-methoxy-carboquinobenzophenone, bis (5-benzoyl-4-hydroxy-1--2-methoxyphenyl) methane, 2-hydroxy-14-methoxy 5-sulfobenzophenone. Drain,

2,2,, 4,4'-tetrahydroxybenzophenone,

2—Hydroquinone 41-benzoyloxybenzophenone,

2-Hydroxy-1-41 (2-Hydroxy-3-Mechanochemical) Propoxy benzophenone,

Benzophenone-based compounds such as; 2- (2-hydroxy-5-methylphenyl) benzotriazole,

2- (2-hydroxy-1,3,5-di-tert-butylphenyl) benzotriazole,

2- (2-hydroxy-3-tert-butyl-5-methylphenyl) -1-5-cyclobutentriazole,

2- (2-Hydroxy-3,5-di-tert-butylphenyl) — 5-chlorobenzotriazole,

2— [2-hydroxy-1-5- (1,1,3,3-tetramethylbutyl) phenyl] benzotriabool,

2- [2-hydroxy-3,5-bis (α, α-dimethylbenzyl) phenyl] 1 2Η-benzotriazole,

Methyl '3 -— [3-tert-butyl-5- (2-hydroxybenzoyl-2-yl-4-ylhydroxyphenyl) propionate condensate with polyethylene glycol,

2- (2-Hydroxy-1,3,5-di-tert-amylphenyl) benzotriazole,

2,2-methylenebis [4- (1.1,3,3-tetramethylbutyl) -1-6-

(2Η-benzotriazole-1-yl) phenol],

2- (2-hydroxy-5-tert-octylphenyl) bembutriabul, 2- [2-hydroxy-13- (3,4,5,6-tetrahydrophthalimidomethyl) -1-5-methylphenyl] Benzotriazole

Benzotriazole compounds such as η-hexadecyl 3,5-di-tert-butyl-4-hydroxybenzoate, 2,4-di-tert-butylphenyl 3,5-di-thi Grade 4-tyl hydroxybenzoate

Benzoate compounds such as; -2-Cyaneau 3, 3-Diphenyl Relate,

Octyl 2—Cyanol 3, 3-Diphenylacrylate

Cyanoacrylate compounds such as;

2-ethylhexylamine nickel

Nickel dimethyldithiocarbamate,

{2,2 * -thiobis [4- (1,1,3,3-tetramethylbutyl) phenolate; I} 1-n-butylamine'nickel,

{2,2'-Thoobis [4-U, 1,33-tetramethylbutyl) phenolate]} Nickel

Nigger compounds such as bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate and bis (1-octyloxy-1,2,2,6,6-tetramethyl-4-piperidyl) cenox Kate,

Bis (1,2,2,6,6-pentymethyl-4-piperidyl) 1-2- (3,5-di-tert-butyl-4-hydroxybenzyl) -2-n-butylmalonate, tetrakis ( 2,2,6,6-tetramethyl-1-piperidyl) 1,1,3,4

Tetrakis (2,2,6,6-tetramethyl-4-piperidyl) 1,2,3,4-butanetetracarboxylate,

Bol {[6-(C 1, 3, 3-tetramethylbutyl) imino s-Triazine-1, 4-diyl] [(2, 2, 6, 6-Tetramethyl-1-piperidyl) imi Nox) hexamethylene [(2,2,6,6-tetramethyl-4-piperidyl) imino]),

Bol {(6-morpholino s-triazine-1,2,4-diyl) [(2, 2, 6, 6-Tetramethyl-4-piperidyl) imino] hexamethylene [(2,2,6,6-tetramethyl-4-piperidyl) imino]) (cyanuric chloride / tertiary octylamine / 1,6-bis (2,2,2) 6, 6-tetramethyl-1,4-biperidylamino) hexane condensate)

1-hydroxyethyl _ 2,2,6,6-tetramethyl-4-piberidinol / succinic acid condensate,

N, N 'monobis (3-aminopropyl) ethyldiamine Z2, monobis [N-butyl-1-N- (1,2,2,6,6-pentanemethyl-4-piperidyl) amino] — 6-chloro-1,3 , 5-triazine condensate

Piperidine compounds such as

And the like. Preferred compounds that can be used as UV absorbers and light stabilizers include

2—hydroxy 4-n—year-old xylosoxybenzophenone,

2- (2-hydroxy-5-methylphenyl) benzotriabool,

2- (2-Hydroxy 3-tert-butyl-1-5-methylphenyl) -1-5-Chlorobenzonitryl,

2- (2-hydroxy-3,5-di-tert-butylphenyl) -1-5-benzobenzotriazole,

Bis (2,2,6,6-tetramethyl-1-piperidyl) sebacate, poly {[6- (1,1,3,3-tetramethylbutyl) imino s-triazine-1,2,4-diyl] [(2,2,6,6-tetramethyl-1-piperidyl) imino] hexamethylene [(2,2,6,6-tetramethyl-4-piperidyl) imino: 1} (cyanuric chloride Z tertiary octylamine 1 , 6-bis (2,2,6,6-tetramethyl-1-piperidylamino) hexane condensate)

And the like. Further, the compound of the present invention may be used in combination with other phosphorus-based antioxidants.

Tris (2,2-tertiary butylphenyl) phosphite,

Tris (2,4-di-tert-butyl-6-methylphenyl) phosphite, tetrakis (2,4-di-tert-butylphenyl) -1,4,4'-biphenylene diphosphonite,

Tetrakis (2,4-di-tert-butyl-5-methylphenyl) -1,4,4'-biphenylenediphosphate,

Bis (2,4-di-tert-butylphenyl) pentaerythritol diphosphite,

Bis (2,6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphate,

2,2'-methylenebis (4,6-di-tert-butylphenyl) -1-ethylhexyl phosphite,

(2,4,6-tri-tert-butyl-phenyl) 1-2-butyl-2-ethyl-1,3-propanediol phosphite,

2,2 ', 2' 'Tri-tris (3,3', 5,5'-tetrabutyl tert-butyl-1,1,1'-biphenyl2,2 'gil) phosphite Stearyl resin, erythritol diphosphite,

1,1,3-tris (2-methyl-4-di-tridecyl phosphite-5-tertiary butylphenyl) butane

And the like. Preferred phosphorus antioxidants include:

Tris (2,4-di-tert-butylphenyl) phosphite,

Tris (2,4-di-tert-butyl-6-methylphenyl) phosphite, Tetrakis (2,4-di-tert-butylphenyl) — 4,4'-biphenylene diphosphonite,

Tetrakis (2,4-di-tert-butyl-5-methylphenyl) —4,4'-biphenylenediphosphite,

Bis (2,4-di-tert-butylphenyl) pentaerythritol diphospho-K

Bis (2,6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphite

And so on.

When the compound of the present invention is used as a stabilizer, if necessary, other additives that do not significantly impair the effect of the compound of the present invention, such as metal stone, heavy metal inactivating agent, and organic tin stabilizer Agent, epoxy compound, pigment, flame retardant, antistatic agent, lubricant, auxiliaries, neutralizer, nucleating agent, plasticizer, coloring agent, filler, foaming agent, etc. You can also. The method for blending the stabilizer with the organic polymer is not particularly limited, and includes a conventionally known method.For example, after mixing the organic polymer and the stabilizer, kneading, extruding, and the like are performed. And a method of processing. Example

Next, the present invention will be described more specifically with reference to examples, but the present invention is not limited thereto. Example 1

29.3 g of triethyleneglycolbis (3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionate)

And 2 8. lg 3 -— (3,5-di-tert-butyl-4-hydroxyphenyl) propionic acid

C (CH ₃ ) ₃ Q

II

HO '' ^ ~ CH ₂ CH ₂ -C-OH

C (CH ₃ ) ₃ was added to 100 g of toluene. The solution was cooled to 110, and 31.5 g of trifluoroacetic anhydride was added dropwise with stirring, and the mixture was reacted at room temperature for 48 hours. Then, it was washed with aqueous sodium carbonate and further washed with water. The toluene layer was濂過, after concentration under reduced pressure, and purified by silica gel column method, a white powder of melting point 8 8~9 4 ^e C was obtained. Elemental analysis, infrared spectroscopy, and nuclear magnetic resonance

