Processing stabilizer, organic material composition, and method for stabilizing organic material.

Abstract

To provide a process stabilizer that is effective in improving thermal stability when processing organic material, and minimizes discoloration caused by oxidative gases, particularly NOx gas.SOLUTION: Provided is a process stabilizer containing a compound (I) with a specific chemical structure including a dioxaphosphepin group, a compound (II) with a specific chemical structure including a dioxaphosphepin group, and an amine compound (A) including a hydroxyalkyl group. Relative to 100 pts.mass of the compound (I), the content of the compound (II) is 0.005-4 pts.mass, and the content of the amine compound (A) is 0.01-15 pts.mass.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a processing stabilizer containing a specific phenolic compound and an amine compound having a hydroxyalkyl group, an organic material composition containing a specific phenolic compound and an amine compound having a hydroxyalkyl group, and a method for stabilizing an organic material using a specific phenolic compound and an amine compound having a hydroxyalkyl group. [Background technology]

[0002] Organic materials such as thermoplastic resins, thermosetting resins, natural or synthetic rubber, mineral oil, lubricating oil, adhesives, and paints are subject to deterioration due to the action of heat and oxygen during production, processing, and even use. This can result in a decrease in the strength properties of the organic materials due to phenomena such as molecular scission and molecular crosslinking, changes in flow properties, coloration, and deterioration in surface properties, which can significantly impair their commercial value.

[0003] In order to prevent such deterioration due to heat or oxygen, various phenolic antioxidants and phosphorus-based antioxidants have been developed, and it is known that adding these to organic materials can stabilize the organic materials (Patent Documents 1 and 2). [Prior art documents] [Patent documents]

[0004] [Patent Document 1] Patent No. 3876479 [Patent Document 2] International Publication No. 2015 / 136717 Summary of the Invention [Problem to be solved by the invention]

[0005] Although various processing stabilizers for organic materials as described above are known, organic materials are used in various environments and may be exposed to combustion gases of fossil fuels, such as automobile exhaust fumes. In such cases, oxidizing gases, such as nitrogen oxides, contained in the combustion gases may accelerate discoloration of the organic materials. Therefore, there is still a demand for processing stabilizers that have processing stabilizing effects but are less likely to cause discoloration due to oxidizing gases, such as NOx gases. Patent Document 1 shows that the phosphite ester compounds of Chemical 1 to Chemical 12 corresponding to the specific formula (I) (Examples 1 to 10) cause less discoloration due to NOx gas compared to the phosphite ester compounds of P-1 and P-3 not corresponding to the specific formula (I) (Comparative Examples 1 and 2). However, the effect of reducing discoloration due to NOx gas is sometimes insufficient, and further improvement in discoloration reduction is still required. Furthermore, Patent Document 2 describes a processing stabilizer containing a compound represented by a specific formula (I) and a compound represented by a specific formula (II), but does not pay any attention to discoloration caused by NOx gas, and there are cases where discoloration caused by NOx gas cannot be sufficiently reduced. Therefore, an object of the present invention is to provide a processing stabilizer that is effective in improving the thermal stability when processing organic materials and that is less susceptible to discoloration due to oxidizing gases, particularly NOx gases. [Means for solving the problem]

[0006] In order to solve the above problems, the present inventors have conducted extensive research into various compounds and have found that a mixture of specific phenolic compounds (I) and (II) and an amine compound (A) having a hydroxyalkyl group is effective in improving the stability of resins and is also less susceptible to discoloration due to oxidizing gases such as NOx gas, thereby completing the present invention.

[0007] That is, the present invention includes the following preferred embodiments. [1] Formula (I): [ka] [In formula (I), 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 is a single bond, a sulfur atom, or -CH(-R 6 )-group(R 6 represents a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, or a cycloalkyl group having 5 to 8 carbon atoms), A is an alkylene group having 1 to 8 carbon atoms or *-C(=O)-R 7 -group(R 7 represents a single bond or an alkylene group having 1 to 8 carbon atoms, and * represents a bond 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. and a compound (I) represented by formula (II): [ka] [In formula (II), R 1 and R 2 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 is a single bond, a sulfur atom, or -CH(-R 6 )-group(R 6 represents a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, or a cycloalkyl group having 5 to 8 carbon atoms). and an amine compound (A) having a hydroxyalkyl group, A processing stabilizer in which the content of compound (II) is 0.005 to 4 parts by mass and the content of amine compound (A) is 0.01 to 15 parts by mass relative to 100 parts by mass of compound (I). [2] The processing stabilizer according to [1], wherein the amine compound (A) is an alkanolamine. [3] The alkanolamine is represented by the formula (III): [ka] [In formula (III), Y 1 , Y 2 and Y 3 each independently represents a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, or an alkyl group having 1 to 8 carbon atoms and at least one hydroxyl group, provided that Y 1 ~Y 3 at least one of which represents an alkyl group having 1 to 8 carbon atoms and at least one hydroxyl group. or formula (IV): [ka] [In formula (IV), Y 4 , Y 5 , Y 6 and Y 7 each independently represents a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, or an alkyl group having 1 to 8 carbon atoms and at least one hydroxyl group, provided that Y 4 ~Y 7 at least one of represents an alkyl group having 1 to 8 carbon atoms and having at least one hydroxyl group, and B represents an alkylene group having 1 to 4 carbon atoms. The processing stabilizer according to [2], represented by the formula: [4] The processing stabilizer according to [3], wherein the alkanolamine is represented by formula (III): [5] Y in formula (III) 1 , Y 2 and Y 3 and Y in formula (IV) 4 , Y 5 , Y 6 and Y 7 are each independently -CH-CH(OH)-R 6 [In the formula, R6 represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. [6] Formula (I): [ka] [In formula (I), 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 is a single bond, a sulfur atom, or -CH(-R 6 )-group(R 6 represents a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, or a cycloalkyl group having 5 to 8 carbon atoms), A is an alkylene group having 1 to 8 carbon atoms or *-C(=O)-R 7 -group(R 7 represents a single bond or an alkylene group having 1 to 8 carbon atoms, and * represents a bond 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. and a compound (I) represented by formula (II): [ka] [In formula (II), R 1 and R 2 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 is a single bond, a sulfur atom, or -CH(-R 6 )-group(R 6 represents a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, or a cycloalkyl group having 5 to 8 carbon atoms). an amine compound (A) having a hydroxyalkyl group, and an organic material, wherein the content of compound (II) is 0.005 to 4 parts by mass and the content of amine compound (A) is 0.01 to 15 parts by mass relative to 100 parts by mass of compound (I). [7] The organic material composition according to [6], which contains the processing stabilizer according to any one of [1] to [5] as the compound (I), the compound (II), and the amine compound (A). [8] The organic material composition according to [6] or [7], wherein the organic material is a thermoplastic resin. [9] The organic material composition according to [8], wherein the thermoplastic resin is a polyolefin or an engineering plastic.

[10] The organic material comprises a compound of formula (I): [ka] [In formula (I), 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 is a single bond, a sulfur atom, or -CH(-R 6 )-group(R 6 represents a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, or a cycloalkyl group having 5 to 8 carbon atoms), A is an alkylene group having 1 to 8 carbon atoms or *-C(=O)-R 7 -group(R 7 represents a single bond or an alkylene group having 1 to 8 carbon atoms, and * represents a bond 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. and a compound (I) represented by formula (II): [ka] [In formula (II), R 1 and R 2 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 is a single bond, a sulfur atom, or -CH(-R 6 )-group(R 6 represents a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, or a cycloalkyl group having 5 to 8 carbon atoms). and an amine compound (A) having a hydroxyalkyl group are added in amounts such that the content of compound (II) is 0.005 to 4 parts by mass and the content of amine compound (A) is 0.01 to 15 parts by mass relative to 100 parts by mass of compound (I), or A method for stabilizing an organic material, comprising adding the processing stabilizer according to any one of [1] to [5] to the organic material.

[11] The stabilization method according to

[10] , wherein the organic material is a thermoplastic resin.

[12] The stabilization method according to

[11] , wherein the thermoplastic resin is a polyolefin or an engineering plastic. [Effects of the Invention]

[0008] According to the present invention, it is possible to provide a processing stabilizer that is effective in improving the thermal stability when processing organic materials and that is resistant to discoloration due to oxidizing gases, particularly NOx gases. Furthermore, the organic material composition of the present invention has high thermal stability and is resistant to discoloration due to oxidizing gases, particularly NOx gases. DETAILED DESCRIPTION OF THE INVENTION

[0009] Hereinafter, embodiments of the present invention will be described in detail. Note that the scope of the present invention is not limited to the embodiments described herein, and various modifications can be made without departing from the spirit of the present invention. Furthermore, when multiple upper and lower limit values ​​are described for a specific feature, any of these upper and lower limit values ​​can be combined to form a suitable numerical range.

[0010] [Processing stabilizer] The processing stabilizer of the present invention has the formula (I): [ka] [In formula (I), 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 is a single bond, a sulfur atom, or -CH(-R 6 )-group(R 6 represents a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, or a cycloalkyl group having 5 to 8 carbon atoms), A is an alkylene group having 1 to 8 carbon atoms or *-C(=O)-R 7 -group(R 7 represents a single bond or an alkylene group having 1 to 8 carbon atoms, and * represents a bond 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. and a compound (I) represented by formula (II): [ka] [In formula (II), R 1 and R 2 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 is a single bond, a sulfur atom, or -CH(-R 6 )-group(R 6 represents a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, or a cycloalkyl group having 5 to 8 carbon atoms). and an amine compound (A) having a hydroxyalkyl group, This is a processing stabilizer in which the content of compound (II) is 0.005 to 4 parts by mass and the content of amine compound (A) is 0.01 to 15 parts by mass relative to 100 parts by mass of compound (I).

[0011] The processing stabilizer of the present invention, which contains specific amounts of compound (II) and amine compound (A) in addition to compound (I), is effective in improving thermal stability during processing of organic materials and is less susceptible to discoloration due to oxidizing gases. While the reason for this is unclear, it is believed that the use of specific amounts of compound (I), compound (II), and amine compound (A) in combination inhibits the conversion of compound (I) and compound (II) to colored substances, particularly due to oxidizing gases. It is believed that when phenolic compounds discolor due to oxidizing gases, the phenolic compounds are converted to quinones. Surprisingly, this conversion to quinones can be prevented by using specific amounts of compound (I), compound (II), and amine compound (A). It should be noted that the present invention is in no way limited to the above mechanism.

