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CN104276995A - High-photosensibility oxime ester photopolymerization initiator and photopolymerization composition containing same - Google Patents

High-photosensibility oxime ester photopolymerization initiator and photopolymerization composition containing same Download PDF

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Publication number
CN104276995A
CN104276995A CN201310271006.8A CN201310271006A CN104276995A CN 104276995 A CN104276995 A CN 104276995A CN 201310271006 A CN201310271006 A CN 201310271006A CN 104276995 A CN104276995 A CN 104276995A
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China
Prior art keywords
chemical formula
compound
methyl
benzoyl
resin composition
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Inventor
车爀镇
柳美善
朴陈圭
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TAKOMA TECHNOLOGY CO LTD
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TAKOMA TECHNOLOGY CO LTD
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D209/00—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom
    • C07D209/56—Ring systems containing three or more rings
    • C07D209/80—[b, c]- or [b, d]-condensed
    • C07D209/82—Carbazoles; Hydrogenated carbazoles
    • C07D209/86—Carbazoles; Hydrogenated carbazoles with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to carbon atoms of the ring system
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C323/00—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups
    • 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
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D333/00—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom
    • C07D333/02—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings
    • C07D333/04—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings not substituted on the ring sulphur atom
    • C07D333/06—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings not substituted on the ring sulphur atom with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to the ring carbon atoms
    • C07D333/22—Radicals substituted by doubly bound hetero atoms, or by two hetero atoms other than halogen singly bound to the same carbon atom
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D409/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms
    • C07D409/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms containing two hetero rings
    • C07D409/06—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms containing two hetero rings linked by a carbon chain containing only aliphatic carbon atoms
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/46—Polymerisation initiated by wave energy or particle radiation
    • C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
    • G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
    • G02F1/1333—Constructional arrangements; Manufacturing methods
    • G02F1/1335—Structural association of cells with optical devices, e.g. polarisers or reflectors
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
    • G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
    • G02F1/1333—Constructional arrangements; Manufacturing methods
    • G02F1/1339—Gaskets; Spacers; Sealing of cells
    • 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
    • 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

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Nonlinear Science (AREA)
  • General Physics & Mathematics (AREA)
  • Mathematical Physics (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Optics & Photonics (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Indole Compounds (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

The invention provides a high-photosensibility oxime ester photopolymerization initiator and a photopolymerization composition containing the same. Specifically, the initiator is characterized in that a carbon atom in double-bond combination with a nitrogen atom of an oxime ester structure is combined with nitrophenyl. The compound and the photoinitiator composition containing the same not only have the solubility improved but also have good photosensitivity. The photoinitiator plays a beneficial role in LCD black resists, colored resists, surface layers, vertical spacers, organic insulating films and the like.

Description

ISO oxime ester Photoepolymerizationinitiater initiater and comprise the photopolymerization constituent of this compound
Technical field
The present invention relates to and be a kind ofly used as the oxime ester compound of light trigger and utilize the Photoepolymerizationinitiater initiater constituent of this compound.
Background technology
Photosensitive compoistion is the material adding Photoepolymerizationinitiater initiater in a kind of polymerizable compound to having an alkene class unsaturated link(age), owing to realizing polymerizing curable by irradiating the mixed light of 365nm, 405nm, 436nm in this photosensitive compoistion, therefore can be used as light-cured type ink, photosensitive printing plate, the use of various photoresist.Because photosensitive compoistion short wavelength light source to light sensitivity can realize trickle printing, be thus necessary to develop the Photoepolymerizationinitiater initiater outstanding to the light sensitivity of short wavelength light source (especially wavelength is the light source of 365nm).
As the Photoepolymerizationinitiater initiater for this photosensitive compoistion, in published International patent WO02/100903A1, describe a kind of light trigger with oxime ester base, wherein describe structure and the synthesis of the multiple oxime ester compound that can be used as light trigger in detail.But when using oxime ester compound disclosed in these patent documentations for Photoepolymerizationinitiater initiater, the resolvent caused due to light during exposure is attached on mask, and result will cause the pattern in typography bad, and makes productivity decline.And decomposition temperature is less than 240 DEG C, and in heat curing processes after video picture process, there is the decomposition of Photoepolymerizationinitiater initiater, cause the adhesion of photosensitive compoistion and alkali resistance to decline thus.Therefore, need to develop a kind of heat decomposition temperature high, and the volatilization of decomposition of initiator thing that can not bring because of rayed and the Photoepolymerizationinitiater initiater of contaminated polymers or device etc.
Summary of the invention
The object of the present invention is to provide a kind of Photoepolymerizationinitiater initiater comprising oxime ester structure as ISO light trigger, the resolvent that this Photoepolymerizationinitiater initiater avoids caused by light during exposure is attached on mask, there is good resulting visualization, adhesion, alkali resistance simultaneously, and due to the maximum extinction of UV can be made close to 365nm, 405nm, thus there is high sensitivity.
Further, another object of the present invention is to provide a kind of to be dissolved in the photoinitiator compound of the solvent used in photopolymerization constituent with suitable solubleness and to comprise the photosensitive compounds of this compound.
According to another embodiment of the present invention, a kind of photosensitive compoistion that this oxime ester compound is included as light trigger is provided.The resist of the black matrix, colorized optical filtering thing or the longitudinal interval article pattern that especially provide a kind of characteristic for the formation of film to improve, organic insulating film and for outer field photosensitive compoistion.
The present invention proposes to solve technical problem as above, provides the oxime ester compound represented with following chemical formula 1 to 4.
[chemical formula 1]
[chemical formula 2]
[chemical formula 3]
[chemical formula 4]
In described chemical formula 1 to 4, R 1for-CH 3,-C 2h 5, propyl group, butyl, hexyl, octyl group, benzoyl or cyclohexyl, R 2for-CH 3,-C 2h 5, propyl group or benzoyl, R 3for-H, or a is methyl or ethyl and b is-H or methyl
or
Further, in described chemical formula 3 and 4, X is-O-,-S-or-Se-.
And, the invention provides a kind of photosensitive resin composition, comprising: more than one compounds selected from the compound represented by described chemical formula 1 to chemical formula 4; Dissolve in the macromolecular compound of solvent or alkaline aqueous solution and/or there is the photopolymerizable compound of alkene class unsaturated link(age).Described photosensitive resin composition can also comprising toner or pigment.
Further, the invention provides the longitudinal interval thing of a kind of formation from described photosensitive resin composition.
And, the invention provides the black matrix of a kind of formation from described photosensitive resin composition.
Further, the invention provides the colorized optical filtering thing of a kind of formation from described photosensitive resin composition.
And, the invention provides a kind of have formed from the substrate of the organic insulating film of described photosensitive resin composition.
Further, the invention provides a kind of have described photosensitive resin composition is carried out applying and the base material of the film formed.
