CN110546134A - Oxime ester compound and photopolymerization initiator containing the same - Google Patents

Oxime ester compound and photopolymerization initiator containing the same Download PDF

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CN110546134A
CN110546134A CN201880027881.2A CN201880027881A CN110546134A CN 110546134 A CN110546134 A CN 110546134A CN 201880027881 A CN201880027881 A CN 201880027881A CN 110546134 A CN110546134 A CN 110546134A
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三原大树
竹内良智
丸山谅子
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Edico Co
Adeka Corp
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    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C251/00—Compounds containing nitrogen atoms doubly-bound to a carbon skeleton
    • C07C251/32—Oximes
    • C07C251/62—Oximes having oxygen atoms of oxyimino groups esterified
    • C07C251/64—Oximes having oxygen atoms of oxyimino groups esterified by carboxylic acids
    • C07C251/66—Oximes having oxygen atoms of oxyimino groups esterified by carboxylic acids with the esterifying carboxyl groups bound to hydrogen atoms, to acyclic carbon atoms or to carbon atoms of rings other than six-membered aromatic rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D209/00—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom
    • C07D209/56—Ring systems containing three or more rings
    • C07D209/80—[b, c]- or [b, d]-condensed
    • C07D209/82—Carbazoles; Hydrogenated carbazoles
    • C07D209/86—Carbazoles; Hydrogenated carbazoles with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to carbon atoms of the ring system
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/46—Polymerisation initiated by wave energy or particle radiation
    • C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
    • C08F2/50—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light with sensitising agents
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
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    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G03F7/028—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with photosensitivity-increasing substances, e.g. photoinitiators
    • G03F7/031—Organic compounds not covered by group G03F7/029
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/09—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers
    • G03F7/105—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers having substances, e.g. indicators, for forming visible images

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Abstract

Description

Oxime ester compound and photopolymerization initiator containing the same
Technical Field
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
The photosensitive composition is a composition obtained by adding a photopolymerization initiator to an ethylenically unsaturated compound, and is polymerized and cured by irradiation with energy rays (light), and therefore, is used for photocurable inks, photosensitive printing plates, various photoresists, and the like.
As a photopolymerization initiator used for the photosensitive composition, patent document 1 discloses an oxime ester photopolymerization initiator having a carbazole skeleton. Further, patent document 2 discloses a polymerization initiator containing an oxime ester compound having a triarylamine skeleton. However, the oxime ester compounds described in patent documents 1 and 2 cannot achieve a satisfactory balance among sensitivity, heat resistance (low sublimation property), and transparency (high luminance of a color filter) at a satisfactory level.
Further, since a colored alkali-developable photosensitive composition containing a colorant such as a color filter is required to have high sensitivity, it is necessary to set a photopolymerization initiator in a resist to a high concentration. However, the photopolymerization initiator having a high concentration of the photopolymerization initiator causes generation of residue due to deterioration of developability, contamination of a photomask or a heating furnace due to a sublimate, and a luminance difference due to coloring of a cured product.
Documents of the prior art
Patent document
patent document 1: international publication No. 2008/138732
Patent document 2: international publication No. 2017/033880
Disclosure of Invention
Accordingly, an object of the present invention is to provide an oxime ester compound which is 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 oxime ester compound, and to provide a color filter having high luminance and a display device including the color filter.
The present invention solves the above problems by providing the following [1] to [9 ].
[1] An oxime ester compound represented by the following general formula (I).
[ chemical formula 1]
(wherein R1, R2, R3, R4, R5, R6, R7, R8, R9, R10, R11, R12 and R13 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, R21, OR21, SR21, NR22R23, COR21, SOR21, SO2R21 OR CONR22R23,
At least three of R1, R2, R3, R4, R5, R6, R7, R8, R9, R10, R11, R12 and R13 are groups represented by the following general formula (II),
R21, R22 and R23 each independently represents a hydrocarbon group having 1 to 20 carbon atoms or a heterocyclic group having 2 to 20 carbon atoms,
The hydrogen atom in the groups represented by R21, R22 and R23 may be substituted with a halogen atom, a nitro group, a cyano group, a hydroxyl group, an amino group, a carboxyl group, a methacryloyl group, an acryloyl group, an epoxy group, a vinyl ether group, a mercapto group, an isocyanate group or a heterocyclic group having 2 to 20 carbon atoms,
Methylene groups in the groups represented by R21, R22 and R23 are sometimes substituted by-O-, -CO-, -COO-, -OCO-, -NR24-, -NR24CO-, -S-, -CS-, -SO2-, -SCO-, -COS-, -OCS-or CSO-,
r24 represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms,
X1 represents absent, directly bonded, -CO-, -O-or-S-. )
[ chemical formula 2]
(wherein R31 and R32 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,
The hydrogen atom in the group represented by R31 and R32 may be substituted with a halogen atom, a nitro group, a cyano group, a hydroxyl group, an amino group, a carboxyl group, a methacryloyl group, an acryloyl group, an epoxy group, a vinyl ether group, a mercapto group, an isocyanate group or a heterocyclic group having 2 to 20 carbon atoms,
methylene groups in the groups represented by R31 and R32 are sometimes substituted by-O-, -CO-, -COO-, -OCO-, -NR33-, -NR33CO-, -S-, -CS-, -SO2-, -SCO-, -COS-, -OCS-, or CSO-,
R33 represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms,
n represents 0 or 1, and x represents a bonding site. )
[2] The oxime ester compound according to [1], wherein at least one of R3, R6 and R11 in the general formula (I) is a group represented by the general formula (II).
[3] A photopolymerization initiator comprising the oxime ester compound according to [1] or [2 ].
[4] A photosensitive composition comprising the photopolymerization initiator (A) as described in [3] and an ethylenically unsaturated compound (B).
[5] The photosensitive composition according to [4], which further contains a colorant (C).
[6] An alkali-developable photosensitive resin composition comprising the photosensitive composition according to [4] or [5] and an alkali-developable compound (D).
[7] A cured product of the photosensitive composition according to [4] or [5] or the alkali-developable photosensitive resin composition according to [6 ].
[8] A display device comprising the cured product according to [7 ].
[9] A method for producing a cured product, which comprises a 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
The oxime ester compound of the present invention and the photopolymerization initiator (a) containing the compound are described in detail below based on preferred embodiments.
the oxime ester compound of the present invention is a novel compound represented by the above general formula (I). In the oxime ester compound, geometric isomers exist due to the double bond of the oxime, but they are not distinguished.
That is, in the present specification, the compound represented by the general formula (I) and the exemplified compounds thereof represent one of these geometric isomers or a mixture of 2 or more kinds thereof, and are not limited to the structures showing specific isomers.
The hydrocarbyl group having 1 to 20 carbon atoms represented by R21 to R24 in the general formula (I) 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, an arylalkyl group having 7 to 20 carbon atoms, or the like.
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 groups, and an alkyl group having 1 to 10 carbon atoms is particularly preferable.
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-tetradecatrieneallyl. Particularly preferred is an alkenyl group having 1 to 10 carbon atoms.
The cycloalkyl group having 3 to 20 carbon atoms is a saturated monocyclic or saturated 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 groups. Examples of the saturated polycyclic alkyl group include an adamantyl group, a decalinyl group, an octahydropentalene group, and a bicyclo [1.1.1] pentyl group.
The cycloalkylalkyl group having 4 to 20 carbon atoms is a group having 4 to 20 carbon atoms in which a hydrogen atom of an alkyl group is substituted with a cycloalkyl group. Examples thereof include cyclopropylmethyl, 2-cyclobutylethyl, 3-cyclopentylpropyl, 4-cyclohexylbutyl, cycloheptylmethyl, cyclooctylmethyl, 2-cyclononylethyl, 2-cyclodecylethyl, 3-3-adamantylpropyl and decahydronaphthylpropyl.
Examples of the aryl group having 6 to 20 carbon atoms include a phenyl group, a tolyl group, a xylyl group, an ethylphenyl group, a naphthyl group, an anthryl group, a phenanthryl group, a phenyl group substituted with one or more alkyl groups, a biphenyl group, a naphthyl group, an anthryl group, and the like.
The arylalkyl group having 7 to 30 carbon atoms is a group having 7 to 30 carbon atoms obtained by substituting a hydrogen atom of an alkyl group with an aryl group. Examples thereof include benzyl, α -methylbenzyl, α -dimethylbenzyl, phenylethyl, and naphthylpropyl.
Among the hydrocarbon groups having 1 to 20 carbon atoms, an alkyl group having 1 to 12 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, a cycloalkylalkyl group having 4 to 15 carbon atoms, an aryl group having 6 to 15 carbon atoms and an arylalkyl group having 7 to 15 carbon atoms are particularly preferable from the viewpoint of satisfactory sensitivity as a photopolymerization initiator.
Examples of the heterocyclic group having 2 to 20 carbon atoms represented by R21 to R23 and the heterocyclic group having 2 to 20 carbon atoms that may substitute for a hydrogen atom in the group represented by R21 to R23 in the general formula (I) include pyrrolyl, pyridyl, pyridylethyl, pyrimidinyl, pyridazinyl, piperazinyl, piperidinyl, pyranyl, pyranylethyl, pyrazolyl, triazinyl, triazinylmethyl, pyrrolidinyl, quinolyl, isoquinolyl, imidazolyl, benzimidazolyl, triazolyl, furyl (furyl), benzofuryl, thienyl, thiophenyl, benzothiophenyl, thiadiazolyl, thiazolyl, benzothiazolyl, oxazolyl, benzoxazolyl, isothiazolyl, isoxazolyl, indolyl, julolidinyl, morpholinyl, thiomorpholinyl, 2-pyrrolidone-1-yl, 2-piperidone-1-yl group, 2, 4-dioxyimidazolidin-3-yl group, 2, 4-dioxyoxazolidin-3-yl group, and the like.
methylene groups in the groups represented by R21 to R23 in the above general formula (I) may be substituted by-O-, -CO-, -COO-, -OCO-, -NR24-, -NR24CO-, -S-, -CS-, -SO2-, -SCO-, -COS-, -OCS-or CSO-, and the substitution may be 1 or2 or more groups, and in the case of a group which can be continuously substituted, 2 or more groups may be continuously substituted under the condition that oxygen atoms are not adjacent.