[0012] (Compound I) The processing stabilizer of the present invention contains at least one compound (I) represented by the above formula (I). R in formula (I) 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.

[0013] Examples of alkyl groups having 1 to 8 carbon atoms include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, a t-butyl group, an n-pentyl group, a t-pentyl group, a 2-methylbutyl group, a 3-methylbutyl group, a 2-ethylpropyl group, an n-hexyl group, an n-heptyl group, an isoheptyl group, an n-octyl group, an isooctyl group, and a 2-ethylhexyl group.

[0014] Examples of the cycloalkyl group having 5 to 8 carbon atoms include a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, and a cyclooctyl group.

[0015] Examples of the alkylcycloalkyl group having 6 to 12 carbon atoms include a 1-methylcyclopentyl group, a 1-methylcyclohexyl group, and a 1-methyl-4-i-propylcyclohexyl group.

[0016] 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.

[0017] R 1 , R 2 and R 4 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. R 1 and R 4 is more preferably a t-alkyl group such as a t-butyl group, a t-pentyl group, or a t-octyl group, a cyclohexyl group, or a 1-methylcyclohexyl group. R 2 is more preferably an alkyl group having 1 to 5 carbon atoms such as a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, an i-butyl group, a sec-butyl group, a t-butyl group, or a t-pentyl group, and even more preferably a methyl group, a t-butyl group, or a t-pentyl group.

[0018] R 5 is preferably a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, or a cycloalkyl group having 5 to 8 carbon atoms, and more preferably a hydrogen atom, or an alkyl group having 1 to 5 carbon atoms such as a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, an i-butyl group, a sec-butyl group, a t-butyl group, or a t-pentyl group.

[0019] R in formula (I) 3 R 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 as those mentioned above. 3 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.

[0020] X in formula (I) is a single bond, a sulfur atom, or -CH(-R 6 )-group(R 6 represents a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, or a cycloalkyl group having 5 to 8 carbon atoms. 6 Examples of the alkyl group having 1 to 8 carbon atoms and the cycloalkyl group having 5 to 8 carbon atoms represented by the formula (I) include the same as those described above. X is preferably a methylene group substituted with an alkyl group having 1 to 4 carbon atoms such as a methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, i-butyl group, or t-butyl group, or a single bond, and more preferably a single bond.

[0021] In formula (I), A is an alkylene group having 1 to 8 carbon atoms or *-C(=O)-R 7 -group(R 7 represents a single bond or an alkylene group having 1 to 8 carbon atoms, and * represents a bond on the oxygen side. Examples of alkylene groups having 1 to 8 carbon atoms include methylene, ethylene, propylene, butylene, pentamethylene, hexamethylene, octamethylene, and 2,2-dimethyl-1,3-propylene. A is preferably a propylene group. *-C(=O)-R 7 The * in the - group indicates that the carbonyl group is bonded to the oxygen atom of the phosphite group. 7 is preferably a single bond or an ethylene group.

[0022] In formula (I), 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. Examples of the alkyl group having 1 to 8 carbon atoms include the same as those described 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. Preferably, 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 more preferably, Y is a hydroxyl group, and Z is a hydrogen atom or an alkyl group having 1 to 8 carbon atoms.

[0023] The processing stabilizer of the present invention may contain one type of compound (I) represented by the above formula (I), or may contain two or more types of compounds (I) represented by formula (I).

[0024] Specific examples of compound (I) include 2,4,8,10-tetra-t-butyl-6-[3-(3-methyl-4-hydroxy-5-t-butylphenyl)propoxy]dibenzo[d,f][1,3,2]dioxaphosphepine, 6-[3-(3,5-di-t-butyl-4-hydroxyphenyl)propoxy]-2,4,8,10-tetra-t-butyldibenzo[d,f][1,3,2]dioxaphosphepine, 6-[ Examples of suitable compounds include 3-(3,5-di-t-butyl-4-hydroxyphenyl)propoxy]-4,8-di-t-butyl-2,10-dimethyl-12H-dibenzo[d,g][1,3,2]dioxaphosphocin, 6-[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionyloxy]-4,8-di-t-butyl-2,10-dimethyl-12H-dibenzo[d,g][1,3,2]dioxaphosphocin, etc. Compound (I) is preferably 2,4,8,10-tetra-t-butyl-6-[3-(3-methyl-4-hydroxy-5-t-butylphenyl)propoxy]dibenzo[d,f][1,3,2]dioxaphosphepine. Compound (I) may also be a commercially available product, such as Sumilizer (registered trademark) GP (manufactured by Sumitomo Chemical Co., Ltd.).

[0025] (Compound II) The processing stabilizer of the present invention contains at least one compound (II) represented by the above formula (II).

[0026] In formula (II), R 1 and R 2 Regarding the formula (I), R 1 and R 2 The same applies to R in formula (II). 3 Regarding the formula (I), R 3The same applies to X in formula (II). The same applies to X in formula (I).

[0027] Compound (II) includes 6-oxo-2,4,8,10-tetra-t-butyl-dibenzo[d,f][1,3,2]dioxaphosphepine, 6-oxo-4,8-di-t-butyl-2,10-dimethyl-dibenzo[d,g][1,3,2]dioxaphosphepine, 6-oxo-2,4,8,10-tetra-t-butyl-dibenzo[d,f][1,3,2]dioxaphosphocin, 6-oxo-2,4,8,10-tetra-t-butyl-dibenzo[d,f][1,3,2]dioxaphosphepine, Examples of such compounds include 4,8-di-t-butyl-2,10-dimethyl-dibenzo[d,g][1,3,2]dioxaphosphocin, 6-oxo-4,8-di-t-butyl-2,10-dimethyl-12H-dibenzo[d,g][1,3,2]dioxaphosphepine, and 6-oxo-4,8-di-t-butyl-2,10-dimethyl-12H-dibenzo[d,g][1,3,2]dioxaphosphocin. Compound (II) is preferably 6-oxo-2,4,8,10-tetra-t-butyl-dibenzo[d,f][1,3,2]dioxaphosphepine.

[0028] Compound (II) can be produced, for example, according to the description in US Pat. No. 5,475,042 (Examples 1 and 2).

[0029] In the processing stabilizer of the present invention, the content of compound (II) is 0.005 to 4 parts by mass per 100 parts by mass of compound (I). If the content of compound (II) is less than 0.005 parts by mass, the thermal stability during processing of organic materials cannot be sufficiently improved, and discoloration due to oxidizing gases cannot be sufficiently prevented. Furthermore, if the content of compound (II) exceeds 4 parts by mass, discoloration due to oxidizing gases cannot be sufficiently prevented. The content of compound (II) per 100 parts by mass of compound (I) is preferably 0.01 parts by mass or more, more preferably 0.03 parts by mass or more, and even more preferably 0.05 parts by mass or more, from the viewpoints of easily improving the thermal stability during processing of organic materials and easily enhancing the effect of preventing discoloration due to oxidizing gases. Furthermore, the content is preferably 3 parts by mass or less, more preferably 2 parts by mass or less, and even more preferably 1.5 parts by mass or less, from the viewpoints of easily improving the thermal stability during processing of organic materials and easily preventing discoloration due to oxidizing gases.

[0030] The content of compound (II) in the processing stabilizer of the present invention relative to 100 parts by mass of compound (I) may be calculated using an analytical device such as liquid chromatography, or may be calculated from the charge ratio when preparing the processing stabilizer or organic material composition. When the content of compound (II) is measured using liquid chromatography, it is preferable to perform the measurement under the following measurement conditions. <Measurement conditions> Column: Sumipax ODS A-212 (6 mmφ × 150 mm, packing diameter: 5 μm) Column temperature: 40℃ Mobile phase: (Solution A) 0.1% by mass ammonium acetate / water (Solution B) 0.1% by mass ammonium acetate / methanol Mobile phase gradient: 0 → 20 min (A solution: 20 → 0 mass% (1 mass % / min), B solution: 80 → 100 mass % (1 mass % / min)), 20 → 45 min (A solution: 0 mass %, B solution: 100 mass %) Flow rate: 1.0mL / min Detection method: UV (280 nm) Sample concentration: 5 mg / mL Injection volume: 10μL

[0031] (Amine compound (A)) The processing stabilizer of the present invention contains at least one amine compound having a hydroxyalkyl group. The amine compound having a hydroxyalkyl group is also referred to as amine compound (A) in this specification. As amine compound (A), one type of amine compound having a hydroxyalkyl group may be used, or two or more types of amine compounds may be used. In this specification, amine compound (A) is a compound having at least one nitrogen atom and at least one linear or branched alkyl group having at least one hydroxyl group, and may be a monoamine compound, diamine compound, triamine compound, or tetraamine compound. Preferably, it is a monoamine compound or diamine compound, and more preferably a monoamine compound. The amine compound (A) is preferably (A1) a compound in which one or two of three hydrogen atoms of ammonia are substituted with hydroxyalkyl groups, and the remaining hydrogen atoms are unsubstituted or substituted with a substituent such as an aliphatic group or aromatic group; (A2) a compound in which all three hydrogen atoms of ammonia are substituted with hydroxyalkyl groups; (A3) a compound in which two nitrogen atoms are linked by an alkylene group (preferably an alkylene group having 1 to 4 carbon atoms), and one, two, or three of the four hydrogen atoms bonded to the nitrogen atoms are substituted with hydroxyalkyl groups, and the remaining hydrogen atoms are unsubstituted or substituted with a substituent such as an aliphatic group or aromatic group; or (A4) a compound in which two nitrogen atoms are linked by an alkylene group (preferably an alkylene group having 1 to 4 carbon atoms), and all four hydrogen atoms bonded to the nitrogen atoms are substituted with hydroxyalkyl groups. More preferably, the amine compound (A) is an alkanolamine. Alkanolamines are saturated aliphatic amines having a hydroxyl group in the molecule. The amine compound (A) may be a primary amine compound, a secondary amine, or a tertiary amine, but is preferably a tertiary amine compound.

