CN116396699A - Acid-resistant protective film and preparation method thereof - Google Patents
Acid-resistant protective film and preparation method thereof Download PDFInfo
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- CN116396699A CN116396699A CN202310407817.XA CN202310407817A CN116396699A CN 116396699 A CN116396699 A CN 116396699A CN 202310407817 A CN202310407817 A CN 202310407817A CN 116396699 A CN116396699 A CN 116396699A
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- Prior art keywords
- acid
- acrylate
- monomer
- protective film
- parts
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- 239000002253 acid Substances 0.000 title claims abstract description 54
- 230000001681 protective effect Effects 0.000 title claims abstract description 45
- 238000002360 preparation method Methods 0.000 title abstract description 8
- 239000012790 adhesive layer Substances 0.000 claims abstract description 43
- 239000004925 Acrylic resin Substances 0.000 claims abstract description 39
- 229920000178 Acrylic resin Polymers 0.000 claims abstract description 39
- 239000000203 mixture Substances 0.000 claims abstract description 39
- 229920000642 polymer Polymers 0.000 claims abstract description 39
- 239000002904 solvent Substances 0.000 claims abstract description 39
- 239000010410 layer Substances 0.000 claims abstract description 35
- 239000003431 cross linking reagent Substances 0.000 claims abstract description 27
- 239000000758 substrate Substances 0.000 claims abstract description 20
- 239000003292 glue Substances 0.000 claims abstract description 16
- 238000000576 coating method Methods 0.000 claims abstract description 14
- 239000011248 coating agent Substances 0.000 claims abstract description 13
- 238000002156 mixing Methods 0.000 claims abstract description 12
- 239000012948 isocyanate Substances 0.000 claims abstract description 7
- 150000002513 isocyanates Chemical class 0.000 claims abstract description 7
- 230000009477 glass transition Effects 0.000 claims abstract description 6
- 238000001035 drying Methods 0.000 claims abstract description 4
- 239000000178 monomer Substances 0.000 claims description 87
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical group CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 33
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 17
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 claims description 16
- 239000002994 raw material Substances 0.000 claims description 15
- XLPJNCYCZORXHG-UHFFFAOYSA-N 1-morpholin-4-ylprop-2-en-1-one Chemical compound C=CC(=O)N1CCOCC1 XLPJNCYCZORXHG-UHFFFAOYSA-N 0.000 claims description 12
- GOXQRTZXKQZDDN-UHFFFAOYSA-N 2-Ethylhexyl acrylate Chemical compound CCCCC(CC)COC(=O)C=C GOXQRTZXKQZDDN-UHFFFAOYSA-N 0.000 claims description 12
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 claims description 12
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims description 12
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 claims description 12
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 12
- 238000006243 chemical reaction Methods 0.000 claims description 12
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 12
- RPQRDASANLAFCM-UHFFFAOYSA-N oxiran-2-ylmethyl prop-2-enoate Chemical compound C=CC(=O)OCC1CO1 RPQRDASANLAFCM-UHFFFAOYSA-N 0.000 claims description 12
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 claims description 12
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 11
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical group OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 claims description 10
- 150000001408 amides Chemical class 0.000 claims description 9
- FQPSGWSUVKBHSU-UHFFFAOYSA-N methacrylamide Chemical compound CC(=C)C(N)=O FQPSGWSUVKBHSU-UHFFFAOYSA-N 0.000 claims description 9
- 238000003756 stirring Methods 0.000 claims description 8
- 239000003999 initiator Substances 0.000 claims description 7
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 claims description 6
- -1 N-butyl (N-substituted) amide Chemical class 0.000 claims description 6
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 6
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 claims description 6
- 238000001816 cooling Methods 0.000 claims description 4
- FKTHNVSLHLHISI-UHFFFAOYSA-N 1,2-bis(isocyanatomethyl)benzene Chemical compound O=C=NCC1=CC=CC=C1CN=C=O FKTHNVSLHLHISI-UHFFFAOYSA-N 0.000 claims description 3
- IQEWHTMQTSAPLG-UHFFFAOYSA-N 10-hydroxydecyl prop-2-enoate Chemical compound OCCCCCCCCCCOC(=O)C=C IQEWHTMQTSAPLG-UHFFFAOYSA-N 0.000 claims description 3
- AEZJNQZYZFLLIY-UHFFFAOYSA-N 12-hydroxydodecyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCCCCCCCCCCCO AEZJNQZYZFLLIY-UHFFFAOYSA-N 0.000 claims description 3
- NKYRAXWYDRHWOG-UHFFFAOYSA-N 12-hydroxydodecyl prop-2-enoate Chemical compound OCCCCCCCCCCCCOC(=O)C=C NKYRAXWYDRHWOG-UHFFFAOYSA-N 0.000 claims description 3
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 claims description 3
