Oxime ester compound and photopolymerization initiator containing the same

Abstract

The oxime ester compound represented by the following general formula (I): 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 10 , R 11 , R 12 and R 13 At least three of them are groups represented by the following general formula (II). 3 , R 6 and R 11 At least one of them is preferably a group represented by general formula (II).

Description

Technical Field

[0001] The present invention relates to a novel oxime ester compound useful as a photopolymerization initiator used in a photosensitive composition, a photopolymerization initiator containing the compound, and a photosensitive composition containing the photopolymerization initiator and an ethylenically unsaturated compound. Background Art

[0002] The photosensitive composition is a composition in which a photopolymerization initiator is added to an ethylenically unsaturated compound. Since the composition can be polymerized and cured by irradiation with energy rays (light), it is used in photocurable inks, photosensitive printing plates, various photoresists, and the like.

[0003] As a photopolymerization initiator used in the above-mentioned photosensitive composition, an oxime ester photopolymerization initiator having a carbazole skeleton is disclosed in Patent Document 1. In addition, a polymerization initiator containing an oxime ester compound having a triarylamine skeleton is disclosed in Patent Document 2. However, the oxime ester compounds described in Patent Documents 1 and 2 cannot achieve a satisfactory level of sensitivity, heat resistance (low sublimation) and transparency (high brightness of the color filter).

[0004] In addition, since the colored alkali-developable photosensitive composition containing a colorant such as a color filter is required to have high sensitivity, the photopolymerization initiator in the resist needs to be set to a high concentration. However, a photopolymerization initiator with a high concentration may cause the generation of residues due to deterioration of developability, contamination of a photomask or a heating furnace due to sublimation products, and coloration of a cured product resulting in poor brightness.

[0005] Prior art literature

[0006] Patent Literature

[0007] Patent Document 1: International Publication No. 2008 / 138732

[0008] Patent Document 2: International Publication No. 2017 / 033880 Summary of the invention

[0009] Therefore, an object of the present invention is to provide an oxime ester compound useful as a photopolymerization initiator having high sensitivity and high transmittance in the visible light region, a photopolymerization initiator and a photosensitive composition using the compound, a color filter having high brightness, and a display device including the color filter.

[0010] The present invention solves the above-mentioned problems by providing the following [1] to [9].

[0011] [1] An oxime ester compound represented by the following general formula (I).

[0012] [Chemical formula 1]

[0013]

[0014] (Where R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 10 , R 11 , R 12 and R 13 Each independently represents a group represented by the following general formula (II), a hydrogen atom, a halogen atom, a nitro group, a cyano group, a hydroxyl group, a carboxyl group, an amino group, R 21 , OR 21 , SR 21 NR 22 R 23 , COR 21 , SOR 21 、SO2R 21 or CONR 22 R 23 ,

[0015] R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 10 , R 11 , R 12 and R 13 At least three of them are groups represented by the following general formula (II),

[0016] R 21 , R 22 and R 23 Each independently represents a hydrocarbon group having 1 to 20 carbon atoms or a heterocyclic group having 2 to 20 carbon atoms,

[0017] R 21 , R 22 and R 23 The hydrogen atoms in the groups represented may be substituted by halogen atoms, nitro groups, cyano groups, hydroxyl groups, amino groups, carboxyl groups, methacryloyl groups, acryloyl groups, epoxy groups, vinyl groups, vinyl ether groups, mercapto groups, isocyanate groups or heterocyclic groups having 2 to 20 carbon atoms.

[0018] R 21, R 22 and R 23 The methylene group in the group represented by may be replaced by -O-, -CO-, -COO-, -OCO-, -NR 24 -、-NR 24 CO-, -S-, -CS-, -SO2-, -SCO-, -COS-, -OCS- or CSO-substituted,

[0019] R 24 represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms,

[0020] X 1 Indicates absence, direct bonding, -CO-, -O-, or -S-. )

[0021] [Chemical formula 2]

[0022]

[0023] (Where R 31 and R 32 Each independently represents a hydrogen atom, a halogen atom, a nitro group, a cyano group, a hydrocarbon group having 1 to 20 carbon atoms, or a heterocyclic group having 2 to 20 carbon atoms,

[0024] R 31 and R 32 The hydrogen atoms in the groups represented may be substituted by halogen atoms, nitro groups, cyano groups, hydroxyl groups, amino groups, carboxyl groups, methacryloyl groups, acryloyl groups, epoxy groups, vinyl groups, vinyl ether groups, mercapto groups, isocyanate groups or heterocyclic groups having 2 to 20 carbon atoms.

[0025] R 31 and R 32 The methylene group in the group represented by is sometimes also referred to as -O-, -CO-, -COO-, -OCO-, -NR 33 -、-NR 33 CO-, -S-, -CS-, -SO2-, -SCO-, -COS-, -OCS- or CSO-substituted,

[0026] R 33 represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms,

[0027] n represents 0 or 1, and * represents a bonding site. )

[0028] [2] The oxime ester compound according to [1], wherein R in the general formula (I) 3 , R 6 and R 11 At least one of them is a group represented by general formula (II).

[0029] [3] A photopolymerization initiator comprising the oxime ester compound according to [1] or [2].

[0030] [4] A photosensitive composition comprising the photopolymerization initiator (A) according to [3] and an ethylenically unsaturated compound (B).

[0031] [5] The photosensitive composition according to [4], further comprising a colorant (C).

[0032] [6] An alkali-developable photosensitive resin composition comprising the photosensitive composition according to [4] or [5] and an alkali-developable compound (D).

[0033] [7] A cured product, which is a cured product of the photosensitive composition according to [4] or [5] or the alkali-developable photosensitive resin composition according to [6].

[0034] [8] A display device comprising the cured product described in [7].

[0035] [9] A method for producing a cured product, comprising the step of curing the photosensitive composition according to [4] or [5] or the alkali-developable photosensitive resin composition according to [6] by light irradiation or heating. DETAILED DESCRIPTION

[0036] Hereinafter, the oxime ester compound of the present invention and the photopolymerization initiator (A) containing the same will be described in detail based on preferred embodiments.

[0037] The oxime ester compound of the present invention is a novel compound represented by the above general formula (I). In the oxime ester compound, geometrical isomers exist due to the double bond of oxime, but these are not distinguished.

[0038] That is, in the present specification, the compound represented by the above-mentioned general formula (I) and its exemplary compounds represent one or a mixture of two or more of these geometric isomers, and are not limited to structures showing specific isomers.

[0039] In the above general formula (I), R 21 ~R 24 The hydrocarbon group having 1 to 20 carbon atoms is not particularly limited, but preferably represents an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, a cycloalkylalkyl group having 4 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, and an arylalkyl group having 7 to 20 carbon atoms.

[0040] Examples of the alkyl group having 1 to 20 carbon atoms include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, pentyl, isopentyl, tert-pentyl, hexyl, heptyl, octyl, isooctyl, 2-ethylhexyl, tert-octyl, nonyl, isononyl, decyl, isodecyl, undecyl, dodecyl, tetradecyl, hexadecyl, octadecyl and eicosyl, and an alkyl group having 1 to 10 carbon atoms is particularly preferred.

[0041] Examples of the alkenyl group having 2 to 20 carbon atoms include vinyl, ethylene, 2-propenyl, 3-butenyl, 2-butenyl, 4-pentenyl, 3-pentenyl, 2-hexenyl, 3-hexenyl, 5-hexenyl, 2-heptenyl, 3-heptenyl, 4-heptenyl, 3-octenyl, 3-nonenyl, 4-decenyl, 3-undecenyl, 4-dodecenyl, and 4,8,12-tetradecatrienylallyl. Alkenyl groups having 1 to 10 carbon atoms are particularly preferred.

[0042] The cycloalkyl group having 3 to 20 carbon atoms is a saturated monocyclic or polycyclic alkyl group having 3 to 20 carbon atoms. Examples of the saturated monocyclic alkyl group include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl and cyclodecyl. Examples of the saturated polycyclic alkyl group include adamantyl, decalinyl, octahydropentalene and bicyclo[1.1.1]pentyl.

[0043] The cycloalkylalkyl group having 4 to 20 carbon atoms is a group having 4 to 20 carbon atoms in which the hydrogen atoms of the alkyl group are replaced by cycloalkyl groups. Examples thereof include cyclopropylmethyl, 2-cyclobutylethyl, 3-cyclopentylpropyl, 4-cyclohexylbutyl, cycloheptylmethyl, cyclooctylmethyl, 2-cyclononylethyl, 2-cyclodecylethyl, 3-3-adamantylpropyl, and decahydronaphthylpropyl.

[0044] Examples of the aryl group having 6 to 20 carbon atoms include phenyl, tolyl, xylyl, ethylphenyl, naphthyl, anthryl, phenanthryl, phenyl substituted with one or more of the above alkyl groups, biphenyl, naphthyl, anthryl, and the like.

[0045] The arylalkyl group having 7 to 30 carbon atoms is a group having 7 to 30 carbon atoms obtained by replacing the hydrogen atom of an alkyl group with an aryl group, and examples thereof include benzyl, α-methylbenzyl, α,α-dimethylbenzyl, phenylethyl, and naphthylpropyl.

[0046] Among the above-mentioned hydrocarbon groups having 1 to 20 carbon atoms, alkyl groups having 1 to 12 carbon atoms, alkenyl groups having 2 to 10 carbon atoms, cycloalkyl groups having 3 to 10 carbon atoms, cycloalkylalkyl groups having 4 to 15 carbon atoms, aryl groups having 6 to 15 carbon atoms and arylalkyl groups having 7 to 15 carbon atoms are particularly preferred from the perspective of good sensitivity as photopolymerization initiators.

[0047] As R in the above general formula (I) 21 ~R 23 The heterocyclic group having 2 to 20 carbon atoms represented by R 21 ~R 23 Examples of heterocyclic groups in which the number of carbon atoms of hydrogen atoms in the group represented by are 2 to 20 include pyrrolyl, pyridyl, pyridylethyl, pyrimidinyl, pyridazinyl, piperazinyl, piperidinyl, pyranyl, pyranylethyl, pyrazolyl, triazinyl, triazinylmethyl, pyrrolidinyl, quinolyl, isoquinolyl, imidazolyl, benzimidazolyl, triazolyl, furyl, furanyl, benzofuranyl, thienyl, phenylthio, benzophenylthio, thiadiazolyl, thiazolyl, benzothiazolyl, oxazolyl, benzoxazolyl, isothiazolyl, isoxazolyl, indolyl, julolidine, morpholinyl, thiomorpholinyl, 2-pyrrolidon-1-yl, 2-piperidon-1-yl, 2,4-dioxyimidazolidin-3-yl, and 2,4-dioxyoxazolidin-3-yl.

[0048] In the above general formula (I), R 21 ~R 23 The methylene group in the group represented by is sometimes also referred to as -O-, -CO-, -COO-, -OCO-, -NR 24 -、-NR 24 The substitution may be one or more groups. In the case of a continuously substitutable group, two or more groups may be substituted continuously without adjacent oxygen atoms.

[0049] Among the heterocyclic group having 2 to 20 carbon atoms, a heterocyclic group having 2 to 10 carbon atoms is particularly preferred from the viewpoint of good sensitivity as a photopolymerization initiator.

[0050] As R in the above general formula (II) 31 ~R 33 The hydrocarbon group having 1 to 20 carbon atoms represented by can be exemplified by the following: 21 ~R 24 The hydrocarbon groups having 1 to 20 carbon atoms represented are the same hydrocarbon groups.

[0051] In the above general formula (II), R 31 and R 32 The heterocyclic group having 2 to 20 carbon atoms represented by R 31 and R 32 The heterocyclic group having 2 to 20 carbon atoms in the hydrogen atom in the group represented by can be exemplified by the following: 21 ~R 23 The hydrocarbon groups having 1 to 20 carbon atoms represented are the same hydrocarbon groups.

[0052] In the above general formula (II), R 31 and R 32 The methylene group in the group represented by is sometimes also referred to as -O-, -CO-, -COO-, -OCO-, -NR 24 -、-NR 24 The substitution may be one or more groups. In the case of a continuously substitutable group, two or more groups may be substituted continuously without adjacent oxygen atoms.

[0053] Examples of the halogen atom in the general formulae (I) and (II) include fluorine, chlorine, bromine and iodine.

[0054] X in the general formula (I) 1 When an oxime ester compound is used as a photopolymerization initiator, it is excellent in brightness, so it is preferred that X 1 Oxime ester compounds that are directly bonded are particularly preferred because they have excellent sensitivity in addition to brightness. 1 Does not exist in X 1 There is no atom at the position of , and the oxime ester compound represented by the general formula (I) has a triphenolamine skeleton.

[0055] In R 1 ~R 13 In the case of a group other than the general formula (II), R 1 ~R 13 A compound which is a hydrogen atom or a cyano group, particularly a hydrogen atom, is preferred because of easy synthesis.

[0056] R in the general formula (I) 3 , R 6 and R 11 Oxime ester compounds in which at least one, preferably two, and more preferably all of the groups are represented by the general formula (II) are preferred because they have a good yield during synthesis and are easy to purify. 3, R 6 and R 11 When all of them are groups represented by the general formula (II), R 1 , R 2 , R 4 , R 5 , R 7 , R 8 , R 9 , R 10 , R 12 and R 13 Oxime ester compounds having a hydrogen atom are preferred because they are easy to synthesize.

