TWI411606B - Oxime ester, radical polymerization initiator, polymerizable composition, negative resist and image pattern - Google Patents

Abstract

Disclosed are a novel oxime ester compound, which is capable of functioning as a highly sensitive radical polymerization initiator, and a curable composition using the same. Also disclosed are a negative resist material, which is appropriately usable particularly as a photoresist material, and an image pattern-forming method using said negative resist. A radical polymerization initiator (A) is represented by general formula (1). In general formula (1), R1 and R2 are selected from an alkyl group, an aryl group, a heterocyclic group, etc.; R3 to R5 are selected from a hydrogen atom, an alkyl group, etc.; R6 to R9 are selected from a hydrogen atom, an alkyl group, an aryl group, a heterocyclic group, etc.; and R10 to R14 are selected from a hydrogen atom, a cyano group, a nitro group, a haloalkyl group, a sulfinyl group, a sulfonyl group, an acyl group, etc., provided that all of R10 to R14 are not hydrogen atoms at the same time.

Description

An oxime ester compound, a radical polymerization initiator, a polymerizable composition, a negative resist, and an image pattern

The present invention relates to an oxime ester compound, a radical polymerization initiator containing the oxime ester compound, a polymerizable composition using the radical polymerization initiator, a negative resist using the polymerizable composition, and the use of the same A method of forming an image pattern of a negative resist. Further, the present invention relates to a molding resin, a cast resin, a resin for stereolithography, a sealant, a dental polymer resin, a printing ink, a paint, a photosensitive resin for printing plates, and a color for printing. Color proof, resist for color filter, resist for black matrix, photospacer for liquid crystal, screen material for rear-projection, optical fiber, plasma display Rib material, dry film resist, resist for printed circuit board, solder resist, photoresist for semiconductor, resist for microelectronics, micro mechanical parts Manufacturing resist, etching resist, microlens array, insulating material, hologram material, optical switch, waveguide material, overcoat agent, powder coating , an adhesive, an adhesive, a release agent, an optical recording medium, an adhesive, a release coating agent, a composition for using an image technology material using microcapsules, various devices, and the like.

In the past, it has been known that a certain oxime ester compound functions as a radical polymerization initiator (see Non-Patent Document 1 and Patent Documents 1 and 2). Further, a photo-radical polymerization initiator of a composition for a positive or negative photosensitive polyimide precursor exhibits an α-ketoxime ester compound (see Patent Document 3). Further, certain α,α'-diketone oxime ester compounds (see Patent Documents 4 to 8) have been disclosed. Further, a certain o-nonyl oxime ester compound (refer to Patent Documents 9 to 13) has been disclosed. In recent years, in order to respond to various processes of productivity improvement or new proposals, high sensitivity of a polymerization initiator has been generally required. As a result of the research carried out in response to this request, although significant progress has been made, it is still pursuing further improvement in sensitivity and the resulting increase in productivity.

Further, in recent years, a photoresist method using a photosensitive resin has been used in various fields. In the photoresist method, the usual method is as follows: a photosensitive resin layer is formed by coating or transferring from another substrate on the surface of the substrate on which the desired image is to be set, and then the photosensitive image is interposed by the original image. After exposing the energy line to the resin layer and exposing it, the unexposed portion is removed by a developing treatment with a solvent or an alkaline aqueous solution to form an image corresponding to the original image. As an example of the use of such a photoresist method, a negative resist is disclosed as a material for forming a spacer for a display panel (see Patent Documents 14 to 16). In addition, materials for manufacturing electric/electronic parts and printed circuit boards are disclosed as a certain type of negative resist (see Patent Documents 17 to 19). Recently, as a resist agent composition of higher sensitivity, it is known to use a certain o-nonyl decyl ester as a resist composition of a radical polymerization initiator to form a material for displaying a spacer for a plate. In other words, a negative resist is disclosed (see Patent Document 20). In addition, a material for manufacturing an electric/electronic component or a printed circuit board is disclosed as a negative resist (see Patent Document 21). These functions can be used as a resist composition, but in recent years, in order to cope with various improvements in productivity or new proposals, higher resistance functions and additional functions are required for the resist composition. In particular, a resist composition having a higher sensitivity is required, and various resist compositions are actively developed.

[Advanced technical literature] [Patent Literature]

Patent Document 1: US Patent No. 3,558,309

Patent Document 2: US Patent No. 4,255,513

Patent Document 3: Japanese Patent Laid-Open No. 7-140,658

Patent Document 4: US Patent No. 5,019,482

Patent Document 5: Japanese Laid-Open Patent Publication No. 62-184,056

Patent Document 6: Japanese Patent Laid-Open No. 62-273, No. 259

Patent Document 7: JP-A-62-286, 961

Patent Document 8: Japanese Patent Laid-Open No. 62-201, 859

Patent Document 9: Japanese Patent Laid-Open Publication No. 2001-233,842

Patent Document 10: Japanese Laid-Open Patent Publication No. 2000-80,068

Patent Document 11: Japanese Patent Publication No. 2004-534,797

Patent Document 12: International Patent Publication No. 2007/062963

Patent Document 13: International Patent Publication No. 2008/078678

Patent Document 14: Japanese Patent Laid-Open No. Hei 11-174464

Patent Document 15: Japanese Laid-Open Patent Publication No. 2001-226449

Patent Document 16: Japanese Laid-Open Patent Publication No. 2002-341531

Patent Document 17: Japanese Patent Laid-Open No. Hei 10-198033

Patent Document 18: Japanese Laid-Open Patent Publication No. 2002-236362

Patent Document 19: Japanese Laid-Open Patent Publication No. 2002-249644

Patent Document 20: Japanese Laid-Open Patent Publication No. 2001-261761

Patent Document 21: Japanese Laid-Open Patent Publication No. 2001-302871

[Non-patent literature]

Non-Patent Document 1: European Polymer Journal, 1970, 6, 933-943

An object of the present invention is to provide a novel oxime ester compound and a sclerosing composition using the oxime ester compound, which can function as a high-sensitivity radical polymerization initiator, by irradiating an energy ray, In particular, active radicals are efficiently generated by light irradiation, and a radical polymerizable compound can be polymerized in a short time.

Another object of the present invention is to provide a negative resist material having alkaline development properties particularly suitable for a photoresist material, and an image pattern forming method using the negative resist material, the negative resist material system The hardening speed is extremely fast, and it can be applied to very sharp pattern exposure or direct drawing by the energy line, and the adhesion to the substrate is very excellent.

The inventors of the present invention have completed the present invention after carefully studying the above problems and working hard to solve them. That is, one aspect of the present invention relates to a compound represented by the following formula (1).

General formula (1)

(Wherein, R ¹ represents a substituted of unsubstituted alkenyl, substituted of unsubstituted alkyl, substituted or unsubstituted alkoxy group of, the substituted or unsubstituted aryl group, the substituted or unsubstituted aryloxy, substituted Or unsubstituted heterocyclic group, substituted or unsubstituted heterocyclic oxy group, substituted or unsubstituted alkylsulfanyl group, substituted or unsubstituted arylthio group, substituted or unsubstituted alkyl sulfinyl group (alkylsulfinyl), substituted or unsubstituted arylsulfinyl, substituted or unsubstituted alkylsulfonyl, substituted or unsubstituted arylsulfonyl, substituted or unsubstituted fluorenyl, substituted Or unsubstituted anthraceneoxy, substituted or unsubstituted amino group, substituted or unsubstituted phosphinoyl, substituted or unsubstituted carbamoyl, or substituted or unsubstituted amine sulfonate Sulfamoyl; R ² represents a substituted or unsubstituted alkenyl group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted aryl group, a substituted or unsubstituted aryloxy group , substituted or unsubstituted heterocyclic group, substituted or unsubstituted heterocyclic oxy group, substituted or a substituted alkylthio group, a substituted or unsubstituted arylthio group, a substituted or unsubstituted alkylsulfinyl group, a substituted or unsubstituted arylsulfinylene group, a substituted or unsubstituted alkylsulfonyl group, a substituted or unsubstituted arylsulfonyl group, a substituted or unsubstituted anthraceneoxy group, or a substituted or unsubstituted amine group; R ³ to R ⁵ each independently represent a hydrogen atom, a halogen atom, a cyano group, a nitro group Alternate or unsubstituted alkenyl group, substituted or unsubstituted alkyl group, substituted or unsubstituted alkoxy group, substituted or unsubstituted aryl group, substituted or unsubstituted aryloxy group, substituted or unsubstituted heterocyclic ring a substituted, unsubstituted alkylthio group, a substituted or unsubstituted alkylthio group, a substituted or unsubstituted arylthio group, a substituted or unsubstituted fluorenyl group, or a substituted or unsubstituted amine group; R ⁶ And R ⁹ each independently represent a hydrogen atom, a halogen atom, a cyano group, a haloalkyl group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted aryl group, a substituted or unsubstituted group. Aryloxy, substituted or unsubstituted heterocyclic group, substituted or unsubstituted heterocyclic oxy group, substituted or not Alkenyl, substituted or unsubstituted alkylthio, substituted or unsubstituted arylthio, substituted or unsubstituted alkylsulfinyl, substituted or unsubstituted arylsulfinyl, substituted or unsubstituted a substituted alkylsulfonyl group, a substituted or unsubstituted arylsulfonyl group, a substituted or unsubstituted amine group, or a substituent represented by the following formula (2):

(wherein R ¹ 'and R ² ' are the same as R ¹ and R ² ); and R ¹⁰ to R ¹⁴ each independently represent a hydrogen atom, a halogen atom, a cyano group, a nitro group, a haloalkyl group, a substituent or Unsubstituted alkylsulfinyl, substituted or unsubstituted arylsulfinylene, substituted or unsubstituted alkylsulfonyl, substituted or unsubstituted arylsulfonyl, or substituted or unsubstituted The sulfhydryl group, but R ¹⁰ to R ^{14 are} not all hydrogen atoms at the same time).

Further, in one aspect of the invention, in the above compound, at least one of R ¹⁰ to R ¹⁴ is a nitro group or a substituted or unsubstituted fluorenyl group.

Further, in one aspect of the invention, in the above compound, at least one of R ¹⁰ to R ¹⁴ is a nitro group or a compound of the following formula (3):

(wherein R ¹⁵ to R ¹⁹ each independently represent a hydrogen atom, a halogen atom, a cyano group, a nitro group, a haloalkyl group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted group. Aryl, substituted or unsubstituted aryloxy, substituted or unsubstituted heterocyclic group, substituted or unsubstituted heterocyclic oxy group, substituted or unsubstituted alkenyl group, substituted or unsubstituted alkylthio group, substituted Or an unsubstituted arylthio group, a substituted or unsubstituted thiol group, or a substituted or unsubstituted amine group).

Further, in one aspect of the invention, in the above compound, R ¹² is a nitro group or the above formula (3).

Further, one aspect of the present invention relates to a radical polymerization initiator (A) containing the above compound.

Further, an aspect of the present invention relates to a polymerizable composition comprising the above-mentioned radical polymerization initiator (A) and a radical polymerization initiator (B).

Further, in one aspect of the invention, the sensitizer (C) is further contained in the polymerizable composition.

Moreover, one aspect of the present invention relates to the above-mentioned polymerizable composition, which contains a coloring component (D).

Further, in one aspect of the invention, the polymerizable composition contains an alkali soluble resin (E).

Further, an aspect of the present invention relates to a negative resist comprising the above polymerizable composition.

Further, an aspect of the present invention relates to a method for producing a polymer obtained by irradiating an energy ray onto the polymerizable composition to polymerize it.

In addition, an aspect of the present invention relates to a method for forming an image pattern, characterized in that a negative resist is laminated on the substrate, partially irradiated with an energy ray to polymerize, and an alkaline developing solution is used. Part of the irradiation is removed.

Further, an aspect of the present invention relates to an image pattern formed by the above-described image pattern forming method.

The content disclosed in the present application is the subject of Japanese Patent Application No. 2009-143790, the entire disclosure of which is incorporated herein by reference.

The compound of the present invention is an α-ketooxime ester compound characterized by substituting an electron-attracting substituent on a phenyl group of the N-phenylcarbazole skeleton, and is effective by irradiation of an energy ray, particularly by light irradiation. Produces active free radicals. Therefore, a compound having a remarkably good effect as a radical polymerization initiator can be provided.

Further, by using the compound of the present invention as a radical polymerization initiator (A), a polymerizable composition having good characteristics can be provided. For example, molding resin, casting resin, photo-forming resin, sealant, dental polymer resin, printing ink, inkjet ink, paint, photosensitive resin for printing plate, color proof for printing, color filter Resistor, resist for black matrix, optical spacer for liquid crystal, screen material for rear projection, optical fiber, rib for plasma display, dry film resist, resist for printed circuit board, solder resist, photoresist for semiconductor Resistors for microelectronics, resists for the manufacture of parts for micromachines, etch resists, microlens arrays, insulating materials, holographic materials, optical switches, materials for waveguides, coating protectants, powder coatings, adhesives In the field of adhesives, release agents, optical recording media, adhesives, release coating agents, etc., practical oligomers or polymers can be provided in an industrial manner, and can be provided to obtain good properties. A radical polymerization initiator of the cured product and a polymerizable composition using the radical polymerization initiator.

The polymerizable composition of the present invention is particularly suitable for very vivid pattern exposure or direct drawing, and is excellent in adhesion to a substrate. Therefore, it is possible to provide a high-sensitivity negative resist material suitable for a photoresist material, and an image pattern forming method using the negative resist.

Hereinafter, embodiments of the present invention will be described in detail.

First, the compound of the present invention will be explained. The compound of the present invention is represented by the formula (1) and is characterized by being substituted with an electron-attracting substituent on the phenyl group of the N-phenylcarbazole skeleton. Further, since it has such a structure, when the compound of the present invention irradiates light in the wavelength region, it is decomposed very efficiently even without using a sensitizer. As a result, the composition of the present invention can function as a high-sensitivity material which efficiently generates a large amount of radicals.

General formula (1)

In the formula, R ¹ represents a substituted of unsubstituted alkenyl, substituted of unsubstituted alkyl, substituted or unsubstituted alkoxy group of, the substituted or unsubstituted aryl group, the substituted or unsubstituted aryloxy, substituted Or unsubstituted heterocyclic group, substituted or unsubstituted heterocyclic oxy group, substituted or unsubstituted alkylthio group, substituted or unsubstituted arylthio group, substituted or unsubstituted alkyl sulfinyl group, substituted or Unsubstituted arylsulfinyl, substituted or unsubstituted alkylsulfonyl, substituted or unsubstituted arylsulfonyl, substituted or unsubstituted fluorenyl, substituted or unsubstituted decyloxy, substituted Or an unsubstituted amino group, a substituted or unsubstituted phosphonium group, a substituted or unsubstituted amine carbenyl group, or a substituted or unsubstituted amine sulfonyl group. Wherein, in view of the synthesis aspect of the compound, or the performance aspect when used as a starter, etc., a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted aryl group, a substitution Or an unsubstituted aryloxy group, or a substituted or unsubstituted heterocyclic group, and a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted heterocyclic group is Better.

The substituted or unsubstituted alkenyl group in R ¹ may, for example, be a linear, branched, monocyclic or condensed polycyclic alkenyl group having 1 to 18 carbon atoms. These may also have a plurality of carbon-carbon double bonds in the structure. Specific examples include vinyl, 1-propenyl, allyl, 2-butenyl, 3-butenyl, isopropenyl, isobutenyl, 1-pentenyl, 2-pentenyl, 3- Pentenyl, 4-pentenyl, 1-hexenyl, 2-hexenyl, 3-hexenyl, 4-hexenyl, 5-hexenyl, cyclopentenyl, cyclohexenyl, 1,3-butadienyl group, cyclohexadienyl group, cyclopentadienyl group or the like, but is not limited thereto.

The substituted or unsubstituted alkyl group in R ¹ may, for example, be a linear, branched, monocyclic or condensed polycyclic alkyl group having 1 to 18 carbon atoms, or a carbon number of 2 to 18 and optionally contained A linear, branched, monocyclic or condensed polycyclic alkyl group having one or more ether bonds (-O-). Specific examples of the linear, branched, monocyclic or condensed polycyclic alkyl group having 1 to 18 carbon atoms include, for example, a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, and the like. Octyl, fluorenyl, fluorenyl, dodecyl, octadecyl, isopropyl, isobutyl, isopentyl, second butyl, tert-butyl, second pentyl, third pentyl Base, third octyl, neopentyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, adamantyl, norbornyl, borneol, 4-decylcyclohexyl, etc. However, it is not limited to this. Further, specific examples of the linear or branched chain alkyl group having 2 to 18 carbon atoms and optionally one or more ether bonds may be, for example, -CH ₂ -O-CH ₃ or -CH ₂ -CH ₂ -O- CH ₂ -CH ₃ , -CH ₂ -CH ₂ -CH ₂ -O-CH ₂ -CH ₃ , -(CH ₂ -CH ₂ -O) _n -CH ₃ (here, n is 1 to 8), - (CH ₂ -CH ₂ -CH ₂ -O) _m -CH ₃ (here, m is 1 to 5), -CH ₂ -CH(CH ₃ )-O-CH ₂ -CH ₃ , -CH ₂ -CH -(OCH ₃ ) ₂ or the like, but is not limited thereto.

Specific examples of the monocyclic or condensed polycyclic alkyl group having 2 to 18 carbon atoms and optionally one or more ether linkages are listed below, but are not limited thereto.

The substituted or unsubstituted alkoxy group in R ¹ may, for example, be a linear, branched, monocyclic or condensed polycyclic alkoxy group having 1 to 18 carbon atoms, or a carbon number of 2 to 18 and In the case of a linear, branched, monocyclic or condensed polycyclic alkoxy group having one or more ether bonds. Specific examples of the linear, branched, monocyclic or condensed polycyclic alkoxy group having 1 to 18 carbon atoms include, for example, a methoxy group, an ethoxy group, a propoxy group, a butoxy group, and a pentyloxy group. , hexyloxy, heptyloxy, octyloxy, nonyloxy, decyloxy, dodecyloxy, octadecyloxy, isopropoxy, isobutoxy, isopentyloxy, Dibutoxy, tert-butoxy, second pentyloxy, third pentyloxy, trioctyloxy, neopentyloxy, cyclopropoxy, cyclobutoxy, cyclopentyloxy, ring Hexyloxy, adamantyloxy, norbornyloxy, borneoloxy, 4-nonylcyclohexyloxy, and the like, but are not limited thereto. Further, specific examples of the linear or branched alkoxy group having 2 to 18 carbon atoms and optionally one or more ether bonds may be, for example, -O-CH ₂ -O-CH ₃ or -O-CH ₂ - CH ₂ -O-CH ₂ -CH ₃ , -O-CH ₂ -CH ₂ -CH ₂ -O-CH ₂ -CH ₃ , -O-(CH ₂ -CH ₂ -O) _n -CH ₃ (here , n is 1 to 8), -O-(CH ₂ -CH ₂ -CH ₂ -O) _m -CH ₃ (here, m is 1 to 5), -O-CH ₂ -CH(CH ₃ )- O-CH ₂ -CH ₃ , -O-CH ₂ -CH-(OCH ₃ ) ₂ or the like, but is not limited thereto.

