JPS6036501A - Vinyl polymerization inhibitor - Google Patents

Abstract

PURPOSE:The titled inhibitor that is composed of a polyvalent ester containing 2,2,6,6-tetramethylpiperizyl group, thus showing improved storage stability without inhibition of photosetting of a photosetting resin and preventing effectively, monomers from polymerizing under heating up to high temperatures. CONSTITUTION:As a vinyl polymerization inhibitor, is added a polyvalent ester having 2,2,6,6-tetramethylpiperizyl group of formula I [R1 is H, oxyl, alkyl; X is methine, formula II (p is 0, 1; R3 is H, lower alkyl); R2 is alkyl, alkenyl, group of formula III; n is 0-4; Y1 is O, amine; Y2 is O, amine, formula III; A is acyl of 2+n valency, carbamoyl, formula IV; G is divalent phenol, divalent alcohol, divalent amine residue; n is 0-10] to a composition of photosetting resins.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a vinyl polymerization inhibitor, and more specifically, 2.2.
The present invention relates to a vinyl polymerization inhibitor comprising a polyvalent ester compound having a 6.6-titramethylbiveridyl group.

α, β of acrylic acid ester, methacrylic acid ester, etc.
- It is known that vinyl compounds such as unsaturated carboxylic acid esters, styrene, and acrylamide are easily polymerized and often polymerize during manufacturing processes, distillation purification, storage, and transportation.

In order to prevent the polymerization of vinyl compounds, phenolic compounds such as hydroquinone and hydroquinone monoalkyl ether have been used in the past, but the effects of these compounds are still insufficient, and they are still one of the main uses of vinyl compounds. When used in photocurable resin compositions, it has the disadvantage of inhibiting photocuring, and its use is naturally limited.

In addition, Japanese Patent Publication No. 50-10281 proposes a vinyl polymerization inhibitor consisting of a specific cyclic amino derivative, but its effect is still insufficient.

Further, JP-A-56-38301 proposes the use of a specific N-oxyl compound as a popcorn polymerization inhibitor for acrylic acid esters, but the effect was still insufficient.

In view of the current situation, the present inventors have attempted to improve storage stability without inhibiting photocuring when used in photocurable resin compositions, and to prevent polymerization of vinyl compounds even when heated to high temperatures. As a result of extensive research aimed at providing a polymerization inhibitor that effectively inhibits polymerization, the present invention was achieved by discovering that a compound represented by the following general formula (1) achieves the above object.

, p represents 0 or 1, and R3 represents a hydrogen atom or a lower alkyl group. R2 is an alkyl group, a turtle hydrogen atom, an alkyl group, an alkenyl group, or -G-Y2
Does not show H. Y2 represents 10- or -N-, and 5 R5 represents a hydrogen atom, an alkyl group, an alkenyl group, or a 2+n-valent group derived from an inorganic oxygen acid. G represents a residue of dihydric phenols, dihydric alcohols or dihydric amines. m indicates 0 to 1o. ) In the compound represented by the general formula (1), the alkyl group represented by R1 includes methyl, ethyl, propyl, butyl, isobutyl,
Sec-butyl, heptyl, octyl, dodecyl, benzyl, 2-hydroxyethyl, 2-hydroxypropyl, 2
-Hydroxybutyl, acetoxyethyl, propionylethyl, 2,3-epoxyprobyl and the like.

Examples of the lower alkyl group represented by R3 include methyl, ethyl, propyl, isopropyl, butyl, and the like.

The alkyl groups represented by R2, turtle and R5 include methyl, ethyl, propyl, butyl, tertiary butyl, octyl,
Tertiary octyl, 2-ethylhexyl, isooctyl, nonyl, isononyl, decyl, isodecyl, dodecyl, 2
-methylundecyl, 1, lysocyl, 2-methyl-dodecyl, tetradecyl, 2-methyl-tridecyl, hexadecyl, 2-hexadecyl, octadecyl, eicosyl, tocosyl, tetradecyl, 2-decyltetradecyl,
Examples include 2-decyltetradecyl, 2-undecyltetrabutyl, 2-undecylpentadecyl, triacontyl, etc., and examples of the alkenyl group include allyl, decenyl, dodecenyl, tetradecenyl, hexadecenyl, occudecenyl, and the like.