Described film can be used as the surface of the Polarizer used in word processor, computer, TV, Plasmia indicating panel, liquid crystal indicator, and can be used for sun glasses eyeglass, there is the glasses lens of the number of degrees, be used in the finder lens of camera, the capping of apparatus, the glass of automobile, the glass of electric car, and can film or light guiding film be improved as luminance brightness and use.
According to time of the present invention, a kind of active solvent as photosensitive compoistion can be provided and oxime ester compound to favorable solubilities such as propylene glycol monomethyl ether acetate (PGMEA), the minimized as the oxime ester compound for the light trigger in photo-crosslinking can be realized accordingly, and after the photosensitive compoistion film like comprising this compound is applied after solvent flashing, being separated between sizing agent and light trigger can be reduced, thus improve the film characteristics after being cross-linked.The black matrix of high-quality, colorized optical filtering thing, longitudinal interval thing, insulating film, photo-crosslinking overlay film etc. can be manufactured accordingly.
Embodiment
Ketooxime ester compounds of the present invention and alpha-ketoxime ester cpds provide a kind of light trigger and comprise the photosensitive compounds of this light trigger, described light trigger, as a kind of Photoepolymerizationinitiater initiater that can be used as polymerizable compound, has the alkene class unsaturated link(age) of solvability and the light sensitivity that can simultaneously realize for solvent.
The invention provides a kind of compound that can be expressed as in chemical formula 1 to 4 and comprise the photosensitive resin composition that more than one can be expressed as a kind of compound in chemical formula 1 to 4.In following chemical formula 1 to 4, chemical formula 1 and 3 comprises ketoxime ester (ketoximester) structure, and chemical formula 2 and 4 comprises alpha-ketoxime ester structure.And, it is characterized in that, be combined with nitrophenyl with the double linked carbon atom of nitrogen-atoms of the ketoxime ester structure of following chemical formula 1 to 4.
[chemical formula 1]
[chemical formula 2]
[chemical formula 3]
[chemical formula 4]
In described chemical formula 1 to 4, R 1can be-CH 3,-C 2h 5, propyl group, butyl, hexyl, octyl group, benzoyl, cyclohexyl, R 2can be-CH 3,-C 2h 5, propyl group or benzoyl, R 3can be-H, or a is methyl or ethyl and b is-H or methyl
or
And in described chemical formula 2 and 4, X can be-O-,-S-,-Se-.
The preferred embodiment that can be expressed as the compound of described chemical formula 1 to 4 can be expressed as chemical formula.
[chemical formula 5]
[chemical formula 6]
[chemical formula 7]
[chemical formula 8]
[chemical formula 9]
[chemical formula 10]
[chemical formula 11]
[chemical formula 12]
[chemical formula 13]
[chemical formula 14]
[chemical formula 15]
[chemical formula 16]
[chemical formula 17]
[chemical formula 18]
[chemical formula 19]
[chemical formula 20]
[chemical formula 21]
[chemical formula 22]
[chemical formula 23]
[chemical formula 24]
synthesis comprises the ketooxime ester compounds of the chemical formula 1 of carbazole structure
The method manufacturing the compound of chemical formula 1 of the present invention such as can be synthesized by the building-up process described in following reaction formula 1.But be not limited thereto.
[reaction formula 1]
Carbazole compound and carboxylic acid chlorine (Carboxylic acid chloride) are carried out successively reacting with nitrocarboxylic acid chlorine and obtain acyl compounds under aluminum chloride existent condition.Described acyl compounds and oxammonium hydrochloride is made to carry out reacting and obtaining oxime compounds.Then make oxime compounds and carboxylic acid chlorine react under Triethylamine catalyst, just can obtain the light trigger with the oxime ester base that can be expressed as chemical formula 1.
synthesis has the oxime ester of the chemical formula 2 of biphenyl structural
Manufacture the method being expressed as the compound of chemical formula 2 of the present invention such as to be synthesized by the building-up process described in following reaction formula 2.But be not limited thereto.
[reaction formula 2]
Biphenol compound and carboxylic acid chlorine and nitrocarboxylic acid chlorine are carried out successively reacting and obtains acyl compounds under aluminum chloride existent condition.Described acyl compounds and oxammonium hydrochloride is made to carry out reacting and obtaining oxime compounds.Then make oxime compounds and carboxylic acid chlorine carry out reacting under Triethylamine catalyst and obtain being expressed as the ketooxime ester compounds of described chemical formula 2.
synthesis has the alpha-ketoxime ester of the chemical formula 3 of carbazole structure
The method manufacturing the compound of chemical formula 3 of the present invention such as can be synthesized by the building-up process described in following reaction formula 3.But be not limited thereto.
[reaction formula 3]
Carbazole compound and carboxylic acid chlorine and nitrocarboxylic acid chlorine are carried out successively reacting and obtains acyl compounds under aluminum chloride existent condition.Described acyl compounds is made to carry out reacting with isoamyl nitrous acid ester (Isoamyl nitrite) under hydrochloric acid catalyst and obtain alpha-ketoxime compound.Then make alpha-ketoxime compound and carboxylic acid chlorine carry out reacting under Triethylamine catalyst and obtain being expressed as the alpha-ketoxime ester cpds of described chemical formula 3.
synthesis has the alpha-ketoxime ester of the chemical formula 4 of biphenyl structural
Manufacture the method being expressed as the compound of chemical formula 4 of the present invention such as to be synthesized by the building-up process described in following reaction formula 4.But be not limited thereto.
[reaction formula 4]
Biphenol compound and carboxylic acid chlorine and nitrocarboxylic acid chlorine are carried out successively reacting and obtains acyl compounds under aluminum chloride existent condition.Described acyl compounds is made to carry out reacting with isoamyl nitrous acid ester (Isoamyl nitrite) under hydrochloric acid catalyst and obtain alpha-ketoxime compound.Then make alpha-ketoxime compound and carboxylic acid chlorine carry out reacting under Triethylamine catalyst and obtain being expressed as the alpha-ketoxime ester cpds of described chemical formula 4.
Photosensitive resin composition according to the present invention, as a kind of light trigger, is characterized in that, comprises more than one and can be expressed as a kind of oxime ester compound in described chemical formula 1 to 4.
Photosensitive resin composition of the present invention is as a kind of light trigger, both can be used alone a kind of oxime ester compound be expressed as in chemical formula 1 to 4, also two or more mixing can be used, known to these and other light trigger can also be mixed and use.
A kind of oxime ester compound be expressed as in chemical formula 1 to 4 is got more than one when mixing with other known light triggers and use, preferably, comprise in the total amount of whole light trigger more than 50 % by weight according to oxime ester compound of the present invention.That is, by making content reach more than 50 % by weight of whole light trigger total amount, thus the effect increasing solubleness and maintain light sensitivity is reached by means of a kind of oxime ester compound be expressed as in chemical formula 1 to 4.
