TW201420664A - Stabilizer composition - Google Patents

Abstract

A stabilizer composition used in order to stabilize a polymerizable compound, wherein the stabilizer composition is characterized by containing (A) at least one species of semi-hindered phenolic compound selected from the group consisting of semi-hindered phenols and dimers thereof, and (B) at least one species of stabilizer selected from the group consisting of (thio)phosphites, phosphines, and thioethers.

Description

Stabilizer composition

The present invention relates to stabilizer compositions. More specifically, the present invention relates to, for example, a stabilizer composition which can be suitably used as a polymerizable compound of an industrial material for a raw material of a polymer, a curable material, or the like; and a stabilizer composition containing the same a polymerizable composition; a polymer composition obtained from the polymerizable composition.

A representative example of the polymerizable compound is a polymerizable compound of a (meth)acryl fluorenyl group having a polymerizable group (hereinafter, simply referred to as a (meth)acrylic compound). a (meth)acrylic compound having a (meth)acryloyl group bonded by a double bond activated by a conjugation with an adjacent carbonyl group, and polymerized by a radical addition polymerization mechanism (hereinafter, also referred to as a single name) It is a radical polymerization or a radical polymerization). The (meth)acrylic compound is used for coating materials, adhesives, sealants, adhesives, paints, and inks because of its excellent polymerization rate, internal hardenability, durability of chemical bond formation, and economy. Uses of resists, dental materials, optical lenses, molding materials, and the like.

In recent years, a polymerizable ester compound (hereinafter also referred to as an AMA ester) having an α-propylene methoxymethyl methacrylate group (hereinafter also referred to as an AMA group) has the same function as the (meth) acrylonitrile group. The above-mentioned polymerization active radical addition polymerizable compound is proposed (see, for example, Patent Documents 1 to 4).

The polymerizable ester compound having an AMA group forms a main chain skeleton having a 5-membered cyclic ether structure having a methylene group in a two-neutral arrangement as a repeating unit, although it is subjected to side-cyclization polymerization. The AMA ester has a radical polymerization activity equivalent to or higher than that of the acrylate, although the α-position having a carbon-carbon double bond bond is more sterically extruded than the methacrylate. Further, the polymer obtained from the polymerizable composition containing an AMA ester is excellent in heat decomposition resistance, adhesion, tough mechanical properties, fine particle dispersibility, and the like by a specific main chain skeleton produced by polymerization. The AMA ester is a polymerizable compound having properties superior to those of the prior (meth)acrylic compound.

However, AMA ester, which has a high polymerization activity, lacks stability such as high-temperature stability and storage stability (hereinafter, referred to as chemical stability), and is particularly high in the production or use of AMA esters. When used under the conditions, it has the disadvantages of poor operability and storage stability.

Therefore, in the invention described in Patent Document 1, it is proposed to use hydroquinone or a hindered phenol and a phosphorus-based oxidation preventing agent as a monoetherified hydroquinone or a p-methoxyphenol. AMA ester stabilizer.

However, the AMA ester containing the hydroquinone as the stabilizer is excellent in chemical stability, but when it is used as a raw material of a polymer or when it is used as a reactive diluent, it has a disadvantage of inhibiting polymerization. Further, an AMA ester containing the above hydroquinone as a stabilizer and a polymer prepared from a polymerizable composition containing the AMA ester, for example, an inorganic basic compound such as sodium hydroxide or potassium hydroxide, or an amine When a basic substance such as an organic alkali substance such as an ammonium salt is brought into contact, it is remarkably colored even before the polymerization reaction, even before the polymerization reaction. In addition, the AMA ester polymer is stored for a long time under heating or exposed to The weathering test conditions will also be colored. Therefore, the AMA ester containing the above-mentioned hydroquinone as a stabilizer is difficult to apply to a water-soluble resin-based paint which requires a neutralization of a base, a water-based resin emulsion using a basic substance, and transparency requiring weather resistance. Materials, etc., to limit their use.

On the other hand, in the case of monoetherifying hydroquinone or a hindered phenol and a phosphorus-based oxidation preventing agent, in order to sufficiently impart chemical stability to the AMA ester, a large amount of monoetherified hydroquinone or hindered phenol is required. However, when a monoetherified hydroquinone or a hindered phenol is used in an amount sufficient to impart chemical stability to the AMA ester, the polymerization activity or coloration of the AMA ester may be inhibited. On the other hand, when monoetherified hydroquinone or hindered phenol is used in an amount less than the amount sufficient to impart chemical stability to the AMA ester, sufficient chemical stability of the AMA ester cannot be imparted.

[Previous Technical Literature] [Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open Publication No. 2010-254685

[Patent Document 2] International Publication No. 2011/148903

[Patent Document 3] Japanese Patent Laid-Open Publication No. 2011-137123

[Patent Document 4] Japanese Patent Laid-Open No. 2011-074068

The present invention has been made in view of the above prior art, and in order to provide a polymerizable compound, particularly when an AMA ester is used, the chemical stability of the compound can be stabilized with the high polymerization activity originally maintained by the compound. The composition of the agent is the target. The present invention is further provided to prevent inclusion by inclusion The polymerizable composition of the AMA ester or the stabilizer of the coloring agent of the polymer prepared by the polymerizable composition is targeted.

Further, the present invention provides a polymer composition obtained by polymerizing the polymerizable compound, comprising the above-mentioned stabilizer composition and a polymerizable composition of an AMA ester.

The present invention relates to: (1) a stabilizer composition for stabilizing a polymerizable compound, characterized by comprising: (A) at least one selected from the group consisting of semi-hindered phenols and dimers thereof a semi-hindered phenolic compound; and (B) at least one stabilizer selected from the group consisting of (thio)phosphites, phosphines, and thioethers; (2) a polymerizable composition containing alpha-allyl a polymerizable ester compound of an oxymethylpropenyl group, characterized by comprising: (A) at least one semi-hindered phenolic compound selected from the group consisting of semi-hindered phenols and dimers thereof; and (B) selected At least one stabilizer of a group consisting of a free (thio) phosphite, a phosphine, and a thioether; and (3) a polymerizable composition obtained by polymerizing the polymerizable composition described in the above (2).

In the present specification, the term "(meth)acryloyl group" means "acryloyl fluorenyl" and/or "methacryl fluorenyl". "Acrylic" means "methacrylic acid" and/or "methacrylic acid". Further, "(meth) acrylate" means "acrylate" and/or "methacrylate".

The stabilizer composition according to the present invention, in a polymerizable compound In particular, when it is used in particular for the use of an AMA ester, the chemical stability of the compound and the high polymerization activity originally possessed by the compound can be excellent. In addition, by using the stabilizer composition of the present invention in the polymerizable composition containing an AMA ester, it is possible to exhibit an excellent effect of preventing the coloration of the polymerizable composition or the polymer prepared by the polymerizable composition.

The stabilizer composition of the present invention is a stabilizer composition for stabilizing a polymerizable compound as described above, characterized in that (A) is selected from the group consisting of semi-hindered phenols and dimers thereof. At least one semi-hindered phenolic compound of the group [hereinafter, also referred to as component (A)]; (B) at least one stabilizer selected from the group consisting of (thio)phosphite, phosphine and thioether [The following is also called (B) component].

The component (A) is at least one semi-hindered phenol compound which is a group consisting of a free semi-hindered phenol and a dimer thereof as described above. Therefore, the semi-hindered phenol and its dimer may be used alone or in combination of two or more.

The semi-hindered phenol may, for example, be a semi-hindered phenol represented by the formula (I):

In the formula, X ¹ represents a hydrogen atom or a linear alkyl group having 1 to 4 carbon atoms, and X ² to X ⁴ each independently represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms which may have a substituent, and X ⁵ It means a third alkyl group having 4 to 12 carbon atoms or an alkyl group having 6 to 18 carbon atoms. Examples of the above substituents include allyl group, methallyl group, crotyl group, 1,1-dimethyl-2-propenyl group, 2-methyl-butenyl group, and 3-methyl-2-butyl group. a chain-unsaturated hydrocarbon group such as an alkenyl group, a 3-methyl 3-butenyl group, a 2-methyl 3-butenyl group, an oleyl group, a linoleyl group or a linoleyl group; a cyclopentyl group, a cyclopentylmethyl group, a lipid such as cyclohexyl, cyclohexylmethyl, 4-methylcyclohexyl, 4-tert-butylcyclohexyl, tricyclodecyl, isobornyl, adamantyl, dicyclopentyl or dicyclopentenyl Cycloalkyl; glycidyl, β-methylglycidyl, β-ethylglycidyl, 3,4-epoxycyclohexylmethyl, 2-oxetanylmethyl, 3-methyl- 3-oxetanylmethyl, 3-ethyl 3-oxetanylmethyl, tetrahydrofuranyl, tetrahydroindenyl, tetrahydropyranyl, dioxolyl, dioxoalkyl Equivalent cyclic ether group; phenyl, methylphenyl, dimethylphenyl, trimethylphenyl, 4-tert-butylphenyl, methoxyphenyl, hydroxyphenyl, benzyl, di An aryl group such as benzyl, diphenylethyl, triphenylmethyl, cinnamyl, naphthyl or anthranyl; methoxy, ethoxy Alkoxy groups such as methoxyethoxy, cyclohexyloxy, phenoxy, phenoxyethoxy; butylthio, octylthio, laurel, stearylthio, phenylthio, etc. An alkylthio group; an alkyl group, a propionate group, a butyl group, a pentamidine group, a benzamidine group, a tolyl group, a fluorenyl group or the like; an ethoxy group, a propenyloxy group, a butyloxy group, a decyloxy group such as a pentyloxy group, a benzamidineoxy group, a tolyloxy group, a hexyloxy group or a (meth)acryloxy group; a methoxycarbonyl group, an ethoxycarbonyl group, a butoxycarbonyl group, Alkoxycarbonyl group of octyloxycarbonyl, lauryloxycarbonyl, stearyloxycarbonyl, phenoxycarbonyl, benzyloxycarbonyl, etc., butylthiocarbonyl, octylthiocarbonyl, laurylthiocarbonyl, stearic sulfur An alkylthiocarbonyl group such as a carbonyl group, a phenylthiocarbonyl group or a benzylthiocarbonyl group; a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom or an iodine atom; a urea group; an amine group; a cyano group; a hydroxyl group; A group; a phosphate group; a trimethyl fluorenyl group, etc., but the present invention is not limited to the examples.