Specific examples of the monocyclic or condensed polycyclic alkoxy group having 2 to 18 carbon atoms and optionally one or more ether linkages are listed below, but are not limited thereto.

The substituted or unsubstituted aryl group in R ¹ may, for example, be a monocyclic or condensed polycyclic aryl group having 6 to 24 carbon atoms. Specific examples thereof include a phenyl group, a 1-naphthyl group, a 2-naphthyl group, a 1-fluorenyl group, a 9-fluorenyl group, a 2-phenanthryl group, a 3-phenanthryl group, a 9-phenanthryl group, a 1-fluorenyl group, and 5 -5-naphthacenyl, 1-mercapto, 2-azulenyl, 1-acenaphthyl, 2-mercapto, 9-fluorenyl, 3-fluorenyl , o-tolyl, m-tolyl, p-tolyl, 2,3-dimethylphenyl (2,3-xylyl), 2,5-dimethylphenyl, 2,4,6-trimethylphenyl (mesityl), pair -P-cumenyl, p-dodecylphenyl, p-cyclohexylphenyl, 4-biphenylyl, o-fluorophenyl, m-chlorophenyl, p-bromophenyl, Buton-hydroxyphenyl, m-carboxyphenyl, o-nonylphenyl, p-cyanophenyl, m-nitrophenyl, m-azidophenyl, etc., but not limited thereto This is the case.

A substituted or ^{unsubstituted,} R ¹ include the aryloxy group having 6 to 18 carbon atoms such as the monocyclic or condensed polycyclic aryl group. Specific examples thereof include a phenoxy group, a 1-naphthyloxy group, a 2-naphthyloxy group, a 9-decyloxy group, a 9-phenanthryloxy group, a 1-decyloxy group, a 5-fused tetraphenoxy group, and a 1- The methoxy group, the 2-decyloxy group, the 1-decyloxy group, the 9-decyloxy group and the like are not limited thereto.

The substituted or unsubstituted heterocyclic group in R ¹ may, for example, be an aromatic or aliphatic heterocyclic group having 4 to 24 carbon atoms which contains a nitrogen atom, an oxygen atom, a sulfur atom or a phosphorus atom. Specific examples thereof include 2-thienyl, 2-benzothienyl, naphtho[2,3-b]thienyl, 3-thianthrenyl, 2-thiazinyl, 2-furan. Base, 2-benzofuranyl, pyranyl, isobenzofuranyl, chromenyl, xanthenyl, brown Phenoxylinyl, 2H-pyrrolyl, pyrrolyl, imidazolyl, pyrazolyl, pyridyl, pyridyl Base, pyrimidinyl, oxime , indolizinyl, isoindolyl, 3H-indenyl, 2-indolyl, 3-indolyl, 1H-carbazolyl, purinyl, 4H- Quino 4H-quinolizinyl, isoquinolyl, quinolinyl, anthracene (phthalazinyl), naphthyridinyl, quinoxalinyl, quinazolinyl, anthraquinone Cinnolinyl, pteridinyl, 4aH-carbazolyl, 2-oxazolyl, 3-oxazolyl, β-carbolinyl, phenanthridinyl, 2- 2-acridinyl, perimidinyl, phenanthrolinyl, phenanthrene Phenazinyl, arsenic Phenasazinyl, isothiazolyl, thiophene Phenothiazinyl, different Isozolyl, furazanyl, 3-morphine 3-phenoxazinyl, isochromanyl, chromanyl, pyrrolidinyl, pyrrolinyl, imidazolidinyl, imidazolinyl, pyrazolyl, pyrazolinyl, piperidinyl Piper Base, indolinyl, isoindolyl, quinuclidinyl, morpholinyl, thioxanthenyl, 4-quinolinyl, 4-isoquinolinyl, 3- Thiophene 2-morphine Although it is a thio group, a 3-coumarinyl group, etc., it is not limited to this.

The substituted or unsubstituted heterocyclic oxy group in R ¹ may, for example, be a monocyclic or condensed polycyclic heterocyclic oxy group having 4 to 18 carbon atoms which contains a nitrogen atom, an oxygen atom, a sulfur atom or a phosphorus atom. Specific examples thereof include a 2-furyloxy group, a 2-thienyloxy group, a 2-decyloxy group, a 3-decyloxy group, a 2-benzofuranyloxy group, and a 2-benzothiophene group. The group is preferably a group of a oxy group, a 2-oxazolyloxy group, a 3-oxazolyloxy group, a 4-oxazolyloxy group, a 9-acridyloxy group, and the like.

The substituted or unsubstituted alkylthio group in R ¹ may, for example, be a linear, branched, monocyclic or condensed polycyclic alkylthio group having 1 to 18 carbon atoms. Specific examples thereof include methylthio group, ethylthio group, propylthio group, butylthio group, pentylthio group, hexylthio group, octylthio group, sulfonylthio group, dodecylthio group, octadecylthio group, and the like. However, it is not limited to this.

A substituted or ^{unsubstituted,} R ¹ include the arylthio group having 6 to 18 carbon atoms such as the monocyclic or condensed polycyclic aromatic group. Specific examples thereof include, but are not limited to, a phenylthio group, a 1-naphthylthio group, a 2-naphthylthio group, a 9-fluorenylthio group, and a 9-phenanthrylthio group.

The substituted or unsubstituted alkylsulfinyl group in R ¹ may, for example, be an alkylsulfinylene group having 1 to 20 carbon atoms. Specific examples thereof include a methylsulfinyl group, an ethylsulfinyl group, a propylsulfinyl group, an isopropylsulfinyl group, a butylsulfinyl group, a hexylsulfinyl group, and a cyclohexyl group. Sulfosyl, octylsulfinyl, 2-ethylhexylsulfinyl, decylsulfinyl, dodecanoylsulfinyl, octadecylsulfinyl And a cyanomethylsulfinyl group, a methoxymethylsulfinyl group, etc., but it is not limited to this.

The substituted or unsubstituted arylsulfinyl group in R ¹ may, for example, be an arylsulfinylene group having 6 to 30 carbon atoms. Specific examples thereof include a phenylsulfinyl group, a 1-naphthylsulfinyl group, a 2-naphthylsulfinyl group, a 2-chlorophenylsulfinyl group, and a 2-methylphenylsulfinium group. , 2-methoxyphenylsulfinyl, 2-butoxyphenylsulfinyl, 3-chlorophenylsulfinyl, 3-trifluoromethylphenylsulfinyl, 3 -Cyanophenylsulfinyl, 3-nitrophenylsulfinyl, 4-fluorophenylsulfinyl, 4-cyanophenylsulfinyl, 4-methoxyphenyl Sulfhydryl group, 4-methylthiophenylsulfinyl group, 4-phenylthiophenylsulfinyl group, 4-dimethylaminophenylsulfinyl group, etc., but not limited thereto.

The substituted or unsubstituted alkylsulfonyl group in R ¹ may, for example, be an alkylsulfonyl group having 1 to 20 carbon atoms. Specific examples thereof include methylsulfonyl group, ethylsulfonyl group, propylsulfonyl group, isopropylsulfonyl group, butylsulfonyl group, hexylsulfonyl group, cyclohexylsulfonyl group, and octyl group. Sulfonyl, 2-ethylhexylsulfonyl, decylsulfonyl, fluorenylsulfonyl, octadecylsulfonyl, cyanomethylsulfonyl, methoxymethylsulfonate醯基等, etc., but is not limited to this.

The substituted or unsubstituted arylsulfonyl group in R ¹ may, for example, be an arylsulfonyl group having 6 to 30 carbon atoms. Specific examples thereof include a phenylsulfonyl group, a 1-naphthylsulfonyl group, a 2-naphthylsulfonyl group, a 2-chlorophenylsulfonyl group, a 2-methylphenylsulfonyl group, and a 2-methyl group. Oxyphenylsulfonyl, 2-butoxyphenylsulfonyl, 3-chlorophenylsulfonyl, 3-trifluoromethylphenylsulfonyl, 3-cyanophenylsulfonyl, 3-nitrophenylsulfonyl, 4-fluorophenylsulfonyl, 4-cyanophenylsulfonyl, 4-methoxyphenylsulfonyl, 4-methylthiophenylsulfonyl And 4-phenylthiophenylsulfonyl group, 4-dimethylaminophenylsulfonyl group, etc., but it is not limited to this.

The substituted or unsubstituted fluorenyl group in R ¹ may, for example, be a carbonyl group bonded to a hydrogen atom or a linear, branched, monocyclic or condensed polycyclic aliphatic group having 1 to 18 carbon atoms; a 2 to 20 alkoxy-substituted carbonyl group; a carbonyl group bonded to a monocyclic or condensed polycyclic aryl group having 6 to 18 carbon atoms; a monocyclic or condensed polycyclic aromatic aryl group having 6 to 18 carbon atoms; a carbonyl group substituted with a carbonyl group containing a nitrogen atom, an oxygen atom, a sulfur atom, a phosphorus atom, and a monocyclic or condensed polycyclic heterocyclic group having 4 to 18 carbon atoms. Specific examples thereof include a methyl group, an ethyl group, a propyl group, a propyl group, a butyl group, an isobutyl group, a pentamidine group, an isovaleryl group, a pivaloyl group, a lauryl group, and a myristyl group. (myristoyl), palmitoyl, stearyl group, cyclopentylcarbonyl, cyclohexylcarbonyl, acryl oxime, methacryl fluorenyl, crotonoyl, isocrotonyl, oil sulfhydryl , cinnamoyl, methoxycarbonyl, ethoxycarbonyl, propoxycarbonyl, butoxycarbonyl, hexyloxycarbonyl, octyloxycarbonyl, decyloxycarbonyl, octadecylcarbonyl, three Fluoromethoxycarbonyl, benzoyl, toluoyl, 1-naphthoyl, 2-naphthylmethyl, 9-fluorenylcarbonyl, phenoxycarbonyl , 4-methylphenoxycarbonyl, 3-nitrophenoxycarbonyl, 4-dimethylaminophenoxycarbonyl, 2-methylthiophenoxycarbonyl, 1-naphthylmethoxycarbonyl, 2-naphthylmethoxycarbonyl, 9-decyloxycarbonyl, 3-furoyl, 2-thenoyl, nicotinoyl, isoniazid Alkali sulfhydryl or the like, but is not limited thereto .

The substituted or unsubstituted methoxy group in R ¹ may, for example, be a decyloxy group having 2 to 20 carbon atoms. Specific examples thereof include an ethoxycarbonyl group, a propenyloxy group, a butoxy group, a pentyloxy group, a trifluoromethylcarbonyloxy group, a benzhydryloxy group, a 1-naphthylcarbonyloxy group, and a 2-naphthalene group. Alkyloxy group and the like.

The substituted or unsubstituted amino group in R ¹ may, for example, be an amine group, an alkylamino group, a dialkylamino group, an arylamino group, a diarylamino group, an alkylarylamino group or a benzylamino group. , dibenzylamino group and the like.

Here, the alkylamine group may, for example, be a methylamino group, an ethylamino group, a propylamino group, a butylamino group, a pentylamino group, a hexylamino group, a heptylamino group, an octylamino group or an anthracene group. Amino group, mercaptoamine group, dodecylamino group, octadecylamino group, isopropylamino group, isobutylamino group, isoamylamino group, second butylamino group, tert-butyl group Amino, second amylamino, third amylamino, third octylamino, neopentylamino, cyclopropylamino, cyclobutylamino, cyclopentylamino, cyclohexyl The amine group, the cycloheptylamino group, the cyclooctylamino group, the cyclododecylamino group, the 1-adamantylamino group, the 2-adamantylamino group, and the like are not limited thereto.

The dialkylamino group may, for example, be dimethylamino, diethylamino, dipropylamino, dibutylamino, dipentylamino, dihexylamino, diheptylamino, or Octylamino, dimethylamino, dinonylamino, bis(dodecyl)amino, bis(octadecyl)amino, diisopropylamino, diisobutylamino, di Isoamylamino, methylethylamino, methylpropylamino, methylbutylamino, methyl isobutylamino, cyclopropylamino, pyrrolidinyl, piperidinyl, piperidin Base, etc., but is not limited to this.

Examples of the arylamine group include an anilino group, a 1-naphthylamino group, a 2-naphthylamino group, an o-toluidino group, a m-toluidine group, a p-toluidine group, and a 2-biphenylamino group ( 2-biphenylamino), 3-biphenylamino, 4-biphenylamino, 1-nonylamino, 2-nonylamino, 2-thiazolylamino, p-terphenylamino, etc. However, it is not limited to this.

Examples of the diarylamine group include a diphenylamino group, a bis(tolyl)amino group, an N-phenyl-1-naphthylamino group, an N-phenyl-2-naphthylamino group, and the like, but are not limited. This is the case.

The alkylarylamine group may, for example, be N-methylanilino, N-methyl-2-pyridyl, N-ethylanilino, N-propylanilino, N-butylanilino, N-iso Examples of the propylanilino group, the N-pentylanilino group, and the N-methyl-1-naphthylamino group are not limited thereto.

The substituted or unsubstituted phosphino group in R ¹ may, for example, be a phosphinium group having 2 to 50 carbon atoms. Specific examples thereof include dimethylphosphonium, diethylphosphonium, dipropylphosphonium, diphenylphosphonium, dimethoxyphosphonium, diethoxyphosphonium, The bis(benzylidene)phosphonium group or the bis(2,4,6-trimethylphenyl)phosphonium group is not limited thereto.

The substituted or unsubstituted amine carbenyl group in R ¹ may, for example, be an amine carbenyl group having 1 to 30 carbon atoms. Specific examples thereof include N-methylamine methyl sulfonyl group, N-ethylamine methyl fluorenyl group, N-propylamine carbhydryl group, N-butylamine carbhydryl group, and N-hexylamine fluorenyl group. N-cyclohexylamine methyl sulfhydryl, N-octylamine methyl fluorenyl, N-decylamine carbhydryl, N-octadecylaminomethyl, N-phenylamine, fluorenyl, N-2- Methylphenylamine methyl sulfhydryl, N-2-chlorophenylamine carbhydryl, N-2-isopropoxyphenylamine carbhydryl, N-2-(2-ethylhexyl)phenylamine Formyl, N-3-chlorophenylamine, mercapto, N-3-nitrophenylamine, mercapto, N-3-cyanophenylamine, N-4-methoxybenzene Base amide, N-4-cyanophenylamine, fluorenyl, N-4-methylthiophenylamine, N-4-phenylthiophenylamine, N-methyl Base-N-phenylaminecarbamyl, N,N-dimethylaminecarbamyl, N,N-dibutylaminecarbamyl, N,N-diphenylaminecarbamyl, etc., but not Limited to this.

The substituted or unsubstituted sulfonyl group in R ¹ may, for example, be an aminoxime group having a carbon number of 0 to 30. Specific examples thereof include an amine sulfonyl group, an N-alkylamine sulfonyl group, an N-arylamine sulfonyl group, an N,N-dialkylamine sulfonyl group, and an N,N-diarylamine sulfonate. Anthracenyl, N-alkyl-N-arylaminesulfonyl and the like. More specifically, for example, N-methylaminesulfonyl, N-ethylaminesulfonyl, N-propylaminesulfonyl, N-butylaminesulfonyl, N-hexylaminesulfonate , N-cyclohexylamine sulfonyl, N-octylamine sulfonyl, N-2-ethylhexylamine sulfonyl, N-decylamine sulfonyl, N-octadecylamine sulfonyl , N-phenylamine sulfonyl, N-2-methylphenylamine sulfonyl, N-2-chlorophenylamine sulfonyl, N-2-methoxyphenylamine sulfonyl, N -2-Isopropoxyphenylamine sulfonyl, N-3-chlorophenylamine sulfonyl, N-3-nitrophenylamine sulfonyl, N-3-cyanophenylamine sulfonate , N-4-methoxyphenylamine sulfonyl, N-4-cyanophenylamine sulfonyl, N-4-dimethylaminophenylamine sulfonyl, N-4-methyl Thiophenylamine sulfonyl, N-4-phenylthiophenylamine sulfonyl, N-methyl-N-phenylamine sulfonyl, N,N-dimethylamine sulfonyl, N N-dibutylamine sulfonyl group, N,N-diphenylamine sulfonyl group, etc., but it is not limited to this.

R ² is a substituted or unsubstituted alkenyl group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted aryl group, a substituted or unsubstituted aryloxy group, a substituted or unsubstituted one. Heterocyclic group, substituted or unsubstituted heterocyclic oxy group, substituted or unsubstituted alkylthio group, substituted or unsubstituted arylthio group, substituted or unsubstituted alkyl sulfinylene group, substituted or unsubstituted aryl group A sulfinyl group, a substituted or unsubstituted alkylsulfonyl group, a substituted or unsubstituted arylsulfonyl group, a substituted or unsubstituted decyloxy group, or a substituted or unsubstituted amine group. Among them, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkoxy group, a substitution point from the viewpoint of the synthesis of the compound or the performance as a starter. Or an unsubstituted aryl group, a substituted or unsubstituted aryloxy group, a substituted or unsubstituted heterocyclic group, a substituted or unsubstituted heterocyclic oxy group, or a substituted or unsubstituted decyloxy group is preferably substituted Or an unsubstituted alkenyl group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted heterocyclic group is more preferred.

R ² is a substituted or unsubstituted alkenyl group of, the substituted or unsubstituted alkyl group, the substituted or unsubstituted alkoxy group, the substituted or unsubstituted aryl group, the substituted or unsubstituted aryloxy group, a substituted or unsubstituted Heterocyclic group, substituted or unsubstituted heterocyclic oxy group, substituted or unsubstituted alkylthio group, substituted or unsubstituted arylthio group, substituted or unsubstituted alkylsulfinyl group, substituted or unsubstituted An arylsulfinyl group, a substituted or unsubstituted alkylsulfonyl group, a substituted or unsubstituted arylsulfonyl group, a substituted or unsubstituted anthraceneoxy group, and a substituted or unsubstituted amine group are as described above in the R ¹ substituted or unsubstituted alkenyl group, the substituted or unsubstituted alkyl, substituted or unsubstituted alkoxy group of, the substituted or unsubstituted aryl group, the substituted or unsubstituted aryloxy group, a substituted or unsubstituted Heterocyclic group, substituted or unsubstituted heterocyclic oxy group, substituted or unsubstituted alkylthio group, substituted or unsubstituted arylthio group, substituted or unsubstituted alkylsulfinyl group, substituted or unsubstituted Arylsulfinyl, substituted or unsubstituted alkylsulfonyl, substituted or unsubstituted arylsulfonyl , Of a substituted or unsubstituted acyl group, and a substituted or unsubstituted amino group of the same meaning.

