JP6125933B2 - Stabilizer composition - Google Patents

Description

  The present invention relates to a stabilizer composition. More specifically, the present invention relates to a stabilizer composition that can be suitably used for, for example, a polymer compound used in an industrial material such as a polymer raw material or a curable material, and the stabilizer composition. And a polymer composition obtained from the polymerizable composition.

  As a representative example of the polymerizable compound, a polymerizable compound having a (meth) acryloyl group as a polymerizable group [hereinafter also simply referred to as a (meth) acrylic compound] can be given. A (meth) acrylic compound has a (meth) acryloyl group which is a double bond activated by conjugation with an adjacent carbonyl group, and is polymerized by a radical addition polymerization mechanism (hereinafter simply referred to as radical polymerization or radical polymerization). Also called sex). (Meth) acrylic compounds are superior in terms of polymerization rate, internal curability, durability of chemical bonds formed, economy, etc., so coating materials, adhesives, sealants, adhesives, paints , Inks, resists, dental materials, optical lenses, molding materials, etc.

  In recent years, as a radical addition polymerizable compound having a polymerization activity equal to or higher than that of a (meth) acryloyl group, a polymerizable ester compound (hereinafter also referred to as an AMA ester) having an α-allyloxymethylacryloyl group (hereinafter also referred to as an AMA group). ) Has been proposed (see, for example, Patent Documents 1-4).

  A polymerizable ester compound having an AMA group is polymerized while being cyclized to form a main chain skeleton having a 5-membered cyclic ether structure having a methylene group on both sides as a repeating unit. Although the AMA ester has a structure in which the α-position of the carbon-carbon double bond is more sterically crowded than the methacrylic acid ester, the AMA ester has a radical polymerization activity equal to or higher than that of the acrylic acid ester. In addition, a polymer obtained from a polymerizable composition containing an AMA ester is excellent in heat decomposability, adhesion, tough mechanical properties, fine particle dispersibility, etc. due to a unique main chain skeleton generated by polymerization. Therefore, AMA ester is a polymerizable compound having properties that can surpass conventional (meth) acrylic compounds.

  However, AMA ester has high polymerization activity, but lacks stability such as high temperature stability and storage stability (hereinafter also referred to as chemical stability). There is a disadvantage that it is inferior in handleability and storage stability at the time of use below.

  Therefore, in the invention described in Patent Document 1, as a stabilizer for AMA ester, hydroquinones are used alone, or monoetherified hydroquinones such as p-methoxyphenol or hindered phenols and phosphorus antioxidants. A combination has been proposed.

  However, the AMA ester containing the hydroquinone as a stabilizer is excellent in chemical stability, but inhibits polymerization when used as a raw material for a polymer or as a reactive diluent. There is a drawback. The polymer prepared from the AMA ester containing the hydroquinone as a stabilizer and the polymerizable composition containing the AMA ester is, for example, an inorganic alkali compound such as sodium hydroxide or potassium hydroxide, an amine or an ammonium salt. When it comes into contact with a basic substance such as an organic basic substance, it is colored significantly before and after the polymerization reaction. Further, it is colored by storing a polymer of AMA ester for a long time under heating or by exposing it to weathering test conditions. Therefore, the AMA ester containing hydroquinones as a stabilizer is applied to water-based water-soluble resin-type paints that require neutralization with alkali, water-based resin emulsions using basic substances, transparent materials that require weather resistance, and the like. Its use is limited because it is difficult to do.

  On the other hand, when monoetherified hydroquinones or hindered phenols and phosphorus antioxidants are used in combination, a large amount of monoetherified hydroquinones or hinders is required to sufficiently impart chemical stability to the AMA ester. Dophenol is required. However, when monoetherified hydroquinones or hindered phenols are used in an amount that sufficiently imparts chemical stability to the AMA ester, the polymerization activity of the AMA ester may be inhibited or coloring may increase. is there. On the other hand, when monoetherified hydroquinone or hindered phenol is used in an amount less than the amount that sufficiently imparts chemical stability to the AMA ester, chemical stability can be sufficiently imparted to the AMA ester. Can not.

JP 2010-254685 A International Publication No. 2011/148903 Pamphlet JP 2011-137123 A JP 2011-074068 A

  The present invention has been made in view of the prior art, and when used in a polymerizable compound, particularly an AMA ester, the chemical stability of the compound and the maintenance of high polymerization activity inherent in the compound. It aims at providing the stabilizer composition which can be made to make compatible. Another object of the present invention is to provide a stabilizer composition capable of preventing the polymerizable composition containing an AMA ester or a polymer prepared from the polymerizable composition from being colored.

  Another object of the present invention is to provide a polymerizable composition containing the stabilizer composition and the AMA ester, and a polymer composition obtained by polymerizing the polymerizable compound.

The present invention
(1) A stabilizer composition used for stabilizing a polymerizable compound, wherein (A) at least one semihindered phenol selected from the group consisting of a semihindered phenol and a dimer thereof A stabilizer composition comprising: a system compound; and (B) (thio) phosphite, phosphine, and at least one stabilizer selected from the group consisting of thioethers,
(2) A polymerizable composition containing a polymerizable ester compound having an α-allyloxymethylacryloyl group, wherein (A) at least one selected from the group consisting of semi-hindered phenols and dimers thereof A polymerizable composition comprising a semi-hindered phenol compound and (B) (thio) phosphite, a phosphine, and at least one stabilizer selected from the group consisting of thioethers. And (3) a polymer composition obtained by polymerizing the polymerizable composition according to (2).

  In the present specification, “(meth) acryloyl group” means “acryloyl group” and / or “methacryloyl group”. “Acrylic acid” means “methacrylic acid” and / or “(meth) acrylic acid”. “(Meth) acrylate” means “acrylate” and / or “methacrylate”.

  According to the stabilizer composition of the present invention, it is possible to achieve both the chemical stability of the compound and the maintenance of the high polymerization activity inherent to the compound, particularly when used in an AMA ester among polymerizable compounds. An excellent effect of being able to be produced. Furthermore, by using the stabilizer composition of the present invention for a polymerizable composition containing an AMA ester, it is possible to prevent the polymerizable composition or a polymer prepared from the polymerizable composition from being colored. An excellent effect of being able to be produced.

  As described above, the stabilizer composition of the present invention is a stabilizer composition used for stabilizing a polymerizable compound, and comprises (A) a semi-hindered phenol and a dimer thereof. At least one selected from the group consisting of at least one selected semi-hindered phenol compound (hereinafter also referred to as component (A)) and (B) (thio) phosphite, phosphine and thioether And an agent [hereinafter also referred to as component (B)].

  As described above, the component (A) is at least one semi-hindered phenol compound selected from the group consisting of semi-hindered phenols and dimers thereof. Accordingly, the semi-hindered phenol and its dimer may be used alone or in combination of two or more.

  Semi-hindered phenols include, for example, formula (I):

(In the formula, X ¹ is a hydrogen atom or a linear alkyl group having 1 to 4 carbon atoms, and X ^{2 to} X ⁴ are each independently a hydrogen atom or an alkyl having 1 to 5 carbon atoms which may have a substituent. Group, X ⁵ represents a tert-alkyl group having 4 to 12 carbon atoms or an alkyl group having 6 to 18 carbon atoms)
And semi-hindered phenols represented by Examples of the substituent include allyl group, methallyl group, crotyl group, 1,1-dimethyl-2-propenyl group, 2-methyl-butenyl group, 3-methyl-2-butenyl group, 3-methyl-3- Chain unsaturated hydrocarbon groups such as butenyl group, 2-methyl-3-butenyl group, oleyl group, linole group, linolene group; cyclopentyl group, cyclopentylmethyl group, cyclohexyl group, cyclohexylmethyl group, 4-methylcyclohexyl group , Alicyclic hydrocarbon groups such as 4-tert-butylcyclohexyl group, tricyclodecanyl group, isobornyl group, adamantyl group, dicyclopentanyl group, dicyclopentenyl group; glycidyl group, β-methylglycidyl group, β -Ethyl glycidyl group, 3,4-epoxycyclohexylmethyl group, 2-oxetanemethyl group, 3 -Cyclic ether groups such as methyl-3-oxetanemethyl group, 3-ethyl-3-oxetanemethyl group, tetrahydrofuranyl group, tetrahydrofurfuryl group, tetrahydropyranyl group, dioxazolanyl group, dioxanyl group; phenyl group, methylphenyl group Dimethylphenyl group, trimethylphenyl group, 4-tert-butylphenyl group, methoxyphenyl group, hydroxyphenyl group, benzyl group, diphenylmethyl group, diphenylethyl group, triphenylmethyl group, cinnamyl group, naphthyl group, anthranyl group, etc. An aryl group of methoxy group, ethoxy group, methoxyethoxy group, cyclohexyloxy group, phenoxy group, phenoxyethoxy group, etc .; butylthio group, octylthio group, laurylthio group, stearylthio group, Alkylthio groups such as nylthio group; acyl groups such as acetyl group, propionyl group, butyryl group, valeryl group, benzoyl group, trioyl group, caproyl group; acetyloxy group, propionyloxy group, butyryloxy group, valeryloxy group, benzoyloxy group, Acyloxy groups such as trioyloxy group, caproyloxy group, (meth) acryloyloxy group; methoxycarbonyl group, ethoxycarbonyl group, butoxycarbonyl group, octyloxycarbonyl group, lauryloxycarbonyl group, stearyloxycarbonyl group, phenoxycarbonyl group, Alkoxycarbonyl groups such as benzyloxycarbonyl group; butylthiocarbonyl group, octylthiocarbonyl group, laurylthiocarbonyl group, stearylthiocarbonyl group, Alkylthiocarbonyl groups such as nylthiocarbonyl group and benzylthiocarbonyl group; halogen atoms such as fluorine atom, chlorine atom, bromine atom and iodine atom; ureido group; amide group; cyano group; hydroxyl group; phosphite group; Examples include ester groups; trimethylsilyl groups, and the like, but the present invention is not limited to such examples.