Among the semi-hindered phenols represented by the formula (I), an X ¹ -based hydrogen atom or a methyl group, X ² and X ⁴ are each independently a hydrogen atom or a methyl group, and the X ³ group may have a carbon number of a substituent 1~ The alkyl group of ⁵ , the X ⁵ is a semi-hindered phenol of a third butyl group or a third pentyl group, preferably a hydrogen atom or a methyl group of X ¹ , a hydrogen atom of X ² and X ⁴ , and a X ³ group may have a substituent. The alkyl group having 1 to 5 carbon atoms, and the semi-hindered phenol of the X ⁵ -type third butyl group or the third pentyl group is more preferable, further X ¹ -based methyl group, X ² and X ⁴ -based hydrogen atom, and X ³ system may be used. The alkyl group having 1 to 5 carbon atoms having a substituent, and the semi-hindered phenol of the X ⁵ -type third butyl group are preferably a X ¹ -based methyl group, X ² and X ⁴ -based hydrogen atoms, and X ³ -based carbon number 1~ The alkyl group of ⁵ , the semi-hindered phenol of the X ⁵ -type tert-butyl group is further preferably further.

The semi-hindered phenol may, for example, be 6-t-butyl o-cresol, 6-t-butyl-2,4-xylenol, 2,4,8,10-tetrabutyl-3-(-6)-[ 3-(3-methyl-4-hydroxy-5-t-butylphenyl)propoxy]dibenzo[d,f][1,3,2]dioxaphosphorin, 2,4 - dimethyl-6-(1-methylpentadecyl)phenol, 2,4-bis(octylthiomethyl)o-cresol, 2,4-(dodecylmethyl)o-cresol, 2-tert-butylphenol, 2,4-di-t-butylphenol, 2-tripentylphenol, 2,4-di-p-pentylphenol, and the like, but the present invention is not limited to the examples. These semi-hindered phenols may be used alone or in combination of two or more.

The semi-hindered phenol is commercially available, and examples thereof include Sumitomo Chemical Co., Ltd., trade name: SUMILIZER (registered trademark, the same as below) GP, etc., manufactured by BASF Corporation, trade name: CGX AO-145, IRGANOX (registered trademark, the same applies 245), IRGANOX 1520L, IRGANOX 1726, and the like, but the present invention is not limited to the examples.

In the present specification, a semi-hindered phenol dimer also includes the concept of its derivatives.

a semi-hindered phenol dimer, such as methylene bis(oxyethylene) Bis[3-(5-tert-butyl-4-hydroxy-m-tolyl)propionate], triethylene glycol bis[β-(3-tert-butyl-5-methyl-4-hydroxybenzene) Propionate], 4,4'-thiobis(2-methyl-6-tert-butylphenol), bis(3-methyl-4-hydroxy-5-t-butylbenzyl) Thioether, p-xylylene-di(2,6-dimethyl-4-tributyl-3-hydroxybenzyl) sulfide, 3,9-bis[2-[3-(3- Third butyl-4-hydroxy-5-methylphenyl)propanoic acid]-1,1-dimethylethyl]-2,4,8,10-tetraoxaspiro[5.5]undecane, 4,4'-butylidene bis(6-tert-butyl-3-methylphenol), 4,4'-thiobis(6-t-butyl-3-methylphenol), 1,1, 3-tris(2-methyl-4-hydroxy-5-t-butylphenyl)butane, 2,2'-methylenebis(4-methyl-6-tert-butylphenol), 2 , semi-hindered phenol such as 2'-methylenebis(4-ethyl-6-tert-butylphenol), 2,2'-thiobis(4-methyl-6-tert-butylphenol) Dimer; 2-[1-(2-hydroxy-3,5-di-t-pentylphenyl)ethyl]-4,6-di-p-pentyl phenyl acrylate, 2-tert-butyl a derivative of a semi-hindered phenol dimer such as 6-(3-tert-butyl-2-hydroxy-5-methylbenzyl)-4-methylphenyl acrylate, etc., but the present invention is not only Limited to this example . These semi-hindered phenol dimers may be used alone or in combination of two or more.

Suitable dimers of semi-hindered phenols, for example, dimers of semi-hindered phenols represented by formula (II-a):

Wherein X ² to X ⁵ are the same as described above. Y is a divalent linking group; a semi-hindered phenol dimer of the formula (II-b):

Wherein X ¹ , X ³ -X ⁵ and Y are the same as above; a semi-hindered phenol dimer of the formula (II-c):

In the formula, X ¹ , X ² , X ⁴ , X ⁵ and Y are the same as described above.

In the dimer of the semi-hindered phenol represented by the formula (II-a) to the formula (II-c), X ¹ to X ⁵ are the same as described above. X ¹ is a hydrogen atom or a linear alkyl group having 1 to 4 carbon atoms, preferably a hydrogen atom or a methyl group, and more preferably a methyl group. X ² to X ⁴ each independently represent a hydrogen atom or an alkyl group having 1 to 5 carbon atoms which may have a substituent, and X ² and X ⁴ are each independently a hydrogen atom or a methyl group, and a hydrogen atom is more preferable. X ³ is preferably an alkyl group having 1 to 5 carbon atoms which may have a substituent, and more preferably an alkyl group having 1 to 5 carbon atoms. X ⁵ is a third alkyl group having 4 to 12 carbon atoms or an alkyl group having 6 to 18 carbon atoms, preferably a third butyl group or a third pentyl group, and more preferably a third butyl group. Y is not particularly limited as long as it is a divalent linking group. Y is preferably any one of a carbon atom, an oxygen atom and a sulfur atom, and among these atoms, two or more of the same or different atomic bonds are more preferable.

The semi-hindered phenol dimer and its derivative are commercially available, and examples thereof include ADEKA STAB, trade name: ADEKASTAB (registered trademark, the same below) AO-30, ADEKASTAB AO-40 , ADEKASTAB AO-70, ADEKASTAB AO-80, etc.; Sumitomo Chemical Co., Ltd., trade name: SUMILIZER GA-80, SUMILIZER BBM-S, SUMILIZER WX-R, SUMILIZER MDP-S, SUMILIZER GM, SUMILIZER GS, etc., manufactured by BASF Corporation, trade name: IRGANOX 1081, etc.; Kawaguchi Chemical Industry Co., Ltd., trade name: ANTAGE W-300, ANTAGE CRYSTAL, ANTAGE W-400, ANTAGE W-500, etc., but the present invention is not limited to this example.

Among the components (A), a semi-hindered phenol represented by the formula (I) and a semi-hindered phenol dimer represented by the formula (II-a) are preferred from the viewpoint of enhancing chemical stability, and the coloring resistance is improved. In view of the above, a semi-hindered phenol represented by the formula (I), a dimer of a semi-hindered phenol represented by the formula (II-b), and a dimer of a semi-hindered phenol represented by the formula (II-c) are preferred. Among the components (A), chemical stability and coloring resistance are particularly excellent, and the semi-hindered phenol is preferably represented by the formula (I).

The component (B) is at least one stabilizer selected from the group consisting of (thio)phosphites, phosphines, and thioethers. Therefore, (thio)phosphite, phosphine, and thioether may be used alone or in combination of two or more. Furthermore, in the present specification, (thio)phosphite means the meaning of a phosphite and/or a thiophosphite.

The (thio)phosphite may, for example, be hydrogen hydrogen phosphite, bis(2-ethylhexyl phosphite), dilauryl hydrogen phosphite, dioleyl phosphite, or hydrogen phosphite. Hydrogen phosphite such as phenyl ester; triethyl phosphite, tributyl phosphite, tris(2-ethylhexyl phosphite), triisodecyl phosphite, trilauryl phosphite, phosphorous tris ( Trialkyl phosphites such as tridecyl ester), trioleylphosphite, and tristearyl phosphite; phenyl diisononyl phosphite, diphenyl methyl phosphite, 2-ethyl phosphite Hexyldiphenyl ester, isodecyl diphenyl phosphite, tridecyl diphenyl phosphite, bisphosphite bis(2,4-di-t-butyl-6-methylphenyl) Alkyl-aryl mixed phosphites such as esters; triphenyl phosphite, tricresyl phosphite, tris(phenylphenyl) phosphite, tris(2,4-di-t-butylphenyl) phosphite Triaryl phosphite; bis(isoindenyl)isopentitol diphosphite, diisopentyl diphosphite, bis(stearyl)isopentyl diphosphate, two Bis(nonylphenyl)isopentitol phosphite, bis(2,4-di-t-butylphenyl)isopentyl diphosphate, diphosphoric acid bis(2,6-di third Pentaerythritol diphosphite such as butyl-6-methylphenyl)isopentaerythritol; thiophosphite such as trilauryl trithiophosphate, phosphite 4,4- Butylene bis(3-methyl-6-t-butylphenyl diisotridecyl) ester, tetraphenyldipropylene glycol diphosphite, tetraphenyltetraisotetradecyl tetraphosphite, sub Tetrakis(C12-C15 alkyl)-4,4'-isopropylidene phenyl phosphate, tetrakis(dodecyl)-1,1,3-tris(2-methyl-5-t-butyl- 4-hydroxyphenyl)butane diphosphite, 2,4,8,10-tetrabutylbutyl-6-[3-(3-methyl-4-hydroxy-5-t-butylphenyl) Propyloxy]dibenzo[d,f][1,3,2]phosphorus British heptyl, phosphorous acid 2,2-methylenebis (4,6-tert-butylphenyl) 2-ethylhexyl acrylate and the like, but the present invention is not limited to only the embodiments illustrated. These (thio)phosphites may be used alone or in combination of two or more.

