JP2001310972A - Composition for discoloring inhibitor of organic polymer materials by nitrogen oxide gas and organic polymer materials containing the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a composition having excellent inhibiting effect against discoloration by nitrogen oxide gas without affecting the original performances of an organic polymer material such as thermal resistance and processing stability, and to provide an organic polymer material containing the composition. SOLUTION: This composition for inhibiting discoloration of the organic polymer material by nitrogen oxide gas comprises (a) at least one compound expressed by the general formula (1), (b) a phenolic antioxidant and (c) a phosphoric antioxidant, wherein R1 represents an alkyl group having 1 to 18 carbons or an alkenyl group having 2 to 18 carbons; R2 represents an alkyl group having 1 to 5 carbons; R3, R4 and R5 each independently represents a hydrogen atom or an alkyl group having 1 to 5 carbons; and R6 represents a hydrogen atom or an alkyl group having 1 to 5 carbons.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a composition for suppressing discoloration of an organic polymer material caused by nitric oxide gas and a method for suppressing discoloration of an organic polymer material caused by nitric oxide gas.

[0002]

2. Description of the Related Art Organic polymer materials composed of organic compounds such as natural polymers, synthetic polymers, fats and oils, lubricating oils, and hydraulic oils are useful because they are deteriorated or colored by oxidation, heat, light, nitrogen oxide gas and the like. Stabilizers for these have been developed because of their reduced properties. By adding such a stabilizer, an organic polymer material composition which is less susceptible to deterioration and coloring is obtained.

It is known that a 6-hydroxychroman compound is known as an antioxidant for fats and oils and polyolefins, as disclosed in JP-B-42-11064, US Pat.
No. 772, Chemical Abstracts, Vol. 70, No. 25
00 items, 50 volumes, 15104 items, 72 volumes, 1390
0 items, German Patent No. 114916, JP-A-49-
72338 and the like.

Japanese Patent Application Laid-Open No. 49-72338 discloses that polyolefins are synergistically stabilized by blending a 6-hydroxychroman compound and thiodialkanoic acid esters in combination with phosphites. Polyolefins can be more stabilized by using them in combination, and other antioxidants, ultraviolet absorbers, carbon black, or other additives to be blended with the composition, and fillers can be blended at all. It has been described.

[0005] However, JP-A-49-72338 only describes the thermal stability of polyolefins, and does not even suggest the effect of nitrogen oxide gas on suppressing coloration.

Further, WO 99/18154 and W
O99 / 54394 discloses an organic polymer material composition by blending a composition comprising a very small amount of a 6-hydroxychroman compound with various phenolic antioxidants and phosphorus antioxidants in an organic polymer. It is described that the processing stability and heat resistance of the product are remarkably improved, but there is no suggestion as to the effect of suppressing the coloring by the combustion gas or the nitrogen oxide gas.

Phenolic antioxidants were researched and developed in the 1930s, are well known as antioxidants for organic polymer materials, and are widely used.

[0008] Phosphorus-based antioxidants were researched and developed in the 1940's, are well known as antioxidants for organic polymer materials, and are widely used.

Further, in order to simultaneously exert different effects or obtain a synergistic effect, a combination of a plurality of kinds of antioxidants is widely used. For example, JP-B-56-5417 and JP-B-56-33939 describe that a phosphite compound or a phosphonite compound is used in combination with a hindered phenol compound as a stabilizer during processing of an organic polymer material. It is described that by doing so, an organic polymer material having excellent stability during processing and improved coloring can be obtained.

Japanese Patent Application Laid-Open No. Sho 62-30129 discloses 3,9-bis [2- [3- (3-tert-butyl-4).
-Hydroxy-5-methylphenyl) propionyloxy] -1,1-dimethylethyl] -2,4,8,10-tetraoxaspiro [5.5] undecane (hereinafter referred to as GA80
Sometimes. ) Is described as preventing the polyolefin resin from yellowing due to nitric oxide gas. In Examples, GA80 and tris (2,4-di-tertiary butylphenyl) phosphite (hereinafter referred to as 168) are used. And the like) are described as being effective in preventing yellowing due to nitric oxide gas.

Japanese Patent Application Laid-Open No. 10-204284 discloses that G
It is described that a polyurethane composition containing A80 and a specific triazine compound has an excellent effect on nitric oxide gas.

Further, JP-A-63-66248 describes that a polyolefin composition containing an antioxidant and a perchloric oxide is a resin composition having improved gas pollution by nitrogen oxide gas. The examples describe formulation examples in which no perchloric oxide is blended (so-called comparative examples for the inventive composition).
According to the results, tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionyloxymethyl] methane (hereinafter sometimes referred to as TT).
And bis (2,6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphite (hereinafter referred to as P3
Sometimes six. ) Or TT and bis (2,4-di-tert-butylphenyl) erythritol diphosphite (hereinafter sometimes referred to as U626) or TT and 168; The most effective one is a resin composition containing TT and P36, and the second most effective one is a resin composition containing TT and U626. Among them, the least effective one is It is a resin composition containing TT and 168.

As described above, an organic polymer material containing GA80 as a phenolic antioxidant and an organic polymer material containing P36 as a phosphorus antioxidant have excellent anti-tarnishing properties against nitrogen oxide gas. It is known that

Further, JP-A-7-102130 discloses that a specific phenolic antioxidant such as GA80 and P
A polypropylene composition obtained by blending a pentaerythritol-type phosphorus antioxidant such as 36 at a specific ratio is described as a polypropylene composition for fibers having excellent yellowing resistance to nitrogen oxide gas.

Japanese Patent Application Laid-Open No. H5-156094 discloses an acrylate-based antioxidant, a specific phenol-based antioxidant, a specific phosphorus-based antioxidant, and a specific piperidine-based antioxidant. Is described as a polyolefin composition having excellent nitric oxide gas yellowing suppression properties.

However, this prior art includes a biphenylene-type phosphorus antioxidant (phosphorous antioxidant represented by (c-1) in the present specification) and other general-purpose TT containing GA80 and the like. Organic polymer material mixed with a phenolic antioxidant such as n-octadecyl 3- (4-hydroxy-3,5-di-tert-butylphenyl) propionate (hereinafter also referred to as SS) is oxidized No mention is made of an organic polymer material having excellent nitrogen gas yellowing suppression properties.

Further, a phosphorus-based antioxidant, a phenol-based antioxidant, and a 6-hydroxychroman compound (compound represented by the general formula (1) in the present specification) are extremely different from the former two. There is no description that an organic polymer material blended in a small amount (1/10 to 1/100) is an organic polymer material having excellent nitric oxide gas yellowing suppression characteristics.

[0018]

[Problems to be Solved by the Invention] While maintaining heat resistance and processing stability that can cope with high temperatures for high-speed molding and high-temperature molding by alloying with engineering plastics, etc., a small amount of nitrogen oxide gas is used. There is a long-awaited demand for providing an excellent discoloration inhibitor having an effect of suppressing discoloration.

[0019]

Means for Solving the Problems The present inventors have conducted intensive studies to solve the above-mentioned problems, and as a result, a small amount of the following general formula (1) was added in accordance with the phenolic antioxidant and the phosphorus antioxidant. By compounding the compound represented by the formula (1) with the organic polymer material, the organic compound having an excellent effect of suppressing discoloration due to a remarkably excellent nitric oxide gas without losing basic performance such as processing stability and thermal stability. The inventors have found that a molecular material can be obtained, and have completed the present invention. For more information,
A phenolic antioxidant such as GA80, TT, SS and the like and tetrakis (2,4-di-tert-butyl-5-methylphenyl) -4,4′-biphenylenediphosphonite (hereinafter sometimes referred to as 101). ), Tetrakis (2,4)
-Di-tert-butylphenyl) -4,4'-biphenylenediphosphonite (hereinafter sometimes referred to as EPQ)
Combination with biphenylene-type phosphorus antioxidants such as
A combination of a phenolic antioxidant such as GA80, TT, SS and a phosphite type phosphorus antioxidant such as 168, or a phenolic antioxidant such as GA80, TT and SS and a pentaerythritol type phosphorus such as P36 In addition to the combination with the system-based antioxidant, a small amount (approximately 1/10 to 1/100 of the total amount of the phenol-based antioxidant and the phosphorus-based antioxidant) is described later in the general formula (1)
It has been found that by blending a 6-hydroxychroman compound represented by the formula (1) with an organic polymer, an organic polymer material having an excellent effect of suppressing discoloration due to nitric oxide gas can be obtained.

That is, the present invention is as follows. [1] (a) General formula (1)

[0021]

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(Wherein, R ¹ represents an alkyl group having 1 to 18 carbon atoms or an alkenyl group having 2 to 18 carbon atoms, R ² represents an alkyl group having 1 to 5 carbon atoms, R ³ , R ⁴ and R ⁵
May be the same or different and each represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and R ⁶ represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms. ), (B) a phenolic antioxidant, and (c) a phosphorus antioxidant, the discoloration of the organic polymer material caused by nitrogen oxide gas. Inhibitor composition.

[2] R ^{1 of the} compound represented by the general formula (1) is an alkyl group having 1 to 5 carbon atoms.
The discoloration inhibitor composition as described in the above.

[3] The compound represented by the general formula (1) is added to the total amount of the compound represented by the general formula (1), the phenolic antioxidant, and the phosphorus antioxidant in an amount of 0.
The discoloration according to [1] or [2], comprising 5 to 10% by weight, and 90 to 99.5% by weight of the total amount of the phenolic antioxidant and the phosphorus antioxidant. Inhibitor composition.

[4] The compound represented by the general formula (1) is used in an amount of 1 to 3 with respect to the total amount of the compound represented by the general formula (1), the phenolic antioxidant, and the phosphorus antioxidant.
The discoloration inhibitor composition according to [1] or [2], wherein the composition contains 5% by weight, and the total amount of the phenolic antioxidant and the phosphorus-based antioxidant is 95 to 99% by weight. .

[5] The phenolic antioxidant of the component (b) is represented by the general formula (2)

[0027]

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(Wherein, R ⁷ represents an alkyl group having 1 to 5 carbon atoms, R ⁸ represents an alkyl group having 1 to 4 carbon atoms, R ⁹ represents a hydrogen atom or a methyl group, and L represents

[0029]

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Or

[0031]

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Or

[0033]

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Or

[0035]

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Or

[0037]

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Is shown. Is a compound containing at least one structure represented by the following formula in the molecule, and the phosphorus-based antioxidant of the component (c) includes the following (c-1), (c-2), (c-3) and [1] to at least one of the compounds of (c-4)
The discoloration inhibitor composition according to any one of [4]. (C-1): General formula (3)

[0039]

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Alternatively, the general formula (4)

[0041]

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[Wherein Q ¹ is a general formula (5)

[0043]

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[0044] (wherein, R ¹⁰ and R ¹¹ may be the same or different, each represent an alkyl group having 1 to 4 carbon atoms, R ¹² represents a hydrogen atom or a methyl group.) Indicates, Q ² Is independently for each repeating unit the general formula (5)

[0045]

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Wherein R ¹⁰ and R ¹¹ may be the same or different and each represents an alkyl group having 1 to 4 carbon atoms, and R ¹² represents a hydrogen atom or a methyl group. Each repeating unit independently represents 0 or 1, j represents 0 or 1, and n ¹ represents an integer of ¹ to 10. Represented by formula (c-2): General formula (6)

[0047]

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Wherein R ¹³ is an alkyl group or 1 to
A phenyl group which may be substituted with three alkyl groups is shown. And (c-3): a compound having one or more structures represented by the following formulas in the molecule:

[0049]

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(In the formula, R ²⁴ represents an alkyl group or a phenyl group which may be substituted with 1 to 3 substituents selected from the group consisting of an alkyl group, an aryl group and a phenylalkyl group. R ²⁴ represents a phenyl group which may be substituted with an alkyl group or an aryl group.) A compound having one or two or more structures in a molecule represented by the following formula (c-4): (8)

[0051]

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Wherein R ³⁷ represents an alkyl group having 1 to 5 carbon atoms, R ³⁸ represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, R ³⁹ represents a hydrogen atom or a methyl group, ⁴⁰
Represents a direct bond, an alkylene group having 1 to 5 carbon atoms or a sulfur atom. ) Is at least one kind of compound containing one or two or more structures in a molecule.
The discoloration inhibitor composition according to any one of [4].

