WO2017059772A1 - 一种含芴肟酯类光引发剂、其合成、含有其的感光性树脂组合物及其应用 - Google Patents

一种含芴肟酯类光引发剂、其合成、含有其的感光性树脂组合物及其应用 Download PDF

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WO2017059772A1
WO2017059772A1 PCT/CN2016/099745 CN2016099745W WO2017059772A1 WO 2017059772 A1 WO2017059772 A1 WO 2017059772A1 CN 2016099745 W CN2016099745 W CN 2016099745W WO 2017059772 A1 WO2017059772 A1 WO 2017059772A1
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Prior art keywords
group
substituted
linear
branched alkyl
oxime ester
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PCT/CN2016/099745
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English (en)
French (fr)
Inventor
钱晓春
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常州强力电子新材料股份有限公司
常州强力先端电子材料有限公司
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Priority claimed from CN201510645925.6A external-priority patent/CN106749776B/zh
Priority claimed from CN201510646816.6A external-priority patent/CN106565864B/zh
Priority claimed from CN201610210118.6A external-priority patent/CN107272336A/zh
Application filed by 常州强力电子新材料股份有限公司, 常州强力先端电子材料有限公司 filed Critical 常州强力电子新材料股份有限公司
Priority to KR1020187012617A priority Critical patent/KR102189685B1/ko
Priority to JP2018517895A priority patent/JP6641468B2/ja
Publication of WO2017059772A1 publication Critical patent/WO2017059772A1/zh

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Classifications

    • 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
    • G03F7/032—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C251/00—Compounds containing nitrogen atoms doubly-bound to a carbon skeleton
    • C07C251/32—Oximes
    • C07C251/62—Oximes having oxygen atoms of oxyimino groups esterified
    • C07C251/64—Oximes having oxygen atoms of oxyimino groups esterified by carboxylic acids
    • C07C251/66—Oximes having oxygen atoms of oxyimino groups esterified by carboxylic acids with the esterifying carboxyl groups bound to hydrogen atoms, to acyclic carbon atoms or to carbon atoms of rings other than six-membered aromatic rings
    • C—CHEMISTRY; METALLURGY
    • 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
    • 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

Definitions

  • the invention belongs to the field of organic chemistry, and in particular relates to an oxime ester-containing photoinitiator, a synthesis thereof, a photosensitive resin composition containing the same, and an application thereof.
  • a liquid crystal layer is usually disposed between two substrates, and each of the substrates is provided with opposing electrodes, and on the inner side of one of the substrates, opposite to the liquid crystal layer, red (R) is prepared.
  • a color filter layer formed of each of green (G), blue (B), and black. Among them, the color weights of the respective colors of R, G, and B are usually distinguished in the form of a setting matrix.
  • the methods for producing color filters mainly include dyeing method, printing method, pigment dispersion method and anode method, and the pigment dispersion method is most widely used.
  • the pigment dispersion method is to apply a photosensitive resin composition containing a coloring material on a transparent substrate, and then perform image exposure, development, and post-cure as necessary, and repeat the processes to form a color filter image.
  • the color filter pixels obtained by this method have high positioning accuracy and film thickness precision, excellent durability (such as light resistance and heat resistance), and few pinhole defects.
  • BM is usually arranged in a grid, strip shape or mosaic between red, green and blue patterns to prevent the thin film transistor from malfunctioning due to light leakage or to prevent color mixing between colors. Contrast, which requires BM to have a high opacity. Therefore, how to form a high-efficiency BM using a photosensitive resin dispersed with a light-shielding pigment or a dye at low cost has become a research hot spot.
  • the main performance is: the difference in crosslink density between the exposed portion and the unexposed portion and the exposed portion; the pigment insoluble in the developer lowers the developability, thereby causing the linearity of the pattern to be lowered, or the pattern to be peeled off, causing residue; .
  • oxime ester compounds as photoinitiators has been well known to those skilled in the art and their activity is outstanding in color filter films (RGB), black matrix (BM), photo-spacers, ribs (rib). ) and other applications in the field of high-end photoresist.
  • the commonly used oxime ester photoinitiator is mainly composed of carbazole or diphenyl sulfide group, and the cost is high, and the solubility with the matrix resin is often insufficient, so that the sensitivity is not affected. A lower cost and better solubility photoinitiator is the goal pursued.
  • the object of the present invention is to provide a photoinitiator containing an oxime ester, a synthesis thereof, a photosensitive resin composition containing the same, and an application thereof, which is simple in synthesis, low in cost, and good in solubility, and is applied to a photocuring combination. Excellent storage stability and film forming properties.
  • an oxime ester-containing photoinitiator having the structure represented by the following formula (I): Wherein R 1 each independently represents hydrogen, halogen, C 1 -C 20 linear or branched alkyl, C 4 -C 20 cycloalkylalkyl, C 2 -C 20 alkenyl, these groups -CH 2 - in the group may be optionally substituted by -O-; R 2 represents a C 3 -C 20 cycloalkyl group, a C 4 -C 20 cycloalkylalkyl group or an alkylcycloalkyl group, or represents -R 4 -COO-R 5 , wherein R 4 represents a C 1 -C 10 alkylene group, a C 3 -C 10 cycloalkylene group, a C 6 -C 20 arylene group or a substituted arylene group, alkylene group wherein the non-terminal -
  • R 1 each independently represents hydrogen, halogen, a C 1 -C 10 linear or branched alkyl group, a C 4 -C 10 cycloalkylalkyl group, and -CH 2 - in these groups may be It is optionally substituted by -O-.
  • R 1 each independently represents hydrogen, a C 1 -C 6 straight or branched alkyl group, and one or two non-adjacent -CH 2 - in the alkyl group may be optionally -O - replaced.
  • R 2 above represents a C 3 -C 10 cycloalkyl group, a C 4 -C 10 cycloalkylalkyl group or an alkylcycloalkyl group.
  • R 2 represents a C 3 -C 6 cycloalkyl group, a C 1 -C 4 linear or branched alkyl group substituted at the end with a C 3 -C 6 cycloalkyl group, and a C 1 -C 4 alkane A substituted C 3 -C 6 cycloalkyl group.
  • R 4 represents a C 1 -C 8 alkylene group, a C 3 -C 8 cycloalkylene group, a phenylene group, a substituted phenylene group, wherein the non-terminal-CH 2 - in the alkylene group and -CH 2 - in the cycloalkyl group may be optionally substituted by -O-, and CH in the phenyl group may be optionally substituted by N.
  • R 4 represents a C 1 -C 4 alkylene group, a C 3 -C 6 cycloalkylene group, a phenylene group or a pyridylene group.
  • R 5 above represents a C 1 -C 10 linear or branched alkyl group, a C 3 -C 10 cycloalkyl group, a C 4 -C 10 alkylcycloalkyl group or a cycloalkylalkyl group.
  • R 5 represents a C 1 -C 6 linear or branched alkyl group, and a C 1 -C 4 linear or branched alkyl group substituted by a C 3 -C 6 cycloalkyl group.
  • R 3 represents a C 1 -C 10 linear or branched alkyl group, a C 4 -C 10 cycloalkylalkyl group, a phenyl group or a C 2 -C 8 alkenyl group.
  • R 3 represents a C 1 -C 6 linear or branched alkyl group, and a C 1 -C 4 linear or branched alkyl group having a terminal substituted with a C 3 -C 6 cycloalkyl group.
  • a photosensitive resin composition comprising the following components: (A) a compound having an ethylenically unsaturated bond, and the compound having an ethylenically unsaturated bond is used for radical polymerization a reaction; (B) a photoinitiator which is at least one of the compounds having a quinone compound represented by the formula (I):
  • X represents a linker or a carbonyl group;
  • R 1 can form a ring;
  • R 2 and R 3 independently of each other represent a C 1 -C 20 linear or branched alkyl group, a C 3 -C 20 cycloalkyl group,
  • the photosensitive resin composition includes, in parts by mass, 0.1 to 100 parts of a compound having an ethylenically unsaturated bond, 1 to 5 parts of a photoinitiator, and 0 to 50 parts of a coloring agent, preferably having an ethylenically unsaturated bond.
  • the mass portion of the compound is 30 to 80 parts, more preferably 40 to 70 parts; and preferably the mass part of the coloring agent is more than 0 and 80 parts or less, more preferably 5 to 40 parts.
  • the compound having the quinone compound represented by the formula (I) as a main structure has the following structure:
  • A represents hydrogen, nitro, C 1 -C 10 linear or branched alkyl
  • X represents a linker or carbonyl
  • the compound having the quinone compound represented by the formula (I) as a main structure includes the structure shown below:
  • the derivative compound having the oxime compound represented by the formula (I) as a main structure is a compound represented by the formula (III), (IV), (V):
  • M represents a linking group formed by dimerization of R 1 , R 2 and R 3
  • M is an empty, C 1 -C 24 linear or branched alkylene group, and a C 6 -C 36 arylene group Or a heteroarylene group, -CH 2 - in M is optionally substituted by sulfur, oxygen, NH or a carbonyl group, and the hydrogen atom is optionally substituted by OH or NO 2 .
  • the derivative compound having the oxime compound represented by the formula (I) as a main structure is a compound having the following structure:
  • the photosensitive resin composition contains an alkali-soluble resin (D), and preferably the mass-soluble resin is used in an amount of more than 0 and not more than 80 parts, more preferably 20 to 60 parts.
  • D alkali-soluble resin
  • Another object of the present invention is to provide a process for the preparation of the above-mentioned oxime ester-containing photoinitiator having the structure of the formula (I), wherein R 2 in the formula (I) represents a C 3 - C 20 cycloalkyl group, C 4 when -C 20 cycloalkylalkyl or alkylcycloalkyl, the preparation process comprises the steps of:
  • the raw material b is R 2 '-CO-Cl, wherein R 2 ' represents R 2 or R 2 -CH 2 -, specifically, when X in the formula (I) is empty, R 2 ' represents R 2 , when X Is a carbonyl group, then R 2 ' represents R 2 -CH 2 -;
  • intermediate b when X is empty, intermediate a undergoes deuteration reaction under the action of hydroxylamine hydrochloride and sodium acetate to form intermediate b; when X is a carbonyl group, it exists in organic solvent and concentrated hydrochloric acid. Next, intermediate a and nitrite or nitrite at room temperature to carry out the oximation reaction to form intermediate b;
  • R 2 in the formula (I) represents -R 4 -COO-R 5 , wherein R 4 represents a C 1 -C 10 alkylene group, a C 3 -C 10 cycloalkylene group, a C 6 -C 20 arylene or substituted arylene group, alkylene group wherein the non-terminal -CH 2 - cycloalkyl and the -CH 2 - can optionally be replaced by -O-, aryl group may be CH Optionally substituted by N; R 5 represents a C 1 -C 20 linear or branched alkyl group, a C 3 -C 20 cycloalkyl group, a C 4 -C 20 alkylcycloalkyl group or a cycloalkyl group; An alkyl group, a C 6 -C 30 aryl or substituted aryl group, a C 7 -C 30 aralkyl group, a C 2 -C 20 alkenyl group, wherein -
  • R 2 ' represents R 4 or CH 2 -R 4 , specifically, when X in the formula (I) is empty, R 2 ' represents R 4 , and when X is a carbonyl group, R 2 ' Represents CH 2 -R 4 ;
  • intermediate b' is heated and refluxed with starting material c, ie, alcohol R 5 OH in the presence of concentrated sulfuric acid or heteropoly acid, to effect an esterification reaction to obtain intermediate b',
  • the raw materials used are all known compounds in the prior art, and can be easily prepared commercially or by a known synthesis method.
  • steps (1)-(3) and (1')-(4') are conventional reactions in the art for synthesizing similar compounds.
  • the specific reaction conditions are readily ascertainable to those skilled in the art on the basis of the synthetic idea disclosed in the present invention.
  • the reaction temperature is usually -10 to 30 °C.
  • the organic solvent to be used is not particularly limited as long as it can dissolve the raw material and has no adverse effect on the reaction, such as dichloromethane, dichloroethane, benzene, toluene, xylene, and the like.
  • the reaction temperature may be normal temperature, and the organic solvent to be used is not particularly limited as long as it can dissolve the raw materials and has no adverse effect on the reaction, such as dichloromethane, dichloroethane, Benzene, toluene, xylene, etc.
  • Aluminum trichloride or zinc chloride can be introduced into the reaction system by dropwise addition or in portions.
  • the deuteration reaction in the step (2) is carried out in a solvent system, and the solvent to be used is not particularly limited as long as the raw material can be dissolved and the reaction is not adversely affected.
  • the esterification reaction in the step (2') may or may not be carried out as needed.
  • a solvent the kind thereof is not particularly limited as long as it can dissolve the raw material and has no adverse effect on the reaction.
  • the deuteration reaction in the step (2) and the step (3') is carried out in a solvent system, and the solvent to be used is not particularly limited as long as the raw material can be dissolved and the reaction is not adversely affected.
  • the solvent used may be a mixed solvent of an alcohol and water, preferably a mixed solvent of ethanol and water.
  • the reaction is carried out under reflux with heating.
  • X is a carbonyl group
  • the organic solvent used may be dichloromethane, benzene, toluene, tetrahydrofuran or the like
  • the nitrite used may be selected from the group consisting of ethyl nitrite, isoamyl nitrite, isooctyl nitrite, etc.
  • the nitrate may be selected from sodium nitrite, potassium nitrite, and the like.
  • the esterification reaction in the step (3) is carried out in an organic solvent, and the kind of the solvent is not particularly limited as long as it can dissolve the raw material and has no adverse effect on the reaction, such as dichloromethane, dichloroethane, benzene, toluene, and Toluene, etc.
  • the esterification reaction in the step (4') is carried out in an organic solvent, and the type of the solvent is not particularly limited as long as the raw material can be dissolved and the reaction is not adversely affected, and dichloromethane, dichloroethane, benzene, and xylene are preferable. .
