JP5023495B2 - Radical polymerization initiator and polymerizable composition - Google Patents

Description

  The present invention relates to a novel 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 radical polymerization initiator for obtaining a polymer having good physical properties in the field and a polymerizable composition using the same.

  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 highly sensitive radical polymerization initiator capable of efficiently generating active radicals upon irradiation with energy rays, particularly light, and capable of polymerizing a radical polymerizable compound in a short time, and a curable composition using the same. Is to propose. 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 and a polymerizable composition using the same to obtain a cured product having good characteristics.

（式中、Ｘは複素環基を表し、
Ｙは置換基を有してもよいアルキル基、置換基を有してもよいアリール基、置換基を有してもよいアルケニル基、置換基を有してもよいアルキニル基、置換基を有してもよいアルコキシ基、置換基を有してもよいアリールオキシ基、置換基を有してもよい複素環オキシ基、置換基を有してもよいアシルオキシ基、置換基を有してもよいアルキルスルファニル基、置換基を有してもよいアリールスルファニル基、置換基を有してもよいアルキルスルフィニル基、置換基を有してもよいアリールスルフィニル基、置換基を有してもよいアルキルスルホニル基、置換基を有してもよいアリールスルホニル基、置換基を有してもよいアシル基、置換基を有してもよいアルコキシカルボニル基、置換基を有してもよいカルバモイル基、置換基を有してもよいスルファモイル基、置換基を有してもよいアミノ基、置換基を有してもよいホスフィノイル基、または、置換基を有してもよい複素環基を表わす。
ただし、２つのＸは同一の複素環基を表わす。） 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)

(Wherein X represents a heterocyclic group,
Y has an alkyl group which may have a substituent, an aryl group which may have a substituent, an alkenyl group which may have a substituent, an alkynyl group which may have a substituent, and a substituent. 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, and a substituent. Good alkylsulfanyl group, arylsulfanyl group which may have a substituent, alkylsulfinyl group which may have a substituent, arylsulfinyl group which may have a substituent, alkyl which may have a substituent Sulfonyl group, arylsulfonyl group which may have a substituent, acyl group which may have a substituent, alkoxycarbonyl group which may have a substituent, carbamoyl group which may have a substituent, substituted Even if it has a group There sulfamoyl group, an optionally substituted amino group, an optionally substituted phosphinoyl group, or a heterocyclic group which may have a substituent.
However, two X represent the same heterocyclic group. )

  The present invention also relates to a radical polymerization initiator 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).

  Moreover, this invention relates to the said polymeric composition which further contains a sensitizer (c).

  The radical polymerization initiator of the present invention is an α, α′-diketooxime ester compound having the same heterocyclic group at the 1-position and the 3-position, and is irradiated with energy rays, particularly light. Generates active radicals efficiently. 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 radical polymerization initiator (a) of the present invention will be described. The radical polymerization initiator of the present invention is characterized by having a structure represented by the general formula (1). In general formula (1), X represents a heterocyclic group.

  In the general formula (1), examples of the heterocyclic group represented by X include a substituted or unsubstituted aromatic or aliphatic heterocyclic group containing a nitrogen atom, an oxygen atom, a sulfur atom, or a phosphorus atom. As 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, isobenzo Furanyl 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-quinolizini 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, phenanthridinyl group 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, thioxyl group Santolyl group, 4-quinolinyl group, 4-isoquinolyl group, 3-phenothiazinyl group, 2-phenoxathiinyl 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.

  The hydrogen atom of the heterocyclic group represented by X described above may be further substituted with other substituents. Examples of such other substituents include a hydroxyl group, a mercapto group, a cyano group, a nitro group, a halogen atom. Atom, alkyl group, aryl group, heterocyclic group, acyl 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, a 9-phenanthryl group, Examples include 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.

  Examples of the arylamino group include an N-arylamino group, 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 diarylamino group, 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 substituent in X may form a cyclic structure together with another substituent or a hydrogen atom on the ring.

