TW201109304A - Photopolymerization initiator and photosensitive composition - Google Patents

Abstract

Provided is a photopolymerization initiator having high sensitivity and excellent thermal stability, and a photosensitive composition using the same. The photopolymerization initiator of the present invention is represented by the following formula (1). (wherein R1 represents an aryl group having at least one nitro group as substituent(s); moreover, R2 is a C1 to 20 saturated or unsaturated monovalent organic group which may have substituent(s), which may form a branched structure or a ring structure, wherein a hetero atom may present in any position. Furthermore, Ar is a substituent having a carbazole skeleton which has a nitro group.)

Description

[Technical Field] The present invention relates to a novel photopolymerization initiator, a photosensitive composition containing the photopolymerization initiator, and a cured product thereof. [Prior Art] The photosensitive composition is widely used in a form in which a photopolymerization initiator is formulated in a polymerizable compound having an olefin bond, and is used in a photoresist, a photocurable ink, a photocurable coating, and photohardening. The use of a type of adhesive, a photosensitive resin for photo-forming, and a photosensitive printing plate has been put into practical use. The photosensitive composition can be polymerized and hardened by irradiating ultraviolet light or visible light (referred to as exposure) with a mercury lamp, a xenon lamp, a laser or the like as a light source, but it is desirable to obtain a high-efficiency hardening with a small amount of exposure. A photosensitive composition of sensitivity, and thus a high sensitivity photopolymerization initiator is required. As far as the photopolymerization initiator is concerned, many compounds have been proposed so far, for example, an acetophenone compound, a benzophenone compound, a benzoin ether compound, and an α-amine are known. An α-aminoalkylphenone compound, a thioxanthone compound, an organic peroxide, and a meter. A biimidazole compound, a titanocene compound, a triazine compound, an acylphosphine oxide compound, a quinone compound, an oxime ester compound, and the like. However, these are not intended to be sufficient. In recent years, an oxime ester compound having a carbazole skeleton (Patent Documents 1 to 9 below) has been disclosed, and its sensitivity system has significantly exceeded that of the conventional photopolymerization initiator 4 322255 201109304. However, even if the photopolymerization initiator is used, there is still a need for high performance in a photoresist (black resist, RGB resist) used in the manufacture of a color fiiter of a liquid crystal display. It is not always possible to achieve a level of satisfaction. [Prior Art Document] [Patent Document] [Patent Document [Patent Document [Patent Document [Patent Document [Patent Document [Patent Document [Patent Document 1] Japanese Patent Laid-Open Publication No. 2004-359639 2] Japanese Laid-Open Patent Publication No. Hei. No. Hei. No. 2008-160. JP-A-2009-040762 8] W02006/018973 Booklet 9] W02008/078678 Booklet In addition, the photoresist used in the manufacture of filters and color chips for liquid crystal displays is generally in its manufacturing steps. It is burned at a high temperature of around 230 〇C. At this time, the photopolymerization initiator remaining in the photoresist is thermally decomposed. Sometimes the decomposition product generated may contaminate the calciner and impair the reliability of the color filter. Therefore, it is desired to obtain a photopolymerization initiator which does not have the above-mentioned concerns and which is excellent in thermal stability. SUMMARY OF THE INVENTION The present invention has been made in view of the problems of the prior art, and its object is 322255 5 201109304 to provide a photopolymerization initiator having high sensitivity and excellent thermal stability, and the use thereof. A photosensitive composition of a photopolymerization initiator. (Means for Solving the Problem) In order to solve the problem, the present inventors have found that by introducing a specific functional group into an oxime ester compound having a taste saliva skeleton as a photopolymerization initiator, the object is achieved. The present invention has been completed: a photopolymerization initiator: that is, the present invention is as shown in the following formula (1)