  • the oxime ester-containing compound represented by the above formula (I) may also be polymerized by R 1 (one or two), R 2 or R 3 to form a dimer. These dimerization products are believed to exhibit similar application properties to the oxime ester-containing photoinitiators represented by formula (I).
  • Another object of the present invention is to provide the use of the oxime ester-containing photoinitiator represented by the above formula (I) in a photocurable composition (i.e., a photosensitive composition).
  • a photocurable composition i.e., a photosensitive composition
  • the photoinitiator can be applied to color resists (RGB), black matrix (BM), photo-spacers, ribs, dry films, semiconductor photoresists, inks, and the like. aspect.
  • the photoinitiator has excellent solubility in application, good storage stability, low exposure requirement (ie, high sensitivity), and exhibits good developability and pattern integrity.
  • the polymerizable composition of the present invention may be used in combination with an alkali-soluble resin.
  • the alkali-soluble resin (D) preferably functions as a binder, and is preferably soluble alkali-developed for the developer used in the development treatment step when forming an image pattern.
  • the liquid is preferably an alkali-soluble resin containing a carboxyl group-containing copolymer, and particularly preferably a copolymer of an ethylenically unsaturated monomer having one or more carboxyl groups and another copolymerizable ethylenically unsaturated monomer.
  • Another object of the present invention is to provide an application of the above photosensitive resin composition for preparing a color filter film, a black matrix, a photo spacer, a rib gate, and a photoresist for a dry film.
  • composition of the photosensitive resin composition of the present invention is reasonable in composition, and the composition has a very high sensitivity, and can be cross-linked and cured well at a very low exposure dose, and the curing effect is excellent.
  • the film made of the composition has a flat edge without defects, no scum, a clear and clear pattern, and high hardness.
  • the prepared filter has high optical transparency, no light leakage, and is produced at a very low exposure dose, and has high precision, flatness and durability.
  • an exemplary embodiment of the present application provides an oxime ester-containing photoinitiator. It has the structure shown by the following formula (I): Wherein R 1 each independently represents hydrogen, halogen, C 1 -C 20 linear or branched alkyl, C 4 -C 20 cycloalkylalkyl, C 2 -C 20 alkenyl, these groups -CH 2 - in the group may be optionally substituted by -O-; R 2 represents a C 3 -C 20 cycloalkyl group, a C 4 -C 20 cycloalkylalkyl group or an alkylcycloalkyl group, or represents -R 4 -COO-R 5 , wherein R 4 represents a C 1 -C 10 alkylene group, a C 3 -C 10 cycloalkylene group, a C 6
  • the above compounds are simple in synthesis, low in cost, and have good solubility, and have excellent storage stability and film forming properties when applied to a photocurable composition.
  • a photosensitive resin composition comprising the following components: (A) a compound having an ethylenically unsaturated bond, and a compound having an ethylenically unsaturated bond for use in freedom a base polymerization reaction; (B) a photoinitiator, wherein the photoinitiator is at least one of a compound having a quinone compound represented by the formula (I):
  • X represents a linker or a carbonyl group;
  • R 1 can form a ring;
  • R 2 and R 3 independently of each other represent a C 1 -C 20 linear or branched alkyl group, a C 3 -C 20 cycloalkyl group,
  • the compound having the above structure (I) is simple in synthesis, low in cost, and good in solubility, it has excellent storage stability and film forming properties when applied to a photocurable composition.
  • the components of the photosensitive resin composition are reasonable in combination, and the composition has a very high sensitivity, and can be cross-linked and cured at a very low exposure dose, and the curing effect is excellent.
  • the film made of the composition has a flat edge without defects, no scum, a clear and clear pattern, and high hardness.
  • the prepared filter has high optical transparency, no light leakage, and is produced at a very low exposure dose, and has high precision, flatness and durability.
  • the photosensitive resin composition of the present invention has high sensitivity and good developability, high resolution, and excellent adhesion to a substrate, and is very suitable for preparing a black matrix having high light-shielding property, high-definition and high-quality color filter. And liquid crystal display devices, and can also be applied to photo spacers and ribs.
  • the photosensitive resin composition of the present invention contains the components (A), (B) and optional components (C), (D), which will be described in more detail below.
  • the component (A) is a compound having a radically polymerizable ethylenically unsaturated bond or/and an epoxy compound.
  • the compound having a radically polymerizable ethylenically unsaturated bond may have a monomer, an oligomer, a polymer, etc. as long as it has at least one radically polymerizable ethylenically unsaturated bond in the molecule. Chemical form.
  • Examples of such a compound having a radically polymerizable ethylenically unsaturated bond include unsaturated carboxylic acids such as acrylates, methacrylates, itaconic acid, crotonic acid, isocrotonic acid, and maleic acid. And its salts, esters, carbamates, amides and anhydrides, acrylonitrile, styrene, vinyl ethers, as well as various unsaturated polyesters, unsaturated polyethers, unsaturated polyamides, unsaturated polyurethanes and other free radicals
  • the polymerizable compound is not limited to the invention.
  • the acrylic compound of the present invention may be exemplified by methyl acrylate, ethyl acrylate, propyl acrylate, isopropyl acrylate, butyl acrylate, isoamyl acrylate, hexyl acrylate, acrylic acid-2- Ethylhexyl ester, octyl acrylate, decyl acrylate, dodecyl acrylate, octadecyl acrylate, isobornyl acrylate, cyclohexyl acrylate, dicyclopentenyl acrylate, dicyclopentenyl oxyacrylate Ester, benzyl acrylate, 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 2-hydroxy-3-chloropropyl acrylate, 2-hydroxy-3-phenoxypropyl acrylate, acrylic acid 2-hydroxy-3-allyloxypropyl ester, 2-acryloyloxyethyl-2-hydroxypropyl
  • the methacrylic compound of the present invention may be exemplified by methyl methacrylate, ethyl methacrylate, hydroxyethyl methacrylate, propyl methacrylate, isopropyl methacrylate, Butyl methacrylate, isoamyl methacrylate, hexyl methacrylate, 2-hexyl methacrylate, 2-ethylhexyl methacrylate, octyl methacrylate, decyl methacrylate , lauryl methacrylate, octadecyl methacrylate, isobornyl methacrylate, cyclohexyl methacrylate, dicyclopentenyl methacrylate, dicyclopentenyloxy methacrylate Ester, benzyl methacrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, 2-hydroxy-3-chloropropyl methacrylate, 2-hydroxy
  • the present invention may also be exemplified by allyl glycidyl ether, diallyl phthalate, triallyl trimellitate, triallyl isocyanurate, acrylamide, N-hydroxyl Methacrylamide, diacetone acrylamide, N,N-dimethylacrylamide, N,N-diethylacrylamide, N-isopropylacrylamide, acryloylmorpholine, styrene, p-hydroxystyrene , p-chlorostyrene, p-bromostyrene, p-methylstyrene, vinyl acetate, vinyl chloride, vinyl benzoate, vinyl pivalate, vinyl butyrate, vinyl laurate, hexan Acid divinyl ester and the like.
  • the radically polymerizable compound (A) of the present invention may be used singly or in combination of two or more kinds in any ratio in order to improve desired properties.
  • the component (A) may be used in the photosensitive resin composition in an amount of from 0.1 to 100 parts by mass, preferably from 30 to 80 parts by mass, more preferably from 40 to 70 parts by mass.
  • the component (B) photoinitiator used in the present invention is selected from the group consisting of an anthracene compound represented by the formula (I) or the formula (II) and a derivative compound having a compound represented by the formula (I) or the formula (II) as a main structure. At least one.
  • the photoinitiator may be composed only of an anthracene compound represented by the formula (I) or the formula (II) or a derivative compound having a main structure thereof, or a combination of two types of compounds.
  • X represents a linker or a carbonyl group;
  • R 1 can form a ring;
  • R 2 and R 3 independently of each other represent a C 1 -C 20 linear or branched alkyl group, a C 3 -C 20 cycloalkyl group,
  • the quinone compound represented by the formula (I) or the formula (II) includes the compounds 1' to 30' represented by the following structures:
  • the above-mentioned derivative compound having a compound represented by the formula (I) or the formula (II) as a main structure means that the main structure of the compound of the formula (I) or the formula (II) is maintained, and the branches are substituted or linked to each other. And the resulting derivative.
  • the derivative compound having a compound represented by the formula (I) or the formula (II) as a main structure is represented by the following formulas (III), (IV), (V), (VI). , the compound shown in (VIII):
  • M represents a linking group formed by dimerization of R 1 , R 2 , R 3 , R 6 , R 7 and R 8 , and M is an empty, C 1 -C 24 linear or branched alkylene group,
  • An arylene or heteroarylene group of C 6 -C 36 , -CH 2 - in M is optionally substituted by sulfur, oxygen, NH or a carbonyl group, and the hydrogen atom is optionally substituted by OH or NO 2 .
  • the above derivative compound may be a compound of the following structure:
  • the amount of the component (B) used in the photosensitive resin composition is preferably from 1 to 5 parts by mass.
  • the photosensitive resin composition of the present invention may further contain a component (C) colorant.
  • C component
  • the composition of the present invention can be used to form a color filter of a liquid crystal display by containing a colorant; and when an opacifier is used as a colorant, the composition can be used to form a black matrix in a color filter of a display device. Picture tube.
  • the present invention is not particularly limited to the kind of the component (C) coloring agent, and may be those classified as a pigment in a color index (CI; published by The Society of Dyers and Colourists), preferably having The colorant of the following CI number, such as CI Pigment Yellow 1 (hereinafter, "CI Pigment Yellow” is the same, only the serial number is described), 3, 11, 12, 13, 14, 15, 16, 17, 20, 24 , 31, 53, 55, 60, 61, 65, 71, 73, 74, 81, 83, 86, 93, 95, 97, 98, 99, 100, 101, 104, 106, 108, 109, 110, 113 , 114, 116, 117, 119, 120, 125, 126, 127, 128, 129, 137, 138, 139, 147, 148, 150, 151, 152, 153, 154, 155, 156, 166, 167, 168 , 175, 180, 185; CI Pigment Orange 1
  • a black pigment As an opacifier, it is preferred to use a black pigment as an opacifier.
  • the black pigment include carbon black, titanium black, metal oxides such as copper, iron, manganese, cobalt, chromium, nickel, zinc, calcium, and silver, composite oxides, metal sulfides, and metal sulfuric acid. Salt or metal carbonate, etc.
  • carbon black having high light-shielding property is preferably used, and it may be a common carbon black such as channel black, furnace black, thermal black, or lampblack, and it is preferable to use a grooved carbon having excellent light shielding properties. Black; carbon black can also be coated with a resin.
  • the component (C) is used in the photosensitive resin composition in an amount of 0 to 50 parts by mass, preferably 5 to 40 parts by mass.
  • the polymerizable composition of the present invention may be used in combination with an alkali-soluble resin.
  • the alkali-soluble resin (D) preferably functions as a binder, and is preferably soluble alkali-developed for the developer used in the development treatment step when forming an image pattern.
  • the liquid is preferably an alkali-soluble resin as a carboxyl group-containing copolymer, particularly preferably an ethylenically unsaturated monomer having one or more carboxyl groups (hereinafter referred to as "carboxy group-containing unsaturated monomer” (P)) and other copolymerizable olefins.
  • a copolymer of a saturated monomer hereinafter referred to as "copolymerizable unsaturated monomer" (Q)) (hereinafter referred to as "carboxyl-containing copolymer” (R)).
  • carboxyl group-containing unsaturated monomer examples include the following compounds: unsaturated monocarboxylic acids such as acrylic acid, methacrylic acid, crotonic acid, ⁇ -chloroacrylic acid, and cinnamic acid; maleic acid, maleic anhydride, fumaric acid, and itaconol.
  • unsaturated monocarboxylic acids such as acrylic acid, methacrylic acid, crotonic acid, ⁇ -chloroacrylic acid, and cinnamic acid
  • maleic acid maleic anhydride
  • fumaric acid and itaconol.
  • An unsaturated dicarboxylic acid such as acid, itaconic anhydride, citraconic acid, citraconic anhydride or mesaconic acid or an anhydride thereof; a trivalent or higher unsaturated polycarboxylic acid or an anhydride thereof; succinic acid mono(2-acryloyl) Oxyethyl), succinic acid mono(2-methacryloyloxyethyl), phthalic acid mono(2-acryloyloxyethyl), phthalic acid mono(2-methacryloyl) Mono[(meth)acryloyloxyalkyl]esters of divalent or higher polycarboxylic acids such as oxyethyl); ⁇ -carboxypolycaprolactone monoacrylate, ⁇ -carboxypolycaprolactone monomethyl A mono(meth)acrylate or the like of a polymer having a carboxyl group and a hydroxyl group at both terminals, such as a acrylate.
  • examples of the copolymerizable unsaturated monomer include styrene, ⁇ -methylstyrene, o-vinyltoluene, m-vinyltoluene, p-vinyltoluene, p-chlorostyrene, and o-methoxystyrene.
  • An aromatic vinyl compound such as benzyl glycidyl ether or p-vinylbenzyl glycidyl ether; an unsaturated carboxylic acid glycidyl ester such as hydrazine glycidyl acrylate or glycidyl methacrylate such as hydrazine or 1-methyl hydrazine; Vinyl esters such as vinyl acetate, vinyl propionate, vinyl butyrate, vinyl benzoate, unsaturated ethers such as vinyl methyl ether, vinyl ethyl ether, allyl glycidyl ether, acrylonitrile , cyan
  • carboxyl group-containing copolymer (R)) in the present invention is obtained by polymerizing (P) and (Q); the (P) is acrylic acid and/or methacrylic acid.
