CN117706871A - Rapid-curing nano-imprint photoresist and preparation method thereof - Google Patents
Rapid-curing nano-imprint photoresist and preparation method thereof Download PDFInfo
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- 229920002120 photoresistant polymer Polymers 0.000 title claims abstract description 58
- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- 239000004593 Epoxy Substances 0.000 claims abstract description 58
- 239000004925 Acrylic resin Substances 0.000 claims abstract description 41
- 229920000178 Acrylic resin Polymers 0.000 claims abstract description 41
- 239000003607 modifier Substances 0.000 claims abstract description 19
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 claims abstract description 17
- 239000004970 Chain extender Substances 0.000 claims abstract description 13
- 239000000203 mixture Substances 0.000 claims abstract description 13
- 235000015112 vegetable and seed oil Nutrition 0.000 claims abstract description 13
- 239000008158 vegetable oil Substances 0.000 claims abstract description 13
- 238000001723 curing Methods 0.000 claims description 23
- 239000000758 substrate Substances 0.000 claims description 16
- 238000000034 method Methods 0.000 claims description 13
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical group CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 12
- 238000003756 stirring Methods 0.000 claims description 11
- ACTRVOBWPAIOHC-XIXRPRMCSA-N succimer Chemical compound OC(=O)[C@@H](S)[C@@H](S)C(O)=O ACTRVOBWPAIOHC-XIXRPRMCSA-N 0.000 claims description 9
- 239000003054 catalyst Substances 0.000 claims description 8
- 239000002285 corn oil Substances 0.000 claims description 8
- 235000005687 corn oil Nutrition 0.000 claims description 8
- 229960005346 succimer Drugs 0.000 claims description 8
- ZKLQKNDCBYXTBC-UHFFFAOYSA-N 5,6,7,7a-tetrafluoro-3aH-2-benzofuran-1,3-dione Chemical group FC1=C(F)C(F)=CC2C(=O)OC(=O)C21F ZKLQKNDCBYXTBC-UHFFFAOYSA-N 0.000 claims description 6
- 239000003963 antioxidant agent Substances 0.000 claims description 6
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- 238000002156 mixing Methods 0.000 claims description 5
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- 235000019198 oils Nutrition 0.000 claims description 5
- MFGALGYVFGDXIX-UHFFFAOYSA-N 2,3-Dimethylmaleic anhydride Chemical compound CC1=C(C)C(=O)OC1=O MFGALGYVFGDXIX-UHFFFAOYSA-N 0.000 claims description 4
- NLZUEZXRPGMBCV-UHFFFAOYSA-N Butylhydroxytoluene Chemical group CC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 NLZUEZXRPGMBCV-UHFFFAOYSA-N 0.000 claims description 3
- 235000010354 butylated hydroxytoluene Nutrition 0.000 claims description 3
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- 238000000576 coating method Methods 0.000 claims description 3
- 238000001816 cooling Methods 0.000 claims description 3
- 238000007872 degassing Methods 0.000 claims description 3
- 241001655736 Catalpa bignonioides Species 0.000 claims description 2
- 235000019483 Peanut oil Nutrition 0.000 claims description 2
- UOQACRNTVQWTFF-UHFFFAOYSA-N decane-1,10-dithiol Chemical compound SCCCCCCCCCCS UOQACRNTVQWTFF-UHFFFAOYSA-N 0.000 claims description 2
- 238000010438 heat treatment Methods 0.000 claims description 2
- 235000021388 linseed oil Nutrition 0.000 claims description 2
- 239000000944 linseed oil Substances 0.000 claims description 2
- 239000000312 peanut oil Substances 0.000 claims description 2
- 238000002604 ultrasonography Methods 0.000 claims description 2
- 238000005886 esterification reaction Methods 0.000 abstract description 10
- 239000003513 alkali Substances 0.000 abstract description 9
- 230000000052 comparative effect Effects 0.000 description 23
- 238000012360 testing method Methods 0.000 description 14
- 239000011347 resin Substances 0.000 description 7
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- 238000006243 chemical reaction Methods 0.000 description 5
- 239000002994 raw material Substances 0.000 description 5
- NIXOWILDQLNWCW-UHFFFAOYSA-N Acrylic acid Chemical class OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 4
- 238000004090 dissolution Methods 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 230000004580 weight loss Effects 0.000 description 4
- 239000005058 Isophorone diisocyanate Substances 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 150000008064 anhydrides Chemical group 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 125000003700 epoxy group Chemical group 0.000 description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 3
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- QLOAVXSYZAJECW-UHFFFAOYSA-N methane;molecular fluorine Chemical compound C.FF QLOAVXSYZAJECW-UHFFFAOYSA-N 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 239000002243 precursor Substances 0.000 description 3
- 239000003549 soybean oil Substances 0.000 description 3
