CN103298782B - Oxime ester compound and the Photoepolymerizationinitiater initiater containing this compound - Google Patents

Oxime ester compound and the Photoepolymerizationinitiater initiater containing this compound Download PDF

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CN103298782B
CN103298782B CN201280004665.9A CN201280004665A CN103298782B CN 103298782 B CN103298782 B CN 103298782B CN 201280004665 A CN201280004665 A CN 201280004665A CN 103298782 B CN103298782 B CN 103298782B
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methyl
acid
alkyl
alkali
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CN103298782A (en
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村田圣
大石武雄
君岛孝一
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Adeka Corp
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Asahi Denka Kogyo KK
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    • C07C323/23—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and nitrogen atoms, not being part of nitro or nitroso groups, bound to the same carbon skeleton
    • C07C323/46—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and nitrogen atoms, not being part of nitro or nitroso groups, bound to the same carbon skeleton having at least one of the nitrogen atoms, not being part of nitro or nitroso groups, further bound to other hetero atoms
    • C07C323/47—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and nitrogen atoms, not being part of nitro or nitroso groups, bound to the same carbon skeleton having at least one of the nitrogen atoms, not being part of nitro or nitroso groups, further bound to other hetero atoms to oxygen atoms
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    • 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
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    • C07C323/64—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and sulfur atoms, not being part of thio groups, bound to the same carbon skeleton
    • C07C323/65—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and sulfur atoms, not being part of thio groups, bound to the same carbon skeleton containing sulfur atoms of sulfone or sulfoxide groups bound to the carbon skeleton
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    • C07D303/20—Ethers with hydroxy compounds containing no oxirane rings
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    • C07D307/38—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with substituted hydrocarbon radicals attached to ring carbon atoms
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    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
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    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
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    • 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
    • G03F7/0005—Production of optical devices or components in so far as characterised by the lithographic processes or materials used therefor
    • G03F7/0007—Filters, e.g. additive colour filters; Components for display devices
    • 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
    • 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
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    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
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    • 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
    • G03F7/032—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
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    • 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
    • G03F7/038—Macromolecular compounds which are rendered insoluble or differentially wettable
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    • C07C2601/12—Systems containing only non-condensed rings with a six-membered ring
    • C07C2601/14—The ring being saturated

Abstract

The oxime ester compound that following general formula (1) represents.In formula, R 1~ R 4represent OR 11, COOR 11deng, R 11represent the heterocyclic radical of hydrogen atom, the alkyl of C1 ~ 20, the aryl of C6 ~ 30, the aralkyl of C7 ~ 30 or C2 ~ 20, the hydrogen atom of these groups can also by-CR 21=CR 22r 23,-CO-CR 21=CR 22r 23,-O-CO-CR 21=CR 22r 23deng replacement (R 21~ R 23with R 11identical); X represents sulphur atom, NR 33(R 33alkyl etc. for hydrogen atom, C1 ~ 20) etc.; A represents the integer of 0 ~ 4; B represents the integer of 1 ~ 5, R 4in at least one be that there is-CR 21=CR 22r 23,-CO-CR 21=CR 22r 23,-O-CO-CR 21=CR 22r 23deng group.

Description

Oxime ester compound and the Photoepolymerizationinitiater initiater containing this compound
Technical field
The present invention relates to the cured article as useful novel oxime ester cpds, the Photoepolymerizationinitiater initiater containing this compound, the photosensitive composite formed containing this Photoepolymerizationinitiater initiater in the polymerizable compound with ethylenic unsaturated link(age) and this photosensitive composite of the Photoepolymerizationinitiater initiater used in photosensitive composite.
Background technology
Photosensitive composite adds Photoepolymerizationinitiater initiater and obtains in the polymerizable compound with ethylenic unsaturated link(age), due to its polymerizing curable can be made by irradiation energy ray (light), thus can be used for light curable inks, photosensitive printing version, various photo-resists etc.
As the Photoepolymerizationinitiater initiater for above-mentioned photosensitive composite, in patent documentation 1 ~ 3, propose oxime ester compound.
But, in the oxime ester compound recorded in patent documentation 1 ~ 3, can the oxime ester compound of satisfaction luminosity to there is the transmissivity of visible region low, the problem of desired color cannot be obtained (particularly with colour filter, the photosensitive composite of the purposes of the transparency is being required for the protection of film etc., and employ in the colour filter resist of blue pigment or pigment, if be mixed with the compound having absorption at 380 ~ 450nm, then brightness, purity of color can decline), in addition, the oxime ester compound that the transmissivity of visible region is higher also exists the problem that light sensitivity can not fully meet the demands, need the Photoepolymerizationinitiater initiater having both two kinds of characteristics.
In addition, the painted alkali-developable photosensitive resin composition containing tinting material for colour filter etc. requires to have ISO, the Photoepolymerizationinitiater initiater in resist must be arranged to high density.But the Photoepolymerizationinitiater initiater of high density can cause the pollution etc. of the generation of the residue caused because of the deterioration of developability and the photomask caused because of sublimate and process furnace.
Prior art document
Patent documentation
Patent documentation 1: Japanese Unexamined Patent Publication 2000-80068 publication
Patent documentation 2: Japanese Unexamined Patent Publication 2001-233842 publication
Patent documentation 3: patent No. 3860170 publication
Summary of the invention
Problem to be solved by this invention
Problem points to be solved by this invention is, does not also have the light sensitivity that can meet the demands up to now, and the Photoepolymerizationinitiater initiater that the transmissivity of visible region is higher, sublimability is lower.
Therefore, the object of this invention is to provide a kind of excellent in stability, low sublimability, developability transmissivity that is excellent, visible region higher, can efficient absorption 365nm etc. near-ultraviolet light and by the Photoepolymerizationinitiater initiater of ISO activated.
The means of dealing with problems
The present inventors conduct in-depth research, found that, if make the compound that uses as Photoepolymerizationinitiater initiater when making resin combination and the reaction such as resin, or when energy-ray (light) irradiates and the reaction such as resin, then to become situation about existing with the state that compound is original than not reacting with resin etc. low for sublimability.
The present invention completes based on above-mentioned cognition, provides a kind of oxime ester compound represented by following general formula (1) and the Photoepolymerizationinitiater initiater formed containing this compound.
(in formula, R 1, R 2, R 3and R 4separately represent R 11, OR 11, COOR 11, SR 11, SO 2r 11, CONR 12r 13or CN,
R 11, R 12and R 13separately represent hydrogen atom or substituting group, this substituting group to be carbonatoms be 1 ~ 20 alkyl, carbonatoms be 6 ~ 30 aryl, carbonatoms be 7 ~ 30 aralkyl or carbonatoms be the heterocyclic radical of 2 ~ 20,
R 11, R 12and R 13represented substituent hydrogen atom can also further by OR 21, COR 21, SR 21, NR 22r 23, CONR 22r 23,-NR 22-OR 23,-NR 22cO-OCOR 23,-C(=N-OR 21)-R 22,-C(=N-OCOR 21)-R 22, CN, halogen atom ,-COOR 21,-CR 21=CR 22r 23,-CO-CR 21=CR 22r 23,-O-CO-CR 21=CR 22r 23,-N=C=O or epoxy group(ing) replace,
R 21, R 22and R 23separately represent hydrogen atom or substituting group, this substituting group to be carbonatoms be 1 ~ 20 alkyl, carbonatoms be 6 ~ 30 aryl, carbonatoms be 7 ~ 30 aralkyl or carbonatoms be the heterocyclic radical of 2 ~ 20,
R 21, R 22and R 23represented substituent hydrogen atom can also further by CN, halogen atom, hydroxyl or carboxyl substituted,
R 11, R 12, R 13, R 21, R 22and R 23represented substituent alkylene moiety can also by-O-,-S-,-COO-,-OCO-,-NR 24-,-NR 24cOO-,-OCONR 24-,-SCO-,-COS-,-OCS-or-CSO-interrupt 1 ~ 5 time,
R 24represent alkyl that hydrogen atom, carbonatoms are 1 ~ 20, aryl that carbonatoms is 6 ~ 30, carbonatoms be 7 ~ 30 aralkyl or carbonatoms be the heterocyclic radical of 2 ~ 20,
R 11, R 12, R 13, R 21, R 22and R 23represented substituent moieties can have branched building block, also can be cyclic alkyl, in addition, and R 12with R 13and R 22with R 23also ring can be formed together respectively,
X represents Sauerstoffatom, sulphur atom, selenium atom, CR 31r 32, CO, NR 33or PR 34,
R 31, R 32, R 33and R 34separately represent hydrogen atom or substituting group, this substituting group to be carbonatoms be 1 ~ 20 alkyl, carbonatoms be 6 ~ 30 aryl or carbonatoms be the aralkyl of 7 ~ 30,
R 31, R 32, R 33and R 34represented substituent moieties can have branched building block, also can be cyclic alkyl, R 31, R 32, R 33and R 34represented substituent alkyl end also can be unsaturated link(age), R 31, R 32, R 33and R 34also separately ring can be formed together with any one adjacent phenyl ring,
A represents the integer of 0 ~ 4,
B represents the integer of 1 ~ 5,
R 4in at least one be that there is-CR 21=CR 22r 23,-CO-CR 21=CR 22r 23,-O-CO-CR 21=CR 22r 23,-N=C=O or epoxy group(ing) group.）
In addition, the invention provides a kind of photosensitive composite, it is formed containing above-mentioned Photoepolymerizationinitiater initiater and the polymerizable compound with ethylenic unsaturated link(age).
In addition, the invention provides a kind of alkali-developable photosensitive resin composition, it is formed containing the compound giving alkali-developable in above-mentioned photosensitive composite.
In addition, the invention provides a kind of painted alkali-developable photosensitive resin composition, it is formed containing tinting material further in above-mentioned alkali-developable photosensitive resin composition.
In addition, the invention provides a kind of cured article, it is by being formed above-mentioned photosensitive composite, above-mentioned alkali-developable photosensitive resin composition or above-mentioned painted alkali-developable photosensitive resin composition irradiation energy ray.
The effect of invention
Oxime ester compound of the present invention is higher in the transmissivity of visible region, for 365nm(i line) etc. bright line can produce free radical efficiently, be useful as Photoepolymerizationinitiater initiater.In addition, oxime ester compound of the present invention when be matched with as Photoepolymerizationinitiater initiater use in resin combination time, can with the resin reaction with polymerizable group, thus sublimate is less, and then can improve the thermotolerance of cured article.
Embodiment
Below, oxime ester compound of the present invention and the Photoepolymerizationinitiater initiater containing this compound are described in detail.
Oxime ester compound of the present invention is the novel cpd represented by above-mentioned general formula (1).There are 2 kinds of geometrical isomers in this oxime ester compound, but they do not distinguish by the present invention because of the double bond of oxime.
Namely, in this manual, the general formula (2) of preferred configuration of above-mentioned general formula (1), compound represented by the above-mentioned general formula of expression described later (1) and the chemical structural formula of exemplary compounds No.1 ~ No.39 illustrate only a kind in 2 kinds of geometrical isomers, but oxime ester compound of the present invention is not limited to the geometrical isomer represented by these chemical formulas, also can be another kind of geometrical isomer, also can be the mixture of 2 kinds of geometrical isomers.