In the semi-hindered phenol represented by the formula (I), X ¹ is a hydrogen atom or a methyl group, X ² and X ⁴ are each independently a hydrogen atom or a methyl group, and X ³ is a substituent. A semi-hindered phenol which is an optionally substituted alkyl group having 1 to 5 carbon atoms, X ⁵ is a tert-butyl group or a tert-amyl group, X ¹ is a hydrogen atom or a methyl group, ² and X ⁴ are hydrogen atoms, X ³ is an optionally substituted alkyl group having 1 to 5 carbon atoms, and X ⁵ is a tert-butyl group or a tert-amyl group. More preferred is phenol, X ¹ is a methyl group, X ² and X ⁴ are hydrogen atoms, X ³ is an optionally substituted alkyl group having 1 to 5 carbon atoms, and X ⁵ is A tert-butyl group A semi-hindered phenol is more preferable, X ¹ is a methyl group, X ² and X ⁴ are hydrogen atoms, X ³ is an alkyl group having 1 to 5 carbon atoms, and X ⁵ is a tert-butyl group. Hindered phenol is even more preferred.

  Examples of the semi-hindered phenol include 6-tert-butyl-o-cresol, 6-tert-butyl-2,4-xylenol, 2,4,8,10-tetra-tert-butyl-6- [3- (3-Methyl-4-hydroxy-5-t-butylphenyl) propoxy] dibenzo [d, f] [1,3,2] dioxaphosphine, 2,4-dimethyl-6- (1-methylpenta Decyl) phenol, 2,4-bis (octylthiomethyl) -o-cresol, 2,4-bis (dodecylthiomethyl) -o-cresol, 2-tert-butylphenol, 2,4-ditert-butylphenol, 2 -Tert-amylphenol, 2,4-ditert-amylphenol, and the like, but the present invention is not limited to such examples. . These semi-hindered phenols may be used alone or in combination of two or more.

  Semi-hindered phenols can be easily obtained commercially, for example, Sumitomo Chemical Co., Ltd., trade name: Sumilizer (registered trademark, the same applies below) GP, etc .; Names: CGX AO-145, Irganox (registered trademark, the same shall apply hereinafter) 245, Irganox 1520L, Irganox 1726, and the like are included, but the present invention is not limited to such examples.

  In the present specification, the dimer of semi-hindered phenol is a concept including a derivative thereof.

  Examples of the dimer of semi-hindered phenol include methylene bis (oxyethylene) bis [3- (5-tert-butyl-4-hydroxy-m-tolyl) propionate], triethylene glycol bis [β- (3- tert-butyl-5-methyl-4-hydroxyphenyl) propionate], 4,4′-thiobis (2-methyl-6-tert-butylphenol), bis (3-methyl-4-hydroxy-5-tertbutylbenzyl) Sulfide, terephthaloyl-di (2,6-dimethyl-4-tert-butyl-3-hydroxybenzyl sulfide, 3,9-bis [2- [3- (3-tert-butyl-4-hydroxy-5-methylphenyl) ) Propionic acid] -1,1-dimethylethyl] -2,4,8,10-tetraoxas B [5.5] undecane, 4,4′-butylidenebis (6-tert-butyl-3-methylphenol), 4,4′-thiobis (6-tert-butyl-3-methylphenol), 1,1, 3-tris (2-methyl-4-hydroxy-5-tert-butylphenyl) butane, 2,2'-methylenebis (4-methyl-6-tert-butylphenol), 2,2'-methylenebis (4-ethyl- 6-tert-butylphenol), 2,2′-thiobis (4-methyl-6-tert-butylphenol) and other semihindered phenol dimers; 2- [1- (2-hydroxy-3,5-ditert -Pentylphenyl) ethyl] -4,6-ditert-pentylphenylacrylate, 2-tert-butyl-6- (3-tert-butyl- Examples include semi-hindered phenol dimer derivatives such as 2-hydroxy-5-methylbenzyl) -4-methylphenyl acrylate, but the present invention is not limited to such examples. The hindered phenol dimers may be used alone or in combination of two or more.

  Suitable semi-hindered phenol dimers include, for example, formula (II-a):

(In the formula, X ^{2 to} X ⁵ are the same as above. Y represents a divalent linking group.)
A dimer of semi-hindered phenol represented by the formula (II-b):

(Wherein X ¹ , X ^{3 to} X ⁵ and Y are the same as above)
A dimer of semi-hindered phenol represented by the formula (II-c):

(Wherein X ¹ , X ² , X ⁴ , X ⁵ and Y are the same as above)
And a dimer of semi-hindered phenol represented by:

In the dimer of semi-hindered phenol represented by formula (II-a) to 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, more preferably a methyl group. X ^{2 to} X ⁴ are each independently a hydrogen atom or an optionally substituted alkyl group having 1 to 5 carbon atoms, but X ² and X ⁴ are each independently a hydrogen atom or methyl. It is preferably a group, more preferably a hydrogen atom, and X ³ is preferably an alkyl group having 1 to 5 carbon atoms which may have a substituent, and an alkyl having 1 to 5 carbon atoms. More preferably, it is a group. X ⁵ is a tert-alkyl group having 4 to 12 carbon atoms or an alkyl group having 6 to 18 carbon atoms, preferably a tert-butyl group or a tert-amyl group, and preferably a tert-butyl group. More preferred. Y should just be a bivalent coupling group, and is not specifically limited. Y is preferably any one of a carbon atom, an oxygen atom and a sulfur atom, and it is more preferable that two or more of these atoms, which may be the same or different, are bonded. preferable.

  A dimer of semi-hindered phenol and a derivative thereof can be easily obtained commercially. As an example, ADE- manufactured by ADEKA Corporation, trade name: ADK STAB (registered trademark, hereinafter the same) AO- 30, Adeka Stub AO-40, Adeka Stub AO-70, Adeka Stub AO-80, etc .; manufactured by Sumitomo Chemical Co., Ltd., trade name: Sumilyzer GA-80, Sumilyzer BBM-S, Sumilyzer WX-R, Sumilyzer MDP-S, Sumilyzer GM , Sumilyzer GS, etc .; manufactured by BASF, trade name: Irganox 1081, etc .; manufactured by Kawaguchi Chemical Industry Co., Ltd., trade names: ANTAGE W-300, ANTAGE CRYSTAL, ANTAGE W-400, ANTAGE W-500, etc. However, the present invention is not limited to such examples.

  Among the components (A), from the viewpoint of improving chemical stability, a semi-hindered phenol represented by formula (I) and a dimer of semi-hindered phenol represented by formula (II-a) are preferable. From the viewpoint of improving color resistance, a semihindered phenol represented by formula (I), a dimer of semihindered phenol represented by formula (II-b), and a semihinder represented by formula (II-c) A dimer of dophenol is preferred. Among the components (A), semihindered phenols represented by the formula (I) are more preferable because they are particularly excellent in chemical stability and color resistance.

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

  Examples of (thio) phosphite include hydrogen phosphite such as diethyl hydrogen phosphite, bis (2-ethylhexyl) hydrogen phosphite, dilauryl hydrogen phosphite, dioleyl hydrogen phosphite, diphenyl hydrogen phosphite; triethyl phosphite , Trialkyl phosphites such as tributyl phosphite, tris (2-ethylhexyl) phosphite, triisodecyl phosphite, trilauryl phosphite, tris (tridecyl phosphite), trioleyl phosphite, tristearyl phosphite; Diisodecyl phosphite, diphenylmethyl phosphite, 2-ethylhexyl diphenyl phosphite, isodecyl diphenyl phosphite, Alkyl-aryl mixed phosphites such as decyl diphenyl phosphite and bis (2,4-ditert-butyl-6-methylphenyl) ethyl phosphite; triphenyl phosphite, tricresyl phosphite, tris (nonylphenyl) phos Triaryl phosphites such as phyto, tris (2,4-ditert-butylphenyl) phosphite; bis (isodecyl) pentaerythritol diphosphite, bis (tridecyl) pentaerythritol diphosphite, bis (stearyl) pentaerythritol di Phosphite, bis (nonylphenyl) pentaerythritol diphosphite, bis (2,4-ditert-butylphenyl) pentaerythritol diphosphite, bis (2,6-ditert-butyl-6-methyl) Phenyl) pentaerythritol diphosphite such as pentaerythritol diphosphite; thiophosphite such as trilauryl trithiophosphite and 4,4-butylidenebis (3-methyl-6-tert-butylphenyldiisotridecyl) phosphite , Tetraphenyldipropylene glycol diphosphite, tetraphenyltetra (tridecyl) pentaerythritol tetraphosphite, tetra (C12-C15 alkyl) -4,4′-isopropylidene diphenylphosphite, tetra (tridecyl) -1,1, 3-tris (2-methyl-5-tert-butyl-4-hydroxyphenyl) butanediphosphite, 2,4,8,10-tetratert-butyl-6- [3- (3-methyl-4-hydroxy -5-te rt-butylphenyl) propoxy] dibenzo [d, f] [1,3,2] dioxaphosphine, 2,2-methylenebis (4,6-tert-butylphenyl) -2-ethylhexyl phosphite and the like. However, the present invention is not limited to such examples. These (thio) phosphites may be used alone or in combination of two or more.

  Among (thio) phosphites, from the viewpoint of improving hydrolysis resistance and suppressing odor, formula (III):

(Wherein R ¹ , R ² and R ³ each independently represents an alkyl group having 6 to 20 carbon atoms)
(Thio) phosphite represented by the formula (III) is preferred, and (thio) phosphite in which R ¹ , R ² and R ³ are each independently an alkyl group having 8 to 18 carbon atoms is more preferred. When two groups out of R ¹ , R ² and R ³ are bonded to form a ring, the group forming the ring may have 5 or less carbon atoms.

  Among the (thio) phosphites, (thio) phosphites that are liquid at normal temperature (for example, 23 ° C.) are preferable from the viewpoint of improving handleability and chemical stability. Among (thio) phosphites, those which are liquid at room temperature and can be easily obtained include, for example, triphenyl phosphite, tris (nonylphenyl) phosphite, triisodecyl phosphite, bis (nonyl) Phenyl) pentaerythritol diphosphite and the like can be mentioned, but the present invention is not limited to such examples. These (thio) phosphites may be used alone or in combination of two or more.