Among the (thio)phosphites, from the viewpoint of improving hydrolysis resistance and suppressing odor, the (thio)phosphite represented by the formula (III) is preferred: P(OR ¹ )(OR ² )( OR ³ ) (III)

(wherein R ¹ , R ² and R ³ are each independently represented by an alkyl group having 6 to 20 carbon atoms.) In the formula (III), each of R ¹ , R ² and R ³ is independently a carbon number. The alkyl (thio) phosphite of 8 to 18 is more preferred. Further, when two of R ¹ , R ² and R ³ are bonded to form a ring, the number of carbon atoms forming the ring may be 5 or less.

Among the (thio)phosphites, a (thio)phosphite which is liquid at normal temperature (for example, 23 ° C) is preferred from the viewpoint of workability and chemical stability. Among the (thio)phosphites, those which are liquid at normal temperature and which are easily obtained include, for example, triphenyl phosphite, tris(phenylphenyl) phosphite, triisodecyl phosphite, and diphosphoric acid. Bis(nonylphenyl)isopentyl glycol ester or the like, but the present invention is not limited to the examples. These phosphites may be used alone or in combination of two or more.

(Thio) phosphites are commercially available, and examples thereof include ADEKASTAB 3010, ADEKASTAB TPP, ADEKASTAB 2112, ADEKASTAB 260, ADEKASTAB 522A, ADEKASTAB 329K, ADEKASTAB 1178. , ADEKASTAB 1500, ADEKASTAB C, ADEKASTAB 135A, ADEKASTAB PEP-4C, ADEKASTAB PEP-8, ADEKASTABPEP-24G, ADEKASTABPEP-36, ADEKASTABHP-10, etc.; BASF company, trade name: IRGAFOS 168, IRGAFOS 38, etc.; Chengbei Chemical Industry (share) system, article number: JP-360, JP-3CP, JP-650, JPM-308, JPM-311, JPM-313, JP-308E, JP-312L, JP-333E, JP-318-O, JP-318E, JPS-312, JA-805, JPP-100, JPP-613M, JPP-31, JPE-10, JPE-13R, JPP-2000PT, etc.; SC organic chemistry (stock) system, trade name: Chelex D , Chelex TD, Chelex OL, Chelex S, Chelex LT-3, etc., but the invention is not limited to the illustration.

The phosphine may, for example, be triethylphosphine, tributylphosphine, tris(2-ethylhexyl)phosphine or triphenylphosphine, but the invention is not limited to the examples. These phosphines may be used alone or in combination of two or more.

Among the phosphines, the odor is suppressed while the toxicity is low, and the triaryl group Phosphine is preferred, and triphenylphosphine is preferred.

The thioether may, for example, be 3-laurylthiopropionic acid, methyl 3-laurylthiopropionate, (3-octylthiopropionic acid) isopentenyl tetraester, (3-mercaptothio group) Propionate) pentaerythritol tetraester, (3-laurylthiopropionic acid) pentaerythritol tetraester, (3-oleylthiopropionic acid) pentaerythritol tetraester, (3-stearyl group) Thioponic acid) pentaerythritol tetraester, (3-laurylthiopropionic acid)-4,4'-thiobis(3-methyl-5-tert-butyl-4-phenol) ester, etc. 3-alkylthiopropionic acid or ester thereof; dioctyl thiodipropionate, dimercapto thiodipropionate, dilauryl thiodipropionate, dimyristyl thiodi a thiocarboxylate such as propionate, distearyl thiodipropionate, lauryl stearyl thiodipropionate, distearyl-β, β'-thiodibutyrate 2 ester thioether of the base; thioether of methyl dimethyl ether, methyl dodecyl sulfide, dilauryl sulfide, distearyl sulfide, etc., 2,4-double (sim The thiomethyl group) o-cresol, 2,4-bis(dodecylthiomethyl)o-cresol or the like, but the present invention is not limited to the examples. These thioethers may be used alone or in combination of two or more.

Among the thioethers, from the viewpoint of suppressing odor, the thioether represented by the formula (IV) is preferred: R ⁴ -SR ⁵ (IV)

Wherein R ⁴ and R ⁵ each independently represent an alkyl group having 1 to 18 carbon atoms or have the formula:

(wherein R ⁶ represents an alkyl group having 1 to 24 carbon atoms which may have a substituent and having a carbon number of 1 to 24), and the alkyl group having 1 to 6 carbon atoms is represented by the formula (IV), and R ⁴ and R ⁵ Separately, the thioether having an alkyl group having 2 to 4 carbon atoms which is substituted with an alkyl group having 8 to 18 carbon atoms or an alkoxycarbonyl group having 6 to 20 carbon atoms is more preferable. Among the thioethers, from the viewpoint of improving workability, it is preferably a liquid thioether at normal temperature, and has a long-chain alkylthio group (at least one of R ⁴ and R ^{5 )} from the viewpoint of improving chemical stability. The thioether of the long-chain alkyl group is preferred. A thioether having a preferred long-chain alkylthio group, for example, (3-laurylthiopropionic acid) isopentenyl tetraester, (3-laurylthiopropionic acid)-4,4' - thiobis(3-methyl-5-tert-butyl-4-phenol) ester, 2,4-bis(octylthiomethyl)o-cresol, 2,4-bis(dodecyl) Thiomethyl) o-cresol or the like, but the present invention is not limited to the examples. These thioethers may be used alone or in combination of two or more.

Sulfide is commercially available, and examples thereof include ADEKA, trade name: ADEKASTAB AO-23, ADEKASTAB AO-412S, ADEKASTAB AO-503, etc. Sumitomo Chemical Co., Ltd. :SUMILIZER TPL-R, SUMILIZER TPM, SUMILIZER TPS, etc.; manufactured by BASF Corporation, trade name: IRGANOX 1520L, IRGANOX 1726, etc., but the present invention is not limited to this example.

Among the components (B), from the viewpoint of improving the safety of the human body, (thio)phosphites and thioethers are preferred, and (thio)phosphites and thioethers may be used alone or in combination. both.

The mass ratio of the component (A) to the component (B) [(A) component/(B) component] is preferably 0.01 to 50, more preferably 0.02 to 25, and further preferably 0.04 to 10, from the viewpoint of suppressing polymerization. The range is good.

The stabilizer composition of the present invention can be easily prepared by mixing the component (A) and the component (B) in a desired ratio.

The stabilizer composition of the present invention can be suitably used, for example, as a raw material for a polymer, a polymerizable compound such as a curable material, etc., and particularly, it can be suitably used for chemical stability and maintenance of an AMA ester. AMA The coexistence of the high polymerization activity of the ester. Therefore, the stabilizer composition of the present invention can be suitably used for an AMA ester, a polymerizable composition containing the AMA ester, and the like.

The stabilizer composition of the present invention can be used for an AMA ester, and can also be suitably used for a polymerizable composition containing an AMA ester.

The polymerizable composition of the present invention is characterized in that it contains a polymerizable composition of an AMA ester, and comprises a component (A) and a component (B).

The AMA ester may, for example, be an AMA ester represented by the formula (V):

Wherein R ⁷ represents a monovalent organic group. The AMA ester is a compound which can be used satisfactorily in the present invention.

In the formula (V), R ⁷ is a monovalent organic group. The monovalent organic group may, for example, be a hydrocarbon group which may have a substituent such as an ether group or a halogen atom. R ^{7 may be} in the form of a linear chain or a branched chain, and may also have a cyclic structure. The hydrocarbon group may, for example, be a chain-like saturated hydrocarbon group having 1 or more carbon atoms, a chain-like unsaturated hydrocarbon group having 3 or more carbon atoms, an alicyclic hydrocarbon group having 3 or more carbon atoms, or an aromatic hydrocarbon group having 6 or more carbon atoms. Among these, a chain-like saturated hydrocarbon group having 1 to 30 carbon atoms, a chain-like unsaturated hydrocarbon group having 3 to 30 carbon atoms, an alicyclic hydrocarbon group having 4 to 30 carbon atoms, and an aromatic hydrocarbon group having 6 to 30 carbon atoms are preferred. The substituent may, for example, be a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom or an iodine atom, a cyano group or a trimethylsulfonyl group, but the present invention is not limited to the examples.

The above chain saturated hydrocarbon group may, for example, be methyl, ethyl or n-propyl Base, isopropyl, n-butyl, t-butyl, tert-butyl, n-pentyl, second pentyl, third pentyl, neopentyl, n-hexyl, second hexyl, n-butyl, positive Octyl, second octyl, trioctyl, 2-ethylhexyl, octyl, decyl, decyl, eleven, lauryl, tridecyl, tetradecyl, fifteen, sixteen The group, the heptadecyl group, the stearyl group, the 19th group, the hexyl group, the twenty-sixth group, the thirtie group, and the like, but the invention is not limited to the illustration.

The above chain unsaturated hydrocarbon group may, for example, be crotyl, 1,1-dimethyl-2-propenyl, 2-methylbutenyl, 3-methyl-2-butenyl or 3-methyl 3-butenyl group, 2-methyl 3-butenyl group, oleyl group, linoleyl group, linoleyl group and the like, but the invention is not limited to the examples.

Examples of the alicyclic hydrocarbon group include a cyclopentyl group, a cyclopentylmethyl group, a cyclohexyl group, a cyclohexylmethyl group, a 4-methylcyclohexyl group, a 4-tert-butylcyclohexyl group, a tricyclodecyl group, an isobornyl group, and Adamantyl, dicyclopentyl, dicyclopentenyl, and the like, but the present invention is not limited to the examples.

The above aromatic hydrocarbon group such as phenyl, methylphenyl, dimethylphenyl, trimethylphenyl, 4-tert-butylphenyl, benzyl, diphenylmethyl, diphenylethyl, triphenyl The aryl group such as a methyl group, a cinnamyl group, a naphthyl group or an anthranyl group is not limited to this example.