Among the heterocyclic group having 2 to 20 carbon atoms, a heterocyclic group having 2 to 10 carbon atoms is particularly preferable from the viewpoint of good sensitivity as a photopolymerization initiator.
Examples of the hydrocarbon group having 1 to 20 carbon atoms represented by R31 to R33 in the general formula (II) include the same hydrocarbon groups as those having 1 to 20 carbon atoms represented by R21 to R24 in the general formula (I).
Examples of the heterocyclic group having 2 to 20 carbon atoms represented by R31 and R32 and the heterocyclic group having 2 to 20 carbon atoms which may substitute for a hydrogen atom in the group represented by R31 and R32 in the general formula (II) include the same hydrocarbon groups as those having 1 to 20 carbon atoms represented by R21 to R23 in the general formula (I).
In the above general formula (II), methylene groups in the groups represented by R31 and R32 may be substituted by-O-, -CO-, -COO-, -OCO-, -NR24-, -NR24CO-, -S-, -CS-, -SO2-, -SCO-, -COS-, -OCS-, or CSO-, and the substitution may be 1 or2 or more groups, and in the case of a group which can be continuously substituted, 2 or more groups may be continuously substituted under the condition that oxygen atoms are not adjacent.
Examples of the halogen atom in the general formulae (I) and (II) include fluorine, chlorine, bromine, and iodine.
The oxime ester compound in which X1 is absent or directly bonded in the general formula (I) is preferable because it has excellent brightness when used as a photopolymerization initiator, and the oxime ester compound in which X1 is directly bonded is particularly preferable because it has excellent sensitivity in addition to brightness. In the present invention, the absence of X1 means that the oxime ester compound represented by the general formula (I) has a triphenolamine skeleton without any atom at the position X1.
When R1 to R13 are groups other than those of the general formula (II), compounds in which R1 to R13 are each a hydrogen atom or cyano group, particularly a hydrogen atom, are preferable because they can be synthesized easily.
The oxime ester compound in which at least one, preferably two, and more preferably all of R3, R6, and R11 in the general formula (I) are groups represented by the general formula (II) is preferable because it is excellent in yield in synthesis and easy to purify. When all of R3, R6, and R11 in the general formula (I) are groups represented by the general formula (II), oxime ester compounds in which R1, R2, R4, R5, R7, R8, R9, R10, R12, and R13 are hydrogen atoms are preferable because synthesis is easy.
The use of an oxime ester compound of the general formula (II) wherein n is 1 as the photopolymerization initiator (a) is preferable because the cured product is excellent in transparency and brightness.
The compound of the general formula (II) wherein R31 is an alkyl group having 1 to 12 carbon atoms, particularly an alkyl group having 1 to 7 carbon atoms, is preferable because of its high solubility in organic solvents. A compound in which R32 is an alkyl group having 1 to 4 carbon atoms, particularly a methyl group, an ethyl group or a phenyl group, is preferable because of its high reactivity.
Preferable specific examples of the oxime ester compound of the present invention represented by the above general formula (I) include the following compound Nos. 1 to 261. However, the present invention is not limited to the following compounds.
[ chemical formula 3]
[ chemical formula 4]
[ chemical formula 5]
[ chemical formula 6]
[ chemical formula 7]
[ chemical formula 8]
[ chemical formula 9]
[ chemical formula 10]
[ chemical formula 11]
[ chemical formula 12]
[ chemical formula 13]
[ chemical formula 14]
[ chemical formula 15]
[ chemical formula 16]
[ chemical formula 17]
[ chemical formula 18]
[ chemical formula 19]
[ chemical formula 20]
[ chemical formula 21]
[ chemical formula 22]
[ chemical formula 23]
The oxime ester compound of the present invention represented by the general formula (I) is not particularly limited, and can be synthesized, for example, by the following method.
When n in the general formula (II) is 0, the synthesis can be carried out by the following reaction scheme. Specifically, a known nitrogen-containing compound is reacted with a known and commercially available acid chloride to obtain a ketone compound 1, and the obtained ketone compound 1 is reacted with hydroxylamine hydrochloride to obtain an oxime compound 1. Then, the acid chloride is reacted with the oxime compound 1 in the presence of Triethylamine (TEA) to obtain the oxime ester compound 1 of the present invention represented by the above general formula (I).
The oxime compound and the oxime ester compound can also be produced by the method described in International publication No. 2008/078678.
[ chemical formula 24]
In the above reaction formulae, R1, R2, R3, R4, R5, R6, R7, R8, R9, R10, R11, R12, R13, R31, R32 and X1 are the same as R1, R2, R3, R4, R5, R6, R7, R8, R9, R10, R11, R12, R13, R31, R32 and X1 in the general formula (I) and the general formula (II).
When n in the general formula (II) is 1, the compound can be produced by the following method according to the following reaction formula.
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. Then, the oxime ester compound 2 of the present invention represented by the above general formula (I) is obtained by reacting an acid anhydride or acid chloride with the oxime compound 2.
[ chemical formula 25]
In the above reaction formulae, R1, R2, R3, R4, R5, R6, R7, R8, R9, R10, R11, R12, R13, R31, R32 and X1 are the same as R1, R2, R3, R4, R5, R6, R7, R8, R9, R10, R11, R12, R13, R31, R32 and X1 in the general formula (I) and the general formula (II).
The novel oxime ester compound of the present invention described above is useful in medicines, agricultural chemicals, base generators, photopolymerization initiators, and the like, and is particularly useful as a radical polymerization initiator (photo radical polymerization initiator or thermal radical polymerization initiator) among photopolymerization initiators. In addition, the novel oxime ester compound of the present invention can also be suitably used as a sensitizer.
The photosensitive composition of the present invention contains the photopolymerization initiator (a) and the ethylenically unsaturated compound (B) of the present invention, and contains, as optional components, a colorant (C), an alkali-developable compound (D), an inorganic compound, a solvent, and other components in combination.
The photopolymerization initiator (A) of the present invention contains at least 1 oxime ester compound of the present invention represented by the 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.
the photopolymerization initiator (a) of the present invention is useful as a photopolymerization initiator for the ethylenically unsaturated compound (B).
The photopolymerization initiator other than the one represented by the general formula (I) is not particularly limited as long as it generates radicals by light irradiation, and conventionally known compounds can be used, and preferable examples thereof include oxime ester compounds, acetophenone compounds, benzil compounds, benzophenone compounds, thioxanthone compounds, phosphine oxide compounds, titanocene compounds, and the like.
the oxime ester compound includes compounds having a group represented by the general formula (II), and the like, and is preferably used in the photosensitive composition of the present invention because the photopolymerization initiator has good sensitivity.
The hydrocarbon group having 1 to 20 carbon atoms represented by R31 to R33 in the general formula (II) is the same as the hydrocarbon group having 1 to 20 carbon atoms described in the general formula (I).
The group containing a heterocycle, which is modified with the group represented by R31 and R32, and R31 or R32 in the general formula (II), may have 2 to 20 carbon atoms, as in the group containing a heterocycle described in the general formula (I), which has 2 to 20 carbon atoms.
among the oxime ester compounds having a group represented by the above general formula (II), compounds represented by the following general formula (III) are particularly highly sensitive and therefore are preferably used in the photosensitive composition of the present invention.
Among the oxime ester compounds having a group represented by the general formula (I), compounds represented by the following general formula (III) are particularly highly sensitive and therefore are preferably used in the photosensitive composition of the present invention.
[ chemical formula 26]
(wherein R31, R32 and n are the same as R31, R32 and n in the formula (II) respectively,
R41 and R42 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 including a heterocyclic ring,
X11 represents an oxygen atom, a sulfur atom, a selenium atom, CR43R44, CO, NR45 or PR46,
X12 represents a non-bonded, directly bonded, C1-20 hydrocarbon group or CO, R43 to R46 each independently represents a hydrogen atom, a C1-20 hydrocarbon group or a C2-20 heterocyclic-containing group, the hydrogen atoms in the groups represented by R43 to R46 may be substituted with a halogen atom, a nitro group, a cyano group, a hydroxyl group, an amino group, a carboxyl group, a methacryloyl group, an acryloyl group, an epoxy group, a vinyl group, a mercapto group, an isocyanate group or a heterocyclic-containing group, and the methylene groups in the groups represented by R41 to R46 may be substituted with-O-, -CO-, -COO-, -OCO-, -S-, -SO2-, -SCO-or-COS-under the condition that oxygen is not adjacent,
R41 to R46 each independently form a ring together with any adjacent benzene ring,
a represents a number of 0 to 4,
b represents a number of 0 to 3. )
The hydrocarbon group having 1 to 20 carbon atoms represented by R41 to R46 in the general formula (III) is the same as the hydrocarbon group having 1 to 20 carbon atoms described in the general formula (I).
The heterocyclic ring-containing group having 2 to 20 carbon atoms represented by R41 to R46 in the general formula (III) is the same as the heterocyclic ring-containing group having 2 to 20 carbon atoms described in the general formula (I).
examples of the preferred oxime ester compounds represented by the general formula (III) include compounds No. A2-1 to No. A2-28 shown below. However, the polymerization initiator (a) used in the present invention is not limited at all by the following compounds.
[ chemical formula 27]
[ chemical formula 28]
[ chemical formula 29]
[ chemical formula 30]
In the general formula (III), when X1 is a sulfur atom and X2 is a non-bonded group, the oxime ester compound having a diphenyl sulfide skeleton represented by the above-mentioned compounds No. A2-1 to A2-7 is preferable in that a photosensitive composition having good sensitivity can be obtained by using the oxime ester compound of the present invention in combination as a polymerization initiator.
In the general formula (III), when X1 is NR55 and X2 is a direct bond, the oxime ester compound having a carbazole skeleton represented by the compounds No. A2-8 to A2-28 is particularly preferable in view of obtaining a photosensitive composition having good sensitivity.
Examples of the acetophenone-based compound include diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 4' -isopropyl-2-hydroxy-2-methylpropiophenone, 2-hydroxymethyl-2-methylpropiophenone, 2-dimethoxy-1, 2-diphenylethan-1-one, p-dimethylaminoacetophenone, p-tert-butyldichloroacetophenone, p-tert-butyltrichloroacetophenone, p-azidobenzylideneacetophenone, 1-hydroxycyclohexylphenylketone, 2-methyl-1- [4- (methylthio) phenyl ] -2-morpholinoacetone-1, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1, and, 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-propan-1-one.
