CN111777583A - Degradable photoresist resin monomer synthesized from pyran-3, 5-dione and synthesis method thereof - Google Patents
Degradable photoresist resin monomer synthesized from pyran-3, 5-dione and synthesis method thereof Download PDFInfo
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- CN111777583A CN111777583A CN202010557266.1A CN202010557266A CN111777583A CN 111777583 A CN111777583 A CN 111777583A CN 202010557266 A CN202010557266 A CN 202010557266A CN 111777583 A CN111777583 A CN 111777583A
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- resin monomer
- pyran
- reaction
- dione
- photoresist resin
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- 229920005989 resin Polymers 0.000 title claims abstract description 44
- 239000011347 resin Substances 0.000 title claims abstract description 44
- 239000000178 monomer Substances 0.000 title claims abstract description 38
- 229920002120 photoresistant polymer Polymers 0.000 title claims abstract description 27
- 238000001308 synthesis method Methods 0.000 title claims abstract description 9
- SMIQVIXGQSMHKF-UHFFFAOYSA-N oxane-3,5-dione Chemical compound O=C1COCC(=O)C1 SMIQVIXGQSMHKF-UHFFFAOYSA-N 0.000 title claims description 10
- HFBMWMNUJJDEQZ-UHFFFAOYSA-N acryloyl chloride Chemical compound ClC(=O)C=C HFBMWMNUJJDEQZ-UHFFFAOYSA-N 0.000 claims abstract description 10
- -1 alkyl Grignard reagent Chemical class 0.000 claims abstract description 10
- 239000007818 Grignard reagent Substances 0.000 claims abstract description 8
- 238000005886 esterification reaction Methods 0.000 claims abstract description 7
- VHRYZQNGTZXDNX-UHFFFAOYSA-N methacryloyl chloride Chemical compound CC(=C)C(Cl)=O VHRYZQNGTZXDNX-UHFFFAOYSA-N 0.000 claims abstract description 7
- 238000003747 Grignard reaction Methods 0.000 claims abstract description 6
- 150000001924 cycloalkanes Chemical class 0.000 claims abstract description 5
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims abstract description 5
- 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
- 239000001257 hydrogen Substances 0.000 claims abstract description 3
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 33
- 238000006243 chemical reaction Methods 0.000 claims description 14
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 12
- 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
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 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
- 238000000746 purification Methods 0.000 claims description 4
- 230000015572 biosynthetic process Effects 0.000 claims description 3
- 238000003786 synthesis reaction Methods 0.000 claims description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 3
- 239000011261 inert gas Substances 0.000 claims description 2
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 2
- 238000010791 quenching Methods 0.000 claims description 2
- 230000000171 quenching effect Effects 0.000 claims description 2
- 238000000034 method Methods 0.000 abstract description 14
- 239000002952 polymeric resin Substances 0.000 abstract description 11
- 229920003002 synthetic resin Polymers 0.000 abstract description 9
- 238000005530 etching Methods 0.000 abstract description 7
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 abstract description 3
- 238000001259 photo etching Methods 0.000 abstract description 3
- 230000002349 favourable effect Effects 0.000 abstract 1
- 239000000543 intermediate Substances 0.000 description 14
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 13
- 150000001875 compounds Chemical class 0.000 description 13
- 239000002253 acid Substances 0.000 description 12
- 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
- 125000004309 pyranyl group Chemical group O1C(C=CC=C1)* 0.000 description 8
- 229940102396 methyl bromide Drugs 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 238000004090 dissolution Methods 0.000 description 4
- 239000012074 organic phase Substances 0.000 description 4
- 125000004430 oxygen atom Chemical group O* 0.000 description 4
- 238000006116 polymerization reaction Methods 0.000 description 4
- 238000009835 boiling Methods 0.000 description 3
- 239000012295 chemical reaction liquid Substances 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 239000005457 ice water Substances 0.000 description 3
- 230000006872 improvement Effects 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 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
- 230000009286 beneficial effect Effects 0.000 description 2
- 229920006037 cross link polymer Polymers 0.000 description 2
- 238000004132 cross linking Methods 0.000 description 2
- 239000012043 crude product Substances 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
- 150000002632 lipids Chemical class 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 229910052757 nitrogen Inorganic materials 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
- 238000004528 spin coating Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 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
- 239000008346 aqueous phase 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
- 239000012071 phase Substances 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
- 238000010189 synthetic method Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D309/00—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only ring hetero atom, not condensed with other rings
- C07D309/02—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only ring hetero atom, not condensed with other rings having no double bonds between ring members or between ring members and non-ring members
- C07D309/08—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only ring hetero atom, not condensed with other rings having no double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D309/10—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
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
- Spectroscopy & Molecular Physics (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 pyran-3, 5-diketone and a synthesis method thereof, relating to the field of photoresist resin monomers, wherein the structural formula is as follows:
wherein R is1Is hydrogen or methyl, R2Is saturated alkane or cycloalkane. The synthesis method comprises the following steps: 2H-pyran-3, 5(4H,6H) -diketone (I) and alkyl Grignard reagent or cycloalkyl Grignard reagent are subjected to Grignard reaction to obtain an intermediate (II); and (3) carrying out esterification reaction on the intermediate (II) and acryloyl chloride or methacryloyl chloride to obtain a resin monomer (III). The resin monomer provided by the invention has better etching resistance, and the difference of the dissolving speed increases before and after exposureThe method is favorable for improving the edge roughness of the developed pattern, greatly improves the resolution of the photoetching pattern, and increases the solubility of the polymer resin containing the method in an ester solvent.