As the R in above-mentioned general formula (1) 11, R 12, R 13, R 21, R 22, R 23, R 24, R 31, R 32, R 33, R 34represented carbonatoms is the alkyl of 1 ~ 20, can list such as methyl, ethyl, propyl group, sec.-propyl, butyl, isobutyl-, sec-butyl, the tertiary butyl, amyl group, isopentyl, tert-pentyl, hexyl, heptyl, octyl group, iso-octyl, 2-ethylhexyl, tertiary octyl group, nonyl, different nonyl, decyl, isodecyl, undecyl, dodecyl, tetradecyl, hexadecyl, octadecyl, eicosyl, cyclopentyl, cyclohexyl, cyclohexyl methyl etc.
As the R in above-mentioned general formula (1) 11, R 12, R 13, R 21, R 22, R 23, R 24, R 31, R 32, R 33, R 34represented carbonatoms is the aryl of 6 ~ 30, can list such as phenyl, tolyl, xylyl, ethylphenyl, naphthyl, anthryl, phenanthryl, by the phenyl, xenyl, naphthyl, anthryl etc. after the abovementioned alkyl replacement of more than 1.
As the R in above-mentioned general formula (1) 11, R 12, R 13, R 21, R 22, R 23, R 24, R 31, R 32, R 33, R 34represented carbonatoms is the aralkyl of 7 ~ 30, can list such as benzyl, α-methylbenzyl, alpha, alpha-dimethylbenzyl, phenylethyl etc.
As the R in above-mentioned general formula (1) 11, R 12, R 13, R 21, R 22, R 23, R 24the represented carbonatoms that can be substituted is the heterocyclic radical of 2 ~ 20, preferably can list 5 ~ 7 yuan of heterocycles such as such as pyridyl, pyrimidyl, furyl, thienyl, tetrahydrofuran base, dioxolyl, benzoxazole-2-base, THP trtrahydropyranyl, pyrrolidyl, imidazolidyl, pyrazolidyl, thiazolidyl, isothiazole alkyl, oxazolidinyl, isoxazole alkyl, piperidyl, piperazinyl, morpholinyl.
In above-mentioned general formula (1), as R 12with R 13, R 22with R 23the ring that can be formed together and R 31, R 32, R 33and R 34the ring that can be formed together with adjacent phenyl ring, preferably can list 5 ~ 7 rings such as such as pentamethylene ring, cyclohexane ring, cyclopentenes ring, phenyl ring, piperidine ring, morpholine ring, lactonic ring, lactam nucleus.
In addition, in above-mentioned general formula (1), as replacing R 11, R 12, R 13, R 21, R 22, R 23halogen atom, fluorine, chlorine, bromine, iodine can be listed.
In addition, R 11, R 12, R 13, R 21, R 22, R 23represented substituent alkylene moiety also can by-O-,-S-,-COO-,-OCO-,-NR 24-,-NR 24cOO-,-OCONR 24-,-SCO-,-COS-,-OCS-or-CSO-interrupt 1 ~ 5 time, the link group now interrupted also can be one kind or two or more group, when the group for interrupting continuously, also can the link group of more than 2 interrupt continuously.In addition, above-mentioned substituent moieties can have branched building block, also can be cyclic alkyl.
In oxime ester compound of the present invention, in above-mentioned general formula (I), X is sulphur atom or NR 33, and R 33be can have branched building block, can be the compound of the alkyl of 1 ~ 20 for the carbonatoms of cyclic alkyl; And the compound that represents of following general formula (2) due to light sensitivity high especially, and easy to manufacture, so be preferred.
(in formula, R 1, R 2, R 3, R 4, X with a be identical with the definition in above-mentioned general formula (1), R 5definition and above-mentioned general formula (1) in R 4identical, at least R 5there is at least one be selected from-CR 21=CR 22r 23,-CO-CR 21=CR 22r 23,-O-CO-CR 21=CR 22r 23, structure in-N=C=O and epoxy group(ing) group, c represents the integer of 0 ~ 4.）
In the compound that above-mentioned general formula (2) represents, R 5there is-CR 21=CR 22r 23,-CO-CR 21=CR 22r 23or-O-CO-CR 21=CR 22r 23compound high due to reactivity, high thermotolerance can be shown by combining with the resin combination with unsaturated double-bond, because of but preferred, in addition, R 5the compound with-N=C=O or epoxy group(ing) can show high thermotolerance by the resin combination having an active hydrogen with alcohol, amine, acid amides etc., is thus preferred equally.
In addition, playing in effect of the present invention higher, the R in above-mentioned general formula (1) and (2) 1and R 2being preferably carbonatoms is that to be particularly preferably carbonatoms be 1 ~ 10 to 1 ~ 20(, especially be preferably carbonatoms be 1 ~ 4) alkyl, a in above-mentioned general formula (1) and (2) is preferably 0 ~ 1, and the b in above-mentioned general formula (1) is preferably 1 ~ 2, and the c in above-mentioned general formula (2) is preferably 0 ~ 1.
Playing in effect of the present invention higher, above-mentioned R 3be preferably hydrogen atom.Due to same reason, above-mentioned X is preferably sulphur atom.Due to same reason, preferably: above-mentioned R 4for OR 11or COOR 11, and this R 11for carbonatoms be 1 ~ 20, particularly carbonatoms be 1 ~ 10, especially carbonatoms be the alkyl of 1 ~ 6, this R 11at least one in the hydrogen atom had is by-OCO-CR 21=CR 22r 23replace, at this-OCO-CR 21=CR 22r 23in, R 21for hydrogen atom or methyl, R 22and R 23for hydrogen atom.Now, when instead of OR 11r 11during the hydrogen atom had ,-OCO-CR 21=CR 22r 23preferably with from this OR 11the carbon atom bonding of Sauerstoffatom position farthest, when instead of COOR 11r 11during the hydrogen atom had ,-OCO-CR 21=CR 22r 2preferably with from this COOR 11the carbon atom bonding of COO base position farthest.In addition, preferably: b is 1, and R 4relative to the carbon atom bonding of X institute bonding in contraposition.
As the preferred object lesson of the oxime ester compound of the present invention that above-mentioned general formula (1) represents, can list following compound N o.1 ~ compound of No.39.But, the present invention is not by any restriction of following compound.
The oxime ester compound of the present invention that above-mentioned general formula (1) represents is not particularly limited, such as, can manufacture according to the method recorded in Japanese Unexamined Patent Publication No. 2000-80068 public Reported.As one of method, according to following reaction formula 1, following method can be used manufacture.First, ketoboidies is reacted with (methyl) vinylformic acid in the presence of a lewis acid, thus obtains (methyl) acrylate body.Then, make this (methyl) acrylate body and nitrous acid ester react in presence of hydrochloric acid, then with acid anhydrides or acyl chloride reaction, obtain the oxime ester compound of the present invention that above-mentioned general formula (1) represents.Describe situation when X is sulphur atom in following reaction formula 1, but X is Sauerstoffatom, selenium atom, CR 31r 32, NR 33or PR 34time situation also can manufacture according to above-mentioned method.
Reaction formula 1
Ketoboidies (methyl) acrylate body
Oxime body oxime ester of the present invention body
(in formula, R 1and R 2identical with the definition in above-mentioned general formula (1).）
Novel oxime ester cpds of the present invention described above is useful as Photoepolymerizationinitiater initiater.
Photoepolymerizationinitiater initiater of the present invention contains at least one oxime ester compound of the present invention, and the Photoepolymerizationinitiater initiater particularly as the polymerizable compound with ethylenic unsaturated link(age) is useful.The content of the oxime ester compound of the present invention in Photoepolymerizationinitiater initiater of the present invention is preferably 30 ~ 100 quality %, is more preferably 50 ~ 100 quality %.Photoepolymerizationinitiater initiater of the present invention, except containing except oxime ester compound of the present invention, can also contain other Photoepolymerizationinitiater initiater.As other Photoepolymerizationinitiater initiater, in the past known compound can be used, such as benzophenone can be listed, phenyl biphenyl ketone, 1-hydroxyl-1-benzoyl group hexanaphthene, bitter almond oil camphor, the two methyl ether of benzil, 1-benzyl-1-dimethylin-1-(4 '-morpholino benzoyl group) propane, 2-morpholinyl-2-(4 '-methyl mercapto) benzoyl group propane, thioxanthone, the chloro-4-propoxythioxanthone of 1-, isopropyl thioxanthone, diethyl thioxanthone, EAQ, 4-benzoyl group-4 '-methyldiphenyl sulfide, benzoin butyl ether, 2-hydroxyl-2-benzoyl group propane, 2-hydroxyl-2-(4 '-sec.-propyl) benzoyl group propane, 4-butylbenzene acyl group trichloromethane, 4-phenoxy group benzoyl group methylene dichloride, benzoyl group methyl-formiate, two (9 '-acridyl) heptane of 1,7-, two (the 2 '-morpholino isobutyryl) carbazole of 9-normal-butyl-3,6-, two (the trichloromethyl)-s-triazine of 2-methyl-4,6-, two (the trichloromethyl)-s-triazine of 2-phenyl-4,6-, two (the trichloromethyl)-s-triazine of 2-naphthyl-4,6-, two (the 2-chloro-phenyl-)-4,5 of 2,2-, 4 ', 5 '-tetraphenyl-1-2 '-bisglyoxaline, 4,4-Diisopropyl azodicarboxylate, triphenylphosphine, camphorquinone, N-1414, N-1717, N-1919, PZ-408, NCI-831, NCI-930(ADEKA Co., Ltd. manufactures), IRGACURE369, IRGACURE907, IRGACUREOXE01, IRGACUREOXE02(BASF company manufactures), benzoyl peroxide, the compound etc. that following general formula (4) ~ (6) represent.When using these Photoepolymerizationinitiater initiaters except oxime ester compound of the present invention, one or more can be used to combinationally use.
(in formula, R 1, R 2and R 33identical with the definition in above-mentioned general formula (1), Y 3represent halogen atom or alkyl, n is 0 ~ 5.）
(in formula, R 1, R 2and R 33identical with the definition in above-mentioned general formula (1), Y 3identical with above-mentioned general formula (4) with the definition of n, R ' 1and R ' 2definition and R 1and R 2identical, R ' 33definition and R 33identical, Y ' 3definition and Y 3identical, R 8represent diol residue or two thiol residue, Z 5represent Sauerstoffatom or sulphur atom.）
(in formula, R 1, R 2and R 33identical with the definition in above-mentioned general formula (1), Y 3identical with above-mentioned general formula (4) with the definition of n, Z 6represent Sauerstoffatom, sulphur atom or selenium atom, A represents heterocyclic radical, and t is the integer of 0 ~ 5, and u is 0 or 1.）
Below, photosensitive composite of the present invention is described in detail.
In photosensitive composite of the present invention, as neccessary composition, have the polymerizable compound of ethylenic unsaturated link(age) containing (A) Photoepolymerizationinitiater initiater of the present invention and (B), as any composition, combination is containing (C) mineral compound, composition such as (D) tinting material, solvent etc.
