TW201100379A - Oxime ester, radical polymerization initiator, polymerizable composition, negative resist and image pattern - Google Patents

Abstract

The present application provides a novel oxime ester compound acting as a high sensitive radical polymerization initiator, and a curable composition using the same. This application further provides a negative resist material especially useful as photoresist material, and an image pattern forming method using the negative resist material. The radical polymerization initiator (A) is represented by the following formula (1) [wherein, R1 or R2 is alkyl group, aryl group, heterocyclic group; R3 to R5 are hydrogen atom, alkyl group; R6 to R9 are hydrogen atom, alkyl group, aryl group, heterocyclic group; R10 to R14 are selected from hydrogen atom, cyano group, nitro group, haloalkyl group, sulfinyl group, sulfonyl group or acyl group, provide that all R10 to R14 are not hydrogen atom at the same time.]

Description

[Technical Field] 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, and the like A negative resist of a polymerizable composition, and an image pattern forming method using the 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 coating material, a photosensitive resin for printing plates, and printing. Use color proof, resist for color filter, resist for black matrix (biack matrix), optical spacer for liquid crystal (ph〇t〇 spacer), rear projection type (rear-projection) , rib materials for optical fibers and plasma displays, dry film resists, resists for printed substrates, solder resists, photoresists for semiconductors, resistance to microelectronics Agent, micromachined parts manufacturing resist, etching resist, microlens array, insulating material, hologram material, optical switch (0pticai switch), waveguide material, coating agent (overcoat agent) 'Powder coating, adhesive, adhesive, release agent, optical recording medium, adhesive, release coating agent, composition for image technology materials using microcapsules, various devices, and the like. It has been known that a certain oxime ester compound functions as a radical polymerization initiator (see Non-Patent Document 专利, Patent Documents i and 2). Further, a photo-radical polymerization initiator of a positive or negative photosensitive polyimide precursor composition reveals a compound such as α-ketooxime (a _ket〇xime 321778 201100379 ester) (refer to Patent Document 3) ). The ester compound (refer to Patent Documents 4 to 8) has a sister, an α,α-diketodecyl decyl ester compound (refer to Patent 7^. In addition, some neighbors, in order to correspond to productivity improvement or; In recent years, the high sensitivity of the polymerization initiator has been required. In view of the results of the two-way '曰 study of the sample, although significant progress has been seen, '= = = = the improvement of the line sensitivity and the productivity improvement caused by it. The photoreceptor method of the photosensitive (four) m is used in the photoresist method. The usual method is as follows: The surface of the substrate of the shirt image is formed by coating or forming from other bases. The photosensitive resin layer is next exposed to the photosensitive tree of the photosensitive tree layer 4 through the original image, and then the unexposed portion is removed by a developing process with a solvent or an alkaline aqueous solution to form an image corresponding to the original image. As for the case of using such a photoresist method, a material such as a negative resist which is used to form a spacer for a display panel has been disclosed (see Patent Documents 14 to 16). In addition, electrical/electronic parts manufacturing, printed circuit board manufacturing The material is disclosed as a negative resist (refer to Patent Documents 17 to 19). Recently, in the case of a higher sensitivity resist composition, it is known to use a certain ortho-based vinegar as a radical polymerization initiation. The resist composition of the agent is a negative resist (see Patent Document 20) for forming a material for displaying a spacer for a plate. Furthermore, for electric/electronic parts manufacturing and printing. The material for substrate production discloses a negative resist (see Patent Document 21). These functions as a resist composition, but in recent years, in order to cope with productivity improvement or new proposals, various types of materials have been used. The process requires higher functionality and additional new features for the composition of the 5 321778 201100379 agent. In particular, it requires a higher sensitivity resist composition, and actively develops various resist compositions. [Progressive Technical Literature] [ [Patent Document 1] Patent Document 1: US Patent No. 3, 558, 309, Patent Document 2: US Patent No. 4, 255, 513, Patent Document 3: Japanese Patent Application Laid-Open No. 7-14, No. 658 Patent Document 4: US Patent No. 5, 0 Japanese Patent Laid-Open No. Sho 62-184, No. 056, Patent Document 6: Japanese Patent Laid-Open No. 62-273, No. 259, Patent Document 7: 曰本特开昭 62-286, 961 [Patent Document 8] Japanese Patent Laid-Open Publication No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. Patent Publication No. 2004-534, No. 2007-062963, Patent Document No. JP-A No. Hei. No. Hei. No. Hei. No. 2001-226. Japanese Unexamined Patent Application Publication No. JP-A- No. No. No. Publication No. JP-A No. No. Publication No. Publication No. JP-A No. No. Publication No. Publication No. No. No. No. No. No. No. No. No. No. No Japanese Patent Publication No. 2001-302871 [Non-Patent Document] Non-Patent Document 1: European Polymer Journal, 6 933-943 [Invention] (Invention Solution to Problem) 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. From the irradiation energy, it is particularly effective to generate active radicals by light, and to polymerize the radically polymerizable compound in a short time. Another object of the present invention is to provide a negative resist material which is particularly suitable for use in a photoresist material, and an image pattern forming method using the negative resist, the negative resist material 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. (Method for Solving the Problem) The present invention has been completed with respect to one kind / the present inventors carefully studied after considering each of the above problems and working hard to solve the problem. That is, the compound of the present invention is represented by the following formula (1). General formula (1) 321778 7 201100379

Wherein n is substituted or unsubstituted, substituted or unsubstituted alkyl, substituted or unsubstituted alkoxy, substituted or unsubstituted aryl, substituted or unsubstituted aryloxy, substituted or unsubstituted a heterocyclic group, a substituted or unsubstituted heterocyclic oxy group, a substituted or unsubstituted alkylthio group (alkyisulfany U, a substituted or unsubstituted arylthio group, a substituted or unsubstituted alkyl sulphide group, Substituted or unsubstituted arylsulfinyl, substituted or unsubstituted alkylsuifonyl, substituted or unsubstituted arylsulfonyl, substituted or unsubstituted fluorenyl, substituted or unsubstituted An oxy group, a substituted or unsubstituted amino group, a substituted or unsubstituted phosphinoyl group, a substituted or unsubstituted carbam〇yi group, or a substituted or unsubstituted sulfonamide group (sulfam〇yl); R2 represents a substituted or unsubstituted alkenyl group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted oxy group, a substituted or unsubstituted aryl group, a substituted or unsubstituted aryloxy group, a substituent Or unsubstituted, substituted or unsubstituted hetero-oxyl, substituted Unsubstituted thiol group 'substituted or unsubstituted aryl group, substituted or unsubstituted alkylidene group, substituted or unsubstituted sulphate, substituted or cleavable surface group, substituted or substituted Unsubstituted aryl Yin' 醯 | | substituted or unsubstituted oxy, or substituted or unsubstituted 321778 8 201100379 amine; R to R5 each independently represents a halogen atom, a halogen atom, a cyano group, a nitro group , substituted or unsubstituted alkenyl, substituted or unsubstituted alkyl, substituted or unsubstituted alkoxy, substituted or unsubstituted, substituted or unsubstituted aryloxy, substituted or unsubstituted Heterocyclic group, substituted or unsubstituted heterocyclic oxy group, substituted or unsubstituted alkylthio group, substituted or unsubstituted aromatic bowl group, substituted or unsubstituted fluorenyl group, or substituted or unsubstituted amine group R to R each independently represent a halogen atom, a halogen atom, a cyano group, a halogenated C) group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted aryl group, a substitution group; Or unsubstituted aryloxy, substituted or unsubstituted heterocyclic group, substituted or unsubstituted heteroepoxy , substituted or unsubstituted alkenyl group, substituted or unsubstituted thiol group, substituted or unsubstituted aryl group, substituted or unsubstituted ketone group, substituted or unsubstituted aryl arsenic group a substituted or unsubstituted alkyl fluorenyl group, a substituted or unsubstituted aryl fluorenyl group, a substituted or unsubstituted amine group, or a substituted fluorenyl group represented by the following formula (2): R2* Ο *| II „·一分-C=N - 〇"~仁一R1 〇 (wherein R1' and R2' have the same meaning as R1 and R2); R10 to R14 each independently represent hydrogen Atom, halogen atom, cyano group, nitro group, 'haloalkyl group, substituted or unsubstituted alkylsulfinyl group, substituted or unsubstituted-arylsulfinyl group, substituted or unsubstituted alkylsulfonate a substituted, unsubstituted arylsulfonyl group, or a substituted or unsubstituted fluorenyl group, but R1() to R14 9 321778 201100379 are not all hydrogen atoms at the same time). Further, in one aspect of the invention, in the above compound, at least one of R1 (1 to R14 is a nitro group or a substituted or unsubstituted anthracene group. Further, one aspect of the invention relates to the above compound Wherein at least one of R1CI to R14 is a nitro group or a formula (3): a formula (3)

(wherein R15 to R19 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 aromatic 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 Substituted arylthio, substituted or unsubstituted fluorenyl, or substituted or unsubstituted amine). Further, in one aspect of the invention, in the above compound, R12 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 above polymerizable composition. Further, an aspect of the present invention relates to the above polymerizable composition, in which the coloring component (D) is contained in 10 321778 201100379. Further, in one aspect of the invention, the above-mentioned polymerizable property or composition is further provided with 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 which is obtained by irradiating an energy ray onto the polymerizable composition. In addition, one 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 it, and an alkaline developing solution is used. The unirradiated portion is removed. Further, an aspect of the present invention relates to an image pattern formed by the above-described method of forming an image pattern. The content disclosed in this case is the subject of the application of Japanese Patent Application No. 2_-143. on June 17, 2009, and the entire system of the application is hereby incorporated by reference. 〇(Effect of the invention) The compound of Ray 2 is a compound of the α-keto group which is characterized by a substitution of a fluorene-substituted substituent on the phenyl group of the phenyl group, which is characterized by The activity is freely produced by light irradiation: therefore, a compound which is effective as a radical polymerization can be provided. The latter is good in providing polymerizable (tetra) having good properties by using the compound of the present invention as a free-agent. For example, such as Japanese, resin, light-shaped resin, sealant, dental 321778 11 201100379 Μ ' (4), printed ship photosensitive liquid crystal with optical spacer Γ black matrix resist, show crying touch the moon ~ type of screen material, optical fiber, plasma display 35 dry film, dry film resist, printed circuit board resist, solder resist, semi-conductor two agents, microelectronics resist, micro-machine parts manufacturing resistance Agent, waveguide material, coating arm (four) image-forming material, optical switch, chest, 'covering U, powder coating, adhesive, adhesive, media, adhesive, peel coating A method for obtaining a practical oligomer or polymer, and providing and using a free radical polymerization initiator of a white/characteristic cured product, and a polymerization of a radical polymerization initiator Sexual composition. The polymerizable composition of the present invention is particularly suitable for use in very sharp exposure or direct drawing, and is excellent in substrate properties. Therefore, a negative resistance (four) material having high sensitivity to the photoresist material, and an image pattern forming method using the negative resist. [Embodiment]

Hereinafter, embodiments of the present invention will be described in detail. I Formula (1) 1 First, the compound of the present invention will be described. The compound of the present invention is characterized, for example, by the substitution of an electron withdrawing group on the stupid group of the fluorenyl-phenyl-wow skeleton. Further, since it has such a structure, the present invention 2: =, when the light of the wavelength region is emitted, is decomposed secondarily without using the sensitizer in combination. 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) 321778 12 201100379

In the formula, R1 represents a substituted silk-substituted alkenyl group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted oxy group, a substituted or unsubstituted aryl group, a fluorene-substituted silk reduced pure base, and a substituted county a heterocyclic oxy group, a substituted or unsubstituted thiol group, a substituted or unsubstituted thiol group, a substituted or unsubstituted arylthio group, a substituted or unsubstituted carbaryl group, a substituted or unsubstituted aryl group A fluorenyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted aryl fluorenyl group, a substituted or unsubstituted fluorenyl group, a substituted or unsubstituted acid oxy group, a substituted or unsubstituted amine group, Substituted or unsubstituted phosphinyl, substituted or unsubstituted urethane, or substituted or unsubstituted amine. Wherein, in view of the synthesis aspect of the compound, or the performance aspect when used as a starter, etc., a substituted or unsubstituted leukoyl group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted aryl group, a substitution Or an unsubstituted square gas group, or a substituted or unsubstituted heterocyclic group, and a substituted or unsubstituted aryl group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted heterocyclic group is Better. The substituted or unsubstituted dilute group in R1 may, for example, be a chain number of a carbon number, a branched chain, a monocyclic ring or a condensed polycyclic ring. These may also have a plurality of t carbon double bonds in the structure. Specific examples thereof include, for example, a vinyl group, 321778 13 201100379 - allyl group, allyl group, 2-butenyl group, 3-butenyl group, isopropenyl group, isobutenyl group, becenyl group, pentyl group, 3-pentyl group Alkenyl, 4-pentenyl, 1-hexenyl, 2-hexenyl, 3-hexyl, 4-hexenyl, 5-hexenyl, cyclopentenyl, cyclohexenyl, 1 3—butadienyl, cyclohexadienyl, cyclopentadienyl, etc., but are not limited thereto. The substituted or unsubstituted alkyl group may, for example, be a linear, branched, monocyclic or condensed polycyclic alkyl group having a carbon number of 丨 to 18, or a carbon number of 2 to 18 and optionally A linear, branched, monocyclic or condensed polycyclic alkyl group of the above ether bond (_〇_). Specific examples of the straight-chain or branched-bonded mono- or sub-cyclic polyalkyl 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, and a heptyl group. 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 (norb〇rnyi) 'borneol base, 4_fluorenyl ring It has been based on, but is not limited to, etc. Further, specific examples of the linear or branched chain alkyl group having 2 to 18 carbon atoms and optionally one or more ether bonds include ^'CH2~0-CH3'-CH2-CH2-0-CH2-CH3' -CH2-CH2-CH2-0-CH2-CH3, -(CH2-CH2-0)n-CH3 (here, η is 1 to 8), _(10) 仏-〇VCH3 (here, m is 1 to 5) -CH2-CH(CH〇-〇-CH2-CH3, 2~CH2-CH-(0CH3)2, etc., but is not limited thereto. A single carbon number of 2 to 18 and optionally containing more than one ether bond Specific examples of the cyclic or polycyclic alkyl group include those listed below, but are not limited thereto. (疋 321778 14 201100379 X) ^ The substituted or unsubstituted alkoxy group in R1 may, for example, be carbon. a straight chain, branched chain, monocyclic or condensed polycyclic alkoxy group of 1 to 18, or a linear or branched chain shape having 2 to 18 carbon atoms and optionally 1 or more ether bonds a monocyclic or condensed polycyclic alkoxy group. Specific examples of the linear, branched, monocyclic or condensed polycyclic alkoxy group having 1 to 18 carbon atoms include decyloxy group and ethoxy group. Base, propoxy, butoxy, pentyloxy, hexyloxy, heptyloxy, octyloxy, decyloxy, decyloxy, Dodecyloxy, octadecyloxy, isopropoxy, isobutoxy, isopentyloxy, second butoxy, third butoxy, second pentyloxy, third pentoxide , third octyloxy, neopentyloxy, cyclopropoxy, cyclobutoxy, cyclopentyloxy, cyclohexyloxy, adamantyloxy, norbornyloxy, borneoloxy, 4-anthracene The cyclohexyloxy group and the like are not limited thereto, and 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. -CH2-O-CH3-O-CH2-CH2-O-CH2-CH3'-O-CH2-CH2-CH2-O-CH2_CH3,-〇-(CH2-CH2-〇)n-CH3 (here' η is 1 to 8), 0_(CH2-CH2-CH2-〇)fCH3 (here, m is 1 to 5), -0-CH2-CH(CH3)-0-CH2-CH3, _0-CH2_CH-( 0CH3)2, etc. 'But is not limited to this. 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 Not limited to 15 321778 201100379 for this.

-0〇 -o^

- 〇 < ο The substituted or unsubstituted aryl group in R1 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 naphthyl group, a 2-I group, a 1-keto group, a 9-enyl group, a 2-phenanthryl group, a 3-phenanthryl group, a 9-phenanthryl group, an I-you group, and a 5-fused tetraphenyl group. (5~naphthacenyl), 1-mercapto, 2-azulenyl, i-acenaphthyl, 2-diyl, 9-fluorenyl, 3-floweryl, ortho-phenyl , m-phenyl, p-tolyl, 2, 3-diphenyl (2, 3-Xyiyl), 2, 5-dimethylphenyl, 2, 4, 6-trimethylbenzene (mesityl), para-iso P-cumenyl, p-dodecylphenyl, p-cyclohexylphenyl, 4-biphenyl, o-fluorophenyl, m-chlorophenyl, p-bromo, and & base group, m-carboxy stupyl group, o-nonylphenyl group, p-cyanophenyl group, inter-succinyl stupid base nitrogen base stupidization - pulling this plus ^ ^ ^ etc. but not limited This is the case. ^ 中================================================================================================ The case is tetraphenyloxy, phenoxy, 2,9-non-milk, budoxy, 5-accumulate, but is not limited thereto. And a substituted or unrun oxygen atom, a sulfur atom, or a heterogeneous group in R such as a fluorenyl group, a decyloxy group, a 9-oxy group, etc., may be exemplified by money 4 to 24 containing a nitrogen atom and a scorpion. A heterocyclic group of aromatic or aliphatic 321778 16 201100379. Specific examples thereof include a 2-thienyl group, a 2-benzothienyl group, a naphtho[2,3-b]°-septenyl group, a 3-°ianthrenyl group, a 2-indenyl group, and a 2-thiol group. 2-indolyl, 2-benzopyranyl, pyranyl, isobenzoxyl, chromenyl, xanthenyl, which (phenoxathiinyl), 2Η-πΛ洛基, 吼η基, miso, pyrazolyl, pyridyl, pyridinyl, pyrimidinyl, hydrazine, indolizinyl, isodecyl (isoindolyl), 3Η-mercapto, 2H-quinolizinyl, isoquinolyl, phthalazinyl, naphthyridinyl, anthraquinone喔琳基 (911丨11〇乂&1丨1171), 喧Wahlinky (911丨1132〇111171), cinnolinyl, pteridinyl, 4aH-flavored β, base (phenanthridinyl), 2-acridinyl, perimidinyl, phenanthrolinyl, phenazinyl, phenarsazinyl, isoindole Phinthyl Zinyl), isoxazole (is〇xazolyl), furazanyl, 3-phenoxazinyl, isochromanyl, chromanyl, pyrrolidinyl, pyrroline , imidazolidinyl, imidazolinyl, "rhoquinone, .π than soul base, ° bottom bite, alpha bottom well base, ϋ 嗓 基 基 (i ndo 1 i ny 1) , ° 朵 朵 朵 、, quinuclidinyl, morpholinyl, thioxanthenyl, 4-quinolinyl, 4-isoquinolinyl, 3-morphinyl, 2- a glycine-based group, a 3-coumarinyl group, etc., but not limited to 17 321778 201100379 Such a substituted, substituted or unsubstituted heterocyclic oxy group may be exemplified by a nitrogen-containing m-hetero, sulfur atom. A single ring or a condensation of a carbon atom of 4 to 18 in the atom:::: an epoxy group. Specific examples thereof include 2-oxooxy group, 2-rolling oxime 2, -(tetra)yloxy group, 3-anthyloxy group, 2-benzo-bite-fermented soil, 2 benzophenyloxy group, 2 It is a succinyloxy group, a 3-saltyloxy group, a fluorenyloxy group, and a -9. Silky oxygen (four), but is rare here. The substituted or unsubstituted sulfur-burning group in RI may, for example, be a linear 77-chain, monocyclic or condensed polycyclic sulfur-burning group having a hindrance of 1 to 18. 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. , but not limited to this. The substituted or unsubstituted arylthio group in R may, for example, be a monocyclic or condensed polycyclic arylthio group having a carbon number of β to 18. Specific examples thereof include, but are not limited to, a phenylthio group, a 1-nathio group, a 2-naphthylthio group, a 9-fluorenylthio group, and a 9-phenanthrylthio group. The substituted or unsubstituted alkylsulfinyl group in R1 may, for example, be an alkylsulfinyl group having a carbon number of i to 20. Specific examples thereof include mercaptosulfinyl group, ethyl sulphate, propylsulfinyl group, isopropylsulfinyl group, butylsulfinyl group, hexylsulfinyl group, cyclohexyl group. Sulfonyl, octylsulfinyl, 2~ethylhexyl fluorenyl, fluorenyl sulphate, dodecanoyl sulfinyl, octadecyl sulfinium The group is a cyanoindenylsulfinyl group or a decyloxymethylsulfinyl group, but is not limited thereto. The substituted or unsubstituted arylsulfinyl group in R1 may, for example, be an arylsulfinylene group having a carbon number of 6 1S 321778 201100379 to 30. Specific examples thereof include, for example, phenylsulfinylene, 1-caiyl continuation, 2-methylphenyl sulfonate, 2-chlorophenyl sulfonium, 2-methylphenylsulfinium , 2-methoxyphenylsulfinyl, 2-butoxyphenylsulfinyl, 3-chlorophenylsulfinyl, 3-trifluoromethylphenylsulfinyl, 3 - cyanophenylsulfinyl, 3-nitrophenylsulfinyl, 4-fluorophenylsulfinyl, 4-cyanophenylsulfinic acid, 4-methoxyphenyl Sulfhydryl group, 4-decylthiophenylsulfinyl group, 4-phenylthiophenylsulfinyl group, 4-dimethylaminophenylsulfinyl group, etc., but not limited thereto. The substituted or unsubstituted alkylsulfonyl group in R may, for example, be a decyl group having a carbon number of 1 to 20. Specific examples thereof include a methyl group, an ethyl sulfonium group, a propyl sulfonyl group, an isopropyl sulfonyl group, a butyl sulfonyl group, a hexyl sulfonyl group, a cyclohexyl sulfonyl group, and an octyl sulfonium group. Base, 2-ethylhexylsulfonyl, decylsulfonyl, fluorenylsulfonyl, octadecylsulfonyl, cyanomethylsulfonyl, decyloxymethylsulfonyl Etc., but not limited to this. The substituted or unsubstituted arylsulfonyl group in R1 may, for example, be an arylsulfonyl group having 6 to 30 carbon atoms. Specific examples thereof include a phenylsulfonyl group, a 1-naphthyl yellow wine base, a 2-methyl group, a 2-chlorophenyl group, a 2-methylphenyl group, a 2-oxo group. Phenyl sulfonyl, 2-butoxyphenylsulfonyl, 3-chlorophenylsulfonyl, 3-trifluorodecylphenylsulfonyl, 3-cyanophenylsulfonyl, 3 _Shi Xiaoji phenyl continuation base, 4 _ phenyl phenyl ketone, 4 _ entyl.· Benzene, continuation, brewing, 4-methoxyphenylsulfonyl, 4-methylthiophenyl Sulfhydryl group, 4-phenylthiophenylsulfonyl group, 4-dimethylaminophenylsulfonyl group, etc., but is not limited thereto. The substituted or unsubstituted thiol group in R1 may, for example, be a carbonyl group bonded to a hydrogen atom or a linear, branched, monocyclic or condensed polycyclic group having a carbon number of 1 to 18, 19 321778 201100379 aliphatic group. a carbonyl group substituted with an alkoxy group having 2 to 20 carbon atoms; a carbonyl group bonded to a monocyclic or condensed polycyclic aryl group having 6 to 18 carbon atoms; a monocyclic or condensed polycyclic ring having 6 to 18 carbon atoms; An aryloxy-substituted carbonyl group; a carbonyl group bonded to a monocyclic or condensed polycyclic heterocyclic group having 4 to 18 carbon atoms, which is a nitrogen atom, an oxygen atom, a sulfur atom or a phosphorus atom. Specific examples thereof include a mercapto group, an ethyl fluorenyl group, a propyl fluorenyl group, a butyl fluorenyl group, an isobutyl fluorenyl group, a amyl group, an isovaleryl group, a pivaloyl group, a laurel tortoise group, and a myristyl group. (myristoyl), palmitoyl, stearyl sulfonyl, cyclopentylcarbonyl, cyclohexylcarbonyl, acryl fluorenyl, methacryl fluorenyl, crotonoyl, isocrotonyl, oil Cinnamoyl, benzyloxy, benzyloxycarbonyl, ethoxycarbonyl, propoxycarbonyl, butoxycarbonyl, hexyloxycarbonyl, octyloxycarbonyl, decyloxycarbonyl, octadecyl Carbocarbonyl, trifluoromethoxycarbonyl, benzoyl, toluoyl, 1-naphthoyl, 2-naphthylmethyl, 9-fluorenylcarbonyl, Phenoxycarbonyl, 4-mercaptophenoxycarbonyl, 3-nitrophenoxycarbonyl, 4-dimethylaminophenoxycarbonyl, 2-methylthiophenoxycarbonyl, 1-naphthoquinone Oxycarbonyl, 2-naphthylmethoxycarbonyl, 9-decyloxycarbonyl, 3-furoyl, 2-thenoyl, 2-thenoyl Nicotinoyl ), is different from the test base, etc., but is not limited to this. The substituted or unsubstituted methoxy group in the above may, for example, be a decyloxy group having 2 to 20 carbon atoms. Specific examples thereof include an ethyl ethoxy group, a propenyloxy group, a butoxy group, a pentyloxy group, a trifluoromethyl group, an oxy-oxy group, a 1-naphthylcarboyloxy group, and the like. 2-naphthylcarbonyloxy group and the like. The substituted or unsubstituted amino group in R1 may, for example, be an amine group, an alkylamino group, 20 321778 201100379 dialkylamino group, arylamino group, diarylamino group, alkylarylamino group, benzyl group Amine group, bisarylamino 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, third 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, hydrazine Diisoamylamino, methylethylamino, methylpropylamino, decylbutylamino, decylisobutylamino, cyclopropylamino. More than a bite base, a bite base, a piperage base, etc., but it is not limited to this. Examples of the arylamine group include an anilino group, a naphthylamino group, a 2-naphthylamino group, an o-toluidino group, an m-anilino group, a p-toluidine group, and a 2-biphenylamino group. , 3-phenylanilino, 4-biphenylamino, 1-nonylamino, 2-aminol, 2-thiazolamine, p-terphenylamino, etc., but not limited This is the case. Examples of the diarylamine group include a diphenylamino group, a bis(indenyl)amino group, 21 321778 201100379 N-phenyl-1-naphthylamino group, phenyl-2-naphthyl group, and the like. . The alkylarylamine group may, for example, be N-methylanilino or methyl I. Specific alkyl, N-ethylanilino, N-propylanilino, N-butylamino, isopropyl, N-pentylanilide, N-ethylanilino, 1-methyl-b-amine Base, etc., but is not limited to this. The substituted or unsubstituted (10) group in the soil R may, for example, be a carbon number 2 to a squaring base. Specific examples thereof include, for example, a sulfhydryl group, a diethylphosphine aryl group, a -propyl group, a diphenylphosphine aryl group, a dimethoxy phosphine aryl group, a diethoxy phosphine aryl group, and a second a phosphine base, a bis (2, 4, 6-tridecyl group, etc., but is not limited thereto. 'The substituted or unsubstituted amine group in the R can be exemplified by a carbon number ^ to a 胺 1 amine group Specific examples thereof include N-methylamine methyl sulfonyl group, N-ethylamine methyl sulfonyl group, propylamine methyl aryl group, Ν_τ-ylamine aryl group, hexylamine amide group, fluorene ring Hexylamine, Ν-octylamine, mercapto, Ν 癸 胺 胺 I Ν Ν 十八 十八 十八 十八 十八 十八 十八 十八 十八 十八 十八 十八 十八 十八 2 2 2 2 Amine-based, Ν2-ylphenylaminocarboxamyl, fluoren-2-isopropoxyphenyl f-mercapto H(2-ethylhexyl)phenylamine, Ν-3_ Phenyl phenyl group, Ν-3' wall-based phenylamine carboxylic acid group, Ν-3-cyanophenylamine 曱醯 Ν Ν 4~ methoxyphenylamine aryl, N-4- Cyanophenylamine fluorenyl, methylthiophenylamine methyl, ^4_phenylthiophenylamine, fluorene, hydrazine, hydrazine And the unsubstituted sulfonyl group can be exemplified by, for example, a carbon number 〇 to a hydrazinyl group, a di-butylene group, a hydrazinyl group, and the like. 30 321 778 22 201100379 Amine continuation base. Specific examples thereof include, for example, an amine sulfonyl group, an N-alkylamine aryl group, an N-arylamine sulfhydryl group, and an N,N-dialkylamine hydrazino group. , N,N-diarylamine, fluorenyl group, N-alkyl-N-arylamine acid group, etc. More specifically, N-decylamine sulfonyl group, N-ethylamine Sulfonyl, sulfamidino, hydrazine-butylamine sulfonyl, hydrazine-hexylamine sulfonyl, fluorene-cyclohexylamine, fluorenyl-octylamine sulfonyl, fluorene-2-ethyl Hexylamine sulfonyl sulfonyl group, hydrazine-hydrazinyl sulfonyl sulfonyl group, fluorenyl-octadecylamine fluorenyl group, hydrazine-demethylamine hydrazino group, ν_2-methylphenylguanamine sulfonyl group, Ν-2 -Phenylaminosulfonyl, Ν_2_decyloxyphenylamine sulfonyl, fluoren-2-isopropenylamine, ν-3-chlorophenylamine hydrazino, hydrazine- 3-nitrophenylamine decyl, indole-3-cyanophenylamine, Ν_4-methoxyphenylamine sulfonyl, Ν-4-cyanophenylamine sulfonyl, Ν_4 _ dimethyl Amino-aminophenylamine hydrazino, Ν_4_methylthiophenylamine sulfonyl, fluorenyl-4-phenylthiophenyl sulfonyl sulfonyl, fluorenyl-fluorenyl-hydrazine-phenylamine sulfonate Base, hydrazine, hydrazine-diguanidylamine stone, styrene, Ν' Ν-dibutylamine hydrazino group, ν, diphenylamine fluorenyl group, etc., but not limited thereto. 〇R2 is substituted Or unsubstituted alkenyl group, substituted or unsubstituted alkyl group, substituted or unsubstituted decyloxy group, substituted or unsubstituted aryl group, substituted or unsubstituted aryloxy group, substituted or unsubstituted heterocyclic group, Substituted or unsubstituted heterocyclic oxy, substituted or unsubstituted alkylthio, substituted or unsubstituted arylthio, substituted or unsubstituted alkylsulfinyl, substituted or unsubstituted arylsulfinyl^ Alkyl, substituted or unsubstituted alkylsulfonyl, substituted or unsubstituted aryl, substituted or unsubstituted alkoxy, or substituted or unsubstituted amine. Wherein 'alkyl, substituted or unsubstituted alkoxy substituted with substituted or unsubstituted dilute, substituted or unsubstituted 23 321778 201100379 from the point of view of the synthesis of the compound or the performance as the starting agent A aryl 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, or a substituted or unsubstituted decyloxy group is preferred. The substituted or unsubstituted alkenyl group, substituted or unsubstituted alkyl group, substituted or unsubstituted aryl group, or substituted or unsubstituted heterocyclic group is more preferred. 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 in R Heterocyclic group, substituted or unsubstituted heterocyclic oxy group, substituted or unsubstituted fluorenyl group, substituted or unsubstituted aryl fluorenyl group, substituted or unsubstituted decyl 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 anthraceneoxy group, and a substituted or unsubstituted amine group, and the aforementioned R1 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 heterocyclic group Cycloalkyl, substituted or unsubstituted heterocyclic oxy, substituted or unsubstituted thiol, substituted or unsubstituted arylthio, substituted or unsubstituted alkylsulfinyl, substituted or unsubstituted aryl Sulfosyl, substituted or unsubstituted alkylsulfonyl, substituted or unsubstituted aromatic The sulfonyl group, the substituted or unsubstituted methoxy group, and the substituted or unsubstituted amine group have the same meaning. R, to R5 each independently represent a hydrogen atom, a halogen atom, a cyano group, a nitro group, a substituted or undrawn filament, a substituted filament substituted 2 group, a substituted or unsubstituted oxy group, a substituted silk substituted aryl group. , substituted or unsubstituted arsenic earth, substituted or unsubstituted heterocyclic group, substituted or unsubstituted heterocyclic oxy group, 321778 24 201100379 substituted or unsubstituted alkylthio group, substituted or unsubstituted, 孑 基And substituting an unsubstituted thiol group or a substituted or unsubstituted amine group. 〆仏 〆仏 人 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 The unsubstituted aryl group, the substituted or unsubstituted heterocyclic group is preferred, and a hydrogen atom, a nitro group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group 2 is more preferable. The halogen atom in the ring "R3" to R5 may, for example, be a fluorine atom, a gas atom, a bromine atom or a broken atom. The substituted or unsubstituted alkenyl group, substituted or de-substituted group, substituted or unsubstituted in R to R5 Alkoxy, substituted or unsubstituted aryl, aryloxy group substituted or unsubstituted, substituted or unsubstituted heterocyclic group, substituted or unsubstituted heterofluorenyloxy group, substituted or unsubstituted alkylthio group a substituted or unsubstituted arylthio group, a substituted or unsubstituted aryl group, and a substituted or unsubstituted amino group, which is a substituted or unsubstituted alkenyl group, a substituted or unsubstituted alkyl fluorenyl group in the above R1, 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 The alkylthio group, the substituted or unsubstituted arylthio group, the substituted or unsubstituted fluorenyl group, and the substituted or unsubstituted amine group have the same meaning. R6 to R9 each independently represent a hydrogen atom, a halogen atom, a cyano group, or a halogen. Alkyl, substituted or unsubstituted alkyl, substituted or unsubstituted alkoxy , substituted or unsubstituted, aryloxy, substituted or unsubstituted aryloxy, substituted or unsubstituted heterocyclic, substituted or unsubstituted heterocyclic oxy, substituted or unsubstituted olefin 25 321778 201100379, substituted or Unsubstituted alkylthio, substituted or unsubstituted arylthio, substituted or unsubstituted alkylsulfinyl, substituted or unsubstituted aryl fluorenyl, substituted or unsubstituted alkylsulfonyl a substituted or unsubstituted arylsulfite group, a substituted or unsubstituted amino group, or a substituent represented by the following formula (2): wherein, from the synthesis of the compound, or as a starter From the standpoint of performance, etc., a hydrogen atom, a halogen atom, a cyano group, a haloalkyl group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted heterocyclic group, or The substituted or unsubstituted amino group is preferably a hydrogen atom, a decanoyl group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, and the like.

