JP2003119205A - Polymerization inhibitor composition - Google Patents

Abstract

(57) [Problem] To provide a polymerization inhibitor which effectively prevents polymerization of a vinyl compound even when heated to a high temperature. (A) Specific N-oxyl-2,2,2
6,6-Tetramethyl-4-piperidine derivative, particularly preferably a compound represented by the following general formula (1-1) and (B) (b-1) a phenolic polymerization inhibitor, (b-2)
A polymerization inhibitor composition comprising at least one polymerization inhibitor selected from a phenothiazine-based polymerization inhibitor, (b-3) a metal salt-based polymerization inhibitor, and (b-4) a nitroso-based polymerization inhibitor. Embedded image

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a polymerization inhibitor composition, and more specifically, it comprises an N-oxyl-2,2,6,6-tetramethyl-4-piperidine derivative and another specific polymerization inhibitor. It relates to a polymerization inhibitor composition containing the same.

[0002]

2. Description of the Related Art α, β-Unsaturated carboxylic acid esters such as acrylic acid esters and methacrylic acid esters, and vinyl compounds such as styrene and acrylamide are easily polymerized, and the production process, distillation purification It is known to polymerize often during storage, storage or transportation. Conventionally, phenol compounds such as hydroquinone and hydroquinone monoalkyl ether have been used to prevent the polymerization of the vinyl compound, but these compounds have not been sufficiently effective.

Japanese Patent Publication No. 45-1054 discloses that
A method for stabilizing an acrylic acid monomer by adding 2,6,6-tetramethyl-4-hydroxypiperidine-1-oxyl or the like has been proposed, and is disclosed in Japanese Examined Patent Publication No. Sho 54-3853.
In the publication, as the polymerization inhibitor, 2,2,6,6-tetramethyl-4-hydroxypiperidyl-1-oxyl,
A method for producing methacrylic acid using copper dithiocarbamate is described. JP-A-6-345681 discloses N-oxyl compounds such as 2,2,6,6-tetramethylpiperidinooxyl and hydroquinone. Use phenol compounds such as phenothiazine compounds (meta)
A method for preventing polymerization of acrylic acid and its ester is described, and a manganese salt compound, a copper salt compound, 2,2,6 together with an N-oxyl compound such as 2,2,6,6-tetramethylpiperidinooxyl. , 6-Tetramethylpiperazine compounds and nitroso compounds are used to describe the method of inhibiting polymerization of (meth) acrylic acid and its esters using one or more compounds selected from the group consisting of nitroso compounds. However, 2,2,6,6-tetramethyl-4-, which is proposed here,
When a lower compound such as hydroxypiperidyl-1-oxyl is used, there is a drawback that it volatilizes and loses its effect in an environment exposed to high temperatures such as during distillation.

On the other hand, JP-A-60-36501 proposes a polymerization inhibitor composed of a polyfunctional N-oxyl-2,2,6,6-tetramethyl-4-piperidine derivative. When it was used alone, its effect was insufficient.

Therefore, an object of the present invention is to provide a polymerization inhibitor which effectively prevents the polymerization of vinyl compounds even when heated to a high temperature.

[0006]

As a result of intensive studies, the present inventors have found that N-oxyl-2,2,6,6-tetramethyl-4-piperidine derivative and other specific polymerization inhibitors are selected. It was found that the polymerization inhibitor composition obtained by combining them can achieve the above object.

That is, the present invention was made based on the above findings, and (A) an N-oxyl-2,2,6,6-tetramethyl-4-piperidine derivative represented by the following general formula (1): And (B) (b-1) phenol-based polymerization inhibitor, (b-2) phenothiazine-based polymerization inhibitor, (b-
3) A polymerization inhibitor composition containing at least one polymerization inhibitor selected from a metal salt polymerization inhibitor and (b-4) a nitroso polymerization inhibitor.

[0008]

[Chemical 3]

[0009]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the polymerization inhibitor composition of the present invention having the above-mentioned gist will be described in detail.

First, (A) of the polymerization inhibitor composition of the present invention.
N-oxyl-2 represented by the general formula (1),
The 2,6,6-tetramethyl-4-piperidine derivative will be described.