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 from pyran-3, 5-dione and a synthesis method thereof.
In order to solve the technical problems, the invention provides the following technical scheme:
the invention relates to a novel resin monomer, which has the structural formula as follows:
wherein R is1Is hydrogen or methyl, R2Is saturated alkane or cycloalkane.
Preferably, the specific structure of the resin monomer comprises:
in addition, a degradable photoresist resin monomer synthesized by pyran-3, 5-diketone and a synthesis method thereof are provided, wherein 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, reacting 2H-pyran-3, 5(4H,6H) -diketone (I) with alkyl Grignard reagent or cycloalkyl Grignard reagent, adding water for quenching after the reaction is finished, and carrying out post-treatment and purification to obtain an intermediate (II); the preferable reaction temperature is 0-30 ℃, and the preferable solvent of the Grignard reaction is anhydrous tetrahydrofuran;
a second step of 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); the reaction temperature is preferably 0-70 ℃, the solvent for the esterification reaction is preferably tetrahydrofuran, toluene or chloroform, and in order to ensure the alkalinity of the system, a base is added into the system, and the preferred base is triethylamine or pyridine.
Compared with the prior art, the invention has the following beneficial effects:
the invention provides a new photoresist resin monomer, the resin monomer contains two unsaturated carbon-carbon double bonds, can generate cross linking in the polymerization process with other resin monomers (including acid-sensitive resin monomer containing only one polymerization group), form three-dimensional network structure polymer resin, the generated cross-linked polymer resin has better anti-etching performance, when exposed, the photo-acid generator generates acid, in the exposure area, (methyl) acrylic ester on the main chain is broken under the acid condition, the main chain of the polymer resin is broken to generate products with smaller molecular weight, the solubility of the exposed resin in the developing solution is increased, because the difference of the dissolution speed of the polymer resin before and after exposure in the developing solution is increased, the edge roughness of the developed pattern is improved, the resolution of the photoetching pattern is greatly improved, and the resin monomer contains pyran ring structure, although the increase of the etching resistance of the pyran ring containing an oxygen atom is weaker than that of the cycloalkane, the pyran ring containing an oxygen atom contributes to the improvement of the resolution; in addition, the pyran rings are high in lipid solubility, and the solubility of the polymer resin in an ester solvent before spin coating is better.
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 (4.3g, 177mmol) into anhydrous ether (15mL), adding one iodine tablet, dissolving methyl bromide (17g, 179mmol) in ether (25mL) to prepare a solution, adding ethyl ether solution (6mL) of methyl bromide into the reaction solution under the protection of nitrogen, after a few minutes, slightly boiling the reaction solution, removing the color of iodine, continuously dropwise adding the rest ethyl ether solution of methyl bromide under stirring, adding ethyl ether (20mL), heating to keep slightly boiling, and refluxing for half an hour; b. synthesis of intermediates 1-2: cooling the prepared methyl Grignard reagent by using ice water, dropwise adding an ether (20mL) solution of 2H-pyran-3, 5(4H,6H) -diketone 1-1(10g, 87.6mmol) under stirring, controlling the dropwise adding speed, keeping the reaction liquid slightly boiling, continuing to stir at 25 ℃ for half an hour after the dropwise adding is finished, separating white solid in the reaction liquid, cooling the reaction liquid by using ice water, dropwise adding slowly 20% dilute sulfuric acid (20mL), separating an ether layer after the dropwise adding is finished, extracting a water phase for three times by using ethyl acetate (100mL multiplied by 3), combining organic phases, concentrating, and purifying by column chromatography to obtain an intermediate 1-2(10.6g, 72.5mmol, 82.7%);
the second step is that: dissolving the intermediate 1-2(10.6g, 72.5mmol) in tetrahydrofuran (120mL), adding triethylamine (30g, 296mmol), cooling to 0 ℃ with ice water, slowly adding a tetrahydrofuran (50mL) solution of acryloyl chloride (13.5g, 149mmol) dropwise under the protection of nitrogen, heating the reaction solution to 25 ℃, continuing to react for 5 hours, concentrating the reaction solution under vacuum to remove the solvent, adding ethyl acetate (50mL), adding a saturated aqueous sodium bicarbonate solution (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(15.2g, 59.8mmol, 82.4%).
