JP5450314B2 - Photopolymerization initiator and photosensitive composition - Google Patents

Description

  The present invention relates to a novel photopolymerization initiator, a photosensitive composition containing the same, and a cured product thereof.

  Photosensitive compositions are widely used in a form in which a photopolymerization initiator is blended with a polymerizable compound having an olefinic bond. Photoresist, photocurable ink, photocurable paint, photocurable adhesive, photofabrication It has been put to practical use in applications such as photosensitive resins and photosensitive printing plates. The photosensitive composition can be cured by causing a polymerization reaction by irradiating with ultraviolet light or visible light (referred to as exposure) using a mercury lamp, xenon lamp, laser or the like as a light source. A highly sensitive photosensitive composition that can be cured is desired, and a highly sensitive photopolymerization initiator is required for this purpose.

  Many compounds have been proposed as photopolymerization initiators so far, and acetophenone compounds, benzophenone compounds, benzoin ether compounds, α-aminoalkylphenone compounds, thioxanthone compounds, organic peroxides, biimidazole compounds, titanocene compounds, Triazine compounds, acylphosphine oxide compounds, quinone compounds, oxime ester compounds and the like are known. However, none of these has sufficient sensitivity.

  In recent years, oxime ester compounds having a carbazole skeleton have been disclosed (Patent Documents 1 to 9 below), and sensitivity far exceeding that of conventional photopolymerization initiators has been reported. However, even with such a photopolymerization initiator, it is not always satisfactory for applications requiring high performance such as photoresists (black resist, RGB resist) used in the production of color filters for liquid crystal displays. There was a problem of not reaching.

  In the case of a photoresist used for manufacturing a color filter of a liquid crystal display, it is common to receive a baking process at a high temperature of about 230 ° C. in the manufacturing process. At this time, the photopolymerization initiator remaining in the photoresist may undergo thermal decomposition, and the generated decomposition product may contaminate the baking furnace and impair the reliability of the color filter. Therefore, a photopolymerization initiator excellent in thermal stability that does not cause such a concern has been desired.

Japanese Patent Laid-Open No. 2004-359639 Japanese Patent Laying-Open No. 2005-097141 Japanese Patent Laid-Open No. 2005-220097 JP 2006-160634 A JP 2008-094770 A Special table 2008-509967 JP 2009-040762 A WO2006 / 018953 pamphlet WO2008 / 078678 pamphlet

  This invention is made | formed in view of the subject of this prior art, and aims at providing the photoinitiator which is highly sensitive and excellent in thermal stability, and the photosensitive composition using the same.

  As a result of studies to solve the above problems, the present inventors have found that the object can be achieved by introducing a specific functional group into an oxime ester compound having a carbazole skeleton as a photopolymerization initiator. completed.

（ただし、Ｒ¹は置換基として少なくとも１つのニトロ基を有するアリール基を表し、また、Ｒ²は置換基を有していてもよい炭素原子数１〜２０の飽和または不飽和の一価の有機基であって、分岐構造や環構造を形成していてもよく、任意の位置にヘテロ原子が存在していてもよい。更に、Ａｒはカルバゾール骨格を有した置換基であって、該カルバゾール骨格はニトロ基を有する。） That is, the present invention is a photopolymerization initiator represented by the following general formula (1).

(However, R ¹ represents an aryl group having at least one nitro group as a substituent, and R ² is a saturated or unsaturated monovalent having 1 to 20 carbon atoms which may have a substituent. An organic group, which may form a branched structure or a ring structure, and may have a hetero atom at an arbitrary position, and Ar is a substituent having a carbazole skeleton, The skeleton has a nitro group.)

Here, R ² is preferably a methyl group. Moreover, this invention is the photosensitive composition containing the polymeric compound which has the said photoinitiator and an olefin bond, and also is the hardened | cured material which hardened | cured the said photosensitive composition.