In the general formula (1), examples of the lower alkyl group represented by R ₃ include methyl, ethyl, propyl, butyl and the like. Also, R ₂ , R ₄ and R
_{As the} alkyl group represented by ₅ , for example, methyl, ethyl, propyl, butyl, isobutyl, sec-butyl, sec-butyl, amyl, sec-amyl, hexyl, heptyl,
Octyl, isooctyl, tertiary octyl, 2-ethylhexyl, dodecyl, 2-methylundecyl, 2-methyldodecyl, tetradecyl, 2-methyltridecyl, hexadecyl, 2-hexadecyl, octadecyl, eicosyl, docosyl, tetracosyl, 2-decyl. Examples thereof include tetradecyl, 2-decylpentadecyl, 2-undecyltetradecyl, 2-undecylpentadecyl, and triacontyl. Examples of the alkenyl group include allyl and
Examples include decenyl, dodecenyl, tetradecenyl, hexadecenyl, octadecenyl and the like.

The acyl group represented by A is A (OH)
_{2 + n} is a carboxylic acid residue, and examples of the carboxylic acid include oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, suberic acid, sebacic acid, decamethylenedicarboxylic acid, and maleic acid. Acid, itaconic acid, acetylenedicarboxylic acid, bis (3,5-di-tert-butyl-4)
-Hydroxybenzyl) malonic acid, thiodipropionic acid, thiodiglycolic acid, methylenebisthiodiglycolic acid, iminodiacetic acid, tartaric acid, malic acid, thiomalic acid, dihydrotartaric acid, epoxysuccinic acid, 3,4-dioxythiophenedicarboxylic acid Acid, 1,4-biscarboxyethylenepiperazine, phthalic acid, isophthalic acid, terephthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, 5-bicyclo [2.2.1] heptene-2,3-dicarboxylic acid, 5- Bicyclo [2.2.2] heptenedicarboxylic acid, tricarballylic acid, citric acid, acetylcitric acid, butane-1,2,3-tricarboxylic acid, 3-butene-1,2,3-tricarboxylic acid, trimellitate Acid, butane-1,2,3,4-tetracarboxylic acid, 1,1,
2,2-ethenetetracarboxylic acid, 7-bicyclo [2.
2.2] Octene-2,3,5,6-tetracarboxylic acid, 1,1,2,3-propanetetracarboxylic acid, pyromellitic acid, 1,6,7,8,9,14-tetradecanehexacarboxylic acid Acid, 1,6,8,14-tetradecanetetracarboxylic acid, nitrilotriacetic acid, nitrilotripropionic acid and the like can be mentioned.

The carbamoyl group represented by A is 2
It is derived from + n-valent polyisocyanate, and examples of the polyisocyanate include tolylene diisocyanate, diphenylmethane diisocyanate, isocyanatomethylcyclohexane isocyanate, hydrogenated diphenylmethane diisocyanate, hexamethylene diisocyanate, and isophorone diisocyanate. Further, as the inorganic oxygen acid in the 2 + n-valent group from the inorganic oxygen acid represented by A, for example,
Phosphoric acid, phosphorous acid, phosphonic acid, phosphonous acid, substituted phosphonic acid, substituted phosphonous acid, silicic acid, diorganosilicic acid,
Examples thereof include boric acid and carbonic acid.

The dihydric phenols capable of providing G include, for example, hydroquinone and 4,4 '.
-Isopropylidene bisphenol (bisphenol A), 4,4'-cyclohexylidene bisphenol,
4,4'-methylenebisphenol, 4,4'-sulfobisphenol, 2,5-di-tert-butylhydroquinone, 2,3,6-trimethylhydroquinone, 2-methylresorcin, 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'-n-butylidenebis (4,6-dimethylphenol), bis-1,1-
(2'-hydroxy-3 ', 5'-dimethylphenyl)
-3,5,5-Trimethylhexane, 2,2'-cyclohexylidenebis (4-ethyl-6-tert-butylphenol), 2,2'-isopropylbenzylidenebis (4
-Ethyl-6-tert-butylphenol), 2,2'-thiobis (4-tert-butyl-6-methylphenol),
2,2'-thiobis (4-methyl-6-tert-butylphenol), 2,2'-thiobis (4,6-di-tert-butylphenol), 4,4'-methylenebis (2-methyl-)
6-tert-butylphenol), 4,4'-isopropylidenebis (2-phenylethylphenol), 4,4 '
-N-butylidene bis (3-methyl-6-tert-butylphenol), 4,4'-cyclohexylidene bis (2-
Tert-butylphenol), 4,4'-cyclohexylidenebis (2-cyclohexylphenol), 4,4'-
Benzylidene bis (2-tert-butyl-5-methylphenol), 4,4'-oxobis (3-methyl-6-isopropylphenol), 4,4'-thiobis (2-methyl-6-tert-butylphenol), 4,4'-thiobis (3-methyl-6-tert-butylphenol), 4,4 '
-Sulfobis (3-methyl-6-tert-butylphenol), bis (2-methyl-4-hydroxy-5-tert-butylbenzyl) sulfide and the like can be mentioned.