Example 2
The first step is as follows: the operation steps and the charge amount of the raw materials are the same as the first step of the reaction in the example 1, and the reaction obtains a compound 2-2(10.8g, 73.9mmol and 84.3%);
the second step is that: the procedure was the same as in the second reaction of example 1, intermediate 1-2(10.6g, 72.5mmol) was replaced with intermediate 2-2(10.8g, 73.9mmol), acryloyl chloride (13.5g, 149mmol) was replaced with methacryloyl chloride (15.5g, 148mmol), giving compound 2-3(16.7g, 59.2mmol, 80.1%).
Example 3
The first step, the same procedure as the first step of example 1, wherein methyl bromide (17g, 179mmol) was changed to ethyl bromide (19.2g, 176mmol), gave compound 3-2(12.3g, 70.6mmol, 80.5%);
the second step is that: the procedure was the same as in the second step of example 1, substituting 3-2(12.3g, 70.6mmol) for intermediate 1-2(10.6g, 72.5mmol), triethylamine (30g, 296mmol) for triethylamine (29g, 287mmol), and acryloyl chloride (13.5g, 149mmol) for acryloyl chloride (13g, 144mmol) to give compound 3-3(16.5g, 58.4mmol, 82.8%).
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(12.5g, 71.7mmol, 81.9%);
the second step is that: the procedure was the same as in the second step of example 3, substituting compound 3-2(12.3g, 70.6mmol) for compound 4-2(12.5g, 71.7mmol), triethylamine (29g, 287mmol) for triethylamine (29.4g, 290.3mmol), acryloyl chloride (13g, 144mmol) for methacryloyl chloride (15.2g, 145.1mmol) to give compound 4-3(17.6g, 56.7mmol, 79%).
Example 5
The first step is as follows: the procedure was the same as in the first step of example 1, wherein methyl bromide (17g, 179mmol) was replaced with cyclohexyl bromide (28.6g, 175mmol), affording compound 5-2(19.5g, 69mmol, 78.8%);
the second step is that: the procedure was the same as in the second step of example 1, except that intermediate 1-2(10.6g, 72.5mmol) was replaced with intermediate 5-2(19.5g, 69mmol) and triethylamine (30g, 296mmol) was replaced with triethylamine (28g, 277 mmol); acryloyl chloride (13.5g, 149mmol) was replaced with methacryloyl chloride (12.5g, 138mmol) to give compound 5-3(21g, 53.8mmol, 77.9%).
Example 6
The first step is as follows: the procedure was identical to the first step of example 5 to give compound 6-2(19.2g, 67.98mmol, 77.6%);
the second step is that: the procedure was the same as in the second step of example 1, except that intermediate 1-2(10.6g, 72.5mmol) was replaced with intermediate 6-2(19.2g, 67.98mmol), triethylamine (30g, 296mmol) was replaced with triethylamine (27.5g, 272mmol), acryloyl chloride (13.5g, 149mmol) was replaced with methacryloyl chloride (14.2g, 136mmol), to give compound 6-3(22.8g, 54.47mmol, 80%).
Compared with the prior art, the invention has the following beneficial effects:
the invention provides a new photoresist resin monomer, the resin monomer contains two unsaturated carbon-carbon double bonds, can generate cross linking in the polymerization process with other resin monomers (including acid-sensitive resin monomer containing only one polymerization group), form three-dimensional network structure polymer resin, the generated cross-linked polymer resin has better anti-etching performance, when exposed, the photo-acid generator generates acid, in the exposure area, (methyl) acrylic ester on the main chain is broken under the acid condition, the main chain of the polymer resin is broken to generate products with smaller molecular weight, the solubility of the exposed resin in the developing solution is increased, because the difference of the dissolution speed of the polymer resin before and after exposure in the developing solution is increased, the edge roughness of the developed pattern is improved, the resolution of the photoetching pattern is greatly improved, and the resin monomer contains pyran ring structure, although the increase of the etching resistance of the pyran ring containing an oxygen atom is weaker than that of the cycloalkane, the pyran ring containing an oxygen atom contributes to the improvement of the resolution; in addition, the pyran rings are high in lipid solubility, and the solubility of the polymer resin in an ester solvent before spin coating is better.