  (Thio) phosphite can be easily obtained commercially. Examples thereof include: ADEKA Corporation, trade name: ADK STAB 3010, ADK STAB TPP, ADK STAB 2112, ADK STAB 260, ADK STAB 522A, ADK STAB 329K, ADK STAB 1178, ADK STAB 1500, ADK STAB C, ADK STAB 135A, ADK STAB PEP-4C, ADK STAB PEP-8, ADK STAB PEP-24G, ADK STAB PEP-36, ADK STAB HP-10, etc .; manufactured by BASF, trade name: Irgaphos 168, Irgafos 38, etc .; manufactured by Johoku Chemical Industry Co., Ltd., product 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 Product name: Chelex D, Chelex TD, Chelex OL, Chelex S, Chelex LT-3, etc. are listed, but the present invention is not limited to such illustrations.

  Examples of the phosphine include triethylphosphine, tributylphosphine, tris (2-ethylhexyl) phosphine, triphenylphosphine, and the like, but the present invention is not limited to such examples. These phosphines may be used alone or in combination of two or more.

  Among phosphines, triarylphosphine is preferable and triphenylphosphine is more preferable because it suppresses odor and has low toxicity.

  Examples of the thioether include 3-laurylthiopropionic acid, methyl 3-laurylthiopropionate, (3-octylthiopropionic acid) pentaerythritol tetraester, (3-decylthiopropionic acid) pentaerythritol tetraester, (Laurylthiopropionic acid) pentaerythritol tetraester, (3-oleylthiopropionic acid) pentaerythritol tetraester, (3-stearylthiopropionic acid) pentaerythritol tetraester, (3-laurylthiopropionic acid) -4,4'- 3-alkylthiopropionic acid or esters thereof such as thiodi (3-methyl-5-tert-butyl-4-phenol) ester; dioctylthiodipropionate, didecylthiodipropionate, dill Dimerized thioethers of thiocarboxylic acid alkyl esters such as rilthiodipropionate, dimyristyl thiodipropionate, distearyl thiodipropionate, lauryl stearyl thiodipropionate, distearyl-β, β′-thiodibutyrate; 2,4-bis (octylthiomethyl) -o-cresol, 2,4-bis (dodecylthiomethyl) -o-cresol, including dialkyl sulfides such as sulfide, methyldodecyl sulfide, dilauryl sulfide, distearyl sulfide, etc. However, the present invention is not limited to such examples. These thioethers may be used alone or in combination of two or more.

  Among thioethers, from the viewpoint of suppressing odor, formula (IV):

[Wherein, R ⁴ and R ⁵ each independently represents an alkyl group having 1 to 18 carbon atoms or a group represented by the formula:

(Wherein R ⁶ represents an alkyl group having 1 to 6 carbon atoms having an alkoxycarbonyl group represented by the following formula: R ⁶ represents an optionally substituted hydrocarbon group having 1 to 24 carbon atoms)]
In formula (IV), R ⁴ and R ⁵ are each independently an alkyl group having 8 to 18 carbon atoms or an alkoxycarbonyl group having 6 to 20 carbon atoms and 2 carbon atoms. More preferred is a thioether which is an alkyl group of ˜4. Among thioethers, a thioether that is liquid at normal temperature is preferable from the viewpoint of improving handleability, and has a long-chain alkylthio group from the viewpoint of improving chemical stability (at least one group of R ⁴ and R ^5). Preferred is a thioether where is a long chain alkyl group. Suitable thioethers having a long-chain alkylthio group include, for example, (3-laurylthiopropionic acid) pentaerythritol tetraester, (3-laurylthiopropionic acid) -4,4′-thiodi (3-methyl-5-tert) -Butyl-4-phenol) ester, 2,4-bis (octylthiomethyl) -o-cresol, 2,4-bis (dodecylthiomethyl) -o-cresol, and the like. It is not limited to only. These thioethers may be used alone or in combination of two or more.

  Thioethers can be easily obtained commercially. Examples include ADEKA Corporation, trade names: ADK STAB AO-23, ADK STAB AO-412S, ADK STAB AO-503, etc .; Sumitomo Chemical Co., Ltd. ), Trade name: Sumilizer TPL-R, Sumilizer TPM, Sumilizer TPS, etc .; manufactured by BASF, trade names: Irganox 1520L, Irganox 1726, etc., but the present invention is limited to such examples only. is not.

  Among the components (B), (thio) phosphite and thioether are preferable from the viewpoint of improving safety to the human body, and (thio) phosphite and thioether may be used alone or in combination. .

  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, from the viewpoint of suppressing polymerization. More preferably, it is the range of 0.04-10.

  The stabilizer composition of this invention can be easily prepared by mixing (A) component and (B) component so that it may become a desired ratio.

  The stabilizer composition of the present invention can be suitably used, for example, as a polymer compound used as a raw material for polymer, a curable material, and the like, and in particular, the chemical stability of AMA ester and AMA. It can be preferably used when maintaining both high polymerization activity inherent in 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.

  Although the stabilizer composition of this invention can be used for AMA ester, it can be used suitably also for the polymeric composition containing AMA ester.

  The polymerizable composition of the present invention is a polymerizable composition containing an AMA ester and is characterized by containing a component (A) and a component (B).

  As the AMA ester, for example, the formula (V):

(Wherein R ⁷ represents a monovalent organic group)
AMA ester represented by the following. An AMA ester is a compound that can be suitably used in the present invention.

In the formula (V), R ⁷ is a monovalent organic group. Examples of the monovalent organic group include an ether group and a hydrocarbon group which may have a substituent such as a halogen atom. R ⁷ may be linear or branched and may contain a cyclic structure. Examples of the hydrocarbon group include a chain saturated hydrocarbon group having 1 or more carbon atoms, a chain unsaturated hydrocarbon group having 3 or more carbon atoms, an alicyclic hydrocarbon group having 3 or more carbon atoms, and a carbon group having 6 or more carbon atoms. An aromatic hydrocarbon group etc. are mentioned. Among these, a chain saturated hydrocarbon group having 1 to 30 carbon atoms, a chain unsaturated hydrocarbon group having 3 to 30 carbon atoms, an alicyclic hydrocarbon group having 4 to 30 carbon atoms, and 6 to 30 carbon atoms. The aromatic hydrocarbon group is preferred. Examples of the substituent include halogen atoms such as a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, a cyano group, and a trimethylsilyl group. However, the present invention is not limited to such examples.

  Examples of the chain saturated hydrocarbon group include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, a tert-butyl group, an n-amyl group, and a sec-amyl group. Tert-amyl group, neopentyl group, n-hexyl group, sec-hexyl group, n-heptyl group, n-octyl group, sec-octyl group, tert-octyl group, 2-ethylhexyl group, capryl group, nonyl group, Examples include decyl group, undecyl group, lauryl group, tridecyl group, myristyl group, pentadecyl group, cetyl group, heptadecyl group, stearyl group, nonadecyl group, eicosyl group, seryl group, and melyl group. It is not limited to only.

  Examples of the chain unsaturated hydrocarbon group include crotyl group, 1,1-dimethyl-2-propenyl group, 2-methyl-butenyl group, 3-methyl-2-butenyl group, 3-methyl-3-butenyl. Group, 2-methyl-3-butenyl group, oleyl group, linole group, linolene group and the like are exemplified, but the present invention is not limited to such 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 tricyclodecanyl group, an isobornyl group, and an adamantyl group. Group, dicyclopentanyl group, dicyclopentenyl group and the like can be mentioned, but the present invention is not limited to such examples.

  Examples of the aromatic hydrocarbon group include phenyl group, methylphenyl group, dimethylphenyl group, trimethylphenyl group, 4-tert-butylphenyl group, benzyl group, diphenylmethyl group, diphenylethyl group, triphenylmethyl group, Although a cinnamyl group, a naphthyl group, an anthranyl group, etc. are mentioned, this invention is not limited only to this illustration.

  Examples of the hydrocarbon group having an ether bond include a chain ether group such as a methoxyethyl group, a methoxyethoxyethyl group, a methoxyethoxyethoxyethyl group, a 3-methoxybutyl group, an ethoxyethyl group, and an ethoxyethoxyethyl group; A group having both an alicyclic hydrocarbon group and a chain ether group such as a pentoxyethyl group, a cyclohexyloxyethyl group, a cyclopentoxyethoxyethyl group, a cyclohexyloxyethoxyethyl group, a dicyclopentenyloxyethyl group; a phenoxyethyl group, A group having both an aromatic hydrocarbon group such as a phenoxyethoxyethyl group and a chain ether group; a glycidyl group, a β-methylglycidyl group, a β-ethylglycidyl group, a 3,4-epoxycyclohexylmethyl group, a 2-oxetanemethyl group, 3-methyl-3-oki Examples include cetanemethyl group, 3-ethyl-3-oxetanemethyl group, tetrahydrofuranyl group, tetrahydrofurfuryl group, tetrahydropyranyl group, dioxazolanyl group, dioxanyl group and the like, but the present invention is only such examples. It is not limited to.

