Polymerizable composition and method for producing polymerizable ester compound having α-allyloxymethylacryloyl group

Abstract

The purpose of the present invention is to provide: a polymerizable composition which contains a polymerizable ester compound having an AMA group and excellent long-term stability; and a method for producing a polymerizable ester compound having an AMA group and excellent long-term stability. The present invention provides a polymerizable composition which contains: a polymerizable ester compound having an α-allyloxymethylacryloyl group represented by general formula (1); and at least one compound that is selected from the group consisting of a phenol compound represented by general formula (2), a (thio)phosphite compound, a phosphine compound, a thioether compound, and a thiol compound. (In formula (1), R1 represents a substituent having 6 or more carbon atoms.) (In formula (2), R21 represents a substituent having 2 or more carbon atoms. R22 moieties are the same or different, and each represent an organic group. a represents an integer of 0 to 2.)

Description

Polymerizable composition and method for producing polymerizable ester compound having α-allyloxymethylacryloyl group

[0001] The present invention relates to a polymerizable composition, particularly to a polymerizable composition that is inhibited from yellowing over time, and a method for producing a polymerizable ester compound having an α-allyloxymethylacryloyl group.

[0002] Polymerizable ester compounds having an α-allyloxymethylacryloyl group (hereinafter also referred to as an AMA group) are known as radically polymerizable compounds having polymerization activity equal to or greater than that of a (meth)acryloyl group. Polymerizable compositions containing polymerizable ester compounds having an AMA group not only have excellent polymerization rate and internal curing properties like radically polymerizable compounds having a (meth)acryloyl group, but also have excellent thermal decomposition resistance, adhesion, mechanical properties, and fine particle dispersibility, and are therefore used in a wide range of applications such as coating agents, adhesives, sealants, pressure-sensitive adhesives, paints, optical lenses, and molding materials.

[0003] Although polymerizable ester compounds having an AMA group have high polymerization activity, they have a problem of lacking storage stability. As a method for improving such storage stability, a method of adding an antioxidant or a stabilizer is known (see, for example, Patent Documents 1 and 2).

[0004] International Publication No. 2010 / 114077 Japanese Patent Application Laid-Open No. 2014-31510

[0005] However, various polymerizable ester compounds having an AMA group, particularly those having a large number of carbon atoms in the ester moiety, have a problem of being prone to yellowing over time. The yellowing becomes particularly pronounced when stored at high temperatures. Thus, there is still room for improvement in the stability over time of the polymerizable ester compounds having large molecules.

[0006] The present invention has been made in view of the above-described current situation, and an object of the present invention is to provide a polymerizable composition containing a polymerizable ester compound having an AMA group and having excellent stability over time, and a method for producing a polymerizable ester compound having an AMA group and having excellent stability over time.

[0007] The present inventors have conducted extensive research on polymerizable ester compounds having an AMA group, and have found that by combining a polymerizable ester compound having an AMA group with a large number of carbon atoms in the ester moiety with at least one of a specific phenol compound, a (thio)phosphite compound, a phosphine compound, a thioether compound, or a thiol compound, the yellowing of the polymerizable ester compound over time can be significantly suppressed, leading to the completion of the present invention.

[0008] That is, the present invention provides the following aspects: <1> A polymerizable composition comprising a polymerizable ester compound having an α-allyloxymethylacryloyl group, represented by the following general formula (1), and at least one compound selected from the group consisting of a phenol compound, a (thio)phosphite compound, a phosphine compound, a thioether compound, and a thiol compound, represented by the following general formula (2):

[0009] (In the formula, R １ represents a substituent having 6 or more carbon atoms.

[0010]

[0011] (In the formula, R ２１ represents a substituent having 2 or more carbon atoms. ２２ are the same or different and represent an organic group. a represents an integer of 0 to 2.) <2> The polymerizable composition according to <1> above, wherein the phenol compound is a hindered phenol compound represented by the following general formula (2-1):

[0012]

[0013] (In the formula, R ２１ represents a substituent having 2 or more carbon atoms. ２３ and R ２４ are the same or different and represent a hydrogen atom or a tert-butyl group. ２３ and R ２４at least one of which is a tert-butyl group.) <3> The polymerizable composition according to <1> or <2> above, characterized in that the polymerizable composition contains the phenol compound and at least one compound selected from the group consisting of (thio)phosphite compounds, phosphine compounds, thioether compounds, and thiol compounds. <4> The polymerizable composition according to any one of <1> to <3> above, characterized in that the content of the at least one compound selected from the group consisting of phenol compounds, (thio)phosphite compounds, phosphine compounds, thioether compounds, and thiol compounds is 100 to 10,000 ppm in the polymerizable composition. <5> A method for producing a polymerizable ester compound having an α-allyloxymethylacryloyl group, the method comprising a step of subjecting an α-(allyloxymethyl)acrylic acid ester and an alcohol to a transesterification reaction in the presence of a catalyst, wherein a phenol compound represented by the following general formula (2) is added in the transesterification reaction step:

[0014]

[0015] (In the formula, R ２１ represents a substituent having 2 or more carbon atoms. ２２ are the same or different and represent an organic group. a represents an integer of 0 to 2.) <6> The method for producing a polymerizable ester compound having an α-allyloxymethylacryloyl group according to <5> above, wherein the alcohol has 6 or more carbon atoms.

[0016] The polymerizable composition of the present invention has excellent stability over time. Furthermore, the method for producing a polymerizable ester compound having an α-allyloxymethylacryloyl group of the present invention can efficiently produce the polymerizable ester compound having excellent stability over time.

[0017] The present invention will be described in detail below. Note that a combination of two or more of the individual preferred embodiments of the present invention described below is also a preferred embodiment of the present invention.

[0018] The polymerizable composition of the present invention is characterized by containing a polymerizable ester compound having an α-allyloxymethylacryloyl group represented by the above general formula (1) and at least one compound selected from the group consisting of a phenol compound represented by the above general formula (2), a (thio)phosphite compound, a phosphine compound, a thioether compound, and a thiol compound.

[0019] The polymerizable ester compound having an α-allyloxymethylacryloyl group contained in the polymerizable composition of the present invention has a problem of yellowing over time, with the yellowing becoming particularly pronounced when stored at high temperatures. The yellowing of the polymerizable ester compound is thought to be caused by the presence of residual reactants of additive components used as polymerization inhibitors during the synthesis of the polymerizable ester compound. When the produced polymerizable ester compound has a low molecular weight and a low boiling point, the residual reactants can be separated and removed from the polymerizable ester compound by distilling the resulting polymerizable ester compound. However, when the polymerizable ester compound has a relatively large number of carbon atoms in the ester moiety, the boiling point becomes high, making purification by distillation difficult and preventing sufficient removal of the residual reactants. The polymerizable composition of the present invention, by combining specific components, can suppress the yellowing of the polymerizable ester compound over time, even when the polymerizable ester compound is difficult to purify by distillation. The reason why the polymerizable composition of the present invention has such excellent stability over time is presumably that the specific phenol compound or the like contained in the polymerizable composition captures peroxy radicals generated by the reaction between oxygen and radical species produced by oxidation of the polymerizable compound, or donates hydrogen radicals to convert them into hydroperoxides, thereby suppressing the polymerization reaction (autoxidation reaction) caused by peroxy radicals, and that the (thio)phosphite compound or the like reduces hydroperoxides and phenol radicals, thereby suppressing the generation of radicals from hydroperoxides and the generation of colored substances derived from phenol radicals.

[0020] Each component contained in the polymerizable composition is described below. <Polymerizable ester compound (A) having an α-allyloxymethylacryloyl group> The polymerizable ester compound having an α-allyloxymethylacryloyl group (hereinafter also referred to as "polymerizable ester compound (A)") contained in the polymerizable composition is a compound represented by the general formula (1).

[0021] In the above general formula (1), R １ represents a substituent having 6 or more carbon atoms. １ The number of carbon atoms of the substituent represented by R is preferably 6 to 30, more preferably 6 to 25, and even more preferably 6 to 20. １ The substituent represented by the formula (I) is preferably an organic group.

[0022] R １ Examples of the substituent represented by the formula (I) include a hydrocarbon group which may have a substituent (substituent a), or a hydrocarbon group which may have a substituent and -O-, -CO-, -COO-, -NH-, -S-, -SO- or -SO ２ The group containing the hydrocarbon group and the bonding group may be a group consisting of a combination of a plurality of hydrocarbon groups and a plurality of bonding groups.

[0023] Examples of the hydrocarbon group include monovalent or divalent aliphatic hydrocarbon groups, alicyclic hydrocarbon groups, aromatic hydrocarbon groups, etc. Examples of the monovalent aliphatic 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, a sec-amyl group, a tert-amyl group, a neopentyl group, a hexyl group, a heptyl group, an octyl group, a sec-octyl group, a tert-octyl group, a 2-ethylhexyl group, a nonyl group, a decyl group, an undecyl group, a lauryl group, a tridecyl group, a myristyl group, a pentadecyl group, a sucralose group, ... ethyl group, an ethyl group, an ethyl group, an ethyl group, an ethyl group, an ethyl group, an ethyl group, an ethyl group, an ethyl group, an ethyl group, an ethyl group, an ethyl group, an ethyl group, an ethyl group, an ethyl group, an ethyl group, an ethyl group, an ethyl group, an ethyl group, an ethyl group, an ethyl group, an ethyl group, an ethyl group, an Examples of the alkyl group include linear or branched saturated aliphatic hydrocarbon groups such as a vinyl group, an allyl group, a crotyl group, a 1,1-dimethyl-2-propenyl group, a 2-methyl-butenyl group, a 3-methyl-2-butenyl group, a 3-methyl-3-butenyl group, a 2-methyl-3-butenyl group, an oleyl group, a linole group, and a linolene group.

[0024] Examples of the monovalent 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 3,3,5-trimethylcyclohexyl group, a tricyclodecanyl group, a bornyl group, an isobornyl group, an adamantyl group, a dicyclopentanyl group, and a dicyclopentenyl group.

