CN117250827A - Negative photosensitive resin with high heat resistance, yellowing resistance and chemical corrosion resistance - Google Patents
Negative photosensitive resin with high heat resistance, yellowing resistance and chemical corrosion resistance Download PDFInfo
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- CN117250827A CN117250827A CN202311051933.9A CN202311051933A CN117250827A CN 117250827 A CN117250827 A CN 117250827A CN 202311051933 A CN202311051933 A CN 202311051933A CN 117250827 A CN117250827 A CN 117250827A
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- 239000000126 substance Substances 0.000 title claims abstract description 31
- 238000004383 yellowing Methods 0.000 title claims abstract description 24
- 239000011347 resin Substances 0.000 title claims abstract description 21
- 229920005989 resin Polymers 0.000 title claims abstract description 21
- 230000007797 corrosion Effects 0.000 title claims abstract description 17
- 238000005260 corrosion Methods 0.000 title claims abstract description 17
- 239000004593 Epoxy Substances 0.000 claims abstract description 13
- 239000003431 cross linking reagent Substances 0.000 claims abstract description 13
- 229920006243 acrylic copolymer Polymers 0.000 claims abstract description 12
- 239000000178 monomer Substances 0.000 claims abstract description 10
- 239000002904 solvent Substances 0.000 claims abstract description 8
- 239000004973 liquid crystal related substance Substances 0.000 claims abstract description 6
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 35
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 12
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 claims description 8
- OUPZKGBUJRBPGC-UHFFFAOYSA-N 1,3,5-tris(oxiran-2-ylmethyl)-1,3,5-triazinane-2,4,6-trione Chemical compound O=C1N(CC2OC2)C(=O)N(CC2OC2)C(=O)N1CC1CO1 OUPZKGBUJRBPGC-UHFFFAOYSA-N 0.000 claims description 7
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 6
- 239000006087 Silane Coupling Agent Substances 0.000 claims description 6
- MPIAGWXWVAHQBB-UHFFFAOYSA-N [3-prop-2-enoyloxy-2-[[3-prop-2-enoyloxy-2,2-bis(prop-2-enoyloxymethyl)propoxy]methyl]-2-(prop-2-enoyloxymethyl)propyl] prop-2-enoate Chemical compound C=CC(=O)OCC(COC(=O)C=C)(COC(=O)C=C)COCC(COC(=O)C=C)(COC(=O)C=C)COC(=O)C=C MPIAGWXWVAHQBB-UHFFFAOYSA-N 0.000 claims description 6
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 claims description 6
- 239000004094 surface-active agent Substances 0.000 claims description 6
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 5
- 239000005977 Ethylene Substances 0.000 claims description 5
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 claims description 4
- PTJWCLYPVFJWMP-UHFFFAOYSA-N 2-[[3-hydroxy-2-[[3-hydroxy-2,2-bis(hydroxymethyl)propoxy]methyl]-2-(hydroxymethyl)propoxy]methyl]-2-(hydroxymethyl)propane-1,3-diol Chemical compound OCC(CO)(CO)COCC(CO)(CO)COCC(CO)(CO)CO PTJWCLYPVFJWMP-UHFFFAOYSA-N 0.000 claims description 4
- 239000002253 acid Substances 0.000 claims description 4
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 claims description 4
- BDJSOPWXYLFTNW-UHFFFAOYSA-N methyl 3-methoxypropanoate Chemical compound COCCC(=O)OC BDJSOPWXYLFTNW-UHFFFAOYSA-N 0.000 claims description 3
- IFPMZBBHBZQTOV-UHFFFAOYSA-N 1,3,5-trinitro-2-(2,4,6-trinitrophenyl)-4-[2,4,6-trinitro-3-(2,4,6-trinitrophenyl)phenyl]benzene Chemical compound [O-][N+](=O)C1=CC([N+](=O)[O-])=CC([N+]([O-])=O)=C1C1=C([N+]([O-])=O)C=C([N+]([O-])=O)C(C=2C(=C(C=3C(=CC(=CC=3[N+]([O-])=O)[N+]([O-])=O)[N+]([O-])=O)C(=CC=2[N+]([O-])=O)[N+]([O-])=O)[N+]([O-])=O)=C1[N+]([O-])=O IFPMZBBHBZQTOV-UHFFFAOYSA-N 0.000 claims description 2
- ALVZNPYWJMLXKV-UHFFFAOYSA-N 1,9-Nonanediol Chemical compound OCCCCCCCCCO ALVZNPYWJMLXKV-UHFFFAOYSA-N 0.000 claims description 2
- LCZVSXRMYJUNFX-UHFFFAOYSA-N 2-[2-(2-hydroxypropoxy)propoxy]propan-1-ol Chemical compound CC(O)COC(C)COC(C)CO LCZVSXRMYJUNFX-UHFFFAOYSA-N 0.000 claims description 2
- TXBCBTDQIULDIA-UHFFFAOYSA-N 2-[[3-hydroxy-2,2-bis(hydroxymethyl)propoxy]methyl]-2-(hydroxymethyl)propane-1,3-diol Chemical compound OCC(CO)(CO)COCC(CO)(CO)CO TXBCBTDQIULDIA-UHFFFAOYSA-N 0.000 claims description 2
- 239000004793 Polystyrene Substances 0.000 claims description 2
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 claims description 2
- 125000003647 acryloyl group Chemical group O=C([*])C([H])=C([H])[H] 0.000 claims description 2
- 235000019437 butane-1,3-diol Nutrition 0.000 claims description 2
- 150000001875 compounds Chemical class 0.000 claims description 2
- FOTKYAAJKYLFFN-UHFFFAOYSA-N decane-1,10-diol Chemical compound OCCCCCCCCCCO FOTKYAAJKYLFFN-UHFFFAOYSA-N 0.000 claims description 2
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 claims description 2
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 claims description 2
- 229920002223 polystyrene Polymers 0.000 claims description 2