The acyl group represented by 8 is a residue of a carboxylic acid represented by A-4011) zten, and the carboxylic acid includes the following.

Namely, oxalic acid, malonic acid, succinic acid, glucuric acid, adipic acid, speric acid, cehatic acid, decamethylene dicarboxylic acid, maleic acid, itaconic acid, acetylene dicarboxylic acid, bis(3,5-di-43-)' (4-hydroxybenzyl) malonic acid, thiodipropionic acid, thiodiglycolic acid, methylenebisthioglycolic acid, iminodiacetic acid, tartaric acid, malic acid, thiomalic acid, dihydrotartaric acid, epoxysuccinic acid, 3,4-dioxythiophene Dicarboxylic acid, 1,4-biscarboxyethylpiperazine, 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]hebutene-2,3-dicarboxylic acid, tricarballylic acid, citric acid, acetylcitric acid, butane-1,2,3-tricarboxylic acid, 3--butene-1, 2,3-tricarboxylic acid, trimellitic 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, ],, ]1,2.3-propanetetracarboxylic acid pyromellitic acid, 1,6,7°8.9.14-tetradecane Examples include hexacarboxylic acid, 1.6.8.14-tetradecanehexacarboxylic acid, nitrilo-1-lyacetic acid, nitrilotripropionic acid, and the like.

Further, the carbamoyl group represented by A is derived from a 2+ni& polyisocyanate, and examples of the polyisocyanate include 1-lyene diisocyanate-1-, diphenylmethane diisocyanate, isocyanate l-medylcyclohexane isocyanate. , hydrogenated diphenylmethane isocyanate 1-, hexamethylene diamine diisocyanate, isophorone diisocyanate 1-
etc. can be mentioned.

Examples of inorganic oxygen acids represented by A include phosphoric acid, phosphorous acid, phosphonic acid, phosphorous acid, substituted phosphonic acid, substituted phosphonic acid, silicic acid, diorganic silicic acid, boric acid, and carbonic acid. It will be done.

Examples of the residues of dihydric phenols, dihydric alcohols, or dihydric amines represented by G include residues of dihydric phenols, dihydric alcohols, and dihydric amines, which are not shown below.

Examples of dihydric phenols include hydroquinone, 4,
4'-isopropylidene diphenol (bisphenol A>, 4,4'-cyclohexylidene diphenol,
4.4°-methylenebisphenol, 4.4°-sulfobisphenol, 2°5-di-tert-butylhydroquinone, 2,3,6-trimethylhydroquinone, 2-methylresorcinol, 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°-di-methylphenyl>3.5°5-1.limethylbexane, 2,2”-
Cyclohexylidene bis(4-ethyl-6-tert-butylphenol), 2.2”-isopropylbenzylidene-
bis(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-tert-butylphenol) butylfurol), 4,4'-methylenebis(2
-methyl---6=tert-butylphenol), 4.4'
-isopropylidene bis(2-phenylethylphenol), 4.4°-n-butylidene bis(3-methyl-6
-tert-butylphenol), 4.4"-cyclohexylidene bis(2-tert-butylphenol), 4.4°-cyclohexylidene bis(2-cyclohexylphenol), 4,4"-benzylidene bis(2- Tertiary butyl-5
-methylphenol), 4,4'-oxobis(3-methyl-6-iprobylphenol), 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-3-ffi3-butyl Examples of dihydric alcohols include ethylene glycol, diethylene glycol, triethylene glycol,
■, 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-cyclohexane dimetatool, 1.4
-Phenyldimethanol, hydrogenated bisphenol A, 3.
9-bis(l,1-dimethyl-2-hydroxyethyl)
-2,4゜8.10-tetraoxaspiro(5,5)undecane, etc., and divalent amines include ethylenediamine, propylenediamine, hexamethylenediamine, undecamethylenediamine, bis(aminomethyl)cyclohexane, 3 ,9-bis(3-aminopropyl)-
2,4,8,10-tetraoxaspiro(5,5)undecane, N,N'-dimethylhexamethylenediamine,
N,N'-bis(2,2,6,6-tetramethyl-4
-piperidyl)hexamethylene diamine, etc.