Hereinafter, the present invention will be described in detail.
The photopolymerization initiator of the present invention has a structure represented by the general formula (1). Here, the C = N double bond of the oxime moiety may have E-form and Z-form geometric isomers, but these are handled without particular distinction in the present invention. Therefore, the structure represented by the general formula (1) and the following formulas (2) to (13) represents a mixture of these geometric isomers or any one of them.

In general formula (1), a more preferable structure is represented by the following general formula (2).

Here, R ¹ represents an aryl group having at least one nitro group as a substituent. In view of availability, R ¹ is preferably a phenyl group having at least one nitro group as a substituent, for example, a 2-nitrophenyl group, a 3-nitrophenyl group, a 4-nitrophenyl group, 2,4 -Dinitrophenyl group, 2,5-dinitrophenyl group, 2,6-dinitrophenyl group, 3,4-dinitrophenyl group, 3,5-dinitrophenyl group, 2,3,5-trinitrophenyl group, 2, A 4,6-trinitrophenyl group or the like is advantageous. In addition, the hydrogen atom on the benzene ring of the phenyl group having at least one nitro group is a halogen atom (fluorine atom, chlorine atom, bromine atom, iodine atom, etc.), alkyl group (methyl group, ethyl group, propyl group). , A butyl group, etc.), a halogenated alkyl group (trifluoromethyl group, chloromethyl group, etc.), a derivative substituted with a cyano group, etc. are also preferable, for example, 2-halo-3-nitrophenyl group (halo is a halogen atom substitution) A 2-halo-4-nitrophenyl group, a 2-halo-5-nitrophenyl group, a 2-halo-6-nitrophenyl group, a 3-halo-2-nitrophenyl group, 3- Halo-4-nitrophenyl group, 3-halo-5-nitrophenyl group, 5-halo-2-nitrophenyl group, 4-halo-2-nitrophenyl group, 4-halo-3-nitro Phenyl group, 4-halo-3,5-dinitrophenyl group, 2-alkyl-3-nitrophenyl group, 2-alkyl-4-nitrophenyl group, 2-alkyl-5-nitrophenyl group, 2-alkyl-6 -Nitrophenyl group, 3-alkyl-2-nitrophenyl group, 3-alkyl-4-nitrophenyl group, 3-alkyl-5-nitrophenyl group, 5-alkyl-2-nitrophenyl group, 4-alkyl-2 -Nitrophenyl group, 4-alkyl-3-nitrophenyl group, 4-alkyl-3,5-dinitrophenyl group, 2-nitro-4- (trifluoromethyl) phenyl group, 3-nitro-5- (trifluoro A methyl) phenyl group, a 4-cyano-2-nitrophenyl group, a 3-cyano-5-nitrophenyl group, and the like can also be used. Furthermore, R ¹ may be a polycyclic aryl group having at least one nitro group as a substituent, for example, a naphthyl group, an anthryl group, a phenanthryl group, and the like.