- WDQMWEYDKDCEHT-UHFFFAOYSA-N 2-ethylhexyl 2-methylprop-2-enoate Chemical compound CCCCC(CC)COC(=O)C(C)=C WDQMWEYDKDCEHT-UHFFFAOYSA-N 0.000 claims description 3
- IEVADDDOVGMCSI-UHFFFAOYSA-N 2-hydroxybutyl 2-methylprop-2-enoate Chemical compound CCC(O)COC(=O)C(C)=C IEVADDDOVGMCSI-UHFFFAOYSA-N 0.000 claims description 3
- GNSFRPWPOGYVLO-UHFFFAOYSA-N 3-hydroxypropyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCCO GNSFRPWPOGYVLO-UHFFFAOYSA-N 0.000 claims description 3
- QZPSOSOOLFHYRR-UHFFFAOYSA-N 3-hydroxypropyl prop-2-enoate Chemical compound OCCCOC(=O)C=C QZPSOSOOLFHYRR-UHFFFAOYSA-N 0.000 claims description 3
- CYUZOYPRAQASLN-UHFFFAOYSA-N 3-prop-2-enoyloxypropanoic acid Chemical compound OC(=O)CCOC(=O)C=C CYUZOYPRAQASLN-UHFFFAOYSA-N 0.000 claims description 3
- NDWUBGAGUCISDV-UHFFFAOYSA-N 4-hydroxybutyl prop-2-enoate Chemical compound OCCCCOC(=O)C=C NDWUBGAGUCISDV-UHFFFAOYSA-N 0.000 claims description 3
- XFOFBPRPOAWWPA-UHFFFAOYSA-N 6-hydroxyhexyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCCCCCO XFOFBPRPOAWWPA-UHFFFAOYSA-N 0.000 claims description 3
- OCIFJWVZZUDMRL-UHFFFAOYSA-N 6-hydroxyhexyl prop-2-enoate Chemical compound OCCCCCCOC(=O)C=C OCIFJWVZZUDMRL-UHFFFAOYSA-N 0.000 claims description 3
- JSZCJJRQCFZXCI-UHFFFAOYSA-N 6-prop-2-enoyloxyhexanoic acid Chemical compound OC(=O)CCCCCOC(=O)C=C JSZCJJRQCFZXCI-UHFFFAOYSA-N 0.000 claims description 3
- YPMOAQISONSSNL-UHFFFAOYSA-N 8-hydroxyoctyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCCCCCCCO YPMOAQISONSSNL-UHFFFAOYSA-N 0.000 claims description 3
- JSCDRVVVGGYHSN-UHFFFAOYSA-N 8-hydroxyoctyl prop-2-enoate Chemical compound OCCCCCCCCOC(=O)C=C JSCDRVVVGGYHSN-UHFFFAOYSA-N 0.000 claims description 3
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 claims description 3
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 claims description 3
- 239000005057 Hexamethylene diisocyanate Substances 0.000 claims description 3
- CNCOEDDPFOAUMB-UHFFFAOYSA-N N-Methylolacrylamide Chemical compound OCNC(=O)C=C CNCOEDDPFOAUMB-UHFFFAOYSA-N 0.000 claims description 3
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims description 3
- LDHQCZJRKDOVOX-NSCUHMNNSA-N crotonic acid Chemical compound C\C=C\C(O)=O LDHQCZJRKDOVOX-NSCUHMNNSA-N 0.000 claims description 3
- 125000005442 diisocyanate group Chemical group 0.000 claims description 3
- GMSCBRSQMRDRCD-UHFFFAOYSA-N dodecyl 2-methylprop-2-enoate Chemical compound CCCCCCCCCCCCOC(=O)C(C)=C GMSCBRSQMRDRCD-UHFFFAOYSA-N 0.000 claims description 3
- SUPCQIBBMFXVTL-UHFFFAOYSA-N ethyl 2-methylprop-2-enoate Chemical compound CCOC(=O)C(C)=C SUPCQIBBMFXVTL-UHFFFAOYSA-N 0.000 claims description 3
- 239000001530 fumaric acid Substances 0.000 claims description 3
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 claims description 3
- PBOSTUDLECTMNL-UHFFFAOYSA-N lauryl acrylate Chemical compound CCCCCCCCCCCCOC(=O)C=C PBOSTUDLECTMNL-UHFFFAOYSA-N 0.000 claims description 3
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 claims description 3
- 239000011976 maleic acid Substances 0.000 claims description 3
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 claims description 3
- 229940088644 n,n-dimethylacrylamide Drugs 0.000 claims description 3
- YLGYACDQVQQZSW-UHFFFAOYSA-N n,n-dimethylprop-2-enamide Chemical group CN(C)C(=O)C=C YLGYACDQVQQZSW-UHFFFAOYSA-N 0.000 claims description 3
- DNTMQTKDNSEIFO-UHFFFAOYSA-N n-(hydroxymethyl)-2-methylprop-2-enamide Chemical compound CC(=C)C(=O)NCO DNTMQTKDNSEIFO-UHFFFAOYSA-N 0.000 claims description 3
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 claims description 3
- LDHQCZJRKDOVOX-UHFFFAOYSA-N trans-crotonic acid Natural products CC=CC(O)=O LDHQCZJRKDOVOX-UHFFFAOYSA-N 0.000 claims description 3
- 230000001070 adhesive effect Effects 0.000 abstract description 13
- 239000000463 material Substances 0.000 abstract description 13
- 239000000853 adhesive Substances 0.000 abstract description 11
- 238000002791 soaking Methods 0.000 abstract description 8
- 150000002500 ions Chemical class 0.000 abstract description 5
- 239000012466 permeate Substances 0.000 abstract description 4
- 150000001732 carboxylic acid derivatives Chemical class 0.000 abstract description 2
- 230000035515 penetration Effects 0.000 abstract 1
- 239000011521 glass Substances 0.000 description 24
- 230000000052 comparative effect Effects 0.000 description 9
- 238000000034 method Methods 0.000 description 8
- 239000003795 chemical substances by application Substances 0.000 description 7
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 239000007788 liquid Substances 0.000 description 6
- 238000010998 test method Methods 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 4
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 4
- 238000005406 washing Methods 0.000 description 4
- 238000005520 cutting process Methods 0.000 description 3
- 238000005530 etching Methods 0.000 description 3
- 239000012528 membrane Substances 0.000 description 3
- 238000003825 pressing Methods 0.000 description 3
- 235000012431 wafers Nutrition 0.000 description 3