  • it may further contain, depending on the case, succinic acid mono(2-acryloyloxyethyl), succinic acid mono(2-methacryloyloxyethyl), ⁇ -carboxypolycaprolactone monoacrylate And a carboxyl group-containing unsaturated monomer component of at least one compound of ⁇ -carboxypolycaprolactone monomethacrylate; said (Q) being selected from the group consisting of styrene, methyl acrylate, methyl methacrylate, and acrylic acid 2-hydroxyethyl ester, 2-hydroxyethyl methacrylate, allyl acrylate, allyl methacrylate, benzyl acrylate, benzyl methacrylate, glycerin monoacrylate, glycerol monomethacrylate At least one of N-phenylmaleimide, polystyrene macromonomer, and polymethyl methacrylate macromonomer.
  • carboxyl group-containing copolymer (R) examples include (meth)acrylic acid/methyl (meth)acrylate copolymer, (meth)acrylic acid/benzyl (meth)acrylate copolymer, and (methyl).
  • the alkali-soluble resin (D) may be used singly or in combination of two or more.
  • the component (D) is used in the photosensitive resin composition in an amount of from 0 to 80 parts by mass, preferably from 20 to 60 parts by mass.
  • one or more macromolecules or polymer compounds may be added to the composition as needed to improve the application performance of the composition during use.
  • the macromolecular or high molecular compound may be a polyol or Polyester polyols may also be optionally added to polymers which do not contain reactive functional groups. These polymers are usually resins containing acidic functional groups such as phenolic hydroxyl groups and hydroxyl groups, and may also be used in combination with other photoinitiators.
  • auxiliary agents conventionally used in the art, including but not limited to sensitizers, dispersants, surfactants, solvents and the like, may be optionally added to the photosensitive resin composition of the present invention.
  • the polymerizable composition of the present invention is polymerized by imparting energy generated by ultraviolet rays, visible rays, near infrared rays, or the like during the polymerization reaction, and a target polymer can be obtained.
  • a light source for imparting energy a light source having a dominant wavelength that emits light in a wavelength region of 250 nm to 450 nm is preferable.
  • Examples of the light source having a dominant wavelength of light emitted in a wavelength region of 250 nm to 450 nm include an ultrahigh pressure mercury lamp, a high pressure mercury lamp, a medium pressure mercury lamp, a mercury xenon lamp, a metal halide lamp, and a high power metal halide lamp.
  • xenon lamp pulsed xenon lamp, xenon lamp, Led lamp, fluorescent lamp, Nd-YAG3 double-wave laser, He-Cd laser, nitrogen laser, Xe-Cl excimer laser, Xe-F excimer laser, semiconductor excited solid laser, etc.
  • kind of light source
  • the photosensitive resin composition of the present invention can be obtained by weighing each component by weight and uniformly mixing it, which is a well-known conventional technique to those skilled in the art.
  • the method generally comprises the steps of: i) dissolving the photosensitive resin composition in a suitable organic solvent, mixing uniformly to obtain a liquid composition; ii) using a coater such as a spin coater, a wire bar coater, a shaft a coating machine or a spray coater or the like, uniformly coating the liquid composition on the substrate; iii) performing pre-baking drying to remove the solvent; iv) attaching the mask to the sample for exposure, and then developing to remove the unexposed area ; v) post-baking to obtain a dry film of photoresist having a desired shape.
  • a coater such as a spin coater, a wire bar coater, a shaft a coating machine or a spray coater or the like
  • a photoresist film containing a black pigment is a black matrix BM
  • a photoresist film containing red, green, and blue pigments is a corresponding R, G, and B photoresist.
  • the material was slowly poured into diluted hydrochloric acid of 800 g of ice water and 100 mL of concentrated hydrochloric acid (37%), and stirred while stirring. Pour into the separatory funnel, separate the lower layer of methylene chloride, and continue to wash the aqueous layer with 50 mL of dichloromethane, and combine the methylene chloride layer, and wash with a 5% aqueous solution of sodium bicarbonate (300 mL each time, 3 times) The methylene chloride layer was washed with water to a neutral pH. The methylene chloride layer was dried over 150 g of anhydrous magnesium sulfate. After filtration, the methylene chloride product solution was evaporated. The methanol was recrystallized and dried in an oven at 70 ° C for 2 h to obtain 141 g. intermediate 1a, yield 78%, purity 98%, MS (m / z ): 364 (m + 1) +.
  • the structure of the product was confirmed by nuclear magnetic resonance spectroscopy and mass spectrometry.
  • the material was slowly poured into diluted hydrochloric acid of 800 g of ice water and 100 mL of concentrated hydrochloric acid (37%), and stirred while stirring. Pour into the separatory funnel, separate the lower layer of methylene chloride, and continue to wash the aqueous layer with 50 mL of dichloromethane, and combine the methylene chloride layer, and wash with a 5% aqueous solution of sodium bicarbonate (300 mL each time, 3 times) The methylene chloride layer was washed with water to a neutral pH. The methylene chloride layer was dried over 150 g of anhydrous magnesium sulfate. After filtration, the methylene chloride product solution was evaporated. The crystals were recrystallized from methanol and dried at 70 ° C for 2 h to give 127 g. intermediate 2a, yield 79%, purity 98%, MS (m / z ): 322 (m + 1) +.
  • the structure of the product was confirmed by nuclear magnetic resonance spectroscopy and mass spectrometry.
  • the methylene chloride layer was washed with a 5% aqueous sodium hydrogencarbonate solution (300 mL each time), and then the methylene chloride layer was washed with water until the pH was neutral.
  • the methylene chloride layer was dried over 150 g of anhydrous magnesium sulfate. After filtration, the methylene chloride product solution was evaporated, and then recrystallized from methanol, and dried in an oven at 70 ° C for 2 h to obtain 143 g of intermediate 13a, yield 87%, purity 99%, MS ( m/z): 326(M+1) + .
  • the structure of the product was confirmed by nuclear magnetic resonance spectroscopy and mass spectrometry.
  • the aqueous layer was further washed with 50 mL of dichloromethane, and the methylene chloride layer was combined.
  • the methylene chloride layer was washed with a 5% aqueous sodium hydrogencarbonate solution (300 mL each time), and then the methylene chloride layer was washed with water until the pH was neutral.
  • the methylene chloride layer was dried over 150 g of anhydrous magnesium sulfate. After filtration, the methylene chloride product solution was evaporated, and then recrystallized from methanol and dried in oven at 70 ° C for 2 h to obtain 134 g of intermediate 14a, yield 86%, purity 99%, MS (m /z): 312(M+1) + .
  • the structure of the product was confirmed by nuclear magnetic resonance spectroscopy and mass spectrometry.
  • the solubility of the photoinitiator in PGMEA is one of the index parameters representing its solubility properties and the performance of the photoinitiator.
  • the compounds of the formula (I) of the present invention were compared with the existing nitrooxazolium ester-based photoinitiators as compared, and their solubility in PGMEA at 25 ° C was tested, respectively, and the results are shown in Table 2.
  • the two existing nitrooxazolium ester-based photoinitiators as comparative compounds are substantially insoluble in PGMEA, while the compounds of the present invention have good solubility in PGMEA. Both meet the requirements of more than 8% by weight of solubility in industrial applications.
  • the storage stability and film forming properties of the photoinitiator represented by the formula (I) of the present invention were evaluated by formulating an exemplary photocurable composition.
  • the photoinitiator is an oxime ester-containing compound represented by the formula (I) disclosed in the present invention or a photoinitiator known in the prior art (for comparison).
  • the degree of precipitation of the substance was visually evaluated according to the following criteria: A: no precipitation was observed; B: precipitation was slightly observed; C: significant precipitation was observed.
  • An exemplary photocurable composition having the above composition was stirred under a yellow light, and a film was formed by roll coating on a PET template, and dried at 90 ° C for 2 minutes to obtain a coating film having a dry film thickness of 2 ⁇ m.
  • the substrate on which the coating film was formed was cooled to room temperature, a mask was attached, and a long-wavelength radiation was realized by a FWHM filter using a high-pressure mercury lamp 1 PCS light source.
  • the coating film was exposed to ultraviolet light at a wavelength of 370-420 nm through a slit of a mask, and then immersed in a 2.5% sodium carbonate solution for 20 s at 25 ° C, washed with ultrapure water, air-dried, and hard baked at 220 ° C. Bake for 30 minutes to fix the pattern and evaluate the obtained pattern.
  • the minimum exposure amount at which the residual film ratio is 90% or more after development in the light irradiation region in the exposure step is evaluated as the exposure demand amount.
  • the substrate pattern was observed with a scanning electron microscope (SEM) to evaluate developability and pattern integrity.
  • the developability was evaluated according to the following criteria: ⁇ : no residue was observed in the unexposed portion; ⁇ : a small amount of residue was observed in the unexposed portion, but the residue was acceptable; ⁇ : Obvious residue was observed in the unexposed portion.
  • the pattern integrity was evaluated according to the following criteria: ⁇ : no pattern defects were observed; ⁇ : a small portion of the pattern was observed to be somewhat defective; ⁇ : Many pattern defects were clearly observed.
  • the photocurable composition containing the oxime ester-containing photoinitiator of the present invention has good storage stability and exposure requirements compared to the existing nitrooxazolium ester-based photoinitiator.
  • the amount is low, both lower than 60 mJ/cm 2 , and the development effect and pattern integrity are better, and the film forming property is very excellent.
  • the oxime ester-containing photoinitiator of the formula (I) disclosed in the present invention has superior application performance, low raw material and low preparation cost, and has a good application prospect.
  • the photosensitive resin composition prepared according to the formulation shown in Table 4 was dissolved in 100 parts by mass of solvent propylene glycol monomethyl ether acetate (PGMEA), and uniformly mixed to form a liquid composition;
  • PGMEA solvent propylene glycol monomethyl ether acetate
  • the liquid composition was coated on a glass substrate by a spin coater, and then the solvent was removed by drying at 100 ° C for 5 minutes to form a coating film having a film thickness of 10 ⁇ m; in order to obtain the coating film of the above thickness, the coating process may be completed once. Can also be divided into multiple times;
  • LED light source Ilethora LED UV curing irradiation device, maximum irradiation intensity 400mW/cm 2 ), pass the gap of the mask plate at the wavelength of 370-420nm Exposing the coating film under ultraviolet irradiation;
  • the minimum exposure amount at which the residual film ratio is 90% or more after development in the light irradiation region in the exposure step is evaluated as the exposure demand amount, and the smaller the exposure demand amount, the higher the sensitivity.
  • the pattern on the substrate was observed with a scanning electron microscope (SEM) to evaluate developability and pattern integrity.
  • the developability was evaluated according to the following criteria:
  • Pattern integrity is evaluated according to the following criteria:
  • Evaluation is carried out in accordance with GB/T 6739-1996 "Coating film hardness pencil measurement method". Use a film pencil scratch hardness tester to observe the scratch marks of the paint film, and use a pencil with no scratches as the pencil hardness of the coating film.
  • the filter photoresists produced by the compositions of Examples 53-60 have excellent developability and pattern integrity, and are excellent in adhesion and hardness, and Comparative Example 5 -8 is clearly insufficient in these areas. It is to be noted that the exposure doses of Examples 53 to 60 were each not higher than 70 mJ/cm 2 , which was far lower than Comparative Examples 5 to 8, and exhibited extremely excellent photosensitivity.
  • the photosensitive resin composition of the present invention exhibits very excellent application properties and has broad application prospects.

