CN113861878B - High temperature resistant protection film - Google Patents
High temperature resistant protection film Download PDFInfo
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- CN113861878B CN113861878B CN202111056172.7A CN202111056172A CN113861878B CN 113861878 B CN113861878 B CN 113861878B CN 202111056172 A CN202111056172 A CN 202111056172A CN 113861878 B CN113861878 B CN 113861878B
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- monomer
- acrylic
- acrylate
- acrylic ester
- sensitive adhesive
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- 239000000178 monomer Substances 0.000 claims abstract description 104
- 239000010410 layer Substances 0.000 claims abstract description 74
- 239000004820 Pressure-sensitive adhesive Substances 0.000 claims abstract description 73
- 230000001681 protective effect Effects 0.000 claims abstract description 62
- -1 acrylic ester Chemical class 0.000 claims abstract description 47
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 37
- 239000004925 Acrylic resin Substances 0.000 claims abstract description 35
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims abstract description 32
- 229920000178 Acrylic resin Polymers 0.000 claims abstract description 29
- 239000000758 substrate Substances 0.000 claims abstract description 27
- 239000002131 composite material Substances 0.000 claims abstract description 12
- 238000010526 radical polymerization reaction Methods 0.000 claims abstract description 5
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 28
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 14
- 229910052710 silicon Inorganic materials 0.000 claims description 14
- 239000010703 silicon Substances 0.000 claims description 14
- 239000004593 Epoxy Substances 0.000 claims description 13
- 239000012948 isocyanate Substances 0.000 claims description 13
- 150000002513 isocyanates Chemical class 0.000 claims description 13
- 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
- PBOSTUDLECTMNL-UHFFFAOYSA-N lauryl acrylate Chemical compound CCCCCCCCCCCCOC(=O)C=C PBOSTUDLECTMNL-UHFFFAOYSA-N 0.000 claims description 11
- FSAJWMJJORKPKS-UHFFFAOYSA-N octadecyl prop-2-enoate Chemical compound CCCCCCCCCCCCCCCCCCOC(=O)C=C FSAJWMJJORKPKS-UHFFFAOYSA-N 0.000 claims description 10
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims description 9
- 229910052731 fluorine Inorganic materials 0.000 claims description 9
- 239000011737 fluorine Substances 0.000 claims description 9
- ZNAOFAIBVOMLPV-UHFFFAOYSA-N hexadecyl 2-methylprop-2-enoate Chemical compound CCCCCCCCCCCCCCCCOC(=O)C(C)=C ZNAOFAIBVOMLPV-UHFFFAOYSA-N 0.000 claims description 9
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 8
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims description 7
- DXPPIEDUBFUSEZ-UHFFFAOYSA-N 6-methylheptyl prop-2-enoate Chemical compound CC(C)CCCCCOC(=O)C=C DXPPIEDUBFUSEZ-UHFFFAOYSA-N 0.000 claims description 6
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 claims description 6
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 claims description 6
- QZPSOSOOLFHYRR-UHFFFAOYSA-N 3-hydroxypropyl prop-2-enoate Chemical compound OCCCOC(=O)C=C QZPSOSOOLFHYRR-UHFFFAOYSA-N 0.000 claims description 5
- 229920002799 BoPET Polymers 0.000 claims description 5
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 claims description 5
- FDLQZKYLHJJBHD-UHFFFAOYSA-N [3-(aminomethyl)phenyl]methanamine Chemical compound NCC1=CC=CC(CN)=C1 FDLQZKYLHJJBHD-UHFFFAOYSA-N 0.000 claims description 5
- KXBFLNPZHXDQLV-UHFFFAOYSA-N [cyclohexyl(diisocyanato)methyl]cyclohexane Chemical compound C1CCCCC1C(N=C=O)(N=C=O)C1CCCCC1 KXBFLNPZHXDQLV-UHFFFAOYSA-N 0.000 claims description 5
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical class C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 claims description 5
- 239000004841 bisphenol A epoxy resin Substances 0.000 claims description 5
- 239000003822 epoxy resin Substances 0.000 claims description 5
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 claims description 5
- 239000000463 material Substances 0.000 claims description 5
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 claims description 5
- 229920000647 polyepoxide Polymers 0.000 claims description 5
- FKTHNVSLHLHISI-UHFFFAOYSA-N 1,2-bis(isocyanatomethyl)benzene Chemical class O=C=NCC1=CC=CC=C1CN=C=O FKTHNVSLHLHISI-UHFFFAOYSA-N 0.000 claims description 4
- WKJICCKTDQDONB-UHFFFAOYSA-N 2-(oxiran-2-ylmethoxycarbonyl)cyclohexane-1-carboxylic acid Chemical compound OC(=O)C1CCCCC1C(=O)OCC1OC1 WKJICCKTDQDONB-UHFFFAOYSA-N 0.000 claims description 4
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 claims description 4
- 239000005058 Isophorone diisocyanate Substances 0.000 claims description 4
- OMRDSWJXRLDPBB-UHFFFAOYSA-N N=C=O.N=C=O.C1CCCCC1 Chemical compound N=C=O.N=C=O.C1CCCCC1 OMRDSWJXRLDPBB-UHFFFAOYSA-N 0.000 claims description 4
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 claims description 4
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 abstract description 13
- 239000003292 glue Substances 0.000 abstract description 6
- 238000012545 processing Methods 0.000 abstract description 5
- 238000006243 chemical reaction Methods 0.000 description 22
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 21
- 229920000139 polyethylene terephthalate Polymers 0.000 description 18
- 239000005020 polyethylene terephthalate Substances 0.000 description 18
- 239000003999 initiator Substances 0.000 description 15
- 239000003085 diluting agent Substances 0.000 description 13
- 239000011248 coating agent Substances 0.000 description 11
- 238000000576 coating method Methods 0.000 description 11
- 238000004132 cross linking Methods 0.000 description 11
- 239000007788 liquid Substances 0.000 description 10
- 238000000034 method Methods 0.000 description 10
- 238000004321 preservation Methods 0.000 description 10
- 230000001070 adhesive effect Effects 0.000 description 9
- 229920000058 polyacrylate Polymers 0.000 description 8
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 7
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 7
- 230000008569 process Effects 0.000 description 7
- 239000000853 adhesive Substances 0.000 description 6
- 238000000418 atomic force spectrum Methods 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- 125000005396 acrylic acid ester group Chemical group 0.000 description 5
- 150000001875 compounds Chemical class 0.000 description 5
- 238000001816 cooling Methods 0.000 description 5
- 238000001035 drying Methods 0.000 description 5
