CN107272336A - A kind of photosensitive polymer combination of photoinitiator containing fluorenes and its application - Google Patents
A kind of photosensitive polymer combination of photoinitiator containing fluorenes and its application Download PDFInfo
- Publication number
- CN107272336A CN107272336A CN201610210118.6A CN201610210118A CN107272336A CN 107272336 A CN107272336 A CN 107272336A CN 201610210118 A CN201610210118 A CN 201610210118A CN 107272336 A CN107272336 A CN 107272336A
- Authority
- CN
- China
- Prior art keywords
- formula
- photosensitive resin
- resin composition
- branched alkyl
- substituted
- 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.)
- Pending
Links
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
-
- 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
Landscapes
- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
- Spectroscopy & Molecular Physics (AREA)
- Materials For Photolithography (AREA)
Abstract
The present invention discloses a kind of photosensitive polymer combination, comprising ultraviolet photosensitive resin resin, activity diluting monomer, light trigger and optional colouring agent and alkali soluble resins, the light trigger is selected from oxime ester compound shown in formula (I) and using compound shown in formula (II) as at least one of derivative compound of agent structure.Said composition has ISO and good developability, high resolution and with substrate excellent adhesion, it is especially suitable for preparing the colour filter and liquid crystal display device of the black matrix", fine and high-quality of high light-proofness, and can be also applied in terms of light spacer and rib grid, photoresist, wet film, dry film.
Description
Technical Field
The invention belongs to the field of organic chemistry, and particularly relates to a photosensitive resin composition containing a fluorene photoinitiator and application thereof in preparation of a color filter film (RGB), a Black Matrix (BM), a photoresist, a photo-spacer (photo-spacer), a rib (rib), a wet film, a dry film and the like.
Background
In a display device such as a liquid crystal display, a liquid crystal layer is generally provided between two substrates, opposing electrodes are disposed on each substrate, and a color filter layer formed of red (R), green (G), blue (B), black, and other pixels is disposed on the inner side of one of the substrates, opposing the liquid crystal layer. The R, G, B color weights are usually distinguished in the form of an arrangement matrix.
At present, methods for producing color filters mainly include a dyeing method, a printing method, a pigment dispersion method, and an anodic method, and among them, the pigment dispersion method is most widely used. The pigment dispersion method is a method in which a photosensitive resin composition containing a coloring material is coated on a transparent substrate, followed by image exposure, development and, optionally, post-curing, and a color filter image is formed by repeating these processes. The color filter obtained by the method has high positioning accuracy and film thickness accuracy, excellent durability (such as light resistance and heat resistance) and less pinhole defects.
In the manufacture of color filters, BMs are usually arranged in a lattice, stripe or mosaic pattern between red, green and blue patterns to prevent malfunction of thin film transistors due to light leakage or to improve contrast by preventing color mixing between colors, which requires that the BM should have high light-shielding properties. Therefore, how to form a high-efficiency BM at low cost using a photosensitive resin in which a light-shielding pigment or dye is dispersed has been a hot point of research. In general, it is desirable to improve the light-blocking properties of BM by increasing the film thickness or increasing the content of light-blocking pigments or dyes, but in cases where light-blocking properties are desired over the entire light wavelength region, these measures tend to cause significant impediments to the photosensitive properties of the composition, mainly manifested as: a difference in crosslinking density occurs between the exposed portion and the unexposed portion and the exposed bottom portion; a pigment insoluble in a developer lowers the developability, and further, the linearity of the pattern is lowered, or the pattern is peeled off to generate a residue; and so on.
Currently, the photoinitiator is usually a photosensitive composition containing oxime ester photoinitiators with carbazole or diphenyl sulfide as a main structure, but the cost of the photoinitiator is high, and the application of the photoinitiator is limited to a certain extent, so that the photoinitiator with a proper price needs to be developed.
Summary of The Invention
In view of the above circumstances, an object of the present invention is to provide a novel photosensitive resin composition which is advantageous in that it is relatively inexpensive and has good exposure sensitivity (i.e., high sensitivity) and developability, and in which a cured pattern is complete and clearly developed, resolution is high, and adhesion to a substrate is excellent in the case where the system contains a high content of a light-shielding agent or the amount of an exposure agent is low.
In order to achieve the above purpose, the following technical scheme is adopted.
A photosensitive resin composition comprising the following components:
(A) a radical polymerizable compound;
(B) the photoinitiator is at least one of a fluorene compound shown as a formula (I) or a formula (II) as a main structure compound or a derivative compound thereof:
wherein,
a represents hydrogen, halogen, nitro, C1-C10Straight or branched alkyl of (2), C3-C10Alkylcycloalkyl of (A), C4-C10Alkyl of (2)Cycloalkyl or cycloalkylalkyl, -CH in A2-can be substituted by O, N, S or C (═ O);
x represents a linker or a carbonyl group;
R1represents hydrogen, halogen, C1-C20Straight or branched alkyl of (2), C4-C20Cycloalkylalkyl or C2-C20Alkenyl of (a), R1In (C-CH)2-can be substituted by O, N, S or C (═ O), R1Can form a ring;
R2and R3Independently of one another represent C1-C20Straight or branched alkyl of (2), C3-C20Cycloalkyl of, C4-C20Cycloalkylalkyl or C4-C20Alkylcycloalkyl of R2And R3In (C-CH)2-can be substituted by O, N, S or C (═ O);
R4and R5Independently of one another represent C1-C20Straight or branched alkyl of (2), C3-C20Cycloalkyl of, C4-C20Cycloalkylalkyl or C4-C20Alkylcycloalkyl of R4And R5In (C-CH)2-can be substituted by O, N, S or C (═ O), and R4And R5Are linked to each other to form a ring;
R6represents a hydroxyl, N-morpholino or N-dialkyl photoactive group;
(C) optionally (optinally), a colorant.