In the general formulas (1) and (2), R ² and R ³ each independently represent a saturated or unsaturated monovalent organic group having 1 to 20 carbon atoms, which may have a substituent, A branched structure or a ring structure may be formed, and a hetero atom may exist at an arbitrary position. Specific examples of R ² and R ³ include methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, sec-butyl group, tert-butyl group, pentyl group, isopentyl group, neopentyl group, tert-pentyl, hexyl, heptyl, octyl, 2-ethylhexyl, nonyl, decyl, dodecyl, tetradecyl, hexadecyl, octadecyl, icosyl, cyclopentyl, cyclohexyl, vinyl, allyl Group, ethynyl group, phenyl group, tolyl group, mesityl group, naphthyl group, anthryl group, phenanthryl group, benzyl group, 2-phenylethyl group, 2-phenylvinyl group and the like saturated or unsaturated monovalent hydrocarbon group And pyridyl group, piperidyl group, piperidino group, pyrrolyl group, pyrrolidinyl group And saturated or unsaturated monovalent heterocyclic groups such as imidazolyl group, imidazolidinyl group, furyl group, tetrahydrofuryl group, thienyl group, tetrahydrothienyl group, morpholinyl group, morpholino group, and quinolyl group. Furthermore, at any position such as the above-mentioned hydrocarbon group and heterocyclic group, as a substituent, a halogen atom, hydroxy group, sulfanyl group, carbonyl group, thiocarbonyl group, carboxy group, thiocarboxy group, dithiocarboxy group, formyl Group, cyano group, nitro group, nitroso group, sulfo group, amino group, imino group, silyl group, ether group, thioether group, ester group, thioester group, dithioester group, amide group, thioamide group, urethane group, thiourethane The structure which introduce | transduced group etc. can also be mentioned. R ² and R ³ include not only monovalent organic groups on carbon atoms such as methyl groups, but also monovalent organic groups on heteroatoms such as methoxy groups, methylsulfanyl groups, and dimethylamino groups. included. R ² and R ³ may be appropriately selected according to the molecular weight, sensitivity, solubility, etc. of the target photopolymerization initiator, but may be a saturated or unsaturated monovalent hydrocarbon group having 1 to 20 carbon atoms. In addition, R ² is most preferably a methyl group, and R ³ is most preferably an ethyl group.

Specific examples of the photopolymerization initiator of the present invention are shown below. However, the present invention is not limited to these.

Although the manufacturing method of the photoinitiator of this invention is not restrict | limited in particular, For example, it can implement by the following procedures. First, R ³ is introduced into the 9-position of 9H-carbazole by a nucleophilic substitution reaction or the like, and then the 6-position is nitrated with nitric acid. Furthermore, R ¹ CO is introduced into the 3-position by Friedel-Crafts acylation reaction to obtain a ketone body. This is converted into an oxime with hydroxylamine, and then the oxime is esterified with an acid halide or acid anhydride of R ² COOH to obtain a photopolymerization initiator of the general formula (2). The order of nitration and Friedel-Crafts acylation may be interchanged.

  Moreover, the photosensitive composition of this invention contains the polymeric compound which has a photoinitiator shown by General formula (1), and an olefin bond. As the polymerizable compound having an olefin bond, a known compound conventionally used in a photosensitive composition can be used without particular limitation. Particularly, acrylic acid and methacrylic acid (hereinafter referred to as “(meta ) Derivatives such as diethylene glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, di (Meth) acrylic acid ester derivatives such as pentaerythritol hexa (meth) acrylate, bisphenol A type epoxy di (meth) acrylate, bisphenol F type epoxy di (meth) acrylate, bisphenol fluorene type epoxy di (meth) a Relate, phenol novolak type epoxy poly (meth) acrylate, it can be preferably used cresol novolac epoxy poly (meth) (meth) acrylic acid epoxy ester derivatives of acrylate and the like. In addition, a reaction product of the (meth) acrylic acid derivative and a compound having an (preferably plural) isocyanate group or an acid anhydride group in the structure is also suitable. Furthermore, vinyl resins (acrylic acid (co) polymer, methacrylic acid (co) polymer, maleic acid (co) polymer, styrene (co) polymer, etc.), which are known resins, polyester resins, polyamide resins, Resins in which a (meth) acryloyl group is introduced into the main chain or side chain of a polyimide resin, polyurethane resin, polyether resin or the like by an ester bond, an amide bond, a urethane bond, or the like can also be used. Other than (meth) acrylic acid derivatives, maleic acid derivatives, maleimide derivatives, crotonic acid derivatives, itaconic acid derivatives, cinnamic acid derivatives, vinyl derivatives, vinyl alcohol derivatives, vinyl ketone derivatives, vinyl aromatic derivatives and the like can also be mentioned. . These polymerizable compounds having an olefinic bond may further have a heat-functional functional group such as an epoxy group, an alkali-soluble functional group such as a carboxy group, etc., and a composite function. . These polymerizable compounds having an olefinic bond may be used alone or in combination.