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Abstract

本发明公开一种如下式(I)所示的含芴肟酯类光引发剂、其合成、含有其的感光性树脂组合物及其应用。该化合物合成简单、成本低，应用于光固化领域时溶解性好，具有优异的储存稳定性和成膜性能，曝光需求量低，且显影性和图案完整性优异。感光性树脂组合物包含紫外感光预聚物树脂、活性稀释单体、本申请的含芴肟酯类光引发剂和任选的着色剂及碱溶性树脂，该组合物具有高感光度和良好的显影性，分辨率高且与基板密合性优异，非常适合用以制备高遮光性的黑色矩阵、高精细且高品质的滤色器和液晶显示装置，并且也能够在光间隔物和肋栅、光刻胶、湿膜、干膜等方面得到应用。

Description

一种含芴肟酯类光引发剂、其合成、含有其的感光性树脂组合物及其应用 技术领域
本发明属于有机化学领域，具体涉及一种含芴肟酯类光引发剂、其合成、含有其的感光性树脂组合物及其应用。
背景技术
在液晶显示器等显示装置中，液晶层通常设于两块基板之间，每块基板上配置相对向的电极，且在其中一块基板的内侧，在液晶层对面，配制有由红色(R)、绿色(G)、蓝色(B)及黑色等各像素形成的滤色层。其中，通常以设置矩阵的形式区分R、G、B各色的色重。
目前，生产滤色器的方法主要有染色法、印刷法、颜料分散法和阳极法，其中颜料分散法使用最为广泛。颜料分散法是在透明基片上涂布含有着色材料的感光性树脂组合物，然后进行图像曝光、显影和视情况需要的后固化，通过重复这些过程形成滤色器图像。该方法得到的滤色器像素的定位精度和膜厚度精度高，具有优异的耐久性(如耐光性和耐热性等)，而且针孔缺陷少。
在滤色器制造中，BM通常以格子状、条形状或马赛克状配制在红、绿、蓝图案之间，用以防止薄膜晶体管因漏光而出现故障或通过阻止各种颜色间的混色来提高对比度，而这就要求BM应具有较高的遮光性。因此，如何使用分散有遮光颜料或染料的感光性树脂低成本地形成高效BM成为了研究的一个热点。一般来说，需要通过增加膜厚度或提高遮光颜料或染料的含量来改善BM的遮光性，但在整个光波长区域都需要遮光性的情况下，这些措施易导致组合物的感光特性出现显著障碍，主要表现为：在曝光部分与未曝光部分以及曝光底部出现交联密度差；不溶于显影液的颜料使显影性降低，进而导致图案的直线性降低，或图案发生剥离，产生残渣；等等。
目前常用为含有有咔唑或二苯硫醚为主体结构的肟酯类光引发剂的感光性组合物，但这类光引发剂成本较高，在一定程度上限制了其应用，因此，价格合适的光引发剂需要被开发。
肟酯类化合物作为光引发剂使用已被该领域人员所熟知，其活性突出，在彩色滤光片膜(RGB)、黑色矩阵(BM)、光间隔物(photo-spacer)、肋栅(rib)等高端光刻胶领域中应用广泛。
常用的肟酯类光引发剂以咔唑或二苯硫醚基团为主体基团，成本较高，且与基体树脂的溶解性往往也存在不足，因此在感光度不受影响的前提下开发更低成本且溶解性好的光引发剂是追求的目标。
发明内容
本发明的目的主要在于提供一种含芴肟酯类光引发剂、其合成、含有其的感光性树脂组合物及其应用，该化合物合成简单、成本低，溶解性好，应用于光固化组合物时具有优异的储存稳定性和成膜性能。
为了实现上述目的，根据本发明的一个方面，提供了一种含芴肟酯类光引发剂，具有如下式(I)所示结构：
Figure PCTCN2016099745-appb-000001
其中，R1各自独立地代表氢、卤素、C1-C20的直链或支链烷基、C4-C20的环烷基烷基、C2-C20的链烯基，这些基团中的-CH2-可任选地被-O-取代；R2代表C3-C20的环烷基、C4-C20的环烷基烷基或烷基环烷基，或者代表-R4-COO-R5，其中，R4代表C1-C10的亚烷基、C3-C10的亚环烷基、C6-C20的亚芳基或取代亚芳基，其中亚烷基中的非末端-CH2-和环烷基中的-CH2-可任选地被-O-所取代，芳基中的CH可任选地被N所取代；R5代表C1-C20的直链或支链烷基、C3-C20的环烷基、C4-C20的烷基环烷基或环烷基烷基、C6-C30的芳基或取代芳基、C7-C30的芳烷基、C2-C20的链烯基，其中的-CH2-可任选地被-O-、-S-或-NH-所取代；R3代表C1-C20的直链或支链烷基、C3-C20环烷基、C4-C20的烷基环烷基或环烷基烷基、C6-C30的芳基或取代芳基、C7-C30的芳烷基、C2-C20的链烯基；A代表氢、卤素、硝基、C1-C10的直链或支链烷基、C4-C10的烷基环烷基或环烷基烷基；X代表空或羰基，其中空表示X两端的两个原子直接相连。
进一步地，上述R1各自独立地代表氢、卤素、C1-C10的直链或支链烷基、C4-C10的环烷基烷基，这些基团中的-CH2-可任选地被-O-取代。
进一步地，上述R1各自独立地代表氢、C1-C6的直链或支链烷基，且烷基中的一个或两个不相邻的-CH2-可任选地被-O-取代。
进一步地，上述R2代表C3-C10的环烷基、C4-C10的环烷基烷基或烷基环烷基。
进一步地，上述R2代表C3-C6的环烷基、末端被C3-C6环烷基取代的C1-C4的直链或支链烷基、被C1-C4烷基取代的C3-C6环烷基。
进一步地，上述R4代表C1-C8的亚烷基、C3-C8的亚环烷基、亚苯基、取代亚苯基，其中亚烷基中的非末端-CH2-和环烷基中的-CH2-可任选地被-O-所取代，苯基中的CH可任选地被N所取代。
进一步地，上述R4代表C1-C4的亚烷基、C3-C6的亚环烷基、亚苯基、亚吡啶基。
进一步地，上述R5代表C1-C10的直链或支链烷基、C3-C10的环烷基、C4-C10的烷基环烷基或环烷基烷基。
进一步地，上述R5代表C1-C6的直链或支链烷基、被C3-C6环烷基取代的C1-C4的直链或支链烷基。
进一步地，上述R3代表C1-C10的直链或支链烷基、C4-C10的环烷基烷基、苯基、C2-C8的链烯基。
进一步地，上述R3代表C1-C6的直链或支链烷基、末端被C3-C6环烷基取代的C1-C4的直链或支链烷基。
进一步地，上述A是硝基。
根据本申请的另一方面，提供了一种感光性树脂组合物，包含下列组分：(A)具有烯属不饱和键的化合物，所述具有烯属不饱和键的化合物用于自由基聚合反应；(B)光引发剂，所述光引发剂为以式(I)所示的芴类化合物为主体结构的化合物中的至少一种：
Figure PCTCN2016099745-appb-000002
其中，A代表氢、卤素、硝基、C1-C10的直链或支链烷基、C3-C10的烷基环烷基、C4-C10的烷基环烷基或环烷基烷基,A中的-CH2-能够被O、N、S或C(＝O)所取代；X代表连接符或羰基；R1代表氢、卤素、C1-C20的直链或支链烷基、C4-C20的环烷基烷基或C2-C20的链烯基，R1中的-CH2-能够被O、N、S或C(＝O)所取代,R1之间能够成环；R2和R3相互独立地表示C1-C20的直链或支链烷基、C3-C20的环烷基、C4-C20的环烷基烷基或C4-C20的烷基环烷基，R2和R3中的-CH2-能够被O、N、S或C(＝O)所取代；(C)着色剂。
进一步地，以质量份计，感光性树脂组合物包括：0.1～100份具有烯属不饱和键的化合物、1～5份光引发剂以及0～50份着色剂，优选具有烯属不饱和键的化合物的质量份为30～80份，更优选为40～70份；优选着色剂的质量份为大于0且小于等于80份，更优选为5～40份。
进一步地，以式(I)所示的芴类化合物为主体结构的化合物，结构如下：
Figure PCTCN2016099745-appb-000003
其中，A代表氢、硝基、C1-C10的直链或支链烷基；X代表连接符或羰基；R1代表氢、C1-C20的直链或支链烷基或被O、N、S或C(＝O)所取代的C1-C20的直链或支链烷基；R2和R3相互独立地表示C1-C20的直链或支链烷基、C3-C20的环烷基、C4-C20的环烷基烷基或C4-C20的烷基环烷基，R2和R3中的-CH2-能被O、N、S或C(＝O)所取代。
进一步地，以式(I)所示的芴类化合物为主体结构的化合物，包括如下所示结构：
Figure PCTCN2016099745-appb-000004
Figure PCTCN2016099745-appb-000005
Figure PCTCN2016099745-appb-000006
进一步地，以式(I)所示的芴类化合物为主体结构的衍生化合物为：式(III)、(IV)、(Ⅴ)所示的化合物：
Figure PCTCN2016099745-appb-000007
其中，M表示R1、R2、R3二聚化而形成的连接基团，M为空、C1-C24的直链或支链亚烷基、C6-C36的亚芳基或亚杂芳基，M中的-CH2-任选地被硫、氧、NH或羰基所取代，氢原子任选地被OH或NO2所取代。
进一步地，以式(I)所示的芴类化合物为主体结构的衍生化合物为下列结构的化合物：
Figure PCTCN2016099745-appb-000008
进一步地，上述感光性树脂组合物含有碱溶性树脂(D)，优选碱溶性树脂的质量份为大于0且小于等于80份，更优选为20～60份。
本发明的另一个目的在于提供上述具有式(I)结构的含芴肟酯类光引发剂的制备方法，当式(I)中的R2代表C3-C20的环烷基、C4-C20的环烷基烷基或烷基环烷基时，该制备方法包括以下步骤：
(1)中间体a的合成，原料a与原料b在三氯化铝或氯化锌的催化作用下于有机溶剂中发生傅克酰基化反应，得到中间体a，
Figure PCTCN2016099745-appb-000009
原料b即R2’-CO-Cl中，其中R2’表示R2或者R2-CH2-，具体是，当式(I)中X为空，则R2’表示R2，当X为羰基，则R2’表示R2-CH2-；
(2)中间体b的合成，当X为空时，中间体a在盐酸羟胺、醋酸钠的作用下进行肟化反应，生成中间体b；当X为羰基时，在有机溶剂和浓盐酸存在下，中间体a与亚硝酸酯或亚硝酸盐于常温下进行肟化反应，生成中间体b；
Figure PCTCN2016099745-appb-000010
(3)式(I)化合物的合成，中间体b与酸酐(R3-CO)2O或酰氯化合物R3-CO-Cl进行酯化反应，得到目标产物；
Figure PCTCN2016099745-appb-000011
当式(I)中的R2代表-R4-COO-R5时，其中，R4代表C1-C10的亚烷基、C3-C10的亚环烷基、C6-C20的亚芳基或取代亚芳基，其中亚烷基中的非末端-CH2-和环烷基中的-CH2-可任选地被-O-所取代，芳基中的CH可任选地被N所取代；R5代表C1-C20的直链或支链烷基、C3-C20的环烷基、C4-C20的烷基环烷基或环烷基烷基、C6-C30的芳基或取代芳基、C7-C30的芳烷基、C2-C20的链烯基，其中的-CH2-可任选地被-O-、-S-或-NH-所取代(1)中间体a的合成，所述制备方法包括：
(1’)中间体a的合成，原料a与原料b’在三氯化铝或氯化锌的催化作用下于有机溶剂中发生傅克反应，生成中间体a’，
Figure PCTCN2016099745-appb-000012
原料b’的结构中，R2’表示R4或者CH2-R4，具体是，当式(I)中X为空，则R2’表示R4，当X为羰基，则R2’表示CH2-R4；
(2’)中间体b’的合成，中间体a’在浓硫酸或杂多酸存在条件下与原料c即醇R5OH加热回流，发生酯化反应，得到中间体b’，
Figure PCTCN2016099745-appb-000013
(3’)中间体c’的合成，当X为空时，中间体b’在盐酸羟胺、醋酸钠的作用下进行肟化反应，生成中间体c’；当X为羰基时，在有机溶剂和浓盐酸存在下，中间体b’与亚硝酸酯或亚硝酸盐于常温下进行肟化反应，生成中间体c’；
Figure PCTCN2016099745-appb-000014
(4’)式(I)化合物的合成，中间体c’与酸酐(R3-CO)2O或酰氯化合物R3-CO-Cl进行酯化反应，得到目标产物；
Figure PCTCN2016099745-appb-000015
上述制备方法中，使用的原料均是现有技术中的已知化合物，可通过商业购得或者经已知的合成方法简便地制备而成。
步骤(1)-(3)和(1’)-(4’)中涉及的反应都是本领域合成类似化合物的常规反应。在知晓了本发明公开的合成思路的基础上，具体反应条件对本领域技术人员而言是容易确定的。
步骤(1)的傅克反应中，反应温度通常为-10-30℃。对使用的有机溶剂并没有特别限定，只要能够溶解原料且对反应无不良影响即可，如二氯甲烷、二氯乙烷、苯、甲苯、二甲苯等。
步骤(1’)的傅克反应中，反应温度可以是常温，对使用的有机溶剂并没有特别限定，只要能够溶解原料且对反应无不良影响即可，如二氯甲烷、二氯乙烷、苯、甲苯、二甲苯等。三氯化铝或氯化锌可通过滴加或分批加入的方式进入反应体系。
步骤(2)的肟化反应是在溶剂体系中进行，使用的溶剂并没有特别限定，只要能够溶解原料且对反应无不良影响即可。