[0057] A cured product using an oxime ester compound wherein n=1 in the general formula (II) as the photopolymerization initiator (A) is preferred because it is excellent in transparency and brightness.

[0058] In the above general formula (II), R 31 Compounds having an alkyl group having 1 to 12 carbon atoms, particularly an alkyl group having 1 to 7 carbon atoms, are preferred because they have high solubility in organic solvents. 32 An alkyl group having 1 to 4 carbon atoms, particularly a methyl group, an ethyl group or a phenyl group is preferred because of its high reactivity.

[0059] Preferred specific examples of the oxime ester compound of the present invention represented by the above general formula (I) include the following compounds No. 1 to No. 261. However, the present invention is not limited to the following compounds at all.

[0060] [Chemical formula 3]

[0061]

[0062] [Chemical formula 4]

[0063]

[0064] [Chemical formula 5]

[0065]

[0066] [Chemical formula 6]

[0067]

[0068] [Chemical formula 7]

[0069]

[0070] [Chemical formula 8]

[0071]

[0072] [Chemical formula 9]

[0073]

[0074] [Chemical formula 10]

[0075]

[0076] [Chemical formula 11]

[0077]

[0078] [Chemical formula 12]

[0079]

[0080] [Chemical formula 13]

[0081]

[0082] [Chemical formula 14]

[0083]

[0084] [Chemical formula 15]

[0085]

[0086] [Chemical formula 16]

[0087]

[0088] [Chemical formula 17]

[0089]

[0090] [Chemical formula 18]

[0091]

[0092] [Chemical formula 19]

[0093]

[0094] [Chemical formula 20]

[0095]

[0096] [Chemical formula 21]

[0097]

[0098] [Chemical formula 22]

[0099]

[0100] [Chemical formula 23]

[0101]

[0102] The oxime ester compound of the present invention represented by the above general formula (I) is not particularly limited, and can be synthesized, for example, by the method shown below.

[0103] When n in the general formula (II) is 0, the synthesis can be carried out by the following reaction process. Specifically, a ketone compound 1 is obtained by reacting a known nitrogen-containing compound with a known and commercially available acid chloride, and the obtained ketone compound 1 is reacted with hydroxylamine hydrochloride to obtain an oxime compound 1. Then, the acid chloride and the oxime compound 1 are reacted in the presence of triethylamine (TEA) to obtain the oxime ester compound 1 of the present invention represented by the general formula (I) above.

[0104] The oxime compound and the oxime ester compound can also be produced by the method described in International Publication No. 2008 / 078678.

[0105] [Chemical formula 24]

[0106]

[0107]

[0108] In the above reaction formula, R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 10 , R 11 , R 12 , R 13 , R 31 , R 32 and X 1 and R of the general formula (I) and the general formula (II) 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 10 , R 11 , R 12 , R 13 , R 31 , R32 and X 1 same.

[0109] When n in the general formula (II) is 1, it can be produced by the following method according to the following reaction formula.

[0110] That is, a known nitrogen-containing compound is reacted with an acid chloride to obtain a ketone compound 2, and the ketone compound 2 is reacted with isobutyl nitrite to obtain an oxime compound 2. Next, an acid anhydride or an acid chloride is reacted with the oxime compound 2 to obtain the oxime ester compound 2 of the present invention represented by the general formula (I).

[0111] [Chemical formula 25]

[0112]

[0113]

[0114] In the above reaction formula, R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 10 , R 11 , R 12 , R 13 , R 31 , R 32 and X 1 and R of the general formula (I) and the general formula (II) 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 10 , R 11 , R 12 , R 13 , R 31 , R 32 and X 1 same.

[0115] The novel oxime ester compound of the present invention described above is useful in medicine, pesticide, base generator and photopolymerization initiator, and is useful as a free radical polymerization initiator (photoradical polymerization initiator or thermal radical polymerization initiator) in particular among photopolymerization initiators. In addition, the novel oxime ester compound of the present invention can also be suitably used as a sensitizer.

[0116] The photosensitive composition of the present invention contains the photopolymerization initiator (A) and the ethylenically unsaturated compound (B) of the present invention, and contains a colorant (C), an alkali-developable compound (D), an inorganic compound, a solvent and other components in combination as optional components.

[0117] The photopolymerization initiator (A) of the present invention is a substance containing at least one oxime ester compound of the present invention represented by general formula (I), and other photopolymerization initiators may be used in combination. The content of the oxime ester compound of the present invention in the photopolymerization initiator (A) is preferably 30 to 100% by mass, more preferably 50 to 100% by mass.

[0118] Moreover, the photopolymerization initiator (A) of the present invention is useful as a photopolymerization initiator of the ethylenically unsaturated compound (B).

[0119] As other photopolymerization initiators that do not belong to the general formula (I), there are no particular restrictions as long as they are substances that generate free radicals by light irradiation, and conventionally known compounds can be used. Examples of preferred substances include oxime ester compounds, acetophenone compounds, benzil compounds, benzophenone compounds, thioxanthone compounds, phosphine oxide compounds and titanocene compounds.

[0120] Examples of the oxime ester compound include compounds having a group represented by the general formula (II). Since the oxime ester compound has excellent sensitivity among the photopolymerization initiators, it can be preferably used in the photosensitive composition of the present invention.

[0121] In the above general formula (II), R 31 ~R 33 The hydrocarbon group having 1 to 20 carbon atoms represented is the same as the hydrocarbon group having 1 to 20 carbon atoms described in the general formula (I).

[0122] Sometimes, R in the above general formula (II) 31 and R 32 and R 31 or R 32 The heterocyclic group having 2 to 20 carbon atoms modified by the group represented by is the same as the heterocyclic group having 2 to 20 carbon atoms described in the general formula (I).

[0123] Among the oxime ester compounds having a group represented by the above general formula (II), the compound represented by the following general formula (III) is preferably used in the photosensitive composition of the present invention because of its particularly high sensitivity.

[0124] Among the oxime ester compounds having a group represented by the above general formula (I), the compound represented by the following general formula (III) is preferably used in the photosensitive composition of the present invention because of its particularly high sensitivity.

[0125] [Chemical formula 26]

[0126]

[0127] (Where R 31 , R 32 and n are respectively the same as R in the general formula (II) 31 , R 32 and n are the same,

[0128] R 41 and R 42 each independently represents a direct bond, a hydrogen atom, a nitro group, a cyano group, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an arylalkyl group having 7 to 20 carbon atoms, or a group having 2 to 20 carbon atoms containing a heterocyclic ring,

[0129] X 11 Indicates oxygen atoms, sulfur atoms, selenium atoms, CR 43 R 44 、CO、NR 45 or PR 46 ,

[0130] X 12 represents no bond, direct bond, hydrocarbon group with 1 to 20 carbon atoms, CO, R 43 ~R 46 Each independently represents a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, or a group having 2 to 20 carbon atoms containing a heterocyclic ring, and R 43 ~R 46 The hydrogen atoms in the groups represented by the above may be substituted by halogen atoms, nitro groups, cyano groups, hydroxyl groups, amino groups, carboxyl groups, methacryloyl groups, acryloyl groups, epoxy groups, vinyl groups, mercapto groups, isocyanate groups, or heterocyclic groups. 41 ~R 46 The methylene group in the represented group may also be replaced by -O-, -CO-, -COO-, -OCO-, -S-, -SO2-, -SCO- or -COS- under the condition that the oxygen is not adjacent.

[0131] R 41 ~R 46 Sometimes, they each independently form a ring with any adjacent benzene ring.

[0132] a represents a number from 0 to 4,

[0133] b represents a number from 0 to 3. )

[0134] In the above general formula (III), R 41 ~R 46 The hydrocarbon groups having 1 to 20 carbon atoms represented are the same as the hydrocarbon groups having 1 to 20 carbon atoms described in the above general formula (I).

[0135] In the above general formula (III), R 41 ~R 46 The heterocyclic ring-containing group having 2 to 20 carbon atoms represented is the same as the heterocyclic ring-containing group having 2 to 20 carbon atoms described in the above general formula (I).

[0136] Preferred oxime ester compounds represented by the general formula (III) include, for example, compounds No. A2-1 to No. A2-28 shown below. However, the polymerization initiator (A) used in the present invention is not limited to the following compounds.

[0137] [Chemical formula 27]

[0138]

[0139] [Chemical formula 28]

[0140]

[0141] [Chemical formula 29]

[0142]

[0143] [Chemical formula 30]

[0144]

[0145] In the general formula (III), X 1 is a sulfur atom, X 2 In the case of no bond, an oxime ester compound having a diphenylsulfide skeleton as represented by the above-mentioned compound Nos. A2-1 to A2-7 is preferred from the viewpoint of obtaining a photosensitive composition having good sensitivity by using it together with the oxime ester compound of the present invention as a polymerization initiator.

[0146] In the general formula (III), X 1 NR 55 , and X 2 In the case of direct bonding, an oxime ester compound having a carbazole skeleton as represented by the above-mentioned compound Nos. A2-8 to A2-28 is particularly preferred from the viewpoint of obtaining a photosensitive composition having good sensitivity.

[0147] Examples of the acetophenone compounds include diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropane-1-one, 4'-isopropyl-2-hydroxy-2-methylpropiophenone, 2-hydroxymethyl-2-methylpropiophenone, 2,2-dimethoxy-1,2-diphenylethane-1-one, p-dimethylaminoacetophenone, p-tert-butyldichloroacetophenone, p-tert-butyltrichloroacetophenone, p-azidobenzylideneacetophenone, 1-hydroxy Cyclohexyl phenyl ketone, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropanone-1, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butanone-1, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin-n-butyl ether, benzoin isobutyl ether and 1-[4-(2-hydroxyethoxy)-phenyl]-2-hydroxy-2-methyl-1-propane-1-one, etc.

[0148] Examples of the benzil-based compound include benzil and the like.

[0149] Examples of the benzophenone-based compound include benzophenone, methyl o-benzoylbenzoate, Michler's ketone, 4,4′-bisdiethylaminobenzophenone, 4,4′-dichlorobenzophenone, and 4-benzoyl-4′-methyldiphenyl sulfide.

[0150] Examples of the thioxanthone-based compound include thioxanthone, 2-methylthioxanthone, 2-ethylthioxanthone, 2-chlorothioxanthone, 2-isopropylthioxanthone, and 2,4-diethylthioxanthone.

[0151] Examples of the phosphine oxide compound include phosphine oxide compounds such as 2,4,6-trimethylbenzoyldiphenylphosphine oxide.

[0152] Examples of the titanocene-based compound include bis(cyclopentadienyl)-bis[2,6-difluoro-3-(pyrrol-1-yl)]titanium and the like.

[0153] Examples of commercially available free radical initiators include Adeka Optomer N-1414, N-1717, N-1919, ADEKA ARKLS NCI-831, and NCI-930 (all manufactured by ADEKA Corporation); IRGACURE 184, IRGACURE 369, IRGACURE 651, IRGACURE 907, IRGACURE OXE 01, IRGACURE OXE 02, and IRGACURE 784 (all manufactured by BASF); TR-PBG-304, TR-PBG-305, TR-PBG-309, and TR-PBG-314 (all manufactured by TRONLY); and the like.

[0154] In the photosensitive composition of the present invention, the content of the photopolymerization initiator (A) is not particularly limited, but is preferably 1 to 70 parts by mass, more preferably 1 to 50 parts by mass, and most preferably 5 to 30 parts by mass, based on 100 parts by mass of the ethylenically unsaturated compound (B).

