CN105503755A - Six-membered-carbon-nitrogen-heteroccle-based acrylate resin for colored light resistance and preparing method thereof - Google Patents
Six-membered-carbon-nitrogen-heteroccle-based acrylate resin for colored light resistance and preparing method thereof Download PDFInfo
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- CN105503755A CN105503755A CN201610012938.4A CN201610012938A CN105503755A CN 105503755 A CN105503755 A CN 105503755A CN 201610012938 A CN201610012938 A CN 201610012938A CN 105503755 A CN105503755 A CN 105503755A
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- 238000000034 method Methods 0.000 title claims abstract description 18
- 239000004925 Acrylic resin Substances 0.000 title claims abstract description 14
- 229920002120 photoresistant polymer Polymers 0.000 claims description 26
- 238000006243 chemical reaction Methods 0.000 claims description 25
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical group CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 24
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 20
- 239000003960 organic solvent Substances 0.000 claims description 18
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical group COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 claims description 13
- 239000002994 raw material Substances 0.000 claims description 12
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 6
- CERQOIWHTDAKMF-UHFFFAOYSA-N alpha-methacrylic acid Natural products CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 6
- RJUIDDKTATZJFE-UHFFFAOYSA-N but-2-enoyl chloride Chemical compound CC=CC(Cl)=O RJUIDDKTATZJFE-UHFFFAOYSA-N 0.000 claims description 5
- 150000001875 compounds Chemical class 0.000 claims description 5
- CBOIHMRHGLHBPB-UHFFFAOYSA-N hydroxymethyl Chemical compound O[CH2] CBOIHMRHGLHBPB-UHFFFAOYSA-N 0.000 claims description 5
- 239000003054 catalyst Substances 0.000 claims description 3
- 238000007259 addition reaction Methods 0.000 claims description 2
- 238000005886 esterification reaction Methods 0.000 claims description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 4
- 239000011347 resin Substances 0.000 abstract description 9
- 229920005989 resin Polymers 0.000 abstract description 9
- 230000032683 aging Effects 0.000 abstract description 8
- 239000000126 substance Substances 0.000 abstract description 7
- 239000000463 material Substances 0.000 abstract description 4
- 238000000576 coating method Methods 0.000 description 17
- 239000011248 coating agent Substances 0.000 description 15
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 14
- 239000000047 product Substances 0.000 description 13
- 239000002904 solvent Substances 0.000 description 11
- BPXVHIRIPLPOPT-UHFFFAOYSA-N 1,3,5-tris(2-hydroxyethyl)-1,3,5-triazinane-2,4,6-trione Chemical compound OCCN1C(=O)N(CCO)C(=O)N(CCO)C1=O BPXVHIRIPLPOPT-UHFFFAOYSA-N 0.000 description 8
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 8
- 238000005160 1H NMR spectroscopy Methods 0.000 description 8
- 238000005481 NMR spectroscopy Methods 0.000 description 8
- 238000001035 drying Methods 0.000 description 8
- 238000010907 mechanical stirring Methods 0.000 description 8
- 238000002390 rotary evaporation Methods 0.000 description 8
- 239000007787 solid Substances 0.000 description 8
- -1 2, 3-dihydroxypropyl Chemical group 0.000 description 7
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 7
- HFBMWMNUJJDEQZ-UHFFFAOYSA-N acryloyl chloride Chemical compound ClC(=O)C=C HFBMWMNUJJDEQZ-UHFFFAOYSA-N 0.000 description 7
- 229910052757 nitrogen Inorganic materials 0.000 description 7
- 239000012860 organic pigment Substances 0.000 description 7
- 238000002360 preparation method Methods 0.000 description 7
- 239000007983 Tris buffer Substances 0.000 description 6
- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Chemical compound OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 0.000 description 6
- 239000011247 coating layer Substances 0.000 description 5
- 238000005260 corrosion Methods 0.000 description 5
- 230000007797 corrosion Effects 0.000 description 5
- 239000000706 filtrate Substances 0.000 description 5
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 4
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 4
- 241000011547 Plebejus idas Species 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 238000001291 vacuum drying Methods 0.000 description 4
- 0 *CC*(C(*C(*1CC*)=*)=*)C1=C Chemical compound *CC*(C(*C(*1CC*)=*)=*)C1=C 0.000 description 3
- 239000006227 byproduct Substances 0.000 description 3
- 238000012512 characterization method Methods 0.000 description 3
- 239000003086 colorant Substances 0.000 description 3
- 239000005457 ice water Substances 0.000 description 3
- 239000012948 isocyanate Substances 0.000 description 3