The hydrocarbon group having an ether bond may, for example, be a methoxyethyl group, a methoxyethoxyethyl group, a methoxyethoxyethoxyethyl group, a 3-methoxybutyl group or an ethoxyethyl group. a chain ether group such as ethoxyethoxyethyl; cyclopentyloxyethyl, cyclohexyloxyethyl, cyclopentyloxyethyl, cyclohexyloxyethoxyethyl, bicyclo a pentadienylethyl group or the like having an alicyclic hydrocarbon group and a chain ether group; a phenoxyethyl group, a phenoxyethoxyethyl group or the like having an aromatic hydrocarbon group and a chain ether Base; glycidyl, β-methylglycidyl, β-ethylglycidyl, 3,4-epoxycyclohexylmethyl, 2-oxetanylmethyl, 3-methyl 3-oxetanylmethyl, 3-ethyl-3-oxetanylmethyl, tetrahydrofuranyl, tetrahydroindenyl, tetrahydropyranyl, bisoxazolyl, dioxoalkyl, etc. The cyclic ether group or the like, but the present invention is not limited to the examples.

Specific examples of the AMA ester include α-allyloxymethyl methacrylate, α-allyloxyethyl methacrylate, α-allyloxymethyl methacrylate, and α-allyl oxygen. Isopropyl methacrylate, α-allyloxy methacrylate n-butyl ester, α-allyloxy methacrylate second butyl ester, α-allyloxy methacrylic acid tert-butyl ester, α - allyl propenyl methacrylate, second amyl olefinic methacrylate, third pentyl methacrylate, alpha-allyloxy methacrylate Amyl ester, α-allyloxy methacrylate n-hexyl ester, α-allyloxy methacrylate second hexyl ester, α-allyloxy methacrylate n-butyl ester, α-allyloxymethyl N-octyl acrylate, second octyl α-allyloxymethacrylate, third octyl α-allyloxymethacrylate, 2-ethylhexyl α-allyloxymethacrylate, α - allyloxymethacrylate octyl ester, α-allyloxymethyl methacrylate, α-allyloxymethyl methacrylate, α-allyloxymethyl decyl acrylate, α- Allyloxymethacrylic acid laurel , α-allyloxy methacrylate decyl ester, α-allyloxy methacrylate tetradecyl ester, α-allyloxy methacrylate pentadecyl ester, α-allyloxy methacrylic acid Hexaester, heptadecyl α-allyloxymethacrylate, stearyl α-allyloxymethyl methacrylate, decyl α-allyloxymethacrylate, α-allyloxymethyl Ethyl acrylate, α-allyloxymethylpropene hexadecyl ester, α-allyloxy methacrylate tridecyl ester, α-allyloxy methacrylate crotonate, α-allyloxy group 1,1-dimethyl-2-methacrylate Propylene ester, 2-methylbutenyl α-allyloxymethacrylate, 3-methyl-2-butenyl α-allyloxymethacrylate, α-allyloxymethacrylic acid 3 -methyl-3-butenyl ester, 2-methyl 3-butenyl α-allyloxymethyl acrylate, α-allyloxy methacrylate oil, α-allyloxy methacrylic acid Linoleic ester, α-allyloxymethyl linolenic acid linolenic acid, α-allyloxymethylcyclohexyl methacrylate, α-allyloxymethylcyclopentyl methyl methacrylate, α-allyloxy Cyclohexyl methacrylate, cyclohexyl methyl α-allyloxy methacrylate, 4-methylcyclohexyl α-allyloxymethyl methacrylate, α-allyloxy methacrylic acid 4- Tributylcyclohexyl ester, tricyclodecyl α-allyloxymethacrylate, isobornyl α-allyloxymethacrylate, aglycolyl α-allyloxymethyl methacrylate, α-allyl Dicyclopentyl oxy methacrylate, dicyclopentadienyl α-allyloxymethyl methacrylate, phenyl α-allyloxy methacrylate, methyl α-allyloxymethyl methacrylate Phenyl ester, dimethylphenyl α-allyloxymethyl methacrylate, α-ene Trimethylphenyl oxymethacrylate, 4-tert-butylphenyl α-allyloxymethacrylate, benzyl α-allyloxymethyl methacrylate, α-allyloxymethacrylic acid Diphenylmethyl ester, diphenylethyl α-allyloxymethacrylate, triphenylmethyl α-allyloxymethacrylate, cinnamyl α-allyloxymethacrylate, α- Allyloxymethacrylate naphthyl ester, α-allyloxy methacrylic acid anthranilate, α-allyloxymethyl methacrylate methoxyethyl ester, α-allyloxymethyl methacrylate methoxy group Ethoxyethyl ester, methoxyethoxyethoxyethyl α-allyloxymethacrylate, 3-methoxybutyl α-allyloxymethacrylate, α-allyloxy Ethoxyethyl methacrylate, ethoxyethoxyethyl α-allyloxymethacrylate, cyclopentyloxyethyl α-allyloxymethacrylate, α-allyloxymethyl Cyclohexyloxyethyl acrylate, cyclopentyloxyethoxyethyl α-allyloxymethacrylate, α-allyloxymethyl methacrylate Ethoxyethoxyethyl ester, dicyclopentenyloxyethyl α-allyloxymethacrylate, phenoxyethyl α-allyloxymethacrylate, α-allyloxymethacrylic acid Phenoxyethoxyethyl ester, α-allyloxyglycidyl methacrylate, α-allyloxymethyl methacrylate β-methyl glycidyl ester, α-allyloxy methacrylic acid β- Ethyl glycidyl ester, α-allyloxymethyl methacrylate 3,4-epoxycyclohexyl methyl ester, α-allyloxymethyl acrylate 2-oxetane methyl ester, α-allyloxy 3-methyl-3-oxetanemethyl methacrylate, 3-ethyl-3-oxetane methyl α-allyloxymethacrylate, α-allyloxymethyl Tetrahydrofuranyl acrylate, tetrahydrofurfuryl α-allyloxymethacrylate, tetrahydropyranyl α-allyloxymethacrylate, dioxazole ester, α-allyloxymethacrylic acid dioxins Ester and the like, but the invention is not limited to the examples. These AMA esters may be used alone or in combination of two or more. Among these AMA esters, it is excellent in dilutable property, and a specific tetrahydrofuran ring structure can be introduced per unit weight of the polymer, and an α-allyloxymethacrylate alkyl group having an alkyl group having 1 to 4 carbon atoms is preferred. However, compared with other AMA esters, chemical stability in a high-temperature environment such as distillation conditions tends to be low.

The stabilizer composition of the present invention is excellent in chemical stability of the α-allyloxyalkyl acrylate having an alkyl group having 1 to 4 carbon atoms among the AMA esters.

The AMA ester can be prepared, for example, by the method described in JP-A-2011-137123.

The polymerizable composition of the present invention may be blended with the stabilizer composition of the present invention and components other than the AMA ester, if necessary, depending on the purpose of use, use, and the like, and may be used, for example, in a resin raw material composition or a curable coating. Laminate Materials and so on. Further, the AMA ester containing the stabilizer composition of the present invention can be used, for example, as a resin raw material or a reactive diluent, and can be used for resin raw material composition by mixing with other components depending on the purpose of use, use, and the like. Materials, hardenable coating materials, etc.

The stabilizer composition of the present invention and a component other than the AMA ester may, for example, be another polymerizable monomer copolymerizable with the AMA ester, a radical polymerization initiator, a curing accelerator, a resin binder, or a solvent. Various components such as additives and the like, but the present invention is not limited to the examples. The type and amount of the components vary depending on the purpose of the use of the stabilizer composition of the present invention and the AMA ester containing the stabilizer composition, the use thereof, etc., and therefore cannot be determined in general, depending on the purpose of use, Appropriate decisions such as use are preferred.

Other polymerizable monomers copolymerizable with the AMA ester can be used within the range not inhibiting the object of the present invention. Other polymerizable monomers which can be copolymerized with the AMA ester include, for example, a compound having a radical polymerizable group such as a carbon-carbon unsaturated bond; and an epoxy group, an oxetane group, or a vinyl group. A compound having a cationically polymerizable group such as an ether group; a compound having a radical polymerizable group and a cationically polymerizable group; and the present invention is not limited to the examples. Among these, it is hardened by the same mechanism as the AMA ester, and a radical polymerizable monomer is preferable.

The other polymerizable monomer which can be copolymerized with the AMA ester, for example, a monofunctional radical polymerizable monomer having one radical polymerizable unsaturated group in a molecule other than the AMA ester; A polyfunctional radical polymerizable monomer having a plurality of radically polymerizable unsaturated groups in the molecule. The polymerizable monomers other than the AMA esters may be used singly or in combination of two kinds. the above.

