CN111689862A - Degradable photoresist resin monomer synthesized from 10-O-acetyl iso-calamus diol and synthesis method thereof - Google Patents
Degradable photoresist resin monomer synthesized from 10-O-acetyl iso-calamus diol and synthesis method thereof Download PDFInfo
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- 229920005989 resin Polymers 0.000 title claims abstract description 45
- 239000011347 resin Substances 0.000 title claims abstract description 45
- 239000000178 monomer Substances 0.000 title claims abstract description 39
- 229920002120 photoresistant polymer Polymers 0.000 title claims abstract description 26
- 150000002009 diols Chemical class 0.000 title claims abstract description 11
- 238000001308 synthesis method Methods 0.000 title abstract description 5
- 238000006243 chemical reaction Methods 0.000 claims abstract description 32
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 16
- 239000001257 hydrogen Substances 0.000 claims abstract description 16
- 239000000758 substrate Substances 0.000 claims abstract description 12
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims abstract description 9
- 238000005886 esterification reaction Methods 0.000 claims abstract description 8
- 239000003054 catalyst Substances 0.000 claims abstract description 7
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 5
- 238000006555 catalytic reaction Methods 0.000 claims abstract description 5
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims abstract description 5
- 230000002378 acidificating effect Effects 0.000 claims abstract description 4
- 238000007259 addition reaction Methods 0.000 claims abstract description 3
- 125000004185 ester group Chemical group 0.000 claims abstract description 3
- 230000003301 hydrolyzing effect Effects 0.000 claims abstract description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 36
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 12
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Natural products CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 10
- 238000000034 method Methods 0.000 claims description 9
- VHYFNPMBLIVWCW-UHFFFAOYSA-N 4-Dimethylaminopyridine Chemical compound CN(C)C1=CC=NC=C1 VHYFNPMBLIVWCW-UHFFFAOYSA-N 0.000 claims description 8
- 238000005984 hydrogenation reaction Methods 0.000 claims description 8
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 7
- HFBMWMNUJJDEQZ-UHFFFAOYSA-N acryloyl chloride Chemical compound ClC(=O)C=C HFBMWMNUJJDEQZ-UHFFFAOYSA-N 0.000 claims description 7
- VHRYZQNGTZXDNX-UHFFFAOYSA-N methacryloyl chloride Chemical compound CC(=C)C(Cl)=O VHRYZQNGTZXDNX-UHFFFAOYSA-N 0.000 claims description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 6
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 5
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 claims description 4
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 4
- 150000002431 hydrogen Chemical group 0.000 claims description 4
- 238000010189 synthetic method Methods 0.000 claims description 4
- FYSNRJHAOHDILO-UHFFFAOYSA-N thionyl chloride Chemical compound ClS(Cl)=O FYSNRJHAOHDILO-UHFFFAOYSA-N 0.000 claims description 4
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 claims description 4
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 3
- 239000002904 solvent Substances 0.000 claims description 3
- 230000015572 biosynthetic process Effects 0.000 claims description 2
- 239000007810 chemical reaction solvent Substances 0.000 claims description 2
- 238000006460 hydrolysis reaction Methods 0.000 claims description 2
- DCUFMVPCXCSVNP-UHFFFAOYSA-N methacrylic anhydride Chemical compound CC(=C)C(=O)OC(=O)C(C)=C DCUFMVPCXCSVNP-UHFFFAOYSA-N 0.000 claims description 2
- UKVIEHSSVKSQBA-UHFFFAOYSA-N methane;palladium Chemical compound C.[Pd] UKVIEHSSVKSQBA-UHFFFAOYSA-N 0.000 claims description 2
- ARJOQCYCJMAIFR-UHFFFAOYSA-N prop-2-enoyl prop-2-enoate Chemical compound C=CC(=O)OC(=O)C=C ARJOQCYCJMAIFR-UHFFFAOYSA-N 0.000 claims description 2
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 2
- 238000003786 synthesis reaction Methods 0.000 claims description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 2
- 125000003944 tolyl group Chemical group 0.000 claims description 2