[0155] The ethylenically unsaturated compound (B) has an ethylenically unsaturated bond. The ethylenically unsaturated compound (B) is not particularly limited, and substances used in conventional photosensitive compositions can be used, such as unsaturated aliphatic hydrocarbons such as ethylene, propylene, butylene, isobutylene, vinyl chloride, vinylidene chloride, vinylidene fluoride, and tetrafluoroethylene; (meth)acrylic acid, α-chloroacrylic acid, itaconic acid, maleic acid, citraconic acid, fumaric acid, nadic acid, crotonic acid, isocrotonic acid, vinylacetic acid, allylacetic acid, cinnamic acid, sorbic acid, mesaconic acid, succinic acid mono[2-(meth)acryloyloxyethyl] ester, phthalic acid mono[2-(meth)acryloyloxyethyl] ester, ω-carboxy polycaprolactone mono(meth)acrylate, and other polymers having carboxyl groups and hydroxyl groups at both ends thereof. Acids; unsaturated polybasic acids such as hydroxyethyl (meth)acrylate maleate, hydroxypropyl (meth)acrylate maleate, dicyclopentadiene maleate or multifunctional (meth)acrylates having one carboxyl group and two or more (meth)acryloyl groups; 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, glycidyl (meth)acrylate, the following compounds No.A1 to No.A4, methyl (meth)acrylate, butyl (meth)acrylate, isobutyl (meth)acrylate, tert-butyl (meth)acrylate, cyclohexyl (meth)acrylate, n-octyl (meth)acrylate, isooctyl (meth)acrylate, isononyl (meth)acrylate, stearyl (meth)acrylate , lauryl (meth)acrylate, methoxyethyl (meth)acrylate, dimethylaminomethyl (meth)acrylate, dimethylaminoethyl (meth)acrylate, aminopropyl (meth)acrylate, dimethylaminopropyl (meth)acrylate, ethoxyethyl (meth)acrylate, poly(ethoxy)ethyl (meth)acrylate, butoxyethoxyethyl (meth)acrylate, ethylhexyl (meth)acrylate, phenoxyethyl (meth)acrylate, tetrahydrofuran (meth)acrylate, vinyl (meth)acrylate, allyl (meth)acrylate, benzyl (meth)acrylate, ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, polyethylene glycol Esters of unsaturated monobasic acids and polyols or polyphenols such as di(meth)acrylate, propylene glycol di(meth)acrylate, 1,4-butanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, trimethylolethane tri(meth)acrylate, trimethylolpropane tri(meth)acrylate, dipentaerythritol hexa(meth)acrylate, dipentaerythritol penta(meth)acrylate, pentaerythritol tetra(meth)acrylate, pentaerythritol tri(meth)acrylate, tricyclodecane dimethylol di(meth)acrylate, tri[(meth)acryloylethyl]isocyanurate, and polyester (meth)acrylate oligomers; metal salts of unsaturated polybasic acids such as zinc (meth)acrylate and magnesium (meth)acrylate;Anhydrides of unsaturated polybasic acids such as maleic anhydride, itaconic anhydride, citraconic anhydride, methyltetrahydrophthalic anhydride, tetrahydrophthalic anhydride, trialkyltetrahydrophthalic anhydride, 5-(2,5-dioxotetrahydrofuranyl)-3-methyl-3-cyclohexene-1,2-dicarboxylic anhydride, trialkyltetrahydrophthalic anhydride-maleic anhydride adduct, dodecenylsuccinic anhydride, methylnadic anhydride; (meth)acrylamide, methylenebis-(meth)acrylamide, diethylenetriaminetri(meth)acrylamide, benzyldimethylbis(meth)acrylamide, α-chloro Acrylamide, N-2-hydroxyethyl (meth)acrylamide and other unsaturated monobasic acids and amides of polyamines; unsaturated aldehydes such as acrolein; unsaturated nitriles such as (meth)acrylonitrile, α-chloroacrylonitrile, vinylidene cyanide, and allyl nitrile; unsaturated aromatic compounds such as styrene, 4-methylstyrene, 4-ethylstyrene, 4-methoxystyrene, 4-hydroxystyrene, 4-chlorostyrene, divinylbenzene, vinyltoluene, vinylbenzoic acid, vinylphenol, vinylsulfonic acid, 4-vinylbenzenesulfonic acid, vinylbenzyl methyl ether, and vinylbenzyl glycidyl ether ; unsaturated ketones such as methyl vinyl ketone; unsaturated amine compounds such as vinylamine, allylamine, N-vinylpyrrolidone, and vinylpiperidine; vinyl alcohols such as allyl alcohol and crotyl alcohol; vinyl ethers such as vinyl methyl ether, vinyl ethyl ether, n-butyl vinyl ether, isobutyl vinyl ether, and allyl glycidyl ether; unsaturated imides such as maleimide, N-phenylmaleimide, and N-cyclohexylmaleimide; indenes such as indene and 1-methylindene; aliphatic conjugated dienes such as 1,3-butadiene, isoprene, and chloroprene; polystyrene, poly(methyl)propylene Macromonomers with mono(meth)acryloyl groups at the end of polymer molecular chains such as methyl acrylate, poly(meth)acrylate n-butyl ester, and polysiloxane; vinyl chloride, vinylidene chloride, divinyl succinate, diallyl phthalate, triallyl phosphate, triallyl isocyanurate, vinyl sulfide, vinyl imidazole, vinyl oxazoline, vinyl carbazole, vinyl pyrrolidone, vinyl pyridine, vinyl monomers containing hydroxyl groups and vinyl carbamate compounds of polyisocyanate compounds, vinyl monomers containing hydroxyl groups and vinyl epoxy compounds of polyepoxide compounds. ;

[0156] As the above-mentioned ethylenically unsaturated compound (B), commercially available products can be used, and examples thereof include KAYARADDPHA, DPEA-12, PEG400DA, THE-330, RP-1040, NPGDA, PET30 (manufactured by Nippon Kayaku Co., Ltd.), SPC-1000, SPC-3000 (manufactured by Showa Denko Co., Ltd.), ARONIX M-140, M-215, M-350 (manufactured by Toagosei Co., Ltd.), NK ESTER A-DPHA-TMPT, A-DCP, A-HD-N, A-9300, TMPT, DCP, NPG and HD-N (manufactured by Shin-Nakamura Chemical Industry Co., Ltd.), etc.

[0157] Among them, mono(meth)acrylates of polymers having carboxyl groups and hydroxyl groups at both ends, polyfunctional (meth)acrylates having one carboxyl group and two or more (meth)acryloyl groups, and esters of unsaturated monobasic acids, polyols, or polyphenols are suitable for the alkali-developable photosensitive resin composition of the present invention.

[0158] The ethylenically unsaturated compound may be used alone or in combination of two or more. When two or more are used in combination, they may be copolymerized in advance to form a copolymer.

[0159] [Chemical formula 31]

[0160]

[0161] [Chemical formula 32]

[0162]

[0163] [Chemical formula 33]

[0164]

[0165] [Chemical formula 34]

[0166]

[0167] The photosensitive composition of the present invention may further contain a colorant (C) to prepare a colored photosensitive composition. Examples of the colorant (C) include pigments, dyes, and natural pigments. These colorants (C) may be used alone or in combination of two or more.

[0168] As the above-mentioned pigment, for example, nitroso compounds, nitro compounds, azo compounds, diazo compounds, xanthene compounds, quinoline compounds, anthraquinone compounds, coumarin compounds, phthalocyanine compounds, isoindolinone compounds, isoindolinone compounds, quinacridone compounds, anthraquinone compounds, perynone compounds, perylene compounds, dione pyrrolopyrrole compounds, thioindigo compounds, dioxazine compounds, triphenylmethane compounds, quinophthalone compounds, naphthalenetetracarboxylic acids; metal complexes of azo dyes and cyanine dyes; lake pigments; Carbon black obtained by furnace process, tank process or thermal cracking process, or carbon black such as acetylene black, ketjen black or lamp black; a substance obtained by adjusting or coating the above carbon black with epoxy resin, a substance obtained by pre-dispersing the above carbon black with resin in a solvent and allowing it to adsorb 20 to 200 mg / g of resin, a substance obtained by subjecting the above carbon black to acidic or alkaline surface treatment, a substance having an average particle size of 8 nm or more and a DBP oil absorption of 90 ml / 100 g or less, a total oxygen content calculated from CO and CO2 in the volatile components at 950°C relative to 100 m2 of the surface area of ​​the carbon black 2 Substances with a concentration of 9 mg or more; graphite, graphitized carbon black, activated carbon, carbon fiber, carbon nanotube, helical carbon fiber (Carbon microcoil), carbon nanohorn, carbon aerogel, fullerene; aniline black, pigment black 7, titanium black; organic or inorganic pigments such as chromium oxide green, Milori blue, cobalt green, cobalt blue, manganese series, ferrocyanide, phosphate ultramarine, Prussian blue, ultramarine, cobalt sky blue, emerald green, emerald green, lead sulfate, chrome yellow, zinc yellow, red iron oxide (red iron (III) oxide), cadmium red, synthetic iron black, and umber. These pigments may be used alone or in combination.

[0169] As the above-mentioned pigment, commercially available pigments may be used, and examples thereof include Pigment Red 1, 2, 3, 9, 10, 14, 17, 22, 23, 31, 38, 41, 48, 49, 88, 90, 97, 112, 119, 122, 123, 144, 149, 166, 168, 169, 170, 171, 177, 179, 180, 184, 185, 192, 200, 202, 209, 215, 216, 217, 220, 223, 224, 226, 227, 228, 240, 254; pigment orange 13, 31, 34, 36, 38, 43, 46, 48, 49, 51, 52, 55, 59, 60, 61, 62, 64, 65, 71; pigment Yellow 1, 3, 12, 13, 14, 16, 17, 20, 24, 55, 60, 73, 81, 83, 86, 93, 95, 97, 98, 100, 109, 110, 113, 114, 117, 120, 125, 126, 127, 129, 137, 138, 139, 147, 148, 150, 151, 15 2, 153, 154, 166, 168, 175, 180, 185; Pigment Green 7, 10, 36; Pigment Blue 15, 15:1, 15:2, 15:3, 15:4, 15:5, 15:6, 22, 24, 56, 60, 61, 62, 64; Pigment Violet 1, 19, 23, 27, 29, 30, 32, 37, 40, 50, etc.

[0170] Examples of the dyes include azo dyes, anthraquinone dyes, indigoid dyes, triarylmethane dyes, xanthene dyes, alizarin dyes, acridine dyes, stilbene dyes, thiazole dyes, naphthol dyes, quinoline dyes, nitro dyes, indamine dyes, oxazine dyes, phthalocyanine dyes, and cyanine dyes, and a plurality of these may be used in combination.

[0171] In the photosensitive composition of the present invention, the content of the colorant (C) is preferably 10 to 200 parts by mass, more preferably 10 to 100 parts by mass, based on 100 parts by mass of the ethylenically unsaturated compound (B).

[0172] The photosensitive composition of the present invention may further contain an alkali-developable compound (D) to form an alkali-developable photosensitive resin composition. A composition containing both a colorant (C) and an alkali-developable compound (D) is also referred to as a colored alkali-developable photosensitive resin composition.

[0173] The alkali-developable compound (D) is not particularly limited as long as it is soluble in an aqueous alkali solution, and examples thereof include resins described in JP-A-2004-264414.

[0174] In addition, as the above-mentioned alkali-developable compound (D), a copolymer of acrylates, a phenol novolac epoxy resin, a cresol novolac epoxy resin, a polyphenylmethane-type epoxy resin having a multifunctional epoxy group, an epoxy acrylate resin, a polymer having a carboxyl group, and a resin obtained by reacting an unsaturated monobasic acid with an epoxy group of an epoxy compound such as an epoxy compound represented by the following general formula (IV) and further reacting a polyacid anhydride with the epoxy compound can be used.

[0175] The epoxy acrylate resin is obtained by reacting (meth)acrylic acid with an epoxy compound, and examples thereof include Ripoxy SPC-2000, DICLITE UE-777 manufactured by DIC Corporation, and Upika 4015 manufactured by U-PICA Corporation.

[0176] Among these compounds, epoxy acrylate resins and polymers having a carboxyl group are preferred.

[0177] The above-mentioned polymer having a carboxyl group is not particularly limited as long as it has a structural unit containing a carboxyl group (hereinafter referred to as "structural unit (U1)". The above-mentioned polymer having a carboxyl group preferably has, in addition to the structural unit (U1), a structural unit containing a crosslinking group such as a methacryloyl group, an acryloyl group, an epoxy group, a vinyl group, a vinyl ether group, a mercapto group, and an isocyanate group (hereinafter referred to as "structural unit (U2)"), and a structural unit containing a silyl group (hereinafter referred to as "structural unit (U3)".).

[0178] The above-mentioned polymer having a carboxyl group may have a structural unit other than the above-mentioned structural units (U1) to (U3) (hereinafter referred to as "structural unit (U4)").

[0179] The structural unit (U1) is preferably a structural unit derived from at least one compound selected from the group consisting of unsaturated carboxylic acids and unsaturated carboxylic anhydrides (hereinafter referred to as “compound (u1)”).

[0180] Examples of the compound (u1) include monocarboxylic acids, dicarboxylic acids, and anhydrides of dicarboxylic acids.

[0181] Examples of the monocarboxylic acid include acrylic acid, methacrylic acid, crotonic acid, 2-acryloyloxyethylsuccinic acid, 2-methacryloyloxyethylsuccinic acid, 2-acryloyloxyethylhexahydrophthalic acid, and 2-methacryloyloxyethylhexahydrophthalic acid.

[0182] Examples of the dicarboxylic acid include maleic acid, fumaric acid, and citraconic acid.

[0183] Examples of the anhydride of the dicarboxylic acid include the anhydrides of the dicarboxylic acids described above.

[0184] Among these compounds, acrylic acid, methacrylic acid, 2-acryloyloxyethylsuccinic acid, 2-methacryloyloxyethylsuccinic acid or maleic anhydride is particularly preferred from the viewpoint of copolymerization reactivity and solubility of the obtained copolymer in a developer.

[0185] The above-mentioned polymer having a carboxyl group may have one structural unit (U1) derived from one compound (u1), or may have two or more structural units (U1) derived from two or more compounds (u1).

[0186] The structural unit (U2) is preferably a structural unit derived from a polymerizable unsaturated compound having an epoxy group or an oxetanyl group (hereinafter referred to as “compound (u2)”).

[0187] The compound (u2) is preferably at least one selected from the group consisting of a polymerizable unsaturated compound having an epoxy group and a polymerizable unsaturated compound having an oxetanyl group.

[0188] Examples of the polymerizable unsaturated compound having an epoxy group include oxiranyl (cyclo)alkyl (meth)acrylates, oxiranyl (cyclo)alkyl α-alkylacrylates, and glycidyl ether compounds having a polymerizable unsaturated bond.

[0189] As a polymerizable unsaturated compound which has an oxetane group, (meth)acrylate etc. which have an oxetane group are mentioned, for example.