[0025] Examples of the monovalent aromatic hydrocarbon group include a phenyl group, a methylphenyl group, a dimethylphenyl group, a benzyl group, a diphenylmethyl group, a triphenylmethyl group, a 4-tert-butylphenyl group, a diphenylethyl group, a cinnamyl group, a naphthyl group, and an anthranyl group.

[0026] Examples of the divalent aliphatic hydrocarbon group, alicyclic hydrocarbon group, and aromatic hydrocarbon group include divalent groups obtained by removing one hydrogen atom from the above-mentioned monovalent aliphatic hydrocarbon group, alicyclic hydrocarbon group, and aromatic hydrocarbon group, respectively.

[0027] The hydrocarbon group may contain a heteroatom such as an oxygen atom, a nitrogen atom, or a sulfur atom.

[0028] Examples of the substituent a include a halogen atom (e.g., a fluorine atom, a chlorine atom, a bromine atom, an iodine atom), an alkoxy group, an α-allyloxymethylacryloyl group, etc. When the substituent a includes an α-allyloxymethylacryloyl group, the polymerizable ester compound (A) becomes a polyvalent polymerizable ester compound including two or more α-allyloxymethylacryloyl groups.

[0029] Among them, R １ The substituent represented by the formula (I) is preferably a hydrocarbon group which may have a substituent a, or a group containing a hydrocarbon group which may have a substituent a and -O-; more preferably an aliphatic hydrocarbon group which may have a substituent a, or a group containing an aliphatic hydrocarbon group which may have a substituent a and -O-; still more preferably a saturated aliphatic hydrocarbon group which may have a substituent a, or a group containing a saturated aliphatic hydrocarbon group which may have a substituent a and -O-; and particularly preferably a saturated aliphatic hydrocarbon group which may have a substituent a and a group containing -O-.

[0030] Specific examples of the polymerizable ester compound (A) include n-hexyl α-(allyloxymethyl)acrylate, sec-hexyl α-(allyloxymethyl)acrylate, n-heptyl α-(allyloxymethyl)acrylate, n-octyl α-(allyloxymethyl)acrylate, 2-ethylhexyl α-(allyloxymethyl)acrylate, nonyl α-(allyloxymethyl)acrylate, decyl α-(allyloxymethyl)acrylate, undecyl α-(allyloxymethyl)acrylate, ... Lauryl acrylate, Tridecyl α-(allyloxymethyl)acrylate, Myristyl α-(allyloxymethyl)acrylate, Pentadecyl α-(allyloxymethyl)acrylate, Cetyl α-(allyloxymethyl)acrylate, Heptadecyl α-(allyloxymethyl)acrylate, Stearyl α-(allyloxymethyl)acrylate, Nodecyl α-(allyloxymethyl)acrylate, Eicosyl α-(allyloxymethyl)acrylate, Seryl α-(allyloxymethyl)acrylate, Melissyl α-(allyloxymethyl)acrylate alkyl α-(allyloxymethyl)acrylates such as cyclohexyl α-(allyloxymethyl)acrylate, cyclohexylmethyl α-(allyloxymethyl)acrylate, 4-methylcyclohexyl α-(allyloxymethyl)acrylate, 3,3,5-trimethylcyclohexyl α-(allyloxymethyl)acrylate, 4-tert-butylcyclohexyl α-(allyloxymethyl)acrylate, tricyclodecanyl α-(allyloxymethyl)acrylate, isobornyl α-(allyloxymethyl)acrylate, alicyclic α-(allyloxymethyl)acrylic esters such as adamantyl α-(allyloxymethyl)acrylate, dicyclopentanyl α-(allyloxymethyl)acrylate, and dicyclopentenyl α-(allyloxymethyl)acrylate; triethylene glycol di(α-(allyloxymethyl))acrylate, tetraethylene glycol di(α-(allyloxymethyl))acrylate, pentaethylene glycol di(α-(allyloxymethyl))acrylate, and hexaethylene glycol di(α-(allyloxymethyl))acrylate,Heptaethylene glycol di(α-(allyloxymethyl))acrylate, octaethylene glycol di(α-(allyloxymethyl))acrylate, nonaethylene glycol di(α-(allyloxymethyl))acrylate, decaethylene glycol di(α-(allyloxymethyl))acrylate, dipropylene glycol di(α-(allyloxymethyl))acrylate, tripropylene glycol di(α-(allyloxymethyl))acrylate, tetrapropylene glycol di(α-(allyloxymethyl))acrylate, pentapropylene glycol Pyrene glycol di(α-(allyloxymethyl))acrylate, hexapropylene glycol di(α-(allyloxymethyl))acrylate, heptapropylene glycol di(α-(allyloxymethyl))acrylate, octapropylene glycol di(α-(allyloxymethyl))acrylate, nonapropylene glycol di(α-(allyloxymethyl))acrylate, decapropylene glycol di(α-(allyloxymethyl))acrylate, 1,6-hexanediol di(α-(allyloxymethyl))acrylate, 1,7-hexanediol di(α-(allyloxymethyl))acrylate, Butanediol di(α-(allyloxymethyl))acrylate, 1,8-heptanediol di(α-(allyloxymethyl))acrylate, 1,9-nonanediol di(α-(allyloxymethyl))acrylate, 1,10-decanediol di(α-(allyloxymethyl))acrylate, 1,12-dodecanediol di(α-(allyloxymethyl))acrylate, polyethylene glycol di(α-(allyloxymethyl))acrylate, polypropylene glycol di(α-(allyloxymethyl))acrylate, hexanediol di( α-(allyloxymethyl))acrylate, neopentyl glycol di(α-(allyloxymethyl))acrylate, 1,4-cyclohexanediol di(α-(allyloxymethyl))acrylate, 1,3-cyclohexanediol di(α-(allyloxymethyl))acrylate, 1,2-cyclohexanediol di(α-(allyloxymethyl))acrylate, 1,4-cyclohexanedimethanol di(α-(allyloxymethyl))acrylate, 1,3-cyclohexanedimethanol di(α-(allyloxymethyl))acrylate,1,3-adamantanediol di(α-(allyloxymethyl))acrylate, tricyclodecane dimethanol di(α-(allyloxymethyl))acrylate, benzenedimethanol di(α-(allyloxymethyl))acrylate, 1,4-bis(2-hydroxyethoxy)-naphthalene di(α-(allyloxymethyl))acrylate, xylylene glycol di(α-(allyloxymethyl))acrylate, hydroquinone di(α-(allyloxymethyl))acrylate, bisphenol A di(α-(allyloxymethyl))acrylate, Divalent allyloxymethyl acrylates such as bisphenol F di(α-(allyloxymethyl))acrylate, bisphenol S di(α-(allyloxymethyl))acrylate, bisphenol fluorene di(α-(allyloxymethyl))acrylate, and bis(hydroxypivalaldehyde) pentaerythritol acetal cyclic acetal di(α-(allyloxymethyl))acrylate; glycerin tri(α-(allyloxymethyl))acrylate, and glycerin alkylene glycol adduct tri(α-(allyloxymethyl))acrylate; tri- or higher valent allyloxymethyl acrylates such as α-(allyl)acrylate, sorbitol tri(α-(allyloxymethyl))acrylate, trimethylolpropane tri(α-(allyloxymethyl))acrylate, ditrimethylolpropane tri(α-(allyloxymethyl))acrylate, dipentaerythritol tri(α-(allyloxymethyl))acrylate, isocyanuric acid tris(2-hydroxyethyl)tri(α-(allyloxymethyl))acrylate, and polyglycerin tri(α-(allyloxymethyl))acrylate; α-(allyloxymethyl)phenyl acrylate, α-(allyloxymethyl)methylphenyl acrylate, α-(allyloxymethyl)dimethylphenyl acrylate, α-(allyloxymethyl)trimethylphenyl acrylate, α-(allyloxymethyl)4-tert-butylphenyl acrylate, α-(allyloxymethyl)benzyl acrylate, α-(allyloxymethyl)1-naphthylmethyl acrylate, α-(allyloxymethyl)3-phenoxybenzyl acrylate, α-(allyloxymethyl)2-(2-biphenylyloxy)ethyl acrylate,4-phenylbenzyl α-(allyloxymethyl)acrylate, 9-fluorenylmethyl α-(allyloxymethyl)acrylate, diphenylethyl α-(allyloxymethyl)acrylate, cinnamyl α-(allyloxymethyl)acrylate, naphthyl α-(allyloxymethyl)acrylate, anthracenyl α-(allyloxymethyl)acrylate, orthophenylphenyl α-(allyloxymethyl)acrylate, 2-(1-naphthyloxy)ethyl α-(allyloxymethyl)acrylate, α-(allyloxymethyl)acrylate aromatic α-(allyloxymethyl)acrylate esters such as 2-(2-naphthyloxy)ethyl acrylate, 8-quinolinyl α-(allyloxymethyl)acrylate, 2-(9H-carbazol-9-yl)ethyl α-(allyloxymethyl)acrylate, and 2-(2-naphthylthio)ethyl α-(allyloxymethyl)acrylate; and α-(allyloxymethyl)acrylic acid ester compounds having 6 or more carbon atoms in the ester moiety among the compounds described in paragraphs

[0044] to

[0047] of WO 2010 / 114077.

[0031] These compounds can be obtained by transesterifying a lower ester compound of α-(allyloxymethyl)acrylic acid, such as methyl α-(allyloxymethyl)acrylate, with a monohydric alcohol. Examples of the monohydric alcohol include alcohols having a linear or branched saturated aliphatic hydrocarbon group, such as hexanol, sec-hexanol, heptanol, n-octanol, 2-ethylhexanol, nonanol, decanol, undecanol, dodecanol (lauryl alcohol), tridecanol, myristyl alcohol, pentadecanol, cetyl alcohol, heptadecanol, stearyl alcohol, nodecyl alcohol, eicosyl alcohol, and melissyl alcohol; alcohols having an alicyclic hydrocarbon group, such as cyclopentylmethanol, cyclohexanol, cyclohexylmethanol, 4-methylcyclohexanol, 4-tert-butylcyclohexanol, 3,3,5-trimethylcyclohexanol, tricyclodecane dimethanol, borneol, isoborneol, adamantanol, dicyclopentanyl alcohol, and dicyclopentenyl alcohol (hydroxydicyclopentadiene); alcohols having a linear or branched ether group-based saturated hydrocarbon group, such as 2-(2-butoxyethoxy)ethanol, 2-(2-hexyloxyethoxy)ethanol, 2-(2-butoxyethoxy)ethanol, 2-(2-hexyloxyethoxy)ethanol, and 2,2-dimethyl-1,3-dioxolane-4-methanol; and alcohols having an aromatic hydrocarbon group or an aromatic heterocyclic group, such as phenol, methylphenol, dimethylphenol, trimethylphenol, 4-tert-butylphenol, benzyl alcohol, 1-naphthalenemethanol, 3-phenoxybenzyl alcohol, 2-(2-biphenylyloxy)ethanol, 4-phenylbenzyl alcohol, 9-fluorenylmethanol, diphenylethanol, cinnamyl alcohol, naphthol, anthrol, orthophenylphenol, 2-(1-naphthyloxy)ethanol, 2-(2-naphthyloxy)ethanol, 8-quinolinol, 2-(9H-carbazol-9-yl)ethanol, and 2-(2-naphthylthio)ethanol.

