Stabilizer, organic material composition, and method for stabilizing organic material

Abstract

The present invention relates to a stabilizer containing a compound (A) and a compound (B), the content of the compound (B) being 0.01-50 parts by mass per 100 parts by mass of the compound (A), the compound (A) being selected from the group consisting of a compound represented by formula (1) and a compound represented by formula (2), the compound (B) being represented by formula (3) (# imgabs0 # [in formula (1), in formula (2), in formula (3); in the formula, R1, R2, R4 and R5 each independently represent a hydrogen atom, an alkyl group having 1-8 carbon atoms, a cycloalkyl group having 5-8 carbon atoms, an alkylcycloalkyl group having 6-12 carbon atoms, an aralkyl group having 7-12 carbon atoms, or a phenyl group, R3 each independently represents a hydrogen atom or an alkyl group having 1-8 carbon atoms, X represents a single bond, a sulfur atom, or a-CH (-R13)-group (R13 represents a hydrogen atom, an alkyl group having 1-8 carbon atoms, or a cycloalkyl group having 5-8 carbon atoms), and R6 represents a hydrogen atom, an alkyl group having 1-8 carbon atoms, or a phenyl group. In formula (1), A represents an alkylene group having 1-8 carbon atoms or a *-C (= O)-R14-group (R14 represents a single bond or an alkylene group having 1-8 carbon atoms, and * represents a linking site on the oxygen side), either Y or Z represents a hydroxyl group, an alkoxy group having 1-8 carbon atoms, or an arylalkoxy group having 7-12 carbon atoms, and the other represents a hydrogen atom or an alkyl group having 1-8 carbon atoms) # imgabs1 # [in formula (2), R6 and R8 each independently represent a hydrogen atom, a methyl group, or an alkyl group having 5-8 carbon atoms, and in formula (2), R6 and R8 each independently represent a hydrogen atom, a methyl group, or an alkyl group having 5-8 carbon atoms. In formula (1), R7 independently represents a hydrogen atom or a hydroxyl group, R9 independently represents a hydrogen atom or a-C15H25-31 group (where at least one R6, R7, R8 or R9 is not a hydrogen atom), # imgabs2 # [in formula (3), R10, R11 and R12 independently represent a hydrogen atom, an alkyl group having 1-12 carbon atoms, or an aralkyl group having 7-20 carbon atoms in total (where at least one of R10, R11 and R12 is not a hydrogen atom).

Description

Technical Field

[0001] The present invention relates to a stabilizer containing a specific compound, an organic material composition, and a method for stabilizing an organic material using the specific compound. Background Art

[0002] Organic materials such as thermoplastic resins, thermosetting resins, natural or synthetic rubbers, mineral oils, lubricating oils, adhesives, and coatings may deteriorate during manufacturing, processing, and use due to the effects of oxidizing substances such as heat, oxygen, and ozone. This may be accompanied by a decrease in the strength and physical properties of the organic materials due to phenomena such as molecular scission and molecular cross-linking, changes in fluidity, coloration, and a decrease in surface properties, which may sometimes significantly damage the value of the product.

[0003] In order to prevent such degradation caused by heat and / or oxidizing substances such as oxygen and ozone, various phenolic antioxidants and phosphorus antioxidants have been developed, and it is known that these antioxidants can stabilize organic materials by adding them to organic materials (Patent Documents 1 and 2).

[0004] Prior art literature

[0005] Patent Literature

[0006] Patent Document 1: Japanese Patent No. 3876479

[0007] Patent Document 2: International Publication No. 2015 / 136717 Summary of the invention

[0008] Problems to be solved by the invention

[0009] Organic materials are used in various environments, for example, they are exposed to combustion gases of fossil fuels such as automobile exhaust. In this case, the discoloration of organic materials is sometimes promoted by oxidizing gases such as nitrogen oxides contained in the combustion gases. So far, various stabilizers for organic materials are known, but stabilizers that fully prevent such discoloration are unknown. Therefore, there is still a need for stabilizers that effectively improve the stability of oxidizing substances represented by heat and / or oxygen and ozone when processing organic materials, and are not prone to discoloration caused by oxidizing gases such as NOx gas.

[0010] In Patent Document 1, although the phosphite compounds of Chemical Formulas 1 to 12 (Examples 1 to 10) corresponding to the specific formula (I) show less coloration caused by NOx gas than the phosphite compounds of P-1 and P-3 (Comparative Examples 1 and 2) which are not corresponding to the specific formula (I) show less coloration caused by NOx gas, the effect of reducing coloration caused by NOx gas is sometimes insufficient, and further improvement in coloration reduction is required.

[0011] Patent Document 2 describes a processing stabilizer comprising a compound represented by a specific formula (I) and a compound represented by a specific formula (II), but no attention is paid to coloration caused by NOx gas, and coloration caused by NOx gas may not be sufficiently reduced.

[0012] Therefore, an object of the present invention is to provide a stabilizer which is effective in improving the stability during processing of an organic material and is less likely to be discolored by an oxidizing gas, particularly by NOx gas.

[0013] Means for solving problems

[0014] The present inventors have repeatedly conducted detailed studies on various compounds in order to solve the above problems, and have found that stabilizers containing specific compounds are effective, thereby completing the present invention. That is, the present invention includes the following preferred embodiments.

[0015] [1] A stabilizer comprising a compound (A) and a compound (B), wherein the content of the compound (B) is 0.01 to 50 parts by mass relative to 100 parts by mass of the compound (A), the compound (A) is selected from the compound represented by formula (1) and the compound represented by formula (2), and the compound B is represented by formula (3), wherein:

[0016]

Chemical formula 1

[0017]

[0018] [In formula (1),

[0019] R 1 , R 2 , R 4 and R 5 each independently represents a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, a cycloalkyl group having 5 to 8 carbon atoms, an alkylcycloalkyl group having 6 to 12 carbon atoms, an aralkyl group having 7 to 12 carbon atoms, or a phenyl group,

[0020] R 3 each independently represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms,

[0021] X represents a single bond, a sulfur atom or -CH(-R 13 )-base (R 13 represents a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, or a cycloalkyl group having 5 to 8 carbon atoms),

[0022] A represents an alkylene group having 1 to 8 carbon atoms or *-C(=O)-R 14 -Base (R 14 represents a single bond or an alkylene group having 1 to 8 carbon atoms, and * represents the connecting position on the oxygen side).

[0023] One of Y and Z represents a hydroxyl group, an alkoxy group having 1 to 8 carbon atoms, or an aralkyloxy group having 7 to 12 carbon atoms, and the other represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms],

[0024]

Chemical formula 2

[0025]

[0026] [In formula (2),

[0027] R 6 and R 8 each independently represents a hydrogen atom, a methyl group, or an alkyl group having 5 to 8 carbon atoms,

[0028] R 7 each independently represents a hydrogen atom or a hydroxyl group,

[0029] R 9 Each independently represents a hydrogen atom or -C 15 H 25-31 base,

[0030] Among them, at least 1 R 6 , R 7 , R 8 or R 9 not a hydrogen atom],

[0031]

Chemical formula 3

[0032]

[0033] [In formula (3), R 10 , R 11 and R 12 Each independently represents a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, or an aralkyl group having 7 to 20 carbon atoms in total, wherein R 10 , R 11 and R 12 At least one of them is not a hydrogen atom].

[0034] [2] The stabilizer according to [1], wherein

[0035] In formula (2),

[0036] R 6 each independently represents a hydrogen atom or a methyl group,

[0037] R 7 each independently represents a hydrogen atom or a hydroxyl group,

[0038] R 8 represents a hydrogen atom,

[0039] R 9Each independently represents -C 15 H 25-31 base.

[0040] [3] The stabilizer according to [1], wherein

[0041] In formula (2), R 6 and R 8 Each independently represents a hydrogen atom or an alkyl group having 5 to 8 carbon atoms, wherein at least one R 6 or R 8 It is not a hydrogen atom, R 7 and R 9 Represents a hydrogen atom.

[0042] [4] The stabilizer according to any one of [1] to [3], wherein

[0043] In formula (3), R 11 Represents a hydrogen atom.

[0044] [5] An organic material composition comprising the above-mentioned compound (A) and compound (B), or the stabilizer described in [1], and at least one organic material, wherein the content of compound (B) is 0.01 to 50 parts by mass relative to 100 parts by mass of compound (A).

[0045] [6] The organic material composition according to [5], wherein the content of the compound (A) is 0.01 to 1 part by mass and the content of the compound (B) is 0.0001 to 0.5 part by mass, based on 100 parts by mass of the organic material.

[0046] [7] The organic material composition according to [5] or [6], wherein the organic material is a thermoplastic resin.

[0047] [8] The organic material composition according to [7], wherein the thermoplastic resin is a polyolefin or an engineering plastic.

[0048] [9] A method for stabilizing an organic material, comprising adding the above-mentioned compound (A) and compound (B), or adding the stabilizer described in [1] to the organic material, wherein the content of compound (B) is 0.01 to 50 parts by mass relative to 100 parts by mass of compound (A).

[0049]

[10] The stabilization method according to [9], wherein the organic material is a thermoplastic resin.

[0050]

[11] The stabilization method according to

[10] , wherein the thermoplastic resin is a polyolefin or an engineering plastic.

[0051] Effects of the Invention

[0052] According to the present invention, a stabilizer can be provided, which is effective in improving the stability when processing an organic material and is not easily discolored by oxidizing gases, especially by NOx gases. In addition, the organic material composition of the present invention has high stability and is not easily discolored by oxidizing gases, especially by NOx gases. DETAILED DESCRIPTION

[0053] Hereinafter, embodiments of the present invention will be described in detail. In addition, the scope of the present invention is not limited to the embodiments described herein, and various changes can be made within the scope of the gist of the present invention. In addition, when a plurality of upper and lower limits are recorded for a specific feature, any upper and lower limits in these upper and lower limits can be combined to form a suitable numerical range.

[0054] 〔Stabilizer〕

[0055] The stabilizer of the present invention comprises a compound (A) and a compound (B), wherein the content of the compound (B) is 0.01 to 50 parts by mass relative to 100 parts by mass of the compound (A), the compound (A) is selected from the compound represented by formula (1) and the compound represented by formula (2), and the compound (B) is represented by formula (3), wherein:

[0056]

Chemical formula 4

[0057]

[0058] [In formula (1),

[0059] R 1 , R 2 , R 4 and R 5 each independently represents a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, a cycloalkyl group having 5 to 8 carbon atoms, an alkylcycloalkyl group having 6 to 12 carbon atoms, an aralkyl group having 7 to 12 carbon atoms, or a phenyl group,

[0060] R 3 each independently represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms,

[0061] X represents a single bond, a sulfur atom or -CH(-R 13 )-base (R 13 represents a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, or a cycloalkyl group having 5 to 8 carbon atoms),

[0062] A represents an alkylene group having 1 to 8 carbon atoms or *-C(=O)-R 14 -Base (R 14 represents a single bond or an alkylene group having 1 to 8 carbon atoms, and * represents the connecting position on the oxygen side).

[0063] One of Y and Z represents a hydroxyl group, an alkoxy group having 1 to 8 carbon atoms, or an aralkyloxy group having 7 to 12 carbon atoms, and the other represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms],

[0064]

Chemical formula 5

[0065]

[0066] [In formula (2),

[0067] R 6 and R 8 each independently represents a hydrogen atom, a methyl group, or an alkyl group having 5 to 8 carbon atoms,

[0068] R 7 each independently represents a hydrogen atom or a hydroxyl group,

[0069] R 9 Each independently represents a hydrogen atom or -C 15 H 25-31 base,

[0070] Among them, at least 1 R 6 , R 7 , R 8 or R 9 not a hydrogen atom],

[0071]

Chemical formula 6

[0072]

[0073] [In formula (3), R 10 , R 11 and R 12 Each independently represents a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, or an aralkyl group having 7 to 20 carbon atoms in total, wherein R 10 , R 11 and R 12 At least one of them is not a hydrogen atom].

[0074] The stabilizer of the present invention, which comprises a compound (A) selected from the compound represented by formula (1) and the compound represented by formula (2), and a compound (B) represented by formula (3), and the content of the compound (B) is 0.01 to 50 parts by mass relative to 100 parts by mass of the compound (A), is effective for improving the stability during processing of organic materials, and is not prone to discoloration caused by oxidizing gases. The reason is not clear, but it is believed that the compound (A) is effective for improving stability, and the interaction between the compound (A) and the compound (B) brought about by the coexistence of the compound (B) suppresses the change of the compound (A) into a coloring substance. It should be noted that the present invention is not limited by the above mechanism.

