JP2019026736A - Stabilizer composition and organic material composition - Google Patents

Abstract

To achieve both of improvement in the process stability and suppression of discoloration of an organic material composition.SOLUTION: A stabilizer composition is provided, comprising a compound represented by formula (I), another phosphorus-based antioxidant different from the compound represented by formula (I), and a compound represented by formula (III), in which a weight ratio of the total amount of the compound represented by formula (I) and another phosphorus-based antioxidant to the amount of the compound represented by formula (III) ((total amount of the compound represented by formula (I) and another phosphorus-based antioxidant):(amount of the compound represented by formula (III))) is 1:0.05 to 1:0.2. Definitions of groups in the formulae are as described in the specification.SELECTED DRAWING: None

Description

  The present invention relates to a stabilizer composition and an organic material composition.

  Organic materials such as thermoplastic resins are deteriorated by the action of heat, oxygen, and the like during processing into products and use after processing. Therefore, a stabilizer is often added to the organic material in order to improve stability during processing (processing stability) and stability during use. As such a stabilizer, for example, phosphites described in Patent Document 1 are known.

JP-A-10-273494

  When a stabilizer is used, the processing stability of the organic material composition is improved, but there is a problem that the organic material composition is discolored. The present invention has been made paying attention to such circumstances, and an object thereof is to achieve both improvement in processing stability of the organic material composition and suppression of discoloration.

The present invention that can achieve the above object is as follows.
[1] Formula (I):

[In formula (I), R < ¹ >, R < ² >, R < ⁴ > and R < ⁵ > are respectively independently a hydrogen atom, a _C1-8 alkyl group, a _C5-8 cycloalkyl group, a _C6-12 alkylcycloalkyl group. _Represents a C _7-12 aralkyl group or a C _6-14 aryl group,
R ³ represents a hydrogen atom or a C _1-8 alkyl group,
X is a divalent group represented by a single bond, a sulfur atom or —CHR ⁶ — (wherein R ⁶ represents a hydrogen atom, a C _1-8 alkyl group or a C _5-8 cycloalkyl group). Represents
A is a C _2-8 alkylene group or * -COR ⁷ -group (in the above formula, R ⁷ represents a single bond or a C _1-8 alkylene group, and * is bonded to the oxygen atom side) And any one of Y and Z represents a hydroxy group, a C _1-8 alkoxy group or a C _7-12 aralkyloxy group, and the other represents a hydrogen atom or C Represents a _1-8 alkyl group. ]
A compound represented by
Another phosphorus antioxidant different from the compound represented by formula (I),
Formula (III):

[In Formula (III), R ³¹ and R ³² each independently represent a hydrogen atom or a methyl group, and R ³³ represents a C _1-20 alkyl group or a C _2-20 alkenyl group. ]
And a compound represented by
Weight ratio of the total amount of the compound represented by formula (I) and other phosphorus antioxidants to the amount of the compound represented by formula (III) (compounds represented by formula (I) and other phosphorous oxidations) A stabilizer composition in which the total amount of the inhibitor: the amount of the compound represented by formula (III) is 1: 0.05 to 1: 0.2.
[2] Another phosphorus-based antioxidant is represented by the formula (II-1):

Wherein ^{(II-1), R 8} ~R 10 are each _{independently, C 1-10} or an alkyl group, or a _{C 1-10} alkyl _{group, C 5-8} cycloalkyl _{group, C 6-12} It represents a phenyl group which may have at least one substituent selected from the group consisting of an alkylcycloalkyl group, a C _7-12 aralkyl group and a phenyl group. ]
A compound represented by
Formula (II-2):

[In formula (II-2), two R ^{11 s} independently represent a hydrogen atom, a C _1-10 alkyl group, a C _5-8 cycloalkyl group, a C _6-12 alkyl cycloalkyl group, a C _{7- 12} represents an aralkyl group or a phenyl group, and two R ^{12 s} independently represent a hydrogen atom, a C _1-10 alkyl group, a C _5-8 cycloalkyl group, a C _6-12 alkyl cycloalkyl group, a C _{7. -12} represents an aralkyl group or a phenyl group. ]
A compound represented by
Formula (II-3):

[In Formula (II-3), R ¹³ and R ¹⁴ each independently represent a C _1-20 alkyl group, or a C _1-10 alkyl group optionally having a phenyl group, C _{5- It} represents a phenyl group which may have at least one substituent selected from the group consisting of an ₈ cycloalkyl group, a C _6-12 alkylcycloalkyl group, a C _7-12 aralkyl group and a phenyl group. ]
A compound represented by
Formula (II-4):

[In formula (II-4), R ¹⁵ represents a C _1-20 alkyl group, or a C _1-10 alkyl group optionally having a phenyl group, a C _5-8 cycloalkyl group, C _{6. Represents a} phenyl group _optionally having at least one substituent selected from the group consisting of a _-12 alkylcycloalkyl group, a C _7-12 aralkyl group and a phenyl group, and R ¹⁶ and R ¹⁷ are each independently , Represents a C _1-10 alkyl group. ]
A compound represented by
Formula (II-5):

[In the formula (II-5), three R ^{18 s} independently represent a hydrogen atom, a C _1-10 alkyl group, a C _5-8 cycloalkyl group, a C _6-12 alkyl cycloalkyl group, a C _{7- 12} represents an aralkyl group or a phenyl group,
Three R ^{19 s} each independently represent a hydrogen atom, a C _1-10 alkyl group, a C _5-8 cycloalkyl group, a C _6-12 alkyl cycloalkyl group, a C _7-12 aralkyl group or a phenyl group,
Three R ^{20 s} each independently represent a hydrogen atom, a C _1-10 alkyl group, a C _5-8 cycloalkyl group, a C _6-12 alkyl cycloalkyl group, a C _7-12 aralkyl group or a phenyl group,
Three R ^{21 s} each independently represent a hydrogen atom, a C _1-10 alkyl group, a C _5-8 cycloalkyl group, a C _6-12 alkyl cycloalkyl group, a C _7-12 aralkyl group or a phenyl group,
Three L ^{1 s} each independently represent a single bond, a sulfur atom, or —C (R ²² ) (R ²³ ) — (wherein R ²² and R ²³ have a total carbon number of 7 or less. Each independently represents a hydrogen atom or a C _1-7 alkyl group.), And three L ² are each independently a C _2-8 alkylene group. Represents. ]
And a compound of formula (II-6):

[In the formula (II-6), R ^{24 to} R ²⁷ are each independently a hydrogen atom, a C _1-10 alkyl group, a C _5-8 cycloalkyl group, a C _6-12 alkyl cycloalkyl group, a C _{7- 12} represents an aralkyl group or a phenyl group,
R ²⁸ represents a halogen atom or a C _1-10 alkoxy group, or consists of a C _1-10 alkyl group, a C _5-8 cycloalkyl group, a C _6-12 alkyl cycloalkyl group and a C _7-12 aralkyl group. Represents a phenyloxy group which may have at least one substituent selected from the group, and L ³ represents a single bond, a sulfur atom or —C (R ²⁹ ) (R ³⁰ ) — (wherein R ²⁹ and R ³⁰ each independently represents a hydrogen atom or a C _1-7 alkyl group on condition that the total number of carbon atoms is 7 or less.} Represents a divalent group represented by
The stabilizer composition according to [1], wherein the stabilizer composition is at least one selected from the group consisting of compounds represented by:
[3] The stabilizer composition according to [2], wherein the other phosphorus-based antioxidant is a compound represented by the formula (II-1).
[4] The stabilizer composition according to any one of [1] to [3], wherein the compound represented by the formula (III) is α-tocopherol.
[5] The stabilizer composition according to any one of [1] to [4], wherein the amount of the other phosphorus-based antioxidant is equal to or greater than the amount of the compound represented by the formula (I) by weight. object.
[6] The stabilizer composition according to any one of [1] to [5], which is in the form of a granulated product.

[7] An organic material composition comprising an organic material and the stabilizer composition according to any one of [1] to [6].
[8] With organic materials,
Formula (I):

[In formula (I), R < ¹ >, R < ² >, R < ⁴ > and R < ⁵ > are respectively independently a hydrogen atom, a _C1-8 alkyl group, a _C5-8 cycloalkyl group, a _C6-12 alkylcycloalkyl group. _Represents a C _7-12 aralkyl group or a C _6-14 aryl group,
R ³ represents a hydrogen atom or a C _1-8 alkyl group,
X is a divalent group represented by a single bond, a sulfur atom or —CHR ⁶ — (wherein R ⁶ represents a hydrogen atom, a C _1-8 alkyl group or a C _5-8 cycloalkyl group). Represents
A is a C _2-8 alkylene group or * -COR ⁷ -group (in the above formula, R ⁷ represents a single bond or a C _1-8 alkylene group, and * is bonded to the oxygen atom side) And any one of Y and Z represents a hydroxy group, a C _1-8 alkoxy group or a C _7-12 aralkyloxy group, and the other represents a hydrogen atom or C Represents a _1-8 alkyl group. ]
A compound represented by
Another phosphorus antioxidant different from the compound represented by formula (I),
Formula (III):

[In Formula (II), R ³¹ and R ³² each independently represent a hydrogen atom or a methyl group, and R ³³ represents a C _1-20 alkyl group or a C _2-20 alkenyl group. ]
And a compound represented by
Weight ratio of the total amount of the compound represented by formula (I) and other phosphorus antioxidants to the amount of the compound represented by formula (III) (compounds represented by formula (I) and other phosphorous oxidations) An organic material composition in which the total amount of the inhibitor: the amount of the compound represented by the formula (III) is 1: 0.05 to 1: 0.2.
[9] The organic material composition according to [7] or [8], wherein the amount of the compound represented by the formula (III) is 0.005 to 0.02 parts by weight with respect to 100 parts by weight of the organic material. .
[10] The organic material composition according to any one of [7] to [9], wherein the organic material is a thermoplastic resin.
[11] The organic material composition according to [10], wherein the thermoplastic resin is a polyolefin or an engineering resin.

  If the stabilizer composition of this invention is used, the improvement of the process stability of organic material composition and suppression of discoloration can be made compatible.

<Definition>
First, definitions of substituents and the like used in this specification will be described in order.
“C _xy ” means that the number of carbon atoms is x or more and y or less (x and y represent numbers). For example, the term “C _6-12 alkylcycloalkyl group” means that the total number of carbon atoms in the alkylcycloalkyl group (that is, the total number of carbon atoms in the cycloalkyl group and the alkyl group as a substituent thereof) is 6 to 12. It means the following.

  As a halogen atom, a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom are mentioned, for example.

The alkyl group may be linear or branched. Examples of the alkyl group include methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, sec-butyl group, t-butyl group, pentyl group, isopentyl group, neopentyl group, t-pentyl group, 1 -Ethylpropyl group, hexyl group, isohexyl group, 1,1-dimethylbutyl group, 2,2-dimethylbutyl group, 3,3-dimethylbutyl group, 2-ethylbutyl group, heptyl group, octyl group, nonyl group, decyl Group, undecyl group, dodecyl group, tridecyl group, tetradecyl group, pentadecyl group, hexadecyl group, 4,8,12-trimethyltridecyl group, heptadecyl group, octadecyl group, nonadecyl group, icosyl group, heicosyl group, docosyl group, tricosyl Group, tetracosyl group, pentacosyl group, hexacosyl group, heptaco Group, octacosyl group, nonacosyl group and a triacontyl group. In the present specification, “t-” means “tert-” and “t-Bu” means “tert-butyl”. Examples of the “C _1-7 alkyl group” include those having 1 to 7 carbon atoms in the above examples of the alkyl group. The same applies to examples such as “C _1-8 alkyl group”.