In photosensitive composite of the present invention, (A) content of Photoepolymerizationinitiater initiater of the present invention is not particularly limited, but polymerizable compound 100 mass parts that the content of the oxime ester compound of the present invention in photosensitive composite of the present invention has ethylenic unsaturated link(age) relative to (B) is preferably 1 ~ 70 mass parts, be more preferably 1 ~ 50 mass parts, most preferably be 5 ~ 30 mass parts.
There is as above-mentioned (B) polymerizable compound of ethylenic unsaturated link(age), be not particularly limited, can use in the past for the compound of photosensitive composite, the unsaturated fatty hydrocarbons such as such as ethene, propylene, butylene, iso-butylene, vinylchlorid, vinylidene chloride, vinylidene, tetrafluoroethylene can be listed, (methyl) vinylformic acid, α-chloro-acrylicacid, methylene-succinic acid, toxilic acid, citraconic acid, fumaric acid, Na Dike acid (himicacid), β-crotonic acid, iso-crotonic acid, vinyl-acetic ester, allyl acetate, styracin, Sorbic Acid, methylfumaric acid, mono succinate [2-(methyl) acryloyl-oxyethyl] ester, phthalic acid list [2-(methyl) acryloyl-oxyethyl] ester, ω-carboxy-polycaprolactone list (methyl) acrylate etc. have list (methyl) acrylate of the polymkeric substance of carboxyl and hydroxyl at two ends, hydroxyethyl (methyl) acrylate-malate, hydroxypropyl (methyl) acrylate-malate, Dicyclopentadiene (DCPD)-malate or there is the unsaturated polyprotonic acid such as multifunctional (methyl) acrylate of (methyl) acryl of 1 carboxyl and more than 2, (methyl) 2-Hydroxy ethyl acrylate, (methyl) 2-hydroxypropyl acrylate, (methyl) glycidyl acrylate, following compound N o.A1 ~ No.A4, (methyl) methyl acrylate, (methyl) butyl acrylate, (methyl) isobutyl acrylate, (methyl) tert-butyl acrylate, (methyl) cyclohexyl acrylate, (methyl) n-octyl, (methyl) Isooctyl acrylate monomer, (methyl) vinylformic acid ester in the different ninth of the ten Heavenly Stems, (methyl) stearyl acrylate ester, (methyl) lauryl acrylate, (methyl) methoxyethyl acrylate, (methyl) acrylate methyl esters, (methyl) acrylate, (methyl) acrylic-amino propyl ester, (methyl) acrylate propyl ester, (methyl) ethoxyethyl acrylate, (methyl) vinylformic acid gathers (oxyethyl group) ethyl ester, (methyl) acrylate, butoxy ethoxy ethyl ester, (methyl) EHA, (methyl) acrylate, (methyl) vinylformic acid tetrahydrofuran ester, (methyl) vinyl acrylate, (methyl) allyl acrylate, (methyl) benzyl acrylate, ethylene glycol bisthioglycolate (methyl) acrylate, Diethylene Glycol two (methyl) acrylate, triethylene glycol two (methyl) acrylate, polyoxyethylene glycol two (methyl) acrylate, propylene glycol two (methyl) acrylate, BDO two (methyl) acrylate, 1,6-hexylene glycol two (methyl) acrylate, trimethylolethane trimethacrylate (methyl) acrylate, trimethylolpropane tris (methyl) acrylate, Dipentaerythritol six (methyl) acrylate, Dipentaerythritol five (methyl) acrylate, tetramethylolmethane four (methyl) acrylate, tetramethylolmethane three (methyl) acrylate, tristane dihydroxymethyl two (methyl) acrylate, three [(methyl) acryloyl ethyl] isocyanuric acid ester, the ester of the unsaturated monoprotic acid such as polyester (methyl) origoester acrylate and polyvalent alcohol or polyphenol, the metal-salt of the unsaturated polyprotonic acids such as (methyl) zinc acrylate resin, (methyl) Magnesium Acrylate Prepared, maleic anhydride, itaconic anhydride, citraconic anhydride, methyl tetrahydrophthalic anhydride, Tetra Hydro Phthalic Anhydride, trialkyl Tetra Hydro Phthalic Anhydride, 5-(2,5-dioxotetrahydrofuryl) acid anhydrides of the unsaturated polyprotonic acid such as-3-methyl-3-tetrahydrobenzene-1,2-dicarboxylic anhydride, trialkyl Tetra Hydro Phthalic Anhydride-maleic anhydride adduct, dodecenyl succinic anhydride, methylnadic anhydride, the acid amides of the unsaturated monoprotic acid such as (methyl) acrylamide, methylene-bis (methyl) acrylamide, Diethylenetriamine three (methyl) acrylamide, xylylene two (methyl) acrylamide, alpha-chloro acrylamide, N-2-hydroxyethyl (methyl) acrylamides and polyamine, the unsaturated aldehydes such as propenal, the unsaturated nitriles such as (methyl) vinyl cyanide, α-chloroacrylonitrile, vinylidene dicyanide, allyl cyanide, the unsaturated aromatics such as vinylbenzene, 4-vinyl toluene, 4-ethyl styrene, 4-methoxy styrene, 4-Vinyl phenol, 4-chloro-styrene, Vinylstyrene, Vinyl toluene, vinyl benzoic acid, vinylphenol, vinyl sulfonic acid, 4-vinylbenzenesulfonic acid, vinyl benzyl methyl ether, vinylbenzyl glycidyl ether, the beta-unsaturated ketones such as methyl vinyl ketone, the unsaturated amine compounds such as vinyl amine, allyl amine, NVP, vinylpiperidine, the vinyl alcohol such as vinyl carbinol, crotyl alcohol, the vinyl ether such as vinyl methyl ether, EVE, n-butyl vinyl ether, IVE, glycidyl allyl ether, the unsaturated acid imides such as maleimide, N-phenylmaleimide, N-N-cyclohexylmaleimide, the indenes classes such as indenes, 1-methyl indenes, the aliphatic conjugated diene classes such as 1,3-butadiene, isoprene, chloroprene, polystyrene, poly-(methyl) methyl acrylate, the macromonomer class of gathering (methyl) n-butyl acrylate, there is at the end of the polymer molecular chains such as polysiloxane list (methyl) acryl, the vinyl monomer of vinylchlorid, vinylidene chloride, divinyl succinate base ester, Phthalic acid, diallyl ester, triallyl phosphate, cyanacrylate, vinyl sulfide, vinyl imidazole, Yi Xi Ji oxazole, vinylcarbazole, vinyl pyrrolidone, vinyl pyridine, hydroxyl and the vinyl urethane compound of polyisocyanate compounds, the vinyl monomer of hydroxyl and the vinyloxirane of polyepoxides.
In addition, have the polymerizable compound of ethylenic unsaturated link(age), can also use the multipolymer of acrylate, phenol and/or cresol novolac epoxy, have epoxy compounds effects such as the polyphenylene methane type epoxy resin of multi-functional epoxy's base, Epocryl and epoxy compounds that unsaturated monoprotic acid and following general formula (3) are represented and then make multi-anhydride and its effect and the resin obtained as (B).Wherein, preferably, epoxy compounds effects such as the epoxy compounds making unsaturated monoprotic acid and following general formula (3) represent and then make multi-anhydride and its effect and the resin obtained.In addition, the unsaturated group of above-claimed cpd preferably containing 0.2 ~ 1.0 equivalent.
(in formula, X 1represent direct key, methylene radical, carbonatoms be 1 ~ 4 alkylidene, carbonatoms be 3 ~ 20 ester ring type alkyl, O, S, SO 2, the substituting group that represents of SS, SO, CO, OCO or following [i], [ii] or [iii], above-mentioned alkylidene also can be replaced by halogen atom, R 51, R 52, R 53and R 54separately represent that hydrogen atom, carbonatoms are alkyl, the carbonatoms alkoxyl group that is 1 ~ 8, carbonatoms be 2 ~ 5 alkenyl or the halogen atom of 1 ~ 5, abovementioned alkyl, alkoxyl group and alkenyl also can be replaced by halogen atom, m is the integer of 0 ~ 10, when m is not 0, the optical isomer of existence can be any one isomer.）
(in formula, Z 3represent hydrogen atom, can by carbonatoms be 1 ~ 10 alkyl or carbonatoms be 1 ~ 10 alkoxyl group replace phenyl can by carbonatoms be 1 ~ 10 alkyl or carbonatoms be 1 ~ 10 alkoxyl group replace carbonatoms be the cycloalkyl of 3 ~ 10, Y 1represent that carbonatoms is alkyl, the carbonatoms alkoxyl group that is 1 ~ 10, carbonatoms be 2 ~ 10 alkenyl or the halogen atom of 1 ~ 10, abovementioned alkyl, alkoxyl group and alkenyl also can be replaced by halogen atom, and d is the integer of 0 ~ 5.）
(in formula, Y 2and Z 4separately represent that the carbonatoms that can be replaced by halogen atom is the alkyl of 1 ~ 10, the carbonatoms that can be replaced by halogen atom is the aryl of 6 ~ 20, the carbonatoms that can be replaced by halogen atom is the aryloxy of 6 ~ 20, the carbonatoms that can be replaced by halogen atom is the arylthio of 6 ~ 20, the carbonatoms that can be replaced by halogen atom is the aralkenyl of 6 ~ 20, the carbonatoms that can be replaced by halogen atom is the aralkyl of 7 ~ 20, the carbonatoms that can be replaced by halogen atom is the heterocyclic radical of 2 ~ 20, or halogen atom, alkylene moiety in abovementioned alkyl and aralkyl also can by unsaturated link(age),-O-or-S-interrupts, adjacent Z 4between also can form ring, p represents the integer of 0 ~ 4, and q represents the integer of 0 ~ 8, and r represents the integer of 0 ~ 4, and s represents the integer of 0 ~ 4, the number of r and s add up to 2 ~ 4 integer.）
As the above-mentioned unsaturated monoprotic acid with above-mentioned epoxy compounds effect, vinylformic acid, methacrylic acid, β-crotonic acid, styracin, Sorbic Acid, HEMA-malate, hydroxyethylmethacry,ate-malate, hydroxy propyl methacrylate-malate, acrylate-malate, Dicyclopentadiene (DCPD)-malate etc. can be listed.
In addition, as the above-mentioned multi-anhydride making it act on after making above-mentioned unsaturated monoprotic acid effect, biphenyl tetracarboxylic dianhydride can be listed, Tetra Hydro Phthalic Anhydride, succinyl oxide, bibenzene tetracarboxylic dianhydride, maleic anhydride, trimellitic acid 1,2-anhydride, pyromellitic dianhydride, 2, 2'-3, 3'-benzophenone tetracarboxylic anhydride, ethylene glycol bis trimellitic acid 1,2-anhydride, glycerol three trimellitic acid 1,2-anhydride, hexahydrophthalic anhydride, methyl tetrahydrophthalic anhydride, carbic anhydride, methylnadic anhydride, trialkyl Tetra Hydro Phthalic Anhydride, hexahydrophthalic anhydride, 5-(2, 5-dioxotetrahydrofuryl)-3-methyl-3-tetrahydrobenzene-1, 2-dicarboxylic anhydride, trialkyl Tetra Hydro Phthalic Anhydride-maleic anhydride adduct, dodecenyl succinic anhydride, methylnadic anhydride etc.
