JP2007210991A - Oxime ester compound, radical polymerization initiator, and polymerizable composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To obtain a new oxime ester compound, a high-sensitivity radical polymerization initiator that efficiently generates an active radical by irradiation with energy rays, especially a light and polymerizes a radically polymerizable compound in a short time and a curable composition using the same. <P>SOLUTION: The compound is represented by general formula (1) (A and B are each independently a substituted or nonsubstituted heterocyclic group or a substituted or nonsubstituted condensed polycyclic hydrocarbon group; X is a monofunctional organic residue with the proviso that A and B are not the same). <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to a novel oxime ester compound, a radical polymerization initiator, and a polymerizable composition using the same. More specifically, free radicals are efficiently generated by irradiation with energy rays, particularly light, and radically polymerizable compounds are reliably polymerized in a short time. For example, molding resins, casting resins, optical modeling resins, sealants, Dental polymerization resin, printing ink, paint, photosensitive resin for printing plate, color proof for printing, resist for color filter, resist for black matrix, photo spacer for liquid crystal, screen material for rear projection, optical fiber, rib material for plasma display , Dry film resist, printed circuit board resist, solder resist, semiconductor photoresist, microelectronic resist, micromachine component resist, etching resist, microlens array, insulating material, hologram material, optical switch, waveguide Materials, overcoat agents, powder coatings, adhesives, adhesives, release agents, optical recording media, adhesives, release coating agents, compositions for image recording materials using microcapsules, various devices, etc. The present invention relates to a novel oxime ester compound, a radical polymerization initiator and a polymerizable composition using the same to obtain a polymer having good physical properties in the field.

Conventionally, it is known that certain oxime ester compounds function as photoinitiators (see Non-Patent Document 1, Patent Documents 1 and 2). Moreover, an α-ketoxime ester compound is disclosed as a radical photopolymerization initiator for a positive or negative photosensitive polyimide precursor composition (see Patent Document 3). In addition, certain α, α′-diketooxime ester compounds are disclosed (see Patent Documents 4 to 8). In addition, certain O-acyloxime ester compounds have been disclosed (see Patent Documents 9 to 11). Any of these can function as a polymerization initiator, but in recent years, there has been a universal demand for higher sensitivity of the polymerization initiator in order to improve productivity and various newly proposed processes.
European polymer Journal, 1970, 6, 933-943 US Pat. No. 3,558,309 US Pat. No. 4,255,513 JP-A-7-140,658 US Pat. No. 5,019,482 Japanese Patent Laid-Open No. 62-184,056 JP-A-62-273,259 JP 62-286,961 A JP-A-62-201,859 JP 2001-233842 A JP 2000-80,068 JP-T-2004-534,797

  An object of the present invention is to provide a novel oxime ester compound, and by using this compound, an active radical can be efficiently generated by irradiation with energy rays, particularly light, and a radical polymerizable compound can be polymerized in a short time. The object is to propose a highly sensitive radical polymerization initiator and a curable composition using the same. For example, industrially provide practical oligomers and polymers in the fields of inks, paints, photosensitive printing plates, proof materials, photoresists, hologram materials, sealants, overcoat materials, stereolithography resins, adhesives, etc. The object of the present invention is to provide a radical polymerization initiator comprising a novel oxime ester compound and a polymerizable composition using the same, in order to obtain a cured product having good characteristics.

  As a result of intensive studies to solve the above problems, the present inventors have arrived at the present invention. That is, the present invention relates to a compound represented by the following general formula (1).

General formula (1)

(In the formula, A and B each independently represent a substituted or unsubstituted heterocyclic group, or a substituted or unsubstituted condensed polycyclic hydrocarbon group,
X represents a monovalent organic residue.
However, A and B are never the same. )

The present invention also relates to the above compound, wherein A is a substituted or unsubstituted carbazolyl group or a substituted or unsubstituted naphthyl group.
(However, a part of substituents on the carbazolyl group and naphthyl group may be bonded to a carbon atom of the carbazolyl group or naphthyl group or a part of other substituents to form a ring structure together. .)

  The present invention also relates to the above compound, wherein A is a group represented by the following general formula (2) which is substituted or unsubstituted, or a general formula (3) which is substituted or unsubstituted.

General formula (2)

General formula (3)

(In general formula (2), Y represents a monovalent organic residue.)

  In the present invention, A is a group represented by the following general formula (2) which is substituted or unsubstituted, and B is a group represented by the following general formula (3) which is substituted or unsubstituted. Relates to compounds.

General formula (2)

General formula (3)

(In general formula (2), Y represents a monovalent organic residue.)

  The present invention also relates to a radical polymerization initiator (a) comprising the above compound.

  The present invention also relates to a polymerizable composition comprising the radical polymerization initiator (a) and the radical polymerizable compound (b).

  The present invention further relates to the polymerizable composition comprising a sensitizer (c).

  The compound of the present invention is an α, α′-diketooxime ester compound characterized by having a heterocyclic group or a condensed polycyclic hydrocarbon group at the 1-position and 3-position, and the compound of the present invention has energy It functions as a radical polymerization initiator that efficiently generates active radicals upon irradiation with light, particularly light. Therefore, the compound which has a remarkably good effect as a radical polymerization initiator of a polymeric substance was able to be provided. Moreover, by using this compound as a radical polymerization initiator, a curable composition having good characteristics could be provided.

  First, the compound of the present invention will be described. The compound of the present invention is characterized by having a structure represented by the general formula (1). In general formula (1), A and B each independently represent a substituted or unsubstituted heterocyclic group or a substituted or unsubstituted condensed polycyclic hydrocarbon group. However, A and B are never the same.

  Examples of the heterocyclic group in the substituted or unsubstituted heterocyclic group in the general formula (1) include aromatic or aliphatic heterocyclic groups containing a nitrogen atom, an oxygen atom, a sulfur atom, and a phosphorus atom. Examples include 2-thienyl group, 2-benzothienyl group, naphtho [2,3-b] thienyl group, 3-thianthenyl group, 2-thianthrenyl group, 2-furyl group, 2-benzofuryl group, pyranyl group, iso Benzofuranyl group, chromenyl group, xanthenyl group, phenoxathiinyl group, 2H-pyrrolyl group, pyrrolyl group, imidazolyl group, pyrazolyl group, pyridyl group, pyrazinyl group, pyrimidinyl group, pyridazinyl group, indolizinyl group, isoindolyl group, 3H -Indolyl group, 2-indolyl group, 3-indolyl group, 1H-indazolyl group, purinyl group, 4H-quinolidine Group, isoquinolyl group, quinolyl group, phthalazinyl group, naphthyridinyl group, quinoxanilyl group, quinazolinyl group, cinnolinyl group, pteridinyl group, 4aH-carbazolyl group, 2-carbazolyl group, 3-carbazolyl group, β-carbolinyl group, phenanthridine Group, 2-acridinyl group, perimidinyl group, phenanthrolinyl group, phenazinyl group, phenalsadinyl group, isothiazolyl group, phenothiazinyl group, isoxazolyl group, furazanyl group, 3-phenixazinyl group, isochromanyl group, chromanyl group, pyrrolidinyl group, Pyrrolinyl group, imidazolidinyl group, imidazolinyl group, pyrazolidinyl group, pyrazolinyl group, piperidyl group, piperazinyl group, indolinyl group, isoindolinyl group, quinuclidinyl group, morpholinyl group, thiol Xanthryl group, 4-quinolinyl group, 4-isoquinolyl group, 3-phenothiazinyl group, 2-phenoxathinyl group, 3-coumarinyl group, dibenzofuranyl group, coumaranyl group, 2-thiocoumarinyl group, xanthonyl group, dibenzothienyl Groups, thioxanthenyl groups, oxazolyl groups, benzoxazolyl groups, benzothiazolyl groups, 1,4-dithianaphthyl groups, and the like, but are not limited thereto. Moreover, it may couple | bond with the carbon atom of General formula (1) in substitution positions other than the above, and if it is a substitution position which can form a covalent bond with a carbon atom, it will not specifically limit.

  As the condensed polycyclic hydrocarbon group in the substituted or unsubstituted condensed polycyclic hydrocarbon group in the general formula (1), a condensed polycyclic hydrocarbon group in which a ring structure is formed of 7 or more carbon atoms is used. Specific examples include indenyl group, 1,3-indandionyl group, naphthyl group, β-tetralonyl group, α-naphthoquinolyl group, pentarenyl group, azulenyl group, heptalenyl group, fluorenyl group, fluorenonyl group, anthryl group, 9 (10H) -anthracenonyl group, anthracenequinonyl group, anthraquinonyl group, phenanthryl group, 9,10-phenanthrenequinonyl group, biphenylenyl group, s-indacenyl group, as-indacenyl group, acenaphthylenyl group, acenaphthenyl group, acenaphthoquinonyl group , Phenalenyl group, naphthacenyl group, chrycenyl Group, pyrenyl group, triphenylenyl group, benzo [a] anthracenyl group, benzo [a] anthraquinonyl group, aceanthrenyl group, aceanthrenyl group, aceanthrenequinolyl group, acephenanthrenylenyl group, fluoranthenyl group, Examples include a preadenyl group, a pentacenyl group, a perylenyl group, a picenyl group, and a benzo [a] pyrenyl group. Among these, a condensed polycyclic hydrocarbon group having 2 or 3 rings is preferable because of easy availability, a decrease in synthesis difficulty, and the like, but is not limited thereto. It may be bonded to the carbon atom of formula (1) at any substitution position, and is not particularly limited as long as it is a substitution position capable of forming a covalent bond with the carbon atom.

  The above-mentioned substituents that the heterocyclic group and the condensed polycyclic hydrocarbon group may have include a hydroxyl group, a mercapto group, a cyano group, a nitro group, a halogen atom, an alkyl group, an aryl group, a heterocyclic group, and an acyl group. Group, alkoxyl group, aryloxy group, heterocyclic oxy group, acyloxy group, alkylthio group, arylthio group, heterocyclic thio group, amino group, alkylamino group, dialkylamino group, arylamino group, diarylamino group, alkylarylamino Group, benzylamino group, dibenzylamino group and the like.

  Here, examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

  Examples of the alkyl group include linear, branched, monocyclic or condensed polycyclic alkyl groups having 1 to 18 carbon atoms, and specific examples include a methyl group, an ethyl group, a propyl group, a butyl group, and a pentyl group. Hexyl group, heptyl group, octyl group, nonyl group, decyl group, dodecyl group, octadecyl group, isopropyl group, isobutyl group, isopentyl group, sec-butyl group, tert-butyl group, sec-pentyl group, tert-pentyl group Tert-octyl group, neopentyl group, cyclopropyl group, cyclobutyl, cyclopentyl group, cyclohexyl group, adamantyl group, norbornyl group, boronyl group, 4-decylcyclohexyl group and the like.

  Examples of the aryl group include monocyclic or condensed polycyclic aryl groups having 6 to 18 carbon atoms. Specific examples include a phenyl group, a 1-naphthyl group, a 2-naphthyl group, a 9-anthryl group, and a 9-phenanthryl group. 1-pyrenyl group, 5-naphthacenyl group, 1-indenyl group, 2-azurenyl group, 1-acenaphthyl group, 9-fluorenyl group and the like.