- 239000002390 adhesive tape Substances 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 238000000113 differential scanning calorimetry Methods 0.000 description 2
- 239000003344 environmental pollutant Substances 0.000 description 2
- 238000005227 gel permeation chromatography Methods 0.000 description 2
- 239000002985 plastic film Substances 0.000 description 2
- 231100000719 pollutant Toxicity 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 238000010306 acid treatment Methods 0.000 description 1
- 229920005601 base polymer Polymers 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000011127 biaxially oriented polypropylene Substances 0.000 description 1
- 229920006378 biaxially oriented polypropylene Polymers 0.000 description 1
- 238000007707 calorimetry Methods 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- KRVSOGSZCMJSLX-UHFFFAOYSA-L chromic acid Substances O[Cr](O)(=O)=O KRVSOGSZCMJSLX-UHFFFAOYSA-L 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000011010 flushing procedure Methods 0.000 description 1
- AWJWCTOOIBYHON-UHFFFAOYSA-N furo[3,4-b]pyrazine-5,7-dione Chemical compound C1=CN=C2C(=O)OC(=O)C2=N1 AWJWCTOOIBYHON-UHFFFAOYSA-N 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 230000005865 ionizing radiation Effects 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 230000000149 penetrating effect Effects 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 238000000053 physical method Methods 0.000 description 1
- 229920006255 plastic film Polymers 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 229920002050 silicone resin Polymers 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 238000004448 titration Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J7/00—Adhesives in the form of films or foils
- C09J7/30—Adhesives in the form of films or foils characterised by the adhesive composition
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J133/00—Adhesives based on homopolymers or 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 only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
- C09J133/04—Homopolymers or copolymers of esters
- C09J133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
- C09J133/062—Copolymers with monomers not covered by C09J133/06
- C09J133/068—Copolymers with monomers not covered by C09J133/06 containing glycidyl groups
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J7/00—Adhesives in the form of films or foils
- C09J7/40—Adhesives in the form of films or foils characterised by release liners
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J2203/00—Applications of adhesives in processes or use of adhesives in the form of films or foils
- C09J2203/326—Applications of adhesives in processes or use of adhesives in the form of films or foils for bonding electronic components such as wafers, chips or semiconductors
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J2301/00—Additional features of adhesives in the form of films or foils
- C09J2301/10—Additional features of adhesives in the form of films or foils characterized by the structural features of the adhesive tape or sheet
- C09J2301/12—Additional features of adhesives in the form of films or foils characterized by the structural features of the adhesive tape or sheet by the arrangement of layers
- C09J2301/122—Additional features of adhesives in the form of films or foils characterized by the structural features of the adhesive tape or sheet by the arrangement of layers the adhesive layer being present only on one side of the carrier, e.g. single-sided adhesive tape
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Adhesive Tapes (AREA)
Abstract
The invention discloses an acid-resistant protective film and a preparation method thereof, wherein the acid-resistant protective film comprises a substrate layer, a glue layer and a release layer which are sequentially attached, wherein the glue layer is prepared by mixing an acrylic resin polymer, an isocyanate cross-linking agent and a solvent, coating the mixture on the substrate layer and then drying the mixture; wherein the molecular weight of the acrylic resin polymer is 70-100W, the glass transition temperature is-25 to-50 ℃, and the acid value is 2-5 mgKOH/g. The adhesive layer in the acid-resistant protective film has high overall strength and molecular chain network density, so that an HF solution cannot permeate into a back adhesive material from a bonding gap and the adhesive layer, and carboxylic acid contained in the adhesive layer can generate a certain amount of H ions, and the penetration of the HF ions to the surface of the back adhesive material through a film material and the adhesive layer can be prevented, so that the adhesive property cannot climb after the HF acid soaking, the adhesive layer is easy to peel off, the HF acid is resistant to seepage, and the adhesive layer is easy to tear and has no residual adhesive after the acid soaking.
Description
Technical Field
The invention relates to the field of membrane materials, in particular to an acid-resistant protective membrane and a preparation method thereof.