(R1, R1 represents an aryl group having at least one nitro group as a substituent). Further, R2 is a saturated or unsaturated monovalent organic group having 1 to 20 carbon atoms which may have a substituent, and may also form a branched structure or The ring structure may also have a hetero atom present at any position; and 'Ar is a substituent having a card, a frame, and the carbazole skeleton has a nitro group. It is preferable that the 'R2 system is a methyl group. Further, the present invention also provides a photopolymerization initiator, and a polymerizable a, 3, and a composition having an olefin bond, and provides a curing of the photosensitive composition; Sigh hardened. The photopolymerization initiator of the present invention has a general formula (1), and an E-form and a Z-form may exist in a C=N double bond at a site. In the structure, the case does not specifically distinguish this. Therefore, the geometry shown by the equations (2) to (10) represents such a core =, and the latter or any of them. Mixture of isomers 322255 6 201109304 in formula (1)

A preferred structure is represented by the following formula (2): Ϊ represents an aryl group having at least one nitro group as a substituent. From the point of view, it is preferred that R1 preferably has at least one nitro group as a substituent = for example, right is 2-nitrophenyl, 3-nitrophenyl, 4-nitrophenyl, t二"!基基基,2,卜二德phenyl, 2,dinitrophenyl, 3,4-monoschyl=yl, 3,5-dinitrophenyl, 2, 3, 5- Trinitrophenyl, 2,4,6-tridecylphenyl (tetra) is advantageous. In addition, it is preferable to have at least the above! The hydrogen atom on the ring of the thiol group is _ atom (a gas atom, a chlorinogen, a bromine atom, an iodine atom, etc.), an alkyl group (methyl, ethyl, propyl, butyl, etc.), halogenated For example, a 2-halo-3-nitrophenyl group (halogen means a substituent of a halogen atom, the same applies hereinafter), a 2-substituted derivative such as a pyridyl group (trifluoromethyl group, a gas group or the like) or a cyano group can be used. Halo-4-nitrophenyl, 2-halo-5-nitrophenyl, 2-halo-6-nitrophenyl, 3-halo-2-nitrophenyl, 3-halo-4-nitro Phenyl, 3-halo-5-nitrophenyl, 5-halo-2-nitrophenyl, 4-halo-2-nitrophenyl, 4-halo-3-nitrophenyl, 4-halo -3,5-dinitrophenyl, 2-alkyl-3-nitrophenyl, 2-alkyl-4-nitrophenyl, 2-alkyl-5-nitrophenyl, 2-alkane 6-nitrophenyl, 3-alkyl-2-nitrophenyl, 3-alkyl-4-yochylphenyl, 3-alkyl-5-nitrophenyl, 5-alkyl -2-nitrophenyl, 4-alkyl-2-nitrophenyl, 4-alkyl-3-nitrophenyl, 4-alkyl-3, 5-dinitrophenyl, 2-nitrate 7 322255 201109304 may also be -4-(trifluoromethyl)phenyl, 3-;; Schottky (trifluoromethyl)phenyl-2-nitrophenyl, 3-cyano-5-nitro base Group. Further, 齓 a polycyclic aromatic group having at least one nitro group as a substituent, a phenanthryl group or the like. The τ' group, in the general formulae (1) and (2), HR3 each independently represents a saturated or unsaturated one having a carbon number of from 1 to 20, which may form a branched structure or a ring structure, and may exist at any position. ^语,子. Specific examples of R2 and R3 include methyl, u, isopropyl, butyl, isobutyl, t-butyl, t-butyl, pentyl, isopentyl, neopentyl, Third amyl, hexyl, heptyl, octyl '2-ethylhexyl, decyl, decyl, dodecyl, tetradecyl, hexadecanol, octadecyl, twentieth Esosyl, cyclopentyl, cyclohexyl, vinyl, allyl, ethynyl, strepto, phenyl (t〇lyl), 2,4,6-trimethylphenyl (mesityl), a saturated or unsaturated monovalent nicotyl group such as naphthyl, anthracenyl, phenanthryl, benzyl, benzyl or 2-benylvinyl, or a pyridinyl, piperidyi, N-piperidin(R), lmidazolidinyl, furyl, tetrahydrofuranyl, thienyl, tetradecyl, morph〇linyi, morph〇lino, A saturated or unsaturated monovalent heterocyclic group such as quinolyl. Further, a structure in which a halogen atom, a hydroxyl group, a sulfanyl group, a carbonyl group, a thiocarbonyl group, a carboxyl group, a thiol group, or a thiol group is introduced at any of the above hydrocarbon group and heterocyclic group may be mentioned. Dithiol, fluorenyl, cyano, nitro, nitroso, acid group, amine group, 8 322255 201109304 imine group, anthracenyl group, ether group 'thioether group, ester group, A structure in which a thioester group, a dithioester group, a brewing amine group, a sulfur-brown amine group, an urethane group, a thiamine group or the like is used as a substituent. Further, R3 includes not only a monovalent organic group such as a methyl group but also a valence organic group such as a decyloxy group, an anthracenylthio group or a dimercaptoamine group which is located on a hetero atom. ^ and R3 may be appropriately selected according to the molecular weight, sensitivity, solubility, etc. of the photopolymerization initiator for the purpose of 'a saturated or unsaturated valence hydrocarbon group having 1 to 20 carbon atoms is preferred' and the R2 methyl group is the most Good, the ethyl is the best. Specific examples of the photopolymerization initiator of the present invention are shown below. It is not limited to this.