R ³ to R ⁵ each independently represent a hydrogen atom, a halogen atom, a cyano group, a nitro group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted group. An aryl group, a substituted or unsubstituted aryloxy group, a substituted or unsubstituted heterocyclic group, a substituted or unsubstituted heterocyclic oxy group, a substituted or unsubstituted alkylthio group, a substituted or unsubstituted arylthio group, A substituted or unsubstituted thiol group, or a substituted or unsubstituted amine group. Among them, a hydrogen atom, a halogen atom, a nitro group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, or a substituent is used from the viewpoint of the synthesis of the compound or the performance as a starter. Or an unsubstituted heterocyclic group is preferred, and a hydrogen atom, a nitro group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group is more preferable.

The halogen atom in R ³ to R ⁵ may, for example, be a fluorine atom, a chlorine atom, a bromine atom or an iodine atom.

A substituted or unsubstituted alkenyl group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted aryl group, a substituted or unsubstituted aryloxy group, a substituent in R ³ to R ⁵ Or unsubstituted heterocyclic group, substituted or unsubstituted heterocyclic oxy group, substituted or unsubstituted alkylthio group, substituted or unsubstituted arylthio group, substituted or unsubstituted fluorenyl group, and substituted or unsubstituted An amine group, which is a substituted or unsubstituted alkenyl group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted aryl group, a substituted or unsubstituted aryloxy group in the above R ¹ a substituted, unsubstituted heterocyclic group, a substituted or unsubstituted heterocyclic oxy group, a substituted or unsubstituted alkylthio group, a substituted or unsubstituted arylthio group, a substituted or unsubstituted fluorenyl group, and a substituted or Unsubstituted amine groups have the same meaning.

R ⁶ to R ⁹ each independently represent a hydrogen atom, a halogen atom, a cyano group, a haloalkyl group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted aryl group, a substituted or not Substituted aryloxy, substituted or unsubstituted heterocyclic group, substituted or unsubstituted heterocyclic oxy group, substituted or unsubstituted alkenyl group, substituted or unsubstituted alkylthio group, substituted or unsubstituted arylthio group , substituted or unsubstituted alkylsulfinyl, substituted or unsubstituted arylsulfinyl, substituted or unsubstituted alkylsulfonyl, substituted or unsubstituted arylsulfonyl, substituted or unsubstituted A substituted amino group or a substituent represented by the following formula (2).

Among them, a hydrogen atom, a halogen atom, a cyano group, a haloalkyl group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted one, from the viewpoint of the synthesis of the compound or the performance as a starting agent. The aryl group, the substituted or unsubstituted heterocyclic group, or the substituted or unsubstituted amino group is preferred, and a hydrogen atom, a cyano group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group is more preferable.

(Wherein, R ^1, and R ^{2, lines} to R ¹ and R ² are the same meaning).

The halogen atom in R ⁶ to R ⁹ has the same meaning as the halogen atom in R ³ to R ⁵ .

The haloalkyl group in R ⁶ to R ⁹ may, for example, be an alkyl group having 1 to 15 carbon atoms in which all hydrogen atoms are substituted by the above halogen atom, and specific examples thereof include trifluoromethyl, trichloromethyl and tribromomethyl. , triiodomethyl, pentafluoroethyl, pentachloroethyl, pentabromoethyl, pentaiodoethyl, trifluorodibromoethyl, tribromodiiodoethyl, heptafluoropropyl, heptachloropropyl , heptabromopropyl, nonafluorobutyl, nonachlorobutyl, nonabromobutyl, undecafluoropentyl, undecylpentyl, undecabromopentyl, decafluorohexyl, tridecylhexyl, ten Pentafluoroheptyl, heptadecafluorooctyl, nonadecylfluoroantimony, hexadecafluoroindenyl, heptatrifluoro (undecyl), twenty-fifrofluoro (dodecyl), etc., but are not limited thereto Wait.

The haloalkyl group is preferably a trifluoromethyl group or a pentafluoroethyl group from the viewpoint of synthesis or properties when used as a radical polymerization initiator (A).

a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted aryl group, a substituted or unsubstituted aryloxy group, a substituted or unsubstituted heterocyclic group in R ⁶ to R ⁹ , Substituted or unsubstituted heterocyclic oxy, substituted or unsubstituted alkenyl, substituted or unsubstituted alkylthio, substituted or unsubstituted arylthio, substituted or unsubstituted alkylsulfinyl, substituted or substituted An unsubstituted arylsulfinyl group, a substituted or unsubstituted alkylsulfonyl group, a substituted or unsubstituted arylsulfonyl group, and a substituted or unsubstituted amine group, which is substituted with the aforementioned R ¹ or Unsubstituted alkyl, substituted or unsubstituted alkoxy, substituted or unsubstituted aryl, substituted or unsubstituted aryloxy, substituted or unsubstituted heterocyclic group, substituted or unsubstituted heterocyclic oxy group , substituted or unsubstituted alkenyl, substituted or unsubstituted alkylthio, substituted or unsubstituted arylthio, substituted or unsubstituted alkylsulfinyl, substituted or unsubstituted arylsulfinyl , substituted or unsubstituted alkylsulfonyl, substituted or unsubstituted arylsulfonyl, and substituted or unsubstituted The amino same meaning.

Here, as long as R ⁶ to R ⁹ are the above-mentioned groups, there is no particular limitation, but when it is considered in terms of synthesis or as a property when used as a radical polymerization initiator (A), it is contained in R ⁶ to R ⁹ . In the case of a group other than hydrogen, R ^{7 is} preferably a group other than hydrogen.

R ¹⁰ to R ¹⁴ each independently represent a hydrogen atom, a halogen atom, a cyano group, a nitro group, a haloalkyl group, a substituted or unsubstituted alkylsulfinyl group, a substituted or unsubstituted arylsulfinylene group, and a substitution. Or an unsubstituted alkylsulfonyl group, a substituted or unsubstituted arylsulfonyl group, or a substituted or unsubstituted fluorenyl group, but R ¹⁰ to R ^{14 are} not all hydrogen atoms at the same time.

The haloalkyl group in R ¹⁰ to R ¹⁴ has the same meaning as the haloalkyl group in the above R ⁶ to R ⁹ , a substituted or unsubstituted alkylsulfinyl group, a substituted or unsubstituted arylsulfinyl group. a substituted or unsubstituted alkylsulfonyl group, a substituted or unsubstituted arylsulfonyl group, and a substituted or unsubstituted indenyl group and a substituted or unsubstituted alkylsulfinyl group in the above R ¹ , The substituted or unsubstituted arylsulfinyl group, the substituted or unsubstituted alkylsulfonyl group, the substituted or unsubstituted arylsulfonyl group, and the substituted or unsubstituted fluorenyl group have the same meaning.

R ¹⁰ to R ^{14 are} based on a nitro group or a substituted or unsubstituted fluorenyl group in terms of synthesis or as a property of the radical polymerization initiator (A), and are based on a nitro group or It is more preferable to show the following general formula (3):

(wherein R ¹⁵ to R ¹⁹ each independently represent a hydrogen atom, a halogen atom, a cyano group, a nitro group, a haloalkyl group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted group. Aryl, substituted or unsubstituted aryloxy, substituted or unsubstituted heterocyclic group, substituted or unsubstituted heterocyclic oxy group, substituted or unsubstituted alkenyl group, substituted or unsubstituted alkylthio group, substituted Or an unsubstituted arylthio group, a substituted or unsubstituted thiol group, or a substituted or unsubstituted amine group).

A substituted or unsubstituted alkyl group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted aryl group, a substituted or unsubstituted aryloxy group, a substituted or unsubstituted heterocyclic oxy group, a substituted or unsubstituted one. An alkylthio group, a substituted or unsubstituted arylthio group, or a substituted or unsubstituted amino group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted alkylthio group, or a substituted or unsubstituted group. The amine group is more preferred.

Wherein, in consideration of the synthesis aspect of the compound or the performance when used as a starter, when R ¹⁵ to R ¹⁹ contain a group other than hydrogen, the position of the substituent other than hydrogen is preferably R ¹⁵ , R ¹⁷ and R ^{19 are more} preferably R ¹⁷ .

The haloalkyl group in R ¹⁵ to R ¹⁹ has the same meaning as the haloalkyl group in the above R ⁶ to R ⁹ , a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted aryl group. Alkyl, substituted or unsubstituted aryloxy, substituted or unsubstituted heterocyclic group, substituted or unsubstituted heterocyclic oxy group, substituted or unsubstituted alkenyl group, substituted or unsubstituted alkylthio group, substituted or not a substituted arylthio group, a substituted or unsubstituted fluorenyl group, and a substituted or unsubstituted amino group and a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted group in the above R ¹ Aryl, substituted or unsubstituted aryloxy, substituted or unsubstituted heterocyclic group, substituted or unsubstituted heterocyclic oxy group, substituted or unsubstituted alkenyl group, substituted or unsubstituted alkylthio group, substituted The unsubstituted arylthio group, the substituted or unsubstituted fluorenyl group, and the substituted or unsubstituted amine group have the same meaning.

Further, when the compound of the present invention is used as the radical polymerization initiator (A), R ¹⁰ to R ¹⁴ are particularly preferred from the viewpoint of compatibility with a solvent or a resin.

Here, R ¹² is preferably a group other than hydrogen from the viewpoint of synthesis or characteristics when used as a radical polymerization initiator (A).

The hydrogen atom of the substituent in the above R ¹ to R ¹⁹ may be substituted with another substituent.

Examples of the substituent include a halogen group such as a fluorine atom, a chlorine atom, a bromine atom or an iodine atom; an alkoxy group such as a methoxy group, an ethoxy group or a second butoxy group; a phenoxy group and a p-tolyloxy group; An aryloxy group; an alkoxycarbonyl group such as a methoxycarbonyl group, a butoxycarbonyl group or a phenoxycarbonyl group; or an aryloxycarbonyl group; a methoxy group such as an ethoxy group, a propyloxy group or a benzyloxy group; a mercapto group such as a mercapto group, a benzhydrazinyl group, an isobutyl fluorenyl group, an acryl fluorenyl group, a methacryl fluorenyl group or a methoxalyl group; an alkylthio group such as a methylthio group or a tert-butylthio group; a phenylthio group; An arylthio group such as p-tolylthio; an alkylamino group such as a methylamino group or a cyclohexylamino group; a dialkylamine such as a dimethylamino group, a diethylamino group, a morpholinyl group or a piperidinyl group; An arylamino group such as a phenylamino group or a p-tolylamino group; an alkyl group such as a methyl group, an ethyl group, a tert-butyl group or a dodecyl group; a phenyl group, a p-tolyl group, a xylyl group and an isopropyl group; An aryl group such as a phenyl group, a naphthyl group, an anthranyl group or a phenanthryl group; a heterocyclic group such as a furyl group or a thienyl group; and the like. In addition, examples thereof include a hydroxyl group, a carboxyl group, a decyl group, a fluorenyl group, a sulfonic acid group, a mesylate group, a p-toluenesulfonyl group, an amine group, a nitro group, a cyano group, and a trifluoromethyl group. , trichloromethyl, trimethyldecyl, phosphinico, phosphono, trimethyl ammonium, dimethyl sulfonium, triphenyl Triphenyl phenacyl phosphoniumyl and the like.

Specific examples of the above-mentioned compounds of the present invention are shown below, but the structure of the compound of the present invention is not limited to these.

The compound represented by the formula (1) is obtained by adjusting an intermediate and adjusting the precursor using the intermediate. The intermediate is a ketone compound represented by the formula (4). Hereinafter, the "intermediate" means a ketone compound unless otherwise specified.

General formula (4)

(Wherein, R ² to R ¹⁴ system and the general formula (1) in the R ² to R ¹⁴ have the same meaning).

In general, a ketone compound can be easily obtained as a raw material. Further, it can be easily obtained by various methods described in the conventional synthesis method, for example, the Japanese Society of Chemistry, 4th edition, New Experimental Chemistry Lecture, Vol. 14, Item 751 (Maruzen). This document is incorporated by reference in its entirety. The following documents are also the same.

In particular, a ketone system of the carbazole compound represented by the formula (4) can be easily obtained by a Friedel-Crafts acylation reaction, for example, according to Japanese Patent No. 3927725 It is obtained by the same method as the method described in the bulletin.

When the compound represented by the formula (1) is synthesized, the precursor is a hydrazine represented by the following formula (5). Hereinafter, as long as there is no special reason, "precursor" means a ruthenium compound.

General formula (5)

(Wherein, R ² to R ¹⁴ system and the general formula (1) in the R ² to R ¹⁴ have the same meaning).

The oxime represented by the formula (5) can be obtained by using the ketone compound represented by the formula (4) as an intermediate, and is based, for example, on Org. React., 7, <1953>, 327 or the Japanese Chemical Society. It is obtained by various methods described in the 4th edition of Experimental Chemistry Lecture, Vol. 14, No. 1316 (Maruzen). And, by some of the commercially available chemistry textbooks (e.g., J. March, Advanced Organic Chemistry, 4 th Edition, Wiley Interscience, 1992) describes the oxime synthesis process.

One of the most suitable synthetic methods for hydrazine is nitrosation by the active methylene group of nitrous acid or alkyl nitrite. The reaction conditions are described, for example, as 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. ., 47, <1925>, 2033, J. Am. Chem. Soc., 117, <1920>, 590, J. Am. Chem. Soc., 51, <1929>, 2264, suitable for the manufacture of hydrazine. Nitrous acid is usually produced by sodium nitrite. The alkyl nitrite is, for example, methyl nitrite, isopropyl nitrite, butyl nitrite or isoamyl nitrite.

The compound represented by the formula (1) is obtained by using a ruthenium compound represented by the formula (5) as a precursor, and a ruthenium chloride or an acid anhydride obtained by a method described in the literature (for example, the method described above) is used. For example, it can be produced by reacting 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 an alkaline solvent such as pyridine.

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

All of the oxime ester groups are present in two stereo configurations (Z) or (E). This isomer can be isolated by conventional methods, but a mixture of isomers can also be used as the light starting species. Accordingly, the invention also relates to mixtures of stereoisomers of the compounds of formula (1).

The present invention of formula (1) compound is shown using the mass analysis value, elemental analysis, ¹ H-NMR, and the like conventionally known method of analysis readily identified.

Next, the case where the compound of the present invention is used as the radical polymerization initiator (A) will be described.

Since the conventionally known α-ketoxime compound does not exhibit absorption for a longer wavelength than the general ultraviolet region, it lacks activity for light from near ultraviolet to near infrared. On the other hand, the radical polymerization initiator (A) represented by the formula (1) of the present invention has an electron-attracting substituent to the phenyl group of the N-phenylcarbazolyl group, so that it is in the near ultraviolet to visible light. There is an absorption band in the region, and it is active in a region from such near ultraviolet rays to longer wavelengths than visible light.

Further, as described above, the radical polymerization initiator (A) of the present invention has a keto-type oxime ester structure as shown in the formula (1). The reason why the radical polymerization initiator (A) of the present invention functions more sensitively than the conventionally known radical polymerization initiator, and is inferred to be the following three reasons (possibility), but the detailed reason is still unknown. .

First reason: the radical polymerization initiator (A) of the present invention has excellent absorption by the carbazole chromophore represented by the formula (1), so that it can be strongly absorbed. The energy of the energy line. Further, since the energy obtained is efficiently used for decomposition of the oxime ester site, the decomposition by the energy ray irradiation is rapid, and a large amount of radicals can be instantaneously generated.

Second reason: Since the radical polymerization initiator (A) of the present invention has a keto-type oxime ester structure, as described below, an inert azoyl radical is rapidly decomposed and acted as an activity. And can reproduce a decomposition product (carbazolyl radical) which can function as an active species. Not only a keto-type oxime ester will generate a large amount of free radicals, but the nitrite-based radicals generated will be slow to be decomposed as long as they are metastable, and the amount of radicals will be less than the theoretical amount. This is greatly affected by the chromophore groups that it has. Since the radical polymerization initiator (A) of the present invention has a structure represented by the formula (1), the nitro-based radical generated by light irradiation is decomposed very rapidly for some reason, resulting in generation. The result of a large amount of free radicals.

The radical polymerization initiator (A) of the present invention is as described above, and it is presumed that the recombination is suppressed because the decomposition of the nitro group is very rapid. When there are many cases of recombination, the active species due to decomposition will be reduced, so that the function as a radical polymerization initiator is lowered.

The third reason is as follows: an effect of the above-described carbazole substituted with an electron-attracting substituent which functions as an excellent chromophore group, and a synergistic effect with the effect of the keto-type oxime ester.

Since the radical polymerization initiator (A) of the present invention functions as a very high-sensitivity radical polymerization initiator due to irradiation of an energy ray, it is possible to reliably realize the use of a conventional radical polymerization in a shorter period of time. The polymerization reaction of the initiator, the crosslinking reaction, and the like. As a result, a large amount of high sensitivity or an increase in characteristics of various uses to which such reactions are applied can be carried out. Hereinafter, a method of using the radical polymerization initiator (A) of the present invention will be described.

The composition containing the radical polymerization initiator (A) of the present invention and the radically polymerizable compound (B) is rapidly and surely cured by irradiation of energy rays, and can be used as a polymerizable property capable of obtaining a cured product having good characteristics. The composition is used.

The radically polymerizable compound (B) of the present invention will be described. The radically polymerizable compound (B) of the present invention is a compound having a radically polymerizable ethylenically unsaturated bond. The compound having a radically polymerizable ethylenically unsaturated bond may be a compound having at least one radically polymerizable ethylenically unsaturated bond in the molecule, and may have a monomer, an oligomer, a polymer, or the like. Chemical type.

Examples of such a compound having a radically polymerizable ethylenically unsaturated bond include unsaturated carboxylic acids such as acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, and maleic acid, and the like. Salt, ester, urethane, guanamine or anhydride, acrylonitrile, styrene, or even free radically polymerizable compounds such as various unsaturated polyesters, unsaturated polyethers, unsaturated polyamines, unsaturated polyurethanes, However, the present invention is not limited to this and the like. Specific examples of the radically polymerizable compound (B) of the present invention are listed below.

