JP2009179619A - Novel oxime ester compound and radical polymerization initiator and polymerizable composition comprising the same - Google Patents

Abstract

（式中、Ｒ¹〜Ｒ⁵、およびＲ¹²〜Ｒ¹⁶は、水素原子、アルキル等を表す。Ｒ⁶〜Ｒ¹¹は、水素原子等を表す。ＸおよびＹは、一価の有機残基を表す。）
【選択図】なしA novel compound that can function as a highly sensitive radical polymerization initiator and a curable composition using the compound are provided.
An oxime ester compound represented by the following general formula (1) and a curable composition using the compound. General formula (1)

(In the formula, R ^{1 to} R ⁵ and R ^{12 to} R ¹⁶ represent a hydrogen atom, alkyl, etc. R ^{6 to} R ¹¹ represent a hydrogen atom, etc. X and Y are monovalent organic residues. Represents.)
[Selection figure] None

Description

  The present invention relates to a novel oxime ester compound, a radical polymerization initiator comprising the same, 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, the alpha-ketoxime ester compound is disclosed as a radical photopolymerization initiator of the composition for positive or negative photosensitive polyimide precursors (refer 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 are disclosed (see Patent Documents 9 to 12). In recent years, high sensitivity of polymerization initiators has been universally demanded and active research has been done to improve productivity and various newly proposed processes. It should be noted that the impact of further sensitivity improvements on productivity and process response is immeasurable. On the other hand, in addition to sensitivity, a low-cost initiator that has various functions such as low odor, low yellowing, solubility, and developability is also desired.

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 Japanese Patent No. 4007399

  An object of the present invention is to provide a novel oxime ester compound capable of efficiently generating active radicals by irradiation of energy rays, particularly light, and functioning as a highly sensitive radical polymerization initiator capable of polymerizing a radical polymerizable compound in a short time, and The object is to propose 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 and a polymerizable composition using the same 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)

(Wherein R ^{1 to} R ⁵ and R ^{12 to} R ¹⁶ each independently represents a hydrogen atom, a halogen atom, a cyano group, a nitro group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, Substituted or unsubstituted alkynyl group, substituted or unsubstituted aryl group, substituted or unsubstituted heterocyclic group, substituted or unsubstituted alkyloxy group, substituted or unsubstituted aryloxy group, substituted or unsubstituted heterocyclic ring Represents an oxy group, a substituted or unsubstituted alkylsulfanyl group, a substituted or unsubstituted arylsulfanyl group, a substituted or unsubstituted acyl group, or a substituted or unsubstituted amino group, and these R ^{1 to} R ⁵ , R ^{12 to} R ¹⁶ may be combined with adjacent substituents to form a ring.
R ^{6 to} R ¹¹ are each independently a hydrogen atom, a halogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkyloxy group, a substituted or unsubstituted aryloxy group, a substituted or unsubstituted alkylsulfanyl. Represents a group, a substituted or unsubstituted arylsulfanyl group, or a substituted or unsubstituted amino group.
X and Y each independently represent a monovalent organic residue. )

In the present invention, at least one of R ^{12 to} R ¹⁶ is a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkyloxy group, a substituted or unsubstituted aryloxy group, a substituted or unsubstituted heterocyclic oxy And a substituted or unsubstituted alkylsulfanyl group, a substituted or unsubstituted arylsulfanyl group, or a substituted or unsubstituted amino group.

The present invention also relates to the above compound, wherein at least one of R ^{12 to} R ¹⁶ is a substituted or unsubstituted alkyloxy group.

  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).

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

  The compound of the present invention is an α, α′-diketooxime ester compound having a benzoylcarbazolyl group at the 1-position and a phenyl group at the 3-position, and is irradiated with energy rays, particularly light. To generate active radicals efficiently. Therefore, the compound which has a remarkably favorable effect as a radical polymerization initiator was able to be provided. Moreover, the curable composition with a favorable characteristic was able to be provided by using the compound of this invention as a radical polymerization initiator (A).

  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). When the compound of the present invention is used as a radical polymerization initiator, it is easier to synthesize than an initiator in which the substituent corresponding to the 3-position phenyl group in the general formula (1) is a condensed polycyclic hydrocarbon group. It becomes an initiator with excellent cost performance due to the availability of raw materials. It is also excellent in sensitivity, solubility and developability.

In general formula (1), R ^{1 to} R ⁵ and R ^{12 to} R ¹⁶ are each independently a hydrogen atom, a halogen atom, a cyano group, a nitro group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted group. Alkenyl group, substituted or unsubstituted alkynyl group, substituted or unsubstituted aryl group, substituted or unsubstituted heterocyclic group, substituted or unsubstituted alkyloxy group, substituted or unsubstituted aryloxy group, substituted or unsubstituted A heterocyclic oxy group, a substituted or unsubstituted alkylsulfanyl group, a substituted or unsubstituted arylsulfanyl group, or a substituted or unsubstituted acyl group, a substituted or unsubstituted amino group. R ^{6 to} R ¹¹ are each independently a hydrogen atom, halogen atom, substituted or unsubstituted alkyl group, substituted or unsubstituted alkyloxy group, substituted or unsubstituted aryloxy group, substituted or unsubstituted It represents an alkylsulfanyl group, a substituted or unsubstituted arylsulfanyl group, or a substituted or unsubstituted amino group.

  Examples of the substituted or unsubstituted alkyl group include a linear, branched, monocyclic or condensed polycyclic alkyl group having 1 to 18 carbon atoms, and specific examples include a methyl group, an ethyl group, and a propyl group. Butyl group, 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. It is not something.

  Examples of the substituted or unsubstituted alkenyl group include alkenyl groups having 2 to 10 carbon atoms, and specific examples include, but are not limited to, a vinyl group, an allyl group, and a styryl group.

  The substituted or unsubstituted alkynyl group is preferably an alkynyl group having 2 to 10 carbon atoms, and examples thereof include, but are not limited to, ethynyl group, propynyl group, propargyl group, phenylethynyl group, and trimethylsilylethynyl group. It is not a thing.

  Examples of the substituted or unsubstituted 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, and a 9-anthryl group. , 9-phenanthryl group, 1-pyrenyl group, 5-naphthacenyl group, 1-indenyl group, 2-azurenyl group, 1-acenaphthyl group, 9-fluorenyl group and the like, but are not limited thereto.

  Examples of the substituted or unsubstituted 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, 2- Examples include thienyl group, 2-indolyl group, 3-indolyl group, 2-benzofuryl group, 2-benzothienyl group, 2-carbazolyl group, 3-carbazolyl group, 4-carbazolyl group, and 9-acridinyl group. It is not limited.

  Examples of the substituted or unsubstituted alkyloxy group include linear, branched, monocyclic or condensed polycyclic alkyloxy groups having 1 to 18 carbon atoms. Specific examples include methoxy group, ethoxy group, propoxy group. 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, Roniruokishi group, 4-decyl cyclohexyl group, 2-tetrahydrofuranyl group, 2-tetrahydrofuranyl group, and the like but not limited thereto.

  Examples of the substituted or unsubstituted 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, 9-anthryloxy group, 9-phenanthryloxy group, 1-pyrenyloxy group, 5-naphthacenyloxy group, 1-indenyloxy group, 2-azurenyloxy group, 1-acenaphthyloxy group, 9-fur Although an oleenyloxy group etc. are mentioned, it is not limited to these.

  Examples of the substituted or unsubstituted 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, 2-thienyloxy group, 2-indolyloxy group, 3-indolyloxy group, 2-benzofuryloxy group, 2-benzothienyloxy group, 2-carbazolyloxy group, 3-carbazolyloxy group, Examples thereof include, but are not limited to, a 4-carbazolyloxy group, a 9-acridinyloxy group, and the like.

  Examples of the alkylsulfanyl group include linear, branched, monocyclic or condensed polycyclic alkylsulfanyl groups having 1 to 18 carbon atoms. Specific examples include a methylsulfanyl group, an ethylsulfanyl group, a propylsulfanyl group, Examples thereof include, but are not limited to, a butylsulfanyl group, a pentylsulfanyl group, a hexylsulfanyl group, an octylsulfanyl group, a decylsulfanyl group, a dodecylsulfanyl group, and an octadecylsulfanyl group.

  Examples of the arylsulfanyl group include monocyclic or condensed polycyclic arylsulfanyl groups having 6 to 18 carbon atoms, and specific examples thereof include phenylsulfanyl group, 1-naphthylsulfanyl group, 2-naphthylsulfanyl group, 9-anthryl. Examples thereof include, but are not limited to, a sulfanyl group and a 9-phenanthrylsulfanyl group.

  Examples of the substituted or unsubstituted acyl group include 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 group having 6 to 18 carbon atoms. Examples include a carbonyl group to which a monocyclic or condensed polycyclic 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. They may have an unsaturated bond in the structure, 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, meta Liloyl group, Crotonoyl 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, but are not limited thereto.

The substituted or unsubstituted amino group 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-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 N-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, etc. Not intended to be.

  Further, the above-mentioned substituted or unsubstituted alkyl group, substituted or unsubstituted alkenyl group, substituted or unsubstituted alkynyl group, substituted or unsubstituted aryl group, substituted or unsubstituted heterocyclic group, substituted or unsubstituted An alkyloxy group, a substituted or unsubstituted aryloxy group, a substituted or unsubstituted heterocyclic oxy group, a substituted or unsubstituted alkylsulfanyl group, a substituted or unsubstituted arylsulfanyl group, or a substituted or unsubstituted acyl group The hydrogen atom of the substituted or unsubstituted amino group may be further substituted with another substituent.