(wherein 'wide and R2 are the same meaning as Rl and R2). The i atom system in R9 in R6 has the same meaning as the 4 atom in R3 to R5. The dentate alkyl group in R9 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 triterpene, trichloromethyl, trimethylol, and triiodomethyl. Base, pentafluoroethyl, pentaerythrine, pentabromoethyl, pentaiodoethyl, trifluorodibromoethyl, tribromodiiodoethyl, heptafluoropropyl, heptachlor, benzyl, sulphate, Nine-I butyl, nonachlorobutyl, nonabromobutyl, deca-fluoropentyl, deca-chloropentyl, deca-amylpentyl, tridecafluoro, tridecafluoro, pentafluoroheptyl , heptadecafluorooctyl, hexadecafluoroindolyl, twenty-four fluorenyl, thirty-one, thirty-one, twenty-fifth (twelve) 321778 26 201100379, etc., but is not limited thereto. The haloalkyl group is preferably a trifluoromethyl group or a pentafluoroethyl group in terms of the characteristics of the synthesis or the use as a radical polymerization initiator (A). a substituted or unsubstituted alkyl group in R to R, 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, substituted or unsubstituted alkenyl, substituted or unsubstituted alkylthio, substituted or unsubstituted anthracenylthio, substituted or unsubstituted alkylsulfinyl, substituted or unsubstituted Substituted arylsulfinyl, substituted or unsubstituted alkylsulfonyl, substituted or unsubstituted arylsulfonyl, and substituted or unsubstituted amine, substituted or unsubstituted in the above R1 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 C) , substituted or unsubstituted alkylsulfonyl, substituted or unsubstituted arylsulfonic acid, and taken Or non-substituted amino group of the same meaning. Here, as long as R6 to R9 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), R6 to R9 contain a group other than hydrogen. In the meantime, R7 is preferably a group other than hydrogen. R10 to R14 each independently represent a hydrogen atom, a halogen atom, a cyano group, a nitro group, a halogen group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted arylsulfinyl group, a substitution or Unsubstituted alkyl sulfonyl, substituted or unsubstituted aryl sulfonyl, 321778 27 201100379, or substituted or unsubstituted sulfhydryl, but! ^. Until rm is not all hydrogen atoms at the same time. The halogen group in R to R has the same meaning as the above-mentioned halogen group in r6 to r9, a substituted or unsubstituted alkyl group, a substituted or unsubstituted arylsulfinyl group, a substituted or not a substituted alkylsulfonyl group, a substituted or unsubstituted arylsulfonyl group, and a substituted or unsubstituted indenyl group and a substituted or unsubstituted homocyclic group in the above R1, substituted or unsubstituted The arylsulfinyl group, the substituted or unsubstituted alkyl group, the substituted or unsubstituted arylsulfonyl group, and the substituted or unsubstituted fluorenyl group have the same meaning. R1(R) to R14 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 The one shown by the following general formula (3) is more preferable: general formula (3)

(wherein R to R 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 aromatic 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 Substituted aragonitic base, substituted or unsubstituted base, or substituted or unsubstituted amine). 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 321778 28 201100379 substituted heterocyclic oxy group, substituted Or an unsubstituted thiol group, a substituted or unsubstituted thio group, or a substituted or unsubstituted amine group, preferably substituted or unsubstituted or unsubstituted or substituted or unsubstituted. The position of the substituent other than the hydrogen other than hydrogen in Rl5 to Rl9 is preferably Rl5, Rl7, r19, and more, the soil is r]7, in terms of the synthesis of the compound, or the performance of the starting day. 〇同立Γ to take the letter of the base in Rl9 and the (4) base in the aforementioned bR9

Mercapto, substituted or unsubstituted heterocyclic oxy, substituted or unS. substituted or unsubstituted fluorenyl, and substituted or unsubstituted =5, substituted or unsubstituted alkyl, substituted or unsubstituted in R == substituted or unsubstituted meimei, > meta-bovine ◎ substituted heterocyclic A aryloxy, substituted or unsubstituted, substituted or unsubstituted or unsubstituted substituted or unreceived or not Substituted arylthio, meaning. The _, and the substituted or unsubstituted amine group are the same meaning (1) like the hydrazine radical polymerization (4) or the compatibility of the resin, in terms of λ: 方 side: or as a radical polymerization starter ^ ” In view of the raw material, R12 is preferably a group other than hydrogen. 321778 29 201100379 The hydrogen atom of the substituent in the above R1 to R19 may be substituted by another substituent. The substituents may be, for example, a fluorine atom or a gas. a halogen group such as an atom, a bromine atom or an iodine atom; an alkoxy group such as a decyloxy group, an ethoxy group or a second butoxy group; an aryloxy group such as a phenoxy group or a p-methyloxy group; a methoxycarbonyl group; An oxycarbonyl group, a aryloxy group, or an aryloxy group; a methoxy group such as an ethoxy group, a propyloxy group or a benzhydryloxy group; an ethyl hydrazino group, a benzhydryl group, an isobutyl fluorenyl group , a fluorenyl group, a methacrylic acid group, a methoxy group such as mdhoxaiyi; an alkylthio group such as a thiol group or a tert-butylthio group; a phenylthio group, a p-fluorenyl group, and the like ^thio group; alkylamino group, cyclohexylamino group and the like alkylamino group; dialkylamino group, diethylamino group, morpholinyl group, piperidinyl group and the like; An arylamino group such as an amine group or a p-tolylamino group; an alkyl group such as a methyl group, an ethyl group, a tributyl group or a dodecyl group; a strepyl group, a p-tolyl group, a dimethylphenyl group, a cumyl group, An aryl group such as a naphthyl group, an anthracenyl group or a phenanthryl group; a heterocyclic group such as a furyl group or a thienyl group; and the like, and examples thereof include a hydroxyl group, a carboxyl group, a fluorenyl group, a fluorenyl group, a sulfonic acid group, and a sulfinyl group ( Mesy 1 ), p-toluene decyl, amine, nitro, cyano, trifluoromethyl, trimethyl, tridecyl decyl, phosphonico, phosphono 'trimethyl ammonium phosphate, dimei:hyl sulfoniumy 1 , two basic phenacyl phosphoniumyl groups, etc. The compounds of the invention are shown below Specific examples, but the structure of the compound of the present invention is not limited to these. 321778 30 201100379

Compound (1 0)

Compound (1 3)

31 321778 201100379

义 meaning. . 9 φ O^CHj φ 〇"S:H3

Compound (1 8) H3trjD^DylCHs Η, ί^^Ο^^Ογ^ 6 0 Compound (16) Compound (17) 0 ^ ^ 〇 Φ crS:H3 φ Λϊη, φ orSiH,

Compound (2 2) Compound (2 0} Compound (2 1)

03⁄4^. Compound (2 3)

Η3(^ HjC^N

〇"S:Hs Φ 9^CHj Compound (2 4) 0g〇 «φ <^CH, ^ο^ΟώαΛοΗ, o Compound (2 7)

Compound (2 9)

32 201100379

Compound (3 9)

33 321778 201100379

X CHs compound (4 8)

Γ2 〇 Ο^Λ〇Η3 ο Compound (5 0)

Compound (5 3)

Η O^CHj , <L^ch3

Compound (6 3) 34 321778 201100379

Compound (7 2) Compound (7 0)

•J u ^ Λ wHv h3c 〇 ch3 compound (7 1)

Fork 02 〇φ 〇Α:Η3

6 ο Compound (7 7)

35 321778 201100379

Compound (8 2)

Compound (8 3)

Compound (8 7)

Compound (8 8)

36 321778 201100379

CN

Compound (1 0 0) CN

Ϊ́φ (p^CHsΟώ&ΛοΗ. II Ο compound (9 8) Φ Ο compound (1 〇 1) CN

Ο compound (1 0 4) ?Ν οφ 9^ch33<^ΟΛη3 Ο compound (1 0 5) a §

Ο compound (1 〇 3) CN

δ ° chemical (10 8: compound (1 0 6) Ο ο^Λη, II Ο compound (1 〇 9) 9Pj

Compound (1 1 2) Compound (10 7) φ O^O^C^CHs II Ο Compound (1 1 〇) ^ ο ρ Shoulder Compound (1 0 8) ^ Λη,

Compound (1 1 1) 0*〇Λη3 ο Compound (1 1 3) Compound (1 1 4) 321778 37 201100379

38 321778 201100379

CH3 H3C person

9

39 321778 201100379

o

Compound (1 4 3)

Qig-CHj

JD o V 〇^CH3

It α o compound (1 4 9) φ is called compound (1 5 2)

Compound (1 50)

Compound (1 5 3)

Ov, rCH3

Ο compound (1 5 5) 〇*5 is

Compound (1 5 6) 40 321778 201100379

Λ

Ο Compound (1 5 8)

Ο

ο

Compound (1 60)

Compound (1 6 1)

Compound (1 6 5)

Ο

p Λη, ο

Compound (1 7 3) Compound (1 7 2) Λ», c*oj_CH3 II Λ ο Compound (1 7 4) 41 321778 201100379

O "〇τΝ;η,

9CftXi 1, CHj

P h3c' , ch3

o

043 Compound (1 8 2) Compound (18 3) Compound (1 8 1)

o

O

, c^CHs CHa 〇

Compound (186) Compound (1 8 4)

321778 42 201100379

Ο compound (1 9 2) ο

Ο

Ο Compound (1 9 5)

Compound (1 9 7)

43 321778 201100379 CH, Compound (2 0 8) Compound (2 0 9)

Compound (2 1 Ο) 〇 φ cT^-CHa ο Compound (2 1 3)

Compound (2 2 0)

Compound (2 2 1)

44 321778 201100379

Compound (2 2 3)

Compound (2 3 5)

〇

45 321778 201100379

Compound (2 4 9> 46 321778 201100379

Compound (2 5 1)

Compound (2 5 5)

Compound (2 5 6)

Compound (2 5 7)

47 321778 201100379

Compound (2 6 1)

Compound (2 6 6)

Compound (2 6 3)

Compound (2 6 7)

Compound (2 6 8)

Compound (2 6 9) 48 321778 201100379

Compound (2 7 1)

Compound (2 7 3)

Compound (2 7 9)

Compound (2 8 1) 49 321778 201100379

Compound (2 8 5)

Ο

Compound (2 8 9)

Compound (2 9 1)

II Μ ο ο

321778 50 201100379

Compound (2 9 4)

Compound (2 9 9)

Compound (2 9 8)

Compound (3 Ο 1)

Compound (3 0 2)

Compound (3 0 3) 51 321778 201100379

Ό Ο Ο ° Compound (3 0 8) Compound (3 0 9)

Compound (3 1 3) Compound (3 1 4)

Compound (3 1 2)

Compound (3 1 5) 52 321778 201100379

Compound (3 2 2)

Compound (3 2 7) The compound represented by the formula (1) is obtained by adjusting an intermediate and adjusting the precursor using the intermediate. The intermediate is a ketoneized product represented by the formula (4). The following "as long as there is no special (four) reason, "intermediate" means deuterated: matter. General formula (4) 321778 53 201100379

R2 (in the formula: to, in the (1), R2 to Rl4 have the same meaning ^ and ", can be obtained as a raw material. In addition, it can be based on well-known synthetic methods, such as the Japanese Chemical Society The fourth edition = the total number of methods described in the 51st article (Maruzen) is easy to use. The (four) system of the ten-seat compound shown can be easily obtained by the Frid-Kraft compound reaction (5), which can be easily obtained, for example, according to the method described in Japanese Patent No. 3992725. Obtained in the same way. When the compound of the formula (1) is synthesized, the precursor is a hydrazine represented by the following formula (5). Hereinafter, the "precursor" means a ruthenium compound as long as there is no particular reason. General formula (5) 321778 54 201100379 R12

(wherein R2 to R14 are the same as those of R2 to R14 in the formula (1)). The ketone compound represented by the formula (5) can be obtained by using the ketone compound represented by the formula (4) as an intermediate, and according to, for example, Org. React., 7, <1953>, 327 or I learned the various methods described in the 4th edition of the Experimental Chemistry Lecture, Vol. 14, No. 1316 (Maruzen). Further, it can also be obtained by a synthetic method described in a commercially available chemical textbook (e.g., J. March, Advanced Organic Chemistry, 4th Edition, Wiley Interscience, 1992). One of the most suitable synthetic methods for hydrazine is the nitrosation of active methylene groups by nitrous acid or alkyl nitrite 0. 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 Soc·, 47, <1925>, 2033, J. Am. Chem. Soc., 117, <1920>, 590, J. Am. Chem. Soc., 51, <1929>, 2264, and Suitable for manufacturing defects. Nitrous acid is usually produced by sodium nitrite. The alkyl nitrite is, for example, decyl nitrite, isopropyl nitrite, butyl nitrite or isocyanuric acid. 55 321778 201100379 μ Γί (1) The compound of 717 is obtained by combining the compound represented by the general formula (5) into a precursor, and the method described in the literature (for example, the method described above) is substituted with a brewing gas or an acid anhydride, for example, four. In the presence of a base (for example, a tertiary amine such as triethylamine) or a basic solvent such as pyridine, the reaction is carried out in a solvent such as hydroquinone, benzene or dimethylmethylamine; Manufacturing. / For those skilled in the relevant art, such reactions are generally performed in 15 C to +50 t, preferably in 〇 to 3 〇〇c. ^All oxime ester systems are present in two stereo configurations (Z) or (E). The isomer can be isolated by the method of 'decamber' but a mixture of isomers can also be used as the starting species of the fluorene. Accordingly, the present invention also relates to a mixture of stereoisomers of the compound of the formula (1). The compound represented by the formula (1) of the present invention can be easily identified by using mass spectrometry values, elemental analysis values, and conventionally known analytical methods such as iH and R. Next, the case where the compound of the present invention is used as the radical polymerization (A) will be described. Since the conventionally known α-ketoxime compound does not exhibit absorption for a longer wavelength than a general ultraviolet region, it lacks activity for light from near ultraviolet to near infrared. In contrast, the radical polymerization initiator (Α) of the present invention has an absorption band in the near ultraviolet to visible region due to the introduction of an electron attracting group to the phenyl group of the phenyl carbazolyl group. It is active in areas ranging from such near ultraviolet rays to longer wavelengths than visible light. Further, as described above, the radical polymerization initiator (Α) of the present invention has a keto-type oxime ester structure as shown in the formula (1), such as 321778 56 201100379. 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. . The first reason: the radical polymerization initiator (A) of the present invention is excellent in absorption because the carbazole chromophore represented by the formula (1) has good absorption. The energy of the energy line. Further, since the obtained energy is efficiently used for the decomposition of the oxime ester moiety, the decomposition by the energy ray irradiation is rapid, and a large-denier radical 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, the inert, /' 2 imyl radical will be rapidly decomposed and made. It is an active species, a decomposition product that can exert the function of an active species (carbazolyl free, ° re-formation of keto-type oxime ester will certainly generate a large number of free radicals, and the resulting female sulfhydryl group will be decomposed as long as it is metastable. It will become slower, and the amount of nitrogen-based free formation will become less than the theoretical amount. This is because the radicals are greatly affected by the radicals. The radical polymerization of the present invention starts from the chromophore and takes the formula (1). The structure is shown, so for some reason ^ = is due to the very rapid decomposition of the nitro-based radicals, which leads to the result of the J-ray. The free radical polymerization initiator of the invention (A) The decomposition of the above nitrous group is very rapid and inhibits recombination. When the recombination is due to a large number of times, the active species produced by the decomposition will be reduced. The function of the initiator is lower than that of the free radical polymerization 321778 57 201100379 The third reason: Synergistic effect by the above-described functions may be used as the chromophore excellent electron attractive group substituted carbazole effect, the keto form and the effect of the ester (synergistic effect) of irradiating energy line: for such.