[0032] Further, examples of the polymerizable ester compound (A) include polyhydric α-(allyloxymethyl)acrylic acid ester compounds obtained by transesterification of a lower α-(allyloxymethyl)acrylic acid ester compound such as methyl α-(allyloxymethyl)acrylate with a polyhydric alcohol.

[0033] The polyhydric alcohols include dihydric alcohols and trihydric or higher alcohols. The number of carbon atoms in the polyhydric alcohols is preferably 6 to 30, more preferably 6 to 25, and even more preferably 6 to 20.

[0034] Specific examples of the polyhydric alcohol include triethylene glycol, tetraethylene glycol, pentaethylene glycol, hexaethylene glycol, heptaethylene glycol, octaethylene glycol, nonaethylene glycol, decaethylene glycol, dipropylene glycol, tripropylene glycol, tetrapropylene glycol, pentapropylene glycol, hexapropylene glycol, heptapropylene glycol, octapropylene glycol, nonapropylene glycol, decapropylene glycol, 1,6-hexanediol, 1,7-heptanediol, 1,8-heptanediol, 1,9-nonanediol, 1,10-decanediol, 1,12-dodecanediol, polyethylene glycol, polypropylene glycol, hexanediol, neopentyl glycol, 1,4-cyclohexanediol, 1,3-cyclohexanediol, 1,2- Dihydric alcohols such as cyclohexanediol, 1,4-cyclohexanedimethanol, 1,3-cyclohexanedimethanol, 1,3-adamantanediol, tricyclodecane dimethanol, benzenedimethanol, 1,4-bis(2-hydroxyethoxy)-naphthalene, xylylene glycol, hydroquinone, bisphenol A, bisphenol F, bisphenol S, bisphenolfluorene, 3,9-bis(1,1-dimethyl-2-hydroxyethyl)-2,4,8,10-tetraoxaspiro[5,5]undecane, and bis(hydroxypivalaldehyde) pentaerythritol acetal cyclic acetal; trihydric or higher alcohols such as glycerin, compounds in which alkylene glycol is added to glycerin, sorbitol, trimethylolpropane, ditrimethylolpropane, dipentaerythritol, tris(2-hydroxyethyl) isocyanurate, and polyglycerin.

[0035] Among these, the polymerizable ester compound (A) is preferably a polyhydric α-(allyloxymethyl)acrylic acid ester compound obtained by transesterifying an α-(allyloxymethyl)acrylic acid lower ester compound with a dihydric alcohol, more preferably a polyhydric α-(allyloxymethyl)acrylic acid ester compound obtained by transesterifying an α-(allyloxymethyl)acrylic acid lower ester compound with a dihydric alcohol having 6 to 20 carbon atoms, and even more preferably a polyhydric α-(allyloxymethyl)acrylic acid ester compound obtained by transesterifying an α-(allyloxymethyl)acrylic acid lower ester compound with tripropylene glycol.

[0036] The content of the polymerizable ester compound (A) in the polymerizable composition is preferably 70 to 99.8 mass%, more preferably 75 to 99.8 mass%, and even more preferably 80 to 99.8 mass%, based on 100 mass% of the polymerizable composition.

[0037] (Method for producing polymerizable ester compound) The method for producing the polymerizable ester compound (A) is not particularly limited as long as the compound can be obtained, and the compound can be produced by a known method described in, for example, WO 2010 / 114077, etc., but it is preferable to include a step (P1) of subjecting an α-(allyloxymethyl)acrylic acid ester and an alcohol to a transesterification reaction in the presence of a catalyst.

[0038] Step (P1) Step (P1) is a step of subjecting an α-(allyloxymethyl)acrylic acid ester and an alcohol to a transesterification reaction in the presence of a catalyst.

[0039] Examples of the α-(allyloxymethyl)acrylic acid ester include α-(allyloxymethyl)acrylic acid ester compounds having an alkyl group having 1 to 5 carbon atoms, such as methyl α-(allyloxymethyl)acrylate, ethyl α-(allyloxymethyl)acrylate, n-propyl α-(allyloxymethyl)acrylate, i-propyl α-(allyloxymethyl)acrylate, n-butyl α-(allyloxymethyl)acrylate, sec-butyl α-(allyloxymethyl)acrylate, tert-butyl α-(allyloxymethyl)acrylate, n-amyl α-(allyloxymethyl)acrylate, sec-amyl α-(allyloxymethyl)acrylate, and tert-amyl α-(allyloxymethyl)acrylate, as well as the above-mentioned α-(allyloxymethyl)acrylic acid ester compounds. Among these, alkyl α-(allyloxymethyl)acrylates are preferred in terms of ease of transesterification, more preferred are α-(allyloxymethyl)acrylic acid ester compounds having an alkyl group having 1 to 3 carbon atoms, and even more preferred is methyl α-(allyloxymethyl)acrylate.

[0040] Examples of the alcohol include monohydric alcohols and polyhydric alcohols. Examples of the monohydric alcohols and polyhydric alcohols include those described above.

[0041] Examples of the catalyst include alkali metal hydroxides (e.g., lithium hydroxide, sodium hydroxide, potassium hydroxide, etc.), alkali metal carbonates (e.g., lithium carbonate, sodium carbonate, potassium carbonate, etc.), alkali metal alkoxides (e.g., lithium methoxide, sodium ethoxide, etc.), alkali metal amides (e.g., lithium amide, sodium amide, potassium amide, etc.), titanium alkoxides (e.g., tetraethyl orthotitanate, tetraisopropyl orthotitanate, etc.), organotin compounds (e.g., dibutyltin oxide), etc. Among these, titanium alkoxides are preferred because the catalyst can be easily removed by washing with water.

[0042] The amount of the catalyst used is not particularly limited, but is preferably 0.1 to 10 mol %, more preferably 0.1 to 5 mol %, and even more preferably 1 to 5 mol %, relative to 100 mol % of the alcohol.

[0043] In the transesterification reaction, it is preferable to use a polymerization inhibitor. The polymerization inhibitor is not particularly limited, and examples thereof include benzoquinone, hydroquinones (e.g., hydroquinone, hydroquinone monomethyl ether, p-tert-butylhydroquinone, p-benzoquinone, etc.), phenols (e.g., 2,6-di-tert-butyl-4-methylphenol, 6-tert-butyl-2,4-xylenol, 2,2'-methylenebis(4-methyl-6-tert-butylphenol), Irganox 245, Irganox 245, etc.), and the like. Irganox 259, Irganox 565, Irganox 1010, Irganox MD1024, Irganox 1035, Irganox 1076, Irganox 1098, Irganox 1135, Irganox 1222, Irganox 1330, Irganox 3114 (all manufactured by BASF), Adekastab AO-20, Adekastab AO-30, Adekastab AO-40, Adekastab AO-50, Adekastab AO-60, Adekastab AO-70, Adekastab AO-80, Adekastab AO-90, Adekastab AO-100, Adekastab AO-112, Adekastab AO-122, Adekastab AO-133, Adekastab AO-140, Adekastab AO-150, Adekastab AO-160, Adekastab AO-170, Adekastab AO-180, Adekastab AO-190, Adekastab AO-200, Adekastab AO-210, Adekastab AO-220, Adekastab AO-230, Adekastab AO-240, Adekastab AO-259, Adekastab 565, Adekastab 1010, Adekastab MD1024, Adekastab MD1035, Adekastab MD1035, Adekastab MD1135, Adekastab MD1222, Adekastab MD1330, Adekastab AO-259, Adekastab MD103 Castab AO-70, Adekastab AO-80, Adekastab AO-330 (all manufactured by ADEKA Corporation), RIANOX 245, RIANOX 330, RIANOX 1010, RIANOX 1019, RIANOX 1035, RIANOX 1076, RIANOX 1098, RIANOX 1135, RIANOX 1790, RIANOX 3114 (all manufactured by Rianlon Corporation), etc.), catechols (for example, p-tert-butylcatechol, etc.), amines Examples of the polymerization inhibitor include known ones such as commercially available products such as amines (e.g., N,N-diethylhydroxylamine, etc.), 1,1-diphenyl-2-picrylhydrazyl, tri-p-nitrophenylmethyl, phenothiazine, piperidine 1-oxyls (e.g., 2,2,6,6-tetramethylpiperidine 1-oxyl, 4-hydroxy-2,2,6,6-tetramethylpiperidine 1-oxyl, etc.), Polystop 7300P, Polystop 7300L (manufactured by Hakuto Co., Ltd.), etc. One type of the polymerization inhibitor may be used alone, or two or more types may be used in combination.

[0044] The amount of the polymerization inhibitor used is not particularly limited, but is preferably 0.01 to 0.5 parts by mass, more preferably 0.01 to 0.3 parts by mass, and even more preferably 0.01 to 0.2 parts by mass, relative to 100 parts by mass of the α-(allyloxymethyl)acrylic acid ester. In addition, when a phenol compound described later also corresponds to the polymerization inhibitor, the amount of the polymerization inhibitor used means the total mass of the polymerization inhibitor including the phenol compound.