The reaction mol ratio of above-mentioned epoxy compounds, above-mentioned unsaturated monoprotic acid and above-mentioned multi-anhydride is preferably as follows setting.
Namely, relative to 1 epoxy group(ing) of above-mentioned epoxy compounds, above-mentioned unsaturated monacid carboxyl is 0.1 ~ 1.0, have with in the epoxy adduct of the structure after this ratio addition, preferably reach following ratio, relative to 1 hydroxyl of this epoxy adduct, the acid anhydride structure of above-mentioned multi-anhydride is 0.1 ~ 1.0.
The reaction of above-mentioned epoxy compounds, above-mentioned unsaturated monoprotic acid and above-mentioned multi-anhydride can conventionally be carried out.
Above-mentioned have in the polymerizable compound of ethylenic unsaturated link(age), when use has the compound of acid number, can give photosensitive composite alkali-developable of the present invention.When use above-mentioned there is the compound of acid number time, its usage quantity is preferably set to 50 ~ 99 quality % in (B) composition.
In addition, the above-mentioned compound with acid number can also by reacting with simple function or multi-functional epoxy compound and regulate acid number to use afterwards.By regulating the above-mentioned acid number with the compound of acid number, the alkali-developable of photoresist can be improved.The above-mentioned acid number with the solids component of the compound (namely can give the polymerizable compound with ethylenic unsaturated link(age) of alkali-developable) of acid number is preferably the scope of 5 ~ 120mgKOH/g, and the usage quantity of simple function or multi-functional epoxy compound is preferably selected according to the mode meeting above-mentioned acid number.
As above-mentioned monofunctional epoxy compound, glycidyl methacrylate can be listed, methyl glycidyl ether, ethyl ether, propyl glycidyl ether, isopropyl glycidyl ether, butylglycidyl ether, isobutyl glycidyl ether, tertiary butyl glycidyl ether, amyl group glycidyl ether, hexyl glycidyl ether, heptyl glycidyl ether, octyl glycidyl ether, nonyl glycidyl ether, decyl glycidyl ether, undecyl glycidyl ether, lauryl diglycidyl ether, tridecyl glycidyl ether, tetradecyl glycidyl ether, pentadecyl glycidyl ether, cetyl glycidyl ether, 2-hexyl glycidyl ether, glycidyl allyl ether, propargyl glycidyl ether, to methoxy ethyl glycidyl ether, phenyl glycidyl ether, to methoxyl group glycidyl ether, p-butylphenol glycidyl ether, cresyl glycidyl ether, 2-methyl toluene base glycidyl ether, 4-nonyl phenyl glycidyl glyceryl ether, benzyl glycidyl ether, to cumyl phenyl glycidyl ether, trityl glycidyl ether, methacrylic acid 2,3-polyglycidyl, epoxidised soybean oil, epoxidised linseed oil, Glycidyl butyrate, vinyl cyclohexane monoxide, 1,2-epoxy-4-vinyl cyclohexane, Styrene oxide 98min., pinene oxide, oxidation methyl vinylbenzene, cyclohexene oxide, propylene oxide, following compound N o.E1, No.E2 etc.
As above-mentioned multi-functional epoxy compound, if use more than one the compound that is selected among biphenol type epoxy compound and Racemic glycidol ethers, then can obtain characteristic better (painted) alkali-developable photosensitive resin composition, because of but preferably.
As above-mentioned biphenol type epoxy compound, except the epoxy compounds represented except above-mentioned general formula (3) can be used, the biphenol type epoxy compounds such as such as hydrogenated bisphenol type epoxy compounds can also be used.
In addition, as above-mentioned Racemic glycidol ethers, ethylene glycol diglycidylether can be used, propylene glycol diglycidylether, 1, 4-butanediol diglycidyl ether, 1, 6-hexanediol diglycidyl ether, 1, 8-ethohexadiol diglycidylether, 1, 10-decanediol diglycidylether, 2, 2-dimethyl-1, ammediol diglycidylether, diethylene glycol diglycidyl glyceryl ether, Triethylene Glycol Diglycidyl Ether, TEG diglycidylether, six ethylene glycol diglycidylethers, 1, 4-cyclohexanedimethanodiglycidyl diglycidyl ether, 1, 1, 1-tri-(glycidoxypropyl methyl) propane, 1, 1, 1-tri-(glycidoxypropyl methyl) ethane, 1, 1, 1-tri-(glycidoxypropyl methyl) methane, 1, 1, 1, 1-tetra-(glycidoxypropyl methyl) methane etc.
In addition, the novolak type epoxy compounds such as phenol novolak-type epoxy compound, biphenyl novolak type epoxy compounds, cresol novolak type epoxy compound, bisphenol A novolac type epoxy compounds, dicyclopentadiene novolac type epoxy compounds can also be used; The cycloaliphatic epoxy such as 3,4-epoxy-6-methylcyclohexylmethyl-3,4-epoxy-6-methylcyclohexanecarboxylic acid ester, 3,4-epoxycyclohexyl-methyl-3,4-epoxycyclohexane carboxylate, 1-epoxy ethyl-3,4-epoxy cyclohexane; The glycidyl ester classes such as o-phthalic acid diglycidyl ester, tetrahydrophthalic acid 2-glycidyl ester, dimer acid glycidyl ester; The glycidyl amines such as four glycidyl group diaminodiphenyl-methane, triglycidyl group p-aminophenol, N, N-diglycidylaniline; The hetero ring type epoxy compoundss such as 1,3-diglycidyl-5,5-T10, triglycidyl group isocyanuric acid ester; The dioxide such as titanium dioxide Dicyclopentadiene (DCPD); Naphthalene type epoxy compounds, triphenylmethane type epoxy compound, dicyclopentadiene type epoxy compound etc.
As above-mentioned (C) mineral compound that can contain in photosensitive composite of the present invention, the metal oxides such as such as nickel oxide, ferric oxide, iridium oxide, titanium oxide, zinc oxide, magnesium oxide, calcium oxide, potassium oxide, silicon-dioxide, aluminum oxide can be listed; Layered clay mineral, milori blue, calcium carbonate, magnesiumcarbonate, cobalt system, manganese system, glass powder (particularly frit (glassfrit)), mica, talcum, kaolin, yellow prussiate, various metal sulfate, sulfide, selenide, pure aluminium silicate, Calucium Silicate powder, aluminium hydroxide, platinum, gold and silver, copper etc.
Wherein, preferred glass material, titanium oxide, silicon-dioxide, layered clay mineral, silver etc.In photosensitive composite of the present invention, the content of (C) mineral compound is, polymerizable compound 100 mass parts relative to (B) with ethylenic unsaturated link(age) is preferably 0.1 ~ 1000 mass parts, is more preferably 10 ~ 800 mass parts.In addition, these mineral compound can use one kind or two or more.
Above-mentioned mineral compound can be used as such as weighting agent, antireflection agent, conductive agent, stablizer, fire retardant, physical strength rising agent, special wavelength absorption agent, anti-ink agent etc.
In addition, as above-mentioned (D) tinting material that can contain in photosensitive composite of the present invention, pigment, dyestuff, natural pigment etc. can be listed.These tinting materials can be used alone or two or more is used in combination.
As above-mentioned pigment, such as nitroso compound can be used; Nitro-compound; Azo-compound; Diazonium compound; Oxa anthracene compound; Quinoline compound; Anthraquinone compounds; Coumarin compound; Phthalocyanine compound; Isoindolinone compounds; Isoindoline compounds; Quinoline Azone compound; Two and anthrone compound; Purple cyclic ketones (perynone) compound; Perylene compound; Diketopyrrolo-pyrrole compound; Thioindigo compound; Dioxazine compound; Triphenylmethane compounds; Quinophthalone compound; Naphthalene tetracarboxylic acid; The metal complex of azoic dyestuff, cyanine dyes; Pigment lake; The carbon black obtained with oven process, channel process, pyrolysis method or acetylene black, Ketjen black or the carbon black such as dim; The material being carried out by above-mentioned carbon black epoxy resin adjusting or cover and obtain, above-mentioned carbon black is carried out dispersion treatment with resin in advance in a solvent, and the material making its resin adsorbing 20 ~ 200mg/g and obtain, above-mentioned carbon black carried out acidity or basic surface process and the material obtained, median size be more than 8nm and DBP oil number be below 90ml/100g carbon black, by CO and CO in the volatile component at 950 DEG C 2the whole oxygen amount calculated is every 100m 2surface-area is the carbon black of more than 9mg; Graphite, graphitized carbon black, gac, carbon fiber, carbon nanotube, screw carbon fibre, Carbon Nanohorn, carbon aerogels, soccerballene; Nigrosine, Pigment black 7, titanium are black; The organic or inorganic pigment such as chromoxide green, milori blue, cobalt green, cobalt blue, manganese system, yellow prussiate, phosphoric acid salt ultramarine, general Shandong soil indigo plant, ultramarine, cerulean blue, viridian (viridian), emerald green, lead sulfate, chrome yellow, zinc yellow, ferric oxide (red iron oxide (III)), cadmium red, synthesis iron oxide black, umber (amber).These pigment can be used alone or multiple used in combination.
As above-mentioned pigment, commercially available pigment can also be used, such as 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 can be listed; Pigment Orange 13,31,34,36,38,43,46,48,49,51,52,55,59,60,61,62,64,65,71; Pigment Yellow 73 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.
As above-mentioned dyestuff, can list the dyestuffs etc. such as azoic dyestuff, anthraquinone dye, indigoide colors, triarylmethane dye, Xanthene dyes, alizarine dyestuff, acridine dye, Stilbene dyestuff, thiazole dye, naphthol dye, quinoline dye, nitro-dye, phenylene blue dyestuff, oxazine dye, phthalocyanine pigment, cyanine dyes, they also can be multiple used in combination.
Time in photosensitive composite of the present invention containing (D) tinting material, the polymerizable compound that its content has ethylenic unsaturated link(age) relative to (B) of 100 mass parts is preferably 50 ~ 350 mass parts, is more preferably 100 ~ 250 mass parts.
In addition, photosensitive composite of the present invention can also give the compound of alkali-developable containing not having ethylenic unsaturated link(age), as this compound, as long as the compound of the alkaline soluble aqueous solution because having acid number, just be not particularly limited, but representatively compound, can list alkali-soluble novolac resin (below simply referred to as " novolac resin ").Novolac resin can make phenols and aldehyde condensation polymer in the presence of acid catalyst and obtain.
As above-mentioned phenols, such as phenol can be used, ortho-cresol, meta-cresol, p-cresol, phlorol, m-ethylphenol, p-ethyl phenol, adjacent butylphenol, between butylphenol, p-butylphenol, 2, 3-xylenol, 2, 4-xylenol, 2, 5-xylenol, 3, 4-xylenol, 3, 5-xylenol, 2, 3, 5-pseudocuminol, p-phenyl phenol, quinhydrones, pyrocatechol, Resorcinol, 2-methylresorcinol, pyrogallol, naphthyl alcohol, dihydroxyphenyl propane, resorcylic acid ester, gallic acid ester etc., in above-mentioned phenols, preferred phenol, ortho-cresol, meta-cresol, p-cresol, 2, 5-xylenol, 3, 5-xylenol, 2, 3, 5-pseudocuminol, Resorcinol, 2-methylresorcinol and dihydroxyphenyl propane.Above-mentioned phenols can be used alone or two or more used in combination.