Background
When micro components such as wafer grinding, various silicon wafers, packaging substrates, ceramics, glass, crystal fine electronic parts, glass, metal plates and the like are processed, a protective film is generally required to be used for surface protection, so that damage caused by movement of the components in the processes of etching and flushing is avoided. In addition, in the etching, rinsing, or coating process, when the partial surface of a component needs to be polished, in order to protect other parts that do not need to be processed from being affected, a protective film is also used to cover the parts that do not need to be processed first, and then the parts are peeled off after the processing is completed. For example, in the glass thinning and wafer etching processes, it needs to be soaked in 30% HF for 30min, washed with weak alkaline liquid medicine for 10min and washed with clear water for 10min, and the process has strong acid soaking, so that the acid-resistant protective film is required to have the following characteristics: the adhesive property is good, the adhesive is resistant to HF acid and seepage, resistant to water washing and seepage, and the film is easy to tear after acid washing.
However, the existing protective film is difficult to meet the above requirements, and in the practical application process, the following problems occur: (1) The material is soaked in HF acid solution for a long time, the HF acid is easy to gasify, has strong corrosiveness and penetrating capacity, and even can penetrate through a membrane material to penetrate to the surface of the material, so that the protected material is damaged. (2) HF permeates to the surface of the material, hydrogen bonds can be formed between the adhesive layer and the back patch, so that the viscosity is increased, the viscosity is increased more, and the adhesive residue is caused on the surface of the patch when the film is torn.
Disclosure of Invention
The invention aims to solve the technical problem of providing an acid-resistant protective film and a preparation method thereof aiming at the defects in the prior art.
In order to solve the technical problems, the invention adopts the following technical scheme: an acid-resistant protective film comprises a substrate layer, a glue layer and a release layer which are sequentially attached, wherein the glue layer is prepared by mixing an acrylic resin polymer, a cross-linking agent and a solvent, coating the mixture on the substrate layer and drying the mixture;
wherein the cross-linking agent is isocyanate cross-linking agent;
wherein the molecular weight of the acrylic resin polymer is 70-100W, the glass transition temperature is-25 to-50 ℃, and the acid value is 2-5 mgKOH/g.
Preferably, the acrylic resin polymer comprises the following raw materials in parts by weight: 20-60 parts of soft monomer, 5-30 parts of hard monomer, 2-15 parts of functional monomer, 0.1-1 part of initiator and 20-50 parts of solvent;
wherein the functional monomer comprises one or more of carboxyl-containing monomers, amide-type monomers and hydroxyl-containing monomers.
Preferably, wherein the soft monomer comprises one or more of ethyl acrylate, n-butyl acrylate, 2-ethylhexyl acrylate, lauryl acrylate, glycidyl acrylate, lauryl methacrylate and 2-ethylhexyl methacrylate.
Preferably, wherein the hard monomer comprises one or more of methyl acrylate, methyl methacrylate, ethyl methacrylate, styrene, acrylonitrile, and acryloylmorpholine.
Preferably, the carboxyl group-containing monomer comprises one or more of acrylic acid, itaconic acid, maleic acid, fumaric acid, crotonic acid, carboxypentyl acrylate and carboxyethyl acrylate.
Preferably, the hydroxyl-containing monomer comprises one or more of hydroxypropyl acrylate, hydroxypropyl methacrylate, hydroxybutyl acrylate, hydroxybutyl methacrylate, hydroxyhexyl acrylate, hydroxyhexyl methacrylate, hydroxyoctyl acrylate, hydroxyoctyl methacrylate, hydroxydecyl acrylate, hydroxylauryl acrylate and hydroxylauryl methacrylate.
Preferably, the amide monomer comprises one or more of acrylamide, methacrylamide, N-dimethylacrylamide, N-dimethylacrylamide and N-butyl (N-substituted) amide monomers;
the N-butyl (N-substituted) amide monomer is one or more of acrylamide, methacrylamide, N-methylolacrylamide, N-methylolmethacrylamide, N-methylolpropane acrylamide and N-methylolpropane methacrylamide.
Preferably, the isocyanate cross-linking agent is one or more of hexamethylene diisocyanate, isoparaffin diisocyanate, 2, 4-toluene diisocyanate, 4' -diphenylmethane diisocyanate and xylylene diisocyanate.
Preferably, the solvent is one or more of ethyl acetate, toluene, butanone and isopropanol.
Preferably, the soft monomer is a mixture of 2-ethylhexyl acrylate, n-butyl acrylate and glycidyl acrylate;
the hard monomer is a mixture of methyl acrylate, methyl methacrylate and acryloylmorpholine;
the functional monomer comprises a mixture of a carboxyl monomer, an amide monomer and a hydroxyl monomer, wherein the carboxyl monomer is acrylic acid, the hydroxyl monomer is hydroxyethyl acrylate, and the amide monomer is N, N-dimethylacrylamide;
the cross-linking agent is toluene diisocyanate, and the solvent is ethyl acetate.
Preferably, the acid-resistant protective film is prepared by the following method:
s1, uniformly mixing a soft monomer, a hard monomer, a functional monomer, an initiator and a solvent according to weight ratio, adding into a reaction kettle, stirring at 60-75 ℃ for reaction for 4-8 hours, cooling after the reaction is finished, and pouring out to obtain an acrylic resin polymer;
s2, mixing the acrylic resin polymer obtained in the step S1, the cross-linking agent and the solvent, and stirring at the speed of 300-800r/min for 10-30min to obtain a glue layer mixture;
s3, coating the adhesive layer mixture obtained in the step S2 on a substrate layer by using a coating device, controlling the thickness of a dry adhesive layer formed by the adhesive layer mixture to be 10-100 mu m, attaching a release film on the adhesive layer, and baking for 1-3 days at 50-65 ℃ to obtain the acid-resistant protective film.