The alkenyl group may be linear or branched. Moreover, the double bond in an alkenyl group may be two or more. Examples of alkenyl groups (particularly C _2-20 alkenyl groups) include those in which one or more single bonds of the alkyl group described above are replaced with one or more double bonds.

The alkoxy group may be linear or branched. Examples of the alkoxy group include a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, a butoxy group, an isobutoxy group, a sec-butoxy group, a t-butoxy group, a t-pentyloxy group, and an isooctyloxy group (alias: 6). -Methylheptyloxy group), t-octyloxy group (alias: 1,1,3,3-tetramethylbutyloxy group), 2-ethylhexyloxy group, nonyloxy group, and decyloxy group. Examples of the “C _1-8 alkoxy group” include those having 1 to 8 carbon atoms in the above examples of alkoxy groups. The same applies to examples such as “C _1-10 alkoxy group”.

Examples of the C _5-8 cycloalkyl group include a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, and a cyclooctyl group.

Examples of the C _6-12 alkylcycloalkyl group include a 1-methylcyclopentyl group, a 2-methylcyclopentyl group, a 1-methylcyclohexyl group, a 2-methylcyclohexyl group, and a 1-methyl-4-isopropylcyclohexyl group.

Examples of the C _7-12 aralkyl group include a benzyl group, an α-methylbenzyl group (alias: 1-phenylethyl group), an α, α-dimethylbenzyl group (alias: 1-methyl-1-phenylethyl group or cumyl). Group).

Examples of the C _7-12 aralkyloxy group include a benzyloxy group, an α-methylbenzyloxy group, and an α, α-dimethylbenzyloxy group.

Examples of the C _6-14 aryl group include a phenyl group, a naphthyl group, a phenanthryl group, an anthryl group, and a biphenylyl group.

The alkylene group may be linear or branched. Examples of the alkylene group include a methylene group, an ethylene group, a propylene group (—CH (CH ₃ ) CH ₂ —, —CH ₂ CH (CH ₃ ) —), a trimethylene group, a tetramethylene group, a pentamethylene group, and a hexamethylene group. Group, octamethylene group, 2,2-dimethyl-1,3-propylene group. Examples of the “C _1-8 alkylene group” include those having 1 to 8 carbon atoms among the above examples of alkylene groups. The same applies to examples such as “C _2-8 alkylene group”.

<Compound represented by formula (I)>
The stabilizer composition and organic material composition of the present invention contain a compound represented by the above formula (I). Hereinafter, the “compound represented by the formula (I)” may be abbreviated as “compound (I)”. Similarly, compounds represented by other formulas may be abbreviated. Compound (I) may be used alone or in combination of two or more. Hereinafter, group which compound (I) has is demonstrated in order.

In formula (I), R ¹ , R ² , R ⁴ and R ⁵ each independently represent a hydrogen atom, a C _1-8 alkyl group, a C _5-8 cycloalkyl group, a C _6-12 alkyl cycloalkyl group, _{Represents a} C _7-12 aralkyl group or a C _6-14 aryl group, preferably a hydrogen atom, a C _1-8 alkyl group, a C _5-8 cycloalkyl group, a C _6-12 alkyl cycloalkyl group, a C _7-12 aralkyl group. Represents a group or a phenyl group.

R ¹ and R ⁴ are each independently more preferably a C _1-8 alkyl group, a C _5-8 cycloalkyl group or a C _6-12 alkyl cycloalkyl group, and even more preferably have a tertiary carbon atom. A C _4-8 alkyl group, a cyclohexyl group or a 1-methylcyclohexyl group, more preferably a t-butyl group, a t-pentyl group or a t-octyl group, and particularly preferably a t-butyl group.

R ² is more preferably a C _1-8 alkyl group, a C _5-8 cycloalkyl group or a C _6-12 alkyl cycloalkyl group, even more preferably a C _1-5 alkyl group, and still more preferably methyl. Group, t-butyl group or t-pentyl group, particularly preferably t-butyl group.

R ⁵ is more preferably a hydrogen atom, a C _1-8 alkyl group or a C _5-8 cycloalkyl group, still more preferably a hydrogen atom or a C _1-5 alkyl group, still more preferably a hydrogen atom or methyl. Group, particularly preferably a methyl group.

In formula (I), R ³ represents a hydrogen atom or a C _1-8 alkyl group, preferably a hydrogen atom or a C _1-5 alkyl group, more preferably a hydrogen atom or a methyl group, still more preferably. Represents a hydrogen atom.

In the formula (I), X represents a single bond, a sulfur atom or —CHR ⁶ — (in the above formula, R ⁶ represents a hydrogen atom, a C _1-8 alkyl group or a C _5-8 cycloalkyl group). Represents the divalent group shown. R ⁶ is preferably a hydrogen atom or a C _1-8 alkyl group. X is preferably a single bond or a —CHR ⁶ — group (wherein R ⁶ represents a hydrogen atom or a C _1-8 alkyl group), and more preferably a single bond.

In the formula (I), A represents a C _2-8 alkylene group or * -COR ⁷ -group (in the above formula, R ⁷ represents a single bond or a C _1-8 alkylene group. * Represents an oxygen atom side. Represents a divalent group represented by the following formula: A is preferably a C _2-8 alkylene group, a carbonyl group, or * —CO— (CH ₂ ) ₂ — (in the above formula, * represents bonding to the oxygen atom side), and more. Preferably it is a _C2-8 alkylene group, More preferably, it is a trimethylene group.

In formula (I), any one of Y and Z represents a hydroxy group, a C _1-8 alkoxy group or a C _7-12 aralkyloxy group, and the other represents a hydrogen atom or a C _1-8 alkyl group. One of Y and Z is preferably a hydroxy group and the other is preferably a hydrogen atom, more preferably Y is a hydroxy group and Z is a hydrogen atom.

As the combination of groups in formula (I), R ¹ , R ² and R ⁴ are each independently a C _1-8 alkyl group, a C _5-8 cycloalkyl group or a C _6-12 alkylcycloalkyl group. R ⁵ is a hydrogen atom, a C _1-8 alkyl group or a C _5-8 cycloalkyl group, R ³ is a hydrogen atom or a C _1-5 alkyl group, and X is a single bond or —CHR ⁶ -group (wherein R ⁶ represents a hydrogen atom or a C _1-8 alkyl group), and A represents a C _2-8 alkylene group, a carbonyl group or * —CO— (CH ₂ ) _2. -(In the above formula, * represents that they are bonded to the oxygen atom side.) A combination in which one of Y and Z is a hydroxy group and the other is a hydrogen atom is preferable.

In the combination of groups in formula (I), R ¹ and R ⁴ are each independently a C _4-8 alkyl group, cyclohexyl group or 1-methylcyclohexyl group having a tertiary carbon atom, and R ² is , A C _1-5 alkyl group, R ⁵ is a hydrogen atom or a C _1-5 alkyl group, R ³ is a hydrogen atom or a methyl group, X is a single bond, and A is a C _2- More preferred is a combination of ₈ alkylene groups, Y is a hydroxy group, and Z is a hydrogen atom.

As a combination of groups in formula (I), R ¹ and R ⁴ are each independently a t-butyl group, a t-pentyl group or a t-octyl group, and R ² is a methyl group, t-butyl group Or a t-pentyl group, R ⁵ is a hydrogen atom or a methyl group, R ³ is a hydrogen atom, X is a single bond, A is a trimethylene group, and Y is a hydroxy group , Z is more preferably a hydrogen atom.

  As compound (I), for example, 6- [3- (3-t-butyl-4-hydroxy-5-methylphenyl) propoxy] -2,4,8,10-tetra-t-butyldibenzo [d, f] [1,3,2] dioxaphosphine, 2,10-dimethyl-4,8-di-t-butyl-6- [3- (3,5-di-t-butyl-4-hydroxy) Phenyl) propoxy] -12H-dibenzo [d, g] [1,3,2] dioxaphosphocine, 2,4,8,10-tetra-t-butyl-6- [3- (3,5-di -T-butyl-4-hydroxyphenyl) propoxy] dibenzo [d, f] [1,3,2] dioxaphosphine, 2,4,8,10-tetra-t-pentyl-6- [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propoxy] -12-methyl 12H-dibenzo [d, g] [1,3,2] dioxaphosphocin, 2,10-dimethyl-4,8-di-t-butyl-6- [3- (3,5-di-t- Butyl-4-hydroxyphenyl) propionyloxy] -12H-dibenzo [d, g] [1,3,2] dioxaphosphocine, 2,4,8,10-tetra-t-pentyl-6- [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionyloxy] -12-methyl-12H-dibenzo [d, g] [1,3,2] dioxaphosphocin, 2,4,8, 10-tetra-t-butyl-6- [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionyloxy] -dibenzo [d, f] [1,3,2] dioxaphosphine Pin, 2,10-dimethyl-4,8-di-t-butyl-6- 3,5-di-t-butyl-4-hydroxybenzoyloxy) -12H-dibenzo [d, g] [1,3,2] dioxaphosphocin, 2,4,8,10-tetra-t-butyl -6- (3,5-di-tert-butyl-4-hydroxybenzoyloxy) -12-methyl-12H-dibenzo [d, g] [1,3,2] dioxaphosphocin, 2,4,8 , 10-Tetra-t-butyl-6- [3- (3-methyl-4-hydroxy-5-t-butylphenyl) propoxy] dibenzo [d, f] [1,3,2] dioxaphosphine 2,10-dimethyl-4,8-di-t-butyl-6- [3- (3-methyl-4-hydroxy-5-t-butylphenyl) propoxy] -12H-dibenzo [d, g] [ 1,3,2] dioxaphosphocin, 2,4,8,10-teto La-t-butyl-6- [3- (3,5-di-t-butyl-4-hydroxyphenyl) propoxy] -12H-dibenzo [d, g] [1,3,2] dioxaphosphocin, 2,10-diethyl-4,8-di-t-butyl-6- [3- (3,5-di-t-butyl-4-hydroxyphenyl) propoxy] -12H-dibenzo [d, g] [1 , 3,2] dioxaphosphocine, 2,4,8,10-tetra-tert-butyl-6- [2,2-dimethyl-3- (3-tert-butyl-4-hydroxy-5-methylphenyl) ) Propoxy] -dibenzo [d, f] [1,3,2] dioxaphosphine.

  Among the compounds (I), 6- [3- (3-t-butyl-4-hydroxy-5-methylphenyl) propoxy] -2,4,8,10-tetra-t-butyldibenzo [d, f] [1,3,2] Dioxaphosphepine (hereinafter sometimes abbreviated as “Compound (Ia)”) is preferred. Compound (Ia) is commercially available as “SUMILIZER (registered trademark) GP” (manufactured by Sumitomo Chemical Co., Ltd.).

  Compound (I) may be a commercially available product or a product produced according to a known method (for example, the method described in JP-A-10-273494).

<Other phosphorus antioxidants>
The stabilizer composition and the organic material composition of the present invention contain another phosphorus-based antioxidant different from the compound (I). Other phosphoric antioxidants may be used alone or in combination of two or more.

  Examples of other phosphorus antioxidants include compounds represented by any one of the above formulas (II-1) to (II-6). These compounds (II-1) to (II-6) may be used alone or in combination of two or more. Hereinafter, compound (II-1) to compound (II-6) will be described in order.