  Specific examples of the AMA ester include methyl α-allyloxymethyl acrylate, ethyl α-allyloxymethyl acrylate, n-propyl α-allyloxymethyl acrylate, isopropyl α-allyloxymethyl acrylate, α-allyloxy N-butyl methyl acrylate, sec-butyl α-allyloxymethyl acrylate, tert-butyl α-allyloxymethyl acrylate, n-amyl α-allyloxymethyl acrylate, sec-amyl α-allyloxymethyl acrylate , Α-allyloxymethyl acrylate tert-amyl, α-allyloxymethyl acrylate neopentyl, α-allyloxymethyl acrylate n-hexyl, α-allyloxymethyl acrylate sec-hexyl, α-allyloxymethyl acrylate n-heptyl, α-Allyloxymethyl acrylate n-octyl, α-allyloxymethyl acrylate sec-octyl, α-allyloxymethyl acrylate tert-octyl, α-allyloxymethyl acrylate 2-ethylhexyl, α-allyloxymethyl acryl Caprylic acid, α-allyloxymethyl acrylate nonyl, α-allyloxymethyl acrylate decyl, α-allyloxymethyl acrylate undecyl, α-allyloxymethyl lauryl acrylate, α-allyloxymethyl acrylate tridecyl, α- Myristyl allyloxymethyl acrylate, pentadecyl α-allyloxymethyl acrylate, cetyl α-allyloxymethyl acrylate, heptadecyl α-allyloxymethyl acrylate, stearyl α-allyloxymethyl acrylate, α- Nonadecyl ryloxymethyl acrylate, eicosyl α-allyloxymethyl acrylate, ceryl α-allyloxymethyl acrylate, melyl α-allyloxymethyl acrylate, crotyl α-allyloxymethyl acrylate, α-allyloxymethyl acrylic acid 1,1-dimethyl-2-propenyl, α-allyloxymethyl acrylate 2-methylbutenyl, α-allyloxymethyl acrylate 3-methyl-2-butenyl, α-allyloxymethyl acrylate 3-methyl-3-butenyl , Α-allyloxymethyl acrylate 2-methyl-3-butenyl, α-allyloxymethyl acrylate oleyl, α-allyloxymethyl acrylate linole, α-allyloxymethyl acrylate linolene, α-allyloxymethyl acrylate Cyclopentyl, α Cyclopentylmethyl allyloxymethyl acrylate, cyclohexyl α-allyloxymethyl acrylate, cyclohexylmethyl α-allyloxymethyl acrylate, 4-methylcyclohexyl α-allyloxymethyl acrylate, 4-tert-allyloxymethyl acrylate 4-tert- Butylcyclohexyl, α-allyloxymethyl acrylate tricyclodecanyl, α-allyloxymethyl acrylate isobornyl, α-allyloxymethyl acrylate adamantyl, α-allyloxymethyl acrylate dicyclopentanyl, α-allyloxymethyl Dicyclopentenyl acrylate, phenyl α-allyloxymethyl acrylate, methyl phenyl α-allyloxymethyl acrylate, dimethylphenyl α-allyloxymethyl acrylate, α-ary Trimethylphenyl oxymethyl acrylate, 4-tert-butylphenyl α-allyloxymethyl acrylate, benzyl α-allyloxymethyl acrylate, diphenylmethyl α-allyloxymethyl acrylate, diphenylethyl α-allyloxymethyl acrylate, α-allyloxymethyl acrylate triphenylmethyl, α-allyloxymethyl acrylate cinnamyl, α-allyloxymethyl acrylate naphthyl, α-allyloxymethyl acrylate anthranyl, α-allyloxymethyl methoxyethyl acrylate, α- Methoxyethoxyethyl allyloxymethyl acrylate, methoxyethoxyethoxyethyl α-allyloxymethyl acrylate, 3-methoxybutyl α-allyloxymethyl acrylate, α-allyloxymethyl acrylate Ethoxyethyl chlorate, ethoxyethoxyethyl α-allyloxymethyl acrylate, cyclopentoxyethyl α-allyloxymethyl acrylate, cyclohexyloxyethyl α-allyloxymethyl acrylate, cyclopentoxyethoxy α-allyloxymethyl acrylate Ethyl, cyclohexyloxyethoxyethyl α-allyloxymethyl acrylate, dicyclopentenyloxyethyl α-allyloxymethyl acrylate, phenoxyethyl α-allyloxymethyl acrylate, phenoxyethoxyethyl α-allyloxymethyl acrylate, α- Glycidyl allyloxymethyl acrylate, β-methyl glycidyl α-allyloxymethyl acrylate, β-ethyl glycidyl α-allyloxymethyl acrylate, α-allyloxymethyl acrylate 3,4-epoxycyclohexylmethyl crylate, 2-oxetanemethyl α-allyloxymethyl acrylate, 3-methyl-3-oxetanemethyl α-allyloxymethyl acrylate, 3-ethyl-3 α-allyloxymethyl acrylate -Oxetanemethyl, α-allyloxymethyl acrylate tetrahydrofuranyl, α-allyloxymethyl acrylate tetrahydrofurfuryl, α-allyloxymethyl acrylate tetrahydropyranyl, dioxazolanyl, α-allyloxymethyl acrylate dioxanyl, etc. However, the present invention is not limited to such examples. These AMA esters may be used alone or in combination of two or more. Among these AMA esters, it is excellent in dilutability and can introduce many tetrahydrofuran ring structures per unit weight of the polymer. Therefore, α-allyloxymethylacrylic having an alkyl group having 1 to 4 carbon atoms. Alkyl acids are preferred, but tend to have lower chemical stability in high temperature environments such as distillation conditions compared to other AMA esters. Among these AMA esters, the stabilizer composition of the present invention is particularly excellent in chemical stability against an alkyl α-allyloxymethyl acrylate having an alkyl group having 1 to 4 carbon atoms.

  The AMA ester can be prepared, for example, according to the method described in JP2011-137123A.

  The polymerizable composition of the present invention is mixed with components other than the stabilizer composition of the present invention and the AMA ester, if necessary, depending on the purpose of use, application, etc., for example, resin raw material composition, curing It can be used as a conductive coating material. In addition, the AMA ester containing the stabilizer composition of the present invention is useful as, for example, a resin raw material, a reactive diluent, and the like. It can be used for resin raw material compositions, curable coating materials, and the like.

  As components other than the stabilizer composition and AMA ester of the present invention, for example, other polymerizable monomers copolymerizable with the AMA ester, radical polymerization initiator, curing accelerator, resin binder, solvent, Although various components, such as an additive, are mentioned, this invention is not limited only to this illustration. Since the types and amounts of these components vary depending on the purpose of use, use, etc. of the stabilizer composition of the present invention and the AMA ester containing the stabilizer composition, it cannot be determined unconditionally. It is preferable to determine appropriately according to the purpose of use, application and the like.

  Other polymerizable monomers that can be copolymerized with the AMA ester can be used as long as the object of the present invention is not impaired. Examples of other polymerizable monomers that can be copolymerized with an AMA ester include compounds having radical polymerizable groups such as carbon-carbon unsaturated bonds, and cationic polymerizable groups such as epoxy groups, oxetanyl groups, and vinyl ether groups. And a compound having a radical polymerizable group and a cationic polymerizable group, but the present invention is not limited to such examples. In these, since it hardens | cures by the same mechanism as AMA ester, a radically polymerizable monomer is preferable.

  Examples of other polymerizable monomers that can be copolymerized with AMA ester include, for example, monofunctional radical polymerizable monomers having one radical polymerizable unsaturated group in a molecule other than AMA ester, and other than AMA ester. Examples thereof include polyfunctional radically polymerizable monomers having a plurality of radically polymerizable unsaturated groups in the molecule. These polymerizable monomers other than the AMA ester may be used alone or in combination of two or more.

  Examples of monofunctional radical polymerizable monomers other than AMA ester include, for example, methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, (meth) N-butyl acrylate, sec-butyl (meth) acrylate, tert-butyl (meth) acrylate, n-amyl (meth) acrylate, sec-amyl (meth) acrylate, tert-amyl (meth) acrylate N-hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, isodecyl (meth) acrylate, tridecyl (meth) acrylate, cyclohexyl (meth) acrylate, cyclohexylmethyl (meth) acrylate, (meth ) Octyl acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate Benzyl (meth) acrylate, phenyl (meth) acrylate, isobornyl (meth) acrylate, adamantyl (meth) acrylate, tricyclodecanyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, ( 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 3-hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, ( 2-methoxyethyl (meth) acrylate, 2-ethoxyethyl (meth) acrylate, phenoxyethyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, glycidyl (meth) acrylate, (meth) acrylic β- Methyl glycidyl, β-ethyl glycidyl (meth) acrylate (Meth) acrylic acid (meth) acrylic acid (3,4-epoxycyclohexyl) methyl, (meth) acrylic acid N, N-dimethylaminoethyl, methyl α-hydroxymethyl acrylate, ethyl α-hydroxymethyl acrylate, etc. Esters; (meth) acrylamides such as N, N-dimethyl (meth) acrylamide and N-methylol (meth) acrylamide; (meth) acrylic acid, crotonic acid, cinnamic acid, vinylbenzoic acid, succinic acid mono (2-acryloyloxy) Ethyl), unsaturated monocarboxylic acids such as mono (2-methacryloyloxyethyl) succinate; unsaturated polycarboxylic acids such as maleic acid, fumaric acid, itaconic acid, citraconic acid, mesaconic acid; maleic anhydride, itaconic anhydride Unsaturated acid anhydrides such as acids; styrene, α-methylstyrene Aromatic vinyl compounds such as vinyltoluene and methoxystyrene; N-substituted maleimides such as methylmaleimide, ethylmaleimide, isopropylmaleimide, cyclohexylmaleimide, phenylmaleimide, benzylmaleimide and naphthylmaleimide; conjugates such as 1,3-butadiene, isoprene and chloroprene Diene: Vinyl esters such as vinyl acetate, vinyl propionate, vinyl butyrate, vinyl benzoate; methyl vinyl ether, ethyl vinyl ether, propyl vinyl ether, butyl vinyl ether, 2-ethylhexyl vinyl ether, n-nonyl vinyl ether, lauryl vinyl ether, cyclohexyl vinyl ether, methoxyethyl Vinyl ether, ethoxyethyl vinyl ether, methoxyethoxyethyl vinyl ether , Vinyl ethers such as methoxypolyethylene glycol vinyl ether, 2-hydroxyethyl vinyl ether, 4-hydroxybutyl vinyl ether; N such as N-vinylpyrrolidone, N-vinylcaprolactam, N-vinylimidazole, N-vinylmorpholine, N-vinylacetamide -Vinyl compounds; unsaturated isocyanates such as isocyanatoethyl (meth) acrylate and allyl isocyanate may be mentioned, but the present invention is not limited to such examples. Monofunctional radically polymerizable monomers other than these AMA esters may be used alone or in combination of two or more.