步骤(2’)的酯化反应中可根据需要使用或不使用溶剂。如果使用溶剂，则对其种类并没有特别限定，只要能够溶解原料且对反应无不良影响即可。
步骤(2)和步骤(3’)的肟化反应是在溶剂体系中进行，使用的溶剂并没有特别限定，只要能够溶解原料且对反应无不良影响即可。当X为空时，使用的溶剂可以是醇和水的混合溶剂，优选乙醇和水的混合溶剂。反应在加热回流状态下进行。当X为羰基时，使用的有机溶剂可以是二氯甲烷、苯、甲苯、四氢呋喃等，所用亚硝酸酯可选自亚硝酸乙酯、亚硝酸异戊酯、亚硝酸异辛酯等，所用亚硝酸盐可选自亚硝酸钠、亚硝酸钾等。
步骤(3)的酯化反应在有机溶剂中进行，对溶剂种类并没有特别限定，只要能够溶解原料且对反应无不良影响即可，如二氯甲烷、二氯乙烷、苯、甲苯、二甲苯等。
步骤(4’)的酯化反应在有机溶剂中进行，对溶剂种类并没有特别限定，只要能够溶解原料且对反应无不良影响即可，优选二氯甲烷、二氯乙烷、苯、二甲苯。
在本发明中，上述式(I)所示的含芴肟酯类化合物还可经由R1(一个或两个)、R2或R3彼此相连聚合以形成二聚化物。这些二聚化产物被认为可表现出与式(I)所示的含芴肟酯类光引发剂相类似的应用性能。
本发明的目的还在于提供上述式(I)所示的含芴肟酯类光引发剂在光固化组合物(即感光性组合物)中的应用。非限制性地，该光引发剂可应用在彩色光阻(RGB)、黑色矩阵(BM)、光间隔物(photo-spacer)、肋栅(rib)、干膜、半导体光刻胶及油墨等方面。该光引发剂在应用中具有优异的溶解性，储存稳定性佳，曝光需求量低(即感光度高)，且表现出了很好的显影性和图案完整性。
本发明的聚合性组合物可以与碱可溶性树脂混合并用，碱溶性树脂(D)只要是起到粘合剂的作用，在形成图像图案时对于显影处理工序中使用的显影液优选可溶性碱性显影液，优选作为含羧基共聚物的碱可溶性树脂、特别优选具有1个以上羧基的烯属不饱和单体和其他可共聚的烯属不饱和单体的共聚物。
本发明的另一个目的在于提供上述感光性树脂组合物在制备彩色滤光片膜、黑色矩阵、光间隔物、肋栅和干膜用光刻胶中的应用。
本发明所述的感光性树脂组合物中各组分组配合理，组合物具有非常高的感光度，在很低的曝光剂量下就可以很好的交联固化，且固化效果极佳。由该组合物制成的膜边缘平整无缺陷，没有浮渣，图案完整清晰，且硬度高。制成的滤光片光学透明度高，不漏光，在很低的曝光剂量下完成制作，并且精度好、平坦、耐久。
具体实施方式
需要说明的是，在不冲突的情况下，本申请中的实施例及实施例中的特征可以相互组合。下面将结合实施例来详细说明本发明。
如背景技术所分析的，现有技术的肟酯类光引发剂与基体树脂的溶解性不足，为了解决该问题，本申请一种典型实施方式提供了一种含芴肟酯类光引发剂，具有如下式(I)所示结 构：
Figure PCTCN2016099745-appb-000016
其中，R1各自独立地代表氢、卤素、C1-C20的直链或支链烷基、C4-C20的环烷基烷基、C2-C20的链烯基，这些基团中的-CH2-可任选地被-O-取代；R2代表C3-C20的环烷基、C4-C20的环烷基烷基或烷基环烷基，或者代表-R4-COO-R5，其中，R4代表C1-C10的亚烷基、C3-C10的亚环烷基、C6-C20的亚芳基或取代亚芳基，其中亚烷基中的非末端-CH2-和环烷基中的-CH2-可任选地被-O-所取代，芳基中的CH可任选地被N所取代；R5代表C1-C20的直链或支链烷基、C3-C20的环烷基、C4-C20的烷基环烷基或环烷基烷基、C6-C30的芳基或取代芳基、C7-C30的芳烷基、C2-C20的链烯基，其中的-CH2-可任选地被-O-、-S-或-NH-所取代；R3代表C1-C20的直链或支链烷基、C3-C20环烷基、C4-C20的烷基环烷基或环烷基烷基、C6-C30的芳基或取代芳基、C7-C30的芳烷基、C2-C20的链烯基；A代表氢、卤素、硝基、C1-C10的直链或支链烷基、C4-C10的烷基环烷基或环烷基烷基；X代表空或羰基，其中空表示X两端的两个原子直接相连。
上述化合物合成简单、成本低，溶解性好，应用于光固化组合物时具有优异的储存稳定性和成膜性能。
在本申请另一种典型的实施方式中，提供了一种感光性树脂组合物，包含下列组分：(A)具有烯属不饱和键的化合物，具有烯属不饱和键的化合物用于自由基聚合反应；(B)光引发剂，所述光引发剂为以式(I)所示的芴类化合物为主体结构的化合物中的至少一种：
Figure PCTCN2016099745-appb-000017
其中，A代表氢、卤素、硝基、C1-C10的直链或支链烷基、C3-C10的烷基环烷基、C4-C10的烷基环烷基或环烷基烷基,A中的-CH2-能够被O、N、S或C(＝O)所取代；X代表连接符或羰基；R1代表氢、卤素、C1-C20的直链或支链烷基、C4-C20的环烷基烷基或C2-C20的链烯基，R1中的-CH2-能够被O、N、S或C(＝O)所取代,R1之间能够成环；R2和R3相互独立地表示C1-C20的直链或支链烷基、C3-C20的环烷基、C4-C20的环烷基烷基或C4-C20的烷基环烷基，R2和R3中的-CH2-能够被O、N、S或C(＝O)所取代；(C)着色剂。
由于具有上述结构是(I)的化合物合成简单、成本低，溶解性好，因此，应用于光固化组合物时具有优异的储存稳定性和成膜性能。
另外，感光性树脂组合物中各组分组配合理，组合物具有非常高的感光度，在很低的曝光剂量下就可以很好的交联固化，且固化效果极佳。由该组合物制成的膜边缘平整无缺陷，没有浮渣，图案完整清晰，且硬度高。制成的滤光片光学透明度高，不漏光，在很低的曝光剂量下完成制作，并且精度好、平坦、耐久。
本发明的上述感光性树脂组合物具有高感光度和良好的显影性，分辨率高且与基板密合性优异，非常适合用以制备高遮光性的黑色矩阵、高精细且高品质的滤色器和液晶显示装置，并且也能够在光间隔物和肋栅等方面得到应用。
本发明的感光性树脂组合物包含组分(A)、(B)以及任选的组分(C)、(D)，以下将对各组分进行更加详细的说明。
<组分(A)自由基聚合性化合物>
本发明的感光性树脂组合物中，组分(A)为具有可自由基聚合的烯属不饱和键的化合物或/和环氧化合物。所谓具有可自由基聚合的烯属不饱和键的化合物只要是在分子中具有至少一个以上可自由基聚合的烯属不饱和键的化合物，上述化合物可以具有单体、低聚物、聚合物等化学形态。
作为这种具有可自由基聚合的烯属不饱和键的化合物的例子可举出丙烯酸酯类、甲基丙烯酸酯类、衣康酸、巴豆酸、异巴豆酸、马来酸等不饱和羧酸及其盐、酯、氨基甲酸酯、酰胺和酸酐，丙烯腈，苯乙烯，乙烯基醚，还有各种不饱和聚酯、不饱和聚醚、不饱和聚酰胺、不饱和聚氨酯等自由基聚合性化合物，本发明并不限于此。
进一步的，本发明所述的丙烯酸类化合物可列举如下化合物：丙烯酸甲酯、丙烯酸乙酯、丙烯酸丙酯、丙烯酸异丙酯、丙烯酸丁酯、丙烯酸异戊酯、丙烯酸己酯、丙烯酸-2-乙基己酯、丙烯酸辛酯、丙烯酸癸酯、丙烯酸十二烷酯、丙烯酸十八烷酯、丙烯酸异冰片酯、丙烯酸环己酯、丙烯酸二环戊烯酯、丙烯酸二环戊烯基氧乙酯、丙烯酸苄酯、丙烯酸-2-羟基乙酯、丙烯酸-2-羟基丙酯、丙烯酸-2-羟基-3-氯丙酯、丙烯酸-2-羟基-3-苯氧基丙酯、丙烯酸-2-羟基-3-烯丙氧基丙酯、2-丙烯酰氧基乙基-2-羟基丙基邻苯二甲酸酯、丙烯酸-2，2，2-三氟乙酯、1，3-丁二醇甲基醚丙烯酸酯、丙烯酸丁氧基乙酯、丙烯酸-β-羧基乙酯、琥珀酸单丙烯酰氧基乙酯、ω-羧基聚己内酯单丙烯酸酯、三甲基甲硅烷氧基乙基丙烯酸酯、二苯基-2-丙烯酰氧基乙基磷酸酯、三乙二醇二丙烯酸酯、四乙二醇二丙烯酸酯、双酚A二丙烯酸酯、EO改性双酚A二丙烯酸酯、PO改性双酚A二丙烯酸酯、氢化双酚A二丙烯酸酯、EO改性氢化双酚A二丙烯酸酯、PO改性氢化双酚A二丙烯酸酯、双酚F二丙烯酸酯、EO改性双酚F二丙烯酸酯、PO改性双酚F二丙烯酸酯、EO改性四溴双酚A二丙烯酸酯、三环癸烷二羟甲基二丙烯酸酯、甘油PO改性三丙烯酸酯、三羟甲基丙烷三丙烯酸酯、季戊四醇四丙烯酸酯、二季戊四醇四丙烯酸酯、二季戊四醇五丙烯酸酯单丙酸酯、二季戊四醇六丙烯酸酯、四羟甲基甲烷四丙烯酸酯等。
进一步的，本发明所述的甲基丙烯酸类化合物可列举如下化合物：甲基丙烯酸甲酯、甲基丙烯酸乙酯、甲基丙烯酸羟乙酯、甲基丙烯酸丙酯、甲基丙烯酸异丙酯、甲基丙烯酸丁酯、甲基丙烯酸异戊酯、甲基丙烯酸己酯、甲基丙烯酸-2-己酯、甲基丙烯酸-2-乙基己酯、甲基丙烯酸辛酯、甲基丙烯酸癸酯、甲基丙烯酸十二烷酯、甲基丙烯酸十八烷酯、甲基丙烯酸异冰片酯、甲基丙烯酸环己酯、甲基丙烯酸二环戊烯酯、甲基丙烯酸二环戊烯基氧乙酯、甲基丙烯酸苄酯、甲基丙烯酸-2-羟基乙酯、甲基丙烯酸-2-羟基丙酯、甲基丙烯酸-2-羟基-3-氯丙酯、甲基丙烯酸-2-羟基-3-苯氧基丙酯、甲基丙烯酸-2，2，2-三氟乙酯、甲基丙烯酸-2，2，3，3-四氟丙酯、甲基丙烯酸-1H-六氟异丙酯、甲基丙烯酸-2-甲氧基乙酯、1，3-丁二醇甲基醚甲基丙烯酸酯、甲基丙烯酸丁氧基乙酯、甲氧基三乙二醇甲基丙烯酸酯、甲氧基聚乙二醇#400甲 基丙烯酸酯、甲氧基二丙二醇甲基丙烯酸酯、甲氧基三丙二醇甲基丙烯酸酯、甲氧基聚丙二醇甲基丙烯酸酯、乙氧基二乙二醇甲基丙烯酸酯、甲基丙烯酸-2-乙基己基卡必醇酯、甲基丙烯酸四氢糠酯、甲基丙烯酸苯氧基乙酯、季戊四醇四甲基丙烯酸酯、二季戊四醇五甲基丙烯酸酯单丙酸酯、二季戊四醇六甲基丙烯酸酯等。
进一步的，本发明所述的还可列举烯丙基缩水甘油醚、邻苯二甲酸二烯丙酯、偏苯三酸三烯丙酯、异氰尿酸三烯丙酯、丙烯酰胺、N-羟甲基丙烯酰胺、二丙酮丙烯酰胺、N，N-二甲基丙烯酰胺、N，N-二乙基丙烯酰胺、N-异丙基丙烯酰胺、丙烯酰基吗啉、苯乙烯、对羟基苯乙烯、对氯苯乙烯、对溴苯乙烯、对甲基苯乙烯、醋酸乙烯酯、单氯醋酸乙烯酯、苯甲酸乙烯酯、特戊酸乙烯酯、丁酸乙烯酯、月桂酸乙烯酯、己二酸二乙烯酯等。
本发明的自由基聚合性化合物(A)可以仅使用一种，为了提高期望的特性也可以按任意比率混合两种或两种以上而使用。
组分(A)在感光性树脂组合物中的用量可以是0.1-100质量份，优选为30-80质量份，更优选为40-70质量份。
<组分(B)光引发剂>
本发明使用的组分(B)光引发剂选自式(I)或式(II)所示芴类化合物和以式(I)或式(II)所示化合物为主体结构的衍生化合物中的至少一种。该光引发剂可以仅由式(I)或式(II)所示芴类化合物或以其为主体结构的衍生化合物构成，也可以是两类化合物的组合。
进一步的，本发明所述的式(I)所示的化合物中：
Figure PCTCN2016099745-appb-000018
其中，A代表氢、卤素、硝基、C1-C10的直链或支链烷基、C3-C10的烷基环烷基、C4-C10的烷基环烷基或环烷基烷基,A中的-CH2-能够被O、N、S或C(＝O)所取代；X代表连接符或羰基；R1代表氢、卤素、C1-C20的直链或支链烷基、C4-C20的环烷基烷基或C2-C20的链烯基，R1中的-CH2-能够被O、N、S或C(＝O)所取代,R1之间能够成环；R2和R3相互独立地表示C1-C20的直链或支链烷基、C3-C20的环烷基、C4-C20的环烷基烷基或C4-C20的烷基环烷基，R2和R3中的-CH2-能够被O、N、S或C(＝O)所取代；R6和R7相互独立地表示C1-C20的直链或支链烷基、C3-C20的环烷基、C4-C20的环烷基烷基或C4-C20的烷基环烷基，R6和R6中的-CH2-能够被O、N、S或C(＝O)所取代，且R6和R7彼此相连以形成环；R8表示羟基、N-吗啉基或N-二烷基光活性基团。
作为优选方案，式(I)或式(II)所示芴类化合物包括下列结构所示的化合物1’至30’：
Figure PCTCN2016099745-appb-000019
Figure PCTCN2016099745-appb-000020
Figure PCTCN2016099745-appb-000021
Figure PCTCN2016099745-appb-000022
上述以式(I)或式(II)所示化合物为主体结构的衍生化合物是指在保持式(I)或式(II)化合物主体结构不变的前提下，通过其支链取代或彼此连接而得到的衍生物。在本发明中作为光引发剂使用时，所述以式(I)或式(II)所示化合物为主体结构的衍生化合物是如下式(III)、(IV)、(Ⅴ)、(Ⅵ)、(Ⅷ)所示的化合物：
Figure PCTCN2016099745-appb-000023
Figure PCTCN2016099745-appb-000024
其中，M表示R1、R2、R3、R6、R7、R8二聚化而形成的连接基团，M为空、C1-C24的直链或支链亚烷基、C6-C36的亚芳基或亚杂芳基，M中的-CH2-任选地被硫、氧、NH或羰基所取代，氢原子任选地被OH或NO2所取代。
示例性地，上述衍生化合物可以是下列结构的化合物：
Figure PCTCN2016099745-appb-000025