  Examples of such substituents include halogen groups such as fluorine atom, chlorine atom, bromine atom and iodine atom, alkyloxy groups such as methoxy group, ethoxy group and tert-butoxy group, phenoxy group and p-tolyloxy group. Alkyloxycarbonyl groups such as aryloxy groups, methoxycarbonyl groups, butoxycarbonyl groups, phenoxycarbonyl groups, acyloxy groups such as acetoxy groups, propionyloxy groups, benzoyloxy groups, acetyl groups, benzoyl groups, isobutyryl groups, acryloyl groups, methacryloyl groups Group, acyl group such as methoxalyl group, methylsulfanyl group, alkylsulfanyl group such as tert-butylsulfanyl group, arylsulfanyl group such as phenylsulfanyl group, p-tolylsulfanyl group, methylamino group, cyclohexane Alkylamino groups such as silamino groups, dimethylamino groups, diethylamino groups, morpholino groups, dialkylamino groups such as piperidino groups, arylamino groups such as phenylamino groups and p-tolylamino groups, methyl groups, ethyl groups, tert-butyl groups In addition to alkyl groups such as dodecyl groups, phenyl groups, p-tolyl groups, xylyl groups, cumenyl groups, naphthyl groups, anthryl groups, phenanthryl groups, and other heterocyclic groups such as furyl groups and thienyl groups, hydroxy groups Group, carboxy group, formyl group, mercapto group, 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, dimethylsulfonium group Triphenyl phenacyl phosphonium Niu mill group, and the like.

In the general formula (1), preferably, at least one of the substituents R ^{12 to} R ¹⁶ is a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkyloxy group, a substituted or unsubstituted aryloxy group, substituted or Any of an unsubstituted heterocyclic oxy group, a substituted or unsubstituted alkylsulfanyl group, a substituted or unsubstituted arylsulfanyl group, and a substituted or unsubstituted amino group, more preferably the substituents R ^{12 to} R ^At least one of ¹⁶ is any one of a substituted or unsubstituted alkyloxy group, a substituted or unsubstituted alkylsulfanyl group, and a substituted or unsubstituted amino group.

  Specific examples include, but are not limited to, a methyloxy group, an ethyloxy group, a methylsulfanyl group, an ethylsulfanyl group, and a dimethylamino group.

Furthermore, as a particularly preferable case, at least one of the substituents R ^{12 to} R ¹⁶ is a substituted or unsubstituted alkyloxy group.

When at least one of R ^{12 to} R ^{16 in} the general formula (1) is substituted by these substituents, when used as a photopolymerization initiator (A), the compound decomposes with a smaller amount of light irradiation. In addition to generating radicals efficiently, it is preferable because it is excellent in all of absorption characteristics, compatibility with resins and solvents, improvement in stability over time, improvement in developability, etc. It is not clear why.

In general formula (1), R ^{6 to} R ¹¹ are each independently a hydrogen atom, a halogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkyloxy group, a substituted or unsubstituted aryloxy group, It represents a substituted or unsubstituted alkylsulfanyl group, a substituted or unsubstituted arylsulfanyl group, or a substituted or unsubstituted amino group.

Here, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkyloxy group, a substituted or unsubstituted aryloxy group, a substituted or unsubstituted alkylsulfanyl group, a substituted or unsubstituted arylsulfanyl group, or a substituted Alternatively, the unsubstituted amino group is a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkyloxy group, a substituted or unsubstituted aryloxy group, a substituted group in R ^{1 to} R ⁵ and R ^{12 to} R ¹⁶ described above. Or it is synonymous with an unsubstituted alkylsulfanyl group, a substituted or unsubstituted arylsulfanyl group, or a substituted or unsubstituted amino group.

The hydrogen atom of the substituent which these R ^{6 to} R ¹¹ can take may be further substituted. Examples of such substituent include halogen groups such as fluorine atom, chlorine atom, bromine atom and iodine atom, and methoxy group. Alkyloxy groups such as ethoxy group and tert-butoxy group, aryloxy groups such as phenoxy group and p-tolyloxy group, alkyloxycarbonyl groups such as methoxycarbonyl group, butoxycarbonyl group and phenoxycarbonyl group, acetoxy group and propionyloxy Group, acyloxy group such as benzoyloxy group, acetyl group, benzoyl group, isobutyryl group, acryloyl group, methacryloyl group, methoxalyl group and other acyl groups, methylsulfanyl group, tert-butylsulfanyl group and other alkylsulfanyl groups, phenylsulfanyl group , P- Arylsulfanyl groups such as rylsulfanyl groups, alkylamino groups such as methylamino groups, cyclohexylamino groups, dimethylamino groups, diethylamino groups, morpholino groups, dialkylamino groups such as piperidino groups, phenylamino groups, p-tolylamino groups, etc. Aryl group such as arylamino group, methyl group, ethyl group, tert-butyl group, dodecyl group, aryl group such as phenyl group, p-tolyl group, xylyl group, cumenyl group, naphthyl group, anthryl group, phenanthryl group, furyl Group, heterocyclic group such as thienyl group, hydroxy group, carboxy group, formyl group, mercapto group, sulfo group, mesyl group, p-toluenesulfonyl group, amino group, nitro group, cyano group, trifluoromethyl group , Trichloromethyl group, trimethylsilyl group, phosphite Co group, a phosphono group, trimethyl ammonium Niu mill group, dimethylsulfoxide Niu mill group, triphenyl phenacyl phosphonium Niu mill group, and the like.

R ^{6 to} R ¹¹ are preferably a hydrogen atom or a substituted or unsubstituted alkyl group from the viewpoint of easy availability of raw materials and ease of synthesis.
In addition, R ^{1 to} R ⁵ and R ^{12 to} R ¹⁶ may be combined with adjacent substituents to form a ring. Specific examples include the following, but the present invention is not limited thereto. It is not something.

  The substituents X and Y in the general formula (1) represent 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. Alkynyl group, optionally substituted alkyloxy group, optionally substituted aryloxy group, optionally substituted heterocyclic oxy group, optionally substituted acyloxy 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, a substitution An alkylsulfonyl group which may have a group, an arylsulfonyl group which may have a substituent, an acyl group which may have a substituent, an alkyloxycarbonyl group which may have a substituent, a substituent Cal that you may have Examples include a moyl group, a sulfamoyl group that may have a substituent, an amino group that may have a substituent, a phosphinoyl group that may have a substituent, and a heterocyclic group that 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, 3-nitroph Nasir group, 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 alkyloxy group which may have a substituent is preferably an alkyloxy group having 1 to 30 carbon atoms. For example, methoxy group, ethoxy group, propyloxy group, isopropyloxy group, butoxy group, isobutoxy group, sec- Butoxy, t-butoxy, pentyloxy, isopentyloxy, hexyloxy, heptyloxy, octyloxy, 2-ethylhexyloxy, decyloxy, dodecyloxy, octadecyloxy, ethoxycarbonylmethyl 2-ethylhexyloxycarbonylmethyloxy group, aminocarbonylmethyloxy group, N, N-dibutylaminocarbonylmethyloxy group, N-methylaminocarbonylmethyloxy group, N-ethylaminocarbonylmethyloxy group, N-octylamino group Boni methyl 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 alkyloxycarbonyl group which may have a substituent is preferably an alkyloxycarbonyl group having 2 to 20 carbon atoms, such as a methoxycarbonyl group, an ethoxycarbonyl group, a propoxycarbonyl group, a butoxycarbonyl group, or a hexyloxycarbonyl group. Octyloxycarbonyl 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-chlorophenyloxy Rubonyl 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 Carbamoyl group N-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 can be mentioned.

  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 N-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 can be mentioned.

  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 alkyloxy 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 group which may have a substituent, and a substituent. 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, and 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 alkyloxycarbonyl group which may have a substituent, and a substituent. Carbamoyl The hydrogen atom of the sulfamoyl group which may have a substituent, the amino group which may have a substituent, or the heterocyclic group which may have a substituent may be further substituted with another substituent. .

  Examples of such substituents include halogen groups such as fluorine atom, chlorine atom, bromine atom and iodine atom, alkyloxy groups such as methoxy group, ethoxy group and tert-butoxy group, phenoxy group and p-tolyloxy group. Alkyloxycarbonyl groups such as aryloxy groups, methoxycarbonyl groups, butoxycarbonyl groups, phenoxycarbonyl groups, acyloxy groups such as acetoxy groups, propionyloxy groups, benzoyloxy groups, acetyl groups, benzoyl groups, isobutyryl groups, acryloyl groups, methacryloyl groups Group, acyl group such as methoxalyl group, methylsulfanyl group, alkylsulfanyl group such as tert-butylsulfanyl group, arylsulfanyl group such as phenylsulfanyl group, p-tolylsulfanyl group, methylamino group, cyclohexane Alkylamino groups such as xylamino groups, dimethylamino groups, diethylamino groups, morpholino groups, dialkylamino groups such as piperidino groups, arylamino groups such as phenylamino groups, p-tolylamino groups, methyl groups, ethyl groups, tert-butyl groups In addition to alkyl groups such as dodecyl groups, phenyl groups, p-tolyl groups, xylyl groups, cumenyl groups, naphthyl groups, anthryl groups, phenanthryl groups, and other heterocyclic groups such as furyl groups and thienyl groups, hydroxy groups Group, carboxy group, formyl group, mercapto group, 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, dimethylsulfonium group Triphenyl phenacyl phosphonium Niu mill group, 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 these substituents Y, a substituted or unsubstituted alkyl group is preferred from the viewpoint of easy availability of raw materials and ease of synthesis.

  Specific examples of the compound of the present invention described above are shown in Table 1, but the structure of the compound of the present invention is not limited thereto.

Table 1

  The starting material for synthesizing the compound represented by the general formula (1) is an oxime represented by the following general formula (2).

General formula (2)

(In the formula, R ^{1 to} R ¹⁶ and Y have the same meaning as in the 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) is obtained by using a oxime represented by the general formula (2) as a starting material and a method described in the literature, for example, an oxime obtained by the above-described method and an acyl chloride or an acid anhydride. For example, 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.

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

  Next, the case where the compound of this invention is used as a radical polymerization initiator (A) is demonstrated.

  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 (A) represented by the general formula (1) has an absorption band from the near ultraviolet to the visible region by introducing a benzoylcarbazolyl group. It is possible to give activity to a region.

