CN112390718A - Degradable photoresist resin monomer synthesized from trimethylbicyclo [2.2.2] octane dione and synthesis method thereof - Google Patents
Degradable photoresist resin monomer synthesized from trimethylbicyclo [2.2.2] octane dione and synthesis method thereof Download PDFInfo
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- CN112390718A CN112390718A CN202011307086.4A CN202011307086A CN112390718A CN 112390718 A CN112390718 A CN 112390718A CN 202011307086 A CN202011307086 A CN 202011307086A CN 112390718 A CN112390718 A CN 112390718A
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- resin monomer
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- trimethylbicyclo
- photoresist resin
- octane
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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 37
- 229920002120 photoresistant polymer Polymers 0.000 title claims abstract description 26
- 238000001308 synthesis method Methods 0.000 title claims abstract description 7
- ASIQHMSATNSWSC-UHFFFAOYSA-N 1,4,5-trimethylbicyclo[2.2.2]octane-2,3-dione Chemical compound CC1C2(C(C(C(C1)(CC2)C)=O)=O)C ASIQHMSATNSWSC-UHFFFAOYSA-N 0.000 title claims description 11
- 238000006243 chemical reaction Methods 0.000 claims abstract description 21
- HFBMWMNUJJDEQZ-UHFFFAOYSA-N acryloyl chloride Chemical compound ClC(=O)C=C HFBMWMNUJJDEQZ-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000007818 Grignard reagent Substances 0.000 claims abstract description 8
- -1 alkyl Grignard reagent Chemical class 0.000 claims abstract description 8
- VHRYZQNGTZXDNX-UHFFFAOYSA-N methacryloyl chloride Chemical compound CC(=C)C(Cl)=O VHRYZQNGTZXDNX-UHFFFAOYSA-N 0.000 claims abstract description 6
- 238000000746 purification Methods 0.000 claims abstract description 6
- 229920006395 saturated elastomer Polymers 0.000 claims abstract description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 3
- 150000001335 aliphatic alkanes Chemical class 0.000 claims abstract description 3
- 150000001924 cycloalkanes Chemical class 0.000 claims abstract description 3
- 239000001257 hydrogen Substances 0.000 claims abstract description 3
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 3
- 239000011261 inert gas Substances 0.000 claims abstract description 3
- 238000010791 quenching Methods 0.000 claims abstract description 3
- 230000000171 quenching effect Effects 0.000 claims abstract description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 39
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 19
- 238000000034 method Methods 0.000 claims description 17
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 8
- 238000005886 esterification reaction Methods 0.000 claims description 8
- 238000003747 Grignard reaction Methods 0.000 claims description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 6
- 239000002904 solvent Substances 0.000 claims description 6
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-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
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 4
- 230000015572 biosynthetic process Effects 0.000 claims description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 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
- 230000002194 synthesizing effect Effects 0.000 claims 5
- 150000001875 compounds Chemical class 0.000 abstract description 12
- 238000005530 etching Methods 0.000 abstract description 6
- 230000009286 beneficial effect Effects 0.000 abstract description 3
- 238000001259 photo etching Methods 0.000 abstract description 3
- XCBBNTFYSLADTO-UHFFFAOYSA-N 2,3-Octanedione Chemical compound CCCCCC(=O)C(C)=O XCBBNTFYSLADTO-UHFFFAOYSA-N 0.000 abstract 1
- 230000000379 polymerizing effect Effects 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 21
- 239000000543 intermediate Substances 0.000 description 17
- GZUXJHMPEANEGY-UHFFFAOYSA-N bromomethane Chemical compound BrC GZUXJHMPEANEGY-UHFFFAOYSA-N 0.000 description 10
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 9
- 239000002952 polymeric resin Substances 0.000 description 9
- 239000002253 acid Substances 0.000 description 8
- 229920003002 synthetic resin Polymers 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- 229940102396 methyl bromide Drugs 0.000 description 5
- 239000012074 organic phase Substances 0.000 description 5
- 239000000376 reactant Substances 0.000 description 5
- 238000006116 polymerization reaction Methods 0.000 description 4
- 238000009835 boiling Methods 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 239000012043 crude product Substances 0.000 description 3
- 239000005457 ice water Substances 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 2