- 239000011347 resin Substances 0.000 description 5
- 229920005989 resin Polymers 0.000 description 5
- 229920006267 polyester film Polymers 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 239000000203 mixture Substances 0.000 description 3
- 239000004342 Benzoyl peroxide Substances 0.000 description 2
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 2
- VEPKQEUBKLEPRA-UHFFFAOYSA-N VX-745 Chemical compound FC1=CC(F)=CC=C1SC1=NN2C=NC(=O)C(C=3C(=CC=CC=3Cl)Cl)=C2C=C1 VEPKQEUBKLEPRA-UHFFFAOYSA-N 0.000 description 2
- 235000019400 benzoyl peroxide Nutrition 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 238000007865 diluting Methods 0.000 description 2
- 238000010790 dilution Methods 0.000 description 2
- 239000012895 dilution Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 230000035945 sensitivity Effects 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- 241000692870 Inachis io Species 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 230000003678 scratch resistant effect Effects 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000006467 substitution reaction 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
- C09J7/38—Pressure-sensitive adhesives [PSA]
- C09J7/381—Pressure-sensitive adhesives [PSA] based on macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
- C09J7/385—Acrylic polymers
-
- 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
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/02—Non-macromolecular additives
- C09J11/06—Non-macromolecular additives organic
-
- 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
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/08—Macromolecular additives
-
- 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
- C09J133/14—Homopolymers or copolymers of esters of esters containing halogen, nitrogen, sulfur or oxygen atoms in addition to the carboxy oxygen
-
- 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
- C09J7/20—Adhesives in the form of films or foils characterised by their carriers
- C09J7/22—Plastics; Metallised plastics
- C09J7/25—Plastics; Metallised plastics based on macromolecular compounds obtained otherwise than by reactions involving only carbon-to-carbon unsaturated bonds
- C09J7/255—Polyesters
-
- 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
-
- 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
- C09J2301/30—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier
- C09J2301/302—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier the adhesive being pressure-sensitive, i.e. tacky at temperatures inferior to 30°C
-
- 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
- C09J2467/00—Presence of polyester
- C09J2467/006—Presence of polyester in the substrate
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Adhesive Tapes (AREA)
- Laminated Bodies (AREA)
Abstract
The invention belongs to the field of protective films, and relates to a high-temperature-resistant protective film which comprises a substrate layer, a pressure-sensitive adhesive layer coated on the surface of the substrate layer and a release film attached with the pressure-sensitive adhesive layer; the pressure-sensitive adhesive layer comprises acrylic resin and a composite curing agent with the acrylic resin as a base, wherein the weight percentage of the composite curing agent is 2-5%; the acrylic resin is prepared by free radical polymerization of a long-chain acrylic monomer, an acrylic soft monomer, an acrylic hard monomer and an acrylic functional monomer, wherein the weight percentages of the long-chain acrylic monomer, the acrylic soft monomer, the acrylic hard monomer and the acrylic functional monomer are as follows: 2-3% of long-chain acrylic ester monomer, 75-83% of acrylic ester soft monomer, 7-10% of acrylic ester hard monomer and 8-12% of acrylic ester functional monomer. The technical scheme of the invention can effectively protect the ITO conductive film or the nano silver conductive film, has no residual glue after high-temperature processing, does not reduce the dyne value of the attached surface of the conductive film and has small warping degree.
Description
Technical Field
The invention belongs to the technical field of protective films, and particularly relates to a high-temperature-resistant protective film.
Background
ITO conductive film and nano silver conductive film belong to the emerging trade in the flexible screen, and market prospect is very good. In the manufacturing process, the surface of the main substrate of the conductive film is not scratch-resistant and is easy to pollute, so that the surface of the conductive film needs to be protected from scratches and pollution by a specific protective film when the conductive film is manufactured.
The manufacturing process of the conductive film needs to be subjected to high-temperature treatment, the high-temperature treatment process is an extremely strict test for the attached product of the protective film, firstly, the pressure-sensitive adhesive layer of the protective film easily generates residual adhesive or adhesive transfer or reduces the attached dyne value to cause unqualified quality of the finished product during the high-temperature treatment; secondly, the high-temperature treatment process is extremely easy to cause the warping of the soft conductive film, and seriously affects the quality of products and even causes defective products. In view of this, it is urgent to develop a high temperature resistant protective film to overcome the above problems.
Although the prior art provides a related technical scheme, for example, chinese patent CN 112280488A discloses a polyester film protective film, which comprises a polyester film and a pressure-sensitive adhesive layer coated on the surface of the polyester film; the pressure-sensitive adhesive layer has a resistance of less than 10 10 Ω/≡; and the pressure-sensitive adhesive layer contains an acrylate resin; the acrylic resin is prepared from a long-chain acrylic monomer, a fluorine-containing acrylic monomer, an acrylic hard monomer, an acrylic soft monomer and an acrylic functional monomer through free radical polymerization, and the upper limit use temperature of the polyester film protective film is improved by utilizing the characteristic of larger C-F bond energy. However, the shrinkage rate of the pressure-sensitive adhesive layer after the high-temperature process is large, and the application range of the pressure-sensitive adhesive layer is limited.