(1) Compound (II-1)
Formula ^{(II-1) R 8 ~R} 10 in each _{independently, C 1-10} or an alkyl group, or a _{C 1-10} alkyl _{group, C 5-8} cycloalkyl _{group, C 6-12} alkyl It represents a phenyl group which may have at least one substituent selected from the group consisting of a cycloalkyl group, a C _7-12 aralkyl group and a phenyl group.

R ⁸ is preferably a hydrogen atom or a C _1-10 alkyl group, or a phenyl group optionally having 1 to 3 C _1-10 alkyl groups, and more preferably a C _{4- 10} or an alkyl group, or a methyl group, t- butyl group, a phenyl group having 1-3 substituents selected from the group consisting of t-pentyl group and a nonyl group, more preferably 2,4 Di-t-butylphenyl group.

R ⁹ and R ¹⁰ are each independently preferably a phenyl group _optionally having 1 to 3 C _1-10 alkyl groups, more preferably a methyl group, a t-butyl group, or a t-pentyl group. A phenyl group having 1 to 3 substituents selected from the group consisting of a group and a nonyl group, more preferably a 2,4-di-t-butylphenyl group.

  Examples of the compound (II-1) include tris (2,4-di-t-butylphenyl) phosphite (hereinafter sometimes abbreviated as “compound (II-1a)”), bis (2,4- Di-t-butyl-6-methylphenyl) ethyl phosphite (hereinafter sometimes abbreviated as “compound (II-1b)”), tris (nonylphenyl) phosphite (TNPP), tris (4-t-pentyl) Phenyl) phosphite, bis (4-t-pentylphenyl) -2,4-di-t-pentylphenyl phosphite and bis (2,4-di-t-pentylphenyl) -4-t-pentylphenyl phosphite Etc. Compound (II-1a) is commercially available as “Irgafos (registered trademark) 168” (manufactured by BASF) and as compound (II-1b) “Irgafos (registered trademark) 38” (manufactured by BASF). Also, tris (4-t-pentylphenyl) phosphite, bis (4-t-pentylphenyl) -2,4-di-t-pentylphenyl phosphite and bis (2,4-di-t-pentylphenyl) A mixture containing -4-t-pentylphenyl phosphite is commercially available as “Weston® 705” (Addivant).

  Compound (II-1) is preferably tris (4-t-pentylphenyl) phosphite, bis (4-t-pentylphenyl) -2,4-di-t-pentylphenylphosphite and bis (2,4 -Di-t-pentylphenyl) -4-t-pentylphenyl phosphite, at least one selected from the group consisting of compound (II-1a), compound (II-1b) and TNPP, more preferably Is tris (4-t-pentylphenyl) phosphite, bis (4-t-pentylphenyl) -2,4-di-t-pentylphenyl phosphite and bis (2,4-di-t-pentylphenyl)- A small amount selected from the group consisting of a mixture containing 4-t-pentylphenyl phosphite, compound (II-1a) and compound (II-1b) Both are one, more preferably a compound (II-1a).

(2) Compound (II-2)
Two R ¹¹ in the formula (II-2) are each independently a hydrogen atom, a C _1-10 alkyl group, a C _5-8 cycloalkyl group, a C _6-12 alkyl cycloalkyl group, or a C _7-12. It represents an aralkyl group or a phenyl group, preferably represents a hydrogen atom or a C _1-10 alkyl group, and more preferably represents a hydrogen atom or a methyl group. Further, the two R ¹¹ are preferably the same. The description and preferred groups of R ¹² are the same as those for R ¹¹ . R ¹¹ and R ¹² are preferably the same.

  As the compound (II-2), for example, (1,1′-biphenyl-4,4′-diyl) bis [bis (2,4-di-t-butylphenoxy) phosphine] (hereinafter “compound (II- 2a) ”, tetrakis (2,4-di-t-butyl-5-methylphenyl) -4,4′-biphenylenediphosphonite (hereinafter“ compound (II-2b) ”) May be included). Compound (II-2a) is commercially available as “Hostanox (registered trademark) P-EPQ” (manufactured by Clariant), and compound (II-2b) is commercially available as “Yoshinox (registered trademark) GSY-P101” (manufactured by API). Yes. Compound (II-2) is preferably at least one selected from the group consisting of compound (II-2a) and compound (II-2b).

(3) Compound (II-3)
R ¹³ and R ^{14 in} formula (II-3) each independently represent a C _1-20 alkyl group, or a C _1-10 alkyl group optionally having a phenyl group, C _5-8. It represents a phenyl group which may have at least one substituent selected from the group consisting of a cycloalkyl group, a C _6-12 alkylcycloalkyl group, a C _7-12 aralkyl group and a phenyl group. R ¹³ and R ¹⁴ are preferably the same.

R ¹³ and R ¹⁴ are each independently preferably a C _1-20 alkyl group or a phenyl group having a C _1-10 alkyl group which may have a phenyl group, more preferably octadecyl. A group, 2,6-di-t-butyl-4-methylphenyl group, 2,4-di-t-butylphenyl group or 2,4-bis (1-methyl-1-phenylethyl) phenyl group.

  As the compound (II-3), for example, 3,9-bis (2,6-di-tert-butyl-4-methylphenoxy) -2,4,8,10-tetraoxa-3,9-diphosphaspiro [5 .5] undecane (hereinafter sometimes abbreviated as “compound (II-3a)”), 3,9-bis (2,4-di-t-butylphenoxy) -2,4,8,10-tetraoxa- 3,9-diphosphaspiro [5.5] undecane (hereinafter sometimes abbreviated as “compound (II-3b)”), 3,9-bis [2,4-bis (1-methyl-1-phenylethyl) Phenoxy] -2,4,8,10-tetraoxa-3,9-diphosphaspiro [5.5] undecane (hereinafter sometimes abbreviated as “compound (II-3c)”), 3,9-bis (octadecyloxy) ) -2, 4, 8, 10- Traoxa-3,9-diphosphaspiro [5.5] undecane (hereinafter sometimes abbreviated as “compound (II-3d)”), diisodecylpentaerythritol diphosphite, bis (2,4-di-t-butylphenyl) ) Pentaerythritol diphosphite, bis (2,4-di-t-butyl-6-methylphenyl) pentaerythritol diphosphite, bis (2,4,6-tri-t-butylphenyl) pentaerythritol diphosphite Etc. Compound (II-3a) is “Adekastb (registered trademark) PEP-36” (manufactured by Adeka), compound (II-3b) is “Ultranox (registered trademark) 626” (manufactured by GE Plastics), compound (II -3c) is commercially available as “Doverphos S-9228” (manufactured by Dover Chemical), and compound (II-3d) is commercially available as “Adekastb (registered trademark) PEP-8” (manufactured by Adeka). Compound (II-3) is preferably at least one selected from the group consisting of Compound (II-3a), Compound (II-3b), Compound (II-3c), and Compound (II-3d).

(4) Compound (II-4)
R ^{15 in} formula (II-4) represents a C _1-20 alkyl group, or a C _1-10 alkyl group optionally having a phenyl group, a C _5-8 cycloalkyl group, C _{6- 12} represents a phenyl group which may have at least one substituent selected from the group consisting of a ₁₂ alkylcycloalkyl group, a C _7-12 aralkyl group and a phenyl group.

R ¹⁵ is preferably a C _1-20 alkyl group or a phenyl group having a C _1-10 alkyl group which may have a phenyl group, more preferably a C _1-10 alkyl group. A phenyl group, more preferably a 2,4,6-tri-t-butylphenyl group.

R ¹⁶ and R ^{17 in} formula (II-4) each independently represent a C _1-10 alkyl group, preferably a C _1-6 alkyl group.

  Compound (II-4) is preferably 5-ethyl-5-butyl-2- (2,4,6-tri-t-butylphenoxy) -1,3,2-dioxaphosphorinane (hereinafter referred to as “compound ( II-4a) ”. Compound (II-4a) is commercially available as “Ultranox® 641” (manufactured by GE Plastics).

(5) Compound (II-5)
In the formula (II-5), three R ^{18 s} independently represent a hydrogen atom, a C _1-10 alkyl group, a C _5-8 cycloalkyl group, a C _6-12 alkyl cycloalkyl group, a C _7-12. It represents an aralkyl group or a phenyl group, preferably a C _1-10 alkyl group, more preferably a t-butyl group. The three R ¹⁸ are preferably the same. Descriptions and preferred groups of R ^{19 to} R ²¹ are the same as those for R ¹⁸ . R ^{18 to} R ²¹ are preferably the same.

The positions of R ¹⁸ and R ¹⁹ are preferably the 2nd and 4th positions when the position of the carbon atom of the benzene ring to which the oxygen atom is bonded is the 1st position. The same applies to the positions of R ²⁰ and R ²¹ .

Three L ¹ in the formula (II-5) are each independently a single bond, a sulfur atom or —C (R ²² ) (R ²³ ) — (wherein R ²² and R ²³ are Each independently represents a hydrogen atom or a C _1-7 alkyl group under the condition that the total number of carbon atoms is 7 or less. The three L ¹ are preferably the same. Examples of the divalent group represented by —C (R ²² ) (R ²³ ) — include —CH ₂ —, —CH (CH ₃ ) —, —CH (C ₂ H ₅ ) —, —C (CH ₃ ) ₂ —, —CH (n—C ₃ H ₇ ) —. Three L ^{1 s} are each independently preferably —CH ₂ — or a single bond, and more preferably a single bond.

Three L < ² _{> in} Formula (II-5) represents a _C2-8 alkylene group each independently. The three L ² are preferably the same. 3 L ² are each independently preferably an ethylene group or trimethylene group, more preferably an ethylene group.

  Compound (II-5) is preferably 6,6 ′, 6 ″-[nitrilotris (ethyleneoxy)] tris (2,4,8,10-tetra-t-butyldibenzo [d, f] [1, 3,2] dioxaphosphepine) (hereinafter sometimes abbreviated as “compound (II-5a)”). Compound (II-5a) is commercially available as “Irgafos (registered trademark) 12” (manufactured by BASF).

(6) Compound (II-6)
R ^{24 to} R ^{27 in} formula (II-6) are each independently a hydrogen atom, a C _1-10 alkyl group, a C _5-8 cycloalkyl group, a C _6-12 alkyl cycloalkyl group, or a C _7-12. It represents an aralkyl group or a phenyl group, preferably a C _1-10 alkyl group, more preferably a t-butyl group. R ^{24 to} R ²⁷ are preferably the same.

The positions of R ²⁴ and R ²⁵ are preferably the 2nd and 4th positions when the position of the carbon atom of the benzene ring to which the oxygen atom is bonded is the 1st position. The same applies to the positions of R ²⁶ and R ²⁷ .

R ^{28 in} formula (II-6) represents a halogen atom or a C _1-10 alkoxy group, or a C _1-10 alkyl group, a C _5-8 cycloalkyl group, a C _6-12 alkyl cycloalkyl group and _{Represents a} phenyloxy group which may have at least one substituent selected from the group consisting of a C _7-12 aralkyl group, preferably a halogen atom or a C _1-10 alkoxy group, more preferably a fluorine atom or Represents a 2-ethylhexyloxy group.

L ³ in the formula (II-6) is a single bond, a sulfur atom, or —C (R ²⁹ ) (R ³⁰ ) — (wherein R ²⁹ and R ³⁰ have a total carbon number of 7 or less. Each independently represents a hydrogen atom or a C _1-7 alkyl group.} Represents a divalent group represented by —C (R ²⁹ ) (R ³⁰ ) —. Examples of the group include —CH ₂ —, —CH (CH ₃ ) —, —CH (C ₂ H ₅ ) —, —C (CH ₃ ) ₂ —, —CH (n—C ₃ H ₇ ) —. L ³ is preferably —CH ₂ — or a single bond, and more preferably —CH ₂ —.