Representative examples of the compound represented by the general formula (1) used in the present invention include the following.

No. 1 Bis-(2,2,6,6-tetramethyl-4-piperidyl)-Sepacade, 11k12 Bis-(1,2,2,6,6-bentamethyl-4-piperidyl)-Sepacade, No. 3 Bis- (2,2,6,6-tetramethyl-
4-piperidinyl-1-oxyl)-sepacade, 4 bis-(2,2,6,6-tetramethyl-4-piperidyl)-dodecanedioate, 5 bis-(2,
2,6,6-tetramethyl-4-piperidyl)-terephthalate, 隘6bis(9-aza-8,8,10,10-tetramethyl-3-ethyl-1,5-dioxaspiro(5,5)
-3-undecylmethyl)methyliminodiacetate, No, 7 bis(1,2,2,6,6-bentamethyl-4-piperidyl)・2-butyl-2-(5,5-di-tert-butyl-4 -Hydroxyhensyl)malonate, 8 Tris(2,2,6,6-tetramethyl-4-piperidyl)citrate, 9 Tris(2,2,6,6-tetramethyl-4-piperidyl)nitrilotriacetate 10 tris (2,
2,6,6-tetramethyl-4-piperidyl-1-oxyl)nitrilotriacetate, N1111 tris(2,2,6,6-tetramethyl-4
-piperidyl)butanetricarboxylate.

Note 12 Tris(2,2,6,6-tetramethyl-4-
Piperidyl-1-oxyl)butane 1-licarboxylate, Tris(2,2,6,6-tetramethyl-4-piperidyl) trimellitate, Magnetic14 Bis(2,2,6,6-tetramethyl-4 -piperidyl)mono(tridecyl) l-limellitate, 15 Tetra(2,2,6,6-tetramethyl-4-
piperidyl) pyromellitate, 16 tetra(2,2,6,6-tetramethyl-4-
piperidyl)-1,3-bis(aminomethyl)cyclohecantetraacetate, 17 Tetra (2,2,
6,6-tetramethyl-4-piperidyl) -1,2,
3,4-butanetetracarboxylate, 18 tetra(2,2,6,6-tetramethyl-4-
piperidyl-1-oxyl)-1,2,3,4-butanetetracarboxylate, 19 tetra(1,2,
2,6,6-bentamethyl-4-piperidyl) -1,
2,3,4-butanetetracarboxylate, 20tris(2,2,6,6-te]-ramethyl-4-
mono(isotridecyl)-1,2,
3,4-butanetetracarboxylate, tris(1,2,2,6,6-bentamethyl-4
-piperidyl) mono(isotridecyl')-1,2
,3,4-butanetetracarboxylate, 22 bis(1,2,2,6,6-pankmethyl-4
-piperidyl) -di(tridecyl)-1.2,3.
4-butanetetracarboxylate, 11h23 bis(2,2,6,6-tetramethyl-4
-piperidyl) di(tridecyl)-1゜2.3.4-
Butane tetracarboxylate, 隘24 bis(2,2,6,6-titramethyl-1
-oxy-4-piperidyl) di(tridecyl)
-1,2,3,4-butanetetracarpoxylate-1, 253.9-bis[1,1-dimethyl-2-(tris(2,2,6,6-tetramethyl-4-piperidyl) (oxycarbonyl)butylcarbonyloxy)ethyl)-
2,4,8,10~tetraoxaspiro(5,5)undecane, 隘263.9-bis[1,1-dimethyl-2-(tris(1,2,2,6,6-pankmethyl-4) -piperidyloxycarbonyl)butylcarbonyloxy)ethyl)-2,4,8,10-tetraoxaspiro[5,5]
Undecane, 隘27N, N'-bis(2,2,6,6-tetramethyl-4-piperidyl)-oxylamide, 2B 2. 4. 6-1-Squirrel-(2,2,6,6
-tetramethyl-4-piperidyloxy)-s-triazine, Na29 2. 4. 6-) Squirrel-(1,2,2,6
゜6-bentamethyl-4-piperidyloxy)-3--
) Riazin, 隘30 2. 4. 6-1-Squirrel-(2,2,6,6
-tetramethyl-4-piperidylamino)-3-) riazine, 隘312-diethylamino-4,6-bis(9-aza-8,8,10,10-tetramethyl-3-ethyl1,
5-dioxaspiro(5,5)-3-undecylmethoxy)-8-triazine, 2-diethylamino-4,6-bis(9-aza-8,8,10,10-tetramethyl-3-ethyl1) ．．
5-dioxaspiro[5,53-9-oxyl-3-undecylmethoxy)-8-triazine, 332-tertiary octylamino-4,6-dichloro-5
-) riazine/N,N'-bis(2,2,6,6-tetramethyl-4-piperidyl)hexamethylenediamine polycondensate, 34 bis(9-aza-8,8,10,10
-tetramethyl-3-ethyl-1,5dioxasubiro [
5,・5]-3-undecylmethyl) carbonate, 隘35 bis(9-others,s,io,io-tetramethyl-3-ethyl-1,5dioxaspiro(5,5)
-3-undecylmethyl)° hydrogenated bisphenol A.
dicarbonate, tris(2,2,6,6-tetramethyl-4-piperidyl) phosphite, tetra(2,2,6,6-tetramethyl-4
-piperidyl)bisphenol A diphosphite, 38tris(2,2,6,6-tetramethyl-4-piperidyl)phosphate, 393.5-di-tert-butyl-4-hydroxybenzyl-bis(2,2, 6,6-tetramethyl-4-piperidyl)phosphonate, 40 phenyl-bis (2,
2,6,6-tetramethyl-4-piperidyl)phosphinate.