(3- (3-tertiary butyl-4-1) (3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionyloxy) -1-methylphenyl) propionate

(Equation (2 7))

Was confirmed. The analysis results of the obtained compound are shown below. Elemental analysis results of the compound synthesized in Example 1

Theoretical value Actual measurement value

Carbon 73.73% 73.73%

Hydrogen 8.94% 8.97% Infrared spectroscopic analysis of the compound synthesized in Example 1 (KB r)

V QH: 3 64 0 cm " ¹

C = 0 1 75 5 cm " 1, 1 74 0 cm" 1 Example 1 Nuclear magnetic resonance analysis of the synthesized compounds (CDC 1 _3, p pm)

δ 1.27 (s, 18 H), 1.44 (s, 36 H), 1.94 (s, 6 H) 2.5 to 3.1 (m, 16 H), 3. 64 (s. 4 H), 3.68 (t, 4 H) 4.24 (t, 4 H), 5.09 (s, 2 H), 6.90 (s, 2 H), 7 0 3 (s, 2H), 7.07 (s, 4H) Example 2

l O g of 4, 4'-thiobis (3-methyl-6-tertiary butyl phenol)

And 20 g of 3— (3,5-di-tert-butyl—4-hydroxyphenyl) propionic acid -OH

Was added to 100 g of toluene. The solution was cooled to 0, 19 g of trifluoroacetic anhydride was added dropwise with stirring, and the mixture was reacted at room temperature for 48 hours. It was washed with sodium carbonate water and further with water. The toluene layer was filtered, concentrated under reduced pressure, and then purified by a silica gel column method to obtain a white powder having a melting point of 135 to 137 ° C.

Elemental analysis and nuclear magnetic resonance analysis showed that thiobis (2-methyl-4-1 (3- (3,5-di-tert-butylbutyl-4-hydroxyphenyl) propionyloxy) -propane-5-tert-butylphenyl) (formula (28))

Was confirmed. The analysis results of the obtained compound are shown below. Elemental analysis results of the compound synthesized in Example 2

Theoretical value Actual measurement value

Carbon 76.49% 76.35%

Hydrogen 8.94% 9.0 1% Nuclear magnetic resonance analysis results of the compound synthesized in Example 2 (CDC 13, p pm) δ 1.17 (s, 18 H), 1.37 (s, 36 H), 2.30 (s , 6 H) 2.8 to 3.1 (m, 8 H), 5.09 (s, 2 H), 6.77 (s, 2 H), 7.03 (s, 2 H), 7.06 (s, 4 H) Example 3

1 9. l g of 4,4'-butylidenebis (3-methyl-6-tert-butylphenol)

And 28. lg of 3- (3,5-di-tert-butyl-4-hydroxyhydroxy) propionic acid

C (CH ₃ ) ₃ was added to 100 g of toluene. The solution was cooled to 11 ° C., 37.9 g of trifluoroacetic anhydride was added dropwise with stirring, and the mixture was reacted at room temperature for 5 hours. After that, it was washed with sodium carbonate water and further washed with water. The toluene layer was filtered, concentrated under reduced pressure, and purified by a silica gel column method to obtain a white powder having a melting point of 73 to 76 ° C. <Elemental analysis, infrared spectroscopy, nuclear magnetic resonance 1-bis (2-methyl-4- (3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionyloxy) -1-5-tert-butylphenyl) butane (Formula (29))

Was confirmed. Elemental analysis of the compound The results of the analysis of the resulting compound was synthesized in _c Example 3 below

Theoretical value Actual measurement value

Carbon 79.76% 79.52%

Hydrogen 9.6 1% 9.72% Infrared spectroscopic analysis of the compound synthesized in Example 3 (KB r)

VO mHi: 3 6 4 Ocm " ¹

v: 1 7 6 Ocm ^-1

C = 0 Example 3 Nuclear magnetic resonance analysis of the synthesized compounds (CDC 1 _3, p pm)

(50.92 (t, 3 H), 1.23 (s, 18 Η), 1.

2Η), 1.4.3 (s, 36 6), 1.8 to 1.9 (m, 2Η), 2.20 (s, 6Η), 2.8 to 3.1 (m, 8Η) ), 4.18 (t, 1Η), 5.08 (s, 2Η), 6.65 (s, 2Η), 7.06 (s, 4Η), 7.14 ( s,

2Η) Example 4

10 g of 2,2'-methylenebis (4-methyl-6-tert-butylphenol)

And 25 g of 3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionic acid

C (CH ₃ ) ₃

Was added to 95 g of toluene. The solution is 0. After cooling to C, 24 g of trifluoroacetic anhydride was added dropwise with stirring, and the mixture was reacted at room temperature for 48 hours. It was washed with sodium carbonate water and further washed with water. The toluene layer was filtered, concentrated under reduced pressure, and purified by silica gel column method to obtain a white powder having a melting point of 71 to 80 ° C. Elemental analysis, infrared spectroscopy, and nuclear magnetic resonance analysis showed that methylenebis (2- (3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionyloxy) 1-3-tert-butyl 5-Methylphenyl) (Formula (30))

Was confirmed. Elemental analysis of the compound The results of the analysis of the resulting compound was synthesized in _c Example 4 below

Theoretical value Actual measurement value

Carbon 79.4 9% 79.6 9% Hydrogen 9.36% 9.44% Hydrogen infrared spectroscopy of the compound synthesized in Example 4 (KB r)

v P_Q: 1 75 5 cm " 1 Example 4 NMR analysis of the synthesized compounds (CDC 1 _3, p pm)

δ 1.25 (s, 18 H), 1.41 (s, 36 H), 2.25 (s, 6 H), 2.6 to 3.0 (m, 8 H), 3.60 (s, 2H), 5.05 (s, 2H), 6.71 (s, 2H), 7.00 (s, 4H), 7.07 (s, 2H) 2 H) Example 5

18.4 g of 2,2'-methylenebis (4-ethyl-6-tertiary butylphenol)

And 33.4 g of 3- (3,5-di-tert-butyl-1-4-hydroxyphenyl) propionic acid

C (CH ₃ ) ₃ was added to 100 g of hexane. The solution was cooled to 15 ° C., 31.5 g of trifluoroacetic anhydride was added dropwise with stirring, and the mixture was reacted at room temperature for 17 hours. It was washed with sodium carbonate water, and further washed with water. The hexane layer is filtered and concentrated. Purification by the Ricagel column method yielded a white powder with a melting point of 81-86 ° C. Elemental analysis, infrared spectroscopy, and nuclear magnetic resonance analysis showed that methylenebis (2- (3- (3,5-di-tert-butyl-4-hydroxyhydroxy) propionyloxy))

3-tert-butyl-5-ethylphenyl (Formula (31))

Was confirmed. The analysis results of the obtained compound are shown _below.c The elemental analysis results of the compound synthesized in Example 5

Theoretical value Actual measurement value

Carbon 79.67 7% 79.49%

9.54% hydrogen 9.54% Hydrogen infrared spectroscopic analysis of the compound synthesized in Example 5 (KB r)

V Q ..: 3 6 4 Ocm ' ¹

_{V ^ = Q: 1 7 5} 5 cm "1 Example 5 Nuclear magnetic resonance analysis of the synthesized compounds (CDC 1 _3, p pm)

δ 1.17 (t, 6H), 1.26 (s, 18H), 1.41 (s, 36H) 2.55 (q, 4H), 2.6-3 0 (m, 8 H), 3.63 (s, 2 H), 5.05 (s, 2H), 6.72 (s, 2H), 7.00 (s, 4 H) ,