- 230000002194 synthesizing effect Effects 0.000 claims 4
- 230000032050 esterification Effects 0.000 claims 1
- 238000005530 etching Methods 0.000 abstract description 10
- 238000004090 dissolution Methods 0.000 abstract description 3
- 230000002349 favourable effect Effects 0.000 abstract 1
- 150000001875 compounds Chemical class 0.000 description 14
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 12
- 238000001035 drying Methods 0.000 description 10
- 239000012074 organic phase Substances 0.000 description 10
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- 239000002952 polymeric resin Substances 0.000 description 8
- 239000003513 alkali Substances 0.000 description 7
- 238000001816 cooling Methods 0.000 description 7
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 6
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical class [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 6
- 239000002253 acid Substances 0.000 description 6
- 229920003002 synthetic resin Polymers 0.000 description 6
- 238000005406 washing Methods 0.000 description 6
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 4
- 239000008346 aqueous phase Substances 0.000 description 4
- 230000009286 beneficial effect Effects 0.000 description 4
- 239000012065 filter cake Substances 0.000 description 4
- 238000001914 filtration Methods 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- KJIFKLIQANRMOU-UHFFFAOYSA-N oxidanium;4-methylbenzenesulfonate Chemical compound O.CC1=CC=C(S(O)(=O)=O)C=C1 KJIFKLIQANRMOU-UHFFFAOYSA-N 0.000 description 4
- 238000006116 polymerization reaction Methods 0.000 description 4
- 229920006395 saturated elastomer Polymers 0.000 description 4
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 230000006872 improvement Effects 0.000 description 3
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium on carbon Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- ZEEBGORNQSEQBE-UHFFFAOYSA-N [2-(3-phenylphenoxy)-6-(trifluoromethyl)pyridin-4-yl]methanamine Chemical compound C1(=CC(=CC=C1)OC1=NC(=CC(=C1)CN)C(F)(F)F)C1=CC=CC=C1 ZEEBGORNQSEQBE-UHFFFAOYSA-N 0.000 description 2
- -1 acrylic ester Chemical class 0.000 description 2
- 229920006037 cross link polymer Polymers 0.000 description 2
- 238000004132 cross linking Methods 0.000 description 2
- 238000010894 electron beam technology Methods 0.000 description 2
- 239000000706 filtrate Substances 0.000 description 2
- 239000005457 ice water Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 230000007935 neutral effect Effects 0.000 description 2
- 238000006552 photochemical reaction Methods 0.000 description 2
- 238000000206 photolithography Methods 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 238000010791 quenching Methods 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- 230000035945 sensitivity Effects 0.000 description 2
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 2
- 235000017557 sodium bicarbonate Nutrition 0.000 description 2
- 239000011780 sodium chloride Substances 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- SAHIZENKTPRYSN-UHFFFAOYSA-N [2-[3-(phenoxymethyl)phenoxy]-6-(trifluoromethyl)pyridin-4-yl]methanamine Chemical compound O(C1=CC=CC=C1)CC=1C=C(OC2=NC(=CC(=C2)CN)C(F)(F)F)C=CC=1 SAHIZENKTPRYSN-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000008569 process Effects 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
- C07C69/52—Esters of acyclic unsaturated carboxylic acids having the esterified carboxyl group bound to an acyclic carbon atom
- C07C69/533—Monocarboxylic acid esters having only one carbon-to-carbon double bond
- C07C69/54—Acrylic acid esters; Methacrylic acid esters
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Materials For Photolithography (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
The invention discloses a degradable photoresist resin monomer synthesized by 10-O-acetyl iso-calamus diol and a synthesis method thereof, relating to the field of photoresist resin monomers, wherein the structural formula is as follows:
Description
Technical Field
The invention relates to the field of photoresist resin monomers, in particular to a resin monomer and a synthetic method thereof.