  Examples of the heterocyclic group include a monocyclic or condensed polycyclic heterocyclic group containing a nitrogen atom, an oxygen atom, a sulfur atom, and a phosphorus atom. Specific examples include a 2-furanyl group, a 2-thienyl group, 2- Indolyl group, 3-indolyl group, 2-benzofuryl group, 2-benzothienyl group, 2-carbazolyl group, 3-carbazolyl group, 4-carbazolyl group, 9-acridinyl group and the like can be mentioned.

  The acyl group includes a hydrogen atom, a carbonyl group to which a linear, branched, monocyclic or condensed polycyclic aliphatic group having 1 to 18 carbon atoms is bonded, or a monocyclic or condensed polyvalent group having 6 to 18 carbon atoms. Examples include a carbonyl group to which a cyclic aryl group is bonded, a carbonyl group to which a monocyclic or condensed polycyclic heterocyclic group having 4 to 18 carbon atoms is bonded, including a nitrogen atom, an oxygen atom, a sulfur atom, and a phosphorus atom. It may have an unsaturated bond, and specific examples thereof include formyl group, acetyl group, propionyl group, butyryl group, isobutyryl group, valeryl group, isovaleryl group, pivaloyl group, lauroyl group, myristoyl group, palmitoyl group , Stearoyl group, cyclopentylcarbonyl group, cyclohexylcarbonyl group, acryloyl group, methacryloyl group, croto Yl group, isocrotonoyl group, oleoyl group, benzoyl group, 2-methylbenzoyl group, 4-methoxybenzoyl group, 1-naphthoyl group, 2-naphthoyl group, cinnamoyl group, 3-furoyl group, 2-thenoyl group, nicotinoyl group , Isonicotinoyl group, 9-anthroyl group, 5-naphthacenoyl group and the like.

  Examples of the alkoxyl group include linear, branched, monocyclic or condensed polycyclic alkoxyl groups having 1 to 18 carbon atoms, and specific examples include methoxy group, ethoxy group, propoxy group, butoxy group, pentyloxy. Group, hexyloxy group, heptyloxy group, octyloxy group, nonyloxy group, decyloxy group, dodecyloxy group, octadecyloxy group, isopropoxy group, isobutoxy group, isopentyloxy group, sec-butoxy group, t-butoxy group, sec-pentyloxy group, t-pentyloxy group, t-octyloxy group, neopentyloxy group, cyclopropyloxy group, cyclobutyloxy group, cyclopentyloxy group, cyclohexyloxy group, adamantyloxy group, norbornyloxy group , Boronyloxy group, 4-de Le cyclohexyloxy group, 2-tetrahydrofuranyl group, 2-tetrahydrofuranyl group, and the like.

  Examples of the aryloxy group include monocyclic or condensed polycyclic aryloxy groups having 6 to 18 carbon atoms. Specific examples include a phenoxy group, a 1-naphthyloxy group, a 2-naphthyloxy group, and 9-anthryloxy. Group, 9-phenanthryloxy group, 1-pyrenyloxy group, 5-naphthacenyloxy group, 1-indenyloxy group, 2-azurenyloxy group, 1-acenaphthyloxy group, 9-fluorenyloxy group, etc. Is mentioned.

  Examples of the heterocyclic oxy group include a monocyclic or condensed polycyclic heterocyclic oxy group containing a nitrogen atom, an oxygen atom, a sulfur atom, and a phosphorus atom. Specific examples include a 2-furanyloxy group and a 2-thienyloxy group. 2-indolyloxy group, 3-indolyloxy group, 2-benzofuryloxy group, 2-benzothienyloxy group, 2-carbazolyloxy group, 3-carbazolyloxy group, 4-carbazolyl group An oxy group, 9-acridinyloxy group, etc. are mentioned.

  The acyloxy group includes a carbonyloxy group to which a hydrogen atom or a linear, branched, monocyclic or condensed polycyclic aliphatic group having 1 to 18 carbon atoms is bonded, or a monocyclic or condensed group having 6 to 18 carbon atoms. A carbonyloxy group to which a monocyclic or condensed polycyclic heterocyclic group having 4 to 18 carbon atoms is bonded, including a carbonyloxy group to which a polycyclic aryl group is bonded, a nitrogen atom, an oxygen atom, a sulfur atom, and a phosphorus atom; Specific examples include acetoxy group, propionyloxy group, butyryloxy group, isobutyryloxy group, valeryloxy group, isovaleryloxy group, pivaloyloxy group, lauroyloxy group, myristoyloxy group, palmitoyloxy group, stearoyloxy group, cyclopentyl Carbonyloxy group, cyclohexylcarbonyloxy group, Royloxy group, methacryloyloxy group, crotonoyloxy group, isocrotonoyloxy group, oleoyloxy group, benzoyloxy group, 1-naphthoyloxy group, 2-naphthoyloxy group, cinnamoyloxy group, 3-furoyloxy group 2-thenoyloxy group, nicotinoyloxy group, isonicotinoyloxy group, 9-anthroyloxy group, 5-naphthathenoyloxy group and the like.

  Examples of the alkylthio group include a linear, branched, monocyclic or condensed polycyclic alkylthio group having 1 to 18 carbon atoms, and specific examples include a methylthio group, an ethylthio group, a propylthio group, a butylthio group, and a pentylthio group. Hexylthio group, octylthio group, decylthio group, dodecylthio group, octadecylthio group and the like.

  Examples of the arylthio group include monocyclic or condensed polycyclic arylthio groups having 6 to 18 carbon atoms, and specific examples thereof include a phenylthio group, a 1-naphthylthio group, a 2-naphthylthio group, a 9-anthrylthio group, and a 9-phenanthri group. And a ruthio group.

  Examples of the heterocyclic thio group include a monocyclic or condensed polycyclic heterocyclic thio group containing a nitrogen atom, an oxygen atom, a sulfur atom, and a phosphorus atom. Specific examples include a 2-furylthio group, a 2-thienylthio group, Examples include 2-pyrrolylthio group, 6-indolylthio group, 2-benzofurylthio group, 2-benzothienylthio group, 2-carbazolylthio group, 3-carbazolylthio group, 4-carbazolylthio group and the like.

  Examples of the alkylamino group include methylamino group, ethylamino group, propylamino group, butylamino group, pentylamino group, hexylamino group, heptylamino group, octylamino group, nonylamino group, decylamino group, dodecylamino group, octadecylamino group Group, isopropylamino group, isobutylamino group, isopentylamino group, sec-butylamino group, tert-butylamino group, sec-pentylamino group, tert-pentylamino group, tert-octylamino group, neopentylamino group, Cyclopropylamino group, cyclobutylamino group, cyclopentylamino group, cyclohexylamino group, cycloheptylamino group, cyclooctylamino group, cyclododecylamino group, 1-adamantamino group, 2-adamantamino group, etc. It is below.

  Dialkylamino group includes dimethylamino group, diethylamino group, dipropylamino group, dibutylamino group, dipentylamino group, dihexylamino group, diheptylamino group, dioctylamino group, dinonylamino group, didecylamino group, didodecylamino group, Dioctadecylamino group, diisopropylamino group, diisobutylamino group, diisopentylamino group, methylethylamino group, methylpropylamino group, methylbutylamino group, methylisobutylamino group, cyclopropylamino group, pyrrolidino group, piperidino group, And piperazino group.

  As an arylamino group, an anilino group, 1-naphthylamino group, 2-naphthylamino group, o-toluidino group, m-toluidino group, p-toluidino group, 2-biphenylamino group, 3-biphenylamino group, 4- Biphenylamino group, 1-fluoreneamino group, 2-fluoreneamino group, 2-thiazoleamino group, p-terphenylamino group and the like can be mentioned.

  Examples of the diarylamino group include a diphenylamino group, a ditolylamino group, an N-phenyl-1-naphthylamino group, and an N-phenyl-2-naphthylamino group.

  Examples of the alkylarylamino group include N-methylanilino group, N-methyl-2-pyridino group, N-ethylanilino group, N-propylanilino group, N-butylanilino group, N-isopropyl, N-pentylanilino group, N -Ethylanilino group, N-methyl-1-naphthylamino group and the like.

  Furthermore, the hydrogen atom of the substituent that the above-described heterocyclic group and condensed polycyclic hydrocarbon group may have may be further substituted with another substituent. Examples of such a substituent include Halogen groups such as fluorine atom, chlorine atom, bromine atom and iodine atom, alkoxy groups such as methoxy group, ethoxy group and tert-butoxy group, aryloxy groups such as phenoxy group and p-tolyloxy group, methoxycarbonyl group and butoxycarbonyl Group, alkoxycarbonyl group such as phenoxycarbonyl group, acetoxy group, propionyloxy group, acyloxy group such as benzoyloxy group, acyl group such as acetyl group, benzoyl group, isobutyryl group, acryloyl group, methacryloyl group, methoxalyl group, methylsulfanyl Group, tert-butylsulfanyl group and the like Arylsulfanyl groups such as sulfanyl group, phenylsulfanyl group, p-tolylsulfanyl group, alkylamino groups such as methylamino group, cyclohexylamino group, dialkylamino groups such as dimethylamino group, diethylamino group, morpholino group, piperidino group, phenyl Aryl group such as amino group, p-tolylamino group, alkyl group such as methyl group, ethyl group, tert-butyl group, dodecyl group, phenyl group, p-tolyl group, xylyl group, cumenyl group, naphthyl group, anthryl group In addition to aryl groups such as phenanthryl group, hydroxy group, carboxy group, formyl group, mercapto group, sulfo group, mesyl group, p-toluenesulfonyl group, amino group, nitro group, cyano group, trifluoromethyl group, trichloro Methyl group, trimethylsilyl , Phosphinico group, a phosphono group, trimethyl ammonium Niu mill group, dimethylsulfoxide Niu mill group, triphenyl phenacyl phosphonium Niu mill group, and the like.

  Furthermore, the substituents in A and B may be combined with other substituents or hydrogen atoms on the ring to form a cyclic structure.

  A and B may be integrated to form an annular structure.

  The substituent X in the general formula (1) represents a monovalent organic residue. The monovalent organic residue may have an alkyl group that may have a substituent, an aryl group that may have a substituent, an alkenyl group that may have a substituent, or a substituent. An alkynyl group, an alkoxy group that may have a substituent, an aryloxy group that may have a substituent, a heterocyclic oxy group that may have a substituent, an acyloxy group that may have a substituent, Alkylsulfanyl group which may have a substituent, arylsulfanyl group which may have a substituent, alkylsulfinyl group which may have a substituent, arylsulfinyl group which may have a substituent, substituent An alkylsulfonyl group that may have a substituent, an arylsulfonyl group that may have a substituent, an acyl group that may have a substituent, an alkoxycarbonyl group that may have a substituent, and a substituent May be carbamoyl , An optionally substituted sulfamoyl group, an optionally substituted amino group, an optionally substituted phosphinoyl group, and heterocyclic group which may have a substituent.