Examples of acrylates:

Examples of monofunctional acrylates: methyl acrylate, ethyl acrylate, propyl acrylate, isopropyl acrylate, butyl acrylate, isoamyl acrylate, hexyl acrylate, 2-ethylhexyl acrylate, octyl acrylate , decyl acrylate, lauryl acrylate, stearyl acrylate, isobornyl acrylate, cyclohexyl acrylate, dicyclopentenyl acrylate, dicyclopentenyloxyethyl acrylate, benzyl acrylate.

Examples of monofunctional hydroxyl-containing acrylates: 2-hydroxypropyl acrylate, 2-hydroxy-3-chloropropyl acrylate, 2-hydroxy-3-phenoxypropyl acrylate, 2-hydroxy-3-ene acrylate Propyloxypropyl ester, 2-propenyloxyethyl-2-hydroxypropyl phthalate.

Examples of monofunctional halogen-containing acrylates: 2,2,2-trifluoroethyl acrylate, 2,2,3,3-tetrafluoropropyl acrylate, 1H-hexafluoroisopropyl acrylate, 1H, 1H acrylic acid ,5H-octafluoropentyl ester, 1H,1H,2H,2H-heptadecafluorodecyl acrylate, 2,6-dibromo-4-butylphenyl acrylate, 2,4,6-tribromophenoxy acrylate Ethyl ester, 2,4,6-tribromophenol 3EO addition acrylate.

Examples of monofunctional ether-containing acrylates: 2-methoxyethyl acrylate, 1,3-butylene glycol methyl ether acrylate, butoxyethyl acrylate, methoxy triethylene glycol acrylate, Methoxy polyethylene glycol #400 acrylate, methoxydipropylene glycol acrylate, methoxy tripropylene glycol acrylate, methoxy polypropylene glycol acrylate, ethoxy diethylene glycol acrylate, ethyl carbene Alcohol acrylate, 2-ethylhexyl carbitol acrylate, tetrahydrofuran methyl acrylate, phenoxyethyl acrylate, phenoxy diethylene glycol acrylate, phenoxy polyethylene glycol acrylate, cresol Polyethylene glycol acrylate, p-nonylphenoxyethyl acrylate, p-nonylphenoxy polyethylene glycol acrylate, glycidyl acrylate.

Examples of monofunctional carboxyl group-containing acrylates: β-carboxyethyl acrylate, monoacryloxyethyl succinate, ω-carboxypolycaprolactone monoacrylate, 2-propenyloxyethyl citrate (2-acryloyloxyethyl hydrogen phthalate), 2-propenyl methoxypropyl citrate, 2-propenyl propyl hexahydrophthalate, 2-propenyl propyl propyl hydroperoxide.

Examples of other monofunctional acrylates: N,N-dimethylaminoethyl acrylate, N,N-dimethylaminopropyl acrylate, morpholinyl acrylate, trimethyldecyloxy acrylate Ethyl ester, diphenyl-2-propenyloxyethyl phosphate, 2-propenyloxyethyl acid phosphate, caprolactone-modified 2-acryloxyethyl acid phosphate.

Examples of difunctional acrylates: 1,4-butanediol diacrylate, 1,6-hexanediol diacrylate, ethylene glycol diacrylate, diethylene glycol diacrylate, triethylene glycol II Acrylate, tetraethylene glycol diacrylate, polyethylene glycol #200 diacrylate, polyethylene glycol #300 diacrylate, polyethylene glycol #400 diacrylate, polyethylene glycol #600 diacrylate , dipropylene glycol diacrylate, tripropylene glycol diacrylate, tetrapropylene glycol diacrylate, polypropylene glycol #400 diacrylate, polypropylene glycol #700 diacrylate, neopentyl glycol diacrylate, neopentyl glycol PO modification Diacrylate, hydroxytrimethylacetic acid neopentyl glycol ester diacrylate, hydroxytrimethylacetic acid neopentyl glycol ester caprolactone adduct diacrylate, 1,6-hexanediol bis (2- Hydroxy-3-propenyloxypropyl)ether, bis(4-propenyloxypolyethoxyphenyl)propane, 1,9-nonanediol diacrylate, pentaerythritol diacrylate, pentaerythritol diacrylate Monostearate, pentaerythritol diacrylate monobenzoate, bisphenol A diacrylate, EO Bisphenol A diacrylate, PO modified bisphenol A diacrylate, hydrogenated bisphenol A diacrylate, EO modified hydrogenated bisphenol A diacrylate, PO modified hydrogenated bisphenol A diacrylate, bisphenol F diacrylate, EO modified bisphenol F diacrylate, PO modified bisphenol F diacrylate, EO modified tetrabromobisphenol A diacrylate, tricyclodecane dimethylol diacrylate, different Cyanuric acid EO modified diacrylate.

Examples of trifunctional acrylates: glycerin PO modified triacrylate, trimethylolpropane triacrylate, trimethylolpropane EO modified triacrylate, trimethylolpropane PO modified triacrylate, different Cyanuric acid EO modified triacrylate, isomeric cyanuric acid EO modified ε-caprolactone modified triacrylate, 1,3,5-tripropylene decyl hexahydrogen , pentaerythritol triacrylate, dipentaerythritol triacrylate tripropionate.

Examples of tetrafunctional or higher acrylates: pentaerythritol tetraacrylate, dipentaerythritol tetraacrylate, dipentaerythritol pentaacrylate monopropionate, dipentaerythritol hexaacrylate, tetramethylol methane tetraacrylate, oligoester 4 Acrylate, tris(propylene decyloxy) phosphate.

Examples of methacrylates:

Examples of monofunctional alkyl methacrylates: methyl methacrylate, ethyl methacrylate, propyl methacrylate, isopropyl methacrylate, butyl methacrylate, isoamyl methacrylate, Hexyl acrylate, 2-hexyl methacrylate, 2-ethylhexyl methacrylate, octyl methacrylate, decyl methacrylate, lauryl methacrylate, stearyl methacrylate, methyl Isobornyl acrylate, cyclohexyl methacrylate, dicyclopentenyl methacrylate, dicyclopentenyloxyethyl methacrylate, benzyl methacrylate.

Examples of monofunctional hydroxyl-containing methacrylates: 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, 2-hydroxy-3-chloropropyl methacrylate, 2-hydroxy methacrylate 3-phenoxypropyl ester, 2-hydroxy-3-allyloxypropyl methacrylate, 2-methylpropenyloxyethyl-2-hydroxypropyl phthalate.

Examples of monofunctional halogen-containing methacrylates: 2,2,2-trifluoroethyl methacrylate, 2,2,3,3-tetrafluoropropyl methacrylate, 1H-hexafluoromethacrylate Isopropyl ester, 1H, 1H, 5H-octafluoropentyl methacrylate, 1H, 1H, 2H, 2H-heptadecafluorodecyl methacrylate, 2,6-dibromo-4-butylbenzene methacrylate Ester, 2,4,6-tribromophenoxyethyl methacrylate, 2,4,6-tribromophenol 3EO addition methacrylate.

Examples of monofunctional ether-containing methacrylates: 2-methoxyethyl methacrylate, 1,3-butanediol methyl ether methacrylate, butoxyethyl methacrylate, methoxy Triethylene glycol methacrylate, methoxy polyethylene glycol #400 methacrylate, methoxy dipropylene glycol methacrylate, methoxy tripropylene glycol methacrylate, methoxy polypropylene glycol Acrylate, ethoxydiethylene glycol methacrylate, 2-ethylhexyl carbitol methacrylate, tetrahydrofuran methacrylate, phenoxyethyl methacrylate, phenoxydiethylene Alcohol methacrylate, phenoxy polyethylene glycol methacrylate, cresol based polyethylene glycol methacrylate, p-nonylphenoxyethyl methacrylate, p-nonylphenoxy Polyethylene glycol methacrylate, glycidyl methacrylate.

Examples of monofunctional carboxyl group-containing methacrylates: β-carboxyethyl methacrylate, monomethacryloxyethyl succinate, ω-carboxy polycaprolactone monomethacrylate, hydrogen citrate 2-methacryloyloxyethyl hydrogen phthalate, 2-methylpropenyl propyl propyl hydride, 2-methylpropenyl propyl hexahydrophthalate, tetrahydrogen 2-methylpropenyl methoxypropyl citrate.

Examples of other monofunctional methacrylates: dimethylaminomethyl methacrylate, N,N-dimethylaminoethyl methacrylate, N,N-dimethylaminopropyl methacrylate Ester, morpholinyl methacrylate, trimethyldecyloxyethyl methacrylate, diphenyl-2-methylpropenyloxyethyl phosphate, 2-methylpropenyloxy acid phosphate Ethyl ester, caprolactone upgrading - 2-methylpropenyloxyethyl acid phosphate.

Examples of difunctional methacrylates: 1,4-butanediol dimethacrylate, 1,6-hexanediol dimethacrylate, ethylene glycol dimethacrylate, diethylene glycol II Methacrylate, triethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, polyethylene glycol #200 dimethacrylate, polyethylene glycol #300 dimethacrylate, poly Ethylene glycol #400 dimethacrylate, polyethylene glycol #600 dimethacrylate, dipropylene glycol dimethacrylate, tripropylene glycol dimethacrylate, tetrapropylene glycol dimethacrylate, polypropylene glycol# 400 dimethacrylate, polypropylene glycol #700 dimethacrylate, neopentyl glycol dimethacrylate, neopentyl glycol PO modified dimethacrylate, hydroxytrimethyl acetic acid neopentyl glycol ester Dimethacrylate, caprolactone adduct dimethacrylate of hydroxytrimethylacetic acid neopentyl glycol ester, 1,6-hexanediol bis(2-hydroxy-3-methylpropenyloxyl) Propyl)ether, 1,9-nonanediol dimethacrylate, pentaerythritol dimethacrylate, pentaerythritol dimethacrylate Ester monostearate, pentaerythritol dimethacrylate monobenzoate, 2,2-bis(4-methylpropenyloxypolyethoxyphenyl)propane, bisphenol A dimethacrylate EO modified bisphenol A dimethacrylate, PO modified bisphenol A dimethacrylate, hydrogenated bisphenol A dimethacrylate, EO modified hydrogenated bisphenol A dimethacrylate, PO modified Hydrogenated bisphenol A dimethacrylate, bisphenol F dimethacrylate, EO modified bisphenol F dimethacrylate, PO modified bisphenol F dimethacrylate, EO modified tetrabromo double Phenol A dimethacrylate, tricyclodecane dimethylol dimethacrylate, isomeric cyanuric acid EO modified dimethacrylate.

Examples of trifunctional acrylates: glycerol PO modified trimethacrylate, trimethylolethane trimethacrylate, trimethylolpropane trimethacrylate, trimethylolpropane EO modified three Methacrylate, trimethylolpropane PO modified trimethacrylate, isomeric cyanuric acid EO modified trimethacrylate, isomeric cyanuric acid EO modified ε-caprolactone modified three Acrylate, 1,3,5-tripropylene decyl hexahydrogen , pentaerythritol trimethacrylate, dipentaerythritol trimethacrylate tripropionate.

Examples of tetrafunctional or higher methacrylates: pentaerythritol tetramethacrylate, dipentaerythritol pentamethyl acrylate monopropionate, dipentaerythritol hexamethacrylate, tetramethylol methane tetramethacrylate, Oligoester tetramethacrylate, tris(methacryloxy)phosphate.

Examples of allylates are allyl glycidyl ether, diallyl phthalate, triallyl trimellitate, and triallyylated isocyanuric acid.

Examples of guanamines: acrylamide, N-methylol acrylamide, diacetone acrylamide, N,N-dimethyl decylamine, N,N-diethyl acrylamide, N-iso Propyl acrylamide, propylene decylmorpholine, methacrylamide, N-methylol methacrylamide, diacetone methacrylamide, N,N-dimethyl methacrylamide, N,N-Diethylmethacrylamide, N-isopropylmethacrylamide, methacryloylmorpholine.

Examples of styrenes: styrene, p-hydroxystyrene, p-chlorostyrene, p-bromostyrene, p-methylstyrene, p-methoxystyrene, p-t-butoxybenzene Ethylene, p-t-butoxycarbonylstyrene, p-t-butoxycarbonyloxystyrene, 2,4-diphenyl-4-methyl-1-pentene.

Examples of other vinyl compounds: vinyl acetate, vinyl monochloroacetate, vinyl benzoate, trimethyl vinyl acetate, vinyl butyrate, vinyl laurate, divinyl adipate, ethylene methacrylate Ester, vinyl crotonate, vinyl 2-ethylhexanoate, N-vinyl carbazole, N-vinyl pyrrolidone, and the like.

The radically polymerizable compound (B) can be easily obtained from a commercial product of the following manufacturer. For example, "light acrylate", "light ester", "epoxy ester", "amine ester acrylate" and "high functional oligo" manufactured by Kyoeisha Oil & Fat Chemicals Co., Ltd. "Nikester" and "NK oligomer" series manufactured by Shin-Nakamura Chemical Co., Ltd.; "FANCRYL" series manufactured by Hitachi Chemical Co., Ltd.; "America Synthetic Chemicals Co., Ltd." "ARONIXM" series; "Functional Monomer" series manufactured by Daiba Chemical Industry Co., Ltd.; "Special Acrylic Monomer" series manufactured by Osaka Organic Chemical Industry Co., Ltd.; manufactured by Mitsubishi Corporation "ACRYESTER" and "DIABEAM oligomers" series; "Kayarad" and "Kayamer" series manufactured by Nippon Kayaku Co., Ltd.; "Acrylic/methacrylate monomer" series manufactured by Nippon Shokubai Co., Ltd. "NICHIGO-UV Violet Amine Ester acrylate" series manufactured by Nippon Synthetic Chemical Industry Co., Ltd.; "Carboxy Carboxylate Monomer" series manufactured by Shin-Etsu Vinyl Acetate Co., Ltd.; The "functional monomer" series of the stock system.

Further, the radically polymerizable compound (B) may also be as described in the literature shown below. For example, there is a "Handbook of Crosslinking Agents" by Yamashita Shinzo (ed., Dacheng Society, 1981), and Kato Qingshi, "UV‧EB Hardening Handbook (Materials)" (1985, Polymer Publishing House), RadTech Research Society, edited by Akamatsu, "The Practical Technology of New ‧ Photosensitive Resin" (CMC, 1987), Endo's "Precision of Thermosetting Polymers" (CMC, 1986), and Rong Yilang, "Shu The Handbook of Ester Resins (In 1988, Nikkan Kogyo Shimbun) and RadTech Research Society, "Application and Market of UV‧EB Hardeners" (2002, CMC).

The radical polymerizable compound (B) of the present invention may be used alone or in combination of two or more kinds in an arbitrary ratio in order to enhance desired properties.

The radical polymerization initiator (A) of the present invention in the polymerizable composition is used in an amount of 0.1 to 100 parts by weight, preferably 3 to 60 parts by weight, based on 100 parts by weight of the radically polymerizable compound (B). .

The polymerizable composition of the present invention can be mixed with a binder such as an organic high molecular polymer and applied to a glass plate or an aluminum plate, another metal plate, or polyethylene terephthalate (PET). Use as a polymer film.

Examples of the binder which can be mixed with the polymerizable composition of the present invention include polyacrylates, poly-α-alkyl acrylates, polyamines, polyvinyl acetals, polymethylamines, and polyurethanes. Polymers and copolymers such as polycarbonates, polystyrenes, and polyvinyl esters. Specific examples thereof include polymethacrylate, polymethyl methacrylate, polyethyl methacrylate, polyvinyl carbazole, polyvinyl pyrrolidone, polyvinyl butyral, and polyvinyl acetate. Ester, novolac resin, phenolic resin, epoxy resin, alkyd resin, other chemicals such as red pine repair "new ‧ photosensitive resin" (1987, CMC) or "10188 chemistry" Commercially known organic high molecular polymers described in pages 657 to 767 (1988, Chemical Industry Daily).

Further, the polymerizable composition of the present invention can be used in combination with other polymerization initiators for the purpose of enhancing sensitivity.

Other polymerization initiators which can be used in combination with the polymerizable composition of the present invention are described in, for example, JP-A-59-1281, JP-A-61-9621, and JP-A-60-60104. Third Japanese Patent Publication No. Sho 59-1504, and Japanese Patent Publication No. Sho 61-243807, Japanese Patent Publication No. Sho 43-23684, Japanese Patent Publication No. Sho 44-6413, and Japanese Patent Publication No. Sho. The organic azide compound described in the specification of the diazonium compound, the specification of USP No. 2848328, the specification of USP No. 2852379, and the specification of USP No. 2940853, Japanese Patent Publication No. Sho 36 Japanese Unexamined Japanese Patent Publication No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. Japanese Patent Publication No. 59-140203 and "MACROMOLECULES", Vol. 10, No. 1307 (1977), various onium compounds, and azo described in JP-A-59-142205 The compound, Japanese Patent Laid-Open No. Hei 1-54440, European Patent No. 109851, European Patent No. 126712, and "Journal of Imaging Science (J. IMAG. Scl.)", Vol. 30, p. 174 (1986) Metal The propylene diene compound, the ferrocene described in JP-A-61-151197, "COORDINATION CHEMISTRY REVIEW", vol. 84, pp. 85 to 277 (1988), and JP-A-2-182701 A transition metal complex containing a transition metal such as ruthenium, and an aluminate complex described in JP-A-3-209477, and a borate compound described in JP-A-2-157760, JP-A-55- 2,4,5-triarylimidazole dimer, carbon tetrabromide, or an organic halogen compound described in JP-A-59-107344, JP-A-60-202437, JP-A-60-202437 An aminoketone compound described in Japanese Patent Laid-Open Publication No. Hei. No. Hei. No. Hei. No. Hei. No. Sho. JP-A-2001-261530, JP-A-2001-261761, JP-A-2000-80068, JP-A-2001-233842, JP-A-2004-534797, and JP-A No. 3558309 (1971) , USP 4202697 (1980) and Japan Special Open 61-24558 An oxime ester compound or the like described in the publication. When such a polymerization initiator is used in an amount of 100 parts by weight based on 100 parts by weight of the radical polymerizable compound (B), it is preferably used in an amount of from 0.01 to 10 parts by weight.

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

Specific examples of the thermal polymerization inhibitor which can be added to the polymerizable composition of the present invention include p-methoxyphenol, hydroquinone, alkyl-substituted hydroquinone, catechol, and third butyl phenol. Thiophene (phenothiazine) and so on. When such a thermal polymerization inhibitor is used with respect to 100 parts by weight of the radically polymerizable compound (B), it is preferably used in an amount of 0.001 to 5 parts by weight.

In addition, a polymerization accelerator or a chain transfer catalyst typified by an amine, a mercaptan, a disulfide or the like may be added for the purpose of further promoting the polymerization of the polymerizable composition of the present invention.