  In the photosensitive composition of the present invention, the blending ratio of the photopolymerization initiator represented by the general formula (1) is not particularly limited, but the photopolymerization initiator is 0.1% relative to 100 parts by weight of the polymerizable compound having an olefin bond. The amount is preferably 1 to 50 parts by weight, and more preferably 1 to 20 parts by weight.

  The photosensitive composition of the present invention may contain other optional components as necessary. For example, a coloring material, a filler, a resin, an additive, a solvent, and the like can be blended. Here, as coloring materials, dyes, organic pigments, inorganic pigments, carbon black pigments, etc., as fillers, silica, talc, etc., as resins, vinyl resins (acrylic acid (co) polymer, methacrylic acid (co) heavy) Coalesce, maleic acid (co) polymer, styrene (co) polymer, etc.), polyester resin, polyamide resin, polyimide resin, polyurethane resin, polyether resin, epoxy resin, melamine resin, etc. Crosslinking agents, dispersants, surfactants, silane coupling agents, viscosity modifiers, wetting agents, antifoaming agents, antioxidants, etc. As solvents, ester solvents, ketone solvents, ether solvents, alcohol solvents And aromatic solvents, aliphatic solvents, amine solvents, amide solvents, and the like. As these optional components, known compounds can be used without particular limitation.

Moreover, in addition to the photoinitiator shown by General formula (1), a well-known photoinitiator, a dye sensitizer, etc. can also be used together for the photosensitive composition of this invention. For example, acetophenone compounds such as acetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, benzyldimethyl ketal, benzophenone, 2,4,6-trimethylbenzophenone, 4,4′-bis (N, N Benzophenone compounds such as -diethylamino) benzophenone, benzoin ether compounds such as benzoin ethyl ether and benzoin-tert-butyl ether, 2-methyl-1- [4- (methylsulfanyl) phenyl] -2-morpholinopropan-1-one, 2 Α-aminoalkylphenone compounds such as benzyl-2- (N, N-dimethylamino) -1- (4-morpholinophenyl) butan-1-one, thioxanthone compounds such as thioxanthone and 2,4-diethylthioxanthone, 3 , 3 ', 4, Organic peroxides such as '-tetra (tert-butylperoxycarbonyl) benzophenone, 2,2'-bis (2-chlorophenyl) -4,4', 5,5'-tetraphenyl-1,2-biimidazole, etc. Biimidazole compounds, titanocene compounds such as bis (η ⁵ -cyclopentadienyl) bis [2,6-difluoro-3- (1-pyrrolyl) phenyl] titanium, 2,4,6-tris (trichloromethyl)- Triazine compounds such as 1,3,5-triazine, 2- [3,4- (methylenedioxy) phenyl] -4,6-bis (trichloromethyl) -1,3,5-triazine, (2,4, Acylphosphine oxy such as 6-trimethylbenzoyl) diphenylphosphine oxide and bis (2,4,6-trimethylbenzoyl) phenylphosphine oxide Compounds, quinone compounds such as camphorquinone, 1- [4- (phenylsulfanyl) phenyl] octane-1,2-dione = 2-O-benzoyloxime, 1- [9-ethyl-6- (2-methylbenzoyl) An oxime ester compound such as) carbazol-3-yl] ethanone = O-acetyloxime can be used without particular limitation.

  As a method for producing a cured product of the photosensitive composition of the present invention, a known method can be used. After applying or injecting the photosensitive composition to an appropriate substrate or mold suitable for the purpose and application, it is cured by exposure. Should just be done. Here, by performing selective exposure using a photomask or the like, and further performing development, processing such as image formation and modeling can be performed. Moreover, you may perform processes, such as baking, as needed.