Disclosure of Invention
In order to solve the defects in the prior art, the technical problem to be solved by the invention is to provide the high-temperature-resistant protective film which can effectively protect the ITO conductive film or the nano silver conductive film, has no residual glue after the high-temperature process, does not reduce the dyne value of the attached surface of the conductive film and has small warping degree.
In order to solve the technical problems, the technical scheme of the invention is as follows: the high temperature resistant protective film comprises a substrate layer, a pressure sensitive adhesive layer coated on the surface of the substrate layer, and a release film attached to the pressure sensitive adhesive layer; the pressure-sensitive adhesive layer comprises acrylic resin and a composite curing agent with the acrylic resin as a base, wherein the weight percentage of the composite curing agent is 2-5%; the acrylic resin is prepared from a long-chain acrylic monomer, an acrylic soft monomer, an acrylic hard monomer and an acrylic functional monomer through free radical polymerization; wherein, the weight percentages of the long-chain acrylic acid monomer, the acrylic ester soft monomer, the acrylic ester hard monomer and the acrylic ester functional monomer are as follows: 2% -3% of long-chain acrylic ester monomer; 75% -83% of acrylic ester soft monomer; 7% -10% of acrylate hard monomer; 8 to 12 percent of acrylate functional monomer.
When the weight percentage of the long-chain acrylic acid monomer is 2-3%, the shrinkage performance of the pressure-sensitive adhesive layer is not obviously reduced when the weight percentage of the long-chain acrylic acid monomer is less than 2%, and when the weight percentage of the long-chain acrylic acid ester monomer is more than 3%, the system viscosity is high and the polymerization reaction is difficult to control because of the wrapping of the long-alkyl side chain on the main chain. The weight percentage of the acrylic ester soft monomer is 75-83%, the weight percentage of the acrylic ester hard monomer is 7-10%, the weight percentage of the acrylic ester functional monomer is 8-12%, when the weight percentage of the acrylic ester hard monomer is lower than 7%, or the weight percentage of the acrylic ester soft monomer is higher than 83%, the cohesive force of the pressure-sensitive adhesive is too low, and the prepared protective film is easy to generate adhesive residue when peeled; when the acrylate hard monomer is higher than 10% or the acrylate soft monomer is lower than 75%, the pressure sensitive adhesive wettability is obviously reduced, the fluctuation of the stripping force curve is large, and the stripping force curve is not smooth; when the acrylic functional monomer is less than 8%, the crosslinking point is insufficient, the cohesive force of the acrylic resin is low, the residual glue is easy to be caused, when the acrylic functional monomer is more than 12%, the excessive crosslinking is caused, the fluctuation of the stripping force curve is large, and even the acrylic resin loses the pressure sensitivity.
The long-chain acrylic ester monomer comprises octadecyl acrylate, hexadecyl methacrylate and dodecyl acrylate, and the weight ratio of the octadecyl acrylate to the hexadecyl methacrylate to the dodecyl acrylate is (0.3-0.5) to (0.2-0.5) to 1. When the proportion of the octadecyl acrylate, the hexadecyl acrylate and the dodecyl acrylate is (0.3-0.5) to (0.2-0.5) to 1, the pressure-sensitive adhesive layer has better flexibility, minimum high-temperature shrinkage resistance and optimal comprehensive performance.
The flexibility and the higher stress relaxation rate of the polyacrylate chain can be maintained after the crosslinking through the long and soft molecular chain of the long-chain acrylate monomer, so that the shrinkage rate of the pressure-sensitive adhesive layer after high-temperature baking is reduced, and the shrinkage rate of the protective film is reduced.
The acrylic ester soft monomer is one or a plurality of ethyl acrylate, butyl acrylate and isooctyl acrylate in any weight ratio.
The acrylate hard monomer is one or more of methyl methacrylate and vinyl acetate in any weight ratio.
The soft monomer provides tackiness and flexibility of the acrylic resin and the hard monomer provides cohesion of the acrylic resin. The pressure-sensitive adhesive layer has proper cohesive force, viscosity and flexibility through the collocation of long chain and soft and hard acrylate monomers; the compactness and the high temperature resistance of the pressure-sensitive adhesive layer network structure are combined, so that the acrylate pressure-sensitive adhesive has the high temperature resistance and no residual adhesive property; the release film without silicon is used in combination, so that the surface dyne value is not reduced when the protective film is faced after being torn.
The acrylate functional monomer is two or more than two of acrylic acid, methacrylic acid, hydroxyethyl acrylate, hydroxypropyl acrylate and glycidyl methacrylate. Hydroxyl and carboxyl are introduced into the functional monomer to react with the isocyanate and epoxy compound curing agent, so that the compactness of the polyacrylate molecular network structure of the pressure-sensitive adhesive layer is improved.
The curing agent of the pressure-sensitive adhesive layer is a composite curing agent of isocyanate and epoxy; the isocyanate curing agent is one of alicyclic diisocyanate such as isophorone diisocyanate, dicyclohexylmethane diisocyanate, cyclohexane diisocyanate and hydrogenated xylylene diisocyanate; the epoxy curing agent is one of hydrogenated bisphenol A epoxy resin, hexahydrophthalic acid glycidyl ester and tetraglycidyl m-xylylenediamine type epoxy resin.
The isocyanate curing agent and hydroxyl groups in the prepared acrylic resin undergo a crosslinking reaction, so that the cohesive force of the pressure-sensitive adhesive layer is increased. The epoxy curing agent and carboxyl in the prepared acrylic resin undergo a crosslinking reaction, so that the cohesive force of the pressure-sensitive adhesive layer is increased.