Figure PCTCN2016099745-appb-000026
组分(B)在感光性树脂组合物中的用量优选为1-5质量份。
<组分(C)着色剂>
本发明的感光性树脂组合物可进一步含有组分(C)着色剂。非限制性地，通过含有着色剂，本发明的组合物可用于形成液晶显示器的滤色器；并且在以遮光剂作为着色剂时，组合物可用于形成显示装置的滤色器中的黑底显像管。
本发明对于组分(C)着色剂的种类没有特别限定，可以是颜色指数(color index)(C.I.；The Society of Dyers and Colourists社发行)中被分类成颜料(Pigment)的那些化合物，优选具有下述C.I.序号的着色剂，如：C.I.颜料黄1(以下由于“C.I.颜料黄”是相同的所以仅记载序号)、3、11、12、13、14、15、16、17、20、24、31、53、55、60、61、65、71、73、74、81、83、86、93、95、97、98、99、100、101、104、106、108、109、110、113、114、116、117、119、120、125、126、127、128、129、137、138、139、147、148、150、151、152、153、154、155、156、166、167、168、175、180、185；C.I.颜料橙1(以下由于“C.I.颜料橙”是相同的所以仅记载序号)、5、13、14、16、17、24、34、36、38、40、43、46、49、51、55、59、61、63、64、71、73；C.I.颜料紫1(以下由于“C.I.颜料紫”是相同的所以仅记载序号)、19、23、29、30、32、36、37、38、39、40、50；C.I.颜料红1(以下由于“C.I.颜料红”是相同的所以仅记载序号)、2、3、4、5、6、7、8、9、10、11、12、14、15、16、17、18、19、21、22、23、30、31、32、37、38、40、41、42、48:1、48:2、48:3、48:4、49:1、49:2、50:1、52:1、53:1、57、57:1、57:2、58:2、58:4、60:1、63:1、63:2、64:1、81:1、83、88、90:1、97、101、102、104、105、106、108、112、113、114、122、123、144、146、149、150、151、155、166、168、170、171、172、174、175、176、177、178、179、180、185、187、188、190、192、193、194、202、206、207、208、209、215、216、217、220、223、224、226、227、228、240、242、243、245、254、255、264、265；C.I.颜料蓝1(以下由于“C.I.颜料蓝”是同样的所以仅记载序号)、2、15、15:3、15:4、15:6、16、22、60、64、66；C.I.颜料绿7、C.I.颜料绿36、C.I.颜料绿37；C.I.颜料棕23、C.I.颜料棕25、C.I.颜料棕26、C.I.颜料棕28；C.I.颜料黑1、C.I.颜料黑7。
在选用遮光剂作为着色剂时，优选使用黑色颜料作为遮光剂。作为黑色颜料，可列举：炭黑，钛黑(titanium black)，铜、铁、锰、钴、铬、镍、锌、钙、银等的金属氧化物、复合氧化物、金属硫化物、金属硫酸盐或金属碳酸盐等。这些黑色颜料中，优选使用具有高遮光性的炭黑，可以是槽法炭黑、炉法炭黑、热裂炭黑、灯烟炭黑等常见炭黑，优选使用遮光性优异的槽法炭黑；还可使用树脂涂覆炭黑。此外，为了调整炭黑的色调，可适宜添加上面列出 的有机颜料作为辅助颜料。实践表明，即使本发明的感光性树脂组合物中使用遮光性高的黑色颜料，也能够表现出非常好的显影性和图案完整性。
组分(C)在感光性树脂组合物中的用量为0-50质量份，优选为5-40质量份。
<组分(D)碱可溶性树脂>
本发明的聚合性组合物可以与碱可溶性树脂混合并用，碱溶性树脂(D)只要是起到粘合剂的作用，在形成图像图案时对于显影处理工序中使用的显影液优选可溶性碱性显影液，优选作为含羧基共聚物的碱可溶性树脂、特别优选具有1个以上羧基的烯属不饱和单体(以下简称“含羧基不饱和单体”(P))和其他可共聚的烯属不饱和单体(以下简称“共聚性不饱和单体”(Q))的共聚物(以下简称“含羧基共聚物”(R))。
作为含羧基不饱和单体可列举如下化合物：丙烯酸、甲基丙烯酸、巴豆酸、α-氯丙烯酸、桂皮酸等不饱和单羧酸类；马来酸、马来酸酐、富马酸、衣康酸、衣康酸酐、柠康酸、柠康酸酐、中康酸等不饱和二羧酸或其酸酐类；三元以上的不饱和多元羧酸或其酸酐类；琥珀酸单(2-丙烯酰氧基乙基)、琥珀酸单(2-甲基丙烯酰氧基乙基)、邻苯二甲酸单(2-丙烯酰氧基乙基)、邻苯二甲酸单(2-甲基丙烯酰氧基乙基)等二元以上的多元羧酸的单[(甲基)丙烯酰氧基烷基]酯类；ω-羧基聚己内酯单丙烯酸酯、ω-羧基聚己内酯单甲基丙烯酸酯等在两末端具有羧基和羟基的聚合物的单(甲基)丙烯酸酯类等。
另外，作为共聚性不饱和单体可举出例如苯乙烯、α-甲基苯乙烯、邻乙烯基甲苯、间乙烯基甲苯、对乙烯基甲苯、对氯苯乙烯、邻甲氧基苯乙烯、间甲氧基苯乙烯、对甲氧基苯乙烯、邻乙烯基苄基甲醚、间乙烯基苄基甲醚、对乙烯基苄基甲醚、邻乙烯基苄基缩水甘油醚、间乙烯基苄基缩水甘油醚、对乙烯基苄基缩水甘油醚等芳香族乙烯基化合物，茚、1-甲基茚等茚类丙烯酸缩水甘油酯、甲基丙烯酸缩水甘油酯等不饱和羧酸缩水甘油酯类，醋酸乙烯酯、丙酸乙烯酯、丁酸乙烯酯、苯甲酸乙烯酯等羧酸乙烯酯类，乙烯基甲醚、乙烯基乙醚、烯丙基缩水甘油醚等不饱和醚类，丙烯腈、甲基丙烯腈、α-氯丙烯腈、氰化乙烯叉等氰化乙烯基化合物，丙烯酰胺、甲基丙烯酰胺、α-氯丙烯酰胺、N-2-羟乙基丙烯酰胺、N-2-羟乙基甲基丙烯酰胺等不饱和酰胺类，马来酰亚胺、N-苯基马来酰亚胺、N-环己基马来酰亚胺等不饱和酰亚胺类，1，3-丁二烯、异戊二烯、氯丁二烯等脂肪族共轭二烯类，聚苯乙烯、聚丙烯酸甲酯、聚甲基丙烯酸甲酯、聚丙烯酸正丁酯、聚甲基丙烯酸正丁酯、聚硅氧烷等聚合物分子链的末端具有单丙烯酰基或单甲基丙烯酰基的大分子单体类等。这些共聚性不饱和单体可以单独使用或者混合2种以上而使用。
本发明中优选的含羧基共聚物(以下称为“含羧基共聚物(R)”)是将(P)和(Q)聚合而得；所述(P)是以丙烯酸和/或甲基丙烯酸作为必要成分，根据情况进一步含有选自琥珀酸单(2-丙烯酰氧基乙基)、琥珀酸单(2-甲基丙烯酰氧基乙基)、ω-羧基聚己内酯单丙烯酸酯和ω-羧基聚己内酯单甲基丙烯酸酯中的至少1种化合物的含羧基不饱和单体成分；所述(Q)是选自苯乙烯、丙烯酸甲酯、甲基丙烯酸甲酯、丙烯酸-2-羟基乙酯、甲基丙烯酸-2-羟基乙酯、丙烯酸烯丙酯、甲基丙烯酸烯丙酯、丙烯酸苄酯、甲基丙烯酸苄酯、甘油单丙烯酸酯、甘油单甲基丙烯酸酯、N-苯基马来酰亚胺、聚苯乙烯大分子单体和聚甲基丙烯酸甲酯大分子单体中的至少1种。
作为含羧基共聚物(R)的具体例可举出(甲基)丙烯酸/(甲基)丙烯酸甲酯共聚物、(甲基)丙烯酸/(甲基)丙烯酸苄酯共聚物、(甲基)丙烯酸/(甲基)丙烯酸-2-羟基乙酯/(甲基)丙烯酸苄酯共聚物、(甲基)丙烯酸/(甲基)丙烯酸甲酯/聚苯乙烯大分子单体共聚物、(甲基)丙烯酸/(甲基)丙烯酸甲酯/聚甲基丙烯酸甲酯大分子单体共聚物、(甲基)丙烯酸/(甲基)丙烯酸苄酯/聚苯乙烯大分子单体共聚物、(甲基)丙烯酸/(甲基)丙烯酸苄酯/聚甲基丙烯酸甲酯大分子单体共聚物、(甲基)丙烯酸/(甲基)丙烯酸-2-羟基乙酯/(甲基)丙烯酸苄酯/聚苯乙烯大分子单体 共聚物、(甲基)丙烯酸/(甲基)丙烯酸-2-羟基乙酯/(甲基)丙烯酸苄酯/聚甲基丙烯酸甲酯大分子单体共聚物、甲基丙烯酸/苯乙烯/(甲基)丙烯酸苄酯/N-苯基马来酰亚胺共聚物、(甲基)丙烯酸/琥珀酸单[2-(甲基)丙烯酰氧基乙基]/苯乙烯/(甲基)丙烯酸苄酯/N-苯基马来酰亚胺共聚物、(甲基)丙烯酸/琥珀酸单[2-(甲基)丙烯酰氧基乙基]/苯乙烯/(甲基)丙烯酸烯丙酯/N-苯基马来酰亚胺共聚物、(甲基)丙烯酸/苯乙烯/(甲基)丙烯酸苄酯/甘油单(甲基)丙烯酸酯/N-苯基马来酰亚胺共聚物、(甲基)丙烯酸/ω-羧基聚己内酯单(甲基)丙烯酸酯/苯乙烯/(甲基)丙烯酸苄酯/甘油单(甲基)丙烯酸酯/N-苯基马来酰亚胺共聚物等含羧基共聚物分子中存在的取代基还可以由其他材料进行修饰。
本发明中，碱可溶性树脂(D)可以单独使用或者混合2种以上而使用。
组分(D)在感光性树脂组合物中的用量为0-80质量份，优选为20-60质量份。
<其它任选组分>
根据产物应用需要，该组合物中还可根据需要添加一种或多种大分子或高分子化合物来提高组合物在使用过程中的应用性能，这种大分子或高分子化合物可以是多元醇或聚酯多元醇，也可选择性的加入不含有反应官能团的聚合物，这些聚合物通常是含有酚羟基、羟基等酸性官能团的树脂，也可和其他光引发剂搭配使用。
另外在本发明的感光性树脂组合物中还可选择性地加入本领域中常用的其它助剂，包括但不限于敏化剂、分散剂、表面活性剂、溶剂等。
本发明的聚合性组合物在聚合反应时通过赋予紫外线、可见光线、近红外线等、电子束等产生的能量而聚合，可以得到作为目标的聚合物。作为赋予能量的光源，优选具有在250nm至450nm的波长区域中发光的主波长的光源。作为具有在250nm至450nm的波长区域中发光的主波长的光源的例子，可以举出超高压汞灯、高压汞灯、中压汞灯、汞氙灯、金属卤化物灯、大功率金属卤化物灯、氙灯、脉冲发光氙灯、氘灯、Led灯、荧光灯、Nd-YAG3倍波激光、He-Cd激光、氮激光、Xe-Cl准分子激光、Xe-F准分子激光、半导体激发固体激光等各种光源。
<制备及应用>
将各组分按量称取后混合均匀，即可获得本发明的感光性树脂组合物，这对于本领域技术人员来说属于公知的常规性技术。
本发明的目的还在于提供上述感光性树脂组合物在制备彩色滤光片膜、黑色矩阵、光间隔物、肋栅和干膜用光刻胶中的应用。
利用感光性树脂组合物通过光固化和光刻工艺制备RGB、BM、光间隔物等的技术已经为本领域的技术人员所熟知。通常包括以下步骤：i)将感光性树脂组合物溶解在合适的有机溶剂中，混合均匀，获得液状组合物；ii)利用涂布机，例如旋转涂布机、绕线棒涂布机、轴涂布机或喷涂布机等，将液状组合物均匀涂布在基板上；iii)进行前烘烤干燥，除去溶剂；iv)将掩膜板附在样品上进行曝光，随后显影除去未曝光区域；v)进行后烘烤，得到具有所希望形状的光致抗蚀剂干膜。
含有黑色颜料的光致抗蚀剂膜就是黑色矩阵BM，含有红、绿、蓝色颜料的光致抗蚀剂膜就是对应的R、G、B光阻。
以下将结合具体实施例对本发明作进一步详细说明，但不应将其理解为对本发明保护范围的限制。
制备实施例
实施例1
Figure PCTCN2016099745-appb-000027
(1)中间体1a的制备
向500mL的四口烧瓶中加入120g原料1a、三氯化铝67g、二氯甲烷100mL，冰水浴降至0℃，滴加80g原料1b与50mL二氯甲烷的混合溶液，控温10℃以下，约2h滴加完，滴加完继续搅拌2h，液相跟踪反应至完全，接着将物料缓慢倒入800g冰水与100mL浓盐酸(37％)配成的稀盐酸中，边加边搅拌，后倒入分液漏斗中，分出下层二氯甲烷层，并用50mL二氯甲烷继续清洗水层，合并二氯甲烷层，用5％的碳酸氢钠水溶液(每次300mL，共3次)清洗二氯甲烷层，接着水洗二氯甲烷层至pH呈中性，用150g无水硫酸镁干燥二氯甲烷层，过滤后旋蒸二氯甲烷产物溶液，甲醇重结晶，70℃烘箱干燥2h，得141g中间体1a，收率78％，纯度98％，MS(m/z):364(M+1)+。
(2)中间体1b的制备
向500mL四口烧瓶中加入73g中间体1a、盐酸羟胺14g、醋酸钠16g、150mL乙醇、50mL水，85℃加热回流搅拌5h，后停止反应，将物料倒入2000mL大烧杯中，加入1000mL水搅拌，使用200mL二氯甲烷萃取，在萃取液中加入50g无水MgSO4干燥，抽滤，将滤液减压旋蒸除去溶剂，旋转瓶中得到油状粘稠物，将粘稠物倒入150mL石油醚中搅拌析出，抽滤，得白色粉末状固体，60℃烘5h，得中间体1b57g，收率75％，纯度98％，MS(m/z):379(M+1)+。
(3)化合物1的合成
向250mL四口烧瓶中加入38g中间体1b、100mL二氯甲烷，室温下搅拌5min，然后滴加11g乙酸酐，约30min滴加完毕，继续搅拌2h，然后加入5％NaHCO3水溶液调pH值至中性，分液漏斗分出有机层，再用200mL水洗2遍，50g无水MgSO4干燥，过滤后旋蒸出溶剂，得粘稠状液体，甲醇重结晶得到白色固体粉末，过滤，得产品36g，收率85％，纯度99％。
产物结构通过核磁共振氢谱和质谱得到确认。
1H-NMR(CDCl3，500MHz)：1.0023-1.1128(3H,d)，1.409-1.4511(7H，m)，1.6157-1.6832(10H，m)，2.0824(3H，s)，8.0121-8.4465(6H，m)。MS(m/z):421(M+1)+。