  Alternatively, the 1-position X and the 3-position X may be integrated to form an annular structure.

The substituent Y in the general formula (1) has an alkyl group which may have a substituent, an aryl group which may have a substituent, an alkenyl group which may have a substituent, and a substituent. An alkynyl group which may have a substituent, an aryloxy group which may have a substituent, a heterocyclic oxy group which may have a substituent, an acyloxy which may have a substituent A group, an alkylsulfanyl group which may have 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, an arylsulfonyl group which may have a substituent, an acyl group which may have a substituent, an alkoxycarbonyl group which may have a substituent, a substituent; Carbamoy that you may have It represents groups, which may have a substituent sulfamoyl group, an optionally substituted amino group, an optionally substituted phosphinoyl group, or an optionally substituted heterocyclic group .

  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, 3-nitrophenac And the like.

  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 group Aryloxy 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.

Specific examples of the radical polymerization initiator (a) in the present invention are shown in Table 1, but the present invention is not limited to these examples.

  The starting material when synthesizing the compound represented by the general formula (1) and the radical polymerization initiator is an oxime represented by the following general formula (2).

General formula (2)

(In the formula, X has the same meaning as in general formula (1).)

  The oxime represented by the general formula (2) 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).

  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 are prepared by using a oxime represented by the general formula (2) as a starting material, a method described in the literature, for example, an oxime and an acyl chloride obtained by the method described above. Or reacting with an acid anhydride in an inert solvent such as tetrahydrofuran, benzene or dimethylformamide, in the presence of a base such as a tertiary amine such as triethylamine, or in a basic solvent such as pyridine. Manufactured by.

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

  Many of the conventionally known α, α′-diketooxime ester compounds generally do not exhibit absorption at wavelengths longer than the ultraviolet region, and thus are less active against near ultraviolet to near infrared light. The radical polymerization initiator represented by the general formula (1) has an absorption band from near ultraviolet to visible region by introducing a heterocyclic group into X, and from these near ultraviolet to visible to longer wavelength region. It is possible to have activity.

  Next, the radically polymerizable compound (b) of the present invention will be described. The radical polymerizable compound 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 ethylenically unsaturated compound capable of radical polymerization in the molecule. Any compound may be used as long as it has at least one bond, and it has 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.

  A sensitizer (c) can be added to the polymerizable composition of the present invention 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, 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 gazette, USP 2,848,328, USP 2,852,379 and USP 2,940,853, organic azide compounds, JP-B 36-22062, JP-B 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. 1099851, 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.

  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 a synthesis example, 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 Synthesis Examples, Examples and Comparative Examples.

Synthesis example 1
Synthesis of compound (81)

  1,3-dithiophen-2-yl-propane-1,3-dione (24.0 g, 102 mmol) was dissolved in a mixed solution of 240 ml of tetrahydrofuran and 120 ml of concentrated hydrochloric acid, and tert-butyl nitrite 12% under stirring at room temperature. .57 g (122 mmol) was added dropwise over 1 hour. 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 1,3-dithiophene-2. 25.4 g of yl-1,2,3-trione 2-oxime was obtained (yield 94.2%).

  Then, 18.0 g (67.8 mmol) of 1,3-dithiophen-2-yl-1,2,3-trione-2-oxime and 5.57 g (67.8 mmol) of sodium acetate were stirred in 250 ml of benzene. Then, 8.31 g (81.4 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 18.7 g of compound (81) (yield: 89.5%).

Synthesis example 2
Synthesis of compound (82)

  18.5 g (54.7 mmol) of 1,3-bis-benzothiazol-2-yl-propane-1,3-dione was dissolved in a mixed solution of 185 ml of tetrahydrofuran and 93 ml of concentrated hydrochloric acid. 6.76 g (65.6 mmol) of tert-butyl nitrate was added dropwise over 40 minutes. After completion of dropping, the mixture was stirred at room temperature for 4 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 1,3-bis- 18.8 g of benzothiazol-2-yl-propane-1,2,3-trione 2-oxime was obtained (yield 93.6%).