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 degree 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 ethylene 58 321778 201100379 unsaturated bond. The ethylenically unsaturated compound which can be freely bonded may be a compound having at least one radically polymerizable fine unsaturated bond in the molecule, and may have a chemical form such as a monomer, an oligomer or a polymer. . Examples of such a compound having a radically polymerizable ethylenically unsaturated bond include unsaturated carboxylic acids such as acrylic acid, methyl acetoacetic acid, itaconic acid, crotonic acid, isocrotonic acid, and maleic acid, and the like. Salt, etc., acetaminophen-), guanamine or anhydride, acrylonitrile, styrene, and even each of me and polyester, unsaturated polyether, unsaturated (tetra) amine, unsaturated polyurethane vinegar, etc. The base polymerizable compound is not limited to this invention. Specific examples of the radical polymerizable compound (B) of the present invention are shown below. Examples of acrylic vinegars: Examples of monofunctional acrylates: methyl acrylate, ethyl acrylate, propyl acrylate, isopropyl acrylate, butyl acrylate, isoamyl acrylate, hexyl acrylate, 2-ethyl acrylate Hexyl ester, octyl acrylate, decyl acrylate, lauryl acrylate, stearyl acrylate, isobornyl acrylate, cyclohexyl acrylate, dicyclopentenyl acrylate, dicyclopentenyloxyethyl acrylate, acrylic acid Benzyl ester. Examples of monofunctional hydroxyl-containing acrylates: hydroxypropyl acrylate, 2-hydroxy-3-chloropropyl acrylate, 2-hydroxy-3~ phenoxypropyl acrylate, 2-hydroxy-3-allyl acrylate Oxypropyl propyl ester, decanoic acid 2~ propylene oxiranyl ethyl 2-hydroxypropyl ester. Examples of monofunctional halogen-containing acrylates: 2, 2, 2-triethyl acrylate, 2, 2, 3, 3-tetrafluoropropyl acrylate, 1H-hexafluoroisopropyl acrylate, 321778 59 201100379 Acrylic acid 1H,1H,5H-octafluoropentyl ester, 1H, 1H, 2H, 2H-heptadecafluorodecyl acrylate, 2,6-dibromo-4-butylphenyl acrylate, 2,4,6-tribromoacrylate Stupid oxyethyl ester, 2, 4, 6-tribromophenol 3E0 addition acrylate. Examples of monofunctional ether-containing acrylates: 2-methoxyethyl acrylate, 1,3-butylene glycol methyl ether acrylate, butoxyethyl acrylate, methoxy triethylene glycol acrylate, Oxime polyethylene glycol #400 acrylate, decyl dipropylene glycol acrylate, decyloxytripropylene glycol acrylate, methoxy polypropylene glycol acrylate, ethoxy diethylene glycol acrylate, ethyl Carbitol propionic acid g, 2-ethylhexyl carbitol acrylate vinegar, isopropyl tetrahydrofuran oxime ester, phenyloxyethyl acrylate, phenoxy diethylene glycol acrylate, phenoxy polyethylene Alcohol acrylate, cresol based polyethylene glycol acrylate, p-nonylphenoxyethyl acrylate, p-nonylphenoxy polyethylene glycol acrylic acid, glycidyl acrylate. Examples of monofunctional carboxyl group-containing acrylates: carboxyethyl acrylate, monoacryloxyethyl succinate, (7)-carboxypolycaprolactone monoacrylic acid vinegar, hydrogen phthalate 2~ propylene methoxyethyl ester ( 2-acryloyl〇xyethyl hydrogen phthalate), 2-propenyl methoxypropyl citrate, 2-propenyl propyl hexahydrophthalate, 2-propenyl hydroxy hydride. Examples of other monofunctional acrylates: N,N-didecylaminoethyl acrylate, N,N-didecylaminopropyl acrylate, morpholinoethyl acrylate, trimethyldecyloxy acrylate Ethyl ester, diphenyl-2-propenyloxyacetic acid phosphate, 2-propenyloxyethyl acid acid acidate, caprolactone modification - acid phosphate 2 - propylene baking oxyethylene. 60 321778 201100379 Examples of difunctional acrylates: 1,4-butanediol diacrylate, 1,6-hexanediol diacrylate, ethylene glycol diacrylate, diethylene glycol diacrylate, triethyl Diol diacrylate, tetraethylene glycol diacrylate, polyethylene glycol # 200 diacrylate, polyethylene glycol # 300 diacrylate, polyethylene glycol diol # 400 diacrylate, polyethylene glycol # 600 diacrylate, dipropylene.  Diol diacrylate, tripropylene glycol diacrylate, tetrapropylene glycol diacrylate, polypropylene glycol # 400 diacrylate, polypropylene glycol # 700 diacrylate, neopentyl glycol diacrylate, neopentyl glycol PO modified decyl diacrylate, hydroxytrimercaptoacetic acid neopentyl glycol diacrylate, hydroxy trimethyl acetic 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 modified bisphenol A diacrylate, PO modified bisphenol A diacrylate, hydrogenated bisphenol A decyl acrylate, 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 dihydroxydecyl dipropylene The acid ester and the isocyanuric acid EO are modified by the acrylic acid. Examples of trifunctional acrylates: glycerol PO modified triacrylate, trihydroxymethyl propane triacrylate, trimethylolpropane EO modified triacrylic acid.  Ester, trihydroxymercaptopropene PO modified triacrylate, isomeric cyanuric acid EO modified triacrylate, isomeric cyanuric acid EO modified ε-caprolactone modified tripropylene 61 321778 201100379 pentaerythritol triacrylic acid Ester, 1,3,5-tripropenyl fluorenyl hexahydrogen, triester, ester, dipentaerythritol triacrylate tripropionate. Examples of tetrafunctional or higher acrylates: pentaerythritol tetraacrylic acid = dipentaerythritol tetrapropyl vinegar vinegar, dipentaerythritol pentapropylene propylene vinegar mono propyl hydrazine, one pentylene domain hexapropyl hexa § §, ton f kejiayuan four (four) Sour vinegar, polyester tetraacrylate, tris(propylene decyloxy) phosphate. Examples of methyl acrylate vinegar: Monomethyl methacrylate (IV): methyl methacrylate, methyl acetoacetate, propyl methacrylate, isopropyl methacrylate , sub-based butyl vinegar, isocyanuric methacrylate, hexyl methacrylate, methyl acetoacetate 2-hexan vinegar, methyl acrylate 2 - ethyl hexanoic acid, methyl acrylate vinegar, A Ethyl acrylate, methyl propyl laurel, methacrylate stearyl sulphate, isopropyl acrylate isobornyl meth, methacrylic acid cyclohexan vinegar, methyl methacrylate dicyclopentadiene, methacrylic acid Dicyclopentenyloxyacetic acid, nordicarboxylic acid. For example, a single palace can contain methyl propyl sulphuric acid vinegar: methyl acrylate 2 _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ 3_ chloropropan vinegar, 2-metho-3-phenoxypropyl acetonate, 2-hydroxy-3-allyloxypropyl methacrylate, 2-methyl propylene oxime Base ethyl _ 2 - per propyl vinegar. Examples of monofunctional halogen-containing methacrylates: 2,2'2-trifluoroethyl methacrylate, 2,2,3,3-tetrafluoropropyl methacrylate, 1H-hexafluoro methacrylate Isopropyl ester, methacrylic acid 1H, 1H-based propylene (4) Gu 2H-seven gas, methyl propylene dioxime; 321778 62 201100379 mono-butyl phenyl ester, methacrylic acid 2, 4, 6-tribromo Phenoxyethyl ester, 2,4,6-tribromophenol 3E0 is added to the mercapto acrylate. Examples of monofunctional ether group-containing methacrylates: 2-methoxyethyl methacrylate, 1,3-butylene glycol methyl ether methacrylate, butyl acetyl methacrylate, decyloxy group Triethylene glycol methacrylate, methoxypolyethylene glycol #400 methacrylate, methoxydipropylene glycol methacrylate, methoxytripropylene glycol methacrylate, methoxypolypropylene glycol methyl Acryl phthalate, ethoxy diethylene glycol methacrylate, 2-ethylhexyl carbitol methacrylate, tetrahydrofuran methacrylate, phenoxyethyl sulfonium methacrylate, phenoxy Ethylene glycol methyl acrylate, phenoxy polyethylene glycol methacrylate, nonylphenol polyethylene glycol methacrylate, fluorenyl propylene hydrazine - mercaptophenoxy polyethylene glycol methyl acrylate, methyl propyl glycosyl glycidyl ester. Examples of monofunctional carboxyl group-containing methacrylates: methyl acetoacetate without monocarboxyethyl ester, succinic acid monodecyl propylene methoxyethyl ester, ω-carboxy polycaprolactone monomethacrylate, 2-methacryloyloxyethyl hydrogen phthalate, 2-methylpropoxypropyl citrate, 2-methylpropenyl hydride hexahydrophthalate Ester, 2-methylpropenyl propyl propyl hydroperoxide. Examples of other monofunctional methacrylates: dimethylaminomethyl methacrylate, N,N-dimethylaminoethyl methacrylate, N,N-dimethylaminopropyl methacrylate Ester, methacrylate ethyl methacrylate, trimethyl decyloxyethyl methacrylate, diphenyl methacryl methoxy ethoxylate, acid quaternary acid 2-mercapto propylene Ethyl acetoacetate, caprolactone modified _ acid type 321778 63 201100379 acid 2-mercapto acrylate acid oxyacetate. Examples of difunctional thio-acrylic vinegars: 1,4-butanediol dimethyl acrylate, 1,6-hexanediol dimethacrylate, ethylene glycol dimethyl acrylate, Diethylene glycol dimercapto acrylic acid, diethylene glycol dimethyl acrylate, tetraethylene glycol dimercapto acrylate, polyethylene glycol #2 〇〇 dimercapto acrylate , polyethylene glycol # 300 dimercapto acrylate, polyethylene glycol #4 〇〇 dimethyl propyl benzoic acid S, polyethylene glycol #6 〇〇 dimethyl acrylate acid, the purpose, dipropylene glycol Mercapto acrylate, tripropylene glycol dimercapto acrylate, tetrapropylene glycol dimethacrylate, polypropylene glycol # 400 dimercapto acrylate, polypropylene glycol # 700 dimethacrylate, neopentyl glycol dimercapto Acrylate, neopentyl glycol PO modified dimercapto acrylate, hydroxytrimercaptoacetic acid neopentyl glycol ester dimethacrylate, hydroxytrimethyl acetic acid neopentyl glycol ester caprolactone adduct Mercapto acrylate, 1,6-hexanediol bis(2-hydroxy-3-methylpropenyloxypropyl)ether, 1,9-nonanediol dimethacrylate, pentaerythritol dimethyl propyl Acid ester, pentaerythritol dimethacrylate monostearate, pentaerythritol dimethacrylate monobenzoate, 2,2-bis(4-methylpropenyloxy χ ethoxy phenyl) propane, Bisphenol A dimethacrylate, bisphenol A dimethacrylate, p 〇 modified bisphenol octamethyl methacrylate hydrogenated double discretion ' A dimethyl acrylate, modified hydrogenation double A dimethyl propylene acid g, P 〇 modified hydrogenated double A dimethyl acetoacetate, double F methacrylate, EO modified bisphenol F dimethacrylate, p 〇 Modified acrylic acid g, EG modified tetrabromobis(tetra) dimethylglycolic acid-曰-fatal oxime monomethylol dimethacrylate, isomeric cyanuric acid E 〇 modified monomethyl propylene Sour vinegar. 64 321778 201100379 : Examples of functional di-saturated acid hydrazines: glycerol p〇? quality trimethyl acrylate--& methyl ethane dimethacrylate, trimethylolpropane trimethyl propyl埽 酉 、 , 三 三 三 三 三 三 三 三 三 三 三 三 三 三 三 三 三 三 三 三 三 三 三 三 三 三 三 三 三 三 三 三 三 三 三 三 三 三 三 三 三 三 三 三 三 三 三 三 三 三 三 三 三 三 三 三 三 三 三 三 三 三 三 三 三 三 三 三 三 三 三 三 三 三 三 三 三 三 三 三 三 三 三 三 三 三 三 三 三Acetone 日g day|Cyanuric acid modification £----------------------------------------------------------------------------------------------------- S, two seasons of fine alcohol trimethyl acrylate _ tripropionate. Luyue b X on the thiol propionate group of examples: pentaerythritol tetramethyl methacrylate g 曰, pentaerythritol pentadecyl acrylate monopropionate, dipentaerythritol hexamethacrylate, tetramethylol methane Tetramethacrylate, oligoester tetradecyl acrylate, tris(methacryloxy)phosphoric acid ester. Examples of the allylate are allyl glycidyl ether, diallyl phthalate, triallyl trimellitate, and triallyl isocyanuric acid. Examples of guanamines: acrylamide, N-methylol acrylamide, diacetone oxime amide, N,N-dimercapto acrylamide, N,N-diethyl acrylamide, N- Isopropyl acrylamide, propylene decylmorpholine, mercapto acrylamide, 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-butoxy Ethylene, p-t-butoxycarbonylstyrene, p-t-butoxycarbonyloxystyrene, 2,4-diphenyl-4-methyl-1-pentene. 65 321778 201100379 Examples of other vinyl compounds: vinyl acetate, monogas vinyl acetate, vinyl benzoate, vinyl tridecyl acetate, vinyl butyrate, vinyl laurate, divinyl adipate, Vinyl methacrylate, vinyl crotonate, vinyl 2-ethylhexanoate, N-vinylcarbazole, N-ethylene group, σ, hexanone, and the like. The above radical polymerizable compound (Β) can be easily obtained from a commercially available product of the following manufacturer. For example, "1 ight aery late", "light 酉", "epoxy ester", "amine ester acrylate", and "high", such as Kyoei Oil & Fat Chemical Industry Co., Ltd. "Functional oligo" series; "NK ESTER" and "Dish Concentrate" series manufactured by Shin-Nakamura Chemical Co., Ltd.; "FANCRYL" series manufactured by Hitachi Chemical Co., Ltd.; East Asia Synthetic Chemicals Co., Ltd. "AR0NIXM" series made by the company; "functional monomer" series made by Daeba Chemical Industry Co., Ltd.; "Special acrylic monomer" series made by Osaka Organic Chemical Industry Co., Ltd.; Mitsubishi "ACRYESTER" and "DI ABEAM Concentrate" series made by the company; "Kayarad" and "Kayamer" series manufactured by Sakamoto Chemical Co., Ltd.; "Acrylic/methyl" manufactured by Nippon Shokubai Co., Ltd. "Acrylate monomer" series; "NICHIG0-UV violet urethane acrylate oligomer" manufactured by Nippon Synthetic Chemical Industry Co., Ltd., 彳 & acetic acid vinegar (stock) company Ethylene vine monomer ; Hing people club (shares) system of "functional monomer" series. Further, the radical compound (B) can also be enumerated as described in the following documents. For example, there is a "Handbook of Crosslinking Agents" by Yamashita Shinzo (ed., "Dacheng" in 1981), and "The υν· Εβ Hardening Handbook (Materials)" (1985, Polymer Publishing Association) edited by Kato Qingshi. RadTech Research 321778 66 201100379 The editor, Akamatsu, edited "The Practical Technology of New Photosensitive Resin" (CMC, 1987), Endo, "Precision of Thermosetting Polymers" (1986, CMC), Yoshiyama Eiichiro The "Polyester Resin Handbook" (in 1988, 曰刊工业新闻) and the RadTech Research Society edited "Application and Market of UV·EB Hardeners" (2002, CMC). The radically 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. V / with respect to 100 parts by weight of the radically polymerizable compound (B), the radical polymerization initiator (A) of the present invention in the polymerizable composition is used in an amount of 0.  From 1 to 100 parts by weight, preferably from 3 to 60 parts by weight. The polymerizable composition of the present invention can be mixed with a binder such as an organic high molecular polymer and coated on a glass plate or a nameplate, another metal plate, or polyethylene terephthalate (PET). ) used as a polymer film. The binder which can be mixed with the polymerizable composition of the present invention may, for example, be a polyacrylate, a poly-α-alkyl acrylate, a polydecylamine, a polyvinyl acetal, a polyformamide or a polyurethane. Polymers and copolymers such as polycarbonates, polystyrenes, and polyvinyl esters. Specifically, for example, polydecyl acrylate, polymethyl methacrylate, polyethyl methacrylate, polyvinyl carbazole, polyvinyl σ pyrrolidone, polyvinyl butyral, poly 'Ethyl acetate S, acid and varnish (novo 1 ac) resin, resin, epoxy resin, alkyd resin, and other technologies such as the new technology of new photosensitive resin 1987, CMC) or "Chemical Products of 10188" 67 321778 201100379 Pages 657 to 767 (1988, Chemical Industry Daily) are well-known organic south molecular polymers. 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 include, for example, Japanese Patent Publication No. 59-107281, Japanese Patent Publication No. Sho 61-9621, and Japanese Patent Laid-Open No. 60-60104. The morphine derivative, the organic peroxide described in Japanese Patent Laid-Open Publication No. Sho 59- 504807, and the Japanese Patent Publication No. SHO-43-243684, Japanese Patent Publication No. Sho 43-23413, and Japanese Patent Publication No. 44-6413 An 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, which are described in the specification of the Japanese Patent No. 3,576,453, Japanese Patent Publication No. Sho 36-22062, Japanese Patent Publication No. Sho 37-13109, Japanese Patent Publication No. Sho 38-18015, and Japanese Patent Publication No. 45-9610, respectively. Japanese Patent Publication No. 39162, Japanese Patent Laid-Open No. 59-140203, and "MACROMOLECULES", Vol. 10, p. 1307 (1977), various rust salts (onium) compounds, such as the lock compound described in Japanese Patent Laid-Open No. 59-142205 The azo compound described in the Japanese Patent Publication No. Hei 1-54440, 'European Patent No. 109851, European Patent No. 126712, and Journal of Imaging Science (J.)  IMAG.  Scl. ) The metal propylene diene compound described in vol. 30, p. 174 (1986), and the ferrocene, described in JP-A-61-151197, 68 321778 201100379 "COORDINATION CHEMISTRY REVIEW", Volume 84 The transition metal complex containing a transition metal such as ruthenium described in JP-A-H02-182701, and the alumino-acid complex described in JP-A-3-209477; Japanese Patent Publication No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. The organic ruthenium halogen compound described in JP-A-59-107344, or the oxime complex or the keto oxime complex described in JP-A-H05-255347, JP-A-54-99185 The aminoketone compound described in Japanese Laid-Open Patent Publication No. SHO-63-264560, JP-A-2001-264530, JP-A-2001-261761, JP-A-2000-80068, and JP-A Publication No. 2001-233842, Japanese Special Table 2004-534797 JP, USP No. 3,558,309 instruction manual (1971), USP No. 4,202,697 and Japanese Patent Laid-Open Publication Sho No. 61-24558 describes oxime ester compound of the specification (1980). With respect to 100 parts by weight of the radical polyadhesive compound (B), when such a polymerization initiator is used, it is used in an amount of 0.  A range of from 01 to 10 parts by weight is preferred. 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 second butyl. , ph〇thiazine, etc. When the thermal polymerization inhibitor is used in an amount of 1 part by weight based on the radically polymerizable compound (B), the amount used is added by adding hydrazine.  It is preferably from 1 to 5 parts by weight. Further, 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. Illustrated in the specification of the Japanese Patent Publication No. 4414312, the thiol described in JP-A-64-13144, the disulfide described in JP-A No. 2-291561, the specification of US Pat. No. 3,558,322, and the Japanese Patent Publication No. Sho 64-17048. The thione type, o-acylthiohydroxamate or N-oxo oxime thione 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. Antihalation agent, glare brightener, surfactant, colorant, extender, plasticizer, flame retardant, antioxidant, UV absorber, foaming agent, mold inhibitor, antistatic agent, An additive, a diluent solvent, or the like which imparts a magnetic substance or other various characteristics is used. The polymerizable composition of the present invention may further contain a sensitizer (C) for the purpose of promoting polymerization. Since the sensitizer enhances the activity of light in the ultraviolet to near-infrared region, it is preferable to add a sensitizer when the polymerizability is to be promoted. Specific examples of such sensitizers include, for example, chalcone (chalcone). a derivative or dibenzaiacetone, etc. as a representative of 70 321778 201100379 saturated ketones, 1,2-dione derivatives, benzophenones represented by benzil or camphorquinone Benzoin derivatives, anthraquinone derivatives, radican i derivatives, 蒽S Kun derivatives, xanthene derivatives, thioxanthene derivatives, xanthone derivatives , • thioxanthone derivatives, coumarin derivatives, ketocoumarin derivatives, cyanine derivatives, merocyanine derivatives, keto alcohols (methonol) derivatives such as polymethine pigments, acridine derivatives, azine derivatives, thiazine derivatives, oxazine derivatives, porphyrin derivatives , laying a derivative, rusting (azulenium) Biological, squarylium derivative, porphyrin derivative, tetraphenylporphyrin derivative, triarylmethane derivative, tetrabenzoporphyrin derivative, tetrapyridinium tetraazaindole Derivatives of tetrapyrazinoporphyrazine, dichlorinated derivatives, tetraazatetrazole externally (^61:^23 mouths 0 117 『32丨116), tetraterpene and tetraazapine derivatives, Naphthalocyanine anthracene derivative, Subphthalocyanine derivative, pyrylium derivative, thiopyranium rust derivative, tetraphylline derivative, annuiene Derivatives, spirulina, snails, snails, snails. Specific derivatives, miso derivatives, metal arene complexes, organic hydrazine complexes, Michler's ketone derivatives, and the like. In addition, the specific examples are more specific - for example, "Heart Handbook" (1986, Kodansha), Dahe Yuanxin, etc., "Chemistry of Functional Pigments" (C, CMC), Chi Senzhong Sanlang et al. edited the "Special Functional Materials" (1986, CMC) sensitizer 71 321778 201100379 '. Further, for example, a sensitizer that exhibits absorption of light in the ultraviolet to near-infrared region can be cited. The sensitizer is not limited to the above exemplification. Sensitization = It is also possible to use two or more types at any ratio as needed. Among the above sensitizers, the sensitizing 2 series which is particularly suitable for sensitizing the radical polymerization initiator of the present invention are, for example, thiazolidine and rice-based derivatives. More specifically, it may, for example, be 2,4-diethylthianone, 2-chlorothiazepinone, 2,4-one gas, melon, and 2-isopropylthioxanthone, 4_ Isopropyl thioxanthone, Bu -4-propyloxy thioxanthone, 4,4,-bis(didecylamino)benzidine 5 4,4 bis(ethylethylamino) Benzene or the like, but is not limited thereto. When the sensitizer (C) of the present invention is used in an amount of 100 parts by weight based on 100 parts by weight of the radical polymerizable compound (β), it is used in an amount of from 0.1 to 6 parts by weight.  〇 1 to 30 I is better than ,. It is more preferred to 丨 to 1 part by weight. - In the polymer composition of the present invention, the coloring component (D) may be added for the purpose of coloring. As the coloring component (8), a conventionally known pigment can be used. Further, in the case of obtaining a desired hue, the dye may be contained in a range in which heat resistance and financial property are not lowered. In order to obtain a desired color density and a hue, it may be used singly or in combination of two or more kinds. For the pigment, for example, an organic pigment, an inorganic pigment, or carbon black (e.g., B-black, channel black, f_ace Mack, etc.) may be used, and the pigment may be used in combination of two or more kinds. The organic pigment may, for example, be a diketop bar B and a π ratio (diketopyrrolopyrrole) system (four), an azo pigment (for example, azo, disazo, polyazo) or a phthalocyanine pigment (for example, copper october , toothed copper phthalocyanine, metal-free phthalocyanine, etc.), 蒽酉Kun-type pigments (such as amine-based 蒽酉, 321778 72 201100379 diamine-based 蒽 蒽, 蒽 ° 密. (3111:11^卩71'丨11^(1丨116), flavanthrone, anthanthrone, indanthrone, pyranthrone, violanthrone, etc. A quinacridone pigment, a dioxazine pigment, a perinone pigment, an anthraquinone pigment, a thioindigo pigment, an isoindoline pigment, and an isophthalate pigment.杀 杀 杀 酮 系 系 系 颜料 quin quin quin quin quin quin 杀 杀 杀 杀 杀 杀 杀 杀 杀 杀 杀 杀 杀 杀 杀 杀 杀 杀 杀 杀 杀 杀 杀 杀 杀 杀 杀 杀 杀 杀 杀 杀 杀 杀 杀 杀 杀 杀 杀 杀, stone acid #5, sedimentary barium sulfate, white carbon, white oxidation (alumina white), still Earth clay, talc, bentonite, black iron oxide, carbon black, red, Bengala, blush, tange, chrome verm ili on, yellow, ore Yellow iron oxide, yellow, chromia, viridian, titanium cobalt green, cobalt green, cobalt chrome green, Victoria green, ultramarine blue, Prussian blue, Ming blue, cerulean blue, oxidized indigo, cobalt-zinc oxide ruthenium blue, manganese violet, or cobalt violet, etc. Carbon black can be exemplified by "Special Black 350, 250, 100, 550, 5, manufactured by Degussa. 4, 4A, 6", "PrintexU, 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 CABOT, "MA7, 8, 11, 77, 100, i〇〇R, i" manufactured by Mitsubishi Chemical Corporation 〇s, 220, 230", "# 2700, # 2650, # 2600, # 200, # 2350, # 2300, #2200, # 1000, 73 321778 201100379 # 990, # 980, # 970, # 960 #950,#900,#850,#750,#650,#52,#50,#47,#45,#45L,#44,#4〇,#33,#332,#30,#25,# 20, #10, #5, CF9, #95, #260", etc. In addition, the following is based on the color index (co 1 or i ndex, also known as c.  I. The pigments which can be used in the polymer composition of the present invention are listed. Red pigments can be used, for example, C.  I. 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 not limited to this. Yellow pigments can be used, for example, C.  I. Pigment Yellow 1, 2, 3, 4, 5, 6, 10, 12, 13, 14, 15, 16, 17, 18, 20, 24, 3, 32, 32, 34, 35, 35: 1, 36, 36 : 1, 37, 37 : 1, 40, 42, 43, 53, 55, 60, 6 Bu 62, 63, 65, 73, 74, 77, 81, 83, 86, 93, 94, 95, 97, 98, 100, 1 (Π, 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, 15 152, 153, 154, 155, 156, 16 162, 164, 166, 167, 168, 169, 170, 17 172, 173, 174, 175, 176, 177, 179, 180, 181, 182, 185, 187, 188, 193, 194, 199, etc., but not limited thereto. For orange pigments, for example, C.  I. Pigment orange 36, 43, 51, 55, 59, 74 321778 201100379 61, etc., but is not limited thereto. Green pigments can be used, for example, C.  I. Pigment greens are green pigments such as 7, 1 , 36, and 37, but are not limited thereto. Blue pigments can be used, for example, C.  I. Pigment blue 15, 15 : 1, 15 : 2, 15 : 3, 15 : 4, 15 : 6, 16, 22, 60, 64, etc., but is not limited to this. Purple pigments can be used, for example, C·I. Pigment violet 1, 19, 23, 27, 29, 〇 30 ' 32, 37, 40, 42, 50, etc., but is not limited thereto. Black pigments can be used, for example, C.  I. Pigment violet 1, 6, 7, 12, 20, 31, etc. 'but is not limited thereto. These pigments can be used in combination of two or more kinds in any ratio. In the case of the radical polymerizable compound (B), the amount of the pigment used as the coloring component (D) is 〇.  The 〇1 to 1 part by weight is preferably 1 to 60 parts by weight.吸收 Visible light absorption coefficient (appropriate degree of spectrum) and transparency. 〇 The 'particle size of the pigment is preferably sufficiently small for the visible wavelength. That is, the pigment has an average primary particle size of 0 01/zm or more and 0 3_ or less: ΐ其ΐ 〇. 01 (four) or more. 1/^ is better. Further, the - secondary particle diameter was taken from the center of the core, and the diameter of the early lining particles was measured by an electron microscope. For the 'human particle size, you can use the dispersion device of Ba, Zhizhi'. For example, sander = rid null), kneader, 2-axis roll, etc., to adjust the target circumference. In addition, when the pigment is added to the polymer composition of the present invention, the pigment dispersion and polymerization composition can be increased. For the purpose of preservation stability, ^ 321778 75 201100379 pigment derivative or pigment dispersant. 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, Japanese Patent Publication No. Sho 63-305173, Japanese Patent Publication No. Sho 57-15620, Japanese Patent Publication No. Sho 59-40172, Japanese Patent Publication No. Sho 63-17102, Japanese Patent Publication No. Hei 5-9469 Japanese Patent Publication No. Hei 06-306301, JP-A-2001-220520, and JP-A-2003-238842. These can be used alone or in combination of two or more. As the pigment dispersant, for example, a carboxylic acid ester containing a hydroxyl group, a salt of a long-chain polyamine-based amine 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, polyoxyethylene ethyl decyl ether, stearyl amine acetate, and the like. Specific examples of the pigment dispersant include "Anti-Terra-U (polyamine guanamine phosphate)" manufactured by BYK Chemie Co., Ltd., "Ant丨_Term-2〇3/204 (molecular weight poly-lysate)", "Disperbyk_1Q1 (polyamine-based amine sulphate and acid ester), 107 (hydroxyl-containing phthalate), 11 〇, 111 (acid-containing copolymer), 130 (polyamide), 16 162, 163, 164, 165, 166, Π〇 (also molecular copolymer), "400", "Bykumen" (high molecular weight not enough 321778 76 201100379 and acid ester), "BYK-P104, P105 (high molecular weight unsaturated poly "Citrate"", "P104S, 240S (high molecular weight unsaturated acid polycarboxylic acid and lanthanide)", "Lactimon (long-chain amine and unsaturated acid tannic acid and Shi Xi)". Further, as Efka Chemicals Co., Ltd., "Efka 44, 46, 47, 48, 49, 54, 63, 64, 65, 66, 7 728, 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 Company company "FLOWLEN TG-710 (amine ester oligomer)", "FLOWLEN SH-290, SP-1000", "POLYFLOW No.  50E, No.  300 (acrylic copolymer), "DISPARLONKS-860, 873SN, 874 (high molecular dispersant), #2150 (aliphatic polycarboxylic acid), #7004 (polyether ester type)" manufactured by Nanben Chemical Co., Ltd.