  As the alkyl group which may have a substituent, an alkyl group having 1 to 30 carbon atoms is preferable, for example, methyl group, ethyl group, propyl group, butyl group, hexyl group, octyl group, decyl group, dodecyl group, Okudadecyl group, isopropyl group, isobutyl group, sec? Butyl group, t? Butyl group, 1-ethylpentyl group, cyclopentyl group, cyclohexyl group, trifluoromethyl group, 2-ethylhexyl group, phenacyl group, 1-naphthoylmethyl group, 2-naphthoylmethyl group, 4-methylsulfanylphenacyl group, 4-phenylsulfanylphenacyl group, 4-dimethylaminophenacyl group, 4-cyanophenacyl group 4-methylphenacyl group, 2-methylphenacyl group, 3-fluorophenacyl group, 3-trifluoromethylphenacyl group, Examples include 3-nitrophenacyl group.

  As the aryl group which may have a substituent, an aryl group having 6 to 30 carbon atoms is preferable, and a phenyl group, a biphenyl group, a 1-naphthyl group, a 2-naphthyl group, a 9-anthryl group, a 9-phenanthryl group, 1-pyrenyl group, 5-naphthacenyl group, 1-indenyl group, 2-azurenyl group, 9-fluorenyl group, terphenyl group, quarterphenyl group, o-, m-, and p-tolyl group, xylyl group, o- , M-, and p-cumenyl group, mesityl group, pentarenyl group, binaphthalenyl group, turnaphthalenyl group, quarternaphthalenyl group, heptaenyl group, biphenylenyl group, indacenyl group, fluoranthenyl group, acenaphthylenyl group, aceanthrylenyl group, Phenalenyl group, fluorenyl group, anthryl group, bianthracenyl group, teranthra Nyl group, quarter anthracenyl group, anthraquinolyl group, phenanthryl group, triphenylenyl group, pyrenyl group, chrysenyl group, naphthacenyl group, preadenyl group, picenyl group, perylenyl group, pentaphenyl group, pentacenyl group, tetraphenylenyl group, Examples include a hexaphenyl group, a hexacenyl group, a rubicenyl group, a coronenyl group, a trinaphthylenyl group, a heptaphenyl group, a heptacenyl group, a pyranthrenyl group, and an ovalenyl group.

  As an alkenyl group which may have a substituent, a C2-C10 alkenyl group is preferable, for example, a vinyl group, an allyl group, a styryl group etc. are mentioned.

  The alkynyl group which may have a substituent is preferably an alkynyl group having 2 to 10 carbon atoms, and examples thereof include an ethynyl group, a propynyl group, and a propargyl group.

  The alkoxy group which may have a substituent is preferably an alkoxy group having 1 to 30 carbon atoms, for example, a methoxy group, an ethoxy group, a propyloxy group, an isopropyloxy group, a butoxy group, an isobutoxy group, or a sec-butoxy group. T-butoxy group, pentyloxy group, isopentyloxy group, hexyloxy group, heptyloxy group, octyloxy group, 2-ethylhexyloxy group, decyloxy group, dodecyloxy group, octadecyloxy group, ethoxycarbonylmethyl group, 2 -Ethylhexyloxycarbonylmethyloxy group, aminocarbonylmethyloxy group, N, N-dibutylaminocarbonylmethyloxy group, N-methylaminocarbonylmethyloxy group, N-ethylaminocarbonylmethyloxy group, N-octylaminocarbonyl Yloxy group, N- methyl -N- benzylaminocarbonyl methyloxy group, a benzyloxy group, and a cyanomethyloxy group.

  The aryloxy group which may have a substituent is preferably an aryloxy group having 6 to 30 carbon atoms, such as a phenyloxy group, a 1-naphthyloxy group, a 2-naphthyloxy group, a 2-chlorophenyloxy group, 2-methylphenyloxy group, 2-methoxyphenyloxy group, 2-butoxyphenyloxy group, 3-chlorophenyloxy group, 3-trifluoromethylphenyloxy group, 3-cyanophenyloxy group, 3-nitrophenyloxy group, Examples include 4-fluorophenyloxy group, 4-cyanophenyloxy group, 4-methoxyphenyloxy group, 4-dimethylaminophenyloxy group, 4-methylsulfanylphenyloxy group, 4-phenylsulfanylphenyloxy group, and the like.

  Examples of the heterocyclic oxy group that may have a substituent include a monocyclic or condensed polycyclic heterocyclic oxy group containing a nitrogen atom, an oxygen atom, a sulfur atom, and a phosphorus atom. Furanyloxy group, 2-thienyloxy group, 2-indolyloxy group, 3-indolyloxy group, 2-carbazolyloxy group, 2-benzofuryloxy group, 2-benzothienyloxy group, 3-carbazolyl An oxy group, 4-carbazolyloxy group, 9-acridinyloxy group, etc. are mentioned.

  The acyloxy group which may have a substituent is preferably an acyloxy group having 2 to 20 carbon atoms, such as an acetyloxy group, a propanoyloxy group, a butanoyloxy group, a pentanoyloxy group, or trifluoromethylcarbonyloxy. Group, benzoyloxy group, 1-naphthylcarbonyloxy group, 2-naphthylcarbonyloxy group and the like.

  The alkylsulfanyl group which may have a substituent is preferably an alkylsulfanyl group having 1 to 20 carbon atoms. For example, a methylsulfanyl group, an ethylsulfanyl group, a propylsulfanyl group, an isopropylsulfanyl group, a butylsulfanyl group, or a hexylsulfanyl group. Group, cyclohexylsulfanyl group, octylsulfanyl group, 2-ethylhexylsulfanyl group, decanoylsulfanyl group, dodecanoylsulfanyl group, octadecanoylsulfanyl group, cyanomethylsulfanyl group, methoxymethylsulfanyl group and the like.

  The arylsulfanyl group which may have a substituent is preferably an arylsulfanyl group having 6 to 30 carbon atoms, such as a phenylsulfanyl group, 1-naphthylsulfanyl group, 2-naphthylsulfanyl group, 2-chlorophenylsulfanyl group, 2-methylphenylsulfanyl group, 2-methoxyphenylsulfanyl group, 2-butoxyphenylsulfanyl group, 3-chlorophenylsulfanyl group, 3-trifluoromethylphenylsulfanyl group, 3-cyanophenylsulfanyl group, 3-nitrophenylsulfanyl group, 4-fluorophenylsulfanyl group, 4-cyanophenylsulfanyl group, 4-methoxyphenylsulfanyl group, 4-methylsulfanylphenylsulfanyl group, 4-phenylsulfanylphenylsulfuric group Aniru group, 4-dimethylamino-phenylsulfanyl group and the like.

  The alkylsulfinyl group which may have a substituent is preferably an alkylsulfinyl group having 1 to 20 carbon atoms. For example, a methylsulfinyl group, an ethylsulfinyl group, a propylsulfinyl group, an isopropylsulfinyl group, a butylsulfinyl group, and a hexylsulfinyl group. Group, cyclohexylsulfinyl group, octylsulfinyl group, 2-ethylhexylsulfinyl group, decanoylsulfinyl group, dodecanoylsulfinyl group, octadecanoylsulfinyl group, cyanomethylsulfinyl group, methoxymethylsulfinyl group and the like.

  The arylsulfinyl group which may have a substituent is preferably an arylsulfinyl group having 6 to 30 carbon atoms, such as a phenylsulfinyl group, 1-naphthylsulfinyl group, 2-naphthylsulfinyl group, 2-chlorophenylsulfinyl group, 2-methylphenylsulfinyl group, 2-methoxyphenylsulfinyl group, 2-butoxyphenylsulfinyl group, 3-chlorophenylsulfinyl group, 3-trifluoromethylphenylsulfinyl group, 3-cyanophenylsulfinyl group, 3-nitrophenylsulfinyl group, 4-fluorophenylsulfinyl group, 4-cyanophenylsulfinyl group, 4-methoxyphenylsulfinyl group, 4-methylsulfanylphenylsulfinyl group, 4-phenylsulfanylphenylsulfuric group Iniru group, 4-dimethylaminophenyl sulfinyl group and the like.

  The alkylsulfonyl group which may have a substituent is preferably an alkylsulfonyl group having 1 to 20 carbon atoms. For example, a methylsulfonyl group, an ethylsulfonyl group, a propylsulfonyl group, an isopropylsulfonyl group, a butylsulfonyl group, a hexylsulfonyl group. Group, cyclohexylsulfonyl group, octylsulfonyl group, 2-ethylhexylsulfonyl group, decanoylsulfonyl group, dodecanoylsulfonyl group, octadecanoylsulfonyl group, cyanomethylsulfonyl group, methoxymethylsulfonyl group and the like.

  The arylsulfonyl group which may have a substituent is preferably an arylsulfonyl group having 6 to 30 carbon atoms, such as a phenylsulfonyl group, a 1-naphthylsulfonyl group, a 2-naphthylsulfonyl group, a 2-chlorophenylsulfonyl group, 2-methylphenylsulfonyl group, 2-methoxyphenylsulfonyl group, 2-butoxyphenylsulfonyl group, 3-chlorophenylsulfonyl group, 3-trifluoromethylphenylsulfonyl group, 3-cyanophenylsulfonyl group, 3-nitrophenylsulfonyl group, 4-fluorophenylsulfonyl group, 4-cyanophenylsulfonyl group, 4-methoxyphenylsulfonyl group, 4-methylsulfanylphenylsulfonyl group, 4-phenylsulfanylphenylsulfonyl group, 4-dimethylaminopheny Sulfonyl group, and the like.

  The acyl group which may have a substituent is preferably an acyl group having 2 to 20 carbon atoms, for example, acetyl group, propanoyl group, butanoyl group, trifluoromethylcarbonyl group, pentanoyl group, benzoyl group, 1-naphthoyl. Group, 2-naphthoyl group, 4-methylsulfanylbenzoyl group, 4-phenylsulfanylbenzoyl group, 4-dimethylaminobenzoyl group, 4-diethylaminobenzoyl group, 2-chlorobenzoyl group, 2-methylbenzoyl group, 2-methoxybenzoyl Group, 2-butoxybenzoyl group, 3-chlorobenzoyl group, 3-trifluoromethylbenzoyl group, 3-cyanobenzoyl group, 3-nitrobenzoyl group, 4-fluorobenzoyl group, 4-cyanobenzoyl group, 4-methoxybenzoyl Groups and the like.

  The alkoxycarbonyl group which may have a substituent is preferably an alkoxycarbonyl group having 2 to 20 carbon atoms, such as a methoxycarbonyl group, ethoxycarbonyl group, propoxycarbonyl group, butoxycarbonyl group, hexyloxycarbonyl group, octyl. Oxycarbonyl group, decyloxycarbonyl group, octadecyloxycarbonyl group, phenoxycarbonyl group, trifluoromethyloxycarbonyl group, 1-naphthyloxycarbonyl group, 2-naphthyloxycarbonyl group, 4-methylsulfanylphenyloxycarbonyl group, 4- Phenylsulfanylphenyloxycarbonyl group, 4-dimethylaminophenyloxycarbonyl group, 4-diethylaminophenyloxycarbonyl group, 2-chlorophenyloxycarbonyl group Group, 2-methylphenyloxycarbonyl group, 2-methoxyphenyloxycarbonyl group, 2-butoxyphenyloxycarbonyl group, 3-chlorophenyloxycarbonyl group, 3-trifluoromethylphenyloxycarbonyl group, 3-cyanophenyloxycarbonyl group , 3-nitrophenyloxycarbonyl group, 4-fluorophenyloxycarbonyl group, 4-cyanophenyloxycarbonyl group, 4-methoxyphenyloxycarbonyl group and the like.