[6] The phenolic antioxidant of the component (b) is n-octadecyl-3- (3,5-di-third
Tert-butyl-4-hydroxyphenyl) propionate,
Tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionyloxymethyl] methane, 1,3,5-tris (3,5-di-tert-butyl-
4-hydroxybenzyl) isocyanurate, 1,3
5-trimethyl-2,4,6-tris (3,5-di-tert-butyl-4-hydroxybenzyl) benzene and 3,9-bis [2- [3- (3-tert-butyl- 4-hydroxy-5-methylphenyl) propionyloxy]
-1,1-dimethylethyl] -2,4,8,10-tetraoxaspiro [5,5] undecane, and the phosphorus-based antioxidant is tris (2,4 -Di-tert-butylphenyl) phosphite, tetrakis (2,4-di-tert-butylphenyl)
-4,4'-biphenylenediphosphonite, tetrakis (2,4-di-tert-butyl-5-methylphenyl)-
4,4′-biphenylenediphosphonite, bis (2,4
-Di-tert-butylphenyl) pentaerythritol diphosphite, bis (2,6-di-tert-butyl-4-)
Methylphenyl) pentaerythritol diphosphite, 2,2′-methylenebis (4,6-di-tert-butylphenyl) -2-ethylhexylphosphite, bis- (2-methyl-4,6-di-tert. Butylphenyl)
Ethyl phosphite, 2,2 ′, 2 ″ -nitrilo [triethyltris (3,3 ′, 5,5′-tetra-tert-butyl-1,1′-biphenyl-2,2′-diyl) phospho Fight], and 6- [3- (3-tert-butyl-4)
-Hydroxy-5-methylphenyl) propoxy]-
2,4,8,10-tetra-tert-butyldibenzo
The discoloration inhibitor composition according to any one of [1] to [4], which is at least one selected from the group consisting of [d, f] [1,3,2] dioxaphosphepin.

[7] An organic polymer material comprising the discoloration inhibitor composition according to any one of [1] to [6].

[8] The organic polymer material according to [7], further comprising at least one compound selected from a sulfur-based antioxidant and a light stabilizer.

[9] An organic polymer material comprising the discoloration inhibitor composition according to [1], wherein the organic polymer material 1
An organic compound having an excellent discoloration inhibiting effect on nitrogen oxide gas, characterized in that the compound represented by the general formula (1) is compounded in an amount of 0.0005 to 0.025 parts by weight with respect to 00 parts by weight. Polymer material.

[10] The compound represented by the general formula (1) is added to 100 parts by weight of the organic polymer material. 0 0
1-0. The organic polymer material according to [9], which is blended in a range of 0 to 10 parts by weight.

[11] The phenolic antioxidant of the component (b) is represented by the general formula (2)

[0059]

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(Wherein, R ⁷ represents an alkyl group having 1 to 5 carbon atoms, R ⁸ represents an alkyl group having 1 to 4 carbon atoms, R ⁹ represents a hydrogen atom or a methyl group, and L represents

[0061]

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Or

[0063]

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Or

[0065]

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Or

[0067]

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Or

[0069]

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FIG. Is a compound containing at least one structure represented by the following formula in the molecule, and the phosphorus-based antioxidant of the component (c) includes the following (c-1), (c-2), (c-3) and The organic polymer material according to [9] or [10], which is at least one compound of (c-4). (C-1): General formula (3)

[0071]

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Alternatively, the general formula (4)

[0073]

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(Wherein Q ¹ is a general formula (5)

[0075]

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[0076] (wherein, R ¹⁰ and R ¹¹ may be the same or different, each represent an alkyl group having 1 to 4 carbon atoms, R ¹² represents a hydrogen atom or a methyl group.) Indicates, Q ² Is independently for each repeating unit the general formula (5)

[0077]

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Wherein R ¹⁰ and R ¹¹ may be the same or different and each represents an alkyl group having 1 to 4 carbon atoms, and R ¹² represents a hydrogen atom or a methyl group. Each repeating unit independently represents 0 or 1, j represents 0 or 1, and n ¹ represents an integer of ¹ to 10. Represented by formula (c-2): General formula (6)

[0079]

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Wherein R ¹³ is an alkyl group or 1 to
A phenyl group which may be substituted with three alkyl groups is shown. And (c-3): a compound having one or more structures represented by the following formulas in the molecule:

[0081]

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(Wherein R ²⁴ represents an alkyl group or a phenyl group which may be substituted with 1 to 3 substituents selected from the group consisting of an alkyl group, an aryl group and a phenylalkyl group. R ²⁴ represents a phenyl group which may be substituted with an alkyl group or an aryl group.) A compound having one or two or more structures in a molecule represented by the following formula (c-4): (8)

[0083]

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(Wherein, R ³⁷ represents an alkyl group having 1 to 5 carbon atoms, R ³⁸ represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, R ³⁹ represents a hydrogen atom or a methyl group, ⁴⁰
Represents a direct bond, an alkylene group having 1 to 5 carbon atoms or a sulfur atom. A) a compound containing one or more of the structures represented by the above in the molecule.

[12] The phenolic antioxidant of the component (b) is n-octadecyl-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate, tetrakis [3- (3 , 5-di-tert-butyl-4
-Hydroxyphenyl) propionyloxymethyl] methane, 1,3,5-tris (3,5-di-tert-butyl-4-hydroxybenzyl) isocyanurate,
3,5-trimethyl-2,4,6-tris (3,5-di-tert-butyl-4-hydroxybenzyl) benzene and 3,9-bis [2- [3- (3-tert-butyl) -4-
Hydroxy-5-methylphenyl) propionyloxy] -1,1-dimethylethyl] -2,4,8,10-tetraoxaspiro [5,5] undecane, at least one member selected from the group consisting of phosphorus compounds When the antioxidant is tris (2,4-di-tert-butylphenyl) phosphite, tetrakis (2,4-di-tert-butylphenyl)
-4,4'-biphenylenediphosphonite, tetrakis (2,4-di-tert-butyl-5-methylphenyl)-
4,4′-biphenylenediphosphonite, bis (2,4
-Di-tert-butylphenyl) pentaerythritol diphosphite, bis (2,6-di-tert-butyl-4-)
Methylphenyl) pentaerythritol diphosphite, 2,2′-methylenebis (4,6-di-tert-butylphenyl) -2-ethylhexylphosphite, bis- (2-methyl-4,6-di-tert. Butylphenyl)
Ethyl phosphite, 2,2 ′, 2 ″ -nitrilo [triethyltris (3,3 ′, 5,5′-tetra-tert-butyl-1,1′-biphenyl-2,2′-diyl) phospho Fight], and 6- [3- (3-tert-butyl-4)
-Hydroxy-5-methylphenyl) propoxy]-
2,4,8,10-tetra-tert-butyldibenzo
The organic polymer material according to [9] or [10], which is at least one selected from the group consisting of [d, f] [1,3,2] dioxaphosphepin.

[13] The organic polymer is a synthetic resin
The organic polymer material according to any one of [7] to [12].

[14] The organic polymer material according to [13], wherein the synthetic resin is a polyolefin resin.

[15] The polyolefin resin is a polyethylene resin, a polypropylene resin, an admixture or a compatible polymer of a polyethylene resin and a polypropylene resin, or a compatible polymer containing a polyethylene resin and / or a polypropylene resin. The organic polymer material according to [14], which is a copolymer, an ethylene-vinyl acetate copolymer, or an ethylene-propylene copolymer.

[16] The organic polymer material according to any one of [9] to [14], further comprising at least one compound selected from a sulfur-based antioxidant and a light stabilizer.

[17] The organic polymer material may be prepared by adding (a) the general formula (1)

[0091]

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(Wherein, R ¹ represents an alkyl group having 1 to 18 carbon atoms or an alkenyl group having 2 to 18 carbon atoms; R ² represents an alkyl group having 1 to 5 carbon atoms; R ³ , R ⁴ and R ⁵
May be the same or different and each represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and R ⁶ represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms. ), (B) a phenolic antioxidant, and (c) a phosphorus antioxidant, the discoloration of the organic polymer material caused by nitrogen oxide gas. Suppression method.

[0093]

BEST MODE FOR CARRYING OUT THE INVENTION The substituents in the compound of the general formula (1) which is a component of the discoloration inhibitor composition of the present invention will be described.

[0094]

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R ^{1 of the} compound represented by the general formula (1)
Is an alkyl group having 1 to 18 carbon atoms or 2 to 18 carbon atoms.
And the alkyl group or the alkenyl group may be linear or branched, and examples thereof include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, and a secondary group. Butyl group, tertiary butyl group, pentyl group, 2-pentyl group, 3-pentyl group, 2-methylbutan-1-yl group, 2-methylbutan-2-yl group, 2-methylbutan-3-yl group, 2-methylbutan-4-yl group, neopentyl group, hexyl group, isohexyl group, heptyl group, octyl group, 2-ethylhexyl group, nonyl group, decyl group, undecyl group,
Dodecyl group, tridecyl group, tetradecyl group, pentadecyl group, hexadecyl group, heptadecyl group, octadecyl group, 4-methylpent-3-enyl group (—CH ₂ CH ₂
CH = C (CH ₃ ) —CH ₃ group), 4,8,12-trimethyltridecyl group (— [CH ₂ CH ₂ CH ₂ CH (CH ₃ )])
_3- CH ₃ group), 4,8,12-trimethyl-3,7,
11 tri tetradecatrienyl group _{(- [CH 2 CH 2 CH} = C
(CH ₃ )] ₃ —CH ₃ group).

R ^{1 of the} compound represented by the general formula (1)
Is preferably an alkyl group having 1 to 5 carbon atoms, or an alkyl group or alkenyl group having 12 to 18 carbon atoms, and the alkyl group or alkenyl group may be either linear or branched. Particularly preferred examples include, for example, a methyl group, a 4,8,12-trimethyltridecyl group (— [CH ₂ CH ₂ CH ₂ CH (CH ₃ )] ₃ —CH ₃
Group), 4,8,12-trimethyl-3,7,11-tri tetradecatrienyl group _{(- [CH 2 CH 2 CH} = C (CH 3)] 3
—CH ₃ group) and the like, and a methyl group, 4,8,12
- trimethyl tridecyl group _{(- [CH 2 CH 2 CH} 2 CH
(CH ₃ )] ₃ —CH ₃ groups) are particularly preferred. Of these, a methyl group is most preferred.

R ^{2 of the} compound represented by the general formula (1)
Is an alkyl group having 1 to 5 carbon atoms, and the alkyl group may be either linear or branched, for example,
Methyl, ethyl, propyl, isopropyl, butyl, isobutyl, secondary butyl, tertiary butyl, pentyl, 2-pentyl, 3-pentyl, 2
-Methylbutan-1-yl group, 2-methylbutane-2-
Examples include an yl group, a 2-methylbutan-3-yl group, a 2-methylbutan-4-yl group, and a neopentyl group.

R ^{2 of the} compound represented by the general formula (1)
Is preferably a methyl group.

R ³ , R ⁴ and R ^{5 in the} compound represented by the general formula (1) may be the same or different and each is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. May be straight-chain or branched, and examples thereof include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a secondary butyl group, and a tertiary butyl group. .

Preferred examples of R ³ , R ⁴ and R ^{5 in} the compound represented by the general formula (1) may be the same or different and include a hydrogen atom, a methyl group, an isopropyl group and a tertiary butyl group. Examples of the group include a hydrogen atom and a methyl group, with a methyl group being most preferred.

R ^{6 of the} compound represented by the general formula (1)
Is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms,
The alkyl group may be linear or branched, for example, methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, secondary butyl group, tertiary butyl group, Pentyl group, 2-pentyl group, 3
-Pentyl group, 2-methylbutan-1-yl group, 2-methylbutan-2-yl group, 2-methylbutan-3-yl group, 2-methylbutan-4-yl group, neopentyl group and the like.

R ^{6 of the} compound represented by the general formula (1)
Is preferably a hydrogen atom.