Further, for example, "Demol RN, N (sodium salt of naphthalenesulfonic acid condensate), MS, C, SN-B (aromatic salt of aromatic sulfonic acid famarin condensate), EP", "" Homogenol L-18 (Polyuremic Acid Polymer), "Emulgen 920, 930, 93 Bu 935, 950, 985 (polyoxyethylidene phenyl)), "Acetamin 24 (coconutamine acetate) ), 86 (stearylamine acetate), "sol sperse 5000 (made by phthalocyanine), 13940 (polyester amine), 17000 (fatty acid amine), 24000GR, 32000, 33000," 39000, 41000, 53000", Nikon Chemical Co., Ltd. "NIKK0L T106 (polyoxyethylene sorbitan monooleate), MYS-IEX (polyoxyethylene ethyl succinate), Hexagline 4-0 ( "AjISPER PB821, 822, 824" manufactured by Fine-Techno Co., Ltd. 77 321778 201100379, etc. The amount of the pigment and the pigment dispersing agent to be added is not particularly limited, and is preferably from 0.1 to 40 parts by weight, more preferably from 0.1 to 30 parts by weight, per part 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 c. 丨. acid jaundice, c. 丨. acid orange 7, CI § red, 37, acid red 180, CI acid blue 29, CI direct red 28, CI direct red 83, CI Direct yellow 12, CI direct orange 26, C. L direct green 28, C · I. direct green 59, CI reaction yellow 2, C. 丨. reaction red 17, CI reaction red 12 〇, c. L reaction black 5, c. 丨, dispersed orange 5, c. [Disperse red 58, C · 丨. Disperse blue 165, C · I. Basic blue 41, CI alkaline green 18 CI mordant red 7 (c · I. M〇rdant Red 7), CI mordant yellow 5, C. I. mordant black 7, etc., but is not limited thereto. Examples of the lanthanide dyes include αι. Reduction Blue 4 (CI Vat Blue 4) C. 酸性. Acid Blue 40, c. L Acid Green 25, CI Reaction Blue 19, CI Reaction Blue 49, C. 1 • Disperse Red 60 c. I. Disperse blue 56, CI disperse blue 60, etc. 'but is not limited thereto. Other examples of the phthalocyanine-based dyes include C i. Reduction Blue 5 and the like, and ruthenium imide = wood, for example, C·L Blue 3, C······················ CI Solvent Yellow 33,

C. I. Acid yellow 3, c. j. Disperse yellow 64, etc., and the base dye may be, for example, c. L 321778 78 201100379 Acid Yellow 1, C. I. Acid Orange 3, C. I. Disperse Yellow 42, etc., but is not limited thereto. With respect to 100 parts by weight of the radically polymerizable compound (B), when these dyes are added, the amount thereof is from 0.01 to 100 parts by weight, preferably from 1 to 60 parts by weight, but as described above, from heat resistance. Or from the point of view of weather resistance, it is not good if too much is used. When the polymerizable composition of the present invention is used for the purpose of forming an image or the like as a material for a so-called alkaline development type photoresist, it is also possible to mix and use the solvent (E). The testable resin (E) of the present invention functions as a binder, and it is preferable that the developer used in the development process, particularly the alkaline developer, is soluble when forming an image. No _ Special limited. 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 hydrazine (hereinafter simply referred to as "copolymer containing a carboxyl group") of a monounsaturated monomer (hereinafter referred to as "copolymerizable unsaturated monomer") 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 y Unsaturated dicarboxylic acid or its anhydrides such as keonic acid, itaconic anhydride, citraconic acid, citraconic anhydride, mesaconic acid, and unsaturated polycarboxylic acids of 3 or more or anhydrides thereof ; succinic acid mono (2-propenyl methoxyethyl ester), succinic acid mono (2-• methacrylic acid oxyethyl s), i large acid mono (2-propenyl methoxy ethoxy vinegar), acid donation (2-methylpropenyl methoxyethyl ester) and the like of a polyvalent carboxylic acid of 2 or more. 321778 201100379 [(Meth) propylene decyloxyalkyl] ester; ω-carboxypolycaprolactone monoacrylate A mono(meth)acrylate having a polymer having a carboxyl group and a hydroxyl group at both terminals, such as ω-carboxypolycaprolactone monodecyl acrylate. Among these carboxyl group-containing unsaturated monomers, succinic acid mono(2-propyleneoxyethyl ester) and citric acid mono(2-propenyloxyethyl ester) are Μ-53〇〇 and Μ-54, respectively. The trade name of 〇〇 (Southeast Synthetic Co., Ltd.) is sold on the market. The carboxyl group-containing unsaturated monomers may be used singly or in combination of two or more. Further, 'copolymerizable unsaturated monomers can be exemplified by: stupid ethylene, methyl stupid ethylene, o-vinyltoluene, m-vinyl oxime, p-vinyl fluorene, p-chloro styrene, o- methoxy Styrene, m-nonyloxystyrene, p-nonyloxystyrene, o-vinylbenzyl methyl ether, m-vinylbenzyl ether, p-vinylbenzyl methyl ether, o-ethylene Aromatic vinyl compounds such as benzyl glycidyl ether, m-vinylbenzyl glycidyl ether, p-vinylbenzyl glycidyl ether; anthracene, hydrazine, etc.; decyl acrylate, methyl methacrylate , ethyl acrylate, ethyl methacrylate, n-propyl propionate, n-propyl methacrylate, isopropyl acrylate, isopropyl methacrylate, n-butyl acrylate, n-butyl methacrylate, acrylic acid Isobutyl ester, isobutyl methacrylate, second butyl acrylate, second butyl methacrylate 't-butyl acrylate, second butyl methacrylate, 2-hydroxyethyl acrylate, methacrylic acid 2 _hydroxyethyl ester, 2-hydroxypropyl acrylate, methacryl 2_Hydroxypropyl ester, acrylic acid 3_ mercaptopropyl phthalocyanine, mercaptopropyl benzoate 3-propyl propyl acrylate, acrylic acid 2 butyl butyl acrylate, 2-hydroxybutyl methacrylate, 3 hydroxy butyl acrylate Ester, mercapto 321778 80 201100379 3-hydroxybutyl ester, 4-hydroxybutyl acrylate, methacrylic acid [hydroxybutyl ester, allyl acrylate, allyl methacrylate, benzyl acrylate, benzyl methacrylate Cyclohexyl acrylate, cyclohexyl methacrylate phenyl acrylate, phenyl methacrylate, 2-methoxyethyl acrylate, 2-propyloxyethyl methacrylate, 2-benzene acrylate Oxyethyl ester, 2-phenoxyethyl methacrylate, methoxy diethylene glycol acrylate, methoxy diethylene glycol methacrylate, methoxy triethylene glycol acrylate, methoxy Triethylene glycol methacrylate, methoxypropylene glycol acrylate, methoxypropylene glycol methacrylate, methoxydipropylene glycol acrylate, propylene dipropylene glycol methacrylate, isobornyl acrylate, Isobornyl methacrylate, dicyclopentadienyl acrylate, methacrylic acid Acid dicyclopentadienyl ester, propionic acid 2_hydroxy-3-phenoxypropyl ester, 2-hydroxy-3-phenoxypropyl methacrylate, glyceryl monoacrylate, glyceryl monomethacrylate Isounsaturated carboxylic acid esters; 2-aminoethyl acrylate, 2-aminoethyl methacrylate, bismuth 2-didecylaminoethyl acrylate, 2-didecylaminoethyl methacrylate , 2-aminopropyl acrylate, 2-aminopropyl methacrylate, 2-didecylaminopropyl acrylate, 2-dimethylaminopropyl methacrylate, 3-amino acrylate Ethyl ester, 3-aminoethyl methacrylate, 3-dimethylaminopropyl acrylate, 3-didecylaminopropyl decyl acrylate, etc.; Glycidyl esters of unsaturated carboxylic acid such as acid glycidyl ester and glycidyl methacrylate; vinyl acetates such as vinyl acetate, vinyl propionate, vinyl butyrate, vinyl benzoate; vinyl ether ether Vinyl 81 321778 201100379 Unsaturated ethers such as diethyl ether and allyl glycidyl ether; acrylonitrile, methyl acrylonitrile, alpha chloroacrylonitrile, dicyanoacetate Vinylidene cyanide), such as vinyl cyanide compound; acrylamide, mercapto acrylamide, a- amphetamine, N-2-hydroxyethyl decylamine, N 2 hydroxyethyl methacrylamide, etc. Saturated guanamines; maleimide, N-phenyl maleimide, n-cyclohexylmaleimine and other unsaturated quinones, 〗 〖, butadiene, isoprene , diuretic and dilute (chior〇prene) and other aliphatic common vehicles; polystyrene, polyacrylic acid, polymethyl methacrylate, polybutyl acrylate, polybutyl methacrylate A macromolecular monomer (maCrom〇nomer) having a monopropenyl fluorenyl group or a monomethacryl fluorenyl group at the end of the polymer molecular chain, such as a polyoxyalkylene. These copolymerizable unsaturated monomers may 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, depending on the case, it is selected from the group consisting of abreast (2-propene oxyethylene), a succinic acid (2 mercapto propylene oxide, vinegar), ω- a carboxyl group-containing unsaturated monomer component of at least j compounds of the group consisting of a slow-base polycaprolactone and a polyacrylic acid monomethacrylate vinegar; (Q) is selected from the group consisting of styrene, Acrylic acid, methacrylate, 2-hydroxyethyl acrylate, 2-methic acid ethyl ester, allyl acrylate, allyl methacrylate, acrylate, methyl = dilute Acid 34, glycerol monoglyceride, glycerol monothioglycolic acid, phenyl phenyl maleimide, polystyrene macromonomer and polyheptyl acrylate macromonomer At least one of the groups formed. 321778 82 201100379 Specific examples of the carboxyl group-containing copolymer (R) include (meth)acrylic acid/methyl (meth)acrylate copolymer, (meth)acrylic acid/benzyl (meth)acrylate copolymer, (mercapto)acrylic acid/(methyl)propionic acid 2-light ethyl acetonate/benzyl (meth) acrylate copolymer, (methyl)propionic acid/methyl (meth) acrylate/polyphenyl Ethylene macromonomer copolymer, (mercapto) acrylic acid / methacrylate methacrylate / polymethyl methacrylate macromolecular copolymer, (meth) acrylate / (meth) acrylate Benzyl ester/polystyrene large hazelnut monomer copolymer, (mercapto) propionate/benzyl (meth) acrylate/polymethyl methacrylate macromolecular copolymer, (meth)acrylic acid /(Meth)ethyl 2-hydroxyethyl acrylate / benzyl (meth) acrylate / polystyrene macromolecular copolymer, (mercapto) acrylic / (mercapto) acrylic acid 2-ethylidene ethyl ester / (A Benzyl acrylate/poly(decyl) acrylate macromer copolymer, methacrylic acid/styrene/benzyl benzyl acrylate/N-phenyl mala Amine copolymer; (meth)acrylic acid / succinic acid mono [2_(methyl) propylene methoxyethyl ester] / styrene / benzyl (meth) acrylate / N phenyl maleimide copolymer, (Mercapto)acrylic acid/succinic acid mono[2-(methyl)acryloxyethyl ester]/styrene/(methyl)propionate allyl ester/N-phenyl maleimide copolymer , (meth)acrylic acid/styrene/benzyl (meth)acrylate/glycerol mono(meth)acrylate/N-phenylmaleimide copolymer, (meth)acrylic acid/ω-carboxypoly Internal vinegar mono(meth)acrylic acid vinegar / benzophenone / (meth) acrylate vinegar / mono (meth) glyceryl acrylate / IV - phenyl maleimide copolymer. In the copolymer containing a lean group, the substituent present in the molecule can be modified by other materials. For example, the moieties-portion present in the polymer may also be modified by reacting with a monomer having a 201100379 functional group which has a radical reaction such as a glycidyl group, and thus may be in the molecule. Set crosslinks that can participate in free radical polymerization. As the monomer, glycidyl (meth) acrylate acid can be used, and examples thereof include glycidyl (meth) (10) acid, glycidyl (meth) acrylate, and glycidyl (A). Base) ethyl acrylate, glycidyl (meth) propionate butyl vinegar, glycidyl (meth) propylene oxime 2 ethyl hexanoic acid. Further, the radicals present in the polymer may also be prepared by the use of the hypomorphic acid 2-propenyloxyacetate, 2-methylpropenylacetic acid isocyanate (Showa Denko) Karenz _") is condensed to provide the same polymerization crosslinking point. 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, and in the case of more than 5% by weight, the alkali image is formed. When the solubility of the liquid becomes too A', when the visible imaging liquid is developed, there is a tendency that the resist film is detached from the substrate or the film on the image surface becomes thick. The polystyrene-reduced 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, 〇〇〇 to 3 〇〇, 〇〇〇, better 5,000 to 1 〇〇, 〇〇〇. Further, the polystyrene alternating average molecular weight (hereinafter referred to as "Μη") measured by gel permeation chromatography (GPC, elution solvent: tetrahydrofuran) in the alkali-soluble resin of the present invention is preferably 3, 〇〇〇 To 60' 000, more preferably 5, 〇〇〇 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 Μη. Therefore, an image pattern having a sharp pattern pattern of 321778 84 201100379 can be formed, and at the same time, residue, scum, residual film, and the like are less likely to occur on the substrate on the unirradiated portion and on the light shielding layer during development. Further, the ratio (Mw/Mn) of Mw and Μη of the test 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 substance is 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 kinds thereof. The amount of the solvent-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 rays, or near-infrared rays to obtain a desired polymer. 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 0 in the 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 i ion lamp, a high power metal i lamp, a xenon lamp, and a pulse. Luminescent xenon lamp, deuterium lamp, fluorescent lamp, M-YAG3 double-wave laser, He-Cd laser, nitrogen laser, Xe-Cl excimer laser, Xe-F excimer laser Semiconductors excite 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 K.K. 85 321778 201100379 Black, 1=The polymerizable composition of the present invention is applied to various inks, inkjet printings, 'Science is protective lacquer, various brush materials, photoresists, photographic photos, direct slab materials, optical fibers, Photographic material recording media such as holographic materials, even adhesives, spears, and other types of adhesives, adhesives, adhesives, release coating agents, sealants, and various coatings. [Image Pattern Forming Method] The polymerizable composition of the present invention containing the resin (E) can be used as a negative resist. The negative resist is applied to a substrate and partially exposed by an energy ray. Hardening, lining, _ users who use liquid to remove unexposed parts to form an image pattern. The image pattern forming method using the negative resist of the present invention containing the resin (8) will be described. First, after coating the liquid composition of the negative resist on the surface of the substrate, prebake is performed to evaporate the solvent to form a coating film. Next, the coating film was exposed to a pattern through a photomask, and then developed with an electrophotographic liquid 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 from 0.1 to 200 #m, more preferably from 2 to 100 // m. In addition, the negative resist layer of the present invention may be provided on a base film composed of polyester or polypropylene I lanthanum mainly represented by polyethylene terephthalate, and may be provided as needed. The negative-type resist layer is sandwiched by a protective film 321778 86 201100379: the type of dry film known as the dry film is used in the present invention. In the dry film, the protective film is usually peeled off to form a substrate of a resist pattern, and if necessary, it is laminated on the substrate under heating or even with an additive. The negative-type sword Sword 4 of the present invention is used in the form of a dry film, and the pattern exposure can be carried out without peeling off the base film, and the base film is removed after exposure and subjected to test development. Q 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 polymerized composition of the present invention. Therefore, the negative resist of the present invention containing the 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, an iSl lamp, a pulsed xenon lamp, a carbon arc lamp (car). N-arc lamp), metal halide lamp, fluorescent lamp, tungsten lamp, argon ion laser, cadmium cadmium laser, helium ion laser, helium ion laser, various semiconductor lasers, YAG laser, light emitting diode The energy of various light sources such as polar body, CRT light source, plasma light source, electron beam, r-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. 5至lOOOOOO/m2。 The amount of exposure is not uniform, but it is usually 0.5 to 1000OO/m2. The substrate used in the image pattern forming method of the present invention may, for example, be glass, ruthenium, polycarbonate, polyester, aromatic polyamine, polyamidolimine, 87 321778 201100379 polyimine, glass epoxy (6) The film or substrate made of ass-Ep〇xy) is set here. In addition, these substrates can also be used as desired (medical treatment, plasma treatment, ion plating, sputtering, gas phase reaction, vacuum evaporation by decane coupling agent, etc.) Pre-treatment before plating (10) The development method used in the image pattern forming method of the present invention may be, for example, a puddle method, a dipping method, a shower method, a spray method, or the like. The development time is preferably 5 i 3 (10) seconds at 2G to 3{rc. In addition, the alkaline imaging solution can be used: sodium hydroxide, nitrogen oxidizing, sodium carbonate, sodium citrate, sodium metasilicate, Inorganic bases such as ammonia; amines such as ethylamine; secondary amines such as diethylamine and di-n-propylamine; trimethylamine, methyldiethylamine, ethyldimethylamine, Triethylamine and the like three: amines; dimercaptoethanolamine, mercapto diethanolamine 'triethanolamine and other tertiary alkanolamines; scale n N-methyl (four), Nm each bite, ^ dioxane bicyclo [5 ·4.0]-7-deca-ene, 1,5-diazabicyclo[4.3 〇]_ 5-decene and other tertiary amines; tetraammonium hydroxide, tetraethylammonium hydroxide, etc. Salt test Further, an aqueous solution of the compound may be added to the aqueous solution of the basic compound in an appropriate amount, such as a water-soluble organic solvent such as methanol or ethanol, and/or a surfactant. The compound of the present invention may be irradiated with an energy ray, especially due to irradiation of light. Since the active radical is efficiently produced, it can function as a high-sensitivity radical polymerization initiator. Therefore, the radical polymerizable composition containing the radical polytropic initiator (Α) of the present invention can be used. A high-sensitivity polymerizable composition which is polymerized in a short period of time. Therefore, by using the polymerizable composition of the present invention, it is possible to provide a basic developing property suitable for a photoresist material. 321778 88 201100379 Negative Resist A material and an image pattern forming method using the negative resist material. Further, by using the image pattern forming method, a preferred image pattern can be provided. (Embodiment) Hereinafter, the present invention will be specifically described based on examples. However, the present invention is not limited to the following embodiments, and the "parts" in the examples mean "parts by weight" unless otherwise specified. The compound of the present invention is shown in the synthesis example. <Example 1> Free radical polymerization initiator: Synthesis of compound (1) First, a compound (A) which is an intermediate of the compound (1) is synthesized as follows.

Compound (A) 100 g of N-dibenzophenone carbazole was dissolved in chloroform (1 mL), and 85.0 g of aluminum chloride was added thereto, and the mixture was stirred at 0 ° C for 2 hours to dissolve chloroform in 500 mL. A solution of propylene chloride 32. Og was added dropwise. 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 compound (A) 10.5 g (yield 89 321 778 2011 00 379 rate 90.5%). Next, using the obtained compound (A), the compound (B) which is a precursor of the compound (1) is synthesized as follows.

The compound (B) was dissolved in a mixture of 100 mL of tetrahydrofuran (100 mL) and concentrated hydrochloric acid (500 mL). 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 x 3 times), dried over magnesium sulfate, and the mixture was dried and the solvent was removed, and the residue was washed with hexane to give the compound (B) 99. 8 g (yield 93.0%). Next, using the obtained compound (B), the compound (1) was synthesized as follows. After the compound (B) 30. Og was stirred in ethyl acetate (300 mL), acetic acid anhydride (6.3 g, sodium acetate, 10.6 g) was 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. -hexane was recrystallized to obtain 31.4 g of a compound (1) (yield: 95.4%). &lt;Example 2&gt; 90 321778 201100379 Radical polymerization initiator: Synthesis of compound (2) First, a compound (C) which is an intermediate of the compound (2) is synthesized as follows.

The compound (c) is dissolved in 100% of chloroform, and then added with 80.0 g of aluminum chloride, and stirred at 0 ° C for 2 hours to dissolve butyl chloride in 500 mL of chloroform. 36. 8 g of the solution was added dropwise. 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 crystallised from chloroform/methanol to afford compound (c) 10.3 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.

Compound (C) 100 g of the compound (C) was dissolved in a mixed solution of tetrahydrofuran 100 mL and concentrated hydrochloric acid 91 321778 201100379 500 mL, and then stirred at room temperature for 1 hour to drip the third butyl nitrite 37. Og. After the completion of the dropwise addition, the mixture was stirred at room temperature for 5 hours. The reaction solution was poured into 160 mL of ice water, and extracted with 160 mL of a gas. The organic layer was washed with water (500 mL x 3 times), dried over magnesium sulfate, filtered, and evaporated to dryness. Next, using the obtained compound (D), the compound (2) was synthesized as follows. After the compound (D) 30. Og was stirred in ethyl acetate (300 mL). Then, the reaction solution 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 with sulfuric acid, and then filtered and evaporated to remove solvent. The ester-hexane was recrystallized to obtain a compound (2) 30. Og (yield: 91. 4%). 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 8 g of tetrahydrofuran (300 mL) was stirred at room temperature for 1 hour and then at 50 ° C for 2 hours. Then, 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. Ethylene-hexane was recrystallized to obtain Compound (7) 33·0 g (yield 97.4%). <Example 4 &gt; 92 321778 201100379 Radical polymerization initiator: Synthesis of compound (46) (8) First, a compound which is an intermediate of the compound (10) is synthesized as follows:

〇 Τ Τ 基 基 基 基 咔 〇 〇 〇 . 溶解 溶解 溶解 溶解 溶解 溶解 溶解 溶解 溶解 溶解 溶解 溶解 溶解 溶解 溶解 溶解 溶解 溶解 溶解 溶解 溶解 溶解 溶解 溶解 溶解 溶解 溶解 溶解 溶解 溶解 溶解 溶解 溶解 溶解 溶解 溶解 溶解 溶解 溶解 溶解 溶解End of the transfer and transfer for 4 hours. The reaction solution was poured into ice water 2_ and extracted with ^. The residue is recrystallized with fluoroform/methanol to give compound (8) 122. 5 g (yield 91, 4%). G ShaoίΤ, using the obtained compound (8), to synthesize the servant belonging to the precursor of the compound C46 as follows, „

The compound (F) is dissolved in a mixture of the tetrahydrogen surface and the concentrated hydrochloric acid L. After the completion of the dropwise addition, it was allowed to stand at room temperature for 5 hours. 321778 93 201100379 The reaction solution was poured into 1600 niL of ice water, and was taken at 1500 inL. The organic layer was washed with water (500 mL x 3 times), dried over magnesium sulfate, filtered and evaporated to dryness, and the residue was washed with n-hexane to give compound (F) 102·8 g (yield 95.9%). Next, using the obtained compound (F), the compound (46) was synthesized as follows. After the compound (F) 50. Og was stirred in 50 mL of ethyl acetate, 18.5 g of acetic anhydride, 10.9 g of sodium acetate was added, and the mixture was heated under reflux for 3 hours. Then, the reaction solution 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 the solvent. The ester (hexane) was recrystallized to give the compound (46) 55.2 g (yield 88.7%). &lt;Example 5 &gt; Free radical polymerization initiator: Synthesis of compound (244) First, a compound (6) which is an intermediate of the compound (244) was synthesized as follows.

The compound (G) is dissolved in a gas-like lOOOOmL, and then added with an aluminum chloride of 126.7 g, and stirred at 0 ° C for 2 hours to dissolve the chloroform in 500 mL. 6g of a solution of acid chloride was added dropwise. After the completion of the dropwise addition, the mixture was stirred at 94 321778 201100379 25C for 4 hours. The reaction solution was poured into 2 g of ice water and transferred to 2,000 mL of chloroform. The organic layer was dried over magnesium sulfate, and the residue was evaporated, and the residue was recrystallized from chloroform/methanol to give compound (6) (10) (IV) yield 82.7%. Next, using the obtained compound (G), a compound (jj) belonging to the precursor of the compound (244) was synthesized as follows.

3克。 The compound (G) 10G · Gg was dissolved in a mixture of tetrahydro-sulphuric acid i-cai and concentrated hydrochloric acid 500mL, and stirred at room temperature, spent 丨 hours into the third butyl nitrite 67. 3g. 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 i6 〇〇 mL. The organic layer was washed with water (500 mL x 3 times), dried over magnesium sulfate, and the residue was filtered, and the solvent was evaporated. Next, the compound (244) was synthesized by the following using the obtained compound (H). After 50.0 g of the compound (H) was added to 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 solution was poured into 500 mL of ice water, and the product was extracted with ethyl acetate. The 321778 95 201100379 layer was washed with water (40 〇mL×3 times), dried over magnesium sulfate, and the desiccant was filtered and the solvent was distilled off. The residue was recrystallized from ethyl acetate-hexane to give compound (244) 58·3 g (yield: 97.7%). &lt;Example 6 &gt; Free radical polymerization initiator: Synthesis of compound (259) First, the compound (I) which is an intermediate of the compound (10)) was synthesized as follows.

Compound (I) Dissolve N-dimethylene ketone sulfonate 〇g in gas imitation · rainbow, add 128.6g of chlorinated salt, and dissolve phenyl b in 300mL of gas imitation under stirring for 2 hours. _ 49 ★ The solution is dripping. After the end of the dropwise addition, the mixture was stirred at 25 ° C for 4 hours. Further, the reaction solution was dispensed, and it took 2 hours to drip a solution of propylene - 33.8 g dissolved in chloroform 2_L. After the completion of the dropwise addition, the mixture was stirred at 25 tons for 3 hours. The reaction solution was poured into ice water g, and extracted with chloroform (2000 mL). The organic layer was dried with sulphuric acid, and the residue was evaporated to give crystals (yield: 85.6%). Next, using the obtained compound (1), the compound (j) which is a precursor of the compound (259) is synthesized as follows. 321778 96 201100379