- 235000012424 soybean oil Nutrition 0.000 description 3
- 230000002194 synthesizing effect Effects 0.000 description 3
- 125000003396 thiol group Chemical group [H]S* 0.000 description 3
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 2
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 2
- MWSKJDNQKGCKPA-UHFFFAOYSA-N 6-methyl-3a,4,5,7a-tetrahydro-2-benzofuran-1,3-dione Chemical compound C1CC(C)=CC2C(=O)OC(=O)C12 MWSKJDNQKGCKPA-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- OWIKHYCFFJSOEH-UHFFFAOYSA-N Isocyanic acid Chemical compound N=C=O OWIKHYCFFJSOEH-UHFFFAOYSA-N 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 125000001931 aliphatic group Chemical group 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 2
- -1 derivatives thereof Substances 0.000 description 2
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 125000001183 hydrocarbyl group Chemical group 0.000 description 2
- 238000003384 imaging method Methods 0.000 description 2
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000006552 photochemical reaction Methods 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 230000009257 reactivity Effects 0.000 description 2
- 238000007142 ring opening reaction Methods 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 239000011593 sulfur Substances 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- YRCWQPVGYLYSOX-UHFFFAOYSA-N synephrine Chemical compound CNCC(O)C1=CC=C(O)C=C1 YRCWQPVGYLYSOX-UHFFFAOYSA-N 0.000 description 2
- 238000002834 transmittance Methods 0.000 description 2
- XMLYCEVDHLAQEL-UHFFFAOYSA-N 2-hydroxy-2-methyl-1-phenylpropan-1-one Chemical compound CC(C)(O)C(=O)C1=CC=CC=C1 XMLYCEVDHLAQEL-UHFFFAOYSA-N 0.000 description 1
- DZTLWXJLPNCYDV-UHFFFAOYSA-N 3,4-difluorofuran-2,5-dione Chemical compound FC1=C(F)C(=O)OC1=O DZTLWXJLPNCYDV-UHFFFAOYSA-N 0.000 description 1
- 239000002028 Biomass Substances 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- XLJMAIOERFSOGZ-UHFFFAOYSA-N anhydrous cyanic acid Natural products OC#N XLJMAIOERFSOGZ-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
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- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical group 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
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- 238000000354 decomposition reaction Methods 0.000 description 1
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- 238000006731 degradation reaction Methods 0.000 description 1
- 125000005442 diisocyanate group Chemical group 0.000 description 1
- 239000003085 diluting agent Substances 0.000 description 1
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- 238000005516 engineering process Methods 0.000 description 1
- 230000032050 esterification Effects 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- 125000001153 fluoro group Chemical group F* 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000012948 isocyanate Substances 0.000 description 1
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 1
- 150000002513 isocyanates Chemical class 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 230000000269 nucleophilic effect Effects 0.000 description 1
- 229960003684 oxedrine Drugs 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 238000000016 photochemical curing Methods 0.000 description 1
- LGRFSURHDFAFJT-UHFFFAOYSA-N phthalic anhydride Chemical group C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 description 1
- 230000010287 polarization Effects 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 238000007712 rapid solidification Methods 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
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- 238000009210 therapy by ultrasound Methods 0.000 description 1
- 238000002411 thermogravimetry Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- 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
Landscapes
- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
- Epoxy Resins (AREA)
Abstract
The invention discloses a fast-curing nano-imprint photoresist and a preparation method thereof. The nano-imprint photoresist comprises a modified epoxy acrylic resin and a photoinitiator. The invention obtains a mixture through esterification reaction of a modifier and hydroxyethyl acrylate and esterification reaction of a graft body and hydroxyethyl acrylate, and then cross-links the mixture with epoxy vegetable oil, and then cross-links the mixture with a chain extender to obtain the modified epoxy acrylic resin. The modified epoxy acrylic resin and the photoinitiator are prepared into photoresist under the action of ultraviolet light. Compared with the prior art, the rapid curing nano-imprint photoresist prepared by the invention has the advantages of good alkali solubility, high refractive index, high precision, good thermal stability and the like.