[0075] [Compound (A)]

[0076] The compound (A) contained in the stabilizer of the present invention may be a compound represented by formula (1).

[0077]

Chemical formula 7

[0078]

[0079] R in formula (1) 1 , R 2 , R 4 and R 5 Each independently represents a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, a cycloalkyl group having 5 to 8 carbon atoms, an alkylcycloalkyl group having 6 to 12 carbon atoms, an aralkyl group having 7 to 12 carbon atoms, or a phenyl group. 1 They may be the same or different from each other. 2 and R 3 , the same is true.

[0080] Examples of the alkyl group having 1 to 8 carbon atoms include methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, n-pentyl, tert-pentyl, 2-methylbutyl, 3-methylbutyl, 2-ethylpropyl, n-hexyl, n-heptyl, isoheptyl, n-octyl, isooctyl, and 2-ethylhexyl.

[0081] Examples of the cycloalkyl group having 5 to 8 carbon atoms include cyclopentyl, cyclohexyl, cycloheptyl, and cyclooctyl.

[0082] Examples of the alkylcycloalkyl group having 6 to 12 carbon atoms include 1-methylcyclopentyl, 1-methylcyclohexyl, and 1-methyl-4-isopropylcyclohexyl.

[0083] Examples of the aralkyl group having 7 to 12 carbon atoms include a benzyl group, an α-methylbenzyl group, and an α,α-dimethylbenzyl group.

[0084] R 1 , R 2 and R 4 It is preferably an alkyl group having 1 to 8 carbon atoms, a cycloalkyl group having 5 to 8 carbon atoms, or an alkylcycloalkyl group having 6 to 12 carbon atoms.

[0085] R 1 and R 4 More preferred is a tertiary alkyl group such as a tert-butyl group, a tert-pentyl group, and a tert-octyl group, a cyclohexyl group, or a 1-methylcyclohexyl group.

[0086] R 2 More preferred are alkyl groups having 1 to 5 carbon atoms, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, and tert-pentyl. Still more preferred are methyl, tert-butyl, and tert-pentyl.

[0087] R 5 Preferred are hydrogen atoms, alkyl groups having 1 to 8 carbon atoms, or cycloalkyl groups having 5 to 8 carbon atoms, and more preferred are hydrogen atoms, alkyl groups having 1 to 5 carbon atoms such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, and tert-amyl.

[0088] R in formula (1) 3 Each independently represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms. Examples of the alkyl group having 1 to 8 carbon atoms include the same groups as those mentioned above. 3 It is preferably a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and more preferably a hydrogen atom or a methyl group.

[0089] In formula (1), X represents a single bond, a sulfur atom or -CH(-R 13 )-base (R 13 represents a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, or a cycloalkyl group having 5 to 8 carbon atoms). 13 The alkyl group having 1 to 8 carbon atoms and the cycloalkyl group having 5 to 8 carbon atoms shown in the above-mentioned group may be the same as those mentioned above. X is preferably a methylene group substituted with an alkyl group having 1 to 4 carbon atoms such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, and tert-butyl, or a single bond, and more preferably a single bond.

[0090] A in formula (1) represents an alkylene group having 1 to 8 carbon atoms or *-C(=O)-R 14 -Base (R 14 represents a single bond or an alkylene group having 1 to 8 carbon atoms, and * represents a connecting position on the oxygen side). Examples of the alkylene group having 1 to 8 carbon atoms include methylene, ethylene, propylene, butylene, pentamethylene, hexamethylene, octamethylene, and 2,2-dimethyl-1,3-propylene. A is preferably propylene. *-C(=O)-R 14 The * in the - group indicates that the carbonyl group is bonded to the oxygen atom of the phosphite group. 14 Preferred is a single bond or an ethylene group.

[0091] In formula (1), one of Y and Z represents a hydroxyl group, an alkoxy group having 1 to 8 carbon atoms, or an aralkyloxy group having 7 to 12 carbon atoms, and the other represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms. Here, examples of the alkyl group having 1 to 8 carbon atoms include the same alkyl groups as those mentioned above. Examples of the aralkyloxy group having 7 to 12 carbon atoms include a benzyloxy group, an α-methylbenzyloxy group, and an α,α-dimethylbenzyloxy group. It is preferred that one of Y and Z is a hydroxyl group and the other is a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, and it is more preferred that Y is a hydroxyl group and Z is a hydrogen atom or an alkyl group having 1 to 8 carbon atoms.

[0092] Specific examples of the compound represented by formula (1) include 2,4,8,10-tetra-tert-butyl-6-[3-(3-methyl-4-hydroxy-5-tert-butylphenyl)propoxy]dibenzo[d,f][1,3,2]dioxaphosphopene, 6-[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propoxy]-2,4,8,10-tetra-tert-butyldibenzo[d,f][1,3,2]dioxaphosphopene, 2,4,8,10-tetra-tert-butyl-6-〔3-(3-methyl-4-hydroxy-5-tert-butylphenyl)propoxy〕dibenzo〔d,f〕〔1,3,2〕dioxaphosphocine, etc. The compound represented by formula (1) is preferably 2,4,8,10-tetra-tert-butyl-6-〔3-(3-methyl-4-hydroxy-5-tert-butylphenyl)propoxy〕dibenzo〔d,f〕〔1,3,2〕dioxaphosphocine.

[0093] As the compound represented by formula (1), a commercially available product may be used. Examples of the commercially available product include Sumilizer (registered trademark) GP (manufactured by Sumitomo Chemical Co., Ltd.).

[0094] The stabilizer of the present invention may contain at least one compound selected from the compound represented by the above-mentioned formula (1) and the compound represented by the formula (2) described later as compound (A). It may contain one compound represented by formula (1), or two or more compounds represented by formula (1), or one compound represented by formula (2), or two or more compounds represented by formula (2), or both the compound represented by formula (1) and the compound represented by formula (2).

[0095] The compound (A) contained in the stabilizer of the present invention may be a compound represented by formula (2).

[0096]

Chemical formula 8

[0097]

[0098] R in formula (2) 6 and R 8 Each independently represents a hydrogen atom, a methyl group, or an alkyl group having 5 to 8 carbon atoms. Examples of the alkyl group having 5 to 8 carbon atoms include n-pentyl, tert-pentyl, 2-methylbutyl, 3-methylbutyl, 2-ethylpropyl, n-hexyl, n-heptyl, isoheptyl, n-octyl, isooctyl, and 2-ethylhexyl. 6 They may be the same or different from each other. 8, the same is true.

[0099] R in formula (2) 7 Each independently represents a hydrogen atom or a hydroxyl group. 7 They can be the same or different from each other.

[0100] R in formula (2) 9 Each independently represents a hydrogen atom or -C 15 H 25-31 Base. R 9 Can be the same or different. -C 15 H 25-31 The group is a straight-chain hydrocarbon group having 0 to 3 double bonds, and examples thereof include groups represented by the following formulae (R1-1) to (R1-4).

[0101]

Chemical formula 9

[0102]

[0103] R in formula (2) 6 ~R 9 Each independently represents a hydrogen atom or the above groups, at least one R 6 , R 7 , R 8 or R 9 It is not a hydrogen atom. It should be noted that at least one R 6 , R 7 , R 8 or R 9 Not a hydrogen atom means that there are three R 6 ~R 9 At least one of the total 12 groups is not a hydrogen atom.

[0104] In a preferred embodiment of the present invention, the compound represented by formula (2) is 6 Each independently represents a hydrogen atom or a methyl group, R 7 Each independently represents a hydrogen atom or a hydroxyl group, R 8 represents a hydrogen atom, R 9 Each independently represents -C 15 H 25-31 The compound is a compound represented by formula (2-1),

[0105]

Chemical formula 10

[0106]

[0107] [In formula (2-1),

[0108] R 6’ each independently represents a hydrogen atom or a methyl group,

[0109] R 7’ each independently represents a hydrogen atom or a hydroxyl group,

[0110] R 9’ Each independently represents -C 15 H 25-31 base].

[0111] In one embodiment of the present invention, from the viewpoint of easily improving the effect as a stabilizer and the viewpoint of effectively utilizing resources for non-edible parts, the compound represented by formula (2-1) is preferably derived from a cashew nut shell oil extract. As cashew nut shell oil extract, cardanol, cardanol and methyl cardanol contained in cashew nut shell oil can be cited. The compound represented by formula (2-1) is derived from a cashew nut shell oil extract, which means that the compound represented by formula (2-1) is prepared using cardanol, cardanol and / or methyl cardanol as a cashew nut shell oil extract as a raw material.

[0112] In another preferred embodiment of the present invention, the compound represented by formula (2) is 6 and R 8 Each independently represents a hydrogen atom or an alkyl group having 5 to 8 carbon atoms, wherein at least one R 6 or R 8 Not a hydrogen atom, R 7 and R 9 The compound is a compound represented by formula (2-2),

[0113]

Chemical formula 11

[0114]

[0115] [In formula (2-2),

[0116] R 6’’ and R 8’’ Each independently represents a hydrogen atom or an alkyl group having 5 to 8 carbon atoms, wherein at least one R 6’’ or R 8’’ Not a hydrogen atom].

[0117] Examples of the alkyl group having 5 to 8 carbon atoms include: 6 and R 8 In the above-mentioned groups. 6’’ and R 8’’ Preferred are n-pentyl, tert-pentyl and 2-methylbutyl, and more preferred are tert-pentyl.

[0118] Specific examples of the compound represented by formula (2-2) include Weston (registered trademark) 705 (manufactured by SI GROUP).

[0119] [Compound (B)]

[0120] The compound (B) contained in the stabilizer of the present invention is a compound represented by formula (3),

[0121]

Chemical formula 12

[0122]

[0123] [In formula (3), R 10 , R 11 and R 12 Each independently represents a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, or an aralkyl group having 7 to 20 carbon atoms in total, wherein R 10 , R 11 and R 12 At least one of them is not a hydrogen atom].

[0124] It is known that by making the compound (B) exist together with the above-mentioned compound (A), it is surprisingly found that the discoloration caused by oxidizing gas, especially the discoloration caused by NOx gas, can be effectively prevented. The reason is not clear, but it is believed that the interaction between the compound (A) and the compound (B) brought about by the coexistence of the compound (B) inhibits the compound (A) from changing into a colored substance.

[0125] Regarding R in formula (3) 10 , R 11 and R 12 As the alkyl group having 1 to 12 carbon atoms, for example, there can be mentioned methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, n-pentyl, tert-pentyl, 2-methylbutyl, 3-methylbutyl, 2-ethylpropyl, n-hexyl, n-heptyl, isoheptyl, n-octyl, isooctyl, 2-ethyl-hexyl, n-nonyl, decyl, undecyl, dodecyl, etc. The alkyl group having 1 to 12 carbon atoms is preferably methyl, isopropyl, tert-butyl, tert-pentyl, or n-nonyl, and more preferably tert-butyl, tert-pentyl, or n-nonyl.

[0126] The aralkyl group having a total carbon number of 7 to 20 is an alkyl group having a total carbon number of 7 to 20 in which at least one hydrogen atom is substituted by an aryl group (preferably a phenyl group). Examples of such a group include -R 15 -Ar(R 15 is an alkylene group, Ar is an aryl group, preferably a phenyl group). 15, for example, alkylene groups having 1 to 14 carbon atoms can be cited, specifically, methylene, ethylene, propylene (n-propylene, methylethylene, dimethylmethylene), butylene, pentamethylene, hexamethylene, octamethylene, and 2,2-dimethyl-1,3-propylene, etc. As Ar, phenyl or naphthyl groups whose hydrogen atoms may be substituted by alkyl groups can be cited, preferably phenyl groups. As aralkyl groups having a total carbon number of 7 to 20, benzyl, cumyl, 2-phenylethyl, 3-phenylpropyl, 4-phenylbutyl, 5-phenylpentyl, 6-phenylhexyl, 7-phenylheptyl, 8-phenyloctyl, 10-phenyldecyl, 12-phenyldodecyl, naphthylmethyl and naphthylethyl groups can be cited, preferably benzyl, cumyl, 2-phenylethyl, and more preferably cumyl.