- 239000004973 liquid crystal related substance Substances 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 238000000967 suction filtration Methods 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 2
- 230000002411 adverse Effects 0.000 description 2
- 230000005587 bubbling Effects 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- 238000013021 overheating Methods 0.000 description 2
- XOFYZVNMUHMLCC-ZPOLXVRWSA-N prednisone Chemical compound O=C1C=C[C@]2(C)[C@H]3C(=O)C[C@](C)([C@@](CC4)(O)C(=O)CO)[C@@H]4[C@@H]3CCC2=C1 XOFYZVNMUHMLCC-ZPOLXVRWSA-N 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 238000005979 thermal decomposition reaction Methods 0.000 description 2
- WDFKEEALECCKTJ-UHFFFAOYSA-N CCCNC(C=C)=O Chemical compound CCCNC(C=C)=O WDFKEEALECCKTJ-UHFFFAOYSA-N 0.000 description 1
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 1
- GLLRIXZGBQOFLM-UHFFFAOYSA-N Xanthorin Natural products C1=C(C)C=C2C(=O)C3=C(O)C(OC)=CC(O)=C3C(=O)C2=C1O GLLRIXZGBQOFLM-UHFFFAOYSA-N 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- VFHVQBAGLAREND-UHFFFAOYSA-N diphenylphosphoryl-(2,4,6-trimethylphenyl)methanone Chemical compound CC1=CC(C)=CC(C)=C1C(=O)P(=O)(C=1C=CC=CC=1)C1=CC=CC=C1 VFHVQBAGLAREND-UHFFFAOYSA-N 0.000 description 1
- 238000002845 discoloration Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000005562 fading Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- VHRYZQNGTZXDNX-UHFFFAOYSA-N methacryloyl chloride Chemical compound CC(=C)C(Cl)=O VHRYZQNGTZXDNX-UHFFFAOYSA-N 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 238000011895 specific detection Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 238000012719 thermal polymerization Methods 0.000 description 1
- 238000002834 transmittance Methods 0.000 description 1
- 239000000080 wetting agent Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D251/00—Heterocyclic compounds containing 1,3,5-triazine rings
- C07D251/02—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings
- C07D251/12—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members
- C07D251/26—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members with only hetero atoms directly attached to ring carbon atoms
- C07D251/30—Only oxygen atoms
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
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- Physics & Mathematics (AREA)
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- General Physics & Mathematics (AREA)
- Spectroscopy & Molecular Physics (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
The invention discloses a six-membered-carbon-nitrogen-heteroccle-based acrylate resin for colored light resistance. The acrylate resin is shown in the formula I, can obviously improve the mechanical property, the ageing resistance, the heat resistance and the chemical resistance of a product after being applied to the colored light resistance and has good application prospects in the field of colored light resistance materials. In addition, a preparing method of the resin is simple, efficient, environmentally friendly and mild in condition. The formula I is shown in the specification.
Description
Technical Field
The invention belongs to the field of organic chemistry, and particularly relates to a mosaic-based acrylate resin for a color photoresist and a preparation method thereof.
Background
Liquid crystal display is the mainstream technology of flat panel display, and a color filter is a key component for realizing color display of a liquid crystal display device, and the color filter utilizes the principle of filtering light to generate various colors by mixing three primary colors of red, green and blue. The color photoresist is a key material of the color filter, and the performance of the color photoresist directly affects the performance of the color filter, such as color saturation, color purity, transmittance, weather resistance and the like. Therefore, the development of a color photoresist material with excellent performance is of great significance to the field of liquid crystal display.
Disclosure of Invention
The invention aims to provide a mosaic acrylate resin for a color photoresist. Compared with the common acrylate resin in the color photoresist, the product structure of the invention introduces a mosaic structure, namely a hexabasic carbon nitrogen heterocycle with a rigid structure, can obviously improve the mechanical property, the aging resistance, the heat resistance and the chemical corrosion resistance of the product after being applied to the color photoresist, and has good application prospect in the field of color photoresist materials. In addition, the preparation method of the resin is simple, efficient, green and environment-friendly, and has mild conditions.