Description
Technical Field
The invention relates to the technical field of photoresist, in particular to a rapidly-cured nano-imprint photoresist and a preparation method thereof.
Background
With the continued rapid growth of the electronic information industry, the demand for Printed Circuit Boards (PCBs) for key electronic components has increased in recent years. Photoresist is a key and fundamental material for obtaining etched electronic component printed circuit boards with engineered structures. Photoresists, also known as photoresists, are relatively sensitive organic mixtures to light, are a carrier medium for lithographic imaging, and can utilize photochemical reactions to convert diffracted, filtered light information in a lithographic system into chemical energy, thereby transferring a fine pattern from a reticle to a substrate to be processed. The method is widely applied to processing and manufacturing of micro pattern circuits in the photoelectric information industry, and is a key material of micro processing technology.
Photoresists differ from negative photoresists and positive photoresists in terms of their development principle: after the positive photoresist is irradiated by illumination, the exposed part is dissolved by the developing solution, the covered part of the mask is reserved, and generally, the positive photoresist can obtain higher resolution; in contrast, the negative photoresist is irradiated by light, the part covered by the mask plate and not exposed is dissolved by the developing solution, and the cost is lower and cheaper than that of the positive photoresist.
The composition of the photoresist typically includes a resin, a photoinitiator, reactive diluents, and additives. The properties of the photoresist, including adhesion, hardness, toughness, thermal stability, viscosity, etc., are determined by the resin. In the manufacture of electronic component printed circuit boards, a photoresist is coated on a metal substrate and then exposed through a photomask to cure and deposit the photoresist on the substrate. Thereafter, the non-exposed areas of the photoresist are removed using a photographic developer. In addition, the etchant is used to etch unwanted portions of the substrate that are not protected by the photoresist film. However, the photoresist film is removed by using a good solvent (usually an acid solution or an alkali solution) to successfully obtain the printed circuit board of the electronic component having the designed structure. In this regard, the photoresist resin should have a structure having a photoreactive group sensitive to a light source and capable of imparting a photocurable property to the resin so as to satisfy the photocuring film-forming requirement of the photoresist resin. In addition, the cured film of the photoresist resin must have solubility, particularly acid-solubility or alkali-solubility.
CN105093826a discloses photoresists and processes by providing a photoresist comprising a hydrocarbon backbone; a highly etch resistant structure attached to the hydrocarbon backbone; and bonding the decomposed groups to the highly etch-resistant structure. The photoresist has high etching resistance, but has poor thermal stability, and can affect the pattern stamping effect in the use process.
CN105353587a discloses a nanoimprint resist and a method for preparing the same, the nanoimprint resist comprising: organic small molecule solvent, resin, graphite fluoride, derivatives thereof, surfactant and additive. The nano-imprinting photoresist prepared by the invention has improved performance by adding graphite fluoride and derivatives thereof. Because graphite fluoride and derivatives thereof have low surface energy, the problems of pattern defects, template damage and the like in demolding caused by overlarge bonding force between the traditional high-surface-energy photoresist and the template are solved, however, the photoresist prepared by the method has low refractive index, and the imprinting precision of the photoresist is affected, so that the quality of imprinted patterns is low.