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 claims 11
- 239000013538 functional additive Substances 0.000 claims 2
- 239000003513 alkali Substances 0.000 claims 1
- 239000010408 film Substances 0.000 description 10
- 229920002120 photoresistant polymer Polymers 0.000 description 10
- 239000011521 glass Substances 0.000 description 9
- 239000011342 resin composition Substances 0.000 description 8
- 238000002834 transmittance Methods 0.000 description 8
- 238000002474 experimental method Methods 0.000 description 5
- 238000000034 method Methods 0.000 description 5
- 239000000654 additive Substances 0.000 description 4
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- LLHKCFNBLRBOGN-UHFFFAOYSA-N propylene glycol methyl ether acetate Chemical compound COCC(C)OC(C)=O LLHKCFNBLRBOGN-UHFFFAOYSA-N 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 description 2
- 229910021642 ultra pure water Inorganic materials 0.000 description 2
- 239000012498 ultrapure water Substances 0.000 description 2
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 206010017472 Fumbling Diseases 0.000 description 1
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000002390 adhesive tape Substances 0.000 description 1
- 125000002947 alkylene group Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 229940028356 diethylene glycol monobutyl ether Drugs 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000011010 flushing procedure Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- JCGNDDUYTRNOFT-UHFFFAOYSA-N oxolane-2,4-dione Chemical compound O=C1COC(=O)C1 JCGNDDUYTRNOFT-UHFFFAOYSA-N 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 125000003356 phenylsulfanyl group Chemical group [*]SC1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 238000012216 screening Methods 0.000 description 1
- 238000004544 sputter deposition Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 238000001039 wet etching Methods 0.000 description 1
Classifications
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- G—PHYSICS
- G02—OPTICS
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
- G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour
- G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on liquid crystals, e.g. single liquid crystal display cells
- G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
- G02F1/1333—Constructional arrangements; Manufacturing methods
- G02F1/133345—Insulating layers
-
- G—PHYSICS
- G02—OPTICS
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
- G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour
- G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on liquid crystals, e.g. single liquid crystal display cells
- G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
- G02F1/1333—Constructional arrangements; Manufacturing methods
- G02F1/1335—Structural association of cells with optical devices, e.g. polarisers or reflectors
- G02F1/133509—Filters, e.g. light shielding masks
-
- 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
- G03F7/0045—Photosensitive materials with organic non-macromolecular light-sensitive compounds not otherwise provided for, e.g. dissolution inhibitors
-
- 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
- G03F7/0048—Photosensitive materials characterised by the solvents or agents facilitating spreading, e.g. tensio-active agents
-
- 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
- G03F7/033—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders the binders being polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds, e.g. vinyl polymers
-
- 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
- G03F7/038—Macromolecular compounds which are rendered insoluble or differentially wettable
Landscapes
- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
- Nonlinear Science (AREA)
- Chemical & Material Sciences (AREA)
- Spectroscopy & Molecular Physics (AREA)
- Mathematical Physics (AREA)
- Crystallography & Structural Chemistry (AREA)
- Optics & Photonics (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Optical Filters (AREA)
- Materials For Photolithography (AREA)
Abstract
The invention discloses a negative photosensitive resin with high heat resistance, yellowing resistance and chemical corrosion resistance, which is used for an insulating layer between electrodes or a cover layer of RGB color resistance in a liquid crystal panel and comprises an alkali-soluble acrylic copolymer, an ethylenically unsaturated double bond monomer, a photoinitiator, a solvent and an epoxy crosslinking agent. The negative photosensitive resin obtained by the invention can form an insulating layer between electrodes or a cover layer of RGB color resistance in a liquid crystal panel, and has excellent heat resistance yellowing resistance and chemical corrosion resistance.