Wherein, known light trigger comprises methyl phenyl ketone (acetophenone), 2, the acetophenones such as 2-diethoxy acetophenone (2,2-diethoxy acetophenone), p-dimethyl acetophenone, p-dimethylamino Propiophenone (p-dimethyl amino propiophenone), dichloroacetophenone (dichloro acetophenone), Trichloroacetophenon, p-tributyl methyl phenyl ketone (p-tert-butyl acetophenone), the benzophenone classes such as benzophenone, 2-chlormezanone, the two dimethylamino benzophenones of p, p'-, the st-yrax ethers such as benzyl, st-yrax, benzoin methyl ether, benzoin isopropyl ether, benzoin isobutyl ether, the sulphur compound such as benzyl dimethyl ketal, tea rubber xanthine (Tea-Oak Xanthine), 2-chlorine tea rubber xanthine, 2,4-diethyl tea rubber xanthine, 2-methyl tea rubber xanthine, 2-sec.-propyl tea rubber xanthine, the Anthraquinones such as 2-ethyl-anthraquinone, pungent tectoquinone (octa methyl anthraquinone), 1,2-benzo anthraquinone (1,2-benzanthraquinone), 2,3-biphenyl anthraquinones, the organo-peroxides such as Diisopropyl azodicarboxylate (azobisisobutyronitrile), benzoyl peroxide (Benzoyl peroxide), cumene hydroperoxide (Cumene peroxide), sulfydryl (thiol) compounds such as 2-mercaptobenzimidazole (2-mercapto benzoimidazole), 2-mercaptobenzoxazole (2-mercapto benzo oxazol), 2-mercaptobenzothiazole (2-mercapto benzo thiazole), the imidazolium compoundss such as 2-(o-chlorobenzene)-4,5-bis-(m-methoxyphenyl)-imidazoles dimer, the triaizine compounds such as p-methoxyl group triazine, 2, 4, 6-tri-(trichloromethyl)-s-triazine, 2-methyl-4, two (the trichloromethyl)-s-triazine of 6-, 2-[2-(5-methyl furan-2-base) vinyl]-4, two (the trichloromethyl)-s-triazine of 6-, 2-[2-(furans-2-base) vinyl]-4, two (the trichloromethyl)-s-triazine of 6-, 2-[2-(4-diethylamino-2-toluene) vinyl]-4, two (the trichloromethyl)-s-triazine of 6-, 2-[2-(3, 4-syringol) vinyl]-4, two (the trichloromethyl)-s-triazine of 6-, 2-(4-methoxyphenyl)-4, two (the trichloromethyl)-s-triazine of 6-, 2-(4-ethoxystyrene base)-4, two (the trichloromethyl)-s-triazine of 6-, 2-(4-n-butoxyphenyl)-4, two (the trichloromethyl)-s-triazines of 6-etc. have the triaizine compounds of monochloromethyl, or 2-benzyl-2-dimethylamino-1-(4-morpholinyl phenyl)-butane-1-to and so on aminoketone compounds.
And photosensitive resin composition of the present invention, as a kind of sensitizer, can also comprise cationic dyestuff such as fiber crops element (c ynin), xanthine, oxazines, thiazine, diarylmethanes, triarylmethane, pyrans etc.; The neutral dye such as merocyanine, tonka bean camphor, indigo element, aromatic amine, phthalocyanine (Phthalocyanine), azo, quinone, tea rubber xanthine photosensitizing dye; And the compound such as benzophenone class, acetophenones, st-yrax class, tea rubber xanthine, Anthraquinones, imidazoles, non-imidazole class, coumarins, ketone tonka bean camphor, three benzopyrans, triazines, phenylformic acid.
The macromolecular compound dissolving in solvent or alkaline aqueous solution can be comprised separately in photosensitive resin composition of the present invention, or comprise these macromolecular compounds and the mixture of photopolymerizable compound with alkene class unsaturated link(age).Wherein, specifically vinylformic acid is comprised in the macromolecular compound dissolving in solvent or alkaline aqueous solution or the photopolymerizable compound with alkene class unsaturated link(age), methacrylic acid, fumaric acid, toxilic acid, monomethyl fumarate, monomethyl ester, 2-Hydroxyethyl acrylate, 2-hydroxyethyl methylacrylate, ethylene glycol monomethyl ether acrylate (ethylene glycol monomethyl ether acrylate), ethylene glycol monomethyl ether methyl acrylate (ethylene glycol monomethyl ether methacrylat e), ethylene glycol list ethyl ether acrylate (ethylene glycol monoethyl ether acrylate), ethylene glycol list ether methyl acrylate (ethylene glycol monoethyl ether methacrylat e), glyceryl acrylate, glycerine methyl acrylate, acrylic acid amides, methacrylic, vinyl cyanide, methacrylonitrile, methacrylic ester, methyl methacrylate, ethyl propylene acid esters, ethyl methyl acrylate, isobutyl acrylate, isobutyl-methyl acrylate, 2-ethyl-hexyl acrylate ester, 2-ethyl-hexyl acrylate methyl esters, benzyl acrylate, benzyl acrylic methyl esters, ethylene glycol diacrylate, ethylene glycol diacrylate methyl esters, divinyl glycol diacrylate, tri-ethylene glycol diacrylate, tri-ethylene glycol diacrylate methyl esters, four ethylene glycol diacrylates, four ethylene glycol diacrylate methyl esters, methyltrimethylene glycol diacrylate methyl esters, propyleneglycoles diacrylate, propyleneglycoles diacrylate methyl esters, Viscoat 295, trimethylolpropane tris methyl acrylate, tetra methylol tetraacrylate, tetra methylol propane tetrapropylene acid methyl esters, penta butantetraol triacrylate, penta butantetraol three methyl acrylate, penta butantetraol tetraacrylate, penta butantetraol tetrapropylene acid methyl esters, diamyl butantetraol five acrylate, diamyl butantetraol five methyl acrylate, diamyl butantetraol six acrylate, diamyl butantetraol six methyl acrylate, 1,6 hexanediol diacrylate, 1,6-hexanediyl methyl esters, the monomer of cardo-epoxy diacrylate etc. and oligopolymer class, polyurethane acroleic acid (first) ester, obtain by the following method: the acid of polyvalent alcohols and single alkali or the sour condensation of many alkali are obtained polyester prepolyer, (methyl) vinylformic acid and this polyester prepolyer is made to carry out reacting and obtaining polyester acrylic (first) ester, make after this polyester acrylic (first) ester, polynary alcohol radical and the compound with two isocyanate group react, then (methyl) vinylformic acid is dropped into and reacts and obtain, epoxy acrylic (first) ester resin, obtains by the following method: the epoxy resin such as bisphenol A type epoxy resin, bisphenol f type epoxy resin, bisphenol-s epoxy resin, phenol or cresol novolak type epoxy resin, first rank phenol aldehyde type epoxy resin, triphenol methylmethane type epoxy resin, poly carboxylic acid poly glycidyl ester, poly alcohol poly glycidyl ester, aliphatics or cycloaliphatic epoxy resin, epoxy-amine resin, dihydroxyl benzene-type epoxy resin and (methyl) vinylformic acid carried out reacting and obtain.Further, the resin that described epoxy acrylic (first) ester resin and many alkali acid dehydrate are reacted and obtained can be used.These photopolymerizable compound also can be cardo system resins.