7. 08 (s, 2H) Example 6

16.4 g of 3,5-tris (3-tert-butyl-4-hydroxy-5-methylbenzyl) isocyanurate

And 27.3 g of 3— (3,5-di-tert-butyl—4-hydroxyphenyl) propionic acid

CH ₃ ) ₃ o

II

ΗΟ-》 -CH ₂ CH ₂ -C-OH

/

C (CH ₃ ) ₃ was added to 100 g of toluene. The solution was cooled to 115 ° C, 32.5 g of trifluoroacetic anhydride was added dropwise with stirring, and the mixture was reacted at room temperature for 32 hours. It was washed with sodium carbonate water, and further washed with water. The toluene layer was filtered, concentrated under reduced pressure, and then purified by silica gel column method to obtain a white powder having a melting point of 1122 ° C. Elemental analysis, infrared spectroscopy, and nuclear magnetic resonance analysis revealed that 3,5-tris (3-tri-tert-butyl-4-1- (3- (3,5-di-tert-butyl) -4-hydroquinophenyl) Propionyloxy) 5-methylbenzyl) isocyanurate (Formula (32)) (3 2))

Was confirmed. Elemental analysis of the compound The results of the analysis of the resulting compound was synthesized in _c Example 6 below

Theoretical value Actual measurement value

Carbon 75.1 1% 74.776%

Hydrogen 8.6 3% 8.6 3%

2.92% 2.91% Infrared spectroscopic analysis of the compound synthesized in Example 6 (KB r)

OH: 3 6 4 5 cm 1

V o_g: 1 7 6 0 cm "1, 1 6 9 5 cm -1 NMR analysis of the compound synthesized in Example _{6 (CDC 1 3, p pm} )

5 1.25 (s, 27H), 1.44 (s, 54H), 1.93 (s, 9H)

1 9 2.8 to 3.1 (m, 12H), 4.95 (s, 6H), 5.08 (s, 3H), 7.06 (s, 6H), 7.22 ( s, 3H), 7.39 (s, 3H) Example 7

15 g of n-octadecyl 3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionate

And 10 g of 3- (3,5-di-tert-butyl-1-4-hydroxyphenyl) propionic acid

C (CH ₃ ) ₃ was added to 95 g of toluene. The solution was cooled to 0 "C, and 12 g of trifluoroacetic anhydride was added dropwise with stirring, and the mixture was reacted at room temperature for 48 hours. Thereafter, the mixture was washed with sodium carbonate water, and further washed with water. Was filtered, concentrated under reduced pressure, and purified by a silica gel column method to obtain an oily substance, which was analyzed by elemental analysis, infrared spectroscopy, and nuclear magnetic resonance analysis to obtain n-octadecyl 3- (3 -Tertiary butyl 4-(3-(3, 5-Gee tertiary butyl-4-hydroxyphenyl) propion-2-ioquinone) 1-5-methylphenyl) propionate (Formula (33))

C (CH ₃ ) ₃ CH ₃ Was confirmed. The analysis results of the obtained compound are shown below. Elemental analysis results of the compound synthesized in Example 7

Theoretical value Actual measurement value

Carbon 78.5 6% 78, 23

Hydrogen 10.7696 10.93% Infrared spectroscopic analysis of the compound synthesized in Example 7 (KB r)

0 „: 3 64 0 cm" ¹

: 1 76 0 cm- ', 1 74 Ocm -1 NMR analysis of the compound synthesized in Example _{7 (CDC 1 3, p pm} )

δ 0.88 (t, 3Η), 1.26 (s, 30Η), 1.27 (s, 9Η), 1.44 (s, 18Η), 1.5 to 1. 7 (m, 2Η), 1.94 (s, 3Η) 2.5 to 3.1 (m, 8Η), 4.06 (t, 2Η), 5.08 (s, 3,) 1Η), 6.90 (s, 1Η), 7.03 (s, 1Η), 7.06 (s, 2Η)

1 5. 1 g of tetrakis (methylene-3- (3-tertiary butyl-4-hydroxy-5-methylphenyl) propionate) methane

And 25. lg of 3— (3,5-di-tertiary tert-butyl 4-hydroxyxnil) propionic acid

CCCH ₃ ) ₃ was added to 100 g of toluene. The solution was —10. After cooling to C, 31.5 g of trifluoroacetic anhydride was added dropwise with stirring, followed by stirring at room temperature for 24 hours. Washed with sodium carbonate water and washed with water. After passing through the toluene layer and purifying, purification by a silica gel column gave a white powder having a melting point of 88 to 94. Elemental analysis, infrared spectroscopy, and nuclear magnetic resonance analysis showed that tetrakis (methylene-1- (3-tertiary-butyl--4-(3- (3,5-di-tertiary-butyl-4-hydroxydiphenyl)) Propionyloxy) 1-5-methylphenyl) propionate) Methane (Formula (34))

Was confirmed. The analysis results of the obtained compound are shown _below.c The elemental analysis results of the compound synthesized in Example 8

Theoretical value Actual measurement value

Carbon 75.53% 75.1 9%

Hydrogen 8.86% 8.87% Infrared spectroscopic analysis of the compound synthesized in Example 8 (KBr)

y Q „: 364 Ocm ^-1

v _{c = 0} : 1 750 cm " ¹ Nuclear magnetic resonance analysis of the compound synthesized in Example _{8 (CDC 1 3, p pm} ) 5 1. 2 7 (s, 3 6 H), 1. 4 3 (s, 7 2 H), 1. 9 4 (s, 12H), 2.59 to 3.04 (m, 32H), 4.10 (s, 8H), 5.08 (s, 4H), 6.90 (s, 4H), 7.02 (s, 4H), 7.06 (s, 8H)

5 g of 3,9-bis [2- (3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionyloxy) 1, 1 -dimethylethyl] 1, 2,8,10 -tetra Oxaspiro [5.5] pendecane

And 5 g of 3— (3,5—tertiary butyl-4-hydroxyphenyl) propionic acid

C (CH ₃ ) ₃₀

HO cH ₂ CH ₂ -C_OH

C (CH ₃ ) ₃ was added to 95 g of toluene. The solution was cooled to 0 ° C, 5 g of trifluoroacetic anhydride was added dropwise with stirring, and the mixture was reacted at room temperature for 48 hours. After that, it was washed with sodium carbonate water and further washed with water. The toluene layer was filtered, concentrated under reduced pressure, and then purified by a silica gel column method to obtain a white powder having a melting point of 82 to 88 ° C. Elemental analysis, infrared spectroscopy, and nuclear magnetic resonance analysis revealed that 3,9-bis [2- (3- (3--tert-butyl- 4-(3-(3,5-di-tertiary-butyl-4-) Hydroxyfeni L) Propionyloxy) 1-5-methylphenyl) propionyloxy) 1-dimethylethyl] 1,2,4,8,10-tetraoxaspiro [5.5] didecane (Formula (35))

Was confirmed. The analysis results of the obtained compound are shown _below.c The elemental analysis result of the compound synthesized in Example 9

Theoretical value Actual measurement value

Carbon 73.30% 73.10%

Hydrogen 8.95% 9.07% Infrared spectroscopic analysis of the compound synthesized in Example 9 (KB r)

V 3 6 4 0 cm-1

OH

V n c = -o 1 7 5 & cm "1 7 4 0 cm 1 1

Example 10

17.9 g of 4,4-thiobis (3-methyl-6-tert-butylphenol)

23.6 g of 3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionic acid

Was added to 100 g of toluene. The solution was cooled to an 1 o ^e c, under stirring, it was added dropwise 3 1. 5 g anhydride bets Rifuruoro acetic and reacted for 48 hours at room temperature. Then, after washing with sodium carbonate water, further washing with water was performed. The toluene layer was filtered, concentrated under reduced pressure, and purified by a silica gel column method to obtain a white powder having a melting point of 64 to 73 ° C. Elemental analysis, infrared spectroscopy, and nuclear magnetic resonance analysis revealed that thiobis (3-tert-butyl-4- (3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionyloxy) -propionyloxy) 1-6-methylphenyl ) (Equation (3 6))

Was confirmed. The analysis results of the obtained compound are shown below. Elemental analysis results of the compound synthesized in Example 10

Theoretical value Actual measurement value

75.5 1% 75.3 6%

Hydrogen 8.38% 8.49% Infrared spectroscopic analysis of the compound synthesized in Example 10 (KBr) OH: 35 2 Ocm ^-1

V r- 1 7 5 Ocm "

