CN111534248B - Pressure-sensitive adhesive, preparation method thereof, surface protective film and element - Google Patents
Pressure-sensitive adhesive, preparation method thereof, surface protective film and element Download PDFInfo
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- CN111534248B CN111534248B CN202010449622.8A CN202010449622A CN111534248B CN 111534248 B CN111534248 B CN 111534248B CN 202010449622 A CN202010449622 A CN 202010449622A CN 111534248 B CN111534248 B CN 111534248B
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- Prior art keywords
- sensitive adhesive
- meth
- pressure
- acrylate
- comonomer
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- 239000004820 Pressure-sensitive adhesive Substances 0.000 title claims abstract description 105
- 230000001681 protective effect Effects 0.000 title claims abstract description 46
- 238000002360 preparation method Methods 0.000 title abstract description 10
- 239000000178 monomer Substances 0.000 claims abstract description 59
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims abstract description 50
- -1 methacrylate ester Chemical class 0.000 claims abstract description 50
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims abstract description 28
- 239000002202 Polyethylene glycol Substances 0.000 claims abstract description 23
- 229920001223 polyethylene glycol Polymers 0.000 claims abstract description 23
- 238000004132 cross linking Methods 0.000 claims abstract description 22
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 20
- 125000003700 epoxy group Chemical group 0.000 claims abstract description 19
- 229920005862 polyol Polymers 0.000 claims abstract description 15
- 150000003077 polyols Chemical class 0.000 claims abstract description 15
- 229920006035 cross-linked graft co-polymer Polymers 0.000 claims abstract description 4
- 238000000034 method Methods 0.000 claims description 32
- 239000003054 catalyst Substances 0.000 claims description 30
- 229920000642 polymer Polymers 0.000 claims description 28
- 238000006116 polymerization reaction Methods 0.000 claims description 26
- 239000013522 chelant Substances 0.000 claims description 24
- 229910052751 metal Inorganic materials 0.000 claims description 24
- 239000002184 metal Substances 0.000 claims description 24
- 239000010410 layer Substances 0.000 claims description 21
- 239000002216 antistatic agent Substances 0.000 claims description 19
- 238000006243 chemical reaction Methods 0.000 claims description 17
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 15
- 239000000463 material Substances 0.000 claims description 14
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 claims description 12
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 12
- 125000003368 amide group Chemical group 0.000 claims description 11
- 239000003431 cross linking reagent Substances 0.000 claims description 11
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 claims description 10
- 150000001252 acrylic acid derivatives Chemical class 0.000 claims description 9
- 229910001413 alkali metal ion Inorganic materials 0.000 claims description 9
- 150000001875 compounds Chemical class 0.000 claims description 9
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- 239000005057 Hexamethylene diisocyanate Substances 0.000 claims description 6
- 239000005058 Isophorone diisocyanate Substances 0.000 claims description 6
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 6
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 6
- 239000012752 auxiliary agent Substances 0.000 claims description 6
- 125000004432 carbon atom Chemical group C* 0.000 claims description 6
- LZCLXQDLBQLTDK-UHFFFAOYSA-N ethyl 2-hydroxypropanoate Chemical compound CCOC(=O)C(C)O LZCLXQDLBQLTDK-UHFFFAOYSA-N 0.000 claims description 6
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 claims description 6
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- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Chemical compound OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 0.000 claims description 6
- 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 6
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- HASUCEDGKYJBDC-UHFFFAOYSA-N 1-[3-[[bis(oxiran-2-ylmethyl)amino]methyl]cyclohexyl]-n,n-bis(oxiran-2-ylmethyl)methanamine Chemical compound C1OC1CN(CC1CC(CN(CC2OC2)CC2OC2)CCC1)CC1CO1 HASUCEDGKYJBDC-UHFFFAOYSA-N 0.000 claims description 3
- STMDPCBYJCIZOD-UHFFFAOYSA-N 2-(2,4-dinitroanilino)-4-methylpentanoic acid Chemical compound CC(C)CC(C(O)=O)NC1=CC=C([N+]([O-])=O)C=C1[N+]([O-])=O STMDPCBYJCIZOD-UHFFFAOYSA-N 0.000 claims description 3
- 125000000954 2-hydroxyethyl group Chemical group [H]C([*])([H])C([H])([H])O[H] 0.000 claims description 3
- UVRCNEIYXSRHNT-UHFFFAOYSA-N 3-ethylpent-2-enamide Chemical compound CCC(CC)=CC(N)=O UVRCNEIYXSRHNT-UHFFFAOYSA-N 0.000 claims description 3
- SXIFAEWFOJETOA-UHFFFAOYSA-N 4-hydroxy-butyl Chemical group [CH2]CCCO SXIFAEWFOJETOA-UHFFFAOYSA-N 0.000 claims description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 3
- WRQNANDWMGAFTP-UHFFFAOYSA-N Methylacetoacetic acid Chemical compound COC(=O)CC(C)=O WRQNANDWMGAFTP-UHFFFAOYSA-N 0.000 claims description 3
- CNCOEDDPFOAUMB-UHFFFAOYSA-N N-Methylolacrylamide Chemical compound OCNC(=O)C=C CNCOEDDPFOAUMB-UHFFFAOYSA-N 0.000 claims description 3
- WHNWPMSKXPGLAX-UHFFFAOYSA-N N-Vinyl-2-pyrrolidone Chemical compound C=CN1CCCC1=O WHNWPMSKXPGLAX-UHFFFAOYSA-N 0.000 claims description 3
- 229920002873 Polyethylenimine Polymers 0.000 claims description 3
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- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 claims description 3
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- 229940116333 ethyl lactate Drugs 0.000 claims description 3
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 claims description 3
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 claims description 3
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 3
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 claims description 3