Especially, dissolve in the high molecular polymer of polymer as a kind of high transparent of solvent or alkaline aqueous solution, dissolve in image-developing liquor (solvent or alkaline aqueous solution).There are thermosetting resin, thermoplastic resin, photoresist etc. in this high molecular polymer, can be used alone or two or more mixing is used.Especially, the good person of thermotolerance, solvent resistance, reagent resistance is preferably used.
As the compound with alkene class unsaturated link(age), from the viewpoint of exposed photosensitive degree and each patience after telling on, select multi-functional (methyl) acrylic monomer may be advantageously.
In addition, the example as photosensitive resin composition can comprise pigment or tinting material, to be used as colorized optical filtering thing or the resist for the formation of black matrix.
Such as can have the blue-greenish colour of redness, green, blue and mazarine mixed system in tinting material, and magenta, yellow, black pigment.C.I. pigment yellow 12,13,14,17,20,24,55,83,86,93,109,110,117,125,137,139,147,148,153,154,166,168 such as can be had in pigment; C.I. pigment orange 36,43,51,55,59,61; C.I. pigment redness 9,97,122,123,149,168,177,180,192,215,216,217,220,223,224,226,227,228,240; C.I. pigment purple 19,23,29,30,37,40,50; C.I. pigment blueness 15,15:1,15:4,15:6,22,60,64; C.I. pigment green 7,36; C.I. pigment brown 23,25,26; C.I. pigment black 7; And titanium black etc.
According to time of the present invention, the substrate with longitudinal interval thing, black matrix, colorized optical filtering thing, organic insulating film is provided by this photosensitive resin composition, and the equipment of film that there is coating photosensitive resin composition and formed, film wherein can be the surface of the Polarizer used in plasma display panel, liquid crystal indicator, sun glasses eyeglass, the glasses lens with the number of degrees, the finder lens being used in camera, the capping of apparatus, the glass of automobile, the glass of electric car, luminance brightness improve film in film or light guiding film.
This use photosensitive compoistion and formed in the method for pattern and such as can have following method: apply photosensitive resin composition on substrate, and remove the volatile components such as desolventizing from the photosensitive compoistion layer of coating, then by photomask, the layer removing volatile component is exposed and video picture.The present invention is just being to provide this cured film obtained by process of setting.
Substrate such as can have the substrate of the surfacings such as glass substrate, silicon substrate, polycarbonate substrate, polyester substrate, aromatic polyamide substrate, polyamideimide-based plate, polyimide substrate, aluminium base, gallium arsenide substrate.
The method that substrate applies photosensitive resin composition is not particularly limited, and spin coater etc. can be used to be coated on substrate by known coating methods such as spin-coating method, casting, roller painting, slit & spin coating methods as an example.
Then the volatile component volatilizations such as solvent are made by heating.So will the layer formed by the solid substance of photosensitive compoistion be formed on substrate.Then the layer that the solid substance of photosensitive compoistion is formed is exposed, such as, can pass through photomask elective irradiation active energy ray.Exposure light source preferably uses Cooper-Hewitt lamp, middle medium pressure mercury lamp, high pressure mercury vapour lamp, extra-high-pressure mercury vapour lamp, xenon lamp, metal halid lamp etc. usually.And laser beams etc. also can with being the active energy line of exposure.
In addition, electric wire, α line, β line, γ line, x-ray, neutron line etc. can also be used.Irradiate active energy ray by photomask, wherein photomask can be such as the photomask being provided with the light shield layer for blocking active energy ray in glass pane surface.The part that light shield layer is not set in sheet glass be active energy ray rely through transmittance section, photosensitive compoistion is exposed to the pattern of this transmittance section and forms the non-irradiated regions of not irradiating active energy ray and irradiated the irradiation area of active energy ray.
The substrate of such exposure such as can carry out video picture with dilute alkaline aqueous solution.Photosensitive compoistion layer after such as can making exposure during video picture contacts with dilute alkaline aqueous solution, specifically, will can be formed with the substrate immersion of photosensitive compoistion layer on the surface in dilute alkaline aqueous solution, or sprays dilute alkaline aqueous solution with shower type.Basic cpd aqueous solution such as sodium carbonate, salt of wormwood, sodium hydroxide, potassium hydroxide, tetramethylammonium hydroxide (Tetramethylammonium hydroxide), organic amine and so on such as can be had in dilute alkaline aqueous solution.The non-irradiated regions of not irradiating active energy ray in photosensitive compoistion layer is removed by video picture.In addition, active energy ray irradiation area will maintain the original state and form pattern.
Usually can wash the substrate through video picture described above and dry and obtain required pattern.
Below by way of embodiments of the invention, the present invention is described in more detail.But these embodiments are just in order to illustrate the present invention, scope of the present invention is not limited to these embodiments.
[embodiment 1]
synthesis (chemical formula 5)
First step: the synthesis of (9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl) (4-nitrophenyl) m ethanone
The N-ethyl carbazole (N-ethylcarbazole) of 30.0g and the CH of 180ml oven dry is added in nitrogen atmosphere 2cl 2and dissolved.The AlCl of 21.1g is slowly dropped into after reactant being cooled to 0 DEG C 3.Now, under the internal temperature below 5 DEG C, the 2-methyl benzoyl chloride of 24.46g is slowly instilled wherein.Make temperature of reactor reach 0 DEG C after stirring 5 hours at normal temperatures again, then drop into the AlCl of 21.1g 3and the 4-nitrobenzoyl chloride of 29.37g is slowly dripped to avoid exceeding 5 DEG C.Stir after 3 hours, internal temperature adjusted to less than 0 DEG C, and slowly add the solution of reactor in the frozen water of 200ml, stir and carry out layer separation after 1 hour, then with the 1%NaOH of 200ml carry out neutralizing, wash after use MgSO 4dry organic layer, then remove desolventizing with convolution vaporizer, and refine with ethyl acetate and methylene dichloride and obtain the yellow solid that yield is the 55g of 77%.