Hydroxyl and carboxyl are introduced through acrylate functional monomers to react with isocyanate and epoxy compound curing agents, so that the compactness of the polyacrylate network structure of the pressure-sensitive adhesive layer is improved; and the composite curing agent is a high-temperature-resistant curing agent, so that the high-temperature resistance of the pressure-sensitive adhesive layer is improved.
The thickness of the pressure-sensitive adhesive layer is 5-25 mu m, the pressure-sensitive adhesive layer is tested after being subjected to high temperature resistance for 60min at 150 ℃, the stripping force of the pressure-sensitive adhesive layer on the hardened surface of the ITO conductive film or the nano silver conductive film is between 5gf/in and 50gf/in, no residual adhesive is stripped on the hardened surface, and the variation value of the dyne value of the hardened surface is less than or equal to 2dyn.
The protective film substrate layer is a PET film, the thickness of the protective film substrate layer is 23-125 mu m, and the thermal shrinkage rates TD1 and MD1 are tested after high temperature resistance for 60min at 150 ℃ and are matched with the thermal shrinkage rates TD2 and MD2 of the ITO conductive film or the nano silver conductive film: 0.10 percent or less (TD 1-TD 2) or less than 0.25 percent, 0.20 percent or less (MD 1-MD 2) or less than 0.35 percent.
The protective film coated with the pressure-sensitive adhesive layer is tested for heat shrinkage rates TD3 and MD3 after being subjected to high temperature resistance for 60min at 150 ℃ and is matched with the heat shrinkage rate of the ITO conductive film or the nano silver conductive film to be protected: 0% or more (TD 3-TD 2) or less than 0.15%,0% or less (MD 3-MD 2) or less than 0.15%.
The method has the advantages that the TD3 is more than or equal to TD2 and the MD3 is more than or equal to MD2, so that the conductive film attached with the protective film basically does not warp or slightly warp towards the direction of the protective film after high-temperature processing, the warp is less than 3mm, and the conductive film can be better attached to a display screen after the protective film is torn off in the downstream use process.
The release film is a non-silicon release film with release force between 10gf/in and 15gf/in or a fluorine release film with release force between 5gf/in and 10 gf/in.
The non-silicon release film does not use an organic silicon release agent, and the fluorine release film is prepared from a fluorinated organic silicon release agent and has the characteristics of stable release force and high temperature resistance. A non-silicon release film or a fluorine release film with low organosilicon release agent content is selected, and the release film has high residual adhesion rate of 92-98%, so that the release film has no silicon transfer pollution to the pressure-sensitive adhesive layer of the protective film; and the high-temperature-resistant acrylate pressure-sensitive adhesive is combined, so that the covered surface of the protective film is torn after high-temperature baking, and the surface dyne value is not reduced. The non-silicon release film with the speed of 10gf/in to 15gf/in and the fluorine release film with the speed of 5gf/in to 10gf/in are both release films with light release force, so as to meet the release film requirement of the high-temperature resistant protective film for the conductive film.
The residual adhesion rate of the release film is 92-98%.
The residual aftertackiness adhesion is expressed as a percentage and is the ratio of the adhesion strength of the standard tape that contacted the release film to the standard test plate to the adhesion strength of the standard tape that did not contact the release film to the standard test plate. Lower residual adhesion can reduce the tackiness of the tape or protective film, affecting the end product's performance.
The beneficial effects are that:
1. Hydroxyl and carboxyl are introduced through acrylate functional monomers to react with isocyanate and epoxy compound curing agents, so that the compactness of the polyacrylate molecular network structure of the pressure-sensitive adhesive layer is improved; and the composite curing agent is a high-temperature-resistant curing agent, so that the high-temperature resistance of the pressure-sensitive adhesive layer is improved.
2. The pressure-sensitive adhesive layer has proper cohesive force, viscosity and flexibility through the collocation of long chain and soft and hard acrylate monomers; the compactness and the high temperature resistance of the pressure-sensitive adhesive layer network structure are combined, so that the acrylate pressure-sensitive adhesive has the high temperature resistance and no residual adhesive property; the release film without silicon is used in combination, so that the surface dyne value is not reduced when the protective film is faced after being torn.
3. The flexibility and the higher stress relaxation rate of the polyacrylate chain can be maintained after the crosslinking through the long and soft molecular chain of the long-chain acrylate monomer, so that the shrinkage rate of the pressure-sensitive adhesive layer after high-temperature baking is reduced, and the shrinkage rate of the protective film is reduced; combining the protective film base materials with matched shrinkage rates, so that the thermal shrinkage rates TD3 and MD3 of the protective film coated with the pressure-sensitive adhesive are very close to those of the protected conductive film: 0% or more (TD 3-TD 2) or less than 0.15%,0% or less (MD 3-MD 2) or less than 0.15%. Therefore, the protective film and the conductive film shrink in the same amplitude after the high-temperature process, so that the warping degree of the conductive film attached with the protective film is less than 3mm, and the use requirement of downstream users is met.
Detailed Description
In order that the invention may be readily understood, a more particular description of the invention will be rendered by reference to specific embodiments that are illustrated below. This invention may, however, be embodied in many different forms and should not be construed as limited to the embodiments set forth herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used herein in the description of the invention is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention.
The present invention will be described in further detail with reference to the following embodiments.
A high temperature resistant protective film comprises a protective film substrate layer, a pressure sensitive adhesive layer coated on the surface of the substrate layer and a release film attached with the pressure sensitive adhesive layer; the pressure-sensitive adhesive layer consists of acrylic resin and a curing agent; the acrylic resin is prepared from long-chain acrylic ester monomers, acrylic ester soft monomers, acrylic ester hard monomers and acrylic ester functional monomers through free radical polymerization.