Background
The photolithography technique is a fine processing technique for transferring a pattern designed on a mask plate to a pattern on a substrate by using the chemical sensitivity of a photolithography material (particularly a photoresist) under the action of visible light, ultraviolet rays, electron beams and the like through the processes of exposure, development, etching and the like.
The main components of the photoresist are resin, photoacid generator, and corresponding additives and solvents, and these materials have chemical sensitivity with light (including visible light, ultraviolet light, electron beam, etc.) and undergo a photochemical reaction to change their solubility in a developing solution. According to the difference of photochemical reaction mechanism, the photoresist is divided into a positive photoresist and a negative photoresist: after exposure, the solubility of the photoresist in a developing solution is increased, and the photoresist with the same pattern as that of the mask is obtained and is called as a positive photoresist; after exposure, the photoresist has reduced solubility or even no solubility in a developing solution, and a negative photoresist with a pattern opposite to that of the mask is obtained.
The resin is a polymer polymerized by a plurality of resin monomers, wherein the acid-sensitive resin monomer is an important component for realizing the dissolution difference of the resin in the developing solution before and after exposure, the common acid-sensitive resin monomer only has one acid-sensitive group, the resin monomer is a linear polymer and has weaker etching resistance, and the dissolution difference in the developing solution after exposure is only determined by the acid-sensitive resin monomer, so that the phenomenon of insufficient resolution is caused.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provides a degradable photoresist resin monomer synthesized by 10-O-acetyl iso-calamus diol and a synthesis method thereof.
In order to solve the technical problems, the invention provides the following technical scheme:
a novel resin monomer having the formula:
The invention also provides a synthetic method of the degradable photoresist resin monomer synthesized by 10-O-acetyl iso-calamus diol, which comprises the following steps:
wherein R is hydrogen or methyl, and the synthesis steps are as follows:
the first step of hydrolysis reaction, hydrolyzing ester group in 10-O-acetyl iso-calamus diol (I) under alkaline condition, adjusting system to acidity to obtain intermediate II, wherein in order to ensure alkaline condition of reaction, the added alkali is sodium hydroxide or potassium hydroxide;
a second step of hydrogenation reaction, wherein an unsaturated carbon-carbon double bond of the intermediate II and hydrogen are subjected to addition reaction under the catalysis of a catalyst a to obtain an intermediate III, preferably, the catalyst a is palladium-carbon, and a solvent is selected from one of methanol, ethanol and tetrahydrofuran;
and step three, carrying out esterification reaction on the intermediate III and another reaction substrate to generate a target resin monomer.
In a preferred embodiment of the present invention, when R is hydrogen, the other reaction substrate in the esterification reaction is acrylic acid, acryloyl chloride, or acrylic anhydride.
In a preferred embodiment of the present invention, when R is methyl, the other reaction substrate of the esterification reaction is methacrylic acid, methacryloyl chloride, or methacrylic anhydride.
As a preferred technical scheme of the invention, when another reaction substrate is acrylic acid or methacrylic acid, one of p-toluenesulfonic acid, sulfuric acid, thionyl chloride and hydrochloric acid is required to be added as a catalyst in the reaction, and the reaction solvent is selected from toluene or ethylbenzene.
As a preferable technical scheme of the invention, when another reaction substrate is acryloyl chloride or methacryloyl chloride, the reaction is carried out under alkaline conditions, the acryloyl chloride or methacryloyl chloride reacts with the intermediate III under the catalysis of 4-dimethylaminopyridine to generate the target resin monomer, and one of triethylamine and pyridine is added into the reaction system to ensure the alkaline conditions of the reaction.