Compound (j) The compound (1) 胤〇g is dissolved in a mixed solution of tetrakis(7) 〇mL and concentrated hydrochloric acid (500 mL), and then stirred at room temperature, and the third butyl phthalate is added dropwise for 1 hour. 59. 3g. After the completion of the dropwise addition, ii) hours were given at room temperature. The reaction solution was poured into 1600 mL of medium ice water to extract with a gas i6 〇〇 mL. The organic layer was washed with water (500 mL x 3 times), and dried over magnesium sulfate. The desiccant was filtered and the solvent was removed to give the compound (j) 101. 7 g (yield: 91.5%). Next, using the obtained compound (J), the compound (259) was synthesized as follows. 5 After stirring 50.0 g of the compound (J) in 5 mL of ethyl acetate, 26.4 g of acetic anhydride and 15.6 g of sodium acetate were added and heated under reflux for 3 hours. Then, the reaction solution 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). After drying over magnesium sulfate, the desiccant was filtered and the solvent was taken out. The product (259) 50. 8 g (yield 88.8%) was obtained. And a mixture of the compound (H) 3〇· 〇g, triethyl 321778 97 201100379 amine 17.6g, the synthesis of the compound (263). Benzyl helium gas (9.8 g) and tetrahydrofuran (300 mL) were stirred at room temperature for 1 hour and then at 50 ° C for 2 hours. After the reaction mixture was cooled in an ice bath, 5. 5 g of acetonitrile was added, and the mixture was stirred at room temperature for 1 hour and then 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 with sulphuric acid sulfate, then filtered and evaporated to remove solvent, and the residue was chromatographed. The product (7) 25.3 g (yield 65.7%) was obtained by the purification (hexane/chloroform). &lt;Examples 8 to 108&gt; 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 the reaction] Conditions (A): Process conditions (B) synthesized from acetic anhydride and sodium acetate in the same manner as in Example 1 : Synthesis of helium and triethylamine in the same manner as in Example 3. Method condition (B)': a method of synthesizing two kinds of ruthenium chloride and triethylamine in the same manner as in Example 98 321778 201100379 [Table 1] Example Synthesis Compound Compoundization Reaction Esterification Reaction Reaction Condition 8 Region Chlorine or acid needle reaction conditions 1 1 (1) Example 1 Ο 〇 II II H3crc, crc, cH3 Condition (A) 2 2 (2) Example 2 (same as in Example 1) Ο 〇 II II h3 £Tc, Ctc, ch3 condition (A) 3 3 (7) Example 3 (same as in the first embodiment) 0 01^0x^.0143 Condition CB) 4 4 (46) Example 4 (same as in the first embodiment) Ο ο II II H3crc, crc, cH3 Conditions (A) 5 5 (244) Example 5 (Same as Example 1) Ο ο Μ II H3CX, crC, CH3 Conditions (A) 6 6 (259) Example 6 (with examples 1 same) ο ο II II h3c, c, ctc, ch3 Condition (A) 7 7 (263) Example 7 (same as in Example 1) c, ^ch3. Cr^l Condition (B)' 8 8 (5 ) Same as in Example 1. ο II II h3c Tc, ox, ch3 Condition (A) 9 9 (13) Same as Example 1 o II II H3crc, crc, cH3 Condition (A) 10 10 (19) The same as in Example 1 0 Cl Upper ό η 3 Condition (B) 11 11 (23) Same as in the first embodiment. ο II II h3c'c, ox, ch3 condition (A) 12 12 (24) Same as in the first embodiment ο it II n3crc, (rc, cH3 condition (A) 13 13 (29) Same as Example 1. o II II H3crc, crc'cH3 Condition (A) 14 14 (30) Same as Example 1 o II II h3c^ox'ch3 Condition (A) 99 321778 201100379 Example Synthesis Example Compounds Esterification Reaction Reaction Conditions S Disk Chlorine or Anhydride Reaction Conditions 15 15 (35) Same as Example 1 9 9 h3cx'ox'ch3 Conditions (A) 16 16 (36) The same conditions as in Example 1 (B) 17 17 (37) Same as in the first embodiment ο II II h3 (Tc, ox, ch3 condition (A) 18 18 (40) Same as in the first embodiment ο 视 1 It h3ctc, ox, ch3 conditions ( A) 19 19 (41) Same as Example 1 9 9 H3CX'〇&quot;C''CH3 Condition (A) 20 20 (43) Same as Example 1 o ci^ch3 Condition (B) 21 21 (44) Same as Example 1 oo II II H3C&quot;C^C'CH3 (A) 22 22 (48) The same as in Example 1 O 0 II II h3ctc, ox, ch3 Condition (A) 23 23 (51) Same as Example 1 0 II CIXv^CH3 Condition (B) 24 24 (53 Similarly to Example 1, o qj^Cv^CH3 Condition (B) 25 25 (59) Same as Example 1 oo II It h3ctc, ox'ch3 Condition (A) 26 26 (62) Same as Example 1 oo II II H3 (TC'&lt;rC, CH3 condition (A) 27 27 (65) 9 9 h3cx'ox'ch3 condition (A) 28 28 (67) The same as in Example 1 (B) 100 321778 201100379 EXAMPLES Synthesis of Compounds 躬·Chemical Reaction Esterification Reaction Reaction Conditions Chlorine or Acid Reaction Conditions 29 29 (69) The same as in Example 1 〇II II H3C/Wh3 Condition (A) 30 30 (73) The same as in Example 1. 〇II II h3ctc, ox, ch3 Condition (A) 31 31 (76) Same as Example 1 0 Ο II II H3CTe'〇X'CH3 Condition (A) 32 32 (79) Similarly to the first embodiment, ο ι η h3cx, ctc, and ch3 conditions (A) 33 33 (80) are the same as in the first embodiment. II CIX'CH3 condition (B) 34 34 (83) Same as in the first embodiment ο II II h3ctc, ox, ch3 conditions (A) 35 35 (85) Example 1 is the same as ο violent 1 II h3c&quot;c^c'ch3 condition (A) 36 36 (87) The same as in the first embodiment ο criS〇i condition (B) 37 37 (90) The same as the first embodiment 0 ο II II h3c^c'o, Cvch3 Condition (A) 38 38 (93) Same as Example 1 Condition (B) 39 39 (97) Same as Example 1 0 ο 11 It h3c^c'o^Cvch3 Conditions (A) 40 40 0〇〇) Same as Example 1. o 11 II H3 (Tc, crc, cH3 Condition (A) 41 41 (104) Same as Example 1 Condition (B) 101 321778 201100379 Example Synthesis Example compound, the esterification reaction, the esterification reaction, the reaction conditions, the helium or the acid anhydride, the reaction conditions, 42 42 (108) The same conditions as in the first embodiment, (B) 43 43 (109) The same as the first embodiment, 9 9 h3c, c, cTc, ch3 conditions (A) 44 44 (110) The same as in the first embodiment q|^C^-CH3 condition (B) 45 45 (114) The same as in the first embodiment 0 cr^〇 condition (B) 46 46 (119) and examples 1 is the same as ο ch3 condition (B) 47 47 (120) 9 9 h3c, c, ox, ch3 condition (A) 48 48 (123) The same as 9th, 9 9 3 cc, ox, ch3 conditions ( A) 49 49 (124) Same as in Example 1 »ch3 cr Ui~CH3 ch3 Condition (B) 50 50 (128) Similarly to Example 1, o crCv^vCH3 Condition (B) 51 51 (132) Same as Example 1 9 9 H3 (TC, 〇X, CH3 Condition (A) 52 52 (134) Same as Example 1 o Condition (B) 53 53 (136) The same as Example 1 0 CV^CH2 Condition (B) 102 321778 201100379 Example Synthesis Example Compounding Chemical Reaction Esterification Reaction Conditions Stuffing Gas or acid Sf Reaction conditions 54 54 (141) Same as Example 1 9 9 h3cx 'ox'ch3 Condition (A) 55 55 (145) Same as Example 1 9 9 h3cWh3 Condition (A) 56 56 (148) In the same manner as in the first embodiment, 9 9 h3cx, ctc, and ch3 conditions (A) 57 57 (150) In the same manner as in the first embodiment, the condition (B) 58 58 (152) is the same as in the first embodiment. 9 9 H3 CTC, CrC, and CH3 Condition (A) 59 59 (154) Same as Example 1 9 9 h3cx 'ox'ch3 Condition (A) 60 60 (157) Same as Example 1 9 〇h3c&quot;cox'ch3 Condition (A) 61 61 (158 9 9 h3cWh3 Condition (A) 62 62 (159) Same as Example 1 9 9 h3c&quot;c^c'ch3 Condition (A) 63 63 (160) The same as in Example 1 o cr^ Condition (B) 64 64 (163) and examples 1 the same a 〇 L 〇 condition (B) 65 65 (170) The same as in Example 1 9 9 h3c ^ co ^ ch3 Condition (A) 103 321778 201100379 Example Synthesis Example Compounds Staining Reaction S The reaction reaction conditions 醯 chlorine Or anhydride reaction conditions 66 66 (173) The same as in Example 1 9 9 HaC^'O^CHa Condition (A) 67 67 (174) Same as Example 1 9 9 h3 (Tc, ox, ch3 Condition (A) 68 68 (177) In the same manner as in the first embodiment, 9 9 H3C &quot;C' 〇 X'CH3 condition (A) 69 69 (180) The same conditions as in the first embodiment (B) 70 70 (181) The same as the first embodiment 9 9 h3ctc , ox, ch3 condition (A) 71 71 (184) The same as in the first embodiment ο cr^〇 condition (B) 72 72 (187) The same as in the first embodiment 9 9 Condition (A) 73 73 (190) and the embodiment 1 same o condition (B) 74 74 (192) 9 9 h3cx, ox, ch3 condition (A) 75 75 (195) The same as in the first embodiment o 〇j a Cn^CH3 condition (B) 76 76 (199) 9 9 H3 (rc, crc, cH3 condition (A) 77 77 (200) The same as in the first embodiment o crC^CH3 condition (B) 78 78 (204) The same as in the first embodiment 9 9 H3£rC, 0, C, CH3 Condition (A) 104 321778 20 1100379 EXAMPLES Synthesis Example Compound Deuteration Reaction Esterification Reaction Reaction Conditions Chlorine or Anhydride Reaction Conditions 79 79 (206) Same as Example 1 9 9 h3cx, cTc, ch3 Conditions (A) 80 80 (209) and Example 1 Similarly, 9 9 h3cx, o, c, and ch3 conditions (A) 81 81 (211) The same as in the first embodiment 9 9 H3CTC '〇X, CH3 conditions (A) 82 82 (218) The same as in the first embodiment 9 conditions (B 83 83 (220) Same as in the first embodiment. Condition (B) 84 84 (221) Same as in the first embodiment. 0 Condition (B) 85 85 (225) The same as the first embodiment 9 9 h3c^cox'ch3 condition ( A) 86 86 (227) 9 9 H3 (TC'〇X, CH3 condition (A) 87 87 (228) Same as Example 1 9 9 H3CTC'〇/C'CH3 Condition (A) 88 88 (232) Same as Example 1 9 9 Condition (A) 89 89 (233) Same as Example 1 9 9 HaC^'O^CHa Condition (A) 90 90 (234) The same o condition as in Example 1 ( B) 91 91 (235) The same as in Example 1 9 9 H3CxCOX 'CH3 Condition (A) 105 321778 201100379 Example Synthesis Example Compound Deuteration Reaction Western Reaction Reaction Conditions Chlorine or Anhydride Reaction Conditions 92 92 (238) real Example 1 is the same as 〇cr^'^x^'CH3 condition (B) 93 93 (241) The same as in the first embodiment 9 9 h3cx, o two ch3 conditions (A) 94 94 (242) The same as in the first embodiment 9 9 H3CxC, 〇X, CH3 Conditions (A) 95 95 (243) The same as in Example 1 »ch3 Crui-CH3 ch3 Condition (B) 96 96 (249) The same as Example 1 9 9 H3C/C, 〇X, CH3 Condition (A) 97 97 (252) Same as Example 1 9 9 H3CX, CTC, CH3 Condition (A) 98 98 (268) The same as Example 1 9 9 H3crc, crc, cH3 Condition (A) 99 99 (274 9 9 h3 in the same manner as in the first embodiment (Tc, ox, and ch3 conditions (A) 100 100 (280) The same as in the first embodiment, 9 9 h3cTc, ox, and ch3 conditions (A) 101 101 (286) The same as in the first embodiment 9 0 ^ Η 3 crcCH3N cr ° ^ condition (B) ' 102 102 (291) The same as in the first embodiment 9 9 h3c / c, o ch3 condition (A) 103 103 (292) The same as the first example 9 9 h3c Ox, ch3 condition (B) 104 104 (298) The same as in Example 1 9 9 H3C/C, CTC, CH3 Condition (A) 106 321778 201100379 Example Synthesis Example Compoundization Reaction Esterification Reaction Conditions Chlorine or Anhydride Reaction conditions 105 105 (300) Same as Example 1 Condition (B) 106 106 (302) In the same manner as in the first embodiment, 9 9 n3trc, crc, and cH3 conditions (A) 107 107 (306) The same conditions as in the first embodiment (B) 108 108 (308) The same as the first embodiment 9 9 H3cx, crc, cH3 Condition (A) 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 results of the elemental analysis are shown in Table 2, and the results of the mass analysis are shown in Table 3. 107 321778 201100379 [Table 2] Elemental analysis results of the synthesized compounds C Η Ν C Η Ν The theoretical value of the compound 75.94 4. 67 5.90 The theoretical value of the compound 76.08 4.38 5.07 (1) The measured value is 75.93 4.66 5.91 (36) The measured value is 76.09 4.38 5. 07 Theoretical value of the compound 76.21 4. 95 5· 73 The theoretical value of the compound 71. 13 4.38 5.53 (2) Measured value 76.21 4.95 5.73 (37) Measured value 71. 13 4.37 5.53 The theoretical value of the compound 76.21 4.95 5.73 The theoretical value of the compound 75.28 4.21 5.32 (7) Found 76.22 4. 95 5.74 (40) Found 75.29 4.21 5.31 Calculated value of compound 68.26 5.07 9. 19 Calculated value of compound 71.31 4.22 4.89 (46) found 68.26 5.07 9.19 (41) found 71.32 4.23 4.88 Theoretical value 69.88 4.52 6.98 Calculated value of compound 66.50 4.12 10.12 (244) Found 69.88 4. 52 6.98 (43) Found 66.50 4.12 10.12 Calculated value of compound 72.39 4.40 6.33 Calculated value of compound 67.13 4.46 9.79 (259) Measured value 72.39 4, 40 6.33 (44) Calculated value 67.12 4.45 9.79 Theoretical value of compound 72.39 4.40 6.33 Theoretical value of compound 69.26 5.61 8.65 (263) Found 72.40 4.41 6.33 (48) Found: 69.26 5.62 8.64 Compound: 76.96 5.70 5.28 Calculated compound value 67.71 4. 77 9.48 (5) found 76.95 5.70 5.29 (51) found value 67.71 4.77 9.48 compound theoretical value 76.96 5.70 5.28 Compound theoretical value 68.26 5.07 9.19 (13) Found 76.96 5.70 5.28 (53) Found 68.25 5.07 9.18 Calculated compound value 77.40 6. 13 5.01 Compound value 68.78 5.34 8.91 09) Found 77.41 6. 14 5.01 (59) Found 68.79 5. 35 8.92 Theoretical value 77.47 5. 57 5. 16 Theoretical value 65.24 4.89 8.15 (23) Found 77.48 5.56 5.15 (62) Found 65.23 4.88 8. 15 Theoretical value 78.34 4.51 5.22 Theoretical value of compound 69. 55 5.21 8.69 (24) Measured value 78.34 4.51 5.22 (65) Measured value 69.55 5. 22 8.69 The theoretical value of the compound 74.84 5.73 7.70 The theoretical value of the compound 70. 94 5. 08 7. 30 (29) Measured value 74.82 5.74 7.72 ( 67) Found 70.93 5.07 7. 30 Compound theoretical value 74.71 5.53 5.12 Compound theoretical value 68.38 5. 04 7.25 (30) Measured value 7171 5.52 5.12 (69) Measured value 68.37 5.05 7.25 Compound theoretical value 76.08 4.38 5.07 Compound theoretical value 65.35 4.61 9.15 (35) Measured value 76.09 4.38 5.08 (73) Measured value 65.35 4.62 9.14 108 321778 201100379

C Η Ν C Η Ν The theoretical value of the compound 66.53 4.04 8.03 The theoretical value of the compound 65.72 5.16 10.06 (76) Found 66.54 4. 04 8.03 (119) Found 65.73 5.165 10.06 The theoretical value of the compound 63. 42 4.05 8.88 The theoretical value of the compound 68.38 4.26 10.47 (79) Found 63.42 4.04 8.88 (120) Found 68.38 4.25 10.46 Calculated compound value 66.09 5.12 11.86 Calculated compound value 64.27 4.49 6. 25 (80) Found 66. 09 5.12 11.85 (123) Measured value 64.28 4.50 6.24 Compound theory Value 72.80 4.89 6.79 Compound theoretical value 67.65 6.06 5.26 (83) Found 72.80 4.88 6.78 (124) Found 67.64 6.06 5.25 Calculated compound value 70.85 4.76 5.51 Calculated compound value 65.54 6.00 4. 63 (85) Measured value 70.84 4.76 5.52 (128) Found 65.55 6.01 4.62 Calculated compound value 75.94 4.67 5.90 Calculated compound value 68. 22 4. 34 5.49 (87) found 75.94 4.66 5.91 (132) found 68.21. 4. 33 5. 48 compound theoretical value 70.58 5.01 6.33 The theoretical value of the compound 71.46 4.10 4.39 (90) measured value 70.58 5.01 6.32 (134) measured value 71.47 4. 11 4.38 Theoretical value 71.24 5,01 5.36 The theoretical value of the compound 66.85 4. 85 4.21 (93) Found 71.24 5.02 5.37 (136) Found 66.84 4.85 4.21 The theoretical value of the compound 73. 74 5.69 4.65 The theoretical value of the compound 67.25 4.97 6.27 (97 Found 73.75 5.69 4. 65 (141) Found 67.26 4. 97 6. 28 Calculated value of compound 73.74 5.00 9.92 Calculated value of compound 69.30 6. 02 5.57 (100) Found 73.74 5.01 9· 92 (145) Measured value 69.30 6.03 5.56 The theoretical value of the compound 74.12 5. 30 9.60 The theoretical value of the compound 66.93 4.16 5.78 (104) Found 74.12 5.30 9.61 (148) Found 66.92 4.17 5.78 The theoretical value of the compound 70.71 5. 34 8.25 The theoretical value of the compound 70.23 5.10 4. 43 (108 Found 70.71 5. 35 8. 25 (150) Found 70·23 5.11 4.44 The theoretical value of the compound 66.75 3.91 13.00 The theoretical value of the compound 73. 67 4.59 4.91 (109) Measured value 66. 74 3. 92 13.00 (152) Measured Value 73.66 4.59 4. 90 Compound theoretical value 66.95 4. 54 12.22 Calculated compound value 74. 54 5.24 4.04 (110) Found 66.94 4.53 12.22 (154) Measured value 74. 5 3 5.23 4.05 Compound theoretical value 69.60 3.83 11.39 Compound theoretical value 71.13 4.41 7.21 (114) Found 69.60 3.84 11.38 (157) Found 71.14 4.42 7.22 109 321778 201100379 C Η Ν C Η 化合物 Compound (]58) Theoretical value 71. 63 4.76 6.96 Compound (199) Theoretical value 66.52 5.17 8. 62 Measured value 71.62 4. 75 6.96 Found 66.51 5. 17 8. 61 Compound (159) Theoretical value 69.36 4. 89 6.47 Compound (200) Theoretical value 72. 03 5.10 7.88 Found 69.37 4.88 6.47 Found 72.03 5.11 7.89 Compound (160) Theory: 64. 10 4.27 5.16 Compound (204) Theory: 72.45 4.62 4.58 Measured value 64. 10 4.26 5. 37 Measured value 72. 46 4.62 4.58 Compound (163 Theoretical value 64.37 2.89 5.36 Compound (206) Theoretical value 72. 60 4.23 7.06 Found 64.36 2.89 5.35 Found: 72.61 4.23 7.05 Compound (170) Theoretical value 63.16 5. 12 5.08 Compound (209) Theoretical value 65.24 4.59 4.91 Measured value 63 17 5. 13 5.08 Measured value 65.24 4.58 4. 92 Compound (173) Theoretical value 75.94 4. 67 5.90 Compound (211) Theoretical value 67. 18 5.64 6.72 Measured value 75 .93 4. 66 5.91 Measured value 67.17 5.65 6.72 Compound (174) Theoretical value 76.48 5.21 5.57 Compound (218) Theoretical value 73.45 5.48 4.76 Found 76.48 5.21 5.57 Measured value 73.46 5. 48 4. 77 Compound (177) Theoretical value 77.40 6. 13 5.01 Compound (220) Theoretical value 72. 77 4.17 4. 14 Measured value 77.41 6. 14 5.02 Measured value 72. 78 4.18 4.14 Compound (180) Theoretical value 80.25 4.38 4.68 Compound (221) Theoretical value 76. 67 5.04 7.25 Measured value 80.25 4.37 4.68 found 76.67 5.03 7. 26 Compound (181) Theory: 75.28 4. 21 5.32 Compound (225) Theory 68. 63 4. 17 8.28 Measured value 75.29 4.21 5.32 Measured value 68. 62 4.17 8.27 (184) Theoretical value 72.41 4. 34 6.03 Compound (227) Theoretical value 65.19 3.85 8.45 Found 72.41 4.34 6.02 Measured 65.]8 3.86 8.44 Compound (187) Theoretical value 72.32 5.71 4.96 Compound (228) Theoretical value 67.03 4.31 7.82 Found 72.32 5.72 4.95 Found 67.04 4.32 7.81 Compound (190) Theoretical value 81.47 4.35 4.32 Compound (232) Theoretical value 66.37 4. 23 6.19 Measured value 81.48 4.35 4.33 Found 66.36 4.22 6. 18 Compound (192) Theoretical value 66.50 4.12 10.12 Compound (233) Theory 66.37 4.23 6.19 Found 66.51 4. 12 10.11 Found 66.37 4.24 6.18 Compound 095) Theoretical value 67.71 4.77 9.48 Compound (234) Theory Value 77.70 5.18 7.99 Actual value 67.72 4.76 9.47 Actual value 77. 71 5.17 7.98 110 321778 201100379

C Η Ν The theoretical value of the compound 72.90 4.33 10.63 (235) Found 72.91 4. 34 10.62 The theoretical value of the compound 69.30 6.02 5.57 (238) Found 69.30 6.01 5. 56 The theoretical value of the compound 68. 22 4. 34 5.49 (241) Measured value 68.21 4. 35 5.49 Theoretical value of the compound 66.65 4.47 5.18 (242) Found 66.66 4.46 5.18 Calculated value of compound 71.74 5. 02 4. 65 (243) Measured value 71.74 5.01 4.66 Calculated value of compound 73.25 5.87 5. 70 (249) Measured value 73.24 5.86 5.71 Theoretical value 70.23 4.75 6.83 (252) Found 70.22 4.76 6.82 Calculated value of compound 61.99 4.09 10.33 (268) Found: 61.98 70 5. 26 9.15 (280) Found 64. 71 5.25 9.15 Theoretical value 66.84 5.33 7.80 (286) Found 66.83 5. 34 7.81 Calculated value of compound 71.22 5. 36 6· 39 (291) Measured value 71.22 5. 35 6.38 Theoretical value of the compound 65.17 5.47 8. 94 (292) Found 65.18 5.46 8.94 The theoretical value of the compound 64. 70 5.26 9.15 (298) Measured value 64.71 5.25 9.14 Compound theoretical value 72.46 3.96 7. 86 (300) Found 72.46 3· 95 7.87 C Η 化合物 Compound (302) Theoretical value 66.36 4.52 6.27 Actual value 66.35 4.51 6.27 Compound (306) Theoretical value 65.36 4. 63 6.78 Measured value 65.37 4.62 6.78 Compound (308) Theoretical value 59.55 3.97 6.13 Measured value 59.54 3.96 6.14 111 321778 201100379 [Table 3] Mass analysis of synthesized compounds Compound analysis results Compound analysis results Compound analysis results Compound analysis results Compound analysis (1) Theoretical value 474.2 Compound (36) Theory: 552.2 Compound (76): calc. Value 473.1 Compound (120) Theory 544.2 found 488.3 found 506.2 found 473. 1 found 544. 1 Compound (7) Theory 488.2 Compound (40) Theory: 526.2 Compound (80) Theory 472.2 Compound (123) Theoretical value 448. 1 measured value 488.2 measured value 526 .2 Measured value 472.3 Found 448.2 Compound (46) calcd. 457.2 Compound (41) </RTI> </RTI> </RTI> </RTI> <RTIgt; </ RTI> </ RTI> </ RTI> </ RTI> </ RTI> </ RTI> </ RTI> </ RTI> </ RTI> <RTIgt; 244) Theoretical value 601.2 Compound (43) Theoretical value 415.1 Compound (85) Theory: 508.2 Compound (128) Theory of value 604.2 found value 601.3 found value 415.2 found value 508.2 found value 604.3 compound (259) Value 429.1 Compound (87) Theoretical value 474.2 Compound (132) Theory: 510.1 Found: 663.3 Found: 429.1 Found: 474.3 Found: 510.1 Compound (263) Calculated value 663.2 Compound (48) Theoretical value 485.2 Compound (90) Theoretical value 442.2 Compound (134) Theoretical value 638.2 Found 663.1 Found 485.2 Found 442.2 Found 638.2 Compound (5) Theory: 530.1 measured value 443.3 measured value 522.3 measured value 664.3 compound (13) Theoretical value 530.2 Compound (53) Theory: 457.2 Compound (97) calcd. s s s s s s s s s s s s s s s s s s s s s s s s s s s s s s s s s s s s s s s s Theoretical value 471.2 Compound (100) Theoretical value 423.2 Compound (145) Theory 502.2 found 558.2 found 471.1 found 423.3 found 502.3 Compound (23) Theory 542.2 Compound (62) Theory: 515.2 Compound (104) 437.2 Compound (148) Theory 484.1 found 542.1 found 515.2 found 437.3 found 484.0 Compound (24) </RTI> <RTI ID=0.0></RTI> </RTI> <RTIgt; </RTI> <RTIgt; 536.3 Measured value 483.3 Found 509.3 Found 632.3 Compound (29) Theory 545.2 Compound (67) Theory: 575.2 Compound Compound Compound Compound Compound Compound Compound Compound Compound Compound Compound Compound Compound Compound (30) Theoretical value 546,2 Compound (69) Value 579.2 Compound (110) Theoretical value 466.2 Compound (154) Theory: 692.2 Found: 546.3 Found: 579.1 Found: 466.1 Found: 692.2 Compound (35) Theory: 552.2 Compound (73) Theory of value 459.1 Compound (114) Theoretical value 500.1 Compound (157) Theory 388.1 Found 552.2 Measured 459.2 Measured 500.2 Measured value 388.2 112 321778 201100379 Compound Analysis Results Compounds * N Result Compound Analysis Results Compound Analysis Results Compound Value 402.1 Compound Theory 487. 2 Compound Theory 395.1 Calculated value of compound 669.2 (158) found 402.2 (199) found 487. 1 (235) found 395.2 (302) found value: 669.3 s. s. s. s. s. s s s s s s s s s s s s s s s s s s s s 159) Found 432.2 (200) found 533.3 (238) found 502.1 (306) found value 826.1 compound value 542.1 compound value 414.1 compound value 510.1 compound value 685.1 (160) found 542.0 (204) measured value 414.2 (241) Real Value 510.2 (308) Found 685.2 Compound calcd. 522.1 Compound calc. 595.2 Compound calc. 54 s s s s s s s s s s s s s s s s s s s s s s s s s s s s s s s s s s s (170) Found 550.2 (209) found 570.2 (243) found 602.1 calcd. s s s s s s s s s s s s s s s s s s s s s s s s s s s s s s s s s s s s s s s s s s s s Value 502.2 Compound calcd 588.2 Compound calcd. 615.2 (174) Found: 50. ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( Value 676.1 (268) Found 542.2 Calculated compound value 598.2 Compound calcd. 579.2 Compound calc. 666.2 (180) Found: 598.1 (221) Found: 579.2 (274) Found: 666.3 Calculated value of compound 526.2 Compound value 507.1 Found: 612.2 (181) found 526.3 (225) found 507.1 (280) found: 612.3 calcd. s. 46 s s s s s s s s s s s s s s s s s s s s s s s s s s s s s s s s s s s s s s Found 718.4 Calculated for compound value 564.2 Calculated for compound value 537.1 Compound found: 657.3 (187) Found: 564.3 (228) Found: 537.2 (291) Found: 657.4 Calculated value of compound 648.2 Calculated compound value 452.1 Compound value 626.2 (190) Measured value 648.3 (232) Measured value 452.2 (292) found calcd. 626.3 calcd. </ s </ s </ s </ s s s s s s s s s s s s s s s s s s s s s s s s s s s s s s s s s s s s s s s s s s s s s s s 525.2 Theoretical value 712.2 (195) Found 443.3 (234) Found 525.3 (300) Found 712.3 113 321778 201100379 <Examples 109 to 254, Comparative Examples 1 to 12> Next, the obtained general formula (1) The compound of the present invention is used as a radical polymerization Initiator (A), as hereinafter be added to the polymerizable composition, the curable polymers of the survey. [Curability 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) 1 part by weight of a diallyl resin) and 8 parts by weight of bis(trihydroxydecylpropenyl) tetraacrylic acid vinegar, and 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 following comparative examples). 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 (130 W/cm, 1 lamp) at a conveying speed of 40 m/min, 40 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, after the ultraviolet ray is irradiated, if it is at a high transport speed, it is judged to be preferable if it is not damaged. [Evaluation Criteria] 5: No damage was observed in the film 4: Very little damage was confirmed in the film 3: Minor damage was confirmed in the film 2: Damage was confirmed in the film 1: Multiple damage was confirmed in the film 114 321778 201100379 [Table 4] Ο Compound (310) Η3〇&lt;^ΓΗ3 6^ch3 Compound (314) YH3 Compound (311) HsC^ (Λη3 Ο Compound (315) Ο Compound (312) Ο Irgacure ΟΧΕ 01 (Ciba Specialty Chemicals Co., Ltd. Compound (316) H3C^^〇Η3 H3^N'〇Ltfj〇rN'^CH3 EAB-F (manufactured by Hodogaya Chemical Co., Ltd.) Compound (313) h?V^VH3 S Irgacure OXE 02 (Ciba Specialty Chemicals Co., Ltd. Compound (317) xh3 Kayacure DETX-S (manufactured by Sakamoto Chemical Co., Ltd.) 115 321778 201100379 [Table 5] Example No. Radical polymerization initiator sensitizer Result Compound parts by weight 40 m/s 45 m/s 50 m/s Example 109 Compound (1) None - 5 5 4 Example 110 Compound (2) None - 5 5 4 Example 111 Compound (7) None - 5 5 4 Example 1 12 Compound (46) None - 5 5 4 Example 113 Compound (244) None - 5 5 4 Example 114 Compound (259) None - 5 5 4 Example 115 Compound (263) None - 5 5 4 Example 1 1 6 Compound (5) None - 5 5 4 Example 117 Compound (13) None - 5 5 4 Example 118 Compound (1 9) None - 5 5 4 Example 119 Compound (23) None - 5 5 4 Example 120 Compound (24) None - 5 5 4 Example 121 Compound (29) None - 5 5 4 Example 122 Compound (30) None - 5 5 4 Example 123 Compound (35) None - 5 5 4 Example 124 Compound (36) None - 5 5 4 Example 125 Compound (37) None - 5 5 4 Example 126 Compound (40) None - 5 5 4 Example 127 Compound (4i None - 5 5 4 Example 128 Compound (43) None - 5 5 4 Example 129 Compound (44) None - 5 5 4 Example 130 Compound (48) None - 5 5 4 Example 131 Compound (51) None — 5 5 4 Example 132 Compound (53) None - 5 5 4 Example 133 Compound (59) None - 5 5 4 Example 134 Compound (62) None - 5 5 4 Example 135 Compound (65) None - 5 5 4 Example 136 Compound (67) None - 5 5 4 Example 137 Compound (69) None - 5 5 4 Example 138 Compound (73) None - 5 5 4 Example 139 Compound (76) N - 5 5 4 Example 140 Compound (79) None - 5 5 4 Example 141 Compound (80) None - 5 5 4 Example 142 Compound (83) None - 5 5 1 Example 143 Compound (85) N - 5 5 1 Example 144 Compound (87) None - 5 5 1 Example 145 Compound (90) None - 5 5 1 Example 146 Compound (93) None - 5 5 1 Example 147 Compound (97) None - 5 5 1 Example] 48 Compound (100) None - 5 5 1 Example 149 Compound (104) None 5 3 1 Example 150 Compound ( 108) None - 5 3 1 116 321778 201100379 Example No. Radical polymerization initiator sensitizer Result Compound parts by weight 40 m/s 45 m/s 50 m/s Example 151 Compound (109) None - 5 3 1 Example 152 Compound (110) None - 5 3 1 Example 153 Compound (114) None - 5 3 1 Example 154 Compound (119) None - 5 3 1 Example 15 5 Compound (120) None - 5 3 1 Example 156 Compound ( 123) none - 5 3 1 Example 157 Compound (124) None - 5 3 1 Example 158 Compound (128) None - 5 3 1 Example 159 Compound (132) None - 5 3 1 Example 160 Compound (134) None - 5 3 1 Example 161 Compound (136) None - 5 3 1 Example 162 Compound (141) None - 5 3 1 Example 163 Compound (145) N - 5 3 1 Example 164 Compound (148) N - 5 3 1 Example 165 Compound (150) None 5 3 1 Example 166 Compound (152) None - 5 3 1 Example 167 Compound (154) None - 5 3 1 Example 168 Compound (157) None - 5 3 1 Example 169 Compound (158) None - 5 3 1 Example 170 Compound (159 None - 5 3 1 Example 171 Compound (160) None - 5 3 1 Example 172 Compound (163) None - 5 3 1 Example 173 Compound (170) None - 5 3 1 Example 174 Compound (173) None — 5 5 2 Example 175 Compound (174) None - 5 5 2 Example 176 Compound (177) N- 5 5 2 Example 177 Compound (180) None - 5 5 2 Example 178 Compound (181) None 5 2 Example 179 Compound (184) None - 5 4 1 Example 180 (187) None - 5 4 1 Example 181 Compound (190) N - 5 4 1 Example 182 Compound (192) N - 5 5 3 Example 183 Compound (195) None - 5 5 3 Example 184 Compound ( 199) none - 5 5 3 Example 185 Compound (200) None 1 5 5 3 Example 186 Compound (204) None - 5 3 1 Example 187 Compound (206) None - 5 5 5 Example 188 Compound (209) None 5 3 1 Example 189 Compound (211) None - 5 1 1 Example 190 Compound (218) N - 5 5 5 Example 191 Compound (220) N - 5 5 5 Example 192 Compound (221) None - 5 5 5 117 321778 201100379 Example No. Radical Polymerization Starter Sensitizer Results 4 Hydrate Weight 40 m/s 45 m/s 50 m/s Example 1 93 Compound (225) None - 5 5 5 Example 194 Compound (227) None - 5 5 5 Example 2 95 Compound (228) None ~ 5 5 5 Example 196 Compound (232) No~ 5 1 1 Example 197 Compound (233) None - 5 1 1 Example 198 Compound ( 234) None - 5 1 Example 199 Compound (235) None - 5 1 Example 200 Compound (238) None - 5 1 1 Example 201 Compound (241) None - 5 1 1 Example 202 Compound (242) None - 5 1 1 Example 203 Compound (243) None - 5 1 1 Example 204 Compound (249) None - 5 5 4 Example 205 Compound (252) None - 5 5 4 Example 206 Compound (268) N - 5 5 4 Example 207 Compound (274) None - 5 5 4 Example 208 Compound (280 None - 5 5 4 Example 209 Compound (286) None ~ 5 5 4 Example 210 Compound (291) None~ 5 5 2 Example 211 Compound (292) None - 5 5 3 Example 212 Compound (298) None — 5 5 3 Example 213 Compound (300) None - 5 3 1 Example 214 Compound (302) None~ 5 3 1 Example 215 Compound (306) None~ 5 4 1 Example 216 Compound (308) None - 5 5 1 Example 217 Compound (1) Compound (316) 1 5 5 5 Example 218 Compound (317) 1 5 5 δ Example 219 Compound (2) Compound (316) 1 5 5 5 Example 220 Compound (317) 1 5 5 5 Example 221 Compound (23) Compound (316) 1 5 5 5 Example 222 Compound (317) 1 5 5 5 Example 223 Compound (174) Compound (316) 1 5 5 5 Example 224 Compound (317) 1 5 5 4 Example 225 Compound (43) Compound (316) 1 5 5 5 Example 226 Compound (317) 1 5 5 5 Example 227 Compound (46) Compound (316) 1 5 5 5 Example 228 Compound (317) 1 5 5 5 Example 229 Compound (62) Compound (316) 1 5 5 5 Example 230 Compound (317) 1 5 5 5