  Examples of polyfunctional radical polymerizable monomers other than AMA esters include ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, and butylene glycol. 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, ditrimethylolpropane tetra (meth) acrylate, glycerin tri (meth) acrylate, pentaerythritol tetra (meth) acrylate Dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, ethylene oxide-added trimethylolpropane tri (meth) acrylate, ethylene oxide-added ditrimethylolpropane tetra (meth) acrylate, ethylene oxide-added pentaerythritol tetra (meth) Acrylate, ethylene oxide-added dipentaerythritol hexa (meth) acrylate, propylene oxide-added trimethylolpropane tri (meth) acrylate, propylene oxide-added ditrimethylolpropane tetra (meth) acrylate, propylene oxide-added pentaerythritol tetra (meth) acrylate, propylene oxide Additive dipentaerythritol hexa (meth) acrelan , Ε-caprolactone-added trimethylolpropane tri (meth) acrylate, ε-caprolactone-added ditrimethylolpropane tetra (meth) acrylate, ε-caprolactone-added pentaerythritol tetra (meth) acrylate, ε-caprolactone-added dipentaerythritol hexa (meth) Polyfunctional (meth) acrylate such as acrylate; ethylene glycol divinyl ether, diethylene glycol divinyl ether, polyethylene glycol divinyl ether, propylene glycol divinyl ether, butylene glycol divinyl ether, hexanediol divinyl ether, bisphenol A alkylene oxide divinyl ether, bisphenol F alkylene oxide Divinyl ether, trimethylolpropane Livinyl ether, ditrimethylolpropane tetravinyl ether, glycerin trivinyl ether, pentaerythritol tetravinyl ether, dipentaerythritol pentavinyl ether, dipentaerythritol hexavinyl ether, ethylene oxide-added trimethylolpropane trivinyl ether, ethylene oxide-added ditrimethylolpropane tetravinyl ether, ethylene oxide-added pentaerythritol Polyfunctional vinyl ethers such as tetravinyl ether, ethylene oxide-added dipentaerythritol hexavinyl ether; 2-vinyloxyethyl (meth) acrylate, 3-vinyloxypropyl (meth) acrylate, 1-methyl-2-vinyloxyethyl (meth) acrylate, ( (Meth) acrylic acid 2-vinyli Xylpropyl, 4-vinyloxybutyl (meth) acrylate, 4-vinyloxycyclohexyl (meth) acrylate, 5-vinyloxypentyl (meth) acrylate, 6-vinyloxyhexyl (meth) acrylate, (meth) acrylic acid 4 -Vinyloxymethylcyclohexylmethyl, p-vinyloxymethylphenylmethyl (meth) acrylate, 2- (vinyloxyethoxy) ethyl (meth) acrylate, 2- (vinyloxyethoxyethoxyethoxy) ethyl (meth) acrylate, etc. Vinyl ether group-containing (meth) acrylic acid ester; ethylene glycol diallyl ether, diethylene glycol diallyl ether, polyethylene glycol diallyl ether, propylene glycol diallyl ether, butylene glycol diallyl ether, hexa Diol diallyl ether, bisphenol A alkylene oxide diallyl ether, bisphenol F alkylene oxide diallyl ether, trimethylolpropane triallyl ether, ditrimethylolpropane tetraallyl ether, glycerin triallyl ether, pentaerythritol tetraallyl ether, dipentaerythritol pentaallyl ether Polyfunctional allyl ethers such as dipentaerythritol hexaallyl ether, ethylene oxide-added trimethylolpropane triallyl ether, ethylene oxide added ditrimethylolpropane tetraallyl ether, ethylene oxide added pentaerythritol tetraallyl ether, ethylene oxide added dipentaerythritol hexaallyl ether; Meta Allyl group-containing (meth) acrylic acid esters such as allyl acrylate; tri (acryloyloxyethyl) isocyanurate, tri (methacryloyloxyethyl) isocyanurate, alkylene oxide-added tri (acryloyloxyethyl) isocyanurate, alkylene oxide-added tri ( Polyfunctional (meth) acryloyl group-containing isocyanurates such as methacryloyloxyethyl) isocyanurate; polyfunctional allyl group-containing isocyanurates such as triallyl isocyanurate; polyfunctional isocyanates such as tolylene diisocyanate, isophorone diisocyanate, xylylene diisocyanate and ( Hydroxyl-containing (meth) acrylic acid esters such as 2-hydroxyethyl (meth) acrylate and 2-hydroxypropyl (meth) acrylate; Multifunctional urethane (meth) acrylate obtained by the reaction; the like polyfunctional aromatic vinyl such as divinylbenzene, the present invention is not limited only to those exemplified. These polyfunctional radically polymerizable monomers other than the AMA ester may be used alone or in combination of two or more.

  The amount of component (A) per 100 parts by mass of the total amount of AMA ester and other polymerizable monomers copolymerizable with the AMA ester is preferably 0.005 mass from the viewpoint of sufficiently suppressing polymerization. Part or more, more preferably 0.01 part by weight or more, further preferably 0.02 part by weight or more, most preferably 0.03 part by weight or more, preferably from the viewpoint of maintaining the radical polymerization activity of the radical polymerization composition. Is 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 most preferably 0.1 parts by mass or less.

  Further, the amount of the component (B) per 100 parts by mass of the total amount of the AMA ester and other polymerizable monomers copolymerizable with the AMA ester is preferably from the viewpoint of sufficiently suppressing the polymerization. 005 parts by mass or more, more preferably 0.01 parts by mass or more, further preferably 0.02 parts by mass or more, and most preferably 0.04 parts by mass or more, obtained from the radical polymerizable composition or the polymerizable composition. From the viewpoint of improving the solubility in the obtained polymer, it is preferably 3 parts by mass or less, more preferably 2 parts by mass or less, still more 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 amounts of polymerizable monomers other than AMA esters, radical polymerization initiators, curing accelerators, resin binders, solvents and additives cannot be unconditionally determined because they vary depending on the composition of the polymerizable composition of the present invention. Therefore, it is preferable to determine appropriately according to the composition.

  Examples of the radical polymerization initiator include a thermal radical polymerization initiator that generates radicals by heating, a photo radical polymerization initiator that generates radicals by irradiation of active energy rays, and the like. You may use independently and may use 2 or more types together.

  Examples of the thermal radical polymerization initiator include a peroxide polymerization initiator and an azo polymerization initiator.

  Examples of peroxide polymerization initiators include methyl ethyl ketone peroxide, cyclohexanone peroxide, methylcyclohexanone peroxide, methyl acetoacetate peroxide, acetyl acetate peroxide, 1,1-bis (tert-hexylperoxy) -3. , 3,5-trimethylcyclohexane, 1,1-bis (tert-hexylperoxy) cyclohexane, 1,1-bis (tert-butylperoxy) -3,3,5-trimethylcyclohexane, 1,1-bis ( tert-butylperoxy) -2-methylcyclohexane, 1,1-bis (tert-butylperoxy) cyclohexane, 1,1-bis (tert-butylperoxy) cyclododecane, 1,1-bis (tert-butyl) Peroxy Butane, 2,2-bis (4,4-ditert-butylperoxycyclohexyl) propane, p-menthane hydroperoxide, diisopropylbenzene hydroperoxide, 1,1,3,3-tetramethylbutyl hydroperoxide, Cumene hydroperoxide, tert-hexyl hydroperoxide, tert-butyl hydroperoxide, α, α'-bis (tert-butylperoxy) diisopropylbenzene, dicumyl peroxide, 2,5-dimethyl-2,5- Bis (tert-butylperoxy) hexane, tert-butylcumyl peroxide, ditert-butyl peroxide, 2,5-dimethyl-2,5-bis (tert-butylperoxy) hexyne-3, isobutyryl peroxide 3,5,5-trimethylhexanoyl peroxide, octanoyl peroxide, lauroyl peroxide, stearoyl peroxide, succinic acid peroxide, m-toluoyl benzoyl peroxide, benzoyl peroxide, di-n-propyl peroxide Oxydicarbonate, diisopropyl peroxydicarbonate, bis (4-tert-butylcyclohexyl) peroxydicarbonate, di-2-ethoxyethyl peroxydicarbonate, di-2-ethoxyhexyl peroxydicarbonate, di-3- Methoxybutyl peroxydicarbonate, di-sec-butylperoxydicarbonate, di (3-methyl-3-methoxybutyl) peroxydicarbonate, α, α'-bis (neodecanoyl pero C) Diisopropylbenzene, cumylperoxyneodecanoate, 1,1,3,3-tetramethylbutylperoxyneodecanoate, 1-cyclohexyl-1-methylethylperoxyneodecanoate, tert-hexyl Peroxyneodecanoate, tert-butylperoxyneodecanoate, tert-hexylperoxypivalate, tert-butylperoxypivalate, 1,1,3,3-tetramethylbutylperoxy-2-ethyl Hexanoate, 2,5-dimethyl-2,5-bis (2-ethylhexanoylperoxy) hexanoate, 1-cyclohexyl-1-methylethylperoxy-2-ethylhexanoate, tert-hexylperoxy- 2-ethylhexanoate, tert-butyl pero Ci-2-ethylhexanoate, tert-hexylperoxyisopropyl monocarbonate, tert-butylperoxyisobutyrate, tert-butylperoxymalate, tert-butylperoxy-3,5,5-trimethylhexanoate Tert-butyl peroxylaurate, tert-butyl peroxyisopropyl monocarbonate, tert-butyl peroxy-2-ethylhexyl monocarbonate, tert-butyl peroxyacetate, tert-butyl peroxy-m-toluylbenzoate, tert -Butylperoxybenzoate, bis (tert-butylperoxy) isophthalate, 2,5-dimethyl-2,5-bis (m-toluylperoxy) hexane, tert-hexylperoxy Benzoate, 2,5-dimethyl-2,5-bis (benzoylperoxy) hexane, tert-butylperoxyallyl monocarbonate, tert-butyltrimethylsilyl peroxide, 3,3 ′, 4,4′-tetra (tert- (Butylperoxycarbonyl) benzophenone, 2,3-dimethyl-2,3-diphenylbutane and the like may be mentioned, but the present invention is not limited to such examples. These peroxide polymerization initiators may be used alone or in combination of two or more.