(4) 322255 9 (5 )201109304 Ο., /CH〇

'NT v v 'N〇2 0h2ch(c2h5)c4h9 0^/CH3

C2h5 (6 )

10 322255 201109304

11 322255 201109304

The method for producing the photopolymerization initiator of the present invention is not particularly limited, and for example, it can be carried out in the following order. First, R3 is introduced into the 9-position of 9Η-σ card D by a nucleophilic substitution reaction or the like, and then 6 positions are nitration with tartaric acid. Further, the ketone body was obtained by introducing FCO ' at the 3-position by Friedel-Crafts Acylation Reaction. This is converted into a hydrazine by a hydroxylamine, and then esterified with hydrazine or an acid anhydride of r2cooh to obtain a photopolymerization initiator of the formula (2). In addition, the order of nitrification and Ryd-Kraft is also interchangeable. The photosensitive composition of the present invention contains a photopolymerization initiator of the formula U) and a polymerizable compound having an olefin bond. With respect to the polymerizable compound having an olefin bond, a known compound used in the conventional photosensitive composition can be used without particular limitation, and in particular, acrylic acid and methacrylic acid (hereinafter, both 12 322255 201109304 &amp; Derivatives of propionate, etc.) are advantageous, preferably using, for example, diethylene glycol di(meth)acrylate, trimethylolpropane tri(meth)acrylate, pentaerythritol (pentaerythrit〇l) a (meth) acrylate derivative such as tetra (meth) acrylate, mono (dimethylolpropane) tetrakis(meth) acrylate, dipentaerythritol hexa(indenyl) acrylate, or bisphenol A-type epoxy di(meth)acrylate, bisphenol F-type epoxy di(meth)acrylate, bisphenol i-type epoxy di(meth)acrylate, phenol novolac (phen〇1 A (meth)acrylic acid epoxy ester derivative such as a novolac) type epoxy group poly(meth)acrylate or an anthranol novolak type epoxy group poly(indenyl) acrylate. Further, a reaction product of the above (fluorenyl)acrylic acid derivative and a compound having a (preferably plural) isocyanate group or an acid anhydride group in the structure is also suitable. Further, a vinyl resin (acrylic (co)polymer, mercaptoacrylic (co)polymer, maleic acid (co)polymer, styrene (co)polymer, etc.) which is a known resin may be used. , a polyester resin, a polyamide resin, a polyimide resin, a polyurethane resin, a polyether resin, etc., and a mercapto group is introduced into the main chain or the side chain by an ester bond, a guanamine bond, an amine ester bond or the like. Base resin, etc. Further, in addition to the (meth)acrylic acid derivative, there may be mentioned, for example, a maleic acid derivative, a maleic imide derivative, a crotonic acid derivative, an itaconic acid derivative, a cinnamic acid derivative, or a vinyl derivative. A vinyl alcohol derivative, a ketene derivative, a vinyl aromatic derivative or the like. The polymerizable compound having an olefin bond may be a compound having a thermoreactive functional group such as an epoxy group or an alkali-soluble functional group such as a carboxyl group. These compounds having a dilute t bond may be used singly or in combination of plural kinds. 