1H-NMR(δ,ppm)DMSOd 6:1.37(t,3H),2.23(s,3H),4.58(q,2H),7.32(m,2H),7.38(d,1H),7.45(t,1H),7.83(s,2H),7.87(d,1H),7.99～8.01(m,3H),8.39(d,2H),8.73(d,2H)
Second step: the 2. synthesis of (E)-(9-ethyl-6-((hydroxyimino) (4-nitrophenyl) methyl)-9H-carb azol-3-yl) (o-tolyl) methanone
The 20g compound obtained in described first step is added in the ethanol of 68mL and the distilled water of 11mL.The oxammonium hydrochloride (hydroxylamine hydrochloride) of 3.3g and the sodium acetate of 6.4g is added in this reactant.After making reaction soln circulate 7 hours, add cold distilled water and form precipitation.The precipitation that filtration is formed also uses distilled water wash.The white solid of acquisition is obtained by cold washing with alcohol post-drying the faint yellow solid that yield is the 18.0g of 87%.
1H-NMR(δ,ppm)DMSOd 6:1.37(t,3H),2.23(s,3H),4.58(q,2H),7.32(m,2H),7.38(d,1H),7.45(t,1H),7.83(s,2H),7.87(d,1H),7.99～8.01(m,3H),8.39(d,2H),8.73(d,2H),10.9(s,1H,-OH)
Third step: the synthesis of (E)-1-((((9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl) (4-nitrop henyl) methylene) amino) oxy) ethanone
Under nitrogen atmosphere internal temperature is adjusted to less than 0 DEG C, and add the compound (15.0g), the methylene dichloride of 90mL and the triethylene amine (Triethylene amin e) of 3.27g that obtain in described second step, then slowly add the methylene dichloride Acetyl Chloride 98Min. of 2.54g being dissolved in 5mL and the solution obtained.Stir 3 hours after internal temperature being risen to 10 DEG C.In reaction soln, repeatedly add water and clean organic layer, and the solid chemical compound obtained by underpressure distillation is added in the acetonitrile (acet onitrile) of 100mL and the methylene dichloride of 100mL and carry out 1 hour circulate, then internal temperature is reduced to 0 DEG C and places after 3 hours and carry out filtering and obtaining the pale yellow crystals that yield is the 10.2g of 61%.Through confirming, described pale yellow crystals is compound shown in the chemical formula 5 as target product.Analytical results is shown below.
< analytical results >
(1) fusing point: 167.3 DEG C
（2） 1H-NMR(δ,ppm)CDCl 3:1.37(t,3H),2.23(s,3H),2.35(s,3H),4.58(q,2H),7.32(m,2H),7.38(d,1H),7.45(t,1H),7.83(s,2H),7.87(d,1H),7.99～8.01(m,3H),8.39(d,2H),8.73(d,2H)
(3) UV spectrometry result (methylene dichloride): λ max:263,299,342
(4) decomposition temperature (under stream of nitrogen gas, heat-up rate is 10 DEG C/min, and weight reduces by the temperature of 5%): 278.6 DEG C
[embodiment 2]
synthesis (chemical formula 9)
The synthesis of first step: 2-(4-nitrophenyl) acetyl chloride
The thionyl chloride of 2-(4-nitrophenyl) acetic acid and 140g of putting into 60g in nitrogen atmosphere also slowly improves temperature and circulate 4 hours at 95 DEG C.Water distilling apparatus is set after 4 hours at the same temperature and distills thionyl chloride at ambient pressure.Vacuum distillation plant is utilized to remove remaining thionyl chloride after the temperature of reactor is cooled to normal temperature.After-tack liquid is precipitated in sherwood oil and carries out filtering and obtaining yellow crystal.The quality of yellow crystal is 61g and yield is 90%.
1H-NMR(δ,ppm)CDCl 3:4.1(s,2H),7.67(d,2H),8.21(d,2H)
The synthesis of second step: 1-(9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl)-2-(4-nitrophen yl) ethanone
The N-ethyl carbazole (N-ethylcarbazole) of 50.0g and the CH of 300ml oven dry is added in nitrogen atmosphere 2cl 2and dissolved.By the AlCl of 35.2g after reactant being cooled to 0 DEG C 3be divided into three times slowly to drop into.Now, under the internal temperature below 3 DEG C, the 2-methyl benzoyl chloride (2-methylbenzoyl chloride) of 40.7g is slowly instilled wherein.Make temperature of reactor reach 0 DEG C after stirring 8 hours again at 15 DEG C, then drop into the AlCl of 35.2g 3and 2-(4-nitrophenyl) Acetyl Chloride 98Min. of 52.7g is slowly dripped to avoid exceeding 5 DEG C.Stir after 3 hours, internal temperature be reduced to less than 0 DEG C, and slowly add the solution of reactor in the frozen water of 500ml, stir and carry out layer separation after 1 hour, then with the 1%NaOH of 200ml carry out neutralizing, wash after use MgSO 4dry organic layer, then remove desolventizing with convolution vaporizer, and obtain with methyl alcohol and methylene dichloride recrystallization the yellow solid that yield is the 85g of 75%.
1H-NMR(δ,ppm)DMSOd 6:1.29(t,3H),2.48(s,3H),4.13(s,2H),4.53(q,2H),7.16(d,1H),7.36(t,1H),7.52(t,1H),7.66(m,4H),7.83(d,1H),7.98(d,1H),8.14(d,2H),8.65(s,1H),8.74(s,1H)
The synthesis of third step: 1-(9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl)-2-(4-nitrophen yl) ethanone
In reactor, put into the tetrahydrofuran (THF) (Tetrahydrofuran) of 300mL and add compound that second step described in 50g obtains and dissolved.35% hydrochloric acid of 52mL is slowly dripped after the temperature of reactant being cooled to less than 3 DEG C.In this reactant, the isoamyl nitrous acid ester (Isopentyl nitrite) of 12.6g is slowly dripped under internal temperature being maintained the condition of less than 3 DEG C.8 hours have been stirred after being warming up to 10 DEG C after dropping.The methylene dichloride of 400mL, the water of 400mL and washing is added removed the tetrahydrofuran (THF) as solvent by underpressure distillation after.Neutralize with saturated potassium carbonate and use MgSO after washing 4dry underpressure distillation after organic layer and obtain aqueous compound.In this aqueous compound, add ethanol and methylene dichloride and carry out recrystallization.Obtain the yellow crystal of 35g, and yield is 66%.
1H-NMR(δ,ppm)DMSOd 6:1.29(t,3H),2.48(s,3H),4.53(q,2H),7.16(d,1H),7.36(t,1H),7.55(m,2H),7.66(d,1H),7.74(d,1H),7.83(d,1H),7.98(d,1H),8.09(d,2H),8.33(d,2H),8.60(s,1H),8.74(s,1H),10.1(s,1H,-OH)
4th the step: (synthesis of (E)-2-(acetoxyimino)-1-(9-ethyl-6-(2-methylbenzoyl)-9H-carbaz ol-3-yl)-2-(4-nitrophenyl) ethanone
Under nitrogen atmosphere internal temperature is reduced to less than 0 DEG C, add the compound (30.0g), the methylene dichloride of 180mL and the triethylene amine of 6.18g that obtain in described third step, and slowly add the methylene dichloride Acetyl Chloride 98Min. of 4.80g being dissolved in 10mL and the solution obtained.Stir 3 hours after internal temperature being brought up to 10 DEG C.In reaction soln, repeatedly add water and clean organic layer, and the solid chemical compound obtained by underpressure distillation is added in ethyl acetate and methylene dichloride circulate 1 hour, then internal temperature is reduced to 0 DEG C and places after 3 hours and carry out filtering and obtaining the pale yellow crystals that yield is the 25g of 77%.Through confirming, described pale yellow crystals is the compound represented with chemical formula 9 as target product.Analytical results is shown below.