[0190] Specific examples of oxiranyl (cyclo)alkyl (meth)acrylates include glycidyl (meth)acrylate, 2-methyl glycidyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate glycidyl ether, 3,4-epoxybutyl (meth)acrylate, 6,7-epoxyheptyl (meth)acrylate, 3,4-epoxycyclohexyl (meth)acrylate, 3,4-epoxycyclohexylmethyl (meth)acrylate, and 3,4-epoxytricyclo[5.2.1.0 2.6 ]Decyl (meth)acrylate, etc.

[0191] Specific examples of the α-alkyl acrylate oxiranyl (cyclo)alkyl ester include, for example, α-ethyl glycidyl acrylate, α-n-propyl glycidyl acrylate, α-n-butyl glycidyl acrylate, α-ethyl acrylate 6,7-epoxyheptyl, and α-ethyl acrylate 3,4-epoxycyclohexyl.

[0192] Specific examples of the glycidyl ether compound having a polymerizable unsaturated bond include o-vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl ether, and p-vinylbenzyl glycidyl ether.

[0193] Specific examples of the (meth)acrylate having an oxetane group include 3-((meth)acryloyloxymethyl)oxetane, 3-((meth)acryloyloxymethyl)-3-ethyloxetane, 3-((meth)acryloyloxymethyl)-2-methyloxetane, 3-((meth)acryloyloxyethyl)-3-ethyloxetane, 2-ethyl-3-((meth)acryloyloxyethyl)oxetane, 3-methyl-3-(meth)acryloyloxymethyloxetane, and 3-ethyl-3-(meth)acryloyloxymethyloxetane.

[0194] Among these compounds, glycidyl methacrylate, 2-methylglycidyl methacrylate, 3,4-epoxycyclohexyl methacrylate, 3,4-epoxycyclohexylmethyl methacrylate, 3,4-epoxytricyclo[5.2.1.0 2.6 ]decyl methacrylate, 3,4-epoxytricyclo[5.2.1.0 2.6 ] Decyl acrylate, 3-methacryloyloxymethyl-3-ethyloxetane, 3-methyl-3-methacryloyloxymethyloxetane or 3-ethyl-3-methacryloyloxymethyloxetane is preferred from the viewpoint of polymerizability.

[0195] The above-mentioned polymer having a carboxyl group may have one structural unit (U2) derived from one compound (u2), or may have two or more structural units (U2) derived from two or more compounds (u2).

[0196] Among the structural units (U2), as the structural unit having a methacryloyl group or an acryloyl group as a crosslinkable group, a structural unit having a (meth)acryloyloxy group can be preferably used.

[0197] The structural unit having a (meth)acryloyloxy group is obtained by reacting a (meth)acrylate having an epoxy group with a carboxyl group in a polymer. The structural unit having a (meth)acryloyloxy group after the reaction is preferably a structural unit represented by the following formula (U).

[0198] [Chemical formula 34A]

[0199]

[0200] (Where R 1000 and R 1001 each independently represents a hydrogen atom or a methyl group,

[0201] u represents an integer from 1 to 6,

[0202] R 1002represents a divalent group represented by the following formula (Uα) or the following formula (Uβ),

[0203] *Indicates bonding location. )

[0204] [Chemical formula 34B]

[0205]

[0206] (Where R 1003 represents a hydrogen atom or a methyl group,

[0207] *Indicates bonding location. )

[0208] In the case where a compound such as glycidyl methacrylate or 2-methylglycidyl methacrylate is reacted with a copolymer having a carboxyl group, R in the formula (U) is 1002 In the case where a compound such as 3,4-epoxycyclohexylmethyl methacrylate is reacted with a copolymer having a carboxyl group, R in the formula (U) 1002 It becomes the formula (Uβ).

[0209] The reaction of the carboxyl group in the above-mentioned polymer with an unsaturated compound such as (meth)acrylate having an epoxy group is preferably carried out as follows: in the presence of a suitable catalyst as needed, an unsaturated compound having an epoxy group is preferably added to a solution of a polymer containing a polymerization inhibitor and stirred for a predetermined time under heating. As the above-mentioned catalyst, for example, tetrabutylammonium bromide, etc. can be listed. As the above-mentioned polymerization inhibitor, for example, p-methoxyphenol, etc. can be listed. The reaction temperature is preferably 70°C to 100°C. The reaction time is preferably 8 hours to 12 hours.

[0210] In the structural unit ratio of the polymer having a carboxyl group, the content ratio of the structural unit having a (meth)acryloyloxy group as a crosslinkable group is preferably 10 mol% to 70 mol% of all structural units of the polymer having a carboxyl group, and more preferably 20 mol% to 50 mol%. When the structural unit ratio having a (meth)acryloyloxy group is within the above range, heat resistance and poor development during development are reduced, and the generation of development residues can be suppressed.

[0211] The structural unit (U3) is preferably a structural unit derived from a polymerizable unsaturated compound having a silyl group (hereinafter referred to as "compound (u3)").

[0212] Examples of the compound (u3) include 3-(meth)acryloxypropylmethyldimethoxysilane, 3-(meth)acryloxypropylethyldimethoxysilane, 3-(meth)acryloxypropyltrimethoxysilane, and 3-(meth)acryloxypropyltriethoxysilane.

[0213] When the polymer having a carboxyl group has a structural unit U3, it may have one structural unit (U3) derived from one compound (u3), or may have two or more structural units (U3) derived from two or more compounds (u3).

[0214] The structural unit (U4) is a structural unit other than the above-mentioned (U1) to (U3), and is preferably a structural unit derived from a polymerizable unsaturated compound other than the above-mentioned (u1) to (u3) (hereinafter referred to as "compound (u4)").

[0215] Examples of the compound (u4) include alkyl (meth)acrylates, cycloalkyl (meth)acrylates, aryl (meth)acrylates, aralkyl (meth)acrylates, unsaturated dicarboxylic acid dialkyl esters, (meth)acrylates having an oxygen-containing 5-membered ring or an oxygen-containing 6-membered ring, vinyl aromatic compounds, conjugated diene compounds, and other polymerizable unsaturated compounds.

[0216] Specific examples of the alkyl (meth)acrylate include methyl acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, sec-butyl (meth)acrylate, and tert-butyl (meth)acrylate.

[0217] Specific examples of cycloalkyl (meth)acrylates include cyclohexyl (meth)acrylate, 2-methylcyclohexyl (meth)acrylate, tricyclo[5.2.1.0 2,6 ] decane-8-yl ester, (meth) acrylic acid 2-(tricyclo[5.2.1.0 2,6 ]decane-8-yloxy)ethyl ester and isobornyl (meth)acrylate, etc.

[0218] Specific examples of the aryl (meth)acrylate include phenyl acrylate and the like.

[0219] Specific examples of the aralkyl (meth)acrylate include benzyl (meth)acrylate and the like.

[0220] Specific examples of the unsaturated dicarboxylic acid dialkyl ester include diethyl maleate and diethyl fumarate.

[0221] Specific examples of the (meth)acrylate having an oxygen-containing 5-membered ring or an oxygen-containing 6-membered ring include tetrahydrofuran-2-yl (meth)acrylate, tetrahydropyran-2-yl (meth)acrylate, and 2-methyltetrahydropyran-2-yl (meth)acrylate.

[0222] Specific examples of the vinyl aromatic compound include styrene and α-methylstyrene.

[0223] Specific examples of the conjugated diene compound include 1,3-butadiene and isoprene.

[0224] Specific examples of other polymerizable unsaturated compounds include 2-hydroxyethyl (meth)acrylate, acrylonitrile, methacrylonitrile, acrylamide, and methacrylamide.

[0225] Among the compounds (u4) listed above, n-butyl methacrylate, 2-methylglycidyl methacrylate, benzyl methacrylate, tricyclo[5.2.1.0 2,6 ]decane-8-yl ester, styrene, p-methoxystyrene, tetrahydrofuran-2-yl methacrylate and 1,3-butadiene, etc.

[0226] When the above-mentioned polymer having a carboxyl group has a structural unit (U4), it may have one structural unit (U4) derived from one compound (u4), or may have two or more structural units (U4) derived from two or more compounds (u4).

[0227] The preferred polymer having a carboxyl group in the present embodiment can be synthesized by copolymerizing a mixture of polymerizable unsaturated compounds containing the above-mentioned compounds (u1) to (u4) at the following ratios.

[0228] Furthermore, by reacting a (meth)acrylate having an epoxy group with a carboxyl group in a structural unit derived from the compound (u1) in the obtained copolymer, a polymer having a structural unit containing a (meth)acryloyloxy group can be obtained.

[0229] Compound (u1): preferably 0.1 mol% to 30 mol%, more preferably 1 mol% to 20 mol%, further preferably 5 mol% to 15 mol%

[0230] Compound (u2): preferably 1 mol% to 95 mol%, more preferably 10 mol% to 60 mol%, further preferably 20 mol% to 30 mol%

[0231] Compound (u3): preferably 50 mol% or less, more preferably 1 mol% to 40 mol%, further preferably 10 mol% to 30 mol%

[0232] Compound (u4): preferably 80 mol% or less, more preferably 1 mol% to 60 mol%, further preferably 25 mol% to 50 mol%

[0233] A polymerizable composition containing a polymer having a carboxyl group obtained by copolymerizing a mixture of polymerizable unsaturated compounds containing compounds (u1) to (u4) in the above-mentioned range is preferred from the perspective of being able to obtain a cured film with a highly adjusted balance of physical properties even for a high-precision pattern, because it can achieve high resolution without impairing good coating properties.

[0234] The weight average molecular weight (Mw) of the polymer having a carboxyl group is preferably 2000 to 100000, more preferably 5000 to 50000. By using a polymer having a carboxyl group having an Mw within this range, a high resolution can be achieved without impairing good coating properties, so that a cured film having a highly adjusted balance of properties can be provided even for a high-definition pattern.

[0235] The weight average molecular weight (Mw) in the present invention refers to a polystyrene-equivalent weight average molecular weight (Mw) measured by gel permeation chromatography (GPC).

[0236] The polymer having a carboxyl group can be produced by polymerizing the mixture of the above-mentioned polymerizable unsaturated compounds preferably in an appropriate solvent, preferably in the presence of a radical polymerization initiator.

[0237] Examples of the solvent used in the polymerization of the mixture of polymerizable unsaturated compounds include diethylene glycol monoethyl ether acetate, diethylene glycol diethyl ether, diethylene glycol ethyl methyl ether, diethylene glycol dimethyl ether, propylene glycol monomethyl ether, ethylene glycol monobutyl ether acetate, propylene glycol monomethyl ether acetate (PGMEA), dipropylene glycol monomethyl ether acetate, 3-methoxybutyl acetate, cyclohexanol acetate, benzyl alcohol, 3-methoxybutanol, etc. These solvents may be used alone or in combination of two or more.

[0238] The free radical polymerization initiator is not particularly limited, and examples thereof include azo compounds such as 2,2'-azobisisobutyronitrile, 2,2'-azobis-(2,4-dimethylvaleronitrile), 2,2'-azobis-(4-methoxy-2,4-dimethylvaleronitrile), 4,4'-azobis(4-cyanovaleric acid), dimethyl-2,2'-azobis(2-methylpropionate), and 2,2'-azobis(4-methoxy-2,4-dimethylvaleronitrile). These free radical polymerization initiators may be used alone or in combination of two or more.

[0239] Among the above-mentioned polymers having a carboxyl group, preferred are polymers described in JP-A-2005-234362 and polymers obtained by reacting an unsaturated monobasic acid with an epoxy group of an epoxy compound represented by the following general formula (VI) and further reacting the epoxy group with a polybasic acid anhydride.

[0240] In addition, as the above-mentioned alkali-developable compound (D), a copolymer of acrylates, a phenol and / or cresol novolac epoxy resin, a polyphenylmethane type epoxy resin having a multifunctional epoxy group, an epoxy acrylate resin, a resin obtained by reacting an unsaturated monobasic acid with an epoxy group of an epoxy compound such as an epoxy compound represented by the following general formula (III) and further reacting a polyacid anhydride with the epoxy compound can be used. The epoxy acrylate resin referred to here is a resin obtained by reacting (meth)acrylic acid with the above-mentioned epoxy compound, and examples thereof include Ripoxy SPC-2000, DICLITE UE-777 manufactured by DIC Corporation, and Upika 4015 manufactured by U-PICA Corporation.

[0241] Among them, epoxy acrylate resins and resins obtained by reacting an unsaturated monobasic acid with an epoxy group of an epoxy compound represented by the following general formula (IV) and further reacting the epoxy group with a polybasic acid anhydride are preferred.

[0242] The alkali-developable compound which may have an ethylenically unsaturated bond preferably contains 0.2 to 1.0 equivalent of an unsaturated group.

[0243] [Chemical formula 35]

[0244]

[0245] (Where X 21 represents a direct bond, a methylene group, an alkylene group having 1 to 4 carbon atoms, an alicyclic hydrocarbon group having 3 to 20 carbon atoms, -O-, -S-, -SO-2, -SS-, -SO-, -CO-, -OCO-, or a group represented by the following [Chemical Formula 36], [Chemical Formula 37], or [Chemical Formula 38], wherein the above alkylene group may be substituted by a halogen atom, and R 51 and R 52 Each independently represents an alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, an alkenyl group having 2 to 5 carbon atoms, or a halogen atom. The alkyl group, alkoxy group, and alkenyl group may be substituted with a halogen atom.

[0246] In R 51 and R 52 When there are multiple of each, there are cases where they are the same and cases where they are different.