[0127] In a preferred embodiment of the present invention, from the viewpoint of more easily preventing discoloration caused by oxidizing gas, R in formula (3) 11 represents a hydrogen atom. It is considered that R in formula (3) 11 When R represents a hydrogen atom, the compound (B) and the compound (A) are likely to interact with each other, and the compound (A) is likely to be suppressed from changing into a colored substance. 10 and R 12 Each independently represents a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, or an aralkyl group having 7 to 20 carbon atoms in total, wherein R 10 and R 12 In this embodiment, R in formula (3) 10 and R 12 Preferably, it is a hydrogen atom, a methyl group, an isopropyl group, a tert-butyl group, a tert-amyl group, a n-nonyl group, a benzyl group, a cumyl group, or a 2-phenylethyl group, wherein R 10 and R 12 At least one of the groups is not a hydrogen atom, and more preferably is a tert-butyl group, a tert-amyl group, an n-nonyl group or a cumyl group.

[0128] Specific examples of the compound represented by formula (3) include 2-methylphenol, 4-methylphenol, 2,4-dimethylphenol, 2,6-dimethylphenol, 2,4,6-trimethylphenol, 2-ethylphenol, 4-ethylphenol, 2,4-diethylphenol, 2,6-diethylphenol, 2,4,6-triethylphenol, 2-phenylphenol, 4-phenylphenol, 2,4-diphenylphenol, 2,6-diphenylphenol, 2,4,6-triphenylphenol, 2,6-di-tert-butyl-4-methylphenol, 2-tert-butyl-4,6-dimethylphenol, 2,6-di ... Butyl-4-ethylphenol, 2,6-di-tert-butyl-4-n-butylphenol, 2,6-di-tert-butyl-4-isobutylphenol, 2,4,6-tri-tert-butylphenol, 2,4-di-tert-butylphenol, 2-tert-butylphenol, 4-tert-butylphenol, 2,4,6-tri-tert-amylphenol, 2,4-di-tert-amylphenol, 2-tert-amylphenol, 4-tert-amylphenol, 2,4,6-tricumylphenol, 2,4-dicumylphenol, 2-cumylphenol, 4-cumylphenol, 2,4,6-trinonylphenol, 2,4-dinonylphenol, 2-nonylphenol, 4-nonylphenol, etc. Preferably, the compound is selected from 2,4-di-tert-butylphenol, 2-tert-butylphenol, 4-tert-butylphenol, 2,4,6-tri-tert-amylphenol, 2,4-di-tert-amylphenol, 2-tert-amylphenol, 4-tert-amylphenol, 2,4,6-tricumylphenol, 2,4-dicumylphenol, 2-cumylphenol, 4-cumylphenol, 2,4,6-trinonylphenol, 2,4-dinonylphenol, 2-nonylphenol and 4-nonylphenol, and more preferably, the compound is selected from 2,4-di-tert-butylphenol, 2,4-di-tert-amylphenol, 2-tert-amylphenol, 4-tert-amylphenol and 2,4-dicumylphenol. The stabilizer of the present invention may contain at least one compound represented by the above formula (3) as compound (B), and may contain one compound represented by the formula (3) or two or more compounds represented by the formula (3).

[0129] The stabilizer of the present invention comprises the above-mentioned compound (A) and compound (B), and the content of compound (B) is 0.01 to 50 parts by mass relative to 100 parts by mass of compound (A). When the content of compound (B) is less than 0.01 parts by mass relative to 100 parts by mass of compound (A), and when the content exceeds 50 parts by mass, discoloration caused by oxidizing gases cannot be fully prevented. From the viewpoint of more easily improving the effect of preventing discoloration caused by oxidizing gases, the content of compound (B) in the stabilizer of the present invention is preferably 0.1 to 50 parts by mass relative to 100 parts by mass of compound (A), more preferably 0.1 to 20 parts by mass, and further preferably 1 to 20 parts by mass.

[0130] The content of the compound (B) in the stabilizer of the present invention relative to 100 parts by mass of the compound (A) can be calculated using an analytical device such as a liquid chromatograph, or can be calculated from the feed ratio when preparing the stabilizer. When the content of the compound (B) is measured using a liquid chromatograph, it is preferably measured under the following measurement conditions.

[0131] <Measurement conditions>

[0132] Column: Sumipax ODS A-212 (6 mm φ × 150 mm, filler diameter: 5 μm)

[0133] Column temperature: 40°C

[0134] Mobile phase: (Solution A) 0.1 mass% ammonium acetate / water

[0135] (Liquid B) 0.1 mass% ammonium acetate / methanol

[0136] Mobile phase gradient: 0→25 min (solvent A: 20→0 mass % (1 mass % / min), solution B: 80→100 mass % (1 mass % / min)), 25→45 min (solvent A: 0 mass %, solution B: 100 mass %)

[0137] Flow rate: 1.0mL / min

[0138] Detection method: UV (280nm)

[0139] Sample concentration: 5mg / mL

[0140] Injection volume: 5μL

[0141] By adding the stabilizer of the present invention comprising compound (A) and a specific amount of compound (B) to an organic material such as a thermoplastic resin, the processing stability of the organic material can be improved. In addition, according to the stabilizer of the present invention, discoloration caused by oxidizing gases can be prevented. The stabilizer can be a material containing a compound (A) selected from the compound represented by the above formula (1) and the compound represented by the formula (2), and a compound (B) represented by the formula (3) in the above ratio, or a material containing at least one of the other additives that can be included in the organic material composition described later in addition to the compound (A) and the compound (B). In addition, the stabilizer of the present invention can be a material containing at least one organic material in addition to the compound (A) and the compound (B). Such a material is also called a masterbatch, for example.

[0142] [Organic material composition and method for stabilizing organic material]

[0143] By adding the stabilizer of the present invention to an organic material, or by adding a compound (A) selected from the compound represented by formula (1) and the compound represented by formula (2) and a compound (B) represented by formula (3) in a specific ratio, it is possible to suppress the degradation of the organic material during processing, improve processing stability, and prevent discoloration caused by oxidizing gases such as NOx gas. Therefore, the stabilizer of the present invention is suitable as a stabilizer for organic materials.

[0144] The present invention also provides a method for stabilizing an organic material by adding the above-mentioned stabilizer, and a method for stabilizing an organic material by adding compound (A) and compound (B) in a specific ratio. In addition, a stabilized organic material composition is provided, which has an organic material and the stabilizer of the present invention, or compound (A) and compound (B) in a specific ratio.

[0145] Examples of organic materials that can be stabilized by the stabilizer of the present invention or the compounds (A) and (B) in a specific ratio include, but are not limited to, the following organic materials. The organic material may be one organic material or a mixture of two or more organic materials.

[0146] (1) Polyethylene, such as high-density polyethylene (HD-PE), low-density polyethylene (LD-PE), linear low-density polyethylene (LLDPE),

[0147] (2) Polypropylene,

[0148] (3) Methylpentene polymer,

[0149] (4) EEA (ethylene / ethyl acrylate copolymer) resin,

[0150] (5) Ethylene / vinyl acetate copolymer resin,

[0151] (6) Polystyrenes, such as polystyrene, poly(p-methylstyrene), poly(α-methylstyrene),

[0152] (7) AS (acrylonitrile / styrene copolymer) resin,

[0153] (8) ABS (acrylonitrile / butadiene / styrene copolymer) resin,

[0154] (9) AAS (special acrylic rubber / acrylonitrile / styrene copolymer) resin,

[0155] (10) ACS (acrylonitrile / chlorinated polyethylene / styrene copolymer) resin,

[0156] (11) Chlorinated polyethylene, polychloroprene, chlorinated rubber,

[0157] (12) Polyvinyl chloride, polyvinylidene chloride,

[0158] (13) Methacrylic resin,

[0159] (14) Ethylene / vinyl alcohol copolymer resin,

[0160] (15) Fluororesin,

[0161] (16) Polyacetal,

[0162] (17) Grafted polyphenylene ether resin and polyphenylene sulfide resin,

[0163] (18) Polyurethane,

[0164] (19) Polyamide,

[0165] (20) Polyester resins, such as polyethylene terephthalate, polybutylene terephthalate,

[0166] (21) Polycarbonate,

[0167] (22) Polyacrylate,

[0168] (23) Polysulfone, polyetheretherketone, polyethersulfone,

[0169] (24) Thermoplastic resins such as aromatic polyester resins,

[0170] (25) Epoxy resin,

[0171] (26) Diallyl phthalate prepolymer,

[0172] (27) Silicone resin,

[0173] (28) Unsaturated polyester resin,

[0174] (29) Acrylic modified benzoguanamine resin,

[0175] (30) Benzoguanamine / melamine resin,

[0176] (31) Urea-formaldehyde resin and other thermosetting resins,

[0177] (32) Polybutadiene,

[0178] (33) 1,2-polybutadiene,

[0179] (34) Polyisoprene,

[0180] (35) Styrene / butadiene copolymer,

[0181] (36) Butadiene / acrylonitrile copolymer,

[0182] (37) Ethylene / propylene copolymers,

[0183] (38) Silicone rubber,

[0184] (39) Epichlorohydrin rubber,

[0185] (40) Acrylic rubber,

[0186] (41) Natural rubber,

[0187] (42) Chloro-rubber coatings,

[0188] (43) Polyester resin coating,

[0189] (44) Urethane resin coating,

[0190] (45) Epoxy resin coating,

[0191] (46) Acrylic resin coating,

[0192] (47) Vinyl resin coating,

[0193] (48) Amino alkyd resin coatings,

[0194] (49) Alkyd resin coatings,

[0195] (50) Nitrocellulose resin coating,

[0196] (51) Oil-based paint,

[0197] (52) Wax,

[0198] (53) Lubricating oil, etc.

[0199] Among them, it is preferably used for thermoplastic resins, especially polyethylene, polyolefins such as HD-PE, LD-PE, LLDPE and polypropylene, polyamide, polyethylene terephthalate, polybutylene terephthalate and engineering plastics such as polycarbonate.

[0200] As polyolefin, there is no particular limitation, for example, it can be a polyolefin obtained by free radical polymerization, or it can be a polyolefin manufactured by polymerization using a catalyst containing a metal of Group IVb, Vb, VIb or VIII of the Periodic Table. As such a catalyst containing a metal, there can be cited a metal complex having more than one ligand, for example, an oxide, a halogen compound, an alkoxide, an ester, an aryl, etc. coordinated by a π or σ bond. These complexes can be directly metal complexes, or they can be supported on substrates such as magnesium chloride, titanium chloride, aluminum oxide, silicon oxide, etc. As polyolefin, it is preferred to use a polyolefin manufactured, for example, using a Ziegler-Natta catalyst, a TNZ catalyst, a metallocene catalyst, a Phillips catalyst, etc.

[0201] Engineering plastics are not particularly limited. Polyamide resin is a polyamide resin having an amide bond in a polymer chain and capable of being heated and melted. Polyamide resin can be manufactured by any method, for example, polyamide resins manufactured by methods such as condensation reaction of diamines and dicarboxylic acids, condensation reaction of aminocarboxylic acids, and ring-opening polymerization of lactams can be cited. As examples of polyamide resins, nylon 66, nylon 69, nylon 610, nylon 612, poly-bis-(p-aminocyclohexyl) methane lauramide, nylon 46, nylon 6, nylon 12, copolymers such as nylon 66 / 6 and nylon 6 / 12 as copolymers of nylon 66 and nylon 6, etc. can be cited. As long as the polyester resin has an ester bond in the polymer chain and can be heated and melted, for example, polyesters obtained by polycondensation of dicarboxylic acids and dihydroxy compounds can be cited. The polyester resin can be any one of homopolyesters and copolyesters. As long as the polycarbonate resin has a carbonate bond in the polymer chain and can be heated and melted, for example, polycarbonates obtained by reacting carbonate precursors such as phosgene and diphenyl carbonate with aromatic hydroxy compounds or aromatic hydroxy compounds and a small amount of polyhydroxy compounds in the presence of a solvent, an acid acceptor, or a molecular weight regulator can be enumerated. The polycarbonate resin can be linear or branched, or a copolymer.