[0045] In the transesterification reaction, it is also preferable to add a phenolic compound represented by the general formula (2). By carrying out the transesterification reaction in the presence of the phenolic compound represented by the general formula (2) and adding the compound (B) described below to the resulting polymerization solution, a polymerizable composition with even better stability over time can be obtained. The phenolic compounds may be used alone or in combination of two or more. The phenolic compounds will be described in detail later.

[0046] The amount of the phenol compound added is preferably 0.01 to 0.5 parts by mass, more preferably 0.01 to 0.3 parts by mass, and even more preferably 0.01 to 0.2 parts by mass, relative to 100 parts by mass of the α-(allyloxymethyl)acrylic acid ester.

[0047] A solvent may be used in the transesterification reaction. The solvent to be used is not particularly limited as long as it does not affect the reaction, and examples thereof include hydrocarbon solvents such as benzene, toluene, xylene, hexane, heptane, octane, and cyclohexane, and ether solvents such as dioxane and tetrahydrofuran. The above solvents may be used alone or in combination of two or more.

[0048] The reaction conditions for the transesterification reaction are not particularly limited and may be any known reaction conditions, and the reaction temperature is preferably 50 to 120° C., more preferably 50 to 110° C. The transesterification reaction may be carried out under normal pressure or under reduced pressure.

[0049] The method for producing the polymerizable ester compound (A) may further include, before the above-mentioned step (P1), a step (P0) of etherifying an α-hydroxymethyl acrylic acid alkyl ester with an unsaturated alcohol.

[0050] The alkyl α-hydroxymethyl acrylate is preferably methyl α-hydroxymethyl acrylate because of its ease of etherification, and the unsaturated alcohol is preferably allyl alcohol because of its ease of etherification.

[0051] For example, methyl α-(allyloxymethyl)acrylate can be produced by etherifying methyl α-hydroxymethylacrylate with allyl alcohol. The reaction conditions for the etherification reaction are not particularly limited and may be appropriately selected based on known methods.

[0052] The method for producing the polymerizable ester compound (A) may further include a step (P2) of washing the transesterification reaction product obtained in the step (P1) with water, and a step (P3) of purifying the crude product after washing with water.

[0053] Step (P2) After step (P1), the resulting transesterification reaction product is preferably washed with water. This water-washing step removes unnecessary components, such as the catalyst and lower alcohol, contained in the transesterification reaction product, thereby further improving the stability over time of the resulting polymerizable ester compound.

[0054] The water washing can be carried out by any known method, such as adding an acidic aqueous solution (e.g., an oxalic acid aqueous solution) or water (e.g., distilled water, ion-exchanged water) to the organic phase containing the transesterification reaction product, stirring, and allowing to stand to separate the oil and water.

[0055] Step (P3) The crude product obtained after washing with water in step (P2) may be further purified. The purification method is not particularly limited and may be appropriately selected from known purification methods such as extraction and filtration. The crude product is purified to obtain a purified polymerizable ester compound having an α-allyloxymethylacryloyl group.

[0056] The method for producing the polymerizable ester compound (A) may further include other steps, such as a dilution step, a drying step, a concentration step, a solvent substitution step, a dissolution step, a solvent evaporation step, a thin film distillation step, and a steam distillation step. These steps can be carried out by known methods.

[0057] As described above, the method for producing a polymerizable ester compound having an α-allyloxymethylacryloyl group includes at least the above step (P1). In particular, it is preferable to use a phenol compound represented by the above general formula (2) in the above step (P1). By using the above phenol compound, it is possible to obtain a polymerizable ester compound having an α-allyloxymethylacryloyl group that has excellent stability over time. Such a method for producing a polymerizable ester compound having an α-allyloxymethylacryloyl group, which method includes a step of subjecting an α-(allyloxymethyl)acrylic acid ester and an alcohol to a transesterification reaction in the presence of a catalyst, and which is characterized by adding a phenol compound represented by the above general formula (2) in the transesterification reaction step, also constitutes one aspect of the present invention.

[0058] The method for producing a polymerizable ester compound having an α-allyloxymethylacryloyl group of the present invention is effective for producing polymerizable ester compounds having a relatively small number of carbon atoms in the ester moiety of 1 to 5, such as methyl α-(allyloxymethyl)acrylate, but is particularly effective for producing compounds having a relatively large number of carbon atoms in the ester moiety of 6 or more, which are difficult to separate and remove by distillation from reaction residues that cause yellowing. Therefore, the number of carbon atoms in the alcohol used in the transesterification reaction step is preferably 6 or more, more preferably 6 to 25, and even more preferably 6 to 20.

[0059] The transesterification reaction step in the production method of the present invention is the same as the above-mentioned step (P1).

[0060] The production method of the present invention may further include the above-mentioned steps (P2) and (P3). In the purification step of step (P3), distillation may be performed if distillation is possible. The distillation method is not particularly limited, and may be performed by a known method, and may be performed in multiple stages.

[0061] <Compound (B)> The polymerizable composition further contains at least one compound selected from the group consisting of a phenol compound represented by the general formula (2), a (thio)phosphite compound, a phosphine compound, a thioether compound, and a thiol compound (hereinafter also referred to as "compound (B)"). By combining the polymerizable ester compound (A) with a specific compound (B), it is possible to improve stability over time. Each component of compound (B) is described below.

[0062] (Phenol Compound) The phenol compound is a compound represented by the general formula (2). In the general formula (2), R ２１ represents a substituent having 2 or more carbon atoms. ２１ The number of carbon atoms of the substituent represented by R is preferably 2 to 70, more preferably 2 to 60, even more preferably 2 to 50, still more preferably 2 to 30, and particularly preferably 2 to 25. ２１ The substituent represented by the formula (I) is preferably an organic group.

[0063] R ２１ Examples of the substituent represented by the formula (I) include a hydrocarbon group which may have a substituent b, or the above hydrocarbon group and —O—, —CO—, —COO—, —NH—, —S—, —SO— or —SO ２ - and a linking group such as -. The group formed by the combination of the hydrocarbon group and a linking group may be a group formed by the combination of multiple hydrocarbon groups and multiple linking groups. Examples of the hydrocarbon group include the aliphatic hydrocarbon group, alicyclic hydrocarbon group, and aromatic hydrocarbon group described above.

[0064] The hydrocarbon group may contain a heteroatom such as an oxygen atom, a nitrogen atom, or a sulfur atom.

[0065] Examples of the substituent b include a halogen atom, a hydroxyl group, and a phosphate ester group. Examples of the phosphate ester group include —PO(OR ａ ) ２ (R ａ represents an alkyl group having 1 to 3 carbon atoms.

[0066] Among them, R ２１ The substituent represented by the formula (I) is preferably a hydrocarbon group which may have a substituent b, or a group which contains the above hydrocarbon group and at least one bonding group selected from the group consisting of -O-, -CO-, -COO-, and -S-, and more preferably a hydrocarbon group which may have a substituent b, or a group which contains the above hydrocarbon group and at least one bonding group selected from the group consisting of -COO- and -S-.

[0067] In the above general formula (2), R ２２ are the same or different and represent an organic group. ２２ is preferably an alkyl group, more preferably an alkyl group having 1 to 4 carbon atoms, and even more preferably a tert-butyl group (t-butyl group).

[0068] In the above general formula (2), a represents an integer of 0 to 2. a is preferably an integer of 1 to 2, and more preferably 2.

[0069] Among these, the phenol compound is preferably a hindered phenol compound represented by the following general formula (2-1), in that it further improves stability over time.

[0070] (In the formula, R ２１ is the same as above. ２３ and R ２４ are the same or different and represent a hydrogen atom or a tert-butyl group. ２３ and R ２４ At least one of the groups is a tert-butyl group.

[0071] Specific examples of the phenolic compounds include Irganox 245, Irganox 259, Irganox 565, Irganox 1010, Irganox MD1024, Irganox 1035, Irganox 1076, Irganox 1098, Irganox 1135, Irganox 1222, Irganox 1330, Irganox 3114 (all manufactured by BASF), Adeka STAB AO-20, Adeka STAB AO-30, Adeka STAB AO-40, Adeka STAB AO-50, Adeka STAB AO-60, Adeka STAB AO-70, Adeka STAB AO-80, Adeka STAB AO-90, Adeka STAB AO-100, Adeka STAB AO-110, Adeka STAB AO-120, Adeka STAB AO-130, Adeka STAB AO-140, Adeka STAB AO-150, Adeka STAB AO-160, Adeka STAB AO-170, Adeka STAB AO-180, Adeka STAB AO-190, Adeka STAB AO-200, Adeka STAB AO-210, Adeka STAB AO-220, Adeka STAB AO-230, Adeka STAB AO-240, Adeka STAB AO-250, Adeka STAB AO-260, Adeka STAB AO-270, Adeka STAB AO-280, Adeka STAB AO-290, Adeka STAB AO-30, Adeka STAB AO-40, Adeka STAB AO-50, Adeka STAB AO-60, Adeka ST Examples include STAB AO-70, ADK STAB AO-80, ADK STAB AO-330 (all manufactured by ADEKA Corporation), RIANOX 245, RIANOX 330, RIANOX 1010, RIANOX 1019, RIANOX 1035, RIANOX 1076, RIANOX 1098, RIANOX 1135, RIANOX 1790, RIANOX 3114 (all manufactured by Rianlon Corporation), and 2,2'-thiodiethylbis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate] (manufactured by Tokyo Chemical Industry Co., Ltd.). Among these, in terms of further improved stability over time, Irganox 259, Irganox 565, Irganox 1010, Irganox MD1024, Irganox 1035, Irganox 1076, Irganox 1098, Irganox 1135, Irganox 1222, Irganox 1330, Irganox 3114 (all manufactured by BASF), Adekastab AO-20, Adekastab AO-50, Adekastab AO-60, Adekastab AO-330 (all manufactured by ADEKA Corporation), and RIANOX 33 are particularly preferred. 0, RIANOX 1010, RIANOX 1019, RIANOX 1035, RIANOX 1076, RIANOX 1098, RIANOX 1135, RIANOX 3114 (all manufactured by Rianlon) are preferred, and Irganox 1010, Irganox 1035, Irganox 3114 (all manufactured by BASF), Adekastab AO-20, Adekastab AO-60 (all manufactured by ADEKA), RIANOX 1010, RIANOX 1035, RIANOX 3114 (all manufactured by Rianlon) are more preferred.A preferred embodiment of the present invention also includes a compound having a hindered phenol moiety of the general formula (2-1) as a partial structure, which is obtained by converting the phenol compound through a reaction.