< analytical results >
(1) fusing point: 158.6 DEG C
（2） 1H-NMR(δ,ppm)CDCl 3:1.28(t,3H),2.48(s,3H),2.28(s,3H),4.48(q,2H),7.16(d,1H),7.36(t,1H),7.45(d,1H),7.52(t,1H),7.66(m,2H),7.92(d,1H),8.09(d,3H),8.33(d,2H),8.51(s,1H),8.87(s,1H)
(3) UV spectrometry result (methylene dichloride): λ max:263,298,344
(4) decomposition temperature (under stream of nitrogen gas, heat-up rate is 10 DEG C/min, and weight reduces by the temperature of 5%): 256.4 DEG C
[embodiment 3]
synthesis (chemical formula 13)
First step: the synthesis of (4-nitrophenyl) (4-(phenylthio) phenyl) methanone
The diphenyl sulfide of 50.0g and the CH of 300ml oven dry is added in nitrogen atmosphere 2cl 2and dissolved.The AlCl of 36.87g has slowly been dropped into after reactant being cooled to 0 DEG C 3.Now, the 4-nitrobenzoyl chloride of 51.3g is slowly dripped wherein to prevent from exceeding 5 DEG C.Stir after 3 hours and internal temperature is reduced to less than 0 DEG C, and slowly add the solution of reactor in the frozen water of 500ml, stir and carry out layer separation after 1 hour, then neutralize with the 1%NaOH of 200ml and use MgSO after washing 4dry organic layer, then remove desolventizing with convolution vaporizer, and refine with methyl alcohol and methylene dichloride and obtain the yellow solid that yield is the 72g of 80%.
1H-NMR(δ,ppm)CDCl 3:7.19～7.25(m,3H),7.41(d,2H),7.51(d,2H),7.58(d,2H),8.04(d,2H),8.39(d,2H)
The synthesis of second step: (Z)-(4-nitrophenyl) (4-(phenylthio) phenyl) methanone oxime
The 50g compound obtained in described first step is added in the ethanol of 350mL and the distilled water of 100mL.In described mixture, add the oxammonium hydrochloride (hydroxylamine hydrochl oride) of 10.67g and the sodium acetate of 20.9g and react.After making described reaction soln carry out 8 h cycle flowings, add cold distilled water and define precipitation.The precipitation that filtration is formed also uses distilled water wash.The post-drying of the yellow solid obtained by cold washing with alcohol and obtain the yellow solid that yield is the 46g of 88%.
1H-NMR(δ,ppm)DMSOd 6:7.19～7.25(m,3H),7.43(m,4H),7.63(d,2H),8.24(d,2H),8.50(d,2H),10.2(s,1H-OH)
The synthesis of third step: (Z)-(4-nitrophenyl) (4-(phenylthio) phenyl) methanone oxime
In nitrogen atmosphere, put into the methylene dichloride of 240ml and internal temperature is reduced to less than 0 DEG C.In this solution, add compound and 11.9g triethylene amine that 40.0g obtains from described second step, and slowly add the methylene dichloride Acetyl Chloride 98Min. of 9.23g being dissolved in 20mL and the solution obtained.3 hours have been stirred after internal temperature being brought up to 10 DEG C.In reaction soln, repeatedly add water and wash organic layer, and the solid chemical compound obtained by underpressure distillation is added in normal hexane and methylene dichloride carry out 1 hour circulate, internal temperature is reduced to 0 DEG C and places after 3 hours and carry out filtering and obtaining the pale yellow crystals that yield is the 38g of 85%.Through confirming, described pale yellow crystals is the compound represented with chemical formula 13 as target product.Analytical results is arranged as follows.
< analytical results >
(1) fusing point: 124.3 DEG C
（2） 1H-NMR(δ,ppm)CDCl 3:2.09(s,3H),7.23(m,3H),7.42(m,4H),7.65(d,2H),8.21(d,2H),8.49(d,2H)
(3) UV spectrometry result (methylene dichloride): λ max:241,328
(4) decomposition temperature (under stream of nitrogen gas, heat-up rate is 10 DEG C/min, and weight reduces by the temperature of 5%): 258.6 DEG C
[embodiment 4]
synthesis (chemical formula 19)
The synthesis of first step: 2-(4-nitrophenyl) acetyl chloride
Put into the thionyl chloride of 2-(4-nitrophenyl) acetic acid of 60g and 140g under nitrogen atmosphere and slowly improve temperature and at 95 DEG C, carry out 4 hours circulate.Water distilling apparatus is set after 4 hours at the same temperature and distills thionyl chloride at ambient pressure.Vacuum distillation plant is utilized to eliminate remaining thionyl chloride after the temperature of reactor is cooled to normal temperature.The viscous liquid remained is precipitated in sherwood oil and carries out filtering and obtaining yellow crystal.The quality of yellow crystal is 61g and yield is 90%.
1H-NMR(δ,ppm)CDCl 3:4.1(s,2H),7.67(d,2H),8.21(d,2H)
The synthesis of second step: 2-(4-nitrophenyl)-1-(4-(phenylthio) phenyl) ethanone
Add the CH that the diphenyl sulfide of 50.0g and 300ml were dried under nitrogen atmosphere 2cl 2and dissolved.The AlCl of 36.87g has slowly been dropped into after reactant being cooled to 0 DEG C 3.Now, 2-(4-nitrophenyl) Acetyl Chloride 98Min. of 55.18g is slowly dripped under the internal temperature below 5 DEG C wherein.Temperature of reaction is adjusted to normal temperature and after carrying out the stirring of 5 hours, internal temperature is reduced to less than 0 DEG C, and in the frozen water of 300ml, slowly add the solution of reactor, stir after 1 hour and carry out layer separation, then neutralize with the 1%NaOH of 200ml and use MgSO after washing 4dry organic layer, then remove desolventizing with convolution vaporizer, and refine with methyl alcohol and methylene dichloride and obtain the yellow solid that yield is the 75g of 80%.