  Examples of the compound (II-6) include 2,4,8,10-tetra-t-butyl-6-[(2-ethylhexyl) oxy] -12H-dibenzo [d, g] [1,3,2]. ] Dioxaphosphocin (hereinafter sometimes abbreviated as "Compound (II-6a)") and 2,4,8,10-tetra-t-butyl-6-fluoro-12-methyl-12H-dibenzo [d , G] [1,3,2] dioxaphosphocin (hereinafter sometimes abbreviated as “compound (II-6b)”), and the like. Compound (II-6a) is commercially available as “Adekastb (registered trademark) HP-10” (manufactured by Adeka), and compound (II-6b) is commercially available as “Ethanox (registered trademark) 398” (sold by Ethyl Corporation). . Compound (II-6) is preferably at least one selected from the group consisting of compound (II-6a) and compound (II-6b).

  The other phosphorus-based antioxidant is preferably at least one selected from the group consisting of compound (II-1) to compound (II-6), more preferably compound (II-1), and further preferably Is tris (4-t-pentylphenyl) phosphite, bis (4-t-pentylphenyl) -2,4-di-t-pentylphenyl phosphite and bis (2,4-di-t-pentylphenyl)- It is at least one selected from the group consisting of a mixture containing 4-t-pentylphenyl phosphite, compound (II-1a), compound (II-1b) and TNPP, particularly preferably tris (4-t-pentylphenyl). ) Phosphite, bis (4-t-pentylphenyl) -2,4-di-t-pentylphenyl phosphite and bis (2,4-di-t-pe) Tilphenyl) -4-t-pentylphenyl phosphite, at least one selected from the group consisting of compound (II-1a) and compound (II-1b), most preferably compound (II-1a) is there.

  From the viewpoint of improving processing stability and suppressing discoloration, the amount of the other phosphorus antioxidant is preferably not less than the amount of compound (I) by weight. The weight ratio of the amount of compound (I) to the amount of other phosphorus antioxidant (the amount of compound (I): the amount of other phosphorus antioxidant) is more preferably 1: 1 to 1:10. More preferably, it is 1: 1 to 1: 5.

<Compound represented by formula (III)>
The stabilizer composition and organic material composition of the present invention contain a compound represented by the above formula (III). Compound (III) may be used alone or in combination of two or more.

R ³¹ and R ^{32 in} formula (III) each independently represent a hydrogen atom or a methyl group, preferably a methyl group.
R ³³ in formula (III) represents a C _1-20 alkyl group or a C _2-20 alkenyl group, preferably a group represented by formula (iii-1) or formula (iii-2), more preferably Represents a group represented by the formula (iii-1) (in the following formula, * represents a bonding position).

  Compound (III) is preferably at least one selected from the group consisting of tocopherol and tocotrienol (that is, α-tocopherol, β-tocopherol, γ-tocopherol, δ-tocopherol, α-tocotrienol, β-tocotrienol, γ-tocotrienol) And at least one selected from the group consisting of δ-tocotrienol), more preferably tocopherol (ie, at least one selected from the group consisting of α-tocopherol, β-tocopherol, γ-tocopherol and δ-tocopherol). More preferably α-tocopherol.

  From the viewpoint of improving processing stability and suppressing discoloration, the weight ratio of the total amount of compound (I) and other phosphorus antioxidants to the amount of compound (III) (compound (I) and other phosphorus systems) Total amount of antioxidant: amount of compound (III)) is 1: 0.05 to 1: 0.2, preferably 1: 0.05 to 1: 0.175, more preferably 1: 0.055. ~ 1: 0.175.

<Organic materials>
The organic material composition of the present invention includes an organic material. Only 1 type may be used for an organic material and it may use 2 or more types together. Examples of the organic material include the following.

(1) Polyethylene, for example, high density polyethylene (HD-PE), low density polyethylene (LD-PE), linear low density polyethylene (LLDPE)
(2) Polypropylene (3) Methylpentene polymer (4) EEA (ethylene / ethyl acrylate copolymer) resin (5) Ethylene / vinyl acetate copolymer resin (6) Polystyrenes such as polystyrene, poly (p-methylstyrene) ), Poly (α-methylstyrene)
(7) AS (acrylonitrile / styrene copolymer) resin (8) ABS (acrylonitrile / butadiene / styrene copolymer) resin (9) AAS (special acrylic rubber / acrylonitrile / styrene copolymer) resin (10) ACS (acrylonitrile / chlorine) Polyethylene / styrene copolymer) resin (11) chlorinated polyethylene, polychloroprene, chlorinated rubber (12) polyvinyl chloride, polyvinylidene chloride (13) methacrylic resin (14) ethylene / vinyl alcohol copolymer resin (15) fluorine Resin (16) Polyacetal (17) Grafted polyphenylene ether resin and polyphenylene sulfide resin (18) Polyurethane (19) Polyamide (20) Polyester such as polyethylene terephthalate, polybutylene terephthalate ( 1) Polycarbonate (22) Polyacrylate (23) Polysulfone, polyether ether ketone, polyether sulfone (24) a thermoplastic resin such as an aromatic polyester resin

(25) epoxy resin (26) diallyl phthalate prepolymer (27) silicone resin (28) unsaturated polyester resin (29) acrylic modified benzoguanamine resin (30) benzoguanamine / melamine resin (31) thermosetting resin such as urea resin

(32) Polybutadiene (33) 1,2-polybutadiene (34) Polyisoprene (35) Styrene / butadiene copolymer (36) Butadiene / acrylonitrile copolymer (37) Ethylene / propylene copolymer (38) Silicone rubber ( 39) Epichlorohydrin rubber (40) Acrylic rubber (41) Natural rubber

(42) Chlorine rubber paint (43) Polyester resin paint (44) Urethane resin paint (45) Epoxy resin paint (46) Acrylic resin paint (47) Vinyl resin paint (48) Amino alkyd resin paint (49) Alkyd resin paint (50) Nitrocellulose resin paint (51) Oil paint (52) Wax (53) Lubricating oil

  The organic material is preferably a thermoplastic resin, more preferably a polyolefin (eg, polyethylene, polypropylene) or an engineering resin (eg, polyamide, polyester, polycarbonate).

  From the viewpoint of processability, the melt flow rate (MFR) of the polyolefin at a temperature of 230 ° C. and a load of 21.18 N is preferably 0.1 to 200 g / 10 minutes, more preferably 0.2 to 150 g / 10 minutes, and still more preferably. Is 0.5 to 100 g / 10 min. MFR can be measured according to JIS K6922-2.

  From the viewpoint of processability, the melt flow rate (MFR) of polyethylene at a temperature of 190 ° C. and a load of 21.18 N is preferably 0.1 to 100 g / 10 minutes, more preferably 0.2 to 75 g / 10 minutes, and still more preferably. Is 0.5 to 50 g / 10 min.

The polyolefin may be a homopolymer (for example, a propylene homopolymer, an ethylene homopolymer) or a copolymer (for example, a copolymer of propylene and ethylene, propylene, ethylene and a C _4-8 α-olefin). A copolymer of ethylene and a C _4-8 α-olefin), or a mixture thereof. Examples of the C _4-8 α-olefin include 1-butene, 4-methyl-1-pentene, 1-hexene, 1-octene and the like. Of the copolymers of ethylene and C _4-8 α-olefin, linear low density polyethylene (LLDPE) is preferred.

  Any polyamide that is an engineering resin may be used as long as it has an amide bond in the polymer chain and can be melted by heating. The polyamide may be produced by any method such as a condensation reaction of diamines and dicarboxylic acids, a condensation reaction of aminocarboxylic acids, or ring-opening polymerization of lactams. Representative examples of polyamides include polyamide 66, polyamide 69, polyamide 610, polyamide 612, poly-bis (p-aminocyclohexyl) methane dodecamide, polyamide 46, polyamide 6, polyamide 12, polyamide 66/6, polyamide 6/12. Is mentioned.

  The polyester that is an engineering resin may be any polyester that has an ester bond in the polymer chain and can be melted by heating. Examples of the polyester include those obtained by polycondensation of dicarboxylic acids and dihydroxy compounds. The polyester may be either a homopolymer or a copolymer. Typical examples of polyester include polyethylene terephthalate and polybutylene terephthalate.

  As the engineering resin polycarbonate, any polycarbonate may be used as long as it has a carbonate bond in the polymer chain and can be melted by heating. The polycarbonate can be obtained, for example, by reacting an aromatic hydroxy compound or a small amount of a polyhydroxy compound with a carbonate precursor such as phosgene or diphenyl carbonate in the presence of a solvent, an acid acceptor and a molecular weight modifier. Things. The polycarbonate may be either a homopolymer or a copolymer, and may be either linear or branched.

  The thermoplastic resin is more preferably polyolefin, particularly preferably polyethylene or polypropylene, and most preferably linear low density polyethylene (LLDPE) or propylene homopolymer.

<Additives>
As long as the stabilizer composition and the organic material composition of the present invention do not inhibit the effects of the present invention (improvement of processing stability and suppression of discoloration), the above-mentioned compound (I), other phosphorus-based antioxidants, The compound (III) and other additives different from the organic material may be contained. Only 1 type may be used for another additive and it may use 2 or more types together. Hereinafter, other additives will be described in order.

  Other additives include, for example, neutralizers, acid-bonded metal salts, phenolic antioxidants, sulfur antioxidants, UV absorbers, light stabilizers, metal deactivators, peroxide scavengers, polyamides Stabilizers, lubricants, nucleating agents, fillers and antistatic agents can be mentioned. Any of these may be used alone or in combination of two or more. The other additives are not limited to the above and the following examples.

Examples of neutralizing agents include the following:
Calcium stearate, zinc stearate, magnesium stearate, hydrotalcite (basic magnesium, aluminum, hydroxy, carbonate, hydrate), melamine, amine, polyamide, polyurethane and mixtures thereof.

  When the organic material composition of the present invention contains a neutralizer, the amount of the neutralizer is preferably 0.001 to 0.2 parts by weight, more preferably 0.01 to 0.1 parts by weight with respect to 100 parts by weight of the organic material. 0.1 parts by weight.

Examples of the acid-bonded metal salt include hydrotalcites. Examples of hydrotalcites include the following formula:
M ²⁺ _1-x · M ³⁺ _x · (OH ⁻ ) ₂ · (A ⁿ⁻ ) _{x / n} · pH ₂ O
(In the formula, M ²⁺ represents Mg, Ca, Sr, Ba, Zn, Pb, Sn and / or Ni, M ³⁺ represents Al, B or Bi, and n represents a value of 1 to 4. , x is represents a value of 0 to 0.5, p is ^{.A n-is} representing a value of 0 to 2, represents an anion of valency n.)
The thing shown by is mentioned.

A The ^n-, for ^{example, OH -, Cl -, Br} -, I -, ClO 4 -, HCO 3 -, C 6 H 5 COO -, CO 3 2-, SO 2-, - OOCCOO -, (CHOHCOO ) ₂ ²⁻ , C ₂ H ₄ (COO) ₂ ²⁻ , (CH ₂ COO) ₂ ²⁻ , CH ₃ CHOHCOO ⁻ , SiO ₃ ²⁻ , SiO ₄ ⁴⁻ , Fe (CN) ₆ ⁴⁻ , BO ^{3 −} , PO ₃ ³⁻ , HPO ₄ ²⁻ .