The beneficial effects of the invention are as follows:
the invention adopts the acrylic resin polymer with the molecular weight of 70-100W, the glass transition temperature of-25-50 ℃ and the acid value of 2-5mgKOH/g, and uses the isocyanate crosslinking agent to prepare the adhesive layer of the protective film, thereby improving the overall crosslinking density of the adhesive layer while ensuring the wettability, improving the overall strength and the molecular chain network density of the adhesive layer, leading the HF solution not to permeate into the back paste from the bonding gap and the adhesive layer, leading the carboxylic acid contained in the adhesive layer to generate a certain amount of H ions, and preventing the HF ions from permeating the film material and the adhesive layer to the surface of the back paste, thereby ensuring that the adhesiveness is not climbed after the HF acid soaking, the HF acid is easy to peel off, the HF acid is not permeated, and the adhesive is easy to tear after the acid washing and has no residual adhesive;
the adhesive layer in the acid-resistant protective film can still keep higher viscosity at 60 ℃, so that acid-base liquid cannot permeate to the surface of a substrate, the adhesive layer structure cannot be damaged after baking at 200 ℃, the peeling force cannot be increased too much after the adhesive layer is restored to normal temperature, and the adhesive layer is still easier to peel; the acid-resistant protective film has excellent comprehensive performance, can provide effective protection for components in a strong acid environment, and has wide application prospect.
Detailed Description
The present invention is described in further detail below with reference to examples to enable those skilled in the art to practice the same by referring to the description.
It will be understood that terms, such as "having," "including," and "comprising," as used herein, do not preclude the presence or addition of one or more other elements or groups thereof.
The test methods used in the following examples are conventional methods unless otherwise specified. The material reagents and the like used in the following examples are commercially available unless otherwise specified. The following examples were conducted under conventional conditions or conditions recommended by the manufacturer, without specifying the specific conditions. The reagents or apparatus used were conventional products commercially available without the manufacturer's attention.
The invention provides an acid-resistant protective film, which comprises a substrate layer, a glue layer and a release layer which are sequentially attached, wherein the glue layer is prepared by mixing an acrylic resin polymer, a cross-linking agent and a solvent, coating the mixture on the substrate layer and then drying;
among them, the crosslinking agent is an isocyanate crosslinking agent, and more preferably, one or more of hexamethylene diisocyanate, isophalcone diisocyanate, 2, 4-toluene diisocyanate, 4' -diphenylmethane diisocyanate, and xylylene diisocyanate, but not limited thereto. The content of the crosslinking agent may be adjusted according to the desired adhesive force, and is typically 0.1 to 10 parts by weight, more preferably 0.5 to 3 parts by weight, relative to 100 parts by weight of the base polymer.
Wherein the molecular weight of the acrylic resin polymer is 70-100W (inclusive), the glass transition temperature is-25 to-50 ℃ (inclusive), and the acid value is 2-5mgKOH/g (inclusive).
Wherein, the substrate layer can be made of plastic film or sheet material such as PET, PE, CPP, PC, BOPP, PI. The thickness of the base material is usually 300 μm or less, preferably 20 to 100 μm, more preferably about 50 to 75 μm, but is not limited thereto. The surface of the substrate 1 is subjected to a conventional surface treatment before preparation, for example, a coating treatment with a release agent such as silicone resin or fluororesin, a chromic acid treatment, an ozone exposure, a flame exposure, a high-pressure impact exposure, an ionizing radiation treatment, an oxidation treatment by a chemical or physical method, or the like.
In the invention, the acrylic resin polymer comprises the following raw materials in parts by weight: 20-60 parts of soft monomer, 5-30 parts of hard monomer, 2-15 parts of functional monomer, 0.1-1 part of initiator and 20-50 parts of solvent; wherein the functional monomer comprises one or more of carboxyl-containing monomer, amide-type monomer and hydroxyl-containing monomer.
In a preferred embodiment, the soft monomer comprises one or more of ethyl acrylate, n-butyl acrylate, 2-ethylhexyl acrylate, lauryl acrylate, glycidyl acrylate, lauryl methacrylate, and 2-ethylhexyl methacrylate, but is not limited thereto.
In a preferred embodiment, the hard monomer comprises one or more of methyl acrylate, methyl methacrylate, ethyl methacrylate, styrene, acrylonitrile, and acryloylmorpholine, but is not limited thereto.
In a preferred embodiment, the carboxyl group-containing monomer includes one or more of acrylic acid, itaconic acid, maleic acid, fumaric acid, crotonic acid, carboxypentyl acrylate and carboxyethyl acrylate, but is not limited thereto.
In a preferred embodiment, the hydroxyl-containing monomer includes one or more of hydroxypropyl acrylate, hydroxypropyl methacrylate, hydroxybutyl acrylate, hydroxybutyl methacrylate, hydroxyhexyl acrylate, hydroxyhexyl methacrylate, hydroxyoctyl acrylate, hydroxyoctyl methacrylate, hydroxydecyl acrylate, hydroxylauryl acrylate, and hydroxylauryl methacrylate, but is not limited thereto.