Disclosure of Invention
In view of the above-mentioned drawbacks of the prior art, the present invention aims to provide a nano imprint photoresist with good alkali dissolution property, fast curing, good thermal stability and higher imprint precision.
In order to achieve the above purpose, the invention provides a fast-curing nano-imprint photoresist, which comprises the following components in parts by weight: 10-40 parts of modified epoxy acrylic resin and 1-5 parts of photoinitiator; the modified epoxy acrylic resin is prepared from epoxy vegetable oil, a modifier, a chain extender, hydroxyethyl acrylate and a grafting body.
Preferably, the preparation method of the modified epoxy acrylic resin comprises the following steps in parts by weight:
step 1, uniformly mixing 5-14 parts of modifier, 7-23 parts of hydroxyethyl acrylate, 0.02-1 part of catalyst and 0.01-3 parts of antioxidant, heating to 100-130 ℃ in an oil bath, stirring at 200-300rpm for 20-60min, adding 10-30 parts of grafting body, and continuously stirring at 100-130 ℃ at 200-300rpm for 1-4h;
step 2, adding 25-50 parts of epoxy vegetable oil and 0.5-3 parts of catalyst into the mixture obtained in the step 1, and stirring at 200-300rpm for 1-4 hours at 100-130 ℃;
and 3, cooling the product obtained in the step 2 to 70-85 ℃, adding 2-10 parts of chain extender, and stirring at 200-300rpm for 0.5-2h to obtain the modified epoxy acrylic resin.
Preferably, the modifier is any one of meso-2, 3-dimercaptosuccinic acid, 3, 4-difluoro maleic anhydride and 2, 3-dimethyl maleic anhydride.
Preferably, the chain extender is any one of dodecylbenzene-2, 4-diisocyanate, decane-1, 10-diisocyanate and toluene-2, 5-diisocyanate.
Preferably, the epoxy vegetable oil is any one of epoxy peanut oil, epoxy corn oil, epoxy linseed oil and epoxy catalpa oil.
Preferably, the antioxidant is 2, 6-di-tert-butyl-4-methylphenol.
Preferably, the graft is 2,3,4, 5-tetrafluorophthalic anhydride.
Preferably, the catalyst is triethylamine.
The use method of the fast-curing nano-imprint photoresist comprises the following steps:
s1, cleaning a substrate;
s2, mixing the modified epoxy acrylic resin and the photoinitiator for 20-50min at room temperature, degassing for 5-15min in ultrasound, coating the mixture on a substrate, and curing the surface of the substrate by using a template;
s3, after the pressure is reduced to normal pressure, the template is stripped, and the nano imprinting pattern can be obtained.
In this formulation, the raw materials and their actions are as follows:
and (3) a modifier: the modifier is used as one of the raw materials for synthesizing the modified epoxy acrylic resin and participates in the crosslinking curing process of the modified epoxy acrylic resin. The modifier contains carboxylic acid functional groups or anhydride functional groups, and can be subjected to esterification reaction with hydroxyethyl acrylate to form a modified acrylic acid precursor. The main function of the modifier is to chemically modify the epoxy acrylic resin to improve its properties. In the invention, the viscosity, the curing speed, the hardness, the toughness and the like of the modified epoxy acrylic resin can be changed, and the modified epoxy acrylic resin is used as one of the raw materials of the photoresist, so that the performances of the photoresist such as thermal stability, alkali solubility, rapid curing, nano-imprinting photoresist precision and the like can be improved.