[0202] As an organic material that can be stabilized by the stabilizer of the present invention or the compounds (A) and (B) in a specific ratio, a recycled resin of the above-mentioned organic material is also suitable. As such a recycled resin, for example, recycled polyethylene resin, recycled polypropylene resin, recycled styrene-butadiene block copolymer, recycled propylene-ethylene block copolymer, etc. can be cited. It should be noted that the recycled resin refers to a resin that is, for example, a resin that is once formed into a shape such as a film and then recycled. For example, in many cases, a formed product such as a film is processed into a pellet or powder and used.

[0203] By adding a conventionally known stabilizer to the recycled resin as appropriate, and adding the stabilizer of the present invention to the resin, or adjusting the ratio of the compounds (A) and (B) in the resin to be within a specific range, the recycled resin can be stabilized and the discoloration of the resin caused by oxidizing gas can be prevented. As an example of a composition containing a recycled resin that can be stabilized and prevented from discoloration by oxidizing gas by such a method, the following compositions 1 to 24 containing recycled resins can be cited. It should be noted that the compounds used in the preparation of the composition are as follows.

[0204] Compound (A-1): 2,4,8,10-tetra-tert-butyl-6-[3-(3-methyl-4-hydroxy-5-tert-butylphenyl)propoxy]dibenzo[d,f][1,3,2]dioxaphosphine (Sumilizer (registered trademark) GP, manufactured by Sumitomo Chemical Co., Ltd.)

[0205] Compound (A-2): Phosphite compound obtained in Preparation Example 1 of Examples of this specification

[0206] Compound (D): 2,2'-dimethyl-2,2'-(2,4,8,10-tetraoxaspiro[5.5]undecane-3,9-diyl)dipropane-1,1'-diyl=bis[3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propionate] (Sumilizer (registered trademark) GA-80, manufactured by Sumitomo Chemical Co., Ltd.)

[0207] Compound (E): 2-tert-butyl-6-(3-tert-butyl-2-hydroxy-5-methylbenzyl)-4-methylphenyl acrylate (Sumilizer (registered trademark) GM, manufactured by Sumitomo Chemical Co., Ltd.)

[0208] Compound (F): 2-[1-(2-hydroxy-3,5-di-tert-pentylphenyl)ethyl]-4,6-di-tert-pentylphenyl acrylate (Sumilizer (registered trademark) GS, manufactured by Sumitomo Chemical Co., Ltd.)

[0209] Compound (G): 4,4'-thiobis(2-tert-butyl-5-methylphenol) (Sumilizer (registered trademark) WX-R, manufactured by Sumitomo Chemical Co., Ltd.)

[0210] (Preparation of Composition 1)

[0211] 100 parts by mass of a recycled polyethylene resin (MI value: 2 g / 10 minutes, manufactured by NISSEN POLYTEC), 0.05 parts by mass of calcium stearate (manufactured by Nitto Kasei Kogyo Co., Ltd.), and 0.1 parts by mass of compound (A-1) were dry-blended, and the resulting mixture was kneaded using a twin-screw extruder (BTN-32, PLABOR) with a barrel diameter of 32 mm under a nitrogen atmosphere at a temperature of 190° C. and a screw speed of 80 rpm to obtain pellets of composition 1.

[0212] (Preparation of Compositions 2 to 6)

[0213] Instead of using compound (A-1) in the preparation of composition 1, composition 2: compound (A-2), composition 3: compound (D), composition 4: compound (E), composition 5: compound (F), or composition 6: compound (G) were used in each composition. The same preparation method as composition 1 was followed to obtain pellets of compositions 2 to 6.

[0214] It should be noted that the melt flow rates (MFR) of the pellets of the above compositions 1 to 6 were measured using a melt indexer (model L246-3537, manufactured by Technol Seven Co., Ltd.) at a temperature of 190°C and a load of 21.18 N. The results were 2.10 g / 10 min (composition 1), 2.11 g / 10 min (composition 2), 2.08 g / 10 min (composition 3), 2.12 g / 10 min (composition 4), 2.14 g / 10 min (composition 5), and 2.11 g / 10 min (composition 6). In addition, the MFR of compositions 7 to 24 described below can also be measured in the same manner.

[0215] (Preparation of Composition 7)

[0216] 100 parts by mass of recycled polypropylene resin, 0.05 parts by mass of calcium stearate (manufactured by Nitto Kasei Kogyo Co., Ltd.), and 0.0500 parts by mass of compound (A-1) were dry-blended, and the resulting mixture was kneaded using a twin-screw extruder (BTN-32, PLABOR) with a barrel diameter of 32 mm under a nitrogen atmosphere at a temperature of 220° C. and a screw speed of 80 rpm to obtain pellets of composition 7.

[0217] (Preparation of Compositions 8 to 12)

[0218] Instead of using compound (A-1) in the preparation of composition 7, composition 8: compound (A-2), composition 9: compound (D), composition 10: compound (E), composition 11: compound (F), or composition 12: compound (G) are used in each composition. Except for this, the same operation as the preparation method of composition 7 is carried out to obtain pellets of compositions 8 to 12.

[0219] (Preparation of Compositions 13 to 18)

[0220] Pellets of compositions 13 to 18 were obtained in the same manner as the preparation methods of compositions 7 to 12, except that a recycled styrene-butadiene block copolymer was used instead of the recycled polypropylene resin used in the preparation of composition 7. Here, composition 13 contained compound (A-1), composition 14 contained compound (A-2), composition 15 contained compound (D), composition 4 contained compound (E), composition 5 contained compound (F), and composition 6 contained compound (G).

[0221] (Preparation of Compositions 19 to 24)

[0222] Pellets of compositions 19 to 24 were obtained in the same manner as in the preparation methods of compositions 7 to 12, except that a recycled propylene-ethylene block copolymer was used instead of the recycled polypropylene resin used in the preparation of composition 7. Here, composition 19 contains compound (A-1), composition 20 contains compound (A-2), composition 21 contains compound (D), composition 22 contains compound (E), composition 23 contains compound (F), and composition 24 contains compound (G).

[0223] By adding a compound (A) selected from the compound represented by formula (1) and the compound represented by formula (2), and a compound (B) represented by formula (3) to an organic material, the processing stability of the organic material can be improved, and discoloration of the organic material caused by oxidizing gas can be prevented. In this case, the compound (A) and the compound (B) are added to the organic material in an amount of 0.01 to 50 parts by mass relative to 100 parts by mass of the compound (A). The content of the compound (B) relative to 100 parts by mass of the compound (A) is preferably 0.1 to 50 parts by mass, more preferably 0.1 to 20 parts by mass, and further preferably 1 to 20 parts by mass, from the viewpoint of easily improving the effect of preventing discoloration caused by oxidizing gas obtained by using the compound (A) and the compound (B) in combination.

[0224] The addition of the compound (A) selected from the compound represented by formula (1) and the compound represented by formula (2) and the compound (B) represented by formula (3) to the organic material can be carried out by adding the stabilizer of the present invention. In either case, the compound (A) and the compound (B) are contained in a specific amount ratio in the organic material.

[0225] When the stabilizer of the present invention or a compound (A) selected from the compound represented by formula (1) and the compound represented by formula (2) and a compound (B) represented by formula (3) are added to an organic material to stabilize the organic material, from the viewpoint of stabilizing the organic material and preventing discoloration caused by oxidizing gas, the content of the compound (A) is preferably 0.01 to 1 part by mass, more preferably 0.02 to 0.3 parts by mass, and further preferably 0.03 to 0.1 parts by mass relative to 100 parts by mass of the organic material. In addition, from the same viewpoint, the content of the compound (B) is preferably 0.0001 to 0.5 parts by mass, more preferably 0.0002 to 0.15 parts by mass, further preferably 0.0003 to 0.05 parts by mass, and further preferably 0.0005 to 0.01 parts by mass relative to 100 parts by mass of the organic material.

[0226] In addition, from the viewpoint of stabilizing the organic material and preventing discoloration caused by the oxidizing gas, the total weight of the compound (A) and the compound (B) is preferably 0.005 parts by mass or more, more preferably 0.01 parts by mass or more, and further preferably 0.05 parts by mass or more, relative to 100 parts by mass of the organic material. In addition, from the viewpoint of efficiently stabilizing the organic material and economical efficiency, the total weight of the compound (A) and the compound (B) is usually 5 parts by mass or less, preferably 3 parts by mass or less, and more preferably 1 part by mass or less, relative to 100 parts by mass of the organic material.

[0227] When a compound (A) selected from the compound represented by formula (1) and the compound represented by formula (2) and a compound (B) represented by formula (3) are added to an organic material, other additives such as a sulfur-based antioxidant, a phosphorus-based antioxidant, an anti-aging agent, an ultraviolet absorber, a light stabilizer, a peroxide scavenger, a polyamide stabilizer, a hydroxylamine, a lubricant, a plasticizer, a flame retardant, a nucleating agent, a metal deactivator, an antistatic agent, a pigment, a filler, a pigment, an anti-blocking agent, a surfactant, a processing aid, a foaming agent, an emulsifier, a glossing agent, a stearic acid, etc. may be further added to the organic material as needed. Neutralizing agents such as calcium sulfate and hydrotalcite, coloring improvers such as 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, auxiliary stabilizers such as benzofurans and indolines described in U.S. Patents 4,325,853, 4,338,244, 5,175,312, 5,216,053, 5,252,643, 4,316,611, DE-A-4,316,622, 4,316,876, EP-A-589,839, EP-A-591,102, etc. These additives may be added to the organic material simultaneously with the compounds (A) and (B) contained in the stabilizer of the present invention, or may be added to the organic material at a stage different from the addition of the compounds (A) and (B) contained in the stabilizer of the present invention. As the additive, one kind of additive may be used, or two or more kinds of additives may be used in combination.

[0228] Examples of phenolic antioxidants include the following. As phenolic antioxidants, the following compounds may be used alone or in combination of two or more. It should be noted that compounds corresponding to formula (3) are excluded.

[0229] (1) Examples of alkylated monophenols

[0230] 2,6-dicyclopentyl-4-methylphenol, 2-(α-methylcyclohexyl)-4,6-dimethylphenol, 2,6-dioctadecyl-4-methylphenol, 2,4,6-tricyclohexylphenol, 2,6-di-tert-butyl-4-methoxymethylphenol, 2,4-dimethyl-6-(1'-methylundecyl-1'-yl)phenol, 2,4-dimethyl-6-(1'-methylheptadecyl-1'-yl)phenol, 2,4-dimethyl-6-(1'-methyltridecyl-1'-yl)phenol and mixtures thereof, etc.

[0231] (2) Examples of alkylthiomethylphenols

[0232] 2,4-Dioctylthiomethyl-6-tert-butylphenol, 2,4-dioctylthiomethyl-6-methylphenol, 2,4-dioctylthiomethyl-6-ethylphenol, 2,6-didodecylthiomethyl-4-nonylphenol and mixtures thereof, etc.

[0233] (3) Examples of hydroquinone and alkylated hydroquinone

[0234] 2,6-di-tert-butyl-4-methoxyphenol, 2,5-di-tert-butylhydroquinone, 2,5-di-tert-amylhydroquinone, 2,6-diphenyl-4-octadecyloxyphenol, 2,6-di-tert-butylhydroquinone, 2,5-di-tert-butyl-4-hydroxyanisole, 3,5-di-tert-butyl-4-hydroxyphenyl stearate, bis(3,5-di-tert-butyl-4-hydroxyphenyl) adipate and mixtures thereof, etc.

[0235] (4) Example of tocopherol

[0236] α-tocopherol, β-tocopherol, γ-tocopherol, δ-tocopherol and mixtures thereof, etc.

[0237] (5) Example of hydroxylated thiodiphenyl ether

[0238] 2,2'-Thiobis(6-tert-butylphenol), 2,2'-thiobis(4-methyl-6-tert-butylphenol), 2,2'-thiobis(4-octylphenol), 4,4'-thiobis(3-methyl-6-tert-butylphenol), 4,4'-thiobis(2-methyl-6-tert-butylphenol), 4,4'-thiobis(3,6-di-tert-amylphenol), 4,4'-(2,6-dimethyl-4-hydroxyphenyl) disulfide, etc.