Examples of the benzil-based compound include benzil and the like.
examples of the benzophenone-based compound include benzophenone, methyl benzoylbenzoate, michler's ketone, 4' -bisdiethylaminobenzophenone, 4 '-dichlorobenzophenone, and 4-benzoyl-4' -methylbenzophenone.
Examples of the thioxanthone compound include thioxanthone, 2-methylthioxanthone, 2-ethylthioxanthone, 2-chlorothioxanthone, 2-isopropylthioxanthone, and 2, 4-diethylthioxanthone.
The phosphine oxide compound includes a phosphine oxide compound such as 2,4, 6-trimethylbenzoyldiphenylphosphine oxide.
Examples of the titanocene-based compound include bis (cyclopentadienyl) -bis [2, 6-difluoro-3- (pyrrol-1-yl) ] titanium and the like.
Examples of commercially available radical initiators include Adeka Optomer N-1414, N-1717, N-1919, ADEKA ARKLS NCI-831 and NCI-930 (manufactured by ADEKA Co., Ltd.); IRGACURE184, IRGACURE369, IRGACURE651, IRGACURE907, IRGACURE OXE 01, IRGACURE OXE 02, and IRGACURE784 (manufactured by BASF); TR-PBG-304, TR-PBG-305, TR-PBG-309, and TR-PBG-314 (manufactured by TRONLY), and the like.
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, relative to 100 parts by mass of the ethylenically unsaturated compound (B).
The ethylenically unsaturated compound (B) has an ethylenically unsaturated bond. The ethylenically unsaturated compound (B) is not particularly limited, and those conventionally used in photosensitive compositions can be used, and examples thereof include unsaturated aliphatic hydrocarbons such as ethylene, propylene, butylene, isobutylene, vinyl chloride, vinylidene fluoride, and tetrafluoroethylene; mono (meth) acrylates of polymers having a carboxyl group and a hydroxyl group at both ends, such as (meth) acrylic acid, α -chloroacrylic acid, itaconic acid, maleic acid, citraconic acid, fumaric acid, norbornenedioic 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, and ω -carboxy polycaprolactone mono (meth) acrylate; unsaturated polybasic acids such as hydroxyethyl (meth) acrylate maleate, hydroxypropyl (meth) acrylate maleate, dicyclopentadiene maleate, or polyfunctional (meth) acrylate having 1 carboxyl group and 2 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, t-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, poly (ethoxy) acrylate, poly (meth) acrylate, poly (, Butoxyethoxyethyl (meth) acrylate, ethylhexyl (meth) acrylate, phenoxyethyl (meth) acrylate, tetrahydrofurfuryl (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 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, propylene glycol di (meth) acrylate, propylene, Esters of unsaturated monobasic acids and polyhydric alcohols or polyhydric phenols such as pentaerythritol tri (meth) acrylate, tricyclodecane dimethylol di (meth) acrylate, tris [ (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-dioxotetrahydrofuryl) -3-methyl-3-cyclohexene-1, 2-dicarboxylic anhydride, trialkyltetrahydrophthalic anhydride-maleic anhydride adducts, dodecenylsuccinic anhydride, and methylnadic anhydride; amides of unsaturated monobasic and polyamine such as (meth) acrylamide, methylenebis- (meth) acrylamide, diethylenetriamine tri (meth) acrylamide, xylylenebis (meth) acrylamide, α -chloroacrylamide, and N-2-hydroxyethyl (meth) acrylamide; unsaturated aldehydes such as acrolein; unsaturated nitriles such as (meth) acrylonitrile, α -chloroacrylonitrile, vinylidene cyanide, and allylnitrile; 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; macromonomers having a mono (meth) acryloyl group at the terminal of the molecular chain of a polymer such as polystyrene, poly (methyl (meth) acrylate), poly (n-butyl (meth) acrylate), or polysiloxane; vinyl chloride, vinylidene chloride, divinyl succinate, diallyl phthalate, triallyl phosphate, triallyl isocyanurate, vinyl thioether, vinyl imidazole, vinyl oxazoline, vinyl carbazole, vinyl pyrrolidone, vinyl pyridine, a vinyl urethane compound of a hydroxyl group-containing vinyl monomer and a polyisocyanate compound, a vinyl epoxy compound of a hydroxyl group-containing vinyl monomer and a polyepoxide compound.
as THE above-mentioned ethylenically unsaturated compound (B), commercially available compounds can be used, and examples thereof include KAYARAD DPHA, DPEA-12, PEG400DA, THE-330, RP-1040, NPGDA, PET30 (manufactured by Nippon Kagaku Co., Ltd.) SPC-1000, SPC-3000 (manufactured by Showa Denko K.K.), ARONIX M-140, M-215, M-350 (manufactured by Toyo Seisaku K.), NK ESTER A-DPHA-TMPT, A-DCPA, A-HD-N, A-9300, TMPT, DCP, NPG and HD-N (manufactured by Newzhonghua chemical industries).
Among them, mono (meth) acrylates of polymers having carboxyl groups and hydroxyl groups at both ends, polyfunctional (meth) acrylates having 1 carboxyl group and 2 or more (meth) acryloyl groups, unsaturated monobasic acids, and esters of polyhydric alcohols or polyphenols are suitable for the alkali-developable photosensitive resin composition of the present invention.
The ethylenically unsaturated compound may be used alone or in combination of 2 or more, or when 2 or more are used in combination, they may be copolymerized in advance to prepare a copolymer.
[ chemical formula 31]
[ chemical formula 32]
[ chemical formula 33]
[ chemical formula 34]
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 2 or more.
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, isoindoline compounds, quinacridone compounds, anthanthrone compounds, perinone (perynone) compounds, perylene compounds, pyrrolopyrroledione compounds, thioindigo compounds, dioxazine compounds, triphenylmethane compounds, quinophthalone compounds, naphthalene tetracarboxylic acid; metal complexes of azo dyes, cyanine dyes; a lake pigment; carbon black obtained by a furnace method, a tank method or a thermal cracking method, or carbon black such as acetylene black, ketjen black or lamp black; a substance obtained by adjusting or coating the carbon black with an epoxy resin, a substance obtained by dispersing the carbon black in a solvent with a resin in advance and adsorbing 20 to 200mg/g of the resin, a substance obtained by subjecting the carbon black to an acidic or basic surface treatment, a substance having an average particle diameter of 8nm or more and a DBP oil absorption of 90ml/100g or less, and a substance having a total oxygen amount calculated from CO and CO2 in volatile components at 950 ℃ of 9mg or more relative to the surface area of the carbon black of 100m 2; graphite, graphitized Carbon black, activated Carbon, Carbon fiber, Carbon nanotube, helical Carbon fiber (Carbon microcoil), Carbon nanohorn, Carbon aerogel, fullerene; nigrosine, pigment black 7, titanium black; organic or inorganic pigments such as chromium oxide green, milori blue, cobalt green, cobalt blue, manganese-based, ferrocyanide, ultramarine, prussian blue, ultramarine, cobalt azure, emerald green, lead sulfate, chrome yellow, zinc yellow, iron oxide red (red iron oxide (III)), cadmium red, synthetic iron black, and umber. These pigments may be used alone or in combination of two or more.
As the 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, 152, 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.
Examples of the dye 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, cyanine dyes, and the like, and a plurality of these dyes may be used in combination.
In the photosensitive composition of the present invention, the content of the colorant (C) is preferably 10 to 200 parts by mass, and more preferably 10 to 100 parts by mass, based on 100 parts by mass of the ethylenically unsaturated compound (B).
The photosensitive composition of the present invention may further contain an alkali-developable compound (D) to prepare an alkali-developable photosensitive resin composition. The composition containing both the colorant (C) and the alkali-developable compound (D) is also referred to as a colored alkali-developable photosensitive resin composition.
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 2004-a 264414.
Further, as the alkali-developable compound (D), there can be used a copolymer of acrylic acid ester, phenol novolac epoxy resin, cresol novolac epoxy resin, polyphenylmethane type epoxy resin having a polyfunctional epoxy group, epoxy acrylate resin, polymer having a carboxyl group, and 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 polybasic acid anhydride with the epoxy group.
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, Upika 4015 manufactured by U-PICA, and the like.
Among these compounds, epoxy acrylate resins and polymers having carboxyl groups are preferable.
the 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 polymer having a carboxyl group preferably has, in addition to the structural unit (U1), a structural unit containing a crosslinkable group such as a methacryloyl group, an acryloyl group, an epoxy 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)").
The polymer having a carboxyl group may have a structural unit (hereinafter referred to as "structural unit (U4)") other than the structural units (U1) to (U3).
The structural unit (U1) is preferably a structural unit derived from at least 1 compound selected from the group consisting of unsaturated carboxylic acids and unsaturated carboxylic acid anhydrides (hereinafter referred to as "compound (U1)").
Examples of the compound (u1) include monocarboxylic acids, dicarboxylic acids, and anhydrides of dicarboxylic acids.
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.
Examples of the dicarboxylic acid include maleic acid, fumaric acid, and citraconic acid.
Examples of the anhydrides of the dicarboxylic acids include anhydrides of the dicarboxylic acids mentioned above.
Among these compounds, acrylic acid, methacrylic acid, 2-acryloyloxyethylsuccinic acid, 2-methacryloyloxyethylsuccinic acid, and maleic anhydride are particularly preferable from the viewpoint of copolymerization reactivity and solubility of the resulting copolymer in a developer.
The polymer having a carboxyl group may have 1 structural unit (U1) derived from 1 compound (U1) or2 or more structural units (U1) derived from 2 or more compounds (U1).
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)").
The compound (u2) is preferably at least 1 selected from the group consisting of a polymerizable unsaturated compound having an epoxy group and a polymerizable unsaturated compound having an oxetanyl group.
Examples of the polymerizable unsaturated compound having an epoxy group include an ethylene oxide (cyclo) alkyl (meth) acrylate, an ethylene oxide (cyclo) alkyl α -alkylacrylate, and a glycidyl ether compound having a polymerizable unsaturated bond.
Examples of the polymerizable unsaturated compound having an oxetanyl group include (meth) acrylates having an oxetanyl group and the like.