  However, the radical polymerization initiator in which the substituent corresponding to the 3-position phenyl group of the general formula (1) is a condensed polycyclic hydrocarbon group often absorbs too much wavelength, and the compound itself has a color. Such a compound is not so preferable because the initiator itself becomes a coloring component. However, the radical polymerization initiator (A) represented by the general formula (1) of the present invention does not reach the colored region and can be used for applications where high transparency is required.

  Furthermore, when the radical polymerization initiator (A) represented by the general formula (1) of the present invention is used, the substituent corresponding to the 3-position phenyl group of the general formula (1) is a condensed polycyclic hydrocarbon group or a heterocycle. Yellowing can be reduced compared to a radical polymerization initiator that is a cyclic group. This is because degradation products generated by light irradiation of radical polymerization initiators generally cause yellowing because the recombined compound has absorption in the long wavelength region, but the phenyl group that is a decomposition component is It is considered that the degradation product possessed has less conjugation than the corresponding condensed polycyclic degradation product, but the details are not clear.

  Furthermore, in the radical polymerization initiator (A) represented by the general formula (1) of the present invention, the substituent corresponding to the 3-position phenyl group of the general formula (1) is a condensed polycyclic hydrocarbon group or a heterocyclic group. It is more compatible with various resins than the radical polymerization initiator. If the solubility is poor, a problem occurs in handling properties such as precipitation of the initiator, but the radical polymerization initiator (A) of the present invention, which is excellent in solubility, does not cause such a problem.

  Furthermore, in the radical polymerization initiator (A) represented by the general formula (1) of the present invention, the substituent corresponding to the 3-position phenyl group of the general formula (1) is a condensed polycyclic hydrocarbon group or a heterocyclic group. It is more developable than the radical polymerization initiator. Although details of the reason are not clear, developability is important in reducing the number of processes demanded in recent years, and the radical polymerization initiator (A) of the present invention is an initiator that can contribute more.

  Furthermore, in the radical polymerization initiator (A) represented by the general formula (1) of the present invention, the substituent corresponding to the 3-position phenyl group of the general formula (1) is a condensed polycyclic hydrocarbon group or a heterocyclic group. It is more stable over time than the radical polymerization initiator.

  Further, as described above, when the radical polymerization initiator (A) of the present invention introduces an electron-donating substituent onto the 3-position phenyl group in the general formula (1), the above-described absorption characteristics, sensitivity, Improvement is seen in all of solubility, developability, and stability. Although the detailed reason is not clear at present, it is considered that the electronic contribution of the electron-donating substituent has a good effect on the compound.

  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.

  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, 4,4′-bis (diethylamino) benzophenone, but are not limited thereto.

  The ratio of the radical polymerization initiator (A) and the sensitizer (C) of the present invention is arbitrary, but is preferably in the range of 100/1 to 1/100 (weight ratio), more preferably 50/1 to 1 /. It is the range of 50, More preferably, it is the range of 20/1-1/30.

  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. 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 special Transition metal complexes containing a transition metal such as ruthenium described in JP-A-2-182701, aluminate complexes described in JP-A-3-209477, borate compounds described in JP-A-2-157760, No. 55-127550 and JP-A-60-202437, 2,4,5-triarylimidazole dimer, carbon tetrabromide and organic halogen compounds described in JP-A-59-107344, A sulfonium complex or an oxosulfonium complex described in JP-A-5-255347, an aminoketone compound described in JP-A-54-99185 and JP-A-63-264560, JP-A-2001-264530, JP-A-2001-261661. JP, JP 2000-80068, JP 2001-233842 A No. 2004-534797, USP 3558309 specification (1971), USP4202697 specification (1980) and Japanese Patent Application Laid-Open No. 61-24558, etc. The agent is preferably contained in the range of 0.01 to 10 parts by weight per 100 parts by weight of the compound having an ethylenically unsaturated bond capable of radical polymerization.

  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-alkyloxypyridinethiones 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.

Table 2

Synthesis Example Example 1
Synthesis of Compound (1) 1- [9-Ethyl-6- (2-methyl-benzoyl) -9H-carbazol-3-yl] -3- (4-methoxy-phenyl) -yl-propane-1,3- When 90.0 g (183.8 mmol) of dione was dissolved in a mixed solution of 900 ml of tetrahydrofuran and 450 ml of concentrated hydrochloric acid, 22.8 g (220.6 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 5 hours. The reaction solution was poured into 1600 ml of ice water and extracted with 1600 ml of chloroform. The organic layer was washed with water (500 ml × 3 times), dried over magnesium sulfate, the desiccant was filtered off to remove the solvent, and the residue was washed with n-hexane to give 1- [9-ethyl- 90.6 g of 6- (2-methyl-benzoyl) -9H-carbazol-3-yl] -3- (4-methoxy-phenyl) -yl-propane-1,2,3-trione-2-oxime was obtained. (Yield 95.0%).

    Next, 1- [9-ethyl-6- (2-methyl-benzoyl) -9H-carbazol-3-yl] -3- (4-methoxy-phenyl) -yl-propane-1,2,3-trione -2-goxime 40.0 g (77.1 mmol) and sodium acetate 6.3 g (77.1 mmol) were stirred in benzene 500 ml, acetic anhydride 9.5 g (92.6 mmol) was added, and 3 hours Heated to reflux. 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 recrystallized from ethyl acetate-hexane to obtain 39.7 g of compound (1) (yield 91.8%).

Example 2
Synthesis of Compound (2) 1- [9-Ethyl-6- (2-methyl-benzoyl) -9H-carbazol-3-yl] -3- (3,4-dimethoxy-phenyl) -yl-propane-1, When 30.0 g (96.2 mmol) of 3-dione was dissolved in a mixed solution of 1000 ml of tetrahydrofuran and 500 ml of concentrated hydrochloric acid, 11.9 g (115.5 mmol) of tert-butyl nitrite was added over 1 hour with stirring at room temperature. It was dripped. 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 washed with n-hexane to give 1- [9-ethyl- 69.3 g of 6- (2-methyl-benzoyl) -9H-carbazol-3-yl] -3- (3,4-dimethoxy-phenyl) -yl-propane-1,2,3-trione-2-oxime Obtained (yield 93.4%).

    Next, 1- [9-ethyl-6- (2-methyl-benzoyl) -9H-carbazol-3-yl] -3- (3,4-dimethoxy-phenyl) -yl-propane-1,2,3 -When 21.0 g (38.3 mmol) of trione-2-oxime and 3.14 g (38.3 mmol) of sodium acetate were stirred in 300 ml of benzene, 4.74 g (45.9 mmol) of acetic anhydride was added, 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 20.8 g of compound (2) (yield 92.0%).

Example 3
Synthesis of Compound (3) 1- [9-Ethyl-6- (2-methyl-benzoyl) -9H-carbazol-3-yl] -3- (4-diethylamino-phenyl) -yl-propane-1,3- To a solution obtained by dissolving 64.0 g (120.6 mmol) of dione in a mixed solution of 640 ml of tetrahydrofuran and 320 ml of concentrated hydrochloric acid, 14.9 g (144.7 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 a place where 600 ml of 10% sodium hydroxide solution was cooled in an ice bath, and extracted with 600 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 washed with n-hexane to give 1- [9-ethyl- 60.3 g of 6- (2-methyl-benzoyl) -9H-carbazol-3-yl] -3- (4-diethylamino-phenyl) -yl-propane-1,2,3-trione-2-oxime was obtained. (Yield 89.4%).

    Then 1- [9-ethyl-6- (2-methyl-benzoyl) -9H-carbazol-3-yl] -3- (4-diethylamino-phenyl) -yl-propane-1,2,3-trione After mixing 25.0 g (44.7 mmol) of 2-oxime, 18.1 g (178 mmol) of triethylamine, 16.5 g (178 mmol) of propionyl chloride and 500 ml of tetrahydrofuran, the mixture was stirred at room temperature for 1 hour. The mixture was further stirred at 50 ° C. for 2 hours. Thereafter, the reaction solution is poured into 600 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 off, and the solvent is distilled off. The residue was recrystallized from dichloroethane-hexane to obtain 26.2 g of compound (3) (yield 95.4%).

Example 4
Synthesis of Compound (4) 1- [9-Ethyl-6- (2-methyl-benzoyl) -9H-carbazol-3-yl] -3- (4-diethylamino-phenyl) -yl-propane-1,2, As the 3-trione-2-oxime, the compound synthesized in Example 3 was used.

    1- [9-Ethyl-6- (2-methyl-benzoyl) -9H-carbazol-3-yl] -3- (4-diethylamino-phenyl) -yl-propane-1,2,3-trione-2- When oxime 25.0 g (44.7 mmol) and sodium acetate 3.66 g (45.1 mmol) were stirred in benzene 500 ml, acetic anhydride 5.53 g (54.1 mmol) was added and heated to reflux for 3 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 recrystallized from dichloroethane-hexane to obtain 25.2 g of compound (4) (yield 93.7%).

Example 5
Synthesis of Compound (5) 1- [9-Ethyl-6- (2-methyl-benzoyl) -9H-carbazol-3-yl] -3- (2,3-dimethyl-phenyl) -yl-propane-1, To a solution obtained by dissolving 28.0 g (53.9 mmol) of 3-dione in a mixed solution of 300 ml of tetrahydrofuran and 150 ml of concentrated hydrochloric acid, 6.67 g (64,7 mmol) of tert-butyl nitrite was added over 1 hour while stirring at room temperature. It was dripped. After completion of dropping, the mixture was stirred at room temperature for 5 hours. The reaction solution was poured into 600 ml of ice water and extracted with 600 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 washed with n-hexane to give 1- [9-ethyl- 28.5 g of 6- (2-methyl-benzoyl) -9H-carbazol-3-yl] -3- (2,3-dimethyl-phenyl) -yl-propane-1,2,3-trione-2-oxime Obtained (yield 96.3%).