The invention relates to a mosaic acrylate resin for a color photoresist, which has a structure shown in the following general formula (I):
wherein,
R1represents-CH2CH2OCOCR2＝CH2、-CH2CH2OCONH(CH2)nOCOCR2＝CH2、-CH2CH(OCOCR2＝CH2)CH2OCOCR2＝CH2or-CH2CH[OCONH(CH2)nOCOCR2＝CH2]CH2OCONH(CH2)nOCOCR2＝CH2；
R2represents-CH3or-H;
n represents 2,3, 4, 5, 6, 7, 8, 9, 10, 11 or 12.
Correspondingly, the invention also relates to a preparation method of the seek-based acrylate resin for the color photoresist, which comprises the following steps: the compound of formula (I) is prepared by reacting hydroxyl-containing seek compound with (methyl) acrylic acid, (methyl) acryloyl chloride or (methyl) acrylic acid-isocyanate alkyl ester.
Specifically, the preparation method comprises the following steps:
(1) raw material S1And S2Carrying out esterification reaction in an organic solvent; or
(2) Raw material S1And S3Carrying out addition reaction in an organic solvent;
wherein,
R1' represents-CH2CH2OH or-CH2CH(OH)CH2OH；
R2represents-CH3or-H;
R3represents-Cl or-OH;
n represents 2,3, 4, 5, 6, 7, 8, 9, 10, 11 or 12.
The starting materials used in the above-described processes are all known compounds and can be obtained commercially or conveniently by known synthetic methods. The reactions involved in the process are conventional in the field of organic chemistry, and the specific reaction conditions are readily determinable to those skilled in the art, given the knowledge of the synthetic concepts disclosed herein.
In the above method (1), the type of the organic solvent is not particularly limited as long as it can dissolve the reaction raw material and does not adversely affect the reaction, and may be, for example, ethylene glycol monomethyl ether or N, N-dimethylformamide, and the amount thereof may be adjusted as required, and S is preferable13.0-3.5 times of the mass. Preferably, when S2When the (methyl) acryloyl chloride is used, the reaction system also comprises S2An equimolar amount of a catalyst selected from triethylamine or sodium hydroxide.
In the above-mentioned directionIn the method (2), the type of the organic solvent is not particularly limited as long as the reaction raw material can be dissolved and the reaction is not adversely affected, and may be ethylene glycol monomethyl ether, for example. The reaction temperature is controlled at 35-45 ℃. Raw material S3It is preferably added dropwise to the reaction system at a rate of 0.01 to 0.03 equivalent per minute. Unless otherwise specified, "equivalent" in the present invention means S in the reaction system1In terms of the molar amount of S in the reaction system1The molar amount of (a) is 1 equivalent.
As a preferable mode, in the method (1), when the raw material S2When the (methyl) acryloyl chloride is used, the method comprises the following steps: mixing the raw material S1And triethylamine in a molar ratio of 1: 3.1-3.5 (S)1In R1' get-CH2CH2OH) or 6.1 to 6.5 (S)1In R1' get-CH2CH(OH)CH2OH) into a three-neck flask equipped with mechanical stirring, a constant-temperature ice-water bath, a thermometer and nitrogen protection; ethylene glycol monomethyl ether is used as solvent and the dosage is S13.0-3.5 times of the mass; dropwise adding S with the same molar quantity as triethylamine at the speed of 0.01-0.03 equivalent per minute2，S2Stirring at room temperature for 2-3 hours after the dripping is finished, removing the organic solvent from the filtrate after suction filtration by rotary evaporation, and drying in vacuum to obtain the product.
As a preferable mode, in the method (1), when the raw material S2When the (methyl) acrylic acid is used, the method comprises the following steps: mixing the raw material S1And S2According to a molar ratio of 1: 3.02-3.08 (S)1In R1' get-CH2CH2OH) or 6.02-6.08 (S)1In R1' get-CH2CH(OH)CH2OH) into a three-necked flask equipped with mechanical stirring, thermometer and pressure reduction means; n, N-dimethyl formamide (DMF) is used as solvent, and the dosage is S13.0-3.5 times of the mass; the reaction temperature is 60-75 ℃, the pressure is reduced to remove the byproduct water after 4-5 hours of reaction, the organic solvent is removed by rotary evaporation after the reaction is completed, and the product is obtained by vacuum drying.