In a preferred embodiment, the amide-based monomer includes one or more of acrylamide, methacrylamide, N-dimethylacrylamide, N-butyl (N-substituted) amide monomers, but is not limited thereto.
The N-butyl (N-substituted) amide monomer is one or more of acrylamide, methacrylamide, N-methylolacrylamide, N-methylolmethacrylamide, N-methylolpropane acrylamide, N-methylolpropane methacrylamide, but is not limited thereto.
In a preferred embodiment, the solvent is one or more of ethyl acetate, toluene, butanone, isopropanol.
In some further preferred embodiments, the soft monomer is a mixture of 2-ethylhexyl acrylate, n-butyl acrylate, and glycidyl acrylate; the hard monomer is a mixture of methyl acrylate, methyl methacrylate and acryloylmorpholine; the functional monomer comprises a mixture of a carboxyl monomer, an amide monomer and a hydroxyl monomer, wherein the carboxyl monomer is acrylic acid, the hydroxyl monomer is hydroxyethyl acrylate, and the amide monomer is N, N-dimethylacrylamide; the cross-linking agent is toluene diisocyanate and the solvent is ethyl acetate.
In the invention, the acid-resistant protective film is prepared by the following method:
s1, uniformly mixing a soft monomer, a hard monomer, a functional monomer, an initiator and a solvent according to weight ratio, adding into a reaction kettle, stirring at 60-75 ℃ for reaction for 4-8 hours, cooling after the reaction is finished, and pouring out to obtain an acrylic resin polymer;
s2, mixing the acrylic resin polymer obtained in the step S1, the cross-linking agent and the solvent, and stirring at the speed of 300-800r/min for 10-30min to obtain a glue layer mixture;
s3, coating the adhesive layer mixture obtained in the step S2 on a substrate layer by using a coating device, controlling the thickness of a dry adhesive layer formed by the adhesive layer mixture to be 10-100 mu m, attaching a release film on the adhesive layer, and baking for 1-3 days at 50-65 ℃ to obtain the acid-resistant protective film.
The foregoing is a general inventive concept and the following detailed examples and comparative examples are provided on the basis thereof to further illustrate the invention.
In the following examples and comparative examples:
the substrate layer and the release layer are the same, the substrate layer is PET, the thickness of the substrate layer is 50 mu m, the release layer is PET release film, and the thickness of the PET release film is 50 mu m;
the preparation method of the acid-resistant protective film is the same, and comprises the following specific steps:
s1, preparing an acrylic resin polymer: uniformly mixing a soft monomer, a hard monomer, a functional monomer, an initiator and a solvent A according to the weight ratio, adding the mixture into a reaction kettle, stirring the mixture at 66-67 ℃ for reaction for 6 hours, cooling the mixture after the reaction is finished, and pouring the mixture out to obtain an acrylic resin polymer;
s2, preparing a glue layer mixture: mixing the acrylic resin polymer obtained in the step S1, the cross-linking agent and the solvent, and stirring at the speed of 500r/min for 20min to obtain a glue layer mixture;
s3, coating the adhesive layer mixture obtained in the step S2 on a substrate layer by using a coating device, controlling the thickness of a dry adhesive layer formed by the adhesive layer mixture to be 60 mu m, attaching a release film on the adhesive layer, and baking at 555 ℃ for 1-3 days to obtain the acid-resistant protective film.
The main difference is the preparation of the starting materials in step S1 and S2.
Example 1
In this example, the acrylic resin polymer prepared in step S1 comprises the following raw materials in parts by weight: the acrylic resin polymer was 40 parts of 2-ethylhexyl acrylate, 20 parts of N-butyl acrylate, 10 parts of methyl methacrylate, 5 parts of hydroxyethyl acrylate, 2 parts of glycidyl acrylate, 3 parts of acryloylmorpholine (hard monomer), 5 parts of acrylic acid, 5 parts of N, N-dimethyl (meth) acrylamide and 30 parts of a solvent.
The adhesive layer mixture prepared in the step S1 comprises the following raw materials in parts by weight: 100 parts of acrylic resin polymer, 1 part of cross-linking agent and 30 parts of solvent.
Wherein the curing agent is toluene diisocyanate and the solvent is ethyl acetate.
Example 2
In this example, the acrylic resin polymer prepared in step S1 comprises the following raw materials in parts by weight: the acrylic resin polymer was 45 parts of 2-ethylhexyl acrylate, 25 parts of N-butyl acrylate, 10 parts of methyl methacrylate, 2 parts of hydroxyethyl acrylate, 4 parts of glycidyl acrylate, 3 parts of acryloylmorpholine (hard monomer), 2 parts of acrylic acid, 2 parts of N, N-dimethyl (meth) acrylamide and 30 parts of a solvent.
The adhesive layer mixture prepared in the step S1 comprises the following raw materials in parts by weight: 100 parts of acrylic resin polymer, 2 parts of cross-linking agent and 30 parts of solvent.
Wherein the curing agent is toluene diisocyanate and the solvent is ethyl acetate.