    Next, 1- [9-ethyl-6- (2-methyl-benzoyl) -9H-carbazol-3-yl] -3- (2,3-dimethyl-phenyl) -yl-propane-1,2,3 -When 25.0 g (45.6 mmol) of trione-2-oxime and 3.74 g (45.6 mmol) of sodium acetate were stirred in 500 ml of benzene, 5.64 g (54.7 mmol) of acetic anhydride was added, Heated to reflux for 3 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 recrystallized from ethyl acetate-hexane to obtain 25.6 g of compound (5) (yield 95.2%).

Example 6
Synthesis of Compound (6) 1- [9-Ethyl-6- (2-methyl-benzoyl) -9H-carbazol-3-yl] -3- (4-propyloxy-phenyl) -yl-propane-1,3 -When 60.0 g (115.9 mmol) of dione was dissolved in a mixed solution of 600 ml of tetrahydrofuran and 300 ml of concentrated hydrochloric acid, 14.3 g (139.1 mmol) of tert-butyl nitrite was added dropwise over 1 hour with stirring at room temperature. did. After completion of dropping, the mixture was stirred at room temperature for 5 hours. The reaction solution was poured into 1500 ml of ice water and extracted with 1500 ml of chloroform. The organic layer was washed with water (600 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- [9-ethyl- 69.2 g of 6- (2-methyl-benzoyl) -9H-carbazol-3-yl] -3- (4-propyloxy-phenyl) -yl-propane-1,2,3-trione-2-oxime was obtained. (Yield 93.5%).

    Next, 1- [9-ethyl-6- (2-methyl-benzoyl) -9H-carbazol-3-yl] -3- (4-propyloxy-phenyl) -yl-propane-1,2,3- When 50.0 g (91.5 mmol) of trione-2-oxime and 3.70 g (45.1 mmol) of sodium acetate were stirred in 1000 ml of benzene, 5.53 g (54.1 mmol) of acetic anhydride was added, and 3 Heated to reflux for hours. Thereafter, the reaction solution is poured into 1000 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 off, and the solvent is distilled off. The residue was recrystallized from ethyl acetate-hexane to obtain 30.2 g of Compound (6) (yield 92.1%).

Example 7
Synthesis of Compound (7) 1- [9-Ethyl-6- (2-methyl-benzoyl) -9H-carbazol-3-yl] -3- (4-methylsulfanyl-phenyl) -yl-propane-1,3 -Dissolve 52.0 g (102.8 mmol) of dione in a mixed solution of 600 ml of tetrahydrofuran and 300 ml of concentrated hydrochloric acid, and add dropwise 12.73 g (123.4 mmol) of tert-butyl nitrite over 1 hour with stirring at room temperature. did. After completion of dropping, the mixture was stirred at room temperature for 5 hours. The reaction solution was poured into 1200 ml of ice water and extracted with 1200 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 washed with n-hexane to give 1- [9-ethyl- 50.1 g of 6- (2-methyl-benzoyl) -9H-carbazol-3-yl] -3- (4-methylsulfanyl-phenyl) -yl-propane-1,2,3-trione-2-oxime are obtained. (Yield 91.1%).

    Next, 1- [9-ethyl-6- (2-methyl-benzoyl) -9H-carbazol-3-yl] -3- (4-methylsulfanyl-phenyl) -yl-propane-1,2,3- When 20.0 g (37.4 mmol) of trione-2-oxime and 3.07 g (37.4 mmol) of sodium acetate were stirred in 500 ml of benzene, 4.63 g (44.9 mmol) of acetic anhydride was added, and 3 Heated to reflux for 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 recrystallized from ethyl acetate-hexane to obtain 20.2 g of compound (7) (yield 93.7%).

Example 8
Synthesis of Compound (8) 1- [9-Ethyl-6- (2-methyl-benzoyl) -9H-carbazol-3-yl] -3- (4-methyl-phenyl) -yl-propane-1,3- When 70.0 g (147.8 mmol) of dione was dissolved in a mixed solution of 700 ml of tetrahydrofuran and 350 ml of concentrated hydrochloric acid, 18.29 g (177.4 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 1500 ml of ice water and extracted with 1500 ml of chloroform. The organic layer was washed with water (700 ml × 3 times), dried over magnesium sulfate, the desiccant was filtered to remove the solvent, and the residue was washed with n-hexane to give 1- [9-ethyl- 69.0 g of 6- (2-methyl-benzoyl) -9H-carbazol-3-yl] -3- (4-methyl-phenyl) -yl-propane-1,2,3-trione-2-oxime was obtained. (Yield 92.9%).

    Next, 1- [9-ethyl-6- (2-methyl-benzoyl) -9H-carbazol-3-yl] -3- (4-methyl-phenyl) -yl-propane-1,2,3-trione -2-oxime 30.0 g (59.7 mmol) and sodium acetate 4.90 g (59.7 mmol) were stirred in 600 ml of benzene, and then 7.39 g (71.6 mmol) of acetic anhydride was added for 3 hours. Heated to reflux. Thereafter, the reaction solution is poured into 600 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 30.7 g of compound (8) (yield 94.5%).

Example 9
Synthesis of Compound (9) 1- [9-Ethyl-6- (2-methyl-benzoyl) -9H-carbazol-3-yl] -3- (4-methyloxy-phenyl) -yl-propane-1,3 -The compound synthesize | combined in Example 1 was used for dione.

    Next, 1- [9-ethyl-6- (2-methyl-benzoyl) -9H-carbazol-3-yl] -3- (4-methyloxy-phenyl) -yl-propane-1,2,3- After mixing 40.0 g (77.1 mmol) of trione-2-oxime, 31.2 g (308.5 mmol) of triethylamine, 28.6 g (308.5 mmol) of propionyl chloride and 800 ml of tetrahydrofuran with cooling in an ice bath, And then stirred at 50 ° C. for 2 hours. Thereafter, the reaction solution was poured into 900 ml of ice water, the composition organism was extracted with ethyl acetate, the organic layer was washed with water (400 ml × 3 times), dried over magnesium sulfate, the desiccant was filtered to remove the solvent, The residue was recrystallized from ethyl acetate-hexane to obtain 38.3 g of compound (9) (yield: 88.5%).

Example 10
Synthesis of Compound (10) 1- [9-Ethyl-6-benzoyl-9H-carbazol-3-yl] -3- (2-ethyloxy-phenyl) -yl-propane-1,3-dione 36.0 g (73 0.5 mmol) was dissolved in a mixed solution of 360 ml of tetrahydrofuran and 180 ml of concentrated hydrochloric acid, and 9.10 g (88.2 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 700 ml of ice water and extracted with 800 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 washed with n-hexane to give 1- [9-ethyl- There was obtained 33.1 g of 6-benzoyl-9H-carbazol-3-yl] -3- (2-ethyloxy-phenyl) -yl-propane-1,2,3-trione-2-oxime (yield 86.9). %).

    Next, 1- [9-ethyl-6-benzoyl-9H-carbazol-3-yl] -3- (2-ethyloxy-phenyl) -yl-propane-1,2,3-trione-2-oxime30. To a stirred solution of 0 g (57.9 mmol) and sodium acetate 4.75 g (57.9 mmol) in 600 ml of benzene, 7.16 g (69.4 mmol) of acetic anhydride was added and heated to reflux for 3 hours. Thereafter, the reaction solution is poured into 800 ml of ice water, the composition organism is extracted with ethyl acetate, the organic layer is washed with water (400 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 29.8 g of Compound (10) (yield 92.0%).

Example 11
Synthesis of Compound (11) 1- [9-Pentyl-6- (4-diethylamino-benzoyl) -9H-carbazol-3-yl] -3- (3,4-dimethylsulfanyl-phenyl) -yl-propane-1 , 3-dione (26.0 g, 39.9 mmol) was dissolved in a mixed solution of 300 ml of tetrahydrofuran and 150 ml of concentrated hydrochloric acid, and 4.94 g (47.9 mmol) of tert-butyl nitrite was added over 1 hour with stirring at room temperature. And dripped. After completion of dropping, the mixture was stirred at room temperature for 5 hours. The reaction solution was poured into 800 ml of ice water and extracted with 800 ml of chloroform. The organic layer was washed with water (300 ml × 3 times), dried over magnesium sulfate, the desiccant was filtered to remove the solvent, and the residue was washed with n-hexane to give 1- [9-pentyl- 6- (4-Diethylamino-benzoyl) -9H-carbazol-3-yl] -3- (3,4-dimethylsulfanyl-phenyl) -yl-propane-1,2,3-trione-2-oxime 24.2 g (Yield 89.1%).

Next, 1- [9-pentyl-6- (4-dimethyl-benzoyl) -9H-carbazol-3-yl] -3- (3,4-dimethylsulfanyl-phenyl) -yl-propane-1,2, When 20.0 g (29.4 mmol) of 3-trione-2-oxime and 2.41 g (29.4 mmol) of sodium acetate were stirred in 400 ml of benzene, 3.64 g (35.3 mmol) of acetic anhydride was added. Heated to reflux for 3 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 20.2 g of compound (11) (yield 95.2%).
Example 12
Synthesis of Compound (12) 1- [9- (2-Ethyloxy-ethyl) -6- (3-ethyl-benzoyl) -9H-carbazol-3-yl] -3- (2-dimethylamino-phenyl) -yl -Propane-1,3-dione (37.0 g, 66.0 mmol) was dissolved in a mixed solution of tetrahydrofuran (400 ml) and concentrated hydrochloric acid (200 ml), and the mixture was stirred at room temperature with tert-butyl nitrite (8.17 g, 79.2 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 800 ml of ice water and extracted with 800 ml of chloroform. The organic layer was washed with water (300 ml × 3 times), dried over magnesium sulfate, the desiccant was filtered to remove the solvent, and the residue was washed with n-hexane to give 1- [9- (2 -Ethyloxy-ethyl) -6- (3-ethyl-benzoyl) -9H-carbazol-3-yl] -3- (2-dimethylamino-phenyl) -yl-propane-1,2,3-trione-2- 35.5 g of oxime was obtained (91.1% yield).