322255 13 201109304 In the photosensitive composition of the present invention, the compounding ratio of the photopolymerization initiator represented by the formula (1) is not particularly limited, and photopolymerization is carried out with respect to 100 parts by weight of the polymerizable compound having an olefin bond. The initiator is preferably from 1 to 50 parts by weight, more preferably from 1 to 20 parts by weight. The photosensitive composition of the present invention may contain other optional components as needed, for example, a coloring material, a filler, a resin, an additive, a solvent, or the like. Here, examples of the coloring material include a dye, an organic pigment, an inorganic pigment, and a carbon black pigment. Examples of the filler include silica, talc, and the like, and examples of the resin include a vinyl resin (acrylic (co)polymer, Mercaptoacrylic acid (co)polymer, maleic acid (co)polymer, styrene (co)polymer, etc., polyester resin, polyamide resin, polyimide resin, polyurethane resin, polyether resin, Examples of the epoxy resin, the melamine resin, and the like include a curing agent, a crosslinking agent, a dispersing agent, a surfactant, a decane coupling agent, a viscosity adjusting agent, a wetting agent, an antifoaming agent, an antioxidant, and the like, and the solvent may, for example, be an ester. Examples of the solvent, the ketone solvent, the ether solvent, the alcohol solvent, the aromatic solvent, the aliphatic solvent, the amine solvent, the guanamine solvent, and the like. Any of the optional components can be used without any particular limitation. Further, in the photosensitive composition of the present invention, in addition to the photopolymerization initiator represented by the formula (1), a known photopolymerization initiator or a color sensitizer may be used in combination. For example, it can be used without particular limitation: acetophenone, 2-hydroxy-2-indolyl-1-phenylpropan-1-ene (2-hydroxy-2-methy) I-phenylpropan-Ι-one , acetophenone compounds such as benzyl dimethyl ketal; benzophenone, 2, 4' 6-trimethylbenzophenone, 4, 4 ,-bis(N,N-diethylamine 14 322255 201109304) benzophenone (4, 4'-bis(N,N-diethylamino)benzophenone); benzoin ethyl ether (benzoin ethyl ether), benzoin tert-butyl ether and other benzoin compounds, 2-methyl-l-[4-(methylthio)phenyl]-2-(N- 2-methyl-l-[4-(methylsulfanylphenyl)-2-morpholinopropan-l-one), 2-benzyl-2-(N,N-didecyl) Amino)-1-(4-(N-morpholinyl)phenyl)butane-1 —_(2-benzyl-2-(N, Nd i methy1ami no)-1-(4-morpho1i nopheny1)butan -1-〇ne), such as a-aminoalkyl benzophenone compound; thioxanthone compound such as thioxanthone or 2, 4-diethylthioxanthone; 3, 3, 4 , 4,-four ( Organic peroxide such as 3,3'4, 4,-tetra (tert-butylperoxycarbonyl) benzophenone; 2, 2'-bis(2-chlorophenyl)-4 , 4'5, 5'-tetraphenyl-1,2-biimidazole (2, 2'-bis(2-chlorophenyl)-4, 4' 5, 5'-tetraphenyl-l, 2-biimidazole), etc. Biimidazole compound; bis(7/5-cyclopentadienyl)bis[2,6-difluoropyryl)phenyl]titanium (1^3(775-cyclopentadienyl)bis[2, 6TMdifluoro-3 -(l-pyrrolyl)phe ie 1]1; ^&1^11111) and other ferrocene compounds; 2,4,6-tris(tris): 1,3, 5-5_(2,4 ,6-tris(trichloromethyl)-l,3,5-triazine), 2-[3,4-(indenylenedioxy)phenyl]-4,6-bis(trimethyl)-1,3 , 3-terpene (2_[3, 4-(methylenedioxy)phenyl]-4, 6-bis(trichloromethyl)-l,3, 5-triazine), etc.; (2, 4, 6-trimethyl) (2, 4, 6-trimethylbenzoyl) diphenylphosphine oxide) ' 15 322255 201109304 Bis(2, 4, 6-trimethylbenzylbenzyl) phenylphosphine oxide (bis( 2,4,6-trimethylbenzoyl)phenylphosphine oxide) a compound such as camphorqu i none; 1-[4-(phenylthio)phenyl]octane-1,2-dione = 2-0-benzylindenyl hydrazine (1-[4- (pheny1su1fany 1)pheny1]octane-1, 2-dione 2_0_benzoyloxime), l-[9_ethyl_6-(2_indenyl-based carbaryl)ethanone=0-acetamidoxime (1- An oxime ester compound such as [9-ethyl-6-(2-methylbenzoy1)carbazo1-3-y1]ethan〇ne-0-acetyloxime. The method for producing the cured product of the photosensitive composition of the present invention can be carried out by a known method as long as the photosensitive composition is coated or injected into a suitable substrate or mold for the purpose of blending or use, and then hardened by exposure. . Here, by using a photomask or the like and performing selective exposure, it is possible to perform image formation, shape formation, and the like even further by performing development. Further, treatment such as calcination may be carried out as needed. (Effects of the Invention) The photopolymerization initiator of the present invention is highly useful because it can provide a photosensitive composition having excellent sensitivity and high sensitivity and can be efficiently cured with a small amount of exposure. When the photopolymerization initiator of the present invention efficiently absorbs ultraviolet light and visible light to be in an excited state, the oxime ester bond is rapidly broken to generate a radical species having high activity, and the photosensitive composition is contained therein. The hydrazine has a stimulating polymerizable compound to carry out a polymerization reaction at a high speed. In addition, the unrecognized photopolymerization initiator is excellent in thermal stability, so even in the manufacturing process, as in the photoresist used for the manufacture of the color film of the liquid crystal display device, 322^ 322255 16 201109304 • 23G° In the calcination treatment at a high temperature of about C, there is no decomposition product of the residual photopolymerization initiator, which impairs the reliability of the color filter. [Embodiment] The present invention will be described in more detail below based on examples, but the present invention is not limited thereto. [Example 1] &lt;(9-Ethyl-6-nitro-xyl-3-yl)(4-_decylphenyl)formamidine=〇_乙醯基肟&gt;(Light of formula (3) Polymerization initiator (Synthesis of photopolymerization initiator) The above photopolymerization initiator was synthesized by the reaction of the four steps. The reaction was carried out using a glass reactor under normal pressure. Step 1 : Using a nitromethane as a solvent, 9-ethyl carbazole (manufactured by Tokyo Chemical Industry Co., Ltd.) 0·10 mol, 4-nitrobenzyl oxime (manufactured by Tokyo Chemical Industry Co., Ltd.) 0. 15 m, And gasification of aluminum crucible. 15 moles in the 〇 to 5. The reaction was carried out for 6 hours. The reaction was dropped into ice water, and the precipitated solid was recovered and washed thoroughly to obtain (9-ethyloxazol-3-yl)(4-nitrophenyl)fluorenone equivalent to 0.07 mol. Crude product. Step 2: using acetic acid as a solvent, the total amount of the product of the step 1 and the acid was 0.14 mol at 801: reaction for 6 hours. The reaction solution was dropped into ice water, and the precipitated solid was recovered and washed thoroughly to obtain (9-ethyl-6-hexyloxazol-3-yl) (4-nitrobenzene) equivalent to 6 mol. Crude product of ketone. Step 3: Using tetrahydrofuran as a solvent, the total amount of the product of Step 2 and hydroxylamine hydrochloride were adjusted. 