Specific examples of the oxirane (cyclo) alkyl (meth) acrylate include glycidyl (meth) acrylate, 2-methylglycidyl (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 [5.2.1.02.6] decyl (meth) acrylate.
Specific examples of the ethylene oxide (cyclo) alkyl α -alkylacrylate include, for example, glycidyl α -ethylacrylate, glycidyl α -n-propylacrylate, glycidyl α -n-butylacrylate, 6, 7-epoxyheptyl α -ethylacrylate, and 3, 4-epoxycyclohexyl α -ethylacrylate.
specific examples of the glycidyl ether compound having a polymerizable unsaturated bond include o-vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl ether, p-vinylbenzyl glycidyl ether and the like.
Specific examples of the (meth) acrylate having an oxetanyl group include, for example, 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.
Among these compounds, glycidyl methacrylate, 2-methylglycidyl methacrylate, 3, 4-epoxycyclohexyl methacrylate, 3, 4-epoxycyclohexylmethyl methacrylate, 3, 4-epoxytricyclo [5.2.1.02.6] decyl acrylate, 3-methacryloxymethyl-3-ethyloxetane, 3-methyl-3-methacryloxymethyloxetane or 3-ethyl-3-methacryloxymethyloxetane are particularly preferable from the viewpoint of polymerizability.
the polymer having a carboxyl group may have 1 structural unit (U2) derived from 1 compound (U2) or2 or more structural units (U2) derived from 2 or more compounds (U2).
among the above-mentioned 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.
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).
[ chemical formula 34A ]
(wherein R1000 and R1001 each independently represents a hydrogen atom or a methyl group,
u represents an integer of 1 to 6,
R1002 represents a 2-valent group represented by the following formula (U.alpha.) or the following formula (U.beta.),
Denotes the bonding site. )
[ chemical formula 34B ]
(wherein R1003 represents a hydrogen atom or a methyl group,
Denotes the bonding site. )
In the case where a compound such as glycidyl methacrylate or 2-methylglycidyl methacrylate is reacted with a copolymer having a carboxyl group with respect to the structural unit represented by the formula (U), R1002 in the formula (U) is represented by the formula (U α). When a compound such as 3, 4-epoxycyclohexylmethyl methacrylate is reacted with a copolymer having a carboxyl group, R1002 in the formula (U) is represented by the formula (U β).
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: if necessary, in the presence of an appropriate catalyst, it is preferable to add an unsaturated compound having an epoxy group to a polymer solution containing a polymerization inhibitor and stir the mixture for a predetermined time under heating. Examples of the catalyst include tetrabutylammonium bromide and the like. Examples of the polymerization inhibitor include p-methoxyphenol and the like. The reaction temperature is preferably 70 ℃ to 100 ℃. The reaction time is preferably 8 to 12 hours.
In the above-mentioned ratio of the structural units 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 to 70 mol%, more preferably 20 to 50 mol%, based on the total structural units of the polymer having a carboxyl group. When the ratio of the structural unit having a (meth) acryloyloxy group is in the above range, heat resistance and development failure during development are reduced, and generation of development residue can be suppressed.
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)").
Examples of the compound (u3) include 3- (meth) acryloyloxypropylmethyldimethoxysilane, 3- (meth) acryloyloxypropylethyldimethoxysilane, 3- (meth) acryloyloxypropyltrimethoxysilane and 3- (meth) acryloyloxypropyltriethoxysilane.
When the polymer having a carboxyl group has the structural unit U3, it may have 1 structural unit (U3) derived from 1 compound (U3) or2 or more structural units (U3) derived from 2 or more compounds (U3).
The structural unit (U4) is a structural unit other than the above (U1) to (U3), and is preferably a structural unit derived from a polymerizable unsaturated compound other than the above (U1) to (U3) (hereinafter referred to as "compound (U4)").
examples of the compound (u4) include alkyl (meth) acrylates, cycloalkyl (meth) acrylates, aryl (meth) acrylates, aralkyl (meth) acrylates, dialkyl unsaturated dicarboxylates, (meth) acrylates having an oxa-5-membered ring or an oxa-6-membered ring, vinyl aromatic compounds, conjugated diene compounds, and other polymerizable unsaturated compounds.
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.
Specific examples of the cycloalkyl (meth) acrylate include cyclohexyl (meth) acrylate, 2-methylcyclohexyl (meth) acrylate, tricyclo [5.2.1.02,6] decan-8-yl (meth) acrylate, 2- (tricyclo [5.2.1.02,6] decan-8-yloxy) ethyl (meth) acrylate, isobornyl (meth) acrylate, and the like.
specific examples of the aryl (meth) acrylate include phenyl acrylate and the like.
Specific examples of the aralkyl (meth) acrylate include benzyl (meth) acrylate and the like.
Specific examples of the unsaturated dicarboxylic acid dialkyl ester include diethyl maleate, diethyl fumarate, and the like.
specific examples of the (meth) acrylate having an oxa-5-membered ring or an oxa-6-membered ring include tetrahydrofuran-2-yl (meth) acrylate, tetrahydropyran-2-yl (meth) acrylate, and 2-methyltetrahydropyran-2-yl (meth) acrylate.
Specific examples of the vinyl aromatic compound include styrene and α -methylstyrene.
Specific examples of the conjugated diene compound include 1, 3-butadiene and isoprene.
specific examples of the other polymerizable unsaturated compounds include 2-hydroxyethyl (meth) acrylate, acrylonitrile, methacrylonitrile, acrylamide, methacrylamide, and the like.
among the above-listed compounds (u4), n-butyl methacrylate, 2-methylglycidyl methacrylate, benzyl methacrylate, tricyclo [5.2.1.02,6] decan-8-yl methacrylate, styrene, p-methoxystyrene, tetrahydrofuran-2-yl methacrylate, 1, 3-butadiene and the like are preferable from the viewpoint of copolymerization reactivity.
When the polymer having a carboxyl group has a structural unit (U4), it may have 1 structural unit (U4) derived from 1 compound (U4) or2 or more structural units (U4) derived from 2 or more compounds (U4).
The polymer having a carboxyl group preferred in the present embodiment can be synthesized by copolymerizing a mixture of polymerizable unsaturated compounds containing the above-mentioned compounds (u1) to (u4) in the following proportions.
Further, a polymer having a structural unit containing a (meth) acryloyloxy group can be produced 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.
Compound (u 1): preferably 0.1 to 30 mol%, more preferably 1 to 20 mol%, and still more preferably 5 to 15 mol%
Compound (u 2): preferably 1 to 95 mol%, more preferably 10 to 60 mol%, and still more preferably 20 to 30 mol%
Compound (u 3): preferably 50 mol% or less, more preferably 1 to 40 mol%, and still more preferably 10 to 30 mol%
Compound (u 4): preferably 80 mol% or less, more preferably 1 to 60 mol%, and still more preferably 25 to 50 mol%
A polymerizable composition containing a polymer having a carboxyl group obtained by copolymerizing a mixture of polymerizable unsaturated compounds containing the compounds (u1) to (u4) in the above-described ranges is preferable because high resolution can be achieved without impairing good coatability, and a cured film having a highly adjusted physical property balance even with a highly fine pattern can be obtained.
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 with Mw in this range, a high resolution can be achieved without impairing good coatability, and therefore, a cured film with a highly adjusted balance of characteristics even in a highly fine pattern can be provided.
The weight average molecular weight (Mw) in the present invention means a weight average molecular weight (Mw) in terms of polystyrene measured by Gel Permeation Chromatography (GPC).
The polymer having a carboxyl group can be produced by polymerizing a mixture of the polymerizable unsaturated compounds described above, preferably in an appropriate solvent, preferably in the presence of a radical polymerization initiator.
examples of the solvent used for 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, and 3-methoxybutanol. These solvents may be used alone in 1 kind, or may also be used in a mixture of 2 or more kinds.
The radical polymerization initiator is not particularly limited, and examples thereof include azo compounds such as 2,2 '-azobisisobutyronitrile, 2' -azobis- (2, 4-dimethylvaleronitrile), 2 '-azobis- (4-methoxy-2, 4-dimethylvaleronitrile), 4' -azobis (4-cyanovaleric acid), dimethyl-2, 2 '-azobis (2-methylpropionate), and 2, 2' -azobis (4-methoxy-2, 4-dimethylvaleronitrile). These radical polymerization initiators may be used alone in 1 kind, or may be used in combination of 2 or more kinds.
Among the above-mentioned polymers having a carboxyl group, preferred is a polymer obtained by reacting an unsaturated monoacid with an epoxy group of an epoxy compound represented by the following general formula (VI) and further reacting a polybasic acid anhydride with the epoxy group, as described in JP 2005-234362A.
The alkali-developable compound (D) may be an acrylic acid ester copolymer, a phenol and/or cresol novolak epoxy resin, a polyphenylmethane-type epoxy resin having a polyfunctional epoxy group, an epoxy acrylate resin, or 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 polybasic acid anhydride with the epoxy group. The epoxy acrylate resin is obtained by reacting (meth) acrylic acid with the epoxy compound, and examples thereof include Ripoxy SPC-2000, DICLITE UE-777 manufactured by DIC, Upika 4015 manufactured by U-PICA, and the like.
among them, preferred are 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 a polybasic acid anhydride with the epoxy group.
The alkali developable compound which may have an ethylenically unsaturated bond preferably contains 0.2 to 1.0 equivalent of an unsaturated group.
[ chemical formula 35]
(wherein X21 represents a direct bond, methylene, 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-, a group represented by the following formula 36, formula 37 or formula 38, the alkylene group may be substituted by a halogen atom, R51 and R52 each independently represent 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, the alkoxy group and the alkenyl group may be substituted by a halogen atom,
When there are a plurality of R51 and R52, the same may be the case, and different cases may be the case,
c is an integer of 0 to 4,
d is an integer of 0 to 4,
m is an integer of 0 to 10,
The optical isomer present in the case where m is not 0 may be any isomer. )
[ chemical formula 36]
(wherein Z1 represents a hydrogen atom, a phenyl group which may be substituted with 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 with an alkyl group having 1 to 10 carbon atoms or an alkoxy group having 1 to 10 carbon atoms, Y1 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 alkyl group, the alkoxy group, and the alkenyl group may be substituted with a halogen atom, and e represents an integer of 0 to 5, and represents a bonding site.)