C = 0 Example 1 0 Nuclear magnetic resonance analysis of the synthesized compounds (CDC 1 _3, p pm)

δ 1.17 (s, 18 H), 1.41 (s, 18 H), 2.22 (s, 6 H) 2.30 (s, 6 H), 2.8 ~ 3.1 (m, 8H), 4.69 (s, 2H),

6.77 (s, 2H), 6.90 (s, 2H), 7.03 (s, 2H),

7.04 (s, 2H) Example 11 A

1 9. l g of 4,4'-butylidenebis (3-methyl-6-tertiary butylphenol)

And 13.9 g of 3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionic acid

C (CH ₃ ) ₃ 0 HO-CH ₂ CH ₂ -C-OH

No

C (CH ₃ ) ₃ was dissolved in 100 g of black form. The solution was cooled to 11 oc, 21 g of trifluoroacetic anhydride was added dropwise with stirring, and the mixture was reacted at room temperature for 5 hours. Then, it was washed with aqueous sodium carbonate and further washed with water. The filter layer is filtered and concentrated under reduced pressure. After that, the residue was purified by a silica gel column method and recrystallized from toluene to obtain white crystals having a melting point of 188 to 189 ° C. Elemental analysis, infrared spectroscopy, nuclear magnetic resonance analysis, and mass spectroscopy revealed that 2-tert-butyl-4- (1-1- (2-methyl-4-hydroxy-5-tert-butylphenyl) butyl) -5 —Methylphenyl 3-— (3,5-di-tert-butyl-4-hydroxyphenyl) probionate (Formula (178))

Was confirmed. The analysis results of the obtained compound are shown below. Example 11 Elemental analysis results of compound synthesized in 1A

Theoretical value Actual measurement value

80.3 1% 80.3%

Hydrogen 9.74% 9.84% Example 11 Infrared spectroscopic analysis of compound synthesized in 1A (KB r)

D: 3 6 4 0 cm " ¹ , 3 4 7 0 cm" ¹

: 1 7 3 5 cm " ¹ Example 1 1 B

16.1 g of 2-tert-butyl-4— (1- (2-methyl-4-hydroxy-1-5-tert-butylphenyl) butyl) -5-methylphenyl 3 -— (3,5-di- Tertiary butyl—4-hydroxyphenyl) Probionate

1 2

And 13.9 g of 3- (3,5-di-tert-butyl-4-hydroxyhydroxy) propionic acid

C (CH ₃ ) ₃

And were dissolved in 100 g of black form. The solution was cooled to -1 ° C, 21 g of trifluoroacetic anhydride was added dropwise with stirring, and the mixture was reacted at room temperature for 8 hours. Then, it was washed with aqueous sodium carbonate and further washed with water. The filter layer was filtered, concentrated under reduced pressure, and purified by silica gel column method to obtain white powder of 1,1-bis (2-methyl-41- (3- (3,5-di-tert-butyl- 4-Hydroxyphenyl) propionyloxy)-5-tert-butylphenyl) butane (Formula (29))

was gotten. Example 12 A

17 g of 2,2'-methylenebis (4-methyl-6-tert-butylphenol)

CH, and-, 13.9 g of 3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionic acid

C (CH ₃ ) _: O

HO〇〇- CH ₂ CH ₂ -C- OH

/

C (CH ₃ ) ₃

Was added to 100 g of toluene. The solution was cooled to 11 ° C., 21 g of trifluoroacetic anhydride was added dropwise with stirring, and the mixture was reacted at room temperature for 25 hours. It was washed with sodium carbonate water and further washed with water. The toluene layer was filtered, concentrated under reduced pressure, and then purified by a silica gel column method to obtain a white powder having a melting point of 75 to 80 ° C. Elemental analysis, infrared spectroscopy, nuclear magnetic resonance analysis, and mass spectroscopy revealed that 2-tert-butyl-4-methyl-6- (2-hydroxy-3-tert-butyl-5-methylbenzyl) phenyl 3- (3 , 5-Di-tert-butyl-4-hydroxyhydroxypropionate (Formula (179))

Was confirmed. Analysis results of the obtained compound are shown _below.c Elemental analysis result of the compound synthesized in Example 12A. Theoretical value Actual measurement value

7 9.94% 79.84%

Hydrogen 9.41% 9.49%

Example 12 Infrared spectroscopic analysis of the compound synthesized in 2A (KBr)

3 6 4 Ocm " ¹ , 3500 cm" ^]

OH

V c = o 17 4 0 cm " ¹ Example 1 2 B

15 g of 2-tert-butyl-4-methyl-6- (2-hydroquinone-3-tert-butyl-5-methylbenzyl) phenyl 3- (3,5-di-tert-butyl-4-monohydroxyphenyl) propionate

And 1.3.9 2 of 3— (3,5-di-tert-butyl 4-hydroxyphenyl) propionic acid

C (CH ₃ ) ₃ was added to 100 g of toluene. The solution was cooled to 11 ° C., 21 g of trifluoroacetic anhydride was added dropwise with stirring, and the mixture was allowed to react at room temperature for 10 hours. It was washed with sodium carbonate water and further washed with water. The toluene layer was filtered, concentrated under reduced pressure, and then purified by silica gel column method. As a result, white powder of methylenebis (2- (3— (3,5-di-tert-butyl-4-4-hydroxyphenyl) propionyloxy)) — 3— No. Tertiary butyl-5-methylphenyl) (Formula (30))

<Example 13 A

18.4 g of 2,2-methylenebis (4-ethyl-6-tertiary butylphenol)

And 16.7 g of 3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionic acid

C (CH ₃ ) ₃ was added to 100 g of toluene. The solution was cooled to 11 ° C., 21 g of trifluoroacetic anhydride was added dropwise with stirring, and the mixture was reacted at room temperature for 5 hours. It was washed with aqueous sodium carbonate and then with water. The toluene layer was filtered, concentrated under reduced pressure, and purified by a silica gel column method to obtain a white powder having a melting point of 59 to 65 ° C. By elemental analysis, infrared spectroscopy, nuclear magnetic resonance analysis, and mass spectrometry, 2-tert-butyl-4-ethyl-6- (2-hydroxy-3-tert-butyl-5-ethylbenzyl) phenyl 3- (3,5-di-tert-butyl-4-hydroxyphenyl) probionate (Formula (180))

Was confirmed. The analysis results of the obtained compound are shown below. Example 13 Elemental analysis results of compound synthesized in 3A

Theoretical value Actual measurement value

80.19% carbon 80.1.2%

Hydrogen 9.63% 9.8 1% Example 13 Infrared Spectroscopy Analysis of Compound Synthesized in 13A (KB r)

V QLI: 3640 cm " ¹ , 3500 cm" ¹

v: 1740 cm- ¹ Example 13 B

15.7 g of 2-tert-butyl-4-ethyl-1-6— (2-hydr CJxy3—tert-butyl-5-ethylbenzyl) phenyl 3- (3,5-di-tert-butyl1-4 -Hydroxyphenyl) Propionate

And 13.9 g of 3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionic acid

C (CH ₃ ) ₃ was added to 100 g of toluene. The solution was cooled to 11 ° C., 21 g of trifluoroacetic anhydride was added dropwise with stirring, and the mixture was reacted at room temperature for 8 hours. Washed with sodium carbonate water and then with water. The toluene layer was filtered, concentrated under reduced pressure, and then purified by a silica gel column method. As a result, methylenebis (2- (3- (3,5-di-tert-butyl-4-hydroxyhydroxy) propionyloxy) white powder was obtained. 3—Tertiary butyl 5-ethylethyl (formula (31))

It was obtained _£ Example 1 4 A

16.4 g of 1,3,5-tris (3-tert-butyl-4-hydroxy-5-methylbenzyl) isocyanurate C (CH ₃ ) ₃

And 13.9 lb of 3- (3,5-di-tert-butyl-4-hydroxoxyphenyl) propionic acid

C (CH ₃ ) ₃

Was added to 100 g of toluene. The solution was cooled to 11 ° C., 21 g of trifluoroacetic anhydride was added dropwise with stirring, and the mixture was reacted at room temperature for 28 hours. It was washed with sodium carbonate water and further washed with water. The toluene layer was filtered, concentrated under reduced pressure, and then purified by a silica gel column method to obtain a white powder having a melting point of 118 to 126. Elemental analysis, infrared spectroscopy, and nuclear magnetic resonance analysis revealed that 3-di- (3-tertiary butyl 4- (3- (3,5-di-tertiary butyl-4-hydroxyphenyl) propionyloxy)) — 5—Methylbenzyl) 1 5— (3—tert-butyl-4-hydroxy-5-methylbenzyl) isocyanurate (Formula (181))

Was confirmed. The analysis results of the obtained compound are shown _below.c Elemental analysis results of the compound synthesized in Example 14A.