The dihydric alcohols capable of providing G include, for example, ethylene glycol, diethylene glycol, triethylene glycol, 1,2-
Propanediol, 1,3-Propanediol, 1,2
-Butanediol, 1,3-butanediol, 1,4-
Butanediol, neopentyl glycol, thiodiethylene glycol, 1,6-hexanediol, 1,10
-Decanediol, 1,4-cyclohexanediol,
1,4-cyclohexanedimethanol, 1,4-phenyldimethanol, hydrogenated bisphenol A, 3,9-bis (1,1-dimethyl-2-hydroxyethyl) -2,
Examples include 4,8,10-tetraoxaspiro [5.5] undecane.

As the divalent amines capable of providing G, for example, ethylenediamine, propylenediamine, hexamethylenediamine, undecamethylenediamine, bis (aminomethyl) cyclohexane, 3,
9-bis (3-aminopropyl) -2,4,8,10-
Tetraoxaspiro [5.5] undecane, N, N'-
Examples thereof include dimethylhexamethylenediamine, N, N'-bis (2,2,6,6-tetramethyl-4-piperidyl) hexamethylenediamine and the like.

Thus, the N-oxyl-2,2,6,6-tetramethyl-4-piperidine derivative represented by the above general formula (1) of the component (A) of the polymerization inhibitor composition of the present invention. Specifically, for example, bis (1-oxyl-2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis (1-oxyl-2,2,6,6-tetramethyl-) 4-piperidyl) dodecanedionate, bis (1-oxyl-2,2,6,6-tetramethyl-4-
Piperidyl) terephthalate, bis (1-oxyl-
2,2,6,6-tetramethyl-4-piperidyl) phthalate, bis (9-oxyl-9-aza-8,8,1
0,10-Tetramethyl-3-ethyl-1,5-dioxaspiro [5.5] -3-undecylmethyl) methyliminodiacetate, bis (1-oxyl-2,2,6,6)
6-Tetramethyl-4-piperidyl) .2-butyl-2
-(3,5-di-tert-butyl-4-hydroxybenzyl)
Malonate, Tris (2,2,6,6-tetramethyl-
4-piperidyl) citrate, tris (1-oxyl-)
2,2,6,6-tetramethyl-4-piperidyl) nitrilotriacetate, tris (1-oxyl-2,2,
6,6-Tetramethyl-4-piperidyl) butane tricarboxylate, tris (1-oxyl-2,2,6,6)
6-tetramethyl) trimellitate, bis (1-oxyl-2,2,6,6-tetramethyl) mono (tridecyl) trimellitate, tetra (1-oxyl-2,2,2
6,6-Tetramethyl) pyromellitate, tetra (1-
Oxyl-2,2,6,6-tetramethyl-4-piperidyl) -1,3-bis (aminomethyl) cyclohexanetetraacetate, tetra (1-oxyl-2,2,2
6,6-Tetramethyl-4-piperidyl) -1,2,
3,4-butane tetracarboxylate, tris (1-
Oxyl-2,2,6,6-tetramethyl-4-piperidyl) -mono (isotridecyl) -1,2,3,4-butanetetracarboxylate, bis (1-oxyl-)
2,2,6,6-Tetramethyl-4-piperidyl) -di (isotridecyl) -1,2,3,4-butanetetracarboxylate, 3,9-bis [1,1-dimethyl-2
-(Tris (1-oxyl-2,2,6,6-tetramethyl-4-piperidyloxycarbonyl) butylcarbonyloxy) ethyl] -2,4,8,10-tetraoxaspiro [5.5] undecane, N, N'-bis (1-
Oxyl-2,2,6,6-tetramethyl-4-piperidyl) oxamide, 2,4,6-tris (1-oxyl-2,2,6,6-tetramethyl-4-piperidyloxy) -s- Triazine, 2-diethylamino-4,6
-Bis (9-oxyl-9-aza-8,8,10,10
-Tetramethyl-3-ethyl-1,5-dioxaspiro [5.5] undecylmethoxy) -s-triazine, 2
-Tertiary octylamino-4,6-dichloro-s-triazine / N, N'-bis (1-oxyl-2,2,6,6)
-Tetramethyl-4-piperidyl) hexamethylenediamine polycondensate, bis (9-oxyl-9-aza-8,
8,10,10-Tetramethyl-3-ethyl-1,5-
Dioxaspiro [5.5] -3-undecylmethyl) carbonate, bis (9-oxyl-9-aza-8,8,
10,10-Tetramethyl-3-ethyl-1,5-dioxaspiro [5.5] -3-undecylmethyl) -hydrogenated bisphenol A-carbonate, tris (1-oxyl-2,2,6,6-) Tetramethyl-4-piperidyl)
Phosphite, tetra (1-oxyl-2,2,6,6
-Tetramethyl-4-piperidyl) -bisphenol A
-Diphosphite, tris (1-oxyl-2,2,
6,6-Tetramethyl-4-piperidyl) phosphate, 3,5-ditert-butyl-4-hydroxybenzyl-
Bis (1-oxyl-2,2,6,6-tetramethyl-
4-piperidyl) phosphonate, phenyl-bis (1-
Examples thereof include oxyl-2,2,6,6-tetramethyl-4-piperidyl) phosphinate.