As above-mentioned aldehydes, such as formaldehyde, paraformaldehyde, acetaldehyde, propionic aldehyde, phenyl aldehyde, phenylacetic aldehyde, α-phenylpropyl aldehyde, β-phenylpropionaldehyde, salicylaldhyde, m-hydroxybenzaldehyde, p-Hydroxybenzaldehyde, o-chlorobenzaldehyde, m chlorobenzaldehyde, 4-chloro-benzaldehyde, Ortho Nitro Benzaldehyde, m-nitrobenzaldehyde, paranitrobenzaldehyde, o-tolualdehyde, a tolyl aldehyde, p-tolyl aldehyde, p-ethylbenzaldehyde can be used, align butyl benzaldehyde etc., in above-claimed cpd, preferred formaldehyde, acetaldehyde and phenyl aldehyde.Above-mentioned aldehydes can be used alone or two or more used in combination.Relative to the phenols of every 1 mole, aldehydes preferably with 0.7 ~ 3 mole, particularly preferably use with the ratio of 0.7 ~ 2 mole.
As above-mentioned acid catalyst, can the organic acid such as mineral acid and formic acid, oxalic acid, acetic acid such as example example hydrochloric acid, nitric acid, sulfuric acid.The usage quantity of above-mentioned acid catalyst is that the phenols of every 1 mole is preferably 1 × 10 -4~ 5 × 10 -1mole.In the condensation reaction, usually use water as reaction medium, if but the phenols used in condensation reaction is insoluble to the aqueous solution of aldehydes, and initial reaction stage just becomes nonhomogeneous system, then hydrophilic solvent also can be used as reaction medium.As above-mentioned hydrophilic solvent, alcohols or the ring-type such as tetrahydrofuran (THF), the diox ethers such as such as methyl alcohol, ethanol, propyl alcohol, butanols can be listed.The reaction raw materials of normally every 100 mass parts of usage quantity of above-mentioned reaction medium is 20 ~ 1000 mass parts.The temperature of reaction of condensation reaction suitably can adjust according to the reactivity of reaction raw materials, but is generally 10 ~ 200 DEG C, is preferably 70 ~ 150 DEG C.After condensation reaction terminates, in order to remove the unreacting material, acid catalyst and the reaction medium that exist in system, interior temperature generally to be made to rise to 130 ~ 230 DEG C, and under reduced pressure heat up in a steamer volatile component, then the novolac resin curtain coating of melting be reclaimed to stainless bringing of steel.
In addition, after condensation reaction terminates, also reaction mixture can be dissolved in aforesaid hydrophilic solvent, and add in the precipitation agents such as water, normal hexane, normal heptane, make novolac resin separate out thus, be separated precipitate, heat drying and reclaiming.
As the example except above-mentioned novolac resin, polycarboxylated styrene or derivatives thereof, styrene-maleic anhydride copolymer, polyvinyl hydroxy-benzoic acid etc. can be listed.
In photosensitive composite of the present invention, solvent can also be added further as required.As this solvent, normally can dissolve or disperse the solvent of above-mentioned each composition ((A) Photoepolymerizationinitiater initiater of the present invention and (B) have the polymerizable compound etc. of ethylenic unsaturated link(age)), the ketones such as such as methylethylketone, methylpentanone, diethyl ketone, acetone, Methyl isobutyl ketone, mibk, pimelinketone, 2-heptanone can be used; The ether series solvents such as ether, diox, tetrahydrofuran (THF), 1,2-glycol dimethyl ether, 1,2-diethoxyethane, dimethyl ether; The ester series solvents such as methyl acetate, ethyl acetate, n-propyl acetate, isopropyl acetate, n-butyl acetate, hexalin acetate, ethyl lactate, Succinic acid dimethylester, alcohol ester; The cellosolve such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether series solvent; The alcohol series solvents such as methyl alcohol, ethanol, XOR n-propyl alcohol, XOR propyl carbinol, amylalcohol; The ether-ether series solvents such as ethylene glycol monomethyl acetic ester, ethylene glycol list ethylhexoate, propylene glycol-1-monomethyl ether-2-acetic ester, dipropylene glycol monomethyl ether acetic ester, 3-methoxybutyl acetic ester, ethoxy ethyl propionate; The BTX series solvents such as benzene,toluene,xylene; The aliphatic hydrocarbon series solvents such as hexane, heptane, octane, hexanaphthene; The terpenic series hydrocarbon ils such as turps, D-limonene, firpene; Mineral turpentine, Swazol#310(Cosmo Guia Hill oil Co., Ltd.), Solvesso#100(Exxon KCC) etc. paraffinic hydrocarbons series solvent; The halogenated aliphatic hydrocarbon system solvents such as tetracol phenixin, chloroform, trieline, methylene dichloride, 1,2-ethylene dichloride; The halogenated aromatic hydrocarbon system solvents such as chlorobenzene; Trivalin SF series solvent; Aniline; Triethylamine; Pyridine; Acetic acid; Acetonitrile; Dithiocarbonic anhydride; DMF; N-Methyl pyrrolidone; Methyl-sulphoxide; Water etc., these solvents can use a kind, also can use mixed solvent of more than two kinds.
Wherein ketone, ether-ether series solvent etc. particularly propylene glycol-1-monomethyl ether-2-acetic ester, pimelinketone etc. make the consistency of resist and Photoepolymerizationinitiater initiater in photosensitive composite become good, thus preferably.
In photosensitive composite of the present invention, the content of solvent is not particularly limited, as long as the amount that each uniform composition can be made to disperse or dissolve and make photosensitive composite of the present invention to present be suitable for the aqueous of each purposes or pasty state is just passable, the amount of the preferred solids component (the whole compositions beyond desolventizing) according to making in photosensitive composite of the present invention is that the scope of 10 ~ 50 quality % is to containing solvent usually.
In photosensitive composite of the present invention, the dispersion agent making (C) mineral compound and/or the dispersion of (D) tinting material can also be added.As this dispersion agent, as long as can disperse and stablize the dispersion agent of (C) mineral compound or (D) tinting material, just do not limit, the BYK series etc. of commercially available dispersion agent, such as BYK Inc. can be used.Particularly, by there is macromolecule dispersing agent that the polyester of basic functionality, polyethers or urethane forms, there is nitrogen-atoms as basic functionality, and the functional group with nitrogen-atoms is amine and/or its quaternary ammonium salt, and amine value is that the dispersion agent of 1 ~ 100mgKOH/g can preferably use.
In addition, in photosensitive composite of the present invention, while there is the polymerizable compound of ethylenic unsaturated link(age) in use (B), use other organic polymer, the characteristic of cured article can also be improved.As this organic polymer, such as polystyrene can be listed, polymethylmethacrylate, Eudragit NE30D, poly-(methyl) vinylformic acid, vinylbenzene-(methyl) acrylic copolymer, (methyl) acryl acid-methyl methacrylate copolymer, ethylene-vinyl chloride copolymer, ethylene-vinyl base co-polymer, polyvinyl chloride (PVC) RESINS, ABS resin, nylon 6, nylon66 fiber, nylon 12, urethane resin, polycarbonate polyvinyl butyral acetal, cellulose ester, polyacrylamide, saturated polyester, resol, phenoxy resin, polyamide-imide resin, polyamic acid resin, epoxy resin etc., wherein preferred polystyrene, (methyl) acryl acid-methyl methacrylate copolymer, epoxy resin.
When using other organic polymer, its usage quantity has the above-mentioned polymerizable compound of ethylenic unsaturated link(age) relative to (B) of 100 mass parts, is preferably 10 ~ 500 mass parts.
Can further also with chain-transfer agent, sensitizing agent, tensio-active agent, silane coupling agent, melamine compound etc. in photosensitive composite of the present invention.
As above-mentioned chain-transfer agent, sensitizing agent, the general compound using sulfur atom-containing.Such as Thiovanic acid can be listed, mercaptosuccinic acid, thiosalicylic acid, 2 mercaptopropionic acid, 3-thiohydracrylic acid, 3-mercaptobutyric acid, N-(2-mercapto radical propionyl group) glycine, 2-mercaptonicotinic acid, 3-[N-(2-mercaptoethyl) formamyl] propionic acid, 3-[N-(2-mercaptoethyl) amino] propionic acid, N-(3-mercapto radical propionyl group) L-Ala, mistabrom, 3-thiohydracrylic acid, 4-sulfydryl fourth sulfonic acid, dodecyl (4-methylthio group) phenyl ether, 2 mercapto ethanol, 3-Mercapto-1，2-propanediol, 1-sulfydryl-2-propyl alcohol, 3-sulfydryl-2-butanols, mercapto-phenol, 2-MEA, 2-mercaptoimidazole, 2-mercaptobenzimidazole, 2-sulfydryl-3-pyridol, 2-mercaptobenzothiazole, Thiovanic acid, trimethylolpropane tris (3-mercaptopropionic acid ester), the sulfhydryl compounds such as tetramethylolmethane four (3-mercaptopropionic acid ester), the disulphide that the oxidation of this sulfhydryl compound is obtained, iodoacetic acid, iodopropionic acid, ethylene iodohydrin, 2-iodine ethyl sulfonic acid, the iodo-alkyl compounds such as 3-iodine propanesulfonic acid, trimethylolpropane tris (3-mercaptoisobutanoic acid esters), butyleneglycol two (3-mercaptoisobutanoic acid esters), ethanthiol, the last of the ten Heavenly stems two mercaptan, Isosorbide-5-Nitrae-dimethyl sulfydryl benzene, butyleneglycol two sulphur propionic ester, butyleneglycol two THIOGLYCOLLIC ACID ester, ethylene glycol bisthioglycolate THIOGLYCOLLIC ACID ester, trimethylolpropane tris THIOGLYCOLLIC ACID ester, butyleneglycol two sulphur propionic ester, trimethylolpropane tris sulphur propionic ester, trimethylolpropane tris THIOGLYCOLLIC ACID ester, tetramethylolmethane four sulphur propionic ester, tetramethylolmethane four THIOGLYCOLLIC ACID ester, trihydroxy-ethyl trithio propionic ester, diethyl thioxanthone, diisopropylthioxanthone, following compound N o.C1, the aliphatics multi-functional thiol compounds such as tri-thiol propionic acid three (2-hydroxyethyl) isocyanuric acid ester, the KarenzMTBD1 of Showa electrician Inc., PE1, NR1 etc.
As above-mentioned tensio-active agent, the fluorochemical surfactant such as perfluoralkyl phosphate, perfluoroalkyl carboxylate can be used; The negatively charged ion system tensio-active agents such as higher aliphatic acid-alkali salt, alkylsulfonate, alkyl-sulphate; The positively charged ion system tensio-active agents such as higher amines halate, quaternary ammonium salt; The nonionogenic tensides such as polyethylene glycol alkyl ether, cithrol, sorbitan-fatty acid ester, glycerine monofatty ester; Amphoterics; The tensio-active agents such as silicone-based tensio-active agent, they also can combine use.