Description
Technical Field
The invention belongs to the technical field of photoresist masks, and particularly relates to negative photosensitive resin with good heat yellowing resistance and chemical corrosion resistance.
Background
In the array process COA (color filter on array) of the TFT-LCD (Thin film transistor liquid crystal display) panel of the present stage, a photosensitive resin composition is generally used as an organic insulating film for filling gaps between RGB color resistors and for covering metal electrodes. Therefore, the photosensitive resin composition has high requirements on the light transmittance blocking rate of the lower RGB color resistance, namely, high light transmittance for the wavelength of visible light region is required. In view of the subsequent ITO sputtering and wet etching processes, there is also a need for higher chemical resistance requirements for the organic insulating film.
However, the resin composition generally used for the organic insulating film does not have excellent heat yellowing resistance, and has a phenomenon that the yield of the array substrate is poor due to poor chemical resistance in the COA process.
Disclosure of Invention
The invention provides a negative photosensitive resin with high heat resistance, yellowing resistance and chemical corrosion resistance, which aims at the defects of the prior art.
In order to achieve the technical purpose, the invention adopts the following technical scheme: a negative photosensitive resin with high heat resistance, yellowing resistance and chemical corrosion resistance is used for an insulating layer between electrodes or a cover layer of RGB color resistance in a liquid crystal panel, and comprises the following components in parts by weight:
alkali-soluble acrylic copolymer 100 parts
10-200 parts of monomer containing ethylene unsaturated double bond
1-50 parts of photoinitiator
50-400 parts of solvent
8-35 parts of epoxy cross-linking agent
0-10 parts of additive
The epoxy crosslinking agent has the following chemical general formula (I),
（Ⅰ）
in the chemical formula, R 1 、R 2 、R 3 And each is a C1 to C12 alkylene group.
Preferably, the additive is a silane coupling agent and/or a surfactant.
Preferably, the weight average molecular weight of the alkali-soluble acrylic copolymer is 5000-20000 in terms of polystyrene and the acid value is 30-200mg/g.
Preferably, the ethylenically unsaturated double bond-containing monomer is a compound having two or more (meth) acryloyl groups.
Preferably, the ethylenically unsaturated double bond-containing monomer is ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, glycerol di (meth) acrylate, tripropylene glycol di (meth) acrylate, 1, 3-butanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, 1, 4-butanediol di (meth) acrylate, 1, 6-hexanediol di (meth) acrylate, 1, 9-nonanediol di (meth) acrylate, 1, 10-decanediol di (meth) acrylate; one or more of glycerol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, ethoxylated pentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, tripentaerythritol hepta (meth) acrylate, tripentaerythritol octa (meth) acrylate, tetrapentaerythritol nona (meth) acrylate, tetrapentaerythritol deca (meth) acrylate, pentapentaerythritol undec (meth) acrylate, and pentapentaerythritol dodeca (meth) acrylate.
Further, the negative photosensitive resin with high heat resistance, yellowing resistance and chemical corrosion resistance comprises the following components in parts by weight:
acrylic copolymer 100 parts
Dipentaerythritol hexaacrylate DPHA 24 parts
8 parts of photoinitiator
350 parts of methyl 3-methoxypropionate
Triglycidyl isocyanurate 16 parts
Silane coupling agent 1 part
1 part of surfactant.
The beneficial effects are that: compared with the prior art, the negative photosensitive resin obtained by screening the proportion of acrylic acid to be a copolymer, the monomer containing ethylene unsaturated double bonds, the photoinitiator (c), the solvent (d) and the specific epoxy crosslinking agent and fumbling to obtain the optimal content of each component has more excellent heat-resistant yellowing performance and chemical corrosion resistance.
The present invention is further illustrated below in conjunction with specific embodiments, it being understood that these embodiments are meant to be illustrative of the invention only and not limiting the scope of the invention, and that modifications of the invention, which are equivalent to those skilled in the art to which the invention pertains, will fall within the scope of the invention as defined in the claims appended hereto.