[0247] c is an integer from 0 to 4,

[0248] d is an integer from 0 to 4,

[0249] m is an integer from 0 to 10,

[0250] When m is not 0, the optical isomers present may be any isomers.)

[0251] [Chemical formula 36]

[0252]

[0253] (Where Z 1 represents a hydrogen atom, a phenyl group which may be substituted by an alkyl group having 1 to 10 carbon atoms or an alkoxy group having 1 to 10 carbon atoms, or a cycloalkyl group having 3 to 10 carbon atoms which may be substituted by an alkyl group having 1 to 10 carbon atoms or an alkoxy group having 1 to 10 carbon atoms, and Y 1 represents an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, or a halogen atom. The above alkyl groups, alkoxy groups, and alkenyl groups may be substituted by halogen atoms. e represents an integer of 0 to 5, and * represents a bonding site.

[0254] [Chemical formula 37]

[0255]

[0256] (Wherein, * indicates the bonding site.)

[0257] [Chemical formula 38]

[0258]

[0259] (Where Y 2 and Z 2 each independently represents an alkyl group having 1 to 10 carbon atoms which may be substituted by a halogen atom, an aryl group having 6 to 20 carbon atoms which may be substituted by a halogen atom, an aryloxy group having 6 to 20 carbon atoms which may be substituted by a halogen atom, an arylthio group having 6 to 20 carbon atoms which may be substituted by a halogen atom, an arylalkenyl group having 6 to 20 carbon atoms which may be substituted by a halogen atom, an arylalkyl group having 7 to 20 carbon atoms which may be substituted by a halogen atom, a heterocyclic group having 2 to 20 carbon atoms which may be substituted by a halogen atom, or a halogen atom, and Y 2 The methylene group in the group represented by may be substituted by an unsaturated bond, -O- or -S-. 2 It can also be done through the adjacent Z 2 They form a ring with each other, f represents an integer of 0 to 4, g represents an integer of 0 to 8, h represents an integer of 0 to 4, i represents an integer of 0 to 4, the total of h and i is an integer of 2 to 4, and * represents a bonding site).

[0260] Examples of the unsaturated monobasic acid that reacts with the epoxy compound include acrylic acid, methacrylic acid, crotonic acid, cinnamic acid, sorbic acid, hydroxyethyl methacrylate / maleate, hydroxyethyl acrylate / maleate, hydroxypropyl methacrylate / maleate, hydroxypropyl acrylate / maleate, and dicyclopentadiene / maleate.

[0261] Examples of the polybasic acid anhydride to be reacted after the unsaturated monobasic acid is allowed to react include biphenyltetracarboxylic anhydride, tetrahydrophthalic anhydride, succinic anhydride, diphthalic anhydride, maleic anhydride, trimellitic anhydride, pyromellitic anhydride, 2,2'-3,3'-benzophenonetetracarboxylic anhydride, ethylene glycol ditrimellitic anhydride, glycerol trimellitic anhydride, hexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, nadic anhydride, methyl nadic anhydride, trialkyltetrahydrophthalic anhydride, hexahydrophthalic anhydride, 5-(2,5-dioxotetrahydrofuranyl)-3-methyl-3-cyclohexene-1,2-dicarboxylic anhydride, trialkyltetrahydrophthalic anhydride-maleic anhydride adduct, dodecenylsuccinic anhydride, and methylnadic anhydride.

[0262] The reaction molar ratio of the epoxy compound, the unsaturated monobasic acid, and the polybasic acid anhydride is preferably set as follows.

[0263] That is, in the epoxy adduct having a structure in which 0.1 to 1.0 carboxyl groups of the unsaturated monobasic acid are added to one epoxy group of the epoxy compound, it is preferred that the anhydride structure of the polybasic acid anhydride is present in a ratio of 0.1 to 1.0 to one hydroxyl group of the epoxy adduct.

[0264] The reaction of the epoxy compound, the unsaturated monobasic acid and the polybasic acid anhydride can be carried out according to a conventional method.

[0265] The alkali-developable photosensitive resin composition of the present invention, which is one embodiment of the photosensitive composition of the present invention, contains a photopolymerization initiator (A), an ethylenically unsaturated compound (B) and an alkali-developable compound (D) as essential components, and contains inorganic compounds, solvents and other components in combination as optional components. It should be noted that among the alkali-developable photosensitive resin compositions of the present invention, the composition containing a colorant (C) is also particularly referred to as a colored alkali-developable photosensitive resin composition of the present invention.

[0266] The alkali-developable compound (D) may be used alone or in combination of two or more.

[0267] When the alkali-developable compound (D) has an ethylenically unsaturated bond, the alkali-developable compound (D) is sometimes included in the category of the ethylenically unsaturated compound (B). When the alkali-developable compound (D) is also an ethylenically unsaturated compound (B), the composition containing the alkali-developable compound (D) is a photosensitive composition and also an alkali-developable photosensitive resin composition.

[0268] In order to improve the developability of the (colored) alkali-developable photosensitive resin composition of the present invention by adjusting the acid value, a monofunctional or polyfunctional epoxy compound may be further used together with the above-mentioned alkali-developable compound which may also have an ethylenically unsaturated bond. The above-mentioned alkali-developable compound which may also have an ethylenically unsaturated bond preferably has an acid value of 5 to 120 mgKOH / g in solid content, and the amount of the monofunctional or polyfunctional epoxy compound used is preferably selected so as to satisfy the above-mentioned acid value.

[0269] Examples of the monofunctional epoxy compound include glycidyl methacrylate, methyl glycidyl ether, ethyl glycidyl ether, propyl glycidyl ether, isopropyl glycidyl ether, butyl glycidyl ether, isobutyl glycidyl ether, tert-butyl glycidyl ether, amyl glycidyl ether, hexyl glycidyl ether, heptyl glycidyl ether, octyl glycidyl ether, nonyl glycidyl ether, decyl glycidyl ether, undecyl glycidyl ether, dodecyl glycidyl ether, tridecyl glycidyl ether, tetradecyl glycidyl ether, pentadecyl glycidyl ether, hexadecyl glycidyl ether, 2-ethylhexyl glycidyl ether, allyl glycidyl ether, propargyl glycidyl ether, Glyceryl ether, p-methoxyethyl glycidyl ether, phenyl glycidyl ether, p-methoxy glycidyl ether, p-butylphenol glycidyl ether, cresyl glycidyl ether, 2-methylcresyl glycidyl ether, 4-nonylphenyl glycidyl ether, benzyl glycidyl ether, p-cumylphenyl glycidyl ether, trityl glycidyl ether, 2,3-epoxypropyl methacrylate, epoxidized soybean oil, epoxidized linseed oil, butyric acid glycidyl ester, vinylcyclohexane monoxide, 1,2-epoxy-4-vinylcyclohexane, styrene oxide, pinane oxide, methylstyrene oxide, cyclohexane oxide, propylene oxide, the above compound No.A2, No.A3, etc.

[0270] As the polyfunctional epoxy compound, it is preferred to use one or more compounds selected from the group consisting of bisphenol epoxy compounds and glycidyl ethers, because a (colored) alkali-developable photosensitive resin composition having further excellent properties can be obtained.

[0271] As the bisphenol type epoxy compound, in addition to the epoxy compound represented by the general formula (IV), for example, a bisphenol type epoxy compound such as a hydrogenated bisphenol type epoxy compound can be used.

[0272] Examples of the glycidyl ethers include ethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, 1,4-butanediol diglycidyl ether, 1,6-hexanediol diglycidyl ether, 1,8-octanediol diglycidyl ether, 1,10-decanediol diglycidyl ether, 2,2-dimethyl-1,3-propanediol diglycidyl ether, diethylene glycol diglycidyl ether, triethylene glycol diglycidyl ether, tetraethylene glycol diglycidyl ether, hexaethylene glycol diglycidyl ether, 1,4-cyclohexanedimethanol diglycidyl ether, 1,1,1-tris(glycidyloxymethyl)propane, 1,1,1-tris(glycidyloxymethyl)ethane, 1,1,1-tris(glycidyloxymethyl)methane, and 1,1,1,1-tetra(glycidyloxymethyl)methane.

[0273] In addition, novolac epoxy compounds such as phenol novolac epoxy compounds, biphenyl novolac epoxy compounds, cresol novolac epoxy compounds, bisphenol A novolac epoxy compounds, and dicyclopentadiene novolac epoxy compounds can also be used; alicyclic epoxy compounds such as 3,4-epoxy-6-methylcyclohexylmethyl-3,4-epoxy-6-methylcyclohexanecarboxylate, 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, and 1-oxiranyl-3,4-epoxycyclohexane; phthalic acid Glycidyl esters such as diglycidyl formate, diglycidyl tetrahydrophthalate, and glycidyl dimer acid ester; glycidyl amines such as tetraglycidyl diaminodiphenylmethane, triglycidyl p-aminophenol, and N,N-diglycidyl aniline; heterocyclic epoxy compounds such as 1,3-diglycidyl-5,5-dimethylhydantoin and triglycidyl isocyanurate; dioxide compounds such as dicyclopentadiene dioxide; naphthalene-type epoxy compounds; triphenylmethane-type epoxy compounds; dicyclopentadiene-type epoxy compounds, etc.

[0274] In particular, when the photosensitive composition of the present invention is made into an alkali-developable photosensitive resin composition, the content of the alkali-developable compound which may have an ethylenically unsaturated bond is 1 to 20% by mass, particularly preferably 3 to 12% by mass in the alkali-developable photosensitive resin composition of the present invention.

[0275] A solvent may be further added to the photosensitive composition of the present invention. Examples of the solvent include solvents that can dissolve or disperse the above-mentioned components (photopolymerization initiator (A) and ethylenically unsaturated compound (B)) as required, such as ketones such as methyl ethyl ketone, methyl amyl ketone, diethyl ketone, acetone, methyl isopropyl ketone, methyl isobutyl ketone, cyclohexanone, and 2-heptanone; ether solvents such as ethyl ether, dioxane, tetrahydrofuran, 1,2-dimethoxyethane, 1,2-diethoxyethane, and dipropylene glycol dimethyl ether; and methyl acetate. , ethyl acetate, n-propyl acetate, isopropyl acetate, n-butyl acetate, cyclohexyl acetate, ethyl lactate, dimethyl succinate, 2,2,4-trimethyl-1,3-pentanediol monoisobutyrate (Texanol) and other ester solvents; ethylene glycol monomethyl ether, ethylene glycol monoethyl ether and other cellosolve solvents; methanol, ethanol, isopropanol or n-propanol, isobutanol or n-butanol, amyl alcohol and other alcohol solvents; ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, propylene glycol-1- Ether ester solvents such as monomethyl ether-2-acetate, dipropylene glycol monomethyl ether acetate, 3-methoxybutyl ether acetate, and ethoxyethyl ether propionate; BTX solvents such as benzene, toluene, and xylene; aliphatic hydrocarbon solvents such as hexane, heptane, octane, and cyclohexane; terpene hydrocarbon oils such as turpentine, D-limonene, and pinene; mineral spirits, SWAZOL#310 (manufactured by COSMO Songshan Oil Company), SOLVESSO#100 (manufactured by Exxon Chemical Company) Halogenated aliphatic hydrocarbon solvents such as carbon tetrachloride, chloroform, trichloroethylene, dichloromethane, 1,2-dichloroethane, etc.; halogenated aromatic hydrocarbon solvents such as chlorobenzene; carbitol solvents; aniline; triethylamine; pyridine; acetic acid; acetonitrile; carbon disulfide; N,N-dimethylformamide; N,N-dimethylacetamide (DMAc); N-methylpyrrolidone; dimethyl sulfoxide; water, etc. These solvents can be used alone or as a mixed solvent of two or more.

[0276] Among them, ketones, ether ester solvents and the like, particularly propylene glycol-1-monomethyl ether-2-acetate, cyclohexanone and the like are preferred because they have good compatibility with the resist and the photopolymerization initiator (A) in the photosensitive composition.

[0277] In addition, the photosensitive composition of the present invention may contain conventional additives such as p-anisole, hydroquinone, pyrocatechol, tert-butylcatechol, inorganic compounds, latent additives, organic polymers, chain transfer agents, sensitizers, surfactants, silane coupling agents, melamine compounds, thermal polymerization inhibitors; plasticizers; adhesion promoters; fillers; defoamers; leveling agents; surface conditioners; antioxidants; ultraviolet absorbers; dispersing aids; anti-agglomeration agents; catalysts; effect promoters; crosslinking agents; thickeners, etc., as needed.

[0278] A dispersant for dispersing the colorant (C) and / or the inorganic compound may be added to the photosensitive composition of the present invention. The dispersant is not limited as long as it is a substance that can disperse and stabilize the colorant (C) or the inorganic compound, and commercially available dispersants such as BYK series manufactured by BYK-Chemie Japan Co., Ltd. can be used. It is particularly suitable to use a polymer dispersant containing polyester, polyether, or polyurethane having a basic functional group; a dispersant having a nitrogen atom as a basic functional group, and the functional group having the nitrogen atom is an amine and / or a quaternary ammonium salt thereof, and the amine value is 1 to 100 mgKOH / g.

[0279] The above-mentioned potential additives are represented by the following general formulas (A) to (C).