As above-mentioned silane coupling agent, the silane coupling agent of such as chemical company of SHIN-ETSU HANTOTAI can be used, wherein, KBE-9007, KBM-502, KBE-403 etc. have isocyanate group, methacryloyl, epoxy group(ing) silane coupling agent can preferably use.
As above-mentioned melamine compound, the active methylol (CH in the nitrogen compounds such as (gathering) melamine methylol, (gathering) methylol glycoluril, (gathering) methylol guanamine, (gathering) methylolurea can be listed 2oH yl) all or part of (at least two) by the compound etc. after alkyl etherified.
Wherein, as the alkyl forming alkyl oxide, methyl, ethyl or butyl can be listed, mutually can be identical, also can be different.In addition, not alkyl etherified methylol can carry out from condensation in a molecule, also can two intermolecularly carry out condensation, result forms oligopolymer composition.
Particularly, HMMM, six butoxymethyl trimeric cyanamides, tetramethoxymethylglycoluril, four butoxymethyl glycolurils etc. can be used.
Wherein, preferred HMMM, six butoxymethyl trimeric cyanamides etc. alkyl etherified after trimeric cyanamide.
In addition, in photosensitive composite of the present invention, can add as required thermal polymerization inhibitors such as methyl-phenoxide, quinhydrones, pyrocatechol, tert-butyl catechol, thiodiphenylamine; Softening agent; Adhesion promoters; Weighting agent; Defoamer; Flow agent; Surface conditioner; Antioxidant; UV light absorber; Dispersing auxiliary; Antithrombotics; Catalyzer; Effect promotor; Linking agent; The additive that tackifier etc. are usual.
In photosensitive composite of the present invention, any composition except the polymerizable compound that (A) Photoepolymerizationinitiater initiater of the present invention and (B) have ethylenic unsaturated link(age) (wherein, (C) except mineral compound, (D) tinting material and solvent) usage quantity suitably can select according to its application target, be not particularly limited, but preferably, there is relative to (B) polymerizable compound 100 mass parts of ethylenic unsaturated link(age), the total amount of any composition is set as below 50 mass parts.
Photosensitive composite of the present invention can make cured article by irradiation energy ray.This cured article can be formed as suitable shape according to purposes.Such as when forming membranaceous cured article, photosensitive composite of the present invention can be applied in the support substrate such as soda glass, silica glass, semiconductor substrate, metal, paper, plastics by spinner, sized roller applicator, rod coaters, mould painting device, curtain coaters, various printing, the known means of impregnating.In addition, after also can temporarily implementing in the support substrate such as film, be transferred in other support substrate, its application method does not limit.
As the light source of energy-ray used when making photosensitive composite of the present invention solidify, having of obtaining from ultrahigh pressure mercury lamp, high voltage mercury lamp, medium pressure mercury lamp, low pressure mercury lamp, mercury vapour arc lamp, xenon arc lamp, carbon arc lamp, metal halide lamp, luminescent lamp, tungsten lamp, Excimer lamp, germicidal lamp, photodiode, CRT light source etc. can be utilized extremely the high-energy rays such as electromagnetic wave energy or electron beam, X-ray, radioactive rays of wavelength, sending the ultrahigh pressure mercury lamp, mercury vapour arc lamp, carbon arc lamp, xenon arc lamp etc. that wavelength is the light of 300 ~ 450nm can preferably use.
In addition, during exposure light source use laser, do not use mask and directly draw method not only from productivity from the view point of the laser that computer digital information directly forms image, and be also useful from improving the viewpoint of resolving power and positional precision etc., as this laser, the light of the wavelength of preferred use 340 ~ 430nm, but the laser sent from visible to the light of region of ultra-red such as excimer laser, N_2 laser, argon laser, helium cadmium laser, He-Ne Lasers, krypton ion laser, various semiconductor laser and YAG laser also can use.When using above-mentioned laser, preferably add Absorbable rod from visible to the sensitizing coloring matter of this infrared area light.
Photosensitive composite of the present invention may be used for light solidified coating or varnish; Photocurable adhesive agent; Printed base plate; Colour filter in the liquid crystal display device of the colour such as colour television set, PC watch-dog, portable information terminal, digital camera display; The colour filter of ccd image sensor; The electrode materials of plasma display; Powder coating; Printing-ink; Press plate; Caking agent; Dental composition; Gel coat; The photo-resist of electrotechnics; Platedresist; Etching resist; Dry film; Scolding tin resist; For the manufacture of the colour filter of various display purposes or in the manufacturing process of plasma display, electroluminescence display unit and LCD for the formation of the resist of these structures; For sealing electrically or the composition of electronic unit; Solder resist; Magnetic recording material; Milli machine parts; Waveguide; Optical switch; Plating mask; Etching mask; Color test system; Glass fiber cable coatings; Silk screen printing masterplate; For being manufactured the material of three-dimensional body by stereolithography; Holographic recording material; Image recording material; Fine circuits; Decoloring material; For the decoloring material of image recording material; Use the decoloring material of the image recording material of micro-capsule; Printed wiring board-use photo anti-corrosion agent material; The photo anti-corrosion agent material of UV and visible laser through image system; For the formation of in the various uses such as photo anti-corrosion agent material or protective membrane of the dielectric layer in the successively lamination of tellite, its purposes is not particularly limited.
Photosensitive composite of the present invention also can be for the formation of the object of display panels spacer and the object for the formation of vertical alignment-type liquid crystal display device projection.Particularly as being used for being formed the projection of vertical alignment-type liquid crystal display device and the photosensitive composite of spacer and useful simultaneously.
Above-mentioned display panels spacer is formed preferably by following operation: the operation that the operation that (1) forms the operation of the film of photosensitive composite of the present invention on substrate, the mulch film after exposure develops to the roasting procedure after the operation of this film irradiation energy ray (light), (3) exposure, (4) across the mask of the pattern form with regulation by (2), (5) heat this mulch film after development.
The photosensitive composite of the present invention that with the addition of (D) tinting material is suitable as the resist of each pixels such as the RGB formed in colour filter or forms the black matrix" resist in next door of each pixel.And then, add the situation of the black matrix" resist of anti-ink agent, be preferred for the ink-jet color filter next door that tooth profile angle (profileangle) is more than 50 °.As this anti-ink agent, preferably use fluorine system tensio-active agent and the composition containing fluorine system tensio-active agent.
When for above-mentioned ink-jet color filter next door, the next door formed by photosensitive composite of the present invention divides on transfer printing body, give drop to the recess on the transfer printing body after division by ink jet method, thus form pixel region, manufacture optical element by the method.Now, preferred above-mentioned drop contains tinting material, above-mentioned pixel region is colored, and in this case, the optical element made by above-mentioned manufacture method becomes the element in the next door of each painted areas at least on substrate with pixel group and this pixel group of isolation be made up of multiple painted areas.
Photosensitive composite of the present invention can also be used as protective membrane or insulation film composition.Now, (methyl) acrylate monomer and/or the silica gel of 1 or 2 officials' energy containing alcohol hydroxyl group in UV light absorber, alkylation modification trimeric cyanamide and/or acrylic acid modified trimeric cyanamide, molecule can be contained.
As the photosensitive composite of said protection film, insulating film, be take following compositions as the resin combination of principal constituent:
(A) Photoepolymerizationinitiater initiater of the present invention,
(B) have ethylenic unsaturated link(age) polymerizable compound (be preferably 2,000 ~ 40 containing weight-average molecular weight, 000, acid number is the carboxylic polymerizable compound of 50 ~ 200mgKOH/g) and
(X) epoxy compounds,
Preferably, relative to (B) composition 100 weight part, it is 0.01 ~ 2.0 weight part that (A) composition is scaled oxime ester compound amount of the present invention, and (X) composition is 10 ~ 40 weight parts.
Above-mentioned insulating film may be used for this insulating resin layer be provided with on the support base material that can peel off in the duplexer of insulating resin layer, and this duplexer can develop with alkali aqueous solution, and the thickness of insulating resin layer is preferably 10 ~ 100 μm.
Photosensitive composite of the present invention, by containing (C) mineral compound, can be used as photosensitivity paste composition.This photosensitivity paste composition may be used for forming the roast patterns such as the partition pattern of plasma display, dielectric material pattern, electrode pattern and black matrix pattern.
Embodiment
Below by enumerating embodiment and comparative example, the present invention will be described in more detail, but the present invention is not limited to these embodiments etc.
The manufacture o.1 of (embodiment 1) compound N
< step 1 > methacrylated
By containing 1-(4-(4-(2-hydroxyl-oxethyl) thiophenyl) phenyl) propane-1-ketone (below also referred to as ketoboidies a) 19.8g(65mmol), methacrylic acid 56.2g(653mmol), tosic acid monohydrate 5.0g(26mmol), BHT1.2g(5.6mmol) and the solution stirring of ethylene dichloride 121g reflux 10.5 hours.After cooling, add ethyl acetate and water carries out oily water separation.According to the sequential purge organic layer of water, sodium bicarbonate aqueous solution, water.After organic over anhydrous dried over mgso, carry out desolventizing, obtain 26.3g following methacrylic ester body a.
< step 2 > oximate
26.0g(70mmol by containing the methacrylic ester body a obtained in 1 in steps), concentrated hydrochloric acid 7.3g(70mmol) and the solution of dimethyl formamide 70g be cooled to 5 DEG C, add isobutyl nitrite 10.8g(105mmol), at room temperature stirring 3 hours.Add ethyl acetate and water carries out oily water separation, according to the sequential purge organic layer of water, sodium bicarbonate aqueous solution, water.After organic over anhydrous dried over mgso, carry out desolventizing, obtain 23.8g following oxime body a.
The esterification of < step 3 > oxime
23.8g(60mmol by containing the oxime body a obtained in 2 in steps), diacetyl oxide 9.1g(90mmol) and the solution of ethyl acetate 79g stir 4 hours at 70 DEG C.After cooling, add water and carry out oily water separation.According to the sequential purge organic layer of water, sodium bicarbonate aqueous solution, water.After organic over anhydrous dried over mgso, carry out desolventizing.The crude product 27.2g column chromatography obtained is refined, obtains 2.3g compound N o.1.The compound obtained by analysis confirmation is target compound.Analytical results is shown in (table 1) ~ (table 3).