[ chemical formula 37]
(wherein denotes a bonding site.)
[ chemical formula 38]
(wherein Y2 and Z2 each independently represents an alkyl group having 1 to 10 carbon atoms which may be substituted with a halogen atom, an aryl group having 6 to 20 carbon atoms which may be substituted with a halogen atom, an aryloxy group having 6 to 20 carbon atoms which may be substituted with a halogen atom, an arylthio group having 6 to 20 carbon atoms which may be substituted with a halogen atom, an arylalkenyl group having 6 to 20 carbon atoms which may be substituted with a halogen atom, an arylalkyl group having 7 to 20 carbon atoms which may be substituted with a halogen atom, a heterocyclic group having 2 to 20 carbon atoms which may be substituted with a halogen atom, or a halogen atom, methylene groups in the group represented by Y2 may be substituted with an unsaturated bond, -O-or-S-, Z2 may form a ring with each other by adjacent Z2, 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, and the sum of h and i is an integer of 2 to 4, and represents a bonding site).
Examples of the unsaturated monobasic acid which acts on 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, dicyclopentadiene maleate and the like.
Examples of the polybasic acid anhydride to be acted upon by the unsaturated monobasic acid include biphenyltetracarboxylic dianhydride, tetrahydrophthalic anhydride, succinic anhydride, bisphthalic anhydride, maleic anhydride, trimellitic anhydride, pyromellitic anhydride, 2 '-3, 3' -benzophenone tetracarboxylic anhydride, ethylene glycol bistrimellitic anhydride, glycerol trimetallic anhydride, hexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, nadic anhydride, methylnadic anhydride, trialkyltetrahydrophthalic anhydride, hexahydrophthalic anhydride, 5- (2, 5-dioxotetrahydrofuryl) -3-methyl-3-cyclohexene-1, 2-dicarboxylic anhydride, trialkyltetrahydrophthalic anhydride-maleic anhydride adduct, dodecenylsuccinic anhydride, succinic anhydride, maleic, Methyl nadic anhydride, and the like.
The reaction molar ratio of the epoxy compound, the unsaturated monobasic acid and the polybasic acid anhydride is preferably set as follows.
That is, in the epoxy adduct having a structure in which 0.1 to 1.0 carboxyl group of the unsaturated monobasic acid is added to 1 epoxy group of the epoxy compound, the following ratio is preferably achieved: the anhydride structure of the polybasic acid anhydride is 0.1 to 1.0 per 1 hydroxyl group of the epoxy adduct.
The reaction of the epoxy compound, the unsaturated monobasic acid and the polybasic acid anhydride can be carried out according to a conventional method.
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 components such as an inorganic compound and a solvent as optional components in combination. In the alkali developable photosensitive resin composition of the present invention, the composition containing the colorant (C) is also referred to as a colored alkali developable photosensitive resin composition of the present invention.
The alkali-developable compound (D) may be used alone in 1 kind, or may be used in combination with 2 or more kinds.
When the alkali-developable compound (D) has an ethylenically unsaturated bond, the alkali-developable compound (D) may be included in the category of the ethylenically unsaturated compound (B). In the case where the alkali-developable compound (D) is also the ethylenically unsaturated compound (B), the composition containing the alkali-developable compound (D) is a photosensitive composition, and is also an alkali-developable photosensitive resin composition.
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 compound having alkali-developability which may have an ethylenically unsaturated bond. The alkali-developable compound which may have an ethylenically unsaturated bond preferably has a solid acid value in the range of 5 to 120mgKOH/g, and the amount of the monofunctional or polyfunctional epoxy compound to be used is preferably selected so as to satisfy the acid value.
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, p-methoxyethyl glycidyl ether, phenyl glycidyl ether, p-methoxyglycidyl ether, n-butylglycidyl ether, n, P-butylphenol glycidyl ether, tolyl glycidyl ether, 2-methyltolyl 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, glycidyl butyrate, vinylcyclohexane monoxide, 1, 2-epoxy-4-vinylcyclohexane, styrene oxide, pinane oxide, methylstyrene oxide, cyclohexane oxide, propylene oxide, the above-mentioned compounds No. a2, No. a3 and the like.
The polyfunctional epoxy compound is preferably used in that 1 or more compounds selected from the group consisting of bisphenol epoxy compounds and glycidyl ethers can provide an (colored) alkali-developable photosensitive resin composition having further excellent properties.
As the bisphenol epoxy compound, in addition to the epoxy compound represented by the general formula (IV), for example, a bisphenol epoxy compound such as a hydrogenated bisphenol epoxy compound can be used.
as the above-mentioned glycidyl ethers, 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-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, 1, 1-bis (glycidyloxymethyl) methane, and mixtures thereof can be used, 1,1,1, 1-tetrakis (glycidyloxymethyl) methane, and the like.
In addition, novolak-type epoxy compounds such as phenol novolak-type epoxy compounds, biphenol novolak-type epoxy compounds, cresol novolak-type epoxy compounds, bisphenol a novolak-type epoxy compounds, dicyclopentadiene novolak-type epoxy compounds, and the like; alicyclic epoxy compounds such as 3, 4-epoxy-6-methylcyclohexylmethyl-3, 4-epoxy-6-methylcyclohexanecarboxylate, 3, 4-epoxycyclohexylmethyl-3, 4-epoxycyclohexane carboxylate, and 1-epoxyethyl-3, 4-epoxycyclohexane; glycidyl esters such as diglycidyl phthalate, diglycidyl tetrahydrophthalate, and glycidyl dimer acid; glycidyl amines such as tetraglycidyl diaminodiphenylmethane, triglycidyl-p-aminophenol and N, N-diglycidylaniline; heterocyclic epoxy compounds such as 1, 3-diglycidyl-5, 5-dimethylhydantoin and triglycidyl isocyanurate; dioxide compounds such as dicyclopentadiene dioxide; a naphthalene type epoxy compound; triphenylmethane type epoxy compounds; dicyclopentadiene type epoxy compounds, and the like.
In particular, when the photosensitive composition of the present invention is an alkali-developable photosensitive resin composition, the content of the compound having alkali-developability which may have an ethylenically unsaturated bond is 1 to 20% by mass, and particularly preferably 3 to 12% by mass, in the alkali-developable photosensitive resin composition of the present invention.
The photosensitive composition of the present invention may further contain a solvent. Examples of the solvent generally include solvents in which the above-mentioned components (the photopolymerization initiator (a), the ethylenically unsaturated compound (B), and the like) can be dissolved or dispersed as necessary, and 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; ester-based solvents such as methyl acetate, ethyl acetate, n-propyl acetate, isopropyl acetate, n-butyl acetate, cyclohexyl acetate, ethyl lactate, dimethyl succinate, and 2,2, 4-trimethyl-1, 3-pentanediol monoisobutyrate (Texanol); cellosolve solvents such as ethylene glycol monomethyl ether and ethylene glycol monoethyl ether; alcohol solvents such as methanol, ethanol, isopropanol or n-propanol, isobutanol or n-butanol, and pentanol; ether ester solvents such as ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, propylene glycol-1-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; paraffinic solvents such as mineral spirits, SWAZOL #310 (manufactured by COSMO Songshan oil Co., Ltd.), SOLVESSO #100 (manufactured by Exxon chemical Co., Ltd.); halogenated aliphatic hydrocarbon solvents such as carbon tetrachloride, chloroform, trichloroethylene, methylene chloride and 1, 2-dichloroethane; halogenated aromatic hydrocarbon solvents such as chlorobenzene; a carbitol-based solvent; aniline; triethylamine; pyridine; acetic acid; acetonitrile; carbon disulfide; n, N-dimethylformamide; n, N-dimethylacetamide (DMAc); n-methyl pyrrolidone; dimethyl sulfoxide; water, etc., and 1 or2 or more kinds of these solvents can be used as a mixed solvent.
of these, ketones, ether ester solvents, and the like, particularly propylene glycol-1-monomethyl ether-2-acetate, cyclohexanone, and the like are preferable because of their good compatibility between the resist and the photopolymerization initiator (A) in the photosensitive composition.
Further, to the photosensitive composition of the present invention, anisole, hydroquinone, pyrocatechol, t-butylcatechol, inorganic compounds, latent additives, organic polymers, chain transfer agents, sensitizers, surfactants, silane coupling agents, melamine compounds, thermal polymerization inhibitors; a plasticizer; an adhesion promoter; a filler; defoaming agents; leveling agent; a surface conditioner; an antioxidant; an ultraviolet absorber; a dispersing aid; an anti-agglomerating agent; a catalyst; an effect-promoting agent; a crosslinking agent; thickening agents and the like.
The photosensitive composition of the present invention may contain a dispersant for dispersing the colorant (C) and/or the inorganic compound. The dispersant is not limited as long as it can disperse and stabilize the colorant (C) and the inorganic compound, and commercially available dispersants such as BYK series manufactured by BYK-Chemie Japan can be used. It is particularly suitable to use a polymeric dispersant comprising a polyester, polyether, or polyurethane having a basic functional group; a dispersant which contains a nitrogen atom as a basic functional group and a functional group containing a nitrogen atom as an amine and/or a quaternary ammonium salt thereof, and has an amine value of 1 to 100 mgKOH/g.
The latent additive is represented by the following general formulae (A) to (C).