Specific examples of the polymerization accelerator or the chain transfer catalyst which may be added to the polymerizable composition of the present invention include amines such as N-phenylglycine, triethanolamine and N,N-diethylaniline. The thiol described in the specification of the Japanese Patent Publication No. 4414312 or the Japanese Patent Publication No. Sho 64-13144, the disulfide described in JP-A No. 2-291561, the specification of US Pat. No. 3,558,322, or the Japanese Patent Laid-Open No. 64-17048 The thione type described in the publication, o-acylthiohydroxamate or N-alkoxypyridinone described in JP-A-2-291560.

The polymerizable composition of the present invention may also be used in combination with dyes, organic and inorganic pigments, phosphine, phosphonate, phosphorous acid and other oxygen scavengers or reducing agents, antifogging agents, anti-fading agents, and anti-fogging agents. Anti-halation agent, fluorescent whitening agent, surfactant, coloring agent, extender, plasticizer, flame retardant, antioxidant, ultraviolet absorber, foaming agent, mold inhibitor, anti- An electrostatic agent, an additive that imparts a magnetic substance or other various characteristics, a diluent solvent, or the like is used.

The polymerizable composition of the present invention may further contain a sensitizer (C) for the purpose of promoting polymerization. Since the sensitizer increases the activity of light in the ultraviolet to near-infrared region, it is preferable to add a sensitizer when it is necessary to promote the polymerizability.

Specific examples of such sensitizers include unsaturated ketones represented by chalcone derivatives or dibenzalacetone, and benzil or camphorquinone. As a representative 1,2-dione derivative, benzoin derivative, anthracene derivative, naphthoquinone derivative, anthracene derivative, xanthene derivative, thioxanthene a derivative, a xanthone derivative, a thioxanthone derivative, a coumarin derivative, a ketocoumarin derivative, an anthocyanin derivative, a part Polymethine pigments such as melocyanine derivatives and oxonol derivatives, acridine derivatives, anthraquinones (azine) derivative, thio (thiazine) derivative, (oxazine) derivative, porphyrin derivative, anthracene derivative, azulenium derivative, squarylium derivative, porphyrin derivative, tetraphenylporphyrin derivative, Sanfang Methane derivative, tetrabenzoporphyrin derivative, tetrapyridyl And a tetrapyrazinoporphyrazine derivative, a phthalocyanine derivative, a tetrazaporphyrazine, a tetraquinoxaline porphyrazine derivative, a naphthalocyanine derivative , Subphthalocyanine derivative, pyrylium derivative, thiopyranidine derivative, tetraphylline derivative, annulene derivative, spiropyran derivative ,screw Derivatives, thiol spiropyran derivatives, carbazole derivatives, metal arene complexes, organic hydrazine complexes, Michler's ketone derivatives, and the like. In addition, examples of the specific examples include the "Pigment Handbook" (Taiwan, 1986, Kodansha), Dahe Yuanxin, etc., "Chemistry of Functional Pigments" (1981, CMC), Chisen Zhongsanlang Et al. edited the sensitizer described in "Special Functional Materials" (1986, CMC). Further, a sensitizer which exhibits absorption of light such as ultraviolet to near-infrared region can be cited. The sensitizer is not limited to the above exemplification. The sensitizer may be used in any ratio of two or more depending on the need. Among the above sensitizers, a series of sensitizers which are particularly suitable for sensitizing the radical polymerization initiator of the present invention are, for example, a thioxanthone derivative or a mazinone derivative. More specifically, for example, 2,4-diethylthianone, 2-chlorothiazinone, 2,4-dichlorothiazinone, 2-isopropylthioxanthone, 4 - isopropyl thioxanthone, 1-chloro-4-propoxy thioxanthone, 4,4'-bis(dimethylamino)benzophenone, 4,4'-double (diethyl The group is a benzophenone or the like, but is not limited thereto.

The sensitizer (C) of the present invention is used in an amount of 0.01 to 60 parts by weight, preferably 0.01 to 30 parts by weight, based on 100 parts by weight of the radically polymerizable compound (B), and preferably 0.1 to 10 parts by weight. The serving is better.

In the polymer composition of the present invention, the coloring component (D) may be added for the purpose of coloring. As the coloring component (D), a conventionally known pigment can be used. Further, in order to obtain a desired hue, the dye may be contained in a range in which heat resistance and weather resistance are not lowered. In order to obtain a desired color density and a hue, these may be used alone or in combination of two or more.

For the pigment, for example, an organic pigment, an inorganic pigment, or carbon black (for example, acetylene black, channel black, furnace black, or the like) may be used, and the pigment may be used in combination of two or more kinds.

The organic pigment may, for example, be a diketopyrrolopyrrole pigment, an azo pigment (for example, azo, disazo, polyazo) or a phthalocyanine pigment (for example, copper phthalocyanine or copper ruthenium halide). Cyanine, metal-free phthalocyanine, etc., lanthanide pigments (eg, amine guanidine, diamino dioxime, anthrapyrimidine, flavanthrohe, anthanthrone, indanthrone) (indanthrone), pyranthrone, violanthrone, etc., quinacridone pigment, two (dioxazine) is a pigment, a perinone pigment, an anthraquinone pigment, a thioindigo pigment, an isoindoline pigment, an isoindolinone pigment, quinophthalone (quinophthalone) A pigment, a threne pigment, or a metal complex pigment.

Examples of the inorganic pigments include titanium oxide, zinc oxide, zinc sulfide, lead white, calcium carbonate, precipitated barium sulfate, white carbon, alumina white, kaolin clay, talc, bentonite, black iron oxide, Carbon black, cadmium red, iron (Bengala), molybdenum red, orange molybdate, chrome vermilion, chrome yellow, cadmium yellow, yellow iron oxide, titanium yellow, chromium oxide, chrome green (viridian), titanium Cobalt green, cobalt green, cobalt chrome green, Victoria green, ultramarine blue, Prussian blue, cobalt blue, cerulean blue, cobalt ruthenium blue, cobalt zinc oxidized indigo, Manganese violet, or cobalt violet.

Examples of carbon black include "Special Black 350, 250, 100, 550, 5, 4, 4A, 6" by Degussa, "Printex U, V, 140U, 140V, 95, 90, 85, 80, 75, 55. , 45, 40, P, 60, L6, L, 300, 30, 3, 35, 25, A, G", "REGAL 400R, 660R, 330R, 250R", "MOGUL E, L", manufactured by CAB0T. "MA7, 8, 11, 77, 100, 100R, 100S, 220, 230", "# 2700, # 2650, # 2600, # 200, # 2350, # 2300, # 2200, # 1000, manufactured by Mitsubishi Chemical Corporation #990,#980,#970,#960,#950,#900,#850,#750,#650,#52,#50,#47,#45,#45L,#44,#40,#33 , #332, #30, #25, #20, #10, #5, CF9, #95, #260", etc.

Further, the pigments which can be used in the polymer composition of the present invention are listed below based on the color index (i.e., C.I.) number.

Red pigments can be used, for example, CI Pigment Red 7, 9, 14, 41, 48:1, 48:2, 48:3, 48:4, 81:1, 81:2, 81:3, 97, 122, 123, 146, 149, 168, 177, 178, 180, 184, 185, 187, 192, 200, 202, 208, 210, 215, 216, 217, 220, 223, 224, 226, 227, 228, 240, 246, 254, 255, 264, 272, etc., but are not limited thereto.

The yellow pigment can be used, for example, CI Pigment Yellow 1, 2, 3, 4, 5, 6, 10, 12, 13, 14, 15, 16, 17, 18, 20, 24, 31, 32, 32, 34, 35, 35:1, 36, 36:1, 37, 37:1, 40, 42, 43, 53, 55, 60, 61, 62, 63, 65, 73, 74, 77, 81, 83, 86, 93, 94, 95, 97, 98, 100, 101, 104, 106, 108, 109, 110, 113, 114, 115, 116, 117, 118, 119, 120, 123, 125, 126, 127, 128, 129, 137, 138, 139, 147, 148, 150, 151, 152, 153, 154, 155, 156, 161, 162, 164, 166, 167, 168, 169, 170, 171, 172, 173, 174, 175, 176, 177, 179, 180, 181, 182, 185, 187, 188, 193, 194, 199, etc., but are not limited thereto.

As the orange pigment, for example, C.I. Pigment Orange 36, 43, 51, 55, 59, 61 and the like can be used, but it is not limited thereto.

As the green pigment, for example, a green pigment such as C.I. Pigment Green 7, 10, 36, 37 can be used, but it is not limited thereto.

As the blue pigment, for example, C.I. Pigment Blue 15, 15:1, 15:2, 15:3, 15:4, 15:6, 16, 22, 60, 64 and the like can be used, but it is not limited thereto.

As the purple pigment, for example, C.I. Pigment Violet 1, 19, 23, 27, 29, 30, 32, 37, 40, 42, 50, etc. may be used, but it is not limited thereto.

As the black pigment, for example, C.I. Pigment Black 1, 6, 7, 12, 20, 31 and the like can be used, but it is not limited thereto.

These pigments can be used in combination of two or more kinds in any ratio.

When such a pigment as the coloring component (D) is added to 100 parts by weight of the radical polymerizable compound (B), it is used in an amount of from 0.01 to 100 parts by weight, preferably from 1 to 60 parts by weight.

From the viewpoint of the absorption coefficient of visible light (appropriate degree of spectrum) and transparency, the particle diameter of the pigment is preferably sufficiently small for the wavelength of visible light. That is, the pigment has an average primary particle diameter of preferably 0.01 μm or more and 0.3 μm or less, particularly preferably 0.01 μm or more and 0.1 μm or less. Further, the primary particle diameter means the diameter of the smallest unit of the pigment particles, which is measured by an electron microscope.

The primary particle diameter of the pigment can be adjusted to an appropriate range using a known dispersing device such as a sand mill, a kneader, a 2-axis roll or the like.

Further, when a pigment is added to the polymer composition of the present invention, a pigment derivative or a pigment dispersant can be used for the purpose of improving pigment dispersibility and preserving stability of the polymer composition.

Here, the pigment derivative means a compound obtained by introducing a substituent into an organic dye. The organic coloring matter also contains a pale yellow aromatic polycyclic compound such as a quinone imine, a naphthalene, a naphthoquinone, an anthraquinone or an anthracene which are not generally called a pigment.

For the pigment derivative, JP-A-63-305173, JP-A-57-15620, JP-A-59-40172, JP-A-63-17102, and JP-A-5-9469 Japanese Patent Publication No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. These can be used individually or in mixture of 2 or more types.

As the pigment dispersant, for example, a carboxylic acid ester containing a hydroxyl group, a salt of a long-chain polyamine guanamine and a high molecular weight acid ester, a salt of a high molecular weight polycarboxylic acid, a salt of a long-chain polyamine guanamine and a polar acid ester, High molecular weight unsaturated acid ester, polymer copolymer, modified polyurethane, modified polyacrylate, polyether ester type anionic active agent, naphthalenesulfonic acid formalin condensate salt, aromatic sulfonic acid famarin condensate salt, Polyoxyalkylene ethyl alkyl phosphate, polyoxyethylidene phenyl ether, stearylamine acetate, and the like.

Specific examples of the pigment dispersant include "Anti-Terra-U (polyamine guanamine phosphate)", "Anti-Terra-203/204 (high molecular weight polycarboxylate)", "Disperbyk" manufactured by BYK Chemie Co., Ltd. -101 (polyamine decylamine phosphate and acid ester), 107 (hydroxyl-containing carboxylic acid ester), 110, 111 (acid group-containing copolymer), 130 (polyamide), 161, 162, 163, 164, 165, 166, 170 (polymer copolymer), "400", "Bykumen" (high molecular weight unsaturated acid ester), "BYK-P104, P105 (high molecular weight unsaturated polycarboxylic acid)", "P104S , 240S (high molecular weight unsaturated acid polycarboxylic acid and lanthanide)", "Lactimon (long-chain amine and unsaturated acid carboxylic acid and hydrazine)".

Further, as Efka Chemicals Co., Ltd., "Efka 44, 46, 47, 48, 49, 54, 63, 64, 65, 66, 71, 701, 764, 766", "Efka Polymer 100 (modified polyacrylate) ), 150 (aliphatic modified polymer), 400, 401, 402, 403, 450, 451, 452, 453 (modified polyacrylate), 745 (copper phthalocyanine), Kyoeisha Chemical Co., Ltd. "FLOWLEN TG-710 (Amine Ester)", "FLOWLEN SH-290, SP-1000", "POLYFLOW No. 50E, No. 300 (Acrylic Copolymer)", "DISPARLON KS" manufactured by Kanemoto Kasei Co., Ltd. -860, 873SN, 874 (polymer dispersant), #2150 (aliphatic polycarboxylic acid), #7004 (polyether ester type).

Further, for example, "Demol RN, N (naphthalenesulfonic acid hydrazine marine condensate sodium salt), MS, C, SN-B (aromatic sulfonic acid hydrazine condensate sodium salt), EP", "Homogenol L-18 (polycarboxylic acid type polymer)", "Emulgen 920, 930, 931, 935, 950, 985 (polyoxyethylidene phenyl ether)", "Acetamin 24 (coconutamine acetate) Ester), 86 (stearylamine acetate), "solsperse 5000 (phthalocyanine ammonium)", 13940 (polyester amine), 17000 (fatty acid amine), 24000GR, 32000, 33000, manufactured by Avecia. 39000, 41000, 53000", Nissan Chemical Co., Ltd. "NIKKOL T106 (polyoxyethylene sorbitan monooleate), MYS-IEX (polyoxyethylidene monostearate), Hexagline 4-0 ( "AJISPER PB821, 822, 824" manufactured by Fine-Techno Co., Ltd., and azetin.

The amount of the pigment derivative and the pigment dispersant to be added is not particularly limited, and is preferably 0.1 to 40 parts by weight, more preferably 0.1 to 30 parts by weight, per 100 parts by weight of the pigment.

Examples of the dye which may be contained in order to obtain a desired hue include an azo dye, an anthraquinone dye, a phthalocyanine dye, a quinonimine dye, a quinoline dye, a nitro dye, A carbonyl dye, a methine dye, or the like.

Examples of the azo dyes include CI Acid Yellow 11, CI Acid Orange 7, CI Acid Red 37, CI Acid Red 180, CI Acid Blue 29, CI Direct Red 28, CI Direct Red 83, CI Direct Yellow 12, and CI Direct Orange. 26, CI Direct Green 28, CI Direct Green 59, CI Reaction Yellow 2, CI Reaction Red 17, CI Reaction Red 120, CI Reaction Black 5, CI Disperse Orange 5, CI Disperse Red 58, CI Disperse Blue 165, CI Alkaline Blue 41, CI alkaline green 18, CI mordant red 7 (CI Mordant Red 7), CI mordant yellow 5, CI mord black 7, etc., but are not limited thereto.

Examples of the lanthanide dyes include CI Reduction Blue 4 (CIVat Blue 4), CI Acid Blue 40, CI Acid Green 25, CI Reaction Blue 19, CI Reaction Blue 49, CI Disperse Red 60, CI Disperse Blue 56, and CI Dispersion. Blue 60, etc., but is not limited to this.

Other examples of the phthalocyanine dye include CI reduction blue 5, and the quinone imine dye may, for example, be CI basic blue 3 or CI basic blue 9, and the quinoline dye may be, for example, CI Solvent Yellow 33 (CIsolvent). Yellow 33), CI Acid Yellow 3, CI Disperse Yellow 64, etc., and the nitro dye may, for example, be CI Acid Yellow 1, CI Acid Orange 3, CI Disperse Yellow 42, etc., but is not limited thereto.

The dye is used in an amount of 0.01 to 100 parts by weight, preferably 1 to 60 parts by weight, based on 100 parts by weight of the radically polymerizable compound (B), but as described above, from heat resistance or weather resistance From the point of view, if the amount used is too much, it is not good.

When the polymerizable composition of the present invention is used for the purpose of forming a video or the like as a so-called alkaline development type photoresist material, an alkali-soluble resin (E) may be used in combination. The alkali-soluble resin (E) of the present invention functions as a binder, and it is preferable that the image developing liquid used in the development processing step, particularly the alkaline developing solution, is soluble when forming an image. There is no special limit. Among them, an alkali-soluble resin which is a copolymer containing a carboxyl group is preferred, and an ethylenically unsaturated monomer having one or more carboxyl groups (hereinafter simply referred to as "carboxy group-containing unsaturated monomer") and other copolymerizable ethylene are preferable. A copolymer of a monounsaturated monomer (hereinafter referred to as "copolymerizable unsaturated monomer") (hereinafter simply referred to as "copolymer containing a carboxyl group") is more preferable.

Examples of the carboxyl group-containing unsaturated monomer include unsaturated monocarboxylic acids such as acrylic acid, methacrylic acid, crotonic acid, α-chloroacrylic acid, and cinnamic acid; maleic acid, maleic anhydride, fumaric acid, and itaconic acid; An unsaturated dicarboxylic acid such as acid, itaconic acid anhydride, citraconic acid, citraconic anhydride, mesaconic acid or an anhydride thereof; an unsaturated polycarboxylic acid having 3 or more elements or an anhydride thereof; Succinic acid mono(2-propenyloxyethyl ester), succinic acid mono(2-methylpropenyloxyethyl), decanoic acid mono(2-propenyloxyethyl), citric acid mono(2- Mono[(meth)acryloxyalkylene] ester of a polyvalent carboxylic acid of 2 or more or more, such as methacryloxyethyl ester); ω-carboxypolycaprolactone monoacrylate, ω-carboxy poly A mono (meth) acrylate having a polymer having a carboxyl group and a hydroxyl group at both terminals, such as a lactone monomethacrylate. Among these carboxyl group-containing unsaturated monomers, succinic acid mono(2-propenyloxyethyl ester) and citric acid mono(2-propenyloxyethyl ester) are M-5300 and M-5400, respectively. The trade name of the synthetic (share) system is sold on the market. The carboxyl group-containing unsaturated monomers may be used singly or in combination of two or more kinds.