The preparation method of the acrylic resin comprises the following steps: an initiator dilution was prepared by first diluting 0.3g of benzoyl peroxide in 99.7g of ethyl acetate. Then 100g of the total weight of acrylate monomers was added to the reaction vessel in weight percent and warmed to the set temperature. 70g of initiator diluent is evenly added dropwise, the dropwise adding time is controlled to be 3 hours, and the reaction is kept at a constant temperature for 2 hours. Continuously dripping 30g of initiator diluent, controlling the dripping time to be 1 hour, and keeping the temperature for reaction for 1 hour. Finally, the reaction mixture is cooled to room temperature to obtain the acrylic resin. Wherein, the weight percentages of the long-chain acrylic acid monomer, the acrylic ester soft monomer, the acrylic ester hard monomer and the acrylic ester functional monomer are as follows: 2% -3% of long-chain acrylic ester monomer; 75% -83% of acrylic ester soft monomer; 7% -10% of acrylate hard monomer; 8 to 12 percent of acrylate functional monomer.
The long-chain acrylic ester monomer comprises octadecyl acrylate, hexadecyl methacrylate and dodecyl acrylate, and the weight ratio of the octadecyl acrylate to the hexadecyl methacrylate to the dodecyl acrylate is (0.3-0.5) to (0.2-0.5) to 1.
The flexibility and the higher stress relaxation rate of the polyacrylate chain can be maintained after the crosslinking through the long and soft molecular chain of the long-chain acrylate monomer, so that the shrinkage rate of the pressure-sensitive adhesive layer after high-temperature baking is reduced, and the shrinkage rate of the protective film is reduced.
The acrylic ester soft monomer is one or a plurality of ethyl acrylate, butyl acrylate and isooctyl acrylate in any weight ratio.
The acrylate hard monomer is one or more of methyl methacrylate and vinyl acetate in any weight ratio.
The pressure-sensitive adhesive layer has proper cohesive force, viscosity and flexibility through the collocation of long chain and soft and hard acrylate monomers; the compactness and the high temperature resistance of the pressure-sensitive adhesive layer network structure are combined, so that the acrylate pressure-sensitive adhesive has the high temperature resistance and no residual adhesive property; the release film without silicon is used in combination, so that the surface dyne value is not reduced when the protective film is faced after being torn.
The acrylate functional monomer is two or more than two of acrylic acid, methacrylic acid, hydroxyethyl acrylate, hydroxypropyl acrylate and glycidyl methacrylate. Hydroxyl and carboxyl are introduced into the functional monomer to react with the isocyanate and epoxy compound curing agent, so that the compactness of the polyacrylate molecular network structure of the pressure-sensitive adhesive layer is improved.
The weight percentage of the long-chain acrylic acid monomer is 2-3%, when the weight part of the long-chain acrylic acid monomer is lower than 2%, the shrinkage performance of the pressure-sensitive adhesive layer is not obviously reduced, and when the weight part of the long-chain acrylic acid ester monomer is higher than 3%, the system viscosity is high and the polymerization reaction is difficult to control because of the wrapping of the long-alkyl side chain on the main chain; when the proportion of the octadecyl acrylate, the hexadecyl acrylate and the dodecyl acrylate is between (0.3 and 0.5) and 1, the pressure-sensitive adhesive layer has better flexibility, minimum high-temperature shrinkage resistance and optimal comprehensive performance.
The weight percentage of the acrylic ester soft monomer is 75-83%, the weight percentage of the acrylic ester hard monomer is 7-10%, the weight percentage of the acrylic ester functional monomer is 8-12%, when the weight percentage of the acrylic ester hard monomer is lower than 7%, or the weight percentage of the acrylic ester soft monomer is higher than 83%, the cohesive force of the pressure-sensitive adhesive is too low, and the prepared protective film is easy to generate adhesive residue when peeled; when the acrylate hard monomer is higher than 10% or the acrylate soft monomer is lower than 75%, the pressure sensitive adhesive wettability is obviously reduced, the fluctuation of the stripping force curve is large, and the stripping force curve is not smooth; when the acrylic functional monomer is less than 8%, the crosslinking point is insufficient, the cohesive force of the acrylic resin is low, the residual glue is easy to be caused, when the acrylic functional monomer is more than 12%, the excessive crosslinking is caused, the fluctuation of the stripping force curve is large, and even the acrylic resin loses the pressure sensitivity.
The curing agent of the pressure-sensitive adhesive layer is a composite curing agent of isocyanate and epoxy.
The isocyanate curing agent is one of alicyclic diisocyanate such as isophorone diisocyanate, dicyclohexylmethane diisocyanate, cyclohexane diisocyanate and hydrogenated xylylene diisocyanate; the isocyanate curing agent and hydroxyl groups in the prepared acrylic resin undergo a crosslinking reaction, so that the cohesive force of the pressure-sensitive adhesive layer is increased.
The epoxy curing agent is one of hydrogenated bisphenol A epoxy resin, hexahydrophthalic acid glycidyl ester and tetraglycidyl m-xylylenediamine type epoxy resin; the epoxy curing agent and carboxyl in the prepared acrylic resin undergo a crosslinking reaction, so that the cohesive force of the pressure-sensitive adhesive layer is increased.
Hydroxyl and carboxyl are introduced through acrylate functional monomers to react with isocyanate and epoxy compound curing agents, so that the compactness of the polyacrylate network structure of the pressure-sensitive adhesive layer is improved; and the composite curing agent is a high-temperature-resistant curing agent, so that the high-temperature resistance of the pressure-sensitive adhesive layer is improved.