[0072] ((Thio)phosphite Compound) In this specification, the (thio)phosphite compound means a phosphite and / or a thiophosphite.Examples of the (thio)phosphite compound include hydrogen phosphites such as diethyl hydrogen phosphite, bis(2-ethylhexyl) hydrogen phosphite, dilauryl hydrogen phosphite, and diphenyl hydrogen phosphite; trialkyl phosphites such as triethyl phosphite, tributyl phosphite, tris(2-ethylhexyl) phosphite, and trilauryl phosphite; phenyl diisodecyl phosphite, diphenyl methyl phosphite, and 2-ethylhexyl diphenyl phosphite; alkyl-aryl mixed phosphites such as bis(2,4-ditert-butyl-6-methylphenyl)ethyl phosphite; triaryl phosphites such as triphenyl phosphite, tricresyl phosphite, tris(nonylphenyl)phosphite, tris(2,4-ditert-butylphenyl)phosphite; bis(isodecyl)pentaerythritol diphosphite, bis(tridecyl)pentaerythritol diphosphite, bis(stearyl)pentaerythritol diphosphite, bis(2,4-di pentaerythritol diphosphites such as 4,4-butylidenebis(3-methyl-6-tert-butylphenyldiisotridecyl)phosphite, tetraphenyldipropylene glycol diphosphite, tetraphenyltetra(tridecyl)pentaerythritol tetraphosphite, tetra(C12-C15 alkyl)-4,4'-isopropylidenediphenyl phosphite, tetra(tridecyl)pentaerythritol tetraphosphite, tetra(tridecyl ... Examples of such phosphites include 2,4,8,10-tetra-tert-butyl-6-[3-(3-methyl-4-hydroxy-5-tert-butylphenyl)propoxy]dibenzo[d,f][1,3,2]dioxaphosphepine, 2,2-methylenebis(4,6-tert-butylphenyl)-2-ethylhexyl phosphite, and the (thio)phosphites described in paragraph

[0036] of JP-A-2014-03150.

[0073] Commercially available (thio)phosphite compounds may also be used, such as 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 (all manufactured by ADEKA Corporation), Irgafos 168, Irgafos 38 (all manufactured by BASF Corporation), JP-360, J P-650, JP-351, JPP-2000PT, JP-310, JP-302, JP-304, JP-308, JP-312L, JP-333E, JP-318-O, JP-318E, JPE-10, JPE-13R, JP-3CP, JPP-88, JPP-100, JPH-1200, JPH-3800, JPM-308, JPM-311, JPM-312, JPM-313 (all manufactured by Johoku Chemical Industry Co., Ltd.), Sumilizer GP (all manufactured by Sumitomo Chemical Co., Ltd.), RIANOX 450, RIANOX 626, RIANOX 686 (all manufactured by Rianlon), Chelex D, Chelex TD, Chelex OL (all manufactured by SC Organic Chemical Industry Co., Ltd.), and the (thio)phosphites described in paragraph

[0041] of JP-A-2014-03150.

[0074] Among these, thiophosphites are preferred in that they have better stability over time.

[0075] The (thio)phosphite compound preferably has 3 to 100 carbon atoms, more preferably 3 to 90 carbon atoms, and even more preferably 3 to 80 carbon atoms.

[0076] (Phosphine Compound) Examples of the phosphine compound include triethylphosphine, tributylphosphine, tris(2-ethylhexyl)phosphine, triphenylphosphine, etc. Of these, triphenylphosphine is preferred.

[0077] (Thioether Compound) Examples of the thioether compound include 3-alkylthiopropionic acids or esters thereof such as 3-laurylthiopropionic acid, methyl 3-laurylthiopropionate, (3-octylthiopropionic acid) pentaerythritol tetraester, (3-laurylthiopropionic acid) pentaerythritol tetraester (ADEKA: Adekastab AO-412S, Sumitomo Chemical: Sumilizer TP-D, Rianlon: RIANOX412S), (3-stearylthiopropionic acid) pentaerythritol tetraester, and (3-laurylthiopropionic acid)-4,4′-thiodi(3-methyl-5-tert-butyl-4-phenol) ester; Examples of the thioether include dimerized thioethers of alkyl thiocarboxylates such as octyl thiodipropionate, didecyl thiodipropionate, dilauryl thiodipropionate, ditridecyl thiodipropionate, distearyl thiodipropionate, and lauryl stearyl thiodipropionate; dialkyl sulfides such as dimethyl sulfide, methyl dodecyl sulfide, dilauryl sulfide, and distearyl sulfide; phenolic thioethers such as 2,4-bis(octylthiomethyl)-o-cresol and 2,4-bis(dodecylthiomethyl)-o-cresol, as well as the thioether compounds described in paragraph

[0044] of JP 2014-31510 A. Among these, the 3-alkylthiopropionic acid esters, dimerized thioethers of alkyl thiocarboxylates, and phenolic thioethers are preferred.

[0078] The thioether compound preferably has 2 to 90 carbon atoms, more preferably 2 to 80 carbon atoms, and even more preferably 2 to 70 carbon atoms.

[0079] Among these, the thioether compound is preferably a compound represented by the following general formula (3): ３１ -S-R ３２ (3) (wherein, R ３１ and R ３２ are the same or different and represent an organic group having 1 to 90 carbon atoms.

[0080] The above R ３１ and R ３２The organic group represented by the formula (I) preferably has 2 to 90 carbon atoms, more preferably 2 to 80 carbon atoms, and even more preferably 2 to 70 carbon atoms.

[0081] The above R ３１ and R ３２ Examples of the organic group represented by the formula (I) include a hydrocarbon group which may have a substituent, and a group consisting of a hydrocarbon group which may have a substituent and -O-, -CO-, -COO- or -S-. ３１ and R ３２ is preferably a hydrocarbon group which may have a substituent, or a group consisting of a hydrocarbon group which may have a substituent and -COO- or -S-, and -COO-R ｂ - (R ｂ represents an alkylene group. ２ -CH ２ -COO-R ｂ - (R ｂ represents an alkylene group. It is more preferable that the hydrocarbon group contains a group represented by the following formula: The hydrocarbon group is preferably an aliphatic hydrocarbon group or an aromatic hydrocarbon group, and more preferably an aliphatic hydrocarbon group. Examples of the substituent of the hydrocarbon group include a hydroxyl group.

[0082] As the thioether compound, commercially available products can also be used, and examples thereof include products manufactured by ADEKA CORPORATION under the trade names of Adekastab AO-23, Adekastab AO-26, Adekastab AO-412S, and Adekastab AO-503; products manufactured by Sumitomo Chemical Co., Ltd. under the trade names of Sumilizer TPL-R, Sumilizer TPM, Sumilizer TPS, and Sumilizer TP-D; products manufactured by BASF under the trade names of Irganox 1520L, Irganox 1726, Irganox PS800FL, and Irganox PS802FL; and products manufactured by Rianlon under the trade names of RIANOX 412S, RIANOX DLTP, and RIANOX DSTP.

[0083] (Thiol Compound) Examples of thiol compounds include methyl mercaptan, 2-mercaptobenzimidazole, methanethiol, ethanethiol, propanethiol, butanethiol, pentanethiol, hexanethiol, heptanethiol, octanethiol, nonanethiol, decanethiol, 2-phenylethanethiol, triphenylmethanethiol, 4-methylbenzenethiol, and Sakai Chemical Industry Co., Ltd., trade names: TMMP, PEMP, DPMP, TEMPIC, EGMP-4, EHMP, MBMP, and Multiol Y-4.

[0084] The thiol compound preferably has 3 to 30 carbon atoms, more preferably 3 to 25 carbon atoms, and even more preferably 3 to 20 carbon atoms.

[0085] The polymerizable composition may contain only one type of the compound (B) or may contain two or more types of the compound (B), but it is preferable that the polymerizable composition contains at least the phenol compound among the compounds (B).

[0086] The polymerizable composition preferably contains, as the compound (B), the phenol compound (b1) and at least one compound (b2) selected from the group consisting of (thio)phosphite compounds, phosphine compounds, thioether compounds, and thiol compounds. By using these two compounds in combination as the compound (B), the stability over time of the polymerizable ester compound (A) can be further improved. Among the compounds (b2), thioether compounds are preferred.

[0087] When the phenol compound (b1) is used in combination with at least one compound (b2) selected from the group consisting of (thio)phosphite compounds, phosphine compounds, thioether compounds, and thiol compounds, the mass ratio (b1) / (b2) thereof is preferably 1 / 68 to 74 / 1, more preferably 1 / 40 to 44 / 1, and even more preferably 1 / 27 to 30 / 1.

[0088] The content of the compound (B) in the polymerizable composition is preferably 100 to 10,000 ppm. The content of the compound (B) in the polymerizable composition is more preferably 100 to 5,000 ppm, even more preferably 100 to 3,000 ppm, and still more preferably 100 to 2,000 ppm. When two or more types of compound (B) are contained, the content of the compound (B) refers to the total mass of the compounds.

[0089] <Other Components (C)> The polymerizable composition may contain, in addition to the polymerizable ester compound (A) and compound (B), other components (C) as long as they do not affect the effects of the present invention. Examples of the other components (C) include radically polymerizable monomers copolymerizable with the polymerizable ester compound (A), radical polymerization initiators, curing accelerators, binder resins, solvents, fillers, colorants, dispersants, adhesion improvers, release agents, plasticizers, UV absorbers, matting agents, antifoaming agents, leveling agents, antistatic agents, slip agents, surface modifiers, silane-based, aluminum-based, titanium-based, or other coupling agents, and acid generators. These include, for example, known compounds such as those described in International Publication No. 2010 / 114077.

[0090] In particular, the polymerizable composition preferably contains a radical polymerization initiator or a curing accelerator as the other component (C) in terms of improving the curability.