  Examples of the azo polymerization initiator include 2-phenylazo-4-methoxy-2,4-dimethylvaleronitrile, 1-[(1-cyano-1-methylethyl) azo] formamide, 1,1′-azobis ( Cyclohexane-1-carbonitrile), 2,2′-azobis (2-methylbutyronitrile), 2,2′-azobisisobutyronitrile, 2,2′-azobis (2,4-dimethylvaleronitrile) 2,2′-azobis (2,4-dimethyl-4-methoxyvaleronitrile), 2,2′-azobis (2-methylpropionamidine) dihydrochloride, 2,2′-azobis (2-methyl-N—) Phenylpropionamidine) dihydrochloride, 2,2′-azobis [N- (4-chlorophenyl) -2-methylpropionamidine] dihydrochloride 2,2′-azobis [N- (4-hydrophenyl) -2-methylpropionamidine] dihydrochloride, 2,2′-azobis [2-methyl-N- (phenylmethyl) propionamidine] dihydrochloride, 2, 2′-azobis [2-methyl-N- (2-propenyl) propionamidine] dihydrochloride, 2,2′-azobis [N- (2-hydroxyethyl) -2-methylpropionamidine] dihydrochloride, 2,2 '-Azobis [2- (5-methyl-2-imidazolin-2-yl) propane] dihydrochloride, 2,2'-azobis [2- (2-imidazolin-2-yl) propane] dihydrochloride, 2,2 '-Azobis [2- (4,5,6,7-tetrahydro-1H-1,3-diazepin-2-yl) propane] dihydro Loride, 2,2′-azobis [2- (3,4,5,6-tetrahydropyrimidin-2-yl) propane] dihydrochloride, 2,2′-azobis [2- (5-hydroxy-3,4,4) 5,6-tetrahydropyrimidin-2-yl) propane] dihydrochloride, 2,2′-azobis {2- [1- (2-hydroxyethyl) -2-imidazolin-2-yl] propane} dihydrochloride, 2, 2'-azobis [2- (2-imidazolin-2-yl) propane], 2,2'-azobis {2-methyl-N- [1,1-bis (hydroxymethyl) -2-hydroxyethyl] propionamide }, 2,2′-azobis {2-methyl-N- [1,1-bis (hydroxymethyl) ethyl] propionamide}, 2,2′-azobis [2-methyl-N- (2-H Droxyethyl) propionamide], 2,2′-azobis (2-methylpropionamide), 2,2′-azobis (2,4,4-trimethylpentane), 2,2′-azobis (2-methylpropane), And dimethyl-2,2-azobis (2-methylpropionate), 4,4′-azobis (4-cyanopentanoic acid), 2,2′-azobis [2- (hydroxymethyl) propionitrile] and the like. However, the present invention is not limited to such examples. These azo polymerization initiators may be used alone or in combination of two or more.

  When using a thermal radical polymerization initiator, a radical polymerization accelerator may be used. Examples of the radical polymerization accelerator include metal salts or metal complexes such as cobalt, copper, tin, zinc, manganese, iron, zirconium, chromium, vanadium, calcium, potassium; primary amines, secondary amines, amines such as 3 Examples include compounds; quaternary ammonium salts; thiourea compounds; ketone compounds, but the present invention is not limited to such examples. Specific examples of the radical polymerization accelerator include cobalt octylate, cobalt naphthenate, zinc octylate, zinc naphthenate, zirconium octylate, zirconium naphthenate, copper octylate, copper naphthenate, manganese octylate, manganese naphthenate, Examples include dimethylaniline, triethanolamine, triethylbenzylammonium chloride, di (2-hydroxyethyl) p-toluidine, ethylenethiourea, acetylacetone, and methyl acetoacetate.

  Examples of the radical photopolymerization initiator include 2,2-diethoxyacetophenone, 2,2-dimethoxy-2-phenylacetophenone, 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-phenylpropane-1- ON, 1- [4- (2-hydroxyethoxy) phenyl] -2-hydroxy-2-methyl-1-propan-1-one, 2-hydroxy-1- {4- [4- (2-hydroxy-2 -Methylpropionyl) benzyl] phenyl} -2-methylpropan-1-one, 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1 -(4-morpholinophenyl) -butanone-1,2- (dimethylamino) -2-[(4-methylphenyl) methyl Alkylphenone compounds such as -1- [4- (4-morpholinyl) phenyl] -1-butanone; benzophenone compounds such as benzophenone, 4,4′-bis (dimethylamino) benzophenone and 2-carboxybenzophenone; benzoin Benzoin compounds such as methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether; thioxanthone, 2-ethylthioxanthone, 2-isopropylthioxanthone, 2-chlorothioxanthone, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone Thioxanthone compounds such as 2- (4-methoxyphenyl) -4,6-bis (trichloromethyl) -sec-triazine, 2- (4-methoxynaphthyl) -4,6-bi (Trichloromethyl) -sec-triazine, 2- (4-ethoxynaphthyl) -4,6-bis (trichloromethyl) -sec-triazine, 2- (4-ethoxycarboquinylnaphthyl) -4,6-bis (trichloro Halomethylated triazine compounds such as methyl) -sec-triazine; 2-trichloromethyl-5- (2′-benzofuryl) -1,3,4-oxadiazole, 2-trichloromethyl-5- [β- (2 Halomethylated oxadiazole compounds such as' -benzofuryl) vinyl] -1,3,4-oxadiazole, 4-oxadiazole, 2-trichloromethyl-5-furyl-1,3,4-oxadiazole 2,2′-bis (2-chlorophenyl) -4,4 ′, 5,5′-tetraphenyl-1,2′-biimidazole, 2,2; -Bis (2,4-dichlorophenyl) -4,4 ', 5,5'-tetraphenyl-1,2'-biimidazole, 2,2'-bis (2,4,6-trichlorophenyl) -4, Biimidazole compounds such as 4 ′, 5,5′-tetraphenyl-1,2′-biimidazole; bis (η5-2,4-cyclopentadien-1-yl) -bis (2,6-difluoro-3) -Titanocene compounds such as-(1H-pyrrol-1-yl) -phenyl) titanium; benzoic acid ester compounds such as p-dimethylaminobenzoic acid and p-diethylaminobenzoic acid; acridine compounds such as 9-phenylacridine However, the present invention is not limited to such examples. These photo radical polymerization initiators may be used alone or in combination of two or more.

  When using a photoradical polymerization initiator, a photosensitizer, a radical polymerization accelerator or the like may be used. Examples of photosensitizers and radical polymerization accelerators include dye compounds such as xanthene dyes, coumarin dyes, 3-ketocoumarin compounds, and pyromethene dyes; ethyl 4-dimethylaminobenzoate, 2-dimethylaminobenzoate 2- Examples include dialkylaminobenzene-based compounds such as ethylhexyl; mercaptan-based hydrogen donors such as 2-mercaptobenzothiazole, 2-mercaptobenzoxazole, and 2-mercaptobenzimidazole, but the present invention is limited only to such examples. It is not a thing. 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 preferably 0.01 to 30 per 100 parts by mass in total of the polymerizable monomer other than the AMA ester and the AMA ester, from the viewpoints of curability and economical efficiency of the polymerizable composition. It is 0.05-20 mass parts, More preferably, it is 0.1-15 mass parts more preferably.

  Examples of the curing accelerator include trimethylolpropane tris (3-mercaptopropionate), pentaerythritol tetrakis (3-mercaptopropionate), pentaerythritol tetrakis (3-mercaptobutyrate), dipentaerythritol hexakis ( 3-mercaptopropionate), 1,4-bis (3-mercaptobutyryloxy) butane, 1,3,5-tris (3-mercaptobutyloxyethyl) -1,3,5-triazine-2, Examples include 4,6- (1H, 3H, 5H) -trione, but the present invention is not limited to such examples. These curing accelerators may be used alone or in combination of two or more.

  Examples of the resin binder include carboxyl group-modified vinyl ester resins, alkali-soluble oligomers such as (meth) acrylic acid polymers, alkali-soluble polymers, and (meth) acrylic acid ester polymers. It is not limited only to such illustration. These resin binders may be used alone or in combination of two or more. By adding a resin binder, the polymerizable composition of the present invention can be used, for example, in applications such as a solder resist, an alkali developing resist such as a color filter resist, a protective film resist, a paint, and an ink.

  Further, since the AMA ester is excellent in solubility and dilutability, it is possible to dissolve a resin that is the same as or similar to the resin constituting the base material. By using it as a binder, it can be suitably used as a primer, an adhesive or the like for the substrate. Examples of the resin binder include polyvinyl alcohol resins, (meth) acrylic resins, polyolefin resins, cyclic olefin resins, polyester resins, cellulose resins, polycarbonates, and the like. It is not limited to only.

  Examples of the solvent include water, monoalcohols such as methanol, ethanol, isopropanol, n-butanol and sec-butanol; polyhydric alcohols such as ethylene glycol and propylene glycol; cyclic ethers such as tetrahydrofuran and dioxane; ethylene glycol monomethyl. Glycol monomers such as ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monobutyl ether, 3-methoxybutanol Ether; ethylene glycol Glycol ethers such as dimethyl ether, ethylene glycol diethyl ether, ethylene glycol ethyl methyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol ethyl methyl ether, propylene glycol dimethyl ether, propylene glycol diethyl ether; ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate , Ethylene glycol monobutyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, propylene glycol monomethyl ether acetate, propylene Glycol monoethyl ether acetate, propylene glycol monobutyl ether acetate, dipropylene glycol monomethyl ether acetate, dipropylene glycol monoethyl ether acetate, dipropylene glycol monobutyl ether acetate, esters of glycol monoether such as 3-methoxybutyl acetate; methyl acetate, Ethyl acetate, propyl acetate, isopropyl acetate, butyl acetate, methyl propionate, ethyl propionate, butyl propionate, methyl lactate, ethyl lactate, butyl lactate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, 3-ethoxy Alkyl esters such as methyl propionate, ethyl 3-ethoxypropionate, methyl acetoacetate and ethyl acetoacetate; Ketones such as seton, methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone; aromatic hydrocarbon compounds such as benzene, toluene, xylene and ethylbenzene; aliphatic hydrocarbon compounds such as hexane, cyclohexane and octane; dimethylformamide, dimethylacetamide and N-methyl Examples include amides such as pyrrolidone, but the present invention is not limited to such examples. These solvents may be used alone or in combination of two or more.

  Examples of additives include fillers, coloring materials, dispersants, adhesion improvers, mold release agents, plasticizers, UV absorbers, matting agents, antifoaming agents, leveling agents, antistatic agents, slip agents, and surfaces. Although a modifier, a coupling agent, etc. are mentioned, this invention is not limited only to this illustration.

  The polymerizable composition of the present invention includes, for example, an AMA ester, a component (A), a component (B), and other polymerizable monomers that can be copolymerized with an AMA ester, a radical polymerization initiator, and a curing accelerator, if necessary. It can be prepared by mixing an agent, a resin binder, a solvent, an additive and the like. The order of mixing these components is arbitrary, and the present invention is not limited by the order of mixing.

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

  When a thermal radical polymerization initiator is used in the polymerizable composition of the present invention, the heating temperature of the polymerizable composition varies depending on the composition of the polymerizable composition, the type of the thermal radical polymerization initiator, etc. However, the temperature suitable for curing of the polymerizable composition is usually selected from the range of preferably 30 to 400 ° C, more preferably 70 to 350 ° C, and still more preferably 100 to 350 ° C.