Among hydrotalcites, the following formula:
Mg _1-x Al _x (OH) ₂ (CO ₃ ) _{x / 2} · pH ₂ O
(Wherein x and p are as defined above.)
Is preferred.

  Hydrotalcites may be natural products or synthetic products, and can be used regardless of their crystal structure, crystal particle diameter, and the like.

  Furthermore, ultrafine zinc oxide described in JP-A-6-329830, inorganic compounds described in JP-A-7-278164, and the like can also be used as acid-bonded metal salts.

Examples of phenolic antioxidants include the following:
(1) Alkylated monophenol 2,6-di-t-butyl-4-methylphenol, 2,4,6-tri-t-butylphenol, 2,6-di-t-butylphenol, 2-t-butyl- 4,6-dimethylphenol, 2,6-di-t-butyl-4-ethylphenol, 2,6-di-t-butyl-4-n-butylphenol, 2,6-di-t-butyl-4- Isobutylphenol, 2,6-dicyclopentyl-4-methylphenol, 2- (α-methylcyclohexyl) -4,6-dimethylphenol, 2,6-diocudadecyl-4-methylphenol, 2,4,6-tricyclohexyl Phenol, 2,6-di-t-butyl-4-methoxymethylphenol, 2,6-di-nonyl-4-methylphenol, 2,4-dimethyl-6- (1'-methyl) Luundecyl-1′-yl) phenol, 2,4-dimethyl-6- (1′-methylheptadecyl-1′-yl) phenol, 2,4-dimethyl-6- (1′-methyltridecyl-1 ′) -Yl) phenols and mixtures thereof.

(2) alkylthiomethylphenol 2,4-dioctylthiomethyl-6-t-butylphenol, 2,4-dioctylthiomethyl-6-methylphenol, 2,4-dioctylthiomethyl-6-ethylphenol, 2,6- Didodecylthiomethyl-4-nonylphenol and mixtures thereof.

(3) Hydroquinone and alkylated hydroquinone 2,6-di-t-butyl-4-methoxyphenol, 2,5-di-t-butylhydroquinone, 2,5-di-t-amylhydroquinone, 2,6-diphenyl -4-octadecyloxyphenol, 2,6-di-t-butylhydroquinone, 2,5-di-t-butyl-4-hydroxyanisole, 3,5-di-t-butyl-4-hydroxyphenyl stearate, Bis (3,5-di-tert-butyl-4-hydroxyphenyl) adipate and mixtures thereof.

(4) Hydroxylated thiodiphenyl ether 2,2′-thiobis (6-tert-butylphenol), 2,2′-thiobis (4-methyl-6-tert-butylphenol), 2,2′-thiobis (4-octylphenol) 4,4'-thiobis (3-methyl-6-tert-butylphenol), 4,4'-thiobis (2-methyl-6-tert-butylphenol), 4,4'-thiobis (3,6-di-) t-amylphenol), 4,4 '-(2,6-dimethyl-4-hydroxyphenyl) disulfide.

(5) Alkylidenebisphenol and derivatives thereof 2,2′-methylenebis (4-methyl-6-tert-butylphenol), 2,2′-methylenebis (4-ethyl-6-tert-butylphenol), 2,2′-methylenebis [4-methyl-6- (α-methylcyclohexyl) phenol)], 2,2′-methylenebis (4-methyl-6-cyclohexylphenol), 2,2′-methylenebis (4-methyl-6-nonylphenol), 2,2′-methylenebis (4,6-di-t-butylphenol), 2,2′-ethylidenebis (4,6-di-t-butylphenol), 2,2′-ethylidenebis (4-isobutyl-6) -T-butylphenol), 2,2′-methylenebis [6- (α-methylbenzyl) -4-nonylphenol], 2,2′-methylenebis [ -(Α, α-dimethylbenzyl) -4-nonylphenol], 4,4′-methylenebis (6-tert-butyl-2-methylphenol), 4,4′-methylenebis (2,6-di-tert-butylphenol) ), 4,4′-butylidenebis (3-methyl-6-tert-butylphenol), 1,1-bis (4-hydroxyphenyl) cyclohexane, 1,1-bis (5-tert-butyl-4-hydroxy-2) -Methylphenyl) butane, 2,6-bis (3-tert-butyl-5-methyl-2-hydroxybenzyl) -4-methylphenol, 1,1,3-tris (5-tert-butyl-4-hydroxy) -2-methylphenyl) butane, 1,1-bis (5-t-butyl-4-hydroxy-2-methylphenyl) -3-n-dodecylmercaptobutane, ethylene glycol bis [ 3,3-bis-3′-tert-butyl-4′-hydroxyphenyl) butyrate], bis (3-tert-butyl-4-hydroxy-5-methylphenyl) dicyclopentadiene, bis [2- (3 ′ -T-butyl-2'-hydroxy-5'-methylbenzyl) -6-t-butyl-4-methylphenyl] terephthalate, 1,1-bis (3,5-dimethyl-2-hydroxyphenyl) butane, 2 , 2-bis (3,5-di-tert-butyl-4-hydroxyphenyl) propane, 2,2-bis (5-tert-butyl-4-hydroxy-2-methylphenyl) -4-n-dodecyl mercapto Butane, 1,1,5,5-tetra (5-t-butyl-4-hydroxy-2-methylphenyl) pentane, 2-t-butyl-6- (3′-t-butyl-5′-methyl-) 2'-Hydroxybenz ) -4-methylphenyl acrylate, 2,4-di -t- pentyl-6- [1- (2-hydroxy-3,5-di -t- pentylphenyl) ethyl] phenyl acrylate, and mixtures thereof.

(6) O-, N- and S-benzyl derivatives 3,5,3 ', 5'-tetra-t-butyl-4,4'-dihydroxydibenzyl ether, octadecyl-4-hydroxy-3,5-dimethyl Benzyl mercaptoacetate, tris (3,5-di-t-butyl-4-hydroxybenzyl) amine, bis (4-t-butyl-3-hydroxy-2,6-dimethylbenzyl) dithioterephthalate, bis (3,5 -Di-tert-butyl-4-hydroxybenzyl) sulfide, isooctyl-3,5-di-tert-butyl-4-hydroxybenzyl mercaptoacetate and mixtures thereof.

(7) Hydroxybenzylated malonate derivative dioctadecyl-2,2-bis (3,5-di-t-butyl-2-hydroxybenzyl) malonate, dioctadecyl-2- (3-t-butyl-4-hydroxy- 5-methylbenzyl) malonate, didodecylmercaptoethyl-2,2-bis (3,5-di-t-butyl-4-hydroxybenzyl) malonate, bis [4- (1,1,3,3-tetramethyl) Butyl) phenyl] -2,2-bis (3,5-di-tert-butyl-4-hydroxybenzyl) malonate and mixtures thereof.

(8) Aromatic hydroxybenzyl derivative 1,3,5-trimethyl-2,4,6-tris (3,5-di-t-butyl-4-hydroxybenzyl) benzene, 1,4-bis (3,5 -Di-t-butyl-4-hydroxybenzyl) -2,3,5,6-tetramethylbenzene, 2,4,6-tris (3,5-t-butyl-4-hydroxybenzyl) phenol and their blend.

(9) Triazine derivative 2,4-bis (n-octylthio) -6- (4-hydroxy-3,5-di-t-butylanilino) -1,3,5-triazine, 2-n-octylthio-4, 6-bis (4-hydroxy-3,5-di-t-butylanilino) -1,3,5-triazine, 2-n-octylthio-4,6-bis (4-hydroxy-3,5-di-t -Butylphenoxy) -1,3,5-triazine, 2,4,6-tris (3,5-di-tert-butyl-4-phenoxy) -1,3,5-triazine, tris (4-t- Butyl-3-hydroxy-2,6-dimethylbenzyl) isocyanurate, tris (3,5-di-t-butyl-4-hydroxybenzyl) isocyanurate, 2,4,6-tris (3,5-di-) t-Butyl-4-hydroxypheny Ruethyl) -1,3,5-triazine, 2,4,6-tris (3,5-di-tert-butyl-4-hydroxyphenylpropyl) -1,3,5-triazine, tris (3,5- Dicyclohexyl-4-hydroxybenzyl) isocyanurate, tris [2- (3 ′, 5′-di-t-butyl-4′-hydroxycinnamoyloxy) ethyl] isocyanurate and mixtures thereof.

(10) Benzylphosphonate derivative Dimethyl-3,5-di-t-butyl-4-hydroxybenzylphosphonate, diethyl-3,5-di-t-butyl-4-hydroxybenzylphosphonate, dioctadecyl-3,5-di -T-butyl-4-hydroxybenzylphosphonate, dioctadecyl-5-t-butyl-4-hydroxy-3-methylbenzylphosphonate, calcium of 3,5-di-t-butyl-4-hydroxybenzylphosphonic acid monoester Salts and mixtures thereof.

(11) Acylaminophenol derivatives 4-hydroxylauric acid anilide, 4-hydroxystearic acid anilide, octyl-N- (3,5-di-tert-butyl-4-hydroxyphenyl) carbamate and mixtures thereof.

(12) Esters of β- (3,5-di-t-butyl-4-hydroxyphenyl) propionic acid and the following mono- or polyhydric alcohols: methanol, ethanol, octanol, octadecanol, ethylene glycol, 1, 3-propanediol, 1,4-butanediol, 1,6-hexanediol, 1,9-nonanediol, neopentyl glycol, diethylene glycol, thioethylene glycol, spiro glycol, triethylene glycol, pentaerythritol, tris (hydroxyethyl) ) Isocyanurate, N, N′-bis (hydroxyethyl) oxamide, 3-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol, trimethylolpropane, 4-hydroxymethyl-1-phospha-2,6 , 7- Trioxabicyclo [2,2,2] octane and mixtures thereof.

(13) Esters of β- (5-tert-butyl-4-hydroxy-3-methylphenyl) propionic acid and the following mono- or polyhydric alcohols: methanol, ethanol, octanol, octadecanol, ethylene glycol, 1, 3-propanediol, 1,4-butanediol, 1,6-hexanediol, 1,9-nonanediol, neopentyl glycol, diethylene glycol, thioethylene glycol, spiro glycol, triethylene glycol, pentaerythritol, tris (hydroxyethyl) ) Isocyanurate, N, N′-bis (hydroxyethyl) oxamide, 3-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol, trimethylolpropane, 4-hydroxymethyl-1-phospha-2,6 , 7-Trioxabicyclo [2,2,2] octane and mixtures thereof.

(14) Esters of β- (3,5-dicyclohexyl-4-hydroxyphenyl) propionic acid and the following mono- or polyhydric alcohols: methanol, ethanol, octanol, octadecanol, ethylene glycol, 1,3-propanediol 1,4-butanediol, 1,6-hexanediol, 1,9-nonanediol, neopentyl glycol, diethylene glycol, thioethylene glycol, spiro glycol, triethylene glycol, pentaerythritol, tris (hydroxyethyl) isocyanurate, N, N′-bis (hydroxyethyl) oxamide, 3-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol, trimethylolpropane, 4-hydroxymethyl-1-phospha-2,6,7 -Trioxabicyclo [2,2,2] octane and mixtures thereof.

(15) Esters of 3,5-di-t-butyl-4-hydroxyphenylacetic acid and the following mono- or polyhydric alcohols: methanol, ethanol, octanol, octadecanol, ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,6-hexanediol, 1,9-nonanediol, neopentyl glycol, diethylene glycol, thioethylene glycol, spiro glycol, triethylene glycol, pentaerythritol, tris (hydroxyethyl) isocyanurate, N , N′-bis (hydroxyethyl) oxamide, 3-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol, trimethylolpropane, 4-hydroxymethyl-1-phospha-2,6,7-trioxabici B [2,2,2] octane and mixtures thereof.