[0091] The radical polymerization initiator may be a thermal radical polymerization initiator that generates radicals upon heating or a photoradical polymerization initiator that generates radicals upon irradiation with active energy rays. The radical polymerization initiator may be used singly or in combination of two or more.

[0092] Examples of the thermal radical polymerization initiator include organic peroxide-based polymerization initiators described in paragraph

[0079] of JP-A No. 2014-31510, such as methyl ethyl ketone peroxide, cyclohexanone peroxide, methylcyclohexane peroxide, methyl acetoacetate peroxide, and acetyl acetate peroxide; and azo-based polymerization initiators described in paragraph

[0080] of JP-A No. 2014-31510, such as 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), and 2,2'-azobisisobutyronitrile.

[0093] Examples of the photoradical polymerization initiator include alkylphenone compounds such as 2,2-diethoxyacetophenone, 2,2-dimethoxy-2-phenylacetophenone, and 1-hydroxycyclohexyl phenyl ketone; benzophenone compounds such as benzophenone and 4,4'-bis(dimethylamino)benzophenone; benzoin compounds such as benzoin and benzoin methyl ether; thioxanthone compounds such as thioxanthone, 2-ethylthioxanthone, and 2-isopropylthioxanthone; halomethylated triazine compounds such as 2-(4-methoxyphenyl)-4,6-bis(trichloromethyl)-s-triazine; halomethylated oxadiazole compounds such as 2-trichloromethyl-5-(2'-benzofuryl)-1,3,4-oxadiazole; biimidazole compounds such as bis(η5-2,4 Examples of the azo polymerization initiator include titanocene compounds such as (2,6-difluoro-3-(1H-pyrrol-1-yl)-phenyl)titanium; benzoate ester compounds such as p-dimethylaminobenzoic acid and p-diethylaminobenzoic acid; and acridine compounds such as 9-phenylacridine, as described in paragraph

[0082] of JP-A-2014-31510.

[0094] The content of the radical polymerization initiator is preferably 0.1 to 30 parts by mass, more preferably 0.1 to 25 parts by mass, and even more preferably 0.1 to 20 parts by mass, relative to 100 parts by mass of the curable component. When the curable component contains the polymerizable ester compound (A) or a radically polymerizable monomer copolymerizable with the polymerizable ester compound (A), the curable component refers to a component obtained by combining the polymerizable monomer and the polymerizable ester compound (A).

[0095] Examples of the curing accelerator include trimethylolpropane tris(3-mercaptopropionate), pentaerythritol tetrakis(3-mercaptopropionate), and pentaerythritol tetrakis(3-mercaptobutyrate).

[0096] The content of the curing accelerator is preferably 0.1 to 30 parts by mass, more preferably 0.1 to 25 parts by mass, and even more preferably 0.1 to 20 parts by mass, per 100 parts by mass of the curable component.

[0097] The content of the other component (C) may be appropriately determined using known techniques depending on the purpose of the various components to be added.

[0098] <Preparation of Polymerizable Composition> The polymerizable composition can be prepared by mixing the above-described polymerizable ester compound (A), compound (B), and, if necessary, other component (C). Mixing can be performed by mixing and dispersing using various known mixers or dispersers. In addition, the polymer obtained by using the phenol compound represented by general formula (2) in producing the polymerizable ester compound (A) contains the polymerizable ester compound (A) and compound (B), and therefore may be used as is as the polymerizable composition, or compound (B) may be further added to prepare the polymerizable composition.

[0099] <Curing of Polymerizable Composition> The curing of the polymerizable composition is not particularly limited, and may be carried out by heating, irradiation with active energy rays, or a combination thereof.

[0100] The temperature conditions for heat curing may be appropriately set depending on the composition of the polymerizable composition, and are, for example, preferably 30 to 400° C., more preferably 70 to 350° C. The heat curing may be carried out in one step or in two or more separate steps, and may be carried out before or after curing by irradiation with active energy rays.

[0101] As the active energy ray, any commonly used ray can be used, including electromagnetic waves such as gamma rays, X-rays, ultraviolet rays, visible light, and infrared rays, and particle rays such as electron beams, neutron beams, and proton beams. Of these, ultraviolet rays are preferred.

[0102] <Applications of Polymerizable Composition> The polymerizable composition has excellent stability over time. Therefore, it is suitable for use in applications requiring suppression of yellowing over time or due to heat. The polymerizable composition can be suitable for use in, for example, coating agents, adhesives, sealants, pressure-sensitive adhesives, primers, paints, inks, resists, dental materials, lenses, molding materials, etc.

[0103] The present invention will be described in more detail below with reference to examples, but the present invention is not limited to these examples. Unless otherwise specified, "parts" means "parts by mass" and "%" means "% by mass".

[0104] Example 1 Synthesis Example 1 Production of a Polymerizable Ester Compound Having an α-Allyloxymethylacryloyl Group 1 Into a reactor were weighed 210 parts of tripropylene glycol (manufactured by ADEKA Corporation), 515 parts of methyl α-(allyloxymethyl)acrylate, 0.52 parts of 6-tert-butyl-2,4-xylenol (manufactured by Tokyo Chemical Industry Co., Ltd.), 0.52 parts of Polystop 7300P (manufactured by Hakuto Co., Ltd.), and 75.3 parts of normal heptane (manufactured by Toa Oil Co., Ltd.). The normal heptane was stored in a holder, the system was reduced in pressure to 300 Torr, and a mixed gas (N ２ / O ２ While bubbling a mixture of 200 ml of 2-hydroxybenzoates (200 ml / min) and 200 ml of 2-hydroxybenzoates (200 ml / min), the mixture was heated to reflux at an internal temperature of 100-110°C for 1 hour. The internal temperature was then lowered to below 100°C, the liquid in the holder was recovered, and the dehydration process was completed. The temperature was then raised while the pressure in the system was reduced to 550 Torr. When the internal temperature reached 100°C, a titanium solution containing 6.2 parts of titanium tetraisopropoxide (manufactured by Mitsubishi Gas Chemical Company, Inc.) and 6.2 parts of normal heptane was added, and a transesterification reaction was carried out. The temperature was then raised, and when the internal temperature reached 110°C, normal heptane was added dropwise at a rate of approximately 81 parts / hour, and the reaction was carried out while maintaining the internal temperature at 110°C. The reaction was continued until high-performance liquid chromatography analysis showed that the area ratio of tripropylene glycol di(2-(allyloxymethyl))acrylate to tripropylene glycol mono(2-(allyloxymethyl))acrylate was >94%. Mixed gas (N ２ / O２ While bubbling a mixture of 2,000 ml of methyl α-(allyloxymethyl)acrylate and 2,000 ml of methyl α-(allyloxymethyl)acrylate (93 / 7 (v / v)) into the system, the pressure inside the system was reduced to 150 Torr, and the internal temperature was raised to 110°C, thereby distilling off normal heptane. Thereafter, while maintaining the internal temperature at 100 to 105°C, the pressure inside the system was reduced to 50 Torr, and trace amounts of normal heptane remaining in the system were removed. Thereafter, the internal temperature was lowered to around 50°C, and when it reached around 50°C, the pressure inside the system was reduced to 5 Torr. After reaching 5 Torr, the internal temperature was raised to 115°C, thereby distilling off methyl α-(allyloxymethyl)acrylate, and the removal of low-boiling components was completed.

[0105] Mixed gas (N ２ / O ２ While bubbling a 93 / 7 (v / v) mixture, 153 parts of normal heptane was added, the internal temperature was adjusted to 70°C, and 133 parts of a 7% aqueous oxalic acid solution was added and heated with stirring for 60 minutes. After that, the mixture was allowed to stand for 60 minutes, and the aqueous phase was removed. Next, 133 parts of water was added, and the mixture was heated with stirring for 30 minutes. After that, the mixture was allowed to stand for 30 minutes, and the aqueous phase was removed. 133 parts of water was added again, and the same water-washing operation was carried out, and the water-washing was completed. By this water-washing operation, titanium tetraisopropoxide used as a catalyst was removed.

[0106] 0.03 parts of Polystop 7300P (manufactured by Hakuto Co., Ltd.) and 0.37 parts of triphenyl phosphite (manufactured by Tokyo Chemical Industry Co., Ltd.) were added, and a mixed gas (N ２ / O ２While bubbling a mixture of ethanol (CO₂ / CO₂ / 93 / 7 (v / v)) and ethanol (CO₂ / CO₂ / 93 / 7 (v / v)), the pressure inside the system was reduced to 300 Torr, and the internal temperature was raised to 110°C, thereby removing normal heptane and water. Thereafter, while maintaining the internal temperature at 100 to 105°C, the pressure inside the system was reduced to 150 Torr, and when the pressure reached 150 Torr, the internal temperature was raised to 110°C, and traces of remaining normal heptane were removed. Thereafter, while maintaining the internal temperature at 100 to 105°C, the pressure inside the system was reduced to 50 Torr, and when the pressure reached 50 Torr, the internal temperature was raised to 110°C, and traces of remaining normal heptane were removed. Thereafter, the internal temperature was lowered to around 50°C, and when it reached around 50°C, the pressure inside the system was reduced to 5 Torr. After reaching 5 Torr, the internal temperature was raised to 110°C, and low-boiling components were removed. The resulting liquid was filtered through a 0.5 μm PTFE membrane filter to obtain 415 parts of the target polymerizable ester compound tripropylene glycol di(2-(allyloxymethyl))acrylate. The resulting tripropylene glycol di(2-(allyloxymethyl))acrylate contained 4.4% tripropylene glycol mono(2-(allyloxymethyl))acrylate, 3.1% methyl α-(allyloxymethyl)acrylate, and 0.02% normal heptane.

[0107] (Preparation of Polymerizable Composition) Irganox 1010 (manufactured by BASF) was added to a polymerization solution containing the polymerizable ester compound tripropylene glycol di(2-(allyloxymethyl))acrylate obtained in Synthesis Example 1 above to a concentration of 5000 ppm, and the mixture was stirred at 40°C for 30 minutes to obtain a polymerizable composition.