As the compound represented by the general formula (1)
Include, but are not limited to, the following compounds
It is not something to be done. 2,2-dimethyl-6-hydroxychroman 2,2,5-trimethyl-7-tert-butyl-6-hydroxide
Loxycycloman 2,2,5-trimethyl-8-tert-butyl-6-hydride
Loxycycloman 2,2,7,8-tetramethyl-6-hydroxy chroma
2,2,5,7-tetramethyl-6-hydroxy chroma
2,2,5,8-tetramethyl-6-hydroxy chroma
2,2-dimethyl-7-tert-butyl-6-hydroxy
Chroman 4-isopropyl-2,2,5-trimethyl-7-third
Tert-butyl-6-hydroxychroman 2,2,5,7,8-pentamethyl-6-hydroxyc
Roman 4-isopropyl-2,2-dimethyl-7-tertiary butyl
Le-6-hydroxychroman 2,2-dimethyl-5-tert-butyl-6-hydroxy
Chroman 2,5,7,8-tetramethyl-2- (4-methylpen
To-3-enyl) -6-hydroxychroman 2,5-dimethyl-8-tert-butyl-2- (4-methyl
Rupent-3-enyl) -6-hydroxychroman 2-methyl-2- (4-methylpent-3-enyl)-
6-hydroxychroman 2,2,5-trimethyl-6-hydroxychroman 2,2,7-trimethyl-6-hydroxychroman 2,2,8-trimethyl-6-hydroxychroman α-tocopherol (R¹Is 4,8,12-trimethyl
Tridecyl group, R^TwoIs a methyl group, R^ThreeAnd R^FourAnd R^FiveTogether
Methyl group, R⁶Is a hydrogen atom. Β-tocopherol (R¹Is 4,8,12-trimethyl
Tridecyl group, R^TwoIs a methyl group, R^ThreeAnd R^FiveTogether
R group, R^FourIs a hydrogen atom, R⁶Is a hydrogen atom. Γ-tocopherol (R¹Is 4,8,12-trimethyl
Tridecyl group, R^TwoIs a methyl group, R^FourAnd R^FiveTogether
R group, R^ThreeIs a hydrogen atom, R⁶Is a hydrogen atom δ-tocopherol (R¹Is 4,8,12-trimethyl
Tridecyl group, R^TwoIs a methyl group, R^ThreeAnd R^FourAre both hydrogen
Atom, R^FiveIs a methyl group, R⁶Is a hydrogen atom.¹Is 4,8,12-trimethyltridecyl
Group, R^TwoIs a methyl group, R ^ThreeAnd R^FourAnd R^FiveAre both hydrogen atoms,
R⁶Is a hydrogen atom ε-tocopherol (R¹Is 4,8,12-trimethyl
-3,7,11-tridecatrienyl group, R^TwoIs methyl
Group, R^ThreeAnd R^FiveAre both methyl groups, R^FourIs a hydrogen atom, R⁶Is
Hydrogen atom) ξ₁-Tocopherol (R¹Is 4,8,12-trimethyl
-3,7,11-tridecatrienyl group, R^TwoIs methyl
Group, R^ThreeAnd R^FourAnd R^FiveAre both methyl groups, R⁶Is a hydrogen atom)_Two-Tocopherol (R¹Is 4,8,12-trimethyl
Tridecyl group, R^TwoIs a methyl group, R^ThreeAnd R^FourTogether
R group, R^FiveIs a hydrogen atom, R⁶Is a hydrogen atom. Η-tocopherol (R¹Is 4,8,12-trimethyl
Tridecyl group, R^TwoIs a methyl group, R^ThreeAnd R^FiveAre both hydrogen
Atom, R^FourIs a methyl group, R⁶Is a hydrogen atom)

As the compound represented by the general formula (1), 2,2,5,7,8-pentamethyl-6-hydroxychroman and various tocopherols are preferable, and among them, 2,2,5,7,8- Pantamethyl-6-hydroxychroman is particularly preferred. In the present invention, component (a)
May be a compound represented by the general formula (1) or a mixture thereof, for example, the above-mentioned various tocopherols or a mixture thereof.

The phenolic antioxidant, one of the components of the discoloration inhibitor composition of the present invention, has the general formula (2)

[0106]

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(Wherein, R ⁷ represents an alkyl group having 1 to 5 carbon atoms, R ⁸ represents an alkyl group having 1 to 4 carbon atoms, R ⁹ represents a hydrogen atom or a methyl group, and L represents

[0108]

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Or

[0110]

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Or

[0112]

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Or

[0114]

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Or

[0116]

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Is shown. And a compound having one or more of the structures represented by the formula (1) in the molecule.

As these compounds, specifically, for example, n-octadecyl-3- (4-hydroxy-3,5
-Di-tert-butylphenyl) propionate, tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionyloxymethyl] methane, 1,3
5-tris (3,5-ditert-butyl-4-hydroxybenzyl) isocyanurate, 1,3,5-trimethyl-2,4,6-tris (3,5-ditert-butyl-4-
Hydroxybenzyl) benzene, 1,1,3-tris [2-methyl-4- [3- (3,5-ditert-butyl-
4-hydroxyphenyl) propionyloxy] -5-
Tert-butylphenyl] butane, bis (3-tert-butyl-4-hydroxy-5-methylphenyl) dicyclopentadiene, 1,3,5-tris (4-tert-butyl-
3-hydroxy-2,6-dimethylbenzyl) isocyanuric acid, 3,9-bis [2- [3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionyloxy] -1,1- Dimethylethyl] -2,4,8,1
0-tetraoxaspiro [5.5] undecane, 2,6
Di-tert-butyl-4-methylphenol, 2,4-dimethyl-6-tert-butylphenol, 2,6-ditert
Tert-butyl-4-hydroxymethylphenol, 2,6-
Di-tert-butyl-4-ethylphenol, 2,4,6-
Tritertiary butylphenol, butylated hydroxyanisole, isooctyl-3- (4-hydroxy-3,5
-Di-tert-butylphenyl) propionate, distearyl- (4-hydroxy-3-methyl-5-tert-butyl) benzylmalonate, 2,2'-methylenebis (4
-Methyl-6-tert-butylphenol), 2,2'-
Methylenebis (4-ethyl-6-tert-butylphenol), 4,4'-methylenebis (2,6-ditert-butylphenol), 2,2'-butylidenebis (4-ethyl-6-tert-butylphenol) , 4,4'-butylidenebis (3-methyl-6-tert-butylphenol), 2,2'-thiobis (4-methyl-6-tert-butylphenol), 4,4'-thiobis (3-methyl-
6-tert-butylphenol), styrenated phenol, N, N'-hexamethylenebis (3,5-ditert-butyl-4-hydroxyhydrocinnamide), bis (3,5-ditert-butyl) Ethyl-4-hydroxybenzylphosphonate) calcium, 1,1,3-tris (2
-Methyl-4-hydroxy-5-tert-butylphenyl) butane, 1,6-hexanediol-bis [3-
(3,5-di-tert-butyl-4-hydroxyphenyl)
Propionate], 2,2′-methylenebis (4-methyl-6-cyclohexylphenol), 2,2′-methylenebis [6- (1-methylcyclohexyl) -4-methylphenol], triethylene glycol-bis [3
-(3-tert-butyl-4-hydroxy-5-methylphenyl) propionate], ethylene glycol-bis (3,3-bis (3-tert-butyl-4-hydroxyphenyl) butyrate), 2-tert-butyl Tertiary butyl-6- (3-
Tertiary butyl-5-methyl-2-hydroxybenzyl)
-4-methylphenyl acrylate, 2,2'-oxamido-bis [ethyl-3- (3,5-di-tert-butyl-
4-hydroxyphenyl) propionate], 6- (4
-Hydroxy-3,5-di-tert-butylanilino)-
2,4-dioctylthio-1,3,5-triazine, bis [2-tert-butyl-4-methyl-6- (2-hydroxy-3-tert-butyl-5-methylbenzyl) phenyl] terephthalate , 3,9-bis [2- [3- (3,
5-di-tert-butyl-4-hydroxyphenyl) propionyloxy] -1,1-dimethylethyl] -2,4.
8,10-tetraoxaspiro [5.5] undecane,
1,3,5-tris [3- (3,5-di-tert-butyl-
4-hydroxyphenyl) propionyloxy] ethyl isocyanate, 2,2-thiodiethylene-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 acrylate, 1,3,5-tris (4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl) Isocyanuric acid, 2,4-di-octylthiomethyl-6-methylphenol and the like,
Also, 2,4-bis [(octylthio) methyl] -o-
The respective compounds of cresol, propyl gallate, octyl gallate and dodecyl gallate are also exemplified, but not limited thereto.

Preferred phenolic antioxidants include n-octadecyl-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate and tetrakis [3- (3,5-di-tert-butyl). -4-hydroxyphenyl) propionyloxymethyl] methane, 1,3,
5-tris (3,5-ditert-butyl-4-hydroxybenzyl) isocyanurate, 1,3,5-trimethyl-2,4,6-tris (3,5-ditert-butyl-4-
Hydroxybenzyl) benzene, 1,1,3-tris [2-methyl-4- [3- (3,5-ditert-butyl-
4-hydroxyphenyl) propionyloxy] -5-
Tert-butylphenyl] butane, 2,4-di-octylthiomethyl-6-methylphenol, bis (3-tert-butyl-4-hydroxy-5-methylphenyl) dicyclopentadiene, 1,3,5 -Tris (4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl) isocyanuric acid, 3,9-bis [2- [3- (3-tert-butyl-4-hydroxy-5-methyl) Phenyl) propionyloxy] -1,1-dimethylethyl] -2,4,
8,10-tetraoxaspiro [5.5] undecane and the like.

Particularly preferred phenolic antioxidants include n-octadecyl-3- (3,5-ditertiarybutyl-4-hydroxyphenyl) propionate and tetrakis [3- (3,5-ditertiary). Butyl-4-hydroxyphenyl) propionyloxymethyl] methane, 1,
3,5-tris (3,5-di-tert-butyl-4-hydroxybenzyl) isocyanurate, 1,3,5-trimethyl-2,4,6-tris (3,5-di-tert-butyl-
4-hydroxybenzyl) benzene, 3,9-bis [2
-[3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionyloxy] -1,1-dimethylethyl] -2,4,8,10-tetraoxaspiro [5.5] undecane Etc., but among them,
n-octadecyl 3- (3,5-di-tert-butyl-4)
-Hydroxyphenyl) propionate, tetrakis [3- (3,5-ditert-butyl-4-hydroxyphenyl) propionyloxymethyl] methane, 3,9-bis [2- [3- (3-tert-butyl) -4-hydroxy-
5-methylphenyl) propionyloxy] -1,1-
Dimethylethyl] -2,4,8,10-tetraoxaspiro [5.5] undecane is particularly preferred.

In the present invention, one or more of these phenolic antioxidants can be used in combination.

The compound of the general formula (3) or (4), which is a phosphorus antioxidant of (c-1), which is a component of the discoloration inhibitor composition of the present invention, will be described. General formula (3)

[0123]

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Or the general formula (4)

[0125]

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[Wherein Q ¹ is a general formula (5)

[0127]

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[0128] (wherein, R ¹⁰ and R ¹¹ may be the same or different, each represent an alkyl group having 1 to 4 carbon atoms, R ¹² represents a hydrogen atom or a methyl group.) Indicates, Q ² Is independently for each repeating unit the general formula (5)

[0129]

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Wherein R ¹⁰ and R ¹¹ may be the same or different and each represents an alkyl group having 1 to 4 carbon atoms, and R ¹² represents a hydrogen atom or a methyl group. Each repeating unit independently represents 0 or 1, j represents 0 or 1, and n ¹ represents an integer of ¹ to 10. ] It is a compound represented by these. More preferably, the phosphorus-based antioxidant of (c-1) is represented by the general formula (9)

[0131]

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Or the general formula (10)

[0133]

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[Wherein Q ³ is a group represented by the general formula (11)

[0135]

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(Wherein R ¹² represents a hydrogen atom or a methyl group), and Q ⁴ independently represents a repeating unit of the general formula (11)

[0137]

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(Wherein R ¹² represents a hydrogen atom or a methyl group), i independently represents 0 or 1 for each repeating unit, j represents 0 or 1, and n ² represents 1 Represents an integer of 1 to 3. ] It is a compound represented by this.

Preferred examples of the phosphorus antioxidant (c-1) will be described in more detail. General formula (5) which is a substituent Q ¹ or Q ² in general formula (3) or (4)

[0140]

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R ¹⁰ and R ¹¹ in R ¹ and R 4 may be the same or different and each is an alkyl group having 1 to 4 carbon atoms, and the alkyl group may be either linear or branched. , A methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group and a tertiary butyl group, and a tertiary butyl group is preferable. It is particularly preferred that both R ¹⁰ and R ¹¹ are tertiary butyl groups.