[0032] In one preferred embodiment of the present invention, the amine compound (A) is preferably an alkanolamine, more preferably an amine compound represented by formula (III): [ka] [In formula (III), Y 1 , Y 2 and Y 3 each independently represents a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, or an alkyl group having 1 to 8 carbon atoms and at least one hydroxyl group, provided that Y 1 ~Y 3 at least one of which represents an alkyl group having 1 to 8 carbon atoms and at least one hydroxyl group. or formula (IV): [ka] [In formula (IV), Y 4 , Y 5 , Y 6 and Y 7 each independently represents a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, or an alkyl group having 1 to 8 carbon atoms and at least one hydroxyl group, provided that Y 4 ~Y 7 at least one of represents an alkyl group having 1 to 8 carbon atoms and having at least one hydroxyl group, and B represents an alkylene group having 1 to 4 carbon atoms. The alkanolamines represented by formula (III) or (IV) easily interact with compound (I) and compound (II), and are therefore thought to be able to easily prevent, for example, compound (I) from being converted to a quinone form by an oxidizing gas, and therefore to easily prevent discoloration due to the oxidizing gas.

[0033] Examples of the alkyl group having 1 to 8 carbon atoms include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, a t-butyl group, an n-pentyl group, a t-pentyl group, a 2-methylbutyl group, a 3-methylbutyl group, a 2-ethylpropyl group, an n-hexyl group, an n-heptyl group, an isoheptyl group, an n-octyl group, an isooctyl group, and a 2-ethylhexyl group. The number of carbon atoms in the alkyl group is preferably 1 to 6, and more preferably 1 to 4.

[0034] Examples of the alkyl group having 1 to 8 carbon atoms and at least one hydroxyl group include the alkyl groups exemplified above in which at least one hydrogen atom has been substituted with a hydroxyl group. Specific examples include a hydroxymethyl group, a hydroxyethyl group, a hydroxypropyl group, and a hydroxybutyl group. The number of hydroxyl groups in the alkyl group having 1 to 8 carbon atoms and at least one hydroxyl group is preferably 1 to 3, more preferably 1 or 2, and even more preferably 1.

[0035] Examples of alkylene groups having 1 to 4 carbon atoms include methylene, ethylene, n-propylene, isopropylene, n-butylene, and isobutylene. The alkylene group having 1 to 4 carbon atoms is preferably a linear alkylene group having 1 to 4 carbon atoms, more preferably a methylene, ethylene, or n-propylene group, even more preferably a methylene or ethylene group, and even more preferably an ethylene group. The number of carbon atoms in the alkylene group is preferably 1 to 3, more preferably 1 or 2, and even more preferably 2.

[0036] Specific examples of the compound represented by formula (III) include monoethanolamine, diethanolamine, triethanolamine, monoisopropanolamine, diisopropanolamine, triisopropanolamine, tributanolamine, tripentanolamine, methylethanolamine, methylisopropanolamine, methyldiethanolamine, methyldiisopropanolamine, diethanolisopropanolamine, diisopropanolethanolamine, and tris(2-hydroxybutyl)amine.

[0037] Specific examples of the compound represented by formula (IV) include tetrahydroxyethylethylenediamine and N,N,N',N'-tetrakis(2-hydroxypropyl)ethylenediamine.

[0038] Y in formula (III) 1 , Y 2 and Y 3 and Y in formula (IV) 4 , Y 5 , Y 6 and Y 7 are preferably each independently —CH—CH(OH)—R 6 [In the formula, R 6 represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms.

[0039] In the processing stabilizer of the present invention, the content of the amine compound (A) is 0.01 to 15 parts by mass per 100 parts by mass of the compound (I). If the content of the amine compound (A) is less than 0.01 part by mass, discoloration due to oxidizing gases cannot be sufficiently prevented. Furthermore, if the content of the compound (II) is more than 15 parts by mass, discoloration due to oxidizing gases cannot be sufficiently prevented. From the viewpoint of easily preventing discoloration due to oxidizing gases, the content of the amine compound (A) per 100 parts by mass of the compound (I) is preferably 0.05 parts by mass or more, more preferably 0.1 parts by mass or more, and even more preferably 0.5 parts by mass or more. From the same viewpoint, the content is preferably 12 parts by mass or less, more preferably 10 parts by mass or less, and even more preferably 7 parts by mass or less. From the viewpoint of further enhancing the effect of preventing discoloration due to oxidizing gases, the content may be, for example, 4% by mass or less, 3% by mass or less, or 2% by mass or less.

[0040] The content of the amine compound (A) in the processing stabilizer of the present invention relative to 100 parts by mass of the compound (I) may be calculated using an analytical device such as liquid chromatography, or may be calculated from the charging ratio when preparing the processing stabilizer or the organic material composition.

[0041] The processing stabilizer of the present invention, which contains compound (I) and specific amounts of compound (II) and amine compound (A), can be added to an organic material such as a thermoplastic resin to reduce thermal and oxidative degradation of the organic material and stabilize the organic material, thereby preventing, for example, viscosity loss and discoloration. Furthermore, the processing stabilizer of the present invention can prevent discoloration due to oxidizing gases. The processing stabilizer may be a material containing only compound (I) represented by formula (I), compound (II) represented by formula (II), and amine compound (A) in the above-mentioned proportions, or it may be a material containing, in addition to compound (I), compound (II), and amine compound (A), at least one other additive that can be contained in the organic material composition described below. The processing stabilizer of the present invention may also be a material containing at least one organic material in addition to compound (I), compound (II), and amine compound (A). Such a material is also referred to as a masterbatch.

[0042] [Organic material composition and method for stabilizing organic material] By adding the processing stabilizer of the present invention to an organic material, or by adding the compound (I) represented by formula (I), the compound (II) represented by formula (II), and the amine compound (A) in a specific ratio, thermal degradation and oxidative degradation of the organic material can be reduced, and the organic material can be stabilized, for example, preventing a decrease in viscosity, preventing coloration, and further preventing discoloration due to oxidizing gases. Therefore, the processing stabilizer of the present invention is suitable as a stabilizer for organic materials. The present invention also provides a method for stabilizing an organic material by adding the above-mentioned processing stabilizer, and a method for stabilizing an organic material by adding a compound (I) represented by formula (I), a compound (II) represented by formula (II), and an amine compound (A) in a specific ratio. Furthermore, the present invention also provides a stabilized organic material composition containing an organic material and the processing stabilizer of the present invention, or a compound (I) represented by formula (I), a compound (II) represented by formula (II), and an amine compound (A) in a specific ratio.

[0043] Examples of organic materials that can be stabilized by the processing stabilizer of the present invention include, but are not limited to, the following organic materials: The organic material may be one type of organic material or a mixture of two or more types of organic materials.

[0044] (1) Polyethylene, such as high density polyethylene (HD-PE), low density polyethylene (LD-PE), linear low density polyethylene (LLDPE), (2) Polypropylene, (3) methylpentene polymers, (4) EEA (ethylene / ethyl acrylate copolymer) resin, (5) ethylene / vinyl acetate copolymer resin, (6) Polystyrenes, such as polystyrene, poly(p-methylstyrene), poly(α-methylstyrene), (7) AS (acrylonitrile / styrene copolymer) resin, (8) ABS (acrylonitrile / butadiene / styrene copolymer) resin, (9) AAS (special acrylic rubber / acrylonitrile / styrene copolymer) resin, (10) ACS (acrylonitrile / chlorinated polyethylene / styrene copolymer) resin,

[0045] (11) Chlorinated polyethylene, polychloroprene, chlorinated rubber, (12) Polyvinyl chloride, polyvinylidene chloride, (13) methacrylic resin, (14) ethylene / vinyl alcohol copolymer resin, (15) Fluorine resin, (16) Polyacetal, (17) Grafted polyphenylene ether resins and polyphenylene sulfide resins, (18) polyurethane, (19) polyamide, (20) Polyester resins, such as polyethylene terephthalate and polybutylene terephthalate;

[0046] (21) polycarbonate, (22) polyacrylate, (23) Polysulfone, polyetheretherketone, polyethersulfone, (24) Thermoplastic resins such as aromatic polyester resins, (25) epoxy resin, (26) Diallyl phthalate prepolymer, (27) silicone resin, (28) unsaturated polyester resin, (29) Acrylic-modified benzoguanamine resin, (30) benzoguanamine / melamine resin, (31) Thermosetting resins such as urea resins,

[0047] (32) polybutadiene, (33) 1,2-polybutadiene, (34) polyisoprene, (35) styrene / butadiene copolymer, (36) butadiene / acrylonitrile copolymer, (37) ethylene / propylene copolymer, (38) silicone rubber, (39) epichlorohydrin rubber, (40) acrylic rubber, (41) natural rubber,

[0048] (42) Chlorinated rubber paints, (43) Polyester resin paint, (44) urethane resin paint, (45) Epoxy resin paint, (46) Acrylic resin paint, (47) Vinyl resin paint, (48) Amino alkyd resin paint, (49) Alkyd resin paint, (50) Nitrocellulose resin paint, (51) Oil paint, (52) wax, (53) Lubricants, etc.

[0049] Among these, thermoplastic resins, particularly polyolefins such as polyethylene, for example, HD-PE, LD-PE, LLDPE and polypropylene, polyamides, engineering plastics such as polyethylene terephthalate, polybutylene terephthalate and polycarbonate are preferably used.

[0050] The polyolefin is not particularly limited and may be, for example, one obtained by radical polymerization or one produced by polymerization using a catalyst containing a metal of Group IVb, Vb, VIb, or VIII of the periodic table. Examples of such metal-containing catalysts include metal complexes having one or more ligands, such as oxides, halides, alcoholates, esters, and aryls, coordinated by π or σ bonds. These complexes may be in the form of metal complexes themselves or may be supported on substrates such as magnesium chloride, titanium chloride, alumina, and silicon oxide. Preferred polyolefins are those produced using, for example, Ziegler-Natta catalysts, TNZ catalysts, metallocene catalysts, and Phillips catalysts.

[0051] Engineering plastics are not particularly limited. Polyamide resins may be any resins that have amide bonds in the polymer chain and can be melted by heating. Polyamide resins may be produced by any method, including condensation reactions between diamines and dicarboxylic acids, condensation reactions between aminocarboxylic acids, and ring-opening polymerization of lactams. Examples of polyamide resins include nylon 66, nylon 69, nylon 610, nylon 612, poly-bis-(p-aminocyclohexyl)methandodecamide, nylon 46, nylon 6, nylon 12, and copolymers such as nylon 66 / 6 and nylon 6 / 12, which are copolymers of nylon 66 and nylon 6. Polyester resins may be any resins that have ester bonds in the polymer chain and can be melted by heating, including polyesters obtained by polycondensation of dicarboxylic acids and dihydroxy compounds. Polyester resins may be either homopolyesters or copolyesters. The polycarbonate resin may be any resin having a carbonate bond in the polymer chain and capable of being melted by heating, such as a polycarbonate obtained by reacting an aromatic hydroxy compound or a small amount of a polyhydroxy compound with a carbonate precursor such as phosgene or diphenyl carbonate in the presence of a solvent, an acid acceptor, and a molecular weight modifier. The polycarbonate resin may be linear or branched, or may be a copolymer.