Among these N-oxyl-2,2,6,6-tetramethyl-4-piperidine derivatives, ester compounds represented by the following general formula (1-1) are particularly preferably used.

[0019]

[Chemical 4]

Next, (B) of the polymerization inhibitor composition of the present invention
The component polymerization inhibitor will be described. Examples of the (b-1) phenolic polymerization inhibitor used as the component (B) of the present invention include hydroquinone, p-methoxyphenol, catechol and the like, with hydroquinone and p-methoxyphenol being preferred. .

Examples of the (b-2) phenothiazine-based polymerization inhibitor used as the component (B) of the present invention include phenothiazine, bis (α-methylbenzyl) phenothiazine, 3,7-dioctylphenothiazine and bis. Examples thereof include (α, α-dimethylbenzyl) phenothiazine, and phenothiazine is preferable.

The (b-3) metal salt polymerization inhibitor used as the component (B) of the present invention includes, for example, dimethyldithiocarbamic acid, diethyldithiocarbamic acid, dipropyldithiocarbamic acid, dibutyldithiocarbamic acid, diphenyl. Examples thereof include copper salts or manganese salts of dithiocarbamic acid, formic acid, acetic acid, octanoic acid, naphthenic acid, ethylenediaminetetraacetic acid, etc., preferably dimethyldithiocarbamic acid, diethyldithiocarbamic acid, dipropyldithiocarbamic acid, dibutyldithiocarbamic acid, diphenyldithiocarbamine. It is a dialkyldithiocarboxylic acid metal salt compound such as an acid.

(B) used as the component (B) of the present invention
-4) Examples of the nitroso-based polymerization inhibitor include p-nitrosophenol, N-nitrosodiphenylamine, N
Examples thereof include ammonium salts of nitrosophenylhydroxyamine (cuperone), and ammonium salts of N-nitrosophenylhydroxyamine (cuperone) are preferable.

The polymerization inhibitor composition of the present invention has the above (A)
The component (B) is preferably contained in an amount of 10 to 200 parts by weight, more preferably 50 to 150 parts by weight, based on 100 parts by weight of the component.