12 moles were reacted under reflux for 24 hours. After cooling, the reaction was dropped into water, and the precipitated solid was recovered and washed thoroughly to obtain 17 322255 201109304 equivalent to 0.05 mM (9-ethyl-6-nitrocarbazole _3_ group) ( 4_Nitrophenyl) A == crude product. Step 4: using pyridine as a solvent, the total amount of the product of the step 3 and the acetic acid needle 0. 10 moles were reacted at 80 ° C for 6 hours. After cooling, the reaction was dropped into water, and the precipitated solid was recovered and washed thoroughly to obtain (9-ethyl-6-nitrooxazol-3-yl) (4-(4-ethyl-6-nitrooxazol-3-yl) Nitro-phenyl) fluorenone = 〇_ crude product of acetamidine. 0摩尔。 Pure refining of the phthalate column to obtain a pure 0.02 molar. When the obtained pure compound was identified by iH-NMR (CDC13), the following results were shown.占=8. 94(s,lH), 8.47(d,lH), 8.43(d,2H)8·16(s,1H), 7·96 (d,1H), 7.59 (d,2H) , 7. 52 ( d, 1H), 7. 46 ( d, 1H), 4.44 (q, 2H), 2.12 (s'3H), 1.53 (t, 3H) (production of photosensitive composition) Propylene glycol monomethyl ether acetate of an alkali-developing photosensitive resin (polymerizable compound having an olefin bond) having a double-type epoxy group diacrylate structure of 0.4% by weight of a photopolymerization initiator 2重量%。 The solution (V-259ME), a solid concentration of 55.6 wt%, 5. 5 wt%, neopentyl alcohol tetraacrylate (polymeric compound with olefin bond) 1. 0% by weight重量重量。 The carbon black pigment (coloring material) is dispersed in a propylene glycol monomethyl ether acetate dispersion (carbon black pigment concentration of 25.3% by weight, solid content concentration of 31.6 weight %) 27. 7 weight, Si 1 icone surfactant ("FZ-2122" manufactured by Dow Corning Toray Co., Ltd.) 0.05% by weight, 3-(glycidoxy)propyltrimethoxydecane (decane coupling agent) 0.05 weight %, Propylene glycol monomethyl key 322 255 18 201 109 304, said G B pack ® agent Valley) 22.2 wt%, and cyclohexanone (solvent) 43.4 wt% _ be formulated according to the ratio, to prepare a photosensitive composition. The photosensitive composition has a solid concentration of 13.2% by weight, and the carbon black pigment concentration in the solid portion is 531. 0 can be used as a photoresist (black resist) for the manufacture of a color filter of a liquid crystal display. use. Here, the solid portion referred to herein means a component other than the solvent. (Evaluation of Photosensitive Composition) 吏Used: The above-mentioned photosensitive composition was applied to a non-glass substrate by a transfer coater', and dried on a hot plate at 8 G ° C for 1 minute to prepare a test piece. The coating condition (suspected number of rotations) was adjusted so that the cured film having a film thickness of 1.0 μm was obtained. Next, use a reticle with a transmittance of 0 to 100% P white & 丨 丨 照 隐 隐 之 之 之 之 之 之 超 超 超 超 超 超 对于 对于 对于 对于 对于 对于 对于 对于 对于 对于 对于 对于 对于 对于exposure. Then, the test piece was taken as 26. (: 1G dilution of the test imaging solution (V 2401 ID manufactured by Niigata Iron Chemical Co., Ltd.)) was treated for 1 minute, and then washed with water to visualize the image. Finally, the test piece was calcined in a hot air oven of 2303⁄4 for 3 minutes to obtain a cured film of the photosensitive composition. The exposure amount required for image hardening determined by the image was 26 mJ/cm. The optical density of the cured film is 4. 