[0280] [Chemical formula 39]

[0281]

[0282] (wherein, ring A 1 is a six-membered alicyclic ring, aromatic ring or heterocyclic ring, R 81 , R 82 , R 83 , R 84 and R 85 represents a hydrogen atom, a halogen atom, a cyano group, a hydroxyl group, a nitro group, a carboxyl group, an alkyl group having 1 to 40 carbon atoms which may have a substituent, an aryl group having 6 to 20 carbon atoms, an arylalkyl group having 7 to 20 carbon atoms, a heterocyclic group having 2 to 20 carbon atoms, or -OR 66 ,

[0283] R 81 , R 82 , R 83 , R 84 and R 85 At least one of them is not a hydrogen atom,

[0284] R 86 represents an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an arylalkyl group having 7 to 20 carbon atoms, a heterocyclic group having 2 to 20 carbon atoms, or a trialkylsilyl group.

[0285] [Chemical formula 40]

[0286]

[0287] (wherein, ring A 1 and R 91 Same as the above general formula (A),

[0288] X 7 is a group represented by the following general formula (1), R92 , R 93 , R 94 and R 95 represents a hydrogen atom, a halogen atom, a cyano group, a hydroxyl group, a nitro group, a carboxyl group, an alkyl group having 1 to 40 carbon atoms which may have a substituent, an aryl group having 6 to 20 carbon atoms, an arylalkyl group having 7 to 20 carbon atoms, or a heterocyclic group having 2 to 20 carbon atoms, R 92 , R 93 , R 94 and R 95 At least one of them is not a hydrogen atom.)

[0289] [Chemical formula 41]

[0290] *-Z 5 -X 8 -Z 6 -* (1)

[0291] (In the above general formula (1), X 8 Indicates -CR 97 R 98 -、-NR 99 -, a divalent aliphatic hydrocarbon group having 1 to 35 carbon atoms, an aromatic hydrocarbon group having 6 to 35 carbon atoms, or a heterocyclic group having 2 to 35 carbon atoms, or any substituent represented by the following [Chemical Formula 42] to [Chemical Formula 44],

[0292] The methylene group in the aliphatic hydrocarbon group may be substituted with -O-, -S-, -CO-, -COO-, -OCO- or -NH-, or a bonding group obtained by combining these when the oxygen atoms are not adjacent.

[0293] R 97 and R 98 represents a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, an aryl group having 6 to 20 carbon atoms, or an arylalkyl group having 7 to 20 carbon atoms, and Z 5 and Z 6 Each independently represents a direct bond, -O-, -S-, >CO, -CO-O-, -O-CO-, -SO2-, -SS-, -SO- or >NR 100 , R 99 and R 100 represents a hydrogen atom, an aliphatic hydrocarbon group having 1 to 35 carbon atoms which may have a substituent, an aromatic hydrocarbon group having 6 to 35 carbon atoms which may have a substituent, or a heterocyclic group having 2 to 35 carbon atoms which may have a substituent, and * represents a bonding site. )

[0294] [Chemical formula 42]

[0295]

[0296] (In the above formula, R 101 represents a hydrogen atom, a phenyl group which may have a substituent, or a cycloalkyl group having 3 to 10 carbon atoms, and R 102 represents an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, or a halogen atom, and the above alkyl group, alkoxy group, and alkenyl group may have a substituent, f is an integer of 0 to 5, and * represents a bonding site.

[0297] [Chemical formula 43]

[0298]

[0299] (Wherein, * indicates the bonding site.)

[0300] [Chemical formula 44]

[0301]

[0302] (In the above formula, R 103 and R 104 each independently represents an alkyl group having 1 to 10 carbon atoms which may have a substituent, an aryl group having 6 to 20 carbon atoms which may have a substituent, an aryloxy group having 6 to 20 carbon atoms which may have a substituent, an arylthio group having 6 to 20 carbon atoms which may have a substituent, an arylalkenyl group having 6 to 20 carbon atoms which may have a substituent, an arylalkyl group having 7 to 20 carbon atoms which may have a substituent, a heterocyclic group having 2 to 20 carbon atoms which may have a substituent, or a halogen atom, and the methylene group in the alkyl group and the arylalkyl group may be interrupted by an unsaturated bond, -O- or -S-. R 103 It can also be done through the adjacent R 103 They form a ring with each other, b represents a number from 0 to 4, c represents a number from 0 to 8, g represents a number from 0 to 4, h represents a number from 0 to 4, and the total number of g and h is 2 to 4.)

[0303] [Chemical formula 45]

[0304]

[0305] (In the formula, k = 2 to 6, X 9 When k=2, it is a group represented by the above general formula (2); when k=3, it is a group represented by the following general formula (3); when k=4, it is a group represented by the following general formula (4); when k=5, it is a group represented by the following general formula (5); when k=6, it is a group represented by the following general formula (6); R 111 , R 112 , R 113 and R 114represents a hydrogen atom, a halogen atom, a cyano group, a hydroxyl group, a nitro group, a carboxyl group, an alkyl group having 1 to 40 carbon atoms which may have a substituent, an aryl group having 6 to 20 carbon atoms, an arylalkyl group having 7 to 20 carbon atoms, or a heterocyclic group having 2 to 20 carbon atoms, R 111 , R 112 , R 113 and R 114 At least one of the atoms in ring A is not a hydrogen atom. 1 and R 86 Same as the above general formula (A).

[0306] [Chemical formula 46]

[0307]

[0308] (In the above general formula (2), Y 11 represents a trivalent aliphatic hydrocarbon group having 3 to 35 carbon atoms, an alicyclic hydrocarbon group having 3 to 35 carbon atoms, an aromatic hydrocarbon group having 6 to 35 carbon atoms, or a heterocyclic group having 2 to 35 carbon atoms, and Z 11 , Z 12 and Z 13 Each independently represents a direct bond, -O-, -S-, >CO, -CO-O-, -O-CO-, -SO2-, -SS-, -SO-, -NR 121 -、-PR 121 - or an aliphatic hydrocarbon group having 1 to 35 carbon atoms which may have a substituent, an aromatic hydrocarbon group having 6 to 35 carbon atoms which may have a substituent, or a heterocyclic group having 2 to 35 carbon atoms which may have a substituent,

[0309] R 121 represents a hydrogen atom, an aliphatic hydrocarbon group having 1 to 35 carbon atoms which may have a substituent, an aromatic hydrocarbon group having 6 to 35 carbon atoms which may have a substituent, or a heterocyclic group having 2 to 35 carbon atoms which may have a substituent, and the methylene group in the aliphatic hydrocarbon group may also be substituted by a carbon-carbon double bond, -O-, -CO-, -O-CO-, -CO-O- or -SO2-.)

[0310] [Chemical formula 47]

[0311]

[0312] (In the above general formula (3), Y 12 represents a carbon atom, or a tetravalent aliphatic hydrocarbon group having 1 to 35 carbon atoms, an aromatic hydrocarbon group having 6 to 35 carbon atoms, or a heterocyclic group having 2 to 35 carbon atoms, wherein the methylene group in the aliphatic hydrocarbon group may be substituted by -COO-, -O-, -OCO-, -NHCO-, -NH- or -CONH-, and Z11 ~Z 14 are independently the same as Z in the above general formula (2) 11 ~Z 13 The same range of groups as those represented. )

[0313] [Chemical formula 48]

[0314]

[0315] (In the above general formula (4), Y 13 represents a pentavalent aliphatic hydrocarbon group having 2 to 35 carbon atoms, an aromatic hydrocarbon group having 6 to 30 carbon atoms, or a heterocyclic group having 2 to 30 carbon atoms, wherein the aliphatic hydrocarbon group may be interrupted by -COO-, -O-, -OCO-, -NHCO-, -NH- or -CONH-, and Z 11 ~Z 15 are independently the same as Z in the above general formula (2) 11 ~Z 13 The same range of groups as those represented. )

[0316] [Chemical formula 49]

[0317]

[0318] (In the above general formula (5), Y 14 represents a hexavalent aliphatic hydrocarbon group having 2 to 35 carbon atoms, an aromatic hydrocarbon group having 6 to 35 carbon atoms, or a heterocyclic group having 2 to 35 carbon atoms, and the aliphatic hydrocarbon group may be interrupted by -COO-, -O-, -OCO-, -NHCO-, -NH- or -CONH-, and Z 11 ~Z 16 are independently the same as Z in the above general formula (2) 11 ~Z 13 The same range of groups as those represented. )

[0319] By using the above-mentioned organic polymer [excluding the ethylenically unsaturated compound (B)], the properties of the cured product can also be improved. As the organic polymer, for example, polystyrene, polymethyl methacrylate, methyl methacrylate-ethyl acrylate copolymer, poly(meth)acrylic acid, styrene-(meth)acrylic acid copolymer, (meth)acrylic acid-methyl methacrylate copolymer, ethylene-vinyl chloride copolymer, ethylene-vinyl ester copolymer, polyvinyl chloride resin, ABS resin, nylon 6, nylon 66, nylon 12, polyurethane resin, polycarbonate, polyvinyl butyral, cellulose ester, polyacrylamide, saturated polyester, phenolic resin, phenoxy resin, polyamide-imide resin, polyamic acid resin, epoxy resin, etc. can be listed, among which polystyrene, (meth)acrylic acid-methyl methacrylate copolymer, epoxy resin, etc. are preferred.

[0320] When an organic polymer is used, the amount used is preferably 10 to 500 parts by mass based on 100 parts by mass of the polymerizable compound having an ethylenically unsaturated bond.

[0321] As the chain transfer agent or the sensitizer, a sulfur atom-containing compound is generally used. Examples thereof include thioglycolic acid, thiomalic acid, thiosalicylic acid, 2-mercaptopropionic acid, 3-mercaptopropionic acid, 3-mercaptobutyric acid, N-(2-mercaptopropionyl)glycine, 2-mercaptonicotinic acid, 3-[N-(2-mercaptoethyl)carbamoyl]propionic acid, 3-[N-(2-mercaptoethyl)amino]propionic acid, N-(3-mercaptopropionyl)alanine, 2-mercaptoethanesulfonic acid, 3-mercaptopropanesulfonic acid, 4-mercaptobutanesulfonic acid, Dialkyl (4-methylthio) phenyl ether, 2-mercaptoethanol, 3-mercapto-1,2-propanediol, 1-mercapto-2-propanol, 3-mercapto-2-butanol, mercaptophenol, 2-mercaptoethylamine, 2-mercaptoimidazole, 2-mercaptobenzimidazole, 2-mercapto-3-pyridinol, 2-mercaptobenzothiazole, thioglycolic acid, trimethylolpropane tris (3-mercaptopropionate), pentaerythritol tetrakis (3-mercaptopropionate) and other mercapto compounds, Disulfide compounds obtained by oxidation of the mercapto compounds, iodoacetic acid, iodopropionic acid, 2-iodoethanol, 2-iodoethanesulfonic acid, 3-iodopropanesulfonic acid and other iodinated alkyl compounds, trimethylolpropane tris(3-mercaptoisobutyrate), butanediol bis(3-mercaptoisobutyrate), hexanedithiol, decanedithiol, 1,4-dimethylmercaptobenzene, butanediol dithiopropionate, butanediol dithioacetate, ethylene glycol dithioacetate, trimethylolpropane trithio acetate, butanediol dithiopropionate, trimethylolpropane trithiopropionate, trimethylolpropane trithioacetate, pentaerythritol tetrathiopropionate, pentaerythritol tetrathioacetate, trihydroxyethyl trithiopropionate, diethyl thioxanthone, diisopropyl thioxanthone, the following compound No. C1, aliphatic multifunctional thiol compounds such as tris(2-hydroxyethyl)trimercaptopropionate, KarenzMT BD1, PE1, NR1 manufactured by Showa Denko K.K., etc.

[0322] [Chemical formula 50]

[0323]

[0324] As the above-mentioned surfactant, fluorine-based surfactants such as perfluoroalkyl phosphates and perfluoroalkyl carboxylates; anionic surfactants such as higher fatty acid alkali metal salts, alkyl sulfonates, and alkyl sulfates; cationic surfactants such as higher amine halides and quaternary ammonium salts; nonionic surfactants such as polyethylene glycol alkyl ethers, polyethylene glycol fatty acid esters, sorbitan fatty acid esters, and fatty acid monoglycerides; amphoteric surfactants; surfactants such as silicone-based surfactants can be used, and they can also be used in combination.

[0325] As the silane coupling agent, for example, a silane coupling agent manufactured by Shin-Etsu Chemical Co., Ltd. can be used, and among them, silane coupling agents having an isocyanate group, an acryloyl group, a methacryloyl group, or an epoxy group, such as KBE-9007, KBM-5103, KBM-502, and KBE-403, are preferably used.

[0326] Examples of the above-mentioned melamine compounds include compounds in which all or part (at least 2) of the active methylol groups (CH2OH groups) in nitrogen compounds such as (poly)hydroxymethylmelamine, (poly)hydroxymethylglycoluril, (poly)hydroxymethylbenzoguanamine, and (poly)hydroxymethylurea are alkyl-etherified.

[0327] Here, the alkyl group constituting the alkyl ether includes methyl, ethyl or butyl, which may be the same or different from each other. In addition, the methylol group that is not alkyl-etherified may self-condense within one molecule or between two molecules to form an oligomer component.

[0328] Specifically, hexamethoxymethylmelamine, hexabutoxymethylmelamine, tetramethoxymethylglycoluril, tetrabutoxymethylglycoluril, etc. can be used. Among them, alkyl-etherified melamines such as hexamethoxymethylmelamine and hexabutoxymethylmelamine are preferred.