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- UUORTJUPDJJXST-UHFFFAOYSA-N n-(2-hydroxyethyl)prop-2-enamide Chemical compound OCCNC(=O)C=C UUORTJUPDJJXST-UHFFFAOYSA-N 0.000 claims description 3
- OMNKZBIFPJNNIO-UHFFFAOYSA-N n-(2-methyl-4-oxopentan-2-yl)prop-2-enamide Chemical compound CC(=O)CC(C)(C)NC(=O)C=C OMNKZBIFPJNNIO-UHFFFAOYSA-N 0.000 claims description 3
- SJPFBRJHYRBAGV-UHFFFAOYSA-N n-[[3-[[bis(oxiran-2-ylmethyl)amino]methyl]phenyl]methyl]-1-(oxiran-2-yl)-n-(oxiran-2-ylmethyl)methanamine Chemical compound C1OC1CN(CC=1C=C(CN(CC2OC2)CC2OC2)C=CC=1)CC1CO1 SJPFBRJHYRBAGV-UHFFFAOYSA-N 0.000 claims description 3
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- 239000010936 titanium Substances 0.000 claims description 3
- 229910052719 titanium Inorganic materials 0.000 claims description 3
- 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 3
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 2
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical compound [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 claims 1
- 238000010382 chemical cross-linking Methods 0.000 abstract description 8
- 239000002904 solvent Substances 0.000 description 14
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- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
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- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
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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
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
- C08F283/06—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polyethers, polyoxymethylenes or polyacetals
-
- 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
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- 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
- C09J151/00—Adhesives based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Adhesives based on derivatives of such polymers
- C09J151/08—Adhesives based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Adhesives based on derivatives of such polymers grafted on to macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/017—Additives being an antistatic agent
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- 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
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- 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
- C09J2451/00—Presence of graft polymer
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- 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
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Abstract
The invention provides a pressure-sensitive adhesive, a preparation method thereof, a surface protective film and an element. The pressure-sensitive adhesive comprises a crosslinked graft copolymer formed from a primary monomer, a comonomer and a grafting agent, wherein the primary monomer comprises a methacrylate ester, the comonomer comprises an acrylic derivative containing an epoxy group, the grafting agent comprises a polymeric polyol, and the monomer forming the pressure-sensitive adhesive does not contain polyethylene glycol acrylate. The pressure-sensitive adhesive has rich chemical crosslinking sites, physical crosslinking sites and high cohesive energy, so that the pressure-sensitive adhesive has low stripping force, good compatibility among all components and low surface resistance, can realize excellent antistatic performance when used as a surface protective film, and is not easy to remain after stripping even under the conditions of high temperature and high humidity.
Description
Technical Field
The invention relates to the technical field of materials, in particular to a pressure-sensitive adhesive, a preparation method thereof, a surface protective film and an element.
Background
Currently, in optical elements or electronic elements, for example, the surfaces of display devices such as LCDs and organic EL displays are required to be attached with a surface protective film, which can prevent the surfaces of the elements from being damaged due to collision during processing, assembly, inspection, and transportation. When the surface of these elements is required to be attached with other members, the surface protective film needs to be peeled off when the surface protective film is not required to be reused. Therefore, in the steps of manufacturing, processing, inspection, transportation, and the like of the above-described element, the surface protective film is often required, and the operations of attaching, peeling, reattaching, and re-peeling the surface protective film are inevitably performed a plurality of times. However, on the one hand, a surface protective film is attached to the surface of the above-mentioned element for a long period of time, and the pressure-sensitive adhesive layer in the surface protective film may leave a residual adhesive on the surface of the element after peeling due to temperature, humidity, etc.; on the other hand, when the surface protective film is attached to the surface of the element for the first time, no air bubbles are generated, but when the surface protective film is peeled off and reattached, air bubbles are easily generated, sometimes the air bubbles are tiny and difficult to distinguish, the air bubbles exist for a long time after attachment, and a mark is generated at the air bubbles when the surface protective film is peeled off again; on the other hand, static electricity is generated when the surface protective film is peeled off from the surface of the above-mentioned element, and the generation of static electricity may cause malfunction of the circuit in the above-mentioned element, which requires the addition of an antistatic agent to the pressure-sensitive adhesive of the surface protective film, but since the antistatic agent is poor in compatibility with other components in the pressure-sensitive adhesive, there is often a case where the antistatic agent remains on the surface of the element when the surface protective film is peeled off.
Thus, the related art of pressure-sensitive adhesives in existing surface protective films has yet to be improved.