实施例2
Figure PCTCN2016099745-appb-000028
(1)中间体2a的制备
向500mL的四口烧瓶中加入105g原料2a、三氯化铝67g、二氯甲烷100mL，冰水浴降至0℃，滴加74g原料2b与50mL二氯甲烷的混合溶液，控温10℃以下，约2h滴加完，滴加完继续搅拌2h，液相跟踪反应至完全，接着将物料缓慢倒入800g冰水与100mL浓盐酸(37％)配成的稀盐酸中，边加边搅拌，后倒入分液漏斗中，分出下层二氯甲烷层，并用50mL二氯甲烷继续清洗水层，合并二氯甲烷层，用5％的碳酸氢钠水溶液(每次300mL，共3次)清洗二氯甲烷层，接着水洗二氯甲烷层至pH呈中性，用150g无水硫酸镁干燥二氯甲烷层，过滤后旋蒸二氯甲烷产物溶液，甲醇重结晶，70℃烘箱干燥2h，得127g中间体2a，收率79％，纯度98％，MS(m/z):322(M+1)+。
(2)中间体2b的制备
向250mL四口烧瓶中加入64g中间体2a、37％的盐酸20g、亚硝酸异戊酯23g、100mL四氢呋喃，常温搅拌5h，停止反应；将物料倒入2000mL大烧杯中，加入1000mL水搅拌，使用200mL二氯甲烷萃取，在萃取液中加入50g无水MgSO4干燥，抽滤，将滤液减压旋蒸除去溶剂，旋转瓶中得到油状粘稠物，将粘稠物倒入150mL石油醚中搅拌析出，抽滤，得白色粉末状固体，60℃烘5h，得中间体1b57g，收率78％，纯度98％，MS(m/z):351(M+1)+。
(3)化合物2的合成
向250mL四口烧瓶中加入35g中间体2b、100mL二氯甲烷，室温下搅拌5min，然后滴加10g丙酰氯，约30min滴加完毕，继续搅拌2h，然后加入5％NaHCO3水溶液调pH值至中性，分液漏斗分出有机层，再用200mL水洗2遍，50g无水MgSO4干燥，过滤后旋蒸出溶剂，得粘稠状液体，甲醇重结晶得到白色固体粉末，过滤，得产品35g，收率86％，纯度99％。
产物结构通过核磁共振氢谱和质谱得到确认。
1H-NMR(CDCl3，500MHz)：1.0162-1.1057(3H,t)，1.5069-1.5161(5H，m)，1.6755-1.6992(4H，m)，2.2624-2.3004(2H，m)，3.8774(2H，s)7.9151-8.3325(6H，m)。MS(m/z):407(M+1)+。
实施例3
参照实施例1和2的方法，利用相应原料合成了如下表1中所示的化合物3-12。
实施例13
Figure PCTCN2016099745-appb-000029
(1)中间体13a的制备
向1L的四口烧瓶中加入原料13a 120g、原料13b即丙二酸酐43g、二氯甲烷150mL，常温搅拌，并于1h内分批加入67g三氯化铝，加完后继续搅拌2h，液相跟踪反应至完全，接着将物料缓慢倒入1200g冰水与100mL浓盐酸(37％)配成的稀盐酸中，边加边搅拌，后倒入分液漏斗中，分出下层二氯甲烷层，并用50mL二氯甲烷继续清洗水层，合并二氯甲烷层，用5％的碳酸氢钠水溶液(每次300mL，共3次)清洗二氯甲烷层，接着水洗二氯甲烷层至pH呈中性，用150g无水硫酸镁干燥二氯甲烷层，过滤后旋蒸二氯甲烷产物溶液，甲醇重结晶，70℃烘箱干燥2h，得143g中间体13a，收率87％，纯度99％，MS(m/z):326(M+1)+。
(2)中间体13b的制备
向500mL四口烧瓶中加入中间体13a 130g、98％的浓硫酸5g、乙醇100mL，连接蒸馏装置，80℃加热回流，边加热边收集反应生成的水，液相跟踪反应至不再发生变化，关闭反应，将反应液倒入500mL去离子水中，二氯甲烷萃取(每次100mL，共3次)，合并二氯甲烷层，水洗，旋蒸得中间体13b 110g，收率78％，纯度98％，MS(m/z):354(M+1)+。
(3)中间体13c的制备
向250mL四口烧瓶中加入71g中间体13b、盐酸羟胺14g、醋酸钠15g、100mL乙醇、30mL水，85℃加热回流反应5h，接着将物料倒入2000mL大烧杯中，加入1000mL水搅拌，析出大量固体，抽滤，水洗，甲醇重结晶，得白色粉末状固体，60℃烘5h，得中间体13c 70g，收率95％，纯度98％，MS(m/z):369(M+1)+。
(4)化合物13的合成
向250mL四口烧瓶中加入37g中间体13c、100mL二氯甲烷，室温下搅拌5min，然后滴加11g乙酸酐，约30min滴加完毕，继续搅拌2h，然后加入5％NaHCO3水溶液调pH值至中性，分液漏斗分出有机层，再用200mL水洗2遍，50g无水MgSO4干燥，过滤后旋蒸出溶剂，得粘稠状液体，甲醇重结晶得到白色固体粉末，过滤，得产品36g，收率89％，纯度99％。
产物结构通过核磁共振氢谱和质谱得到确认。
1H-NMR(CDCl3，500MHz)：1.2892-1.3061(3H,t)，1.6849(6H,s)，2.0812(3H，s)，3.6832(2H，s)，4.1168-4.2000(2H,m)，7.8121-8.7466(6H，m)。MS(m/z):411(M+1)+。
实施例14
Figure PCTCN2016099745-appb-000030
(1)中间体14a的制备
向1L的四口烧瓶中加入原料14a 106g、原料14b即丁二酸酐50g、二氯甲烷150mL，常温搅拌，并于1h内分批加入67g三氯化铝，加完继续搅拌2h，液相跟踪反应至完全，接着将物料缓慢倒入1200g冰水与100mL浓盐酸(37％)配成的稀盐酸中，边加边搅拌，后倒入分液漏斗中，分出下层二氯甲烷层，并用50mL二氯甲烷继续清洗水层，合并二氯甲烷层，用5％的碳酸氢钠水溶液(每次300mL，共3次)清洗二氯甲烷层，接着水洗二氯甲烷层至pH呈中性，用150g无水硫酸镁干燥二氯甲烷层，过滤后旋蒸二氯甲烷产物溶液，甲醇重结晶，70℃烘箱干燥2h，得134g中间体14a，收率86％，纯度99％，MS(m/z):312(M+1)+。
(2)中间体14b的制备
向500mL四口烧瓶中加入中间体14a 124g、98％的浓硫酸5g、环丁基甲醇100mL，连接蒸馏装置，140℃加热回流，边加热边收集反应生成的水，液相跟踪反应至不再发生变化，关闭反应，将反应液倒入500mL去离子水中，二氯甲烷萃取水层(每次100mL，共3次)，合并二氯甲烷层，水洗，旋蒸得中间体14b 117g，收率77％，纯度98％，MS(m/z):380(M+1)+。
(3)中间体14c的制备
向250mL四口烧瓶中加入76g中间体14b、亚硝酸异戊酯24g、37％的盐酸10g、50mL四氢呋喃，常温搅拌5h，停止反应；将物料倒入2000mL大烧杯中，加入1000mL水搅拌，使用200mL二氯甲烷萃取，在萃取液中加入50g无水MgSO4干燥，抽滤，将滤液减压旋蒸除去溶剂，旋转瓶中得到油状粘稠物，将粘稠物倒入150mL石油醚中搅拌析出，抽滤，得白色粉末状固体，60℃烘5h，得中间体14c 78g，收率95％，纯度98％，MS(m/z):409(M+1)+。
(4)化合物14的合成
向250mL四口烧瓶中加入41g中间体14c、100mL二氯甲烷，室温下搅拌5min，然后滴加11g丁酰氯，约30min滴加完毕，继续搅拌2h，然后加入5％NaHCO3水溶液调pH值至中 性，分液漏斗分出有机层，再用200mL水洗2遍，50g无水MgSO4干燥，过滤后旋蒸出溶剂，得粘稠状液体，甲醇重结晶得到白色固体粉末，过滤，得产品43g，收率90％，纯度99％。
产物结构通过核磁共振氢谱和质谱得到确认。
1H-NMR(CDCl3，500MHz)：1.0001-1.1102(3H，t)，1.5981-1.6002(2H,m)，1.9167-2.1621(6H，m)，2.3346-2.5842(5H，m)，3.8813(2H，s)，3.9768-4.0130(2H,m)，7.8046-8.7573(6H，m)。MS(m/z):479(M+1)+。
实施例15
参照实施例13和14的方法，利用相应原料合成了如下表1中所示的化合物15-30。
表1
Figure PCTCN2016099745-appb-000031
Figure PCTCN2016099745-appb-000032
Figure PCTCN2016099745-appb-000033
Figure PCTCN2016099745-appb-000034
Figure PCTCN2016099745-appb-000035
Figure PCTCN2016099745-appb-000036
性能评价
1、溶解性能测试
光引发剂在PGMEA中的溶解度大小，是代表其溶解性能及衡量光引发剂应用性能的指标参数之一。选用本发明的式(I)化合物与作为对比的现有含硝基咔唑肟酯类光引发剂，分别测试了25℃时它们在PGMEA中的溶解度，结果如表2中所示。
表2
Figure PCTCN2016099745-appb-000037
Figure PCTCN2016099745-appb-000038
Figure PCTCN2016099745-appb-000039
从上表可以看出，作为对比的化合物A和B两种现有含硝基咔唑肟酯类光引发剂在PGMEA中基本不溶解，而本发明的化合物在PGMEA中有很好的溶解度，且均满足工业化应用中溶解度需大于8％重量比的要求。
2、储存稳定性和成膜性能测试
通过配制示例性光固化组合物，对本发明式(I)所示光引发剂的储存稳定性和成膜性能进行评价。
(1)配制如下组成的光固化组合物
丙烯酸酯共聚物           200质量份
[甲基丙烯酸苄酯/甲基丙烯酸/甲基丙烯酸羟乙酯(摩尔比70/10/20)共聚物(Mv:10000)]
二季戊四醇六丙烯酸酯     100质量份
光引发剂                 5质量份
丁酮(溶剂)               900质量份
上述组合物中，光引发剂为本发明公开的式(I)所示含芴肟酯类化合物或现有技术中已知光引发剂(作为对比)。
(2)储存稳定性
将液态的光固化组合物在室温下自然储存1个月后，根据以下标准在视觉上评价物质的沉淀程度：A：没有观察到沉淀；B：略微观察到沉淀；C：观察到明显沉淀。
(3)成膜性能
将具有上述组成的示例性光固化组合物在黄光灯下搅拌，取料于PET模板上利用滚涂成膜，在90℃下干燥2min，得到干膜厚为2μm的涂膜。将形成有涂膜的基板冷却至室温，附上掩膜板，用高压汞灯1PCS光源，通过FWHM滤光片实现长波长辐射。通过掩膜板的缝隙在370-420nm波长的紫外线对涂膜进行曝光，随后于25℃下在2.5％的碳酸钠溶液中浸渍20s显影，再用超纯水洗，风干，在220℃下硬烘烤30min使图形定影，对得到的图形进行评价。
①感光度
曝光时，将在曝光步骤中光辐照区域显影后残膜率在90％或以上的最小曝光量评价为曝光需求量。曝光需求量越小表示灵敏度越高。
②显影性和图案完整性
用扫描电子显微镜(SEM)观察基板图案，以评价显影性和图案完整性。
显影性根据以下标准评价：○：在未曝光部分未观察到残留物；◎：在未曝光部分观察到少量残留物，但残留物可以接受；●：在未曝光部分观察到明显残留物。
图案完整性根据以下标准评价：◇：没有观察到图案缺陷；□：观察到小部分图案有些许缺陷；◆：明显观察到许多图案缺陷。
评价结果如表3中所示。
表3
Figure PCTCN2016099745-appb-000040
从表3中可以看出，相比于现有的含硝基咔唑肟酯类光引发剂，含有本发明的含芴肟酯类光引发剂的光固化组合物储存稳定性好，曝光需求量低，均低于60mJ/cm2，且显影效果和图案完整性更佳，具有非常优异的成膜性能。
整体而言，本发明公开的式(I)所示的含芴肟酯类光引发剂应用性能优越，且原料和制备成本低，具有很好的应用前景。
组合物的相关试验
按照表4所列配方，配制实施例53-60和比较例5-8的感光性树脂组合物。其中，比较例5-9中的光引发剂A1-A4的结构如下所示：
Figure PCTCN2016099745-appb-000041
表4
Figure PCTCN2016099745-appb-000042
Figure PCTCN2016099745-appb-000043
注：以上均为质量份
将依照表4所示配方配制好的感光性树脂组合物溶解在100质量份的溶剂丙二醇单甲醚醋酸酯(PGMEA)中，混合均匀，形成液态组合物；
利用旋转涂布机将液态组合物涂覆在玻璃基板上，然后在100℃下干燥5min除去溶剂，形成膜厚为10μm的涂膜；为获得上述厚度的涂膜，涂覆过程可以是一次完成也可以分多次进行；
将带有涂膜的基板冷却至室温，附上掩膜板，采用LED光源(依瓦塔LED UV固化照射装置，最大照射强度400mW/cm2)，通过掩膜板的缝隙在370-420nm波长的紫外线照射下对涂膜进行曝光；
在25℃温度下，使用1％的NaOH水溶液显影，再用超纯水洗涤，风干；