Preferably, the method (2) comprises the steps of: mixing the raw material S1Joining assemblyA three-neck flask with mechanical stirring, a cooling device, a thermometer and nitrogen protection; ethylene glycol monomethyl ether is used as solvent and the dosage is S13.0-3.5 times of the mass; the reaction temperature is controlled between 40 and 45 ℃, and the S equivalent is dripped at the speed of 0.01 to 0.03 equivalent per minute13 (S)1In R1' get-CH2CH2OH) or6 (S)1In R1' get-CH2CH(OH)CH2OH) equivalent of S3And after the dripping is finished, continuously stirring for 5-7 hours, then removing the organic solvent by rotary evaporation, and drying in vacuum to obtain the product.
The invention discloses the mosaic-based acrylate resin with the mosaic structure and the acrylic double bond structure, which can be used for preparing color photoresist, has excellent mechanical property, aging resistance, heat resistance and chemical corrosion resistance, excellent comprehensive performance, simple preparation, high efficiency, environmental protection and mild conditions.
Detailed Description
The present invention will be described in further detail with reference to specific examples, which should not be construed as limiting the scope of the present invention.
Preparation examples
Example 1
Adding tris (2-hydroxyethyl) isocyanurate and triethylamine into a three-neck flask equipped with mechanical stirring, a constant-temperature ice water bath, a thermometer and nitrogen protection according to a molar ratio of 1:3.1, taking ethylene glycol monomethyl ether as a solvent, using the amount of the ethylene glycol monomethyl ether to be 3.5 times of the mass of the tris (2-hydroxyethyl) isocyanurate, dropwise adding acryloyl chloride which is equal to the triethylamine and the like at a speed of 0.02 equivalent per minute, reacting the acryloyl chloride with violent heat release, and observing the temperature change of the system to prevent the thermal polymerization of double bonds of acrylic acid caused by overheating. After the dripping of the acryloyl chloride, stirring the mixture at room temperature for 2 hours, rotatably evaporating the filtrate after suction filtration to remove the organic solvent, and drying the filtrate in vacuum at the temperature of 40 ℃ for 4 hours to obtain a white solid.
The product structure was confirmed by nuclear magnetic resonance.
1H-NMR(400MHz,ACETONE-D,ppm),:3.46(t,6H)；4.58(t,6H)；5.59(d,3H)；6.05(m,3H)；6.27(d,3H)；
13C-NMR(100MHz,ACETONE-D,ppm),:44.6,60.2,128.2,131.3,148.6,166.5。
Example 2
Adding tris (2, 3-dihydroxypropyl) isocyanurate and triethylamine into a three-neck flask equipped with mechanical stirring, a constant-temperature ice-water bath, a thermometer and nitrogen protection according to a molar ratio of 1:6.5, taking ethylene glycol monomethyl ether as a solvent, using 3.0 times of the mass of tris (2, 3-dihydroxypropyl) isocyanurate, dropwise adding acryloyl chloride which is equal to the moles of triethylamine at a speed of 0.02 equivalent per minute, reacting the acryloyl chloride with violent heat release, and observing the temperature change of the system to prevent the double bond heat polymerization of acrylic acid caused by overheating. After the dripping of the acryloyl chloride, stirring the mixture at room temperature for 3 hours, rotatably evaporating the filtrate after suction filtration to remove the organic solvent, and drying the filtrate in vacuum at the temperature of 40 ℃ for 4 hours to obtain a white solid.
The product structure was confirmed by nuclear magnetic resonance.
1H-NMR(400MHz,ACETONE-D,ppm),:3.25～3.27(m,6H)；4.26～4.51(m,6H)；5.18(m,3H)；5.59(d,6H)；6.05(m,6H)；6.27(d,6H)；
13C-NMR(100MHz,ACETONE-D,ppm),:45.2,64.4,68.1,128.2,131.3,148.9,165.2,166.5。
Example 3
Referring to example 2, replacing acryloyl chloride with methacryloyl chloride ultimately yielded a white solid.
The product structure was confirmed by nuclear magnetic resonance.