Disclosure of Invention
The present invention aims to solve at least one of the technical problems in the related art to some extent. Therefore, an object of the present invention is to provide a pressure-sensitive adhesive which has a rich chemical crosslinking site, has a rich physical crosslinking site, has high cohesive energy, low peeling force, good compatibility between components, has low surface resistance, can realize excellent antistatic properties when used as a surface protective film, or is less likely to cause residue even when peeled under high temperature and high humidity conditions when used as a surface protective film.
In one aspect of the invention, the invention provides a pressure sensitive adhesive. According to an embodiment of the present invention, the pressure-sensitive adhesive contains a crosslinked graft copolymer formed from a main monomer, a comonomer, and a grafting agent, wherein the main monomer includes a methacrylate, the comonomer includes an acrylic derivative containing an epoxy group, the grafting agent includes a polymeric polyol, and the monomer forming the pressure-sensitive adhesive does not contain polyethylene glycol acrylate. The inventor finds that the pressure-sensitive adhesive has abundant chemical crosslinking sites, physical crosslinking sites and high cohesive energy, so that the pressure-sensitive adhesive has low stripping force, good compatibility among components and low surface resistance, can realize excellent antistatic performance when used as a surface protective film, and is not easy to be left after stripping even under the conditions of high temperature and high humidity.
According to an embodiment of the present invention, the number of carbon atoms in the methacrylate is 4 to 10.
According to an embodiment of the present invention, the methacrylate includes at least one of hexyl (meth) acrylate, isobutyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, n-octyl (meth) acrylate, isooctyl (meth) acrylate, n-nonyl (meth) acrylate, isononyl (meth) acrylate, n-decyl (meth) acrylate, or isodecyl (meth) acrylate.
According to an embodiment of the present invention, the crosslinking agent includes at least one of an isocyanate compound, an epoxy compound, an aziridine compound, or a metal chelate.
According to an embodiment of the present invention, the isocyanate compound includes at least one of hexamethylene diisocyanate, isophorone diisocyanate, toluene diisocyanate, an isocyanurate body of hexamethylene diisocyanate, an isocyanurate body of isophorone diisocyanate, or an addition product of a polyol and an isocyanate.
According to an embodiment of the present invention, the epoxy compound includes at least one of N, N' -tetraglycidyl-m-xylylenediamine or 1, 3-bis (N, N-diglycidyl aminomethyl) cyclohexane.
According to an embodiment of the invention, the aziridine compound comprises at least one of a polyethylenimine crosslinker, saC-100, or an NWIITC aqueous crosslinker.
According to an embodiment of the present invention, the metal chelate includes at least one of a metal aluminum chelate, a metal iron chelate, a metal tin chelate, a metal titanium chelate, and a metal nickel chelate.
According to an embodiment of the present invention, in the metal chelate, the ligand includes at least one of acetylene, methyl acetoacetate or ethyl lactate.
According to an embodiment of the present invention, the comonomer further comprises at least one of an acrylic derivative containing a hydroxyl group or an acrylic derivative containing an amide group.
According to an embodiment of the present invention, the acrylic derivative containing an epoxy group includes at least one of glycidyl methacrylate, methyl glycidyl methacrylate, or allyl glycidyl ether.
According to an embodiment of the present invention, the hydroxyl group-containing acrylic derivative includes at least one of 8-hydroxyoctyl (meth) acrylate, 6-hydroxyhexyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, N-hydroxy (meth) acrylamide, N-hydroxymethyl (meth) acrylamide, or N-hydroxyethyl (meth) acrylamide.
According to an embodiment of the present invention, the amide group-containing acrylic derivatives include acrylamide, methacrylamide, diethylacrylamide, N-vinylpyrrolidone, N ' -dimethylacrylamide, N ' -dimethylmethacrylamide, N ' -diethylacrylamide, N, at least one of N ' -diethyl methacrylamide, N ' -methylene bisacrylamide, N ' -dimethyl aminopropyl acrylamide, N ' -dimethyl aminopropyl acrylamide, diacetone acrylamide, N-methylolacrylamide and N-hydroxyethyl acrylamide.
According to an embodiment of the present invention, the raw materials for forming the pressure-sensitive adhesive include: 100 parts by weight of the main monomer; 0.001 to 0.8 part by weight of the comonomer; 0.1 to 10 parts by weight of grafting agent; and 2.5 to 2.8 parts by weight of the crosslinking agent.
According to an embodiment of the invention, the comonomer comprises: 0.001 to 0.15 parts by weight of an acrylic derivative containing an epoxy group; 0.01 to 0.5 parts by weight of an acrylic acid derivative containing a hydroxyl group; and 0.001 to 0.15 part by weight of an acrylic derivative containing an amide group.
According to an embodiment of the invention, the weight average molecular weight of the polymeric polyol is not greater than 2000Da.
According to an embodiment of the invention, the polymeric polyol is polyethylene glycol.
According to an embodiment of the invention, the pressure sensitive adhesive further comprises an antistatic agent.
According to an embodiment of the present invention, the antistatic agent includes at least one of a salt containing an alkali metal ion or an ionic liquid containing an alkali metal ion.
According to an embodiment of the invention, the alkali metal ion comprises Li + 、Na + Or K + At least one of them.
