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WO2017059772A1 - Photo-initiateur contenant de l'ester d'oxime fluorène, synthèse de ce dernier, composition de résine photosensible le contenant et son utilisation - Google Patents

Photo-initiateur contenant de l'ester d'oxime fluorène, synthèse de ce dernier, composition de résine photosensible le contenant et son utilisation Download PDF

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Publication number
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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WIPO (PCT)
Prior art keywords
group
substituted
linear
branched alkyl
oxime ester
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
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PCT/CN2016/099745
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English (en)
Chinese (zh)
Inventor
钱晓春
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Changzhou Tronly New Electronic Materials Co Ltd
Changzhou Tronly Advanced Electronic Materials Co Ltd
Original Assignee
Changzhou Tronly New Electronic Materials Co Ltd
Changzhou Tronly Advanced Electronic Materials Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
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 Changzhou Tronly New Electronic Materials Co Ltd, Changzhou Tronly Advanced Electronic Materials Co Ltd filed Critical Changzhou Tronly New Electronic Materials Co Ltd
Priority to KR1020187012617A priority Critical patent/KR102189685B1/ko
Priority to JP2018517895A priority patent/JP6641468B2/ja
Publication of WO2017059772A1 publication Critical patent/WO2017059772A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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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

L'invention concerne un photo-initiateur contenant un ester d'oxime fluorène, tel que représenté par la formule suivante (I), la synthèse de ce dernier, une composition de résine photosensible le contenant, et son utilisation. Le composé est simple à synthétiser et peu coûteux, et il présente une bonne solubilité lors d'une application dans le domaine du photo-durcissement, il présente une stabilité de conservation et une caractéristique filmogène excellentes, il exige une faible exposition, et possède une propriété de développement et une intégralité de motifs excellentes. La composition de résine photosensible contient une résine de prépolymère photosensible aux ultraviolets, un monomère de dilution actif, le photo-initiateur contenant un ester d'oxime fluorène de la présente application, et éventuellement, un colorant et une résine soluble dans les alcalis. La composition présente une sensibilité élevée et une bonne propriété de développement, une résolution élevée et une excellente adhérence à un substrat ; elle est particulièrement appropriée pour la préparation d'une matrice noire dotée d'une propriété de protection importante contre la lumière, et un filtre de couleur et un dispositif d'affichage à cristaux liquides de grande finesse et de qualité élevée ; et peut également être appliquée dans des aspects tels que dans un élément espacement de lumière et une grille nervurée, une résine photosensible, un film humide et un film sec.
PCT/CN2016/099745 2015-10-08 2016-09-22 Photo-initiateur contenant de l'ester d'oxime fluorène, synthèse de ce dernier, composition de résine photosensible le contenant et son utilisation Ceased WO2017059772A1 (fr)

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JP2018517895A JP6641468B2 (ja) 2015-10-08 2016-09-22 フルオレン含有オキシムエステル類光開始剤、その合成、それを含有する感光性樹脂組成物及びその使用

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WO2018060110A1 (fr) * 2016-09-28 2018-04-05 Merck Patent Gmbh Matériau polymérisable à cristaux liquides et film polymérisé à cristaux liquides
JP2018537518A (ja) * 2015-09-23 2018-12-20 キスコＫｉｓｃｏ 耐熱安定性に優れたオキシムエステル化合物、それを含む光重合開始剤及び感光性樹脂組成物
WO2021023144A1 (fr) * 2019-08-07 2021-02-11 常州强力电子新材料股份有限公司 Composé d'ester de fluorénoxime, son procédé de préparation et son application
JP2021507058A (ja) * 2017-12-22 2021-02-22 常州強力先端電子材料有限公司Ｃｈａｎｇｚｈｏｕ Ｔｒｏｎｌｙ Ａｄｖａｎｃｅｄ Ｅｌｅｃｔｒｏｎｉｃ Ｍａｔｅｒｉａｌｓ Ｃｏ．，Ｌｔｄ． フッ素含有フルオレンオキシムエステル系光開始剤、それを含む光硬化組成物およびその適用
WO2022048679A1 (fr) * 2020-09-07 2022-03-10 常州强力电子新材料股份有限公司 Photoamorceur ester d'oxime contenant une structure thiophène, procédé de préparation et composition de résine photosensible
CN117756974A (zh) * 2023-12-19 2024-03-26 波米科技有限公司 一种具有高分子聚合物结构的光引发剂、感光性树脂组合物及其应用
CN120554889A (zh) * 2025-07-30 2025-08-29 苏州华源控股股份有限公司 一种pet基材表面处理用疏水油墨材料及其制备方法
WO2025258982A1 (fr) * 2024-06-12 2025-12-18 동우 화인켐 주식회사 Composé ester d'oxime et photoinitiateur le comprenant

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JP6788971B2 (ja) * 2016-01-14 2020-11-25 東京応化工業株式会社 感光性組成物
JP6813398B2 (ja) * 2017-03-10 2021-01-13 東京応化工業株式会社 感光性組成物、ドライフィルム、及びパターン化された硬化膜を形成する方法
CN108117616B (zh) * 2017-11-22 2019-08-09 惠州市华泓新材料股份有限公司 二丁基芴基衍生物与其作为光引发剂的应用

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JP2018537518A (ja) * 2015-09-23 2018-12-20 キスコＫｉｓｃｏ 耐熱安定性に優れたオキシムエステル化合物、それを含む光重合開始剤及び感光性樹脂組成物
WO2018060110A1 (fr) * 2016-09-28 2018-04-05 Merck Patent Gmbh Matériau polymérisable à cristaux liquides et film polymérisé à cristaux liquides
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JP6999039B2 (ja) 2017-12-22 2022-02-04 常州強力先端電子材料有限公司 フッ素含有フルオレンオキシムエステル系光開始剤、それを含む光硬化組成物およびその適用
WO2021023144A1 (fr) * 2019-08-07 2021-02-11 常州强力电子新材料股份有限公司 Composé d'ester de fluorénoxime, son procédé de préparation et son application
WO2022048679A1 (fr) * 2020-09-07 2022-03-10 常州强力电子新材料股份有限公司 Photoamorceur ester d'oxime contenant une structure thiophène, procédé de préparation et composition de résine photosensible
CN117756974A (zh) * 2023-12-19 2024-03-26 波米科技有限公司 一种具有高分子聚合物结构的光引发剂、感光性树脂组合物及其应用
WO2025258982A1 (fr) * 2024-06-12 2025-12-18 동우 화인켐 주식회사 Composé ester d'oxime et photoinitiateur le comprenant
CN120554889A (zh) * 2025-07-30 2025-08-29 苏州华源控股股份有限公司 一种pet基材表面处理用疏水油墨材料及其制备方法

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