[0329] As the leveling agent, any existing leveling agent can be used as long as it has a leveling effect, and among them, silicone-based leveling agents and fluorine-based leveling agents can be particularly preferably used.

[0330] As the silicone-based leveling agent, a commercially available silicone-based leveling agent can be used, for example, BYK-300, BYK-306, BYK-307, BYK-310, BYK-315, BYK-313, BYK-320, BYK-322, BYK-323, BYK-325, BYK-330, BYK-331, BYK-333, BYK-337, BYK-341, BYK-342, BYK-343, BYK-344, BYK-345, BYK-346, BYK-347, BYK-348, BYK-349, BYK-350, BYK-351, BYK-352, BYK-353, BYK-354, BYK-355, BYK-356, BYK-357, BYK-358, BYK-359, BYK-360, BYK-361, BYK-362, BYK-363, BYK-364, BYK-365, BYK-366, BYK-367, BYK-368, BYK-369, BYK-370, BYK-371, BYK-372, BYK-373, BYK-374, BYK-375, BYK-376, BYK-377, BYK-378, BYK-379, BYK-380, BYK-381, BYK-382, BYK-383, BYK-384, BYK-385 BYK-344, BYK-347, BYK-348, BYK-349, BYK-370, BYK-375, BYK-377, BYK-378, BYK-UV3500, B YK-UV3510, BYK-UV3570, BYK-3550, BYK-SILCLEAN3700, BYK-SILCLEAN3720 (the above is BYK-Chemie Japan); ACFS180, ACFS360, AC S20 (all made by Algin Chemie); Polyflow KL-400X, Polyflow KL-400HF, Polyflow KL-401, Polyflow KL-402, Polyflow KL-403, Polyflow KL-404 (all made by Kyoeisha Chemical); KP-323, KP-326, KP-341, KP-104, KP-110, KP-112 (all made by Shin-Etsu Chemical); LP-7001, LP-7002, 8032ADDITIVE, 57ADDITIVE, L-7604, FZ-2110, FZ-2105, 67ADDITIVE, 8618ADDITIVE, 3ADDITIVE, 56ADDITIVE (all made by Toray-Dow Corning) and other commercially available products.

[0331] As the fluorine-based leveling agent, a commercially available fluorine-based leveling agent can be used, for example, OPTOOL DSX, OPTOOL DAC-HP (all manufactured by DAIKIN Industries); SURFLON S-242, SURFLON S-243, SURFLON S-420, SURFLON S-611, SURFLON S-651, SURFLON S-386 (all manufactured by AGC SEIMI CHEMICAL); BYK-340 (manufactured by BYK-Chemie Japan); AC110a, AC100a (all manufactured by Algin Chemie); MEGAFACE F-114, MEGAFACE F-410, MEGAFACE F-444, MEGAFACE EXPTP-2066, MEGAFACE F-430, MEGAFACE F-472SF, MEGAFACE F-477, MEGAFACE F-552, MEGAFACE F-553, MEGAFACE F-554, MEGAFACE F-555, MEGAFACE R-94, MEGAFACE RS-72-K, MEGAFACE RS-75, MEGAFACE F-556, MEGAFACEEXPTF-1367, MEGAFACE EXPTF-1437, MEGAFACE F-558, MEGAFACE EXPTF-1537 (all made by DIC); FC-4430, FC-4432 (all made by Sumitomo 3M); FTERGENT 100, FTERGENT 100C, FTERGENT 110, FTERGENT 150, FTERGENT 150CH, FTERGENT AK, FTERGENT 501, FTERGENT 250, FTERGENT251, FTERGENT Commercially available products include 222F, FTERGENT 208G, FTERGENT 300, FTERGENT 310, FTERGENT 400SW (all manufactured by NEOS); PF-136A, PF-156A, PF-151N, PF-636, PF-6320, PF-656, PF-6520, PF-651, PF-652, PF-3320 (all manufactured by Kitamura Chemical Industry).

[0332] In the photosensitive composition of the present invention, the amount of any component other than the polymerization initiator (A), the ethylenically unsaturated compound (B), the colorant (C), the alkali-developable compound (D), the solvent, the inorganic compound, and the organic polymer is appropriately selected according to the intended use and is not particularly limited, but is preferably set to 50 parts by mass or less in total relative to 100 parts by mass of the ethylenically unsaturated compound (B).

[0333] The photosensitive composition, alkali-developable photosensitive resin composition or cured product of the present invention can be used for photocurable coatings or varnishes; photocurable adhesives; printed substrates; color filters in liquid crystal display elements for color displays of display devices (color TVs, PC monitors, portable information terminals, digital cameras, etc.); color filters for CCD image sensors; electrode materials for plasma display panels; powder coatings; printing inks; printing plates; adhesives; dental compositions; gel coatings; photoresists for electronic engineering; plating resists; etching resists; dry films; solder resists; resists for forming structures of various display devices; compositions for encapsulating electrical and electronic components; resists Flux; magnetic recording material; micro-mechanical parts; waveguide; optical opening; mask for plating; etching mask; color test system; glass fiber cable coating; screen printing template; materials for manufacturing three-dimensional objects by stereolithography, materials for holographic recording, image recording materials, microelectronic circuits, decolorizing materials, decolorizing materials for image recording materials, decolorizing materials for image recording materials using microcapsules, photoresist materials for printed wiring boards, photoresist materials for UV and visible laser direct imaging systems; photoresist materials or protective films used in the formation of dielectric layers in the sequential lamination of printed circuit boards, etc., and there is no particular limitation on the use thereof.

[0334] The photosensitive composition or alkali-developable photosensitive resin composition of the present invention can also be used for the purpose of forming a spacer for a liquid crystal display panel and the purpose of forming a protrusion for a vertically aligned liquid crystal display element. In particular, it is useful as a photosensitive composition for simultaneously forming a protrusion and a spacer for a vertically aligned liquid crystal display element.

[0335] The curing method of the photosensitive composition or alkali-developable photosensitive resin composition of the present invention will be described in detail below.

[0336] The photosensitive composition or alkali-developable photosensitive resin composition of the present invention can be applied to a supporting substrate such as soda glass, quartz glass, semiconductor substrate, metal, paper, plastic, etc. by a spin coater, a roll coater, a rod coater, a die coater, a curtain coater, various printing, dipping, etc., and can also be applied to a supporting substrate such as a film once and then transferred to another supporting substrate. There is no limitation on the application method.

[0337] In addition, as a light source of energy rays used when curing the photosensitive composition alkali-developable photosensitive resin composition of the present invention, electromagnetic wave energy with a wavelength of 2000 to 7000 angstroms obtained from ultra-high pressure mercury lamps, high pressure mercury lamps, medium pressure mercury lamps, low pressure mercury lamps, mercury vapor arc lamps, xenon arc lamps, carbon arc lamps, metal halide lamps, fluorescent lamps, tungsten lamps, excimer lamps, germicidal lamps, light-emitting diodes, CRT light sources, etc., or high energy rays such as electron beams, X-rays, and radiation can be utilized. Preferably, ultra-high pressure mercury lamps, mercury vapor arc lamps, carbon arc lamps, xenon arc lamps, etc. that can emit light with a wavelength of 300 to 450 nm can be listed.

[0338] Furthermore, by using a laser in an exposure light source, the laser direct drawing method that directly forms an image by digital information such as a computer without using a mask is useful because it can not only seek to improve productivity, but also seek to improve clarity or position accuracy, etc. As this laser, it is suitable to use light with a wavelength of 340 to 430 nm, and it is also possible to use lasers that can emit light from the visible to infrared region such as excimer lasers, nitrogen lasers, argon ion lasers, helium-cadmium lasers, helium-neon lasers, krypton ion lasers, various semiconductor lasers and YAG lasers. When using these lasers, a sensitizing dye that absorbs this region from the visible to the infrared can be added.

[0339] The above-mentioned spacer for liquid crystal display panel is preferably formed by the following steps: (1) a step of forming a coating film of the photosensitive composition of the present invention on a substrate; (2) a step of irradiating the coating film with radiation via a mask having a predetermined pattern shape; (3) a baking step after exposure; (4) a step of developing the exposed coating film; and (5) a step of heating the developed coating film.

[0340] The photosensitive composition of the present invention to which an ink-proofing agent is added is useful as a resin composition for forming a partition wall for an inkjet method, and the composition is used as a color filter, and is particularly preferably used for a partition wall for an inkjet method color filter having a tooth angle of 50° or more. As the ink-proofing agent, a fluorine-based surfactant and a composition containing a fluorine-based surfactant are preferably used.

[0341] An optical element is manufactured by a method of partitioning a transfer body by partitions formed by the photosensitive composition of the present invention, and applying droplets to the concave portions on the partitioned transfer body by an inkjet method to form image areas. In this case, it is preferred that the droplets contain a colorant and the image area is colored, and it is preferred to use an optical element having at least a pixel group including a plurality of colored areas and partitions isolating each colored area of ​​the pixel group on a substrate, and manufactured by the above-mentioned method for manufacturing an optical element.

[0342] Example

[0343] Hereinafter, the present invention will be described in further detail with reference to Examples and Comparative Examples, but the present invention is not limited to these Examples and the like.

[0344] [Examples 1-1 to 1-3] Preparation of Compound No. 1

[0345] [Example 1-1] Preparation of Intermediate 1A (Ketone Compound)

[0346] After placing triphenylamine (3.3 g) and dichloroethane (15 g) in a four-necked flask, aluminum chloride (5.8 g) and acetyl chloride (3.3 g) were added under ice-cooling. After stirring at room temperature for 3 hours, the reaction solution was poured into ice-cooled 5% dilute hydrochloric acid and stirred to separate oil and water. The organic layer was washed twice with a 5% HCl aqueous solution and further washed four times with water. After the product layer was desolvated, it was purified by passing through a silica gel column (hexane / ethyl acetate = 65 / 35) to obtain Intermediate 1A (2.6 g: yield 52%).

[0347] [Chemical formula 51]

[0348] Intermediate 1A

[0349]

[0350] [Example 1-2] Preparation of Intermediate 1B (Oxime Compound)

[0351] In a four-necked flask, intermediate 1A (2.6 g), ethanol (24 g), water (12 g), and hydroxylamine hydrochloride (1.6 g) were placed and heated under reflux for 10 hours. After cooling to room temperature, the precipitate was filtered and fully dried to obtain intermediate 1B (2.8 g: yield 96%).

[0352] [Chemical formula 52]

[0353] Intermediate 1B

[0354]

[0355] [Example 1-3] Preparation of Compound No. 1 (Oxime Ester Compound of the Present Invention)

[0356] After intermediate 1B (2.1 g) and dimethylformamide (15 g) were added to a four-necked flask, triethylamine (1.7 g) and acetyl chloride (1.3 g) were added under ice cooling. After stirring at room temperature for 2 hours, ion exchange water (15 g) and ethyl acetate (30 g) were added to separate oil and water. The organic layer was washed with water three times, and after removing the solvent, it was purified by silica gel column (hexane / ethyl acetate = 50 / 50) to obtain compound No. 1 (1.4 g: yield 50%). The NMR data of the obtained compound No. 1 are shown in [Table 1].

[0357] [Chemical formula 53]

[0358]

[0359] [Examples 2-1 to 2-3] Preparation of Compound No. 2

[0360] [Example 2-1] Preparation of Intermediate 2A (Ketone Compound)

[0361] After placing triphenylamine (5.9 g) and dichloroethane (40 g) in a four-necked flask, aluminum chloride (10.5 g) and propionyl chloride (7.1 g) were added under ice-cooling. After stirring at room temperature for 5 hours, the reaction solution was poured into ice-cooled 5% dilute hydrochloric acid and stirred to separate oil and water. The organic layer was washed twice with 5% HCl aqueous solution and further washed 4 times with water. After the product layer was desolvated, it was purified by silica gel column (hexane / ethyl acetate = 80 / 20) to obtain intermediate 2A (3.9 g: yield 39%).

[0362] [Chemical formula 54]

[0363]

[0364] [Example 2-2] Preparation of Intermediate 2B (Oxime Compound)

[0365] Weigh the intermediate 2A (3.9 g) and dimethylformamide (24 g) into a four-necked flask, add 35% hydrochloric acid (3.9 g) and isobutyl nitrite (3.9 g) dropwise under ice cooling, and stir at room temperature for 20 hours. Add ion exchange water (24 g) and ethyl acetate (48 g), separate the oil and water, and wash the organic layer with water three times. After removing the solvent from the organic layer, the intermediate NCIx175-b (4.5 g: yield 96%) was obtained.

[0366] [Chemical formula 55]

[0367] Intermediate 2B

[0368]

[0369] [Example 2-3] Preparation of Compound No. 2 (Oxime Ester Compound of the Present Invention)

[0370] In a four-necked round-bottom flask, intermediate 2B (4.5 g) and tetrahydrofuran (23 g) were added dropwise, triethylamine (3.0 g) and acetyl chloride (2.2 g) were added dropwise in sequence under ice cooling, and stirred at room temperature for 2 hours. After adding ion exchange water (17 g) and ethyl acetate (46 g), oil-water separation was performed, and the organic layer was washed with water 5 times. After the organic layer was desolvated, it was purified by silica gel column (hexane / ethyl acetate = 50:50) to obtain compound No. 2 (2.7 g: yield 48%). The NMR data of the obtained compound No. 2 are shown in [Table 1].