According to an embodiment of the invention, in the salt or ionic liquid, the anion comprises a halide, CH 3 COO - 、CF 3 SO 3 - 、(CF 3 SO 2 ) 2 N - 、(C 2 F 5 SO 2 ) 2 N - 、(C 3 F 7 SO 2 ) 2 N - 、(C 4 F 9 SO 2 ) 2 N - 、(FSO 2 ) 2 N - Or (CF) 3 SO 2 ) 3 C - At least one of them.
According to an embodiment of the invention, the pressure sensitive adhesive further comprises an auxiliary agent.
According to an embodiment of the invention, the auxiliary agent comprises at least one of a catalyst, a catalyst promoter, a surfactant, a diluent, a plasticizer, a filler, a crosslinking inhibitor, an antioxidant, or an anti-aging agent.
According to an embodiment of the present invention, the catalyst includes at least one of a tin-based catalyst, an iron-based catalyst, a copper-based catalyst, a phosphorus-containing catalyst, or an amine-based catalyst.
In another aspect of the invention, the invention provides a method of making the pressure sensitive adhesive described previously. According to an embodiment of the invention, the method comprises: polymerizing the main monomer and the comonomer to obtain a first polymer; under the condition of 60-90 ℃, the first polymer and the grafting agent are subjected to grafting reaction for 4-8 hours to obtain a second polymer; and (3) carrying out a crosslinking reaction on the second polymer and the crosslinking agent so as to obtain the pressure-sensitive adhesive. The inventor finds that the method is simple and convenient to operate, easy to realize industrial production and capable of effectively preparing the pressure-sensitive adhesive.
According to an embodiment of the present invention, the step of polymerizing the main monomer and the comonomer to obtain the first polymer further comprises: under the conditions of 60-90 ℃ and inert gas, partial main monomers and partial comonomers are subjected to a first polymerization reaction for 15-75 min to obtain prepolymer; and (2) carrying out a second polymerization reaction on the prepolymer, part of the main monomer and part of the comonomer for 3-10 hours at the temperature of 60-90 ℃ so as to obtain the first polymer.
According to an embodiment of the present invention, the mass ratio of the main monomer in which the first polymerization reaction occurs to the main monomer in which the second polymerization reaction occurs is (2 to 4): (2-5).
According to an embodiment of the present invention, the mass ratio of the comonomer in which the first polymerization reaction occurs to the comonomer in which the second polymerization reaction occurs is (2 to 3): (2-3).
In yet another aspect of the invention, the invention provides a surface protective film. According to an embodiment of the present invention, the surface protective film includes: a substrate layer; and a pressure-sensitive adhesive layer provided on at least a part of the surface of the base material layer, wherein at least a part of the pressure-sensitive adhesive layer is formed of the pressure-sensitive adhesive described above or is prepared by the method described above. The inventors found that the surface protective film can realize excellent antistatic properties, is less likely to remain after peeling even under high temperature and high humidity conditions, and has all the features and advantages of the pressure-sensitive adhesive described above, and will not be described in detail herein.
In yet another aspect of the invention, the invention provides an element. According to an embodiment of the invention, the element comprises: a body; and the surface protective film is attached to at least part of the surface of the body, and the pressure-sensitive adhesive layer is in contact with the body. The inventors found that the surface protective film of the element can realize excellent antistatic properties, is less likely to remain after peeling even under high temperature and high humidity conditions, and has all the features and advantages of the pressure-sensitive adhesive and the surface protective film described above, and will not be described in detail herein.
Drawings
FIG. 1 shows a schematic flow chart of a method of preparing a pressure-sensitive adhesive according to one embodiment of the invention.
FIG. 2 shows a schematic flow diagram of the steps of forming a first polymer according to one embodiment of the invention.
Fig. 3 shows a schematic cross-sectional structure of a surface protective film according to an embodiment of the present invention.
Fig. 4 shows a schematic cross-sectional structure of an element according to an embodiment of the present invention.
Reference numerals:
10: element 100: body 200: surface protective film 210: the base material layer 220: pressure sensitive adhesive layer
Detailed Description
In one aspect of the invention, the invention provides a pressure sensitive adhesive. According to an embodiment of the present invention, the pressure-sensitive adhesive contains a crosslinked graft copolymer formed from a main monomer, a comonomer, and a grafting agent, wherein the main monomer includes a methacrylate, the comonomer includes an acrylic derivative containing an epoxy group, the grafting agent includes a polymeric polyol, and the monomer forming the pressure-sensitive adhesive does not contain polyethylene glycol acrylate. The inventor finds that the pressure-sensitive adhesive has abundant chemical crosslinking sites, physical crosslinking sites and high cohesive energy, so that the pressure-sensitive adhesive has low stripping force, good compatibility among components and low surface resistance, can realize excellent antistatic performance when used as a surface protective film, and is not easy to be left after stripping even under the conditions of high temperature and high humidity.
According to the embodiment of the invention, in the pressure-sensitive adhesive, the acrylic derivative containing the epoxy group can form a relatively stable crosslinking structure with the crosslinking agent; and epoxy groups can also form intramolecular cross-linking with hydroxyl groups in the polymer polyol, so that molecules of the pressure-sensitive adhesive have higher cohesive energy, the stripping force can be smaller than 0.5N/25m, the pressure-sensitive adhesive belongs to the category of ultra-low stripping force pressure-sensitive adhesives, the stripping force is lower under the conditions of low speed and high speed, and the stripping force is balanced under the conditions of low speed and high speed, so that the pressure-sensitive adhesive is not easy to remain in stripping when the pressure-sensitive adhesive is used as a surface protective film.