  The carbamoyl group which may have a substituent is preferably a carbamoyl group having 1 to 30 carbon atoms, for example, an N-methylcarbamoyl group, an N-ethylcarbamoyl group, an N-propylcarbamoyl group, or an N-butylcarbamoyl group. N-hexylcarbamoyl group, N-cyclohexylcarbamoyl group, N-octylcarbamoyl group, N-decylcarbamoyl group, N-octadecylcarbamoyl group, N-phenylcarbamoyl group, N-2-methylphenylcarbamoyl group, N-2- Chlorophenylcarbamoyl group, N-2-isopropoxyphenylcarbamoyl group, N-2- (2-ethylhexyl) phenylcarbamoyl group, N-3-chlorophenylcarbamoyl group, N-3-nitrophenylcarbamoyl group, N-3-cyanophenyl A carbamoyl group, -4-methoxyphenylcarbamoyl group, N-4-cyanophenylcarbamoyl group, N-4-methylsulfanylphenylcarbamoyl group, N-4-phenylsulfanylphenylcarbamoyl group, N-methyl-N-phenylcarbamoyl group, N, N -Dimethylcarbamoyl group, N, N-dibutylcarbamoyl group, N, N-diphenylcarbamoyl group and the like.

  The sulfamoyl group which may have a substituent is preferably a sulfamoyl group having 0 to 30 carbon atoms, for example, a sulfamoyl group, an N-alkylsulfamoyl group, an N-arylsulfamoyl group, N, N- Examples thereof include a dialkylsulfamoyl group, an N, N-diarylsulfamoyl group, and an N-alkyl-N-arylsulfamoyl group. More specifically, N-methylsulfamoyl group, N-ethylsulfamoyl group, N-propylsulfamoyl group, N-butylsulfamoyl group, N-hexylsulfamoyl group, N-cyclohexylsulfur group. Famoyl group, N-octylsulfamoyl group, N-2-ethylhexylsulfamoyl group, N-decylsulfamoyl group, N-octadecylsulfamoyl group, N-phenylsulfamoyl group, N-2- Methylphenylsulfamoyl group, N-2-chlorophenylsulfamoyl group, N-2-methoxyphenylsulfamoyl group, N-2-isopropoxyphenylsulfamoyl group, N-3-chlorophenylsulfamoyl group, N-3-nitrophenylsulfamoyl group, N-3-cyanophenylsulfamoyl group, N-4-methoxyphenyl Nylsulfamoyl group, N-4-cyanophenylsulfamoyl group, N-4-dimethylaminophenylsulfamoyl group, N-4-methylsulfanylphenylsulfamoyl group, N-4-phenylsulfanylphenylsulfamoyl Group, N-methyl-N-phenylsulfamoyl group, N, N-dimethylsulfamoyl group, N, N-dibutylsulfamoyl group, N, N-diphenylsulfamoyl group and the like.

The amino group which may have a substituent is preferably an amino group having 0 to 50 carbon atoms in total, for example, —NH ₂ , N-alkylamino group, N-arylamino group, N-acylamino group, N— Examples include sulfonylamino group, N, N-dialkylamino group, N, N-diarylamino group, N-alkyl-N-arylamino group, N, N-disulfonylamino group and the like. More specifically, N-methylamino group, N-ethylamino group, N-propylamino group, N-isopropylamino group, N-butylamino group, Nt-butylamino group, N-hexylamino group, N-cyclohexylamino group, N-octylamino group, N-2-ethylhexylamino group, N-decylamino group, N-octadecylamino group, N-benzylamino group, N-phenylamino group, N-2-methylphenylamino Group, N-2-chlorophenylamino group, N-2-methoxyphenylamino group, N-2-isopropoxyphenylamino group, N-2- (2-ethylhexyl) phenylamino group, N-3-chlorophenylamino group, N-3-nitrophenylamino group, N-3-cyanophenylamino group, N-3-trifluoromethylphenylamino group, -4-methoxyphenylamino group, N-4-cyanophenylamino group, N-4-trifluoromethylphenylamino group, N-4-methylsulfanylphenylamino group, N-4-phenylsulfanylphenylamino group, N- 4-dimethylaminophenylamino group, N-methyl-N-phenylamino group, N, N-dimethylamino group, N, N-diethylamino group, N, N-dibutylamino group, N, N-diphenylamino group, N N-diacetylamino group, N, N-dibenzoylamino group, N, N- (dibutylcarbonyl) amino group, N, N- (dimethylsulfonyl) amino group, N, N- (diethylsulfonyl) amino group, N N- (dibutylsulfonyl) amino group, N, N- (diphenylsulfonyl) amino group and the like.

  The phosphinoyl group which may have a substituent is preferably a phosphinoyl group having 2 to 50 carbon atoms, for example, dimethylphosphinoyl group, diethylphosphinoyl group, dipropylphosphinoyl group, diphenylphosphinoyl group. Group, dimethoxyphosphinoyl group, diethoxyphosphinoyl group, dibenzoylphosphinoyl group, bis (2,4,6-trimethylphenyl) phosphinoyl group and the like.

  The heterocyclic group that may have a substituent is preferably an aromatic or aliphatic heterocyclic ring containing a nitrogen atom, an oxygen atom, a sulfur atom, or a phosphorus atom. For example, thienyl group, benzo [b] thienyl group, naphtho [2,3-b] thienyl group, thiantenyl group, furyl group, pyranyl group, isobenzofuranyl group, chromenyl group, xanthenyl group, phenoxathinyl group, 2H-pyrrolyl group, pyrrolyl group, imidazolyl group, pyrazolyl group, pyridyl group, pyrazinyl group, pyrimidinyl group, pyridazinyl group, indolizinyl group, isoindolyl group, 3H-indolyl group, indolyl group, 1H-indazolyl group, purinyl group, 4H- Quinolidinyl group, isoquinolyl group, quinolyl group, phthalazinyl group, naphthyridinyl group, quinoxanilyl group, quinazolinyl group, cinnolinyl group, pteridinyl group, 4aH-carbazolyl group, carbazolyl group, β-carbolinyl group, phenanthridinyl group, acridinyl group, perimidinyl group Nyl group, phenanthrolinyl group, phenazinyl group, phenalsadinyl group, isothiazolyl group, phenothiazinyl group, isoxazolyl group, furazanyl group, phenoxazinyl group, isochromanyl group, chromanyl group, pyrrolidinyl group, pyrrolinyl group, imidazolidinyl group, imidazolinyl group, pyrazolidinyl group Group, pyrazolinyl group, piperidyl group, piperazinyl group, indolinyl group, isoindolinyl group, quinuclidinyl group, morpholinyl group, thioxanthryl group and the like.

  Furthermore, the alkyl group which may have a substituent mentioned above, the aryl group which may have a substituent, the alkenyl group which may have a substituent, the alkynyl group which may have a substituent, a substituent An alkoxy group which may have a substituent, an aryloxy group which may have a substituent, an acyloxy group which may have a substituent, an alkylsulfanyl group which may have a substituent, and a substituent An arylsulfanyl group which may have a substituent, an alkylsulfinyl group which may have a substituent, an arylsulfinyl group which may have a substituent, an alkylsulfonyl group which may have a substituent, and a substituent. An arylsulfonyl group, an optionally substituted acyl group, an optionally substituted alkoxycarbonyl group, an optionally substituted carbamoyl group, an optionally substituted sulfamoyl group, Amino group which may have a group, hydrogen atom of the heterocyclic group which may have a substituent may be further substituted with other substituents.

  Examples of such substituents include halogen groups such as fluorine atom, chlorine atom, bromine atom and iodine atom, alkoxy groups such as methoxy group, ethoxy group and tert-butoxy group, aryl groups such as phenoxy group and p-tolyloxy group. Oxy group, methoxycarbonyl group, butoxycarbonyl group, alkoxycarbonyl group such as phenoxycarbonyl group, acetoxy group, propionyloxy group, acyloxy group such as benzoyloxy group, acetyl group, benzoyl group, isobutyryl group, acryloyl group, methacryloyl group, Acyl group such as methoxalyl group, alkylsulfanyl group such as methylsulfanyl group, tert-butylsulfanyl group, arylsulfanyl group such as phenylsulfanyl group, p-tolylsulfanyl group, methylamino group, cyclohexyla Alkyl groups such as alkyl groups, dimethylamino groups, diethylamino groups, morpholino groups, piperidino groups and other dialkylamino groups, phenylamino groups, p-tolylamino groups and other arylamino groups, methyl groups, ethyl groups, tert-butyl groups In addition to alkyl groups such as dodecyl group, phenyl groups, p-tolyl groups, xylyl groups, cumenyl groups, naphthyl groups, anthryl groups, phenanthryl groups, etc., hydroxy groups, carboxy groups, formyl groups, mercapto groups, Sulfo group, mesyl group, p-toluenesulfonyl group, amino group, nitro group, cyano group, trifluoromethyl group, trichloromethyl group, trimethylsilyl group, phosphinico group, phosphono group, trimethylammonium group, dimethylsulfonyl group, Triphenylphenacylphosphoniumyl group, etc. And the like.

  In these substituents X, an alkyl group which may have a substituent, an aryl group which may have a substituent, an acyl group which may have a substituent, and a phosphinyl which may have a substituent Group, a heterocyclic group that may have a substituent, and the like, more preferably, an alkyl group that may have a substituent, and an aryl group that may have a substituent. Examples include a methyl group, an ethyl group, a propyl group, a butyl group, a t-butyl group, a trifluoromethyl group, a phenyl group, and a benzyl group, but the present invention is not limited to these examples.

  In the compound represented by the general formula (1) of the present invention, preferred is a compound wherein A in the general formula (1) is a substituted or unsubstituted carbazolyl group or a substituted or unsubstituted naphthyl group. . In this case, a part of the substituents on the carbazolyl group and naphthyl group may be bonded to a carbon atom of the carbazolyl group or naphthyl group or a part of another substituent to form a ring structure together. In addition, the carbazolyl group and the naphthyl group may be bonded at any substitution position as long as they can form a covalent bond with the adjacent carbon atom of the general formula (1).

  The carbazolyl group and naphthyl group may be substituted with other substituents. Examples of such other substituents include the same substituents as those mentioned as the substituents that A and B may have. Can be mentioned.

  In the compound represented by the general formula (1), it is more preferable that A in the general formula (1) is represented by the substituted or unsubstituted general formula (2) or the substituted or unsubstituted general formula (3). It is a compound that is a group. The groups represented by the general formula (2) and the general formula (3) are bonded at any substitution position as long as they can form a covalent bond with the adjacent carbon atom of the general formula (1). May be.

  In the general formula (2), Y represents a monovalent organic residue, and examples thereof include the same monovalent organic residues as in the above substituent X. Ease of availability of raw materials and easiness of synthesis Therefore, a substituted or unsubstituted alkyl group is preferable.