1H-NMR(δ,ppm)CDCl 3:4.14(s,2H),7.19～7.25(m,3H),7.41(d,2H),7.52(d,2H),7.68(d,2H),7.74(d,2H),8.14(d,2H)
Third step: the synthesis of (E)-2-(hydroxyimino)-2-(4-nitrophenyl)-1-(4-(phenylthio) pheny l) ethanone
Put into the tetrahydrofuran (THF) of 420mL in the reactor and add compound that 70g obtains from described second step and dissolved.35% hydrochloric acid of 22.9mL has slowly been dripped after the temperature of reactant being cooled to less than 3 DEG C.Under internal temperature being maintained the condition of less than 3 DEG C, the isoamyl nitrous acid ester of 35.2g is slowly instilled in this reactant.Then 8 hours have been stirred after being warming up to 10 DEG C.The methylene dichloride of 400mL, the water of 400mL washing is added removed the tetrahydrofuran (THF) as solvent by underpressure distillation after.Neutralize with saturated potassium carbonate and use MgSO after washing 4carry out underpressure distillation after drying organic layer and obtain aqueous compound.In this aqueous compound, add sherwood oil and methylene dichloride and carried out recrystallization.Obtain the yellow crystal of 50g, and yield is 66%.
1H-NMR(δ,ppm)DMSOd 6:7.19～7.25(m,3H),7.41(d,2H),7.52(d,2H),7.68(d,2H),7.74(d,2H),8.14(d,2H),12.5(s,1H,-OH)
4th step: the synthesis of (E)-2-(acetoxyimino)-2-(4-nitrophenyl)-1-(4-(phenylthio) phenyl) ethanone
Under nitrogen atmosphere internal temperature is reduced to less than 0 DEG C, add compound, the methylene dichloride of 300mL and the triethylene amine of 13.77g that 50g obtains from described third step, and slowly add the methylene dichloride Acetyl Chloride 98Min. of 10.68g being dissolved in 15mL and the solution obtained.3 hours have been stirred after internal temperature being brought up to 10 DEG C.In reaction soln, repeatedly add water and clean organic layer, and the solid chemical compound obtained by underpressure distillation is added in sherwood oil and methylene dichloride having carried out recrystallization.Obtain the pale yellow crystals that yield is the 45g of 81% after filtration.Through confirming, described pale yellow crystals is compound shown in the chemical formula 15 as target product.Analytical results is shown below.
< analytical results >
(1) fusing point: 116.2 DEG C
（2） 1H-NMR(δ,ppm)CDCl 3:2.28(s,3H)7.19～7.25(m,3H),7.41(d,2H),7.52(d,2H),7.68(d,2H),8.09(d,2H),8.33(d,2H)
(3) UV spectrometry result (methylene dichloride): λ max:242,332
(4) decomposition temperature (under stream of nitrogen gas, heat-up rate is 10 DEG C/min, and weight reduces by the temperature of 5%): 251.3 DEG C
[embodiment 5 ~ embodiment 10]
Compound as shown in table 1 below has been synthesized according to the manufacture method of described embodiment 1 to 4.
[table 1]
[embodiment 11]
Manufacture transparent anti-corrosion composition
In the acrylic copolymer of 17g, drop into the propyleneglycoles list ether of the diamyl erythritol Ethyl acrylate of 13.6g, the compound obtained from embodiment 1 of 1.5g and 67g, and fully stir and obtain transparent feel photosensitiveness anti-corrosion composition.
[embodiment 12]
Manufacture black anti-corrosion constituent
In the acrylic copolymer of 10g, drop into the compound, the melanochrome of 7.48g and the propyleneglycoles list ether of 25g that obtain from embodiment 1 of the diamyl erythritol Ethyl acrylate of 13.6g, 2.0g, and fully stir and obtain black-colored photosensitive anti-corrosion composition.
[embodiment 13]
Manufacture red anti-corrosion composition
In the acrylic copolymer of 10g, drop into the propyleneglycoles list ether of the diamyl erythritol Ethyl acrylate of 13.6g, the compound obtained from embodiment 1 of 1.5g, the haematochrome of 192.25g and 49g, and fully stir and obtain red sensitive anti-corrosion composition.
[embodiment 14]
Manufacture transparent anti-corrosion composition
In the acrylic copolymer of 17g, drop into the propyleneglycoles list ether of the diamyl erythritol Ethyl acrylate of 13.6g, the compound obtained from embodiment 4 of 1.5g and 67g, and fully stir and obtain transparent feel photosensitiveness anti-corrosion composition.
[embodiment 15]
Manufacture black anti-corrosion constituent
In the acrylic copolymer of 10g, drop into the propyleneglycoles list ether of the diamyl erythritol Ethyl acrylate of 13.6g, the compound obtained from embodiment 4 of 2.0g, the melanochrome of 7.48g and 25g, and fully stir and obtain black-colored photosensitive anti-corrosion composition.
[embodiment 16]
Manufacture red anti-corrosion composition
In the acrylic copolymer of 10g, drop into the propyleneglycoles list ether of the diamyl erythritol Ethyl acrylate of 13.6g, the compound obtained from embodiment 4 of 1.5g, the haematochrome of 192.25g and 49g, and fully stir and obtain red sensitive anti-corrosion composition.
Comparative example
Manufacture the photosensitivity anti-corrosion composition comprising the compound being expressed as chemical formula 25 and chemical formula 26.
[chemical formula 25]
[chemical formula 26]
[comparative example 1]
Manufacture transparent anti-corrosion composition
In 17g acrylic copolymer, drop into the propyleneglycoles list ether of the diamyl erythritol Ethyl acrylate of 13.6g, the compound representated by described chemical formula 25 of 1.5g and 67g, and fully stir and obtain transparent feel photosensitiveness anti-corrosion composition.
[comparative example 2]
Manufacture black anti-corrosion constituent
In the acrylic copolymer of 10g, drop into the propyleneglycoles list ether of the diamyl erythritol Ethyl acrylate of 13.6g, the compound representated by described chemical formula 25 of 2.0g, the melanochrome of 7.48g and 25g, and fully stir and obtain black-colored photosensitive anti-corrosion composition.
[comparative example 3]
Manufacture red anti-corrosion composition
In the acrylic copolymer of 10g, drop into the propyleneglycoles list ether of the diamyl erythritol Ethyl acrylate of 13.6g, the compound representated by described chemical formula 25 of 1.5g, the haematochrome of 192.25g and 49g, and fully stir and obtain red sensitive anti-corrosion composition.
[comparative example 4]
Manufacture transparent anti-corrosion composition
In 17g acrylic copolymer, drop into the propyleneglycoles list ether of the diamyl erythritol Ethyl acrylate of 13.6g, the compound representated by described chemical formula 26 of 1.5g and 67g, and fully stir and obtain transparent feel photosensitiveness anti-corrosion composition.
[comparative example 5]
Manufacture black anti-corrosion constituent
In the acrylic copolymer of 10g, drop into the propyleneglycoles list ether of the diamyl erythritol Ethyl acrylate of 13.6g, the compound representated by described chemical formula 26 of 2.0g, the melanochrome of 7.48g and 25g, and fully stir and obtain black-colored photosensitive anti-corrosion composition.