5# claw, which has high light-shielding property. [Example 2] &lt;(9-Hexyl-6-stone succinyl hydrazine _3_yl) (4-nitrophenyl) formamidine ♦ Ethyl hydrazone loss (Photopolymerization initiator of the formula (4)) The synthesis was carried out in the same manner as in Example 1. When the pure compound obtained by 19 322255 201109304 was identified by 1H-NMR (CDC13), the following The result is 8.92 (s, 1H), 8.49 (d, lH), 8.47 (d, 2H), 8. 14 (s, 1H), 7. 96 (d, 1H)' 7· 61 (d, 2H), 7. 48 (d, 1H), 7. 46 (d, 1H), 4. 30 (q, 2H), 2. 12 (s, 3H), 1. 90-1. 83 (m, 2H), 1.43-1. 35 (m, 2H), 1.35 - 1.23 (m, 4H), 0.86 (t, 3H) Further, photosensitive property was produced in the same manner as in Example 1. The amount of exposure required for photohardening was 26 mJ/cm 2 . [Example 3] &lt; (9-(2-ethylhexyl)-6-nitrooxazol-3-yl) (4- (Nitrophenyl) _ =0-ethyl fluorenyl hydrazine (photopolymerization initiator of the formula (5)) The synthesis was carried out in the same manner as in Example 1. The obtained pure compound was obtained by iH_^R (CDCh). At the time of identification, the following results are displayed: (5 = 8.93 ( s, 1H), 8. 46 (d, 2H), 8. 41 (d, 1H), 8. 15 (s, 1H), 7. 95 (d,1H), 7.60 (d,2H), 7·48 (d,1H), 7.45 (d,1H), 4.17(q,2H), 2.16(s,3H) , 2. 07 (m, 1H), 1. 45-1. 30 (m, 4H), 1.30-1.26 (m, 4H), 0.92 (t, 3H), 0.86 (t, 3H) In addition, with the embodiment (1) A photosensitive composition was produced and evaluated in the same manner, and the exposure amount required for photohardening was 26 mJ/cm<2> [Example 4] &lt;(9-ethyl-6-demethyl-indol-3-yl) (3) -Nitrophenyl)methanone = oxime-ethyl ruthenium ruthenium (Photopolymerization initiator of the formula (6)) The synthesis was carried out in the same manner as in Example 1. The obtained pure compound was carried out as 1H--R (CDC13). At the time of identification, the following results are displayed. (5 = 8· 94 ( s, 1H), 8. 59 ( s, 1H ), 8. 54-8· 50 ( ro, 2H), 8. 47 322255 20 201109304 « (d, 1H), 8.43 (d , 1H), 8. 16 (s, 1H), 7. 96 (d, 1H), 7 52 (d, 1H), 7. 46 (d, 1H), 4· 42 (q, 2H), 2. 15 ( s, 3H), ! 5l '(t, 3H) ' Further, a photosensitive composition was produced and evaluated in the same manner as in Example 1. The exposure amount required for photocuring was 26 mJ/cm 2 . [Example 5] &lt;(9-Ethyl-6-nitrooxazol-3-yl)(3,5-dinitrophenyl)A@同吲〜乙醯基肟&gt;(Photopolymerization of formula (7) The starting compound was synthesized in the same manner as in Example 1. When the obtained pure compound was identified by iH_NMR (CDCh), the following results were obtained. <5 = 9.29 (s, 1H), 8. 95 (m, 3H), 8.43 (d, 1H), 8. 14 (s, 1H), 7. 93 (d, 1H), 7. 53 (d, 1H), 7. 48 (d, 1H), 4. 48 (q, 2H), 2.17 (s, 3H), and 1.52 (t, 3H) Further, a photosensitive composition was produced in the same manner as in Example 1 and evaluated to have an exposure amount of 26 mJ/cm 2 . Comparative Example 1] The photopolymerization initiator of Example 1 was changed to 1-(9-ethylnitrooxazol-3-yl) Ethyl ketone = 0-acetyl hydrazine (compound represented by the following formula (14)), and a photosensitive composition was prepared and evaluated in the same manner as in Example 1. As a result, the exposure amount required for photohardening was 30 mJ/ Cm2, compared to the embodiment, shows a lower sensitivity (the less the amount of light required for photohardening, the higher the sensitivity). 322255 21 201109304