(D) Optionally (optinally), an alkali soluble resin
The polymerizable composition of the present invention may be used in combination with an alkali-soluble resin, and the alkali-soluble resin (D) is preferably a soluble alkali developer as long as it functions as a binder for a developer used in a development treatment step when forming an image pattern, and is preferably an alkali-soluble resin as a carboxyl group-containing copolymer, and particularly preferably a copolymer of an ethylenically unsaturated monomer having 1 or more carboxyl groups and another copolymerizable ethylenically unsaturated monomer.
Another object of the present invention is to provide the use of the above photosensitive resin composition for preparing a photoresist for a color filter film, a black matrix, a photo spacer, a rib, and a dry film.
The photosensitive resin composition disclosed by the invention is reasonable in component combination, has very high sensitivity, can be well crosslinked and cured under very low exposure dose, and is excellent in curing effect. The film prepared from the composition has flat edge, no defect, no scum, complete and clear pattern and high hardness. The manufactured optical filter has high optical transparency, does not leak light, is manufactured under very low exposure dose, and has good precision, flatness and durability.
Detailed Description
The photosensitive resin composition of the invention has high sensitivity, good developability, high resolution and excellent adhesion with a substrate, is very suitable for preparing a black matrix with high light-shielding property, a high-precision and high-quality color filter and a liquid crystal display device, and can also be applied to aspects such as a photo spacer, a rib grid and the like.
The photosensitive resin composition of the present invention comprises components (a), (B) and optionally components (C), (D), each of which will be described in more detail below.
< component (A) radically polymerizable Compound >
In the photosensitive resin composition of the present invention, 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 chemical form such as a monomer, an oligomer, or a polymer, as long as it has at least one radically polymerizable ethylenically unsaturated bond in the molecule.
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 salts, esters, urethanes, amides, and anhydrides thereof, acrylonitrile, styrene, vinyl ethers, and also radically polymerizable compounds such as various unsaturated polyesters, unsaturated polyethers, unsaturated polyamides, and unsaturated polyurethanes, but the present invention is not limited thereto.
Further, the acrylic compound of the present invention may be exemplified by the following compounds: methyl acrylate, ethyl acrylate, propyl acrylate, isopropyl acrylate, butyl acrylate, isoamyl acrylate, hexyl acrylate, 2-ethylhexyl acrylate, octyl acrylate, decyl acrylate, dodecyl acrylate, octadecyl acrylate, isobornyl acrylate, cyclohexyl acrylate, dicyclopentenyl acrylate, dicyclopentenyloxyethyl acrylate, benzyl acrylate, 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 2-hydroxy-3-chloropropyl acrylate, 2-hydroxy-3-phenoxypropyl acrylate, 2-hydroxy-3-allyloxypropyl acrylate, 2-acryloyloxyethyl-2-hydroxypropyl phthalate, methyl acrylate, ethyl acrylate, decyl acrylate, dodecyl acrylate, isobutyl acrylate, dodecyl acrylate, 2, 2, 2-trifluoroethyl acrylate, 1, 3-butanediol methyl ether acrylate, butoxyethyl acrylate, beta-carboxyethyl acrylate, monoacryloxyethyl succinate, omega-carboxypolycaprolactone monoacrylate, trimethylsiloxyethyl acrylate, diphenyl-2-acryloxyethyl phosphate, triethylene glycol diacrylate, tetraethylene glycol diacrylate, bisphenol A diacrylate, EO-modified bisphenol A diacrylate, PO-modified bisphenol A diacrylate, hydrogenated bisphenol A diacrylate, EO-modified hydrogenated bisphenol A diacrylate, PO-modified hydrogenated bisphenol A diacrylate, bisphenol F diacrylate, EO-modified bisphenol F diacrylate, PO-modified bisphenol F diacrylate, EO-modified tetrabromobisphenol A diacrylate, bisphenol A diacrylate, Tricyclodecane dihydroxymethyl diacrylate, glycerol PO modified triacrylate, trimethylolpropane triacrylate, pentaerythritol tetraacrylate, dipentaerythritol pentaacrylate monopropionate, dipentaerythritol hexaacrylate, tetramethylolmethane tetraacrylate, and the like.
Further, the methacrylic compound of the present invention includes the following compounds: methyl methacrylate, ethyl methacrylate, hydroxyethyl methacrylate, propyl methacrylate, isopropyl methacrylate, butyl methacrylate, isoamyl methacrylate, hexyl methacrylate, 2-ethylhexyl methacrylate, octyl methacrylate, decyl methacrylate, dodecyl methacrylate, octadecyl methacrylate, isobornyl methacrylate, cyclohexyl methacrylate, dicyclopentenyl methacrylate, dicyclopentenyloxyethyl methacrylate, benzyl methacrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, 2-hydroxy-3-chloropropyl methacrylate, 2-hydroxy-3-phenoxypropyl methacrylate, methyl methacrylate, hexyl methacrylate, 2-ethylhexyl methacrylate, octyl methacrylate, decyl methacrylate, dodecyl methacrylate, octadecyl methacrylate, isobornyl methacrylate, cyclohexyl methacrylate, dicyclopentenyl methacrylate, benzyl methacrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, n-butyl methacrylate, n-, 2, 2, 2-trifluoroethyl methacrylate, 2, 2, 3, 3-tetrafluoropropyl methacrylate, 1H-hexafluoroisopropyl methacrylate, 2-methoxyethyl methacrylate, 1, 3-butanediol methyl ether methacrylate, butoxyethyl methacrylate, methoxytriethylene glycol methacrylate, methoxypolyethylene glycol #400 methacrylate, methoxypropylene glycol methacrylate, ethoxydiethylene glycol methacrylate, 2-ethylhexyl carbitol methacrylate, tetrahydrofurfuryl methacrylate, phenoxyethyl methacrylate, pentaerythritol tetramethacrylate, dipentaerythritol pentamethacrylate monopropionate, pentaerythritol penta (meth) acrylate, poly, Dipentaerythritol hexamethacrylate, and the like.