The negative photosensitive resin with high heat resistance and yellowing resistance and chemical corrosion resistance is an insulating layer between electrodes or a cover layer of RGB color resistance in a liquid crystal panel, has excellent heat resistance and yellowing resistance and chemical corrosion resistance, and comprises an alkali-soluble acrylic copolymer (a), an ethylenically unsaturated double bond monomer (b), a photoinitiator (c), a solvent (d) and an epoxy crosslinking agent (e) in the following chemical formula 1.
[ chemical formula 1]
In the chemical formula, R1, R2 and R3 are respectively alkylene groups of C1-C12. Preferably, the negative-type photosensitive resin composition is characterized by comprising:
a) Acrylic copolymer 100 parts by weight
b) 10-200 parts by weight of monomer containing ethylene unsaturated double bond
c) 1-50 parts by weight of a photoinitiator
d) 50-400 parts by weight of a solvent
e) 8-30 parts by weight of an epoxy crosslinking agent in the chemical formula 1.
The composition, preparation method and application property effects of the negative-type photosensitive resin of the present invention are described in detail below by way of specific examples and comparative examples.
Examples
The negative-type photosensitive resin composition of the present invention may further contain some known conventional additives, preferably, the additives may be a silane coupling agent and a surfactant, depending on physical properties required for actual production.
The preparation process is as follows: 100 parts of acrylic copolymer (weight average molecular weight Mw 8700, acid value 86 mg/g), 24 parts of dipentaerythritol hexaacrylate (DPHA), 8 parts of photoinitiator (OXE 01), 16 parts of epoxy cross-linking agent (TGIC), 1 part of silane coupling agent and 1 part of surfactant are mixed in proportion, and then 350 parts of solvent methyl 3-methoxypropionate is added and stirred for dissolution, so that the corresponding negative photosensitive resin composition is obtained. The photoinitiator is 1- [4- (phenylthio) phenyl ] -1, 2-octane diketone 2- (O-benzoyl oxime) (OXE 01) manufactured by BASF, and the epoxy crosslinking agent is triglycidyl isocyanurate TGIC.
Examples 2 to 10
This example differs from the example in the types and amounts of the components, as detailed in Table 1.
TABLE 1 content of the components in the examples of the invention
The evaluation was then carried out by the following steps and methods:
photoresist film layer and development experiments: the resin composition was spin-coated on a glass plate, and then most of the solvent was removed by low-pressure suction, followed by thermal baking on a hot plate at 100 ℃ for 90s to obtain a resist film layer having a thickness of about 3 μm. Exposing the photoresist film glass covered with the photomask with exposure of 50 mJ/cm2, then developing for 90s with 2.48% tetramethyl ammonium hydroxide aqueous solution, then washing with ultrapure water, and then baking for 30 min in a 230 ℃ oven, thus obtaining the photoresist glass sheet with corresponding patterns.
Heat resistance yellowing experiment: the above-mentioned photoresist glass sheet was baked in an oven at 250℃for 1 hour, and then tested for light transmittance at 400 and nm wavelengths. The light transmittance is larger than 96% and indicated by 'O', the light transmittance is 90-96% and indicated by 'delta', and the light transmittance is smaller than 90% and indicated by 'X'.
Chemical corrosion resistance experiment: drawing a hundred grid pattern on the non-pattern photoresist glass sheet by using a hundred grid knife, respectively placing the non-pattern photoresist glass sheet in Propylene Glycol Methyl Ether Acetate (PGMEA), N-methylpyrrolidone (NMP), 1% oxalic acid aqueous solution (acidic aqueous solution) and diethylene glycol monobutyl ether solution (alkaline organic solution) containing 10% triethanolamine for 10 min, taking out the non-pattern photoresist glass sheet, flushing the non-pattern photoresist glass sheet by using ultrapure water, airing the non-pattern photoresist glass sheet, treating a film layer by using 3M adhesive tape according to a hundred grid pattern experiment, and grading ATSM (automatic teller machine).
Table 2 shows the results of the performance test of each example
As can be seen from table 2, after TGIC was added as an epoxy crosslinking agent, the photosensitive resin was obtained with more excellent heat yellowing resistance and chemical corrosion resistance than the general epoxy crosslinking agent (GMA) photosensitive resin composition or the example containing no epoxy crosslinking agent. Meanwhile, when the TGIC addition amount is in the range of 8-30 parts by weight, the photosensitive resin film has optimal 400nm light transmittance, thermal yellowing resistance and corrosion resistance. When the addition amount is less than 8 parts, the heat yellowing resistance and the chemical corrosion resistance of the film layer are drastically reduced; when the addition amount is more than 30 parts, scum occurs in the resin developing process, resulting in the problem of unclear pattern after development, and chemical resistance and yellowing are also remarkably reduced.