Compared with the prior art, the invention has the beneficial effects that:
the invention provides a new photoresist resin monomer, which contains two unsaturated carbon-carbon double bonds, can generate cross-linking in the polymerization process with other resin monomers (including an acid-sensitive resin monomer containing only one polymerization group) to form a polymer resin with a three-dimensional network structure, the generated cross-linked polymer resin has better etching resistance, and the resin monomer contains a bridge ring, has higher carbon-hydrogen ratio and further increases the etching resistance, in addition, (methyl) acrylic ester on a main chain is broken under the acidic condition, the main chain of the polymer resin is broken to generate smaller molecular weight segments, the solubility of the exposed resin in a developing solution is increased, and the difference of the dissolving speed of the polymer resin before and after exposure in the developing solution is increased, thereby being beneficial to improving the edge roughness of a developed pattern and greatly improving the resolution of the developed pattern, moreover, the resin monomer contains a bridge ring structure, so that the etching resistance of an unexposed area is improved, and the resin monomer also obviously contributes to the improvement of the resolution.
Detailed Description
The preferred embodiments of the present invention will be described in conjunction with the following examples, which are set forth to illustrate and explain the present invention and are not to be construed as limiting the present invention.
Example 1
The first step is as follows: dissolving sodium hydroxide (3.5g, 87.5mmol) in water (20mL) to prepare an alkali solution, cooling the alkali solution to 25 ℃, adding the cooled alkali solution into a methanol (80mL) solution of 10-O-acetyl-iso-gladiole 1-1(10g, 35.7mmol), reacting for 2 hours at 25 ℃, cooling the reaction solution with ice water, adding diluted hydrochloric acid to adjust the pH to be neutral, directly spin-drying the reaction solution, adding methanol (100mL) into the solid for washing, and spin-drying the methanol solution after drying with anhydrous sodium sulfate to obtain a compound 1-2(8.2g, 34.4mmol, 96.5%);
secondly, adding the compound 1-2(8.2g, 34.4mmol) into a hydrogenation kettle, dissolving with methanol (80mL), slowly adding Pd-C (0.3g) under nitrogen flow, screwing the hydrogenation kettle, replacing the air in the reaction kettle with nitrogen for three times, replacing with hydrogen for three times, reacting for 16 hours at normal temperature under hydrogen, filtering the reaction solution with diatomite, washing a filter cake with methanol (25mL multiplied by 3) for three times (the filter cake cannot be filtered out during filtering), concentrating and drying the filtrate to obtain the compound 1-3(7.8g, 32mmol, 94.3%);
the third step: compound 1-3(7.8g, 32mmol), acrylic acid (4.7g, 65mmol) were dissolved in toluene (100mL), p-toluenesulfonic acid monohydrate (1.5g, 8.7mmol) was added thereto, heated under reflux for 16 hours, cooled to 25 deg.C, the reaction was washed with saturated sodium bicarbonate solution (50mL), the organic phase was dried over anhydrous sodium sulfate, and concentrated under vacuum to give compound 1-4(10.6g, 30.4mmol, yield 93.7%).
Example 2
The first step is as follows: dissolving sodium hydroxide (3.5g, 87.5mmol) in water (20mL) to prepare an alkali solution, cooling the alkali solution to 25 ℃, adding the cooled alkali solution into a methanol (80mL) solution of 10-O-acetyl-iso-gladiole 2-1(10g, 35.7mmol), reacting for 2 hours at 25 ℃, cooling the reaction solution with ice water, adding diluted hydrochloric acid to adjust the pH to be neutral, directly spin-drying the reaction solution, adding methanol (100mL) into the solid for washing, and spin-drying the methanol solution after drying with anhydrous sodium sulfate to obtain a compound 2-2(8.4g, 35.2mmol, 98.8%);
secondly, adding the compound 2-2(8.4g, 35.2mmol) into a hydrogenation kettle, dissolving the compound with methanol (80mL), slowly adding Pd-C (0.3g) under nitrogen flow, screwing the hydrogenation kettle, replacing air in the reaction kettle with nitrogen for three times, replacing the air with hydrogen for three times, reacting for 16 hours at 25 ℃ under hydrogen, filtering the reaction solution with diatomite, washing a filter cake with methanol (25mL multiplied by 3) for three times (the filter cake cannot be filtered out during filtering), concentrating and drying the filtrate to obtain the compound 2-3(8g, 33.3mmol, 94.4%);
the third step: dissolving the compound 2-3(8g, 33.3mmol) in anhydrous dichloromethane (250mL), adding triethylamine (14g, 138mmol), adding 4-dimethylaminopyridine (0.3g, 2.4mmol), cooling to 0 ℃, slowly adding acryloyl chloride (6.2g, 68.5mmol) dropwise, heating to 25 ℃ for reaction for 16 hours, slowly adding the reaction solution into ice saturated aqueous sodium bicarbonate solution (50mL) to quench, separating an aqueous phase and an organic phase, extracting the aqueous phase three times with dichloromethane (50 mL. times.3), combining the organic phases, washing the organic phase with saturated aqueous sodium chloride solution (100mL), drying the organic phase with anhydrous sodium sulfate, and concentrating to obtain the compound 2-4(10.8g, 31mmol, 93.1% yield).