R ¹² in the group represented by the above formula (5) is a hydrogen atom or a methyl group. When R ¹² is a methyl group, R ¹² is the 5-position on the phenyl ring of the formula (5). Alternatively, those substituted at the 6-position are particularly preferred, and those substituted at the 5-position are most preferred.

Particularly preferred examples of the group represented by the general formula (5) include a 2,4-di-tert-butylphenoxy group and a 2,4-di-tert-butyl-5-methylphenoxy group. .

N ¹ in the general formula (3) or (4) is an integer of 1 to 10, preferably 1 or 2, and particularly preferably 1. i and j are 0 or 1, and 0
It is preferred that

Particularly preferred examples of the groups represented by the general formulas (5) and (11) include 2,4-dithi
Tert-butylphenoxy group, 2,4-ditertiarybutyl-5-
A methylphenoxy group is exemplified.

When the component (c) is (c-1), the compound of the general formula (3) or (9) is preferably the main component, and the compound of the general formula (4) or (10) May not be included.

The compound represented by the general formula (3) or (4) or the general formula (9) or (10), which is one of the components of the discoloration inhibitor composition of the present invention, is as follows. Can be 4,4'-biphenylenediphosphonite compounds represented by tetrakis (2,4-di-tert-butylphenyl) -4,4'-biphenylenediphosphonite described in JP-B-50-35096; Tetrakis (2,4-di-tert-butylphenyl) -4, described in JP-A-1-254744
Composition containing 4'-biphenylenediphosphonite and corresponding biphenylene monophosphonite
No. 70892, tetrakis (2, 4
-Di-tert-butyl-6-methylphenyl) -4,4'-
A composition comprising biphenylenediphosphonite or the like; a composition comprising tetrakis (2,4-ditert-butylphenyl) -4,4'-biphenylenediphosphonate described in JP-A-5-202078; JP 5
Tetrakis (2,4-ditert-butyl-5-methylphenyl)-described in JP-178870A
4,4'-biphenylenediphosphonite compound, 2,4-di-tert-butylphenyl bis [4'-bis (2,4-di-tert-butylphenoxy) described in JP-A-8-231568 ) Phosphanylbiphenyl-4-yl] phosphinite (or (2,4
-Di-tert-butylphenoxy) bis [4 '-[bis (2,4-di-tert-butylphenoxy) phosphino] biphenyl-4-yl] phosphine), 2,
4-di-tert-butylphenyl [4'-bis (2,4-di-tert-butylphenoxy) phosphanylbiphenyl-4
-Yl] [4'-bis (2,4-di-tert-butylphenoxy) phosphorylbiphenyl-4-yl] phosphinite, 2,4-di-tert-butylphenylbis [4'-bis (2,4- Di-tert-butylphenoxy) phosphanylbiphenyl-4-yl] phosphinate, 2,4-di-tert-butylphenyl [4'-bis (2,4-di-tert-butylphenoxy) phosphanylbiphenyl-4- Yl] [4'-bis (2,4-di-tert-butylphenoxy) phosphorylbiphenyl-4-yl] phosphinate, 2,4-di-tert-butylphenyl bis [4'-bis (2,4-di- Tertiary butylphenoxy) phosphorylbiphenyl-4-yl] phosphinite, 2,4-ditertiary
Tert-butylphenyl bis [4'-bis (2,4-ditert.
Tert-butylphenoxy) phosphorylbiphenyl-4-yl] phosphinate, 2,4-ditert-butyl-5-methylphenylbis [4'-bis (2,4-ditert-butyl-5-methylphenoxy) phosph Fanylbiphenyl-4-yl] phosphinite (or (2,4-tert-butyl-5-methylphenoxy) bis [4 '-[bis (2,4-ditert-butyl-5-methylphenoxy) phosphino] Biphenyl-4-yl] phosphine), 2,4-di-tert-butyl-5-methylphenyl [4 '-[bis (2,4-di-tert-butyl-5-methylphenoxy) phosphanylbiphenyl -4-yl]
[4 '-[bis (2,4-ditert-butyl-5-methylphenoxy) phosphorylbiphenyl-4-yl] phosphinite, 2,4-ditert-butyl-5-methylphenylbis [4'- [Bis (2,4-ditert-butyl-5)
-Methylphenoxy) phosphanylbiphenyl-4-yl] phosphinate, 2,4-di-tert-butyl-5-methylphenyl [4 '-[bis (2,4-di-tert-butyl-5-methylphenoxy) Phosphanylbiphenyl-
4-yl] [4'-bis (2,4-di-tert-butyl-5
-Methylphenoxy) phosphorylbiphenyl-4-yl] phosphinate, 2,4-ditert-butyl-5-methylphenylbis [4 '-[bis (2,4-ditert-butyl-5-methylphenoxy) Phosphorylbiphenyl-4-yl] phosphinite, 2,4-ditert-butyl-5-methylphenylbis [4 '-[bis (2,4-
Ditertiary butyl-5-methylphenoxy) phosphorylbiphenyl-4-yl] phosphinate, 2,4-ditertiary
Tert-butylphenyl (biphenyl-4-yl) [4'-bis (2,4-di-tert-butylphenoxy) phosphanylbiphenyl-4-yl] phosphinite, 2,4-di-tert-butyl-5-methyl Phenyl (biphenyl-4-yl) [4′-bis (2,4-di-tert-butyl-5-methylphenoxy) phosphanylbiphenyl-4-yl] phosphinite, 2,4-di-tert-butyl-6 -Methylphenyl (biphenyl-4-yl) [4'-bis (2,4
-Di-tert-butyl-6-methylphenoxy) phosphanylbiphenyl-4-yl] phosphinite, 2,4-di-tert-butylphenyl (biphenyl-4-yl) [4 '
-[Bis (2,4-di-tert-butylphenoxy) phosphorylbiphenyl-4-yl] phosphinite, 2,4-
Di-tert-butylphenyl (biphenyl-4-yl)
[4 '-[bis (2,4-di-tert-butylphenoxy)
Phosphanylbiphenyl-4-yl] phosphinate,
Compounds such as 2,4-di-tert-butylphenyl (biphenyl-4-yl) [4′-bis (2,4-di-tert-butylphenoxy) phosphorylbiphenyl-4-yl] phosphinate are exemplified.

The compound represented by (c-1) includes tetrakis (2,4-di-tert-butylphenyl)-
4,4'-biphenylenediphosphonite, tetrakis (2,4-ditert-butyl-5-methylphenyl)-
4,4'-biphenylenediphosphonite is particularly preferred, and tetrakis (2,4-di-tert-butylphenyl)-
4,2′-biphenylenediphosphonite as a main component, and (2,4-di-tert-butylphenoxy) bis [4 ′
-[Bis (2,4-di-tert-butylphenoxy) phosphino] biphenyl-4-yl] phosphine, [(2,4
-Di-tert-butylphenoxy) phosphino] biphenyl, a composition containing tris (2,4-di-tert-butylphenyl) phosphite or the like, or tetrakis (2,
4-ditert-butyl-5-methylphenyl) -4,4 '
-Biphenylenediphosphonite as a main component, (2,
4-di-tert-butyl-5-methylphenoxy) bis [4 ′-[bis (2,4-di-tert-butyl-5-methylphenoxy) phosphino] biphenyl-4-yl] phosphine, [(2, Compositions containing 4-di-tert-butyl-5-methylphenoxy) phosphino] biphenyl, tris (2,4-di-tert-butyl-5-methylphenyl) phosphite and the like are most preferred.

The phosphorus antioxidant (c-2), which is a component of the discoloration inhibitor composition of the present invention, has the general formula (6)

[0150]

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(Wherein R ¹³ is an alkyl group, or 1 to
A phenyl group which may be substituted with three alkyl groups is shown. Is a compound having one or two or more structures represented by the following formula in the molecule.

In the general formula (6), R ¹³ has 1 to 1 carbon atoms.
An alkyl group of 18 or a phenyl group which may be substituted by an alkyl group having 1 to 3 carbon atoms, and more preferably, R ¹³ is a group represented by the general formula (12)

[0153]

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(In the formula, R ¹⁴ and R ¹⁵ may be the same or different and each represents an alkyl group having 1 to 4 carbon atoms, and R ¹⁶ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. ). As the phosphorus-based antioxidant of (c-2), more preferably, the general formula (1)
3)

[0155]

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Or the general formula (14)

[0157]

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[Wherein R ¹⁷ may be the same or different and each represents an alkyl group having 1 to 18 carbon atoms, a phenyl group, a phenyl group substituted by an alkyl group having 1 to 9 carbon atoms, or a general formula: (15)

[0159]

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Wherein R ²¹ and R ²² may be the same or different and each represents an alkyl group having 1 to 4 carbon atoms, and R ²³ represents a hydrogen atom or a methyl group. R ¹⁸ represents an alkyl group having 1 to 18 carbon atoms, a phenylalkyl group having 7 to 9 carbon atoms, a cyclohexyl group, a phenyl group, a phenyl group substituted with an alkyl group having 1 to 9 carbon atoms, or a general formula (15)

[0161]

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(In the formula, R ²¹ and R ²² may be the same or different and each represents an alkyl group having 1 to 4 carbon atoms, and R ²³ represents a hydrogen atom or a methyl group.) Wherein R ¹⁹ is a hydrogen atom or a group having 1 to 1 carbon atoms.
4 represents an alkyl group, R ²⁰ represents an alkyl group having 1 to 4 carbon atoms, and L ¹ represents a 1,1,3-butanetriyl group. ] The compound represented by this is mentioned.

Preferred examples of the phosphorus antioxidant (c-2) will be described in more detail. R ^{17 of} the general formulas (13) and (14), and R ^{18 of the} general formula (14)
The alkyl group having 1 to 18 carbon atoms in may be linear or branched, and examples thereof include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group and a secondary butyl group. Tertiary butyl group, pentyl group, 2-pentyl group, 3-pentyl group, 2-methylbutan-1-yl group, 2-methylbutan-2-yl group, 2-
Methylbutan-3-yl group, 2-methylbutan-4-yl group, neopentyl group, hexyl group, isohexyl group,
Heptyl group, octyl group, 2-ethylhexyl group, nonyl group, decyl group, undecyl group, dodecyl group, tridecyl group, tetradecyl group, pentadecyl group, hexadecyl group, heptadecyl group, octadecyl group, and the like.
Preferred are a methyl group, an ethyl group, a dodecyl group, a tridecyl group and an octadecyl group.

R in the general formulas (13) and (14)
¹⁷ , and 1 to 9 carbon atoms at R ¹⁸ in the general formula (13).
Examples of the phenyl group substituted with an alkyl group include a methylphenyl group, an ethylphenyl group, a propylphenyl group, an isopropylphenyl group, a butylphenyl group, an isobutylphenyl group, a secondary butylphenyl group,
Examples include a tertiary butylphenyl group, a pentylphenyl group, a hexylphenyl group, a heptylphenyl group, an octylphenyl group, and a nonylphenyl group.

In the general formula (13), the number of carbon atoms in R ¹⁸ is from 7 to
The phenylalkyl group of No. 9 may have a linear or branched alkyl moiety, and examples thereof include a benzyl group, a phenethyl group, an α-methylbenzyl group, and an α, α-dimethylbenzyl group.

In the general formula (14), R ¹⁹ is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and the alkyl group may be linear or branched.
Examples include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, and a tertiary butyl group.
R ¹⁹ is preferably an alkyl group having 1 to 4 carbon atoms, and more preferably a methyl group.

In the general formula (14), R ¹⁹ is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and the alkyl group may be linear or branched.
Examples include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, and a tertiary butyl group.
R ¹⁹ is preferably an alkyl group having 1 to 4 carbon atoms, and more preferably a methyl group.

In the general formula (14), R ²⁰ has 1 to 1 carbon atoms.
And the alkyl group may be a straight-chain or branched-chain, such as a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, and a tertiary butyl group. And a tertiary butyl group is preferred. R ²⁰ is preferably substituted at the 5- or 6-position on the phenyl ring with respect to L ¹ , particularly preferably substituted at the 5-position.

R ²¹ and R ²² in the group represented by formula (15) may be the same or different and each is an alkyl group having 1 to 4 carbon atoms, and the alkyl group is a straight-chain or branched-chain. May be any of, for example,
Examples include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, and a tertiary butyl group, and a tertiary butyl group is preferable. Among them, it is particularly preferred that both R ²¹ and R ²² are tertiary butyl groups.