Further, the examples of the present invention include allyl glycidyl ether, diallyl phthalate, triallyl trimellitate, triallyl isocyanurate, acrylamide, N-methylolacrylamide, diacetone acrylamide, N-dimethylacrylamide, N-diethylacrylamide, N-isopropylacrylamide, acryloylmorpholine, styrene, p-hydroxystyrene, p-chlorostyrene, p-bromostyrene, p-methylstyrene, vinyl acetate, vinyl monochloroacetate, vinyl benzoate, vinyl pivalate, vinyl butyrate, vinyl laurate, and divinyl adipate.
The radical polymerizable compound (a) of the present invention may be used alone, or two or more kinds may be mixed at an arbitrary ratio to improve desired characteristics.
The amount of the component (A) in the photosensitive resin composition may be 0.1 to 100 parts by mass, preferably 30 to 80 parts by mass, more preferably 40 to 70 parts by mass.
< component (B) photoinitiator >
The component (B) photoinitiator used in the invention is at least one selected from fluorene compounds shown in formula (I) or formula (II) and derivative compounds taking the compounds shown in formula (I) or formula (II) as main structures. The photoinitiator may be composed of only fluorene compounds represented by formula (I) or formula (II) or derivative compounds having the fluorene compounds as a main structure, or may be a combination of the two compounds.
Further, in the compound represented by the formula (I) of the present invention:
wherein,
a represents hydrogen, halogen, nitro, C1-C10Straight or branched alkyl of (2), C3-C10Alkylcycloalkyl of (A), C4-C10Alkylcycloalkyl or cycloalkylalkyl of (A) — CH2-can be substituted by O, N, S or C (═ O);
x represents a linker or a carbonyl group;
R1represents hydrogen, halogen, C1-C20Straight or branched alkyl of (2), C4-C20Cycloalkylalkyl or C2-C20Alkenyl of (a), R1In (C-CH)2-can be substituted by O, N, S or C (═ O), R1Can form a ring;
R2and R3Independently of one another represent C1-C20Straight or branched alkyl of (2), C3-C20Cycloalkyl of, C4-C20Cycloalkylalkyl or C4-C20Alkylcycloalkyl of R2And R3In (C-CH)2-can be substituted by O, N, S or C (═ O);
R4and R5Independently of one another represent C1-C20Straight or branched alkyl of (2), C3-C20Cycloalkyl of, C4-C20Cycloalkylalkyl or C4-C20Alkylcycloalkyl of R4And R5In (C-CH)2-can be substituted by O, N, S or C (═ O), and R4And R5Are linked to each other to form a ring;
R6represents a hydroxyl, N-morpholino or N-dialkyl photoactive group;
preferably, the fluorene compound represented by formula (I) or formula (II) includes compounds represented by the following structures:
the derivative compound having the main structure of the compound represented by the formula (I) or (II) is a derivative obtained by substitution of branches or linkage of the compounds of the formula (I) or (II) while maintaining the main structure of the compound. When used as a photoinitiator in the present invention, the derivative compound having the main structure of the compound represented by formula (I) or formula (II) is a compound represented by the following formulae (III), (IV), (V), (VI), (VIII):
wherein M represents R1、R2、R3、R4、R5A linking group formed by dimerization, M is empty, C1-C24Linear or branched alkylene of (C)6-C36Arylene or heteroarylene of (A), of-CH in M2-optionally substituted by sulfur, oxygen, NH or carbonyl, the hydrogen atom being optionally substituted by OH or NO2And (4) substituting.
Illustratively, the derivative compound may be a compound of the following structure:
compound 31
Compound 32
Compound 33
Compound 34
Compound 35
The amount of the component (B) in the photosensitive resin composition is preferably 1 to 5 parts by mass.
< colorant of component (C) >
The photosensitive resin composition of the present invention may further contain a colorant as a component (C). Without limitation, 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 opacifying agent is used as the colorant, the composition is useful for forming a black matrix tube in a color filter of a display device.
The kind of The colorant as The component (C) in The present invention is not particularly limited, and may be those classified as pigments (pigments) in color index (C.I.; issued by The Society of Dyers and Colourists Co.), and colorants having The following C.I. numbers, such as:
c.i. pigment yellow 1 (hereinafter, the "c.i. pigment yellow" is the same and therefore only referred to by the reference numeral), 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. pigment orange 1 (hereinafter, the "c.i. pigment orange" is the same and is referred to merely as a reference numeral), 5, 13, 14, 16, 17, 24, 34, 36, 38, 40, 43, 46, 49, 51, 55, 59, 61, 63, 64, 71, 73;
c.i. pigment violet 1 (hereinafter, the same as "c.i. pigment violet" and hence the same reference numerals), 19, 23, 29, 30, 32, 36, 37, 38, 39, 40, 50;
c.i. pigment red 1 (hereinafter, the "c.i. pigment red" is the same and is referred to merely as a reference numeral), 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 and 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. pigment blue 1 (hereinafter, the same as "c.i. pigment blue" and hence the same reference numerals), 2, 15, and 15: 3. 15: 4. 15: 6. 16, 22, 60, 64, 66;
c.i. pigment green 7, c.i. pigment green 36, c.i. pigment green 37;
c.i. pigment brown 23, c.i. pigment brown 25, c.i. pigment brown 26, c.i. pigment brown 28;
c.i. pigment black 1, c.i. pigment black 7.