Example 3
In this example, the acrylic resin polymer prepared in step S1 comprises the following raw materials in parts by weight: the acrylic resin polymer was 45 parts of 2-ethylhexyl acrylate, 25 parts of N-butyl acrylate, 10 parts of methyl methacrylate, 3 parts of hydroxyethyl acrylate, 1 part of glycidyl acrylate, 2 parts of acryloylmorpholine (hard monomer), 3 parts of acrylic acid, 4 parts of N, N-dimethyl (meth) acrylamide and 30 parts of a solvent.
The adhesive layer mixture prepared in the step S1 comprises the following raw materials in parts by weight: 100 parts of acrylic resin polymer, 1.5 parts of cross-linking agent and 30 parts of solvent.
Wherein the curing agent is toluene diisocyanate and the solvent is ethyl acetate.
Comparative example 1
In this example, the acrylic resin polymer prepared in step S1 comprises the following raw materials in parts by weight: the acrylic resin polymer was 45 parts of 2-ethylhexyl acrylate, 20 parts of N-butyl acrylate, 10 parts of methyl methacrylate, 2 parts of glycidyl acrylate, 3 parts of acryloylmorpholine (hard monomer), 5 parts of acrylic acid, 5 parts of N, N-dimethyl (meth) acrylamide and 30 parts of a solvent.
The adhesive layer mixture prepared in the step S1 comprises the following raw materials in parts by weight: 100 parts of acrylic resin polymer, 1 part of cross-linking agent and 30 parts of solvent.
Wherein the curing agent is toluene diisocyanate and the solvent is ethyl acetate.
Comparative example 2
In this example, the acrylic resin polymer prepared in step S1 comprises the following raw materials in parts by weight: the acrylic resin polymer was 40 parts of 2-ethylhexyl acrylate, 20 parts of N-butyl acrylate, 10 parts of methyl methacrylate, 5 parts of hydroxyethyl acrylate, 2 parts of glycidyl acrylate, 3 parts of acryloylmorpholine (hard monomer), 5 parts of N, N-dimethyl (meth) acrylamide and 30 parts of a solvent.
The adhesive layer mixture prepared in the step S1 comprises the following raw materials in parts by weight: 100 parts of acrylic resin polymer, 2 parts of cross-linking agent and 30 parts of solvent.
Wherein the curing agent is toluene diisocyanate and the solvent is ethyl acetate.
Comparative example 3
In this example, the acrylic resin polymer prepared in step S1 comprises the following raw materials in parts by weight: the acrylic resin polymer was 40 parts of 2-ethylhexyl acrylate, 20 parts of n-butyl acrylate, 10 parts of methyl methacrylate, 5 parts of hydroxyethyl acrylate, 2 parts of glycidyl acrylate, 3 parts of acryloylmorpholine (hard monomer), 5 parts of acrylic acid, and 30 parts of a solvent.
The adhesive layer mixture prepared in the step S1 comprises the following raw materials in parts by weight: 100 parts of acrylic resin polymer, 1.5 parts of cross-linking agent and 30 parts of solvent.
Wherein the curing agent is toluene diisocyanate and the solvent is ethyl acetate.
The protective films prepared in examples 1 to 3 and comparative examples 1 to 3 were subjected to the following performance tests, and the test items and methods are as follows:
the molecular weight measurement method was GPC (gel chromatography).
The acid number test method is titration with standard KOH solvent.
The glass transition temperature test method is DSC (differential scanning calorimetry) calorimetry.
The peel force test method was ASTM-D3330.
The seepage test method comprises the following steps: cutting the protective film into 5cm by 5cm, sticking the protective film on plain glass, driving and pressing the plain glass twice by using a 2kg roller, standing the plain glass for 20min, soaking the plain glass in 30% HF acid solution for 30min, taking out the plain glass, and observing whether the edge of the glass has a permeated trace or not by using a microscope, wherein the permeated trace is a liquid.
The residual adhesive testing method comprises the following steps: cutting the protective film into 5cm by 5cm, sticking the protective film on plain glass, driving and pressing the plain glass twice by using a 2kg roller, standing the plain glass for 20min, soaking the plain glass in 30% HF acid solution for 30min, taking out the plain glass, tearing the protective film, and observing whether residual pollutants exist on the surface of the glass, and if the residual pollutants are residual glue.
The method for testing whether the HF is easy to peel after soaking for 30min comprises the following steps: cutting the protective film into 5cm by 5cm, sticking the protective film on plain glass, driving and pressing the glass twice by using a 2kg roller, standing the glass for 20min, soaking the glass in 30% HF acid solution for 30min, taking the glass out, sticking the glass on the back of the protective film by using a Nidong 31B adhesive tape, peeling the glass at 180 ℃, and peeling the glass to OK that the protective film can be peeled off by the adhesive tape and not to NG.
The test results are shown in table 1 below:
TABLE 1
As can be seen from the test results in Table 1, the protective films prepared in examples 1-3 are resistant to HF acid and liquid permeation, are easy to tear after acid washing, have no residual adhesive, and have excellent comprehensive properties.