[0371] [Chemical formula 56]

[0372]

[0373] [Examples 3-1 to 3-4] Preparation of Compound No. 133

[0374] [Example 3-1] Preparation of Intermediate 133A

[0375] Fluorobenzene (27.7 g) and dichloroethane (192 g) were added to a four-necked flask, followed by aluminum chloride (40.4 g) and n-octanoyl chloride (46.8 g) under ice cooling. After reacting at room temperature for 1 hour, the reaction solution was poured into ice-cold 5% dilute hydrochloric acid and stirred to separate oil from water. The organic layer was washed twice with 5% dilute hydrochloric acid and three times with ion exchange water, and then the solvent was removed to obtain intermediate 133A (50.0 g: yield 78%).

[0376] [Chemical formula 57]

[0377] Intermediate 133A

[0378]

[0379] [Example 3-2] Preparation of Intermediate 133B (Nitrogen-Containing Compound)

[0380] Carbazole (20.0 g), intermediate 133A (29.3 g), potassium carbonate (24.8 g), and dimethyl sulfoxide (133 g) were placed in a four-necked flask and reacted at 160° C. for 6 hours. Ion exchange water (173 g) was added and extracted with dichloroethane (163 g). The organic layer was washed with water three times and then desolventized to obtain intermediate 133B (41.2 g: yield 93%).

[0381] [Chemical formula 58]

[0382] Intermediate 133B

[0383]

[0384] [Example 3-3] Preparation of Intermediate 133C (Ketone Compound)

[0385] After placing intermediate 133B (41.2 g) and dichloroethane (209 g) in a four-necked flask, aluminum chloride (49.1 g) and n-octanoyl chloride (39.9 g) were added in sequence under ice cooling. After reacting at this temperature for 4 hours, the reaction solution was poured into ice-cold 5% dilute hydrochloric acid and stirred to separate oil and water. The organic layer was washed twice with 5% dilute hydrochloric acid and three times with ion exchange water, and then the solvent was removed to obtain intermediate 133C (50.5 g: 73%).

[0386] [Chemical formula 59]

[0387] Intermediate 133C

[0388]

[0389] [Example 3-4] Preparation of Compound No. 133 (Oxime Ester Compound)

[0390] Add intermediate 133C (10.0 g), dimethylformamide (50 g), hydroxylamine hydrochloride (3.7 g), and pyridine (4.2 g) to a four-necked flask and stir at 80°C for 10 hours. After cooling with ice, triethylamine (5.4 g) and acetyl chloride (4.2 g) were added dropwise in sequence and stirred at room temperature for 5 hours. Add ion exchange water (50 g) and extract with ethyl acetate (100 g). After washing the organic layer with water three times, remove the solvent and purify it with a silica gel column (ethyl acetate / hexane = 1 / 4) to obtain compound No. 133 (2.3 g: yield 18%). The NMR data of the obtained compound No. 133 are shown in [Table 1].

[0391] [Chemical formula 60]

[0392]

[0393] [Examples 4-1 and 4-2] Preparation of Compound No. 134

[0394] [Example 4-1] Preparation of Intermediate 134A (Oxime Compound)

[0395] Intermediate 133C (10.0 g) and DMF (10.0 g) were weighed into a four-necked flask, and 35% hydrochloric acid (6.70 g) and isobutyl nitrite (6.63 g) were added dropwise under ice cooling, and stirred at room temperature for 20 hours. Ion exchange water (22.8 g) and ethyl acetate (34.2 g) were added to separate the oil and water, and the organic layer was washed with water three times. After the organic layer was desolvated, it was purified by silica gel column (ethyl acetate / hexane = 1 / 4) to obtain intermediate 134A (2.8 g: yield 25%).

[0396] [Chemical formula 61]

[0397] Intermediate 134A

[0398]

[0399] [Example 4-2] Preparation of Compound No. 134 (Oxime Ester Compound)

[0400] Place intermediate 134A (2.7 g) and ethyl acetate (10 g) in a four-necked round-bottom flask. Add triethylamine (1.3 g) and acetyl chloride (1.0 g) dropwise in sequence under ice cooling, warm to room temperature, and stir for 3 hours. Add ion exchange water (12 g) to separate the oil from the water, and wash the organic layer with water 5 times. After removing the solvent from the organic layer, purify it through a silica gel column (hexane / ethyl acetate = 85:15) to obtain compound No. 134 (0.89 g: yield 27%).

[0401] The NMR data of the obtained compound No. 134 is shown in [Table 1].

[0402] [Chemical formula 62]

[0403]

[0404] [Table 1]

[0405]

[0406] [Manufacturing Example 1] Manufacture of Blue Pigment Dispersion No. 1

[0407] A blue pigment dispersion was prepared by dispersing DISPERBYK-161 (12.5 parts by mass; manufactured by BYK-Chemie Japan) as a dispersant and Pigment Blue 15:6 (15 parts by mass) as a colorant in PGMEA (72.5 parts by mass) using a bead mill.

[0408] [Examples 5 to 7 and Comparative Examples 1 to 2] Preparation of Photosensitive Compositions

[0409] The components were prepared according to the formulations of [Table 2] and [Table 3] to obtain photosensitive compositions No. 1 to 3 and comparative photosensitive compositions No. 1 to 2. It should be noted that the numbers in the table represent parts by mass. Compounds No. 2, No. 133, No. 134, No. A2-3 and No. A2-11 were used alone as photopolymerization initiators.

[0410] In addition, the symbols in the table represent the following components.

[0411] A-1 Compound No.2

[0412] A-2 Compound No.133

[0413] A-3 Compound No.134

[0414] A'-4 Compound No.A2-3

[0415] A'-5 Compound No.A2-11

[0416] B-1 SPC-3000 * (Ethylenically unsaturated compound having an acid group, solid content 42 wt% PGMEA solution: manufactured by Showa Denko)

[0417] B-2 KAYARAD DPHA (ethylenically unsaturated compound: manufactured by Nippon Kayaku)

[0418] C-1 Blue Pigment Dispersion No.1 (Colorant PGMEA Dispersion)

[0419] D-1 KBE-403 (Silane coupling agent: Shin-Etsu Chemical)

[0420] D-2 F-554 (fluorine-containing and lipophilic group-containing oligomer: manufactured by DIC)

[0421] E-1 PGMEA (Solvent)

[0422] *SPC-3000 is an ethylenically unsaturated compound (B) and also an alkali-developable compound (D).

[0423] [Table 2]

[0424] Example 5 6 7 Photosensitive composition No.1 No.2 No.3 A-1 1 A-2 1 A-3 1 A′-4 A′-5 B-1 22.7 22.7 22.7 B-2 3 3 3 C-1 28.5 28.5 28.5 D-1 0.5 0.5 0.5 D-2 0.01 0.01 0.01 E-1 44.29 44.29 44.29 count 100 100 100

[0425] [Table 3]

[0426] Comparative Example 1 2 Comparison of photosensitive compositions No.1 No.2 A-1 A-2 A-3 A′-4 1 A′-5 1 B-1 22.7 22.7 B-2 3 3 C-1 28.5 28.5 D-1 0.5 0.5 D-2 0.01 0.01 E-1 44.29 44.29 count 100 100

[0427] [Evaluation of Cured Product Obtained from Photosensitive Composition]

[0428] The cured products obtained from the photosensitive compositions Nos. 1 to 3 and the comparative photosensitive compositions Nos. 1 to 2 were evaluated for brightness by the following procedure. The results are collectively shown in [Table 4].

[0429] (brightness)

[0430] The photosensitive compositions No. 1 to 3 and the comparative photosensitive compositions No. 1 to 2 were spin-coated (500 rpm, 2 seconds, 900 rpm, 5 seconds) on a glass substrate, pre-baked at 90° C. for 90 seconds using a hot plate, and then cooled at 23° C. for 40 seconds. Thereafter, the glass substrate was irradiated with a high-pressure mercury lamp at 100 mJ / cm 2 , an evaluation sample was prepared. The Y value was calculated from the transmittance of the obtained sample at 380-780nm according to JIS Z8701. The sample with a Y value of 9.5 or more was set as A, and the sample with a Y value of less than 9.5 was set as B. The higher the BY value, the higher the brightness, which is useful. The sample with a brightness evaluation of A can be preferably used as a color filter, and the sample evaluated as B is not suitable as a color filter.

[0431] [Table 4]

[0432] Photosensitive composition brightness Example 8 Photosensitive composition No.1 A Example 9 Photosensitive composition No.2 A Example 10 Photosensitive composition No.3 A Comparative Example 3 Comparative Photosensitive Composition No. 1 A Comparative Example 4 Comparative Photosensitive Composition No. 2 B

[0433] [Evaluation of photosensitive composition]

[0434] The sensitivity evaluation of the photosensitive compositions No. 1 and 3 and the comparative photosensitive composition No. 1 evaluated as A in the above brightness evaluation was performed by the following procedure. The results are collectively described in [Table 5].

[0435] (Sensitivity)

[0436] The above-mentioned photosensitive compositions No. 1 to 3 and comparative photosensitive compositions No. 1 to 2 were spin-coated (500 rpm, 2 seconds, 900 rpm, 5 seconds) on a glass substrate, and pre-baked at 90°C for 90 seconds using a hot plate, and then cooled at 23°C for 40 seconds. After that, exposure was performed using a high-pressure mercury lamp through a mask. After development using a 2.5 mass % < sodium carbonate aqueous solution as a developer, the pattern was thoroughly washed with water, and then post-baked at 230°C for 30 minutes using an oven to fix the pattern. Observation with an electron microscope showed that the photosensitive composition No. 1 to 3 and the comparative photosensitive composition No. 1 to 2 were pre-baked at 90°C for 90 seconds, and then cooled at 23°C for 40 seconds. 2 The pattern of exposure amount is measured, and the line width of the mask opening is 30μm. The sample with a line width of 35μm or more is set as A, the sample with a line width of 25μm or more is set as B, and the sample with a line width of less than 25μm is set as C. The larger the line width, the better the sensitivity. The photosensitive composition with a sensitivity evaluation of A and B can be used as a color filter, and the photosensitive composition with a sensitivity evaluation of A is particularly preferred. The photosensitive composition with a sensitivity evaluation of C is not suitable for use as a color filter.

[0437] [Table 5]

[0438] Photosensitive composition Sensitivity Embodiment 11 Photosensitive composition No.1 B Example 12 Photosensitive composition No.3 A Comparative Example 5 Comparative Photosensitive Composition No. 1 C

[0439] From the above [Table 3] to [Table 5], it is shown that the oxime ester compound of the present invention has high sensitivity and the cured product of the present invention has high brightness.

[0440] Therefore, the oxime ester compound of the present invention is excellent in photolithography properties and the obtained cured product is excellent in brightness, and therefore is useful as a photopolymerization initiator.

[0441] Industrial Applicability

[0442] The oxime ester compound of the present invention is a novel compound useful as a photopolymerization initiator having high sensitivity and excellent heat resistance (low sublimation), and is particularly useful as a photopolymerization initiator. In particular, the oxime ester compound of the present invention is useful because a color filter having high brightness and a display device containing the color filter can be provided by a photosensitive composition containing the photopolymerization initiator.

Claims

1. An oxime ester compound represented by the following general formula (I): In the formula, R 1 , R 2 , R 4 , R 5 , R 7 , R 8 , R 9 , R 10 , R 12 and R 13 Each independently represents a hydrogen atom, R 3 , R 6 and R 11 is a group represented by the following general formula (II), X 1 indicates absence, direct bonding, -CO-, -O- or -S-, In the formula, R 31 and R 32 Each independently represents a hydrogen atom, a halogen atom, a nitro group, a cyano group, a hydrocarbon group having 1 to 20 carbon atoms, or a heterocyclic group having 2 to 20 carbon atoms, R 31 and R 32 The hydrogen atoms in the groups represented may be substituted by halogen atoms, nitro groups, cyano groups, hydroxyl groups, amino groups, carboxyl groups, methacryloyl groups, acryloyl groups, epoxy groups, vinyl groups, vinyl ether groups, mercapto groups, isocyanate groups or heterocyclic groups having 2 to 20 carbon atoms. R 31 and R 32 The methylene group in the group represented by may also be referred to as -O-, -CO-, -COO-, -OCO-, -NR 33 -、-NR 33 CO-, -S-, -CS-, -SO2-, -SCO-, -COS-, -OCS- or CSO-substituted, R 33 represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, n represents 1, and * represents a bonding site. 2 . A photopolymerization initiator comprising the oxime ester compound according to claim 1 . 3 . A photosensitive composition comprising the photopolymerization initiator (A) according to claim 2 and an ethylenically unsaturated compound (B). The photosensitive composition according to claim 3 , further comprising a colorant (C). 5 . An alkali-developable photosensitive resin composition comprising the photosensitive composition according to claim 3 or 4 and an alkali-developable compound (D). 6 . A cured product, which is a cured product of the photosensitive composition according to claim 3 or 4 or the alkali-developable photosensitive resin composition according to claim 5 .

7. A display device comprising the cured product according to claim 6. 8 . A method for producing a cured product, comprising the step of curing the photosensitive composition according to claim 3 or 4 or the alkali-developable photosensitive resin composition according to claim 5 by light irradiation or heating.

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