Hydroxyethyl acrylate: the hydroxyethyl acrylate is acrylic ester containing active hydroxyl, can be subjected to esterification reaction with a modifier, can be subjected to esterification reaction with a grafting body, can be subjected to reaction with epoxy groups contained in epoxy vegetable oil after being crosslinked, and is used as one of raw materials for synthesizing the modified epoxy acrylic resin to participate in the crosslinking curing process of the modified epoxy acrylic resin.
Catalyst: the catalyst has the main function of accelerating the synthesis speed of the modified epoxy acrylic resin.
Antioxidant: the antioxidant mainly prevents the modified epoxy acrylic resin from undergoing oxidation reaction during the preparation and use process.
Grafting body: the grafting body is used as one of the raw materials for synthesizing the modified epoxy acrylic resin and participates in the crosslinking curing process of the modified epoxy acrylic resin. The grafting body contains phthalic anhydride functional group, and can be subjected to esterification reaction with hydroxyethyl acrylate to obtain another modified acrylic acid precursor.
Epoxy vegetable oil: the vegetable oil has reactive groups on the main component structure, is one of rich renewable biomass resources, is epoxy group-containing vegetable oil, can carry out ring-opening reaction with products of hydroxyethyl acrylate and a modifier, and hydroxyethyl acrylate and grafts to form a cross-linked structure, and in the process, a large number of ester bonds with alkaline solution dissolving capacity are generated, and acrylic acid introduces terminal double bonds and can be solidified by ultraviolet light to form modified epoxy acrylic resin with good ultraviolet solidification performance and alkaline solubility.
Chain extender: the chain extender contains isocyanate functional groups and has the main function of forming longer molecular chains through reaction with hydroxyl groups in the modified epoxy acrylic resin, so that the molecular weight of the modified epoxy acrylic resin is increased, and the thermal stability, mechanical property and alkali dissolution property of the photoresist are improved.
And (3) a photoinitiator: the photoinitiator has the main function of generating free radicals or ions under the irradiation of ultraviolet light to initiate the curing reaction of the modified epoxy acrylic resin. So that the modified epoxy acrylic resin can be quickly cured to form photoresist.
The invention has the beneficial effects that:
1. compared with the prior art, the preparation method has the advantages that the modifier is used for esterification reaction with the hydroxyethyl acrylate, the grafting body is used for esterification reaction with the hydroxyethyl acrylate, the mixture is subjected to ring-opening reaction with the epoxy vegetable oil, the chain extender containing isocyanic acid is introduced to modify the epoxy acrylic resin, and the modified epoxy acrylic resin and the photoinitiator are used for preparing the photoresist under the action of ultraviolet light, so that the obtained photoresist has the characteristics of good thermal stability, rapid solidification and alkali dissolution performance.
2. Compared with the prior art, the sulfhydryl functional group contained in the modifier added during preparation can further react with the isocyanic acid functional group contained in the chain extender to generate the multi-sulfhydryl polymer with the structural unit of-NH-CO-S-, and the refractive index of the modified epoxy acrylic resin is improved, so that the precision of the photoresist can be improved.
Detailed Description
Parameters of specific chemicals are used, sources.
Meso-2, 3-dimercaptosuccinic acid, CAS number: 304-55-2.
3, 4-difluoromaleic anhydride, CAS number: 669-78-3.
2,3,4, 5-tetrafluorophthalic anhydride, CAS number: 52-12-0.
Dodecylbenzene-2, 4-diisocyanate, CAS number: 93859-04-2.
Epoxy corn oil, model: c8267 Jiangsu Meiger Biotech Co., ltd.
Epoxidized soybean oil, model: ESO, synephrine chemical industry limited.
The substrate is a quartz substrate, and the goods number is as follows: BKTMDC123116-02, northc nanotechnology Co., ltd.