  In the compound represented by the general formula (1), it is more preferable that A in the general formula (1) is a group represented by the substituted or unsubstituted general formula (2), and B is a substituted or unsubstituted group. It is a compound which is group represented by General formula (3).

  The groups represented by the general formula (2) and the general formula (3) may be substituted with other substituents, and as such other substituents, the substituents that A and B may have Examples of the substituent are the same as those described for the group. The other substituent in the general formula (2) is preferably an acyl group, more preferably a substituted or unsubstituted benzoyl group or a substituted or unsubstituted alkylcarbonyl group.

Specific examples of the compound in the present invention are shown in Table 1, but the present invention is not limited to these examples.

Table 1

  Next, the radical polymerization initiator (a) of the present invention will be described. The radical polymerization initiator of the present invention is characterized by comprising a compound having the structure represented by the general formula (1), and examples thereof include the same compounds as those mentioned above for the compound of the present invention. .

  In the radical polymerization initiator (a) of the present invention, preferred is a compound in which A in the general formula (1) is a substituted or unsubstituted carbazolyl group or a substituted or unsubstituted naphthyl group. In this case, a part of the substituents on the carbazolyl group and naphthyl group may be bonded to a carbon atom of the carbazolyl group or naphthyl group or a part of another substituent to form a ring structure together. In addition, the carbazolyl group and the naphthyl group may be bonded at any substitution position as long as they can form a covalent bond with the adjacent carbon atom of the general formula (1).

  The carbazolyl group and naphthyl group may be substituted with other substituents. Examples of such other substituents include the same substituents as those mentioned as the substituents that A and B may have. Can be mentioned. When A in the general formula (1) is a substituted or unsubstituted carbazolyl group or a substituted or unsubstituted naphthyl group, the availability of raw materials, the ease of synthesis, and details at present The reason for this is not clear, but it is preferable because the compound is decomposed by light irradiation and the efficiency of generating radicals is increased.

  In the compound represented by the general formula (1), it is more preferable that A in the general formula (1) is represented by the substituted or unsubstituted general formula (2) or the substituted or unsubstituted general formula (3). It is a compound that is a group. The groups represented by the general formula (2) and the general formula (3) are bonded at any substitution position as long as they can form a covalent bond with the adjacent carbon atom of the general formula (1). May be.

  In the general formula (2), Y represents a monovalent organic residue, and examples thereof include the same monovalent organic residues as in the above substituent X. Ease of availability of raw materials and easiness of synthesis From the viewpoint of improving the solubility in the solvent or resin used in combination, a substituted or unsubstituted alkyl group is preferred.

  The group represented by the general formula (2) and the group represented by the general formula (3) may be substituted with other substituents, and examples of such other substituents include A and B. Examples of the substituent are the same as those described above for the substituent that may be included. When A in the general formula (1) is a group represented by the general formula (2) which is substituted or unsubstituted, or the general formula (3) which is substituted or unsubstituted, the availability of raw materials and the synthesis The ease of treatment and the detailed reason are not clear at present, but it is preferable because the compound is decomposed by light irradiation and the efficiency of generating radicals is increased.

  In the compound represented by the general formula (1), it is more preferable that A in the general formula (1) is a group represented by the substituted or unsubstituted general formula (2), and B is a substituted or unsubstituted group. It is a compound which is group represented by General formula (3). In this case, although the detailed reason is not clear at present, the compound is decomposed by light irradiation, the efficiency of generating radicals is increased, and it functions as a more sensitive initiator.

  The other substituent in the group represented by the general formula (2) is preferably an acyl group, and more preferably a substituted or unsubstituted benzoyl group or a substituted or unsubstituted alkylcarbonyl group. When the group represented by the general formula (2) is substituted by these substituents, the compound is decomposed with a smaller amount of light irradiation, and it is preferable to generate radicals efficiently. However, the detailed reason is not clear.

  The starting material for the synthesis of the compound represented by the general formula (1) and the radical polymerization initiator (a) is an oxime represented by the following general formula (4).

General formula (4)

(In the formula, A and B are synonymous with the general formula (1).)

  The oxime represented by the general formula (4) is described in, for example, Org. React., 7, <1953>, 327, edited by The Chemical Society of Japan, 4th edition, Experimental Chemistry Course, Vol. 14, page 1316 (Maruzen). It can be obtained by various methods. Furthermore, it can also be obtained from a method for synthesizing oximes described in commercially available chemistry texts (for example, J. March, Advanced Organic Organic Chemistry, 4th Edition, Wiley Interscience, 1992). The β-diketone that is a starting material for oxime synthesis is, for example, Tetrahedron: Asymmetry, 14, <2003>, 2739, Chem. Ber., 113, <1980>, 1507, Helvetica Chimica Acta, 84, <2001 >, 2316, Organic Syntheses, Coll. Vol. III, pp 251; Bull. Chem. Soc. Jpn., 71, <1998>, 2253.

  One of the most convenient methods of synthesizing oximes is nitrosation of active methylene groups with nitrous acid or alkyl nitrites. The reaction conditions are, for example, Organic Syntheses Coll. Vol. VI, pp 840, Organic Syntheses Coll. Vol. III, pp 191 and 513, Organic Syntheses Coll. Vol. II, pp 202, 204 and 363, J. Am. Chem. Soc., 47, <1925>, 2033, J. Chem. Soc., 117, <1920>, 590, J. Am. Chem. Soc., 51, <1929>, 2264. Suitable for manufacturing. Nitrous acid is usually produced from sodium nitrite. The nitrite alkyl ester is, for example, methyl nitrite, isopropyl nitrite, butyl nitrite, isoamyl nitrite.

  The compound represented by the general formula (1) and the radical polymerization initiator (a) are prepared by a method described in the literature, for example, an oxime obtained by the method described above, using the oxime represented by the general formula (4) as a starting material. And an acyl chloride or anhydride and in an inert solvent such as tetrahydrofuran, benzene or dimethylformamide, in the presence of a base, for example a tertiary amine such as triethylamine, or in a basic solvent such as pyridine. Produced by reacting.

  Such reactions are known to those skilled in the art and are generally carried out at -15 ° C to + 50 ° C, preferably 0-30 ° C.

  All oxime ester groups exist in two configurations, (Z) or (E). The isomers can be separated by conventional methods, but mixtures of isomers can also be used as photoinitiating species. The invention therefore also relates to a mixture of configurational isomers of the compound of general formula (1).

The compound represented by the general formula (1) and the radical polymerization initiator (a) of the present invention can be identified by elemental analysis and ¹ H-NMR.

  Many of radical polymerization initiators composed of conventionally known α, α′-diketooxime ester compounds usually do not absorb at wavelengths longer than the ultraviolet region, and are therefore active against light from near ultraviolet to near infrared. Although it is scarce, the radical polymerization initiator (a) comprising the oxime ester compound represented by the general formula (1) of the present invention is obtained by introducing a heterocyclic group or a condensed polycyclic hydrocarbon group into A and B in the near ultraviolet region. It is possible to have an absorption band from the visible region to the visible region, and to have activity from the near ultraviolet region to a region having a longer wavelength than the visible region.

  Furthermore, in the radical polymerization initiator (a) represented by the general formula (1) of the present invention, since A and B are not the same, substituents having different absorption wavelength regions and absorption intensities can be combined. The wavelength region of the absorption band and the absorption intensity can be easily controlled. Moreover, it is possible to improve the solubility to the solvent and monomer used together.

  Next, the radically polymerizable compound (b) of the present invention will be described. The radical polymerizable compound (b) of the present invention is a compound having an ethylenically unsaturated bond capable of radical polymerization, and the compound having an ethylenically unsaturated bond capable of radical polymerization is an ethylene capable of radical polymerization in the molecule. Any compound having at least one ionic unsaturated bond may be used, and it may have a chemical form such as a monomer, an oligomer or a polymer. These may be used alone or may be a system in which two or more kinds are mixed at an arbitrary ratio in order to improve the intended characteristics.

  Examples of such a compound having an ethylenically unsaturated bond capable of radical polymerization include unsaturated carboxylic acids such as acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid and their salts, esters, Examples include urethane, amides and anhydrides, acrylonitrile, styrene, various unsaturated polyesters, unsaturated polyethers, unsaturated polyamides, unsaturated polyurethanes, and other radical polymerizable compounds, but the present invention is not limited thereto. It is not something.

  Specifically, 2-ethylhexyl acrylate, 2-hydroxyethyl acrylate, butoxyethyl acrylate, carbitol acrylate, cyclohexyl acrylate, tetrahydrofurfuryl acrylate, benzyl acrylate, bis (4-acryloxypolyethoxyphenyl) propane, neo Pentyl glycol diacrylate, 1,6-hexanediol diacrylate, ethylene glycol diacrylate, diethylene glycol diacrylate, triethylene glycol diacrylate, tetraethylene glycol diacrylate, polyethylene glycol diacrylate, polypropylene glycol diacrylate, pentaerythritol diacrylate , Pentaerythritol triacrylate, pentaerythritol Tetraacrylate, dipentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, trimethylolpropane triacrylate, tetramethylol methane tetraacrylate, oligoester acrylate, N-methylol acrylamide, diacetone acrylamide, epoxy acrylate, etc. Acrylic acid derivatives, methyl methacrylate, n-butyl methacrylate, 2-hexyl methacrylate, benzyl methacrylate, dimethylaminomethyl methacrylate, 1,6-hexanediol dimethacrylate, ethylene glycol dimethacrylate, triethylene glycol dimethacrylate, polyethylene glycol di Methacrylate, polypropylene Methacrylic acid derivatives such as recall dimethacrylate, trimethylolethane trimethacrylate, trimethylolpropane trimethacrylate, 2,2-bis (4-methacryloxypolyethoxyphenyl) propane, allyl glycidyl ether, diallyl phthalate, triallyl trimelli Derivatives of allyl compounds such as tate, etc., and more specifically, edited by Shinzo Yamashita et al., “Crosslinking Agent Handbook” (1981, Taiseisha), edited by Sato Kato, “UV / EB Curing Handbook (raw material) Ed.) "(1985, Polymer Press Society), edited by Radtech Research Group," Application and Market of UV / EB Curing Technology ", 79, (1989, CMC), Akamatsu Kiyoshi edited, Practical Technology of Resin Resin ”(1987, CMC), Shinichiro Takiyama,“ Polyester Resin Handbook ", (1988, Nikkan Kogyo Shimbun Co., Ltd.) or radically polymerizable or crosslinkable monomers, oligomers and polymers known in the industry.

  The amount of the radical polymerization initiator (a) used in the present invention is usually 0.01 to 60 parts by weight, preferably 0.01 to 30 parts by weight with respect to 100 parts by weight of the radical polymerizable compound (b). More preferably 0.1 to 10 parts by weight.

  In the polymerizable composition of the present invention, a sensitizer (c) can be added for the purpose of further promoting polymerization. A sensitizer increases the activity with respect to light from the ultraviolet to the near infrared region, and therefore it is preferable to add a sensitizer when it is necessary to promote polymerization.