Theoretical value Actual measurement value

73.9 6% 74.1 0%

Hydrogen 8.26% 8.56%

3.70% 3.58% Example 14 Infrared Spectroscopy Results of Compound Synthesized in 4A (KBr)

V 3 6 4 0 cm "3 5 2 0 cm-1

OH

V r- 1 76 Ocm " ¹ , 1 695 cm" ¹

c = o Example 1 4 B

11.4 ^ 1,3-di (3-tert-butyl-4-(3-(3,5-di_tert-butyl-4-hydroxydiphenyl) propionyloxy)-5-methylbenzyl ) — 5— (3-tert-butyl-4-hydroxy-5-methylbenzyl) isocyanurate

And 5.6 g of 3- (3,5-di-tert-butyl-4-hydroxyhydroxy) p-pionic acid

C (CH ₃ ) ₃ was added to 80 g of toluene. The solution was cooled to 110 ° C, 1 lg of trifluoroacetic anhydride was added dropwise with stirring, and the mixture was reacted at room temperature for 12 hours. It was washed with aqueous sodium carbonate and then with water. The toluene layer was filtered, concentrated under reduced pressure, and then purified by a silica gel column method. As a result, white powders of 1,3,5-tris (3-tertiary butyl 4 -— (3- (3,5-di- Tertiary butyl-4-hydroxyphenyl) propionyloxy-1-5-methylbenzyl) isocyanurate (Formula (32))

Was obtained <Example 15 A

10.1 g of tetrakis (methylene-3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionate) methane

And 8.4 g of 3- (3,5-di-tert-butyl-4-hydroxyphenyl) -p-pionic acid

C (CH ₃ ) ₃

Was added to 67 g of toluene. The solution was cooled to 110, 21 g of trifluoroacetic anhydride was added dropwise with stirring, and the mixture was stirred at room temperature for 24 hours. Washed with aqueous sodium carbonate and washed with water. Purification by a silica gel column method after concentration and concentration of the toluene layer yielded a white powder with a melting point of 76-83. By elemental analysis, infrared spectroscopy, and nuclear magnetic resonance analysis, bis (methylene-1- (3-tertiary butyl

(3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionyloxy) -1-5-methylphenyl) propionate) bis (methylene-1- (3-

Tertiary butyl-1-hydroquinone 5-methylphenyl) propionate Methane

(Equation (18 2))

Was confirmed. The analysis results of the obtained compound are shown below. <Element analysis result of compound synthesized in Example 15A

Theoretical value Actual measurement value

Carbon 7 4.5 6% 7 4.4 7%

Hydrogen 8.71% 8.70% Example 15 Infrared Spectroscopy Results of Compound Synthesized in 5A (KBr)

v Q_Q: 1 7 4 5 cm " ¹

Example 15 B

15.3 g of bis (methylene-1- (3-tertiary-butyl-4-1) (3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionyloxy) -1-5-methylphenyl ) Propionate) bis (methylene-1- (3-tert-butyl_4-hydroxy-5-methylphenyl) propionate) methane

And 5.6 g of 3- (3,5-di-tert-butyl-4-hydroxyhydroxy) -p-pionic acid

C (CH ₃ ) ₃ was added to 80 g of toluene. The solution was cooled to 110 ° C, 1 lg of trifluoroacetic anhydride was added dropwise with stirring, and the mixture was stirred at room temperature for 14 hours. Washed with aqueous sodium carbonate and water. The toluene layer was filtered, concentrated, and purified by a silica gel column method to obtain a white powder of tetrakis (methylene-3- (3—tertiary butyl-41- (3— (3,5-di-tertiary butyl— 4-hydroxyphenyl) propioni Roxy) 1-5-methylphenyl) propionate) Methane (Formula (34))

was gotten. Example 16 A

6, 3 g of 3,9-bis [2- (3- (3-tertiary butyl-4-hydroquinine-5-methylphenyl) propionyloxy) 1 1,1—dimethylethyl] 1,2,4,8 1 0—tetraoxaspiro [5.5] pendecane

And 2.4 g of 3- (3,5-di-tert-butyl-4-hydroxyphenyl) -p-pionic acid

C (CH ₃ ) ₃ was added to 5 O g of toluene. The solution was cooled to 0 ° C, 3.7 g of trifluoroacetic anhydride was added dropwise with stirring, and the mixture was reacted at room temperature for 18 hours. Then, it was washed with sodium carbonate water and further washed with water. The toluene layer was filtered, concentrated under reduced pressure, and then purified by silica gel column method to obtain a white powder having a melting point of 72 to 78. By elemental analysis, infrared spectroscopy, and nuclear magnetic resonance analysis, 3-[2-(3-(3-3rd Tert-butyl-4-1 (3- (3,5-di-tert-butyl-4-hydroquinphenyl) propionyloxy) -1-5-methylphenyl) propionyloxy) 1 1-dimethylethyl] — 9-1 [2-( 3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionyloxy) -1,1,1-dimethylethyl] -1,2,48, · 10-tetraoxaspiro [5.5] pentadecane (formula (1 8 3))

Was confirmed. The analysis results of the obtained compound are shown below. Example 16 Elemental analysis results of compound synthesized in 6A

Theoretical value Actual measurement value

Carbon 71.95% 72.0%

Hydrogen 8.87% 8.98% Example 16 Infrared Spectroscopy Results of Compound Synthesized in 16A (KB r)

0 _H : 3 6 4 0 cm ^-1 , 3 5 0 0 cm— ¹

v-: 1 7 3 5 cm " ¹ Example 16 B

5 g of 3 — [2 — (3-(3 — tertiary butyl 4 _ (3 — (3, 5 — g Tert-butyl-1-hydroxyphenyl) propionyloxy) -5-methylphenyl) propionyloxy) —1,1,1-dimethylethyl] 19— [2— (3— (3 tert-butyl-4-hydroxy—5 —Methylphenyl) propionyloquin) 1, 1 —Dimethylethyl] — 2,4,8,10—tetraoxaspiro [5.5] pentane

And 2.8 g of 3- (3,5-tert-butylhydroxyphenyl) propionic acid

C (CH ₃ ) ₃ was added to 50 g of toluene. The solution was cooled to 110, 4.2 g of trifluoroacetic anhydride was added dropwise with stirring, and the mixture was reacted at room temperature for 8 hours. After that, it was washed with sodium carbonate water and further washed with water. The toluene layer was filtered, concentrated under reduced pressure, and purified by a silica gel column method. As a result, white powdered 3,9-bis [2- (3- (3-tertiary tert-butyl-41- (3- (3,5-G) Tertiary butyl 4-hydroxyphenyl) propionyloxy) 1-5-methylphenyl) propionyloxy)-1, 1-dimethylethyl] 1, 2, 4, 8, 10-tetraoxaspiro [5.5] Pendecane (Formula (35))

H

was gotten. Experimental example 1

Polymerized by a slurry method using a Ziegler-Natta catalyst and having a limiting viscosity of 1.9 as measured in tetralin at 135 ° C and an atactic content of 98% Polypropylene powder 100% by weight Then, the compounds shown in Table 1 were blended into a part, and the mixture was sufficiently mixed by a mixer. The mixture was then melt-kneaded with an extruder having an LZD of 20 and a discharge diameter of 20 mm at a cylinder temperature of 230, and granulated. The obtained pellets were press-molded into a sheet of 23 (TC, 0.5 mm thick), and a test piece having a length of 5 Omnu and a width of 25 mm was cut out. The obtained test piece was subjected to a hot water resistance test. That is, put a test piece and 12 ml of distilled water in a stainless steel pressure-resistant container with a lid (inner diameter 38 mm, depth 55 mm), seal the container, and put the entire container in an oven at 140 ° C to deteriorate. The test piece was taken out every 24 hours, distilled water was replaced, the presence or absence of embrittlement was visually observed, and the time required for the test piece to become embrittled was taken as the life of the test piece, and the same blending test was performed. The average of the life of the three pieces was taken as the hot water resistance of the compound material.