When a light-screening agent is selected as the coloring agent, a black pigment is preferably used as the light-screening agent. As the black pigment, there can be mentioned: carbon black, titanium black (titanium black), metal oxides, composite oxides, metal sulfides, metal sulfates, metal carbonates, and the like of copper, iron, manganese, cobalt, chromium, nickel, zinc, calcium, silver, and the like. Among these black pigments, carbon black having high light-shielding properties is preferably used, and common carbon black such as channel black, furnace black, thermal black, lampblack black and the like is used, and channel black having excellent light-shielding properties is preferably used; resin coated carbon blacks may also be used. In addition, in order to adjust the color tone of carbon black, the organic pigments listed above may be suitably added as auxiliary pigments. It has been found that the photosensitive resin composition of the present invention exhibits excellent developability and pattern integrity even when a black pigment having high light-shielding properties is used.
The amount of component (C) in the photosensitive resin composition is 0 to 50 parts by mass, preferably 5 to 40 parts by mass.
< component (D) alkali-soluble resin >
The polymerizable composition of the present invention can be used in combination with an alkali-soluble resin, and the alkali-soluble resin (D) is preferably a soluble alkali developer as long as it functions as a binder for a developer used in a developing step when forming an image pattern, and is preferably an alkali-soluble resin of a carboxyl group-containing copolymer, particularly preferably a copolymer of an ethylenically unsaturated monomer having 1 or more carboxyl groups (hereinafter referred to as "carboxyl group-containing unsaturated monomer" (P)) and another copolymerizable ethylenically unsaturated monomer (hereinafter referred to as "copolymerizable unsaturated monomer" (Q)) (hereinafter referred to as "carboxyl group-containing copolymer" (R)).
Examples of the carboxyl group-containing unsaturated monomer include the following compounds: unsaturated monocarboxylic acids such as acrylic acid, methacrylic acid, crotonic acid, α -chloroacrylic acid, cinnamic acid, etc.; unsaturated dicarboxylic acids such as maleic acid, maleic anhydride, fumaric acid, itaconic anhydride, citraconic acid, citraconic anhydride, and mesaconic acid, or anhydrides thereof; three or more membered unsaturated polycarboxylic acids or anhydrides thereof; mono [ (meth) acryloyloxyalkyl ] esters of dibasic or higher polycarboxylic acids such as succinic acid mono (2-acryloyloxyethyl), succinic acid mono (2-methacryloyloxyethyl), phthalic acid mono (2-acryloyloxyethyl) and phthalic acid mono (2-methacryloyloxyethyl); and mono (meth) acrylates of polymers having carboxyl groups and hydroxyl groups at both ends, such as ω -carboxy polycaprolactone monoacrylate and ω -carboxy polycaprolactone monomethacrylate.
Further, examples of the copolymerizable unsaturated monomer include aromatic vinyl compounds such as styrene, α -methylstyrene, o-vinyltoluene, m-vinyltoluene, p-chlorostyrene, o-methoxystyrene, m-methoxystyrene, p-methoxystyrene, o-vinylbenzyl methyl ether, m-vinylbenzyl methyl ether, p-vinylbenzyl methyl ether, o-vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl ether, p-vinylbenzyl glycidyl ether and the like, unsaturated carboxylic acid glycidyl esters such as indene-based glycidyl acrylate, 1-methylindene and the like, carboxylic acid vinyl esters such as vinyl acetate, vinyl propionate, vinyl butyrate, vinyl benzoate and the like, unsaturated ethers such as vinyl methyl ether, vinyl ethyl ether, allyl glycidyl ether and the like, vinyl cyanide compounds such as acrylonitrile, methacrylonitrile, α -chloroacrylonitrile and vinylidene cyanide, unsaturated amides such as acrylamide, methacrylamide, α -chloroacrylamide, N-2-hydroxyethylacrylamide and N-2-hydroxyethylmethacrylamide, unsaturated imides such as maleimide, N-phenylmaleimide and N-cyclohexylmaleimide, aliphatic conjugated dienes such as 1, 3-butadiene, isoprene and chloroprene, and macromonomers having a monoacryl group or a monomethacryl group at the end of a polymer molecular chain such as polystyrene, polymethyl acrylate, polymethyl methacrylate, poly-N-butyl acrylate, poly-N-butyl methacrylate and polysiloxane. These copolymerizable unsaturated monomers may be used alone or in combination of 2 or more.
The carboxyl group-containing copolymer (hereinafter referred to as "carboxyl group-containing copolymer (R)") preferable in the present invention is obtained by polymerizing (P) and (Q); the (P) is a carboxyl group-containing unsaturated monomer component containing acrylic acid and/or methacrylic acid as an essential component and further containing at least 1 compound selected from the group consisting of succinic acid mono (2-acryloyloxyethyl group), succinic acid mono (2-methacryloyloxyethyl group), omega-carboxy polycaprolactone monoacrylate and omega-carboxy polycaprolactone monomethacrylate, as the case may be; the (Q) is at least 1 selected from the group consisting of styrene, methyl acrylate, methyl methacrylate, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, allyl acrylate, allyl methacrylate, benzyl acrylate, benzyl methacrylate, glycerol monoacrylate, glycerol monomethacrylate, N-phenylmaleimide, polystyrene macromonomer and polymethyl methacrylate macromonomer.