[0108] (Evaluation of color resistance (stability over time)) The obtained polymerizable composition was allowed to stand at 70°C for one week, and then the Hazen color number (APHA) was determined using a TZ-6000 transmitted color measuring instrument (manufactured by Nippon Denshoku Corporation) and evaluated according to the following criteria. The results are shown in Table 1. (Evaluation criteria) S: Hazen color number less than 150 A: Hazen color number 150 or more but less than 300 B: Hazen color number 300 or more but less than 999 C: Hazen color number 999 (upper limit of measurement)

[0109] Examples 2 to 11 In Example 1, compound (B) shown in Table 1 was added instead of Irganox 1010, and polymerizable compositions were obtained in the same manner as in Example 1, and discoloration resistance was evaluated. Samples in which residual dissolution was confirmed after 30 minutes of stirring at 40°C were further stirred for 30 minutes at 70°C. After that, polymerizable compositions in which residual dissolution was confirmed were filtered to obtain test samples. The results are shown in Table 1.

[0110] Comparative Example 1 A polymerizable composition was obtained in the same manner as in Example 1, except that Irganox 1010 was not added, and the coloration resistance was evaluated. The results are shown in Table 1.

[0111]

[0112] Compound (B) in Table 1 is as follows: Irg1010: Irganox 1010, manufactured by BASF Corporation, hindered phenol type Irg1222: Irganox 1222, manufactured by BASF Corporation, hindered phenol type Irg1520L: Irganox 1520L, manufactured by BASF Corporation, thioether type Compound 1: 2,2'-thiodiethylbis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], manufactured by Tokyo Chemical Industry Co., Ltd., hindered phenol type TPP: triphenyl phosphite, manufactured by Tokyo Chemical Industry Co., Ltd., phosphite type PEP-36: Adekastab PEP-36, manufactured by ADEKA Corporation, phosphite type PEP-8: Adekastab PEP-8, manufactured by ADEKA Corporation, phosphite type Compound 2: Trilauryl trithiophosphite, manufactured by Tokyo Chemical Industry Co., Ltd., thiophosphite type TPD: Sumilizer TP-D, manufactured by Sumitomo Chemical Co., Ltd., thioether type Compound 3: Dilauryl 3,3'-thiodipropionate, manufactured by Tokyo Chemical Industry Co., Ltd., thioether type Compound 4: 2-mercaptobenzimidazole, manufactured by Tokyo Chemical Industry Co., Ltd., thiol type

[0113] From Table 1, it was found that the polymerizable compositions obtained in the examples were superior in discoloration resistance compared to the polymerizable compositions of the comparative examples. In particular, it was found that the polymerizable compositions to which a thioether-based compound was added were particularly superior in discoloration resistance.

[0114] Example 12 Synthesis Example 2 Production of a Polymerizable Ester Compound Having an α-Allyloxymethylacryloyl Group 2 609 parts of tripropylene glycol (manufactured by ADEKA Corporation), 1,486 parts of methyl α-(allyloxymethyl)acrylate, 1.49 parts of Polystop 7300P (manufactured by Hakuto Co., Ltd.), and 221 parts of normal heptane (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) were weighed into a reactor. The normal heptane was stored in a holder, the system was reduced in pressure to 300 Torr, and a mixed gas (N ２ / O ２ While bubbling a mixture of ethanol (200 ml / min. / 200 sachets / ml) and ethanol (200 ml / min. / 200 sachets / ml) (93 / 7 (v / v)), the mixture was heated to reflux at an internal temperature of 100-110°C for 1 hour. The internal temperature was lowered to 100°C or below, the liquid in the holder was recovered, and the dehydration process was completed. The temperature was raised while the pressure in the system was reduced to 550 Torr, and when the internal temperature reached 100°C, a titanium solution containing 18.0 parts of titanium tetraisopropoxide (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) and 18.0 parts of normal heptane was added, and a transesterification reaction was carried out. The temperature was then raised, and when the internal temperature reached 110°C, normal heptane was added dropwise at a rate of approximately 230 parts / hour, and the reaction was carried out while maintaining the internal temperature at 110°C. The reaction was continued until the area ratio of tripropylene glycol di(2-(allyloxymethyl))acrylate to tripropylene glycol mono(2-(allyloxymethyl))acrylate was >94% by high performance liquid chromatography. ２ / O ２ While bubbling a mixed gas (N 2 O 3 / N 2 O 4 O 5 ... ２ / O ２While bubbling a mixed gas (N = 93 / 7 (v / v)), 359 parts of normal heptane were added, and the internal temperature was adjusted to 70°C. Then, 311 parts of a 7% aqueous oxalic acid solution were added, and the mixture was heated and stirred for 60 minutes from the time the internal temperature exceeded 68°C. After that, the mixture was left to stand for 60 minutes, and the aqueous phase was removed. Next, 311 parts of water were added, and the mixture was heated and stirred for 30 minutes from the time the internal temperature exceeded 68°C. After that, the mixture was left to stand for 30 minutes, and the aqueous phase was removed. 311 parts of water were added again, and the same water washing operation was carried out, and the water washing was completed. By this water washing operation, titanium tetraisopropoxide used as a catalyst was removed. ２ / O ２ While bubbling a mixture of ethanol (CO₂ / CO₂ / 93 / 7 (v / v)) and ethanol (CO₂ / CO₂ / 93 / 7 (v / v)), the pressure inside the system was reduced to 300 Torr, and the internal temperature was raised to 110°C, thereby removing normal heptane and water. Thereafter, while maintaining the internal temperature at 100 to 105°C, the pressure inside the system was reduced to 150 Torr, and when the pressure reached 150 Torr, the internal temperature was raised to 110°C, and traces of remaining normal heptane were removed. Thereafter, while maintaining the internal temperature at 100 to 105°C, the pressure inside the system was reduced to 50 Torr, and when the pressure reached 50 Torr, the internal temperature was raised to 110°C, and traces of remaining normal heptane were removed. Thereafter, the internal temperature was lowered to around 50°C, and when it reached around 50°C, the pressure inside the system was reduced to 5 Torr. After reaching 5 Torr, the internal temperature was raised to 110°C, and low-boiling components were removed. The resulting liquid was filtered through a 0.5 μm PTFE membrane filter to obtain 1,058 parts of the target polymerizable ester compound tripropylene glycol di(2-(allyloxymethyl))acrylate. The resulting tripropylene glycol di(2-(allyloxymethyl))acrylate contained 5.1% tripropylene glycol mono(2-(allyloxymethyl))acrylate, 3.6% methyl α-(allyloxymethyl)acrylate, and 0.01% normal heptane.

[0115] (Preparation of Polymerizable Composition) Irganox 1010 (manufactured by BASF) was added to a polymerization solution containing the polymerizable ester compound tripropylene glycol di(2-(allyloxymethyl))acrylate obtained in Synthesis Example 2 above to a concentration of 5000 ppm, and the mixture was stirred at 40°C for 30 minutes to obtain a polymerizable composition.

[0116] (Evaluation of Coloration Resistance) The obtained polymerizable composition was allowed to stand at 70°C for 2 weeks, and then the Hazen color scale (APHA) was determined using a transmitted color measuring instrument TZ-6000 (manufactured by Nippon Denshoku Corporation) and evaluated according to the same criteria as in Example 1. The results are shown in Table 2.

[0117] Examples 13 to 33, Comparative Examples 2 and 3 In Example 12, instead of Irganox 1010, compound (B) shown in Table 2 was added in an amount shown in Table 2, and a polymerizable composition was obtained in the same manner as in Example 12, and the discoloration resistance was evaluated. The results are shown in Table 2.

[0118]

[0119] Compound (B) in Table 2 is the same as in Table 1. Compound (B) not listed in Table 1 is as follows: AO20: Adekastab AO-20, manufactured by ADEKA Corporation, hindered phenol type AO330: Adekastab AO-330, manufactured by ADEKA Corporation, hindered phenol type AO80: Adekastab AO-80, manufactured by ADEKA Corporation, hindered phenol type Compound 5: 4-[[4,6-bis(n-octylthio)-1,3,5-triazin-2-yl]amino]-2,6-di-tert-butylphenol, manufactured by Tokyo Chemical Industry Co., Ltd., hindered phenol type Top A: 6-tert-butyl-2,4-xylenol, manufactured by Tokyo Chemical Industry Co., Ltd., hindered phenol type BHT: dibutylhydroxytoluene, manufactured by Fujifilm Wako Pure Chemical Industries, Ltd., hindered phenol type

[0120] From Table 2, it was found that the polymerizable compositions obtained in each Example were superior in discoloration resistance compared to the polymerizable compositions of Comparative Examples. It was found that the polymerizable compositions to which a thioether-based compound was added and the polymerizable compositions to which a hindered phenol compound and a thioether-based compound were used in combination were particularly superior in discoloration resistance.