(16) Amide of β- (3,5-di-t-butyl-4-hydroxyphenyl) propionic acid N, N′-bis [3- (3 ′, 5′-di-t-butyl-4′- Hydroxyphenyl) propionyl] hydrazine, N, N′-bis [3- (3 ′, 5′-di-t-butyl-4′-hydroxyphenyl) propionyl] hexamethylenediamine, N, N′-bis [3- (3 ′, 5′-di-tert-butyl-4′-hydroxyphenyl) propionyl] trimethylenediamine and mixtures thereof.

Examples of sulfur-based antioxidants include the following:
Dilauryl 3,3'-thiodipropionate, tridecyl 3,3'-thiodipropionate, dimyristyl 3,3'-thiodipropionate, distearyl 3,3'-thiodipropionate, lauryl stearyl 3,3 '-Thiodipropionate, neopentanetetrayltetrakis (3-laurylthiopropionate).

Examples of ultraviolet absorbers include the following:
(1) Salicylate derivatives Phenyl salicylate, 4-t-butylphenyl salicylate, 2,4-di-t-butylphenyl 3 ′, 5′-di-t-butyl-4′-hydroxybenzoate, 4-t-octylphenyl Salicylate, bis (4-t-butylbenzoyl) resorcinol, benzoylresorcinol, hexadecyl 3 ′, 5′-di-t-butyl-4′-hydroxybenzoate, octadecyl 3 ′, 5′-di-t-butyl-4 ′ -Hydroxybenzoate, 2-methyl-4,6-di-tert-butylphenyl 3 ', 5'-di-tert-butyl-4'-hydroxybenzoate and mixtures thereof.

(2) 2-hydroxybenzophenone and derivatives thereof 2-hydroxybenzophenone, 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-octoxybenzophenone, 2,2′-dihydroxy-4- Methoxybenzophenone, bis (5-benzoyl-4-hydroxy-2-methoxyphenyl) methane, 2,2 ′, 4,4′-tetrahydroxybenzophenone and mixtures thereof.

(3) 2- (2′-hydroxyphenyl) benzotriazole and derivatives thereof 2- (2′-hydroxyphenyl) benzotriazole, 2- (2-hydroxy-5-methylphenyl) benzotriazole, 2- (3 ′, 5'-di-t-butyl-2'-hydroxyphenyl) benzotriazole, 2- (5'-t-butyl-2'-hydroxyphenyl) benzotriazole, 2- (2'-hydroxy-5'-t- Octylphenyl) benzotriazole, 2- (3-t-butyl-2-hydroxy-5-methylphenyl) -5-chlorobenzotriazole, 2- (3′-s-butyl-2′-hydroxy-5′-t -Butylphenyl) benzotriazole, 2- (2'-hydroxy-4'-octyloxyphenyl) benzotriazole, 2- (3 ', 5'-di-t- Mil-2′-hydroxyphenyl) benzotriazole, 2- [2′-hydroxy-3 ′, 5′-bis (α, α-dimethylbenzyl) phenyl] -2H-benzotriazole, 2-[(3′-t -Butyl-2'-hydroxyphenyl) -5 '-(2-octyloxycarbonylethyl) phenyl] -5-chlorobenzotriazole, 2- [3'-t-butyl-5'-[2- (2-ethylhexyl) Oxy) carbonylethyl] -2′-hydroxyphenyl] -5-chlorobenzotriazole, 2- [3′-tert-butyl-2′-hydroxy-5 ′-(2-methoxycarbonylethyl) phenyl] -5-chloro Benzotriazole, 2- [3′-t-butyl-2′-hydroxy-5 ′-(2-methoxycarbonylethyl) phenyl] benzotriazole, 2- [3′-t-butyl Tyl-2'-hydroxy-5- (2-octyloxycarbonylethyl) phenyl] benzotriazole, 2- [3'-t-butyl-2'-hydroxy-5 '-[2- (2-ethylhexyloxy) carbonyl Ethyl] phenyl] benzotriazole, 2- [2-hydroxy-3- (3,4,5,6-tetrahydrophthalimidomethyl) -5-methylphenyl] benzotriazole, 2- (3,5-di-t-butyl 2-hydroxyphenyl) -5-chlorobenzotriazole, 2- (3′-dodecyl-2′-hydroxy-5′-methylphenyl) benzotriazole and 2- [3′-t-butyl-2′-hydroxy- A mixture of 5 '-(2-isooctyloxycarbonylethyl) phenyl] benzotriazole, 2,2'-methylenebis [6- (2H- Nzotriazol-2-yl) -4- (1,1,3,3-tetramethylbutyl) phenol, 2,2′-methylenebis [4-t-butyl-6- (2H-benzotriazol-2-yl) ) Phenol], poly (3-11) (ethylene glycol) and 2- [3′-tert-butyl-2′-hydroxy-5 ′-(2-methoxycarbonylethyl) phenyl] benzotriazole, polycondensate A condensate of (3-11) (ethylene glycol) with methyl 3- [3- (2H-benzotriazol-2-yl) -5-tert-butyl-4-hydroxyphenyl] propionate, 2-ethylhexyl 3- [ 3-t-butyl-5- (5-chloro-2H-benzotriazol-2-yl) -4-hydroxyphenyl] propionate, octyl 3- [3-t-butyl- -(5-Chloro-2H-benzotriazol-2-yl) -4-hydroxyphenyl] propionate, methyl 3- [3-tert-butyl-5- (5-chloro-2H-benzotriazol-2-yl)- 4-hydroxyphenyl] propionate, 3- [3-t-butyl-5- (5-chloro-2H-benzotriazol-2-yl) -4-hydroxyphenyl] propionic acid and mixtures thereof.

Examples of light stabilizers include the following:
(1) Hindered amine light stabilizer bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis ((2,2,6,6-tetramethyl-4-piperidyl) succinate, bis (1 , 2,2,6,6-pentamethyl-4-piperidyl) sebacate, bis (N-octoxy-2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis (N-benzyloxy-2,2) , 6,6-tetramethyl-4-piperidyl) sebacate, bis (N-cyclohexyloxy-2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis (1,2,2,6,6- Pentamethyl-4-piperidyl) 2- (3,5-di-t-butyl-4-hydroxybenzyl) -2-butylmalonate, bis (1-acryloyl-2,2,6,6-tetra Methyl-4-piperidyl) 2,2-bis (3,5-di-t-butyl-4-hydroxybenzyl) -2-butylmalonate, bis (1,2,2,6,6-pentamethyl-4- Piperidyl decandioate, 2,2,6,6-tetramethyl-4-piperidyl methacrylate, 4- [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionyloxy] -1- [2 -(3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionyloxy) ethyl] -2,2,6,6-tetramethylpiperidine, 2-methyl-2- (2,2,6 , 6-Tetramethyl-4-piperidyl) amino-N- (2,2,6,6-tetramethyl-4-piperidyl) propionamide, tetrakis (2,2,6,6-tetramethyl-4-piperidyl) 1, , 3,4-Butanetetracarboxylate, tetrakis (1,2,2,6,6-pentamethyl-4-piperidyl) 1,2,3,4-butanetetracarboxylate, 1,2,3,4-butane Mixed esterified products of tetracarboxylic acid and 1,2,2,6,6-pentamethyl-4-piperidinol and 1-tridecanol, 1,2,3,4-butanetetracarboxylic acid and 2,2,6,6- Mixed esterified product of tetramethyl-4-piperidinol and 1-tridecanol, 1,2,3,4-butanetetracarboxylic acid and 1,2,2,6,6-pentamethyl-4-piperidinol and 3,9-bis (2-hydroxy-1,1-dimethylethyl) -2,4,8,10-tetraoxaspiro [5.5] undecane mixed ester product, 1,2,3 -Butanetetracarboxylic acid and 2,2,6,6-tetramethyl-4-piperidinol and 3,9-bis (2-hydroxy-1,1-dimethylethyl) -2,4,8,10-tetraoxaspiro [5.5] Mixed esterified product with undecane, polycondensate of dimethyl succinate and 1- (2-hydroxyethyl) -4-hydroxy-2,2,6,6-tetramethylpiperidine, poly [(6- Morpholino-1,3,5-triazine-2,4-diyl) ((2,2,6,6-tetramethyl-4-piperidyl) imino) hexamethylene ((2,2,6,6-tetramethyl- 4-piperidyl) imino)], poly [(6- (1,1,3,3-tetramethylbutyl) imino-1,3,5-triazine-2,4-diyl ((2,2,6,6) -Tetramethyl-4 Piperidyl) imino) hexamethylene ((2,2,6,6-tetramethyl-4-piperidyl) imino)], N, N′-bis (2,2,6,6-tetramethyl-4-piperidyl) hexa A polycondensate of methylenediamine and 1,2-dibromoethane, N, N ′, 4,7-tetrakis [4,6-bis (N-butyl-N- (2,2,6,6-tetramethyl- 4-piperidyl) amino) -1,3,5-triazin-2-yl] -4,7-diazadecane-1,10 diamine, N, N ′, 4-tris [4,6-bis (N-butyl-) N- (2,2,6,6-tetramethyl-4-piperidyl) amino) -1,3,5-triazin-2-yl] -4,7-diazadecane-1,10-diamine, N, N ′ , 4,7-tetrakis [4,6-bis (N-butyl-N- (1,2, , 6,6-pentamethyl-4-piperidyl) amino) -1,3,5-triazin-2-yl] -4,7-diazadecane-1,10-diamine, N, N ′, 4-tris [4, 6-bis (N-butyl-N- (1,2,2,6,6-pentamethyl-4-piperidyl) amino) -1,3,5-triazin-2-yl] -4,7-diazadecane-1 , 10-diamine and mixtures thereof.

(2) Acrylate-based light stabilizer Ethyl α-cyano-β, β-diphenyl acrylate, isooctyl α-cyano-β, β-diphenyl acrylate, methyl α-carbomethoxycinnamate, methyl α-cyano-β-methyl-p -Methoxycinnamate, butyl α-cyano-β-methyl-p-methoxycinnamate, methyl α-carbomethoxy-p-methoxycinnamate and N- (β-carbomethoxy-β-cyanovinyl) -2-methylindoline and A mixture of them.

(3) Nickel-based light stabilizer Nickel complex of 2,2′-thiobis- [4- (1,1,3,3-tetramethylbutyl) phenol], nickel dibutyldithiocarbamate, nickel salt of monoalkyl ester, ketoxime Nickel complexes and mixtures thereof.

(4) Oxamide-based light stabilizer 4,4′-dioctyloxyoxanilide, 2,2′-diethoxyoxanilide, 2,2′-dioctyloxy-5,5′-di-t-butylanilide, 2,2′-didodecyloxy-5,5′-di-t-butylanilide, 2-ethoxy-2′-ethyloxanilide, N, N′-bis (3-dimethylaminopropyl) oxamide, 2- Ethoxy-5-t-butyl-2'-ethoxyanilide, 2-ethoxy-5,4'-di-t-butyl-2'-ethyloxanilide and mixtures thereof.