Example 3:
the first two steps are the same as in example 1, starting with 10-O-acetylisocalanediol (10g, 35.7mmol) to finally obtain the compound 3-3(7.6g, 31.6 mmol);
the third step: compound 3-3(7.6g, 31.6mmol), methacrylic acid (5.5g, 63.9mmol) were dissolved in toluene (100mL), p-toluenesulfonic acid monohydrate (1.5g, 8.7mmol) was added thereto, heating and refluxing were carried out for 16 hours, cooling was carried out to 25 degrees Celsius, the reaction solution was washed with saturated sodium bicarbonate solution (50mL), the organic phase was dried over anhydrous sodium sulfate, and concentration under vacuum was carried out to obtain compound 3-4(11g, 30.4mmol, yield 92.4%).
Example 4:
the first two steps are the same as in example 2, starting with 10-O-acetylisocalanediol (10g, 35.7mmol) to give the compound 4-3(7.7g, 32 mmol);
the third step: dissolving compound 4-3(7.7g, 32mmol) in anhydrous dichloromethane (250mL), adding triethylamine (14g, 138mmol), adding 4-dimethylaminopyridine (0.3g, 2.4mmol), cooling to 0 deg.C, slowly adding methacryloyl chloride (6.7g, 64.1mmol) dropwise, heating to 25 deg.C for reaction for 16 hours, slowly adding the reaction solution into ice saturated aqueous sodium bicarbonate (50mL) to quench, separating the aqueous phase from the organic phase, extracting the aqueous phase three times with dichloromethane (50 mL. times.3), combining the organic phases, washing the organic phase with saturated aqueous sodium chloride (100mL), drying the organic phase with anhydrous sodium sulfate, and concentrating to obtain compound 4-4(11.3g, 30mmol, 93.7% yield).
Compared with the prior art, the invention has the beneficial effects that:
the invention provides a new photoresist resin monomer, which contains two unsaturated carbon-carbon double bonds, can generate cross-linking in the polymerization process with other resin monomers (including an acid-sensitive resin monomer containing only one polymerization group) to form a polymer resin with a three-dimensional network structure, the generated cross-linked polymer resin has better etching resistance, and the resin monomer contains a bridge ring, has higher carbon-hydrogen ratio and further increases the etching resistance, in addition, (methyl) acrylic ester on a main chain is broken under the acidic condition, the main chain of the polymer resin is broken to generate smaller molecular weight segments, the solubility of the exposed resin in a developing solution is increased, and the difference of the dissolving speed of the polymer resin before and after exposure in the developing solution is increased, thereby being beneficial to improving the edge roughness of a developed pattern and greatly improving the resolution of the developed pattern, moreover, the resin monomer contains a bridge ring structure, so that the etching resistance of an unexposed area is improved, and the resin monomer also obviously contributes to the improvement of the resolution.