Vinyl compounds that can be used with the vinyl polymerization inhibitor of the present invention include unsaturated carboxylic acids such as acrylic acid, methacrylic acid, itaconic acid, crotonic acid, maleic acid, and fumaric acid;
Esters of unsaturated carboxylic acids and monohydric or polyhydric alcohols or amides with monohydric or polyhydric amines; (meth)acrylates of polyhydroxy esters obtained from polyhydric carboxylic acids and polyhydric alcohols; unsaturated Unsaturated polyesters or polyamides obtained from dicarboxylic acids (and other dicarboxylic acids) and polyvalent amines; by reaction of urethane compounds with terminal isocyanates obtained from diisocyanates and polyhydric alcohols and hydroxyalkyl (meth)acrylates; Urethane acrylate obtained; Epoxy acrylate obtained by reaction of polyglycidyl ether of bisphenols or polyol with (meth)acrylic acid; Linear polyester obtained by reaction of dicarboxylic acid anhydride and glycidyl (meth)acrylate; Examples include di(meth)acrylic modified polyester or polyamide obtained by reacting polyester or polyamide having a carboxyl group at the terminal with glycidyl (meth)acrylate.

In these compounds, -hydric or polyhydric alcohols include, for example, methanol, ethanol, butanol,
Allyl alcohol, octatool, ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, neopentyl glycol, 1,4
-butanediol, 1,3-butanediol, ■, 6-
Examples include hexanediol, glycerin, trimethylolpropane, trimethylolethane, tris(2-hydroxyethyl)isocyanate, pentaerythritol, diglycerin, di-1-limethylolpropane, dipentaerythritol, etc.; As a -valent or polyvalent amine For example, ammonia, methylamine, butylamine, octylamine, diethylamine, dibutylamine, ethylenediamine, diethylenetriamine, piperazine, ■
, 6-hexamethylene diamine, melamine, etc.; examples of polycarboxylic acids other than unsaturated dicarboxylic acids include fucuric acid, isophthalic acid, terephthalic acid, trimellitic acid, pyromellitic acid, terahydrophthalic acid, and succinic acid. , adipic acid, sebacic acid and the like; examples of the diisocyanate include toluene diisocyanate, diphenylmethane diisocyanate, isocyanatomethylcyclohexane isocyanate, hexamethylene diisocyanate, isophorone diisocyanate and the like.