[0239] (6) Examples of alkylidene bisphenols and their derivatives

[0240] 2,2'-methylenebis(4-methyl-6-tert-butylphenol), 2,2'-methylenebis(4-ethyl-6-tert-butylphenol), 2,2'-methylenebis[4-methyl-6-(α-methylcyclohexyl)phenol)], 2,2'-methylenebis(4-methyl-6-cyclohexylphenol), 2,2'-methylenebis(4-methyl-6-nonylphenol), 2,2'-methylenebis(4,6-di-tert-butylphenol), 2,2'-ethylidenebis(4,6-di-tert-butylphenol), 2,2'-ethylidenebis(4-isobutyl-6-tert-butylphenol), 2,2'-methylenebis[6-(α-methylbenzyl)-4-nonylphenol], 2,2'-methylenebis[4,6-(α,α-dimethylbenzyl)-4-nonylphenol], 4,4'-methylenebis(6-tert-butyl-2-methylphenol), 4,4'-methylenebis(2,6-di-tert-butylphenol), 4,4'-butylidenebis(3-methyl-6-tert-butylphenol), 1,1-bis(4-hydroxyphenyl)cyclohexane, 1,1-bis(5-tert-butyl-4-hydroxy-2-methylphenyl)butane, 2,6-bis(3-tert-butyl-5-methyl-2- 1,1,3-Tris(5-tert-butyl-4-hydroxy-2-methylphenyl)butane, 1,1-bis(5-tert-butyl-4-hydroxy-2-methylphenyl)-3-n-dodecylmercaptobutane, ethylene glycol bis[3,3-bis-3'-tert-butyl-4'-hydroxyphenyl)butyrate], bis(3-tert-butyl-4-hydroxy-5-methylphenyl)dicyclopentadiene, bis[2-(3'-tert-butyl-2'-hydroxy-5'-methylbenzyl)-6-tert-butyl-4-methylphenyl]terephthalate, 1,1-bis(3,5-dimethyl 1-(2-hydroxy-3,5-di-tert-butyl-4-hydroxyphenyl)-4-n-dodecylmercaptobutane, 1,1,5,5-tetrakis(5-tert-butyl-4-hydroxy-2-methylphenyl)pentane, 2-tert-butyl-6-(3'-tert-butyl-5'-methyl-2'-hydroxybenzyl)-4-methylphenyl acrylate, 2,4-di-tert-pentyl-6-[1-(2-hydroxy-3,5-di-tert-pentylphenyl)ethyl]phenyl acrylate and mixtures thereof.

[0241] (7) Examples of O-, N- and S-benzyl derivatives

[0242] 3,5,3',5'-tetra-tert-butyl-4,4'-dihydroxydibenzyl ether, octadecyl-4-hydroxy-3,5-dimethylbenzylthioacetate, tris(3,5-di-tert-butyl-4-hydroxybenzyl)amine, bis(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl)dithioterephthalate, bis(3,5-di-tert-butyl-4-hydroxybenzyl)sulfide, 3,5-di-tert-butyl-4-hydroxybenzylthioacetate and mixtures thereof.

[0243] (8) Examples of Hydroxybenzylated Malonate Derivatives

[0244] 2,2-bis(3,5-di-tert-butyl-2-hydroxybenzyl)malonate, 2-(3-tert-butyl-4-hydroxy-5-methylbenzyl)malonate, 2,2-bis(3,5-di-tert-butyl-4-hydroxybenzyl)malonate, didodecylmercaptoethyl 2,2-bis(3,5-di-tert-butyl-4-hydroxybenzyl)malonate, bis[4-(1,1,3,3-tetramethylbutyl)phenyl]malonate, and mixtures thereof.

[0245] (9) Examples of aromatic hydroxybenzyl derivatives

[0246] 1,3,5-trimethyl-2,4,6-tri(3,5-di-tert-butyl-4-hydroxybenzyl)benzene, 1,4-bis(3,5-di-tert-butyl-4-hydroxybenzyl)-2,3,5,6-tetramethylbenzene, 2,4,6-tri(3,5-tert-butyl-4-hydroxybenzyl)phenol and mixtures thereof, etc.

[0247] (10) Examples of triazine derivatives

[0248] 2,4-Bis(n-octylthio)-6-(4-hydroxy-3,5-di-tert-butylanilino)-1,3,5-triazine, 2-n-octylthio-4,6-bis(4-hydroxy-3,5-di-tert-butylanilino)-1,3,5-triazine, 2-n-octylthio-4,6-bis(4-hydroxy-3,5-di-tert-butylphenoxy)-1,3,5-triazine, 2,4,6-tris(3,5-di-tert-butyl-4-phenoxy)-1,3,5-triazine, tris(4-tert-butyl-3-hydroxy-2,6- isocyanurate, tris(3,5-di-tert-butyl-4-hydroxybenzyl)isocyanurate, 2,4,6-tris(3,5-di-tert-butyl-4-hydroxyphenylethyl)-1,3,5-triazine, 2,4,6-tris(3,5-di-tert-butyl-4-hydroxyphenylpropyl)-1,3,5-triazine, tris(3,5-dicyclohexyl-4-hydroxybenzyl)isocyanurate, tris[2-(3',5'-di-tert-butyl-4'-hydroxycinnamoyloxy)ethyl]isocyanurate and mixtures thereof, etc.

[0249] (11) Examples of benzylphosphonate derivatives

[0250] 3,5-di-tert-butyl-4-hydroxybenzylphosphonic acid dimethyl ester, 3,5-di-tert-butyl-4-hydroxybenzylphosphonic acid diethyl ester, 3,5-di-tert-butyl-4-hydroxybenzylphosphonic acid distearyl ester, 5-tert-butyl-4-hydroxy-3-methylbenzylphosphonic acid distearyl ester, 3,5-di-tert-butyl-4-hydroxybenzylphosphonic acid monoester calcium salt and their mixtures, etc.

[0251] (12) Examples of acylaminophenol derivatives

[0252] 4-Hydroxylauroylanilide, 4-hydroxystearic acid anilide, N-(3,5-di-tert-butyl-4-hydroxyphenyl)carbamic acid octyl ester and mixtures thereof, etc.

[0253] (13) Examples of esters of β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionic acid with the following monohydric or polyhydric alcohols

[0254] Methanol, ethanol, octanol, octadecyl alcohol, ethylene glycol, 1,3-propylene glycol, 1,4-butanediol, 1,6-hexanediol, 1,9-nonanediol, neopentyl glycol, diethylene glycol, thioethylene glycol, spirodiol, triethylene glycol, pentaerythritol, tris(hydroxyethyl)isocyanurate, N,N'-bis(hydroxyethyl)oxamide, 3-thioundecanol, 3-thiopentadecanol, trimethyl hexanediol, trimethylolpropane, 4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo[2,2,2]octane and mixtures thereof.

[0255] (14) Examples of esters of β-(5-tert-butyl-4-hydroxy-3-methylphenyl)propionic acid with the following monohydric or polyhydric alcohols

[0256] Methanol, ethanol, octanol, octadecyl alcohol, ethylene glycol, 1,3-propylene glycol, 1,4-butanediol, 1,6-hexanediol, 1,9-nonanediol, neopentyl glycol, diethylene glycol, thioethylene glycol, spirodiol, triethylene glycol, pentaerythritol, tris(hydroxyethyl)isocyanurate, N,N'-bis(hydroxyethyl)oxamide, 3-thioundecanol, 3-thiopentadecanol, trimethyl hexanediol, trimethylolpropane, 4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo[2,2,2]octane and mixtures thereof.

[0257] (15) Examples of esters of β-(3,5-dicyclohexyl-4-hydroxyphenyl)propionic acid with the following monohydric or polyhydric alcohols

[0258] Methanol, ethanol, octanol, octadecyl alcohol, ethylene glycol, 1,3-propylene glycol, 1,4-butanediol, 1,6-hexanediol, 1,9-nonanediol, neopentyl glycol, diethylene glycol, thioethylene glycol, spirodiol, triethylene glycol, pentaerythritol, tris(hydroxyethyl)isocyanurate, N,N'-bis(hydroxyethyl)oxamide, 3-thioundecanol, 3-thiopentadecanol, trimethyl hexanediol, trimethylolpropane, 4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo[2,2,2]octane and mixtures thereof.

[0259] (16) Examples of esters of 3,5-di-tert-butyl-4-hydroxyphenylacetic acid with the following monohydric or polyhydric alcohols

[0260] Methanol, ethanol, octanol, octadecyl alcohol, ethylene glycol, 1,3-propylene glycol, 1,4-butanediol, 1,6-hexanediol, 1,9-nonanediol, neopentyl glycol, diethylene glycol, thioethylene glycol, spirodiol, triethylene glycol, pentaerythritol, tris(hydroxyethyl)isocyanurate, N,N'-bis(hydroxyethyl)oxamide, 3-thioundecanol, 3-thiopentadecanol, trimethyl hexanediol, trimethylolpropane, 4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo[2,2,2]octane and mixtures thereof.

[0261] (17) Examples of amides of β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionic acid

[0262] N,N'-bis[3-(3',5'-di-tert-butyl-4'-hydroxyphenyl)propionyl]hydrazine, N,N'-bis[3-(3',5'-di-tert-butyl-4'-hydroxyphenyl)propionyl]hexamethylenediamine, N,N'-bis[3-(3',5'-di-tert-butyl-4'-hydroxyphenyl)propionyl]trimethylenediamine and mixtures thereof.

[0263] Examples of the sulfur-based antioxidant include the following.

[0264] 3,3'-dilauryl thiodipropionate, tridecyl 3,3'-thiodipropionate, dimyristyl 3,3'-thiodipropionate, distearyl 3,3'-thiodipropionate, lauryl stearyl 3,3'-thiodipropionate, neopentanetetrayltetrakis (3-laurylthiopropionate), and the like.

[0265] Examples of the phosphorus-based antioxidant include the following: As the phosphorus-based antioxidant, the following compounds may be used alone or in combination of two or more.

[0266] Triphenyl phosphite, tris(nonylphenyl) phosphite, tris(2,4-di-tert-butylphenyl) phosphite, trilauryl phosphite, tri(octadecyl) phosphite, distearyl pentaerythritol diphosphite, diisodecyl pentaerythritol diphosphite, bis(2,4-di-tert-butylphenyl) pentaerythritol diphosphite, bis(2,4-di-tert-butyl-6-methylphenyl) pentaerythritol diphosphite, bis(2,6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphite, bis(2,4,6-tri-tert-butylphenyl) pentaerythritol diphosphite, tristearyl sorbitol triphosphite, tetrakis(2,4-di-tert-butylphenyl)-4,4'-diphenylene diphosphonite, 2,2'-methylenebis(4,6-di-tert-butylphenyl) 2-ethyl 2-(2,4,6-tri-tert-butylphenyl)-5-ethyl-5-butyl-1,3,2-oxaphosphinane, 2,2',2''-nitrilo[triethyl-tris(3,3',5,5'-tetra-tert-butyl-1,1'-biphenyl-2,2'-diyl)phosphite, 6-[3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propoxy]-2,4,8,10-tetra-tert-butyldibenzo[d,f][1,3,2]dioxaphosphinane and mixtures thereof.

[0267] As the anti-aging agent, for example, quinoline anti-aging agents such as polymers of 2,2,4-trimethyl-1,2-dihydroquinoline; monophenol anti-aging agents such as 2,6-di-tert-butyl-4-methylphenol and styrenated phenol; bisphenol anti-aging agents such as tetrakis[methylene-3-(3',5'-di-tert-butyl-4'-hydroxyphenyl) propionate]methane, triphenol anti-aging agents, polyphenol anti-aging agents, etc. can be used alone or in combination of two or more. Among them, quinoline anti-aging agents are preferred.

[0268] As the ultraviolet absorber, for example, the following substances can be mentioned. As the ultraviolet absorber, the following compounds may be used alone or in combination of two or more.

[0269] (1) Examples of salicylic acid ester derivatives

[0270] Phenyl salicylate, 4-tert-butylphenyl salicylate, 2,4-di-tert-butylphenyl 3',5'-di-tert-butyl-4'-hydroxybenzoate, 4-tert-octylphenyl salicylate, bis(4-tert-butylbenzoyl)resorcinol, benzoylresorcinol, hexadecyl 3',5'-di-tert-butyl-4'-hydroxybenzoate, octadecyl 3',5'-di-tert-butyl-4'-hydroxybenzoate, 2-methyl-4,6-di-tert-butylphenyl 3',5'-di-tert-butyl-4'-hydroxybenzoate and mixtures thereof.