  When a radical photopolymerization initiator is used in the polymerizable composition of the present invention, the polymerizable composition can be polymerized by irradiating active energy rays. Examples of active energy rays include gamma rays, X-rays, electromagnetic waves such as ultraviolet rays, visible rays, and infrared rays, particle rays such as electron rays, neutron rays, and proton rays. However, the present invention is limited to such examples. It is not limited. Among these active energy rays, γ rays, X rays, ultraviolet rays, visible rays and electron beams, more preferably ultraviolet rays, visible rays and electron rays, more preferably ultraviolet rays are used from the viewpoint of energy intensity and the like. is there.

  In addition, when using together a thermal radical polymerization initiator and a photoradical polymerization initiator with the polymeric composition of this invention, you may use either heating and irradiation of an active energy ray, or you may use both together.

  By polymerizing the polymerizable composition of the present invention as described above, a polymer composition can be obtained.

  As described above, the polymerizable composition of the present invention can not only achieve both the chemical stability of the AMA ester and the maintenance of the high polymerization activity inherent to the AMA ester, but also the polymerizable composition or Since coloring of the polymer obtained by polymerizing the polymerizable composition can be prevented, for example, a coating material, an adhesive, a sealing material, an adhesive, a primer, a paint, an ink, a resist, a dental material , Lenses, molding materials and the like.

  EXAMPLES Next, although this invention is demonstrated further in detail based on an Example, this invention is not limited only to this Example. In the following, “part” means “part by mass” and “%” means “mass%” unless otherwise specified.

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

  While nitrogen gas containing 7% by volume of oxygen gas was blown into the flask at a flow rate of 5 mL / min, the contents of the flask were heated to 90 ° C. at atmospheric pressure. During the reaction, the top liquid in the distillation tower is separated into an oil phase and an aqueous phase by a phase separator, and the oil phase is returned to the top of the tower as a reflux liquid and reacted at 90 ° C. for 16 hours while extracting the aqueous phase, α-Allyloxymethyl acrylate methyl (hereinafter referred to as MeAMA) was prepared. The obtained reaction mixture was washed with water and distilled to obtain MeAMA as a colorless and transparent liquid.

<Radical polymerization activity of radical polymerizable composition>
Example 1-1
As a stabilizer belonging to 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)), it is liquid at room temperature (23 ° C.). Stabilization belonging to 0.03 g of 6-tert-butyl-2,4-xylenol (hereinafter referred to as TPA) and at least one stabilizer selected from the group consisting of (thio) phosphite, phosphine and thioether A stabilizer composition was prepared by mixing 0.05 g of triphenyl phosphite (hereinafter referred to as TPP) that is liquid at room temperature (23 ° C.) as an agent (hereinafter referred to as (B) group).

  A radical polymerizable composition was obtained by mixing 0.08 g of the stabilizer composition obtained above and 100 g of MeAMA obtained in Preparation Example 1. As physical properties of the obtained radical polymerizable composition, radical polymerization activity in solution polymerization and radical polymerization activity in emulsion polymerization were examined based on the following methods. The results are shown in Table 1.

[Radical polymerization activity in solution polymerization]
Using 2.0 g of a radical polymerizable composition, 18.0 g of toluene, ethyl acetate or methyl ethyl ketone as a solvent, 2,2′-azobis (2-methylbutyronitrile) as a radical polymerization initiator [manufactured by Nippon Finechem Co., Ltd., Trade name: ABN-E (hereinafter referred to as ABN-E)] was placed in a reaction vessel, a reflux tube was attached to the reaction vessel, and the reaction vessel was immersed in an oil bath maintained at 80 ° C. After maintaining the temperature of the contents of the reaction vessel at 80 ° C. for 1 hour with occasional stirring, the contents of the reaction vessel were cooled by immersing the reaction vessel in a 25 ° C. water bath. A small amount of the contents in the reaction vessel was collected, and the remaining amount of MeAMA was measured based on the following method. The polymerization conversion rate was obtained from the result, and used as an index of radical polymerization activity. The higher the polymerization conversion rate, the better the radical polymerization activity.

(Remaining amount of MeAMA)
The remaining 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). It was measured. The measurement conditions at that time are as follows.

(Measurement condition)
Diluting solvent: acetonitrile / methanol = 2/1 (mass ratio)
-Elution solvent: 0.1 mol% phosphoric acid aqueous solution / acetonitrile / methanol mixed solvent-Separation column: manufactured by Shiseido Co., Ltd., trade name: CAPCELL PAK C18 TYPE: AQ

[Radical polymerization activity in emulsion polymerization]
133.0 g of deionized water was charged into a 5 L (liter) flask equipped with a dropping funnel, a stirrer, a nitrogen gas inlet tube, a thermometer, and a reflux condenser. First stage comprising 16.0 g of 25% aqueous solution of emulsifier (trade name: EMAL O, manufactured by Kao Corporation), 24.0 g of deionized water and 100.0 g of the radical polymerizable composition obtained above in a dropping funnel. A pre-emulsion was prepared.

  In the first stage pre-emulsion obtained above, 7.0 g of an amount corresponding to 5% of the pre-emulsion was added into the flask, and the temperature was raised to 75 ° C. with stirring while gently blowing nitrogen gas. did. After the temperature rise, initial polymerization was started by adding 1.0 g of 5% potassium persulfate aqueous solution into the flask, and the content in the flask was heated to 80 ° C. over 20 minutes to carry out the initial polymerization. It was.

  After completion of the initial polymerization, with the temperature of the contents of the flask maintained at 80 ° C., the rest of the pre-emulsion for the first stage and 8.0 g of 2.5% potassium persulfate aqueous solution were placed in the flask over 180 minutes. It was dripped uniformly. A small amount of the contents of the flask was collected at the same time as the dropping was completed, and the remaining amount of MeAMA was measured in the same manner as described above to determine the polymerization conversion rate, which was used as an index of radical polymerization activity. 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
A 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 as shown in Table 1. A radical polymerizable composition was obtained in the same manner as Example 1-1 using the obtained stabilizer composition. As physical properties of the obtained radical polymerizable composition, radical polymerization activity and radical polymerization activity in emulsion polymerization were examined in the same manner as in Example 1-1. The results are shown in Table 1.

In the following table, each abbreviation means the following.
[(A) group]
TPA: 6-tert-butyl-2,4-xylenol (liquid at room temperature)
W400: manufactured by Kawaguchi Chemical Industry Co., Ltd., trade name: Antage W-400 (semi-hindered phenol o-position dimer, solid at room temperature)
[(B) group]
・ TPP: Triphenyl phosphite (liquid at room temperature)
AO412S: manufactured by ADEKA Corporation, trade name: ADK STAB AO-412S (thioether stabilizer, solid at room temperature)
AS2112: manufactured by ADEKA Corporation, trade name: ADK STAB 2112 (phosphite stabilizer, solid at room temperature)
-PEP36: manufactured by ADEKA Corporation, product name: ADK STAB PEP-36 (phosphite stabilizer, solid at room temperature)
-TPLR: manufactured by Sumitomo Chemical Co., Ltd., trade name: Sumilizer TPL-R (thioether stabilizer, solid at room temperature)
[Others]
TBHQ: tert-butylhydroquinone (solid at room temperature)
・ MEHQ: Hydroquinone monomethyl ether (solid at room temperature)
・ Irg1010: BASF Japan Ltd., trade name: Irganox 1010 (hindered phenol stabilizer, solid at room temperature)
〔solvent〕
・ EAC: Ethyl acetate ・ MEK: Methyl ethyl ketone

  From the results shown in Table 1, the radical polymerizable composition containing the stabilizer composition obtained in each example is a radical polymerizable composition not containing the stabilizer composition obtained in Comparative Example 1-1. Similar to the composition, the radical polymerization activity is excellent, and the radical polymerization activity is remarkably superior to the radical polymerizable composition containing tert-butylhydroquinone (TBHQ) obtained in Comparative Example 1-2. I understand.

<Coloring resistance at the time of alkali contact of radical polymerizable composition>
Example 2-1
A stabilizer composition was prepared by mixing 0.03 g TPA and 0.05 g TPP.

  A radical polymerizable composition was obtained by mixing 0.08 g of the stabilizer composition obtained above and 100 g of MeAMA obtained in Preparation Example 1. As physical properties of the obtained radical polymerizable composition, the coloring resistance at the time of alkali contact was examined based on the following method. The results are shown in Table 2.

[Coloring resistance when in contact with alkali]
After mixing 1.0 part of the radical polymerizable composition and 2.7 parts of 10% aqueous sodium hydroxide solution and stirring the resulting solution at room temperature for 1 hour, the color of the solution was confirmed visually, and the coloring level The color type was used as an index of coloration resistance when contacted with alkali.

Examples 2-2 to 2-3 and comparative examples 2-1 to 2-3
A 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 as 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 physical properties of the obtained radical polymerizable composition, the coloring resistance at the time of alkali contact was examined in the same manner as in Example 2-1. The results are shown in Table 2.

  From the results shown in Table 2, the radically polymerizable composition containing the stabilizer composition obtained in each example was a radically polymerizable composition containing the stabilizer composition obtained in each comparative example. In contrast, it can be seen that the coloring resistance at the time of alkali contact is excellent.

<Coloring resistance of polymer solution>
Example 3-1
A stabilizer composition was prepared by mixing 0.03 g TPA and 0.05 g TPP.

  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 consisting only of MeAMA. To 66.0 g of this radically polymerizable composition consisting only of MeAMA, 27.2 g of isobornyl methacrylate [manufactured by Kyoeisha Chemical Co., Ltd., trade name: Light Ester IB-X] and 2-hydroxyethyl methacrylate [Japan Catalyst product] A radical polymerizable composition was obtained by adding and mixing 6.2 g.

  The inside of the reaction vessel equipped with a thermometer, a cooling pipe, a gas introduction pipe and a stirring device in a four-neck separable flask was replaced with nitrogen gas. Under a nitrogen stream, 66.7 g of ethyl acetate and 20.0 g of the radical polymerizable composition obtained above were charged in a reaction vessel, and the temperature was raised to 80 ° C.