The thickness of the pressure-sensitive adhesive layer is 5-25 mu m, the pressure-sensitive adhesive layer is tested after being subjected to high temperature resistance for 60min at 150 ℃, the stripping force of the pressure-sensitive adhesive layer on the hardening surface of the ITO conductive film or the nano silver conductive film is 5-50 gf/in, and the stripping force range avoids the stripping or stripping difficulty of the high temperature resistant protective film; and no residual adhesive is peeled from the hardened surface, so that the variation value of the dyne value of the hardened surface is less than or equal to 2dyn, the surface energy attenuation of the hardened film is smaller, and the excellent printing performance of the hardened surface is ensured.
The protective film substrate layer is a PET film, the thickness of the PET film is 23-125 mu m, and the PET film is tested to have heat shrinkage rates TD1 and MD1 after being subjected to high temperature resistance for 60min at 150 ℃ and is matched with the heat shrinkage rates TD2 and MD2 of the ITO conductive film or the nano silver conductive film: 0.10 percent or less (TD 1-TD 2) or less than 0.25 percent, 0.20 percent or less (MD 1-MD 2) or less than 0.35 percent.
The protective film coated with the pressure-sensitive adhesive layer is tested for heat shrinkage rates TD3 and MD3 after being subjected to high temperature resistance for 60min at 150 ℃ and is matched with the heat shrinkage rate of the ITO conductive film or the nano silver conductive film to be protected: 0% or more (TD 3-TD 2) or less than 0.15%,0% or less (MD 3-MD 2) or less than 0.15%.
The method has the advantages that the TD3 is more than or equal to TD2 and the MD3 is more than or equal to MD2, so that the conductive film attached with the protective film basically does not warp or slightly warp towards the high-temperature-resistant protective film after high-temperature processing, the warp is less than or equal to 3mm, and the conductive film can be better attached to a display screen after the high-temperature-resistant protective film is torn off in the downstream use process.
The release film is one of a non-silicon release film and a fluorine release film, the release force of the release film is between 5gf/in and 15gf/in, and the residual adhesion rate is between 92% and 98%.
For a better explanation of the technical solutions herein, the following details are given in connection with examples:
The preparation method of the initiator diluent in the embodiment comprises the following steps: an initiator dilution was prepared by diluting 0.3g of benzoyl peroxide in 99.7g of ethyl acetate.
Example 1
0.6G of octadecyl acrylate, 0.4g of hexadecyl methacrylate, 2g of dodecyl acrylate, 75g of butyl acrylate, 8g of methyl methacrylate, 2g of vinyl acetate, 2g of acrylic acid, 2g of methacrylic acid and 8g of hydroxyethyl acrylate were weighed and added to a reaction vessel, and the temperature was raised to 70 ℃.70g of initiator diluent is evenly added dropwise, the dropwise adding time is controlled to be 3 hours, and then the reaction is carried out for 2 hours under the heat preservation. 30g of initiator diluent was continuously added dropwise, the dropwise addition time was controlled to be 1 hour, and then the reaction was continued for 1 hour with heat preservation. And then cooling the synthesized resin to room temperature to obtain the acrylic resin.
30G of the above-mentioned acrylate resin, 30g of ethyl acetate, 0.4g of isophorone diisocyanate, and 0.2g of tetraglycidyl m-xylylenediamine type epoxy resin were weighed and uniformly mixed to obtain a coating liquid. The coating liquid is coated on the surface of a 23 mu m thick PET substrate, and the PET substrate is subjected to high temperature resistance for 60min at 150 ℃ and then is tested for heat shrinkage rates TD1 and MD1, and the PET substrate is matched with heat shrinkage rates TD2 and MD2 of an ITO conductive film: TD 1-td2=0.25%, MD 1-md2=0.35%. And after drying, attaching a non-silicon release film with release force of 15gf/in and residual adhesion rate of 98% on the pressure-sensitive adhesive layer surface to obtain the high-temperature-resistant protective film.
Example 2
0.55G of octadecyl acrylate, 0.55g of hexadecyl methacrylate, 1.1g of dodecyl acrylate, 80g of isooctyl acrylate, 7.8g of methyl methacrylate, 2g of methacrylic acid and 8g of hydroxypropyl acrylate were weighed and added to a reaction vessel, and the temperature was raised to 70 ℃. 70g of initiator diluent is evenly added dropwise, the dropwise adding time is controlled to be 3 hours, and then the reaction is carried out for 2 hours under the heat preservation. 30g of initiator diluent was continuously added dropwise, the dropwise addition time was controlled to be 1 hour, and then the reaction was continued for 1 hour with heat preservation. And then cooling the synthesized resin to room temperature to obtain the acrylic resin.
30G of the above acrylate resin, 30g of ethyl acetate, 0.8g of dicyclohexylmethane diisocyanate and 0.4g of hydrogenated bisphenol A epoxy resin were weighed and uniformly mixed to obtain a coating liquid. The coating liquid is coated on the surface of a 50 mu m thick PET substrate, and the PET substrate is subjected to high temperature resistance for 60min at 150 ℃ and then is tested for heat shrinkage rates TD1 and MD1, and the PET substrate is matched with heat shrinkage rates TD2 and MD2 of a nano silver conductive film: TD 1-td2=0.10%, MD 1-md2=0.20%. And (3) after drying, attaching a fluorine release film with release force of 10gf/in and residual adhesion rate of 95% on the pressure-sensitive adhesive layer surface to obtain the high-temperature-resistant protective film.