  Next, 1- [9- (2-ethyloxy-ethyl) -6- (3-ethyl-benzoyl) -9H-carbazol-3-yl] -3- (2-dimethylamino-phenyl) -yl-propane- When 3,0.0 g (50.9 mmol) of 1,2,3-trione-2-oxime and 4.17 g (50.9 mmol) of sodium acetate were stirred in 500 ml of benzene, 6.30 g (61.1 mmol) of acetic anhydride was stirred. ) And heated to reflux for 3 hours. Thereafter, the reaction solution was poured into 700 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 off and the solvent was distilled off. The residue was recrystallized from ethyl acetate-hexane to obtain 29.9 g of compound (12) (yield 93.0%).

Example 13
Synthesis of Compound (13) 1- [9-Ethyl-6- (4-methyloxy-benzoyl) -9H-carbazol-3-yl] -3- (3-cyclohexyloxy-phenyl) -yl-propane-1, To a solution of 4-dione (45.0 g, 78.4 mmol) dissolved in tetrahydrofuran (460 ml) and concentrated hydrochloric acid (230 ml), tert-butyl nitrite (9.71 g, 94.1 mmol) was added over 1 hour with stirring at room temperature. It was dripped. After completion of dropping, the mixture was stirred at room temperature for 5 hours. The reaction solution was poured into 800 ml of ice water and extracted with 800 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 washed with n-hexane to give 1- [9-ethyl- 41.6 g of 6- (4-methyloxy-benzoyl) -9H-carbazol-3-yl] -3- (3-cyclohexyloxy-phenyl) -yl-propane-1,2,3-trione-2-oxime Obtained (yield 87.9%).

  Next, 1- [9-ethyl-6- (4-methyloxy-benzoyl) -9H-carbazol-3-yl] -3- (3-cyclohexyloxy-phenyl) -yl-propane-1,2,3 -A mixture of 40.0 g (66.4 mmol) of trione-2-oxime and 5.44 g (66.4 mmol) of sodium acetate in 700 ml of benzene was added with 5.44 g (66.4 mmol) of acetic anhydride, Heated to reflux for 3 hours. Thereafter, the reaction solution is poured into 1000 ml of ice water, the composition organism is extracted with ethyl acetate, the organic layer is washed with water (400 ml × 3 times), dried over magnesium sulfate, the desiccant is filtered off and the solvent is distilled off. The residue was recrystallized from ethyl acetate-hexane to obtain 39.2 g of compound (13) (yield 91.5%).

Example 14
Synthesis of Compound (14) 1- [9- (2-Ethyloxy-ethyl) -6-benzoyl-9H-carbazol-3-yl] -3- (4-diphenylamino-phenyl) -yl-propane-1,3 -When 39.0 g (59.4 mmol) of dione was dissolved in a mixed solution of 600 ml of tetrahydrofuran and 300 ml of concentrated hydrochloric acid, 7.35 g (71.3 mmol) of tert-butyl nitrite was added dropwise over 1 hour with stirring at room temperature. did. After completion of dropping, the mixture was stirred at room temperature for 5 hours. The reaction solution was poured into 1000 ml of ice water and extracted with 900 ml of chloroform. The organic layer was washed with water (400 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- [9- (2 -Ethyloxy-ethyl) -6-benzoyl-9H-carbazol-3-yl] -3- (4-diphenylamino-phenyl) -yl-propane-1,2,3-trione-2-oxime 36.6 g (Yield 90.0%).

  Next, 1- [9- (2-ethyloxy-ethyl) -6-benzoyl-9H-carbazol-3-yl] -3- (4-diphenylamino-phenyl) -yl-propane-1,2,3- When 35.0 g (51.0 mmol) of trione-2-oxime and 4.19 g (51.0 mmol) of sodium acetate were stirred in 600 ml of benzene, 6.32 g (61.2 mmol) of acetic anhydride was added. Heated to reflux for hours. Thereafter, the reaction solution was poured into 900 ml of ice water, the composition organism was extracted with ethyl acetate, the organic layer was washed with water (400 ml × 3 times), dried over magnesium sulfate, the desiccant was filtered to remove the solvent, The residue was recrystallized from dichloromethane-hexane to obtain 34.6 g of compound (14) (yield 93.1%).

Example 15
Synthesis of Compound (15) 1- [9-Ethyl-6-benzoyl-9H-carbazol-3-yl] -3- (4-methyl-phenyl) -yl-propane-1,2,3-trione-2- As the oxime, the compound synthesized in Example 8 was used.

  Next, 1- [9-ethyl-6-methyl-benzoyl 9H-carbazol-3-yl] -3- (4-methyl-phenyl) -yl-propane-1,2,3-trione-2-oxime 30 0.02 g (59.7 mmol), triethylamine 24.2 g (238.8 mmol), propionyl chloride 22.1 g (238.8 mmol) and tetrahydrofuran 600 ml were mixed with cooling in an ice bath, and then stirred at room temperature for 1 hour. The mixture was further stirred at 50 ° C. for 2 hours. Thereafter, the reaction solution was poured into 800 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 off, and the solvent was distilled off. The residue was recrystallized from dichloroethane-hexane to obtain 30.3 g of compound (3) (yield: 93.3%).

Example 16
Synthesis of Compound (16) 1- [9-Ethyl-6-benzoyl-1-methyl-9H-carbazol-3-yl] -3- (3,4-diethylamino-phenyl) -yl-propane-1,3- To a solution obtained by dissolving 39.0 g (64.8 mmol) of dione in a mixed solution of 700 ml of tetrahydrofuran and 350 ml of concentrated hydrochloric acid, 8.02 g (77.8 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 1200 ml of ice water and extracted with 1000 ml of chloroform. The organic layer was washed with water (500 ml × 3 times), dried over magnesium sulfate, the desiccant was filtered off to remove the solvent, and the residue was washed with n-hexane to give 1- [9-ethyl- 67.6 Benzoyl-1-methyl-9H-carbazol-3-yl] -3- (3,4-diethylamino-phenyl) -yl-propane-1,2,3-trione-2-oxime 37.6 g was obtained. (Yield 91.9%).

  Next, 1- [9-ethyl-6-benzoyl-1-methyl-9H-carbazol-3-yl] -3- (3,4-diethylamino-phenyl) -yl-propane-1,2,3-trione -2-oxime 30.0 g (47.6 mmol) and sodium acetate 3.90 g (47.6 mmol) were stirred in benzene 500 ml, acetic anhydride 5.89 g (57.1 mmol) was added, and 3 hours Heated to reflux. Thereafter, the reaction solution was poured into 800 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 off, and the solvent was distilled off. The residue was recrystallized from ethyl acetate-hexane to obtain 39.2 g of compound (16) (yield 91.5%).

Example 17
Synthesis of Compound (17) 1- [9-Ethyl-6- (2-ethylsulfanyl-benzoyl) -9H-carbazol-3-yl] -3- (3-ethylsulfanyl-phenyl) -yl-propane-1, To a solution of 700 ml of tetrahydrofuran and 350 ml of concentrated hydrochloric acid dissolved in 42.0 g (74.2 mmol) of 3-dione, 9.19 g (89.1 mmol) of tert-butyl nitrite was added over 1 hour with stirring at room temperature. It was dripped. After completion of dropping, the mixture was stirred at room temperature for 5 hours. The reaction solution was poured into 1200 ml of ice water and extracted with 1200 ml of chloroform. The organic layer was washed with water (600 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- [9-ethyl- 61.7 g of 6- (2-ethylsulfanyl-benzoyl) -9H-carbazol-3-yl] -3- (3-ethylsulfanyl-phenyl) -yl-propane-1,2,3-trione-2-oxime Obtained (yield 94.5%).

  Next, 1- [9-ethyl-6- (2-ethylsulfanyl-benzoyl) -9H-carbazol-3-yl] -3- (3-ethylsulfanyl-phenyl) -yl-propane-1,2,3 -After mixing 40.0 g (67.3 mmol) of trione-2-oxime, 27.2 g (269.0 mmol) of triethylamine, 37.8 g (269.0 mmol) of benzoyl chloride and 700 ml of tetrahydrofuran while cooling in an ice bath, After stirring at room temperature for 1 hour, the mixture was further stirred at 50 ° C. for 2 hours. Thereafter, the reaction solution was poured into 900 ml of ice water, the composition organism was extracted with ethyl acetate, the organic layer was washed with water (400 ml × 3 times), dried over magnesium sulfate, the desiccant was filtered to remove the solvent, The residue was recrystallized from dichloroethane-hexane to obtain 42.3 g of compound (17) (yield 89.9%).

Example 18
Synthesis of Compound (18) 1- [9-Ethyl-6- (2-methyl-benzoyl) -9H-carbazol-3-yl] -3- (4-methylsulfanyl-phenyl) -yl-propane-1,2 The compound synthesized in Example 7 was used as 3-trione-2-oxime.

  Next, 1- [9-ethyl-6- (2-methyl-benzoyl) -9H-carbazol-3-yl] -3- (4-methylsulfanyl-phenyl) -yl-propane-1,2,3- After mixing 25.0 g (46.8 mmol) of trione-2-oxime, 18.9 g (187.0 mmol) of triethylamine, 17.3 g (187.0 mmol) of propionyl chloride and 500 ml of tetrahydrofuran with cooling in an ice bath, And then stirred at 50 ° C. for 2 hours. Thereafter, the reaction solution was poured into 800 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 off, and the solvent was distilled off. The residue was recrystallized from dichloroethane-hexane to obtain 25.3 g of Compound (18) (yield 91.6%).

Example 19
Synthesis of Compound (19) 1- [9-Ethyl-6-benzoyl-9H-carbazol-3-yl] -3- (2,3,4-trimethyl-phenyl) -yl-propane-1,3-dione 33 0.07 g (67.7 mmol) was dissolved in a mixed solution of 700 ml of tetrahydrofuran and 350 ml of concentrated hydrochloric acid, and 8.37 g (81.2 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 1000 ml of ice water and extracted with 1000 ml of chloroform. The organic layer was washed with water (500 ml × 3 times), dried over magnesium sulfate, the desiccant was filtered off to remove the solvent, and the residue was washed with n-hexane to give 1- [9-ethyl- 67.6 Benzoyl-9H-carbazol-3-yl] -3- (2,3,4-trimethyl-phenyl) -yl-propane-1,2,3-trione-2-oxime (37.6 g) was obtained. (Rate 91.9%).