The weight average molecular weight Mw 8700 of the acrylic copolymer in the examples of the present invention, the acid value of 86mg/g, and too high a polymerization molecular weight may cause a significant decrease in the light transmittance, thermal yellowing resistance and corrosion resistance of the product resin film, and the weight average molecular weight Mw of the acrylic copolymer is preferably 5000 to 20000 by experiment.
With the above-described preferred embodiments according to the present invention as an illustration, the above-described descriptions can be used by persons skilled in the relevant art to make various changes and modifications without departing from the scope of the technical idea of the present invention. The technical scope of the present invention is not limited to the description, but must be determined according to the scope of claims.
Claims (6)
1. The negative photosensitive resin with high heat resistance, yellowing resistance and chemical corrosion resistance is used for an insulating layer between electrodes or a cover layer of RGB color resistance in a liquid crystal panel, and is characterized by comprising the following components in parts by weight:
alkali-soluble acrylic copolymer 100 parts
10-200 parts of monomer containing ethylene unsaturated double bond
1-50 parts of photoinitiator
50-400 parts of solvent
8-30 parts of epoxy cross-linking agent
0-10 parts of functional additive
The epoxy crosslinking agent has the following chemical general formula (I),
（Ⅰ）
in the chemical formula, R 1 、R 2 、R 3 And each is a C1 to C12 alkylene group.
2. The highly heat-resistant yellowing chemical-resistant negative photosensitive resin according to claim 1, wherein: the functional additive is a silane coupling agent and/or a surfactant.
3. The highly heat-resistant yellowing chemical-resistant negative photosensitive resin according to claim 1, wherein: the weight average molecular weight of the alkali soluble acrylic copolymer is 5000-20000 in terms of polystyrene, and the acid value is 30-200mg/g.
4. The highly heat-resistant yellowing chemical-resistant negative photosensitive resin according to claim 1, wherein: the ethylenically unsaturated double bond-containing monomer is a compound having two or more (meth) acryloyl groups.
5. The highly heat-resistant yellowing chemical-resistant negative photosensitive resin according to claim 4, wherein: the monomer containing ethylene unsaturated double bond is ethylene glycol di (methyl) acrylate, diethylene glycol di (methyl) acrylate, trimethylolpropane tri (methyl) acrylate, glycerol di (methyl) acrylate, tripropylene glycol di (methyl) acrylate, 1, 3-butanediol di (methyl) acrylate, neopentyl glycol di (methyl) acrylate, 1, 4-butanediol di (methyl) acrylate, 1, 6-hexanediol di (methyl) acrylate, 1, 9-nonanediol di (methyl) acrylate, 1, 10-decanediol di (methyl) acrylate; one or more of glycerol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, ethoxylated pentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, tripentaerythritol hepta (meth) acrylate, tripentaerythritol octa (meth) acrylate, tetrapentaerythritol nona (meth) acrylate, tetrapentaerythritol deca (meth) acrylate, pentapentaerythritol undec (meth) acrylate, and pentapentaerythritol dodeca (meth) acrylate.
6. The highly heat-resistant yellowing chemical-resistant negative photosensitive resin according to claim 1, wherein:
the components and the contents are as follows:
acrylic copolymer 100 parts
Dipentaerythritol hexaacrylate DPHA 24 parts
8 parts of photoinitiator
350 parts of methyl 3-methoxypropionate
Triglycidyl isocyanurate 16 parts
Silane coupling agent 1 part
1 part of surfactant.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202311051933.9A CN117250827A (en) | 2023-08-21 | 2023-08-21 | Negative photosensitive resin with high heat resistance, yellowing resistance and chemical corrosion resistance |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202311051933.9A CN117250827A (en) | 2023-08-21 | 2023-08-21 | Negative photosensitive resin with high heat resistance, yellowing resistance and chemical corrosion resistance |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN117250827A true CN117250827A (en) | 2023-12-19 |
Family
ID=89127171
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202311051933.9A Pending CN117250827A (en) | 2023-08-21 | 2023-08-21 | Negative photosensitive resin with high heat resistance, yellowing resistance and chemical corrosion resistance |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN117250827A (en) |
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2023
- 2023-08-21 CN CN202311051933.9A patent/CN117250827A/en active Pending
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