  The photopolymerization initiator of the present invention is extremely useful because it is excellent in sensitivity and can provide a highly sensitive photosensitive composition that can be efficiently cured with a small exposure amount. When the photopolymerization initiator of the present invention absorbs ultraviolet light and visible light efficiently and enters an excited state, it rapidly cleaves the oxime ester bond to generate a highly active radical species, and is contained in the photosensitive composition. It is considered that the polymerizable compound having an olefin bond is polymerized at high speed. In addition, since the photopolymerization initiator of the present invention is excellent in thermal stability, it remains even when subjected to a baking process at a high temperature of about 230 ° C. in the manufacturing process like a photoresist used for manufacturing a color filter of a liquid crystal display. There is no possibility that the decomposition product of the photopolymerization initiator is generated and the reliability of the color filter is impaired.

  EXAMPLES Hereinafter, although an Example demonstrates this invention further in detail, this invention is not limited to these.

[Example 1]
<(9-Ethyl-6-nitrocarbazol-3-yl) (4-nitrophenyl) methanone = O-acetyloxime> (photopolymerization initiator of formula (3))
(Synthesis of photopolymerization initiator)
The above photopolymerization initiator was synthesized by the following four-step reaction. The reaction was carried out under normal pressure using a glass reactor.

  Step 1: Using nitromethane as a solvent, 0.10 mol of 9-ethylcarbazole (Tokyo Chemical Industry Co., Ltd.), 0.15 mol of 4-nitrobenzoyl chloride (Tokyo Chemical Industry Co., Ltd.), and 0.15 mol of aluminum chloride 0 The reaction was carried out at ˜5 ° C. for 6 hours. The reaction solution was dropped into ice water, and the precipitated solid was collected and thoroughly washed to obtain 0.07 mol of a crude product of (9-ethylcarbazol-3-yl) (4-nitrophenyl) methanone. .

  Step 2: Using acetic acid as a solvent, the entire product of Step 1 and 0.14 mol of nitric acid were reacted at 80 ° C. for 6 hours. The reaction solution was added dropwise to ice water, and the precipitated solid was collected, washed thoroughly, and 0.09 mol of a crude product of (9-ethyl-6-nitrocarbazol-3-yl) (4-nitrophenyl) methanone. Got considerable.

  Step 3: Using tetrahydrofuran as a solvent, the total amount of the product of Step 2 and 0.12 mol of hydroxylamine hydrochloride were reacted under reflux for 24 hours. After cooling, the reaction solution was added dropwise to water, and the precipitated solid was collected and washed sufficiently to produce crude (9-ethyl-6-nitrocarbazol-3-yl) (4-nitrophenyl) methanone = oxime. 0.05 mol equivalent was obtained.

Step 4: Using pyridine as a solvent, the total amount of the product of Step 3 and 0.10 mol of acetic anhydride were reacted at 80 ° C. for 6 hours. After cooling, the reaction solution was dropped into water, and the precipitated solid was collected, washed thoroughly, and (9-ethyl-6-nitrocarbazol-3-yl) (4-nitrophenyl) methanone = O-acetyloxime. The crude product corresponding to 0.04 mol was obtained. Furthermore, it refine | purified with the silica gel column, and 0.02 mol of pure products were obtained. When the obtained pure compound was identified by ¹ H-NMR (CDCl ₃ ), the following results were shown.
δ = 8.94 (s, 1H), 8.47 (d, 1H), 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)