In the group represented by the general formula (15), R ²³ is a hydrogen atom or a methyl group. When R ²³ is a methyl group, R ²³ is substituted on the phenyl ring at the 5- or 6-position. preferable.

Preferred examples of the group represented by the general formula (15) include a 2,4-ditertiary butylphenyl group,
2,4-di-tert-butyl-6-methylphenyl group.

Preferred examples of R ¹⁷ in the general formula (13) include a dodecyl group, an octadecyl group, a phenyl group,
A nonylphenyl group, a 2,4-ditertiary butylphenyl group, and a 2,4-ditertiarybutyl-6-methylphenyl group.

Preferred examples of R ¹⁸ in the general formula (13) include a methyl group, an ethyl group, a dodecyl group, an octadecyl group, a phenyl group, a nonylphenyl group, a 2,4-ditertiary butylphenyl group, 4-di-tert-butyl-6-
And a methylphenyl group.

Preferred examples of R ¹⁷ in the general formula (14) include dodecyl, tridecyl, octadecyl, phenyl, nonylphenyl, 2,4-ditertiary butylphenyl, 2,4-diphenyl A tertiary butyl-6-methylphenyl group is exemplified, and a tridecyl group is more preferred.

Examples of the phosphorus antioxidant (c-2) include
For example, tris (2,4-di-tert-butylphenyl) phosphite, bis (2,4-di-tert-butyl-6-methylphenyl) ethyl phosphite, triphenyl phosphite, diphenylalkyl phosphite, phenyl Dialkyl phosphite, tris (nonylphenyl) phosphite, trilauryl phosphite, trioctadecyl phosphite, bis (2,4-di-tertiary butyl-6)
-Methylphenyl) methyl phosphite, hexatridecyl 1,1,3-tris (2-methyl-4-hydroxy-5-tert-butylphenyl) butanetriphosphite and the like.

The phosphorus antioxidant (c-3), which is a component of the discoloration inhibitor composition of the present invention, has the general formula (7):

[0177]

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(In the formula, R ²⁴ represents an alkyl group or a phenyl group which may be substituted with 1 to 3 substituents selected from the group consisting of an alkyl group, an aryl group and a phenylalkyl group. R ²⁴ represents a phenyl group which may be substituted with an alkyl group or an aryl group.) In the molecule.

In the general formula (7), preferably, R ²⁴
Is substituted with an alkyl group having 1 to 18 carbon atoms, or an alkyl group having 1 to 4 carbon atoms, a phenyl group and 1 to 3 substituents selected from the group consisting of phenylalkyl groups having 7 to 9 carbon atoms. R ²⁴ is more preferably an alkyl group having 1 to 18 carbon atoms, or a general formula (16)

[0180]

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(In the formula, R ²⁵ and R ²⁶ may be the same or different and each represents an alkyl group having 1 to 4 carbon atoms or a phenylalkyl group having 7 to 9 carbon atoms, and R ²⁷ is a hydrogen atom or a carbon atom. Represents an alkyl group of Formulas 1 to 4).

As the phosphorus antioxidant (c-3),
More preferably, general formula (17)

[0183]

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Or the general formula (18)

[0185]

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[Wherein q represents 1 or 2, and A represents the case where q represents 1;

[0187]

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(In the formula, R ³¹ and R ³² may be the same or different and each represents an alkyl group having 1 to 4 carbon atoms, and R ³³ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. A represents an alkylene group having 2 to 18 carbon atoms, a p-phenylene group or a p-biphenylene group when q represents 2, and R ²⁸ and R ^28
29 independently represents an alkyl group having 1 to 4 carbon atoms, R ³⁰ independently represents an alkyl group having 1 to 18 carbon atoms, a phenylalkyl group having 7 to 9 carbon atoms, a cyclohexyl group, a phenyl group, Or the general formula (20)

[0189]

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(Wherein R ³⁴ and R ³⁵ may be the same or different and each represents an alkyl group having 1 to 4 carbon atoms or a phenylalkyl group having 7 to 9 carbon atoms, and R ³⁶ represents a hydrogen atom or a carbon atom Represents an alkyl group of Formulas 1 to 4). ] The compound represented by this is mentioned.

Preferred examples of the phosphorus antioxidant (c-3) will be described in more detail. R ³¹ and R ³² in the group represented by the general formula (19) may be the same or different and each is an alkyl group having 1 to 4 carbon atoms, and the alkyl group may be a straight chain or a branched chain. Examples thereof include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group and a tertiary butyl group, and a methyl group and a tertiary butyl group are preferable.

R ³³ in the group represented by the general formula (19) is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and the alkyl group may be either linear or branched. For example, a methyl group, an ethyl group, a propyl group,
Examples include an isopropyl group, a butyl group, an isobutyl group, and a tertiary butyl group. R ³³ is preferably a hydrogen atom or a tertiary butyl group. When R ³³ is an alkyl group having 1 to 4 carbon atoms, R ³³ is preferably substituted at the 5- or 6-position on the phenyl ring, particularly preferably substituted at the 6-position.

Preferred examples of the group represented by the general formula (19) include a 2,4,6-tri-tert-butylphenyl group, a 2,4-di-tert-butylphenyl group, and a 2,6-di-tert-butylphenyl group. A tertiary butyl-4-methylphenyl group is exemplified.

In formula (17), A has 2 to 1 carbon atoms in A.
The alkylene group of 8 may be linear or branched, and examples thereof include an ethylene group, an ethylidene group, a trimethylene group, an isopropylidene group, a tetramethylene group, a pentamethylene group, and a hexamethylene group. .

When q represents 1, preferred examples of A include 2,4,6-tritertiary butylphenyl group, 2,4
-Di-tert-butylphenyl group and 2,6-di-tert-butyl-4-methylphenyl group.

In the general formula (17), q is preferably 1.

R ²⁸ and R in the general formula (17)
²⁹ may be the same or different and each is an alkyl group having 1 to 4 carbon atoms, and the alkyl group may be either linear or branched, for example, a methyl group,
Examples include an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, and a tertiary butyl group.

In formula (18), the number of carbon atoms in R ³⁰ is 1 to 1.
The alkyl group of 18 may be linear or branched, for example, a methyl group, an ethyl group, a propyl group,
Isopropyl group, butyl group, isobutyl group, secondary butyl group, tertiary butyl group, pentyl group, 2-pentyl group,
3-pentyl group, 2-methylbutan-1-yl group, 2-
Methylbutan-2-yl group, 2-methylbutan-3-yl group, 2-methylbutan-4-yl group, neopentyl group, hexyl group, isohexyl group, heptyl group, octyl group, 2-ethylhexyl group, nonyl group, decyl group , Isodecyl group, undecyl group, dodecyl group, tridecyl group, tetradecyl group, pentadecyl group, hexadecyl group, heptadecyl group, octadecyl group and the like,
Preferably it is an octadecyl group.

In the general formula (18), the number of carbon atoms in R ³⁰ is 7 to
The phenylalkyl group of No. 9 may have a linear or branched alkyl moiety, and examples thereof include a benzyl group, a phenethyl group, an α-methylbenzyl group, and an α, α-dimethylbenzyl group.

The alkyl group having 1 to 4 carbon atoms at R ³⁴ and R ³⁵ in the general formula (20) may be linear or branched, for example, methyl, ethyl, propyl, isopropyl Group, butyl group, isobutyl group, tertiary
A tert-butyl group is exemplified, and a methyl group and a tertiary butyl group are preferred.

The phenylalkyl group having 7 to 9 carbon atoms at R ³⁴ and R ³⁵ in the general formula (20) may have a straight-chain or branched alkyl moiety, for example, benzyl group, phenethyl group, α-methylbenzyl group, α, α
-Dimethylbenzyl group and the like.

R ³⁶ in the group represented by the general formula (20) is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and the alkyl group may be linear or branched. For example, a methyl group, an ethyl group, a propyl group,
Examples include an isopropyl group, a butyl group, an isobutyl group, and a tertiary butyl group. R ³⁶ is preferably a hydrogen atom or a tertiary butyl group. When R ³⁶ is an alkyl group having 1 to 4 carbon atoms, R ³⁶ is preferably substituted at the 5- or 6-position on the phenyl ring, particularly preferably substituted at the 6-position.

Preferred examples of R ³⁰ include a 2,4-di-tert-butylphenyl group and a 2,6-di-tert-butyl-4- group.
Methylphenyl group, 2,4-di (1-phenyl-1,1
-Dimethylmethyl) phenyl group, 2,4,6-tritertiary
Tert-butylphenyl group, octadecyl group, and isodecyl group.

As the phosphorus antioxidant (c-3),
For example, bis (2,4-di-tert-butylphenyl) pentaerythritol diphosphite, bis (2,6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphite, distearylpentaerythritol diphosphite Phosphite, bis [2,4-bis (α, α-dimethylbenzyl) phenyl] pentaerythritol diphosphite, (2,4,6-tri-tert-butylphenyl)-
2-butyl-2-ethyl-1,3-propanediol phosphite, (2,4,6-tritert-butylphenyl) -2-butyl-2-ethyl-1,3-propanediol phosphite, bis (2,4,6-tri-tert-butylphenyl) pentaerythritol diphosphite and the like.

As the phosphorus antioxidant of (c-3),
Preferably, bis (2,4-di-tert-butylphenyl)
Pentaerythritol diphosphite, bis (2,6-
Ditertiary butyl-4-methylphenyl) pentaerythritol diphosphite, bis [2,4-bis (α, α-
Dimethylbenzyl) phenyl] pentaerythritol diphosphite, (2,4,6-tritert-butylphenyl) -2-butyl-2-ethyl-1,3-propanediol phosphite, distearylpentaerythritol diphosphite Fight.

The general formula (8) which is a phosphorus antioxidant of (c-4) which is a constituent of the discoloration inhibitor composition of the present invention.

[0207]

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Wherein R ³⁷ represents an alkyl group having 1 to 5 carbon atoms, R ³⁸ represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, R ³⁹ represents a hydrogen atom or a methyl group, ⁴⁰
Represents a direct bond, an alkylene group having 1 to 5 carbon atoms or a sulfur atom. The compound containing one or more of the structures represented by the formula (1) in the molecule will be described.

As the phosphorus antioxidant (c-4),
More preferably, general formula (21)

[0210]

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[Wherein, R ⁴¹ represents an alkyl group having 1 to 5 carbon atoms, R ⁴² represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, R ⁴³ represents a hydrogen atom or a methyl group, ⁴⁴
Represents a direct bond, a methylene group, a —CH (R ⁴⁶ ) — group (R ⁴⁶ represents an alkyl group having 1 to 4 carbon atoms), or a sulfur atom, n ³ represents 1 or 3, and n ³ represents In the case of 3, R ⁴⁵ represents a group represented by N (CH ₂ CH ₂ O—) ₃ , and when n ³ is 1, R ⁴⁵ is an alkyl group having 1 to 18 carbon atoms, a halogen atom, a hydroxyl group, and 1 carbon atom. ~ 8 alkoxy groups, or-
OR ⁴⁷ (R ⁴⁷ is a phenyl (C ₁ -C ₄ ) alkyl group or phenyl (C ₁ -C ₄ ) alkylcarbonyloxy (C ₁
-C ₄ ) alkyl groups, which may have 1 to 3 substituents selected from the group consisting of alkyl groups having 1 to 4 carbon atoms and hydroxyl groups on the phenyl ring. ). ] The compound represented by this is mentioned.

R ⁴¹ in the general formula (21) may be the same or different and each represents an alkyl group having 1 to 5 carbon atoms, and the alkyl group may be either linear or branched. , Methyl group, ethyl group, propyl group,
Isopropyl group, butyl group, isobutyl group, secondary butyl group, tertiary butyl group, pentyl group, 2-pentyl group,
3-pentyl group, 2-methylbutan-1-yl group, 2-
Examples thereof include a methylbutan-2-yl group, a 2-methylbutan-3-yl group, a 2-methylbutan-4-yl group, and a neopentyl group. R ⁴¹ is preferably a tertiary butyl group.

R ⁴² in the general formula (21) may be the same or different and each represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and the alkyl group may be linear or branched. Often, a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, and a tertiary butyl group are exemplified. The R ^42, tert-butyl group is preferable.

R ⁴³ in the general formula (21) may be the same or different and each represents a hydrogen atom or a methyl group, preferably a hydrogen atom.

In the general formula (21), R ⁴⁶ has 1 to 1 carbon atoms.
And the alkyl group may be a straight-chain or branched-chain, such as a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, and a tertiary butyl group. Is mentioned. The R ^46,
A methyl group is preferred.