Specific examples of the carboxyl group-containing copolymer (R) include a (meth) acrylic acid/methyl (meth) acrylate copolymer, a (meth) acrylic acid/benzyl (meth) acrylate copolymer, a (meth) acrylic acid/2-hydroxyethyl (meth) acrylate/benzyl (meth) acrylate copolymer, a (meth) acrylic acid/methyl (meth) acrylate/polystyrene macromonomer copolymer, a (meth) acrylic acid/methyl (meth) acrylate/polymethyl methacrylate macromonomer copolymer, a (meth) acrylic acid/benzyl (meth) acrylate/polystyrene macromonomer copolymer, a (meth) acrylic acid/benzyl (meth) acrylate/polymethyl methacrylate macromonomer copolymer, and a (meth) acrylic acid/2-hydroxyethyl (meth) acrylate/methyl (meth) acrylate macromonomer copolymer A benzyl) acrylate/polystyrene macromonomer copolymer, a (meth) acrylic acid/2-hydroxyethyl (meth) acrylate/benzyl (meth) acrylate/polymethyl methacrylate macromonomer copolymer, a methacrylic acid/styrene/benzyl (meth) acrylate/N-phenylmaleimide copolymer, a (meth) acrylic acid/succinic acid mono [2- (meth) acryloyloxyethyl ]/styrene/allyl (meth) acrylate/N-phenylmaleimide copolymer, a copolymer of benzyl (meth) acrylate/N-phenylmaleimide, a copolymer of benzyl (meth) acrylate/styrene, a copolymer of benzyl (meth) acrylate/N-phenylmaleimide, a copolymer of benzyl (, The substituent present in the molecule of the carboxyl group-containing copolymer such as (meth) acrylic acid/styrene/(meth) acrylic acid benzyl ester/glycerin mono (meth) acrylate/N-phenylmaleimide copolymer, and (meth) acrylic acid/ω -carboxypolycaprolactone mono (meth) acrylate/styrene/(meth) acrylic acid benzyl ester/glycerin mono (meth) acrylate/N-phenylmaleimide copolymer may be modified with other materials.
In the present invention, the alkali-soluble resin (D) may be used alone or in combination of 2 or more.
The amount of component (D) in the photosensitive resin composition is 0 to 80 parts by mass, preferably 20 to 60 parts by mass.
< other optional Components >
According to the application requirement of the product, one or more macromolecules or macromolecular compounds can be added into the composition according to the requirement to improve the application performance of the composition in the use process, the macromolecules or macromolecular compounds can be polyol or polyester polyol, polymers without a reaction functional group can also be selectively added, the polymers are usually resins containing acidic functional groups such as phenolic hydroxyl, hydroxyl and the like, and the polymers can also be matched with other photoinitiators for use.
In addition, other auxiliary agents commonly used in the art, including but not limited to sensitizers, dispersants, surfactants, solvents, etc., may be optionally added to the photosensitive resin composition of the present invention.
The polymerizable composition of the present invention is polymerized by applying energy generated by an electron beam or the like such as ultraviolet light, visible light, near infrared light or the like during polymerization reaction, and a target polymer can be obtained. As the energy-imparting light source, a light source having a dominant wavelength that emits light in a wavelength region of 250nm to 450nm is preferable. Examples of the light source having a dominant wavelength that emits light in a wavelength region of 250 to 450nm include various light sources such as an ultra-high pressure mercury lamp, a medium pressure mercury lamp, a mercury xenon lamp, a metal halide lamp, a high power metal halide lamp, a xenon lamp, a pulse light-emitting xenon lamp, a deuterium lamp, a Led lamp, a fluorescent lamp, an Nd-YAG3 double wave laser, a He-Cd laser, a nitrogen laser, a Xe-Cl excimer laser, a Xe-F excimer laser, and a semiconductor excited solid state laser.
< preparation and use >
The photosensitive resin composition of the present invention can be obtained by weighing the components in a certain amount and mixing them uniformly, which is a well-known conventional technique for those skilled in the art.
The invention also aims to provide application of the photosensitive resin composition in preparing photoresist for color filter films, black matrixes, photo spacers, ribs and dry films.
Techniques for preparing RGB, BM, photo spacers, etc. by photo-curing and photolithography processes using the photosensitive resin composition are well known to those skilled in the art. Generally comprising the steps of:
i) dissolving a photosensitive resin composition in a suitable organic solvent, and uniformly mixing to obtain a liquid composition;
ii) uniformly coating the liquid composition on the substrate using a coater such as a spin coater, a wire bar coater, a spin coater, a spray coater or the like;
iii) pre-baking and drying to remove the solvent;
iv) attaching a mask plate to the sample for exposure, followed by development to remove the unexposed regions;
v) post-baking to obtain the photoresist dry film with the desired shape.
The photoresist film containing the black pigment is the black matrix BM and the photoresist film containing the red, green and blue pigments is the corresponding R, G, B photoresist.
Detailed Description
The present invention is further illustrated by the following examples, which should not be construed as limiting the scope of the invention.
Preparation examples
Photosensitive resin compositions of examples 1 to 8 and comparative examples 1 to 4 were prepared according to the formulation shown in Table 1. The structures of the photoinitiators A1-A4 of comparative examples 1-4 are shown below:
TABLE 1
Note: the above are all mass portions
Dissolving a photosensitive resin composition prepared according to a formula shown in table 1 in 100 parts by mass of Propylene Glycol Monomethyl Ether Acetate (PGMEA) as a solvent, and uniformly mixing to form a liquid composition;
coating the liquid composition on a glass substrate by using a spin coater, and then drying at 100 ℃ for 5min to remove the solvent, thereby forming a coating film with a film thickness of 10 μm; in order to obtain a coating film with the thickness, the coating process can be completed once or carried out for multiple times;
cooling the substrate with the coating film to room temperature, attaching a mask plate, and adopting an LED light source (Eatta tower LED UV curing irradiation device, the maximum irradiation intensity is 400mW/cm2) Exposing the coating film under the irradiation of ultraviolet rays with the wavelength of 370-420nm through the gaps of the mask plate;
developing with 1% NaOH aqueous solution at 25 deg.C, washing with ultrapure water, and air drying;
and finally, post-baking for 30min in a baking oven at 240 ℃ to obtain the pattern transferred by the mask plate.