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 from pyran-3, 5-dione is characterized in that the structural formula of the resin monomer is as follows:
2. The degradable photoresist resin monomer synthesized from pyran-3, 5-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 from pyran-3, 5-diketone 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, reacting 2H-pyran-3, 5(4H,6H) -diketone (I) with alkyl Grignard reagent or 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 (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 degradable photoresist resin monomer synthesized from pyran-3, 5-dione as claimed in claim 3, wherein the temperature of the Grignard reaction is 0-30 ℃.
5. The degradable photoresist resin monomer synthesized from pyran-3, 5-dione as claimed in claim 3, wherein the solvent of the Grignard reaction is anhydrous tetrahydrofuran.
6. The degradable photoresist resin monomer synthesized from pyran-3, 5-dione as claimed in claim 3, wherein the reaction temperature of the esterification reaction is 0-70 ℃.
7. The degradable photoresist resin monomer synthesized from pyran-3, 5-dione as claimed in claim 3, wherein the solvent of the esterification reaction is selected from tetrahydrofuran, toluene or chloroform.
8. The degradable photoresist resin monomer synthesized from pyran-3, 5-dione as claimed in claim 3, wherein triethylamine or pyridine is added to the system to ensure the basic condition of the esterification reaction.
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| Application Number | Priority Date | Filing Date | Title |
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| CN202010557266.1A CN111777583A (en) | 2020-06-18 | 2020-06-18 | Degradable photoresist resin monomer synthesized from pyran-3, 5-dione and synthesis method thereof |
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| CN202010557266.1A CN111777583A (en) | 2020-06-18 | 2020-06-18 | Degradable photoresist resin monomer synthesized from pyran-3, 5-dione and synthesis method thereof |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113416177A (en) * | 2021-06-24 | 2021-09-21 | 徐州博康信息化学品有限公司 | Main chain degradable photoresist resin monomer and preparation method and application thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1885161A (en) * | 2005-06-24 | 2006-12-27 | 株式会社东进世美肯 | Photoresist monomer, polymer thereof and photoresist composition containing photoresist polymer |
| CN111056945A (en) * | 2019-12-25 | 2020-04-24 | 上海博栋化学科技有限公司 | Photoresist resin monomer synthesized from spiro [5.5] undecane-3, 9-dione and synthesis method thereof |
| CN111072482A (en) * | 2019-12-25 | 2020-04-28 | 上海博栋化学科技有限公司 | Photoresist resin monomer synthesized from spiro [2.5] decane-6, 8-dione and synthesis method thereof |
| CN111138287A (en) * | 2019-12-25 | 2020-05-12 | 上海博栋化学科技有限公司 | Photoresist resin monomer synthesized from hexahydro-1H-indene-1, 3(2H) -diketone and synthetic method thereof |
-
2020
- 2020-06-18 CN CN202010557266.1A patent/CN111777583A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1885161A (en) * | 2005-06-24 | 2006-12-27 | 株式会社东进世美肯 | Photoresist monomer, polymer thereof and photoresist composition containing photoresist polymer |
| CN111056945A (en) * | 2019-12-25 | 2020-04-24 | 上海博栋化学科技有限公司 | Photoresist resin monomer synthesized from spiro [5.5] undecane-3, 9-dione and synthesis method thereof |
| CN111072482A (en) * | 2019-12-25 | 2020-04-28 | 上海博栋化学科技有限公司 | Photoresist resin monomer synthesized from spiro [2.5] decane-6, 8-dione and synthesis method thereof |
| CN111138287A (en) * | 2019-12-25 | 2020-05-12 | 上海博栋化学科技有限公司 | Photoresist resin monomer synthesized from hexahydro-1H-indene-1, 3(2H) -diketone and synthetic method thereof |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113416177A (en) * | 2021-06-24 | 2021-09-21 | 徐州博康信息化学品有限公司 | Main chain degradable photoresist resin monomer and preparation method and application thereof |
| CN113416177B (en) * | 2021-06-24 | 2022-10-25 | 徐州博康信息化学品有限公司 | Main chain degradable photoresist resin monomer and preparation method and application thereof |
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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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