118 321778 201100379 Example No. Free Radical Polymerization Sensitizer Results Starting _ 4 Hydrate Parts by Weight 40 m/s 45 m/s 50 m/s Example 231 il- Zv /Wn Ί 0 C, Compound (316) 1 5 5 5 Example 232 Compound (317) 1 5 5 5 Example 233 Compound (109) Compound (316) 1 5 5 3 Example 234 Compound (317) 1 5 5 3 Example 235 Compound (100) Compound (316) 1 5 5 1 Example 236 Compound (317) 1 5 5 3 Example 237 Compound (123) Compound (316) 1 5 5 3 Example 238 Compound (317) 1 5 5 3 Example 239 Compound (132) Compound (316) 1 5 5 1 Example 240 Compound (317) 1 5 5 1 Example 241 Compound (145) Compound (316) 1 5 5 3 Example 242 Compound (317) 1 5 5 3 Example 243 Compound (152) Compound (316) 1 5 5 3 Example 244 Compound (317) 1 5 5 1 Example 245 Compound (157) Compound (316) 1 5 5 3 Example 246 Compound (317) 1 5 5 3 Example 247 Compound (83) Compound 316 1 5 5 5 Example 248 Compound (317) 1 5 5 3 Example 249 Compound 93) Compound (316) 1 5 5 5 Example 250 Compound (317) 1 5 5 5 Example 251 Compound (244) Compound (316) 1 5 5 5 Example 252 Compound (317) 1 5 5 5 Example 253 Compound (280) Compound (316) 1 5 5 5 Example 254 Compound (317) 1 5 5 5 Comparative Example 1 Compound (310) None - 1 1 1 Comparative Example 2 Compound (311) None - 1 1 1 Comparative Example 3 Compound (312) None - 1 1 1 Comparative Example 4 Compound (313) None - 1 1 1 Comparative Example 5 Compound (314) None - 1 1 1 Comparative Example 6 Compound (315) None - 1 1 1 Comparative Example 7 Compound ( 311) Compound (316) 1 1 1 1 Comparative Example 8 Compound (317) 1 1 1 1 Comparative Example 9 Compound (316) 1 1 1 1 Comparative Example 10 1U^ \ O i 0 J Compound (317) 1 3 1 1 Comparative Example 11 Compound (316) 1 3 1 1 Comparative Example 12 103⁄4 ^ \ ύ ) Compound (317) 1 1 1 1

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) 1〇9 to 216) has a higher hardness of 119 321778 201100379. 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, in the case of using a conventionally known keto-type oxime ester as a photopolymerization initiator, the brewing type 1 of the present invention clearly exhibits a high sensitivity. Although the detailed reason has not been clarified, it is presumed that the photopolymerization initiator (A) of the present invention may have a match with a ketone-type oxime structure due to the excellent chromophore group which is not in 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 R1Q to R14 is a nitro group or a substituted or unsubstituted fluorenyl group is used (Examples 109 to 147) , 174 to 185, 187, 190 to 195, 204 to 212, 215, 216) 'the radical polymerization of the present invention as compared with the use of a substituent other than the above substituents using at least one of r7 to r1() In the case of the starting agent (A) (Examples 148 to 173, l86, i88, i89, 196 to 203, 213 to 214), it is known that Wei is right-handed. The detailed reason is not known, but the curability is presumed. Although the initiator can be used as an excellent chromophoric group by substituting the electron for the photopolymerization of the present invention: the base is substituted with the N-position benzene step of the ten-seat group to be substituted into the MW group. Yes, but if you go further into it, it will be obvious. 321778 120 201100379 Further, in the case where at least one of R&quot; to R14 is a Si group represented by the general 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), showing higher hardenability, and in the present embodiment as in the case of the nitro group Shows the highest hardenability. Further, a photopolymerizable composition of the radical polymerization initiator (A) of the present invention wherein R12 is a nitro group (Examples 112, 128 to 141, 193 to 195, ο 206 to 209) is used as compared with In other cases (Examples 182 to 185, 211, and 212), it was found that the curability was excellent. Although the detailed reasons are still unknown, it is speculated that the position of the most effective effect of the nitro group is R12, and the same tendency is exhibited for other substituents (such as thiol groups). That is, when it is known that the same substituent is used, the substitution is preferably in the case of R12. &lt;Examples 255 to 281, and Comparative Examples 13 to 18 &gt; An alkali-soluble resin was prepared and added to the polymerizable composition as described below, and the sputum was subjected to a sclerosing test and development. [Preparation of Acrylic Resin Solution (1)] To the reaction solution, 800 parts by weight of cyclohexane was added, and while nitrogen gas was injected into the vessel, the mixture was heated to 100 ° C, and the same temperature was taken for 1 hour. A mixture of the body and the thermal polymerization initiator is dropped to carry out a polymerization reaction. 6重量份滴份 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 Thereafter, the reaction was further carried out at 10 ° 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 a weight average molecular weight of about 40. , 000 solution of acrylic 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 a non-volatile component in the previously synthesized resin solution to 20%. Ketone, and prepare acrylic resin solution (1). The obtained acrylic resin solution (1) is a solution containing the alkali-soluble resin (E) of the present invention. [Curability test] 100 parts by weight of a dipentaerythritol pentapropan acid (Sartomer, SR399) as a radical polymerizable compound (B), and an acrylic resin solution (1) containing a solution of the test resin (E) 500 parts by weight, 400 parts by weight of cyclohexanone as a solvent, and 6 parts by weight of the compound shown in Table 6 as a radical polymerization initiator (A), and mixed to prepare a uniform polymerizable composition solution.

The above polymerizable composition solution was passed through a 0.2 2 m pore size disc filter (di sc fi 11er) and coated on a stainless steel plate (#600 grinding) using a spin coater in an oven. The medium was removed by heating and drying at 80 ° C for 3 minutes. After drying, the film thickness of the polymerizable composition formed on the stainless steel plate was 2 / / m. For the polymerizable composition film, the light of the 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 of the polymerizable composition film was measured. 122 321778 201100379 Spectrum, absorption by the characteristics of propylene sulfhydryl group 81 The change in the absorption intensity of Ocnf1 is calculated in Table 6 after the light irradiation for 1 G seconds and the propylene oxime before the light irradiation. [Table 6]

321778 123 201100379 Compared with the use of well-known (4) as a radical polymerization initiator (than the ruthenium Example 13 Magic 8) 'Using the radical polymerization initiator of the present invention (phantom polymerizable composition (Example 255) i 281) will efficiently generate free radicals due to light irradiation and polymerize propylene sulfhydryl groups. Even if it is slight, further polymerization of acrylonitrile base has a great influence on the productivity improvement required in recent years, so it can be borrowed The process of using a radical polymerization initiator (human) of the present invention corresponds to a higher sensitivity. 〜 q Further, the polymerizable compositions of Examples 255 to 281 which are formed on a stainless steel plate before irradiation with light are provided under another After immersing in a 2% by weight aqueous solution of tetramethylammonium hydroxide for about one minute, it was dissolved at an appropriate rate, and it was confirmed that the composition of the present invention was developed by an alkaline developing solution. Examples 282 to 353, and Comparative Examples 19 to 33&gt; The alkali-soluble resin was prepared and added to the polymerizable composition to carry out a curing test and development. [Preparation of Acrylic Resin Solution (2)] In the Reaction Solution Add cyclohexanone 37 0 parts by weight, while injecting nitrogen into the vessel, heating to 801, and dropping the mixture of the following monomer and the thermal polymerization initiator at the same temperature for a few hours to carry out polymerization. Methacrylic acid 20. 〇 1 part by weight of mercaptopropionic acid methyl vinegar 10.0 parts by weight of mercaptopropyl benzoic acid n-butyl vinegar 55.0 parts by weight of 2-hydroxyethyl methacrylate 15.0 parts by weight of 2,2'-azobisisobutyronitrile 4.0 parts by weight After cooling to room temperature, about 2 g of the acrylic resin solution was taken for 124 321778 201100379, and dried at 18 (TC for 20 minutes, the non-volatile component was determined, and the non-volatile component in the previously synthesized acrylic resin solution was measured. Adding cyclohexanone to 2% by weight to prepare an acrylic resin solution (2). The obtained weight average molecular weight of the formula is 40,000. The obtained acrylic tree ride liquid (2) is containing the present invention. a solution of the test-soluble resin (E). [, Curability test] Addition of a quaternary phosphonium tetrapentaenoic acid vinegar as a radical polymerizable compound (B) (Sartomer's SR399H00 parts by weight, as a test Resin (E) solution of C 5 parts by weight of the acid resin solution (2), 200 parts by weight of propylene glycol monomethyl ether acetate as a solvent, and a compound shown in Table 7 as a radical polymerization initiator (A) and a sensitizer (C) Each of the polymerizable composition solutions prepared by mixing them into a heavy wound described in Table 7 was prepared by filtering the above polymerizable composition solution in a 0.2/ζπι pore size disk filter and applying it to a rotary coater. The glass plate having a thickness of 1 mm was 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 am. 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. In the development of i minutes, the minimum energy required to make the polymerizable composition insolubilized at an irradiation wavelength of 365 nm was defined as sensitivity, and the results are shown in Table 7. 321778 125 201100379 [Table 7] Example compilation Radical polymerization addition amount sensitizer Adding amount sensitivity initiator (parts by weight) (parts by weight) CmJ/cm2) Example 282 8 No 0 25 Example 283 Compound (1) 8 Compound (3) 6) 2 20 Example 284 8 Compound (3 1 7) 2 20 Example 285 8 No 0 25 Example 286 Compound (2) 8 Compound (31 6) 2 25 Example 287 8 Compound (3) 1 7 ) 2 20 Example 288 8 None 0 25 Example 289 Compound (13) 8 Compound (31 6 ) 2 25 Example 290 8 Compound (317) 2 20 Example 291 8 No 0 25 Example 292 Compound (24) 8 compound (31 6) 2 20 Example 293 8 Compound (3丨7) 2 25 Example 294 8 No 0 30 Example 295 Compound (174) 8 Compound (31 6 ) 2 25 Example 296 8 Compound (317 2 25 Example 297 8 No 0 25 Example 298 Compound (44) 8 Compound (31 6) 2 20 Example 299 8 Compound (3Ϊ7) 2 20 Example 300 8 No 0 25 Example 301 Compound (53) 8 Compound (3 1 6 ) 2 20 Example 302 8 Compound (317) 2 25 Implementation 303 8 no 0 25 Example 304 Compound (6 5) 8 Compound (3 1 6) 2 25 Example 3 0 5 8 Compound (317) 2 20 Example 306 8 No 0 30 Example 30 7 Compound (195) 8 Compound (316) 2 25 Example 308 8 Compound (317) 2 25 Example 309 8 No 0 35 Example 310 Compound (85) 8 Compound (31 6) 2 30 Example 311 8 Compound (317) 2 30 Example 312 8 no 0 35 Example 31 3 Compound (187) 8 Compound (31 6) 2 30 Example 314 8 Compound (317) 2 35 Example 315 8 No 0 40 Example 316 Compound (109) 8 Compound (316) 2 30 Example 317 8 Compound (317) 2 35 Example 318 8 No 0 40 Example 319 Compound (100) 8 Compound (31 6) 2 35 Example 320 8 Compound (317) 2 40 Example 321 8 No 0 40 Example 322 Compound U24) 8 Compound (31 6) 2 35 Example 323 8 Compound (31 7) 2 35 126 321778 201100379

Example No. Radical polymerization initiator Adding amount (parts by weight) Additive amount (parts by weight) Sensitivity CraJ/cm2) Example 324 8 No 0 40 Example 325 Compound (丨34) 8 Compound (316) 2 40 Example 326 8 Compound (317) 2 35 Example 327 8 No 0 40 Example 328 Compound (145) 8 Compound (316) 2 35 Example 329 8 Compound (317) 2 35 Example 330 8 No 0 40 Example 331 Compound (150) 8 Compound (316) 2 40 Example 332 8 Compound (317) 2 40 Example 333 8 No 0 40 Example 334 Compound (157) 8 Compound (316) 2 35 Example 335 8 Compound (317 2 35 Example 336 8 None 0 25 Example 337 Compound (244) 8 Compound (316) 2 20 Example 338 8 Compound (317) 2 20 Example 339 8 No 0 25 Example 340 Compound (252) 8 Compound (316) 2 20 Example 341 8 Compound (317) 2 25 Example 342 8 No 0 25 Example 343 Compound (268) 8 Compound (316) 2 20 Example 344 8 Compound (317) 2 20 Example 345 8 No 0 25 Example 346 (280) 8 Compound (31 6) 2 20 Example 347 8 Compound (317) 2 20 Example 348 8 No 0 30 Example 349 Compound (291) 8 Compound (316) 2 25 Example 350 8 Compound (317) 2 25 Example 351 8 No 0 35 Example 352 Compound (300) 8 Compound (316) 2 30 Example 353 8 Compound (317) 2 30 Comparative Example 19 8 None 0 &gt; 100 Comparative Example 20 Compound (310) 8 Compound (316) 2 &gt; 300 Comparative Example 21 8 Compound (317) 2 &gt; 100 Comparative Example 22 8 None 0 &gt; 100 Comparative Example 23 Compound (311) 8 Compound (31 6 ) 2 &gt; 100 Comparative Example 24 8 Compound (317) 2 &gt; 100 Comparative Example 25 8 No 0 85 Comparative Example 26 Compound (313) 8 Compound (316) 2 80 Comparative Example 2? 8 Compound (31?) 2 80 Comparative Example 28 8 No 0 90 Comparative Example 29 Compound (314) 8 Compound (316) 2 85 Comparative Example 30 8 Compound (317) 2 85 Comparative Example 31 8 No 0 80 Comparative Example 32 Compound (315) 8 Compound (3) 6) 2 75 Comparative Example 33 8 Compound (31 7 ) 2 75 127 321778 201100379 Compared to the use of knowing The case of a polymerization initiator (Comparative Examples 19 to 33), of the present invention using a radical polymerization initiator, the polymerizable composition (A) (Examples 282-353) was significantly more sensitivity based. 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. &lt;Examples 354 to 425, Comparative Examples 34 to 48&gt; [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/zm X 20 // m resolution) The light of a high-pressure mercury lamp having an exposure potential of about 100 // m and a wavelength of 365 nm of 4. 5 mW/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, the unexposed portion was removed, and after washing with pure water, the obtained cured product was heated in an oven at 230 ° C for 30 minutes. . The pattern shape obtained on the glass substrate was evaluated in the following manner. The results are shown in Table 8. (Pattern shape evaluation method) The pattern shape 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. 〇: Good linearity X: Poor linearity A: The pattern cannot be observed due to insufficient hardening 128 321778 201100379 [Table 8]

Example Number of Polymer Compositions Used in Example Numbers Example 3 5 4 Example 282 〇 Example 355 Example 283 〇 Example 356 Example 284 〇 Example 357 Example 285 〇 Example 3 5 8 Example 286 〇 Implementation Example 359 Example 287 〇 Example 360 Example 288 〇 Example 361 Example 289 〇 Example 362 Example 290 〇 Example 363 Example 291 〇 Example 364 Example 292 〇 Example 365 Example 293 Example 366 Example 294 〇 Example 367 Example 295 〇 Example 368 Example 296 〇 Example 369 Example 297 〇 Example 370 Example 298 〇 Example 371 Example 299 〇 Example 372 Example 300 〇 Example 373 Example 301 Example 374 Example 302 Example 375 Example 303 Example 376 Example 304 Example 377 Example 305 Example 378 Example 306 Example 379 Example 307 Example 380 贲Example 308 Example 381 Example 309 Example 382 Example 310 Example 383 Example 311 Example 384 Example 312 〇 Example 385 Example 313 〇 Example 386 Example 314 〇 Example 387 Example 315 〇 Example 388 Example 316 〇 Example 389 Example 317 〇 Example 390 Example 318 〇 Example 391 Implementation Example 319 〇Example 392 Example 320 〇Example 393 Example 321 〇Example 394 Example 322 〇Example 394 Example 322 〇Example 395 Example 323 〇Example 396 Example 324 〇

Example number used polymer composition ffl shape embodiment 397 embodiment 325 〇 embodiment 398 embodiment 326 〇 embodiment 399 embodiment 327 〇 embodiment 400 embodiment 328 〇 embodiment 401 embodiment 329 〇 embodiment 402 330 〇 Embodiment 403 Embodiment 331 〇 Embodiment 404 Embodiment 332 〇 Embodiment 405 Embodiment 333 〇 Embodiment 406 Embodiment 334 〇 Embodiment 407 Embodiment 335 〇 Example 408 Example 336 〇 Example 409 Example 337 〇 Embodiment 410 Embodiment 338 〇 Embodiment 411 Embodiment 339 〇 Embodiment 412 Embodiment 340 〇 Embodiment 413 Example 341 〇 Embodiment 414 Example 342 〇 Example 415 Example 343 〇 Example 416 Example 344 〇 Example 417 Example 345 〇 Example 418 Example 346 〇 Example 419 Example 347 〇 Example 420 Example 348 〇 Example 421 Example 349 〇 Example 422 Example 350 〇 Example 423 Example 351 〇 Implementation Example 424 Example 352 〇 Example 425 Example 353 〇 Comparative Example 34 Comparative Example 19 - Comparative Example 35 Comparative Example 20 - Comparative Example 36 Comparative Example 21 - Comparative Example 37 Comparative Example 22 - Comparative Example 38 Comparative Example 23 - Comparative Example 39 Comparative Example 24 - Comparative Example 40 Comparative Example 25 X Comparative Example 41 Comparative Example 2 6 X Comparative Example 42 Comparative Example 27 X Comparative Example 43 Comparative Example 28 X Comparative Example 44 Comparative Example 29 X Comparative Example 45 Comparative Example 3 0 X Comparative Example 46 Comparative Example 31 X Comparative Example 4 7 Comparative Example 3 2 X Comparative Example 48 Comparative Example 3 3 X 129 321778 201100379 The polymerizable composition (Examples 354 to 425) using the radical polymerization initiator (A) of the present invention has a good linearity in the pattern shape obtained on the glass substrate, and as compared with the above, the ester is freely used. 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. &lt;Examples 426 to 498, Comparative Examples 49 to 63&gt; [Pattern-tightness test] The pattern-formed substrates produced in Examples 354 to 425 and Comparative Examples 34 to 48 were at 121 ° C, 100% RH, 2 atm, After the PCT test (pressure cooker test) was carried out under the conditions of 24 hours, a scotch tape was attached to the 20/zm pattern portion, and 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. 〇: The peeling of the 20//m pattern was not confirmed. X: The peeling of the 20/z m pattern was confirmed. One: It was impossible to evaluate due to insufficient hardening. 130 321778 201100379 [Table 9]

Polymer Composition Pattern Shape Example 426 Example 354 Example 427 Example 355 〇 Example 428 Example 356 〇 Example 429 Example 357 〇 Example 430 Example 358 0 Example 4 31 Implementation Example 359 Example 432 Example 360 Example 433 Example 361 Example 434 Example 362 Example 435 Example 363 Example 436 Example 364 Example 437 Example 365 0 Example 438 Example 366 〇 Example 439 Example 367 〇 Example 440 Example 368 〇 Example 441 Example 369 〇 Example 442 Example 370 〇 Example 443 Example 371 〇 Example 444 Example 372 0 Example 445 Example 373 Example 446 Example 374 实施. Example 447 Example 375 〇 Example 448 Example 376 〇 Example 449 Example 377 〇 Example 450 Example 378 〇 Example 451 Example 379 〇 Example 452 Example 380 Example 453 Example 381 0 Example 454 Example 382 〇 Example 455 Example 383 〇 Example 456 Example 384 Example 457 Example 385 〇 Example 458 Example 386 〇 Example 4 5 9 Example 387 〇 Example 460 Example 388 〇 Example 461 Example 389 〇 Example 462 Example 390 〇 Example 463 Example 391 〇Example 464 Example 392 〇1 Example 465 Example 393 〇 Example 466 Example 394 〇 Example 467 Example 394 〇 Example 468 Example 395 〇 Example 469 Example 396 〇

Example Number of Polymer Composition Shapes Used in Example 470 Example 397 〇 Example 4 71 Example 398 〇 Example 472 Example 399 〇 Example 473 Example 400 〇 Example 474 Example 401 〇 Example 475 Example 402 Example 476 Example 403 Example 477 Example 404 Example 478 Example 405 Example 479 Example 406 Example 480 Example 4 0 7 Example 481 Example 482 Example 482 Example 409 〇 Example 483 Example 410 〇 Example 484 Example 411 〇 Example 485 Example 412 〇 Example 486 Example 413 〇 Example 487 Example 414 〇 Example 488 Example 41 〇 Example 489 Example 416 〇Example 490 Example 417 〇Example 491 Example 418 〇Example 492 Example 419 〇Example 493 Example 420 〇Example 494 Example 421 〇Example 495 Example 422 〇Example 496 Implementation Example 423 〇 Example 497 Example 424 〇 Example 498 Example 425 〇 Comparative Example 49 Comparative Example 34 - Comparative Example 5 0 ratio Example 35 - Comparative Example 51 Comparative Example 36 - Comparative Example 52 Comparative Example 37 - Comparative Example 53 Comparative Example 38 - Comparative Example 54 Comparative Example 39 - Comparative Example 55 Comparative Example 40 X Comparative Example 56 Comparative Example 41 X Comparative Example 5 7 Comparison Example 42 X Comparative Example 5 8 Comparative Example 43 X Comparative Example 5 9 Comparative Example 44 X Comparative Example 60 Comparative Example 4 5 X Comparative Example 61 Comparative Example 46 X Comparative Example 62 Comparative Example 47 X Comparative Example 63 Comparative Example 48 X 131 321778 201100379 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 when the polymerizable composition of the present invention is used, the comparative example is used. 49 to 63), the adhesion of the pattern to the substrate could not be obtained. &lt;Examples 499 to 606, and Comparative Examples 64 to 91 &gt; A pigment dispersion was prepared as follows, and then, a color-developing polymer compound containing the pigment dispersion was prepared. [Preparation of Red Pigment Dispersion] The mixture of the following composition was uniformly stirred and mixed, and then dispersed by an Eiger mill (Eiger mi 1 U (mini model M-250 MK 11 manufactured by Eiger Japan Co., Ltd.) for 2 hours, The red pigment dispersion was prepared by filtration with a filter of 5 // m. Diketopyrrolopyrrole pigment (CI Pigment Red 254) (Irgaphor Red B-CF by Ciba Specialty Chemicals Co., Ltd.) 11. 0 weight 0重量份。 The ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone ketone

[Preparation of Green Pigment Dispersion] A mixture of the following compositions was finely prepared in the same manner as the red pigment dispersion 132 321778 201100379 to prepare a green pigment dispersion. Copper halide phthalocyanine pigment (CI Pigment Green 36) (Toyo Ink Manufacturing Co., Ltd. rLi〇n〇1 Green 6YK) 71 parts by weight of monoazo pigment (CI Pigment Yellow 15〇) ("E4GN-GT" manufactured by LANXESS) 0重量份。 0 parts by weight of the following structure of the triterpenoid pigment derivative 1. 0 parts by weight

Acrylic resin solution cyclohexanone 40. 0 parts by weight 48. 0 parts by weight c2h5

[Preparation of coloring pigment dispersion] A mixture of the following composition was operated in the same manner as in the red pigment dispersion to prepare a blue pigment dispersion. 0重量份以下的结构的。 The ε-type copper phthalocyanine pigment (c. I. Pigment Blue 15: 6) ("Heliogen Blue L-6700F" by BASF) 11.0 parts by weight of 1.0 parts by weight of 40. 0 parts by weight of 48. 0 parts by weight of the following structure Phthalocyanine pigment derivative alkenoic acid resin solution cyclohexanone 133 321778 201100379 wide 3