No hydroxyethyl acrylate is added in comparative example 1, so that the cohesive strength of the adhesive layer is poor, and residual adhesive exists after the adhesive layer is torn, which indicates that the hydroxyethyl acrylate can improve the cohesive strength of the adhesive layer and the bonding force between the adhesive layer and a substrate. The phenomenon such as oozing occurs in comparative example 2 because it does not add acrylic acid, and acrylic acid can prevent effectively that H ion from permeating to the glue film, and the glue film of no acrylic acid can't prevent effectively that HF from permeating, easily produces oozes liquid and viscidity and climbs the phenomenon, leads to glass to be polluted, and can't viscidity climb too high, and the dyestripping is difficult. N, N-dimethyl (meth) acrylamide provides a strong peel force, and comparative example 3 in which N, N-dimethyl (meth) acrylamide was not added, the peel force was weak, resulting in weak bonding force with the adherend, resulting in liquid permeation.
Although embodiments of the present invention have been disclosed above, it is not limited to the use of the description and embodiments, it is well suited to various fields of use for the invention, and further modifications may be readily apparent to those skilled in the art, and accordingly, the invention is not limited to the particular details without departing from the general concepts defined in the claims and the equivalents thereof.
Claims (10)
1. The acid-resistant protective film is characterized by comprising a substrate layer, a glue layer and a release layer which are sequentially attached, wherein the glue layer is prepared by mixing an acrylic resin polymer, a cross-linking agent and a solvent, coating the mixture on the substrate layer and drying the mixture;
wherein the cross-linking agent is isocyanate cross-linking agent;
wherein the molecular weight of the acrylic resin polymer is 70-100W, the glass transition temperature is-25 to-50 ℃, and the acid value is 2-5 mgKOH/g.
2. The acid-resistant protective film according to claim 1, wherein the acrylic resin polymer comprises the following raw materials in parts by weight: 20-60 parts of soft monomer, 5-30 parts of hard monomer, 2-15 parts of functional monomer, 0.1-1 part of initiator and 20-50 parts of solvent;
wherein the functional monomer comprises one or more of carboxyl-containing monomers, amide-type monomers and hydroxyl-containing monomers.
3. The acid-resistant protective film according to claim 2, wherein the soft monomer comprises one or more of ethyl acrylate, n-butyl acrylate, 2-ethylhexyl acrylate, lauryl acrylate, glycidyl acrylate, lauryl methacrylate, and 2-ethylhexyl methacrylate.
4. The acid-resistant protective film according to claim 2, wherein the hard monomer comprises one or more of methyl acrylate, methyl methacrylate, ethyl methacrylate, styrene, acrylonitrile, and acryloylmorpholine.
5. The acid-resistant protective film according to claim 2, wherein the carboxyl group-containing monomer comprises one or more of acrylic acid, itaconic acid, maleic acid, fumaric acid, crotonic acid, carboxypentyl acrylate, and carboxyethyl acrylate.
6. The acid-resistant protective film according to claim 2, wherein the hydroxyl-containing monomer comprises one or more of hydroxypropyl acrylate, hydroxypropyl methacrylate, hydroxybutyl acrylate, hydroxybutyl methacrylate, hydroxyhexyl acrylate, hydroxyhexyl methacrylate, hydroxyoctyl acrylate, hydroxyoctyl methacrylate, hydroxydecyl acrylate, hydroxylauryl acrylate, and hydroxylauryl methacrylate.
7. The acid-resistant protective film according to claim 2, wherein the amide-based monomer comprises one or more of acrylamide, methacrylamide, N-dimethylacrylamide, N-butyl (N-substituted) amide monomers;
the N-butyl (N-substituted) amide monomer is one or more of acrylamide, methacrylamide, N-methylolacrylamide, N-methylolmethacrylamide, N-methylolpropane acrylamide and N-methylolpropane methacrylamide.
8. The acid-resistant protective film according to claim 2, wherein the isocyanate-based crosslinking agent is one or more of hexamethylene diisocyanate, isoparaffin diisocyanate, 2, 4-toluene diisocyanate, 4' -diphenylmethane diisocyanate, and xylylene diisocyanate.
9. The acid-resistant protective film according to claim 2, wherein the soft monomer is a mixture of 2-ethylhexyl acrylate, n-butyl acrylate, and glycidyl acrylate;
the hard monomer is a mixture of methyl acrylate, methyl methacrylate and acryloylmorpholine;
the functional monomer comprises a mixture of a carboxyl monomer, an amide monomer and a hydroxyl monomer, wherein the carboxyl monomer is acrylic acid, the hydroxyl monomer is hydroxyethyl acrylate, and the amide monomer is N, N-dimethylacrylamide;
the cross-linking agent is toluene diisocyanate, and the solvent is ethyl acetate.
10. The acid-resistant protective film according to any one of claims 2 to 9, wherein the acid-resistant protective film is produced by:
s1, uniformly mixing a soft monomer, a hard monomer, a functional monomer, an initiator and a solvent according to weight ratio, adding into a reaction kettle, stirring at 60-75 ℃ for reaction for 4-8 hours, cooling after the reaction is finished, and pouring out to obtain an acrylic resin polymer;
s2, mixing the acrylic resin polymer obtained in the step S1, the cross-linking agent and the solvent, and stirring at the speed of 300-800r/min for 10-30min to obtain a glue layer mixture;
s3, coating the adhesive layer mixture obtained in the step S2 on a substrate layer by using a coating device, controlling the thickness of a dry adhesive layer formed by the adhesive layer mixture to be 10-100 mu m, attaching a release film on the adhesive layer, and baking for 1-3 days at 50-65 ℃ to obtain the acid-resistant protective film.
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