(Preparation of photosensitive composition)
Propylene glycol monomethyl ether acetate solution of the photopolymerization initiator 0.4% by weight obtained above and an alkali development type photosensitive resin (polymerizable compound having an olefin bond) having a bisphenolfluorene type epoxy diacrylate structure (Nippon Steel) “V-259ME” manufactured by Kagaku Co., Ltd., solid content concentration 56.5 wt%) 5.2 wt%, pentaerythritol tetraacrylate (polymerizable compound having an olefin bond) 1.0 wt%, carbon black pigment (colorant) Dispersion of propylene glycol monomethyl ether acetate with a cationic polymer dispersant (carbon black pigment concentration 25.3% by weight, solid content concentration 31.6% by weight) 27.7% by weight, silicone surfactant ( "Toray Dow Corning" FZ-2122 ") 0.05 weight , 3- (glycidyloxy) propyltrimethoxysilane (silane coupling agent) 0.05 wt%, propylene glycol monomethyl ether acetate (solvent) 22.2 wt%, and cyclohexanone (solvent) 43.4 wt% The photosensitive composition was prepared by blending. Such a photosensitive composition has a solid content concentration of 13.2% by weight and a carbon black pigment concentration in the solid content of 53.1% by weight, and is used as a photoresist (black resist) used for manufacturing a color filter of a liquid crystal display. It is possible. In addition, solid content means components other than a solvent here.

(Evaluation of photosensitive composition)
The photosensitive composition was applied to an alkali-free glass substrate using a spin coater, and dried on an 80 ° C. hot plate for 1 minute to prepare a test piece. At this time, the coating conditions (spin rotation speed) were adjusted so that a cured film having a thickness of 1.0 μm was obtained. Next, using a photomask whose transmittance was changed stepwise between 0 to 100%, an ultraviolet ray of 100 mJ / cm ² was irradiated with an ultrahigh pressure mercury lamp with an i-line illuminance of 30 mW / cm ^2. Image exposure was performed. Thereafter, the test piece was treated with an alkali developer at 26 ° C. (10-fold diluted solution of “V-2401ID” manufactured by Nippon Steel Chemical Co., Ltd.) for 1 minute, and further washed with water to develop the image. This image can read the exposure amount required for photocuring. Finally, the test piece was baked in a hot air oven at 230 ° C. for 30 minutes to obtain a cured film of the photosensitive composition. The exposure required for photocuring determined from the image was 26 mJ / cm ² . Moreover, the optical density of the cured film was 4.5 / μm and had high light shielding properties.

[Example 2]
<(9-Hexyl-6-nitrocarbazol-3-yl) (4-nitrophenyl) methanone = O-acetyloxime> (photopolymerization initiator of formula (4))
Synthesis was carried out in the same manner as in Example 1. When the obtained pure compound was identified by ¹ H-NMR (CDCl ₃ ), the following results were shown.
δ = 8.92 (s, 1H), 8.49 (d, 1H), 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)

Moreover, when the photosensitive composition was produced and evaluated similarly to Example 1, the exposure amount required for photocuring was 26 mJ / cm < ² >.

[Example 3]
<[9- (2-Ethylhexyl) -6-nitrocarbazol-3-yl] (4-nitrophenyl) methanone = O-acetyloxime> (photopolymerization initiator of formula (5))
Synthesis was carried out in the same manner as in Example 1. When the obtained pure compound was identified by ¹ H-NMR (CDCl ₃ ), the following results were shown.
δ = 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)

Moreover, when the photosensitive composition was produced and evaluated similarly to Example 1, the exposure amount required for photocuring was 26 mJ / cm < ² >.

[Example 4]
<(9-Ethyl-6-nitrocarbazol-3-yl) (3-nitrophenyl) methanone = O-acetyloxime> (photopolymerization initiator of formula (6))
Synthesis was carried out in the same manner as in Example 1. When the obtained pure compound was identified by ¹ H-NMR (CDCl ₃ ), the following results were shown.
δ = 8.94 (s, 1H), 8.59 (s, 1H), 8.54-8.50 (m, 2H), 8.47 (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), 1.51 (t, 3H)

Moreover, when the photosensitive composition was produced and evaluated similarly to Example 1, the exposure amount required for photocuring was 26 mJ / cm < ² >.