[0052] Adding a compound (I) represented by formula (I), a compound (II) represented by formula (II), and an amine compound (A) to an organic material can stabilize the organic material and prevent discoloration of the organic material due to oxidizing gases. In this case, the compound (I), the compound (II), and the amine compound (A) are added to the organic material in amounts such that the content of compound (II) is 0.005 to 4 parts by mass per 100 parts by mass of compound (I), and the content of amine compound (A) is 0.01 to 15 parts by mass per 100 parts by mass of compound (I). The content of compound (II) per 100 parts by mass of compound (I) is preferably 0.01 parts by mass or more, more preferably 0.03 parts by mass or more, and even more preferably 0.05 parts by mass or more, from the viewpoints of ease of measurement during use, of facilitating the synergistic stabilization of the organic material composition by the combined use of compound (I) and compound (II), and of facilitating the prevention of discoloration due to oxidizing gases. From the viewpoints of efficient stabilization of the organic material composition and of facilitating the prevention of discoloration due to oxidizing gases, the content of compound (II) per 100 parts by mass is preferably 3 parts by mass or less, more preferably 2 parts by mass or less, and even more preferably 1.5 parts by mass or less. The content of amine compound (A) per 100 parts by mass of compound (I) is preferably 0.05 parts by mass or more, more preferably 0.1 parts by mass or more, and even more preferably 0.5 parts by mass or more, from the viewpoints of facilitating the prevention of discoloration due to oxidizing gases. From the viewpoints of facilitating the prevention of discoloration due to oxidizing gases, the content is preferably 12 parts by mass or less, more preferably 10 parts by mass or less, and even more preferably 7 parts by mass or less. From the viewpoint of further enhancing the effect of preventing discoloration due to oxidizing gases, the content may be, for example, 4% by mass or less, 3% by mass or less, or 2% by mass or less.

[0053] Compound (I) represented by formula (I) or compound (II) represented by formula (II) may be added to an organic material by adding the processing stabilizer of the present invention. In either case, compound (I) and compound (II) are contained in the organic material in a specific quantitative ratio.

[0054] When a processing stabilizer or a compound (I) represented by formula (I), a compound (II) represented by formula (II), and an amine compound (A) are added to an organic material to stabilize the organic material, the total weight of compounds (I), (II), and (A) is preferably 0.005 parts by weight or more, more preferably 0.01 parts by weight or more, and even more preferably 0.05 parts by weight or more, per 100 parts by weight of the organic material, from the viewpoint of stabilizing the organic material. Furthermore, the total weight of compounds (I), (II), and (A) is usually 5 parts by weight or less, preferably 3 parts by weight or less, and more preferably 1 part by weight or less, per 100 parts by weight of the organic material, from the viewpoint of efficient stabilization of the organic material and economical considerations.

[0055] When the compound (I) represented by formula (I), the compound (II) represented by formula (II), and the amine compound (A) are added to an organic material, other additives may be added to the organic material as needed, such as a phenolic antioxidant, a sulfur-based antioxidant, a phosphorus-based antioxidant, an antiaging agent, an ultraviolet absorber, a light stabilizer, a peroxide scavenger, a polyamide stabilizer, a hydroxyamine, a lubricant, a plasticizer, a flame retardant, a nucleating agent, a metal deactivator, an antistatic agent, a pigment, a filler, a pigment, an antiblocking agent, a surfactant, a processing aid, a foaming agent, an emulsifier, a gloss agent, calcium stearate, etc. Neutralizing agents such as sodium or hydrotalcite, color improvers such as 9,10-dihydro-9-oxa-10-phosphophenanthrene-10-oxide, and co-stabilizers such as benzofurans and indolines described in U.S. Patent Nos. 4,325,853, 4,338,244, 5,175,312, 5,216,053, 5,252,643, and 4,316,611, DE-A-4,316,622 and 4,316,876, EP-A-589,839, and EP-A-591,102 can also be added. These additives can be added to the organic material simultaneously with compounds (I) and (II) and amine compound (A) contained in the organic material composition of the present invention, or can be added to the organic material at a stage separate from that of compounds (I) and (II) and amine compound (A) contained in the organic material composition 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.

[0056] Examples of phenolic antioxidants include the following: As the phenolic antioxidant, the following compounds may be used alone or in combination of two or more. (1) Examples of alkylated monophenols 2,6-di-t-butyl-4-methylphenol, 2,4,6-tri-t-butylphenol, 2,6-di-t-butylphenol, 2-t-butyl-4,6-dimethylphenol, 2,6-di-t-butyl-4-ethylphenol, 2,6-di-t-butyl-4-n-butylphenol, 2,6-di-t-butyl-4-isobutylphenol, 2,6-dicyclopentyl-4-methylphenol, 2-(α-methylcyclohexyl)-4,6-dimethylphenol, 2 ,6-dioctadecyl-4-methylphenol, 2,4,6-tricyclohexylphenol, 2,6-di-t-butyl-4-methoxymethylphenol, 2,6-di-nonyl-4-methylphenol, 2,4-dimethyl-6-(1'-methylundecyl-1'-yl)phenol, 2,4-dimethyl-6-(1'-methylheptadecyl-1'-yl)phenol, 2,4-dimethyl-6-(1'-methyltridecyl-1'-yl)phenol and mixtures thereof.

[0057] (2) Examples of alkylthiomethylphenols 2,4-dioctylthiomethyl-6-t-butylphenol, 2,4-dioctylthiomethyl-6-methylphenol, 2,4-dioctylthiomethyl-6-ethylphenol, 2,6-didodecylthiomethyl-4-nonylphenol, and mixtures thereof. (3) Examples of hydroquinone and alkylated hydroquinone 2,6-di-t-butyl-4-methoxyphenol, 2,5-di-t-butylhydroquinone, 2,5-di-t-amylhydroquinone, 2,6-diphenyl-4-octadecyloxyphenol, 2,6-di-t-butylhydroquinone, 2,5-di-t-butyl-4-hydroxyanisole, 3,5-di-t-butyl-4-hydroxyphenyl stearate, bis(3,5-di-t-butyl-4-hydroxyphenyl)adipate, and mixtures thereof.

[0058] (4) Examples of tocopherols α-tocopherol, β-tocopherol, γ-tocopherol, δ-tocopherol, and mixtures thereof. (5) Examples of hydroxylated thiodiphenyl ethers 2,2'-thiobis(6-t-butylphenol), 2,2'-thiobis(4-methyl-6-t-butylphenol), 2,2'-thiobis(4-octylphenol), 4,4'-thiobis(3-methyl-6-t-butylphenol), 4,4'-thiobis(2-methyl-6-t-butylphenol), 4,4'-thiobis(3,6-di-t-amylphenol), 4,4'-(2,6-dimethyl-4-hydroxyphenyl) disulfide, etc.

[0059] (6) Examples of alkylidene bisphenols and their derivatives 2,2'-methylenebis(4-methyl-6-t-butylphenol), 2,2'-methylenebis(4-ethyl-6-t-butylphenol), 2,2'-methylenebis[4-methyl-6-(α-methylcyclohexyl)phenol)], 2,2'-methylenebis(4-methyl-6-cyclohexylphenol), 2,2'-methylenebis(4-methyl-6-nonylphenol), 2,2'-methylenebis(4,6-di-t-butylphenol), 2,2'-ethylidenebis(4,6-di-t-butylphenol), 2,2'-ethylidenebis(4-isobutyl-6-t-butylphenol), 2,2'-methylenebis[6-(α-methylbenzyl)-4-nonylphenol], 2,2'-methylenebis[4,6-(α,α- dimethylbenzyl)-4-nonylphenol], 4,4'-methylenebis(6-t-butyl-2-methylphenol), 4,4'-methylenebis(2,6-di-t-butylphenol), 4,4'-butylidenebis(3-methyl-6-t-butylphenol), 1,1-bis(4-hydroxyphenyl)cyclohexane, 1,1-bis(5-t-butyl-4-hydroxy-2-methylphenyl)butane, 2,6-bis(3-t-butyl-5-methyl-2-hydroxybenzyl)-4-methylphenol, 1,1,3-tris(5-t-butyl-4-hydroxy-2-methylphenyl)butane, 1,1-bis(5-t-butyl-4-hydroxy-2-methylphenyl)-3-n-dodecylmercaptobutane, ethylene glycol Bis[3,3-bis-3'-t-butyl-4'-hydroxyphenyl)butyrate], bis(3-t-butyl-4-hydroxy-5-methylphenyl)dicyclopentadiene, bis[2-(3'-t-butyl-2'-hydroxy-5'-methylbenzyl)-6-t-butyl-4-methylphenyl]terephthalate, 1,1-bis(3,5-dimethyl-2-hydroxyphenyl)butane, 2,2-bis(3,5-di-t-butyl-4-hydroxyphenyl)propane, 2,2-bis(5-t-butyl-4-hydroxy-2-methylphenyl)-4-n-dodecylmercaptobutane, 1,1,5,5-tetra(5-t-butyl-4-hydroxy-2-methylphenyl)pentane, 2-t-butyl-6-(3'-t-butyl-5'-methyl-2'-hydroxybenzyl)-4-methylphenyl acrylate, 2,4-di-t-pentyl-6-[1-(2-hydroxy-3,5-di-t-pentylphenyl)ethyl]phenyl acrylate, and mixtures thereof.