[0271] (2) Examples of 2-hydroxybenzophenone derivatives

[0272] 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-octyloxybenzophenone, 2,2'-dihydroxy-4-methoxybenzophenone, bis(5-benzoyl-4-hydroxy-2-methoxyphenyl)methane, 2,2',4,4'-tetrahydroxybenzophenone and mixtures thereof, etc.

[0273] (3) Example of 2-(2'-hydroxyphenyl)benzotriazole

[0274] 2-(2-hydroxy-5-methylphenyl)benzotriazole, 2-(3',5'-di-tert-butyl-2'-hydroxyphenyl)benzotriazole, 2-(5'-tert-butyl-2'-hydroxyphenyl)benzotriazole, 2-(2'-hydroxy-5'-tert-octylphenyl)benzotriazole, 2-(3-tert-butyl-2-hydroxy-5-methylphenyl)-5-chlorobenzotriazole, 2-(3'-sec-butyl-2'-hydroxy-5'-tert-butylphenyl)benzotriazole, 2-(2'-hydroxy-4'-octyloxyphenyl)benzotriazole benzotriazole, 2-(3',5'-di-tert-amyl-2'-hydroxyphenyl)benzotriazole, 2-[2'-hydroxy-3',3'-bis(α,α-dimethylbenzyl)phenyl]-2H-benzotriazole, 2-[(3'-tert-butyl-2'-hydroxyphenyl)-5'-(2-octyloxycarbonylethyl)phenyl]-5-chlorobenzotriazole, 2-[3'-tert-butyl-5'-[2-(2-ethylhexyloxy)carbonylethyl]-2'-hydroxyphenyl]-5-chlorobenzotriazole, 2-[3'-tert-butyl -3'-hydroxy-5'-(2-methoxycarbonylethyl)phenyl]-5-chlorobenzotriazole, 2-[3'-tert-butyl-2'-hydroxy-5'-(2-methoxycarbonylethyl)phenyl]benzotriazole, 2-[3'-tert-butyl-2'-hydroxy-5-(2-octyloxycarbonylethyl)phenyl]benzotriazole, 2-[3'-tert-butyl-2'-hydroxy-5'-[2-(2-ethylhexyloxy)carbonylethyl]phenyl]benzotriazole, 2-[2-hydroxy-3-(3,4,5,6-tetrahydro phthalimidomethyl)-5-methylphenyl]benzotriazole, 2-(3,5-di-tert-butyl-2-hydroxyphenyl)-5-chlorobenzotriazole, a mixture of 2-(3'-dodecyl-2'-hydroxy-5'-methylphenyl)benzotriazole and 2-[3'-tert-butyl-2'-hydroxy-5'-(2-isooctyloxycarbonylethyl)phenyl]benzotriazole, 2,2'-methylenebis[6-(2H-benzotriazol-2-yl)-4-(1,1,3,3-tetramethylbutyl)phenol, 2,2'-methylenebis[4-tert-butyl-6-(2H-benzotriazol-2-yl)phenol], condensation product of poly(3-11)(ethylene glycol) and 2-[3'-tert-butyl-2'-hydroxy-5'-(2-methoxycarbonylethyl)phenyl]benzotriazole, condensation product of poly(3-11)(ethylene glycol) and 3-[3-(2H-benzotriazol-2-yl)-5-tert-butyl-4-hydroxyphenyl]propionic acid methyl ester, 3-[3-tert-butyl-5-(5-chloro- 2H-benzotriazol-2-yl)-4-hydroxyphenyl]propionic acid 2-ethylhexyl ester, 3-[3-tert-butyl-5-(5-chloro-2H-benzotriazol-2-yl)-4-hydroxyphenyl]propionic acid octyl ester, 3-[3-tert-butyl-5-(5-chloro-2H-benzotriazol-2-yl)-4-hydroxyphenyl]propionic acid methyl ester, 3-[3-tert-butyl-5-(5-chloro-2H-benzotriazol-2-yl)-4-hydroxyphenyl]propionic acid and mixtures thereof, etc.

[0275] As the light stabilizer, for example, the following substances can be mentioned. As the light stabilizer, the following compounds may be used alone or in combination of two or more.

[0276] (1) Examples of Hindered Amine Light Stabilizers

[0277] Bis(2,2,6,6-tetramethyl-4-piperidinyl) sebacate, bis(2,2,6,6-tetramethyl-4-piperidinyl) succinate, bis(1,2,2,6,6-pentamethyl-4-piperidinyl) sebacate, bis(N-octyloxy-2,2,6,6-tetramethyl-4-piperidinyl) sebacate, bis(N-benzyloxy-2,2,6,6-tetramethyl-4-piperidinyl) sebacate, bis(N-cyclohexyloxy) 2-butylmalonate, bis(1-acryloyl-2,2,6,6-tetramethyl-4-piperidinyl) 2,2-bis(3,5-di-tert-butyl-4-hydroxybenzyl)-2-butylmalonate, bis(1-acryloyl-2,2,6,6-tetramethyl-4-piperidinyl) 2,2-bis(3,5-di-tert-butyl-4-hydroxybenzyl)-2-butylmalonate, bis(1,2,2,6 ,6-pentamethyl-4-piperidinyl) sebacate, 2,2,6,6-tetramethyl-4-piperidinyl methacrylate, 4-[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionyloxy]-1-[2-(3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionyloxy)ethyl]-2,2,6,6-tetramethylpiperidine, 2-methyl-2-(2,2,6,6-tetramethyl-4-piperidinyl)amino -N-(2,2,6,6-tetramethyl-4-piperidinyl) propionamide, tetrakis(2,2,6,6-tetramethyl-4-piperidinyl) 1,2,3,4-butanetetracarboxylate, tetrakis(1,2,2,6,6-pentamethyl-4-piperidinyl) 1,2,3,4-butanetetracarboxylate, mixed esters of 1,2,3,4-butanetetracarboxylic acid, 1,2,2,6,6-pentamethyl-4-piperidinol and 1-tridecanol,

[0278] Mixed esters of 1,2,3,4-butanetetracarboxylic acid with 2,2,6,6-tetramethyl-4-piperidinol and 1-tridecanol, mixed esters of 1,2,3,4-butanetetracarboxylic acid with 1,2,2,6,6-pentamethyl-4-piperidinol and 3,9-bis(2-hydroxy-1,1-dimethylethyl)-2,4,8,10-tetraoxaspiro[5·5]undecane, mixed esters of 1,2,3,4-butanetetracarboxylic acid with 2,2,6,6-tetramethyl-4-piperidinol and 3,9-bis(2-hydroxy-1,1-dimethylethyl)-2,4,8,10-tetraoxaspiro[5·5]undecane ·5] Undecane mixed esters, polycondensation products of dimethyl succinate and 1-(2-hydroxyethyl)-4-hydroxy-2,2,6,6-tetramethylpiperidine, poly[(6-morpholinyl-1,3,5-triazine-2,4-diyl)((2,2,6,6-tetramethyl-4-piperidinyl)imino)hexamethylene((2,2,6,6-tetramethyl-4-piperidinyl)imino)], poly[(6-(1,1,3,3-tetramethylbutyl)imino-1,3,5-triazine-2,4-diyl((2,2,6,6-tetramethyl-4-piperidinyl)imino)hexamethylene N,N',4,7-tetrakis[4,6-bis(N-butyl-N-(2,2,6,6-tetramethyl-4-piperidinyl)amino)-1,3,5-triazine-2-yl]-4,7-diazadecane-1,10-diamine, N,N',4-tris[4,6-bis(N-butyl-N-(2,2,6,6-tetramethyl-4-piperidinyl)amino)-1,2-dibromoethane polycondensate 3,5-triazine-2-yl]-4,7-diazadecane-1,10-diamine, N,N',4,7-tetrakis[4,6-bis(N-butyl-N-(1,2,2,6,6-pentamethyl-4-piperidinyl)amino)-1,3,5-triazine-2-yl]-4,7-diazadecane-1,10-diamine, N,N',4-tris[4,6-bis(N-butyl-N-(1,2,2,6,6-pentamethyl-4-piperidinyl)amino)-1,3,5-triazine-2-yl]-4,7-diazadecane-1,10-diamine and mixtures thereof.

[0279] (2) Examples of Acrylate Light Stabilizers

[0280] Ethyl α-cyano-β,β-diphenylacrylate, isooctyl α-cyano-β,β-diphenylacrylate, methyl α-methyl cinnamate, methyl α-cyano-β-methyl p-methoxycinnamate, butyl α-cyano-β-methyl p-methoxycinnamate, methyl α-methyl p-methoxycinnamate and N-(β-methyl ester-β-cyanovinyl)-2-methylindoline and mixtures thereof, etc.

[0281] (3) Examples of nickel-based light stabilizers

[0282] Nickel complex of 2,2'-thiobis-[4-(1,1,3,3-tetramethylbutyl)phenol], nickel dibutyldithiocarbamate, nickel salt of monoalkyl ester, nickel complex of ketoxime, and mixtures thereof, etc.

[0283] (4) Examples of oxalamide-based light stabilizers

[0284] 4,4'-dioctyloxy oxalanilide, 2,2'-diethoxy oxalanilide, 2,2'-dioctyloxy-5,5'-di-tert-butylaniline, 2,2'-didodecyloxy-5,5'-di-tert-butylaniline, 2-ethoxy-2'-ethyl oxalanilide, N,N'-bis(3-dimethylaminopropyl)oxalamide, 2-ethoxy-5-tert-butyl-2'-ethoxyaniline, 2-ethoxy-5,4'-di-tert-butyl-2'-ethyl oxalanilide and mixtures thereof.

[0285] (5) Examples of 2-(2-hydroxyphenyl)-1,3,5-triazine-based light stabilizers

[0286] 2,4,6-tris(2-hydroxy-4-octyloxyphenyl)-1,3,5-triazine, 2-(2-hydroxy-4-octyloxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine, 2-[2,4-dihydroxyphenyl-4,6-bis(2,4-dimethylphenyl]-1,3,5-triazine, 2,4-bis(2-hydroxy-4-propoxyphenyl)-6-(2,4-dimethylphenyl)-1,3,5-triazine, 2-(2-hydroxy-4-octyloxyphenyl)-4,6-bis( phenyl)-1,3,5-triazine, 2-[2-hydroxy-4-(2-hydroxy-3-butyloxypropoxy)phenyl]-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine, 2-[2-hydroxy-4-(2-hydroxy-3-octyloxypropoxy)phenyl]-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine, and mixtures thereof.

[0287] Examples of the metal deactivator include the following.

[0288] N,N'-diphenyloxamide, N-salicylaldehyde-N'-salicylic hydrazide, N,N'-bis(salicylic acid)hydrazide, N,N'-bis(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)hydrazide, 3-salicylic acid amino-1,2,4-triazole, bis(benzylidene)oxalyl dihydrazide, oxalyl anilide, isophthaloyl dihydrazide, sebacoyl bisphenyl hydrazide, N,N'-bis(salicylic acid)oxalyl dihydrazide, N,N'-bis(salicylic acid)thiopropionyl dihydrazide and mixtures thereof, etc.

[0289] Examples of the peroxide scavenger include esters of β-thiodipropionic acid, mercaptobenzimidazole, zinc salt of 2-mercaptobenzimidazole, zinc salt of dibutyldithiocarbamic acid, dioctadecyl disulfide, pentaerythritol tetrakis(β-dodecylmercapto)propionate, and mixtures thereof.

[0290] Examples of the polyamide stabilizer include copper or divalent manganese salts of iodides or phosphorus compounds, and mixtures thereof.

[0291] Examples of the hydroxylamine include N,N-dibenzylhydroxylamine, N,N-diethylhydroxylamine, N,N-dioctylhydroxylamine, N,N-dilaurylhydroxylamine, N,N-ditetradecylhydroxylamine, N,N-dihexadecylhydroxylamine, N,N-dioctadecylhydroxylamine, N-hexadecyl-N-octadecylhydroxylamine, N-heptadecyl-N-octadecylhydroxylamine, and mixtures thereof.

[0292] Examples of the neutralizing agent include calcium stearate, zinc stearate, magnesium stearate, hydrotalcite (basic magnesium·aluminum·hydroxy·carbonate·hydrate), melamine, amines, polyamides, polyurethanes, and mixtures thereof.