- BZLVMXJERCGZMT-UHFFFAOYSA-N Methyl tert-butyl ether Chemical compound COC(C)(C)C BZLVMXJERCGZMT-UHFFFAOYSA-N 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 239000008346 aqueous phase Substances 0.000 description 2
- 229920006037 cross link polymer Polymers 0.000 description 2
- 238000004132 cross linking Methods 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000010894 electron beam technology Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 239000000463 material Substances 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
- 239000000047 product Substances 0.000 description 2
- 230000035945 sensitivity Effects 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000010189 synthetic method Methods 0.000 description 2
- ZNDOMJGECLSXDQ-UHFFFAOYSA-N 2,2,4-trimethylbicyclo[2.2.2]octane-3,6-dione Chemical compound C1CC2(C)CC(=O)C1C(C)(C)C2=O ZNDOMJGECLSXDQ-UHFFFAOYSA-N 0.000 description 1
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical class [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- AQNQQHJNRPDOQV-UHFFFAOYSA-N bromocyclohexane Chemical group BrC1CCCCC1 AQNQQHJNRPDOQV-UHFFFAOYSA-N 0.000 description 1
- RDHPKYGYEGBMSE-UHFFFAOYSA-N bromoethane Chemical compound CCBr RDHPKYGYEGBMSE-UHFFFAOYSA-N 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000004440 column chromatography Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical compound II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 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
- 238000004537 pulping Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 230000001502 supplementing effect Effects 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F222/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
- C08F222/10—Esters
- C08F222/1006—Esters of polyhydric alcohols or polyhydric phenols
- C08F222/102—Esters of polyhydric alcohols or polyhydric phenols of dialcohols, e.g. ethylene glycol di(meth)acrylate or 1,4-butanediol dimethacrylate
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/36—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring increasing the number of carbon atoms by reactions with formation of hydroxy groups, which may occur via intermediates being derivatives of hydroxy, e.g. O-metal
- C07C29/38—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring increasing the number of carbon atoms by reactions with formation of hydroxy groups, which may occur via intermediates being derivatives of hydroxy, e.g. O-metal by reaction with aldehydes or ketones
- C07C29/40—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring increasing the number of carbon atoms by reactions with formation of hydroxy groups, which may occur via intermediates being derivatives of hydroxy, e.g. O-metal by reaction with aldehydes or ketones with compounds containing carbon-to-metal bonds
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/14—Preparation of carboxylic acid esters from carboxylic acid halides
-
- 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
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2601/00—Systems containing only non-condensed rings
- C07C2601/12—Systems containing only non-condensed rings with a six-membered ring
- C07C2601/14—The ring being saturated
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2602/00—Systems containing two condensed rings
- C07C2602/36—Systems containing two condensed rings the rings having more than two atoms in common
- C07C2602/44—Systems containing two condensed rings the rings having more than two atoms in common the bicyclo ring system containing eight carbon atoms
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
The invention discloses a new compound consisting of trimethylbicyclo [2.2.2]A degradable photoresist resin monomer synthesized by octane dione and a synthesis method thereof relate to the field of photoresist resin, and the structural formula of the resin monomer is as follows:
wherein R is1Is a saturated alkane or cycloalkane, R2Is hydrogen or methylThe synthesis method comprises the following steps: under the protection of inert gas, 1,3, 3-trimethyl bicyclo [2.2.2]Reacting octane-2, 5-diketone (I) with an alkyl Grignard reagent or a cycloalkyl Grignard reagent, adding water for quenching after the reaction is finished, and carrying out post-treatment and purification to obtain an intermediate (II); and (3) reacting the intermediate (II) with acryloyl chloride or methacryloyl chloride under an alkaline condition, and carrying out post-treatment and purification to obtain a resin monomer (III). The polymerized resin formed by polymerizing the resin monomer and other resin monomers has better etching resistance, is beneficial to improving the edge roughness of a developed pattern, and greatly improves the resolution of a photoetching pattern.