Example 3
2G of hexadecyl methacrylate, 3g of ethyl acrylate, 70g of butyl acrylate, 10g of isooctyl acrylate, 3g of methyl methacrylate, 4g of vinyl acetate, 2g of acrylic acid, 2g of methacrylic acid and 4g of glycidyl methacrylate are weighed, added into a reaction vessel, and heated to 70 ℃. 70g of initiator diluent is evenly added dropwise, the dropwise adding time is controlled to be 3 hours, and then the reaction is carried out for 2 hours under the heat preservation. 30g of initiator diluent was continuously added dropwise, the dropwise addition time was controlled to be 1 hour, and then the reaction was continued for 1 hour with heat preservation. And then cooling the synthesized resin to room temperature to obtain the acrylic resin.
30G of the above acrylate resin, 30g of ethyl acetate, 0.8g of cyclohexane diisocyanate and 0.7g of glycidyl hexahydrophthalate were weighed and uniformly mixed to obtain a coating liquid. The coating liquid is coated on the surface of a PET substrate with the thickness of 100 mu m, and the PET substrate is subjected to high temperature resistance for 60min at 150 ℃ and then is tested for heat shrinkage rates TD1 and MD1, and the PET substrate is matched with heat shrinkage rates TD2 and MD2 of an ITO conductive film: TD 1-td2=0.15%, MD 1-md2=0.25%. And after drying, attaching a non-silicon release film with release force of 10gf/in and residual adhesion rate of 92% on the pressure-sensitive adhesive layer surface to obtain the high-temperature-resistant protective film.
Example 4
2.8G of dodecyl acrylate, 5g of ethyl acrylate, 73g of butyl acrylate, 9.2g of vinyl acetate, 5g of methacrylic acid and 5g of glycidyl methacrylate were weighed and added to a reaction vessel, and the temperature was raised to 70 ℃. 70g of initiator diluent is evenly added dropwise, the dropwise adding time is controlled to be 3 hours, and then the reaction is carried out for 2 hours under the heat preservation. 30g of initiator diluent was continuously added dropwise, the dropwise addition time was controlled to be 1 hour, and then the reaction was continued for 1 hour with heat preservation. And then cooling the synthesized resin to room temperature to obtain the acrylic resin.
30G of the above-mentioned acrylate resin, 30g of ethyl acetate, 0.7g of hydrogenated xylylene diisocyanate, and 0.5g of tetraglycidyl m-xylylene diamine type epoxy resin were weighed and uniformly mixed to obtain a coating liquid. The coating liquid is coated on the surface of a PET substrate with the thickness of 125 mu m, and the PET substrate is subjected to high temperature resistance for 60min at 150 ℃ and then is tested for heat shrinkage rates TD1 and MD1, and the PET substrate is matched with heat shrinkage rates TD2 and MD2 of a nano silver conductive film: TD 1-td2=0.17%, MD 1-md2=0.30%. And (3) after drying, attaching a fluorine release film with release force of 5gf/in and residual adhesion rate of 95% on the pressure-sensitive adhesive layer surface to obtain the high-temperature-resistant protective film.
Comparative example
82.2G of isooctyl acrylate, 7.8g of methyl methacrylate, 2g of methacrylic acid, 8g of hydroxypropyl acrylate were weighed and added to a reaction vessel, and the temperature was raised to 70 ℃. 70g of initiator diluent is evenly added dropwise, the dropwise adding time is controlled to be 3 hours, and then the reaction is carried out for 2 hours under the heat preservation. 30g of initiator diluent was continuously added dropwise, the dropwise addition time was controlled to be 1 hour, and then the reaction was continued for 1 hour with heat preservation. And then cooling the synthesized resin to room temperature to obtain the acrylic resin.
30G of the above acrylate resin, 30g of ethyl acetate, 0.8g of dicyclohexylmethane diisocyanate and 0.4g of hydrogenated bisphenol A epoxy resin were weighed and uniformly mixed to obtain a coating liquid. The coating liquid is coated on the surface of a 50 mu m thick PET substrate, and the PET substrate is subjected to high temperature resistance for 60min at 150 ℃ and then is tested for heat shrinkage rates TD1 and MD1, and the PET substrate is matched with heat shrinkage rates TD2 and MD2 of a nano silver conductive film: TD 1-td2=0.40%, MD 1-md2=0.40%. And (3) after drying, attaching an organosilicon release film with release force of 10gf/in and residual adhesion rate of 92% on the pressure-sensitive adhesive layer surface to obtain the protective film.
The composition tables and performance data of the examples and comparative examples are listed below in tabular form.
The performance test methods in table 2 are as follows:
(1) Thickness of pressure-sensitive adhesive layer: the test was performed using a PEACOCK G-6C pointer thickness gauge.
(2) Peel force: the object to be attached is an ITO conductive film according to the test of standard GB/T2792-1998.
(3) HC face dyne value change value: and (3) using a SHERMANTREATERS dyne pen, tearing off the HC surface dyne value of the protective film before and after the protective film is stuck and subjected to high temperature resistance for 60 minutes at 150 ℃ and calculating a change value.
(4) Heat shrinkage rate: according to the standard GB/T27584-2011, the test condition is 150 ℃ for 60min.
(5) Warpage of the fitting object: the warpage of a laminate composed of a protective film and a protected film material was tested according to standard GB/T25257-2010.
The composition of the components of each of the above examples and comparative examples is shown in Table 1.
Table 1: composition table of the ingredients of examples and comparative examples
The performance data of each of the above examples and comparative examples are shown in table 2.
Table 2: performance data sheet for examples and comparative examples
Note that: PET base material heat shrinkage rates TD1, MD1, material-to-be-adhered heat shrinkage rates TD2, MD2, and protective film heat shrinkage rates TD3, MD3
As can be seen from the performance data in table 2, examples 1 to 4 are high temperature resistant protective films adopting the technical scheme of the invention, have proper peeling force to the HC side of the attached object, can effectively protect the ITO conductive film or the nano silver conductive film, have no residual glue after high temperature processing, hardly reduce the dyne value and the warpage of the attached surface of the conductive film. The comparative example is an acrylic acid ester pressure-sensitive adhesive prepared without long-chain acrylic acid ester monomer, and the protective film prepared by coating the acrylic acid ester pressure-sensitive adhesive on a PET (polyethylene terephthalate) base material with unmatched heat shrinkage rate has residual glue and large warping degree after high-temperature processing and cannot be used as the protective film of the conductive film.