Specific examples of the above-mentioned vinyl compounds include, for example, methyl-
, ethyl-, butyl-, isooctyl- or 2-hydroxyethyl-acrylate, methylamine is ethyl-
Methacrylate-1-, ethylene glycol diacrylate, 1-lyethylene glycol diacrylate, 1,4-
Butanediol diacrylate, trimethylolpropane 1-reacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate,
Tris(2-hydroxyethyl)isocyanurate triacrylate, dipentaerythri]-1-ru-tetra~
Heki No. acrylate, glycerin diacrylate, triethylene glycol dimethacrylate, trimethylolpropane trimethacrylate, pentaerythritol trimethacrylate, ethylene glycol dicrotonate, diallyl maleate, bis(acryloyloxyethylphenyl)propane, acrylamide, methacrylamide, ethylene Bisacrylamide, hexamethylenebisacrylamide, methylenebismethacrylamide, bis(2-acryloyloxyethyl)hexamethylenecicabamate, bis(2-hydroxy-3-acryloyloxypropyl)hexamethylenecicabamate, 6-
Cyanatohexane carbamoyloxyethyl acrylate, 6-cyanatohexane carbamoyloxyethyl meccrylate, diallyl phthalate, diallyl malonate, divinyl adipate, divinyl phthalate, vinyl acetate, isobutyl vinyl ether, ethylene glycol divinyl ether, styrene, acrylonitrile,
Examples include triallyl isocyanurate, triallylphosphate, acrolein, meccrolein, butadiene, styrene, divinylbenzene, α-methylstyrene, vinylpyridine, vinyl chloride, and the like.

The vinyl polymerization inhibitor of the present invention can be added at any stage of production, purification, storage, or transportation of the vinyl compound, and the amount added is preferably 0.001 to 3% by weight based on the vinyl compound.

Hereinafter, the effect of the vinyl polymerization inhibitor of the present invention will be explained in more detail with reference to specific examples, but the present invention is not limited by the following examples.

Example 1 Urethane acrylate (manufactured by Shin Nakamura Chemical, NK-.

To a mixture of 50 parts by weight of ester U-108A (molecular weight approximately 1500) and 50 parts by weight of 1,6-hexanediol diacrylate, 3 parts by weight of hensifhenone, 3 parts by weight of dimethylaminoethanol and 0.3 parts by weight of the sample compound were added. , stirred and mixed thoroughly.

This was placed in a differential thermal analyzer and heated to 200°C to check for the presence or absence of an exothermic peak.

In addition, apply the above mixture onto paper using a bar coater to a thickness of 50 μm.
After applying it uniformly to a thickness of m, a high-pressure mercury lamp (Toshiba iQ;
H-400P) for 30 seconds from a distance of 12 cm. Next, the hardening state of this coating was examined by the pencil hardness method. The results are shown in Table-1.

Table 1 Example 2 An unsaturated polyester was produced by heating and esterifying 1 mole of terephthalic acid, 3.3 moles of propylene glycol, and 2 moles of arsenic maleic anhydride.

55 parts by weight of the above unsaturated polyester and 45 parts by weight of styrene
2 parts by weight of hensifhenone and 0.1 part by weight of the sample compound were added to the mixture of 2 parts by weight, and the mixture was stored in a dark place at 60°C, and the number of days until a gel was formed was observed. The results are shown in Table-2.

Table-2 Example 3 Sample compound 0.0 in 2-hydroxyethyl acrylate
1% by weight was added, placed in a glass tube, sealed, and shaken at 100° C. for 3 hours. Thereafter, the amount of residual double bonds was determined by infrared spectroscopic analysis, and the rate of decrease was determined as the polymerization rate. Table 3 shows the results.
Shown below.

Table 3 Example 4 A test was conducted in the same manner as in Example 3 using methyl methacrylate in place of 2-hydroxyethyl acrylate.

The results are shown in Table-4.

Table-4 Continuation of page 1 ■Int, C1,' Identification code Internal reference number 0 Inventor Shiba 1) Toshihiro Shirahata 5-chome, Urawa City, company

Claims (1)

[Claims] A vinyl polymerization inhibitor comprising a compound represented by the following general formula (I). , p represents 0 or 1, R3 represents a hydrogen atom or a lower alkyl group, R2 is an alkyl group, a113 hydrogen atom, an alkyl group, an alkenyl group, or 5 R5 is a hydrogen atom, an alkyl group, an alkenyl group represents a group or a 2+n-valent group from an inorganic oxygen acid. G does not represent a residue of dihydric phenols, dihydric alcohols or dihydric amines. m represents 0 to 10. )