Preferred examples of R ⁴⁴ in formula (21) include a direct bond, a methylene group and an ethylidene group.

In formula (21), the number of carbon atoms of R ⁴⁵ is 1 to 1.
The alkyl group of 18 may be linear or branched, for example, a methyl group, an ethyl group, a propyl group,
Isopropyl group, butyl group, isobutyl group, secondary butyl group, tertiary butyl group, pentyl group, 2-pentyl group,
3-pentyl group, 2-methylbutan-1-yl group, 2-
Methylbutan-2-yl group, 2-methylbutan-3-yl group, 2-methylbutan-4-yl group, neopentyl group, hexyl group, isohexyl group, heptyl group, octyl group, 2-ethylhexyl group, nonyl group, decyl group , Undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl and the like.

The halogen atom for R ⁴⁵ in the general formula (21) includes a chlorine atom, a bromine atom, a fluorine atom and an iodine atom, and is preferably a fluorine atom.

In formula (21), the number of carbon atoms of R ⁴⁵ is 1 to 1.
The alkoxy group of 8 may be linear or branched, and includes, for example, a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, a butoxy group, a secondary butyloxy group, a tertiary butyloxy group, Examples include a pentyloxy group, a hexyloxy group, a heptyloxy group, an octyloxy group, a 2-ethylhexyloxy group, and a 2-ethylhexyloxy group is preferable.

In the general formula (21), when n ³ is 1, preferred examples of R ⁴⁵ include a fluorine atom and a 2-ethylhexyloxy group. Preferred examples of R ⁴⁷ is (4-hydroxy-5-methylphenyl) propionyloxy group, and a (3-tert-butyl-4-hydroxy-5-methylphenyl) propoxy group.

As the phosphorus antioxidant of (c-4),
For example, 2,2-methylenebis (4,6-di-tert-butylphenyl) -2-ethylhexyl phosphite (or 6-isooctyloxy-2,4,8,10-tetra-tert-butyl-12H-dibenzo) [D, g] -1,3,3
6-fluoro-2,4,8,10-tetra-tert-butyl-12-methyl-dibenzo [d, g] -1,3,2-dioxaphosphosine; 2,2 ′, 2 ″ -nitrilo [triethyltris (3,3 ′, 5,5′-tetra-tert-butyl-1,1 ′
-Biphenyl-2,2'-diyl) phosphite],
2,10-dimethyl-4,8-di-tert-butyl-6-
{2- [3- (3-tert-butyl-4-hydroxy-5
-Methylphenyl) propionyloxy] ethoxy}-
12H-dibenzo [d, f] [1,3,2] dioxaphosphin, 6- [3- (3-tert-butyl-4-hydroxy-5-methylphenyl] propoxy] -2,4,8 ,
10-tetra-tert-butyldibenzo [d, f] [1,
[3,2] dioxaphosphepin and the like.

Examples of the organic polymer whose discoloration due to nitric oxide gas is suppressed by the discoloration inhibitor composition of the present invention include synthetic organic polymers and natural organic polymers.

As the synthetic organic polymer, a thermoplastic resin,
Synthetic resins such as thermosetting resins are exemplified.

Examples of the thermoplastic resin include polyolefin resin, halogen-containing polymer, styrene resin, acrylic resin, thermoplastic polyester resin, polyamide resin, aromatic polycarbonate resin, polyacetal resin, polyethylene oxide resin, and polyphenylene ether. Resin, polysulfone resin, polyurethane resin, petroleum resin, polyvinyl acetate resin, vinyl acetal resin, cellulose (cellulose) resin, polyether sulfone resin,
Polyphenylene sulfide resin, polyether ketone resin, polyether imide resin, polyoxybenzoyl resin, polyimide resin, polymaleimide resin, polyamide imide resin, polyarylate resin, fluororesin, ionomer, thermoplastic elastomer, etc., and mixtures thereof Can also be used.

Examples of the polyolefin resin include low-density polyethylene, linear low-density polyethylene,
Medium-density polyethylene, high-density polyethylene, ultra-high-molecular-weight polyethylene, polypropylene, polybutene-1, polypentene, poly-2-methylbutylene, etc.
Α-olefin homopolymer of No. 8; α such as ethylene / propylene random copolymer, ethylene / propylene block copolymer, ethylene / butene-1 random copolymer, propylene / ethylene / butene-1 random copolymer
-Olefin copolymers; copolymers of α-olefins with other monomers such as maleic anhydride-modified polypropylene, ethylene / vinyl acetate copolymers, etc .; Can be used.

After polymerization of these polyolefin resins,
A catalyst that has been subjected to a slight purification treatment with a step of removing catalyst residues, a relatively highly purified one, a highly active catalyst, a catalyst that has not undergone a catalyst removal step, or is obtained in a simplified manner. Polyolefin-based resins containing residues, especially crystalline polyolefin-based resins obtained using a Ziegler-type catalyst or a chromium-based catalyst using a halogen-containing magnesium compound as a catalyst carrier and not yet subjected to a catalyst residue removal step. Good (Japanese Patent Publication No. 62-4418)
Gazette, Japanese Patent Publication No. 3-56245, U.S. Pat.
No. 5639). Further, a polyolefin resin having a very narrow molecular weight distribution obtained by a metallocene single-site catalyst may be used (Journal of Polymer Science. Polymer Chemistry.
Edition (Journal of Polymer)
Science. Polymer Chemistr
yEdition) 23, 2151 (1985)
Year)).

Examples of the halogen-containing polymer include polyvinyl chloride, polyvinylidene chloride, polyvinyl fluoride, polyvinylidene fluoride, vinyl chloride / alkyl acrylate copolymer, and chlorinated polyethylene.

Examples of the styrene resin include polystyrene, high-impact polystyrene, styrene-acrylonitrile copolymer, styrene-MMA copolymer, AB
S resin, AES resin, ACS resin, AAS resin, EES
Examples thereof include resins and the like, and mixtures thereof.

Examples of the acrylic resin include polyacrylate and polymethacrylate.

As the thermoplastic polyester resin,
For example, polyethylene terephthalate, polybutylene terephthalate and the like can be mentioned.

As the polyamide resin, for example, 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, aramid, and the like, and mixtures thereof.

The thermosetting resin includes unsaturated polyester resin, phenol resin, urea resin, melamine resin, epoxy resin, polyimide resin, silicone resin,
Examples include diallyl phthalate resin, polyurethane resin, and furan resin.

Examples of the natural organic polymer include natural rubber, proteins, derivatives such as cellulose, mineral oil, animal and vegetable oils, waxes, oils and fats.

As the organic polymer used in the organic polymer material of the present invention having an excellent effect of suppressing discoloration to nitrogen oxide gas, polyolefin resins, especially α-olefin homopolymers or α-olefin copolymers, are preferred. It is suitable. When the discoloration inhibitor composition of the present invention is blended with such an organic polymer, an excellent effect of suppressing discoloration due to nitric oxide gas is exhibited. Most preferred as α-olefin is ethylene or propylene.

The formula (1) used in the present invention

[0236]

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(The symbols in the formula are as described above.) The 6-hydroxychroman compound represented by
Can be synthesized according to the method described in JP-A-23146.

The above-mentioned phosphorus antioxidants and phenolic antioxidants are known compounds, and most of them are sold as antioxidants and generally available.

A 6-hydroxychroman compound represented by the general formula (1) (component (a)), a phenolic antioxidant (component (b)) and a phosphorus antioxidant (component (c))
Is 0.5% by weight to 10% by weight based on the total amount of component (a), component (b) and component (c), component (b) and component (c). 99.5% by weight
And preferably 90% by weight to 90% by weight, preferably 1.0% to 5% by weight of component (a) and 9% by weight of component (b) and component (c).
9.0 to 95% by weight, more preferably 2 to 5% by weight of component (a), and components (b) and (c).
Is 98% to 95% by weight.

By using the discoloration inhibitor composition of the present invention containing the 6-hydroxychroman compound represented by the general formula (1) in a small amount within the above range, discoloration due to nitric oxide gas is suppressed, and thermal stability is reduced. In addition, an organic polymer material having excellent processing stability can be obtained.

In the present invention, the weight ratio of the component (b) to the component (c) is 9: 1 to 1: 9, preferably 4: 1 to 1: 4, and more preferably 1: 1. : 0.5 ~
1: 2.

By using the discoloration inhibitor composition of the present invention in which the weight ratio of component (b) to component (c) is within the above range, discoloration due to nitrogen oxide gas is suppressed, and heat stability and processing stability are improved. Also, an excellent organic polymer material can be obtained.

Formula (1) in the organic polymer material of the present invention
The content of the 6-hydroxychroman compound is 0.0005 parts by weight to 100 parts by weight of the organic polymer material.
0.025 parts by weight, preferably 0.001 parts by weight to 0.1 part by weight.
010 parts by weight, more preferably 0.001 to 0.005 parts by weight.

With respect to 100 parts by weight of the organic polymer material of the present invention, a 6-hydroxychroman compound of the general formula (1), a phenolic antioxidant (component (b)) and a phosphorus antioxidant (component (c) )) Is 0.01 to 1 part by weight, preferably 0.02 to 0.2 part by weight. When the amount is 0.01 part by weight to 1 part by weight, discoloration due to nitric oxide gas is suppressed, and an organic polymer material excellent in heat resistance and processing stability can be obtained.

By further mixing a sulfur-based antioxidant with the organic polymer material of the present invention, 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, dimyristyl thiodipropionate, distearyl thiodipropionate, ditridecyl thiodipropionate, tetrakis [(3-lauryl thiopropionyloxy) methyl]
Methane, tetrakis [(3-stearylthiopropionyloxy) methyl] methane, bis [2-methyl-4-
(3-n-alkyl (C12-C14) thiopropionyloxy) -5-tert-butylphenyl] sulfide and the like.

The organic polymer material of the present invention may contain one or more sulfur-based antioxidants.
The sulfur-based antioxidant can be added at a ratio of preferably 0.005 to 5 parts by weight, more preferably 0.01 to 1 part by weight, based on 100 parts by weight of the organic polymer material. 2
When using more than one kind of sulfur-based antioxidants, it is preferable to add them so that the total amount is within the above range.

By blending an ultraviolet stabilizer or a light stabilizer with the organic polymer material of the present invention, an organic polymer material having more excellent stability can be obtained.

Examples of the ultraviolet absorber and light stabilizer include salicylic acid compounds, benzophenone compounds, benzotriazole compounds, benzoate compounds, cyanoacrylate compounds, nickel compounds, and piperidine compounds.

As salicylic acid-based compounds that can be used as an ultraviolet absorber, phenyl salicylate, p-
Tertiary butylphenyl salicylate, p-octylphenyl salicylate and the like can be mentioned.

Examples of the benzophenone-based compounds that can be used as an ultraviolet absorber include 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2,2′-dihydroxy-4,4′-dimethoxybenzophenone, and 2-hydroxybenzophenone. -4-n-octyloxybenzophenone, 2-hydroxy-4-isooctyloxybenzophenone, 2-hydroxy-4-dodecyloxybenzophenone, 2-hydroxy-4-octadecyloxybenzophenone, 2-hydroxy-4-
Methoxy-2'-carboxybenzophenone, bis (5
-Benzoyl-4-hydroxy-2-methoxyphenyl) methane, 2-hydroxy-4-methoxy-5-sulfobenzophenone trihydrate, 2,2 ', 4,
Compounds such as 4′-tetrahydroxybenzophenone and 2-hydroxy-4-benzoyloxybenzophenone are exemplified.

Examples of the benzotriazole-based compound that can be used as an ultraviolet absorber include 2- (2-hydroxy-5-methylphenyl) benzotriazole,
(2-hydroxy-3,5-di-tert-butylphenyl)
Benzotriazole, 2- (2-hydroxy-3-third
Tert-butyl-5-methylphenyl) -5-chlorobenzotriazole, 2- (2-hydroxy-3,5-ditert-butylphenyl) -5-chlorobenzotriazole, 2
-[2-hydroxy-5- (1,1,3,3-tetramethylbutyl) phenyl] benzotriazole, 2- [2
-Hydroxy-3,5-bis (α, α-dimethylbenzyl) phenyl] -2H-benzotriazole, methyl
Condensation product of 3- [3-tert-butyl-5- (2H-benzotriazol-2-yl) -4-hydroxyphenyl] propionate and polyethylene glycol, 2- (2
-Hydroxy-3,5-ditertiary amylphenyl) benzotriazole, 2,2-methylenebis [4- (1,
1,3,3-tetramethylbutyl) -6- (2H-benzotriazol-2-yl) phenol], 2- (2-
Hydroxy-5-tert-octylphenyl) benzotriazole, 2- [2-hydroxy-3- (3,4,5,
6-tetrahydrophthalimidomethyl) -5-methylphenyl] benzotriazole.