  Next, 13.0 g (35.4 mmol) of 1,3-bis-benzothiazol-2-yl-propane-1,2,3-trione-2-oxime and 2.90 g (35.4 mmol) of sodium acetate were mixed with benzene. When stirring in 250 ml, 4.33 g (42.5 mmol) of acetic anhydride was added and heated to reflux for 3 hours. Thereafter, the reaction solution was poured into 250 ml of ice water, the composition organism was extracted with ethyl acetate, the organic layer was washed with water (200 ml × 3 times), dried over magnesium sulfate, the desiccant was filtered off, and the solvent was distilled off. The residue was recrystallized from ethyl acetate-hexane to obtain 14.0 g of compound (82) as pale yellow crystals (yield 96.8%).

Synthesis example 3
Synthesis of compound (83)

  When 18.0 g (39.3 mmol) of 1,3-bis- (9-ethyl-9H-carbazol-3-yl) -propane-1,3-dione was dissolved in a mixed solution of 200 ml of tetrahydrofuran and 100 ml of concentrated hydrochloric acid, While stirring at room temperature, 4.86 g (47.1 mmol) of tert-butyl nitrite was added dropwise over 30 minutes. After completion of dropping, the mixture was stirred at room temperature for 6 hours. The reaction solution was poured into 600 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 recrystallized from chloroform-hexane to give 1,3-bis- 15.9 g of (9-ethyl-9H-carbazol-3-yl) -propane-1,2,3-trione 2-oxime was obtained (yield 83.0%).

  Next, 10.0 g (20.5 mmol) of 1,3-bis- (9-ethyl-9H-carbazol-3-yl) -propane-1,2,3-trione 2-oxime and 1.68 g of sodium acetate ( 20.5 mmol) was stirred in 200 ml of benzene, 2.51 g (24.6 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 (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 8.77 g of compound (83) as pale yellow crystals (yield 80.7%).

Synthesis example 4
Synthesis of compound (84)

  20.0 g (47.6 mmol) of 1,3-bis- (7-methoxy-2-oxo-2H-chromen-3-yl) -propane-1,3-dione was added to a mixed solution of 200 ml of tetrahydrofuran and 100 ml of concentrated hydrochloric acid. When dissolved, 5.89 g (57.1 mmol) of tert-butyl nitrite was added dropwise over 45 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 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 off to remove the solvent, and the residue was recrystallized from dichloromethane-hexane to give 1,3-bis- 19.7 g of (7-methoxy-2-oxo-2H-chromen-3-yl) -propane-1,2,3-trione 2-oxime was obtained (yield 92.1%).

  Next, 1,3-bis- (7-methoxy-2-oxo-2H-chromen-3-yl) -propane-1,2,3-trione 2-oxime 15.0 g (33.4 mmol) and sodium acetate When 2.74 g (33.4 mmol) was stirred in 300 ml of benzene, 4.09 g (40.1 mmol) of acetic anhydride was added and heated to reflux for 4 hours. Thereafter, the reaction solution was poured into 400 ml of ice water, the composition organism was extracted with ethyl acetate, the organic layer was washed with water (300 ml × 3 times), dried over magnesium sulfate, the desiccant was filtered to remove the solvent, The residue was reprecipitated with ethyl acetate-hexane to obtain 15.6 g of compound (84) as pale yellow crystals (yield 94.8%).

  Table 3 shows the results of elemental analysis of the radical polymerization initiators of the present invention synthesized in Synthesis Examples 1 to 4 above.