Evaluation of Performance
1. Evaluation of Exposure sensitivity
The minimum exposure amount at which the residual film ratio after development of the light-irradiated region in the exposure step is 90% or more is evaluated as the exposure demand, and a smaller exposure demand indicates a higher sensitivity.
2. Evaluation of developability and Pattern integrity
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:
o: no residue was observed in the unexposed parts;
very good: a small amount of residue was observed in the unexposed parts, but the residual amount was acceptable;
●: a clear residue was observed in the unexposed parts.
Pattern integrity was evaluated according to the following criteria:
and (delta): no pattern defects were observed;
□: a small part of the pattern was observed to have some defects;
a tangle-solidup: many pattern defects were clearly observed.
3. Evaluation of hardness
Evaluation was carried out with reference to GB/T6739-1996 pencil determination of film hardness. And observing the scratch marks of the paint film by using a film coating pencil scratch hardness instrument, and taking the pencil without the scratch as the pencil hardness of the coating film.
4. Evaluation of adhesion
According to GB9286-88 grid test of paint films of colored paint and varnish, the adhesion of the paint film is evaluated by a grid test method. The grade is 0-5 (6 grades in total) according to the damage degree, wherein the grade is 0, and no small lattice falls off from the film surface; grade 5 was very poor and severe flaking occurred on the membrane surface.
The evaluation results are shown in table 2.
TABLE 2
As can be seen from the results in Table 2, the compositions of examples 1-8 produced filter photoresists having very good developability and pattern integrity, and also excellent in adhesion and hardness, while comparative examples 1-4 clearly had disadvantages in these respects. It is particularly noted that the exposure doses of examples 1-8 are not higher than 70mJ/cm2Significantly lower than comparative examples 1 to 4, and extremely excellent photosensitivity was exhibited.
In conclusion, the photosensitive resin composition of the invention has very excellent application performance and wide application prospect.
Claims (8)
1. A photosensitive resin composition comprising the following components:
(A) a compound having an ethylenically unsaturated bond, which is used for radical polymerization;
(B) the photoinitiator is at least one of compounds taking a fluorene compound shown in a formula (I) or a formula (II) as a main structure, or the photoinitiator is at least one of derivative compounds taking the fluorene compound shown in the formula (I) or the formula (II) as a main structure:
wherein,
a represents hydrogen, halogen, nitro, C1-C10Straight or branched alkyl of (2), C3-C10Alkylcycloalkyl of (A), C4-C10Alkylcycloalkyl or cycloalkylalkyl of (A) — CH2-can be substituted by O, N, S or C (═ O);
x represents a linker or a carbonyl group;
R1represents hydrogen, halogen, C1-C20Straight or branched alkyl of (2), C4-C20Cycloalkylalkyl or C2-C20Alkenyl of (a), R1In (C-CH)2-can be substituted by O, N, S or C (═ O), R1Can form a ring;
R2and R3Independently of one another represent C1-C20Straight or branched alkyl of (2), C3-C20Cycloalkyl of, C4-C20Cycloalkylalkyl or C4-C20Alkylcycloalkyl of R2And R3In (C-CH)2-can be substituted by O, N, S or C (═ O);
R4and R5Independently of one another represent C1-C20Straight or branched alkyl of (2), C3-C20Cycloalkyl of, C4-C20Cycloalkylalkyl or C4-C20Alkylcycloalkyl of R4And R5In (C-CH)2-can be substituted by O, N, S or C (═ O), and R4And R5Are linked to each other to form a ring;
R6represents a hydroxyl, N-morpholino or N-dialkyl photoactive group;
(C) a colorant.
2. The photosensitive resin composition according to claim 1, wherein the fluorene compound represented by formula (I) has a main structure as follows:
wherein,
a represents hydrogen, nitro, C1-C10Linear or branched alkyl of (a);
x represents a linker or a carbonyl group;
R1represents hydrogen, C1-C20Or C substituted by O, N, S or C (═ O)1-C20Linear or branched alkyl of (a);
R2and R3Independently of one another represent C1-C20Straight or branched alkyl of (2), C3-C20Cycloalkyl of, C4-C20Cycloalkylalkyl or C4-C20Alkylcycloalkyl of R2And R3In (C-CH)2-can be substituted by O, N, S or C (═ O).
3. The photosensitive resin composition according to claim 1, wherein the compound having a fluorene compound represented by formula (II) as a main structure comprises the following structure:
wherein,
a represents hydrogen, nitro, C1-C10Linear or branched alkyl of (a);
R1represents hydrogen, C1-C20Or C substituted by O, N, S or C (═ O)1-C20Linear or branched alkyl of (a);
R4and R5Independently of one another represent C1-C20Straight or branched alkyl of (2), C3-C20Cycloalkyl of, C4-C20Cycloalkylalkyl of (C)4-C20Alkyl ring ofAlkyl or C6-C20Aryl of (A), R4And R5In (C-CH)2-can be substituted by O, N, S or C (═ O), and R4And R5Are linked to each other to form a ring;
R6represents a hydroxyl group, an N-morpholino group or an N-dialkyl group.
4. The photosensitive resin composition according to any one of claims 1 to 3, wherein the compound having a fluorene compound represented by formula (I) or formula (II) as a main structure has a structure represented by:
5. the photosensitive resin composition according to claim 1, wherein the derivative compound having a fluorene compound represented by formula (I) or formula (II) as a main structure is: a compound of formula (III), (IV), (V), (VI), (VIII):
wherein M represents R1、R2、R3、R4、R5A linking group formed by dimerization, M is empty, C1-C24Linear or branched alkylene of (C)6-C36Arylene or heteroarylene of (A), of-CH in M2-optionally substituted by sulfur, oxygen, NH or carbonyl, the hydrogen atom being optionally substituted by OH or NO2And (4) substituting.