Cu-pc: copper phthalocyanine residue [Preparation of black pigment dispersion] A mixture of the following compositions is prepared in the same manner as the work pigment dispersion of 盥^ χΑζ ^ , , , , , Into a black pigment dispersion.式 12 12 4 4 4 48 48 48 48 48 48 48 48 48 48 48 48 48 48 48 48 48 48 48 48 48 48 48 48 」 」 」 」 」 」 」 」 」 」 」 」 」 」 」 」 」 」 」 」 」 」 」 」 」 」 」红色 红色 红色 红色 红色 红色 红色 红色 红色 红色 红色 红色 红色 红色 红色 红色 红色 红色 红色 红色 红色 红色 红色 红色 红色 红色 红色 红色 红色 红色 红色 红色 红色 红色 红色 红色 红色 红色 红色 红色 红色 红色 红色 红色 红色 红色 红色 红色 红色 红色 红色 红色 红色 红色 红色 红色 红色 红色 红色 红色The mixture of U and I parts was stirred and mixed uniformly, and the red polymerizable composition of the present invention (Example 499) was obtained by the tear of the transition of 1 // m (Example 499). Composition: 4 parts by weight of a blue pigment dispersion, 4 parts by weight of an acrylic resin solution (2), and 4 parts by weight of methacrylic acid diacid (Xinzhongcun Chemical Ε ΑΤΜΡΤ) The polymerization initiator 〇; 4 parts by weight of the compound (1), and 25 parts by weight of the cyclohexyl group (4) are mixed until homogeneous, and filtered by a 1/zm filter to obtain the blue composition of the present invention (Example 500) ) : - λ σ 321778 134 201100379 [Green polymerizable composition] Green pigment dispersion 67 3 parts by weight of the acrylic resin solution "parts by weight, trimethylolpropane triacrylate ("ESTER" manufactured by Shin-Nakamura Chemical Co., Ltd.), and 2 parts by weight of the compound (1) as a radical polymerization initiator 18 parts by weight of cyclohexanone was stirred and mixed until homogeneous, and then filtered with a filter of 1 to obtain a green polymerizable composition of the present invention (Example 501). &amp; [Black polymerizable composition] 分散 Disperse black pigment 7 parts by weight of a solution of a propionic acid resin solution (2), 9 parts by weight, and 3 parts by weight of trimethyl sulfonium triacetate ("Kappa ESTER" manufactured by Shin-Nakamura Chemical Co., Ltd.) as a radical polymerization The mixture of the starting agent (a), the compound (1), 3 parts by weight, and 13 parts by weight of cyclohexanone, were stirred and mixed until homogeneous, and then filtered through a filter of 1 Am to obtain a green polymerizable composition of the present invention (Example) 502) The colored polymerizable group of the examples 503 to 606 and the comparative examples 64 to 91 were produced as follows. [Red polymerizable composition] In addition to being used as a radical polymerization initiator (A) Compound (1) is replaced by the one shown in Table 10. The red polymerizable composition shown in Table 10 was obtained in the same manner as in Example 499. [Blue polymerizable composition] In addition to the compound (1) which is a radical polymerization initiator (A) The blue polymerizable composition shown in Table 10 was obtained in the same manner as in Example 500 except that the compound shown in Table 10 was used. 135 321778 201100379 [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) of the starting agent (A) was replaced by the compound shown in Table 10. [Black polymerizable composition] The same procedure as in Example 5A was carried out except that the compound as the radical polymerization initiator (A) was replaced with the compound shown in Table 10, and the black polymerization shown in Table 10 was obtained. Sexual composition. 321778 136 201100379 [Table 10] Example No. Radical polymerization initiator coloring polymerization. Modulation of composition color Example 503 Compound (2) Same as Example 499 Red Example 504 Same as Example 500 Blue Example 505 Example 501 is the same green embodiment 506 is the same as the embodiment 502. The black embodiment 507 4 is the same as the embodiment 499. The red embodiment 508 is the same as the embodiment 500. The blue embodiment 509 is the same as the embodiment 501. 510 is the same as Example 502. Black Example 511 Compound (24) Same as Example 499 Red Example 512 Same as Example 500 Blue Example 513 Same as Example 501 Green Example 514 Same as Example 502 Black Example 51 5 Compound (174) Same as Example 499 Red Example 516 Same as Example 500 Blue Example 517 Same as Example 501 Green Example 518 Same as Example 502 Black 贲 Example 519 Compound (44) and Example 499 Similarly, the red embodiment 520 is the same as the embodiment 500, the blue embodiment 521 is the same as the embodiment 501, the green embodiment 522 is the same as the embodiment 502, and the black embodiment 523 is the same. Compound (53) is the same as Example 499. Red Example 524 is the same as Example 500. Blue Example 525 is the same as Example 501. Green Example 526 is the same as Example 502. Black Example 527 Compound (65) is as red as Example 499. Example 5 2 8 Blue as in Example 500 Example 529 Same as Example 501 Green Example 5 3 0 Same as Example 502 Black Example 531 Compound (195) Same as Example 499 Red Example 532 Blue Example 533 is the same as Example 500. Green Example 534 is the same as Example 502. Black Example 535 Compound (85) Same as Example 499 Red Example 536 Same as Example 500 Blue Example 537 Example 501 is similar to Green Example 538 is the same as Example 502. Black Example 539 Compound (187) is the same as Example 499. Red Example 540 is the same as Example 500. Example 541 is the same as Example 501. Green Example 542 Example 502 is the same as Example 543. Compound (109) is the same as Example 499. Example 544 is the same as Example 500. Blue Example 5 4 5 and Example 501 Example Green Example 5 4 6 Example No. 502, Black Example No. Radical Polymerization Starter Coloring Polymerization Composition Color Example 547 Compound (119) Same as Example 499 Red Example 548 Same as Example 500 Blue Example 549 Same as Example 501 Green Example 550 Same as Example 502 Black Example 551 Compound (100) Same as Example 499 Red Example 552 Same as Example 500 Blue Example 553 is the same green as Example 501 Example 554 is the same as Example 502. Black Example 5 5 5 Compound (234) Same as Example 499 Red Example 5 5 6 Same as Example 500 Blue Example 557 Same as Example 50 Green Example 558 and Implementation Example 502 likewise Black Example 559 Compound (124) Same as Example 499 Red Example 560 Same as Example 500 Blue Example 561 Same as Example 501 Green Example 562 Same as Example 502 Black Example 563 Compound (134 The same as in the embodiment 499, the red embodiment 564 is the same as the embodiment 500, the blue embodiment, the fifth embodiment, the same as the embodiment 501, the green embodiment 566 and the real Example 502 likewise Black Example 567 Compound (145) Same as Example 499 Red Example 568 Same as Example 500 Blue Example 569 Same as Example 501 Green Example 570 Same as Example 502 Black Example 571 Compound (150 The same as Example 499, the same red embodiment 572 is the same as the embodiment 500, the blue embodiment 573 is the same as the embodiment 501, the green embodiment 574 is the same as the embodiment 502, the black embodiment 575 compound (157) is the same as the embodiment 499, the red embodiment 576 The same as Example 500, Blue Example 577 is the same as Example 501. Green Example 578 is the same as Example 502. Black Example 579 Compound (244) Same as Example 499 Red Example 580 is the same as Example 500 Blue Example 581 and Example 501 is similar to Green Example 582 is the same as Example 502. Black Example 583 Compound (252) Same as Example 499 Red Example 584 Same as Example 500 Blue Example 585 Same as Example 501 Green Example 586 and Implementation Example 502 likewise black Example 587 Compound (268) Same as Example 499 Red Example 588 is as blue as Example 500 Example 589 is the same as Example 501. Green Example 590 is the same as Example 502. Black 137 321778 201100379 Example No. Radical Polymerization Initiation 剤 Coloring Polymer Composition Modulation Method Color Example 591 is the same as Example 499 — '- Red· EXAMPLE 592 The same procedure as in Example 500 - Basket Example 593 (280) is as green as Example 501 - Example 594 is the same as Example 502. Black Example 5 9 5 Same as Example 499. Fee. Example 596 Compound The same as Example 500. Example 597 (291) The same as Example 501, Green Example 598 is the same as Example 502; tiT - Black Example 599 is the same as Example 499. h. Example 600 The compound is the same as Example 500. Example 601 (298) The same as Example 50, Green Example 602 is the same as Example 502. *----- Black Example 603 is the same as Example 499. The red exemplified compound 604 is the same as Example 500. Example 605 (300) The same as Example 501 - 丨 - Green Example 606 is the same as Example 502. Black Comparative Example 6 4 Same as Example 499 Red Comparative Example 6 5 Compound In the same manner as in Example 500, Comparative Example 66 (310) is the same as Example 50, Green Comparative Example 67, and Example 502 are the same as the number of the radical polymerization initiator coloring polymerization composition. Color Comparison Example 72 4 composition (311) The same as Example 499, the red comparative example 73 is the same as the embodiment 500, the blue comparative example 74 is the same as the embodiment 50, the same green comparative example 7 5 is the same as the embodiment 502, the black comparative example 7 6 compound (312) and the reward Example 499 is similarly red Comparative Example 77 is the same as Example 500. Blue Comparative Example 78 is the same as Example 501. Green Comparative Example 79 is the same as Example 502. Black Comparative Example 80 Compound (313) Same as Example 499 Red Comparative Example 81 and Implementation Example 500 Same Blue Comparative Example 82 Same as Example 501 Green Comparative Example 83 Same as Example 502 Black Comparative Example 84 Compound (314) Same as Example 499 Red Comparative Example 85 Same as Example 500 Comparative Example 8 6 and Implementation Example 501 is the same as Green Comparative Example 8 7 is the same as Example 502. Black Comparative Example 88 Compound (315) Same as Example 499 Red Comparative Example 89 Same as Example 500 Blue Comparative Example 90 and Implementation 501 is the same green _ Comparative Example 91 is as black as Example 502 [pattern formation of the filter segments and the black matrix] so that the thicknesses of the respective colors after post-baking become the film thicknesses shown in Table u, respectively. The obtained colored polymerizable composition was applied by spin coating to a glass substrate of 10 cm x 10 cm and then prebaked at 70 C for 15 minutes in a clean oven (ciean 〇ven). Next, after the substrate was cooled to room temperature, ultraviolet light exposure 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, and then washed with ion-exchanged water and air-dried. Thereafter, it was 23 Torr in a dust-free oven. 〇 After baking for 30 minutes, a stripe-shaped filter segment is formed on the substrate. 321778 138 201100379 [Table 11] Red, blue, green and black film thickness (/zm) 1. 40 1. 80 1. 80 1.10 Film thickness: film thickness of each color filter segment and black matrix [Evaluation] The sensitivity of the resulting colored polymerizable composition and the filter segment or black matrix formed by the above method were evaluated according to the following method. The shape of the pattern. The results are shown in Table 12. (Sensitivity) When a pattern of a filter segment or a black matrix is formed depending on 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 40 mJ/cm2 〇: 40 mJ/cm2 or more and less than 80 mJ/cm2: 80 mJ/cm2 or more and less than 250 mJ/cm2 x : 250 mJ/cm2 or more (pattern shape) The pattern shape of the filter segment or the 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. 〇: Good linearity △: Partially poor linearity 139 321778 201100379 X : Poor linearity For (2), it was observed and evaluated by scanning electron microscopy (SEM). The rating of the assessment is as follows. 〇:forward tapered shape △: non-tapered shape x · inverse tapered shape (remaining tapered shape) to exposure (100 mJ/cm2) The ratio of the film thickness measured after the image and the post-baking step to the film thickness measured after the coating film of each of the colored polymerizable compositions was dried and dried was the residual film ratio. The rating of the assessment is as follows. 〇: 70% or more X : Less than 70% 140 321778 201100379 [Table 12]

Example No. Radical Polymerization Starter Color Sensitivity Pattern Linear Circle Section Shape Residual Film Rate Example 499 Compound (1) Red ◎ 〇 0 〇 Example 500 Blue ◎ 〇〇〇 Example 501 Green ◎ 〇 0 〇 Example 502 Black ◎ 〇 0 〇 Example 503 Compound (2) Red ◎ 〇 0 〇 Example 504 Blue ◎ 〇〇〇 Example 505 Green ◎ 〇〇〇 Example 506 Black ◎ 〇〇〇 Example 507 Compound 03) Red ◎ 〇0 Example 508 Blue ◎ 〇〇〇 Example 509 Green ◎ Example 510 Black ◎ 〇〇〇 Example 511 Compound (24) Red ◎ 〇〇〇 Example 512 Blue ◎ 〇〇〇 Example 513 Green ◎ Example 514: Black ◎ Example 515 Compound (174) Red ◎ Example 516 Blue ◎ Example 517 Green ◎ Example 518 Black 〇〇〇〇贲 Example 519 Compound (44) Red ◎ 〇〇〇 Example 520 Blue ◎ 〇〇〇 Example 521 Green ◎ 〇〇〇 Example 522 Black ◎ 〇 0 〇 Example 5 23 Compound (53) Red ◎ 〇〇〇 Example 524 blue ◎ 〇〇〇 Example 525 Green ◎ 〇〇〇 Example 526 Black ◎ 〇〇〇 Example 527 Compound (65) Red ◎ 〇〇〇 Example 528 Blue 〇〇〇 Example 529 Green ◎ Example 530 Black ◎ Example 531 Compound (195) Red ◎ 〇〇〇 Example 532 Blue ◎ 〇 0 〇 Example 533 Green ◎ 〇〇〇 Example 534 black ◎ 〇〇〇 Example 535 Compound (85) Red ◎ 〇〇〇 Example 536 Blue ◎ 〇〇〇 Example 537 Green 〇〇〇〇 Example 538 Black 〇〇〇〇 Example 539 Compound (187) Red ◎ Example 540 Blue 〇〇〇〇 Example 541 Green 〇〇〇〇 Example 542 〇 〇. 〇〇〇 Example No. Radical polymerization initiator Color sensitivity pattern Linear pattern Carrier shape Residual film rate implementation Example 543 Compound (109) Red ◎ 〇〇〇 Example 544 Blue ◎ 〇〇〇 Example 545 Green 〇〇〇〇 Example 546 Black 〇〇〇〇 Example 547 Compound (119) Red hydrazine Example 548 Blue ◎ 〇〇〇 Example 549 Green 〇〇〇〇 Example 550 Black 〇〇〇〇 Example 551 Compound (100) Red ◎ 〇〇〇 Example 552 Blue ◎ 〇〇〇 Example 553 Green 〇〇〇〇 Example 554 Black 〇〇〇〇 Example 555 Compound (234) Red 〇〇〇〇 Example 556 Blue ◎ 〇〇〇 Example 557 Green 〇〇〇〇 implementation Example 558 Black 〇〇〇〇 Example 559 Compound (124) Red ◎ 〇〇〇 Example 560 Blue ◎ 〇〇〇 Example 561 Recorded Example 562 Black 〇〇〇〇 Example 563 Compound (134) Hung Hom Example 564 Blue ◎ 〇〇〇 Example 565 Green 〇〇〇〇 Example 566 〇〇〇〇贲 〇〇〇〇贲 Example 567 Compound (145) Red ◎ 〇〇〇 Example 568 Blue ◎ 〇〇〇 Example 569 Green 〇〇〇〇 Example 570 Black 〇〇〇〇 Example 571 Compound (150) Red ◎ 〇〇〇 Example 572 Blue 〇〇〇〇 Example 573 Green 〇〇〇〇 Example 574 Black 〇〇〇〇 Example 575 Compound (157) Red 〇〇〇〇 Example 576 Blue 〇〇〇〇 Example 577 Recorded Example 578 Black 〇〇〇 Example 579 Compound (244) Red ◎ 〇〇 0 Example 580 Blue ◎ 〇〇〇 Example 581 Green ◎ 〇〇〇 Example 582 Black ◎ 〇〇〇 Example 583 Compound (252) Red ◎ 〇〇〇 Example 584 Blue ◎ 〇〇〇 Example 585 Record ◎ 〇〇〇贲 Example 586 Black ◎ 〇〇〇 141 321778 201100379

Example No. Free Radical Coupled Starter Color Sensitivity Circle Linear Pattern Cut Shape Residual Film Rate Example 587 Compound (268) Red ◎ 〇〇〇 Example 588 Blue ◎ 〇〇〇 Example 589 Green ◎ 〇〇〇 Example 590: Black ◎ 〇〇〇 Example 591 Compound (280) Red ◎ 〇〇〇 Example 592 Μ ◎ 〇〇〇 Example 593 Green ◎ 〇〇〇 Example 594 Black ◎ 〇〇〇 Example 595 Compound (291 Red 〇〇〇 〇〇〇 Example 596 Basket ◎ 〇〇〇 Example 597 Green 〇〇〇〇 Example 598 Black 〇〇〇〇 Example 599 Compound (298) Red 〇〇〇〇 Example 600 Blue ◎ 〇〇〇 Example 601 Green 0 〇〇〇 Example 602 Black 〇〇〇〇 Example 603 Compound (300) Red 〇〇〇〇 Example 604 Blue 〇〇〇〇 Example 605 Green 〇〇〇〇 Example 606 Black 〇〇 〇〇Comparative Example 64 Compound (310) Red XXXX Comparative Example 65 Μ XXXX t匕 Comparative Example 66 Green XXX .X Comparative Example 67 Black XXXX

Example No. Radical Polymerization Starter Color Sensitivity Ffi Case Linear Pattern Carrier Shape Residual Film Rate Comparative Example 72 Compound ¢ 311) Red XXXX Comparative Example 73 Blue XXXX Comparative Example 74 Green XXXX Comparative Example 75 Black XXXX Comparative Example 76 Compound ( 312) Red XXXX Comparative Example 77 Blue XXXX Comparative Example 78 Green XXXX Comparative Example 79 Black XXXX Comparative Example 80 Compound (313) Red Δ Δ X 〇 Comparative Example 81 Blue Δ Δ Δ 〇 Comparative Example 82 Green XXXX Comparative Example 83 Black XXXX Comparative Example 84 Compound (314) Red Δ XX 〇 Comparative Example 85 Blue Δ Δ Δ 〇 Comparative Example 86 Green XXXX Comparative Example 87 Black XXXX Comparative Example 88 Compound (315) Red Δ Δ Δ 〇 Comparative Example 89 Blue Δ Δ Δ 〇 ratio Example 90 Wire Δ Δ X 〇 Comparative Example 91 Black XXXX As shown in Table 12, the coloring polymerizable composition of the radical polymerization initiator (A) represented by the formula (1) was used (Examples 499 to 606). It is very high-sensitivity, and the linearity and cross-sectional shape of the obtained pattern are also good. In contrast, the coloring polymerization of a known oxime ester compound as a radical polymerization initiator is used. To a composition (Comparative Examples 64 to 91) based differential sensitivity, linearity, and the sectional shape of the pattern are likewise 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 coloring polymerizable composition (Comparative Examples 64 to 91) using a known compound as a radical polymerization initiator was inferior in residual film rate, and was not sufficient in coating film formation 142 321778 201100379. level. It is understood that the photopolymerizable composition using the compound of the present invention as a radical polymerization initiator is curable in comparison with the photopolymerizable property of a conventionally known radical polymerization initiator and a sensitizer. The above is superior. It can be seen that J can contribute to higher sensitivity by the high contribution to the hardenability, and the compound of the present invention having such high hardenability can absorb light well and can greatly improve the efficiency of radical generation. It is presumed that the carbazole chromophore group represented by the formula (1) has an excellent effect of multiplying the erbium-like structure which can be decomposed by light irradiation to generate a large amount of radicals. (industrial availability) -tr (4) related to a novel (four)-based compound, and the use of the (four) 'published (A) ¥ self-based polymerization initiator (A), and the use of the radical polymerization initiation ^ A composition, a negative resist using the polymerizable composition, and a pattern forming method using the negative type. The system of the present invention functions as a zero energy for irradiation. Therefore, the radical-generating polymerization initiator (1) having the sensitivity of the pendant is used, and the free radical of the present invention which can illuminate the P compound is used as a catalyst, and the energy generated by the energy line is rapidly expected to realize the energy supply for various uses. The results of the joint reaction can be divided into various uses: sensitization, or the sensitization of the reaction or the increase of the touch. According to this Wei, I expect high, reaction molding resin, washing scale tree month t, ^ enumeration such as: using polymerization or cross-linking. Branch polymer resin, printing ink, enamel resin, sealant, tooth light tree Moonlight, color proof for printing, t ink, paint, resist for beta color filter for printing plate, black moment 321778 143 201100379 array resistance #!, optical room for liquid crystal (four), rear projection fiber, plasma Display crying 咏 忝 # 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 Adhesive material, coating agent, powder coating, adhesive, use: 脬 Dong type agent, optical recording medium, adhesive, peel coating agent, composition of heart::::r material, None of the various devices. [Main component? Tiger description] None. 321778 144

Claims (1)