1H-NMR(400MHz,ACETONE-D,ppm),:2.01(s,18H)；3.25～3.27(m,6H)；4.26～4.51(m,6H)；5.18(m,3H)；5.59(d,6H)；6.05(m,6H)；6.27(d,6H)；
13C-NMR(100MHz,ACETONE-D,ppm),:17.9,45.2,64.4,68.1,128.2,131.3,148.9,165.2,166.5。
Example 4
Adding tris (2-hydroxyethyl) isocyanurate and acrylic acid into a three-neck flask equipped with a mechanical stirrer, a thermometer and a pressure reducing device according to a molar ratio of 1:3.02, taking N, N-Dimethylformamide (DMF) as a solvent, wherein the amount of the DMF is 3.5 times of the mass of the tris (2-hydroxyethyl) isocyanurate, the reaction temperature is 60 ℃, removing generated byproduct water under reduced pressure after 5 hours of reaction, removing the organic solvent by rotary evaporation after the reaction is completed, and drying in vacuum at 40 ℃ for 4 hours to obtain a white solid.
The product structure was confirmed by nuclear magnetic resonance.
1H-NMR(400MHz,ACETONE-D,ppm),:3.46(t,6H)；4.58(t,6H)；5.59(d,3H)；6.05(m,3H)；6.27(d,3H)；
13C-NMR(100MHz,ACETONE-D,ppm),:44.6,60.2,128.2,131.3,148.6,166.5。
Example 5
Adding tris (2, 3-dihydroxypropyl) isocyanurate and acrylic acid into a three-neck flask equipped with a mechanical stirrer, a thermometer and a pressure reducing device according to a molar ratio of 1:6.08, taking N, N-Dimethylformamide (DMF) as a solvent, wherein the amount of the DMF is 3.0 times of the mass of the tris (2, 3-dihydroxypropyl) isocyanurate, reacting at 75 ℃, removing water generated as a byproduct under reduced pressure after 5 hours of reaction, removing the organic solvent by rotary evaporation after the reaction is completed, and drying in vacuum at 40 ℃ for 4 hours to obtain a white solid.
The product structure was confirmed by nuclear magnetic resonance.
1H-NMR(400MHz,ACETONE-D,ppm),:3.25～3.27(m,6H)；4.26～4.51(m,6H)；5.18(m,3H)；5.59(d,6H)；6.05(m,6H)；6.27(d,6H)；
13C-NMR(100MHz,ACETONE-D,ppm),:45.2,64.4,68.1,128.2,131.3,148.9,165.2,166.5。
Example 6
Adding tris (2-hydroxyethyl) isocyanurate into a three-neck flask equipped with a mechanical stirring device, a cooling device, a thermometer and nitrogen protection, taking ethylene glycol monomethyl ether as a solvent, controlling the using amount to be 3.0 times of the mass of the tris (2-hydroxyethyl) isocyanurate, controlling the reaction temperature to be 40 ℃, dropwise adding 3 equivalents of acrylic acid-2-isocyanate ethyl ester at the speed of 0.02 equivalent per minute, continuing to react for 5 hours after dropwise adding, removing the organic solvent by rotary evaporation, and performing vacuum drying for 4 hours at 40 ℃ to obtain a light yellow solid.
The product structure was confirmed by nuclear magnetic resonance.
1H-NMR(400MHz,ACETONE-D,ppm),:3.15(t,6H)；3.46(t,6H)；4.51～4.58(m,12H)；5.59(d,3H)；6.05(m,3H)；6.27(d,3H)；8.03(s,3H)；
13C-NMR(100MHz,ACETONE-D,ppm),:39.9,44.2,57.5,67.1,128.2,131.3,148.9,157.8,166.5。
Example 7
Adding tris (2, 3-dihydroxypropyl) isocyanurate into a three-neck flask equipped with a mechanical stirring device, a cooling device, a thermometer and nitrogen protection, taking ethylene glycol monomethyl ether as a solvent, controlling the dosage to be 3.5 times of the mass of the tris (2, 3-dihydroxypropyl) isocyanurate, controlling the reaction temperature to be 40 ℃, dropwise adding 6 equivalents of acrylic acid-2-isocyanate ethyl ester at the speed of 0.02 equivalent per minute, continuing the reaction for 7 hours after the dropwise addition is finished, removing the organic solvent by rotary evaporation, and performing vacuum drying for 4 hours at the temperature of 40 ℃ to obtain a light yellow solid.