[ chemical formula 39]
(wherein ring A1 is a six-membered alicyclic, aromatic or heterocyclic ring, R81, R82, R83, R84 and R85 represent a hydrogen atom, a halogen atom, a cyano group, a hydroxyl group, a nitro group, a carboxyl group, an optionally substituted alkyl group having 1 to 40 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-O-R66,
At least one of R81, R82, R83, R84 and R85 is not a hydrogen atom,
R86 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. )
[ chemical formula 40]
(wherein rings A1 and R91 are the same as those of the above general formula (A),
X7 is a group represented by the following general formula (1), R92, R93, R94 and R95 represent a hydrogen atom, a halogen atom, a cyano group, a hydroxyl group, a nitro group, a carboxyl group, an optionally substituted alkyl group having 1 to 40 carbon atoms, 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, and at least one of R92, R93, R94 and R95 is not a hydrogen atom. )
[ chemical formula 41]
*-Z-X-Z-* (1)
(in the general formula (1), X8 represents-CR 97R98-, -NR99-, a divalent aliphatic hydrocarbon group having 1 to 35 carbon atoms, an aromatic hydrocarbon group having 6 to 35 carbon atoms, a heterocyclic group having 2 to 35 carbon atoms, or any substituent group represented by the following [ chemical formula 42] to [ chemical formula 44],
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 groups in the case where oxygen atoms are not adjacent to each other,
R97 and R98 each represent 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, Z5 and Z6 each independently represent a direct bond, -O-, -S-, > CO, -CO-O-, -O-CO-, -SO2-, -SS-, -SO-, or > NR100, R99 and R100 each represent 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 represent a bonding site. )
[ chemical formula 42]
(in the formula, R101 represents a hydrogen atom, a phenyl group which may have a substituent, or a cycloalkyl group having 3 to 10 carbon atoms, R102 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 alkyl group, the alkoxy group, and the alkenyl group may have a substituent, f is an integer of 0 to 5, and represents a bonding site.)
[ chemical formula 43]
(wherein denotes a bonding site.)
[ chemical formula 44]
(in the above formula, R103 and R104 independently represent 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, methylene groups in the alkyl group and the arylalkyl group may be interrupted by an unsaturated bond, -O-or-S-, R103 may form a ring by adjacent R103, b represents a number of 0 to 4, c represents a number of 0 to 8, g represents a number of 0 to 4, h represents a number of 0 to 4, and the sum of g and h is 2 to 4. )
[ chemical formula 45]
(wherein k is 2 to 6, X9 represents a group represented by the general formula (2) when k is 2, a group represented by the general formula (3) when k is 3, a group represented by the general formula (4) when k is 4, a group represented by the general formula (5) when k is 5, or a group represented by the general formula (6) when k is 6, R111, R112, R113, and R114 each represent 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, at least one of R111, R112, R113, and R114 is not a hydrogen atom, and rings a1 and R86 are the same as the general formula (a))
[ chemical formula 46]
(in the general formula (2), Y11 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, Z11, Z12, and Z13 each independently represents a direct bond, -O-, -S-, > CO, -CO-O-, -O-CO-, -SO2-, -SS-, -SO-, -NR121-, -PR121-, 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,
R121 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 methylene groups in the aliphatic hydrocarbon group may be substituted by a carbon-carbon double bond, -O-, -CO-, -O-CO-, -CO-O-, or-SO 2-. )
[ chemical formula 47]
(in the general formula (3), Y12 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, and methylene groups in the aliphatic hydrocarbon group may be substituted with-COO-, -O-, -OCO-, -NHCO-, -NH-, or-CONH-, and Z11 to Z14 are each independently a group in the same range as that of the groups represented by Z11 to Z13 in the general formula (2).)
[ chemical formula 48]
(in the general formula (4), Y13 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, the aliphatic hydrocarbon group may be interrupted by-COO-, -O-, -OCO-, -NHCO-, -NH-, or-CONH-, and Z11 to Z15 are each independently a group in the same range as that represented by Z11 to Z13 in the general formula (2))
[ chemical formula 49]
(in the general formula (5), Y14 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, the aliphatic hydrocarbon group may be interrupted by-COO-, -O-, -OCO-, -NHCO-, -NH-, or-CONH-, and Z11 to Z16 are each independently a group in the same range as that represented by Z11 to Z13 in the general formula (2))
By using the organic polymer [ excluding the ethylenically unsaturated compound (B) ], the characteristics of the cured product can be improved. Examples of the organic polymer include polystyrene, polymethyl methacrylate, a methyl methacrylate-ethyl acrylate copolymer, poly (meth) acrylic acid, a styrene- (meth) acrylic acid copolymer, a (meth) acrylic acid-methyl methacrylate copolymer, an ethylene-vinyl chloride copolymer, an ethylene-vinyl ester copolymer, a polyvinyl chloride resin, an ABS resin, nylon 6, nylon 66, nylon 12, a polyurethane resin, polycarbonate, polyvinyl butyral, a cellulose ester, polyacrylamide, a saturated polyester, a phenol resin, a phenoxy resin, a polyamideimide resin, a polyamic acid resin, an epoxy resin, and the like, and among them, polystyrene, (meth) acrylic acid-methyl methacrylate copolymer, and an epoxy resin are preferable.
when an organic polymer is used, the amount thereof is preferably 10 to 500 parts by mass per 100 parts by mass of the polymerizable compound having an ethylenically unsaturated bond.
As the chain transfer agent or the sensitizer, a compound containing a sulfur atom is generally used. Examples thereof include thioglycolic acid, thiomalic acid, thiosalicylic acid, 2-mercaptopropionic acid, 3-mercaptobutanoic 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, dodecyl (4-methylthio) phenyl ether, 2-mercaptoethanol, 3-mercapto-1, 2-propanediol, 1-mercapto-2-propanol, 3-mercapto-2-butanol, and mixtures thereof, Mercapto compounds such as mercaptophenol, 2-mercaptoethylamine, 2-mercaptoimidazole, 2-mercaptobenzimidazole, 2-mercapto-3-pyridinol, 2-mercaptobenzothiazole, mercaptoacetic acid, trimethylolpropane tris (3-mercaptopropionate), pentaerythritol tetrakis (3-mercaptopropionate), disulfide compounds obtained by oxidizing the mercapto compounds, iodinated alkyl compounds such as iodoacetic acid, iodopropionic acid, 2-iodoethanol, 2-iodoethanesulfonic acid, 3-iodopropanesulfonic acid, trimethylolpropane tris (3-mercaptoisobutyrate), butanediol bis (3-mercaptoisobutyrate), hexanedithiol, decanedithiol, 1, 4-dimethylmercaptobenzene, butanediol bisthiopropionate, butanediol bisthioacetate, ethylene glycol bisthioacetate, and the like, Trimethylolpropane trithioacetate, butanediol bisthiopropionate, trimethylolpropane trithiopropionate, trimethylolpropane trithioacetate, pentaerythritol tetrathiopropionate, pentaerythritol tetrathioacetate, trihydroxyethyl trithiopropionate, diethyl thioxanthone, diisopropyl thioxanthone, the following aliphatic polyfunctional thiol compounds such as compound No. C1 and tris (2-hydroxyethyl) isocyanurate of trimercaptopropionic acid, Karenz MT BD1, PE1 and NR1 manufactured by Showa Denko K.K.
[ chemical formula 50]
As the surfactant, a fluorine-based surfactant such as perfluoroalkyl phosphate ester and perfluoroalkyl carboxylate; anionic surfactants such as higher fatty acid alkali metal salts, alkylsulfonates, and alkylsulfates; 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; an amphoteric surfactant; surfactants such as silicone surfactants, and the like may be used in combination.
As the silane coupling agent, for example, silane coupling agents manufactured by shin-Etsu chemical Co., Ltd are 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 suitably used.
Examples of the melamine compound include compounds obtained by etherification of all or part (at least 2) of the active methylol groups (CH2OH groups) in a nitrogen compound such as (poly) methylolmelamine, (poly) methylolglycoluril, (poly) methylolbenzoguanamine, or (poly) methylolurea with an alkyl group.
here, examples of the alkyl group constituting the alkyl ether include a methyl group, an ethyl group and a butyl group, and they may be the same or different. The methylol group not etherified with an alkyl group may be self-condensed in one molecule or condensed between two molecules, and as a result, an oligomer component is formed.
Specifically, hexamethoxymethylmelamine, hexabutoxymethylmelamine, tetramethoxymethylglycoluril, tetrabutoxymethylglycoluril, or the like can be used. Among them, alkyl-etherified melamines such as hexamethoxy methyl melamine and hexabutoxy methyl melamine are preferable.
As the leveling agent, any conventional leveling agent can be used as long as it has a leveling effect, and among them, a silicone-based leveling agent and a fluorine-based leveling agent can be particularly preferably used.
As the above-mentioned silicone leveling agent, commercially available silicone leveling agents can be used, and examples thereof include 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-344, BYK-347, BYK-348, BYK-349, BYK-370, BYK-375, BYK-377, BYK-378, BYK-UV3500, BYK-UV3510, BYK-UV3570, BYK-3550, BYK-SILCLEAN3700, and BYK-SILCLEAN3720 (manufactured by BYK-Chemie Japan); ACFS180, ACFS360, AC S20 (manufactured by Algin Chemie, supra); polyflow KL-400X, Polyflow KL-400HF, Polyflow KL-401, Polyflow KL-402, Polyflow KL-403, Polyflow KL-404 (manufactured by Kyoeisha Co., Ltd.); KP-323, KP-326, KP-341, KP-104, KP-110, KP-112 (above, the product of the Xinyue chemical industry); LP-7001, LP-7002, 8032ADDITIVE, 57ADDITIVE, L-7604, FZ-2110, FZ-2105, 67ADDITIVE, 8618ADDITIVE, 3ADDITIVE, and 56ADDITIVE (manufactured by Toray-Dow corning, supra).
as the fluorine-based leveling agent, commercially available fluorine-based leveling agents such as OPTOOL DSX and OPTOOL DAC-HP (manufactured by DAIKIN industries, supra); SURLON S-242, SURLON S-243, SURLON S-420, SURLON S-611, SURLON S-651, and SURLON S-386 (AGC SEIMI CHEMICAL, supra); BYK-340(BYK-Chemie Japan); AC110a, AC100a (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, MEGAFACE EXPTF-1367, MEGAFACE EXPTF-1437, MEGAFACE F-558, and MEGAFACE EXPTF-1537 (DIC system); FC-4430, FC-4432 (manufactured by Sumitomo 3M); FTERGENT 100, FTERGENT 100C, FTERGENT 110, FTERGENT 150CH, FTERGENT A-K, FTERGENT 501, FTERGENT 250, FTERGENT 251, FTERGENT 222F, FTERGENT 208G, FTERGENT 300, FTERGENT 310, FTERGENT 400SW (made by NEOS); PF-136A, PF-156A, PF-151N, PF-636, PF-6320, PF-656, PF-6520, PF-651, PF-652, and PF-3320 (manufactured by Nomura chemical industries, Ltd.).
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 depending on the purpose of use thereof, 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).