Table 1 shows the results. table 1

In Table 1,

Compound A: manufactured by Ciba-Geigy Corporation, trade name "IRGANOX l10" Tetrakis [methylene-1- (3,5-di-tert-butyl-14-hydroxyphenyl) propionate] methane

Compound B: manufactured by Ciba Geigy Co., Ltd., trade name ΠRGANOX 1330 ”and 3,5-trimethyl-2,4,6-tris (3,5-di-tert-butyl-4-hydroxybenzyl) benzene As shown in Table 1, the compositions of the present invention containing the compounds of Examples 2 to 8 were prepared by adding a known phenolic antioxidant (compounds A and B) to 100 g of the resin component in the composition. It can be seen that the molar concentration of the hydroxyl group (hereinafter, referred to as phenol molar concentration) has extremely excellent hot water resistance as compared with the composition added to the same extent as the composition of the present invention. Further, from Table 1, the composition of the present invention was compared with a composition in which a known phenolic antioxidant (Compound A) was added so that the phenol molar concentration was twice that of the composition of the present invention. It turns out that it also has excellent hot water resistance. Efficacy test examples 1-6, Efficacy test comparative examples 1-2

The compounds listed in Table 2 were polymerized by a slurry method using a Ziegler-Natta catalyst, and the intrinsic viscosity measured in tetralin at 135 was 1.9, and the isotactic one was 98% polypropylene powder, and the compounds listed in Table 2 were added. After mixing and sufficiently mixing with a mixer, the mixture is melted and kneaded with an extruder with a cylinder temperature of 260, L / D = 28, and a discharge diameter of 20 mm, and this is extruded into strands and cut. An organic polymer material containing an antioxidant as a pellet was obtained.

0.1% by weight of calcium stearate was added to each of the above compositions. Experimental example 2

The pellets (organic polymer material containing an antioxidant) obtained in Efficacy Test Examples 1 to 6 and Efficacy Test Comparative Examples 1 and 2 were placed at 200 ° C by a vertical screw injection molding machine. A test piece having a thickness of 3 mm and a thickness of 90 mm × 50 mm was prepared.

The obtained test piece was subjected to a hot water test. The color change after immersing the test piece in boiling distilled water for a predetermined time (1300 hours) is measured according to JISK-7103 (Plastic yellowing degree and yellowing test method). The degree of yellowing (YI) was measured according to the method.

Table 2 shows the results. In Table 2, compound A is the same compound as described above. Table 2 Compounding compounds Compounding amount (% by weight) Yellowness Yellowness

(Before immersion) (After immersion for 1300 h) Efficacy Test Example 1 Compound of Example 2 0.1 1 9 42 Efficacy Test Example 2 Compound of Example 3 0.1 1 8 23 Efficacy Test Example 3 Example 5 Compound 0.1 1 9 1 9 Efficacy Test Example 4 Compound of Example 8 0.1 1 8 2 1 Efficacy Test Example 5 Compound of Example 2 0.1 1 7 30

Jimi ristylthiodipropionate 0.2

Efficacy Test Example 6 Compound of Example 3 0.1 1 8 1 8

Jimi ristylthiodipropionate 0.2

Efficacy Test Comparative Example 1 Compound A 0.1 1 9 62 Efficacy Test Comparative Example 2 Compound A 0.1

Jimi ristylthiodipropionate 0.2 1 8 77

From the results in Table 2, it is clear that the polypropylene molded article containing the phenol compound of the present invention does not deteriorate in coloring even when it is kept in hot water for a long time, and has excellent durability. That is, when the same amount of the commonly used antioxidants shown in Comparative Examples 1 and 2 was used, the yellowness changed by a factor of 3 and the color was extremely colored. It was confirmed that compositions 1 to 6 had little or no color change. Experiment 3

Example 11 The compounds synthesized in 1B, 12B, 13B, 14B, 15B and 16B also exhibited the effect of preventing oxidative deterioration.

Claims

The scope of the claims

1. Equation (1)

H- (L ² ) _b- (L ¹ ) a- (L

(Wherein the definition of each symbol ^ is as follows.) L, L ′ and L ² in the phenolic compound _c formula (1) represented by )

(Here, R ¹ represents an alkyl group having 1 to 8 carbon atoms, and R ² and R ³ may be the same or different and each represent a hydrogen atom or an alkyl group having 1 to 8 carbon atoms.) are shown, L ² - L ¹ is an acid atom of Fuwenokishi group carbonylation凡基and L ¹ of L ² form a bond by an ester bond, L 'one L is a carbonyl group of L ¹ L And the oxygen atom of the phenolic oxy group forms an anchor by an ester bond, L-10 represents a bond between the carbonyl group of L and the oxygen atom by an ester bond, a represents 1, and b represents Represents an integer of 0 or 1,

(l a): n represents 1, X represents 1, p represents 1, R z represents an alkyl group having 1 to 30 carbon atoms; or

(lb): n represents 1, X represents 1, p represents 1, Rz represents an alkenyl group having 2 to 30 carbon atoms;

(Id): n represents 1, X represents 1, p represents 1, and Rz represents an optionally substituted cycloalkyl group having 3 to 7 carbon atoms; or

(1e): n represents 1, X represents 1, p represents 1, and Rz is the number of carbon atoms which may have a substituent. May have up to 20 aralkyl groups or substituents Represents an aryl group having 6 to 20 carbon atoms; or

(2a): n represents 2, x represents 1, p represents 1, R z represents 1 to 10 sulfur atoms and Z or oxygen atom hetero atoms in the chain. Represents an alkylene group having 1 to 20 carbon atoms; or

(2b): n represents 2, X represents 1, p represents 1, and 1¾2 is a alkynylene group having 2 to 12 carbon atoms, an alkynylene group having 2 to 12 carbon atoms, or a substituent. Represents a cycloalkylene group having 3 to 60 carbon atoms which may have; or

(2c): n represents 2, X represents 1, p represents 1, and Rz represents an arylene group having 6 to 60 carbon atoms which may have a substituent.

(2 d): n represents 2, X represents 0, p represents 1, R z is a formula (3)

R ⁴ R ⁹

R ⁵ , R ⁶ R ⁷ R ⁸

(In the formula, A ′ is an alkylene group having 1 to 6 carbon atoms in which 1 to 3 sulfur atoms and / or a hetero atom of an oxygen atom may be interposed in the pestle, and 1 to 3 sulfur atoms in the chain. C2-5 alkylidene, oxygen, sulfur, sulfinyl (1-SO-) or sulfonyl, which may be interspersed with heteroatoms of atoms and / or oxygen

(- S_〇 ₂ -) indicates, R ⁴ and R ⁹ may be the same or different, their respective an alkyl group having 1 to 8 carbon ^{^{atoms, R 5, R 6, R}} 7 and R ⁸ are They may be the same or different and each represent a hydrogen atom or an alkyl group having 1 to 8 carbon atoms. ) Represents a group represented by; or

(2e): n indicates 2, x indicates 0, p indicates 1, and Rz is a formula (4)

(In the formula, A ² is an alkylene group having 1 to 6 carbon atoms which may have 1 to 3 sulfur atoms and / or a hetero atom of an oxygen atom in the chain, and 1 to 3 sulfur atoms in the chain. An alkylene group having 2 to 5 carbon atoms, an oxygen atom, a sulfur atom, a sulfinyl group (one SO—) or a sulfonyl group may be present even though a heteroatom of an atom and / or an oxygen atom is present.