Example 1
A method for preparing a fast curing nano-imprint photoresist, comprising the following steps:
s1, cleaning a substrate, and performing ultrasonic treatment on the substrate in acetone, ethanol and water at 15KHz for 10min;
s2, mixing 40g of modified epoxy acrylic resin and 2g of 2-hydroxy-2-methyl propiophenone at 25 ℃ for 20min at 200rpm, degassing for 10min in 40KHz ultrasonic, uniformly coating on a substrate with the thickness of 60nm, attaching the template to the substrate after the nano-imprinting photoresist fills the gaps of the template, maintaining the pressure in a cavity of an ultraviolet imprinting machine at 0.2MPa for 1min, and then turning on an ultraviolet lamp with the irradiation distance of 5kW for 2min with the irradiation distance of 10 cm;
s3, closing the ultraviolet lamp, reducing the pressure to normal pressure, and stripping the template to obtain the nano imprinting photoresist.
The preparation method of the modified epoxy acrylic resin comprises the following steps:
step 1, 8g of meso-2, 3-dimercaptosuccinic acid, 22g of hydroxyethyl acrylate, 0.2g of triethylamine and 0.5g of 2, 6-di-tert-butyl-4-methylphenol are stirred at 200rpm for 30min, heated to 120 ℃ in an oil bath, stirred at 200rpm for 30min, 15g of 2,3,4, 5-tetrafluorophthalic anhydride is added, and stirring at 200rpm is continued for 1h at 120 ℃;
step 2, adding 35g of epoxy corn oil and 2g of triethylamine into the mixture obtained in the step 1, and stirring at 200rpm for 2.5 hours at 120 ℃;
and 3, cooling the mixture obtained in the step 2 to 70 ℃, adding 6g of dodecylbenzene-2, 4-diisocyanate, and stirring at 200rpm for 1h to obtain the modified epoxy acrylic resin.
Example 2
Example 2 of the present application differs from example 1 in that 3, 4-difluoromaleic anhydride was used in place of meso-2, 3-dimercaptosuccinic acid in step 1.
Example 3
Example 3 of the present application differs from example 1 in that 2, 3-dimethylmaleic anhydride was used instead of meso-2, 3-dimercaptosuccinic acid in step 1.
Comparative example 1
This comparative example 1 differs from example 1 in that isophorone diisocyanate was used in place of dodecylbenzene-2, 4-diisocyanate in step 3.
Comparative example 2
This comparative example 2 differs from example 1 in that methyl tetrahydrophthalic anhydride was used instead of 2,3,4, 5-tetrafluorophthalic anhydride in step 1.
Comparative example 3
This comparative example 3 differs from example 1 in that maleic anhydride was used instead of meso-2, 3-dimercaptosuccinic acid in step 1.
Comparative example 4
This comparative example 4 differs from example 1 in that epoxidized soybean oil was used instead of epoxidized corn oil in step 2.
Test example 1
The embossed product prepared by the invention is subjected to thermogravimetric analysis to test its thermal stability by counting the temperature at 10wt% of the weight loss and the temperature at 50wt% of the weight loss of the sample. The test results are shown in Table 1.
TABLE 1 thermal stability test results
| Experimental protocol | Weight loss 10wt% temperature (. Degree. C.) | Weight loss 50wt% temperature (. Degree. C.) |
| Example 1 | 298.4 | 352.2 |
| Example 2 | 282.7 | 341.8 |
| Example 3 | 278.6 | 330.9 |
| Comparative example 1 | 275.3 | 329.0 |
| Comparative example 2 | 269.7 | 327.8 |
| Comparative example 3 | 265.4 | 326.3 |
| Comparative example 4 | 264.1 | 324.6 |
Test example 2
Determination of the tensile Properties of plastics according to GB/T1040.3-2006 section 3: test conditions for films and sheets tensile properties were tested on the embossed products prepared according to the invention. The length of the sample is 150mm, the width is 20mm, a 4-type dumbbell specimen is adopted, and the stretching speed is 50mm/min. Test conditions: at room temperature, 5 samples per group, averaged. The test results are shown in Table 2.