[Comparative Example 2] The photopolymerization initiator of Example 1 was changed to (9-ethyl-6-nitrooxazol-3-yl)phenyl fluorenone = 0-ethyl hydrazide (the following formula ( The photosensitive composition was produced and evaluated in the same manner as in Example 1 except for the compound shown in 15). As a result, the amount of exposure required for photohardening was 37 mJ/cm2, which showed a lower sensitivity than the example. O^ch3

OIN 2

5 [Comparative Example 3] The photopolymerization initiator of Example 1 was changed to (9-ethyloxazol-3-yl)(4-nitrophenyl)fluorenone=0-ethylindenyl hydrazide (described below) A photosensitive composition was prepared and evaluated in the same manner as in Example 1 except for the compound represented by the formula (16). As a result, the exposure amount up to 10 OmJ/cm 2 was completely incapable of hardening the light, and showed a lower sensitivity than the example. 22 322255 (16) 201109304 0-^ ^CH,

C2h5 [Comparative Example 4] The photopolymerization initiator of Example 1 was changed to 1-(9-ethyl-6-(2-methylbenzyl) oxazol-3-yl)ethanone = 0-B A bismuth group (a compound represented by the following formula (17), "Irgacure OXE02" manufactured by BASF Corporation) was prepared, and a photosensitive composition was produced and evaluated in the same manner as in Example 1. As a result, the exposure amount required for photohardening was 67 mJ/cm2, which showed a lower sensitivity than the example.

(Evaluation of Thermal Stability) The thermal stability of the photopolymerization initiators of the above Examples 1, 4, and 5 and Comparative Examples 1 and 4 was evaluated by differential scanning calorimetry. The results are shown in Table 1. The decomposition starting points of the photopolymerization initiators of the examples all exceeded 230 ° C, indicating excellent thermal stability. On the other hand, the decomposition starting point of the photopolymerization initiator of the comparative example was less than 230 ° C, and the thermal stability was insufficient. 23 322255 201109304 [Table 1] Photopolymerization initiator melting point / ° C decomposition starting point / ° C Example 1 248 250 Example 4 213 235 Example 5 Unobservable 250 Comparative Example 1 205 220 Comparative Example 4 130 200 ( INDUSTRIAL APPLICABILITY The photopolymerization initiator of the present invention is excellent in high sensitivity and thermal stability, and thus can be suitably used as a photoresist, a photocurable ink, a photocurable coating, a photocurable adhesive, The photoformation is used for a photosensitive resin, a photosensitive printing plate, or the like. In particular, it is most suitable for applications requiring high performance such as photoresists (black resists, RGB resists) used in the manufacture of color filters for liquid crystal displays. [Simple diagram description] None [Main component symbol description] None 24 322255

Claims (1)

201109304 VII. Patent application scope: * i. A photopolymerization initiator, as shown in the following formula G)·· (R1) R1 represents an aryl group having at least one nitro group as a substituent, and R is a saturated or unsaturated monovalent organic group having a substituent of from 丨 to 2〇, and may form a branched structure. Or a ring structure, or a hetero atom may be present at any position; and, as a substituent having a carbazole skeleton, the carbazole skeleton has a nitro group). 2. The photopolymerization initiator according to item 1 of the patent application, wherein R2 is a ^..... 3. a photosensitive composition comprising: claim 1 or 2 of the patent application scope A photopolymerization initiator, and a polymerizable compound having an olefin bond. 4. A cured product obtained by hardening a photosensitive composition of the third application of the patent application. 322255 25 201109304 IV. Designated representative map: There is no schema in this case - (1) The representative representative map of this case is: (). (2) A brief description of the symbol of the representative figure: 5. If there is a chemical formula in this case, please disclose the chemical formula that best shows the characteristics of the invention: 322255