最后，在240℃的烘箱中后烘烤30min，得到掩膜板转移的图案。
性能评价
1、曝光灵敏度评价
将在曝光步骤中光辐照区域显影后残膜率在90％或以上的最小曝光量评价为曝光需求量，曝光需求量越小表示灵敏度越高。
2、显影性和图案完整性评价
用扫描电子显微镜(SEM)观察基板上图案，以评价显影性和图案完整性。
显影性根据以下标准评价：
○：在未曝光部分未观察到残留物；◎：在未曝光部分观察到少量残留物，但残留量可以接受；●：在未曝光部分观察到明显残留物。
图案完整性根据以下标准评价：
△：没有观察到图案缺陷；□：观察到小部分图案有些许缺陷；▲：明显观察到许多图案缺陷。
3、硬度评价
参照GB/T 6739-1996《涂膜硬度铅笔测定法》进行评价。使用涂膜铅笔划痕硬度仪，观察漆膜划痕痕迹，以未见划痕的铅笔为涂膜的铅笔硬度。
4、附着力评价
参照GB9286-88《色漆和清漆漆膜的划格试验》，通过划格实验方法评价涂膜附着力好坏。根据破坏程度分为0-5级(共6个等级),其中最好为0级,膜面没有任一个小格脱落；5级为极差,膜面产生了严重的剥落。
评价结果如表5中所示。
表5
Figure PCTCN2016099745-appb-000044
从表5的结果可以看出，实施例53-60的组合物所制得的滤光片光阻具有很好的显影性和图案完整性，附着力及硬度方面也非常优异，而比较例5-8在这些方面明显存在不足。需要特别注意的是，实施例53-60的曝光剂量均不高于70mJ/cm2，远远低于比较实施例5-8，表现出了极其优异的感光灵敏度。
综上所述，本发明的感光性树脂组合物表现出了非常优异的应用性能，具有广阔的应用前景。
以上所述仅为本发明的优选实施例而已，并不用于限制本发明，对于本领域的技术人员来说，本发明可以有各种更改和变化。凡在本发明的精神和原则之内，所作的任何修改、等同替换、改进等，均应包含在本发明的保护范围之内。

Claims (24)

  1. 一种含芴肟酯类光引发剂，其特征在于，具有如下式(I)所示结构：
    Figure PCTCN2016099745-appb-100001
    其中，
    R1各自独立地代表氢、卤素、C1-C20的直链或支链烷基、C4-C20的环烷基烷基、C2-C20的链烯基，这些基团中的-CH2-可任选地被-O-取代；
    R2代表C3-C20的环烷基、C4-C20的环烷基烷基或烷基环烷基，或者代表-R4-COO-R5，其中，R4代表C1-C10的亚烷基、C3-C10的亚环烷基、C6-C20的亚芳基或取代亚芳基，其中亚烷基中的非末端-CH2-和环烷基中的-CH2-可任选地被-O-所取代，芳基中的CH可任选地被N所取代；R5代表C1-C20的直链或支链烷基、C3-C20的环烷基、C4-C20的烷基环烷基或环烷基烷基、C6-C30的芳基或取代芳基、C7-C30的芳烷基、C2-C20的链烯基，其中的-CH2-可任选地被-O-、-S-或-NH-所取代；
    R3代表C1-C20的直链或支链烷基、C3-C20环烷基、C4-C20的烷基环烷基或环烷基烷基、C6-C30的芳基或取代芳基、C7-C30的芳烷基、C2-C20的链烯基；
    A代表氢、卤素、硝基、C1-C10的直链或支链烷基、C4-C10的烷基环烷基或环烷基烷基；
    X代表空或羰基，其中空表示X两端的两个原子直接相连。
  2. 根据权利要求1所述的含芴肟酯类光引发剂，其特征在于：所述R1各自独立地代表氢、卤素、C1-C10的直链或支链烷基、C4-C10的环烷基烷基，这些基团中的-CH2-可任选地被-O-取代。
  3. 根据权利要求1或2所述的含芴肟酯类光引发剂，其特征在于：所述R1各自独立地代表氢、C1-C6的直链或支链烷基，且烷基中的一个或两个不相邻的-CH2-可任选地被-O-取代。
  4. 根据权利要求1所述的含芴肟酯类光引发剂，其特征在于：所述R2代表C3-C10的环烷基、C4-C10的环烷基烷基或烷基环烷基。
  5. 根据权利要求1或4所述的含芴肟酯类光引发剂，其特征在于：所述R2代表C3-C6的环烷基、末端被C3-C6环烷基取代的C1-C4的直链或支链烷基、被C1-C4烷基取代的C3-C6环烷基。
  6. 根据权利要求1所述的含芴肟酯类光引发剂，其特征在于：所述R4代表C1-C8的亚烷基、C3-C8的亚环烷基、亚苯基、取代亚苯基，其中亚烷基中的非末端-CH2-和环烷基中的-CH2-可任选地被-O-所取代，苯基中的CH可任选地被N所取代。
  7. 根据权利要求1或6所述的含芴肟酯类光引发剂，其特征在于：所述R4代表C1-C4的亚烷基、C3-C6的亚环烷基、亚苯基、亚吡啶基。
  8. 根据权利要求1所述的含芴肟酯类光引发剂，其特征在于：所述R5代表C1-C10的直链或支链烷基、C3-C10的环烷基、C4-C10的烷基环烷基或环烷基烷基。
  9. 根据权利要求1或8所述的含芴肟酯类光引发剂，其特征在于：所述R5代表C1-C6的直链或支链烷基、被C3-C6环烷基取代的C1-C4的直链或支链烷基。
  10. 根据权利要求1所述的含芴肟酯类光引发剂，其特征在于：所述R3代表C1-C10的直链或支链烷基、C4-C10的环烷基烷基、苯基、C2-C8的链烯基。
  11. 根据权利要求1或10所述的含芴肟酯类光引发剂，其特征在于：所述R3代表C1-C6的直链或支链烷基、末端被C3-C6环烷基取代的C1-C4的直链或支链烷基。
  12. 根据权利要求1所述的含芴肟酯类光引发剂，其特征在于：所述A是硝基。
  13. 一种感光性树脂组合物，其特征在于，包含下列组分：
    (A)具有烯属不饱和键的化合物，所述具有烯属不饱和键的化合物用于自由基聚合反应；
    (B)光引发剂，所述光引发剂为以式(I)所示的芴类化合物为主体结构的化合物中的至少一种：
    Figure PCTCN2016099745-appb-100002
    其中，
    A代表氢、卤素、硝基、C1-C10的直链或支链烷基、C3-C10的烷基环烷基、C4-C10的烷基环烷基或环烷基烷基,A中的-CH2-能够被O、N、S或C(＝O)所取代；
    X代表连接符或羰基；
    R1代表氢、卤素、C1-C20的直链或支链烷基、C4-C20的环烷基烷基或C2-C20的链烯 基，R1中的-CH2-能够被O、N、S或C(＝O)所取代,R1之间能够成环；
    R2和R3相互独立地表示C1-C20的直链或支链烷基、C3-C20的环烷基、C4-C20的环烷基烷基或C4-C20的烷基环烷基，R2和R3中的-CH2-能够被O、N、S或C(＝O)所取代；
    (C)着色剂。
  14. 根据权利要求13所述的感光性树脂组合物，其特征在于，A代表氢、硝基、C1-C10的直链或支链烷基；X代表连接符或羰基；R1代表氢、C1-C20的直链或支链烷基或被O、N、S或C(＝O)所取代的C1-C20的直链或支链烷基；R2和R3相互独立地表示C1-C20的直链或支链烷基、C3-C20的环烷基、C4-C20的环烷基烷基或C4-C20的烷基环烷基，R2和R3中的-CH2-能被O、N、S或C(＝O)所取代。
  15. 根据权利要求13或14所述的感光性树脂组合物，其特征在于，以式(I)所示的芴类化合物为主体结构的化合物，包括如下所示结构：
    Figure PCTCN2016099745-appb-100003
    Figure PCTCN2016099745-appb-100004
    Figure PCTCN2016099745-appb-100005
  16. 根据权利要求13所述的感光性树脂组合物，其特征在于，以式(I)所示的芴类化合物为主体结构的衍生化合物为：式(III)、(IV)、(Ⅴ)所示的化合物：
    Figure PCTCN2016099745-appb-100006
    Figure PCTCN2016099745-appb-100007
    其中，M表示R1、R2、R3二聚化而形成的连接基团，M为空、C1-C24的直链或支链亚烷基、C6-C36的亚芳基或亚杂芳基，M中的-CH2-任选地被硫、氧、NH或羰基所取代，氢原子任选地被OH或NO2所取代。
  17. 根据权利要求13或16所述的感光性树脂组合物，其特征在于，以式(I)所示的芴类化合物为主体结构的衍生化合物为下列结构的化合物：
    Figure PCTCN2016099745-appb-100008
    Figure PCTCN2016099745-appb-100009
  18. 权利要求1所述的感光性树脂组合物，其特征在于，所述感光性树脂组合物进一步含有碱溶性树脂(D)，优选所述碱溶性树脂的质量份为大于0且小于等于80份，更优选为20～60份。
  19. 权利要求1-12中任一项所述的含芴肟酯类光引发剂的制备方法，其特征在于，式(I)中的R2代表C3-C20的环烷基、C4-C20的环烷基烷基或烷基环烷基，所述制备方法包括以下步骤：
    (1)中间体a的合成
    原料a与原料b在三氯化铝或氯化锌的催化作用下于有机溶剂中发生傅克酰基化反应，得到中间体a，
    Figure PCTCN2016099745-appb-100010
    原料b即R2’-CO-Cl中，其中R2’表示R2或者R2-CH2-，具体是，当式(I)中X为空，则R2’表示R2，当X为羰基，则R2’表示R2-CH2-；
    (2)中间体b的合成
    当X为空时，中间体a在盐酸羟胺、醋酸钠的作用下进行肟化反应，生成中间体b；
    当X为羰基时，在有机溶剂和浓盐酸存在下，中间体a与亚硝酸酯或亚硝酸盐于常温下进行肟化反应，生成中间体b；
    Figure PCTCN2016099745-appb-100011
    (3)式(I)化合物的合成
    中间体b与酸酐(R3-CO)2O或酰氯化合物R3-CO-Cl进行酯化反应，得到目标产物；
    Figure PCTCN2016099745-appb-100012
    式(I)中的R2代表-R4-COO-R5，其中，R4代表C1-C10的亚烷基、C3-C10的亚环烷基、C6-C20的亚芳基或取代亚芳基，其中亚烷基中的非末端-CH2-和环烷基中的-CH2-可任选地被-O-所取代，芳基中的CH可任选地被N所取代；R5代表C1-C20的直链或支链烷基、C3-C20的环烷基、C4-C20的烷基环烷基或环烷基烷基、C6-C30的芳基或取代芳基、C7-C30的芳烷基、C2-C20的链烯基，其中的-CH2-可任选地被-O-、-S-或-NH-所取代(1)中间体a的合成，所述制备方法包括：
    (1’)中间体a的合成
    原料a与原料b’在三氯化铝或氯化锌的催化作用下于有机溶剂中发生傅克反应，生成中间体a’，
    Figure PCTCN2016099745-appb-100013
    原料b’的结构中，R2’表示R4或者CH2-R4，具体是，当式(I)中X为空，则R2’表示R4，当X为羰基，则R2’表示CH2-R4；
    (2’)中间体b’的合成
    中间体a’在浓硫酸或杂多酸存在条件下与原料c即醇R5OH加热回流，发生酯化反应，得到中间体b’，
    Figure PCTCN2016099745-appb-100014
    (3’)中间体c’的合成
    当X为空时，中间体b’在盐酸羟胺、醋酸钠的作用下进行肟化反应，生成中间体c’；
    当X为羰基时，在有机溶剂和浓盐酸存在下，中间体b’与亚硝酸酯或亚硝酸盐于常温下进行肟化反应，生成中间体c’；
    Figure PCTCN2016099745-appb-100015
    (4’)式(I)化合物的合成
    中间体c’与酸酐(R3-CO)2O或酰氯化合物R3-CO-Cl进行酯化反应，得到目标产物；
    Figure PCTCN2016099745-appb-100016
  20. 根据权利要求19的制备方法，其特征在于：所述步骤(2)和所述步骤(3’)中，当X为空时，使用的溶剂是醇和水的混合溶剂，反应在加热回流状态下进行。
  21. 根据权利要求19所述的制备方法，其特征在于：所述步骤(2)和所述步骤(3’)中，当X为羰基时，所用亚硝酸酯选自亚硝酸乙酯、亚硝酸异戊酯、亚硝酸异辛酯，所用亚硝酸盐选自亚硝酸钠、亚硝酸钾。
  22. 权利要求1-12中任一项所述的具有式(I)结构的含芴肟酯类光引发剂在光固化领域中的应用。
  23. 根据权利要求22所述的应用，其特征在于：所述光固化领域包括彩色光阻、黑色矩阵、光间隔物、肋栅、干膜、半导体光刻胶、油墨的制备。
  24. 权利要求13-18中任一项所述的感光性树脂组合物在制备彩色滤光片膜、光刻、黑色矩阵、光间隔物、肋栅、湿膜和干膜中的应用。
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