TABLE 2 mechanical test results
Test example 3
Alkali solubility test
The nanoimprint photoresists prepared in examples 1 to 3 and comparative examples 1 to 4 were cut to a size of 2cm×2cm, weighed 0.1g, immersed in 10wt% NaOH solution at normal temperature, taken out after 20min immersion, dried over surface solution, and weighed. The results are shown in Table 3.
TABLE 3 alkali dissolution test results
| Experimental protocol | Quality after soaking (g) |
| Example 1 | 0.032 |
| Example 2 | 0.042 |
| Example 3 | 0.045 |
| Comparative example 1 | 0.046 |
| Comparative example 2 | 0.047 |
| Comparative example 3 | 0.046 |
| Comparative example 4 | 0.054 |
Test example 4
Refractive index
The refractive index n was determined using GB/T2410-2008 determination of light transmittance and haze of clear plastics. The test results are shown in Table 4
TABLE 4 refractive index test results
From the test data in tables 1 to 4, it can be seen that the thermal stability, tensile strength, alkali dissolution property and refractive index of the nano-imprint resist prepared in example 1 of the present invention are the best, and the deformation of the nano-imprint resist can be reduced by slightly lower elongation at break. As can be seen from the comparison of examples 1-3 and comparative example 3, examples 1-3 and comparative example 3 differ in the use of different modifiers, the modifier used in examples 1-3 being meso-2, 3-dimercaptosuccinic acid, 3, 4-difluoromaleic anhydride, 2, 3-dimethylmaleic anhydride, respectively, and the modifier used in comparative example 3 being maleic anhydride. The main function of the modifier is to provide anhydride or carboxyl groups, and the refractive index of the imprint resist prepared in example 1 is best, probably because the mesogen-2, 3-dimercaptosuccinic acid has hydroxyl groups in hydroxyethyl acrylate to participate in esterification reaction to prepare the acrylic acid precursor, and the mercapto functional group containing mercapto functional group can react with isocyanate to generate a multi-mercapto polymer containing structural units of-NH-CO-S-which is beneficial to accelerating the curing of the resist. Meanwhile, sulfur and benzene rings which contain substances with high polarizability are introduced into the prepared photoresist polymer. The large polarization rate also means that the dielectric constant is large, and the dielectric medium with the large dielectric constant can reduce the propagation loss of electromagnetic waves such as ultraviolet rays and the like and can effectively improve the refractive index. The high-molar refractive index group of the sulfur element is introduced into the main chain or the side chain of the polymer, so that the refractive index of the photoresist can be better improved, the light transmittance of the photoresist can be improved by improving the refractive index, the photoresist with high refractive index can generate stronger photochemical reaction, the imaging contrast is improved, the sensitivity and resolution of the photoresist can be further improved, and the manufacturing precision and the yield of an integrated circuit and an electronic device are improved.
Example 1 differs from comparative example 1 in that a different chain extender was used. Dodecyl benzene-2, 4-diisocyanate differs from isophorone diisocyanate in that dodecyl benzene-2, 4-diisocyanate is a low modulus, low strength soft segment structure, while isophorone diisocyanate is a rigid segment structure. The soft segment structure diisocyanate is introduced into the modified epoxy acrylic resin, which is helpful for obviously improving the toughness and ductility of the photoresist. In this regard, the film has good tensile properties due to the fact that the soft segments in the crosslinked network are free to move under external forces to counteract the external forces. The thermal stability of the photoresist is mainly determined by the crosslinking density and the structure of the modified epoxy acrylic resin, however, the steric hindrance of the soft long chain is small, so that the dodecylbenzene-2, 4-diisocyanate is easier to participate in crosslinking, and the modified epoxy acrylic resin is formed. The main differences in the degradation process are the decomposition of long aliphatic chain segments and carbonization of crosslinked polymers, whereas dodecylbenzene-2, 4-diisocyanate has longer aliphatic chain segments and the modified epoxy acrylic resin formed by crosslinking has a higher density and thus exhibits better thermal stability.