(5) 2- (2-hydroxyphenyl) -1,3,5-triazine-based light stabilizer 2,4,6-tris (2-hydroxy-4-octyloxyphenyl) -1,3,5-triazine, 2- (2-hydroxy-4-octyloxyphenyl) -4,6-bis (2,4-dimethylphenyl) -1,3,5-triazine, 2- [2,4-dihydroxyphenyl-4,6- Bis (2,4-dimethylphenyl) -1,3,5-triazine, 2,4-bis (2-hydroxy-4-propyloxyphenyl) -6- (2,4-dimethylphenyl) -1,3 5-triazine, 2- (2-hydroxy-4-octyloxyphenyl) -4,6-bis (4-methylphenyl) -1,3,5-triazine, 2- (2-hydroxy-4-dodecyloxyphenyl) ) -4, 6-bis (2,4-dimethylphenyl) -1,3,5-triazine, 2- [2-hydroxy-4- (2-hydroxy-3-butyloxypropoxy) phenyl] -4,6-bis (2 , 4-Dimethylphenyl) -1,3,5-triazine, 2- [2-hydroxy-4- (2-hydroxy-3-octyloxypropoxy) phenyl] -4,6-bis (2,4-dimethylphenyl) ) -1,3,5-triazine and mixtures thereof.

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

Examples of peroxide scavengers include the following:
Esters of β-thiodipropionic acid, mercaptobenzimidazole, zinc salt of 2-mercaptobenzimidazole, zinc salt of dibutyldithiocarbamic acid, dioctadecyl disulfide, pentaerythritol tetrakis (β-dodecylmercapto) propionate and mixtures thereof.

  Polyamide stabilizers include, for example, copper or divalent manganese salts of iodides or phosphorus compounds and mixtures thereof.

Examples of the lubricant include the following:
Aliphatic hydrocarbons such as paraffin and wax, C _8-22 aliphatic acid, C _8-22 aliphatic acid metal (Al, Ca, Mg, Zn) salt, C _8-22 aliphatic alcohol, polyglycol, C _{4 -22} ester of fatty acid and C _4-18 aliphatic monohydric alcohol, C _8-22 aliphatic amide, silicone oil, rosin derivative.

Examples of nucleating agents include the following:
Sodium 2,2′-methylenebis (4,6-di-t-butylphenyl) phosphate, [phosphate-2,2′-methylenebis (4,6-di-t-butylphenyl)] dihydroxyaluminum, bis [ Phosphate-2,2'-methylenebis (4,6-di-t-butylphenyl)] hydroxyaluminum, tris [phosphate-2,2'-methylenebis (4,6-di-t-butylphenyl)] Aluminum, sodium bis (4-tert-butylphenyl) phosphate, benzoic acid metal salts such as sodium benzoate, aluminum pt-butylbenzoate, 1,3: 2,4-bis (O-benzylidene) sorbitol, 1 , 3: 2,4-bis (O-methylbenzylidene) sorbitol, 1,3: 2,4-bis (O-ethylbenzylidene) sorbitol, 1, -O-3,4-dimethylbenzylidene-2,4-O-benzylidene sorbitol, 1,3-O-benzylidene-2,4-O-3,4-dimethylbenzylidene sorbitol, 1,3: 2,4-bis (O-3,4-dimethylbenzylidene) sorbitol, 1,3-O-p-chlorobenzylidene-2,4-O-3,4-dimethylbenzylidene sorbitol, 1,3-O-3,4-dimethylbenzylidene- 2,4-Op-chlorobenzylidene sorbitol, 1,3: 2,4-bis (Op-chlorobenzylidene) sorbitol and mixtures thereof.

Examples of fillers include the following:
Calcium carbonate, silicate, glass fiber, asbestos, talc, kaolin, mica, barium sulfate, carbon black, carbon fiber, zeolite and mixtures thereof.

  Examples of the antistatic agent include a cationic surfactant, an anionic surfactant, a nonionic surfactant, an amphoteric surfactant, and an alkanolamine. Examples of cationic surfactants include quaternary ammonium salt type cationic surfactants, amine salts (primary amine salts, secondary amine salts, tertiary amine salts, quaternary amine salts), pyridine derivatives. Etc. Examples of anionic surfactants include alkyl phosphate type anionic surfactants, sulfated oils, soaps, sulfated ester oils, sulfated amide oils, olefin sulfated ester salts, fatty alcohol sulfate ester salts, alkyl sulfates. Examples include ester salts, fatty acid ethyl sulfonates, alkyl naphthalene sulfonates, alkyl benzene sulfonates, oxalate sulfonates, and phosphate ester salts. Nonionic surfactants include, for example, partial esters of polyhydric alcohol and fatty acid, ethylene oxide adduct of fatty alcohol, ethylene oxide adduct of fatty acid, ethylene oxide adduct of fatty amine or fatty acid amide, ethylene oxide addition of alkylphenol Products, ethylene oxide adducts of partial esters of polyhydric alcohols and fatty acids, polyethylene glycol, and the like. Examples of amphoteric surfactants include betaine-type amphoteric surfactants, carboxylic acid derivatives, and imidazoline derivatives. The alkanolamine may be any of trialkanolamine, dialkanolamine and monoalkanolamine. Examples of the trialkanolamine include triethanolamine, tripropanolamine, and triisopropanolamine. Examples of dialkanolamines include diethanolamine, dipropanolamine, diisopropanolamine, tetraethanolethylenediamine, and tetraisopropanolethylenediamine. Examples of the monoalkanolamine include dibutyl isopropanolamine.

<Stabilizer composition>
The stabilizer composition of the present invention comprises compound (I), another phosphorus antioxidant and compound (III). The stabilizer composition of the present invention may contain other additives as necessary. The amount of the other phosphorus antioxidant in the stabilizer composition and the weight ratio between the amount of compound (I) and the amount of the other phosphorus antioxidant are as described above. Further, the weight ratio of the total amount of compound (I) and other phosphorus antioxidants to the amount of compound (III) in the stabilizer composition is as described above.

  The stabilizer composition of the present invention can be produced by mixing compound (I), other phosphorus antioxidant and compound (III), and other additives as required. The mixing method is not particularly limited, and the above-described components may be mixed using a known apparatus. Mixing may be either dry mixing or wet mixing.

  You may manufacture the stabilizer composition which is the shape of a granulated material by utilizing a granulation method. The granulation method is not particularly limited, and examples thereof include compression granulation method, extrusion granulation method, stirring granulation method, rolling granulation method, spray granulation method, and fluidized bed granulation method. There are no particular limitations on the apparatus used for the granulation method, and examples thereof include a compression granulator, an extrusion granulator, an agitation granulator, a rolling granulator, a spray granulator, and a fluidized bed granulator. Is mentioned. The granulation may be either dry granulation or wet granulation (granulation using a binder or the like).

<Organic material composition>
The organic material composition of the present invention comprises an organic material and the stabilizer composition described above (that is, compound (I), other phosphorus antioxidant and compound (III)). The organic material composition of the present invention may contain other additives as necessary. The amount of other phosphorus antioxidant in the organic material composition and the weight ratio of the amount of compound (I) to the amount of other phosphorus antioxidant are as described above. In addition, the weight ratio of the total amount of compound (I) and other phosphorus antioxidants to the amount of compound (III) in the organic material composition is as described above.

  From the viewpoint of improving processing stability and suppressing discoloration, the amount of compound (III) in the organic material composition is preferably 0.005 to 0.02 parts by weight, more preferably 100 parts by weight of the organic material. Is 0.005 to 0.018 part by weight, more preferably 0.005 to 0.015 part by weight.

  The organic material composition of the present invention may be produced by mixing an organic material, a stabilizer composition produced in advance, and other additives as necessary. The organic material and the compound (I ), Other phosphorus antioxidants, compound (III), and other additives as necessary. The mixing method is not particularly limited, and the above-described components may be mixed using a known apparatus. Mixing may be either dry mixing or wet mixing. “Pre-manufactured stabilizer composition and other additives as required” and “Organic materials, Compound (I), other phosphorus antioxidants, Compound (III) and other additives as required "Is abbreviated as" stabilizer composition of the present invention "hereinafter.

  When the organic material is a solid polymer, (1) the solid polymer and the stabilizer composition of the present invention may be directly dry blended. (2) First, a small amount of the solid polymer and the stabilizer composition of the present invention. May be kneaded to form a master batch, and then the master batch and the solid polymer may be dry blended. When the organic material is a liquid polymer, a solution or dispersion of the stabilizer composition of the present invention may be added to the polymer solution during or after polymerization.

  When the organic material is a liquid such as a lubricating oil, (1) the stabilizer composition of the present invention may be added directly to the liquid organic material, and (2) the stabilizer composition of the present invention is used as a solvent. It is also possible to prepare a solution or dispersion by dissolving or dispersing in the solution, and adding the obtained solution or dispersion to the liquid organic material.

  EXAMPLES Hereinafter, the present invention will be described in more detail with reference to examples. However, the present invention is not limited by the following examples, and appropriate modifications are made within a range that can meet the above and the following purposes. Of course, it is possible to implement them, and they are all included in the technical scope of the present invention. In the following examples and comparative examples, “parts” means “parts by weight” unless otherwise specified.

<Ingredients>
The components used in Examples and Comparative Examples are described below.
(1) Stabilizer (1-1) Phosphorous antioxidant Compound (Ia): “SUMILIZER (registered trademark) GP” manufactured by Sumitomo Chemical Co., Ltd.
Compound (II-1a): “Irgafos (registered trademark) 168” manufactured by BASF
(1-2) Phenol-based antioxidant Phenol-based antioxidant 1: “Irganox (registered trademark) 1076” manufactured by BASF
Phenol-based antioxidant 2: “Irganox (registered trademark) 1010” manufactured by BASF
(1-3) Other stabilizers α-tocopherol: “Irganox (registered trademark) E201” manufactured by BASF

(2) Neutralizing agent Calcium stearate

(3) Organic material LLDPE: linear low density polyethylene manufactured by Sumitomo Chemical Co., Ltd. (melt flow rate (MFR) at a temperature of 190 ° C. and a load of 21.18 N: 2.0 g / 10 min)
PP: Propylene homopolymer manufactured by Sumitomo Chemical Co., Ltd. (melt flow rate (MFR) at a temperature of 230 ° C. and a load of 21.18 N: 3.0 g / 10 min)

Examples 1-5 and Comparative Examples 1-7
(1) Manufacture of pellets (organic material composition) LLDPE (100 parts), calcium stearate (0.05 parts), and the types and amounts of stabilizers shown in Table 1 were dry blended, and the resulting mixture was transferred to a cylinder. Using a single screw extruder (VS30-28 type extruder, manufactured by Tanabe Plastics Co., Ltd.) having a diameter of 30 mm, the mixture was kneaded in an air atmosphere at a temperature of 190 ° C. and a screw rotation speed of 80 rpm to obtain pellets 1. The pellet 1 obtained was kneaded using the single screw extruder under the conditions of an air atmosphere at a temperature of 280 ° C. and a screw rotation speed of 70 rpm to obtain pellets 5 times.