Finally, it should be noted that: although the present invention has been described in detail with reference to the foregoing embodiments, it will be apparent to those skilled in the art that changes may be made in the embodiments and/or equivalents thereof without departing from the spirit and scope of the invention. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (8)
1. A degradable photoresist resin monomer synthesized by 10-O-acetyl iso-calamus diol is characterized in that the structural formula of the resin monomer is as follows:
2. A synthetic method of a degradable photoresist resin monomer synthesized by 10-O-acetyl iso-calamus diol is characterized in that the synthetic route of the synthetic method is as follows:
wherein R is hydrogen or methyl, and the synthesis steps are as follows:
the first step of hydrolysis reaction, hydrolyzing ester group in 10-O-acetyl isocorylalandiol I under alkaline condition, and then adjusting the system to be acidic to obtain an intermediate II;
a second step of hydrogenation reaction, wherein an unsaturated carbon-carbon double bond of the intermediate II and hydrogen are subjected to addition reaction under the catalysis of a catalyst a to obtain an intermediate III;
and step three, carrying out esterification reaction on the intermediate III and another reaction substrate to generate a target resin monomer IV.
3. The method for synthesizing the degradable photoresist resin monomer synthesized from 10-O-acetyl-iso-calamus diol as claimed in claim 2, wherein the catalyst a for the hydrogenation reaction is palladium carbon.
4. The method as claimed in claim 2, wherein the solvent for the hydrogenation reaction is selected from methanol, ethanol, and tetrahydrofuran.
5. The method for synthesizing the degradable photoresist resin monomer synthesized from 10-O-acetyl-iso-calamus diol as claimed in claim 2, wherein when R is hydrogen, the other reaction substrate in the esterification reaction is acrylic acid, acryloyl chloride or acrylic anhydride; when R is methyl, the other reaction substrate in the esterification reaction is methacrylic acid, methacryloyl chloride or methacrylic anhydride.
6. The method as claimed in claim 5, wherein when the other substrate is acrylic acid or methacrylic acid, one of p-toluenesulfonic acid, sulfuric acid, thionyl chloride and hydrochloric acid is added as a catalyst, and the reaction solvent is selected from toluene or ethylbenzene.
7. The method for synthesizing the degradable photoresist resin monomer from 10-O-acetyl-isogladiole as claimed in claim 5, wherein when the other reaction substrate is acryloyl chloride or methacryloyl chloride, the reaction is carried out under alkaline condition, and the acryloyl chloride or methacryloyl chloride reacts with the intermediate III under the catalysis of 4-dimethylaminopyridine to generate the target resin monomer IV.
8. The method for synthesizing a degradable photoresist resin monomer from 10-O-acetyl-isocalamus diol as claimed in claim 7, wherein one of triethylamine and pyridine is added to the reaction system in the third esterification step to ensure the alkaline condition of the reaction.
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2004042477A1 (en) * | 2002-11-04 | 2004-05-21 | Dongjin Semichem Co., Ltd. | Chemically amplified polymer having pendant group with dicyclohexyl and resist composition comprising the same |
| TW201804249A (en) * | 2016-05-13 | 2018-02-01 | 住友化學股份有限公司 | Photoresist composition |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2004042477A1 (en) * | 2002-11-04 | 2004-05-21 | Dongjin Semichem Co., Ltd. | Chemically amplified polymer having pendant group with dicyclohexyl and resist composition comprising the same |
| TW201804249A (en) * | 2016-05-13 | 2018-02-01 | 住友化學股份有限公司 | Photoresist composition |
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Inventor after: Fu Zhiwei Inventor after: He Baoyuan Inventor after: Shao Yanliang Inventor after: Mao Guoping Inventor after: Yu Wenqing Inventor after: Xue Fukui Inventor after: Liu Sifei Inventor before: Fu Zhiwei Inventor before: He Baoyuan Inventor before: Shao Yanliang Inventor before: Mao Guoping Inventor before: Yu Wenqing Inventor before: Xue Fukui Inventor before: Liu Sifei |
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Application publication date: 20200922 |