Example 1 differs from comparative example 2 in that a different graft was used. The fluorine atoms in 2,3,4, 5-tetrafluorophthalic anhydride used in example 1 had strong electronegativity, which enabled the whole molecule to have strong electron-attracting ability. This electronic effect can enhance the activity of the anhydride, making it more susceptible to esterification with the nucleophilic agent hydroxyethyl acrylate, as compared to the lower reactivity of methyltetrahydrophthalic anhydride, which may require higher temperatures or longer reaction times to fully participate in the reaction.
Example 1 and comparative example 4 differ in that different epoxidized vegetable oils are used. The possible reason is that epoxidized corn oil contains more allyl and benzyl groups, which are relatively fewer in epoxidized soybean oil. Allyl and benzyl groups can provide better reactivity and compatibility, facilitating the reaction between the epoxy groups and the chain extender. Meanwhile, the viscosity of the epoxy corn oil is relatively low, and the fluidity is better. This makes the epoxy corn oil easier to mix and disperse when preparing the modified epoxy acrylic resin, thereby improving the uniformity and stability of the modified epoxy acrylic resin.
Claims (9)
1. The fast-curing nano-imprint photoresist is characterized by comprising the following components in parts by weight: 10-40 parts of modified epoxy acrylic resin and 1-5 parts of photoinitiator; the modified epoxy acrylic resin is prepared from epoxy vegetable oil, a modifier, a chain extender, hydroxyethyl acrylate and a grafting body.
2. The rapid curing nanoimprint resist of claim 1, wherein the preparation method of the modified epoxy acrylic resin comprises the following steps in parts by weight:
step 1, uniformly mixing 5-14 parts of modifier, 7-23 parts of hydroxyethyl acrylate, 0.02-1 part of catalyst and 0.01-3 parts of antioxidant, heating to 100-130 ℃ in an oil bath, stirring at 200-300rpm for 20-60min, adding 10-30 parts of grafting body, and continuously stirring at 100-130 ℃ at 200-300rpm for 1-4h;
step 2, adding 25-50 parts of epoxy vegetable oil and 0.5-3 parts of catalyst into the mixture obtained in the step 1, and stirring at 200-300rpm for 1-4 hours at 100-130 ℃;
and 3, cooling the product obtained in the step 2 to 70-85 ℃, adding 2-10 parts of chain extender, and stirring at 200-300rpm for 0.5-2h to obtain the modified epoxy acrylic resin.
3. The rapid curing nanoimprint resist of claim 2, wherein: the modifier is any one of meso-2, 3-dimercaptosuccinic acid, 3, 4-difluoro maleic anhydride and 2, 3-dimethyl maleic anhydride.
4. The rapid curing nanoimprint resist of claim 2, wherein: the chain extender is any one of dodecylbenzene-2, 4-diisocyanate, decane-1, 10-diisocyanate and toluene-2, 5-diisocyanate.
5. The rapid curing nanoimprint resist of claim 2 wherein the epoxidized vegetable oil is any one of epoxidized peanut oil, epoxidized corn oil, epoxidized linseed oil, and epoxidized catalpa oil.
6. The rapid curing nanoimprint resist of claim 2 wherein the antioxidant is 2, 6-di-tert-butyl-4-methylphenol.
7. The rapid curing nanoimprint resist of claim 2, wherein: the grafting body is 2,3,4, 5-tetrafluorophthalic anhydride.
8. The rapid curing nanoimprint resist of claim 2 wherein the catalyst is triethylamine.
9. A method of preparing a fast curing nanoimprint resist as claimed in any one of claims 1 to 8, comprising the steps of:
s1, cleaning a substrate;
s2, mixing the modified epoxy acrylic resin and the photoinitiator for 20-50min at room temperature, degassing for 5-15min in ultrasound, coating the mixture on a substrate, and curing the surface of the substrate by using a template;
s3, after the pressure is reduced to normal pressure, the template is stripped, and the nano imprinting pattern can be obtained.
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