(embodiment 2 ~ 4) compound N o.2, compound N o.3, compound N manufacture o.4
Use corresponding ketoboidies to replace ketoboidies a(and for compound N o.3, use vinylformic acid to replace methacrylic acid), in addition, according to the method recorded in embodiment 1 manufacture respectively compound N o.2, compound N o.3 with compound N o.4.Analytical results is shown in (table 1) ~ (table 3).λ
Table 1
* 1: solvent uses CHCl 3
Table 2
Table 3
The manufacture of (embodiment 5) alkali-developable photosensitive resin composition No.1
The preparation of < step 1 > alkali-developable resin (giving (B) composition of alkali-developable)
In reaction vessel, adding bisphenol fluorene type epoxy resin, (epoxy equivalent (weight) is 231, epoxy compounds represented by above-mentioned general formula (3)) 184g, vinylformic acid 58g, 2,6-di-t-butyl-p-cresol 0.26g, tetra-n-butyl ammonium bromide 0.11g and propylene glycol-1-monomethyl ether-2-acetic ester 23g, stir 16 hours at 120 DEG C.Reaction solution is cooled to room temperature, adds propylene glycol-1-monomethyl ether-2-acetic ester 35g, biphenyl tetracarboxylic acid anhydrides 59g and tetra-n-butyl ammonium bromide 0.24g, stir 4 hours at 120 DEG C.And then, add Tetra Hydro Phthalic Anhydride 20g, at 120 DEG C stir 4 hours, at 100 DEG C stir 3 hours, at 80 DEG C stir 4 hours, at 60 DEG C stir 6 hours, at 40 DEG C stir 11 hours, then propylene glycol-1-monomethyl ether-2-acetic ester 90g is added, obtain the alkali-developable resin No.1(Mw=5000 of the target compound as propylene glycol-1-monomethyl ether-2-acetate solution, Mn=2100, acid number (solids component) is 92.7mgKOH/g).
The preparation of < step 2 > alkali-developable photosensitive resin composition No.1
Using the 14.7g of alkali-developable resin No.1, the Dipentaerythritol five and six acrylate (ARONIXM-402 as (B) composition that obtain in < step 1 > of (B) composition as imparting alkali-developable; Toagosei Co., Ltd's system) 3.0g, tensio-active agent FZ-2122(Japan Unicar Co., Ltd. system) pimelinketone 1% solution 1.8g, propylene glycol-1-monomethyl ether-2-acetic ester 10.0g and pimelinketone 20.2g mix, add the compound N obtained in the embodiment 1 as (A) composition o.10.3g also fully to stir, obtain the alkali-developable photosensitive resin composition No.1 as photosensitive composite of the present invention.
The manufacture of (embodiment 6) alkali-developable photosensitive resin composition No.2
Except o.1 the compound N obtained in embodiment 1 is replaced with the compound N that obtains in embodiment 2 o.2 except, obtain the alkali-developable photosensitive resin composition No.2 as photosensitive composite of the present invention by the method that < step 2 > with embodiment 5 is same.
The manufacture of (embodiment 7) alkali-developable photosensitive resin composition No.3
Except o.1 the compound N obtained in embodiment 1 is replaced with the compound N that obtains in embodiment 3 o.3 except, obtain the alkali-developable photosensitive resin composition No.3 as photosensitive composite of the present invention by the method that < step 2 > with embodiment 5 is same.
The manufacture of (comparative example 1) alkali-developable photosensitive resin composition No.4
Except o.1 the compound N obtained in embodiment 1 being replaced with 2-benzyl-2-dimethylamino-1-(4-morphlinophenyl) except-1-butanone, obtain the alkali-developable photosensitive resin composition No.4 as comparing product by the method that < step 2 > with embodiment 5 is same.
The manufacture of (comparative example 2) alkali-developable photosensitive resin composition No.5
Except o.1 the compound N obtained in embodiment 1 is replaced with ethyl ketone; 1-9-ethyl-6-(2-methylbenzene acyl group)-9H-carbazole-3-base ］-; 1-(O-acetyl oxime) beyond, obtain the alkali-developable photosensitive resin composition No.5 as comparing product by the method that < step 2 > with embodiment 5 is same.
< transmissivity >
As described below the alkali-developable photosensitive resin composition No.1 ~ No.5 obtained is carried out transmissivity test.
That is, spin coating alkali-developable photosensitive resin composition (with 500rpm spin coating 2 second, with 800rpm spin coating 6 second) on the glass substrate, uses hot-plate at 90 DEG C, carry out the prebake conditions in 90 seconds.Then, use high voltage mercury lamp as light source, carry out 150mJ/cm 2exposure after, use baking oven at 230 DEG C, carry out the rear baking of 30 minutes, obtain cured film.To the cured film obtained, extinction photometer is used to measure the transmissivity at 380nm place.Result is shown in (table 4).
Table 4
Alkali-developable photosensitive resin composition Transmissivity (%)
No.1(embodiment 5) 88
No.2(embodiment 6) 86
No.3(embodiment 7) 86
No.4(comparative example 1) 82
No.5(comparative example 2) 80
Described in table 4, use oxime ester compound of the present invention to compare with the photosensitive composite of the comparative example 1 with 2 that employ comparative compound as the photosensitive composite of the present invention of Photoepolymerizationinitiater initiater, transmissivity is higher.
The manufacture of (embodiment 8) conductive composition No.1
Using as give alkali-developable (B) composition embodiment 5 < step 1 > in the alkali-developable resin No.114.1g, the Dipentaerythritol five and six acrylate (ARONIXM-402 as (B) composition that obtain; Toagosei Co., Ltd's system) 7.1g, surfactant B YK-323(BYKJapan Co., Ltd. system) 0.05g, alcohol ester (2,2,4-trimethylammonium-1,3-pentanediol mono isobutyrate) 11.3g, the compound N that obtains in embodiment 1 as (A) composition 0.7g o.1 and carry out mix and blend as the frit 3.1g of (C) composition and silver powder 63.7g, then use 3 roller mills to carry out mixing, obtain the conductive composition No.1 as photosensitive composite of the present invention.
The manufacture of (embodiment 9) painted alkali-developable photosensitive resin composition No.1
The manufacture of < step 1 > blue dispersing liquid
In 500ml polyethylene container, add the pigment Blue 15 of 57.6g blue pigments: 6, dispersant A JISPERPB821(AjinomotoFine-Techno Co., Ltd. system) 20.0g, dispersing auxiliary SOLSPERSE5000(Avecia Co., Ltd. system) 2.4g and propylene glycol-1-monomethyl ether-2-acetic ester 320.0g, use the zirconium oxide bead 350g that particle diameter is 0.5mm, vibrate 10 hours in Paintconditioner after, filter zirconium oxide bead, obtain blue dispersing liquid.
The manufacture of the painted alkali-developable photosensitive resin composition No.1 of < step 2 >
Using as the blue dispersing liquid 10.63g obtained in < step 1 > of (D) composition, give the alkali-developable resin No.12.98g, the Dipentaerythritol five and six acrylate (ARONIXM-402 as (B) composition that obtain in < step 1 > of the embodiment 5 as (B) composition of alkali-developable; Toagosei Co., Ltd's system) 0.31g, urethane acrylate UN3320HS(Negami Chemical Ind Co., Ltd. system as (B) composition) 0.31g, surfactant B YK-323(BYKJapan Co., Ltd. system) pimelinketone 1% solution 0.30g, propylene glycol-1-monomethyl ether-2-acetic ester 4.70g and pimelinketone 10.36g mix, o.10.41g and stir add the compound N that obtains in embodiment 1 as (A) composition, obtain the painted alkali-developable photosensitive resin composition No.1 as photosensitive composite of the present invention.
The manufacture of (comparative example 3) painted alkali-developable photosensitive resin composition No.2
Except o.1 the compound N obtained in embodiment 1 is replaced with ethyl ketone; 1-［ 9-ethyl-6-(2-methylbenzene acyl group)-9H-carbazole-3-base ］-; 1-(O-acetyl oxime) beyond, obtain the painted alkali-developable photosensitive resin composition No.2 as comparing product by the method that < step 2 > with embodiment 9 is same.
The manufacture of (comparative example 4) painted alkali-developable photosensitive resin composition No.3
Except o.1 the compound N obtained in embodiment 1 being replaced with 2-methyl isophthalic acid-(4-methylthio group phenyl)-2-morpholino propane-1-ketone, obtain the painted alkali-developable photosensitive resin composition No.3 as comparing product by the method that < step 2 > with embodiment 9 is same.
The manufacture of (comparative example 5) painted alkali-developable photosensitive resin composition No.4
Except o.1 the compound N obtained in embodiment 1 is replaced with 1; 2-acetyl caproyl; 1-4-(thiophenyl) phenyl ］-; 2-(O-benzoyl group oxime) beyond, obtain the painted alkali-developable photosensitive resin composition No.4 as comparing product by the method that < step 2 > with embodiment 9 is same.
The manufacture of (comparative example 6) painted alkali-developable photosensitive resin composition No.5
Except o.1 the compound N obtained in embodiment 1 being replaced with 2-benzyl-2-dimethylamino-1-(4-morphlinophenyl) except-1-butanone, obtain the painted alkali-developable photosensitive resin composition No.5 as comparing product by the method that < step 2 > with embodiment 9 is same.
< transmissivity >
As described below the painted alkali-developable photosensitive resin composition No.1 ~ No.3 obtained is carried out transmissivity test.
The painted alkali-developable photosensitive resin composition of spin coating (with 500rpm spin coating 7 second), uses hot-plate at 90 DEG C, carry out the prebake conditions in 90 seconds on the glass substrate.Then, high voltage mercury lamp is used to carry out 150mJ/cm as light source 2exposure after, use baking oven at 230 DEG C, carry out the rear baking of 30 minutes, obtain cured film.As thermal test, the cured film obtained is heated 1 hour further at 260 DEG C.To the cured film after thermal test, extinction photometer is used to measure the transmissivity at 420nm place.Result is shown in (table 5).
Table 5
Described in table 5, use oxime ester compound of the present invention to compare with the painted alkali-developable photosensitive composition of the comparative example 3 with 4 that employ comparative compound as the of the present invention painted alkali-developable photosensitive composition of Photoepolymerizationinitiater initiater, transmissivity is higher.
< venting quality >
Venting quality as painted alkali-developable photosensitive resin composition No.1, No.3 of obtaining ~ No.5 is tested, and is cured the mensuration of the weight reduction rates of thing as described below.
That is, the painted alkali-developable photosensitive resin composition of spin coating (500rpm, 7 seconds) on the glass substrate, uses hot-plate at 90 DEG C, carry out the prebake conditions in 90 seconds.Then, high voltage mercury lamp is used to carry out 100mJ/cm as light source 2exposure, obtain cured film.Cut this cured film of lower about 3mg, use cured film under cutting as sample, by TG-DTA(SeikoInstruments Co., Ltd. system) be determined at weight reduction rates when to maintain 30 minutes at 230 DEG C.Result is shown in (table 6).
Table 6
As known from Table 6, use oxime ester compound of the present invention as the photosensitive composite of the present invention of Photoepolymerizationinitiater initiater and painted alkali-developable photosensitive resin composition with employ comparative compound comparative example 4 ~ 6 painted alkali-developable photosensitive resin composition compared with, thermotolerance is more excellent, is vented less.In addition, from this results presumption, react as the oxime ester compound of the present invention of Photoepolymerizationinitiater initiater and resinous principle, thus, the sublimability step-down of oxime ester compound of the present invention and/or resinous principle.