Examples of the monofunctional radically polymerizable monomer other than the AMA ester include methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, and isopropyl (meth)acrylate. N-butyl (meth)acrylate, second butyl (meth)acrylate, tert-butyl (meth)acrylate, n-amyl (meth)acrylate, second amyl (meth)acrylate, (A) Base) triamyl acrylate, n-hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, isodecyl (meth) acrylate, tridecyl (meth) acrylate, (methyl) Cyclohexyl acrylate, cyclohexyl methyl (meth) acrylate, octyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, benzyl (meth) acrylate, ( Phenyl methacrylate, isobornyl (meth)acrylate, adamantyl (meth) acrylate, tricyclodecyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, (methyl) 2-hydroxypropyl acrylate, 3-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 3-hydroxybutyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate ,(Methacrylate 2-methoxyethyl ester, 2-ethoxyethyl (meth)acrylate, phenoxyethyl (meth)acrylate, tetrahydrofurfuryl (meth)acrylate, glycidyl (meth)acrylate , β-methyl glycidyl (meth)acrylate, β-ethyl glycidyl (meth)acrylate, (3,4-epoxycyclohexyl)methyl (meth)acrylate, (methyl) (Meth) acrylate such as N,N-dimethylaminoethyl acrylate, α-hydroxymethyl methacrylate or α-hydroxyethyl methacrylate; N,N-di(methyl) propylene oxime (meth)acrylamide such as amine, (meth) propylene morpholine; cyano-2-propenyl oxyethyl ester such as (meth) acrylonitrile; (meth)acrylic acid, crotonic acid, cinnamic acid An unsaturated monocarboxylic acid such as vinyl benzoic acid, succinic acid (2-propenyloxyethyl ester) or succinic acid (2-methylpropoxy oxirane); maleic acid, fumaric acid, and itaconic acid An unsaturated polycarboxylic acid such as citraconic acid or mesaconic acid; An unsaturated acid anhydride such as maleic anhydride or isocanic anhydride; an aromatic vinyl compound such as styrene, α-methylstyrene, vinyltoluene or methoxystyrene; methylmaleimide or ethyl N substitution of maleic imine, isopropyl maleimide, cyclohexylmaleimide, phenyl maleimide, benzyl maleimide, naphthyl maleimide, etc. Maleic imine; conjugated diene such as 1,3-butadiene, isoprene, chloroprene; vinyl acetate such as vinyl acetate, vinyl propionate, vinyl butyrate, vinyl benzoate Base ester; vinyl ether, ethyl vinyl ether, propyl vinyl ether, butyl vinyl ether, 2-ethylhexyl vinyl ether, n-decyl vinyl ether, lauryl vinyl ether, cyclohexyl ethylene Ether, methoxyethyl vinyl ether, ethoxyethyl vinyl ether, methoxyethoxyethyl vinyl ether, methoxy polyethylene glycol vinyl ether, 2-hydroxyethyl vinyl Vinyl ether, 4-hydroxybutyl vinyl ether, etc., vinyl ether, N-vinyl pyrrolidone, N-vinyl caprolactam, N-vinylimidazole, N-vinylmorpholine, N-B N- vinyl compounds such as acetamide groups; (meth) acrylate, isocyanatoethyl methacrylate, propenyl isocyanate unsaturated isocyanate and the like, but the present invention is not limited only to the embodiments illustrated. The monofunctional radically polymerizable monomers other than the AMA esters may be used alone or in combination of two or more.

Examples of the polyfunctional radical polymerizable monomer other than the AMA ester include ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, and polyethylene glycol di(meth)acrylate. Propylene glycol di(meth)acrylate, butanediol di(meth)acrylate, hexanediol di(meth)acrylate, cyclohexanedimethanol di(meth)acrylate, bisphenol A alkylene oxide Di(meth)acrylate, bisphenol F alkylene oxide di(meth)acrylate, trimethylolpropane tri(meth)acrylate, di-trimethylolpropane tetra(meth)acrylate, Tris(meth)acrylate, different Pentaerythritol tetra(meth)acrylate, diisopentyl alcohol (meth) acrylate, diisopentaerythritol hexa(meth) acrylate, ethylene oxide addition dimethylolpropane tris Acrylate, ethylene oxide addition di-trimethylolpropane tetra(meth)acrylate, ethylene oxide addition pentaerythritol tetra(meth)acrylate, ethylene oxide addition Diisopentaerythritol hexa(meth) acrylate, propylene oxide addition trimethylolpropane tri(meth) acrylate, propylene oxide addition di-trimethylolpropane tetra (meth) acrylate , propylene oxide addition of pentaerythritol tetra (meth) acrylate, propylene oxide addition diisopentaerythritol hexa (meth) acrylate, ε-caprolactone addition trimethylolpropane three ( Methyl) acrylate, ε-caprolactone addition ditrimethylolpropane tetra(meth) acrylate, ε-caprolactone addition pentaerythritol tetra(meth) acrylate, ε-hexine Polyfunctional (meth) acrylate such as diester pentaerythritol hexa(meth) acrylate; ethylene glycol divinyl ether, diethylene glycol divinyl ether, polyethylene glycol divinyl ether , propylene glycol divinyl ether, butanediol II Vinyl ether, hexanediol divinyl ether, bisphenol A alkylene oxide divinyl ether, bisphenol F alkylene oxide divinyl ether, trimethylolpropane trivinyl ether, ditrimethylolpropane Tetravinyl ether, glycerol trivinyl ether, isovaerythritol tetravinyl ether, diisopentaerythritol penta vinyl ether, diisopentaerythritol hexavinyl ether, ethylene oxide addition trimethylol Propane trivinyl ether, ethylene oxide addition ditrimethylolpropane tetravinyl ether, ethylene oxide addition pentaerythritol tetravinyl ether, ethylene oxide addition diisopentaerythritol a polyfunctional vinyl ether such as vinyl ether; 2-vinyloxiranyl (meth)acrylate, 3-vinyloxime (meth)acrylate, 1-methyl-2-ethene (meth)acrylate Ethyloxyethyl ester, 2-enoxonol (meth)acrylate, 4-vinyloxime (meth)acrylate, 4-vinyloxime (meth)acrylate, (meth)acrylic acid 5-vinyloxime pentaester, 6-vinyloxime (meth)acrylate, 4-vinyloxiranylmethylcyclohexyl (meth)acrylate Ester, (meth)acrylic acid to ethylene methoxymethyl phenyl methyl ester, (meth) acrylate 2-(vinyl methoxy ethoxy) ethyl ester, (meth) acrylate 2- (vinyl oxiran oxyethylene) a vinyl ether group-containing (meth) acrylate such as ethoxyethoxyethyl ester; ethylene glycol diallyl ether, diethylene glycol diallyl ether, polyethylene glycol diene Ether, propylene glycol diallyl ether, butanediol diallyl ether, hexanediol diallyl ether, bisphenol A alkylene oxide diallyl ether, bisphenol F alkylene oxide diallyl Ether, trimethylolpropane triallyl ether, di-trimethylolpropane tetraallyl ether, glyceryl triallyl ether, pentaerythritol tetraallyl ether, diisopentaerythritol pentaene Propyl ether, diisopentaerythritol hexenyl ether, ethylene oxide addition trimethylolpropane triallyl ether, ethylene oxide addition di-trimethylolpropane tetraallyl ether a polyfunctional allyl ether such as ethylene oxide addition to isopentaerythritol tetraallyl ether or ethylene oxide addition diisopentaerythritol hexenyl ether; allyl (meth) acrylate Ethyl-containing (meth) acrylate; tris(propylene oxime) Uric acid ester, tris(methacryloxyethyl)isocyanurate, alkylene oxide addition tris(propylene oxyethyl)isocyanurate, alkylene oxide addition tris(methacryl oxime a polyfunctional (meth) acryloxy-containing isocyanurate such as oxyethyl)isocyanurate or a polyfunctional ally-containing isocyanuric acid such as triallyl isocyanurate a polyfunctional isocyanate such as toluene diisocyanate, isophorone diisocyanate or xylene diisocyanate, and a hydroxyl group such as 2-hydroxyethyl (meth)acrylate or 2-hydroxypropyl (meth)acrylate. A polyfunctional urethane (meth) acrylate obtained by a reaction of (meth) acrylate, a polyfunctional aromatic vinyl group such as divinyl benzene, or the like, but the present invention is not limited to the examples. The polyfunctional radical polymerizable monomers other than the AMA esters may be used alone or in combination of two or more.

AMA ester and other polymerizable copolymerizable with the AMA ester The amount of the component (A) which is 100 parts by mass of the total amount of the monomer is preferably 0.005 parts by mass or more, more preferably 0.01 parts by mass or more, and more preferably 0.02 parts by mass or more, from the viewpoint of sufficiently suppressing the polymerization. It is preferably 0.03 parts by mass or more, and is preferably 0.5 parts by mass or less, more preferably 0.3 parts by mass or less, further preferably 0.2 parts by mass or less, and 0.1 or less, from the viewpoint of maintaining the radical polymerization activity of the radical polymerizable composition. The quality department is the best below.

Further, the amount of the (A) component of 100 parts by mass equivalent of the AMA ester and the other polymerizable monomer copolymerizable with the AMA ester is 0.005 or more in excess of the mass portion from the viewpoint of sufficiently suppressing the polymerization. Preferably, it is preferably 0.01 parts by mass or more, more preferably 0.02 parts by mass or more, and most preferably 0.04 parts by mass or more, and the dissolution of the polymer obtained from the radical polymerizable composition or the polymerizable composition is improved. The viewpoint is preferably 3 parts by mass or less, more preferably 2 parts by mass or less, further preferably 1 part by mass or less, and most preferably 0.5 parts by mass or less.

The polymerizable composition of the present invention may further contain a radical polymerization initiator, a curing accelerator, a resin binder, a solvent, an additive, and the like. The amount of the polymerizable monomer, the radical polymerization initiator, the curing accelerator, the resin binder, the solvent, and the additive other than the AMA ester varies depending on the polymerizable composition of the present invention, and therefore cannot be roughly determined, and the composition is determined according to the composition. The appropriate decision is better.

The radical polymerization initiator may, for example, be a thermal radical polymerization initiator which generates a radical by heating, a photoradical polymerization initiator which generates a radical by irradiation of an active energy ray, or the like. The polymerization initiators may be used alone or in combination of two or more.

Thermal radical polymerization initiator, which can be initiated by peroxide polymerization Agent, azo polymerization initiator, and the like.

Examples of the peroxide-based polymerization initiator include lauric acid peroxide, benzamidine peroxide, and dibutylbutyl-2-ethylhexanoate peroxide. However, the present invention is not limited to the examples. . These peroxide-based polymerization initiators may be used alone or in combination of two or more.

Examples of the azo polymerization initiator include 2,2'-azobis(2-methylbutyronitrile), 2,2'-azobisisobutyronitrile, and 2,2'-azobis (2). , 4-dimethylvaleronitrile), dimethyl-2,2-azobis(2-methylpropionate), etc., but the present invention is not limited to the examples. These azo-based polymerization initiators may be used alone or in combination of two or more.