201100379 Patent application scope: Compounds of the following formula (1) Alkenyl, substituted or substituted alkyl, substituted or unsubstituted alkoxy, substituted or unsubstituted: aryl, substituted silk substituted pure, substituted or unsubstituted a heterocyclic 3-, substituted or unsubstituted heterocyclic oxy-substituted or unsubstituted sulphur; (alkylsulfanyl), substituted or unsubstituted arylthio, substituted or substituted hydrazine substituted alkyl sulfonyl, substituted or substituted No 4 aryl amide base, #代代或未代院基基 _ (4)kylsulf〇nyl), substituted or unsubstituted aryl yl κ or unsubstituted fluorenyl, substituted or unsubstituted transradical, Substituted or substituted, unsubstituted or unsubstituted phosphazene (ph〇sphin〇yi) ^ or unsubstituted methoxymethyl, or substituted or unsubstituted amine R2 represents the substituted or unsubstituted county r/: Oxy, or dibasic substituted or unsubstituted heterocyclic 321778 145 201100379 Unsubstituted heterocyclic oxy, substituted or unsubstituted arylthio, substituted or unsubstituted =4, substituted or not Substituted green subunit, substituted = sulfanyl, substituted or substituted or unsubstituted aryl group, substituted a thiol group or a substituted amine group; an unsubstituted oxime group; R3 to R5 each independently represent a hydrogen atom, an unsubstituted or unsubstituted dilute group, a substituted or unsubstituted alkyl group: An unsubstituted alkoxy group, a substituted or unsubstituted aryl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted heterocyclic group, a substituted or unsubstituted heterocyclic oxy group, a substituted or unsubstituted a base group, a substituted or unsubstituted arylthio group, a substituted or unsubstituted hetero- or a substituted-substituted amine group; R6 to R9 each independently represent a hydrogen atom, a _ atom, a cyano group, a nucleus alkyl group, a substituent Or unsubstituted alkyl, substituted or unsubstituted alkoxy, substituted or unsubstituted aryl, substituted or unsubstituted aryloxy, substituted or unsubstituted heterocyclic, substituted or unsubstituted heteroepoxy a substituted or unsubstituted thiol group, a substituted or unsubstituted sulphur group, a substituted or unsubstituted ash, a substituted or unsubstituted aryl group, a substituted or unsubstituted aryl group Sulfosyl, substituted or unsubstituted alkylsulfonyl, substituted or unsubstituted arylsulfonyl a mercapto group, a substituted or unsubstituted amino group, or a substituent represented by the following formula (2), wherein R2' Ο ^C~C=N-〇-C-R1 η R1, and R2 have the same meanings as R1 and R2; 321778 146 201100379 R to R each independently a gas atom, a halogen atom, a cyano group, a nitro group, an alkyl group, a substituted or unsubstituted alkyl sulfinyl group. And a substituted unsubstituted arylsulfinylene group, a substituted or unsubstituted alkylsulfonyl group, a substituted or unsubstituted arylsulfonyl group, or a substituted or unsubstituted fluorenyl group, but R1. Not all of them are hydrogen atoms at the same time. 2. The compound of claim 1, wherein the above ^. At least one of them is a nitro group or a substituted or unsubstituted disc group. The compound according to claim 1 or 2, wherein at least one of the above Ri〇 to R14 is a nitro group or a group represented by the following formula (3): However, in the formula, R15 to R19 each independently represent a hydrogen atom, a halogen atom, a cyano group, a nitro group, an alkyl group, a substituted or unsubstituted alkyl group, a substituted C) or an unsubstituted alkoxy group, a substituted or not a substituted 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, 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. 4. A compound according to claim 3, wherein the ri2 is a nitro group or a group represented by the above formula (3). • 5. A kind of free radical t-initiator (A), which contains the compound of claim 1 321778 147 201100379 to 4 items. A polymerizable composition comprising the radical polymerization initiator (A) and the radical polymerizable compound (β) of claim 5 of the patent application. 7. The polymerizable composition according to item 6 of the patent application, wherein the sensitizer (C) is further contained. 8. The polymerizable composition according to claim 6 or 7, wherein the color component (D) is compounded. 9. The polymerizable composition according to any one of Items 6 to 8, wherein the alkali-soluble resin (Ε) is further contained. 10. A negative-type resist, which is a polymerizable composition containing the ninth application patent. The polymerizable composition of any one of the sixth to ninth aspects of the invention is irradiated with an energy ray to polymerize it. 12. A method for forming an image pattern, characterized in that a negative resist of item 10 of the patent scope is laminated on a substrate, partially irradiated with an energy ray to be polymerized, and an alkaline developing solution is used. The unirradiated portion is removed. 13. The image pattern is formed according to the method of forming the image pattern of claim 12 of the patent application. 321778 148 201100379 ' IV. Designated representative map: There is no schema in this case. (1) The representative representative of the case is: ( ). (2) A brief description of the symbol of the representative figure: Ο 5. If there is a chemical formula in this case, please disclose the chemical formula that best shows the characteristics of the invention: R12 3 321778 201100379 111〇°° "一...-羽" 6. Description of the invention: ^ ^ ? . £ , [Technical field to which the invention pertains] &gt; The present invention relates to an oxime ester compound, a radical polymerization containing the oxime ester compound An initiator, a polymerizable composition using the radical polymerization initiator, a negative resist using the polymerizable composition, and an image pattern forming method using the negative resist. The present invention relates to: "molding resin, cast resin, resin for stereolithography, sealant, dental polymer resin, enamel printing ink, paint, photosensitive resin for printing plate, printing" Color proof, color filter resist, black matrix resist, liquid crystal optical spacer, rear-projection screen material, fiber optics, electricity For slab display, rib material, dry film resist, printed circuit board. Resist, solder resist, semiconductor photoresist (photoresist) Resistor for microelectronics, resist for manufacturing parts for micromachines, resist for residuals, micro lens array (micr〇lenS array), insulating material, hologram material, optical switch (〇pticai switch) , waveguide material, coating agent (overc〇at agent), powder coating, adhesive, adhesive, release agent, optical recording medium, adhesive, release coating agent, I use microcapsule image technology material The composition to be used, various devices, etc. [Prior Art] Conventionally, a certain oxime ester compound has been known to function as a radical polymerization and a two-initiator (see Non-Patent Document 1 and Patent Document 1). ...2&gt;, /^i-type or negative-type sensible S-polyimine precursor precursor composition &quot; soil 5 starter system reveals such as α-ketoester (a-ketoxime 4 321778 201100379 β 乂The substituted or unsubstituted alkoxy group in η R1 may, for example, be a linear, branched, monocyclic or condensed polycyclic alkoxy group having a carbon number of 1 to 18, or a carbon number of 2 to 18 and Linear, branched, monocyclic or condensed containing one or more ether linkages as appropriate A polycyclic alkoxy group. Specific examples of the linear, branched, monocyclic or condensed polycyclic alkoxy group having 1 to 18 carbon atoms include a decyloxy group, an ethoxy group, a propoxy group, and the like. Butoxy, pentyloxy, hexyloxy 'heptyloxy, octyloxy, nonyloxy, decyloxy, dodecyloxy' octadecyloxy, isopropoxy, isobutoxy , isopentyloxy, second butoxy, third butoxy, second pentyloxy, third pentyloxy, third octyloxy, neopentyloxy, cyclopropoxy, cyclobutoxy And a cyclopentyloxy group, a cyclohexyloxy group, an adamantyloxy group, a norbornyloxy group, a borneoloxy group, a 4-fluorenylcyclohexyloxy group, etc., but it is not limited to this. 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-CH2-O-CH3'-O-CH2-CH2-O. -CH2-CH3' -O-CH2-CH2-CH2-O-CH2 -CH3, -0-(CH2-CH2-0)n-CH3 (here, η is 1 to 8), -0-(CH2- CH2-CH2-0)h-CH3 (here, ιώ is 1 to 5), -〇-CH2-CH(CH3)-0-CH2-CH3, -0-CH2-CH-(0CH3)2, etc., but It is not limited to this. 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 the invention is not limited to the patent application No. 99103470 (99) May 3 from 1 Λ 201100379 ψ » This. - β WW』 The substituted or unsubstituted aryl group in R 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 naphthyl group, a 2-indolyl group, a 1-indenyl group, a 9-fluorenyl group, a 2-phenanthrenyl group, a 3-phenanthrenyl group, a 9-phenanthryl group, a diterpene group, and a 5-di-tetraphenyl group. (5-naphthacenyl), 1-mercapto, 2-azulenyl, 1, acenaphthyl, 2-g-based, 9-caiyl, 3-mercapto, ortho-phenyl, Phenylphenyl, p-phenylene, 2,3-diindole, (2,3_Xylyl), 2, diphenyl, 2,4,6-trimethylphenyl (mesityl), p-cumene (P~cumenyl), p-dodecylphenyl'p-cyclohexylphenyl, 4-biphenyl, o-fluorophenyl, m-phenyl, p-bromophenyl, p-light Phenyl, m-phenylene, o-cyanophenyl, p-cyanophenyl, m-nitro-based, m-azidophenyl (ffl-azid〇phenyl), etc., but not limited This is the case. The substituted or unsubstituted aryloxy group in the above may, for example, be a monocyclic or condensed polycyclic aryloxy group having 6 to 18 carbon atoms. Specific examples thereof include a phenoxy group, a naphthyloxy group, a 2-naphthyloxy group, a 9-decyloxy group, a 9-phenanthryloxy group, a phenanthoxy group, and a 5-condensed tetraphenoxy '1-oxime oxygen. The base, 2_oxy group, diterpeneoxy group, 9-mercaptooxy group, etc., k are not limited thereto. The substituted or unsubstituted heterocyclic group in the soil may, for example, be an aromatic or aliphatic having a carbon number of 4 to 24 containing a nitrogen atom, a milk atom, a sulfur atom or a dish atom, 321778 (Revised Edition)] 6 201100379 v * to 30 The arylsulfinyl group. Specific examples thereof include a phenylsulfinyl group, a 1-naphthyl anthracene group, a 2-naphthyl phthalic acid group, a 2-gas phenyl sulfonium group, and a 2-nonylphenyl sulfinium sulfonate. , 2-methoxyphenylsulfinyl, 2-butoxyphenylsulfinyl, 3-chlorophenylsulfinyl, 3-trifluoromethylphenylsulfinyl, fluorenyl, 3-cyanophenylsulfinyl, 3-nitrophenylsulfinyl, 4-fluoro, phenylsulfinyl, 4-cyanophenylsulfinyl, 4-methoxybenzene a sulfinyl group, a 4-sulfonylphenylsulfinyl group, a 4-phenylthiophenylsulfinyl group, a D 4-didecylaminophenylsulfinyl group, etc., but is not limited thereto This is the case. The substituted or unsubstituted alkylsulfonyl group in R1 may, for example, be an alkylsulfonyl group having 1 to 20 carbon atoms. Specific examples thereof include mercaptosulfonyl, ethylsulfonyl, propylsulfonyl, isopropylsulfonyl, butylsulfonyl, hexylsulfonyl, cyclohexylsulfonyl, and octyl Alkylsulfonyl '2-ethylhexylsulfonyl, fluorenylsulfonyl, fluorenylsulfonyl, octadecylsulfonyl, cyanosulfonyl, fluorenyl hydrazine A sulfonyl group or the like, but is not limited thereto. The substituted or unsubstituted arylsulfonyl group in R1 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-nonylphenylsulfonyl group, and a 2-hydrazine group. Oxyphenylsulfonyl, 2-butoxyphenylsulfonyl, 3-chlorophenylsulfonyl, 3-trifluorodecylphenylsulfonyl, 3-cyanophenylsulfonyl, 3-Nitrophenylsulfonyl, 4-fluorophenylsulfonate, 4-cyanophenylsulfonyl, 4-nonyloxyphenylsulfonyl, 4-decylthiophenylsulfonyl And 4-phenylthiophenylsulfonyl group, 4-didecylaminophenylsulfonyl group, etc., but it is not limited to this. The substituted or unsubstituted thiol group in R1 may, for example, be a linear, branched, monocyclic or condensed polycyclic lipid having a hydrogen atom or a carbon number of 1 to 18] 321778 201100379 Patent Application a group of (4) groups; a group substituted by an alkoxy group of 2 to 20; a group bonded to a mono- or condensed polycyclic aryl group having 6 to 18 carbon atoms; a single carbon number of 6 to 18 t a prison group substituted with a cyclic or condensed polycyclic aryloxy group; combined with a radical containing a nitrogen atom, an oxygen atom, a sulfur atom, a phosphorus atom having a carbon number of 4 to 18 or a condensed poly() group. Specific examples thereof include a mercapto group, an acetate group, a propionyl group, a mercapto group, an isobutyl group, an anthranyl group, an isovaleryl group, a piValyl group, a lauryl group, and a nutmeg. Myristoyl, palmitoyl, stearyl, cyclopentylcarbonyl, cyclohexylcarbonyl, acryl oxime, methacryl fluorenyl, crotonoyl, isocrotonyl , oil sulfhydryl, cimianioyl, decyloxycarbonyl, ethoxycarbonyl, propoxycarbonyl, butoxycarbonyl, hexyloxycarbonyl, octyloxycarbonyl, decyloxycarbonyl, octadecyloxy Base Ik group, di It methoxy &amp; base, benzinyl group (benZ〇y丨), phenethyl fluorenyl (10) ―), naphthyl fluorenyl group (bu naphth () yl), naphthoic acid group, two Mercaptocarbonyl 'phenoxycarbonyl' 4-methylphenoxylate, 3_county, -carbyl, 4-dimethylaminophenoxyline, 2~methylamidophenoxy county, Qin 2 Amethyst ethoxylate, 9~ oxime base, 31W base (3-fyl), 2 sold base (Μ-), nicotinoyl 'isonicotinium thiol, etc., 彳It is not limited to this. The substituted or unsubstituted linear oxy group in R may, for example, be a carbonyloxy group having 2 to 20 carbon atoms. Specific examples thereof include an anthraceneoxy group, a (tetra)oxy group, a butyl group, a pentyloxy group, a trifluoromethylcarbonyloxy group, an oxyoxy group, a 2-naphthyloxy group and the like. The substituted or green substituted silk in the decyloxy group, the oxalate group R] can be used as an amine group, an amine group, 32] 77S (revision) 20 201100379 dialkylamino group, arylamine group, diaryl Alkylamino group, alkylarylamino group, benzylamino group, bisarylamino group and the like. Here, the alkylamino 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 or an octyl decylamino group. Mercaptoamine, mercaptoamine, dodecylamino, octadecylamino, ^isopropylamino, isobutylamino, isoamylamino, second butylamino, third Butylamino, second amylamino, third amylamino, tert-octyl0-amino, neopentylamino, cyclopropylamino, cyclobutylamino, cyclopentylamino And a cyclohexylamino group, a cycloheptylamino group, a cyclooctylamino group, a cyclododecylamino group, a 1-adamantylamino group, a 2-adamantylamino group, etc., but it is not limited to this. The dialkylamino group may, for example, be a dinonylamino group, a diethylamino group, a dipropylv-ylamino group, a dibutylamino group, a didecylamino group, a dihexylamino group or a diheptylamino group. Dioctylamino, dinonylamino, dinonylamino, bis(dodecyl)amino, bis(octadecyl)amino, diisopropylamino, diisobutylamino, 〇Diisoamylamino, decylethylamino, methylpropylamino, decylbutylamino, decylisobutylamino, cyclopropylamino, pyrrolidinyl, piperidinyl , piperidinyl and the like, but are not limited thereto. 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-S-amino, 2-1-amino, 2-oxazolidinyl, p-terphenylamino, etc. However, it is not limited to this. The diarylamine group may, for example, be a diphenylamino group or a bis(indenyl)amino group, and the N-phenyl-naphthylamino group, N-phenyl-2-naphthyl group, Patent Application No. 99, 323, 778, pp. An amine group or the like is not limited thereto. Examples of the alkylarylamine group include N-methylanilino, N-methyl-2-indole, N-ethylaminoamino, N-propylanilino, N-butylanilino, N-isopropylanilinoquinone-based m-naphthylamino group, etc., but is not limited thereto. The substituted or unsubstituted phosphinium group in the publication is exemplified by a phosphine group having a carbon number of 2 to 50. Specific examples thereof include, for example, dimethyl fluorenyl 'diethyl sulfanyl group, dipropyl phosphine aryl group, diphenyl phosphine aryl group, dimethoxy phosphine aryl group, diethoxy phosphine 1 group, One (thinning base) phosphinyl group, bis(2,4,6-trimethylphenyl) lining group, etc., but is not limited thereto. The substituted or unsubstituted amine methyl group in the middle may be exemplified by a carbon number of j to 3 〇 1 amine formazan. Specific examples thereof include hydrazine methylamine methyl ketone, ν-ethylamine methyl aryl, fluorenyl propyl methacrylate, hydrazine-butylamine carboxylic acid, hydrazine-hexylamine oxime, and hydrazine. -cyclohexylamine oxime, octylamine amide, oxime amine: awake, Ν 'octadecylaminomethyl hydrazino, hydrazine-phenylamine carbhydryl, Nm ^ benzylamine Base, N-2-gas phenylamine hydrazide, N_""'ethylhexyl)phenyl group, formazanyl group, n_3=^曱醯 group 'N_3-nitrophenylamine fluorenyl group, N_3— Cyanyl benzylamine, N-4-methoxyphenylamine, N+ cyanophenylamine, + methylthiophenylamine, N+ phenylthiobenzoate Sulfhydryl, benzylidene N-phenylamine carbhydryl, N, dimethylamino fluorenyl, n, n-dibutyl acetonide U diphenyl amide, etc., but not limited thereto Etc. The substituted or unsubstituted amine ore base can be exemplified by the number of turns G to 3 〇 321778 (revision) 22 201100379 The patent of the 99103470 patent (May 3, 9 9) 61, etc. The green pigment may be, for example, a green pigment such as C·I. Pigment Green 7, 10, 36, 37, etc., but is not limited thereto. For the blue pigment, for example, c. I. Pigment Blue 15, 15 : 1, 15 : 2, 15 · 3, 15 · 4 ' 15 · 6, 16 ' 22, 60, 64, etc., but not limited thereto For the purple pigment, for example, CI Pigment Violet 1, 19, 23, 27, 29, 〇30, 32, 37, 40, 42, 50, etc. may be used, but is not limited thereto. For the black pigment, for example, C·I may be used. The pigment blacks are 1, 6, 7, 12, 20, 31, etc., but are not limited thereto. These pigments may be used in combination of two or more kinds in any ratio. The weight of the radically polymerizable compound (B) is 1 〇〇. In the case of adding the pigment as the coloring component (D), it is preferably used in an amount of from 1 to 60 parts by weight in terms of Q Q1 to parts by weight. From the viewpoint of absorption coefficient of visible light (appropriate degree of spectrum) and transparency It is preferable that the particle diameter of the pigment is sufficiently small for the wavelength of visible light. That is, the pigment has an average primary particle diameter of 〇〇1#m or more, especially (K01#m or more 〇·1// The following is preferred. In addition, the primary particle size refers to the diameter of the smallest unit of pigment particles, as determined by electron microscopy: The diameter can be increased by using a known dispersing device such as a sand mill (mill), a kneader (kneade small 2 pure "regulated in the dry circumference. ~ In addition" when adding a pigment to the polymer composition of the present invention, it can be promoted 32] 77S (Revised Edition) 75 201100379 Pigment Derivative or Pigment Dispersant for the purpose of pigment dispersion and storage stability. 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 naphthalene, an anthraquinone, or a quinone. For the pigment derivative, Japanese Patent Publication No. Sho 63-305173, Japanese Patent Publication No. Sho 57-15620, Japanese Patent Publication No. Sho 59-40172, Japanese Patent Publication No. SHO 63-17102, No. 5-9469 Japanese Patent Publication No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. These can be used alone or in combination of two or more. 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, polyoxyethylene ethyl decyl ether, stearyl amine acetate, and the like. Specific examples of the pigment dispersant include "Anti-Terra-U (polyamine amide oxime)" and "Anti-Terra-203/204 (high molecular weight polycarboxylate)" manufactured by BYK Chera Inc. "Disperbyk-101 (polyamine decyl 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 not full 76 32) 778 201100379 Compound analysis results Compound analysis results Compound analysis results Compound analysis results Compound theoretical value 402.1 The theoretical value of the compound 487.2 The theoretical value of the compound 395.1 The theoretical value of the compound 669.2 () 58) Found 402.2 (199) Found 487.] (235) Found 395.2 (302) Found: 669.3 Calculated value of compound 432.1 Compound value 533.2 502.2 Theoretical value 826.2 059) Found 432.2 (200) Found 533.3 (238) Found 502.1 (306) Found 826.1 Compound 542.] Compound 414J Compound Theory Value 5] 〇.] The theoretical value of the compound 685" (160) Found 542.0 (204) Found 414.2 (241) Found 5: 0_2 (308) Found 685.2 Compound value 522.1 Compound value 595.2 Compound value 540.1 ( </ RTI> </ RTI> </ RTI> </ RTI> </ RTI> </ RTI> </ RTI> </ RTI> </ RTI> </ RTI> </ RTI> </ RTI> </ RTI> </ RTI> </ RTI> </ RTI> </ RTI> </ RTI> <RTIgt; Theoretical value 474.2 Compound theoretical value 625.2 Calculated compound value 737.3 073) Found 474.3 (211) Found: 625.3 (249) Found: 737.4 Calculated compound value 502.2 Compound value 588.2 Compound value 6] 5. 2 (]74) Measured value 502.2 (218) Found 588.1 (252) found 6]5.] Calculated compound value 558.3 Compound calc. 676.2 Compound calc. 542.1 (177) Found 558.2 (220) Found 676.1 (268) Measured value 542.2 598.2 Theoretical value of compound 579. 2 Theoretical value of compound 666.2 080) Found 598.1 (221) Found 579.2 (274) Found 666.3 Calculated compound value 526.2 Compound calc. 507.] Calculated compound value 612.2 (]8]) found 526.3 (225) found 507.1 (280) found 6] 2_3 compound value 464.1 compound Theoretical value 497.1 Calculated compound value 718.3 (184) Found 464.1 (227) Found 497.2 (286) Found: 718.4 Calculated value of compound 564.2 Compound 537.] Calculated value of compound 657.3 (187) Measured value 564.3 (228) Measured Value 537.2 (29)) Found 657.4 Compound theoretical value 648.2 Compound theoretical value 452.1 Calculated compound value 626.2 (]90) Found 648.3 (232) Found 452.2 (292) Found 626.3 Compound value 4]5.] Compound theory Value 452·] Compound theoretical value 612.2 0 92) Found 415.2 (233) Found 452.0 (298) Found 6]2·] Calculated value of compound 443.2 Compound value 525.2 Compound value 7] 2, 2 095) Measured value 443.3 (234) Measured value 525.3 (300) measured value 712.3 113 321 778 201100379 Patent Application No. 99103470 (May 3b, 9 9; &lt;Examples 109 to 254, Comparative Examples 1 to 12) Next, the compound of the present invention represented by the obtained general formula (1) is used as a radical polymerization The initiator (A) was added to the polymerizable composition as described below, and the curability of the polymer was examined. [Curability test] s weekly free radical polymerization initiator (A) 4 parts by weight, sensitizer 〇 Or 1 part by weight of Daptohto DT 170 (manufactured by Tosoh Tehto Chemical Co., Ltd.) as a radical polymerizable compound (B), 1 part by weight, and 2 (three sulfhydryl-based) 85 parts by weight of a baking vinegar was heated and glazed 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 following comparative examples). The polymerization initiator (^ and 'sensitizer (C)) are shown in Table 5. This coating liquid was applied onto a PET film using a bar coater (#3) at a transfer speed of 40 m/min. Ultraviolet irradiation of the coated material at a condition of 45 m/min or 5 〇m/min (high-yield mercury lamp i 3 〇 W/cm, 1 lamp) The film was wiped with a cotton cloth to confirm whether the film was damaged or not. The results are shown in Table 5. Further, after irradiation with ultraviolet rays, it is judged to be preferable if it is not damaged at a high conveyance speed. 5: No damage was confirmed on the film. 4. Very few damages were confirmed on the film. 3. Minor damage was observed on the film. 2: Damage was confirmed on the film. 1. Multiple lesions were confirmed on the film. 32] 778 (Revised version) 114 201100379 [Table 9] Example No. 聚合 Polymerization Composition Circle Shape Example 426 Example 354 〇 Example 427 Example 355 〇 Example 428 Example 356 〇 Example 429 Example 357 〇 Example 430 Implementation Example 358 〇 Example 43] Example 359 〇 Example 432 Example 360 〇 Example 433 Appreciation Example 36 〇 Example 434 Example 362 Example 435 Example 363 〇 Example 436 Example 364 〇 Example 437 Example 365 Appreciation Example 438 Example 366 Example 439 Example 367 〇 Example 440 Example 368 〇 Example 44 Example 369 0 Example 442 Example 370 Example 443 Example 371 Example 444 Example 372 Example 445 Example 373 Example 446 Example 374 Example 447 Example 375 Example 448 Example 376 Example 449 Example 377 Example 450 Example 378 Example 45] Example 379 Example 452 Example 380 Example 453 Example 38J Example 454 Example 382 Example 455 Example 383 Example 456 Example 384 Example 457 Example 385 Example 458 Example 386 Example 459 Example 387 Example 460 Example 388 Example 46 Example 389 Example 462 Example 390 Example 4 G3 Example 391 Example 464 Example 392 Phytophthora 465 Example 393 〇 Example 466 Example 394 〇 Example 467 Example 394 〇 Example 468 Example 3 ί) 5 〇 Example 469 Example 3 SG 〇 Polymer Composition Shape Example 470 Example 397 Example 471 Example 398 Example 472 Example 399 〇 Example 473 Example 400 〇 Example 474 Example 40] 〇 艳 475 Example 402 〇 Example 476 Example 403 〇贲 Example 477 贲 Example 404 〇 Example 478 Example 405 〇贲 例 479 Example 406 〇 Implementation Example 480 Example 407 〇 Example 48] Example 408 〇 Example 482 Example 409 〇 Example 483 Example 410 铯 Example 484 Example 4 〇 Example 485 Example 412 〇 Example 486 Example 4 3 〇 Example 487 Example 4] 4 〇 Example 488 Example 415 〇 Example 489 Example 416 〇 Example 490 Reward Example 41 7 〇 Example 49 例 Example 418 〇贲 Example 4 S2 Example 419 Example 493 Example 420 〇 Example 4 S4 Example 42 〇 Example 495 Example 422 〇 Example 496 Example 423 Poor Example 497 Example 424 〇 Example 498 Example 425 〇 Comparative Example 49 Comparative Example 34 - Comparative Example 50 Comparative Example 35 - Comparative Example 51 Comparative Example 36 - Comparative Example 52 Ratio: Comparative Example 37 Comparative Example 5 3 Specific Example 38 - Comparative Example 54 Comparative Example 39 - Comparative Example 55 Comparative Example 4 (1 X Comparative Example 5G Comparative Example 4] X Comparative Example 57 Comparative Example 42 X Comparative Example 58 Comparative Example 43 X Comparative Example 59 Comparative Example 44 X Comparative Example 6 0 Comparative Example 45 X Comparative Example 6] Comparative Example 4G X Comparative Example G2 Comparative Example 47 X Comparative Example 63 Comparison Example 4 8 X 131 321778 201100379 Patent No. 9910300, application (sept. 3, 1989), the use of the polymerization of the present invention (99 years on 5/glass substrate, to 498), The closeness of the bricks of ^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^ 63) 'None, the image was placed on the substrate. <Examples 499 to 606, Comparative Examples 64 to 91> Next, a coloring polymer compound containing the pigment component as described below to prepare a pigment dispersion was prepared. Ο [Preparation of red pigment dispersion] The mixture of the following composition was uniformly stirred and mixed, and then dispersed by an Eiger roill ("mini model Μ _25 〇ΜΚ II" manufactured by Eiger japan Co., Ltd.) for 2 hours. A 5//in filter was filtered to produce a red 'color pigment dispersion. v Diketopyrrolopyrrole pigment (CI Pigment Red 254) ("Irgaphor Red B-CF" manufactured by Ciba Specialty Chemicals Co., Ltd.) 11. 〇 Parts by weight of the diketopyrrolopyrrole pigment derivative of the following structure 1. 0 40.0 parts by weight of cyclohexanone 48.0 parts by weight, parts by weight [Preparation of Green Pigment Dispersion] A mixture of the following composition is in the same manner as the red pigment dispersion. 132 32] 77S (Revised Edition) 201100379 Patent Application No. 99103470 (May 3, 2009) [Green Polymerization The composition is as follows: 67 parts by weight of the green pigment dispersion, 11 parts by weight of the acrylic resin solution (2), and 3 parts by weight of trishydroxypropyl propane triacrylate ("NK•ESTER ATMPT" manufactured by Shin-Nakamura Chemical Co., Ltd.). The mixture of the polymerization initiator (A) (2), 2 parts by weight, and 18 parts by weight of cyclohexanone, was stirred and mixed until homogeneous, and then filtered by a 1/zm filter to obtain the green polymerization of the present invention. Sex composition (Example 501). 0 [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 trishydroxypropyl propane triacrylate ("NK ESTER ATMPT" manufactured by Shin-Nakamura Chemical Co., Ltd.) The mixture of the compound (1) as a radical polymerization initiator (A), 3 parts by weight, and 13 parts by weight of cyclohexanone, was stirred and mixed, and then filtered through a 1//ID filter to obtain the present. The black polymerizable composition of the invention (Example 502). The coloring polymerizable groups of Examples 503 to 606 and Comparative Examples 64 to 91 were produced as follows. [Red polymerizable composition] The same procedure as in Example 49 was carried out, except that the compound (1) as the radical polymerization initiator (A) was replaced by the compound shown in Table 10, and the results shown in Table 10 were respectively obtained. Red polymerizable composition. [Blue polymerizable composition] The same operation as in Example 500 except that the compound (1) as the radical polymerization initiator (A) was replaced by the compound shown in Table 10, and Table 10 was respectively obtained. A blue polymerizable composition is shown. 135 32]778 (Revised Edition) 201100379 [Green Polymerizable Composition] The same operation as in Example 501 except that the compound (1) as the radical polymerization initiator (A) was replaced by the compound represented by f 10 The green polymerizable composition shown in Table 10 was obtained, respectively. [Black polymerizable composition] The black polymerization shown in Table 10 was obtained in the same manner as in Example 502 except that the compound as the radical polymerization initiator (A) was replaced with the compound shown in Table 10. Sex composition. 136 321778 201100379 Patent application for the first 〇 〇 〇 ( ( ( ( ( ( ( ( ( ( ( 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 : General formula (1) Aryl, substituted or unsubstituted aryloxy, substituted or unsubstituted heterocyclic group, substituted or unsubstituted heterocyclic oxy group, substituted or unsubstituted alkylsulfanyl 'substituted or unsubstituted aromatic sulphur Alkyl, substituted or unsubstituted alkylsulfinyl, substituted or unsubstituted arylsulfinyl, substituted or unsubstituted alkylsulfonyl, substituted or unsubstituted aryl A substituted or unsubstituted fluorenyl group, a substituted or unsubstituted methoxy group, a substituted or unsubstituted amine group, a substituted or unsubstituted phosphinoyl group, a substituted or unsubstituted amine mercapto group 'Or a substituted or unsubstituted aminoxime; R2 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, substituted or unsubstituted heterocyclic group, substituted or 145 321778 (revision) 201100379 Patent Application No. 99103470 (May 3, 2009) Unsubstituted heterocyclic oxy-substituted or unsubstituted alkylthio, substituted or unsubstituted arylthio, substituted or unsubstituted alkylsulfinyl, substituted or unsubstituted arylsulfinyl, a substituted or unsubstituted alkylsulfonyl group, a substituted or unsubstituted aryl fluorenyl group, a substituted or unsubstituted methoxy group, or a substituted or unsubstituted amine group; R3 to R5 each independently represent a hydrogen atom , halogen atom, cyano group, nitro 'substituted or unsubstituted alkenyl group, substituted or unsubstituted alkyl group, substituted or unsubstituted alkoxy group, substituted or unsubstituted aryl group, substituted or unsubstituted aryloxy group 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 thiol group, or a substituted group Or an unsubstituted amino group; R6 to R9 each independently represent a hydrogen atom, a halogen atom, a cyano group, a halo-alkyl 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 a substituted or unsubstituted heterocyclic oxy group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted thiol group, a substituted or unsubstituted (} arylthio group, a substituted or unsubstituted pyrenyl fluorenyl group, a substituted or unsubstituted arylsulfinyl group, a substituted or unsubstituted alkylsulfonyl group, a substituted or unsubstituted aryl aryl group, a substituted or unsubstituted amine group, or a formula (2) ) the substituent shown, general formula (2) Where R1' and R2' have the same meaning as V and R2 146 32] 778 (Revised Edition) 201100379 Patent Application No. SSI0347 (May 3, 2009) ♦ f to ... each independently represents hydrogen An atom, a halogen atom, a cyano group, a nitro group, a ii alkyl 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, or a substituted or unsubstituted fluorene group, but R]° to R14 are not all hydrogen atoms at the same time. ' 2. A compound according to claim 1 wherein At least one of the foregoing &quot; to Rl4 is a nitro group, or a substituted or unsubstituted acid group. The compound of claim 1 or 2 wherein at least one of R 0 to R 4 is a nitro group or a group represented by the following formula (3): Formula (3) R18 惟 In the formula, R15 to ru each independently represent a hydrogen atom, a halogen atom, a cyano group, a nitro group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkoxy group, or a 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 group, substituted Or an unsubstituted arylthio group, a substituted or unsubstituted thiol group, or a substituted or unsubstituted amine group. 4. The compound according to claim 3, wherein the above r!2 is a nitro group or a group represented by the above formula (3). 5. /A kind of radical polymerization initiator (Α)' contains the patent application scope 1 32I77S (revision) 147 201100379 Patent application No. 99103C0 (the compound of any of the items from May to April 9) 6. A polymerizable composition comprising a radical polymerization initiator (Α) and a radical polymerizable compound (Β) in claim 5 of the patent application. 7. Polymerization as in claim 6 a composition comprising a sensitizer (C). 8. A polymerizable composition according to claim 6 of the patent application, wherein the color component (D) is compounded. 9. If the patent application (four) 6 The polymerizable composition of any one of the eight items, wherein the alkali-soluble resin (Ε) is added. ίο.: The negative (four) agent' contains the polymerizable group of the ninth patent range. The manufacturing method of the object is the polymerization of the polymerizable composition of the sixth to the ninth item of the patent range, and the polymerization of the energy pattern is carried out. The method for forming the pattern of the H-th image is characterized by: 4? type resist is layered on the substrate, partially irradiating energy 1 to make the material, and readability The image liquid will be unirradiated 13·---------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------- IV. Designated representative map: There is no schema in this case. (1) The representative representative figure of this case is: ( ). (2) The symbol of the symbol of the representative figure is simple: 5. If there is a chemical formula in this case, please reveal the best display. Chemical formula of the inventive feature: 3 321778