According to an embodiment of the present invention, further, the number of carbon atoms in the methacrylate may be 4 to 10. Specifically, in some embodiments of the present invention, the number of carbon atoms in the methacrylate may be specifically 4, 5, 6, 7, 8, 9, 10, or the like. Thus, the main monomer and the comonomer described above may have more chemical crosslinking points and physical crosslinking points, and thus the release force of the pressure-sensitive adhesive may be further lowered.
According to an embodiment of the present invention, further, the methacrylate may specifically include hexyl (meth) acrylate, isobutyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, n-octyl (meth) acrylate, isooctyl (meth) acrylate, n-nonyl (meth) acrylate, isononyl (meth) acrylate, n-decyl (meth) acrylate, isodecyl (meth) acrylate, or the like. Thus, the main monomer and the comonomer described above may have more chemical crosslinking points and physical crosslinking points, and thus the release force of the pressure-sensitive adhesive may be further lowered.
According to an embodiment of the present invention, a specific kind of the crosslinking agent may include an isocyanate compound, an epoxy compound, an aziridine compound, a metal chelate compound, or the like. Specifically, in some embodiments of the present invention, the isocyanate compound may include hexamethylene diisocyanate, isophorone diisocyanate, toluene diisocyanate, an isocyanurate body of hexamethylene diisocyanate, an isocyanurate body of isophorone diisocyanate, or an addition product of a polyol and an isocyanate, or the like; in other embodiments of the present invention, the epoxy compound may include N, N' -tetraglycidyl-m-xylylenediamine or 1, 3-bis (N, N-diglycidyl aminomethyl) cyclohexane, etc.; in still other embodiments of the present invention, the aziridine compound may include a polyethylenimine crosslinker SaC-100 or an NWIITC aqueous crosslinker, or the like; in still other embodiments of the present invention, the metal chelate may include a metal aluminum chelate, a metal iron chelate, a metal tin chelate, a metal titanium chelate, a metal nickel chelate, and the like; in addition, in the metal chelate compound, the ligand may include acetylene, methyl acetoacetate, ethyl lactate, or the like. Therefore, the material sources are wide and easy to obtain, the cost is low, the pressure-sensitive adhesive is easy to prepare, the components are crosslinked more fully, the components are intertwined and crosslinked, and the formed pressure-sensitive adhesive has more chemical crosslinking points and physical crosslinking points, so that the cohesive energy is higher, and the stripping force is further lowered.
According to embodiments of the present invention, in particular, the comonomer of the present invention, that is, the acrylic derivative containing an epoxy group may specifically include glycidyl methacrylate, methyl glycidyl methacrylate, allyl glycidyl ether, or the like. Therefore, the material source is wide and easy to obtain, the cost is low, more chemical crosslinking points and physical crosslinking points exist in the pressure-sensitive adhesive, so that the components in the pressure-sensitive adhesive are more tightly crosslinked with each other, the stripping force of the pressure-sensitive adhesive is further reduced, and residues are less prone to occurring when the pressure-sensitive adhesive is taken as a surface protective film.
Further, according to embodiments of the present invention, the comonomer may include an acrylic derivative containing a hydroxyl group or an acrylic derivative containing an amide group, etc., in addition to the aforementioned acrylic derivative containing an epoxy group. Thus, in the pressure sensitive adhesive, a large variety of comonomers are present, hydroxyl groups can react with the crosslinker to form the polymer into a crosslinked network, thereby controlling the wettability and release force of the composition; in addition, it is different from carboxyl, sulfonic acid group, etc. with larger polarity, the hydroxyl has interaction with antistatic agent, thus, make the pressure sensitive adhesive realize better antistatic property; in addition, a plurality of comonomers can cooperate with each other to play a synergistic effect, epoxy groups can also react with hydroxyl groups and amide to form intramolecular crosslinking, and amide groups can also serve as physical crosslinking points, so that the cohesive energy of the pressure-sensitive adhesive is high.
According to an embodiment of the present invention, still further, the hydroxyl group-containing acrylic derivative includes at least one of 8-hydroxyoctyl (meth) acrylate, 6-hydroxyhexyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, N-hydroxy (meth) acrylamide, N-hydroxymethyl (meth) acrylamide, or N-hydroxyethyl (meth) acrylamide. Thus, in the pressure-sensitive adhesive, a large variety of comonomers exist, and the comonomers can cooperate with each other to play a synergistic role, so that the cohesive energy of the pressure-sensitive adhesive is high.
According to an embodiment of the present invention, further, the amide group-containing acrylic acid derivatives include acrylamide, methacrylamide, diethylacrylamide, N-vinylpyrrolidone, N '-dimethylacrylamide, N' -diethylacrylamide, N, at least one of N '-diethyl methacrylamide, N' -methylene bisacrylamide, N '-dimethyl aminopropyl acrylamide, N' -dimethyl aminopropyl acrylamide, diacetone acrylamide, N-methylolacrylamide and N-hydroxyethyl acrylamide. Thus, in the pressure-sensitive adhesive, a large variety of comonomers exist, and the comonomers can cooperate with each other to play a synergistic role, so that the cohesive energy of the pressure-sensitive adhesive is high.