[0060] (7) Examples of O-, N- and S-benzyl derivatives 3,5,3',5'-tetra-t-butyl-4,4'-dihydroxydibenzyl ether, octadecyl-4-hydroxy-3,5-dimethylbenzyl mercaptoacetate, tris(3,5-di-t-butyl-4-hydroxybenzyl)amine, bis(4-t-butyl-3-hydroxy-2,6-dimethylbenzyl)dithioterephthalate, bis(3,5-di-t-butyl-4-hydroxybenzyl)sulfide, isooctyl-3,5-di-t-butyl-4-hydroxybenzyl mercaptoacetate, and mixtures thereof. (8) Examples of hydroxybenzylated malonate derivatives Dioctadecyl-2,2-bis(3,5-di-t-butyl-2-hydroxybenzyl)malonate, dioctadecyl-2-(3-t-butyl-4-hydroxy-5-methylbenzyl)malonate, didodecylmercaptoethyl-2,2-bis(3,5-di-t-butyl-4-hydroxybenzyl)malonate, bis[4-(1,1,3,3-tetramethylbutyl)phenyl]-2,2-bis(3,5-di-t-butyl-4-hydroxybenzyl)malonate, and mixtures thereof. (9) Examples of aromatic hydroxybenzyl derivatives 1,3,5-trimethyl-2,4,6-tris(3,5-di-t-butyl-4-hydroxybenzyl)benzene, 1,4-bis(3,5-di-t-butyl-4-hydroxybenzyl)-2,3,5,6-tetramethylbenzene, 2,4,6-tris(3,5-t-butyl-4-hydroxybenzyl)phenol, and mixtures thereof.

[0061] (10) Examples of triazine derivatives 2,4-bis(n-octylthio)-6-(4-hydroxy-3,5-di-t-butylanilino)-1,3,5-triazine, 2-n-octylthio-4,6-bis(4-hydroxy-3,5-di-t-butylanilino)-1,3,5-triazine, 2-n-octylthio-4,6-bis(4-hydroxy-3,5-di-t-butylphenoxy)-1,3,5-triazine, 2,4,6-tris(3,5-di-t-butyl-4-phenoxy)-1,3,5-triazine, tris(4-t-butyl-3-hydroxy-2,6-dimethylbenzyl)iso cyanurate, tris(3,5-di-t-butyl-4-hydroxybenzyl)isocyanurate, 2,4,6-tris(3,5-di-t-butyl-4-hydroxyphenylethyl)-1,3,5-triazine, 2,4,6-tris(3,5-di-t-butyl-4-hydroxyphenylpropyl)-1,3,5-triazine, tris(3,5-dicyclohexyl-4-hydroxybenzyl)isocyanurate, tris[2-(3',5'-di-t-butyl-4'-hydroxycinnamoyloxy)ethyl]isocyanurate, and mixtures thereof.

[0062] (11) Examples of benzylphosphonate derivatives Dimethyl-3,5-di-t-butyl-4-hydroxybenzylphosphonate, diethyl-3,5-di-t-butyl-4-hydroxybenzylphosphonate, dioctadecyl-3,5-di-t-butyl-4-hydroxybenzylphosphonate, dioctadecyl-5-t-butyl-4-hydroxy-3-methylbenzylphosphonate, calcium salt of 3,5-di-t-butyl-4-hydroxybenzylphosphonic acid monoester, and mixtures thereof. (12) Examples of acylaminophenol derivatives 4-hydroxylauric acid anilide, 4-hydroxystearic acid anilide, octyl-N-(3,5-di-t-butyl-4-hydroxyphenyl)carbamate, and mixtures thereof. (13) Examples of esters of β-(3,5-di-t-butyl-4-hydroxyphenyl)propionic acid with the following monohydric or polyhydric alcohols Methanol, ethanol, octanol, octadecanol, ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,6-hexanediol, 1,9-nonanediol, neopentyl glycol, diethylene glycol, thioethylene glycol, spiroglycol, triethylene glycol, pentaerythritol, tris(hydroxyethyl)isocyanurate, N,N'-bis(hydroxyethyl)oxamide, 3-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol, trimethylolpropane, 4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo[2,2,2]octane, and mixtures thereof.

[0063] (14) Examples of esters of β-(5-t-butyl-4-hydroxy-3-methylphenyl)propionic acid with the following monohydric or polyhydric alcohols Methanol, ethanol, octanol, octadecanol, ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,6-hexanediol, 1,9-nonanediol, neopentyl glycol, diethylene glycol, thioethylene glycol, spiroglycol, triethylene glycol, pentaerythritol, tris(hydroxyethyl)isocyanurate, N,N'-bis(hydroxyethyl)oxamide, 3-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol, trimethylolpropane, 4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo[2,2,2]octane, and mixtures thereof. (15) Examples of esters of β-(3,5-dicyclohexyl-4-hydroxyphenyl)propionic acid with the following monohydric or polyhydric alcohols Methanol, ethanol, octanol, octadecanol, ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,6-hexanediol, 1,9-nonanediol, neopentyl glycol, diethylene glycol, thioethylene glycol, spiroglycol, triethylene glycol, pentaerythritol, tris(hydroxyethyl)isocyanurate, N,N'-bis(hydroxyethyl)oxamide, 3-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol, trimethylolpropane, 4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo[2,2,2]octane, and mixtures thereof.

[0064] (16) Examples of esters of 3,5-di-t-butyl-4-hydroxyphenylacetic acid with the following monohydric or polyhydric alcohols Methanol, ethanol, octanol, octadecanol, ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,6-hexanediol, 1,9-nonanediol, neopentyl glycol, diethylene glycol, thioethylene glycol, spiroglycol, triethylene glycol, pentaerythritol, tris(hydroxyethyl)isocyanurate, N,N'-bis(hydroxyethyl)oxamide, 3-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol, trimethylolpropane, 4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo[2,2,2]octane, and mixtures thereof. (17) Examples of amides of β-(3,5-di-t-butyl-4-hydroxyphenyl)propionic acid N,N'-bis[3-(3',5'-di-t-butyl-4'-hydroxyphenyl)propionyl]hydrazine, N,N'-bis[3-(3',5'-di-t-butyl-4'-hydroxyphenyl)propionyl]hexamethylenediamine, N,N'-bis[3-(3',5'-di-t-butyl-4'-hydroxyphenyl)propionyl]trimethylenediamine, and mixtures thereof.

[0065] Examples of sulfur-based antioxidants include the following: Dilauryl 3,3'-thiodipropionate, tridecyl 3,3'-thiodipropionate, dimyristyl 3,3'-thiodipropionate, distearyl 3,3'-thiodipropionate, lauryl stearyl 3,3'-thiodipropionate, neopentanetetrayltetrakis (3-laurylthiopropionate), etc.

[0066] Examples of phosphorus-based antioxidants include the following: As the phosphorus-based antioxidant, the following compounds may be used alone or in combination of two or more. Triphenyl phosphite, tris(nonylphenyl) phosphite, tris(2,4-di-t-butylphenyl) phosphite, trilauryl phosphite, trioctadecyl phosphite, distearyl pentaerythritol diphosphite, diisodecyl pentaerythritol diphosphite, bis(2,4-di-t-butylphenyl)pentaerythritol diphosphite, bis(2,4-di-t-butyl-6-methylphenyl)pentaerythritol diphosphite, bis(2,6-di-t-butyl-4-methylphenyl)pentaerythritol diphosphite, bis(2,4,6-tri-t-butylphenyl)pentaerythritol Diphosphite, Tristearyl Sorbitol Triphosphite, Tetrakis(2,4-di-t-butylphenyl)-4,4'-diphenylene Diphosphonite, 2,2'-Methylenebis(4,6-di-t-butylphenyl) 2-Ethylhexyl Phosphite, 2,2'-Ethylidenebis(4,6-di-t-butylphenyl) Fluorophosphite, Bis(2,4-di-t-butyl-6-methylphenyl) Ethyl Phosphite, Bis(2,4-di-t-butyl-6-methylphenyl) Methyl Phosphite, 2-(2,4,6-tri-t-butylphenyl)-5-ethyl-5-butyl-1,3,2-oxaphosphorinane, 2,2',2''-Nitrilo[triethyl-tris(3,3',5,5'-tetra-t-butyl-1,1'-biphenyl-2,2'-diyl] phosphites, 6-[3-(3-t-butyl-4-hydroxy-5-methylphenyl)propoxy]-2,4,8,10-tetra-t-butyldibenz[d,f][1,3,2]dioxaphosphepine, and mixtures thereof.

[0067] Examples of antioxidants include quinoline-based antioxidants such as polymers of 2,2,4-trimethyl-1,2-dihydroquinoline; monophenol-based antioxidants such as 2,6-di-t-butyl-4-methylphenol and styrenated phenol; and bis-, tris-, and polyphenol-based antioxidants such as tetrakis-[methylene-3-(3',5'-di-t-butyl-4'-hydroxyphenyl)propionate]methane. These antioxidants may be used alone or in combination of two or more. Among these, quinoline-based antioxidants are preferred.

[0068] Examples of ultraviolet absorbents include the following: As the ultraviolet absorbent, the following compounds may be used alone or in combination of two or more. (1) Examples of salicylate derivatives phenyl salicylate, 4-t-butylphenyl salicylate, 2,4-di-t-butylphenyl 3',5'-di-t-butyl-4'-hydroxybenzoate, 4-t-octylphenyl salicylate, bis(4-t-butylbenzoyl)resorcinol, benzoylresorcinol, hexadecyl 3',5'-di-t-butyl-4'-hydroxybenzoate, octadecyl 3',5'-di-t-butyl-4'-hydroxybenzoate, 2-methyl-4,6-di-t-butylphenyl 3',5'-di-t-butyl-4'-hydroxybenzoate, and mixtures thereof. (2) Examples of 2-hydroxybenzophenone derivatives 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-octoxybenzophenone, 2,2'-dihydroxy-4-methoxybenzophenone, bis(5-benzoyl-4-hydroxy-2-methoxyphenyl)methane, 2,2',4,4'-tetrahydroxybenzophenone, and mixtures thereof.