(- S0 ₂ -) indicates, R ^lfl and R ¹⁵ may be the same or different, their respective an alkyl group having 1 to 8 carbon atoms, R ¹¹ R ^12, R ¹³ and RH are the same or They may be different and each represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms. ) Indicates a group represented by:

(2 f): n represents 2, X represents 1, p represents 1, and R z is the formula (5)

Represents a group represented by; or

(2g): n represents 2, X represents 1, p represents 1, Rz is the formula (6)

Represents a group represented by; or

(2h): n represents 2, X represents 1, p represents 1, R z is a formula (7)

CH Represents a group represented by; or

Represents a group represented by; or

(2 j): n indicates 2, X indicates 1, p indicates 0, and Rz is the equation (9)

—— 0- (CH ₂ CH ₂ 0) _m1 —

(In the formula, ml represents an integer of 1 to 4.) or (2k): n represents 2, X represents 1, p represents 0, and R z represents Formula (10) NH— (CH ₂ ) _m2 — NH

(Wherein, m2 represents an integer of 1 to 6.) or (21): n represents 2, X represents 1, p represents 0, and Rz represents Formula (11) NH-NH

Represents a group represented by; or

(2m): n indicates 2, x indicates 1, p indicates 1, and R z is a formula (1 2)

(Wherein A ³ is an alkylene group having 1 to 6 carbon atoms which may have 1 to 3 sulfur atoms and a hetero atom of Z or oxygen atom in the chain, and 1 to 3 sulfur atoms in the chain An alkylidene group having 2 to 5 carbon atoms, an oxygen atom, a sulfur atom, a sulfinyl group (one SO—) or a sulfonyl group which may be intervened by a heteroatom of an atom and / or an oxygen atom

(_S0 ₂ -) ^{^{indicates, R '8, R 17,}} R 18, R 13, R 2 ° and R ²¹ may be the same or different, each represent a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, carbon And represents an aryl group having 6 to 10 carbon atoms or a cycloalkyl group having 3 to 7 carbon atoms. ) Represents a group represented by (2 n): n indicates 2, x indicates 1, p indicates 1, R z is a formula (1 3)

(In the formula, A ⁴ is an alkylene group having 1 to 6 carbon atoms which may have 1 to 3 sulfur atoms and / or a hetero atom of an oxygen atom in the chain, and 1 to 3 sulfur atoms in the chain. And a hetero atom of oxygen or oxygen may be intervened, and an alkylidene group having 2 to 5 carbon atoms, an oxygen atom, a sulfur atom, a sulfinyl group (—SO—) or a sulfonyl group

(An S0 ₂ -) ^{^{indicates, R 22, R 23, R}} 24, R 25, R 26 and R ²⁷ may be the same or different, each represent a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, carbon atoms It represents an aryl group having 6 to 10 or a cycloalkyl group having 3 to 3 carbon atoms. ) Represents a group represented by

(3a): n represents 3, x represents 1, p represents 1, R z represents a linear or branched alkane-triyl group having 2 to 6 carbon atoms: or

(3b): n represents 3, X represents 0, p represents 1, Rz is the formula (14)

(Wherein, A ⁵ represents an isocyanuric group or 3,5-trimethylphenyl 2,4,6-tolyl group, R ²⁸ represents an alkyl group having 1 to 8 carbon atoms, and R ²⁹ and R ^3e represent Which may be the same or different, and each represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, and m 3 represents an integer of 1 to 3.) represents a group represented by:

(3c): n represents 3, X represents 0, p represents 1, Rz is the formula (15)

(Wherein, A ⁶ represents an isocyanuric group or 1,3,5-trimethylphenyl-1,2,4,6-tolyl group, R ³¹ represents an alkyl group having from 8 to 8 carbon atoms, R ³² and R ³³ May be the same or different, and each represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, and m4 represents an integer of 1 to 3.) represents a group represented by:

(3d): n represents 3, X represents 1, p represents 1, R z is a formula (16)

(In the formula, A ⁷ represents an isocyanuric group or a nitrogen atom, and m 5 represents an integer of 1-3.)

(4a): n represents 4, x represents 1, p represents 1, R z represents a linear or branched alkane-tetrayl group having 2 to 6 carbon atoms; or

(6a): n represents 6, x represents 1, p represents 1, Rz represents a linear or branched alkane-hexyl group having 2 to 6 carbon atoms.

2. Equation (1)

H- (L ² ) _b- (L) _a- (L) _x- (0) _p Rz

(Wherein definitions of the symbols are as follows.) Off X Nord compound represented by _c L, L ′ and L ² in the formula (1) may be the same or different, and the formula (2)

(Here, R ¹ represents an alkyl group having ¹ to 8 carbon atoms, and R ² and R ³ may be the same or different and each represent a hydrogen atom or an alkyl group having 1 to 8 carbon atoms.) are shown, L ² -L ¹ is the L ² carbonylation几基and L 'and oxygen radicals in the phenoxy group form a bond by an ester bond, L' -L represents a carbonyl group of L ¹ and L And the oxygen atom of the phenolic oxy group forms a bond by an ester bond, L-10 forms a bond between the carbonyl group of L and the oxygen atom by an ester bond, a represents 1, and b represents Indicates an integer of 0 or 1,

(la): n represents 1, X represents 1, p represents 1, Rz represents an alkyl group having 1 to 30 carbon atoms; or

(1e): n represents 1, X represents 1, p represents 1, and Rz represents an optionally substituted aralkyl group having 7 to 20 carbon atoms or a substituent. Represents an aryl group having 6 to 20 carbon atoms; or

(2a): n represents 2, x represents 1, p represents 1, R z represents 1 to 10 sulfur atoms in the chain and a σ atom interposed between Z and oxygen atoms. Represents an alkylene group having 1 to 20 carbon atoms; or

(2 d): η indicates 2, X indicates 0, ρ indicates 1, and R 式 is the equation (3)

(In the formula, A ′ is an alkylene group having 1 to 6 carbon atoms which may have 1 to 3 sulfur atoms and / or a hetero atom of an oxygen atom in the chain, and 1 to 3 sulfur atoms in the chain. And Alkylene, oxygen, sulfur, sulfinyl (—SO—) or sulfonyl (—S〇 ₂ —) R ⁴ and R ⁹ may be the same or different, each represents an alkyl group having 1 to 8 carbon atoms, and R ⁵ , R ^e , R ⁷ and R ⁸ may be the same or different It often represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms. ) Represents a group represented by; or

(2e): n indicates 2, x indicates 0, p indicates 1, and Rz is a formula (4)

(In the formula, A ² is an alkylene group having 1 to 6 carbon atoms which may have 1 to 3 sulfur atoms and / or a hetero atom of an oxygen atom in the chain, and 1 to 3 sulfur atoms in the chain. Hetero atom of oxygen and / or oxygen atom C 2-5 carbon atom which may be interposed, oxygen atom, sulfur atom, sulfinyl group (1SO—) or succinyl group

(One S_〇 ₂ -) indicates, R "and R ¹⁵ may be the same or different, their respective an alkyl group having 1 to 8 carbon ^{^{atoms, R u, R 12, R}} 13 and R ^'4 May be the same or different and each represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms.) Represents a group represented by:

† H ₃ 0-C¾2, CH ₂ -0 CH ₃

CH -C- CH, CH- C one CH ₂

I \ ノ \ / I

CH ₃ ° " ^CH 2 CH ₂ _0 CH ₃

Represents a group represented by; or

(2j): n represents 2, X represents 1, p represents 0, and Rz represents the equation (9).