When a thermal radical polymerization initiator is used, a radical polymerization accelerator can also be used. The radical polymerization accelerator may, for example, be a wholly-owned salt or a metal complex of cobalt, copper, tin, zinc, manganese, iron, zirconium, chromium, vanadium, calcium, potassium or the like; a primary amine, a secondary amine, An amine compound of 3; a 4-grade ammonium salt; a thiourea compound; a ketone compound, etc., but the present invention is not limited to the examples.

The photoradical polymerization initiator may, for example, be 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-phenylpropan-1-one or 2-methyl-1-(4- Methylthiophenyl)-2-morpholinylpropan-1-one, 2-benzyl-2-dimethylamino-1-(4-morpholinylphenyl)-butanone-1, etc. An alkylphenol compound; a benzophenone compound such as benzophenone or 4,4'-bis(dimethylamino)benzophenone; benzoin isopropyl ether or benzoin isobutyl ether; A benzoin compound; a thioxanthone compound such as 2,4-dimethylthioxanthone or 2,4-diethylthioxanthone; a halomethylated triazine compound; a halomethylated oxadiazole system a compound; a diimidazole compound; a titanocene compound; an benzoic acid ethyl ester compound; an acridine compound, etc., but the present invention, and It is not limited to this illustration. These photoradical polymerization initiators may be used alone or in combination of two or more.

When a photoradical polymerization initiator is used, a photosensitizer, a radical polymerization accelerator, or the like can also be used. The photosensitizer and the radical polymerization accelerator may, for example, be a dye-based compound such as a xanthene dye, a coumarin dye, a 3-ketocoumarin compound or a pyrromethylene dye; 4-dimethylamino group An alkylamino benzene compound such as ethyl benzoate or 2-ethylhexyl benzoic acid 2-ethylhexyl ester; 2-mercaptobenzothiazole, 2-mercaptobenzoxazole, 2-indole A thiol-based hydrogen donor such as a benzimidazole or the like, but the present invention is not limited to the examples. These photosensitizers and radical polymerization accelerators may be used alone or in combination of two or more.

The amount of the radical polymerization initiator is from 0.01 to 30 parts by mass based on the total mass of 100 parts by mass of the AMA ester and the polymer monomer other than the AMA ester from the viewpoints of the curability and economy of the polymerizable composition. Preferably, the quality is preferably 0.05 to 20, and further preferably 0.1 to 15 parts by mass.

Examples of the hardening accelerator include trimethylolpropane tris(3-mercaptopropionate), pentaerythritol tetrakis(3-mercaptopropionate), and diisopentaerythritol hexa(3-mercaptoproperate). The present invention is not limited to the examples and the curing accelerators, and may be used alone or in combination of two or more.

The resin binder may, for example, be an alkali-soluble oligomer such as a carboxyl group-modified vinyl ester resin or a (meth)acrylic polymer, an alkali-soluble polymer or a (meth)acrylate polymer, but the present invention is not limited to the present invention. Limited to this illustration. These resin binders may be used alone or in combination of two or more. The polymerizable composition of the present invention can be used for alkaline development type resist for use in, for example, a solder resist, a resist for a color filter, a protective film resist, or the like by adding a resin binder. Uses of agents, paints, inks, etc.

Since the AMA ester is excellent in solubility and dilutable property, a resin similar to or similar to the resin constituting the substrate can be dissolved. Therefore, by using such a resin as a resin binder, it can be suitably used as the substrate. The primer and the adhesive. The resin binder may, for example, be a polyvinyl alcohol resin, a (meth)acrylic resin, a polyolefin resin, a cyclic olefin resin, a polyester resin, a cellulose resin, or a polycarbonate. The present invention is not limited to the examples.

The solvent may, for example, be a monoalcohol such as methanol, isopropanol or n-butanol; a polyhydric alcohol such as ethylene glycol or propylene glycol; a cyclic ether such as tetrahydrofuran or dioxane; and ethylene glycol; a glycol monoether such as monomethyl ether, diethylene glycol monomethyl ether or propylene glycol monomethyl ether; glycol ether such as ethylene glycol dimethyl ether, diglyme, propylene glycol dimethyl ether; An ester of a glycol monoether such as methyl ether acetate, propylene glycol monomethyl ether acetate or 3-methoxybutyl acetate; an alkyl group such as ethyl acetate, isopropyl acetate, butyl acetate or ethyl lactate. Ester; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, methyl cyclohexanone; aromatic hydrocarbon compounds such as benzene, toluene, xylene, ethylbenzene; hexane, cyclohexane, octane, etc. An aliphatic hydrocarbon compound; an amine compound such as dimethylformamide, dimethylacetamide or N-methylpyrrolidone, but the present invention is not limited to the examples. These solvents may be used alone or in combination of two or more.

The additive may, for example, be a filler, a color material, a dispersant, an adhesion promoter, a mold release agent, a plasticizer, an ultraviolet absorber, a matting agent, an antifoaming agent, a smoothing agent, a charge preventing agent, a lubricant, and a surface modification. The agent, the coupling agent and the like, but the invention is not limited to the examples.

The polymerizable composition of the present invention may be, for example, an AMA ester, a component (A), a component (B), and another polymerizable monomer copolymerizable with an AMA ester, if necessary, a radical polymerization initiator. And a curing accelerator, a resin binder, a solvent, an additive, and the like are mixed and prepared.

The mixing order of the components is arbitrary, and the present invention is not limited to the mixing order.

The polymerizable composition of the present invention can be polymerized, for example, by heating, irradiation with an active energy ray, or the like.

When a thermal radical polymerization initiator is used as the polymerizable composition of the present invention, the heating temperature of the polymerizable composition varies depending on the composition of the polymerizable composition and the type of the thermal radical polymerization initiator. It is not possible to generalize the determination, and it is usually 30 to 400 ° C, more preferably 70 to 350 ° C, and even more preferably, the temperature suitable for the curing of the polymerizable composition is selected from the range of 100 to 350 ° C.

When a polymerizable composition of the present invention is used as a photoradical polymerization initiator, the polymerizable composition can be polymerized by irradiation with an active energy ray. Examples of the active energy ray include electromagnetic waves such as γ-rays, X-rays, ultraviolet rays, visible rays, and infrared rays, particle lines such as electron beams, neutron beams, and proton wires, and the like, but the present invention is not limited to the examples. Among these active energy rays, gamma rays, X-rays, ultraviolet rays, visible rays, and electron rays are preferred from the viewpoint of energy intensity, and ultraviolet rays, visible rays, and electron wires are more preferable, and ultraviolet rays are more preferable.

In the case where the polymerizable composition of the present invention is used together with a thermal radical polymerization initiator and a photoradical polymerization initiator, either heating or irradiation of an active energy ray or both may be used.

As described above, by polymerizing the polymerizable composition of the present invention, Polymer composition.

As described above, the polymerizable composition of the present invention can prevent not only the chemical stability of the AMA ester but also the high polymerization activity which is maintained by the AMA ester, and the polymerization can be prevented by the polymerizable composition or polymerization. The color of the polymer obtained from the composition can be favorably used for, for example, a coating material, an adhesive, a sealing material, an adhesive, a primer, a paint, an ink, a resist, a dental material, a lens, a molding material, and the like. the use of.

[Examples]

Next, the present invention will be described in more detail based on examples, but the present invention is not limited to the examples. In addition, in the following, unless otherwise mentioned, "part" means "quality" and "%" means "mass%".

Preparation Example 1 [Preparation of α-Allyloxymethyl methacrylate]

In a round bottom flask equipped with a distillation column, a phase separator, and a reflux pump of 5 L (liter), 1625.7 g of α-hydroxymethyl methacrylate and 1219.7 g (1.5 equivalents) of allyl alcohol were placed as a catalyst. 78.5 g (0.05 eq.) of triethylenediamine (DABCO), 84.9 g (0.1 eq.) of acetic acid as acid, and 30.7 g (0.01 eq.) of zinc acetate dihydrate and 30.7 g (0.01 eq.) as a water entraining agent. 429.1 g (0.3 equivalent), 0.8 g of hydroquinone monomethyl ether as a polymerization inhibitor, and 0.8 g of 4-hydroxy-2,2,6,6-tetramethylpiperidine-1-oxo.

Nitrogen gas containing 7 vol% of oxygen was blown into the flask at a flow rate of 5 mL/min, and the contents of the flask were heated to 90 ° C at atmospheric pressure. In the reaction, the top liquid in the fractionation column is separated into an oil phase and an aqueous phase by a phase separator, and the oil phase is taken out as a reflux liquid, and the aqueous phase is extracted and reacted at 90 ° C for 16 hours to prepare a reaction. Alpha-allyloxymethyl methacrylate (hereinafter, referred to as Meama). The resulting reaction mixture was washed with water, and by distillation, MeAMA was obtained as a colorless, transparent liquid.

<Free radical polymerization activity of radical polymerizable composition>

Example 1-1

As a stabilizer for at least one semi-hindered phenol compound selected from the group consisting of semi-hindered phenols and dimers thereof (hereinafter referred to as group (A), liquid at room temperature (23 ° C) 6 - tributyl butyl-2,4-xylenol (hereinafter referred to as TPA): 0.03 g, as at least one stabilizer selected from the group consisting of (thio)phosphites, phosphines, and thioethers The stabilizer (hereinafter referred to as group (B)) is prepared by reacting 0.05 mg of triphenyl phosphite (hereinafter referred to as TPP) at a normal temperature (23 ° C) as a liquid to prepare a stabilizer composition.

0.08 g of the stabilizer composition obtained above and 100 g of MeAMA obtained in Preparation Example 1 were mixed to obtain a radical polymerizable composition. As the physical properties of the obtained radically polymerizable composition, the radical polymerization activity in solution polymerization and the radical polymerization activity in emulsion polymerization were examined by the following methods. The results are shown in Fig. 1.