(2) Evaluation of processing stability Melt flow rate (MFR1) and pellet 2 at a temperature of 190 ° C. and a load of 21.18 N using a melt indexer (model L246-3537, manufactured by Techno Seven Co., Ltd.) The melt flow rate (MFR2) was measured and the MFR2 / MFR1 ratio was calculated. Crosslinking of linear low density polyethylene (LLDPE) proceeds by heat processing, and its MFR decreases. Therefore, the processing stability of the organic material composition containing LLDPE is better as the MFR2 / MFR1 ratio is larger. Based on the obtained MFR2 / MFR1 ratio, the processing stability was evaluated according to the following criteria. The results are shown in Table 1.
Evaluation criteria for processing stability (MFR2 / MFR1 ratio) ◎: 0.70 or more ○: 0.65 or more and less than 0.70 Δ: 0.61 or more and less than 0.65 ×: less than 0.61

(3) Evaluation of discoloration Using a press machine (“PEW-5040” manufactured by Kansai Roll Co., Ltd.) at a temperature of 200 ° C., a sheet having a thickness of 1 mm was obtained from the obtained pellet 2. The yellow index (YI) of the obtained sheet was measured using a color difference meter (“CM-3500d” manufactured by Minolta). As YI is smaller, discoloration is suppressed. Based on the obtained YI, discoloration was evaluated according to the following criteria. The results are shown in Table 1.
Evaluation criteria for discoloration (YI) ○: 0.60 or more and less than 1.10 Δ: 1.10 or more and less than 1.30 ×: 1.30 or more

Examples 6-8 and Comparative Examples 8-10
(1) Manufacture of pellets (organic material composition) PP (100 parts), calcium stearate (0.05 parts), and the types and amounts of stabilizers shown in Table 2 were dry blended, and the resulting mixture was transferred to a cylinder. Using a single screw extruder (VS30-28 type extruder, manufactured by Tanabe Plastics Co., Ltd.) having a diameter of 30 mm, the mixture was kneaded in an air atmosphere at a temperature of 230 ° C. and a screw rotation speed of 80 rpm to obtain pellets 1. The obtained pellet 1 was kneaded in an air atmosphere at a temperature of 280 ° C. and a screw rotation speed of 70 rpm using the single screw extruder to obtain pellets 5 times, whereby pellet 2 was obtained.

(2) Evaluation of processing stability Using a melt indexer (model L246-3537, manufactured by Techno Seven Co., Ltd.), the melt flow rate (MFR1) of pellet 1 and the pellet 2 at 230 ° C. and a load of 21.18 N The melt flow rate (MFR2) was measured and the MFR2 / MFR1 ratio was calculated. Propylene homopolymer (PP) is decomposed by heat processing, and its MFR increases. Therefore, the processing stability of an organic material composition containing PP is better as the MFR2 / MFR1 ratio is smaller. Based on the obtained MFR2 / MFR1 ratio, the processing stability was evaluated according to the following criteria. The results are shown in Table 2.
Evaluation criteria of processing stability (MFR2 / MFR1 ratio) ◎: Less than 2.30 ○: 2.30 or more and less than 2.60 Δ: 2.60 or more and less than 3.00 x: 3.00 or more

(3) Evaluation of discoloration Using a press machine (“PEW-5040” manufactured by Kansai Roll Co., Ltd.) under the condition of a temperature of 210 ° C., a sheet having a thickness of 1 mm was obtained from the obtained pellet 2. The yellow index (YI) of the obtained sheet was measured using a color difference meter (“CM-3500d” manufactured by Minolta). As YI is smaller, discoloration is suppressed. Based on the obtained YI, discoloration was evaluated according to the following criteria. The results are shown in Table 2.
Evaluation criteria for discoloration (YI) ○: Less than 3.40 Δ: 3.40 or more and less than 3.50 ×: 3.50 or more

  The stabilizer composition of the present invention is useful as a stabilizer for organic materials.

Claims (11)

Formula (I):
[In formula (I), R < ¹ >, R < ² >, R < ⁴ > and R < ⁵ > are respectively independently a hydrogen atom, a _C1-8 alkyl group, a _C5-8 cycloalkyl group, a _C6-12 alkylcycloalkyl group. _Represents a C _7-12 aralkyl group or a C _6-14 aryl group,
R ³ represents a hydrogen atom or a C _1-8 alkyl group,
X is a divalent group represented by a single bond, a sulfur atom or —CHR ⁶ — (wherein R ⁶ represents a hydrogen atom, a C _1-8 alkyl group or a C _5-8 cycloalkyl group). Represents
A is a C _2-8 alkylene group or * -COR ⁷ -group (in the above formula, R ⁷ represents a single bond or a C _1-8 alkylene group, and * is bonded to the oxygen atom side) And any one of Y and Z represents a hydroxy group, a C _1-8 alkoxy group or a C _7-12 aralkyloxy group, and the other represents a hydrogen atom or C Represents a _1-8 alkyl group. ]
A compound represented by
Another phosphorus antioxidant different from the compound represented by formula (I),
Formula (III):
[In Formula (III), R ³¹ and R ³² each independently represent a hydrogen atom or a methyl group, and R ³³ represents a C _1-20 alkyl group or a C _2-20 alkenyl group. ]
And a compound represented by
Weight ratio of the total amount of the compound represented by formula (I) and other phosphorus antioxidants to the amount of the compound represented by formula (III) (compounds represented by formula (I) and other phosphorous oxidations) A stabilizer composition in which the total amount of the inhibitor: the amount of the compound represented by formula (III) is 1: 0.05 to 1: 0.2. Another phosphorus antioxidant is represented by the formula (II-1):
Wherein ^{(II-1), R 8} ~R 10 are each _{independently, C 1-10} or an alkyl group, or a _{C 1-10} alkyl _{group, C 5-8} cycloalkyl _{group, C 6-12} It represents a phenyl group which may have at least one substituent selected from the group consisting of an alkylcycloalkyl group, a C _7-12 aralkyl group and a phenyl group. ]
A compound represented by
Formula (II-2):
[In formula (II-2), two R ^{11 s} independently represent a hydrogen atom, a C _1-10 alkyl group, a C _5-8 cycloalkyl group, a C _6-12 alkyl cycloalkyl group, a C _{7- 12} represents an aralkyl group or a phenyl group, and two R ^{12 s} independently represent a hydrogen atom, a C _1-10 alkyl group, a C _5-8 cycloalkyl group, a C _6-12 alkyl cycloalkyl group, a C _{7. -12} represents an aralkyl group or a phenyl group. ]
A compound represented by
Formula (II-3):
[In Formula (II-3), R ¹³ and R ¹⁴ each independently represent a C _1-20 alkyl group, or a C _1-10 alkyl group optionally having a phenyl group, C _{5- It} represents a phenyl group which may have at least one substituent selected from the group consisting of an ₈ cycloalkyl group, a C _6-12 alkylcycloalkyl group, a C _7-12 aralkyl group and a phenyl group. ]
A compound represented by
Formula (II-4):
[In formula (II-4), R ¹⁵ represents a C _1-20 alkyl group, or a C _1-10 alkyl group optionally having a phenyl group, a C _5-8 cycloalkyl group, C _{6. Represents a} phenyl group _optionally having at least one substituent selected from the group consisting of a _-12 alkylcycloalkyl group, a C _7-12 aralkyl group and a phenyl group, and R ¹⁶ and R ¹⁷ are each independently , Represents a C _1-10 alkyl group. ]
A compound represented by
Formula (II-5):
[In the formula (II-5), three R ^{18 s} independently represent a hydrogen atom, a C _1-10 alkyl group, a C _5-8 cycloalkyl group, a C _6-12 alkyl cycloalkyl group, a C _{7- 12} represents an aralkyl group or a phenyl group,
Three R ^{19 s} each independently represent a hydrogen atom, a C _1-10 alkyl group, a C _5-8 cycloalkyl group, a C _6-12 alkyl cycloalkyl group, a C _7-12 aralkyl group or a phenyl group,
Three R ^{20 s} each independently represent a hydrogen atom, a C _1-10 alkyl group, a C _5-8 cycloalkyl group, a C _6-12 alkyl cycloalkyl group, a C _7-12 aralkyl group or a phenyl group,
Three R ^{21 s} each independently represent a hydrogen atom, a C _1-10 alkyl group, a C _5-8 cycloalkyl group, a C _6-12 alkyl cycloalkyl group, a C _7-12 aralkyl group or a phenyl group,
Three L ^{1 s} each independently represent a single bond, a sulfur atom, or —C (R ²² ) (R ²³ ) — (wherein R ²² and R ²³ have a total carbon number of 7 or less. Each independently represents a hydrogen atom or a C _1-7 alkyl group.), And three L ² are each independently a C _2-8 alkylene group. Represents. ]
And a compound of formula (II-6):
[In the formula (II-6), R ^{24 to} R ²⁷ are each independently a hydrogen atom, a C _1-10 alkyl group, a C _5-8 cycloalkyl group, a C _6-12 alkyl cycloalkyl group, a C _{7- 12} represents an aralkyl group or a phenyl group,
R ²⁸ represents a halogen atom or a C _1-10 alkoxy group, or consists of a C _1-10 alkyl group, a C _5-8 cycloalkyl group, a C _6-12 alkyl cycloalkyl group and a C _7-12 aralkyl group. Represents a phenyloxy group which may have at least one substituent selected from the group, and L ³ represents a single bond, a sulfur atom or —C (R ²⁹ ) (R ³⁰ ) — (wherein R ²⁹ and R ³⁰ each independently represents a hydrogen atom or a C _1-7 alkyl group on condition that the total number of carbon atoms is 7 or less.} Represents a divalent group represented by
The stabilizer composition according to claim 1, which is at least one selected from the group consisting of compounds represented by:   The stabilizer composition according to claim 2, wherein the other phosphorus-based antioxidant is a compound represented by the formula (II-1).   The stabilizer composition according to any one of claims 1 to 3, wherein the compound represented by the formula (III) is α-tocopherol.   The stabilizer composition according to any one of claims 1 to 4, wherein the amount of the other phosphorus-based antioxidant is not less than the amount of the compound represented by the formula (I) by weight.   It is the shape of a granulated material, The stabilizer composition as described in any one of Claims 1-5.   The organic material composition containing an organic material and the stabilizer composition as described in any one of Claims 1-6. Organic materials,
Formula (I):
[In formula (I), R < ¹ >, R < ² >, R < ⁴ > and R < ⁵ > are respectively independently a hydrogen atom, a _C1-8 alkyl group, a _C5-8 cycloalkyl group, a _C6-12 alkylcycloalkyl group. _Represents a C _7-12 aralkyl group or a C _6-14 aryl group,
R ³ represents a hydrogen atom or a C _1-8 alkyl group,
X is a divalent group represented by a single bond, a sulfur atom or —CHR ⁶ — (wherein R ⁶ represents a hydrogen atom, a C _1-8 alkyl group or a C _5-8 cycloalkyl group). Represents
A is a C _2-8 alkylene group or * -COR ⁷ -group (in the above formula, R ⁷ represents a single bond or a C _1-8 alkylene group, and * is bonded to the oxygen atom side) And any one of Y and Z represents a hydroxy group, a C _1-8 alkoxy group or a C _7-12 aralkyloxy group, and the other represents a hydrogen atom or C Represents a _1-8 alkyl group. ]
A compound represented by
Another phosphorus antioxidant different from the compound represented by formula (I),
Formula (III):
[In Formula (II), R ³¹ and R ³² each independently represent a hydrogen atom or a methyl group, and R ³³ represents a C _1-20 alkyl group or a C _2-20 alkenyl group. ]
And a compound represented by
Weight ratio of the total amount of the compound represented by formula (I) and other phosphorus antioxidants to the amount of the compound represented by formula (III) (compounds represented by formula (I) and other phosphorous oxidations) An organic material composition in which the total amount of the inhibitor: the amount of the compound represented by the formula (III) is 1: 0.05 to 1: 0.2.   The organic material composition according to claim 7 or 8, wherein the amount of the compound represented by the formula (III) is 0.005 to 0.02 parts by weight with respect to 100 parts by weight of the organic material.   The organic material composition according to any one of claims 7 to 9, wherein the organic material is a thermoplastic resin.   The organic material composition according to claim 10, wherein the thermoplastic resin is a polyolefin or an engineering resin.