Further, the copolymerizable unsaturated monomer may, for example, be styrene, α-methylstyrene, o-vinyltoluene, m-vinyltoluene, p-vinyltoluene, p-chlorostyrene, ortho-methoxy Styrene, m-methoxystyrene, p-methoxystyrene, o-vinylbenzyl methyl ether, m-vinylbenzyl methyl ether, p-vinylbenzyl methyl ether, o-ethylene An aromatic vinyl compound such as benzyl glycidyl ether, m-vinylbenzyl glycidyl ether or p-vinylbenzyl glycidyl ether; anthracene such as hydrazine or 1-methylhydrazine; methyl acrylate and methyl Methyl acrylate, ethyl acrylate, ethyl methacrylate, n-propyl acrylate, n-propyl methacrylate, isopropyl acrylate, isopropyl methacrylate, n-butyl acrylate, n-butyl methacrylate, Isobutyl acrylate, isobutyl methacrylate, second butyl acrylate, second butyl methacrylate, tert-butyl acrylate, third butyl methacrylate, 2-hydroxyethyl acrylate, methacrylic acid 2-hydroxyethyl ester, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, C Acid 3-hydroxypropyl ester, 3-hydroxypropyl methacrylate, 2-hydroxybutyl acrylate, 2-hydroxybutyl methacrylate, 3-hydroxybutyl acrylate, 3-hydroxybutyl methacrylate, acrylic acid 4 -hydroxybutyl ester, 4-hydroxybutyl methacrylate, allyl acrylate, allyl methacrylate, benzyl acrylate, benzyl methacrylate, cyclohexyl acrylate, cyclohexyl methacrylate, benzene acrylate Ester, phenyl methacrylate, 2-methoxyethyl acrylate, 2-methoxyethyl methacrylate, 2-phenoxyethyl acrylate, 2-phenoxyethyl methacrylate, methoxy Diethylene glycol acrylate, methoxy diethylene glycol methacrylate, methoxy triethylene glycol acrylate, methoxy triethylene glycol methacrylate, methoxypropylene glycol acrylate, A Oxypropanediol methacrylate, methoxydipropylene glycol acrylate, methoxydipropylene glycol methacrylate, isobornyl acrylate, isobornyl methacrylate, dicyclopentadienyl acrylate, methacrylic acid Cyclopentadienyl ester, 2-hydroxy-3-phenoxypropyl acrylate, Unsaturated carboxylic acid esters such as 2-hydroxy-3-phenoxypropyl acrylate, glyceryl monoacrylate, and glyceryl monomethacrylate; 2-aminoethyl acrylate and 2-aminoethyl methacrylate , 2-dimethylaminoethyl acrylate, 2-dimethylaminoethyl methacrylate, 2-aminopropyl acrylate, 2-aminopropyl methacrylate, 2-dimethylamine acrylate Propyl propyl ester, 2-dimethylaminopropyl methacrylate, 3-aminoethyl acrylate, 3-aminoethyl methacrylate, 3-dimethylaminopropyl acrylate, methacrylic acid 3 - Aminoalkyl esters of unsaturated carboxylic acids such as dimethylaminopropyl acrylate; glycidyl esters of unsaturated carboxylic acid such as glycidyl acrylate or glycidyl methacrylate; vinyl acetate, vinyl propionate, Vinyl carboxylates such as vinyl butyrate and vinyl benzoate; unsaturated ethers such as vinyl methyl ether, vinyl ethyl ether and allyl glycidyl ether; acrylonitrile, methacrylonitrile, α-chloroacrylonitrile And vinyl cyanide compounds such as vinylidene cyanide; acrylamide, methacrylamide, α-chloropropenylamine, N Unsaturated guanamines such as 2-hydroxyethyl acrylamide and N-2-hydroxyethyl methacrylamide; maleic imine, N-phenyl maleimide, N-cyclohexyl An aliphatic conjugated diene such as unsaturated quinone imine, 1,3-butadiene, isoprene, chloroprene, etc.; polystyrene, polyacrylic acid Methyl ester, polymethyl methacrylate, polybutyl acrylate, polybutyl methacrylate, polyoxyalkylene, etc. have a large propylene group or a monomethacryl fluorenyl group at the end of the polymer molecular chain. Molecular monomer (macromonomer) and the like. These copolymerizable unsaturated monomers can be used singly or in combination of two or more.

The preferred carboxyl group-containing copolymer (hereinafter referred to as "carboxyl group-containing copolymer (R)") is obtained by polymerizing the following (P) and (Q): (P) acrylic acid and/or Methacrylic acid is an essential component, and optionally contains succinic acid mono(2-propenyloxyethyl ester), succinic acid mono(2-methylpropenyloxyethyl ester), and ω-carboxy polycap a carboxyl group-containing unsaturated monomer component of at least one compound of the group consisting of ester monoacrylate and ω-carboxypolycaprolactone monomethacrylate; (Q) is selected from the group consisting of styrene, methyl acrylate, and methyl group Methyl acrylate, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, allyl acrylate, allyl methacrylate, benzyl acrylate, benzyl methacrylate, glyceryl monoacrylate, monomethyl At least one selected from the group consisting of glycerin acrylate, N-phenylmaleimide, polystyrene macromonomer, and polymethyl methacrylate macromonomer.

Specific examples of the carboxyl group-containing copolymer (R) include (meth)acrylic acid/methyl (meth)acrylate copolymer, (meth)acrylic acid/benzyl (meth)acrylate copolymer, and (methyl). Acrylic acid/2-hydroxyethyl (meth)acrylate/benzyl (meth)acrylate copolymer, (meth)acrylic acid/methyl (meth)acrylate/polystyrene macromonomer copolymer, (A) Acrylic acid / methyl (meth) acrylate / polymethyl methacrylate macromolecular copolymer, (meth) acrylate / benzyl (meth) acrylate / polystyrene macropolymer, ( Benzyl methacrylate / benzyl (meth) acrylate / polymethyl methacrylate macromolecular copolymer, (meth) acrylate / 2-hydroxyethyl (meth) acrylate / benzyl (meth) acrylate /Polystyrene macromonomer copolymer, (meth)acrylic acid / 2-hydroxyethyl (meth)acrylate / benzyl (meth) acrylate / polymethyl methacrylate macromer copolymer, A Acrylic acid/styrene/benzyl (meth)acrylate/N-phenylmaleimide copolymer; (meth)acrylic acid/succinic acid mono[2-(methyl)acryloxyethyl ester]/ Styrene / (methyl) Benzene olefinate/N-phenylmaleimide copolymer, (meth)acrylic acid/succinic acid mono[2-(methyl)acryloxyethyl ester]/styrene/(meth)acrylic acid Propyl ester/N-phenylmaleimide copolymer, (meth)acrylic acid/styrene/benzyl (meth)acrylate/glycerol mono(meth)acrylate/N-phenylmaleimide Copolymer, (meth)acrylic acid/ω-carboxypolycaprolactone mono(meth)acrylate/styrene/benzyl (meth)acrylate/glycerol mono(meth)acrylate/N-phenyl Malay Yttrium imide copolymer and the like.

In the copolymer containing a carboxyl group, the substituent present in the molecule may be modified by other materials. For example, a part of the carboxyl group present in the polymer may be modified by reacting with a monomer having a functional group reactive with a carboxyl group such as a glycidyl group, and thus it is possible to participate in the molecule. Crosslinking point of free radical polymerization. As the monomer, a glycidyl (meth) acrylate may be used, and examples thereof include, for example, glycidyl (meth)acrylic acid, glycidyl methyl (meth) acrylate, and glycidyl (meth) acrylate B. Ester, glycidyl butyl (meth) acrylate, glycidyl 2-ethylhexyl (meth) acrylate. Further, the hydroxyl group present in the polymer may be obtained by "Karenz MOI" made of 2-propenyloxyethyl isocyanate or 2-methylpropenylethyl isocyanate (Showa Denko) ") The same polymerization crosslinking point is provided by condensation.

In the copolymer containing a carboxyl group, the copolymerization ratio of the carboxyl group-containing unsaturated monomer is preferably from 5 to 50% by weight. When the copolymerization ratio is less than 5% by weight, the solubility of the obtained resist composition in the alkaline developing solution tends to decrease. On the other hand, if it exceeds 50% by weight, the alkaline developing solution is used. The solubility is too large, and when developing with an alkaline developing solution, there is a tendency that the resist film is detached from the substrate or the film on the image surface becomes rough. The polystyrene-equivalent weight average molecular weight (hereinafter referred to as "Mw") measured by gel permeation chromatography (GPC, elution solvent: tetrahydrofuran) in the alkali-soluble resin of the present invention is preferably 3,000 to 300,000, more preferably 5,000. To 100,000. In addition, the polystyrene-equivalent number average molecular weight (hereinafter referred to as "Mn") measured by gel permeation chromatography (GPC, elution solvent: tetrahydrofuran) in the alkali-soluble resin of the present invention is preferably 3,000 to 60,000, more preferably It is 5,000 to 25,000. In the present invention, a radiation-sensitive composition excellent in developability is obtained by using such an alkali-soluble resin having a specific Mw and Mn. Therefore, an image pattern having a sharp pattern edge can be formed, and at the same time, residue, scum, residual film, and the like are less likely to occur on the substrate of the unirradiated portion and the light shielding layer during development. Further, the ratio (Mw/Mn) of Mw and Mn of the alkali-soluble resin in the present invention is preferably from 1 to 5, more preferably from 1 to 4.

The alkali-soluble resin (E) other than the carboxyl group-containing copolymer may, for example, be a novolac type resin or a resin having a phenolic hydroxyl group such as polyhydroxystyrene, and the modified substances are also included in the alkali-soluble resin of the present invention ( E).

In the present invention, the alkali-soluble resin (E) may be used singly or in combination of two or more.

The amount of the alkali-soluble resin (E) of the present invention used is 10 to 600 parts by weight based on 100 parts by weight of the radically polymerizable compound (B).

When the polymerization composition of the present invention is subjected to a polymerization reaction, it can be polymerized by imparting energy such as ultraviolet rays, visible light rays, or near-infrared rays to obtain a polymer of interest. The light source for imparting energy is preferably a light source having a dominant wavelength of light emitted in a wavelength region of 250 nm to 450 nm. Examples of the light source having a dominant wavelength of light emitted in a wavelength region of 250 nm to 450 nm include, for example, an ultrahigh pressure mercury lamp, a high pressure mercury lamp, a medium pressure mercury lamp, a mercury xenon lamp, a metal halide lamp, a high power metal halide lamp, a xenon lamp, and a pulsed xenon lamp. , deuterium lamps, fluorescent lamps, Nd-YAG3 double-wave lasers, He-Cd lasers, nitrogen lasers, Xe-Cl excimer lasers, Xe-F excimer lasers, semiconductors Excitation of various light sources such as solid lasers. In addition, the definitions of ultraviolet rays, visible rays, and near-infrared rays in the present specification are based on the "Rock Wave Chemistry Dictionary 4th Edition" (1987, Rock Wave) edited by Kubo Koto.

The polymerizable composition of the present invention can be applied to various inks, inkjet inks, protective paints, various brush materials, photoresists, electronic photographs, direct brush materials, optical fibers, holographic materials, and the like. Or various recording media such as microcapsules, or even adhesives, adhesives, adhesives, release coating agents, sealants, and various coating materials.

[Image pattern forming method]

The polymerizable composition of the present invention containing the alkali resin (E) can be used as a negative resist which is applied to a substrate, partially cured by energy ray exposure, and is alkali-treated. The user who removes the unexposed portion to form an image pattern.

The image pattern forming method using the negative resist of the present invention containing the alkali resin (E) will be described. First, a liquid composition of a negative resist is applied onto the surface of a substrate, and then prebaked to evaporate the solvent to form a coating film. Next, the coating film was exposed to a pattern through a photomask, and then developed using an alkaline developing solution to dissolve and remove the unexposed portion of the coating film. Then, postbake is performed as needed to form a desired image pattern.

When the liquid composition of the negative resist is applied to the substrate, a known coating method such as a spray coating method, a spin coating method, a slit coating method, or a roll coating method can be employed. The coating thickness can be appropriately changed depending on the use, and the film thickness after drying is preferably 0.1 to 200 μm, more preferably 0.2 to 100 μm.

Further, the base film formed mainly of polyester, polypropylene, polyethylene or the like mainly represented by polyethylene terephthalate may be provided with the negative resist layer of the present invention and, if necessary, The protective film sandwiches the negative resist layer, and the negative resist of the present invention is used in a so-called dry film type well known in the art. In the dry film, the protective film is usually peeled off to adhere to a substrate on which a resist pattern is to be formed, and if necessary, laminated on a substrate under heating or even under pressure. When the negative resist of the present invention is used in the form of a dry film, the pattern exposure can be carried out without peeling off the base film, in which case the base film is removed after exposure and alkaline development is performed.

The energy to be irradiated in order to polymerize the negative resist of the present invention containing the alkali resin (E) and obtain a polymer is the same as that obtained above when the polymer is obtained from the polymer composition of the present invention.

Therefore, the negative resist of the present invention containing the alkali resin (E) can be imparted to a low-pressure mercury lamp, a medium-pressure mercury lamp, a high-pressure mercury lamp, an ultra-high pressure mercury lamp, a xenon lamp, a pulsed xenon lamp, a carbon-arc lamp, Metal halide lamps, fluorescent lamps, tungsten lamps, argon ion lasers, cadmium cadmium lasers, helium ion lasers, helium ion lasers, various semiconductor lasers, YAG lasers, light emitting diodes, CRT light sources, electricity The energy of various light sources such as plasma light source, electron beam, γ line, ArF excimer laser, KrF excimer laser, F2 laser, etc., to obtain the desired polymer or hardened material.

Therefore, in the image pattern forming method of the present invention, the energy line of the above-mentioned light source can be used at the time of exposure. In particular, an energy line in the range of 190 to 450 nm is preferred. The amount of exposure cannot be generalized depending on the film thickness, but is usually from 0.5 to 100,000 J/m ² .

The substrate used in the image pattern forming method of the present invention may, for example, be glass, ruthenium, polycarbonate, polyester, aromatic polyamide, polyamidimide, polyimide, glass epoxy (Glass- Epoxy) film or substrate, but is not limited thereto. Further, for such substrates, pharmaceutical treatment, plasma treatment, ion plating, sputtering, gas phase reaction, vacuum vapor deposition, etc., which are carried out by a decane coupling agent or the like, may be performed as desired. Before processing.

The developing method used in the image pattern forming method of the present invention may be, for example, any of a puddle method, a dipping method, a shower method, and a spray method. The development time is preferably 5 to 300 seconds at 20 to 30 °C. In addition, alkaline imaging liquid can be used: sodium hydroxide, potassium cyanide, sodium carbonate, sodium citrate, sodium metasilicate, ammonia and other inorganic bases; ethylamine, n-propylamine and other primary amines; a secondary amine such as ethylamine or di-n-propylamine; a tertiary amine such as trimethylamine, methyldiethylamine, ethyldimethylamine or triethylamine; dimethylethanolamine, A Tertiary alkanolamines such as diethanolamine and triethanolamine; pyrrole, piperidine, N-methylpiperidine, N-methylpyrrolidine, 30-diazabicyclo[5.4.0]-7-undecene And a tertiary amine such as 1,5-diazabicyclo[4.3.0]-5-pinene; an aqueous solution of a basic compound such as a tetrabasic ammonium salt such as tetramethylammonium hydroxide or tetraethylammonium hydroxide. Further, a water-soluble organic solvent such as methanol or ethanol and/or a surfactant may be added to the aqueous solution of the basic compound in an appropriate amount.

Since the compound of the present invention efficiently generates active radicals by irradiation with energy rays, in particular, it can function as a high-sensitivity radical polymerization initiator. Therefore, the radically polymerizable composition containing the radical polymerization initiator (A) of the present invention is a high-sensitivity polymerizable composition which can be polymerized in a short time. Therefore, by using the polymerizable composition of the present invention, a negative resist material having an alkali developability suitable for a photoresist material and an image pattern forming method using the negative resist material can be provided. Moreover, by using this image pattern forming method, a better image pattern can be provided.

(Example)

Hereinafter, the present invention will be specifically described based on examples, but the present invention is not limited to the following examples. In addition, the "parts" in the examples mean "parts by weight" unless otherwise stated.

First, the compound of the present invention is shown in a synthesis example.

<Example 1> Free radical polymerization initiator: synthesis of compound (1)

First, the compound (A) which is an intermediate of the compound (1) is synthesized as follows.

100.0 g of N-benzophenone carbazole was dissolved in 1000 mL of chloroform, and 85.0 g of aluminum chloride was further added thereto. After stirring at 0 ° C, a solution of 32.0 g of propional chloride dissolved in 500 mL of chloroform was added thereto. . After the completion of the dropwise addition, the mixture was stirred at 25 ° C for 4 hours. The reaction solution was poured into 2000 g of ice water, and extracted with chloroform (2000 mL). The organic layer was dried over magnesium sulfate, and the residue was filtered, and the residue was recrystallized from chloroform/methanol to afford 105.0 g (yield 90.5%) of compound (A).

Next, using the obtained compound (A), the compound (B) which is a precursor of the compound (1) is synthesized as follows.

100.0 g of the compound (A) was dissolved in a mixed solution of 1000 mL of tetrahydrofuran and 500 mL of concentrated hydrochloric acid, and then, under stirring at room temperature, 38.4 g of tributyl nitrite was added dropwise over 1 hour. After the completion of the dropwise addition, 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, filtered, and evaporated to dryness, and the residue was washed with n-hexane to obtain 99.8 g (yield 93.0%) of compound (B).

Next, using the obtained compound (B), the compound (1) was synthesized as follows.

After 30.0 g of the compound (B) was stirred in 300 mL of ethyl acetate, 6.3 g of acetic anhydride and 10.6 g of sodium acetate were added, and the mixture was heated under reflux for 3 hours. Then, the reaction liquid was poured into 500 mL of ice water, and the product was extracted with ethyl acetate. The organic layer was washed with water (300 mL×3 times), dried over magnesium sulfate, and then filtered and evaporated to remove solvent. Ethyl-hexane was recrystallized to obtain 31.4 g of a compound (1) (yield: 95.4%).

<Example 2> Free radical polymerization initiator: synthesis of compound (2)

First, the compound (C) which is an intermediate of the compound (2) is synthesized as follows.

100.0 g of N-benzophenone carbazole was dissolved in 1000 mL of chloroform, and 84.0 g of aluminum chloride was further added thereto. After stirring at 0 ° C, a solution of 36.8 g of butyric chloride dissolved in 500 mL of chloroform was added thereto. . After the completion of the dropwise addition, the mixture was stirred at 25 ° C for 4 hours. The reaction solution was poured into 2000 g of ice water, and extracted with chloroform (2000 mL). The organic layer was dried over magnesium sulfate, and the residue was filtered, and the residue was recrystallized from chloroform/methanol to afford 105.3 g (yield: 87.6%).

Next, using the obtained compound (C), the compound (D) which is a precursor of the compound (2) is synthesized as follows.

100.0 g of the compound (C) was dissolved in a mixed solution of 1000 mL of tetrahydrofuran and 500 mL of concentrated hydrochloric acid, and then, under stirring at room temperature, 37.0 g of tributyl nitrite was added dropwise over 1 hour. After the completion of the dropwise addition, 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, filtered, and evaporated to dryness, and the residue was washed with n-hexane to obtain 89.3 g (yield: 83.5%) of compound (D).