[Example 5]
<(9-Ethyl-6-nitrocarbazol-3-yl) (3,5-dinitrophenyl) methanone = O-acetyloxime> (photopolymerization initiator of formula (7))
Synthesis was carried out in the same manner as in Example 1. When the obtained pure compound was identified by ¹ H-NMR (CDCl ₃ ), the following results were shown.
δ = 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), 1.52 (t, 3H)

Moreover, when the photosensitive composition was produced and evaluated similarly to Example 1, the exposure amount required for photocuring was 26 mJ / cm < ² >.

[Comparative Example 1]
The photopolymerization initiator of Example 1 was changed to 1- (9-ethyl-6-nitrocarbazol-3-yl) ethanone = O-acetyloxime (a compound represented by the following formula (14)), and the others were examples. In the same manner as in Example 1, a photosensitive composition was prepared and evaluated. As a result, the exposure amount required for photocuring was 30 mJ / cm ² , indicating that the sensitivity was lower than that of the examples (the smaller the exposure amount required for curing, the higher the sensitivity).

[Comparative Example 2]
The photopolymerization initiator of Example 1 was changed to (9-ethyl-6-nitrocarbazol-3-yl) phenylmethanone = O-acetyloxime (a compound represented by the following formula (15)), and the others were examples. In the same manner as in Example 1, a photosensitive composition was prepared and evaluated. As a result, the amount of exposure required for photocuring was 37 mJ / cm ² , indicating that the sensitivity was low compared to the examples.

[Comparative Example 3]
The photopolymerization initiator of Example 1 was changed to (9-ethylcarbazol-3-yl) (4-nitrophenyl) methanone = O-acetyloxime (a compound represented by the following formula (16)), and the others were Examples. In the same manner as in Example 1, a photosensitive composition was prepared and evaluated. As a result, it was shown that photocuring was not possible at all at an exposure amount of up to 100 mJ / cm ^2, and the sensitivity was lower than in the examples.

[Comparative Example 4]
The photopolymerization initiator of Example 1 is 1- (9-ethyl-6- (2-methylbenzoyl) carbazol-3-yl) ethanone = O-acetyloxime (a compound represented by the following formula (17), manufactured by BASF) The composition was changed to “Irgacure OXE02”), and the others were prepared and evaluated in the same manner as in Example 1. As a result, the amount of exposure required for photocuring was 67 mJ / cm ² , indicating that the sensitivity was low compared to the examples.

(Evaluation of thermal stability)
The thermal stability of the photopolymerization initiators of Examples 1, 4, and 5 and the photopolymerization initiators of Comparative Examples 1 and 4 were each evaluated by differential scanning calorimetry. The results are shown in Table 1. The decomposition start points of the photopolymerization initiators in the examples all exceeded 230 ° C., indicating that they were excellent in thermal stability. On the other hand, the decomposition start point of the photopolymerization initiator of the comparative example did not reach 230 ° C., and the thermal stability was insufficient.

  Since the photopolymerization initiator of the present invention is highly sensitive and excellent in thermal stability, it is a photoresist, a photocurable ink, a photocurable paint, a photocurable adhesive, a photosensitive resin for photofabrication, and a photosensitive printing plate. It can be used in a suitable manner. In particular, it is most suitable for applications that require high performance such as a photoresist (black resist, RGB resist) used for manufacturing a color filter of a liquid crystal display.

Claims (4)

A photopolymerization initiator represented by the following general formula (1).

(However, R ¹ represents an aryl group having at least one nitro group as a substituent, and R ² is a saturated or unsaturated monovalent having 1 to 20 carbon atoms which may have a substituent. An organic group, which may form a branched structure or a ring structure, and may have a hetero atom at an arbitrary position, and Ar is a substituent having a carbazole skeleton, The skeleton has a nitro group.) The photopolymerization initiator according to claim 1, wherein R ² is a methyl group.   A photosensitive composition comprising the photopolymerization initiator according to claim 1 or 2 and a polymerizable compound having an olefin bond.   A cured product obtained by curing the photosensitive composition according to claim 3.