  Next, 1- [9-ethyl-6-benzoyl-9H-carbazol-3-yl] -3- (2,3,4-trimethyl-phenyl) -yl-propane-1,2,3-trione-2 -When oxime 30.0 g (58.1 mmol) and sodium acetate 4.76 g (58.1 mmol) were stirred in 600 ml of benzene, 7.19 g (69.7 mmol) of acetic anhydride was added and heated to reflux for 3 hours. did. Thereafter, the reaction solution is poured into 1000 ml of ice water, the composition organism is extracted with ethyl acetate, the organic layer is washed with water (400 ml × 3 times), dried over magnesium sulfate, the desiccant is filtered off and the solvent is distilled off. The residue was recrystallized from ethyl acetate-hexane to obtain 29.6 g of compound (19) (yield 91.3%).

Example 20
Synthesis of Compound (20) 1- [9-Ethyl-6- (2-methyl-benzoyl) -9H-carbazol-3-yl] -3- (3,4-dimethyloxy-phenyl) -yl-propane-1 2,3-trione-2-oxime used the compound synthesized in Example 2.

  Next, 1- [9-ethyl-6- (2-methyl-benzoyl) -9H-carbazol-3-yl] -3- (3,4-dimethyloxy-phenyl) -yl-propane-1,2, After mixing 25.0 g (45.6 mmol) of 3-trione-2-oxime, 18.5 g (182.3 mmol) of triethylamine, 16.9 g (182.3 mmol) of propionyl chloride and 500 ml of tetrahydrofuran with cooling in an ice bath The mixture was stirred at room temperature for 1 hour, and further stirred at 50 ° C. for 2 hours. Thereafter, the reaction solution was poured into 800 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 off, and the solvent was distilled off. The residue was recrystallized from ethyl acetate-hexane to obtain 25.9 g of compound (18) (yield 94.0%).

Example 21
Synthesis of Compound (21) 1- [9-Ethyl-6- (4-benzoyl-benzoyl) -9H-carbazol-3-yl] -3- (3-phenylsulfanyl-phenyl) -yl-propane-1,3 -30.0 g (45.6 mmol) of dione was dissolved in a mixed solution of 700 ml of tetrahydrofuran and 350 ml of concentrated hydrochloric acid, and 5.64 g (54.7 mmol) of tert-butyl nitrite was added dropwise over 1 hour with stirring at room temperature. did. After completion of dropping, the mixture was stirred at room temperature for 5 hours. The reaction solution was poured into 1000 ml of ice water and extracted with 1000 ml of chloroform. The organic layer was washed with water (500 ml × 3 times), dried over magnesium sulfate, the desiccant was filtered off to remove the solvent, and the residue was washed with n-hexane to give 1- [9-ethyl- 6- (4-Benzoyl-benzoyl) -9H-carbazol-3-yl] -3- (3-phenylsulfanyl-phenyl) -yl-propane-1,2,3-trione-2-oxime was obtained in 29.1 g. (Yield 92.9%).

  Next, 1- [9-ethyl-6- (4-benzoyl-benzoyl) -9H-carbazol-3-yl] -3- (3-phenylsulfanyl-phenyl) -yl-propane-1,2,3- When 25.0 g (36.4 mmol) of trione-2-oxime and 2.99 g (36.4 mmol) of sodium acetate were stirred in 600 ml of benzene, 4.50 g (43.7 mmol) of acetic anhydride was added, and 3 Heated to reflux for hours. Thereafter, the reaction solution is poured into 1000 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 off, and the solvent is distilled off. The residue was recrystallized from ethyl acetate-hexane to obtain 25.2 g of compound (21) (yield 95.1%).

Example 22
Synthesis of Compound (22) 1- [9-Ethyl-6- (3-phenyloxy-benzoyl) -9H-carbazol-3-yl] -3- (2-methylsulfanyl-4-methyl-phenyl) -yl- When 36.0 g (60.2 mmol) of propane-1,3-dione was dissolved in a mixed solution of 600 ml of tetrahydrofuran and 300 ml of concentrated hydrochloric acid, 7.45 g (72.3 mmol) of tert-butyl nitrite was added with stirring at room temperature. The solution 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 1000 ml of ice water and extracted with 1000 ml of chloroform. The organic layer was washed with water (500 ml × 3 times), dried over magnesium sulfate, the desiccant was filtered off to remove the solvent, and the residue was washed with n-hexane to give 1- [9-ethyl- 6- (3-Phenyloxy-benzoyl) -9H-carbazol-3-yl] -3- (2-methylsulfanyl-4-methyl-phenyl) -yl-propane-1,2,3-trione-2-oxime 34.6 g was obtained (yield 91.7%).

  Next, 1- [9-ethyl-6- (3-phenyloxy-benzoyl) -9H-carbazol-3-yl] -3- (2-methylsulfanyl-4-methyl-phenyl) -yl-propane-1 , 2,3-trione-2-oxime 30.0 g (54.7 mmol), triethylamine 22.1 g (218.7 mmol), propionyl chloride 23.3 g (218.7 mmol) and tetrahydrofuran 600 ml while cooling in an ice bath After mixing, the mixture was stirred at room temperature for 1 hour, and further stirred at 50 ° C. for 2 hours. Thereafter, the reaction solution was poured into 900 ml of ice water, the composition organism was extracted with ethyl acetate, the organic layer was washed with water (400 ml × 3 times), dried over magnesium sulfate, the desiccant was filtered to remove the solvent, The residue was recrystallized from ethyl acetate-hexane to obtain 30.9 g of Compound (22) (yield: 93.3%).

Example 23
Synthesis of Compound (23) 1- [9- (2-Ethyloxy-ethyl) -6- (4-phenyl-benzoyl) -9H-carbazol-3-yl] -3- (3-pentyl-phenyl) -yl- When 36.0 g (56.6 mmol) of propane-1,3-dione was dissolved in a mixed solution of 600 ml of tetrahydrofuran and 300 ml of concentrated hydrochloric acid, 7.01 g (67.9 mmol) of tert-butyl nitrite was stirred at room temperature. The solution 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 1200 ml of ice water and extracted with 1200 ml 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 washed with n-hexane to give 1- [9- (2 -Ethyloxy-ethyl) -6- (4-phenyl-benzoyl) -9H-carbazol-3-yl] -3- (3-pentyl-phenyl) -yl-propane-1,2,3-trione-2-oxime 36.3 g was obtained (96.5% yield).

  Next, 1- [9- (2-ethyloxy-ethyl) -6- (4-phenyl-benzoyl) -9H-carbazol-3-yl] -3- (3-pentyl-phenyl) -yl-propane-1 , 2,3-trione-2-oxime 35.0 g (52.6 mmol), triethylamine 21.3 g (210.6 mmol), benzoyl chloride 29.6 g (210.6 mmol) and tetrahydrofuran 600 ml while cooling in an ice bath After mixing, the mixture was stirred at room temperature for 1 hour, and further stirred at 50 ° C. for 2 hours. Thereafter, the reaction solution is poured into 1000 ml of ice water, the composition organism is extracted with ethyl acetate, the organic layer is washed with water (400 ml × 3 times), dried over magnesium sulfate, the desiccant is filtered off and the solvent is distilled off. The residue was recrystallized from dichloromethane-hexane to obtain 37.9 g of Compound (23) (yield 93.6%).

Example 24
Synthesis of Compound (24) 1- (9-Butyl-6-benzoyl-9H-carbazol-3-yl) -3- [4- (1-thiofuranyloxy) -phenyl-yl] -propane-1,3 -10.0 g (105.0 mmol) of tert-butyl nitrite was added dropwise over 1 hour while stirring at room temperature when 50.0 g (87.5 mmol) of dione was dissolved in a mixed solution of 900 ml of tetrahydrofuran and 450 ml of concentrated hydrochloric acid. did. After completion of dropping, the mixture was stirred at room temperature for 5 hours. The reaction solution was poured into 1600 ml of ice water and extracted with 1600 ml of chloroform. The organic layer was washed with water (500 ml × 3 times), dried over magnesium sulfate, the desiccant was filtered off to remove the solvent, and the residue was washed with n-hexane to give 1- (9-butyl- 69.0 g of 6-benzoyl-9H-carbazol-3-yl) -3- [4- (1-thiofuranyloxy) -phenyl-yl] -propane-1,2,3-trione-2-oxime are obtained. (Yield 93.3%).

    Next, 1- (9-butyl-6-benzoyl-9H-carbazol-3-yl) -3--4- (1-thiofuranyloxy) -phenyl-yl] -propane-1,2,3-trione -2-oxime 45.0 g (74.9 mmol) and sodium acetate 6.15 g (74.9 mmol) were stirred in 800 ml of benzene, and 9.27 g (89.9 mmol) of acetic anhydride was added for 3 hours. Heated to reflux. Thereafter, the reaction solution is poured into 1200 ml of ice water, the composition organism is extracted with ethyl acetate, the organic layer is washed with water (500 ml × 3 times), dried over magnesium sulfate, the desiccant is filtered off and the solvent is distilled off. The residue was recrystallized from ethyl acetate-hexane to obtain 45.8 g of compound (24) (yield 95.2%).

Example 25
Synthesis of Compound (25) 1- (9-Ethyl-6-benzoyl-9H-carbazol-3-yl) -3- (3,4-methylenedioxy-phenyl-yl) -propane-1,3-dione 42 0.03 g (83.4 mmol) was dissolved in a mixed solution of 900 ml of tetrahydrofuran and 450 ml of concentrated hydrochloric acid, and 10.3 g (100.1 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 1500 ml of ice water and extracted with 1500 ml of chloroform. The organic layer was washed with water (500 ml × 3 times), dried over magnesium sulfate, the desiccant was filtered off to remove the solvent, and the residue was washed with n-hexane to give 1- (9-ethyl- 60.5-benzoyl-9H-carbazol-3-yl) -3- (3,4-methylenedioxy-phenyl-yl) -propane-propane-1,2,3-trione-2-oxime was obtained, 40.5 g. (Yield 91.1%).