[0121] Examples 34 to 35 Synthesis Example 3 Production 3 of a polymerizable ester compound having an α-allyloxymethylacryloyl group 1,237 parts of tripropylene glycol (manufactured by Tokyo Chemical Industry Co., Ltd.), 3,003 parts of methyl α-(allyloxymethyl)acrylate, 3.02 parts of Irganox 1010 (manufactured by BASF), 3.01 parts of Polystop 7300P (manufactured by Hakuto Co., Ltd.), and 442 parts of normal heptane (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) were weighed into a reactor. The normal heptane was stored in a holder, the system was reduced in pressure to 300 Torr, and a mixed gas (N ２ / O ２ While bubbling a mixture of ethanol (2000 kJ / 2000 kcal / 3000 kcal / 4000 kcal / 5000 kcal / 6000 kcal / 7000 kcal / 8000 kcal / 93 / 7 (v / v)), the mixture was heated to reflux at an internal temperature of 100-110°C for 3 hours. The internal temperature was lowered to 100°C or below, the liquid in the holder was recovered, and the dehydration process was completed. The temperature was raised while the pressure in the system was reduced to 550 Torr, and when the internal temperature reached 100°C, a titanium solution containing 35.6 parts of titanium tetraisopropoxide (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) and 35.6 parts of normal heptane was added, and a transesterification reaction was carried out. The temperature was then raised, and when the internal temperature reached 110°C, normal heptane was added dropwise at a rate of approximately 460 parts / hour, and the reaction was carried out while maintaining the internal temperature at 110°C. The reaction was continued until the area ratio of tripropylene glycol di(2-(allyloxymethyl))acrylate to tripropylene glycol mono(2-(allyloxymethyl))acrylate was >94% by high performance liquid chromatography. ２ / O ２ While bubbling a mixed gas (N 2 O 3 / N 2 O 4 O 5 ... ２ / O ２While bubbling a mixture of hexane and hexane (93 / 7 (v / v)), 804 parts of normal heptane were added, and the internal temperature was adjusted to 70°C. 699 parts of a 7% aqueous oxalic acid solution were then added, and the mixture was heated and stirred for 60 minutes from the point at which the internal temperature exceeded 68°C. After standing for 60 minutes, the aqueous phase was removed. Next, 697 parts of water were added, and the mixture was heated and stirred for 30 minutes from the point at which the internal temperature exceeded 68°C. After standing for 30 minutes, the aqueous phase was removed. 698 parts of water were added again, and the same water-washing operation was carried out, completing the water-washing. This water-washing operation removed the titanium tetraisopropoxide used as a catalyst. To 850 parts of the liquid after water-washing, 0.04 parts of Polystop 7300P (manufactured by Hakuto Co., Ltd.) and 0.49 parts of triphenyl phosphite (manufactured by Tokyo Chemical Industry Co., Ltd.) were added, and a mixed gas (N ２ / O ２ While bubbling a mixture of ethanol (CO₂ / CO₂ / 93 / 7 (v / v)) and ethanol (CO₂ / CO₂ / 93 / 7 (v / v)), the pressure inside the system was reduced to 300 Torr, and the internal temperature was raised to 110°C, thereby removing normal heptane and water. Thereafter, while maintaining the internal temperature at 100 to 105°C, the pressure inside the system was reduced to 150 Torr, and when the pressure reached 150 Torr, the internal temperature was raised to 110°C, and traces of remaining normal heptane were removed. Thereafter, while maintaining the internal temperature at 100 to 105°C, the pressure inside the system was reduced to 50 Torr, and when the pressure reached 50 Torr, the internal temperature was raised to 110°C, and traces of remaining normal heptane were removed. Thereafter, the internal temperature was lowered to around 50°C, and when it reached around 50°C, the pressure inside the system was reduced to 5 Torr. After reaching 5 Torr, the internal temperature was raised to 110°C, and low-boiling components were removed. The resulting liquid was filtered through a 0.5 μm PTFE membrane filter to obtain 619 parts of the target polymerizable ester compound tripropylene glycol di(2-(allyloxymethyl))acrylate. The resulting tripropylene glycol di(2-(allyloxymethyl))acrylate contained 5.7% tripropylene glycol mono(2-(allyloxymethyl))acrylate, 3.5% methyl α-(allyloxymethyl)acrylate, and 0.03% normal heptane.

[0122] (Preparation of Polymerizable Composition) To a polymerization solution containing the polymerizable ester compound tripropylene glycol di(2-(allyloxymethyl))acrylate obtained in Synthesis Example 3, an additive (compound (B)) shown in Table 3 was added to give a concentration shown in Table 3, and the mixture was stirred at 40°C for 30 minutes to obtain a polymerizable composition. The discoloration resistance of the obtained polymerizable composition was evaluated in the same manner as in Example 12, except that the composition was allowed to stand at 70°C for 3 weeks instead of 2 weeks. The results are shown in Table 3.

[0123]

[0124] Compound (B) in Table 3 is the same as the compound described in Table 1. Compound (B) not described in Table 1 is as follows: AO-503: Adekastab AO-503, manufactured by ADEKA Corporation, thioether-based

[0125] From Table 3, it was found that the polymerizable compositions obtained in the examples were superior to the polymerizable composition of Comparative Example 1 in coloration resistance.

[0126] Example 36 Synthesis Example 4 Production 4 of a polymerizable ester compound having an α-allyloxymethylacryloyl group 800 parts of tricyclo[5.2.1.0(2,6)]dec-3-en-8-ol, 1636 parts of methyl α-(allyloxymethyl)acrylate, 1.69 parts of Irganox 1010 (manufactured by BASF), 1.69 parts of Polystop 7300L (manufactured by Hakuto Co., Ltd.), and 247 parts of normal heptane (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) were weighed into a reactor. The normal heptane was stored in a holder, the system was reduced in pressure to 300 Torr, and a mixed gas (N ２ / O ２While bubbling a mixture of 29.5 parts titanium tetraisopropoxide (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) and 29.5 parts normal heptane, the mixture was heated to reflux for 1 hour at an internal temperature of 100-110°C. The internal temperature was then lowered to 90°C or below, the liquid in the holder was recovered, and the dehydration process was completed. The system was heated while the pressure was reduced to 300 Torr, and when the internal temperature reached 90°C, a titanium solution containing 29.5 parts titanium tetraisopropoxide (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) and 29.5 parts normal heptane was added, and a transesterification reaction was carried out. The temperature was then raised, and when the internal temperature reached 100°C, normal heptane was added dropwise at a rate of approximately 257 parts / hour, and the reaction was carried out while maintaining the internal temperature at 100°C. The reaction was continued until the area ratio of dicyclopentenyl 2-(allyloxymethyl)acrylate to tricyclo[5.2.1.0(2,6)]dec-3-en-8-ol was >97% by gas chromatographic analysis. ２ / O ２ While bubbling a 7% oxalic acid solution (93 / 7 (v / v)) into the flask, the internal temperature was adjusted to 70°C, and then 477 parts of a 7% oxalic acid aqueous solution was added, and the mixture was heated and stirred for 30 minutes from the point at which the internal temperature exceeded 68°C. After that, the mixture was left to stand for 30 minutes, and the aqueous phase was removed. Next, 477 parts of water was added, and the mixture was heated and stirred for 30 minutes from the point at which the internal temperature exceeded 68°C. After that, the mixture was left to stand for 30 minutes, and the aqueous phase was removed. 476 parts of water was added again, and the same water washing operation was carried out, and the water washing was completed. By this water washing operation, titanium tetraisopropoxide used as a catalyst was removed. A mixed gas (N ２ / O ２While bubbling a mixture of 2,000 ml of methyl α-(allyloxymethyl)acrylate and 2,000 ml of methyl α-(allyloxymethyl)acrylate (93 / 7 (v / v)), the pressure inside the system was reduced to 300 Torr, and the internal temperature was raised to 110°C, thereby removing normal heptane and water. Thereafter, while maintaining the internal temperature at 100-105°C, the pressure inside the system was reduced to 150 Torr, and when the pressure reached 150 Torr, the internal temperature was raised to 110°C, and traces of remaining normal heptane were removed. Thereafter, while maintaining the internal temperature at 100-105°C, the pressure inside the system was reduced to 50 Torr, and when the pressure reached 50 Torr, the internal temperature was raised to 110°C, and traces of remaining normal heptane were removed. 100 g of the resulting liquid was weighed into a reactor, the pressure inside the system was reduced to 5 Torr, and the internal temperature was raised to 115°C, thereby distilling off methyl α-(allyloxymethyl)acrylate, and the removal of low-boiling components was completed. The resulting solution was filtered through a 0.8 μm PTFE membrane filter to obtain 74 parts of the target polymerizable ester compound, dicyclopentenyl 2-(allyloxymethyl)acrylate. The resulting dicyclopentenyl 2-(allyloxymethyl)acrylate contained 1.5% tricyclo[5.2.1.0(2,6)]dec-3-en-8-ol, 4.7% methyl α-(allyloxymethyl)acrylate, and less than 0.1% normal heptane.

[0127] Comparative Example 4 A polymerization solution of a polymerizable ester compound was obtained in the same manner as in Example 36, except that 6-tert-butyl-2,4-xylenol was added instead of Irganox 1010.

[0128] The polymer solutions obtained in Example 36 and Comparative Example 4 were evaluated for coloration resistance in the same manner as in Example 1. The results are shown in Table 4.

[0129]

[0130] Table 4 shows that the polymerization solution of Example 36 obtained by adding Irganox 1010 in the transesterification reaction of the polymerizable ester compound has superior discoloration resistance compared to the polymerization solution of Comparative Example 4 obtained by adding 6-tert-butyl-2,4-xylenol.

Claims

1. A polymerizable composition comprising a polymerizable ester compound having an α-allyloxymethylacryloyl group, represented by the following general formula (1), and at least one compound selected from the group consisting of a phenol compound, a (thio)phosphite compound, a phosphine compound, a thioether compound, and a thiol compound, represented by the following general formula (2): (In the formula, R １ represents a substituent having 6 or more carbon atoms. (In the formula, R ２１ represents a substituent having 2 or more carbon atoms. ２２ are the same or different and represent an organic group; and a represents an integer of 0 to 2.

2. The polymerizable composition according to claim 1, wherein the phenol compound is a hindered phenol compound represented by the following general formula (2-1): (In the formula, R ２１ represents a substituent having 2 or more carbon atoms. ２３ and R ２４ are the same or different and represent a hydrogen atom or a tert-butyl group. ２３ and R ２４ At least one of the groups is a tert-butyl group.

3. The polymerizable composition according to claim 1 or 2, characterized in that the polymerizable composition contains the phenol compound and at least one compound selected from the group consisting of (thio)phosphite compounds, phosphine compounds, thioether compounds, and thiol compounds.

4. The polymerizable composition according to any one of claims 1 to 3, characterized in that the content of at least one compound selected from the group consisting of phenol compounds, (thio)phosphite compounds, phosphine compounds, thioether compounds, and thiol compounds is 100 to 10,000 ppm in the polymerizable composition.

5. A method for producing a polymerizable ester compound having an α-allyloxymethylacryloyl group, the method comprising a step of transesterifying an α-(allyloxymethyl)acrylic acid ester with an alcohol in the presence of a catalyst, and wherein a phenol compound represented by the following general formula (2) is added in the transesterification reaction step: (In the formula, R ２１ represents a substituent having 2 or more carbon atoms. ２２ are the same or different and represent an organic group; and a represents an integer of 0 to 2.

6. The method for producing a polymerizable ester compound having an α-allyloxymethylacryloyl group according to claim 5, wherein the alcohol has 6 or more carbon atoms.

Images