  Specific examples of such sensitizers include unsaturated ketones typified by chalcone derivatives and dibenzalacetone, 1,2-diketone derivatives typified by benzyl and camphorquinone, benzoin derivatives, and fluorene derivatives. , Naphthoquinone derivatives, anthraquinone derivatives, xanthene derivatives, thioxanthene derivatives, xanthone derivatives, thioxanthone derivatives, coumarin derivatives, ketocoumarin derivatives, cyanine derivatives, merocyanine derivatives, oxonol derivatives and other polymethine dyes, acridine derivatives, azine derivatives, thiazine derivatives, Oxazine derivatives, indoline derivatives, azulene derivatives, azurenium derivatives, squarylium derivatives, porphyrin derivatives, tetraphenylporphyrin derivatives, triarylmethane derivatives, tetrabenzopo Filin derivatives, tetrapyrazinoporphyrazine derivatives, phthalocyanine derivatives, tetraazaporphyrazine derivatives, tetraquinoxalyloporphyrazine derivatives, naphthalocyanine derivatives, subphthalocyanine derivatives, pyrylium derivatives, thiopyrylium derivatives, tetraphyrin derivatives, annulene derivatives, spiropyran derivatives , Spirooxazine derivatives, thiospiropyran derivatives, carbazole derivatives, metal arene complexes, organoruthenium complexes, Michler's ketone derivatives, etc. Other specific examples include Ogahara Shin et al., “Dye Handbook” (1986, Kodansha), Okawara Sensitizers described in Shin et al., "Chemicals of Functional Dyes" (1981, CMC), edited by Tadasaburo Ikemori et al., "Special Functional Materials" (1986, CMC) However, the present invention is not limited to these, and other sensitizers that absorb light from the ultraviolet to the near-infrared region can be used, and these may be used in an arbitrary ratio as needed. . Among the sensitizers, examples of the sensitizer capable of particularly suitably sensitizing the photopolymerization initiator of the present invention include thioxanthone derivatives and Michler ketone derivatives. More specifically, 2,4-diethylthioxanthone, 2-chlorothioxanthone, 2,4-dichlorothioxanthone, 2-isopropylthioxanthone, 4-isopropylthioxanthone, 1-chloro-4-propoxythioxanthone, 4,4′-bis Examples thereof include (dimethylamino) benzophenone and 4,4′-bis (diethylamino) benzophenone, but are not limited thereto.

  The ratio of the radical polymerization initiator (a) and the sensitizer (c) represented by the general formula (1) is arbitrary, but is preferably in the range of 100/1 to 1/100 (weight ratio), more preferably It is in the range of 50/1 to 1/50, more preferably in the range of 20/1 to 1/30.

  The polymerizable composition of the present invention can be used by mixing with a binder such as an organic polymer and applying it to a polymer film such as a glass plate, an aluminum plate, another metal plate, or polyethylene terephthalate.

  Examples of binders that can be used by mixing with the polymerizable composition of the present invention include polyacrylates, poly-α-alkyl acrylates, polyamides, polyvinyl acetals, polyformaldehydes, polyurethanes, polycarbonates, polystyrenes, Examples thereof include polymers and copolymers such as polyvinyl esters, and more specifically, polymethacrylate, polymethyl methacrylate, polyethyl methacrylate, polyvinyl carbazole, polyvinyl pyrrolidone, polyvinyl butyral, polyvinyl acetate, novolac resin, phenol resin, Epoxy resin, alkyd resin, etc., supervised by Kiyoshi Akamatsu, “New Photosensitive Resin Technology” (1987, CMC) and “10188 Chemical Products”, pages 657-767 (1988, Chemical Industries Day) Inc.) industry known organic polymer according the like.

  Furthermore, the polymerizable composition of the present invention may be used by adding the following carboxyl group-containing polymer for the purpose of use as a photoresist material for image formation. Since the carboxyl group-containing polymer has solubility in an alkaline aqueous solution, if the film prepared using the photopolymerizable composition of the present invention is partially cured, a so-called negative resist pattern is formed due to the difference in solubility in the alkaline aqueous solution. Can be formed. Here, the carboxyl group-containing polymer includes a copolymer of acrylic acid ester or methacrylic acid ester and acrylic acid, or a copolymer of methacrylic acid ester, methacrylic acid and a vinyl monomer copolymerizable therewith. . These copolymers may be used alone or in combination of two or more.

  Here, as the methacrylic acid ester, methyl acrylate, ethyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, isobornyl acrylate, methyl methacrylate, ethyl methacrylate, butyl methacrylate, 2-ethylhexyl methacrylate, isobornyl methacrylate, etc. Is mentioned.

  Methacrylic acid ester, methacrylic acid and vinyl monomers copolymerizable therewith include tetrahydrofurfuryl acrylate, dimethylaminoethyl acrylate, glycidyl acrylate, 2,2,2-trifluoroethyl acrylate, 2,2,3, Examples include 3-tetrafluoropropyl acrylate, tetrahydrfurfuryl methacrylate, dimethylaminoethyl methacrylate, glycidyl methacrylate, 2,2,2-trifluoroethyl methacrylate, acrylamide, and styrene.

  The polymerizable composition of the present invention can be used in combination with other polymerization initiators for the purpose of further improving sensitivity.

  Examples of other polymerization initiators that can be used in combination with the polymerizable composition of the present invention include triazine derivatives described in JP-B-59-1281, JP-B-61-9621, and JP-A-60-60104. Organic peroxides described in JP-A-59-1504 and JP-A-61-243807, JP-B-43-23684, JP-B-44-6413, JP-B-47-1604 and USP No. 3567453, diazonium compound publication, USP 2,848,328, USP 2,852,379 and USP 2,940,853, organic azide compounds, Japanese Patent Publication No. 36-22062, Japanese Patent Publication No. 37-13109 Disclosed in Japanese Patent Publication No. SHO 38-18015 and SHO 45-9610. Luto-quinonediazides, including iodonium compounds described in JP-B-55-39162, JP-A-59-140203 and “MACROMOLECULES”, Vol. 10, page 1307 (1977) Various onium compounds, azo compounds described in JP-A-59-142205, JP-A-1-54440, European Patent No. 109851, European Patent No. 126712, “Journal of Imaging Science” (J.IMAG.SCI.), Vol. 30, page 174 (1986), titanocenes described in JP-A No. 61-151197, “COORDINATION CHEMISTRY REVIEW 84), 85-277 (1988) and JP-A-2- Transition metal complexes containing transition metals such as ruthenium described in 82701, Aluminate complexes described in JP-A-3-209477, Borate compounds described in JP-A-2-157760, JP-A-55-127550 And 2,4,5-triarylimidazole dimer described in JP-A-60-202437, carbon tetrabromide and organic halogen compounds described in JP-A-59-107344, JP-A-5-255347. Sulfonium complexes or oxosulfonium complexes described in JP-A No. 54-99185, aminoketone compounds described in JP-A No. 54-99185 and JP-A No. 63-264560, JP-A No. 2001-264530, JP-A No. 2001-261661, JP 2000-80068, JP 2001-233842, special table The oxime ester compounds described in 2004-534797, USP3558309 (1971), USP4202697 (1980) and JP61-24558 are listed, and these polymerization initiators are radical polymerizations. It is preferably contained in the range of 0.01 to 10 parts by weight with respect to 100 parts by weight of the compound having a possible ethylenically unsaturated bond.

  In addition, a thermal polymerization inhibitor can be added to the polymerizable composition of the present invention for the purpose of preventing polymerization during storage.

  Specific examples of the thermal polymerization inhibitor that can be added to the polymerizable composition of the present invention include p-methoxyphenol, hydroquinone, alkyl-substituted hydroquinone, catechol, tert-butylcatechol, phenothiazine, and the like. The polymerization inhibitor is preferably added in the range of 0.001 to 5 parts by weight with respect to 100 parts by weight of the compound having an ethylenically unsaturated bond capable of radical polymerization.

  The polymerizable composition of the present invention can further contain a polymerization accelerator represented by amine, thiol, disulfide and the like, a chain transfer catalyst, etc. for the purpose of further promoting the polymerization.

  Specific examples of the polymerization accelerator and chain transfer catalyst that can be added to the polymerizable composition of the present invention include, for example, amines such as N-phenylglycine, triethanolamine, N, N-diethylaniline, USP No. 4414312 Thiols described in the specification, JP-A No. 64-13144, disulfides described in JP-A No. 2-291561, thiones described in USP No. 3558322 and JP-A No. 64-17048, Examples include O-acylthiohydroxamate and N-alkoxypyridinethiones described in JP-A-2-291560.

The polymerizable composition of the present invention can be used by adding a solvent for the purpose of improving workability during coating and film formation. The added solvent can be substantially removed by heat drying or vacuum drying after coating. Specific examples of the solvent that can be added to the polymerizable composition of the present invention include, for example, ketones such as methyl ethyl ketone, cyclohexanone, 2-heptanone, and 3-heptanone; ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol (Poly) alkylene glycol monoalkyl ether acetates such as monomethyl ether acetate, diethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate;
Ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol mono-n-propyl ether, ethylene glycol mono-n-butyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol mono-n-propyl ether, ethylene glycol mono-n -Butyl ether, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol mono-n-propyl ether, propylene glycol mono-n-butyl ether, dipropylene glycol monomethyl ether, Dipropylene glycol monoe Ether, dipropylene glycol mono -n- propyl ether, dipropylene glycol mono -n- butyl ether, tripropylene glycol monomethyl ether, tripropylene glycol monoethyl (poly) alkylene glycol monoalkyl ethers such as ether;
Ethyl acetate, n-butyl acetate, isobutyl acetate, amyl formate, isoamyl acetate, butyl propionate, ethyl butyrate, isopropyl butyrate, butyl butyrate, methyl lactate, ethyl lactate, methyl oxyacetate, ethyl oxyacetate, butyl oxyacetate, methoxy Esters such as methyl acetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, methyl 3-oxypropionate, ethyl 3-oxypropionate, methyl 3-methoxypropionate, 3-methoxypropionic acid Ethyl, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, methyl 2-oxypropionate, ethyl 2-oxypropionate, propyl 2-oxypropionate, methyl 2-methoxypropionate, 2-methoxypropionic acid Til, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate, methyl 2-oxy-2-methylpropionate, ethyl 2-oxy-2-methylpropionate, 2-methoxy-2 -Methyl methyl propionate, ethyl 2-methoxy-2-methylpropionate, methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, methyl 2-oxobutanoate, ethyl 2-oxobutanoate, etc. Esters;
Aromatic hydrocarbons such as toluene and xylene, and amides such as N-methylpyrrolidone and N, N-dimethylacetamide can be exemplified.

  These solvents can be used alone or in admixture of two or more.

  Further, the polymerizable composition of the present invention can be used depending on the purpose, such as dyes, organic and inorganic pigments, phosphine, phosphonate, phosphite and other oxygen scavengers and reducing agents, antifoggants, antifading agents, antihalation agents, fluorescent enhancers. Whitening agents, surfactants, colorants, extenders, plasticizers, flame retardants, antioxidants, UV absorbers, foaming agents, fungicides, antistatic agents, magnetic substances and other additives that impart various properties Further, it may be used by mixing with a diluting solvent or the like.