    Next, 1- (9-ethyl-6-benzoyl-9H-carbazol-3-yl) -3- (3,4-methylenedioxy-phenyl-yl) -propane-1,2,3-trione-2 -When 35.0 g (65.7 mmol) of oxime and 5.39 g (65.7 mmol) of sodium acetate were stirred in 700 ml of benzene, 8.13 g (78.9 mmol) of acetic anhydride was added and heated to reflux for 3 hours. did. Thereafter, the reaction solution is poured into 1000 ml of ice water, the composition organism is extracted with ethyl acetate, the organic layer is washed with water (400 ml × 3 times), dried over magnesium sulfate, the desiccant is filtered off and the solvent is distilled off. The residue was recrystallized from ethyl acetate-hexane to obtain 34.9 g of compound (25) (yield 92.5%).

Example 26
Synthesis of Compound (26) 1- (9-Ethyl-6-benzoyl-9H-carbazol-3-yl) -3- (3,4-ethylenedioxy-phenyl-yl) -propane-1,3-dione 50 To a solution of 0.0 g (96.6 mmol) in a mixed solution of 1000 ml of tetrahydrofuran and 500 ml of concentrated hydrochloric acid, 11.9 g (115.9 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 1800 ml of ice water and extracted with 1800 ml of chloroform. The organic layer was washed with water (700 ml × 3 times), dried over magnesium sulfate, the desiccant was filtered to remove the solvent, and the residue was washed with n-hexane to give 1- (9-ethyl- 69.6 g of 6-benzoyl-9H-carbazol-3-yl) -3- (3,4-ethylenedioxy-phenyl-yl) -propane-1,2,3-trione-2-oxime were obtained. (Rate 94.0%).

    Next, 1- (9-ethyl-6-benzoyl-9H-carbazol-3-yl) -3- (3,4-ethylenedioxy-phenyl-yl) -propane-1,2,3-trione-2 -When oxime 45.0 g (82.3 mmol) and sodium acetate 6.75 g (82.3 mmol) were stirred in 800 ml of benzene, 10.2 g (98.8 mmol) of acetic anhydride was added and heated to reflux for 3 hours. did. Thereafter, the reaction solution is poured into 1200 ml of ice water, the composition organism is extracted with ethyl acetate, the organic layer is washed with water (500 ml × 3 times), dried over magnesium sulfate, the desiccant is filtered off and the solvent is distilled off. The residue was recrystallized from ethyl acetate-hexane to obtain 45.4 g of compound (26) (yield 93.6%).

Example 27
Synthesis of Compound (27) 1- (9-Ethyl-6-benzoyl-9H-carbazol-3-yl) -3- (N-methylindoline-5-yl) -propane-1,3-dione 30.0 g ( 58.3 mmol) was dissolved in a mixed solution of 600 ml of tetrahydrofuran and 300 ml of concentrated hydrochloric acid, and 7.21 g (70.0 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 1600 ml of ice water and extracted with 1600 ml of chloroform. The organic layer was washed with water (500 ml × 3 times), dried over magnesium sulfate, the desiccant was filtered off to remove the solvent, and the residue was washed with n-hexane to give 1- (9-ethyl- 69.7-benzoyl-9H-carbazol-3-yl) -3- (N-methylindoline-5-yl) -propane-1,2,3-trione-2-oxime was obtained (29.7 g). 7%).

    Next, 1- (9-ethyl-6-benzoyl-9H-carbazol-3-yl) -3- (N-methylindoline-5-yl) -propane-1,2,3-trione-2-oxime 25 To a stirred solution of 0.0 g (46.0 mmol) and 3.77 g (46.0 mmol) of sodium acetate in 500 ml of benzene, 5.69 g (55.2 mmol) of acetic anhydride was added and heated to reflux for 3 hours. Thereafter, the reaction solution was poured into 800 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 off, and the solvent was distilled off. The residue was recrystallized from ethyl acetate-hexane to obtain 24.8 g of compound (27) (yield 91.9%).

Example 28
Synthesis of Compound (28) 1- (9-Ethyl-6-benzoyl-9H-carbazol-3-yl) -3- [chroman-6-yl] -propane-1,3-dione 30.0 g (58.2 mmol) ) Was dissolved in a mixed solution of 600 ml of tetrahydrofuran and 300 ml of concentrated hydrochloric acid, and 7.20 g (69.8 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 1000 ml of ice water and extracted with 1000 ml of chloroform. The organic layer was washed with water (400 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- (9-ethyl- 69.4 Benzoyl-9H-carbazol-3-yl) -3- [chroman-6-yl] -propane-1,2,3-trione-2-oxime (29.4 g) was obtained (yield 92.9%). .

    Next, 25.0 g of 1- (9-ethyl-6-benzoyl-9H-carbazol-3-yl) -3- [chroman-6-yl] -propane-1,2,3-trione-2-oxime ( 45.9 mmol) and 3.77 g (45.9 mmol) of sodium acetate were stirred in 500 ml of benzene, 5.68 g (55.1 mmol) of acetic anhydride was added, and the mixture was heated to reflux for 3 hours. Thereafter, the reaction solution is poured into 800 ml of ice water, the composition organism is extracted with ethyl acetate, the organic layer is washed with water (400 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 24.4 g of Compound (28) (yield 90.6%).

Example 29
Synthesis of Compound (29) 1- (9-Ethyl-6-benzoyl-9H-carbazol-3-yl) -3- [thiochroman-6-yl] -propane-1,3-dione 40.0 g (75.2 mmol) ) Was dissolved in a mixed solution of 800 ml of tetrahydrofuran and 400 ml of concentrated hydrochloric acid, and 9.31 g (90.3 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 1400 ml of ice water and extracted with 1500 ml of chloroform. The organic layer was washed with water (500 ml × 3 times), dried over magnesium sulfate, the desiccant was filtered off to remove the solvent, and the residue was washed with n-hexane to give 1- (9-ethyl- 69.6 Benzoyl-9H-carbazol-3-yl) -3- [thiochroman-6-yl] -propane-1,2,3-trione-2-oxime (39.6 g) was obtained. .

    Next, 35.0 g of 1- (9-ethyl-6-benzoyl-9H-carbazol-3-yl) -3- [thiochroman-6-yl] -propane-1,2,3-trione-2-oxime ( 62.4 mmol) and 5.12 g (62.4 mmol) of sodium acetate were stirred in 600 ml of benzene, and 7.72 g (74.9 mmol) of acetic anhydride was added and heated to reflux for 3 hours. Thereafter, the reaction solution was poured into 900 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 recrystallized from ethyl acetate-hexane to obtain 34.9 g of compound (29) (yield 92.8%).

Example 30
Synthesis of Compound (30) 1- [9-Ethyl-6- (3,4-ethylenedioxy-benzoyl) -9H-carbazol-3-yl] -3- (4-methyloxy-phenyl-yl) -propane -1,3-dione 50.0 g (93.7 mmol) was dissolved in a mixed solution of 900 ml of tetrahydrofuran and 450 ml of concentrated hydrochloric acid, and 11.6 g (112.5 mmol) of tert-butyl nitrite was added to 1 with stirring at room temperature. It was added dropwise over time. After completion of dropping, the mixture was stirred at room temperature for 5 hours. The reaction solution was poured into 1600 ml of ice water and extracted with 1600 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 washed with n-hexane to give 1- [9-ethyl- 6- (3,4-Ethylenedioxy-benzoyl) -9H-carbazol-3-yl] -3- (4-methyloxy-phenyl-yl) -propane-1,2,3-trione-2-oxime 50 0.1 g was obtained (yield 95.0%).

    Next, 1- [9-ethyl-6- (3,4-ethylenedioxy-benzoyl) -9H-carbazol-3-yl] -3- (4-methyloxy-phenyl-yl) -propane-1, When 45.0 g (80.0 mmol) of 2,3-trione-2-oxime and 6.56 g (80.0 mmol) of sodium acetate were stirred in 800 ml of benzene, 9.90 g (96.0 mmol) of acetic anhydride was added. In addition, the mixture was heated to reflux for 3 hours. Thereafter, the reaction solution is poured into 1200 ml of ice water, the composition organism is extracted with ethyl acetate, the organic layer is washed with water (500 ml × 3 times), dried over magnesium sulfate, the desiccant is filtered off and the solvent is distilled off. The residue was recrystallized from ethyl acetate-hexane to obtain 45.8 g of compound (30) (yield 94.8%).

  By applying the methods of Examples 1 to 30 described above, it is possible to easily synthesize the compounds of the present invention other than the Examples.

  Table 3 shows the results of elemental analysis of the compounds of the present invention synthesized in Examples 1-30.

  Next, although the application example using the compound of this invention as a radical polymerization initiator (A) is demonstrated, this invention is not limited only to the following.

Examples 31-60, Comparative Example 1
<Curing test 1>
A polymerizable composition comprising 8 parts by weight of a radical polymerization initiator (A), 100 parts by weight of pentaerythritol triacrylate as a radical polymerizable compound (B), 100 parts by weight of polymethyl acrylate as a binder, and 1600 parts by weight of cyclohexanone as a solvent is shown. 4 was 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. The coating film was irradiated with light (9.0 mW / cm ² ) of a high-pressure mercury lamp through a bandpass filter that selectively transmits light of 350 to 380 nm. Table 4 shows the results of rubbing with a cotton cloth when the irradiation time is 20 seconds and confirming the presence or absence of scratches on the cured product.
○: No scratch ×: Scratch

Table 4

  In the polymerization compositions (Examples 31 to 60) using the radical polymerization initiator (A) of the present invention, the substituent corresponding to the 3-position phenyl group of the general formula (1) is a condensed polycyclic hydrocarbon group. Compared with the polymerization composition (Comparative Example 1) using the radical polymerization initiator (A), radicals are generated more efficiently by light irradiation to polymerize acrylic groups. That is, high sensitivity can be achieved by using the compound represented by the general formula (1) of the present invention as the radical polymerization initiator (A).