[0293] Examples of lubricants include paraffin wax, aliphatic hydrocarbons such as wax, higher fatty acids having 8 to 22 carbon atoms, metal (Al, Ca, Mg, Zn) salts of higher fatty acids having 8 to 22 carbon atoms, aliphatic alcohols having 8 to 22 carbon atoms, polyglycols, esters of higher fatty acids having 4 to 22 carbon atoms and aliphatic monohydric alcohols having 4 to 18 carbon atoms, higher aliphatic amides having 8 to 22 carbon atoms, silicone oils, rosin derivatives, and the like.

[0294] Examples of the nucleating agent include the following: sodium 2,2'-methylenebis(4,6-di-tert-butylphenyl) phosphate, dihydroxyaluminum [phosphate-2,2'-methylenebis(4,6-di-tert-butylphenyl)], bis[phosphate-2,2'-methylenebis(4,6-di-tert-butylphenyl)]hydroxyaluminum, tris[phosphate-2,2'-methylenebis(4,6-di-tert-butylphenyl)]aluminum, sodium bis(4-tert-butylphenyl) phosphate, metal benzoates such as sodium benzoate, aluminum p-tert-butylbenzoate, 1,3:2,4-bis(O-benzylidene)sorbitol, 1,3:2,4-bis(O-methylbenzylidene)sorbitol, 1,3:2, 4-Bis(O-ethylbenzylidene)sorbitol, 1,3-O-3,4-dimethylbenzylidene-2,4-O-benzylidene sorbitol, 1,3-O-benzylidene-2,4-O-3,4-dimethylbenzylidene sorbitol, 1,3:2,4-bis(O-3,4-dimethylbenzylidene)sorbitol, 1,3-O-p-chlorobenzylidene-2,4-O-3,4-dimethylbenzylidene sorbitol, 1,3-O-3,4-dimethylbenzylidene-2,4-O-p-chlorobenzylidene sorbitol, 1,3:2,4-bis(O-p-chlorobenzylidene)sorbitol and mixtures thereof.

[0295] Examples of the filler include calcium carbonate, silicate, glass fiber, asbestos, talc, kaolin, mica, barium sulfate, carbon black, carbon fiber, zeolite, and mixtures thereof.

[0296] Preferable additives among these additives are phenolic antioxidants, phosphorus antioxidants, ultraviolet absorbers, hindered amine light stabilizers, peroxide scavengers, and neutralizers.

[0297] As particularly preferred phenolic antioxidants, the following compounds can be mentioned.

[0298] 2,2'-Thiobis(6-tert-butylphenol), 4,4'-thiobis(3-methyl-6-tert-butylphenol), 2,2'-methylenebis(4-methyl-6-tert-butylphenol), 2,2'-methylenebis(4-ethyl-6-tert-butylphenol), 2,2'-methylenebis[4-methyl-6-(α-methylcyclohexyl)phenol)], 2,2'-methylenebis(4-methyl-6-cyclohexylphenol), 2,2'-methylenebis(4,6-di-tert-butylphenol), 2,2'-ethylidenebis(4,6-di-tert-butylphenol), 4,4'-methylenebis(6-tert-butyl-2-methylphenol), 4,4'-methylenebis (2,6-di-tert-butylphenol), 4,4'-butylenebis(3-methyl-6-tert-butylphenol), 1,1-bis(4-hydroxyphenyl)cyclohexane, 1,1-bis(5-tert-butyl-4-hydroxy-2-methylphenyl)butane, 1,1,3-tris(5-tert-butyl-4-hydroxy-2-methylphenyl)butane, ethylene glycol bis[3,3-bis-3'-tert-butyl-4'-hydroxyphenyl)butyrate], 2-tert-butyl-6-(3'-tert-butyl-5'-methyl-2'-hydroxybenzyl)-4-methylphenyl acrylate, 2,4-di-tert-amyl-6-[1-(2-hydroxy-3,5-di-tert-amylphenyl)ethyl]phenyl acrylate,

[0299] 2,4,6-Tris(3,5-di-tert-butyl-4-phenoxy)-1,3,5-triazine, tris(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl) isocyanurate, bis(3,5-di-tert-butyl-4-hydroxybenzyl) isocyanurate, tris[2-(3',5'-di-tert-butyl-4'-hydroxycinnamoyloxy)ethyl] isocyanurate, diethyl-3,5-di-tert-butyl-4-hydroxybenzylphosphonate, di-n-octadecyl-3,5-di-tert-butyl-4-hydroxybenzylphosphonate, calcium salt of 3,5-di-tert-butyl-4-hydroxybenzylphosphonic acid monoester, n-octadecyl 3-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate, neopentanetetrayl tetra(3,5-di-tert-butyl-4-hydroxyphenyl) propionate, butyl-4-hydroxycinnamate), thiodiethylenebis(3,5-di-tert-butyl-4-hydroxycinnamate), 1,3,5-trimethyl-2,4,6-tri(3,5-di-tert-butyl-4-hydroxybenzyl)benzene, 3,6-dioxaoctamethylenebis(3,5-di-tert-butyl-4-hydroxycinnamate), hexamethylenebis(3,5-di-tert-butyl-4-hydroxycinnamate), triethylene glycol bis(5-tert-butyl-4-hydroxy-3-methylcinnamate), N,N'-bis[3-(3',5'-di-tert-butyl-4'-hydroxyphenyl)propionyl]hydrazine, N,N'-bis[3-(3',5'-di-tert-butyl-4'-hydroxyphenyl)propionyl]hexamethylenediamine, etc.

[0300] In addition, as particularly preferred phosphorus-based antioxidants, the following compounds can be mentioned.

[0301] Tris(nonylphenyl) phosphite, tris(2,4-di-tert-butylphenyl) phosphite, distearyl pentaerythritol diphosphite, bis(2,4-di-tert-butylphenyl) pentaerythritol diphosphite, bis(2,4-di-tert-butyl-6-methylphenyl) pentaerythritol diphosphite, bis(2,6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphite, tetrakis(2,4-di-tert-butylphenyl)-4,4'-diphenylene diphosphonite, 2,2'-methylenebis(4,6-di-tert-butylphenyl) 2-ethylhexyl phosphite, 2,2'-ethylidenebis(4,6-di-tert-butylphenyl) 2-(2,4-di-tert-butyl-6-methylphenyl)fluorophosphite, bis(2,4-di-tert-butyl-6-methylphenyl)ethylphosphite, 2-(2,4,6-tri-tert-butylphenyl)-5-ethyl-5-butyl-1,3,2-dioxaphosphinane, 2,2',2''-nitrilo[triethyl-tri(3,3',5,5'-tetra-tert-butyl-1,1'-biphenyl-2,2'-diyl)phosphite, 6-[3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propoxy]-2,4,8,10-tetra-tert-butyldibenzo[d,f][1,3,2]dioxaphosphinane, etc.

[0302] As particularly preferred ultraviolet absorbers, the following compounds can be mentioned.

[0303] Phenyl salicylate, 4-tert-butylphenyl salicylate, 2,4-di-tert-butylphenyl 3',5'-di-tert-butyl-4'-hydroxybenzoate, 4-tert-octylphenyl salicylate, 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-octyloxybenzophenone, 2,2'-dihydroxy-4-methoxybenzophenone, bis(5-benzoyl-4-hydroxy-2-methoxyphenyl)methane, 2,2',4,4'-tetrahydroxybenzophenone, 2-(2-hydroxy-5-methylphenyl)benzotriazole, 2-(3',5'-di-tert-butyl-2'-hydroxyphenyl)benzotriazole benzotriazole, 2-(5'-tert-butyl-2'-hydroxyphenyl)benzotriazole, 2-(2'-hydroxy-5'-tert-octylphenyl)benzotriazole, 2-(3-tert-butyl-2-hydroxy-5-methylphenyl)-5-chlorobenzotriazole, 2-(3'-sec-butyl-2'-hydroxy-5'-tert-butylphenyl)benzotriazole, 2-(2'-hydroxy-4'-octyloxyphenyl)benzotriazole, 2-(3',5'-di-tert-amyl-2'-hydroxyphenyl)benzotriazole, 2-[2'-hydroxy-3',5'-bis(α,α-dimethylbenzyl)phenyl]-2H-benzotriazole, and the like.

[0304] As particularly preferred light stabilizers, the following compounds can be mentioned.

[0305] Bis(2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis(1,2,2,6,6-pentamethyl-4-piperidyl) sebacate, bis(N-octyloxy-2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis(N-benzyloxy-2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis(N-cyclohexyloxy-2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis(1,2,2,6,6-pentamethyl-4-piperidyl) 2-(3,5-di-tert-butyl-4-hydroxybenzyl)-2-butylmalonate, bis(1-acryloyl-2,2,6,6-tetramethyl-4-piperidyl) 2,2-bis(3,5-di-tert-butyl-4-hydroxybenzyl)-2-butylmalonate tert-butyl-4-hydroxybenzyl)-2-butylmalonate, bis(2,2,6,6-tetramethyl-4-piperidinyl) succinate, 2,2,6,6-tetramethyl-4-piperidinyl methacrylate, 4-[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionyloxy]-1-[2-(3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionyloxy)ethyl]-2,2,6,6-tetramethylpiperidine, 2-methyl-2-(2,2,6,6-tetramethyl-4-piperidinyl)amino-N-(2,2,6,6-tetramethyl-4-piperidinyl)propionamide, tetrakis(2,2,6,6-tetramethyl-4-piperidinyl)1,2,3,4-butanetetracarboxylate,

[0306] Tetrakis(1,2,6,6-pentamethyl-4-piperidinyl)1,2,3,4-butanetetracarboxylic acid ester, mixed esters of 1,2,3,4-butanetetracarboxylic acid with 1,2,2,6,6-pentamethyl-4-piperidinol and 1-tridecanol, mixed esters of 1,2,3,4-butanetetracarboxylic acid with 2,2,6,6-tetramethyl-4-piperidinol and 1-tridecanol, mixed esters of 1,2,3,4-butanetetracarboxylic acid with 1,2,2,6,6-pentamethyl-4-piperidinol and 3,9-bis(2-hydroxy-1,1-dimethylethyl)-2,4,8,10-tetraoxaspiro[5·5]undecane, mixed esters of 1,2,3,4-butanetetracarboxylic acid with 2,2,6,6-tetramethyl-4-piperidinol and 3,9-bis(2-hydroxy-1,1-dimethylethyl)-2,4,8,10-tetraoxaspiro[5·5]undecane

[0045] ], poly[(6-morpholino-1,3,5-triazine-2,4-diyl)((2,2,6,6-tetramethyl-4-piperidinyl)imino)hexamethylene((2,2,6,6-tetramethyl-4-piperidinyl)imino)], poly[(6-(1,1,3,3-tetramethylbutyl)-1,3,5-triazine-2,4-diyl)((2,2,6,6-tetramethyl-4-piperidinyl)imino)hexamethylene((2,2,6,6-tetramethyl-4-piperidinyl)imino)], etc.

[0307] All known methods and apparatuses for obtaining a homogeneous mixture can be used to add the stabilizer of the present invention, or a compound (A) selected from the compound represented by formula (1) and the compound represented by formula (2) and a compound (B) represented by formula (3) in a specific ratio, and other additives added as needed to the organic material. For example, when the stabilizer of the present invention is added as an example, when the organic material is a solid polymer, the stabilizer of the present invention and / or other additives added as needed can be directly dry-mixed into the solid polymer, or the stabilizer of the present invention and / or other additives added as needed can be added to the solid polymer in the form of a masterbatch. In the case where the organic material is a liquid polymer, in addition to the above-mentioned addition method, the stabilizer of the present invention and / or other additives added as needed can be formulated in the form of a solution or dispersion in a polymer solution during or just after polymerization. On the other hand, in the case where the organic material is a liquid other than a solid polymer (such as oil, etc.), in addition to the above-mentioned addition method, the stabilizer of the present invention and / or other additives added as needed can be directly added to the organic material and dissolved, or the stabilizer of the present invention and / or other additives added as needed can be added in a state dissolved or suspended in a liquid medium.

[0308] The stabilizer of the present invention has excellent performance as a stabilizer for various organic materials represented by thermoplastic resins such as polyolefins. Organic materials to which the stabilizer of the present invention is added, and organic materials to which a specific ratio of a compound (A) selected from the compound represented by formula (1) and the compound represented by formula (2) and a compound (B) represented by formula (3) are added have good processing stability. In addition, discoloration of the organic material caused by oxidizing gases can be prevented. Such an organic material becomes a high-quality product that is stable to thermal degradation and / or oxidative degradation during manufacturing, processing and use, and also suppresses discoloration caused by oxidizing gases.