[0069] (3) Examples of 2-(2'-hydroxyphenyl)benzotriazole 2-(2-hydroxy-5-methylphenyl)benzotriazole, 2-(3',5'-di-t-butyl-2'-hydroxyphenyl)benzotriazole, 2-(5'-t-butyl-2'-hydroxyphenyl)benzotriazole, 2-(2'-hydroxy-5'-t-octylphenyl)benzotriazole, 2-(3-t-butyl-2-hydroxy-5-methylphenyl)-5-chlorobenzotriazole, 2-(3'-s-butyl-2'-hydroxy-5'-t-butylphenyl)benzotriazole, 2-(2'-hydroxy-4'-octyloxyphenyl)benzotriazole, 2-(3',5'-di-t-amyl-2'-hydroxyphenyl)benzotriazole azole, 2-[2'-hydroxy-3',3'-bis(α,α-dimethylbenzyl)phenyl]-2H-benzotriazole, 2-[(3'-t-butyl-2'-hydroxyphenyl)-5'-(2-octyloxycarbonylethyl)phenyl]-5-chlorobenzotriazole, 2-[3'-t-butyl-5'-[2-(2-ethylhexyloxy)carbonylethyl]-2'-hydroxyphenyl]-5-chlorobenzotriazole, 2-[3'-t-butyl-3'-hydroxy-5'-(2-methoxycarbonylethyl)phenyl]-5-chlorobenzotriazole, 2-[3'-t-butyl-2'-hydroxy-5'-(2-methoxycarbonylethyl)phenyl] Mixture of benzotriazole, 2-[3'-t-butyl-2'-hydroxy-5-(2-octyloxycarbonylethyl)phenyl]benzotriazole, 2-[3'-t-butyl-2'-hydroxy-5'-[2-(2-ethylhexyloxy)carbonylethyl]phenyl]benzotriazole, 2-[2-hydroxy-3-(3,4,5,6-tetrahydrophthalimidomethyl)-5-methylphenyl]benzotriazole, 2-(3,5-di-t-butyl-2-hydroxyphenyl)-5-chlorobenzotriazole, 2-(3'-dodecyl-2'-hydroxy-5'-methylphenyl)benzotriazole and 2-[3'-t-butyl-2'-hydroxy-5'-(2-isooctyloxycarbonylethyl)phenyl]benzotriazole, 2,2'-methylenebis[6-(2H-benzotriazol-2-yl)-4-(1,1,3,3-tetramethylbutyl)phenol, 2,2'-methylenebis[4-t-butyl-6-(2H-benzotriazol-2-yl)phenol], condensation product of poly(3-11)(ethylene glycol) with 2-[3'-t-butyl-2'-hydroxy-5'-(2-methoxycarbonylethyl)phenyl]benzotriazole, condensation product of poly(3-11)(ethylene glycol) with methyl 3-[3-(2H-benzotriazol-2-yl)-5-t-butyl-4-hydroxyphenyl]propionate, 2-ethylhexyl 3-[3-t-butyl-5-(5-chloro-2H-benzotriazol-2-yl)-4-hydroxyphenyl]propionate, octyl 3-[3-t-butyl-5-(5-chloro-2H-benzotriazol-2-yl)-4-hydroxyphenyl]propionate, methyl 3-[3-t-butyl-5-(5-chloro-2H-benzotriazol-2-yl)-4-hydroxyphenyl]propionate, 3-[3-t-butyl-5-(5-chloro-2H-benzotriazol-2-yl)-4-hydroxyphenyl]propionic acid, and mixtures thereof.

[0070] Examples of light stabilizers include the following: As the light stabilizer, the following compounds may be used alone or in combination of two or more. (1) Examples of hindered amine light stabilizers Bis(2,2,6,6-tetramethyl-4-piperidyl)sebacate, bis(2,2,6,6-tetramethyl-4-piperidyl)succinate, bis(1,2,2,6,6-pentamethyl-4-piperidyl)sebacate, bis(N-octoxy-2,2,6,6-tetramethyl-4-piperidyl)sebacate, bis(N-benzyloxy-2,2,6,6-tetramethyl-4-piperidyl)sebacate, bis(N-cyclohexyloxy-2,2,6,6-tetramethyl-4- piperidyl) sebacate, bis(1,2,2,6,6-pentamethyl-4-piperidyl) 2-(3,5-di-t-butyl-4-hydroxybenzyl)-2-butylmalonate, bis(1-acryloyl-2,2,6,6-tetramethyl-4-piperidyl) 2,2-bis(3,5-di-t-butyl-4-hydroxybenzyl)-2-butylmalonate, bis(1,2,2,6,6-pentamethyl-4-piperidyl) decanedioate, 2,2,6,6-tetramethyl-4-piperidyl Methacrylate, 4-[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionyloxy]-1-[2-(3-(3,5-di-t-butyl-4-hydroxyphenyl)propionyloxy)ethyl]-2,2,6,6-tetramethylpiperidine, 2-methyl-2-(2,2,6,6-tetramethyl-4-piperidyl)amino-N-(2,2,6,6-tetramethyl-4-piperidyl)propionyl Pionamide, 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, mixed esters of 1,2,3,4-butanetetracarboxylic acid with 1,2,2,6,6-pentamethyl-4-piperidinol and 1-tridecanol,

[0071] 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 mixed esters of dimethyl succinate and 1-(2-hydroxyethyl)-4-hydroxy-2,2,6,6-tetramethylpiperidine, poly[(6-morpholino-1,3,5-triazine-2,4-diyl)((2,2,6,6-tetramethyl-4-piperidyl)imino)hexamethylene((2,2,6,6-tetramethyl-4-piperidyl)imino)], poly[(6-(1,1,3,3-tetramethylbutyl)imino-1,3,5-triazine-2,4-diyl] N,N'-bis(2,2,6,6-tetramethyl-4-piperidyl)amino)-1,3,5-triazin-2-yl]-4,7-diazadecane-1,10-diamine, N,N',4-tris[4,6-bis(N-butyl-N-(2,2,6,6-tetramethyl-4-piperidyl)amino] ... N,N',4,7-tetrakis[4,6-bis(N-butyl-N-(1,2,2,6,6-pentamethyl-4-piperidyl)amino)-1,3,5-triazin-2-yl]-4,7-diazadecane-1,10-diamine, N,N',4,7-tetrakis[4,6-bis(N-butyl-N-(1,2,2,6,6-pentamethyl-4-piperidyl)amino)-1,3,5-triazin-2-yl]-4,7-diazadecane-1,10-diamine, N,N',4-tris[4,6-bis(N-butyl-N-(1,2,2,6,6-pentamethyl-4-piperidyl)amino)-1,3,5-triazin-2-yl]-4,7-diazadecane-1,10-diamine and mixtures thereof, etc.

[0072] (2) Examples of acrylate light stabilizers Ethyl α-cyano-β,β-diphenylacrylate, isooctyl α-cyano-β,β-diphenylacrylate, methyl α-carbomethoxycinnamate, methyl α-cyano-β-methyl-p-methoxycinnamate, butyl α-cyano-β-methyl-p-methoxycinnamate, methyl α-carbomethoxy-p-methoxycinnamate, N-(β-carbomethoxy-β-cyanovinyl)-2-methylindoline, and mixtures thereof. (3) Examples of nickel-based light stabilizers Nickel complex of 2,2'-thiobis-[4-(1,1,3,3-tetramethylbutyl)phenol], nickel dibutyldithiocarbamate, nickel salts of monoalkyl esters, nickel complex of ketoximes, and mixtures thereof.

[0073] (4) Examples of oxamide light stabilizers 4,4'-dioctyloxyoxanilide, 2,2'-diethoxyoxanilide, 2,2'-dioctyloxy-5,5'-di-t-butylanilide, 2,2'-didodecyloxy-5,5'-di-t-butylanilide, 2-ethoxy-2'-ethyloxanilide, N,N'-bis(3-dimethylaminopropyl)oxamide, 2-ethoxy-5-t-butyl-2'-ethoxyanilide, 2-ethoxy-5,4'-di-t-butyl-2'-ethyloxanilide, and mixtures thereof. (5) Examples of 2-(2-hydroxyphenyl)-1,3,5-triazine light stabilizers 2,4,6-tris(2-hydroxy-4-octyloxyphenyl)-1,3,5-triazine, 2-(2-hydroxy-4-octyloxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine, 2-[2,4-dihydroxyphenyl-4,6-bis(2,4-dimethylphenyl]-1,3,5-triazine, 2,4-bis(2-hydroxy-4-propyloxyphenyl)-6-(2,4-dimethylphenyl)-1,3,5-triazine, 2-(2-hydroxy-4-octyloxyphenyl)-4,6-bis bis(4-methylphenyl)-1,3,5-triazine, 2-(2-hydroxy-4-dodecyloxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine, 2-[2-hydroxy-4-(2-hydroxy-3-butyloxypropoxy)phenyl]-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine, 2-[2-hydroxy-4-(2-hydroxy-3-octyloxypropoxy)phenyl]-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine, and mixtures thereof.

[0074] Examples of metal deactivators include the following: N,N'-diphenyloxamide, N-salicylal-N'-salicyloylhydrazine, N,N'-bis(salicyloyl)hydrazine, N,N'-bis(3,5-di-t-butyl-4-hydroxyphenylpropionyl)hydrazine, 3-salicyloylamino-1,2,4-triazole, bis(benzylidene)oxalyl dihydrazide, oxanilide, isophthaloyl dihydrazide, sebacoyl bisphenylhydrazide, N,N'-bis(salicyloyl)oxalyl dihydrazide, N,N'-bis(salicyloyl)thiopropionyl dihydrazide, and mixtures thereof.

[0075] Examples of peroxide scavengers include esters of β-thiodipropionic acid, mercaptobenzimidazole, zinc salts of 2-mercaptobenzimidazole, zinc salts of dibutyldithiocarbamic acid, dioctadecyl disulfide, pentaerythritol tetrakis(β-dodecylmercapto)propionate, and mixtures thereof. Polyamide stabilizers include, for example, copper or divalent manganese salts of iodides or phosphorus compounds, and mixtures thereof.

[0076] Examples of hydroxyamines include N,N-dibenzylhydroxyamine, N,N-diethylhydroxyamine, N,N-dioctylhydroxyamine, N,N-dilaurylhydroxyamine, N,N-ditetradecylhydroxyamine, N,N-dihexadecylhydroxyamine, N,N-dioctadecylhydroxyamine, N-hexadecyl-N-octadecylhydroxyamine, N-heptadecyl-N-octadecylhydroxyamine, and mixtures thereof.

[0077] Examples of the neutralizing agent include calcium stearate, zinc stearate, magnesium stearate, hydrotalcite (basic magnesium aluminum hydroxy carbonate hydrate), melamine, amine, polyamide, polyurethane, and mixtures thereof.

[0078] Examples of lubricants include aliphatic hydrocarbons such as paraffin and 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, and rosin derivatives.