Description
Technical Field
The invention relates to the field of photoresist resin, 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 trimethylbicyclo [2.2.2] octane dione and a synthesis method thereof.
In order to solve the technical problems, the invention provides the following technical scheme:
the invention provides a novel resin monomer, which has the structural formula as follows:
Preferably, the specific structure of the resin monomer comprises:
the reaction route of the synthetic method of the resin monomer is as follows:
the specific synthetic steps of the resin monomer are as follows:
the first step of Grignard reaction, under the protection of inert gas, 1,3, 3-trimethyl bicyclo [2.2.2] octane-2, 5-diketone (I) reacts with alkyl Grignard reagent or cycloalkyl Grignard reagent, water is added for quenching after the reaction is finished, and the intermediate (II) is obtained after post-treatment and purification;
and (2) performing esterification reaction, namely reacting the intermediate (II) with acryloyl chloride or methacryloyl chloride under an alkaline condition, and performing post-treatment and purification to obtain a resin monomer (III).
As a preferred technical scheme of the invention, the temperature of the Grignard reaction is 0-30 ℃; the solvent of the Grignard reaction is anhydrous diethyl ether.
As a preferable technical scheme of the invention, the reaction temperature of the esterification reaction is 0-70 ℃, and the solvent of the esterification reaction is selected from tetrahydrofuran, toluene or chloroform.
As a preferred technical scheme of the invention, triethylamine or pyridine is required to be added into the system in order to ensure the alkaline condition of the esterification reaction.
Compared with the prior art, the invention has the following beneficial effects:
the invention provides a novel photoresist resin monomer, which contains two unsaturated carbon-carbon double bonds and can generate crosslinking in the polymerization process with other resin monomers (including an acid-sensitive resin monomer containing only one polymerization group) to form a three-dimensional network-structured polymer resin, and the generated crosslinked polymer resin has better etching resistance; during exposure, the photoacid generator generates acid, the (methyl) acrylate on the main chain is broken under an acidic condition in an exposure area, the main chain of the polymer resin is broken to generate a product with smaller molecular weight, the solubility of the resin in a developing solution after exposure is increased, the difference of the dissolving speed of the polymer resin in the developing solution before and after exposure is increased, the edge roughness of a developed pattern is favorably improved, the resolution of a photoetching pattern is greatly improved, and the etching resistance of the polymer resin is also improved due to the structure containing a bridge ring in the structure of the resin monomer.
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: a. preparing a methyl Grignard reagent: adding magnesium chips (2.7g, 111mmol) into anhydrous ether (15mL), adding one iodine tablet, dissolving methyl bromide (10.6g, 112mmol) in ether (25mL) to prepare a solution, adding the ether solution (6mL) of the methyl bromide into the reaction solution under the protection of nitrogen, after several minutes, slightly boiling the reaction solution, removing the color of iodine, stirring, continuously dropwise adding the rest ether solution of the methyl bromide, supplementing ether (20mL), heating to keep slightly boiling, and refluxing for half an hour; b. synthesis of intermediates 1-2: under the protection of nitrogen, cooling the prepared methyl Grignard reagent by ice water, dropwise adding an ether (20mL) solution of 1,3, 3-trimethylbicyclo [2.2.2] octane-2, 5-dione (10.0g, 55mmol) while stirring, controlling the dropwise adding speed, keeping the reaction solution slightly boiling, after dropwise adding, continuing to stir at 25 ℃ for half an hour, separating a white solid in the reaction solution, cooling the reaction solution by ice water, slowly dropwise adding 20% dilute sulfuric acid (20mL), after dropwise adding, separating an ether layer, extracting an aqueous phase for three times by using ethyl acetate (100mL multiplied by 3), combining organic phases, and purifying a crude product obtained after concentrating the organic phase by column chromatography to obtain an intermediate 1-2(9.3g, 44mmol, 78.9%);
the second step is that: dissolving the intermediate 1-2(9.3g, 44mmol) in tetrahydrofuran (120mL), adding triethylamine (17.8g, 176mmol), cooling to 0 ℃ with ice water, slowly adding a tetrahydrofuran (50mL) solution of acryloyl chloride (8g, 88mmol) under nitrogen protection, heating the reaction solution to 25 ℃ to continue reacting for 5 hours, concentrating the reaction solution under vacuum to remove the solvent, adding ethyl acetate (50mL), adding a saturated aqueous solution of sodium bicarbonate (20mL), separating the organic phase, extracting the aqueous phase with ethyl acetate (80 mL. times.3) for three times, combining the organic phases, washing the organic phase with saturated saline, drying with anhydrous sodium sulfate, spin-drying to obtain a crude product, and pulping the crude product with methyl tert-butyl ether to obtain the compound 1-3(12.2g, 38mmol, 86.9%).