[0309] The stabilizer of the present invention can reduce the degradation of the organic material during processing and improve the processing stability by adding the stabilizer to the organic material. In addition, the stabilizer of the present invention can prevent discoloration caused by oxidizing gases, especially NOx gas. Therefore, the stabilizer of the present invention is suitable as an active ingredient of a stabilizer for organic materials. Therefore, the present invention also provides a stabilizer and a stabilization method for organic materials, wherein the stabilizer comprises a specific ratio of a compound (A) selected from the compound represented by formula (1) and the compound represented by formula (2) and a compound (B) represented by formula (3), and the stabilization method of the organic material adds the stabilizer of the present invention or compounds (A) and (B) to the organic material. In addition, a stabilized resin composition is also provided, which comprises an organic material, and the stabilizer or compounds (A) and (B) of the present invention.

[0310] Example

[0311] The present invention will be described in more detail below with reference to Examples and Comparative Examples, but the present invention is not limited thereto. It should be noted that, in the following Examples and Comparative Examples, "parts" means "parts by weight" unless otherwise specified.

[0312] <Ingredients>

[0313] The components used in Examples and Comparative Examples are described below.

[0314] (Thermoplastic resin)

[0315] Low-density polyethylene resin (LLDPE) (MI value: 2 g / 10 min, manufactured by Sumitomo Chemical Co., Ltd.)

[0316] (Stabilizer)

[0317] Compound A-1:

[0318] 2,4,8,10-Tetra-tert-butyl-6-[3-(3-methyl-4-hydroxy-5-tert-butylphenyl)propoxy]dibenzo[d,f][1,3,2]dioxaphosphophene (Sumilizer (registered trademark) GP, manufactured by Sumitomo Chemical Co., Ltd.)

[0319] Compound A-2: Phosphite compound obtained in Preparation Example 1

[0320] Compound A-3: a mixture of tris(4-tert-pentylphenyl) phosphite, bis(4-tert-pentylphenyl)-2,4-di-tert-pentylphenyl phosphite, and bis(2,4-di-tert-pentylphenyl)-4-tert-pentylphenyl phosphite (WESTON (registered trademark) 705, manufactured by SI GROUP)

[0321] Compound B: 2,4-di-tert-butylphenol (produced by Tokyo Chemical Industry)

[0322] Compound C: stearyl 3-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate (IRGANOX 1076, manufactured by BASF)

[0323] (Production Example 1: Production of Compound A-2)

[0324] After 300g of cashew nut shell oil (Cardolite, NX-2025), 114g (1.11 mol) of triethylamine and 790ml of hexane were put into a 4-mouth separable flask, 200mL of a hexane solution of 49.1g (0.35 mol) of phosphorus trichloride was added dropwise in a nitrogen atmosphere in a range of 30 to 40°C for 50 minutes. After the addition was completed, the solution was stirred at 30°C for 4 hours. After the stirring was completed, it was washed twice with 0.65L of purified water and once with 0.65L of saturated brine. The obtained organic layer was dried with sodium sulfate, filtered to remove the sodium sulfate, concentrated and dried to obtain 285g of compound A-2 having a structure shown in the following formula (A-2). It should be noted that in formula (A-2), for example, -H / OH refers to -H or -OH, and the same is true for others.

[0325]

Chemical formula 13

[0326]

[0327] (Example 1)

[0328] 100 parts of LLDPE, 0.05 parts of calcium stearate (manufactured by Nitto Kasei Kogyo Co., Ltd.), 0.0500 parts of compound A-1, and 0.0010 parts of compound B were dry-blended, and the resulting mixture was kneaded using a twin-screw extruder with a barrel diameter of 32 mm (BTN-32, PLABOR) under a nitrogen atmosphere, a temperature of 190°C, and a screw speed of 80 rpm to obtain pellets.

[0329] (Examples 2 to 4, Comparative Examples 1 to 4)

[0330] The pellets of Examples 2 to 4 and Comparative Examples 1 to 3 were obtained in the same manner as in Example 1, except that Compound A-1, Compound B, and / or Compound C were dry-mixed in the amounts described in Table 1. In addition, the pellets of Comparative Example 4 were obtained in the same manner as in Example 1, except that none of Compound A-1, Compound B, or Compound C was added.

[0331] (NOx resistance)

[0332] The pellets obtained in Examples 1 to 4 and Comparative Examples 1 to 4 were pressed at 190°C using a press ("PEW-5040" manufactured by Kansai Roll Co., Ltd.) to obtain sheets having a thickness of 1 mm. The obtained sheets were cut into 4 cm in length by 4 cm in width using a rod-type sample cutter ("SDL-200" manufactured by Dumbbell Co., Ltd.) to obtain test pieces.

[0333] The obtained test piece is hung in a nitrogen oxide test device ("GF-5" manufactured by Suga Testing Instruments Co., Ltd.), and the generated NOx gas is captured in a gas measuring tube according to JIS L 0855 (1998). 10 mL of the captured NOx gas is taken with a gas syringe and injected into the nitrogen oxide test device. After the NOx gas injected into the test piece is exposed to room temperature for 7 days, the test piece is taken out, and the yellow index (YI) is measured using a colorimeter ("CM-3500d" manufactured by Konica Minolta Japan Co., Ltd.), and the ratio of the YI of the obtained test piece to the YI of the test piece obtained in Comparative Example 1 is calculated (YI of the test piece of the embodiment or comparative example / YI of the test piece obtained in Comparative Example 1). If the ratio is less than 1, it means that the NOx resistance is excellent. Based on the ratio of the obtained YI, the NOx resistance is evaluated according to the following criteria. The results are shown in Table 1.

[0334] Evaluation criteria for NOx resistance

[0335] ○: less than 1.0

[0336] ×: 1.0 or more

[0337] (Processing stability)

[0338] The melt flow rates (MFR) of the pellets obtained in Examples 1 to 4 and Comparative Examples 1 to 4 were measured.

[0339] MFR (g / 10min) is measured using a melt indexer (model L246-3537, manufactured by Technol Seven Co., Ltd.) at a temperature of 190°C and a load of 21.18N. LLDPE is crosslinked by heat-based processing, and its MFR decreases. Therefore, for LLDPE, the larger the MFR of the pellets extruded by a twin-screw extruder, the better its processing stability. Based on the obtained MFR, the processing stability was evaluated according to the following criteria. The results are shown in Table 2.

[0340] Evaluation criteria for processing stability

[0341] ○:2.0 or above

[0342] ×: less than 2.0

[0343]

Table 1

[0344]

[0345] (Example 5)

[0346] Pellets were obtained in the same manner as in Example 1 except that Compound A-2 was used instead of Compound A-1.

[0347] (Examples 6 to 7, Comparative Examples 5 to 6)

[0348] Except for dry-blending the compound A-2, the compound B, and / or the compound C in the addition amounts described in Table 2, it carried out similarly to Example 5 to obtain pellets.

[0349] Using the pellets obtained in Examples 5 to 7 and Comparative Examples 5 to 6, the ratio of YI (YI of the test piece of the Example or Comparative Example / YI of the test piece obtained in Comparative Example 5) was calculated according to the above-mentioned evaluation method (NOx resistance), and the evaluation was performed according to the same evaluation criteria. In addition, MFR was measured according to the above-mentioned evaluation method, and processing stability was evaluated. The obtained results are shown in Table 2.

[0350]

Table 2

[0351]

[0352] (Example 8)

[0353] Pellets were obtained in the same manner as in Example 1 except that Compound A-3 was used instead of Compound A-1.

[0354] (Example 9, Comparative Examples 7-8)

[0355] Except for dry-blending the compound A-3, the compound B, and / or the compound C in the addition amounts described in Table 3, it carried out similarly to Example 8 to obtain pellets.

[0356] Using the pellets obtained in Examples 8 to 9 and Comparative Examples 7 to 8, the ratio of YI (YI of the test piece of the Example or Comparative Example / YI of the test piece obtained in Comparative Example 7) was calculated according to the above-mentioned evaluation method (NOx resistance), and the evaluation was performed according to the same evaluation criteria. In addition, MFR was measured according to the above-mentioned evaluation method, and processing stability was evaluated. The obtained results are shown in Table 3.

[0357]

Table 3

[0358]

[0359] It was confirmed that the organic material to which a specific ratio of compound (A) selected from the compound represented by formula (1) and the compound represented by formula (2) and compound (B) represented by formula (3) were added had good processing stability and could prevent discoloration of the organic material caused by oxidizing gas.

[0360] It should be noted that, in the above examples, compound A and compound B are added to LLDPE separately, but compound A and compound B may be mixed in the same amount in advance by dry blending or the like to obtain the stabilizer of the present invention, and then the stabilizer may be added to LLDPE. Even in this case, it is considered that the same results as those shown in the examples can be obtained.

Claims

1. A stabilizer comprising a compound A and a compound B, wherein the content of the compound B is 0.01 to 50 parts by mass relative to 100 parts by mass of the compound A, the compound A is selected from the compound represented by formula (1) and the compound represented by formula (2), and the compound B is represented by formula (3), wherein: In formula (1), R 1 , R 2 , R 4 and R 5 each independently represents a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, a cycloalkyl group having 5 to 8 carbon atoms, an alkylcycloalkyl group having 6 to 12 carbon atoms, an aralkyl group having 7 to 12 carbon atoms, or a phenyl group, R 3 each independently represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, X represents a single bond, a sulfur atom or -CH(-R 13 )-group, where R 13 represents a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, or a cycloalkyl group having 5 to 8 carbon atoms, A represents an alkylene group having 1 to 8 carbon atoms or *-C(=O)-R 14 -base, where R 14 represents a single bond or an alkylene group having 1 to 8 carbon atoms, * represents the bonding position on the oxygen side, One of Y and Z represents a hydroxyl group, an alkoxy group having 1 to 8 carbon atoms, or an aralkyloxy group having 7 to 12 carbon atoms, and the other represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, In formula (2), R 6 and R 8 each independently represents a hydrogen atom, a methyl group, or an alkyl group having 5 to 8 carbon atoms, R 7 each independently represents a hydrogen atom or a hydroxyl group, R 9 Each independently represents a hydrogen atom or -C 15 H 25-31 base, Among them, at least 1 R 6 , R 7 , R 8 or R 9 Not hydrogen atoms, In formula (3), R 10 , R 11 and R 12 Each independently represents a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, or an aralkyl group having 7 to 20 carbon atoms in total, wherein R 10 , R 11 and R 12 At least one of them is not a hydrogen atom.

2. The stabilizer according to claim 1, wherein In formula (2), R 6 each independently represents a hydrogen atom or a methyl group, R 7 each independently represents a hydrogen atom or a hydroxyl group, R 8 represents a hydrogen atom, R 9 Each independently represents -C 15 H 25-31 base.

3. The stabilizer according to claim 1, wherein In formula (2), R 6 and R 8 Each independently represents a hydrogen atom or an alkyl group having 5 to 8 carbon atoms, wherein at least one R 6 or R 8 It is not a hydrogen atom, R 7 and R 9 Represents a hydrogen atom.

4. The stabilizer according to any one of claims 1 to 3, wherein In formula (3), R 11 Represents a hydrogen atom.

5. An organic material composition comprising at least one organic material and the stabilizer according to claim 1 or the compound A and the compound B, wherein the content of the compound B is 0.01 to 50 parts by mass relative to 100 parts by mass of the compound A.

6. The organic material composition according to claim 5, wherein: The content of the compound A is 0.01 to 1 part by mass, and the content of the compound B is 0.0001 to 0.5 parts by mass, based on 100 parts by mass of the organic material.

7. The organic material composition according to claim 5 or 6, wherein: The organic material is a thermoplastic resin.

8. The organic material composition according to claim 7, wherein: Thermoplastic resins are polyolefins or engineering plastics.

9. A method for stabilizing an organic material, wherein: The compound A and the compound B are added to the organic material, or the stabilizer according to claim 1 is added, wherein the content of the compound B is 0.01 to 50 parts by mass relative to 100 parts by mass of the compound A.

10. The stabilization method according to claim 9, wherein: The organic material is a thermoplastic resin.

11. The stabilization method according to claim 10, wherein: Thermoplastic resins are polyolefins or engineering plastics.

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