6. The photosensitive resin composition according to claim 1 or 5, wherein the derivative compound having a fluorene compound represented by formula (I) or formula (II) as a main structure is a compound having the following structure:
7. the photosensitive resin composition according to claim 1, further comprising an alkali-soluble resin.
8. Use of the photosensitive resin composition of any one of claims 1 to 7 for preparing color filter films, photolithography, black matrices, photo spacers, ribs, wet films and dry films.
Priority Applications (11)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610210118.6A CN107272336A (en) | 2016-04-06 | 2016-04-06 | A kind of photosensitive polymer combination of photoinitiator containing fluorenes and its application |
| KR1020187012617A KR102189685B1 (en) | 2015-10-08 | 2016-09-22 | Fluorene-containing oxime ester photoinitiator, its synthesis, photosensitive resin composition containing the same, and its application |
| PCT/CN2016/099745 WO2017059772A1 (en) | 2015-10-08 | 2016-09-22 | Photoinitiator containing fluorene oxime ester, synthesis therefor, photosensitive resin composition containing same and use thereof |
| JP2018517895A JP6641468B2 (en) | 2015-10-08 | 2016-09-22 | Fluorene-containing oxime esters photoinitiators, their synthesis, photosensitive resin compositions containing them and their use |
| PCT/CN2016/100601 WO2017101553A1 (en) | 2015-12-15 | 2016-09-28 | Fluorene multifunctional photoinitiator and preparation and use thereof, and photosensitive resin composition containing fluorene photoinitiator and use thereof |
| EP16874613.9A EP3392232B1 (en) | 2015-12-15 | 2016-09-28 | Fluorene multifunctional photoinitiator and preparation and use thereof, and photosensitive resin composition containing fluorene photoinitiator and use thereof |
| JP2018530699A JP6725663B2 (en) | 2015-12-15 | 2016-09-28 | Fluorene-type polyfunctional photoinitiator, production and use thereof, photosensitive resin composition containing fluorene-type photoinitiator and use thereof |
| US16/061,490 US11054743B2 (en) | 2015-12-15 | 2016-09-28 | Fluorene polyfunctional photoinitiator and preparation and use thereof, and photosensitive resin composition containing fluorene photoinitiator and use thereof |
| KR1020187019720A KR102079026B1 (en) | 2015-12-15 | 2016-09-28 | Fluorene multifunctional photoinitiator and its manufacture and use, and photosensitive resin composition comprising fluorene photoinitiator and use thereof |
| DK16874613.9T DK3392232T3 (en) | 2015-12-15 | 2016-09-28 | MULTIFUNCTIONAL FLUOREN PHOTOINITIATOR AND MANUFACTURE AND APPLICATION THEREOF, AND PHOTOSENSITIVE RESIN COMPOSITION CONTAINING FLUORENE PHOTOINITIATOR AND USE THEREOF |
| TW105139349A TWI591050B (en) | 2015-12-15 | 2016-11-30 | Flourene multifunctional photoinitiator, method of production, and the use thereof, and photopolymer comprising the same and the use thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610210118.6A CN107272336A (en) | 2016-04-06 | 2016-04-06 | A kind of photosensitive polymer combination of photoinitiator containing fluorenes and its application |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN107272336A true CN107272336A (en) | 2017-10-20 |
Family
ID=60052638
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201610210118.6A Pending CN107272336A (en) | 2015-10-08 | 2016-04-06 | A kind of photosensitive polymer combination of photoinitiator containing fluorenes and its application |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN107272336A (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108290828A (en) * | 2015-09-23 | 2018-07-17 | 京仁洋行股份有限公司 | Oxime ester compound having excellent thermal stability, photopolymerization initiator and photosensitive resin composition containing same |
| WO2019101142A1 (en) * | 2017-11-22 | 2019-05-31 | 惠州市华泓新材料股份有限公司 | Dibutylfluorene derivative and application thereof as photoinitiator |
| WO2019210742A1 (en) * | 2018-05-03 | 2019-11-07 | 优缔新材料科技(苏州)有限公司 | Acrylic ketone oxime ester compound, preparation method therefor, and composition thereof |
| CN110760217A (en) * | 2018-07-25 | 2020-02-07 | 常州强力电子新材料股份有限公司 | Active energy photo-curing ink composition and application thereof |
| CN113372757A (en) * | 2021-07-29 | 2021-09-10 | 业成科技（成都）有限公司 | Ultraviolet light curing printing ink |
| CN116082298A (en) * | 2022-11-11 | 2023-05-09 | 材料科学姑苏实验室 | A kind of oxime ester photoinitiator and photosensitive composition containing it |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20140144809A (en) * | 2013-06-11 | 2014-12-22 | 애경화학 주식회사 | Photoinitiators with fluorene structure and reactive liquid crystal compositions, and photoresist compositions comprising the same |
| CN104661997A (en) * | 2012-05-03 | 2015-05-27 | 韩国化学研究院 | Novel oximester fluorine compound, and photopolymerization initiator and photoresist composition comprising same |
| CN104684888A (en) * | 2012-09-28 | 2015-06-03 | 大东凯米克斯株式会社 | Fluorene-based compound, photopolymerization initiator containing the fluorene-based compound, and photosensitive composition containing the photopolymerization initiator |
| WO2015108386A1 (en) * | 2014-01-17 | 2015-07-23 | 주식회사 삼양사 | Novel β-oximester fluorene compound, a photopolymerization initiator comprising same, and photoresist composition |
| WO2016010036A1 (en) * | 2014-07-15 | 2016-01-21 | 東京応化工業株式会社 | Photosensitive composition and compound |
-
2016
- 2016-04-06 CN CN201610210118.6A patent/CN107272336A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104661997A (en) * | 2012-05-03 | 2015-05-27 | 韩国化学研究院 | Novel oximester fluorine compound, and photopolymerization initiator and photoresist composition comprising same |