The photosensitive composition, the alkali developable photosensitive resin composition, or the cured product of the present invention can be used for photocurable coatings or varnishes; a photocurable adhesive; a printed substrate; color filters in liquid crystal display elements for color display of display devices (color televisions, PC monitors, portable information terminals, digital cameras, and the like); a color filter of the CCD image sensor; electrode materials for plasma display panels; powder coating; printing ink; printing plates; an adhesive; a dental composition; gel coating; photoresists for electronics engineering; electroplating a corrosion inhibitor; etching the resist; dry film; a solder resist; resists used for forming structures of various display devices; a composition for encapsulating electric and electronic components; a solder resist; a magnetic recording material; a micro mechanical component; a waveguide; optically switching on light; a mask for plating; etching the mask; a color test system; a fiberglass cable coating; stencil for screen printing; materials for producing three-dimensional objects by stereolithography, materials for hologram recording, image recording materials, fine electronic circuits, decoloring materials for image recording materials using microcapsules, photoresist materials for printed wiring boards, photoresist materials for UV and visible laser direct imaging systems; the application of the photoresist material, the protective film, and the like used for forming the dielectric layer in the successive lamination of the green sheet is not particularly limited.
The photosensitive composition or the alkali developable photosensitive resin composition of the present invention can also be used for the purpose of forming spacers for liquid crystal display panels and for the purpose of forming protrusions for vertical alignment type liquid crystal display elements. Particularly, the photosensitive composition is useful as a photosensitive composition for simultaneously forming a protrusion and a spacer for a vertical alignment type liquid crystal display element.
The method for curing the photosensitive composition or the alkali-developable photosensitive resin composition of the present invention will be described in detail below.
The photosensitive composition or the alkali developable photosensitive resin composition of the present invention can be applied to a support substrate such as soda glass, quartz glass, a semiconductor substrate, metal, paper, plastic, and the like by known means such as a spin coater, a roll coater, a bar coater, a die coater, a curtain coater, various printing, dipping, and the like. Further, the transfer may be performed once on a support substrate such as a film and then transferred to another support substrate, and the method of application is not limited.
The light source of the energy ray used for curing the photosensitive composition of the present invention, which is alkali-developable, can be an electromagnetic wave energy having a wavelength of 2000 to 7000 angstroms obtained from an ultrahigh-pressure mercury lamp, a high-pressure mercury lamp, a medium-pressure mercury lamp, a low-pressure mercury lamp, a mercury vapor arc lamp, a xenon arc lamp, a carbon arc lamp, a metal halide lamp, a fluorescent lamp, a tungsten lamp, an excimer lamp, a germicidal lamp, a light-emitting diode, a CRT light source, or the like, or a high-energy ray such as an electron beam, an X-ray, a radioactive ray, and preferably an ultrahigh-pressure mercury lamp, a mercury vapor arc lamp, a carbon arc lamp, a xenon arc lamp, or the like, which can emit light having a wavelength of 300 to 450.
Further, the laser direct writing method, which uses laser light as an exposure light source to directly form an image from digital information such as a computer without using a mask, is useful because it can improve not only productivity but also resolution and positional accuracy, and as the laser light, light having a wavelength of 340 to 430nm can be suitably used, and a laser emitting light in the visible to infrared region, such as an excimer laser, a nitrogen laser, an argon ion laser, a helium cadmium laser, a helium neon laser, a krypton ion laser, various semiconductor lasers, and a YAG laser, can be used. In the case of using these lasers, a sensitizing pigment that absorbs in this region from visible to infrared can be added.
The spacer for a 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) irradiating the coating film with radiation through a mask having a predetermined pattern shape; (3) a baking step after exposure; (4) a step of developing the exposed coating; (5) and heating the developed film.
The photosensitive composition of the present invention to which an ink repellent is added is useful as a resin composition for forming partition walls for an ink jet system, and the composition is used for color filters, and is particularly preferably used for partition walls for an ink jet system color filter having a tooth form angle of 50 ° or more. As the ink repellent, a fluorine-based surfactant and a composition containing a fluorine-based surfactant are suitably used.
The optical element is produced by a method in which a transfer object is partitioned by a partition wall formed of the photosensitive composition of the present invention, and a liquid droplet is applied to a concave portion on the partitioned transfer object by an ink jet method to form an image region. In this case, it is preferable that the liquid droplets contain a colorant and the image region is colored, and it is preferable to use an optical element which has at least a pixel group including a plurality of colored regions and a partition wall for separating the respective colored regions of the pixel group on a substrate and which is manufactured by the above-described method for manufacturing an optical element.
examples
The present invention will be described in further detail below with reference to examples and comparative examples, but the present invention is not limited to these examples.
[ examples 1-1 to 1-3] production of Compound No.1
EXAMPLE 1-1 preparation of intermediate 1A (ketone Compound)
Triphenylamine (3.3g) and dichloroethane (15g) were charged in a four-necked flask, and then aluminum chloride (5.8g) and acetyl chloride (3.3g) were added thereto under ice cooling. After stirring at room temperature for 3 hours, the reaction solution was poured into ice-cooled 5% diluted hydrochloric acid and stirred to separate oil from water. The organic layer was washed 2 times with 5% aqueous HCl and further 4 times with water. The product layer was desolventized and purified by a silica gel column (hexane/ethyl acetate: 65/35) to obtain intermediate 1A (2.6 g: yield 52%).
[ chemical formula 51]
Intermediate 1A
EXAMPLE 1-2 preparation of intermediate 1B (Oxime Compound)
Intermediate 1A (2.6g), ethanol (24g), water (12g) and hydroxylamine hydrochloride (1.6g) were put into a four-necked flask, and the mixture was refluxed for 10 hours. After cooling to room temperature, the precipitate was collected by filtration and sufficiently dried to obtain intermediate 1B (2.8 g: yield 96%).
[ chemical formula 52]
Intermediate 1B
[ examples 1-3] production of Compound No.1 (Oxime ester Compound of the present invention)
After charging intermediate 1B (2.1g) and dimethylformamide (15g) into a four-necked flask, triethylamine (1.7g) and acetyl chloride (1.3g) were charged under ice-cooling. After stirring at room temperature for 2 hours, ion-exchanged water (15g) and ethyl acetate (30g) were added thereto to conduct oil-water separation. The organic layer was washed with water 3 times, desolvated, and purified by a silica gel column (hexane/ethyl acetate: 50/50) to obtain compound No.1(1.4 g: yield 50%). NMR data of the obtained compound No.1 are shown in [ Table 1 ].
[ chemical formula 53]
[ examples 2-1 to 2-3] production of Compound No.2
EXAMPLE 2-1 production of intermediate 2A (Ketone Compound)
Triphenylamine (5.9g) and dichloroethane (40g) were charged in a four-necked flask, and then aluminum chloride (10.5g) and propionyl chloride (7.1g) were added thereto under ice cooling. After stirring at room temperature for 5 hours, the reaction solution was poured into ice-cooled 5% diluted hydrochloric acid and stirred to separate oil from water. The organic layer was washed 2 times with 5% aqueous HCl and further 4 times with water. The product layer was desolventized and purified by a silica gel column (hexane/ethyl acetate: 80/20) to obtain intermediate 2A (3.9 g: yield 39%).
[ chemical formula 54]
EXAMPLE 2-2 preparation of intermediate 2B (Oxime Compound)
Intermediate 2A (3.9g) and dimethylformamide (24g) were weighed into a four-necked flask, and 35% hydrochloric acid (3.9g) and isobutyl nitrite (3.9g) were added dropwise under ice cooling, followed by stirring at room temperature for 20 hours. Ion-exchanged water (24g) and ethyl acetate (48g) were added thereto, followed by oil-water separation, and the organic layer was washed with water 3 times. After the organic layer was desolventized, intermediate NCIx175-b was obtained (4.5 g: yield 96%).
[ chemical formula 55]
Intermediate 2B
EXAMPLE 2-3 preparation of Compound No.2 (Oxime ester Compound of the present invention)
Intermediate 2B (4.5g) and tetrahydrofuran (23g) were put into a four-necked round-bottomed flask, and triethylamine (3.0g) and acetyl chloride (2.2g) were added dropwise in this order under ice cooling, followed by stirring at room temperature for 2 hours. After ion-exchanged water (17g) and ethyl acetate (46g) were added thereto, oil-water separation was performed, and the organic layer was washed 5 times with water. The organic layer was desolventized and purified by silica gel column (hexane/ethyl acetate 50: 50) to obtain compound No.2(2.7 g: yield 48%). NMR data of the obtained compound No.2 are shown in [ Table 1 ].
[ chemical formula 56]
Example 3-1 to 3-4 production of Compound No.133
EXAMPLE 3-1 preparation of intermediate 133A
Fluorobenzene (27.7g) and dichloroethane (192g) were put into a four-necked flask, and then aluminum chloride (40.4g) and n-octanoyl chloride (46.8g) were put into the flask in this order under ice cooling. After the reaction was carried out at room temperature for 1 hour, the reaction solution was poured into ice-cooled 5% diluted hydrochloric acid and stirred to separate the reaction solution from water. The organic layer was washed 2 times with 5% dilute hydrochloric acid and 3 times with ion-exchanged water, and then desolventized to obtain intermediate 133A (50.0 g: yield 78%)
[ chemical formula 57]
Intermediate 133A
EXAMPLE 3-2 production of intermediate 133B (Nitrogen-containing Compound)
carbazole (20.0g), intermediate 133A (29.3g), potassium carbonate (24.8g), and dimethyl sulfoxide (133g) were charged in a four-necked flask, and reacted at 160 ℃ for 6 hours. Ion-exchanged water (173g) was added thereto, and extraction was performed with dichloroethane (163 g). The organic layer was washed with water 3 times and then desolventized to obtain intermediate 133B (41.2 g: yield 93%).