Next, using the obtained compound (D), the compound (2) was synthesized as follows.

After 30.0 g of the compound (D) was stirred in 300 mL of ethyl acetate, 6.1 g of acetic anhydride and 10.3 g of sodium acetate were added, and the mixture was heated under reflux for 3 hours. Then, the reaction liquid was poured into 500 mL of ice water, and the product was extracted with ethyl acetate. The organic layer was washed with water (300 mL×3 times), dried over magnesium sulfate, and then filtered and evaporated to remove solvent. Ethyl acetate-hexane was recrystallized to obtain 30.0 g of a compound (2) (yield: 91.4%).

<Example 3> Free radical polymerization initiator: synthesis of compound (7)

While cooling with an ice bath, 30.0 g of the compound (B), 10.5 g of triethylamine, 6.8 g of propylamine chloride, and 300 mL of tetrahydrofuran were mixed, and the mixture was stirred at room temperature for 1 hour and then at 50 ° C for 2 hours. Then, the reaction liquid was poured into 600 mL of ice water, and the product was extracted with 300 mL of ethyl acetate. The organic layer was washed with water (200 mL×3 times), dried over magnesium sulfate, and then filtered and evaporated to remove solvent. Dichloroethane-hexane was recrystallized to obtain 33.0 g of a compound (7) (yield 97.4%).

<Example 4> Free radical polymerization initiator: synthesis of compound (46)

First, the compound (E) which is an intermediate of the compound (46) is synthesized as follows.

100.0 g of N-(p-nitrophenyl)carbazole was dissolved in 1000 mL of chloroform, and then 101.8 g of aluminum chloride was added thereto. After stirring at 0 ° C, a solution of 56.0 g of hexyl chloride in 500 mL of chloroform was dissolved. Drop in. After the completion of the dropwise addition, the mixture was stirred at 25 ° C for 4 hours. The reaction solution was poured into 2000 g of ice water, and extracted with chloroform (2000 mL). The organic layer was dried over magnesium sulfate, and the residue was filtered, and the residue was recrystallized from chloroform/methanol to afford 122.5 g of compound (E) (yield 91.4%).

Next, using the obtained compound (E), the compound (F) which is a precursor of the compound (46) is synthesized as follows.

100.0 g of the compound (E) was dissolved in a mixed solution of 1000 mL of tetrahydrofuran and 500 mL of concentrated hydrochloric acid, and then, under stirring at room temperature, 40.0 g of tributyl nitrite was added dropwise over 1 hour. After the completion of the dropwise addition, the mixture was stirred at room temperature for 5 hours. The reaction solution was poured into 1600 mL of ice water, and extracted with chloroform 1500 mL. The organic layer was washed with water (500 mL × 3 times), dried over magnesium sulfate, and the solvent was filtered, and the solvent was evaporated, and the residue was washed with n-hexane to obtain 102.8 g (yield 95.9%) of compound (F).

Next, using the obtained compound (F), the compound (46) was synthesized as follows.

After 50.0 g of the compound (F) was stirred in 500 mL of ethyl acetate, 18.5 g of acetic anhydride and 10.9 g of sodium acetate were added, and the mixture was heated under reflux for 3 hours. Then, the reaction liquid was poured into 500 mL of ice water, and the product was extracted with ethyl acetate. The organic layer was washed with water (500 mL×3 times), dried over magnesium sulfate, and then filtered and evaporated to remove solvent. The ethyl acetate-hexane was recrystallized to obtain 55.2 g of a compound (46) (yield: 88.7%).

<Example 5> Free radical polymerization initiator: synthesis of compound (244)

First, the compound (G) which is an intermediate of the compound (244) is synthesized as follows.

100.0 g of N-benzophenone carbazole was dissolved in 1000 mL of chloroform, and 126.7 g of aluminum chloride was further added thereto. After stirring at 0 ° C, a solution of 58.6 g of propyl chloride in 500 mL of chloroform was added thereto. . After the completion of the dropwise addition, the mixture was stirred at 25 ° C for 4 hours. The reaction solution was poured into 2000 g of ice water, and extracted with chloroform (2000 mL). The organic layer was dried over magnesium sulfate, and the residue was filtered, and the residue was recrystallized from chloroform/methanol to afford 109.3 g (yield: 82.7%).

Next, using the obtained compound (G), the compound (H) which is a precursor of the compound (244) is synthesized as follows.

100.0 g of the compound (G) was dissolved in a mixed solution of 1000 mL of tetrahydrofuran and 500 mL of concentrated hydrochloric acid, and then 67.3 g of tributyl nitrite was added dropwise thereto over 1 hour while stirring at room temperature. After the completion of the dropwise addition, 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, filtered, and evaporated to dryness, and the residue was washed with n-hexane to obtain 103.6 g of compound (H) (yield: 94.3%).

Next, using the obtained compound (H), the compound (244) was synthesized as follows.

After 50.0 g of the compound (H) was stirred in 500 mL of ethyl acetate, 30.4 g of acetic anhydride and 17.7 g of sodium acetate were added, and the mixture was heated under reflux for 3 hours. Then, the reaction liquid was poured into 500 mL of ice water, and the product was extracted with ethyl acetate. The organic layer was washed with water (400 mL×3 times), dried over magnesium sulfate, and then filtered and evaporated to remove solvent. Ethyl acetate-hexane was recrystallized to obtain 58.3 g of a compound (244) (yield: 97.7%).

<Example 6> Free Radical Polymerization Starter: Synthesis of Compound (259)

First, the compound (I) which is an intermediate of the compound (259) is synthesized as follows.

100.0 g of N-benzophenone carbazole was dissolved in 800 mL of chloroform, and then 128.6 g of aluminum chloride was added thereto. After stirring at 0 ° C, a solution of 49.0 g of phenylacetamidine chloride was dissolved in 300 mL of chloroform. Drop in. After the completion of the dropwise addition, the mixture was stirred at 25 ° C for 4 hours. The reaction liquid was further stirred at 0 ° C, and a solution in which 33.8 g of propional chloride was dissolved in 200 mL of chloroform was added dropwise for 2 hours. After the completion of the dropwise addition, the mixture was stirred at 25 ° C for 3 hours. The reaction solution was poured into 1800 g of ice water, and extracted with chloroform (2000 mL). The organic layer was dried over magnesium sulfate, and the residue was filtered, and the residue was recrystallized from chloroform/methanol to afford 128.6 g (yield: 85.6%) of Compound (I).

Next, using the obtained compound (I), a compound (J) which is a precursor of the compound (259) is synthesized as follows.

100.0 g of the compound (I) was dissolved in a mixed solution of 1000 mL of tetrahydrofuran and 500 mL of concentrated hydrochloric acid, and then, under stirring at room temperature, 59.3 g of tributyl nitrite was added dropwise over 1 hour. After the completion of the dropwise addition, 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, filtered, and evaporated to dryness, and the residue was washed with n-hexane to obtain 101.7 g (yield: 91.5%) of compound (J).

Next, using the obtained compound (J), the compound (259) was synthesized as follows.

After 50.0 g of the compound (J) was stirred in 500 mL of ethyl acetate, 26.4 g of acetic anhydride and 15.6 g of sodium acetate were added, and the mixture was heated under reflux for 3 hours. Then, the reaction liquid was poured into 500 mL of ice water, and the product was extracted with ethyl acetate. The organic layer was washed with water (400 mL×3 times), dried over magnesium sulfate, and then filtered and evaporated to remove solvent. The ethyl acetate-hexane was recrystallized to obtain 50.8 g of a compound (259) (yield: 88.8%).

<Example 7> Free Radical Polymerization Starter: Synthesis of Compound (263)

While cooling with an ice bath, 30.0 g of a compound (H), 17.6 g of triethylamine, 9.8 g of benzamidine chloride, and 300 mL of tetrahydrofuran were mixed, and the mixture was stirred at room temperature for 1 hour and then at 50 ° C for 2 hours. After cooling the reaction liquid in an ice bath, 5.5 g of acetonitrile chloride was added, and the mixture was stirred at room temperature for 1 hour, and then stirred at 50 ° C for 2 hours. The reaction solution was poured into 600 mL of ice water, and the product was extracted with 300 mL of ethyl acetate. The organic layer was washed with water (200 mL×3 times), dried over magnesium sulfate, and then filtered and evaporated to remove solvent. Purification by chromatography (hexane/chloroform) gave 25.3 g (yield: 65.7%) of Compound (7).

<Examples 8 to 108>

According to the conditions shown in Table 1, the deuteration and esterification reactions were carried out separately, and the compound of the present invention was obtained.

[Conditions of esterification reaction]

Condition (A): a method of synthesizing acetic anhydride and sodium acetate in the same manner as in Example 1.

Condition (B): a method of synthesizing ruthenium chloride and triethylamine in the same manner as in Example 3.

Condition (B)': a method of synthesizing two kinds of ruthenium chloride and triethylamine in the same manner as in Example 7.

In the table, "compound" means a compound of the present invention obtained by synthesis.

The compounds obtained in Examples 1 to 108 were combined with the results of elemental analysis (C, H, N) (2400‧CHN manufactured by PerkinElmer Co., Ltd.) and mass analysis results of EI-MS (Polaris Q manufactured by Thermo Co., Ltd.). Structure confirmation. The elemental analysis results are shown in Table 2, and the mass analysis results are shown in Table 3.

<Examples 109 to 254, Comparative Examples 1 to 12>

Then, the compound of the present invention represented by the obtained general formula (1) was added as a radical polymerization initiator (A) to the polymerizable composition as described below, and the curability of the polymer was examined.

[Sclerosing test]

4 parts by weight of a radical polymerization initiator (A), 0 or 1 part by weight of a sensitizer, and Daptohto DT 170 (Dongdu Chemical Co., Ltd.) as a radical polymerizable compound (B) 10 parts by weight of 85 parts by weight of bis(trimethylolpropane) tetraacrylate was heated and melted to prepare a coating liquid. The structures of the compounds and sensitizers used in the comparative examples are shown in Table 4 (see also Table 4 in the comparative examples below). The radical polymerization initiator (A) and the sensitizer (C) used are shown in Table 5. This coating liquid was applied onto a PET film using a bar coater (#3). The coating material was subjected to ultraviolet irradiation (high-pressure mercury lamp 130 W/cm, 1 lamp) under the conditions of a conveying speed of 40 m/min, 45 m/min or 50 m/min, and then wiped with a cotton cloth to confirm whether or not the film was damaged. The results are shown in Table 5. Further, it is judged to be preferable if it is not damaged at a high conveyance speed after irradiation with ultraviolet rays.

[Evaluation Benchmark]

5: no damage was confirmed on the film

4: Very few damages were confirmed on the film

3: A slight damage was confirmed on the film.

2: Damage was confirmed on the film

1: Multiple lesions were confirmed on the film

The photopolymerizable composition using the radical polymerization initiator (A) of the present invention is known as a photopolymerizable composition (Comparative Examples 1 to 6) using a conventionally known radical polymerization initiator (Example) 109 to 216) has high hardenability. Further, in comparison with the case of using a conventionally known radical polymerization initiator and a sensitizer (Comparative Examples 7 to 12), it is understood that the radical polymerization initiator (A) of the present invention and the sensitizer are used in combination. The polymerizable compositions (Examples 217 to 254) have high hardenability. In particular, the ketone-type oxime ester compound of the present invention is remarkably higher in sensitivity than the case where a conventionally known keto-type oxime ester is used as a photopolymerization initiator. Although the detailed reason is not known, it is presumed that the photopolymerization initiator (A) of the present invention may be bonded to the keto-oxime structure by the excellent chromophore group represented by the formula (1). And it causes very efficient decomposition of free radicals, so it is highly sensitive to function.

In addition, it is understood that the photopolymerizable composition using the radical polymerization initiator (A) of the present invention exhibits sufficiently high hardenability as it is (Examples 109 to 216), but if a sensitizer (C) is used in combination The hardenability can be further improved (Examples 217 to 254).

Further, a photopolymerizable composition of the radical polymerization initiator (A) of the present invention in which at least one of R ¹⁰ to R ¹⁴ is a nitro group or a substituted or unsubstituted fluorenyl group is used (Example 109) to 147,174 to 195,204 to 185,187,190 to 212,215,216), compared to the use of R ⁷ to R ¹⁰ in at least one of the substituents of the above substituted with a radical group of the present invention In the case of the polymerization initiator (A) (Examples 148 to 173, 186, 188, 189, 196 to 203, 213 to 214), it was found that the system had high hardenability. Although the detailed reason is not known, it is presumed that the photopolymerization initiator of the present invention can be used as an excellent chromophore group by substituting an electron-attracting substituent on the N-phenyl group of the carbazolyl group. The function, but if it is further substituted into a nitro group or a thiol group, it can bring about a significant effect.

Further, in the case where at least one of R ¹⁰ to R ¹⁴ is a mercapto group represented by the formula (3) (Examples 109 to 111, 113 to 127, 174 to 178, 187, 190 to 192, 204, 205) , 210), compared to the case of the sulfhydryl group other than the above (Examples 142 to 147, 179 to 181, 216), showed higher hardenability, and showed the highest in the present embodiment as in the case of the nitro group. Hardening.

Further, a photopolymerizable composition of the radical polymerization initiator (A) of the present invention in which R ¹² is a nitro group (Examples 112, 128 to 141, 193 to 195, 206 to 209) is used as compared with this. In other cases (Examples 182 to 185, 211, and 212), it was found that the curability was excellent. Although the detailed reason is still unknown, it is presumed that the position of the most effective effect of the nitro group is R ¹² , and the same tendency is exhibited for other substituents (thiol groups, etc.). That is, as can be seen while a substituent group, the substituent R ¹² in the case is preferred.

<Examples 255 to 281, Comparative Examples 13 to 18>

The alkali-soluble resin was prepared and added to the polymerizable composition to carry out a curing test and development.

[Modulation of Acrylic Resin Solution (1)]

800 parts by weight of cyclohexanone was added to the reaction solution, and while nitrogen gas was injected into the vessel, the mixture was heated to 100 ° C, and a mixture of the following monomers and a thermal polymerization initiator was dropped at the same temperature for 1 hour. Polymerization.

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 the dropwise addition, the mixture was further reacted at 100 ° C for 3 hours, and then 2.0 parts by weight of azobisisobutyronitrile was dissolved in 50.0 parts by weight of cyclohexanone, and the reaction was continued at 100 ° C for 1 hour to obtain an acrylic acid having a weight average molecular weight of about 40,000. A solution of the resin. After cooling to room temperature, about 2 g of the resin solution was sampled, and dried by heating at 180 ° C for 20 minutes, and the nonvolatile matter was measured to add cyclohexanone in such a manner that the non-volatile component in the previously synthesized resin solution became 20%. And modulating the acrylic resin solution (1). The obtained acrylic resin solution (1) is a solution containing the alkali-soluble resin (E) of the present invention.

[Sclerosing test]

100 parts by weight of dipentaerythritol pentaacrylate (Sartomer Co., Ltd., SR399) as a radical polymerizable compound (B), and 500 parts by weight of an acrylic resin solution (1) as a solution containing an alkali-soluble resin (E), as a solvent 400 parts by weight of cyclohexanone and 6 parts by weight of the compound shown in Table 6 as a radical polymerization initiator (A) were mixed to prepare a uniform polymerizable composition solution.

The above polymerizable composition solution was filtered with a 0.2 μm pore size disc filter, and coated on a stainless steel plate (#600 grinding) using a spin coater, and dried by heating at 80 ° C in an oven. The solvent was removed for 3 minutes. After drying, the film thickness of the polymerizable composition formed on the stainless steel plate was 2 μm. For the polymerizable composition film, light of a high pressure mercury lamp (4.6 mW/cm ² ) was irradiated through a bandpass filter that selectively transmitted light of 350 nm to 380 nm, and the IR spectrum of the polymerizable composition film was measured. The propylene thiol group consumption rate after light irradiation for 10 seconds was calculated from the change in the absorption intensity of 810 cm ^-1 by the characteristics of the acrylonitrile group. The results are shown in Table 6.

The polymerizable composition of the radical polymerization initiator (A) of the present invention (Examples 255 to 281) was used as compared with the case of using a known oxime ester as a radical polymerization initiator (Comparative Examples 13 to 18). Radicals are efficiently generated by light irradiation, and propylene sulfhydryl groups are polymerized. Even if it is slight, further polymerization of the acrylonitrile group has a great influence on the productivity improvement required in recent years, and therefore, the process of higher sensitivity can be achieved by using the radical polymerization initiator (A) of the present invention.

Further, the polymerizable composition before irradiation of light formed on the stainless steel sheets of Examples 255 to 281 was immersed in a 0.2% by weight aqueous solution of tetramethylammonium hydroxide at 20 ° C for about 1 minute, and then appropriate. The rate was dissolved, and it was confirmed that the composition of the present invention was developed by an alkaline developing solution.

<Examples 282 to 353, Comparative Examples 19 to 33>

The alkali-soluble resin was prepared and added to the polymerizable composition to carry out a curing test and development.

[Modulation of Acrylic Resin Solution (2)]

370 parts by weight of cyclohexanone was added to the reaction solution, and while nitrogen gas was injected into the vessel, the mixture was heated to 80 ° C, and the mixture of the following monomer and the thermal polymerization initiator was dropped at the same temperature for 1 hour. Polymerization.

Methacrylic acid 20.0 parts by weight

Methyl methacrylate 10.0 parts by weight

N-butyl methacrylate 55.0 parts by weight

2-hydroxyethyl methacrylate 15.0 parts by weight

2,2'-azobisisobutyronitrile 4.0 parts by weight

After cooling to room temperature, about 2 g of the acrylic resin solution was sampled, and dried by heating at 180 ° C for 20 minutes, and the nonvolatile matter was measured to add a ring in such a manner that the non-volatile component in the previously synthesized acrylic resin solution became 20%. The hexanone is used to prepare an acrylic resin solution (2). The resulting acrylic resin solution had a weight average molecular weight of 40,000. The obtained acrylic resin solution (2) is a solution containing the alkali-soluble resin (E) of the present invention.

[Sclerosing test]

100 parts by weight of dipentaerythritol pentaacrylate (Sartomer Co., Ltd., SR399) as a radical polymerizable compound (B), and 500 parts by weight of an acrylic resin solution (2) as a solution containing an alkali-soluble resin (E), as a solvent 200 parts by weight of propylene glycol monomethyl ether acetate, and the compounds shown in Table 7 as a radical polymerization initiator (A) and a sensitizer (C) are each a part by weight in Table 7, and are mixed and prepared uniformly. A polymerizable composition solution.