The product structure was confirmed by nuclear magnetic resonance.
1H-NMR(400MHz,ACETONE-D,ppm),:3.15(t,12H)；3.27～3.52(m,6H)；4.20～4.45(m,6H)；4.58(t,12H)；5.18(m,3H)；5.59(d,6H)；6.05(m,6H)；6.27(d,6H)；8.03(s,6H)；
13C-NMR(100MHz,ACETONE-D,ppm),:39.9,44.8,61.3,65.0,67.1,128.2,131.3,148.9,155.9,157.8,166.5。
Example 8
Adding tris (2-hydroxyethyl) isocyanurate into a three-neck flask equipped with a mechanical stirring device, a cooling device, a thermometer and nitrogen protection, taking ethylene glycol monomethyl ether as a solvent, controlling the using amount to be 3.0 times of the mass of the tris (2-hydroxyethyl) isocyanurate, controlling the reaction temperature to be 40 ℃, dropwise adding 3 equivalents of acrylic acid-12-isocyanate-based dodecaester at the speed of 0.02 equivalent per minute, continuing to react for 5 hours after dropwise adding, removing the organic solvent by rotary evaporation, and performing vacuum drying for 4 hours at 40 ℃ to obtain a light yellow solid.
The product structure was confirmed by nuclear magnetic resonance.
1H-NMR(400MHz,ACETONE-D,ppm),:1.29～1.62(m,60H)；3.18(m,6H)；3.46(t,6H)；3.97(t,6H)；4.51(t,6H)；5.59(d,3H)；6.05(m,3H)；6.27(d,3H)；8.03(s,3H)；
13C-NMR(100MHz,ACETONE-D,ppm),:25.8,26.4,26.7,29.0,29.3,29.6,40.3,44.2,57.5,65.3,128.2,131.3,148.3,157.8,166.5。
Application examples
Application example 1
100 parts by mass of the resin synthesized in example 4, 100 parts by mass of a solvent ethylene glycol monomethyl ether, about 1 part by mass of a photoinitiator 2-methyl-1- (4-methylthiophenyl) -2-morpholine-1-one, about 1.5 parts by mass of 2-phenylbenzyl-2-dimethylamine-1- (4-morpholine-benzylphenyl) butanone, about 1.5 parts by mass of 2,4, 6-trimethylbenzoyl-diphenylphosphine oxide, about 1 part by mass of an organic pigment C.I. blue 60, and about 1 part by mass of a wetting agent OT75 were mixed and placed in a container, and predispersed on an SFJ-400 type multipurpose machine, and predispersed and mixed for 45 minutes at a rotation speed of 1500 rpm. 3ml of the mixture was filmed on a spin coater at 1000rpm for 10 s. Placing the film-formed glass sheet into an oven at 60 deg.C, baking for 5min, and exposing to light (light source type Fusion-LH6) at an exposure of 2000mJ/cm2Development in 1% strength potassium hydroxide solution, subsequent postbaking at 90 ℃1h, obtaining the photoresist coating layer 1.
Application example 2
Referring to application example 1, the resin synthesized in example 4 was replaced with the resin synthesized in example 6, and the organic pigment c.i. blue 60 was replaced with the organic pigment c.i. yellow 12, and other conditions were not changed to obtain a resist coating layer 2.
Application example 3
Referring to application example 1, the resin synthesized in example 4 was replaced with the resin synthesized in example 7, and the organic pigment c.i. blue 60 was replaced with the organic pigment c.i. red 3, and the other conditions were not changed, to obtain a resist coating layer 3.
Application example 4
Referring to application example 1, the resin synthesized in example 4 was replaced with the resin synthesized in example 8, and the organic pigment c.i. blue 60 was replaced with the organic pigment c.i. black 11, and the other conditions were not changed to obtain a resist coating layer 4.
Performance characterization
The photoresist coatings 1-4 prepared in the application examples 1-4 are subjected to performance characterization, including mechanical properties, aging resistance, heat resistance and chemical corrosion resistance. The specific detection method and steps are as follows:
(1) and (3) measuring the mechanical property: the mechanical property test of the color light resistance coating refers to a detection method of national standard GB/T6739-1996, the pencil hardness is tested and rated, and the higher the rating number is, the better the performance is.