In other embodiments of the present invention, the comonomer may further comprise an acrylic derivative containing a carboxyl group, for example, may comprise at least one of methacrylic acid, carboxyethyl (meth) acrylic acid, carboxypentyl (meth) acrylic acid, 2- (meth) acryloyloxyethyl phthalic acid, 2- (meth) acryloyloxyethyl succinic acid, 2- (meth) acryloyloxyethyl maleic acid, carboxypolycaprolactone mono (meth) acrylate, 2- (meth) acryloyloxyethyl tetrahydrophthalic acid; in still other embodiments of the present invention, the comonomer may also include other monomers, such as at least one of cyano-containing monomers, vinyl monomers, aromatic vinyl monomers, imide-based monomers, epoxy-based monomers, vinyl monomers, or amino monomers. Specifically, the cyano group-containing monomer may include acrylonitrile, methacrylonitrile, and the like; vinyl monomers may include vinyl acetate, vinyl propionate, vinyl laurate, and the like; the aromatic vinyl monomer may include styrene, chlorostyrene, chloromethylstyrene, alpha-methylstyrene, etc.; the imido monomer may include cyclohexylmaleimide, isopropylmaleimide, N-cyclohexylmaleimide, itaconimide, etc.; the amino monomer may include aminoethyl (meth) acrylate, N-dimethylaminoethyl (meth) acrylate, N-dimethylaminopropyl (meth) acrylate, and the like. Thus, the multiple comonomers can cooperate to act synergistically, together to provide the pressure sensitive adhesive with high cohesive energy.
According to an embodiment of the present invention, the raw materials for forming the pressure-sensitive adhesive include: 100 parts by weight of the main monomer; 0.001 to 0.8 part by weight of the comonomer; 0.1 to 10 parts by weight of grafting agent; and 2.5 to 2.8 parts by weight of the crosslinking agent. Specifically, the weight part of the comonomer may be 0.001 weight part, 0.002 weight part, 0.005 weight part, 0.01 weight part, 0.02 weight part, 0.05 weight part, 0.1 weight part, 0.2 weight part, 0.4 weight part, 0.6 weight part, or 0.8 weight part, etc.; the grafting agent may be 0.1 part by weight, 0.2 parts by weight, 0.5 parts by weight, 1 part by weight, 2 parts by weight, 4 parts by weight, 6 parts by weight, 8 parts by weight, 10 parts by weight, or the like; the cross-linking agent may be 2.5 parts by weight, 2.6 parts by weight, 2.7 parts by weight, or 2.8 parts by weight, etc. Therefore, in the pressure-sensitive adhesive, the proportion of each component is proper, and various comonomers can cooperate with each other to play a synergistic effect, so that the cohesive energy of the pressure-sensitive adhesive is high together, the peeling force of the pressure-sensitive adhesive is further lowered, the compatibility among the components is better, the surface resistance is lower, and the pressure-sensitive adhesive is less prone to residue when peeled under the conditions of high temperature and high humidity.
According to an embodiment of the present invention, further, the comonomer may include: 0.001 to 0.15 parts by weight of an acrylic derivative containing an epoxy group; 0.01 to 0.5 parts by weight of an acrylic acid derivative containing a hydroxyl group; and 0.001 to 0.15 parts by weight of an acrylic derivative containing an amide group; 0.01 to 0.5 parts by weight of an acrylic acid derivative containing a carboxyl group. Specifically, the weight part of the epoxy group-containing acrylic derivative may be 0.001 weight part, 0.002 weight part, 0.005 weight part, 0.01 weight part, 0.02 weight part, 0.05 weight part, 0.1 weight part, 0.12 weight part, 0.15 weight part, or the like. Therefore, in the pressure-sensitive adhesive, a plurality of comonomers can cooperate with each other to play a synergistic effect, so that the cohesive energy of the pressure-sensitive adhesive is high together, the peeling force of the pressure-sensitive adhesive is further reduced, the compatibility among the components is better, the surface resistance is lower, and the peeling is less prone to residue under the conditions of high temperature and high humidity; in addition, the amount of the above-mentioned acrylic acid derivative containing carboxyl groups is not excessive, and since the carboxyl groups are reactive and have a weak catalytic action, a smaller amount of the acrylic acid derivative containing carboxyl groups does not result in a short storage time of the composition solution, which is disadvantageous in terms of construction.
According to an embodiment of the invention, in particular, the weight average molecular weight of the polymeric polyol is not greater than 2000Da. In some embodiments of the invention, the weight average molecular weight of the polymeric polyol may be specifically 1000Da, 1200Da, 1400Da, 1600Da, 1800Da, 2000Da, or the like. Therefore, the weight average molecular weight of the grafting agent is not too high, so that polyethylene glycol is self-formed into one phase to lead the polymer to be microphase separated or phase separated, and the grafting agent can be better grafted with main monomers and comonomers, so that the pressure-sensitive adhesive with higher cohesive energy is formed.