[0079] Examples of nucleating agents include sodium 2,2'-methylenebis(4,6-di-t-butylphenyl)phosphate, [2,2'-methylenebis(4,6-di-t-butylphenyl)]dihydroxyaluminum, bis[2,2'-methylenebis(4,6-di-t-butylphenyl)]hydroxyaluminum, tris[2,2'-methylenebis(4,6-di-t-butylphenyl)]aluminum, sodium Bis(4-t-butylphenyl)phosphate, metal salts of benzoic acid such as sodium benzoate, aluminum pt-butylbenzoate, 1,3:2,4-bis(O-benzylidene)sorbitol, 1,3:2,4-bis(O-methylbenzylidene)sorbitol, 1,3:2,4-bis(O-ethylbenzylidene)sorbitol, 1,3-O-3,4-dimethylbenzylidene-2,4-O-benzylidenesorbitol, 1,3-O-benzylidene benzylidene-2,4-O-3,4-dimethylbenzylidene sorbitol, 1,3:2,4-bis(O-3,4-dimethylbenzylidene) sorbitol, 1,3-Op-chlorobenzylidene-2,4-O-3,4-dimethylbenzylidene sorbitol, 1,3-O-3,4-dimethylbenzylidene-2,4-Op-chlorobenzylidene sorbitol, 1,3:2,4-bis(Op-chlorobenzylidene) sorbitol and mixtures thereof.

[0080] Examples of fillers include calcium carbonate, silicates, glass fibers, asbestos, talc, kaolin, mica, barium sulfate, carbon black, carbon fibers, zeolites, and mixtures thereof.

[0081] Among these additives, those preferably used are phenol-based antioxidants, phosphorus-based antioxidants, ultraviolet absorbers, hindered amine-based light stabilizers, peroxide scavengers and neutralizing agents. Particularly preferred phenolic antioxidants include the following compounds: 2,6-di-t-butyl-4-methylphenol, 2,4,6-tri-t-butylphenol, 2,4-dioctylthiomethyl-6-methylphenol, 2,2'-thiobis(6-t-butylphenol), 4,4'-thiobis(3-methyl-6-t-butylphenol), 2,2'-methylenebis(4-methyl-6-t-butylphenol), 2,2'-methylenebis(4-ethyl-6-t-butylphenol), 2,2'-methylenebis[4-methyl-6-(α-methylcyclohexyl)phenol)], 2,2'-methylenebis(4-methyl-6-cyclohexylphenol), 2,2 '-Methylenebis(4,6-di-t-butylphenol), 2,2'-ethylidenebis(4,6-di-t-butylphenol), 4,4'-methylenebis(6-t-butyl-2-methylphenol), 4,4'-methylenebis(2,6-di-t-butylphenol), 4,4'-butylidenebis(3-methyl-6-t-butylphenol), 1,1-bis(4-hydroxyphenyl)cyclohexane, 1,1-bis(5-t-butyl-4-hydroxy-2-methylphenyl)butane, 1,1,3-tris(5-t-butyl-4-hydroxy-2-methylphenyl)butane, ethylene glycol Bis[3,3-bis-3'-t-butyl-4'-hydroxyphenyl)butyrate], 2-t-butyl-6-(3'-t-butyl-5'-methyl-2'-hydroxybenzyl)-4-methylphenyl acrylate, 2,4-di-t-pentyl-6-[1-(2-hydroxy-3,5-di-t-pentylphenyl)ethyl]phenyl acrylate,

[0082] 2,4,6-tris(3,5-di-t-butyl-4-phenoxy)-1,3,5-triazine, tris(4-t-butyl-3-hydroxy-2,6-dimethylbenzyl)isocyanurate, bis(3,5-di-t-butyl-4-hydroxybenzyl)isocyanurate, tris[2-(3',5'-di-t-butyl-4'-hydroxycinnamoyloxy)ethyl]isocyanurate, diethyl-3,5-di-t-butyl-4-hydroxybenzylphosphonate, di-n-octadecyl-3,5-di-t-butyl-4-hydroxybenzylphosphonate, calcium salt of 3,5-di-t-butyl-4-hydroxybenzylphosphonic acid monoester, n-octadecyl 3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate, neopentanetetrayltetrakis(3,5-di-t-butyl-4-hydroxycinnamate), thiodiethylene bis(3,5-di-t-butyl-4-hydroxycinnamate), 1,3,5-trimethyl-2,4,6-tris(3,5-di-t-butyl-4-hydroxybenzyl)benzene, 3,6-dioxaoctamethylene bis(3,5-di-t-butyl-4-hydroxycinnamate), hexamethylene bis(3,5-di-t-butyl-4-hydroxycinnamate), triethylene glycol Bis(5-t-butyl-4-hydroxy-3-methylcinnamate), N,N'-bis[3-(3',5'-di-t-butyl-4'-hydroxyphenyl)propionyl]hydrazine, N,N'-bis[3-(3',5'-di-t-butyl-4'-hydroxyphenyl)propionyl]hexamethylenediamine, and the like.

[0083] Particularly preferred phosphorus-based antioxidants include the following compounds: Tris(nonylphenyl)phosphite, tris(2,4-di-t-butylphenyl)phosphite, distearyl pentaerythritol diphosphite, bis(2,4-di-t-butylphenyl)pentaerythritol diphosphite, bis(2,4-di-t-butyl-6-methylphenyl)pentaerythritol diphosphite, bis(2,6-di-t-butyl-4-methylphenyl)pentaerythritol diphosphite, tetrakis(2,4-di-t-butylphenyl)-4,4'-diphenylenediphosphonite, 2,2'-methylenebis(4,6-di-t-butylphenyl) 2-ethylhexyl phosphite, 2,2'-ethylidenebis(4,6-di-t-butylphenyl) fluorophosphite, bis(2,4-di-t-butyl-6-methylphenyl) Ethyl phosphite, 2-(2,4,6-tri-t-butylphenyl)-5-ethyl-5-butyl-1,3,2-oxaphosphorinane, 2,2',2''-nitrilo[triethyl-tris(3,3',5,5'-tetra-t-butyl-1,1'-biphenyl-2,2'-diyl)phosphite, 6-[3-(3-t-butyl-4-hydroxy-5-methylphenyl)propoxy]-2,4,8,10-tetra-t-butyldibenz[d,f][1,3,2]dioxaphosphepine, and the like.

[0084] Particularly preferred ultraviolet absorbers include the following compounds: Phenyl salicylate, 4-t-butylphenyl salicylate, 2,4-di-t-butylphenyl 3',5'-di-t-butyl-4'-hydroxybenzoate, 4-t-octylphenyl salicylate, 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-octoxybenzophenone, 2,2'-dihydroxy-4-methoxybenzophenone, bis(5-benzoyl-4-hydroxy-2-methoxyphenyl)methane, 2,2',4,4'-tetrahydroxybenzophenone, 2-(2-hydroxy-5-methylphenyl)benzotriazole, 2-(3',5'-di-t-butyl-2'-hydroxyphenyl)benzotriazole, 2-(5'-t-butyl-2'-hydroxyphenyl)benzotriazo benzotriazole, 2-(2'-hydroxy-5'-t-octylphenyl)benzotriazole, 2-(3-t-butyl-2-hydroxy-5-methylphenyl)-5-chlorobenzotriazole, 2-(3'-s-butyl-2'-hydroxy-5'-t-butylphenyl)benzotriazole, 2-(2'-hydroxy-4'-octyloxyphenyl)benzotriazole, 2-(3',5'-di-t-amyl-2'-hydroxyphenyl)benzotriazole, 2-[2'-hydroxy-3',5'-bis(α,α-dimethylbenzyl)phenyl]-2H-benzotriazole, and the like.

[0085] Particularly preferred light stabilizers include the following compounds: Bis(2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis(1,2,2,6,6-pentamethyl-4-piperidyl) sebacate, bis(N-octoxy-2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis(N-benzyloxy-2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis(N-cyclohexyloxy-2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis(1,2,2,6,6-pentamethyl-4-piperidyl) 2-(3,5-di-t-butyl-4-hydroxybenzyl)-2-butylmalonate, bis(1-acroyl-2,2,6,6-tetramethyl-4-piperidyl) 2,2-bis(3,5-di-t-butyl-4-hydroxybenzyl)-2-butylmalonate, bis(2,2,6,6-tetramethyl-4-piperidyl)succinate, 2,2,6,6-tetramethyl-4-piperidyl methacrylate, 4-[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionyloxy]-1-[2-(3-(3,5-di-t-butyl-4-hydroxyphenyl)propionyloxy)ethyl]-2,2,6,6-tetramethylpiperidine, 2-methyl-2-(2,2,6,6-tetramethyl-4-piperidyl)amino-N-(2,2,6,6-tetramethyl-4-piperidyl)propionamide, tetrakis(2,2,6,6-tetramethyl-4-piperidyl) 1,2,3,4-butanetetracarboxylate,

[0086] Tetrakis(1,2,6,6-pentamethyl-4-piperidyl) 1,2,3,4-butanetetracarboxylate, 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- Mixed esters of 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 and 2,2,6,6-tetramethyl-4-piperidinol and 3,9-bis(2-hydroxy-1,1-dimethylethyl)-2,4,8,10-tetraoxaspiro[5·5]undecane, Dimethyl Polycondensation polymer of succinate and 1-(2-hydroxyethyl)-4-hydroxy-2,2,6,6-tetramethylpiperidine, poly[(6-morpholino-1,3,5-triazine-2,4-diyl)((2,2,6,6-tetramethyl-4-piperidyl)imino)hexamethylene((2,2,6,6-tetramethyl-4-piperidyl)imino)], poly[(6-(1,1,3,3-tetramethylbutyl)-1,3,5-triazine-2,4-diyl)((2,2,6,6-tetramethyl-4-piperidyl)imino)hexamethylene((2,2,6,6-tetramethyl-4-piperidyl)imino)], etc.

[0087] The processing stabilizer of the present invention, or a specific ratio of the compound (I) represented by formula (I), the compound (II) represented by formula (II), and the amine compound (A), along with other additives added as needed, can be added to an organic material using any known method and apparatus for obtaining a homogeneous mixture. For example, when adding the processing stabilizer of the present invention, if the organic material is a solid polymer, the processing stabilizer of the present invention and / or other additives added as needed can be dry-blended directly with the solid polymer, or the processing 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. If the organic material is a liquid polymer, in addition to the above-mentioned addition methods, the processing stabilizer of the present invention and / or other additives added as needed can be blended in the form of a solution or dispersion into the polymer solution during or immediately after polymerization. On the other hand, when the organic material is a liquid other than a solid polymer (for example, an oil), in addition to the above-mentioned addition method, the processing stabilizer of the present invention and / or other additives to be added as needed can be added directly to the organic material to dissolve it, or the processing stabilizer of the present invention and / or other additives to be added as needed can be added in a dissolved or suspended state in a liquid medium.