Example 2
The first step is as follows: the operation steps and the raw material charge amount are the same as the first step of the reaction in the example 1, and the reaction obtains a compound 2-2(9.4g, 44mmol, 79.8%);
the second step is that: the procedure was the same as for the second reaction of example 1, with the reactants and charge: intermediate 1-2(9.3g, 44mmol) was replaced with intermediate 2-2(9.4g, 44mmol), acryloyl chloride (8g, 88mmol) was replaced with methacryloyl chloride (9.3g, 89mmol), triethylamine (17.8g, 176mmol) was replaced with triethylamine (18.0g, 178mmol) to afford compound 2-3(13.2g, 38mmol, 85.6%).
Example 3
The first step is as follows: the procedure was the same as in the first step of example 1, wherein methyl bromide (10.6g, 112mmol) was changed to ethyl bromide (12.1g, 111mmol), to give compound 3-2(10.3g, 43mmol, 77.2%);
the second step is that: the procedure was the same as for the second reaction of example 1, with the reactants and charge: intermediate 1-2(9.3g, 44mmol) was replaced with intermediate 3-2(10.3g, 43mmol), acryloyl chloride (8g, 88mmol) was replaced with acryloyl chloride (7.8g, 86mmol), triethylamine (17.8g, 176mmol) was replaced with triethylamine (17.4g, 172mmol) to afford compound 3-3(12.5g, 36mmol, 83.7%).
Example 4
The first step is as follows: the procedure was the same as in the first step of example 3 to give compound 4-2(10.5g, 44mmol, 78.7%);
the second step is that: the procedure was the same as for the second reaction of example 1, with the reactants and charge: intermediate 1-2(9.3g, 44mmol) was replaced with intermediate 4-2(10.5g, 44mmol), acryloyl chloride (8g, 88mmol) was replaced with methacryloyl chloride (9.2g, 88mmol), triethylamine (17.8g, 176mmol) was replaced with triethylamine (17.7g, 175mmol) to afford compound 4-3(13.5g, 36mmol, 82.1%).
Example 5
The first step is as follows: the procedure was the same as in the first step of example 1, wherein methyl bromide (10.6g, 112mmol) was replaced with cyclohexyl bromide (18.1g, 111mmol), to give compound 5-2(12.7g, 36mmol, 65.7%);
the second step is that: the procedure was the same as for the second reaction of example 1, with the reactants and charge: intermediate 1-2(9.3g, 44mmol) was replaced with intermediate 5-2(12.7g, 36mmol), acryloyl chloride (8g, 88mmol) was replaced with acryloyl chloride (6.6g, 73mmol), triethylamine (17.8g, 176mmol) was replaced with triethylamine (14.8g, 146mmol) to afford compound 5-3(12.3g, 27mmol, 73.9%).