Examples 61-72, Comparative Example 2
<Curing test 2>
4 parts by weight of radical polymerization initiator (A), 100 parts by weight of pentaerythritol triacrylate as radically polymerizable compound (B), 0 or 1 part by weight of sensitizer (C), 100 parts by weight of polymethyl acrylate as binder, solvent A polymerizable composition consisting of 1600 parts by weight of cyclohexanone 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 coating film was irradiated with light (9.0 mW / cm ² ) of a high-pressure mercury lamp through a bandpass filter that selectively transmits light of 350 to 380 nm. First, when the irradiation time was 15 seconds, it was rubbed with a cotton cloth, and those that were not damaged were finished. Table 5 shows the results of confirming the presence or absence of scratches on the cured product by preparing a coated film under the same conditions and extending the irradiation time to 25 seconds under the same conditions.
○: No scratch.
Δ: Slight scratches are confirmed.
X: Scratches are clearly confirmed.

Table 5

  The polymerization compositions (Examples 61 to 72) using the radical polymerization initiator (A) of the present invention are highly sensitive radical polymerization initiators without using the sensitizer (C). Further sensitivity can be increased by using (C) in combination. On the other hand, the radical polymerization initiator (A) in which the substituent corresponding to the 3-position phenyl group in the general formula (1) is a condensed polycyclic hydrocarbon group is sufficiently curable even when the sensitizer (C) is used in combination. (Comparative Example 2).

Examples 73-89, comparative example 3
<Developability test>
(Preparation of acrylic resin solution)
Add 800 parts by weight of cyclohexanone to the reaction solution, heat to 100 ° C. while injecting nitrogen gas into the container, and drop the mixture of the following monomers and thermal polymerization initiator at the same temperature over 1 hour to conduct the polymerization reaction. It was.
Styrene 60.0 parts by weight Methacrylic acid 60.0 parts by weight Methyl methacrylate 65.0 parts by weight Butyl methacrylate 65.0 parts by weight Azobisisobutyronitrile 10.0 parts by weight After dropping, the reaction was further carried out at 100 ° C. for 3 hours. Then, 2.0 parts by weight of azobisisobutyronitrile dissolved in 50.0 parts by weight of cyclohexanone was added, and the reaction was further continued at 100 ° C. for 1 hour, so that the weight average molecular weight was about 40,000. An acrylic resin solution was obtained. After cooling to room temperature, sample about 2 g of the resin solution, heat dry at 180 ° C. for 20 minutes, measure the nonvolatile content, and add cyclohexanone to the previously synthesized resin solution so that the nonvolatile content is 20%. To prepare an acrylic resin solution.

  8 parts by weight of the radical polymerization composition (A), 100 parts by weight of dipentaerythritol pentaacrylate (Sartomer, SR399) as the radical polymerizable compound (B), and the acrylic resin solution prepared above as a solution containing an alkali-soluble resin A polymerization composition consisting of 500 parts by weight and 400 parts by weight of cyclohexanone as a solvent was blended in the composition shown in Table 6 to prepare a coating solution.

The polymerizable composition solution is filtered through a 0.2 μm pore size disk filter, coated on a stainless steel plate (# 600 polishing) using a spin coater, and heated and dried in an oven at 80 ° C. for 3 minutes. The solvent was removed. After drying, the film thickness of the polymerizable composition formed on the stainless steel plate was 2 μm. These were immersed in an aqueous tetramethylammonium hydroxide solution having a concentration of 0.2% by weight at 20 ° C. for 45 seconds, further washed with distilled water, and dried for 2 hours in a hot air dryer (60 ° C.) to remove moisture. . Table 6 shows the result of checking the presence or absence of stickiness by tucking the surface of the stainless steel plate with a finger.
○: No stickiness ×: With stickiness

Table 6

  It was confirmed that the polymerizable composition (Examples 73 to 89) using the radical polymerization initiator (A) of the present invention was rapidly developed in a predetermined time with respect to an alkaline developer. On the other hand, when the radical polymerization initiator (A) in which the substituent corresponding to the 3-position-phenyl group in the general formula (1) is a condensed polycyclic hydrocarbon group is used (Comparative Example 3), the radical polymerization initiator (A) is completely removed in a predetermined time. Not developed. Therefore, it has been clarified that the use of the radical polymerization initiator (A) of the present invention has superior characteristics even in a field where alkali developability is required.

Examples 90-119, Comparative Example 4
<Storage stability test>
The polymerizable composition solution prepared in the examples was stored in the dark at 40 ° C. for 3 weeks. Then, the result of having evaluated storage stability by the presence or absence of gelatinization of this polymeric composition solution is shown in Table 7.
○: Storage stability is good (no change before storage. Gelation is not confirmed.)
X: Storage stability was poor (gelation was confirmed).

Table 7

  In the polymerizable compositions (Examples 90 to 119) using the radical polymerization initiator (A) of the present invention, gelation was not observed under storage conditions of 40 ° C. for 3 weeks. That is, by using the compound represented by the general formula (1) of the present invention as the radical polymerization initiator (A), the substituent corresponding to the 3-position-phenyl group of the general formula (1) is condensed polycyclic hydrocarbon. Storage stability can be improved as compared with the polymerization composition (Comparative Example 4) using the radical polymerization initiator (A) as a group.

Examples 120 to 136, Comparative Example 5
<Odor test>
A stainless steel plate hardened under the same conditions as in the curability test is filled in a glass bottle, and after 1 hour at 40 ° C., 5 panelists have to determine the odor relative to 1 (defect) to 3 (good). Table 8 shows the results of evaluation in five stages.

Table 8

  In the photopolymerizable composition (Examples 120 to 136) using the radical polymerization initiator (A) of the present invention, the substituent corresponding to the 3-position phenyl group of the general formula (1) is a condensed polycyclic hydrocarbon group. As compared with the radical polymerization initiator (A) (Comparative Example 5), the odor was found to be excellent. It is presumed that the reason why the photopolymerizable composition of the present invention is excellent in odor is because there is little volatilization of the radical polymerization initiator (A) and its decomposition product after curing.

Examples 137 to 154, Comparative Example 6
<Solubility test>
A polymerization composition comprising 10 parts by weight of the radical polymerization initiator (A) and 100 parts by weight of pentaerythritol triacrylate and 100 parts by weight of cyclohexanone was blended in the composition shown in Table 9. Table 9 shows the results of the evaluation of the solubility based on the presence or absence of undissolved residue visually.
○: No unmelted residue ×: Undissolved residue

Table 9

  The radical polymerization initiator (A) of the present invention (Examples 137 to 154) is a radical polymerization initiator (A) in which the substituent corresponding to the 3-position phenyl group of the general formula (1) is condensed polycyclic hydrocarbon yellow (A ) (Comparative Example 6) was found to be more excellent in solubility. That is, it has been clarified that the photopolymerization initiator (A) of the present invention is excellent in handling property and can be developed for various uses.

Examples 155 to 171 and Comparative Example 7
<Yellowening of cured product>
A polymerizable composition comprising 6 parts by weight of a radical polymerization initiator (A), 100 parts by weight of pentaerythritol triacrylate as a radical polymerizable compound (B), 100 parts by weight of polymethyl acrylate as a binder, and 1600 parts by weight of cyclohexanone as a solvent is shown. The composition shown in Fig. 10 was blended to prepare a coating solution. This coating solution was applied onto a pet film using a bar coater (# 3). The coated product was cut into the coated product under the same conditions as the curability, and 10 panelists relatively determined the yellowing of the coated product. 1 (defect) to 5 (good) ). The results are shown in Table 10.

Table 10

  In the photopolymerizable composition (Examples 155 to 171) using the radical polymerization initiator (A) of the present invention, the substituent corresponding to the 3-position phenyl group of the general formula (1) is a condensed polycyclic hydrocarbon group. Compared with the photopolymerizable composition (Comparative Example 7) using the radical polymerization initiator (A) which is, it is clearly excellent in yellowing. That is, it was revealed that the radical polymerization initiator (A) of the present invention is an initiator that can be developed even in the field where transparency of the cured product is required.

Claims (6)

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

(Wherein R ^{1 to} R ⁵ and R ^{12 to} R ¹⁶ each independently represents a hydrogen atom, a halogen atom, a cyano group, a nitro group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, Substituted or unsubstituted alkynyl group, substituted or unsubstituted aryl group, substituted or unsubstituted heterocyclic group, substituted or unsubstituted alkyloxy group, substituted or unsubstituted aryloxy group, substituted or unsubstituted heterocyclic ring Represents an oxy group, a substituted or unsubstituted alkylsulfanyl group, a substituted or unsubstituted arylsulfanyl group, a substituted or unsubstituted acyl group, or a substituted or unsubstituted amino group, and these R ^{1 to} R ⁵ , R ^{12 to} R ¹⁶ may be combined with adjacent substituents to form a ring.
R ^{6 to} R ¹¹ are each independently a hydrogen atom, a halogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkyloxy group, a substituted or unsubstituted aryloxy group, a substituted or unsubstituted alkylsulfanyl. Represents a group, a substituted or unsubstituted arylsulfanyl group, or a substituted or unsubstituted amino group.
X and Y each independently represent a monovalent organic residue. ) At least one of R ^{12 to} R ¹⁶ is a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkyloxy group, a substituted or unsubstituted aryloxy group, a substituted or unsubstituted heterocyclic oxy group, a substituted or unsubstituted The compound according to claim 1, which is any one of an alkylsulfanyl group, a substituted or unsubstituted arylsulfanyl group, and a substituted or unsubstituted amino group. At least one of R ¹² to R ¹⁶ are, according to claim 1 or 2 A compound according a substituted or unsubstituted alkyl group.   A radical polymerization initiator (A) comprising the compound according to claim 1.   A polymerizable composition comprising the radical polymerization initiator (A) according to claim 4 and a radical polymerizable compound (B).   The polymerizable composition according to claim 5, further comprising a sensitizer (C).