According to embodiments of the present invention, in particular, the polymeric polyol may be in particular polyethylene glycol. Polyethylene glycol in the present invention includes, but is not limited to, monohydroxy polyethylene glycol polymerized thereon with one hydroxyl group as a starting material, monohydroxy polyethylene glycol polymerized thereon with two hydroxyl groups as a starting material, and monohydroxy polyethylene glycol polymerized thereon with a plurality of hydroxyl groups as a starting material. Therefore, the material has wide and easily available sources and lower cost, and can be better grafted with the main monomer and the comonomer to form a pressure-sensitive adhesive with higher cohesive energy, so that the stripping force of the pressure-sensitive adhesive is further lowered; meanwhile, polyethylene glycol can better react with the epoxy groups, and chemical bonds are formed between the polyethylene glycol and the epoxy groups, so that the compatibility between the components is better, the surface resistance is lower, and the stripping is less prone to residue under the conditions of high temperature and high humidity.
According to an embodiment of the present invention, further, the pressure sensitive adhesive may further include an antistatic agent. Thus, the antistatic property of the pressure-sensitive adhesive can be better, and at the same time, since the compatibility of the resin of each component in the pressure-sensitive adhesive and the antistatic agent is better, even if a certain amount of antistatic agent is added into the pressure-sensitive adhesive, the cohesive energy of the pressure-sensitive adhesive is not influenced, so that the pressure-sensitive adhesive can have lower stripping force, and can realize more excellent antistatic property when used as a surface protective film.
According to an embodiment of the present invention, the antistatic agent may specifically include a composition comprisingAt least one of salts of alkali metal ions or ionic liquids containing alkali metal ions. In particular, in some embodiments of the invention, the alkali metal ions may specifically include Li + 、Na + Or K + At least one of (a) and (b); in other embodiments of the invention, the anions may include in particular halogen ions, CH in the salts or ionic liquids 3 COO - 、CF 3 SO 3 - 、(CF 3 SO 2 ) 2 N - 、(C 2 F 5 SO 2 ) 2 N - 、(C 3 F 7 SO 2 ) 2 N - 、(C 4 F 9 SO 2 ) 2 N - 、(FSO 2 ) 2 N - Or (CF) 3 SO 2 ) 3 C - At least one of them. Therefore, the material source is wide and easy to obtain, the cost is low, meanwhile, the antistatic agent is an ionic compound, the dissociation property is high, the melting point is low, the molecular movement capability is strong, the antistatic agent has better antistatic property, cations in the antistatic agent can be complexed with ether bonds, the compatibility of resin and the antistatic agent is further improved, further, the excellent antistatic property can be realized, and the surface resistance of the pressure-sensitive adhesive is reduced.
In other embodiments of the present invention, the pressure sensitive adhesive may further comprise an auxiliary agent. Specifically, the auxiliary agent may include at least one of a catalyst, a catalyst promoter, a surfactant, a diluent, a plasticizer, a filler, a crosslinking inhibitor, an antioxidant, or an anti-aging agent, and more specifically, the catalyst may include at least one of a tin-based catalyst, an iron-based catalyst, a copper-based catalyst, a phosphorus-containing catalyst, or an amine-based catalyst. In addition, the specific kind of the catalyst promoter, the surfactant, the diluent, the plasticizer, the filler, the crosslinking inhibitor, the antioxidant or the antioxidant, and the more specific kind of the catalyst may be selected from the kinds of the auxiliary agents in the related art, and will not be described in detail herein; in addition, the catalyst may promote the reaction, however, an excessive amount of catalyst or a catalyst having a too fast catalytic effect may cause inconvenience in processing, and the catalyst may be used in an amount of 0.0001 to 0.5 parts by weight, specifically, 0.0001, 0.001, 0.01, 0.1 or 0.5 parts by weight, etc., with respect to 100 parts by weight of the aforementioned pressure-sensitive adhesive.
In another aspect of the invention, the invention provides a method of making the pressure sensitive adhesive described previously. According to an embodiment of the invention, referring to fig. 1, the method comprises the steps of:
s100: and polymerizing the main monomer and the comonomer to obtain a first polymer.
According to an embodiment of the present invention, referring to fig. 2, the step of polymerizing the main monomer and the comonomer to obtain the first polymer may further comprise the sub-steps of:
s110: under the condition of 60-90 ℃ and inert gas, partial main monomer and partial comonomer are subjected to a first polymerization reaction for 15-75 min to obtain prepolymer.
According to an embodiment of the present invention, the reaction temperature may be specifically 60 ℃, 70 ℃, 80 ℃, or 90 ℃, and the like, the inert gas may be specifically helium, argon, or the like, and the reaction time of the reaction may be specifically 15min, 25min, 35min, 45min, 55min, 65min, 75min, or the like. Therefore, before all the main monomers and all the comonomers are reacted to obtain a first polymer, part of the main monomers and part of the comonomers are subjected to a first polymerization reaction to obtain a prepolymer, and the additional monomers can enable the reaction to be carried out smoothly because a large amount of heat is generated in the reaction process.
S120: and (2) carrying out a second polymerization reaction on the prepolymer, part of the main monomer and part of the comonomer for 3-10 hours at the temperature of 60-90 ℃ so as to obtain the first polymer.