[Free radical polymerization activity in solution polymerization]

2.0 g of a radical polymerizable composition, 18.0 g of toluene, ethyl acetate or methyl ethyl ketone as a solvent, 2,2'-bis(2-methylbutyronitrile) as a radical polymerization initiator [Japan FINECHEM (shares) The product name: ABN-E (hereinafter referred to as ABN-E)] 0.05 g was placed in a reaction vessel, and a reflux tube was attached to the reaction vessel, and the reaction vessel was immersed in an oil bath maintained at 80 °C. Occasionally, the temperature of the contents of the reaction vessel was maintained at 80 ° C for 1 hour, and then the contents of the reaction vessel were cooled by immersing the reaction vessel in a water bath at 25 ° C. The contents of the reaction vessel The amount of MeAMA remaining was measured in the following manner, and the polymerization conversion ratio was determined as a result of the radical polymerization activity. Furthermore, the higher the polymerization conversion rate, the better the radical polymerization activity.

(Remaining amount of MeAMA)

The residual amount of MeAMA was measured using a high-performance liquid chromatography (HPLC) apparatus [manufactured by Shimadzu Corporation, product number: DGU-20A5, LC-20AD, SIL-20A, SPD-20A, and CTO-20A]. The measurement conditions at this time are as follows.

(measurement conditions)

. Dilution solvent: acetonitrile / methanol = 2 / 1 (mass ratio)

. Extraction solvent: 0.1 mol% phosphoric acid aqueous solution / acetonitrile / methanol mixed solvent

. Separation column: (share) Shiseido system, trade name: CAPCELL PAK C18 TYPE: AQ

[In the radical polymerization activity of emulsion polymerization]

In a 5 L (liter) flask equipped with a dropping funnel, a stirrer, a nitrogen gas introduction tube, a thermometer, and a reflux cooling tube, 133.0 g of deionized water was placed. In the dropping funnel, 16.0 g of a 25% aqueous solution of an emulsifier [manufactured by Kao Co., Ltd., trade name: EMAL O], 24.0 g of deionized water, and 100.0 g of the radical polymerizable composition obtained above were prepared. 1 stage pre-latex.

In the first-stage pre-emulsion obtained above, 7.0 g of an amount corresponding to 5% of the pre-emulsion was added to the flask, and nitrogen gas was slowly blown while stirring to a temperature of 75 ° C under stirring. After the temperature was raised, 1.0 g of a 5% potassium persulfate aqueous solution was added to the flask to initiate initial polymerization, and the contents of the flask were heated to 80 ° C for 20 minutes to carry out initial polymerization.

After the initial polymerization is completed, the temperature of the contents of the flask is maintained. The residue of the pre-latex for the first stage and 8.0 g of a 2.5% potassium persulfate aqueous solution were allowed to stand for 180 minutes in a state of 80 ° C, and uniformly dropped into the flask. At the same time as the completion of the dropwise addition, the contents of a small amount of the flask were taken, and the residual amount of MeAMA was measured in the same manner as above to determine the polymerization conversion ratio as an index of the radical polymerization activity. Furthermore, the higher the polymerization conversion rate, the better the radical polymerization activity.

Examples 1-2 to 1-3 and Comparative Examples 1-1 to 1-2

The stabilizer composition was prepared in the same manner as in Example 1-1 except that the type and amount of the stabilizer composition were changed to those shown in Table 1. A radical polymerizable composition was obtained in the same manner as in Example 1-1 except that the obtained stabilizer composition was used. The radical polymerization activity and the radical polymerization activity of the emulsion polymerization were examined in the same manner as in Example 1-1, as the physical properties of the obtained radically polymerizable composition. The results are shown in the first table.

In addition, in the following table, each short number means the following meaning.

[(A) group]

. TPA: 6-tert-butyl-2,4-xylenol (liquid at room temperature)

. W400: Kawaguchi Chemical Industry Co., Ltd., trade name: ANTAGE W-400 (ortho-dimer of semi-hindered phenol, solid at room temperature)

[(B) group]

. TPP: Triphenyl phosphite (normal temperature is liquid)

. AO412S: (share) made by ADEKA, trade name: ADEKASTAB AO-412S (thioether stabilizer, solid at room temperature)

. AS2112: (stock) made by ADEKA, trade name: ADEKASTAB 2112 (phosphite stabilizer, solid at room temperature)

. PEP36: (share) ADEKA system, trade name: ADEKASTAB PEP-36 (Asia Phosphate ester stabilizer, solid at room temperature)

. TPLR: Sumitomo Chemical Co., Ltd., trade name: Sumilizer TPL-R (thioether stabilizer, solid at room temperature)

[other]

. TBHQ: tert-butyl hydroquinone (solid at room temperature)

. MEHQ: hydroquinone monomethyl ether (solid at room temperature)

. Irg1010: BASF Japan (stock), trade name: Irganox1010 (hindered phenol system stabilizer, solid at room temperature)

[solvent]

. EAC: ethyl acetate

. MEK: methyl ethyl ketone

As a result of the results shown in the first table, the radical polymerizable composition of the stabilizer composition obtained in each of the examples showed that the radical polymerization activity and the radical polymerizability of the stabilizer composition were not obtained in Comparative Example 1-1. Composition Excellent, the radical polymerization activity was remarkably excellent as compared with the radically polymerizable composition containing the third butyl hydroquinone (TBHQ) obtained in Comparative Example 1-2.

<Coloring resistance in the case of alkaline contact of a radical polymerizable composition>

Example 2-1

The stabilizer composition was prepared by mixing TPA 0.03 g and TPP 0.05 g.

0.08 g of the stabilizer composition obtained above and 100 g of MeAMA obtained in Preparation Example 1 were mixed to obtain a radical polymerizable composition. As the physical properties of the obtained radically polymerizable composition, the color resistance at the time of contact with a base was examined by the following method. This result is shown in the second table.

[Color tolerance when in contact with alkali]

The radical polymerizable composition 1.0 was mixed with 2.7 parts of a 10% sodium hydroxide aqueous solution, and the obtained solution was stirred at room temperature for 1 hour, and then the color of the solution was visually confirmed, and the coloring level and the color type were brought into contact with the alkali. The indicator of color tolerance.

Example 2-2~2-3 and Comparative Example 2-1~2-3

The stabilizer composition was prepared in the same manner as in Example 2-1 except that the type and amount of the stabilizer composition were changed to those shown in Table 2. A radical polymerizable composition was obtained in the same manner as in Example 2-1, using the obtained stabilizer composition. As the physical properties of the obtained radical polymerizable composition, the color resistance at the time of contact with a base was examined in the same manner as in Example 2-1. This result is shown in the second table.

From the results shown in the second table, it is understood that the radical polymerizable composition including the stabilizer composition obtained in each of the examples is compared with the radical polymerizable composition containing the stabilizer composition obtained in each of the comparative examples. Excellent color resistance when in contact with a base.

<Coloring tolerance of polymer solution>

Example 3-1

The stabilizer composition was prepared by mixing TPA 0.03 g and TPP 0.05 g.

0.08 g of the stabilizer composition obtained above and 100 g of MeAMA obtained in Preparation Example 1 were mixed to prepare a radical polymerizable composition composed only of MeAMA. By adding 66.0 g of the radically polymerizable composition composed only of the MeAMA, isobornyl methacrylate [manufactured by Kyoeisha Chemical Co., Ltd., trade name: LIGHTESTER IB-X] 27.2 g and methacrylic acid 2 were added. - 6.2 g of hydroxyethyl ester [manufactured by Nippon Shokubai Co., Ltd.] was mixed to obtain a radical polymerizable composition.

The four separable flasks were replaced with nitrogen, and the inside of the reaction vessel equipped with a thermometer, a nitrogen gas introduction tube, and a stirring device was replaced with nitrogen. 66.7 g of ethyl acetate and 20.0 g of the radically polymerizable composition obtained above were placed in the reaction vessel under a nitrogen stream, and the temperature was raised to 80 °C.

On the other hand, 80.0 g of a radical polymerizable composition was placed in the dropping tank A, and 0.43 g of ABN-E and n-dodecyl mercaptan (hereinafter referred to as n-DM) 0.26 g were placed in the dropping tank B. And a mixture of 23.3 g of ethyl acetate (hereinafter referred to as EAC).

After confirming the internal temperature stability of the reaction vessel, a mixture of 0.07-g of ABN-E, 0.05 g of n-DM, and 10.0 g of EAC was added to the reaction vessel. After the completion of the addition, the mixture was dropped into the drip tank A and the drip tank B over 10 minutes, and the internal temperature of the reaction vessel was adjusted to 80 to 83 ° C, and the drip tank A was allowed to flow for 3 hours. The liquid tank B was dropped into the mixture for 4 hours to carry out a polymerization reaction. After the completion of the dropwise addition, the mixture was further stirred at a temperature of 80 to 83 ° C for 2 hours, and the internal temperature of the reaction vessel was cooled to room temperature to obtain a colorless transparent polymer solution.

As the physical properties of the polymer solution obtained above, the color resistance when the polymer solution was brought into contact with a base and the coloring resistance under the storage stability test conditions. The results are shown in Table 3.

[Color resistance of polymer solution in contact with alkali]

3 g of the polymer solution was placed in a spiral tube having a capacity of 10 mL, and after heating to 50 ° C, 0.3 g of monoethanolamine was added to the spiral tube, and the mixture was thoroughly stirred, and the color of the polymer solution was visually confirmed to determine whether or not the color was used as a contact with the alkali. The indicator of color tolerance.

[Coloring resistance of polymer solution under storage stability test conditions]

5 g of the polymer solution obtained above was placed in a spiral tube having a capacity of 10 mL, and the opening of the spiral tube was capped, and the spiral tube was sealed, and stored in a hot air dryer maintained at 50 ° C for one month, and then visually confirmed. The color of the polymer solution, whether or not the coloring is used as the coloring resistance under the storage stability test conditions Standard.