Example 6
The first step is as follows: the procedure was the same as in the first step of example 5 to give compound 6-2(12.5g, 36mmol, 64.6%);
the second step is that: the procedure was the same as for the second reaction of example 1, with the reactants and charge: intermediate 1-2(9.3g, 44mmol) was replaced with intermediate 6-2(12.5g, 36mmol), acryloyl chloride (8g, 88mmol) was replaced with methacryloyl chloride (7.5g, 72mmol), triethylamine (17.8g, 176mmol) was replaced with triethylamine (14.6g, 144mmol) to afford compound 6-3(13g, 27mmol, 74.8%).
Compared with the prior art, the invention has the following beneficial effects:
the invention provides a novel photoresist resin monomer, which contains two unsaturated carbon-carbon double bonds and can generate crosslinking in the polymerization process with other resin monomers (including an acid-sensitive resin monomer containing only one polymerization group) to form a three-dimensional network-structured polymer resin, and the generated crosslinked polymer resin has better etching resistance; during exposure, the photoacid generator generates acid, the (methyl) acrylate on the main chain is broken under an acidic condition in an exposure area, the main chain of the polymer resin is broken to generate a product with smaller molecular weight, the solubility of the resin in a developing solution after exposure is increased, and the difference of the dissolving speeds of the polymer resin before and after exposure in the developing solution is increased, so that the improvement of the edge roughness of a developed pattern is facilitated, and the resolution of a photoetching pattern is greatly improved.
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. The degradable photoresist resin monomer synthesized by trimethyl bicyclo [2.2.2] octane dione is characterized in that the structural formula of the resin monomer is as follows:
2. The degradable photoresist resin monomer synthesized from trimethylbicyclo [2.2.2] octane dione as claimed in claim 1, wherein the specific structure of the resin monomer comprises:
3. the synthesis method of the degradable photoresist resin monomer synthesized by trimethyl bicyclo [2.2.2] octane dione is characterized in that the reaction route of the synthesis method is as follows:
the synthesis steps are as follows:
the first step of Grignard reaction, under the protection of inert gas, 1,3, 3-trimethyl bicyclo [2.2.2] octane-2, 5-diketone (I) reacts with alkyl Grignard reagent or cycloalkyl Grignard reagent, water is added for quenching after the reaction is finished, and the intermediate (II) is obtained after post-treatment and purification;
and (2) performing esterification reaction, namely reacting the intermediate (II) with acryloyl chloride or methacryloyl chloride under an alkaline condition, and performing post-treatment and purification to obtain a resin monomer (III).
4. The method for synthesizing the degradable photoresist resin monomer synthesized from trimethylbicyclo [2.2.2] octane dione as claimed in claim 3, wherein the temperature of the Grignard reaction is 0-30 ℃.
5. The method for synthesizing a degradable photoresist resin monomer synthesized from trimethylbicyclo [2.2.2] octane dione as claimed in claim 3, wherein the solvent of the Grignard reaction is anhydrous diethyl ether.
6. The method for synthesizing the degradable photoresist resin monomer synthesized from trimethylbicyclo [2.2.2] octane dione as claimed in claim 3, wherein the reaction temperature of the esterification reaction is 0-70 ℃.
7. The method for synthesizing a degradable photoresist resin monomer synthesized from trimethylbicyclo [2.2.2] octane dione as claimed in claim 3, wherein the solvent for the esterification reaction is selected from tetrahydrofuran, toluene or chloroform.
8. The method for synthesizing a degradable photoresist resin monomer synthesized from trimethylbicyclo [2.2.2] octane dione as claimed in claim 3, wherein triethylamine or pyridine is added to the system to ensure the alkaline condition of the esterification reaction.
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| CN114380688A (en) * | 2021-12-28 | 2022-04-22 | 徐州博康信息化学品有限公司 | Preparation method of acid-sensitive photoresist resin monomer |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| 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 |
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| 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 |
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| CN114380688A (en) * | 2021-12-28 | 2022-04-22 | 徐州博康信息化学品有限公司 | Preparation method of acid-sensitive photoresist resin monomer |
| CN114380688B (en) * | 2021-12-28 | 2023-12-29 | 徐州博康信息化学品有限公司 | Preparation method of acid-sensitive photoresist resin monomer |
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