Benzoate compounds which can be used as light stabilizers include n-hexadecyl-3,5-ditert-butyl-4-hydroxybenzoate and 2,4-
Di-tert-butylphenyl-3,5-di-tert-butyl-4
Compounds such as -hydroxybenzoate.

Examples of cyanoacrylate compounds that can be used as an ultraviolet absorber include ethyl-2-cyano-3,3-diphenylacrylate, octyl-2-cyano-3,3-diphenylacrylate and the like.

As nickel compounds that can be used as an ultraviolet absorber, 2-ethylhexylamine / nickel, nickel dimethyldithiocarbamate, [2,
2′-thiobis [4- (1,1,3,3-tetramethylbutyl) phenolate]]-n-butylamine nickel, [2,2′-thiobis [4- (1,1,3,3-tetra Methylbutyl) phenolate]] nickel and the like.

Examples of piperidine compounds that can be used as a light stabilizer include bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate and bis (1-octyloxy-2,2,6,6- Tetramethyl-4-piperidyl) sebacate, bis (1,2,2,6,6-pentamethyl-4-piperidyl) -2- (3,5-ditert-butyl-4-hydroxybenzyl) -2 -N-butylmalonate, tetrakis (2,2,6,6-tetramethyl-
4-piperidyl) -1,2,3,4-butanetetracarboxylate, tetrakis (1,2,2,6,6-pentamethyl-4-piperidyl) -1,2,3,4-butanetetracarboxylate, Poly [[6- (1,1,3,
3-tetramethylbutyl) imino-s-triazine-
2,4-diyl] [(2,2,6,6-tetramethyl-
4-piperidyl) imino] hexamethylene [(2,2
6,6-tetramethyl-4-piperidyl) imino]],
Poly [(6-morpholino-s-triazine-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,
6,6-tetramethyl-4-piperidylamino) hexane condensate), 1-hydroxyethyl-2,2,6,6-
Tetramethyl-4-piperidinol / succinic acid condensate,
N, N'-bis (3-aminopropyl) ethyldiamine / 2,4-bis [N-butyl-N- (1,2,2,6
6-pentamethyl-4-piperidyl) amino] -6-chloro-1,3,5-triazine condensate.

Preferred compounds that can be used as an ultraviolet absorber and a light stabilizer include 2-hydroxy-
4-n-octyloxybenzophenone, 2- (2-hydroxy-5-methylphenyl) benzotriazole,
2- (2-hydroxy-3-tert-butyl-5-methylphenyl) -5-chlorobenzotriazole, 2- (2
-Hydroxy-3,5-ditert-butylphenyl) -5
-Chlorobenzotriazole, bis (2,2,6,6-
Tetramethyl-4-piperidyl) sebacate, poly [[6- (1,1,3,3-tetramethylbutyl) imino-s-triazine-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 (2,2,6,6-tetramethyl-4-piperidylamino) hexane condensate).

One or more ultraviolet absorbers or light stabilizers can be added to the organic polymer material of the present invention. The ultraviolet absorber or the light stabilizer can be blended in an amount of preferably 0.005 to 5 parts by weight, more preferably 0.01 to 1 part by weight, based on 100 parts by weight of the organic polymer material. When two or more UV absorbers or light stabilizers are used, they are preferably added so that the total amount is within the above range.

Further, if necessary, other additives such as hydrotalcites, calcium stearate, etc., which do not significantly impair the performance of the organic polymer material of the present invention, which is excellent in the effect of inhibiting discoloration to nitric oxide gas, may be used. Heavy metal deactivators such as metal soaps and hydrazine compounds, monoalkyltin tris (octyl thioglycolate), dialkyltin tris (octyl thioglycolate), monoalkyltin tris (monoalkyl maleate) or dialkyl Organic tin stabilizers such as tin tris (monoalkyl maleate), epoxy compounds such as epoxidized soybean oil or epoxy octyl stearate, various organic pigments, flame retardants such as phosphate esters, cationic or anionic surfactants Agent, antistatic agent, fat Lubricants such as lower alcohol esters of amides, or fatty acids, acrylic polymer processing aids, di-2-ethylhexyl phthalate or di-2
It can also be used in combination with one or more of a plasticizer such as ethylhexyl adipate, a filler such as aluminum oxide, and a foaming agent such as sodium bicarbonate or azodicarbonamide.

The organic polymer material of the present invention can be used in combination with a nucleating agent, a clarifying agent, and the like, if necessary. Bis (p-tert-butylbenzoic acid) hydroxyaluminum, bis (4-tert.
Butylphenyl) sodium phosphate, 2,2 '
Sodium methylenebis (4,6-ditert-butylphenyl) phosphate, 2,2′-methylenebis (4
6-ditert-butylphenyl) phosphate hydroxyaluminum, 1: 1 composition of 2,2'-methylenebis (4,6-ditert-butylphenyl) phosphatehydroxyaluminum and lithium stearate, dibenzylidene sorbitol , Bis (p-methylbenzylidene) sorbitol, bis (p-ethylbenzylidene) sorbitol, bis (p-chlorobenzylidene) sorbitol and the like.

To prepare the discoloration inhibitor composition according to the present invention, the 6-hydroxychroman compound of the present invention or a mixture containing the compound is, if necessary, mixed with a phenolic antioxidant, a phosphorus antioxidant, Sulfur-based antioxidants, ultraviolet absorbers, light stabilizers, or other additives are each weighed in a predetermined amount, and may be mixed with the organic polymer, may be mixed and kneaded, and may be extruded. You can also go through.

In mixing, a mixer conventionally used for mixing an additive with an organic polymer, for example, a ball mill, a pebble mill, a tumble mixer, a change can mixer, a super mixer (Henschel mixer)
When kneading, kneading machines conventionally used when kneading additives to organic polymers, for example, mixing rolls, Banbury mixers, blade-type mixers, high-speed twin-screw continuous mixers And an extruder-type kneader.

The organic polymer material according to the present invention can be produced by various molding methods for organic polymer materials known in the art, for example, injection molding, extrusion molding, calender molding, blow molding, compression molding. For example, it can be formed into a target product. The product is not particularly limited and may be used indoors or outdoors.Specifically, parts for electric products, parts for electronic products, parts for agricultural machinery, agricultural products, fishery machinery Parts, marine products, automobile parts, daily necessities, sundries and the like. More specifically, a coating layer of a steel pipe for transporting heavy oil at a high temperature, a heating pipe (for hot water supply, for underfloor heating, etc.), a jar, a pot, a part of a home appliance such as a washing machine, and the like can be given. By the way, the present inventors did not mix the compound represented by the general formula (1), and added a biphenylene-type phosphorus antioxidant such as P101 or EPQ and a phenolic antioxidant such as TT, SS, and GA80. Is blended with an organic polymer material to prevent discoloration of nitric oxide gas better than previously known without losing basic performance such as processing stability and thermal stability. Was also found.

[0264]

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

[Nitrogen Oxide Gas Generation and Testing Apparatus] JI
According to SL0855 "Testing Method for Color Fastness to Nitric Oxide Gas", 375 ml of distilled water and 6.7 ml of 85% phosphoric acid are put into a magnetic petri dish, and 25 ml of 1% aqueous sodium nitrite is added to generate nitric oxide gas. .
The magnetic petri dish containing the solution and a glass petri dish containing a test sample (pellets having a diameter of about 1.5 mm and a length of 2.0 mm) are put into contact with a closed glass desiccator equipped with a stirrer and brought into contact therewith.

Based on the yellowness of the pellet before and after the contact with the nitric oxide gas, the yellowing degree is determined as follows. <Yellowness> = <Yellowness of pellet after contact with nitric oxide gas> − <Yellowness of non-contact pellet>

Synthesis Example 1 5.0 g of 2,3,6-trimethylhydroquinone, 0.8 g of zinc chloride, 0.3 g of acetic acid were placed in a 50 ml 4-necked corvene.
5 ml, methyl ethyl ketone 4 ml, toluene 15 ml
And heated. At 100 ° C., isoprene 2.5
g in 5 ml of toluene was added dropwise over 2 hours under reflux. After the dropwise addition, the mixture was further refluxed for 4 hours, and then cooled to room temperature. The reaction product was transferred to a separating funnel and washed three times with 50 ml of water, and then the solvent was distilled off to obtain 6.5 g of an oil.

This was recrystallized with 50 ml of petroleum ether,
2.5 g of needle crystals of 2,2,5,7,8-pentamethyl-6-hydroxychroman having a melting point of 94-95 ° C. were obtained.

[0269]

Example 1 Strands were extruded with an extruder having a diameter of 20 mm (die setting temperature: 280 ° C.) using the blends shown in Tables 1 to 3 which were dry-mixed for 5 minutes using a tumbler mixer. I got The pellets were brought into contact with the nitric oxide gas generated by the above method at room temperature for one week, and the yellowness of the pellets was measured using a color difference meter according to JIS.
Measured before and after contact with nitric oxide gas according to -K7103. Based on the yellowness of the pellet before and after the contact with the nitric oxide gas, the yellowing degree was determined from the above formula.

[0271]

[Table 1]

[0272]

[Table 2]

[0273]

[Table 3]

The meanings of the symbols described in Table 1, Table 2 and Table 3 are as follows. PP: polypropylene LLDPE: linear low-density polyethylene Ca-St: calcium stearate S-1: 2,2,5,7,8-pentamethyl-6-hydroxychroman (the one synthesized according to Synthesis Example 1 was used) -E: DL-α-tocopherol (reagent manufactured by Wako Pure Chemical Industries, Ltd.) T-TT: tetrakis [3- (3,5-ditert-butyl-4-hydroxyphenyl) propionyloxymethyl] methane (Yoshitomi Fine Chemical) T-SS: n-octadecyl 3- (4-hydroxy-)
3,5-di-tert-butylphenyl) propionate (trade name: "Tominox SS" manufactured by Yoshitomi Fine Chemical Co., Ltd.) GA-80: 3,9-bis [2- [3- (3-tert-butyl) -4-hydroxy-5-methylphenyl) propionyloxy] -1,1-dimethylethyl] -2,4,8,1
0-Tetraoxaspiro [5.5] undecane (manufactured by Sumitomo Chemical Co., Ltd., trade name: "Sumilyzer-GA-80") P-1: Tetrakis (2,4-di-tertiary butyl-5-)
Methylphenyl) -4,4'-biphenylenediphosphonite (manufactured by Yoshitomi Fine Chemical Co., Ltd., trade name: "G
SY-P101 ") P-2: Tetrakis (2,4-di-tert-butylphenyl) -4,4'-biphenylenediphosphonite (manufactured by Clariant, trade name:" Sandstub P-EPQ ") P- 3: Bis (2,6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphite (Adeka Stab PEP-3, manufactured by Asahi Denka Co., Ltd.)
6 ") P-4: Tris (2,4-di-tert-butylphenyl)
Phosphite (manufactured by Yoshitomi Fine Chemical Co., Ltd., trade name: "Tomiphos 202")

From the results shown in Tables 1 and 2, the phenolic antioxidants (T-TT, T-SS, GA-80)
And phosphorus antioxidants (P-1, P-2, P-3, P-
4) and a 6-hydroxychroman compound (S-1, V-
E) An organic polymer obtained by blending the composition of the present invention containing 2.5% by weight and 5% by weight of the 6-hydroxychroman compound (S-1, VE) with respect to the total amount of It was found that the material composition formulation (formulations 1 to 26) was superior to the comparative example composition formulation (formulations 35 to 42) in the effect of suppressing discoloration due to nitric oxide gas. At the same time, the experimental example composition formulation (formulations 27 to 34) using the phosphorus-based antioxidant (P-1, P-2) is changed to the phosphorus-based antioxidant (P-3,
Comparative Example Composition Formulation Using P-4) (Formulations 35 to 42)
It was also found that the discoloration suppression effect by the nitrogen oxide gas was superior to that of Table 3 (Table 3). This tendency was the same even when GA-80 having a high ability to inhibit discoloration of nitrogen oxide gas was used.