Examples 1-4
Polymerizable composition comprising 6 parts by weight of the radical polymerization initiator (a) of the present invention, 100 parts by weight of pentaerythritol triacrylate as the radical polymerizable compound (b), 100 parts by weight of polymethyl acrylate as the binder, and 1600 parts by weight of cyclohexanone as the solvent. The product was blended with the composition shown in Table 4 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
Table 4 shows a polymerizable composition comprising 6 parts by weight of a radical polymerization initiator, 100 parts by weight of pentaerythritol triacrylate as a radical polymerizable compound, 100 parts by weight of polymethyl methacrylate as a binder, and 1600 parts by weight of cyclohexanone as a solvent. To prepare a coating solution. Table 4 shows the result of calculating the consumption rate of the acrylic monomer at the time point 15 seconds after the start of light irradiation by film-forming and light-irradiating this coating liquid in the same procedures and conditions as in Examples 1 to 6 above. It was.

  The polymerizable composition (Examples 1 to 4) 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 having the same heterocyclic group at the 1-position and the 3-position is used as a radical polymerization initiator. As a result, the sensitivity can be increased.

Examples 5-16
The radical polymerization initiator (a) of the present invention is 5 parts by weight, the radically polymerizable compound (b) is 100 parts by weight of pentaerythritol triacrylate, and the sensitizer (c) is 0 or 1 in the compound (88) or the compound (89). A polymerizable composition comprising 100 parts by weight of polymethyl acrylate as a binder and 1600 parts by weight of cyclohexanone as a solvent was blended in the composition shown in Table 5 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 radical polymerization initiator, 100 parts by weight of pentaerythritol triacrylate as a radical polymerizable compound, 0 or 1 part by weight of compound (88) or compound (89) as a sensitizer, 100 parts by weight of polymethyl acrylate as a binder A polymerizable composition composed of 1600 parts by weight of cyclohexanone as a solvent was blended in the composition shown in Table 5 to prepare a coating solution. This coating liquid was formed and irradiated with light in the same procedures and conditions as in Examples 7 to 18 above, and the consumption rate of acrylic monomer at the time 10 seconds after the start of light irradiation (light irradiation amount: 100 mJ / cm ² ). The results of calculating are shown in Table 5.

The polymerizable compositions using the radical polymerization initiator of the present invention (Examples 5, 8, 11 and 14) 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 6, 7, 9, 10, 12, 13, 15 and 16, which contain a sensitizer in the polymerizable composition, Examples 5, 8, which do not contain a sensitizer in the polymerizable composition, Compared with 11 and 14, the polymerization sensitivity is improved. In addition, Examples 5 to 16 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 high-sensitivity radical polymerization initiator and a polymerizable composition, such as ink, paint, photosensitive printing plate, proof material, photoresist, hologram material, sealant, overcoat material, light, and the like. It can be a material for quickly and reliably obtaining a cured product having good physical properties in the fields of modeling resins, adhesives, various devices and the like.

Claims (4)

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

(Wherein X represents a heterocyclic group,
Y has an alkyl group which may have a substituent, an aryl group which may have a substituent, an alkenyl group which may have a substituent, an alkynyl group which may have a substituent, and a substituent. 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, and a substituent. Good alkylsulfanyl group, arylsulfanyl group which may have a substituent, alkylsulfinyl group which may have a substituent, arylsulfinyl group which may have a substituent, alkyl which may have a substituent Sulfonyl group, arylsulfonyl group which may have a substituent, acyl group which may have a substituent, alkoxycarbonyl group which may have a substituent, carbamoyl group which may have a substituent, substituted Even if it has a group There sulfamoyl group, an optionally substituted amino group, an optionally substituted phosphinoyl group, or a heterocyclic group which may have a substituent.
However, two X represent the same heterocyclic group. ) A radical polymerization initiator comprising the compound according to claim 1. A polymerizable composition comprising the radical polymerization initiator (a) according to claim 2 and a radical polymerizable compound (b). The polymerizable composition according to claim 3, further comprising a sensitizer (c).