[0088] The processing stabilizer of the present invention has excellent performance as a stabilizer for various organic materials, including thermoplastic resins such as polyolefins. Organic materials to which the processing stabilizer of the present invention has been added, as well as organic materials to which specific proportions of compound (I) represented by formula (I), compound (II) represented by formula (II), and amine compound (A) have been added, are stable against thermal and oxidative degradation during production, processing, and use, resulting in high-quality products. Furthermore, discoloration of organic materials due to oxidizing gases can be prevented. [Example]

[0089] 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. In the following examples and comparative examples, "parts" means "parts by mass" unless otherwise specified.

[0090] <Ingredients> The components used in the examples and comparative examples are listed below. (thermoplastic resin) Low-density polyethylene resin (LLDPE) (MI value: 1g / 10min, manufactured by Sumitomo Chemical Co., Ltd.) (processing stabilizer) ·Compound I: 2,4,8,10-tetra-t-butyl-6-[3-(3-methyl-4-hydroxy-5-t-butylphenyl)propoxy]dibenzo[d,f][1,3,2]dioxaphosphepine (Sumilizer® GP, manufactured by Sumitomo Chemical Co., Ltd.) Compound II: 6-Oxo-2,4,8,10-tetra-t-butyl-dibenzo[d,f][1,3,2]dioxaphosphepine Amine compound A: Triisopropanolamine (Tokyo Chemical Industry Co., Ltd.)

[0091] (Preparation of Compound II) 60 g of 2,2'-bis(4,6-di-t-butylphenol) and 770 mL of n-pentane were mixed, and 23 g of phosphorus trichloride was added dropwise. While cooling in an ice bath, 49 g of triethylamine was added dropwise, and the mixture was stirred at room temperature for 6 hours. 2.6 g of water was added to the resulting mixture, and the mixture was stirred at room temperature for 2 hours. Water and ethyl acetate were added to the resulting mixture, and the ethyl acetate layer was separated. The resulting ethyl acetate layer was washed with saturated brine. The washed ethyl acetate layer was dried over anhydrous magnesium sulfate, and the ethyl acetate was distilled off to obtain a solid. The resulting solid was mixed with diethyl ether, and the resulting mixture was then filtered to obtain a white solid. The resulting white solid was dissolved in a hexane / ethyl acetate mixed solvent, filtered, and the hexane and ethyl acetate were distilled off from the filtrate to obtain Compound II. The yield was 61.8%. The compound II obtained was confirmed to be 6-oxo-2,4,8,10-tetra-t-butyl-dibenzo[d,f][1,3,2]dioxaphosphepine by mass spectrometry and 1 This was confirmed by H-NMR.

[0092] Example 1 100 parts of LLDPE, 0.05 parts of calcium stearate (manufactured by Nitto Kasei Kogyo Co., Ltd.), 0.2 parts of Compound I, 0.00006 parts of Compound II, and 0.002 parts of amine compound A were dry-blended, and the resulting mixture was kneaded in a twin-screw extruder (BTN-32, PLABOR Corporation) having a cylinder diameter of 32 mm under conditions of a temperature of 190°C and a screw rotation speed of 80 rpm in a nitrogen atmosphere to obtain pellets.

[0093] (Examples 2 to 7, Comparative Examples 1 to 5) Pellets were obtained in the same manner as in Example 1, except that Compound I, Compound II and Amine Compound A were dry-blended in the addition parts by weight shown in Table 1.

[0094] The resulting pellets of Examples 1 to 7 and Comparative Examples 1 to 5 were used to evaluate processing stability and NOx resistance.

[0095] (Processing stability) The obtained pellets were kneaded five times using a single-screw extruder (VS30-28 type extruder, manufactured by Tanabe Plastics Co., Ltd.) with a cylinder diameter of 30 mm under conditions of a temperature of 280°C and a screw rotation speed of 50 rpm in an air atmosphere to obtain pellets, and the melt flow rate (MFR) of the obtained pellets was measured. The MFR was measured using a melt indexer (Model L246-3537, Techno Seven Co., Ltd.) at a temperature of 190°C and a load of 21.18 N. LLDPE undergoes crosslinking during thermal processing, resulting in a decrease in its MFR. Therefore, the higher the MFR of the pellets after repeated extrusion in a single-screw extruder, the better the processing stability of the LLDPE. Based on the obtained MFR, processing stability was evaluated according to the following criteria. The results are shown in Table 2. Evaluation criteria for processing stability ○: 0.6 or more ×: Less than 0.6

[0096] (NOx resistance) The pellets were pressed into a sheet of 1 mm thickness using a press (Kansai Roll Co., Ltd., "PEW-5040") at 190°C. The sheet was then cut into 4 cm long and 4 cm wide pieces using a lever-type sample cutter (Dumbell Co., Ltd., "SDL-200") to obtain test pieces. The obtained test specimen was suspended in a nitrogen oxide gas test apparatus ("GF-5" manufactured by Suga Testing Instruments Co., Ltd.), and NOx gas generated in accordance with JIS L 0855 (1998) was collected in a gas burette. 10 mL of the collected NOx gas was then injected into the nitrogen oxide gas test apparatus using a gas syringe. The test specimen was exposed to the injected NOx gas at room temperature for 7 days, after which the test specimen was removed and the yellow index (YI) was measured using a colorimeter ("CM-3500d" manufactured by Konica Mirta Japan Co., Ltd.). The smaller the YI, the more suppressed the discoloration and the better the NOx resistance. Based on the obtained YI, NOx resistance was evaluated according to the following criteria. The results are shown in Table 2. NOx resistance evaluation criteria ○: Less than 5.9 ×: 5.9 or higher

[0097] [Table 1]

[0098] [Table 2]

Claims

1. Formula (I): 【Chemistry 1】 [In formula (I), 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 is a single bond, a sulfur atom, or —CH(—R ６ )-group (R ６ represents a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, or a cycloalkyl group having 5 to 8 carbon atoms; A is an alkylene group having 1 to 8 carbon atoms or *-C(=O)-R ７ - group (R ７ represents a single bond or an alkylene group having 1 to 8 carbon atoms, and * represents a bond on the oxygen side, Either Y or 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. and a compound (I) represented by formula (II): 【Chemistry 2】 [In formula (II), R １ and R ２ 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 is a single bond, a sulfur atom, or —CH(—R ６ )-group (R ６ represents a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, or a cycloalkyl group having 5 to 8 carbon atoms. and an amine compound (A) having a hydroxyalkyl group, A processing stabilizer, wherein the content of compound (II) is 0.005 to 4 parts by mass and the content of amine compound (A) is 0.01 to 15 parts by mass relative to 100 parts by mass of compound (I).

2. 2. The processing stabilizer according to claim 1, wherein the amine compound (A) is an alkanolamine.

3. The alkanolamine has the formula (III): 【Transformation 3】 [In formula (III), Y １ , Y ２ and Y ３ each independently represents a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, or an alkyl group having 1 to 8 carbon atoms and at least one hydroxyl group, provided that Y １ ~Y ３ At least one of the groups represents an alkyl group having 1 to 8 carbon atoms and having at least one hydroxyl group. Or formula (IV): 【Chemistry 4】 [In formula (IV), Y ４ , Y ５ , Y ６ and Y ７ each independently represents a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, or an alkyl group having 1 to 8 carbon atoms and at least one hydroxyl group, provided that Y ４ ~Y ７ at least one of B represents an alkyl group having 1 to 8 carbon atoms and having at least one hydroxyl group, and B represents an alkylene group having 1 to 4 carbon atoms. The processing stabilizer according to claim 2, wherein the stabilizer is represented by the formula:

4. 4. The processing stabilizer of claim 3, wherein the alkanolamine is represented by formula (III):

5. Y in formula (III) １ , Y ２ and Y ３ And Y in formula (IV) ４ , Y ５ , Y ６ and Y ７ are each independently —CH ２ —CH(OH)—R ６ [In the formula, R ６ represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms.

6. Formula (I): 【Transformation 5】 [In formula (I), 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 is a single bond, a sulfur atom, or —CH(—R ６ )-group (R ６ represents a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, or a cycloalkyl group having 5 to 8 carbon atoms; A is an alkylene group having 1 to 8 carbon atoms or *-C(=O)-R ７ - group (R ７ represents a single bond or an alkylene group having 1 to 8 carbon atoms, and * represents a bond on the oxygen side, Either Y or 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. and a compound (I) represented by formula (II): 【Transformation 6】 [In formula (II), R １ and R ２ 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 is a single bond, a sulfur atom, or —CH(—R ６ )-group (R ６ represents a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, or a cycloalkyl group having 5 to 8 carbon atoms. an amine compound (A) having a hydroxyalkyl group, and an organic material, wherein the content of compound (II) is 0.005 to 4 parts by mass and the content of amine compound (A) is 0.01 to 15 parts by mass relative to 100 parts by mass of compound (I).

7. 7. The organic material composition according to claim 6, comprising the processing stabilizer according to any one of claims 1 to 5 as compound (I), compound (II), and amine compound (A).

8. 8. The organic material composition according to claim 6, wherein the organic material is a thermoplastic resin.

9. 9. The organic material composition according to claim 8, wherein the thermoplastic resin is a polyolefin or an engineering plastic.

10. The organic material comprises a compound of formula (I): 【Transformation 7】 [In formula (I), 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 is a single bond, a sulfur atom, or —CH(—R ６ )-group (R ６ represents a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, or a cycloalkyl group having 5 to 8 carbon atoms; A is an alkylene group having 1 to 8 carbon atoms or *-C(=O)-R ７ - group (R ７ represents a single bond or an alkylene group having 1 to 8 carbon atoms, and * represents a bond on the oxygen side, Either Y or 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. and a compound (I) represented by formula (II): 【Transformation 8】 [In formula (II), R １ and R ２ 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 is a single bond, a sulfur atom, or —CH(—R ６ )-group (R ６ represents a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, or a cycloalkyl group having 5 to 8 carbon atoms. and an amine compound (A) having a hydroxyalkyl group are added in amounts such that the content of compound (II) is 0.005 to 4 parts by mass and the content of amine compound (A) is 0.01 to 15 parts by mass relative to 100 parts by mass of compound (I), or A method for stabilizing an organic material, comprising adding the processing stabilizer according to any one of claims 1 to 5 to the organic material.

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

12. 12. The stabilization method according to claim 11, wherein the thermoplastic resin is a polyolefin or an engineering plastic.

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