[0276]

The organic polymer material containing the discoloration inhibitor composition of the present invention is excellent in the effect of suppressing discoloration due to nitric oxide gas, and has a known effect on heat resistance and processing stability. , And is extremely effective in suppressing discoloration of a combustion gas, a nitrogen oxide gas, or the like.

Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat II (Reference) C09K 15/06 C09K 15/06 15/08 15/08 15/32 15/32 C (72) Inventor Mamoru Suga Osaka F-term (reference) 4H025 AA63 AA84 4J002 AA001 AB011 AC011 AD001 AE031 AE051 BB001 BB021 BB031 BB051 BB121 BB141 BB141 BB141 BB141 BB141 BB141 1141 BC071 BD041 BD091 BD101 BD131 BD141 BF051 BG041 BG051 BN071 BN101 BN121 BN151 BP021 CC031 CC181 CC211 CD001 CF061 CF071 CF211 CH121 CK021 CL011 CL031 CL061 CM041 CP031 EE039 EJ017 EJ027 EJ047 EJ067 EJ069 EL086 EP017 ET009 EU079 EU179 EU197 EV069 EW068 EW088 EW118 EW128 EW138 EZ009 FD010 FD020 FD077 FD078 FD079 FD206 FD320 GM00 GN00 GQ00

Claims (17)

[Claims] (A) General formula (1) (In the formula, R ¹ represents an alkyl group having 1 to 18 carbon atoms or an alkenyl group having 2 to 18 carbon atoms, and R ² represents 1 to 5 carbon atoms.
R ³ , R ⁴ and R ⁵ may be the same or different and each represents a hydrogen atom or a carbon atom
And R ⁶ represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms. And (b) a phenolic antioxidant;
(C) A discoloration inhibitor composition for an organic polymer material caused by nitric oxide gas, comprising: a phosphorus-based antioxidant. 2. The discoloration inhibitor composition according to claim ¹ , wherein R ^{1 of the} compound represented by the general formula (1) is an alkyl group having 1 to 5 carbon atoms. 3. The compound represented by the general formula (1) is added in an amount of 0.5 to 1 based on the total amount of the compound represented by the general formula (1), the phenolic antioxidant, and the phosphorus antioxidant.
3. The discoloration inhibitor composition according to claim 1, wherein the composition contains 0% by weight, and the total amount of the phenolic antioxidant and the phosphorus-based antioxidant is 90 to 99.5% by weight. . 4. A compound represented by the general formula (1) in an amount of 1 to 5% by weight based on the total amount of the compound represented by the general formula (1), a phenolic antioxidant, and a phosphorus antioxidant. The discoloration inhibitor composition according to claim 1 or 2, wherein the total amount of the phenolic antioxidant and the phosphorus antioxidant is contained in a proportion of 95 to 99% by weight. 5. The phenolic antioxidant of the component (b) is represented by the general formula (2): (Wherein, R ⁷ represents an alkyl group having 1 to 5 carbon atoms, R ⁸ represents an alkyl group having 1 to 4 carbon atoms, R ⁹ represents a hydrogen atom or a methyl group, and L represents Or Or Or Or Is shown. Is a compound containing at least one structure represented by the following formula in the molecule, and the phosphorus-based antioxidant of the component (c) includes the following (c-1), (c-2), (c-3) and (C-4)
The discoloration inhibitor composition according to any one of claims 1 to 4, which is at least one compound of the formula: (C-1): General formula (3) Or, the general formula (4) [Wherein Q ¹ is a general formula (5)] (Wherein, R ¹⁰ and R ¹¹ may be the same or different, each represent an alkyl group having 1 to 4 carbon atoms, R ¹² is. Represents a hydrogen atom or a methyl group) indicates, Q ² is each The repeating unit is independently represented by the general formula (5): Wherein, in the formula, R ¹⁰ and R ¹¹ may be the same or different and each represents an alkyl group having 1 to 4 carbon atoms, and R ¹² represents a hydrogen atom or a methyl group. The unit independently represents 0 or 1, j represents 0 or 1, and n ¹ represents an integer of ¹ to 10. A compound represented by the general formula (6): (Wherein, R ¹³ represents an alkyl group or a phenyl group which may be substituted with 1 to 3 alkyl groups.) A compound having one or more structures represented by the following formulas in the molecule: (C-3): General formula (7) (In the formula, R ²⁴ represents an alkyl group or a phenyl group which may be substituted with 1 to 3 substituents selected from the group consisting of an alkyl group, an aryl group and a phenylalkyl group.) One or two structures in the molecule
Compound having at least one compound of formula (c-4): general formula (8) (Wherein, R ³⁷ represents an alkyl group having 1 to 5 carbon atoms, R ³⁸
Represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms;
³⁹ represents a hydrogen atom or a methyl group, R ⁴⁰ represents a direct bond,
It represents an alkylene group having 1 to 5 carbon atoms or a sulfur atom. )
A compound containing one or two or more structures represented by the following formulas in a molecule. 6. The phenolic antioxidant of the component (b) is n-octadecyl-3- (3,5-di-tertiary butyl).
4-hydroxyphenyl) propionate, tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionyloxymethyl] methane, 1,3,5-tris (3,5-di-tert. Grade butyl-4-
Hydroxybenzyl) isocyanurate, 1,3,5-trimethyl-2,4,6-tris (3,5
-Di-tert-butyl-4-hydroxybenzyl) benzene, and 3,9-bis [2- [3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionyloxy] -1, 1-dimethylethyl] -2,4,8,10
At least one selected from the group consisting of tetraoxaspiro [5,5] undecane, wherein the phosphorus-based antioxidant is tris (2,4-di-tert-butylphenyl) phosphite, tetrakis (2 4-di-tert-butylphenyl)-
4,4'-biphenylenediphosphonite, tetrakis (2,4-di-tert-butyl-5-methylphenyl) -4,4'-biphenylenediphosphonite, bis (2,4-di-tertiary) Butylphenyl) pentaerythritol diphosphite, bis (2,6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphite, 2,2′-methylenebis (4,6-di-tert-butyl) Phenyl) -2-ethylhexyl phosphite, bis- (2-methyl-4,6-di-tert-butylphenyl) ethyl phosphite, 2,2 ′, 2 ″ -nitrilo [triethyl tris (3
3 ', 5,5'-tetra-tert-butyl-1,1'-biphenyl-2,2'-di-yl) phosphite], and 6
-[3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propoxy] -2,4,8,10-tetra-tert-butyldibenzo [d, f] [1,3,2 The discoloration inhibitor composition according to any one of claims 1 to 4, wherein the composition is at least one member selected from the group consisting of dioxaphosphepin. 7. An organic polymer material comprising the discoloration inhibitor composition according to claim 1. 8. The organic polymer material according to claim 7, further comprising at least one compound selected from a sulfur-based antioxidant and a light stabilizer. 9. An organic polymer material containing the discoloration inhibitor composition according to claim 1, wherein the organic polymer material 10
The compound represented by the general formula (1) is compounded in a range of 0.0005 to 0.025 parts by weight with respect to 0 parts by weight, and has an excellent discoloration suppressing effect on nitrogen oxide gas. Organic polymer materials. 10. The compound represented by the general formula (1) is added in an amount of 0.001 to 100 parts by weight of the organic polymer material.
The organic polymer material according to claim 9, which is blended in a range of 0.010 parts by weight. 11. The phenolic antioxidant of the component (b) is represented by the general formula (2): (Wherein, R ⁷ represents an alkyl group having 1 to 5 carbon atoms, R ⁸ represents an alkyl group having 1 to 4 carbon atoms, R ⁹ represents a hydrogen atom or a methyl group, and L represents Or Or Or Or Is shown. Is a compound containing at least one structure represented by the following formula in the molecule, and the phosphorus-based antioxidant of the component (c) includes the following (c-1), (c-2), (c-3) and (C-4)
The organic polymer material according to claim 9, wherein the organic polymer material is at least one compound of the following. (C-1): General formula (3) Or a compound of the general formula (4) [Wherein Q ¹ is a general formula (5)] (Wherein, R ¹⁰ and R ¹¹ may be the same or different, each represent an alkyl group having 1 to 4 carbon atoms, R ¹² is. Represents a hydrogen atom or a methyl group) indicates, Q ² is each The repeating unit is independently represented by the general formula (5): Wherein, in the formula, R ¹⁰ and R ¹¹ may be the same or different and each represents an alkyl group having 1 to 4 carbon atoms, and R ¹² represents a hydrogen atom or a methyl group. The unit independently represents 0 or 1, j represents 0 or 1, and n ¹ represents an integer of ¹ to 10. A compound represented by the general formula (6): (Wherein, R ¹³ represents an alkyl group or a phenyl group which may be substituted with 1 to 3 alkyl groups.) A compound having one or more structures represented by the following formulas in the molecule: (C-3): General formula (7) (In the formula, R ²⁴ represents an alkyl group or a phenyl group which may be substituted with 1 to 3 substituents selected from the group consisting of an alkyl group, an aryl group and a phenylalkyl group.) One or two structures in the molecule
Compound having at least one compound of formula (c-4): general formula (8) (Wherein, R ³⁷ represents an alkyl group having 1 to 5 carbon atoms, R ³⁸
Represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms;
³⁹ represents a hydrogen atom or a methyl group, R ⁴⁰ represents a direct bond,
It represents an alkylene group having 1 to 5 carbon atoms or a sulfur atom. )
A compound containing one or two or more structures represented by the following formulas in a molecule. 12. The phenolic antioxidant of the component (b) is n-octadecyl-3- (3,5-di-tertiary butyl).
4-hydroxyphenyl) propionate, tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionyloxymethyl] methane, 1,3,5-tris (3,5-di-tert. Grade butyl-4-
Hydroxybenzyl) isocyanurate, 1,3,5-trimethyl-2,4,6-tris (3,5
-Di-tert-butyl-4-hydroxybenzyl) benzene, and 3,9-bis [2- [3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionyloxy] -1, 1-dimethylethyl] -2,4,8,10
At least one selected from the group consisting of tetraoxaspiro [5,5] undecane, wherein the phosphorus-based antioxidant is tris (2,4-di-tert-butylphenyl) phosphite, tetrakis (2 4-di-tert-butylphenyl)-
4,4'-biphenylenediphosphonite, tetrakis (2,4-di-tert-butyl-5-methylphenyl) -4,4'-biphenylenediphosphonite, bis (2,4-di-tertiary) Butylphenyl) pentaerythritol diphosphite, bis (2,6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphite, 2,2′-methylenebis (4,6-di-tert-butyl) Phenyl) -2-ethylhexyl phosphite, bis- (2-methyl-4,6-di-tert-butylphenyl) ethyl phosphite, 2,2′2 ″ -nitrilo [triethyl tris (3
3 ′, 5,5′-Tetra-tert-butyl-1,1′-biphenyl-2,2′-di-yl) phosphite], and 6- [3- (3-tert-butyl-4) -Hydroxy-5
-Methylphenyl] propoxy] -2,4,8,10-tetra-tert-butyldibenzo [d, f] [1,3,2] dioxaphosphepin
The organic polymer material according to claim 9 or 10, which is a seed. 13. The organic polymer material according to claim 7, wherein the organic polymer is a synthetic resin. 14. The organic polymer material according to claim 13, wherein the synthetic resin is a polyolefin resin. 15. The polyolefin resin is a polyethylene resin, a polypropylene resin, a mixture or a compatible polymer of a polyethylene resin and a polypropylene resin, or a compatible polymer containing a polyethylene resin and / or a polypropylene resin. The organic polymer material according to claim 14, which is an ethylene-vinyl acetate copolymer or an ethylene-propylene copolymer. 16. The organic polymer material according to claim 9, further comprising at least one compound selected from a sulfur-based antioxidant and a light stabilizer. 17. An organic polymer material comprising (a) a compound represented by the following general formula (1): (In the formula, R ¹ represents an alkyl group having 1 to 18 carbon atoms or an alkenyl group having 2 to 18 carbon atoms, and R ² represents 1 to 5 carbon atoms.
R ³ , R ⁴ and R ⁵ may be the same or different and each represents a hydrogen atom or a carbon atom
And R ⁶ represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms. And (b) a phenolic antioxidant;
(C) A method for suppressing discoloration of an organic polymer material using nitric oxide gas, which comprises adding a phosphorus-based antioxidant.