The polymerizable composition solution was filtered through a disk filter having a pore size of 0.2 μm, and coated on a glass plate having a thickness of 1 mm using a spin coater, and dried by heating at 80 ° C for 3 minutes in an oven to remove the solvent. After drying, the film thickness of the polymerizable composition formed on the glass plate was 5 μm. For the polymerizable composition film, the irradiation energy of the high-pressure mercury lamp, that is, the irradiation time was exposed by a 13-stage change using a spectroscopic SS-2CP spectrophotometer, followed by a 1% sodium carbonate aqueous solution at 20 ° C. The minimum energy required to make the polymerizable composition insolubilized at an irradiation wavelength of 365 nm as 1 minute was defined as sensitivity, and the results are shown in Table 7.

The polymerizable composition of the radical polymerization initiator (A) of the present invention (Examples 282 to 353) was used as compared with the case of using a known oxime ester as a radical polymerization initiator (Comparative Examples 19 to 33). The line is clearly higher sensitivity. Further, the polymerizable composition of the present invention is sufficiently high in sensitivity when the sensitizer is not used in combination, and the sensitizer can be used in combination to further improve the sensitivity.

<Examples 354 to 425, Comparative Examples 34 to 48> [Pattern shape test]

The polymerizable composition films on the glass substrates produced in Examples 282 to 353 and Comparative Examples 19 to 33 were masked in a predetermined pattern (20 μm × 20 μm resolution) at an exposure interval of about 100 μm and an exposure energy of 365 nm was 4.5 mW. The light of the high-pressure mercury lamp of /cm ² was irradiated for 10 seconds. Then, the film was developed with a 0.2% by weight aqueous solution of tetramethylammonium hydroxide at room temperature for 60 seconds to remove the unexposed portion, washed with pure water, and then the obtained cured product was heated in an oven at 230 ° C for 30 minutes. The shape of the pattern obtained on the glass substrate was evaluated in the following manner. The results are shown in Table 8.

(pattern shape evaluation method)

The shape of the pattern obtained on the glass substrate was observed with an optical microscope, and the linearity of the pattern was evaluated. The rating of the assessment is as follows.

○: Good linearity

×: poor linearity

-: The pattern cannot be observed due to insufficient hardening

The polymerizable composition (Examples 354 to 425) of the radical polymerization initiator (A) of the present invention has a good linearity in the pattern shape obtained on the glass substrate, and as a result, a well-known oxime ester is used as a free The polymerizable composition of the base polymerization initiator (Comparative Examples 34 to 48) was inferior in linearity of the pattern shape obtained on the glass substrate, or the shape of the pattern could not be observed due to insufficient curing.

<Examples 426 to 498, Comparative Examples 49 to 63> [pattern adhesion test]

The pattern forming substrates prepared in Examples 354 to 425 and Comparative Examples 34 to 48 were subjected to a PCT test (pressure cooker test) at 121 ° C, 100% RH, 2 atm, and 24 hours, and then a transparent tape was attached to the 20 μm pattern portion. The pattern adhesion was evaluated by performing a peeling test. The results are shown in Table 9.

The rating of the assessment is as follows.

○: peeling of the 20 μm pattern was not confirmed

×: Confirmation of peeling of the 20 μm pattern

-: Unable to evaluate due to insufficient hardening

When the polymerizable composition of the present invention is used (Examples 426 to 498), the adhesion of the pattern obtained on the glass substrate to the substrate is good, and the known oxime ester is used as a radical polymerization initiator. In the case of the polymerizable composition (Comparative Examples 49 to 63), the adhesion of the pattern to the substrate could not be obtained.

<Examples 499 to 606, Comparative Examples 64 to 91>

The pigment dispersion was prepared as follows, and secondly, a color-developing polymer compound containing the pigment dispersion was prepared.

[Modulation of Red Pigment Dispersion]

The mixture of the following composition was uniformly stirred and mixed, and then dispersed by an Eiger mill ("mini model M-250 MK II" manufactured by Eiger Japan Co., Ltd.) for 2 hours, and then filtered by a 5 μm filter. Red pigment dispersion.

[Modulation of Green Pigment Dispersion]

A mixture of the following composition was operated in the same manner as the red pigment dispersion to prepare a green pigment dispersion.

Copper phthalocyanine pigment (C.I. Pigment Green 36) (Toyo Ink Manufacturing Co., Ltd. "Lionol Green 6YK") 7.1 parts by weight

Monoazo pigment (C.I. Pigment Yellow 150) ("E4GN-GT" manufactured by LANXESS Co., Ltd.) 3.9 parts by weight

The following structure a pigment derivative of 1.0 part by weight

Acrylic resin solution 40.0 parts by weight

Cyclohexanone 48.0 parts by weight

[Modulation of Blue Pigment Dispersion]

A mixture of the following composition was operated in the same manner as the red pigment dispersion to prepare a blue pigment dispersion.

Ε-type copper phthalocyanine pigment (C.I. Pigment Blue 15:6) ("Heliogen Blue L-6700F" manufactured by BASF) 11.0 parts by weight

Phthalocyanine pigment derivative having the following structure: 1.0 part by weight

Acrylic resin solution 40.0 parts by weight

Cyclohexanone 48.0 parts by weight

Cu-pc: copper phthalocyanine residue [Modulation of Black Pigment Dispersion]

A mixture of the following composition was operated in the same manner as the red pigment dispersion to prepare a black pigment dispersion.

Carbon black ("MA77" manufactured by Mitsubishi Chemical Corporation) 12.0 parts by weight

Acrylic resin solution 40.0 parts by weight

Cyclohexanone 48.0 parts by weight

[Red polymerizable composition]

58 parts by weight of a red pigment dispersion, 20 parts by weight of an acrylic resin solution (2), and 3 parts by weight of trimethylolpropane triacrylate ("NK ESTER ATMPT" manufactured by Shin-Nakamura Chemical Co., Ltd.) as a radical polymerization initiator The mixture of 2 parts by weight of the compound (1) (1) and 17 parts by weight of cyclohexanone was stirred and mixed until homogeneous, and then filtered through a filter of 1 μm to obtain a red polymerizable composition of the present invention (Example 499).

[Blue polymerizable composition]

54 parts by weight of a blue pigment dispersion, 15 parts by weight of an acrylic resin solution (2), and 4 parts by weight of trimethylolpropane triacrylate ("NK ESTER ATMPT" manufactured by Shin-Nakamura Chemical Co., Ltd.) as a radical polymerization initiation The mixture of 4 parts by weight of the compound (1) of the agent (A) and 25 parts by weight of cyclohexanone was stirred and mixed until homogeneous, and then filtered through a filter of 1 μm to obtain a blue polymerizable composition of the present invention (Example 500).

[Green polymerizable composition]

67 parts by weight of a green pigment dispersion, 11 parts by weight of an acrylic resin solution (2), and 3 parts by weight of trimethylolpropane triacrylate ("NK ESTER ATMPT" manufactured by Shin-Nakamura Chemical Co., Ltd.) as a radical polymerization initiator The mixture of 2 parts by weight of the compound (1) (1) and 18 parts by weight of cyclohexanone was stirred and mixed until homogeneous, and then filtered through a filter of 1 μm to obtain a green polymerizable composition of the present invention (Example 501).

[Black polymerizable composition]

75 parts by weight of a black pigment dispersion, 9 parts by weight of an acrylic resin solution (2), and 3 parts by weight of trimethylolpropane triacrylate ("NK ESTER ATMPT" manufactured by Shin-Nakamura Chemical Co., Ltd.) as a radical polymerization initiator The mixture of 3 parts by weight of the compound (1) (1) and 13 parts by weight of cyclohexanone was stirred and mixed until homogeneous, and then filtered through a filter of 1 μm to obtain a black polymerizable composition of the present invention (Example 502).

The colored polymerizable compositions of Examples 503 to 606 and Comparative Examples 64 to 91 were produced as follows.

[Red polymerizable composition]

The red polymerizable composition shown in Table 10 was obtained in the same manner as in Example 499 except that the compound (1) as the radical polymerization initiator (A) was replaced by the compound shown in Table 10.

[Blue polymerizable composition]

The blue polymerizable composition shown in Table 10 was obtained in the same manner as in Example 500 except that the compound (1) as the radical polymerization initiator (A) was replaced by the compound shown in Table 10.

[Green polymerizable composition]

The green polymerizable composition shown in Table 10 was obtained in the same manner as in Example 501 except that the compound (1) as the radical polymerization initiator (A) was replaced by the compound shown in Table 10.

[Black polymerizable composition]

The black polymerizable composition shown in Table 10 was obtained in the same manner as in Example 502 except that the compound (1) as the radical polymerization initiator (A) was replaced by the compound shown in Table 10.

[Formation of filter segments and black matrix]

The obtained coloring polymerizable composition was applied to a glass substrate of 10 cm × 10 cm by a spin coating method so that the film thicknesses of the respective colors after the post-baking were respectively the film thicknesses shown in Table 11, and then dust-free. Prebaking at 70 ° C for 15 minutes in a clean oven. Next, after the substrate was cooled to room temperature, ultraviolet irradiation was performed through a photomask using an ultrahigh pressure mercury lamp. Then, the substrate was subjected to spray development using a sodium carbonate aqueous solution at 23 ° C, washed with ion-exchanged water, and air-dried. Thereafter, it was baked in a dust-free oven at 230 ° C for 30 minutes, and a stripe-shaped filter segment was formed on the substrate.

[assessment]

The sensitivity of the resulting colored polymerizable composition and the pattern shape of the filter segments or black matrix formed by the above method were evaluated according to the following method. The results are shown in Table 12.

(Sensitivity)

When the pattern of the filter segment or the black matrix is formed according to the image size of the mask, the exposure amount is used as the sensitivity of the resist. The rating of the assessment is as follows.

◎: less than 40mJ/cm ²

○: 40 mJ/cm ² or more and less than 80 mJ/cm ²

△: 80 mJ/cm ² or more and less than 250 mJ/cm ²

×: 250 mJ/cm ² or more

(pattern shape)

The pattern shape of the formed filter segment or black matrix is evaluated in accordance with (1) the linearity of the pattern and (2) the cross-sectional shape of the pattern.

For (1), it was observed with an optical microscope and evaluated. The rating of the assessment is as follows.

○: Good linearity

△: Partially linear defect

×: poor linearity

For (2), it was observed and evaluated by a scanning electron microscope (SEM). The rating of the assessment is as follows.

○: forward tapered shape

△: non-tapered shape

×: inverse tapered shape

(residual film rate evaluation)

The film thickness measured after exposure (100 mJ/cm ² ), development, and post-baking step, the ratio of the film thickness measured after forming the coating film of each colored polymerizable composition and dried is the residual film ratio. . The rating of the assessment is as follows.

○: 70% or more

×: less than 70%

As shown in Table 12, the coloring polymerizable composition (Examples 499 to 606) using the radical polymerization initiator (A) represented by the formula (1) was very high in sensitivity, and the linearity and cross-sectional shape of the obtained pattern were obtained. Also, the coloring polymerizable composition (Comparative Examples 64 to 91) using a known oxime ester compound as a radical polymerization initiator was inferior in sensitivity, and the linearity and cross-sectional shape of the pattern were not good. .

Further, by using the colored polymerizable composition (Examples 499 to 606) using the radical polymerization initiator (A) represented by the formula (1), a high residual film ratio can be obtained and a coating film is formed. In terms of production stability. On the other hand, the colored polymerizable composition (Comparative Examples 64 to 91) using a known oxime ester compound as a radical polymerization initiator was inferior in residual film rate, and did not reach a sufficient level in coating film formation.

It is understood that the photopolymerizable composition using the compound of the present invention as a radical polymerization initiator is harder in comparison with a photopolymerizable composition of a conventionally known radical polymerization initiator and a sensitizer. Excellent. It can be seen that this contributes to a higher sensitivity process due to the high contribution to the hardenability. Further, the compound of the present invention having such a high hardenability can absorb light well and can greatly improve the radical generating efficiency, which is presumably due to the carbazole chromophore group represented by the general formula (1). A keto-type oxime ester structure which decomposes to generate a large amount of radicals by light irradiation exhibits an excellent effect of multiplicity.

(industrial availability)

The present invention relates to a novel oxime ester compound, a radical polymerization initiator (A) using the oxime ester compound, and a polymerizable composition using the radical polymerization initiator (A), and using the polymerization A negative resist of a sexual composition, and an image pattern forming method using the negative resist. The compound of the present invention functions as a radical generator having a very high sensitivity to an irradiation energy ray. Therefore, the radical polymerization initiator (A) of the present invention using the compound of the present invention can rapidly and surely carry out polymerization and crosslinking reaction by irradiating a radical generated by a conventionally used energy ray as a catalyst. It achieves high sensitivity to energy lines for various applications, or enhances various application characteristics due to sufficient reaction. According to the present invention, a series of applications in which high sensitivity or characteristic improvement can be expected are as follows: a molding resin which is subjected to polymerization or crosslinking reaction, a casting resin, a resin for photoforming, a sealant, a dental polymer resin, a printing ink, Inkjet ink, paint, photosensitive resin for printing plate, color proof for printing, resist for color filter, resist for black matrix, optical spacer for liquid crystal, back projection type of screen material, optical fiber, plasma Display ribs, dry film resists, resists for printed substrates, solder resists, photoresists for semiconductors, resists for microelectronics, resists for manufacturing micromachined parts, resists for etching, microlens arrays, Insulating materials, holographic materials, optical switches, waveguide materials, coating agents, powder coatings, adhesives, adhesives, release agents, optical recording media, adhesives, release coating agents, images using microcapsules Compositions, various devices, etc. used in technical materials

Claims (13)

A compound represented by the following formula (1): However, in the formula, R ¹ represents a substituted or unsubstituted alkenyl group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted aryl group, a substituted or unsubstituted aryloxy group, Substituted or unsubstituted heterocyclic group, substituted or unsubstituted heterocyclic oxy group, substituted or unsubstituted alkylsulfanyl group, substituted or unsubstituted arylthio group, substituted or unsubstituted alkyl sulfinium sulfonate An alkylsulfinyl group, a substituted or unsubstituted arylsulfinyl group, a substituted or unsubstituted alkylsulfonyl group, a substituted or unsubstituted arylsulfonyl group, a substituted or unsubstituted fluorenyl group, Substituted or unsubstituted methoxy, substituted or unsubstituted amino, substituted or unsubstituted phosphinoyl, substituted or unsubstituted amide, or substituted or unsubstituted sulfonamide R ² represents a substituted or unsubstituted alkenyl group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted aryl group, a substituted or unsubstituted aryloxy group, a substituted or unsubstituted group; Heterocyclic group, substituted or unsubstituted heterocyclic oxy group, substituted or unsubstituted alkyl sulphide Alkyl, substituted or unsubstituted arylthio, substituted or unsubstituted alkylsulfinyl, substituted or unsubstituted arylsulfinyl, substituted or unsubstituted alkylsulfonyl, substituted or unsubstituted An arylsulfonyl group, a substituted or unsubstituted anthraceneoxy group, or a substituted or unsubstituted amine group; R ³ to R ⁵ each independently represent a hydrogen atom, a halogen atom, a cyano group, a nitro group, a substituted or not Substituted alkenyl, substituted or unsubstituted alkyl, substituted or unsubstituted alkoxy, substituted or unsubstituted aryl, substituted or unsubstituted aryloxy, substituted or unsubstituted heterocyclic, substituted or Unsubstituted heterocyclic oxy group, substituted or unsubstituted alkylthio group, substituted or unsubstituted arylthio group, substituted or unsubstituted fluorenyl group, or substituted or unsubstituted amine group; R ⁶ to R ⁹ each Independently represents a hydrogen atom, a halogen atom, a cyano group, a haloalkyl group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted aryl group, a substituted or unsubstituted aryloxy group, a substituted or unsubstituted heterocyclic group, a substituted or unsubstituted heterocyclic oxy group, a substituted or unsubstituted alkenyl group, Alken or unsubstituted alkylthio, substituted or unsubstituted arylthio, substituted or unsubstituted alkylsulfinyl, substituted or unsubstituted arylsulfinylene, substituted or unsubstituted alkylsulfonate An aryl group, a substituted or unsubstituted arylsulfonyl group, a substituted or unsubstituted amine group, or a substituent represented by the following formula (2), Wherein R ¹ 'and R ² ' have the same meanings as R ¹ and R ² ; R ¹⁰ to R ¹⁴ each independently represent a hydrogen atom, a halogen atom, a cyano group, a nitro group, a haloalkyl group, a substituted or unsubstituted group. Alkylsulfinyl, substituted or unsubstituted arylsulfinyl, substituted or unsubstituted alkylsulfonyl, substituted or unsubstituted arylsulfonyl, or substituted or unsubstituted anthracene Base, but R ¹⁰ to R ^{14 are} not all hydrogen atoms at the same time. The compound of claim 1, wherein at least one of R ¹⁰ to R ¹⁴ is a nitro group or a substituted or unsubstituted fluorenyl group. The compound according to claim 1 or 2, wherein at least one of the foregoing R10 "to the state is a nitro group or a group represented by the following formula (3): However, in the formula, R, 5 to R, 9 each independently represent a hydrogen atom, a halogen atom, a gas group, a nitro group, a halogen group, a substituted or unsubstituted alkyl group, a substituted group, or an unsubstituted alkoxy group, Substituted or unsubstituted aryl, substituted or unsubstituted aryloxy, substituted or unsubstituted heterocyclic group, substituted or unsubstituted heterocyclic gas group, substituted or unsubstituted alkenyl group, substituted or unsubstituted burnt A thio group, a substituted or unsubstituted arylthio group, a substituted or unsubstituted fluorenyl group, or a substituted or unsubstituted gum base. The compound of claim 3, wherein R ¹² is a nitro group or a group represented by the above formula (3). A radical polymerization initiator (A) containing the patent application scope 1 To compounds of any of the four items. A polymerizable composition comprising the radical polymerization initiator (A) and the radical polymerizable compound (B) of claim 5 of the patent application. The polymerizable composition of claim 6, wherein the sensitizer (C) is further contained. The polymerizable composition of claim 6, wherein the coloring component (D) is further contained. The polymerizable composition according to any one of claims 6 to 8, wherein the alkali-soluble resin (E) is further contained. A negative resist comprising a polymerizable composition of claim 9 of the patent application. A method for producing a polymer by irradiating an energy ray to a polymerizable composition according to any one of claims 6 to 9 to polymerize it. A method for forming an image pattern, characterized in that a negative resist of claim 10 of the patent application layer is laminated on a substrate, partially irradiated with an energy ray to be polymerized, and the unexposed is irradiated with an alkaline developing solution. Partially removed. An image pattern formed by a method of forming an image pattern according to claim 12 of the patent application.