  In the polymerization reaction, the polymerizable composition of the present invention can be polymerized by application of energy such as ultraviolet rays, visible rays, near infrared rays, electron beams, etc. to obtain a desired polymer. The definitions of ultraviolet rays, near-ultraviolet rays, visible light, near-infrared rays, infrared rays, and the like referred to in this specification are based on “Iwanami Rikagaku Dictionary 4th Edition” (1987, Iwanami) edited by Ryogo Kubo et al.

  Therefore, the polymerizable composition of the present invention includes a low pressure mercury lamp, a medium pressure mercury lamp, a high pressure mercury lamp, an ultrahigh pressure mercury lamp, a xenon lamp, a carbon arc lamp, a metal halide lamp, a fluorescent lamp, a tungsten lamp, an argon ion laser, a helium cadmium laser, and helium. Neon laser, krypton ion laser, various semiconductor lasers, YAG laser, light emitting diode, CRT light source, plasma light source, electron beam, gamma ray, ArF excimer laser, KrF excimer laser, F2 laser, etc. Polymer or cured product can be obtained.

  Therefore, various inks, various printing plate materials, photoresists, electrophotography, direct printing plate materials, photosensitive materials such as hologram materials and various recording media such as microcapsules, and adhesives, which are coated on a substrate together with a binder and the like, It can be applied to pressure-sensitive adhesives, adhesives, sealants and various paints.

  EXAMPLES Hereinafter, although an Example and a comparative example are shown and this invention is demonstrated in detail, this invention is not limited only to the following.

  Table 2 shows the compounds used in Examples and Comparative Examples.

Table 2

Example 1
Synthesis of Compound (111) 1-Furan-2-yl-3-thiophen-2-yl-propane-1,3-dione (20.0 g, 90.8 mmol) was dissolved in a mixed solution of 200 ml of tetrahydrofuran and 100 ml of concentrated hydrochloric acid. Thereto, 11.24 g (109 mmol) of tert-butyl nitrite was added dropwise over 1 hour with stirring at room temperature. After completion of dropping, the mixture was stirred at room temperature for 5 hours. The reaction solution was poured into 500 ml of ice water and extracted with 500 ml of chloroform. The organic layer was washed with water (300 ml × 3 times), dried over magnesium sulfate, the desiccant was filtered off, the solvent was distilled off, and the residue was washed with n-hexane to give 1-furan-2-yl. 22.3 g of -3-thiophen-2-yl-propane-1,2,3-trione-2-oxime was obtained (yield 93.6%).

  Next, 15.0 g (60.2 mmol) of 1-furan-2-yl-3-thiophen-2-yl-propane-1,2,3-trione-2-oxime and 4.94 g (60.2 mmol) of sodium acetate ) Was stirred in 250 ml of benzene, 7.37 g (72.2 mmol) of acetic anhydride was added, and the mixture was heated to reflux for 3 hours. Thereafter, the reaction solution is poured into 300 ml of ice water, the composition organism is extracted with ethyl acetate, the organic layer is washed with water (200 ml × 3 times), dried over magnesium sulfate, the desiccant is filtered, and the solvent is distilled off. The residue was recrystallized from ethyl acetate-hexane to obtain 16.1 g of compound (111) (yield 92.1%).

Example 2
Synthesis of Compound (112) 1- (4-Methoxy-naphthalen-1-yl) -3-thiophen-2-yl-propane-1,3-dione (18.0 g, 58.0 mmol) in tetrahydrofuran (180 ml) and concentrated hydrochloric acid (90 ml) Then, 7.18 g (69.7 mmol) of tert-butyl nitrite was added dropwise over 30 minutes with stirring at room temperature. After completion of dropping, the mixture was stirred at room temperature for 6 hours. The reaction solution was poured into 500 ml of ice water and extracted with 500 ml of chloroform. The organic layer was washed with water (300 ml × 3 times), dried over magnesium sulfate, the desiccant was filtered off to remove the solvent, and the residue was recrystallized from dichloromethane-hexane to give 1- (4-methoxy -Naphthalen-1-yl) -3-thiophen-2-yl-propane-1,2,3-trione-2-oxime 18.6 g was obtained (yield 94.6%).

  Next, 15.0 g (44.2 mmol) of 1- (4-methoxy-naphthalen-1-yl) -3-thiophen-2-yl-propane-1,2,3-trione-2-oxime and sodium acetate 3 To a stirred solution of .63 g (44.2 mmol) in 300 ml of benzene, 5.41 g (53.0 mmol) of acetic anhydride was added and heated to reflux for 3 hours. Thereafter, the reaction solution is poured into 300 ml of ice water, the composition organism is extracted with ethyl acetate, the organic layer is washed with water (200 ml × 3 times), dried over magnesium sulfate, the desiccant is filtered, and the solvent is distilled off. The residue was recrystallized from ethyl acetate-hexane to obtain 16.4 g of compound (112) as pale yellow crystals (yield 97.3%).

Example 3
Synthesis of Compound (113) 1- (9,9-Dihexyl-9H-fluoren-2-yl) -3- (9,10-dimethoxyphenanthren-2-yl) -propane-1,3-dione 22.0 g ( 34.3 mmol) was dissolved in a mixed solution of 260 ml of tetrahydrofuran and 180 ml of concentrated hydrochloric acid, and 4.25 g (41.2 mmol) of tert-butyl nitrite was added dropwise over 30 minutes with stirring at room temperature. After completion of dropping, the mixture was stirred at room temperature for 8 hours. The reaction solution was poured into 1 L of ice water and extracted with 800 ml of chloroform. The organic layer was washed with water (500 ml × 3 times), dried over magnesium sulfate, the desiccant was filtered to remove the solvent, and the residue was recrystallized from chloroform-hexane to give 1- (9,9 -Dihexyl-9H-fluoren-2-yl) -3- (9,10-dimethoxyphenanthren-2-yl) -propane-1,2,3-trione-2-oxime 18.4 g (yield 80) .2%).

  Next, 1- (9,9-dihexyl-9H-fluoren-2-yl) -3- (9,10-dimethoxyphenanthren-2-yl) -propane-1,2,3-trione-2-oxime 16 To a stirred solution of 0.0g (23.9 mmol) and 1.96 g (23.9 mmol) of sodium acetate in 300 ml of benzene, 2.93 g (28.7 mmol) of acetic anhydride was added and heated to reflux for 5 hours. Thereafter, the reaction solution is poured into 300 ml of ice water, the composition organism is extracted with ethyl acetate, the organic layer is washed with water (200 ml × 3 times), dried over magnesium sulfate, the desiccant is filtered, and the solvent is distilled off. The residue was recrystallized from ethyl acetate-hexane to obtain 13.4 g of compound (113) as yellow crystals (yield 78.9%).

Example 4
Synthesis of Compound (114) 1- (4,6-Bis-dimethylamino- [1,3,5] triazin-2-yl) -3- (9-ethyl-9H-carbazol-3-yl) -propane- When 20.0 g (46.5 mmol) of 1,3-dione was dissolved in a mixed solution of 200 ml of tetrahydrofuran and 100 ml of concentrated hydrochloric acid, 5.75 g (55.7 mmol) of tert-butyl nitrite was added for 40 minutes while stirring at room temperature. It was dripped over. After completion of dropping, the mixture was stirred at room temperature for 5 hours. The reaction solution was poured into 500 ml of ice water and extracted with 500 ml of chloroform. The organic layer was washed with water (200 ml × 3 times), dried over magnesium sulfate, the desiccant was filtered to remove the solvent, and the residue was recrystallized from dichloromethane-hexane to give 1- (4,6 -Bis-dimethylamino- [1,3,5] triazin-2-yl) -3- (9-ethyl-9H-carbazol-3-yl) -propane-1,2,3-trione-2-oxime 18 0.8 g was obtained (yield 88.1%).

  Next, 1- (4,6-bis-dimethylamino- [1,3,5] triazin-2-yl) -3- (9-ethyl-9H-carbazol-3-yl) -propane-1,2 , 3-trione-2-oxime 13.5 g (29.4 mmol) and sodium acetate 2.41 g (29.4 mmol) were stirred in 240 ml of benzene, and 3.60 g (35.3 mmol) of acetic anhydride was added. And heated to reflux for 4 hours. Thereafter, the reaction solution is poured into 300 ml of ice water, the composition organism is extracted with ethyl acetate, the organic layer is washed with water (200 ml × 3 times), dried over magnesium sulfate, the desiccant is filtered, and the solvent is distilled off. The residue was reprecipitated with ethyl acetate-hexane to obtain 13.7 g of compound (114) as a yellow powder (yield 93.2%).

Example 5
Synthesis of Compound (115) 1-Benzo [b] thiophen-2-yl-3-quinolin-4-yl-propane-1,3-dione (17.2 g, 51.9 mmol) was mixed with 320 ml of tetrahydrofuran and 160 ml of concentrated hydrochloric acid. To the solution, 6.42 g (62.3 mmol) of tert-butyl nitrite was added dropwise over 30 minutes with stirring at room temperature. After completion of dropping, the mixture was stirred at room temperature for 5 hours. The reaction solution was poured into 1 L of ice water and extracted with 650 ml of chloroform. The organic layer was washed with water (400 ml × 3 times), dried over magnesium sulfate, the desiccant was filtered to remove the solvent, and the residue was recrystallized from chloroform-hexane to give 1-benzo [b]. 16.0 g of thiophen-2-yl-3-quinolin-4-yl-propane-1,2,3-trione-2-oxime was obtained (yield 85.6%).

  Next, 12.0 g (33.3 mmol) of 1-benzo [b] thiophen-2-yl-3-quinolin-4-yl-propane-1,2,3-trione-2-oxime and 2.73 g of sodium acetate (33.3 mmol) was stirred in 240 ml of benzene, 4.08 g (40.0) of acetic anhydride was added, and the mixture was heated to reflux for 5 minutes. Thereafter, the reaction solution is poured into 300 ml of ice water, the composition organism is extracted with ethyl acetate, the organic layer is washed with water (200 ml × 3 times), dried over magnesium sulfate, the desiccant is filtered, and the solvent is distilled off. The residue was recrystallized from ethyl acetate-hexane to obtain 12.2 g of compound (115) as pale yellow crystals (yield 91.1%).

Example 6
Synthesis of Compound (116) 1-Naphthalen-2-yl-3- (2-oxo-2H-chromen-3-yl) -propane-1,3-dione (25.0 g, 73.0 mmol) was concentrated with 250 ml of tetrahydrofuran. To a solution dissolved in 125 ml of hydrochloric acid, 9.04 g (87.6 mmol) of tert-butyl nitrite was added dropwise over 1 hour with stirring at room temperature. After completion of dropping, the mixture was stirred at room temperature for 3 hours. The reaction solution was poured into 1 L of ice water and extracted with 1 L of chloroform. The organic layer was washed with water (600 ml × 3 times), dried over magnesium sulfate, the desiccant was filtered to remove the solvent, and the residue was recrystallized from dichloromethane-hexane to give 1-naphthalene-2- 25.8 g of yl-3- (2-oxo-2H-chromen-3-yl) -propane-1,2,3-trione-2-oxime was obtained (yield 95.2%).