The manufacture of (embodiment 10) painted alkali-developable photosensitive resin composition No.6
Using the 10.63g of the blue dispersing liquid obtained in < step 1 > of the embodiment 9 as (D) composition, give the 2.93g of alkali-developable resin No.1, the Dipentaerythritol five and six acrylate (ARONIXM-402 as (B) composition that obtain in < step 1 > of the embodiment 5 as (B) composition of alkali-developable, Toagosei Co., Ltd's system) 0.30g, urethane acrylate UN3320HS(Negami Chemical Ind Co., Ltd. system as (B) composition) 0.30g, sensitizing agent DETX-S(Nippon Kayaku K. K system) 0.05g, surfactant B YK-323(BYKJapan Co., Ltd. system) pimelinketone 1% solution 0.30g, propylene glycol-1-monomethyl ether-2-acetic ester 4.72g, and pimelinketone 10.36g mixes, add the compound N 0.41g o.1 obtained in the embodiment 1 as (A) composition also fully to stir, obtain the painted alkali-developable photosensitive resin composition No.6 as photosensitive composite of the present invention.
The manufacture of (comparative example 7) painted alkali-developable photosensitive resin composition No.7
Except o.1 the compound N obtained in embodiment 1 is replaced with ethyl ketone; 1-［ 9-ethyl-6-(2-methylbenzene acyl group)-9H-carbazole-3-base ］-; 1-(O-acetyl oxime) beyond, obtain the painted alkali-developable photosensitive resin composition No.7 as comparing product by method similarly to Example 10.
The manufacture of (comparative example 8) painted alkali-developable photosensitive resin composition No.8
Except o.1 the compound N obtained in embodiment 1 being replaced with 2-methyl isophthalic acid-(4-methylthio group phenyl)-2-morpholino propane-1-ketone, obtain the painted alkali-developable photosensitive resin composition No.8 as comparing product by method similarly to Example 10.
The manufacture of (comparative example 9) painted alkali-developable photosensitive resin composition No.9
Except o.1 the compound N obtained in embodiment 1 is replaced with 1,2-acetyl caproyl, 1-4-(thiophenyl) phenyl ］-, 2-(O-benzoyl oxime) beyond, obtain the painted alkali-developable photosensitive resin composition No.9 as comparing product by method similarly to Example 10.
The manufacture of (comparative example 10) painted alkali-developable photosensitive resin composition No.10
Except o.1 the compound N obtained in embodiment 1 being replaced with 2-benzyl-2-dimethylamino-1-(4-morphlinophenyl) except-1-butanone, obtain the painted alkali-developable photosensitive resin composition No.10 as comparing product by method similarly to Example 10.
< photoetching >
As the evaluation of the photoetching of painted alkali-developable photosensitive resin composition No.6 ~ 10 obtained, to the light sensitivity in following order, adhesivity and residue, following methods is used to evaluate respectively.Result is shown in (table 7).
The painted alkali-developable photosensitive resin composition of spin coating (500rpm, 7 seconds) on the glass substrate, uses hot-plate at 90 DEG C, carry out the prebake conditions in 90 seconds.Then, use high voltage mercury lamp as light source, carry out specified amount (50,100 or 150mJ/cm across mask 2) exposure.Use 2.5 quality % aqueous sodium carbonates as developing solution, develop after 45 seconds with spin developer, fully wash, then use the rear baking that baking oven carries out 30 minutes at 230 DEG C, make pattern fixing.
(light sensitivity)
By the light sensitivity of following 4 painted alkali-developable photosensitive resin compositions of grade evaluation.
That is, the exposure when live width of the pattern of formation being exceeded mask open live width is 50mJ/cm 2situation be set as a, be 100mJ/cm by exposure 2situation be set as b, be 150mJ/cm by exposure 2situation be set as c, even if be 150mJ/cm by exposure 2the situation that also cannot form pattern is set as d.
(adhesivity)
By the adhesivity of following 4 painted alkali-developable photosensitive resin compositions of grade evaluation.
That is, will at 100mJ/cm 2condition under exposure, pattern residual after development the thinnest mask linewidths be that the situation of less than 3 μm is set as A, by more than 3 μm but be that the situation of less than 10 μm is set as B, by more than 10 μm but be that the situation of less than 15 μm is set as C, the situation super more than 15 μm is set as D.
(residue)
After development, the situation glass surface in non-exposed portion not observing completely residue is set as zero, the situation that one side is observed residue is set as ×.
Table 7
As shown in Table 7, the Compound Phase ratio used in oxime ester compound of the present invention and comparative example 7, due to unconfirmed to residue, so developability is more excellent.In addition, when using oxime ester compound of the present invention, with the Compound Phase ratio used in comparative example 8 ~ 10, light sensitivity and adhesivity more excellent.
The manufacture of (embodiment 11) painted alkali-developable photosensitive resin composition No.11
Pigment Blue 15 using in < step 1 > of the embodiment 9 as (D) composition: 6 change to carbon black and make carbon black dispersion liquid 7.06g, give the alkali-developable resin No.13.07g, the Dipentaerythritol five and six acrylate (ARONIXM-402 as (B) composition that obtain in < step 1 > of the embodiment 5 as (B) composition of alkali-developable; Toagosei Co., Ltd's system) 0.53g, surfactant B YK-323(BYKJapan Co., Ltd. system) pimelinketone 1% solution 0.30g, propylene glycol-1-monomethyl ether-2-acetic ester 8.16g and pimelinketone 10.69g mix, add the compound N 0.19g o.1 obtained in the embodiment 1 as (A) composition also fully to stir, obtain the painted alkali-developable photosensitive resin composition No.11 as photosensitive composite of the present invention.
The manufacture of (embodiment 12) painted alkali-developable photosensitive resin composition No.12
Except o.1 the compound N obtained in embodiment 1 is replaced with the compound N that obtains in embodiment 2 o.2 except, obtain as photosensitive composite of the present invention and painted alkali-developable photosensitive resin composition No.12 by method similarly to Example 11.
The manufacture of (embodiment 13) painted alkali-developable photosensitive resin composition No.13
Except o.1 the compound N obtained in embodiment 1 is replaced with the compound N that obtains in embodiment 3 o.3 except, obtain as photosensitive composite of the present invention and painted alkali-developable photosensitive resin composition No.13 by method similarly to Example 11.
The manufacture of (comparative example 11) painted alkali-developable photosensitive resin composition No.14
Except o.1 the compound N obtained in embodiment 1 is replaced with ethyl ketone; 1-［ 9-ethyl-6-(2-methylbenzene acyl group)-9H-carbazole-3-base ］-; 1-(O-acetyl oxime) beyond, obtain the painted alkali-developable photosensitive resin composition No.14 as comparing product by method similarly to Example 11.
The manufacture of (comparative example 12) painted alkali-developable photosensitive resin composition No.15
Except o.1 the compound N obtained in embodiment 1 is replaced with 1,2-acetyl caproyl, 1-4-(thiophenyl) phenyl ］-, 2-(O-benzoyl oxime) beyond, obtain the painted alkali-developable photosensitive resin composition No.15 as comparing product by method similarly to Example 11.
< photoetching >
As the evaluation of the photoetching of painted alkali-developable photosensitive resin composition No.11 ~ 15 obtained, to the light sensitivity in following order, adhesivity and developability, following methods is used to evaluate respectively.Result is shown in (table 8).
The painted alkali-developable photosensitive resin composition of spin coating (500rpm, 7 seconds) on the glass substrate, uses hot-plate at 90 DEG C, carry out the prebake conditions in 90 seconds.Then, use high voltage mercury lamp as light source, carry out specified amount (100 or 120mJ/cm across mask 2) exposure.Use 2.5 quality % aqueous sodium carbonates as developing solution, develop after 45 seconds with spin developer, fully wash, then use the rear baking that baking oven carries out 30 minutes at 230 DEG C, make pattern fixing.
(light sensitivity)
By the light sensitivity of following 3 painted alkali-developable photosensitive resin compositions of grade evaluation.
That is, the exposure when live width of the pattern of formation being exceeded mask open live width is 100mJ/cm 2situation be set as a, be 120mJ/cm by exposure 2situation be set as b, even if be 120mJ/cm by exposure 2the situation that also cannot form pattern is set as c.
(adhesivity)
By the adhesivity of following 3 painted alkali-developable photosensitive resin compositions of grade evaluation.
That is, will at 100mJ/cm 2condition under exposure, pattern residual after development the thinnest mask linewidths be that the situation of less than 3 μm is set as A, by more than 3 μm but be that the situation of less than 5 μm is set as B, the situation super more than 5 μm is set as C.
(developability)
After development, the situation that the glass surface in non-exposed portion does not observe residue is completely set as zero, the situation that whole is all observed residue is set as ×.
Table 8
As shown in Table 8, when using oxime ester compound of the present invention, with the Compound Phase ratio used in comparative example 12, light sensitivity and adhesivity better.In addition, compare with the comparative example 11 of good adhesion with light sensitivity, if use oxime ester compound of the present invention, then developability is more excellent.
The fact following as can be known from the above results.
When using oxime ester compound of the present invention, with the Compound Phase ratio used in comparative example 2,3,7 and 11, transmissivity and the developability of visible region are more excellent.
In addition, when using oxime ester compound of the present invention, with the Compound Phase ratio used in comparative example 4 and 8, the transmissivity of visible region, thermotolerance, light sensitivity and adhesivity are more excellent.
In addition, when using oxime ester compound of the present invention, with the Compound Phase ratio used in comparative example 5,9 and 12, thermotolerance, light sensitivity and adhesivity are more excellent.
In addition, when using oxime ester compound of the present invention, with the Compound Phase ratio used in comparative example 1,6 and 10, the transmissivity of visible region, thermotolerance, light sensitivity and adhesivity are more excellent.
As mentioned above, when using oxime ester compound of the present invention, the transmissivity of visible region is higher, excellent heat resistance, and photoetching is excellent, and oxime ester compound of the present invention is useful as Photoepolymerizationinitiater initiater.

Claims (9)

1. an oxime ester compound, it is represented by following general formula (1),
In formula (1), R 1, R 2and R 3separately represent hydrogen atom or alkyl,
R 4represent OR 11or COOR 11,
R 11represent alkyl,
R 11the hydrogen atom of represented alkyl is further by-O-CO-CR 21=CR 22r 23replace,
R 21, R 22and R 23separately represent hydrogen atom or alkyl,
R 11the alkylene moiety of represented alkyl can by-NR 24cOO-interrupts,
R 24represent hydrogen atom or alkyl,
Described alkyl is methyl, ethyl, propyl group, sec.-propyl, butyl, isobutyl-, sec-butyl, the tertiary butyl, amyl group, isopentyl, tert-pentyl or hexyl,
X represents Sauerstoffatom, sulphur atom or selenium atom,
A represents the integer of 1,
B represents the integer of 1.
2. a Photoepolymerizationinitiater initiater, it is formed containing oxime ester compound according to claim 1.
3. a photosensitive composite, its polymerizable compound having ethylenic unsaturated link(age) containing (A) Photoepolymerizationinitiater initiater according to claim 2 and (B) is formed.
4. photosensitive composite according to claim 3, wherein, described (B) at least one had in the polymerizable compound of ethylenic unsaturated link(age) gives the compound of alkali-developable.
5. the photosensitive composite according to claim 3 or 4, it is formed containing (C) mineral compound further.
6. the photosensitive composite according to claim 3 or 4, it is formed containing (D) tinting material further.
7. photosensitive composite according to claim 5, it is formed containing (D) tinting material further.
8. a cured article, it is formed by the photosensitive composite irradiation energy ray according to any one of claim 3 ~ 7.
9. a colour filter, it uses cured article according to claim 8.
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