| CN104684888A (en) * | 2012-09-28 | 2015-06-03 | 大东凯米克斯株式会社 | Fluorene-based compound, photopolymerization initiator containing the fluorene-based compound, and photosensitive composition containing the photopolymerization initiator |
| KR20140144809A (en) * | 2013-06-11 | 2014-12-22 | 애경화학 주식회사 | Photoinitiators with fluorene structure and reactive liquid crystal compositions, and photoresist compositions comprising the same |
| WO2015108386A1 (en) * | 2014-01-17 | 2015-07-23 | 주식회사 삼양사 | Novel β-oximester fluorene compound, a photopolymerization initiator comprising same, and photoresist composition |
| WO2016010036A1 (en) * | 2014-07-15 | 2016-01-21 | 東京応化工業株式会社 | Photosensitive composition and compound |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108290828A (en) * | 2015-09-23 | 2018-07-17 | 京仁洋行股份有限公司 | Oxime ester compound having excellent thermal stability, photopolymerization initiator and photosensitive resin composition containing same |
| CN108290828B (en) * | 2015-09-23 | 2021-01-26 | 京仁洋行股份有限公司 | Oxime ester compound having excellent thermal stability, photopolymerization initiator containing the same, and photosensitive resin composition |
| WO2019101142A1 (en) * | 2017-11-22 | 2019-05-31 | 惠州市华泓新材料股份有限公司 | Dibutylfluorene derivative and application thereof as photoinitiator |
| US11560362B2 (en) | 2017-11-22 | 2023-01-24 | Huizhou Huahong New Material Co., Ltd. | Dibutylfluorene derivative and application thereof as photoinitiator |
| WO2019210742A1 (en) * | 2018-05-03 | 2019-11-07 | 优缔新材料科技(苏州)有限公司 | Acrylic ketone oxime ester compound, preparation method therefor, and composition thereof |
| CN110760217A (en) * | 2018-07-25 | 2020-02-07 | 常州强力电子新材料股份有限公司 | Active energy photo-curing ink composition and application thereof |
| CN113372757A (en) * | 2021-07-29 | 2021-09-10 | 业成科技（成都）有限公司 | Ultraviolet light curing printing ink |
| CN116082298A (en) * | 2022-11-11 | 2023-05-09 | 材料科学姑苏实验室 | A kind of oxime ester photoinitiator and photosensitive composition containing it |
| CN116082298B (en) * | 2022-11-11 | 2025-04-25 | 材料科学姑苏实验室 | Oxime ester photoinitiator and photosensitive composition containing the same |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| KR101804032B1 (en) | Acrylate photocurable composition | |
| JP6641468B2 (en) | Fluorene-containing oxime esters photoinitiators, their synthesis, photosensitive resin compositions containing them and their use | |
| JP6725663B2 (en) | Fluorene-type polyfunctional photoinitiator, production and use thereof, photosensitive resin composition containing fluorene-type photoinitiator and use thereof | |
| CN107272336A (en) | A kind of photosensitive polymer combination of photoinitiator containing fluorenes and its application | |
| CN104614940B (en) | A kind of photosensitive polymer combination and its application | |
| JP3940535B2 (en) | Radiation sensitive composition for black resist | |
| KR102361595B1 (en) | Black photosensitive resin composition, and black matrix and column spacer for liquid crystal display manufactured thereby | |
| CN106444282A (en) | Photosensitive resin composition containing oxime ester photoinitiator and application of photosensitive resin composition | |
| JP2003043685A (en) | Color composition, and photosensitive color composition for color filter | |
| JPH11209632A (en) | Red resin composition, photosensitive red resin composition, red image-forming photosensitive solution, production of colored image, and production of color filter | |
| KR20140145333A (en) | A colored photosensitive resin composition and color filter comprising the same | |
| KR20160103277A (en) | Color photosensitive resin composition, color filter manufactured thereby and liquid crystal display comprising the same | |
| JPH11142639A (en) | Production of black matrix and color filter and color filter | |
| JPH11209631A (en) | Green resin composition, photosensitive green resin composition, green image-forming photosensitive solution, production of colored image, and production of color filter | |
| JPH11310714A (en) | Red resin composition, photosensitive red resin composition, photosensitive fluid for formation of red image, production of colored image, and production of color filter | |
| KR102529781B1 (en) | Black photosensitive resin composition, black matrix, column sapcer and column spacer combined with black matrix for image display device produced using the same | |
| JPH10239858A (en) | Developing solution, manufacture of color image and manufacture of color filter | |
| KR102206495B1 (en) | A colored photosensitive resin comopsition | |
| KR20100094811A (en) | Colored photosensitive resin composition, color filter and liquid crystal display device prepared by using the same | |
| KR101401488B1 (en) | Colored photosensitive resin composition, and color filter and liquid crystal display device prepared by using the same | |
| KR102384000B1 (en) | Photosensitive Resin Composition and Liquid Crystal Display Device Using the Same | |
| JP2005105114A (en) | Green resin composition, photosensitive green resin composition, photosensitive liquid for formation of green image, and manufacturing methods of green image and color filter | |
| JPH11258819A (en) | Developer, production of color image and production of color filter | |
| JPH10133010A (en) | Production of color filter and color filter | |
| CN118011731A (en) | Colored photosensitive resin composition and application thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20171020 |
|
| RJ01 | Rejection of invention patent application after publication |