[comparative example 6]
Manufacture red anti-corrosion composition
In the acrylic copolymer of 10g, drop into the propyleneglycoles list ether of the diamyl erythritol Ethyl acrylate of 13.6g, the compound representated by described chemical formula 26 of 1.5g, the haematochrome of 192.25g and 49g, and fully stir and obtain red sensitive anti-corrosion composition.
Following evaluation has been carried out to the photosensitive compoistion obtained.
Described photosensitive compoistion is coated with 15 seconds with the rotating speed of 800 ~ 900rpm by spin coater, then toasts 100 seconds with the temperature of 90 DEG C on hot plate.Utilize predetermined mask and using extra-high-pressure mercury vapour lamp as after light source exposes, select at 25 DEG C the potassium hydroxide solution of 0.04% carry out the rotation video picture of 60 seconds after wash.Wash and after drying, at 230 DEG C, carry out the baking of 40 minutes and obtain pattern.Following evaluation has been carried out to the pattern obtained.Table 1 is shown in as the Photoepolymerizationinitiater initiater of each photosensitive compoistion and various evaluation result.
(1) adhesion
According to the test method of JIS D0202, in the film of heating in 30 minutes, grid-like CROSS CUT (cross cut) is put at backward 200 DEG C of exposure imaging, then strip device by glassine paper and carry out stripping test, and evaluate by observing grid-like stripping state.Be expressed as zero in the situation be not stripped completely, and confirm the situation that is stripped be expressed as ×.
(2) alkali resistance
After video picture, will toast 30 minutes at 230 DEG C, then film is soaked in the NaOH of 5% 24 hours, soak in the 4%KOH of 50 DEG C 10 minutes, soak after 5 minutes in the 1%NaOH of 80 DEG C and observe state.There is no appearance change and the situation be not stripped is expressed as zero, occurring that the situation that sign peeled off by resist is expressed as △, and find the situation that resist is peeled off be expressed as ×.
(3) light sensitivity evaluation
The each photosensitive resin composition spin coater formed as mentioned above is coated on glass substrate (S amsung Corning Co., Ltd. manufactures, Eagle2000), and at 90 DEG C, toasted 1 minute with hot-plate.Measure with contact pin type film thickness determination device (KLA-Tencor company manufactures, α-step500) after oven dry, the thickness of result black anti-corrosion film and transparent negativity etchant resist is respectively 1 micron and 5 microns.Then this sample is exposed by mask with high pressure mercury vapour lamp.Then carry out sprinkling video picture with the potassium hydroxide aqueous solution that concentration is 0.04% and obtain corrosion-resisting pattern.Indicate the correct exposure amount (mJ/sqcm) that can form the size identical with the mask pattern of 40 microns.That is, because namely the resist that exposure is few uses less luminous energy also can form image, therefore represent that light sensitivity is high.
(4) albinism
The light trigger of synthesis will be comprised and each photosensitive resin composition spin coater formed is coated on glass substrate.Wherein, produce crystallization when causing rotary coating because of the different solubility of light trigger and make the bad situation of coated side situation be expressed as ×, in drying process, make owing to producing crystallization the gloomy situation in surface be expressed as △ after film is formed, do not produce crystallization because being fully dissolved in anti-corrosion composition when forming film, the situation of clean surface is expressed as zero.
These results are shown in following table 2.
[table 2]
From the above results, the adhesion comprising the photosensitive compoistion of oxime ester based compound and α-oxime ester based compound according to of the present invention and alkali resistance good, and there is not the albinism of film.And, can also see according to the light sensitivity of oxime ester based compound of the present invention and α-oxime ester based compound good.

Claims (12)

1. an oxime ester compound, chemical formula is:
Wherein, R 1for-CH 3,-C 2h 5, propyl group, butyl, hexyl, octyl group, benzoyl or cyclohexyl, R 2for-CH 3,-C 2h 5, propyl group or benzoyl, R 3for-H, or a is methyl or ethyl and b
For-H or methyl
or
2. an alpha-ketoxime ester cpds, chemical formula is:
Wherein, R 1for-CH 3,-C 2h 5, propyl group, butyl, hexyl, octyl group, benzoyl or cyclohexyl, R 2for-CH 3,-C 2h 5, propyl group or benzoyl, R 3for-H, or a is methyl or ethyl and b
For-H or methyl
or and X is-O-,-S-or-Se-.
3. an oxime ester compound, chemical formula is:
Wherein, R 1for-CH 3,-C 2h 5, propyl group, butyl, hexyl, octyl group, benzoyl or cyclohexyl, R 2for-CH 3,-C 2h 5, propyl group or benzoyl, R 3for-H, or a is methyl or ethyl and b
For-H or methyl
or
4. an alpha-ketoxime ester cpds, chemical formula is:
Wherein, R 1for-CH 3,-C 2h 5, propyl group, butyl, hexyl, octyl group, benzoyl or cyclohexyl, R 2for-CH 3,-C 2h 5, propyl group or benzoyl, R 3for-H, or a is methyl or ethyl and b
For-H or methyl
or and X is-O-,-S-or-Se-.
5. a photosensitive resin composition, is characterized in that, comprising:
More than one compounds selected from the compound representated by the compound representated by chemical formula 1 as claimed in claim 1, chemical formula 2 as claimed in claim 2, the compound representated by chemical formula 3 as claimed in claim 3 and the compound representated by chemical formula 4 as claimed in claim 4;
Dissolve in the macromolecular compound of solvent or alkaline aqueous solution and/or there is the photopolymerizable compound of alkene class unsaturated link(age).
6. photosensitive resin composition as claimed in claim 5, it is characterized in that, described constituent is also comprising toner or pigment.
7. a longitudinal interval thing, is characterized in that, is formed from photosensitive resin composition according to claim 5.
8. a black matrix, is characterized in that, is formed from photosensitive resin composition according to claim 5.
9. a colorized optical filtering thing, is characterized in that, is formed from photosensitive resin composition according to claim 5.
10. a substrate, is characterized in that, has the organic insulating film formed from photosensitive resin composition according to claim 5.
11. 1 kinds of base materials, is characterized in that, have and are carried out applying by photosensitive resin composition according to claim 5 and the film formed.
12. base materials as claimed in claim 11, it is characterized in that, described film is used as the surface of the Polarizer used in word processor, computer, TV, plasma display panel, liquid crystal indicator, and for sun glasses eyeglass, the glasses lens with the number of degrees, the finder lens being used in camera, the capping of apparatus, the glass of automobile, the glass of electric car, and can film or light guiding film be improved as luminance brightness and use.
CN201310271006.8A 2013-07-01 2013-07-01 High-photosensibility oxime ester photopolymerization initiator and photopolymerization composition containing same Pending CN104276995A (en)

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