The polymerization inhibitor composition of the present invention is used as a polymerization inhibitor of a vinyl compound, and the vinyl compound is an unsaturated compound such as acrylic acid, methacrylic acid, itaconic acid, crotonic acid, maleic acid or fumaric acid. Carboxylic acid; the unsaturated carboxylic acid and a monohydric or polyhydric alcohol (for example, methanol, ethanol, butanol, allyl alcohol, octanol, ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, neopentyl glycol, 1,4 -Butanediol, 1,3-butanediol, 1,6-hexanediol, glycerin, trimethylolpropane, trimethylolethane, tris (2-hydroxyethyl) isocyanate, pentaerythritol, diglycerin, ditrimethylolpro Down, dipentaerythritol, etc.)
Ester or monohydric or polyhydric alcohol ester or monohydric or polyhydric amine (for example, ammonia, methylamine, octylamine, diethylamine, dibutylamine, ethylenediamine, diethylenetriamine, piperazine, 1,6-hexamethylenediamine , Melamine, etc.); (meth) acrylates of polyhydroxy esters obtained from polycarboxylic acids and polyhydric alcohols; unsaturated dicarboxylic acids (and other carboxylic acids (eg phthalic acid, isophthalic acid, terephthalic acid, Trimetic acid, promellitic acid, tetrahydrophthalic acid, succinic acid, adipic acid, sebacic acid, etc.))
An unsaturated polyester or an unsaturated polyamide obtained from a polyamine and a polyisocyanate; a diisocyanate (for example, toluene diisocyanate, diphenylmethane diisocyanate, isocyanatomethylcyclohexane isocyanate, hexamethylene diisocyanate, isophorone diisocyanate, etc.) and a polyhydric alcohol Urethane acrylate obtained by the reaction of the resulting urethane compound having a terminal isocyanate with hydroxyalkyl (meth) acrylate; Epoxy acrylate obtained by the reaction of polyglycidyl ether of bisphenol or polyol and (meth) acrylic acid; Dicarboxylic acid anhydride Linear polyester obtained by the reaction of a product with glycidyl (meth) acrylate; both ends Polyester or polyamide and a glycidyl (meth) di (meth) obtained by reacting the acrylate acrylic modified polyester or polyamide having a carboxyl group; an aromatic vinyl compound; acrylonitrile, and the like.

Specific examples of the above-mentioned vinyl compound include, for example, methyl-, ethyl-, butyl-, isooctyl- or 2-hydroxyethyl-acrylate, methyl- or ethyl-methacrylate, ethylene glycol diacrylate, triethylene glycol diacrylate. ,
1,4-butanediol diacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, tris (2-hydroxyethyl) isocyanurate triacrylate, dipentaerythritol-tetra-hexaacrylate, glycerin diacrylate, triethylene glycol dimethacrylate, Trimethylolpropane trimethacrylate, pentaerythritol trimethacrylate, ethylene glycol diclonate, diallylmaleate, bis (acryloyloxyethylphenyl) propane, acrylamide, methacrylamide, ethylenebisacrylamide, hexamethylenebisacrylamide, methylenebismethacrylamide, bis ( 2-acryloyloxyethyl) hexamethylene dicarb , Bis (2-hydroxy-3-acryloyloxypropyl) hexamethylene dicarbamate, 6-diisocyanatohexane carbamoyloxy ethyl acrylate, 6-diisocyanatohexane carbamoyloxy methacrylate, diallyl phthalate,
Diallyl malonate, divinyl adipate, divinyl phthalate, vinyl acetate, isobutyl vinyl ether, ethylene glycol divinyl ether, styrene, acrylonitrile, triallyl isocyanurate, triallyl phosphate, acrolein, methacrolein, butadiene, divinylbenzene, α-methylstyrene, vinyl Pyridine, vinyl chloride, styrene, α-methylstyrene,
Examples include vinyltoluene, divinylbenzene, styrenesulfonic acid, acrylonitrile and the like.

The polymerization inhibitor composition of the present invention can be added at any stage of production, purification, storage or transportation of a vinyl compound, and the addition amount thereof is 0.001 to 3% by weight based on the vinyl compound. Is preferred. The polymerization inhibitor composition of the present invention has an effect of trapping radicals generated by heating a vinyl compound. This is N-oxyl-2 which is the component (A) of the polymerization inhibitor composition of the present invention.
This is because the 2,6,6-tetramethyl-4-piperidine derivative becomes a nitroxy radical and thus exerts an effect as a radical scavenger.

[0028]

EXAMPLES The present invention will be specifically described below with reference to Examples and Comparative Examples, but the present invention is not limited to the following Examples.