—— 0- (CH CH ₂ 0) _m1 (Wherein ΙΏ 1 represents an integer of 1 to 4.) or a group represented by: (2k): n represents 2, X represents 1, p represents 0, R z is the formula _{(1 0) NH- (CH 2} ) m2 - NH

(Wherein, m 2 represents an integer of 1 to 6.) A group represented by:

"(2 1): n represents 2, X represents 1, p represents 0, and R z represents the formula (1 1)

NH-NH——

Represents a group represented by; or

(3b): n represents 3, X represents 0, p represents 1, Rz is the formula (14)

(In the formula, A ⁵ represents an isocyanuric group or 1,3,5-trimethylphenyl—2,4,6-tolyl group; R ²⁸ represents an alkyl L group having 1 to 8 carbon atoms; R ²⁹ and R ²⁹ ³ ° may be the same or different and each represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, and m 3 represents an integer of 1 to 3.) represents a group represented by:

(3c): n represents 3, X represents 0, p represents 1, Rz is the formula (15)

(Wherein, Alpha ^beta is Isoshianuru group or 1, 3, 5-Torimechirufue two Lou 2, 4, shows a 6-Toryiru group, R ³¹ represents an alkyl group of - number of carbon atoms 8, R ³² and R ³³ May be the same or different, and each has a hydrogen atom or a carbon number of 1 to 8 M 4 represents an integer of 1 to 3; ) Represents a group represented by

(3d): n represents 3, X represents 1, p represents 1, R z is a formula (16)

(Wherein, A ⁷ represents an isocyanuric group or a nitrogen atom, and 5 represents an integer of 1-3.) Or a group represented by the following formula:

(4a): n represents 4, x represents 1, p represents 1, and Rz represents a straight-chain or branched-chain alkane-tetrayl group having 2 to 6 carbon atoms.

3. L, L ¹ and L ² may be the same or different and each has the formula (17)

CH ₃

Or expression (18)

Or equation (1 9)

3. The phenol compound according to claim 1, which is a group represented by the following formula:

4. In the formula (1), n is 1 or n is 2 or more and the formula (20)

H- (L ² ) _b- (L ¹ ) _a- (L) x

(The symbols in the formula are as defined above.) The phenolic compound according to claim 1, 2 or 3, wherein both groups are the same.

5. The phenolic compound according to claim 1, 2, 3, or 4, wherein b is 0.

6. n is 2, X is 1, p is 0, and R z is of the form (2 1)

—— 0— (CH ₂ CH ₂ 0) ₃ ——

The phenol compound according to any one of claims 1 to 5, wherein the phenol compound is represented by the following formula:

7. n is 2, X is 0, ρ is 1 and R z is of the form (2 2)

(Wherein A ⁸ is a sulfur atom or a butylidene group.) The phenol compound according to any one of claims 1 to 5, which is represented by the following formula:

8. n is 2, X is 0, p is 1 and R z is given by equation (2 3) (H ₃ C) ₃ C ヽ C (CH ₃ ) ₃

11 14

R R

(Wherein A ⁹ is a methylene group or a butylidene group, and R ′ ¹ and R ¹⁴ may be the same or different and are each a methyl group or an ethyl group.) 6. The phenol compound according to claim 5.

9. n is 3, X is 0, p is 1, and rule 2 is given by the formula (24)

(Wherein the phenol compound is an isocyanuric group.) The phenol compound according to any one of claims 1 to 5, which is represented by the following formula:

1 0. η is 1, X is 1, ρ is 1, and R ζ is the equation (2 5)

—— (CH ₂ ) ₁₇ -CH ₃

The phenol compound according to any one of claims 1 to 5, which is (n-octane decyl group).

1 1.n is 4, X is 1, p is 1 and R z is of the formula (26) CH ₂

H2C-C_CH2-

1 2. n is 2, X is 1, p is 1, and R z is of the formula (5)

H3 O-CH2 NO CH ₂ _0 ^H 3

CH ₂ -C— CH input CH-C— CH ₂

CH ₃ O-CH2 CH ₂ -0 CH ₃

13.

Equation (2 7)

Triethylene glycol bis (3- (3-N-tert-butyl-4- (3- (3,5-di-tert-butyl-4-4-hydra-α-phenyl) propionyloxy)) — 5-Methyl Lufenil) propionate),

Equation (2 8)

Thiobis (2-methyl-4- (3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionyloxy) 1-5-tert-butylbutyl),

Equation (2 9)

1, 1-bis (2-methyl-4- (3- (3,5-di-tert-butyl-14-hydropenxoxyphenyl) propionyloxy) -1-5-tert-butylphenyl) butane, formula (3 0)

CH ₃ CH ₃

Methylenebis (2- (3- (3,5-di-tert-butyl-1-4-hydroxypropionyloxy) propionyloxy) -3-tert-butyl-5-methylphenyl), formula (31)

Methylenebis (2- (3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionyloxy) -1-3-tert-butyl-5-ethylphenyl), formula (32)

1,3,5-tris (3-tertiary butyl 4- (3- (3,5-di-tertiary butyl 4-hydroxyphenyl) propionylloquine) 1-5-methylbenzyl) isocyanurate,

Equation (3 3)

n-octadecyl 3- (3-tert-butyl-4-1- (3- (3,5-di-tert-butyl-4-hydroquinphenyl) propionyloxy) —5-methylphenyl) propionate,

Equation (3 4)

Tetrakis (methylene-1- (3-tertiary butyl_4- (3- (3,5-di-tert-butyl-4-hydroquinophenyl) propionyloxy) propionyloxy-1-5-methylphenyl) propionate) methane,

Expression

3,9-bis [2- (3— (3-tert-butyl-4-1) (3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionyloxy) -1-5-methylphenyl ) Propionyloquine) 1, 1-dimethylethyl] 1, 2, 4, 8, 10-tetraoxaspiro [5.5] pentane,

Equation (36)

A phenol compound selected from thiobis (3-tert-butyl-4-1) (3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionyloxy) -16-methylphenyl).

1 4. An organic polymer stabilizer comprising the phenol compound according to any one of claims 1 to 13.

1 5. An organic polymer material comprising the phenol compound according to any one of claims 1 to 13.

16. The stabilizer for an organic polymer material according to claim 14, further comprising a sulfur-based antioxidant.

1 7. The sulfur-based antioxidant

Dilauryl thiodipropionate,

Lauryl stearyl thiodipropionate,

Jimi ristylthiodipropionate,

Distearyl thiodipropionate,

Ditridesi pionate mouth pionate,

Tetrakis [methylene (laurylthiopropionate)] methane,

Tetrakis [methylene (stearylthiopropionate)] methane or bis [2-methyl-41- (3-n-alkyl (C12-C14) thiopropionyloxy) 1-5-tert-butylbutyl] sulfide Claim 16 which is Stabilizer for organic polymer materials.

1 8. A method for stabilizing an organic polymer, comprising adding the phenol compound according to any one of claims 1 to 13 to the organic polymer.

1 9. The method for stabilizing an organic polymer according to claim 8, wherein the organic polymer is an olefin resin.

20. The compounding amount of the phenolic compound according to any one of claims 1 to 13 is 0.01 to 10 parts by weight based on 100 parts by weight of the olefin resin. 19. The method for stabilizing an organic polymer according to claim 18, wherein the method is selected from the range.

21. The method for stabilizing an organic polymer according to claim 18, wherein the orefin-based resin is selected from an α-orefin homopolymer and a one-year-old refin copolymer.

2 2. A composition comprising the compound according to any one of claims 1 to 13 and an organic high molecule.

23. The composition according to claim 22, wherein the organic polymer is an olefin resin.

2 4. The compounding amount of the phenolic compound according to any one of claims 1 to 13 is 0.01 to 10 parts by weight based on 100 parts by weight of the olefin resin. 24. The composition according to claim 23, selected from the range.

25. The composition according to claim 23, wherein the olefin resin is an olefin resin selected from an α-olefin homopolymer and an α-olefin copolymer.

26. The composition according to claim 22, further comprising a sulfur-based antioxidant.

2 7. Sulfur-based antioxidant

Dilauryl thiodib mouth pionate,

Lauryl stearyl thiodipropionate,

Jimi ristylthiodib mouth pionate,

Distearyl thiodib mouth pionate,

Ditridecylthiodipropionate,

Tetrakis [methylene (laurylthiopropionate)] methane,

Tetrakis [methylene (stearylthiopropionate)] methane,

27. The composition according to claim 26, which is bis [2-methyl-4- (3-n-alkyl (C.sub.12-C.sub.14) thiopropionyloxy) -15-tert-butylbutyl] sulfide.

28. A stabilizer for an organic polymer material, comprising the composition according to any one of claims 22 to 27.