  Next, 20.0 g (53.9 mmol) of 1-naphthalen-2-yl-3- (2-oxo-2H-chromen-3-yl) -propane-1,2,3-trione-2-oxime and acetic acid To a stirred solution of 4.42 g (53.9 mmol) of sodium in 400 ml of benzene, 6.60 g (64.6 mmol) of acetic anhydride was added and heated to reflux for 6 hours. Thereafter, the reaction solution is poured into 500 ml of ice water, the composition organism is extracted with ethyl acetate, the organic layer is washed with water (300 ml × 3 times), dried over magnesium sulfate, the desiccant is filtered, and the solvent is distilled off. The residue was recrystallized from ethyl acetate-hexane to obtain 21.0 g of compound (116) as pale yellow crystals (yield 94.4%).

Example 7
Synthesis of Compound (117) 1- (9-Ethyl-9H-carbazol-3-yl) -3-naphthalen-1-yl-propane-1,3-dione 15.0 g (38.3 mmol) was concentrated with tetrahydrofuran 150 ml. To a solution dissolved in 75 ml of hydrochloric acid, 4.74 g (46.0 mmol) of tert-butyl nitrite was added dropwise over 15 minutes with stirring at room temperature. After completion of dropping, the mixture was stirred at room temperature for 24 hours. The reaction solution was poured into 500 ml of ice water and extracted with 500 ml of chloroform. The organic layer was washed with water (200 ml × 2 times), dried over magnesium sulfate, the desiccant was filtered to remove the solvent, and the residue was recrystallized from chloroform-hexane to give 1- (9-ethyl). -9H-carbazol-3-yl) -3-naphthalen-1-yl-propane-1,2,3-trione-2-oxime (14.2 g, yield 88.3%) was obtained.

  Next, 10.0 g (23.8 mmol) of 1- (9-ethyl-9H-carbazol-3-yl) -3-naphthalen-1-yl-propane-1,2,3-trione-2-oxime and acetic acid 1.95 g (23.8 mmol) of sodium was stirred in 200 ml of benzene, 2.9 g (28.4 mmol) of acetic anhydride was added, and the mixture was heated to reflux for 5 hours. Thereafter, the reaction solution is poured into 300 ml of ice water, the composition organism is extracted with ethyl acetate, the organic layer is washed with water (150 ml × twice), dried over magnesium sulfate, the desiccant is filtered off and the solvent is distilled off. The residue was recrystallized from dichloromethane-hexane to obtain 8.7 g of compound (117) as a pale yellow powder (yield 79.0%).

Example 8
Synthesis of Compound (118) 1- [9-Ethyl-6- (2-methyl-benzoyl) -9H-carbazol-3-yl] -3-naphthalen-1-yl-propane-1,3-dione 20.0 g (39.2 mmol) was dissolved in a mixed solution of 200 ml of tetrahydrofuran and 100 ml of concentrated hydrochloric acid, and 4.86 g (47.1 mmol) of tert-butyl nitrite was added dropwise over 20 minutes with stirring at room temperature. After completion of dropping, the mixture was stirred at room temperature for 10 hours. The reaction solution was poured into 700 ml of ice water and extracted with 600 ml of chloroform. The organic layer was washed with water (2 x 300 ml), the solvent was distilled off, and the residue was recrystallized from chloroform-hexane to give 1- [9-ethyl-6- (2-methyl-benzoyl) -9H- 19.3 g of carbazol-3-yl] -3-naphthalen-1-yl-propane-1,2,3-trione-2-oxime was obtained (yield 91.3%).

  Next, 1- [9-ethyl-6- (2-methyl-benzoyl) -9H-carbazol-3-yl] -3-naphthalen-1-yl-propane-1,2,3-trione-2-oxime When 17.0 g (31.6 mmol) and 2.59 g (31.6 mmol) of sodium acetate were stirred in 340 ml of benzene, 3.86 g (37.8 mmol) of acetic anhydride was added and heated to reflux for 4 hours. Thereafter, the reaction solution is poured into 700 ml of ice water, the composition organism is extracted with ethyl acetate, the organic layer is washed with water (300 ml × 2 times), dried over sodium sulfate, the desiccant is filtered off and the solvent is distilled off. The residue was recrystallized from chloroform-hexane to obtain 17.4 g of compound (118) as pale yellow crystals (yield 95.1%).

Table 3 shows the results of elemental analysis of the radical polymerization initiators of the present invention synthesized in Examples 1 to 8 above.

Examples 9-16
6 parts by weight of the compound shown in Table 4 as the radical polymerization initiator (a) of the present invention, 100 parts by weight of pentaerythritol triacrylate as the radical polymerizable compound (b), and polymethyl acrylate (weight average molecular weight of about 30000, number average as the binder) A molecular weight of about 10,000) 100 parts by weight and 1600 parts by weight of cyclohexanone as a solvent were blended to prepare a coating solution. This coating solution was applied onto a stainless steel plate using a spin coater and dried in an oven at 40 ° C. for 10 minutes. The film thickness after removing the solvent by drying was 1.5 μm. While irradiating light (9.0 mW / cm ² ) of a high-pressure mercury lamp through a band-pass filter that selectively transmits light of 350 to 380 nm to this coating film, the IR spectrum of the polymerizable composition The (reflection) was measured, and the intensity at 810 cm ⁻¹ , which is the characteristic absorption of the acrylic group, was monitored. Table 4 shows the result of calculation based on the IR measurement result, with respect to the ratio of acrylic groups consumed by polymerization at the time point 15 seconds after the start of light irradiation, based on the pre-light irradiation.

Comparative Examples 1-3
6 parts by weight of a compound shown in Table 4 as a radical polymerization initiator, 100 parts by weight of pentaerythritol triacrylate as a radical polymerizable compound, 100 parts by weight of polymethyl methacrylate (weight average molecular weight of about 30,000, number average molecular weight of about 10,000) as a binder, solvent 1600 parts by weight of cyclohexanone was blended to prepare a coating solution. Table 4 shows the results of calculating the consumption rate of the acrylic monomer at the time point 15 seconds after the start of light irradiation by forming this coating liquid under the same procedures and conditions as in Examples 9 to 16 and irradiating with light. It was.

Table 4

  The polymerizable composition (Examples 9 to 16) using the radical polymerization initiator of the present invention is a case where a known α, α'-diketooxime ester is used as a radical polymerization initiator (Comparative Examples 1 to 3). Rather than that, radicals are efficiently generated by light irradiation to polymerize acrylic groups. That is, the α, α′-diketooxime ester compound represented by the general formula (1) of the present invention, which has a heterocyclic group or a condensed polycyclic hydrocarbon group at the 1-position and the 3-position By using as a radical polymerization initiator, high sensitivity can be achieved.

Examples 17-31
5 parts by weight of the compound shown in Table 5 as the radical polymerization initiator (a) of the present invention, 100 parts by weight of pentaerythritol triacrylate as the radical polymerizable compound (b), and the compound (122) or compound (c) as the sensitizer (c) 123) was mixed with 0 or 1 part by weight, 100 parts by weight of polymethyl acrylate (weight average molecular weight of about 30,000, number average molecular weight of about 10,000) as a binder, and 1600 parts by weight of cyclohexanone as a solvent to prepare a coating solution. This coating solution was applied onto a stainless steel plate using a spin coater and dried in an oven at 40 ° C. for 10 minutes. The film thickness after removing the solvent by drying was 1.5 μm. The IR spectrum of the polymerizable composition was irradiated to the coated film while irradiating light (10.0 mW / cm ² ) of a high-pressure mercury lamp through a bandpass filter that selectively transmits light of 350 to 380 nm. The (reflection) was measured, and the intensity at 810 cm ⁻¹ , which is the characteristic absorption of the acrylic group, was monitored. Based on the IR measurement results, the ratio of acrylic groups consumed by polymerization at the time 10 seconds after the start of light irradiation (light irradiation amount: 100 mJ / cm ² ) was calculated based on the pre-light irradiation. Are shown in Table 5.

Comparative Examples 4-6
5 parts by weight of a compound shown in Table 5 as a radical polymerization initiator, 100 parts by weight of pentaerythritol triacrylate as a radical polymerizable compound, 0 or 1 part by weight of a compound (122) or compound (123) as a sensitizer, and poly as a binder 100 parts by weight of methyl acrylate (weight average molecular weight of about 30,000, number average molecular weight of about 10,000) and 1600 parts by weight of cyclohexanone as a solvent were blended to prepare a coating solution. Depositing the coating solution in the same procedure and conditions as in Example 17-31, and light irradiation, consumption rate of the acrylic monomer at the time of 10 seconds after the light irradiation start (amount of light irradiation 100 mJ / cm ²⁾ The results of calculating are shown in Table 5.

Table 5

The polymerizable compositions (Examples 17, 20, 23, 26 and 29) using the radical polymerization initiator of the present invention generate radicals with a small exposure amount of 100 mJ / cm ² and polymerize acrylic groups. It is a highly sensitive polymerizable composition. Furthermore, in Examples 18, 19, 21, 22, 24, 25, 27, 28, 30 and 31, which contain a sensitizer in the polymerizable composition, Examples in which no sensitizer is contained in the polymerizable composition Compared with 17, 20, 23, 26 and 29, the polymerization sensitivity is improved. In addition, Examples 17 to 31 of the present invention clearly have higher sensitivity than Comparative Examples 4 to 6 using a known α, α′-diketooxime ester as a radical polymerization initiator. That is, the polymerizable composition of the present invention is highly sensitive even if it does not contain a sensitizer, but it can be a more sensitive polymerizable composition by using a sensitizer together.

The present invention relates to a novel oxime ester compound, a highly sensitive radical polymerization initiator, and a polymerizable composition, such as ink, paint, photosensitive printing plate, proof material, photoresist, hologram material, and sealant. In addition, it can be a material for quickly and reliably obtaining a cured product having good physical properties in the fields of overcoat material, resin for optical modeling, adhesive, various devices and the like.

Claims (7)

A compound represented by the following general formula (1).
General formula (1)

(In the formula, A and B each independently represent a substituted or unsubstituted heterocyclic group, or a substituted or unsubstituted condensed polycyclic hydrocarbon group,
X represents a monovalent organic residue.
However, A and B are never the same. ) The compound according to claim 1, wherein A is a substituted or unsubstituted carbazolyl group or a substituted or unsubstituted naphthyl group.
(However, a part of substituents on the carbazolyl group and naphthyl group may be bonded to a carbon atom of the carbazolyl group or naphthyl group or a part of other substituents to form a ring structure together. .) The compound according to claim 1, wherein A is a group represented by the following general formula (2) which is substituted or unsubstituted, or a general formula (3) which is substituted or unsubstituted.
General formula (2)

General formula (3)

(In general formula (2), Y represents a monovalent organic residue.) The compound according to claim 1, wherein A is a group represented by the following general formula (2) which is substituted or unsubstituted, and B is a group represented by the following general formula (3) which is substituted or unsubstituted.
General formula (2)

General formula (3)

(In general formula (2), Y represents a monovalent organic residue.) A radical polymerization initiator (a) comprising the compound according to claim 1. A polymerizable composition comprising the radical polymerization initiator (a) according to claim 5 and a radical polymerizable compound (b). The polymerizable composition according to claim 6, further comprising a sensitizer (c).