[ chemical formula 58]
Intermediate 133B
EXAMPLE 3-3 production of intermediate 133C (ketone Compound)
After intermediate 133B (41.2g) and dichloroethane (209g) were charged in a four-necked flask, aluminum chloride (49.1g) and n-octanoyl chloride (39.9g) were sequentially charged under ice cooling. After 4 hours of reaction at this temperature, the reaction solution was poured into ice-cooled 5% diluted hydrochloric acid and stirred to separate oil from water. The organic layer was washed 2 times with 5% dilute hydrochloric acid and 3 times with ion-exchanged water, and then desolventized to obtain intermediate 133C (50.5 g: 73%)
[ chemical formula 59]
Intermediate 133C
EXAMPLE 3-4 preparation of Compound No.133 (Oxime ester Compound)
Intermediate 133C (10.0g), dimethylformamide (50g), hydroxylamine hydrochloride (3.7g) and pyridine (4.2g) were added to a four-necked flask, and the mixture was stirred at 80 ℃ for 10 hours. After cooling with ice, triethylamine (5.4g) and acetyl chloride (4.2g) were added dropwise in this order, and the mixture was stirred at room temperature for 5 hours. Ion-exchanged water (50g) was added thereto, and extraction was performed with ethyl acetate (100 g). The organic layer was washed with water 3 times, then, the solvent was removed, and the product was purified by a silica gel column (ethyl acetate/hexane: 1/4), whereby compound No.133 was obtained (2.3 g: yield 18%). NMR data of the obtained compound No.133 are shown in [ Table 1 ].
[ chemical formula 60]
Example 4-1 to 4-2 preparation of Compound No.134
EXAMPLE 4-1 preparation of intermediate 134A (Oxime Compound)
Intermediate 133C (10.0g) and DMF (10.0g) were weighed into a four-necked flask, and 35% hydrochloric acid (6.70g) and isobutyl nitrite (6.63g) were added dropwise under ice cooling, followed by stirring at room temperature for 20 hours. Ion-exchanged water (22.8g) and ethyl acetate (34.2g) were added thereto to separate an oil from water, and the organic layer was washed with water 3 times. The organic layer was desolventized and purified by a silica gel column (ethyl acetate/hexane: 1/4) to obtain intermediate 134A (2.8 g: yield 25%).
[ chemical formula 61]
Intermediate 134A
EXAMPLE 4-2 preparation of Compound No.134 (Oxime ester Compound)
Intermediate 134A (2.7g) and ethyl acetate (10g) were charged in a four-necked round-bottomed flask. Triethylamine (1.3g) and acetyl chloride (1.0g) were added dropwise in this order under ice-cooling, and the mixture was warmed to room temperature and stirred for 3 hours. After ion-exchanged water (12g) was added, oil-water separation was performed, and the organic layer was washed 5 times with water. The organic layer was desolventized and purified by silica gel column (hexane/ethyl acetate 85: 15) to obtain compound No.134(0.89 g: yield 27%).
NMR data of the obtained compound No.134 are shown in [ Table 1 ].
[ chemical formula 62]
[ Table 1]
Production example 1 production of blue pigment Dispersion No.1
DISPERBYK-161(12.5 parts by mass; manufactured by BYK-Chemie Japan) as a dispersant and pigment blue 15 as a colorant were mixed using a bead mill: 6(15 parts by mass) was dispersed in PGMEA (72.5 parts by mass) to prepare a blue pigment dispersion.
[ examples 5 to 7 and comparative examples 1 to 2] preparation of photosensitive composition
The photosensitive compositions No.1 to 3 and comparative photosensitive compositions No.1 to 2 were obtained by preparing the respective components according to the formulations of [ Table 2] and [ Table 3 ]. In the table, the numbers indicate parts by mass. The compounds No.2, No.133, No.134, No. A2-3 and No. A2-11 were used alone as photopolymerization initiators.
In addition, symbols in the table represent the following components.
Compound No.2 of A-1
Compound No.133 of A-2
A-3 Compound No.134
A' -4 Compound No. A2-3
A' -5 Compound No. A2-11
B-1 SPC-3000 (ethylenically unsaturated compound having acid group, PGMEA solution with solid content 42 wt%; manufactured by Showa Denko K.K.)
b-2 KAYARAD DPHA (ethylenically unsaturated Compound: Japanese chemical)
C-1 blue pigment Dispersion No.1 (colorant PGMEA Dispersion)
D-1 KBE-403 (silane coupling agent: manufactured by shin-Etsu chemical Co., Ltd.)
D-2F-554 (fluoro-containing lipophilic group-containing oligomer: DIC product)
E-1 PGMEA (solvent)
SPC-3000 is an ethylenically unsaturated compound (B) and also an alkali-developable compound (D).
[ Table 2]
Examples 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
Meter 100 100 100
[ Table 3]
Comparative example 1 2
Comparative photosensitive composition 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
Meter 100 100
[ evaluation of cured product obtained from photosensitive composition ]
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 also shown in Table 4.
(Brightness)
The photosensitive compositions No.1 to 3 and comparative photosensitive compositions No.1 to 2 were spin-coated (500rpm, 2 seconds, 900rpm, 5 seconds) on a glass substrate, prebaked at 90 ℃ for 90 seconds using a hot plate, and then cooled at 23 ℃ for 40 seconds. Thereafter, 100mJ/cm2 was irradiated with mercury high pressure lamp to prepare an evaluation sample. The Y value was determined from the transmittance at 380 to 780nm of the obtained sample according to JIS Z8701. A is the sample having a Y value of 9.5 or more, and B is the sample having a Y value of less than 9.5. A higher BY value means higher brightness, which is useful. The sample evaluated as a in luminance can be preferably used for a color filter, and the sample evaluated as B is not suitable as a color filter.
[ Table 4]
Photosensitive composition Brightness of light
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
[ evaluation of photosensitive composition ]
The sensitivity evaluation of the photosensitive compositions Nos. 1 and 3 and the comparative photosensitive composition No.1, which were evaluated as A in the above evaluation of the luminance, was carried out by the following procedure. The results are also shown in [ Table 5 ].
(sensitivity)
The photosensitive compositions No.1 to 3 and comparative photosensitive compositions No.1 to 2 were spin-coated (500rpm, 2 seconds, 900rpm, 5 seconds) on a glass substrate, prebaked at 90 ℃ for 90 seconds using a hot plate, and then cooled at 23 ℃ for 40 seconds. Thereafter, exposure was performed using a high-pressure mercury lamp through a mask. After the development was carried out using an aqueous solution of sodium carbonate of 2.5 mass% < sodium carbonate as a developer, the resultant was sufficiently washed with water, and then baked at 230 ℃ for 30 minutes in an oven to fix the pattern. The pattern of exposure light to 40mJ/cm2 was observed with an electron microscope, and the line width of the mask opening was measured to be 30 μm. A represents a sample having a line width of 35 μm or more, B represents a sample having a line width of 25 μm or more, and C represents a sample having a line width of less than 25 μm. The larger the line width, the better the sensitivity. The photosensitive compositions having sensitivity evaluations a and B can be used for color filters, and the photosensitive composition having sensitivity evaluation a is particularly preferable. The photosensitive composition having the sensitivity evaluation C is not suitable for color filter applications.
[ Table 5]
photosensitive composition Sensitivity of the probe
Example 11 Photosensitive composition No.1 B
Example 12 Photosensitive composition No.3 A
Comparative example 5 Comparative photosensitive composition No.1 C
As is clear from the above [ Table 3] to [ Table 5], the oxime ester compounds of the present invention have high sensitivity and the cured products of the present invention have high brightness.
Therefore, the oxime ester compound of the present invention is excellent in the photolithography property and the brightness of the obtained cured product is excellent, and therefore is useful as a photopolymerization initiator.
Industrial applicability
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 property), 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 luminance and a display device including the color filter can be provided by the photosensitive composition containing the photopolymerization initiator.

Claims (9)

1. An oxime ester compound represented by the following general formula (I),
Wherein R1, R2, R3, R4, R5, R6, R7, R8, R9, R10, R11, R12 and R13 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, R21, OR21, SR21, NR22R23, COR21, SOR21, SO2R21 OR CONR22R23,
At least three of R1, R2, R3, R4, R5, R6, R7, R8, R9, R10, R11, R12 and R13 are groups represented by the following general formula (II),
R21, R22 and R23 each independently represents a hydrocarbon group having 1 to 20 carbon atoms or a heterocyclic group having 2 to 20 carbon atoms,
The hydrogen atom in the groups represented by R21, R22 and R23 may be substituted with a halogen atom, a nitro group, a cyano group, a hydroxyl group, an amino group, a carboxyl group, a methacryloyl group, an acryloyl group, an epoxy group, a vinyl ether group, a mercapto group, an isocyanate group or a heterocyclic group having 2 to 20 carbon atoms,
Methylene groups in the groups represented by R21, R22 and R23 are sometimes substituted by-O-, -CO-, -COO-, -OCO-, -NR24-, -NR24CO-, -S-, -CS-, -SO2-, -SCO-, -COS-, -OCS-or CSO-,
R24 represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms,
X1 represents the absence, direct bond, -CO-, -O-, or-S-,
Wherein R31 and R32 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,
The hydrogen atom in the group represented by R31 and R32 may be substituted with a halogen atom, a nitro group, a cyano group, a hydroxyl group, an amino group, a carboxyl group, a methacryloyl group, an acryloyl group, an epoxy group, a vinyl ether group, a mercapto group, an isocyanate group or a heterocyclic group having 2 to 20 carbon atoms,
Methylene groups in the groups represented by R31 and R32 are sometimes substituted by-O-, -CO-, -COO-, -OCO-, -NR33-, -NR33CO-, -S-, -CS-, -SO2-, -SCO-, -COS-, -OCS-, or CSO-,
R33 represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms,
n represents 0 or 1, and x represents a bonding site.
2. The oxime ester compound according to claim 1, wherein at least one of R3, R6 and R11 in the general formula (I) is a group represented by the general formula (II).
3. A photopolymerization initiator containing the oxime ester compound as claimed in claim 1 or 2.
4. a photosensitive composition comprising the photopolymerization initiator (A) as claimed in claim 3 and an ethylenically unsaturated compound (B).
5. The photosensitive composition according to claim 4, further comprising a colorant (C).
6. An alkali-developable photosensitive resin composition comprising the photosensitive composition according to claim 4 or 5 and an alkali-developable compound (D).
7. A cured product of the photosensitive composition according to claim 4 or 5 or the alkali-developable photosensitive resin composition according to claim 6.
8. A display device comprising the cured product according to claim 7.
9. A method for producing a cured product, which comprises a step of curing the photosensitive composition according to claim 4 or 5 or the alkali-developable photosensitive resin composition according to claim 6 by light irradiation or heating.
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