Example 1 In a flask equipped with a distillation apparatus, 2
-Hydroxyethyl acrylate and the compounding ingredients and compounding amounts of the test compounds shown in Table 1, Table 2 and Table 3 below were added, and about half of the charged amount was distilled, and those obtained by distillation and those remaining in the flask The amount of the residual double bond was determined by infrared spectroscopic analysis, and the reduction rates were defined as the polymerization rate A and the polymerization rate B, respectively. The results are shown in Table 1, Table 2 and Table 3 below.

In the following Tables 1, 2 and 3, the unit of the compounding amount of the test compound is ppm, and each symbol in the column of the test compound represents the following compound. HA-1: Bis (1-oxyl-2,2,6,6-tetramethyl-4-piperidyl) sebacate HA-2: Bis (1-oxyl-2,2,6,6-tetramethyl-4-piperidyl) ) Terephthalate HA-3: Bis (1-oxyl-2,2,6,6-tetramethyl-4-piperidyl) phthalate HA-4: Tetra (1-oxyl-2,2,6,6-tetramethyl-4) -Piperidyl) -1,2,3,4-butanetetracarboxylate HA-5: 1-oxyl-2,2,6,6-tetramethyl-4-piperidinol PH-1: hydroquinone PH-2: p-methoxy Phenol PT-1: phenothiazine CU-1: dibutylaminodithiocarboxylic acid copper salt

[0031]

[Table 1]

[0032]

[Table 2]

[0033]

[Table 3]

As is clear from the results shown in Tables 1, 2 and 3, the polymerization proceeds easily by heating when no polymerization inhibitor is used (Comparative Example 1-1). Even when the polymerization inhibitor is used, the effect of suppressing the polymerization is not obtained when the component (A) or the component (B) of the present invention is used alone (Comparative Examples 1-2 to 1-6). Still not enough. Further, among N-oxyl-2,2,6,6-tetramethyl-4-piperidyl compounds, a compound different from the component (A) of the present invention is used in combination with another polymerization inhibitor (Comparative Example 1-7. Also in 1-8), only a small polymerization inhibiting effect can be obtained.

On the other hand, the (A) component N-oxyl-2,2,6,6-tetramethyl-4-piperidyl derivative and the (B) component phenol-based polymerization inhibitor, phenothiazine-based polymerization inhibitor, When the polymerization inhibitor composition of the present invention in combination with a metal salt polymerization inhibitor or a nitroso polymerization inhibitor is used (Examples 1-1 to 1-10), a large polymerization inhibition effect is obtained.

[0036]

INDUSTRIAL APPLICABILITY The polymerization inhibitor composition of the present invention can effectively prevent the polymerization of vinyl compounds even when heated to a high temperature.

   ─────────────────────────────────────────────────── ─── Continued front page    (72) Inventor Ryoji Kimura             Asahi, 5-2-13 Shirahata, Saitama City, Saitama Prefecture             Denka Kogyo Co., Ltd. (72) Inventor Yoko Nambu             Asahi, 5-2-13 Shirahata, Saitama City, Saitama Prefecture             Denka Kogyo Co., Ltd. F-term (reference) 4J011 NA02 NA15 NA16 NA18 NA26                       NA29

Claims (6)

[Claims] 1. (A) N- represented by the following general formula (1):
Oxyl-2,2,6,6-tetramethyl-4-piperidine derivative and (B) (b-1) phenol-based polymerization inhibitor, (b-2) phenothiazine-based polymerization inhibitor, (b-
3) A polymerization inhibitor composition containing at least one polymerization inhibitor selected from metal salt polymerization inhibitors and (b-4) nitroso polymerization inhibitors. [Chemical 1] 2. (A) N-oxyl-2,2,6,6-
The tetramethyl-4-piperidine derivative is represented by the following general formula (1
The polymerization inhibitor composition according to claim 1, which is a compound represented by -1). [Chemical 2] 3. The polymerization inhibitor composition according to claim 1, wherein the (b-1) phenol-based polymerization inhibitor is hydroquinone or p-methoxyphenol. 4. The polymerization inhibitor composition according to claim 1, wherein the phenothiazine-based polymerization inhibitor (b-2) is phenothiazine. 5. The polymerization inhibitor composition according to claim 1 or 2, wherein the metal salt polymerization inhibitor (b-3) is a dithiocarbamic acid metal salt compound. 6. The (b-4) nitroso-based polymerization inhibitor is N-
The polymerization inhibitor composition according to claim 1 or 2, which is an ammonium salt of nitrosophenylhydroxyamine.