(2) The method for measuring and evaluating the aging resistance comprises the following steps: the color light resistance coating is placed on an ATLAS-UV2000 aging instrument to be continuously irradiated for 200 hours, then the light resistance coating is tested by a desktop color difference spectrophotometer Datacolor600 for the color difference (delta E) before and after the light resistance coating, and the smaller the delta E value is, the better the aging resistance of the light resistance coating is.
(3) Heat resistance measurement and evaluation methods: color photoresists were tested for thermal decomposition temperature (T) using TGA-Q500d)，TdThe larger the value, the photoresist coating is indicatedThe better the heat resistance.
(4) Chemical resistance test: and (3) putting the color photoresist coating into a vacuum oven at 60 ℃ for baking for 8 hours, taking out the color photoresist coating, completely soaking the color photoresist coating into an analytically pure acetone solution for 30 minutes, then putting the color photoresist coating into a blast drying oven at 40 ℃ for drying for 1 hour, and observing whether the color photoresist coating has wrinkling, bubbling, discoloring and fading phenomena.
The characterization results are shown in the following table:
as can be seen from the above table, the photoresist coatings of various colors prepared by using the inventive seek-based acrylate resin have very high hardness and small color difference Delta E. Thermal decomposition temperature (T) of the respective coating layersd) The temperature of the coating exceeds 400 ℃, the heat resistance is excellent, and further experiments show that the surface morphology and the chromaticity of the coating are basically not changed after the coating is baked for 5 minutes at the high temperature of 280 ℃. After being soaked in an analytically pure acetone solution for 30 minutes and dried, the photoresist coating has no phenomena of wrinkling, bubbling, discoloration and color loss and shows good chemical corrosion resistance.
In conclusion, the invention can be used for preparing color photoresist, has excellent mechanical property, aging resistance, heat resistance and chemical corrosion resistance, has excellent comprehensive performance and has good application prospect.
Claims (8)
1. A kind of mosaic acrylate resin for color photoresist has the following general formula (I):
wherein,
R1represents-CH2CH2OCOCR2＝CH2、-CH2CH2OCONH(CH2)nOCOCR2＝CH2、-CH2CH(OCOCR2＝CH2)CH2OCOCR2＝CH2or-CH2CH[OCONH(CH2)nOCOCR2＝CH2]CH2OCONH(CH2)nOCOCR2＝CH2；
R2represents-CH3or-H;
n represents 2,3, 4, 5, 6, 7, 8, 9, 10, 11 or 12.
2. The method for preparing the seek-based acrylate resin for color photoresist of claim 1, comprising: the compound of formula (I) is prepared by reacting hydroxyl-containing seek compound with (methyl) acrylic acid, (methyl) acryloyl chloride or (methyl) acrylic acid-isocyanate alkyl ester.
3. The method of manufacturing according to claim 2, comprising:
(1) raw material S1And S2Carrying out esterification reaction in an organic solvent; or
(2) Raw material S1And S3Carrying out addition reaction in an organic solvent;
wherein,
R1' represents-CH2CH2OH or-CH2CH(OH)CH2OH；
R2represents-CH3or-H;
R3represents-Cl or-OH;
n represents 2,3, 4, 5, 6, 7, 8, 9, 10, 11 or 12.
4. The production method according to claim 3, characterized in that: in the method (1), the organic solvent is ethylene glycol monomethyl ether or N, N-dimethylformamide.
5. The production method according to claim 3, characterized in that: in the method (1), when S is2When the (methyl) acryloyl chloride is used, the reaction system also comprises S2Equimolar amounts of catalyst.
6. The method of claim 5, wherein: the catalyst is selected from triethylamine or sodium hydroxide.
7. The production method according to claim 3, characterized in that: in the method (2), the organic solvent is ethylene glycol monomethyl ether.
8. Use of the seek-based acrylate resin for color resists according to claim 1 for producing color resists.
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| CN114716421B (en) * | 2020-12-22 | 2023-10-31 | 常州强力电子新材料股份有限公司 | Oxetane modified isocyanurates, method for the production thereof, energy-curable compositions and use thereof |
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