Although embodiments of the present invention have been shown and described, it will be understood by those skilled in the art that various changes, modifications, substitutions and alterations can be made therein without departing from the principles and spirit of the invention, the scope of which is defined in the appended claims and their equivalents.
Claims (7)
1. The high temperature resistant protective film comprises a substrate layer, a pressure sensitive adhesive layer coated on the surface of the substrate layer and a release film attached to the pressure sensitive adhesive layer, and is characterized in that the pressure sensitive adhesive layer comprises acrylic resin and a composite curing agent with the acrylic resin as a base, wherein the weight percentage of the composite curing agent is 2% -5%, and the acrylic resin is prepared by free radical polymerization of long-chain acrylic ester monomers, acrylic ester soft monomers, acrylic ester hard monomers and acrylic ester functional monomers; the weight percentages of the long-chain acrylic ester monomer, the acrylic ester soft monomer, the acrylic ester hard monomer and the acrylic ester functional monomer are as follows: 2-3% of long-chain acrylic ester monomer, 75-83% of acrylic ester soft monomer, 7-10% of acrylic ester hard monomer and 8-12% of acrylic ester functional monomer; the long-chain acrylic ester monomer comprises octadecyl acrylate, hexadecyl methacrylate and dodecyl acrylate, wherein the weight ratio of the octadecyl acrylate to the hexadecyl methacrylate to the dodecyl acrylate is (0.3-0.5): 0.2-0.5): 1;
the curing agent of the pressure-sensitive adhesive layer is a composite curing agent of isocyanate and epoxy; the isocyanate curing agent comprises isophorone diisocyanate, dicyclohexylmethane diisocyanate, cyclohexane diisocyanate and hydrogenated xylylene diisocyanate; the epoxy curing agent is one of hydrogenated bisphenol A epoxy resin, hexahydrophthalic acid glycidyl ester and tetraglycidyl m-xylylenediamine type epoxy resin;
The acrylate functional monomer is the combination of more than one of acrylic acid and methacrylic acid and more than one of hydroxyethyl acrylate, hydroxypropyl acrylate and glycidyl methacrylate.
2. The high temperature resistant protective film according to claim 1, wherein the acrylic ester soft monomer is one or more of ethyl acrylate, butyl acrylate, and isooctyl acrylate.
3. The high temperature resistant protective film according to claim 1, wherein the acrylate hard monomer is one or more of methyl methacrylate and vinyl acetate.
4. The high temperature resistant protective film according to claim 1, wherein the pressure sensitive adhesive layer has a thickness of 5 μm to 25 μm.
5. The high temperature resistant protective film according to claim 1, wherein the protective film base material layer is a PET film having a thickness of 23 μm to 125 μm.
6. The high temperature resistant protective film according to claim 1, wherein the release film is one of a non-silicon release film having a release force of between 10gf/in and 15gf/in, or a fluorine release film having a release force of between 5gf/in and 10 gf/in.
7. The high temperature resistant protective film according to claim 6, wherein the release film has a residual adhesion rate of 92% to 98%.
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| CN115466584B (en) * | 2022-09-09 | 2024-03-26 | 苏州市贝特利高分子材料股份有限公司 | High-surface tension waterproof adhesive with durable bonding strength |
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103387804A (en) * | 2013-07-12 | 2013-11-13 | 斯迪克新型材料（江苏）有限公司 | High-temperature resistance matte acrylic acid adhesive |
| CN108485556A (en) * | 2018-02-07 | 2018-09-04 | 东莞市方恩电子材料科技有限公司 | A kind of solvent acrylates type acid and alkali-resistance pressure sensitive adhesive adhesive tape and its preparation method and application |
| CN110591596A (en) * | 2019-09-17 | 2019-12-20 | 上海亥博胶粘材料有限公司 | Adhesive tape for sealing photovoltaic cell frame and preparation method thereof |
| CN112159637A (en) * | 2020-09-30 | 2021-01-01 | 广东东立新材料科技股份有限公司 | Acrylate copolymer, protective film and preparation method thereof |
| CN112457791A (en) * | 2020-12-09 | 2021-03-09 | 江苏日久光电股份有限公司 | High-temperature-resistant protective film, preparation process thereof and ITO conductive film |
-
2021
- 2021-09-09 CN CN202111056172.7A patent/CN113861878B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103387804A (en) * | 2013-07-12 | 2013-11-13 | 斯迪克新型材料（江苏）有限公司 | High-temperature resistance matte acrylic acid adhesive |
| CN108485556A (en) * | 2018-02-07 | 2018-09-04 | 东莞市方恩电子材料科技有限公司 | A kind of solvent acrylates type acid and alkali-resistance pressure sensitive adhesive adhesive tape and its preparation method and application |
| CN110591596A (en) * | 2019-09-17 | 2019-12-20 | 上海亥博胶粘材料有限公司 | Adhesive tape for sealing photovoltaic cell frame and preparation method thereof |
| CN112159637A (en) * | 2020-09-30 | 2021-01-01 | 广东东立新材料科技股份有限公司 | Acrylate copolymer, protective film and preparation method thereof |
| CN112457791A (en) * | 2020-12-09 | 2021-03-09 | 江苏日久光电股份有限公司 | High-temperature-resistant protective film, preparation process thereof and ITO conductive film |
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