  On the other hand, 80.0 g of the radical polymerizable composition is put into the dropping tank A, and 0.43 g of ABN-E, 0.26 g of n-dodecyl mercaptan (hereinafter referred to as n-DM) and ethyl acetate (hereinafter referred to as EAC) are added to the dropping tank B. ) 23.3 g of the mixture was added.

  After confirming that the internal temperature of the reaction vessel was stable, a mixture of ABN-E 0.08 g, n-DM 0.05 g and EAC 10.0 g was added to the reaction vessel. When 10 minutes have elapsed after completion of the addition, the mixture is dropped from the dropping tank A and the dropping tank B, and the internal temperature of the reaction tank is adjusted to 80 to 83 ° C. From the dropping tank B, the mixture was dropped over 4 hours to carry out a polymerization reaction. After 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 and transparent polymer solution.

  As the physical properties of the polymer solution obtained above, the color resistance of the polymer solution upon contact with alkali and the color resistance under storage stability test conditions were examined based on the following methods. The results are shown in Table 3.

[Coloring resistance of polymer solution when contacted with alkali]
After putting 3 g of the polymer solution into a 10 mL screw tube and heating to 50 ° C., add 0.3 g of monoethanolamine into the screw tube, sufficiently stirring, visually confirming the color of the polymer solution, and coloring The presence or absence of color was used as an index of coloring resistance at the time of alkali contact.

[Coloring resistance of polymer solution under storage stability test conditions]
Put 5 g of the polymer solution obtained above in a 10 mL screw tube, seal the screw tube by closing the opening of the screw tube, and store it in a hot air dryer maintained at 50 ° C. for 1 month. Then, the color of the polymer solution was visually confirmed, and the presence or absence of coloring was used as an index of coloring resistance under storage stability test conditions.

Example 3-2 and Comparative Example 3-1
A 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 as shown in Table 3. Using the obtained stabilizer composition, a polymer solution was obtained in the same manner as in Example 3-1. As physical properties of the obtained polymer solution, the coloration resistance under alkali contact and the coloration resistance under storage stability test conditions were examined in the same manner as in Example 3-1. The results are shown in Table 3.

  From the results shown in Table 3, the polymer solutions obtained in each example were colored under the conditions of coloring resistance and storage stability when contacted with an alkali as compared with the polymer solutions obtained in the comparative examples. It turns out that it is excellent in tolerance.

<Coloring resistance under weathering test conditions of cured product>
Example 4-1
A stabilizer composition was prepared by mixing 0.03 g TPA and 0.05 g TPP.

  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 consisting only of MeAMA. To 8.0 g of this radically polymerizable composition consisting only of MeAMA, 2.0 g of dipentaerythritol hexaacrylate [manufactured by Kyoeisha Chemical Co., Ltd., trade name: Light acrylate DPE-6A] and Irgacure 184D [BASF as a photoradical initiator Japan Co., Ltd.] 0.3 g was added and mixed to obtain a radical polymerizable composition.

Using a polyethylene terephthalate film (hereinafter referred to as PET film) having a thickness of 100 μm as a spacer, 0.5 g of the radical polymerizable composition is sandwiched between the PET film having been subjected to a release treatment together with the spacer, and further sandwiched between transparent glass plates. It is. Using a belt conveyor type ultraviolet irradiation device, after irradiating the transparent glass plate with ultraviolet rays so that the integrated light quantity becomes 4 (J / cm ² ), the PET film subjected to the release treatment is peeled off, and the thickness is increased. A 100 μm film-like cured product was obtained.

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

[Coloring resistance under weathering test conditions]
The yellowness (b value) of the film-like cured product obtained above was measured using an equation difference meter, and the obtained value was defined as the initial b value.

  Next, after placing the film-like cured product under the following weathering test conditions, the b value was measured again, and the obtained value was defined as the b value after the test. In addition, it shows that yellowing degree is so small that b value is small.

(Weather resistance test conditions)
Tester: Suga Test Instruments Co., Ltd., trade name: Xenon Weather Meter X75SC
Irradiance: 60 W / m ²
Black panel temperature: 63 ° C
Humidity: 50% relative humidity
Test time: 500 hours

Comparative Examples 4-1 to 4-3
A radical containing 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 as shown in Table 4. The coloring resistance of the film-like cured product obtained from the polymerizable composition under the weather resistance test conditions was examined. The results are shown in Table 4.

  From the results shown in Table 4, the cured product obtained in Example 4-1 is small in initial yellowing because the initial b value is small compared to the cured product obtained in each comparative example. Furthermore, since the b value after test is small, it can be seen that the coloring resistance under the weathering test condition is excellent.

<Storage stability of radically polymerizable composition>
Example 5-1
A stabilizer composition was prepared by mixing 0.05 g TPA and 0.5 g TPP.

  A radical polymerizable composition was obtained by mixing 0.55 g of the stabilizer composition obtained above and 100 g of MeAMA obtained in Preparation Example 1. 3 g of the obtained radical polymerizable composition is put into a 10 mL screw tube, a lid is attached to the opening of the screw tube, the screw tube is hermetically sealed, put into a 50 ° C. incubator, and screw tube every month. Was taken out of the incubator and the storage stability was examined based on the following method. The results are shown in Table 5.

[Storage stability]
(1) Presence or absence of polymer The contents (liquid) of the screw tube are taken out and dropped into n-hexane at room temperature (about 23 ° C.). If no precipitate is formed, it is judged that there is no polymer. When a precipitate was formed, it was judged that there was a polymer. However, when the contents of the screw tube were clearly thickened or gelled, it was judged that there was a polymer unconditionally.

  In the column of “Presence / absence of polymer” in Table 5, if a polymer is produced from when the contents are dropped into n-hexane until 9 months have passed, the course of the occurrence of the polymer is shown. The number of months was described, and “None” was described when no polymer was formed by the lapse of 9 months from when the contents were dropped into n-hexane.

(2) Presence or absence of coloration When the polymer was not produced by the lapse of 9 months from when the content was dropped into n-hexane, the colored state of the content was visually observed.

  In the column of “Presence / absence of coloring” in Table 5, the coloring state of the contents is described. In addition, "-" was described when the polymer was produced until nine months passed since the contents were dropped into n-hexane.

Examples 5-2 to 5-23 and comparative examples 5-1 to 5-8
A radical containing 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 as shown in Table 5. The storage stability of the polymerizable composition was examined. The results are shown in Table 5.

  From the results shown in Table 5, it can be seen that the radical polymerizable composition obtained in each example is superior in storage stability as compared with the radical polymerizable composition obtained in each comparative example. .

<High temperature stability of radically polymerizable composition (90 ° C.)>
Example 6-1
A stabilizer composition was prepared by mixing 0.03 g TPA and 0.1 g TPP.

  A radical polymerizable composition was obtained by mixing 0.13 g of the stabilizer composition obtained above and 100 g of MeAMA obtained in Preparation Example 1.

  5 g of the radical polymerizable composition obtained above is put in a 15 mL screw-cap test tube, a lid is attached to the opening of the test tube, the test tube is sealed, put in a thermostat, and at a temperature of 90 ° C. Heated for 24 hours. After heating for 24 hours, the test tube was taken out of the thermostat and the high temperature stability (90 ° C.) was examined based on the following method. The results are shown in Table 6.

[High temperature stability]
(1) Presence / absence of polymer The presence / absence of polymer is determined by taking out the content (liquid) from a test tube and dropping it into n-hexane at room temperature. Judgment was made, and when a precipitate was formed, it was judged that a polymer was present. However, when the contents were clearly thickened or gelled, it was judged that there was a polymer unconditionally.

  In the column “Presence / absence of polymer” in Table 6, “Yes” is described when a polymer is generated, and “None” is described when no polymer is generated.

(2) Presence / absence of coloring When no polymer was formed, the colored state of the contents was visually observed. In the column of “Presence / absence of coloring” in Table 6, the coloring state is described. In addition, "-" was described when the polymer produced.

Examples 6-2 to 6-11 and Comparative Example 6-1
A radical containing 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 as shown in Table 6. The high temperature stability (90 ° C.) of the polymerizable composition was examined. The results are shown in Table 6.

  From the results shown in Table 6, the radically polymerizable composition obtained in each example has high temperature stability (90 ° C.) as compared with the radically polymerizable composition obtained in Comparative Example 6-1. It turns out that it is excellent.

<High temperature stability of radically polymerizable composition (110 ° C.)>
Example 7-1
A stabilizer composition was prepared by mixing 0.05 g TPA and 0.5 g TPP.

  A radical polymerizable composition was obtained by mixing 0.55 g of the stabilizer composition obtained above and 100 g of MeAMA obtained in Preparation Example 1.

  5 g of the radical polymerizable composition obtained above is placed in a 15 mL screw-cap test tube, a lid is attached to the opening of the test tube, the test tube is sealed, placed in a thermostat, and at a temperature of 110 ° C. Heated for 24 hours. After heating for 24 hours, the test tube was taken out of the thermostatic chamber, and the high temperature stability (110 ° C.) was examined in the same manner as in Example 6-1. The results are shown in Table 7.

Examples 7-2 to 7-24 and Comparative Examples 7-1 to 7-14
A radical containing 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 as shown in Table 7. The high temperature stability (110 ° C.) of the polymerizable composition was examined. The results are shown in Table 7.

  From the results shown in Table 7, the radical polymerizable composition obtained in each example is superior in high temperature stability (110 ° C.) as compared with the radical polymerizable composition obtained in each comparative example. I understand that.

The stabilizer composition of the present invention can be suitably used for, for example, a polymerizable compound used for a polymer raw material, a curable material, and the like. Since the polymerizable composition of the present invention contains the stabilizer composition, the chemical stability of the AMA ester and the maintenance of the high polymerization activity inherent in the AMA ester can be achieved at the same time. Since coloring of the composition or its polymer can be prevented, it is used for applications such as coating materials, adhesives, sealants, adhesives, paints, inks, resists, dental materials, optical lenses, molding materials, etc. Is expected to do.

Claims (2)

A polymerizable composition comprising a polymerizable ester compound having an α -allyloxymethylacryloyl group, wherein (A) at least one semihindered selected from the group consisting of semihindered phenols and dimers thereof A polymerizable composition comprising a phenol compound and (B) (thio) phosphite, a phosphine, and at least one stabilizer selected from the group consisting of thioethers. A polymer composition obtained by polymerizing the polymerizable composition according to claim 1 .