Example 3-2 and Comparative Example 3-1

The stabilizer composition was prepared in the same manner as in Example 3-1 except that the type and amount of the stabilizer composition were changed to those shown in Table 3. A polymer solution was obtained in the same manner as in Example 3-1, using the obtained stabilizer composition. As the physical properties of the obtained polymer solution, the color resistance at the time of contact with a base and the coloring resistance under the storage stability test conditions were examined in the same manner as in Example 3-1. This result is shown in the third table.

From the results shown in the third table, it was found that the polymer solution obtained in each of the examples was superior to the polymer solution obtained in the comparative example in coloring resistance upon contact with a base and coloring resistance under the storage stability test conditions.

<Coloring resistance under the weathering test conditions of the cured product>

Example 4-1

The stabilizer composition was prepared by mixing TPA 0.03 g and TPP 0.05 g.

0.08 g of the stabilizer composition obtained above and 100 g of MeAMA obtained in Preparation Example 1 were mixed to prepare a radical polymerizable composition composed only of MeAMA. 8.0 g of the radical polymerizable composition composed only of MeAMA Diisopentaerythritol hexaacrylate [manufactured by Kyoeisha Chemical Co., Ltd., trade name: LIGHT ACRYLATE DPE-6A] 2.0 g and IRGACURE 184D as a photoradical initiator (BASF Japan Co., Ltd.) 0.3 g is mixed to obtain a radical polymerizable composition.

A polyethylene terephthalate film (hereinafter referred to as a PET film) having a thickness of 100 μm was used as a spacer, and 0.5 g of the above radical polymerizable composition was placed together with a spacer to release a PET film package. The clip is further clipped with a transparent glass plate. The transparent glass plate was irradiated with ultraviolet rays with an integrated light amount of 4 (J/cm ² ) using a conveyor belt type ultraviolet irradiation device, and then the release-treated PET film was peeled off to obtain a film-like cured product having a thickness of 100 μm.

As the physical properties of the obtained film-like cured product, the coloring resistance under the weathering test conditions was examined by the following method. The results are shown in Table 4.

[Coloring tolerance under weathering test conditions]

The yellowness (b value) of the film-form cured product obtained above was measured using a differential meter, and the obtained value was made into the initial b value.

Next, after the film-like cured product was placed under the following weathering test conditions, the b value was measured again, and the obtained value was taken as the b value after the test. Furthermore, the smaller the b value, the smaller the yellowing degree.

(weathering test conditions)

Testing machine: SUGA testing machine (share) system, trade name: Xenon arc lamp weathering testing machine X75SC

Radiation: 60W/m ²

Blackboard temperature: 63 ° C

Humidity: relative humidity 50%

Test time: 500 hours

Comparative Example 4-1~4-3

The stabilizer composition was prepared in the same manner as in Example 4-1 except that the type and amount of the stabilizer composition were changed to the fourth table, and the radical polymerization property of the stabilizer composition was examined. The color resistance of the film-like cured product obtained from the composition under weathering test conditions. This result is shown in the fourth table.

From the results shown in Table 4, it is understood that the cured product obtained in Example 4-1 has a smaller initial b value than the cured product obtained in each comparative example, so that the initial yellow change degree is small, and further, after the test, b The value is small, so the color resistance under the weathering test conditions is good.

<Storage stability of radical polymerizable composition>

Example 5-1

The stabilizer composition was prepared by mixing 0.05 g of TPA and 0.5 g of TPP.

0.55 g of the stabilizer composition obtained above and 100 g of MeAMA obtained in Preparation Example 1 were mixed to obtain a radical polymerizable composition. Collecting the resulting free radicals The synergistic composition 3g was placed in a spiral tube having a capacity of 10 mL, the opening of the spiral tube was capped, the spiral tube was sealed, and placed in a thermostat at 50 ° C, and the spiral tube was taken out by a thermostat every other month, for example. Methods investigate storage stability. This result is shown in the fifth table.

[Storage Stability]

(1) With or without polymer

The content (liquid) of the spiral tube was taken out, and n-hexane was added dropwise at room temperature (about 23 ° C). When no precipitate occurred, it was judged that there was no polymer, and when a precipitate occurred, it was judged that a polymer was present. However, if the contents of the spiral tube are significantly viscous or gelled, it is unconditionally judged to have a polymer.

In the column of "the presence or absence of the polymer" in the fifth table, the content of the polymer is counted in the case where the content is dropped into n-hexane until the polymer is generated for 9 months, and the content is dropped into n-hexane. When no polymer occurred between the time of 9 months, it was described as "None".

(2) Whether there is coloring

When the content was dropped into n-hexane until the polymer did not occur for 9 months, the color state of the content was visually observed.

In the column of "the presence or absence of coloring" in the fifth table, the coloring state of the contents is described. In addition, when the content was dropped into n-hexane until the polymer was formed for 9 months, it was described as "-".

Examples 5-2 to 5-23 and Comparative Examples 5-1 to 5-8

The stabilizer composition was prepared in the same manner as in Example 5-1 except that the type and amount of the stabilizer composition were changed to those shown in Table 5, and the radical polymerizable composition including the stabilizer composition was examined. Storage stability of the object. will The results are shown in Table 5.

From the results shown in the fifth table, it was found that the radically polymerizable composition obtained in each of the examples had better storage stability than the radically polymerizable composition obtained in each of the comparative examples.

<High temperature stability (90 ° C) of radical polymerizable composition>

Example 6-1

The stabilizer composition was prepared by mixing TPA 0.03 g and TPP 0.1 g.

0.13 g of the stabilizer composition obtained above and 100 g of MeAMA obtained in Preparation Example 1 were mixed to obtain a radical polymerizable composition.

5 g of the radically polymerizable composition obtained above was placed in a screw-molded test tube having a capacity of 15 mL, and the tube was sealed with a lid attached to the opening of the tube, placed in a thermostat, and heated at a temperature of 90 ° C for 24 hours. After heating for 24 hours, the test tube was taken out from the thermostat, and the high temperature stability (90 ° C) was investigated as follows. This result is shown in the sixth table.

[High temperature stability]

(1) With or without polymer

The presence or absence of the polymer was taken out from the contents of the test tube (liquid), and n-hexane was added dropwise at room temperature. When no precipitate occurred, it was judged that there was no polymer, and when a precipitate occurred, it was judged that a polymer was present. However, if the contents of the spiral tube are significantly viscous or gelled, it is unconditionally judged to have a polymer.

In the column of "The presence or absence of the polymer" in the sixth table, "Yes" is described when the polymer is generated, and "None" is not found when the polymer is not produced.

(2) Whether there is coloring

When the polymer did not occur, the content was visually observed in a colored state. This color state is described in the column of "the presence or absence of coloring" in the sixth table. Furthermore, aggregation occurs The object is recorded as "-".

Examples 6-2 to 6-11 and Comparative Example 6-1

The stabilizer composition was prepared in the same manner as in Example 6-1 except that the type and amount of the stabilizer composition were changed to those shown in Table 6, and the radical polymerizable composition including the stabilizer composition was examined. High temperature stability (90 ° C). This result is shown in the sixth table.

From the results shown in the sixth table, it was found that the radical polymerizable composition obtained in each of the examples had better high-temperature stability (90 ° C) than the radical polymerizable composition obtained in Comparative Example 6-1.

<High temperature stability (110 ° C) of radical polymerizable composition>

Example 7-1

The stabilizer composition was prepared by mixing TPA 0.05g and TPP0.5.

0.55 g of the stabilizer composition obtained above and 100 g of MeAMA obtained in Preparation Example 1 were mixed to obtain a radical polymerizable composition.

5 g of the radically polymerizable composition obtained above was placed in a test tube having a capacity of 15 mL, and the tube was sealed with a lid attached to the opening of the tube, placed in a thermostat, and heated at a temperature of 110 ° C for 24 hours. After heating for 24 hours, the test tube was taken out from the thermostat, and the high temperature stability (110 ° C) was investigated as follows. This result is shown in the seventh table.

Examples 7-2 to 7-24 and Comparative Examples 7-1 to 7-14

The stabilizer composition was prepared in the same manner as in Example 7-1 except that the type and amount of the stabilizer composition were changed to those shown in Table 7, and the radical polymerizable composition including the stabilizer composition was examined. High temperature stability of the material (110 ° C). This result is shown in the seventh table.

From the results shown in the seventh table, it was found that the radical polymerizable composition obtained in each of the examples had better high-temperature stability (110 ° C) than the radical polymerizable composition obtained in each of the comparative examples.

[Industry profitability]

The stabilizer composition of the present invention can be suitably used, for example, as a polymerizable material such as a raw material for a polymer or a curable material. Since the polymerizable composition of the present invention contains the stabilizer composition, the chemical stability of the AMA ester can be prevented and the high polymerization activity of the AMA ester can be maintained, and the polymerizable composition or the polymerizable composition can be prevented. Since the polymer is colored, it can be expected to be used for, for example, a coating material, an adhesive, a sealing material, an adhesive, a paint, an ink, a resist, a dental material, an optical lens, a molding material, or the like.

Claims (3)

A stabilizer composition for stabilizing a polymerizable compound, characterized by comprising: (A) at least one semi-hindered phenolic compound selected from the group consisting of semi-hindered phenols and dimers thereof; B) at least one stabilizer selected from the group consisting of (thio)phosphites, phosphines and thioethers. A polymerizable composition containing a polymerizable ester compound of α-allyloxymethylpropenyl group, characterized in that it comprises: (A) at least one selected from the group consisting of semi-hindered phenols and dimers thereof a semi-hindered phenolic compound; and (B) at least one stabilizer selected from the group consisting of (thio)phosphites, phosphines, and thioethers. A polymerizable composition obtained by polymerizing a polymerizable composition of the second aspect of the patent application.