According to an embodiment of the present invention, the reaction temperature may be specifically 60 ℃, 70 ℃, 80 ℃, 90 ℃ or the like, the inert gas may be specifically helium, argon or the like, and the reaction time of the reaction may be specifically 3 hours, 4 hours, 5 hours, 6 hours, 7 hours, 8 hours, 9 hours, 10 hours or the like. Therefore, the polymerization degree of the first polymer is higher, and finally the pressure-sensitive adhesive with higher internal energy can be prepared.
According to an embodiment of the present invention, further, the mass ratio of the main monomer in which the first polymerization reaction occurs to the main monomer in which the second polymerization reaction occurs is (2 to 4): (2-5). In some embodiments of the present invention, the mass ratio may be specifically 1: 1. 1: 2. 2: 5. 3: 2. 3: 4. 3: 5. 2: 1. 4: 3. 4:5, etc. Thus, the quality of the main monomer subjected to the first polymerization reaction and the quality of the main monomer subjected to the second polymerization reaction are better, and the pressure-sensitive adhesive with better performance in all aspects can be formed.
According to an embodiment of the present invention, further, the mass ratio of the comonomer in which the first polymerization reaction occurs to the comonomer in which the second polymerization reaction occurs is (2 to 3): (2-3). In some embodiments of the present invention, the mass ratio may be specifically 1: 1. 2: 3. 3:2, etc. Thus, the comonomer undergoing the first polymerization reaction is of a better quality than the comonomer undergoing the second polymerization reaction, and a pressure sensitive adhesive having better performance in all respects can be formed.
S200: and (3) carrying out grafting reaction on the first polymer and the grafting agent for 4-8 hours at the temperature of 60-90 ℃ to obtain a second polymer.
According to an embodiment of the present invention, the reaction temperature may be specifically 60 ℃, 70 ℃, 80 ℃, 90 ℃ or the like, the inert gas may be specifically helium, argon or the like, and the reaction time of the reaction may be specifically 4 hours, 5 hours, 6 hours, 7 hours, 8 hours or the like. Therefore, the polymerization degree of the second polymer is higher, and the pressure-sensitive adhesive with higher internal energy can be finally prepared, and the preparation method is simple and convenient to operate, easy to realize and easy to realize industrial production.
S300: and (3) carrying out a crosslinking reaction on the second polymer and the crosslinking agent so as to obtain the pressure-sensitive adhesive.
According to the embodiment of the present invention, the specific conditions of the crosslinking reaction are not particularly limited, and a person skilled in the art can flexibly select the crosslinking reaction according to actual needs, and will not be described in detail herein.
In a specific embodiment of the invention, the method may comprise: uniformly mixing at least 20-40 parts by weight of methacrylate containing 4-10 carbon atoms, 0-5 parts by weight of acrylic derivative containing epoxy groups, 0-5 parts by weight of acrylic derivative containing amide groups, 0.075-1 part by weight of initiator and 40-60 parts by weight of solvent, fully dissolving, heating to 60-90 ℃ under the protection of inert gas, and preserving heat for 15-75 min to obtain the prepolymer; slowly adding a dropwise adding mixture of at least 20-50 parts by weight of 20-40 parts by weight of methacrylic acid ester containing 4-10 carbon atoms, 0.5-5 parts by weight of acrylic acid derivative containing epoxy groups, 0-5 parts by weight of acrylic acid derivative containing amide groups, 0.1-1 part by weight of initiator and 0-20 parts by weight of solvent into the prepolymer, and preserving heat for 3-10 hours after finishing 2-4 hours; adding 0.5-8 parts by weight of polyethylene glycol, continuing to react for 4-8 hours, and finally crosslinking by a crosslinking agent to obtain the pressure-sensitive adhesive.
According to an embodiment of the present invention, further, the acrylic derivative containing an epoxy group is 0 to 10 parts by weight in the prepolymer and 0.01 to 10 parts by weight in the dropping mixture; the methacrylate monomer having more than two ether bonds accounts for 0 to 10 parts by weight in the prepolymer and 0.01 to 10 parts by weight in the dropwise addition mixture.
According to the embodiment of the invention, specifically, the solvent may include common solvents such as ethyl acetate, butyl acetate, butanone, acetone, DMF, DMAc, benzene, toluene, and the like, and one or more solvents may be selected. Because of the solubility difference of polyacrylate and polyethylene glycol in the solvents, two or more solvents can be selected as preferable solvents to be used together, for example, ethyl acetate, toluene, ethyl acetate and butanone are used together according to a certain proportion, and a plurality of solvents can be mixed and added at one time or can be reacted in one solvent and then added into the other solvent.
According to embodiments of the present invention, the polymerization methods described herein include, but are not limited to, bulk polymerization, solution polymerization, emulsion polymerization, and suspension polymerization, preferably solution polymerization.
In yet another aspect of the invention, the invention provides a surface protective film. Referring to fig. 3, according to an embodiment of the present invention, the surface protective film 200 includes: a substrate layer 210; and a pressure-sensitive adhesive layer 220, the pressure-sensitive adhesive layer 220 being disposed on at least a portion of the surface of the base material layer 210, wherein at least a portion of the pressure-sensitive adhesive layer 220 is formed of the pressure-sensitive adhesive described previously or is prepared by the method described previously. The inventors found that the surface protective film can realize excellent antistatic properties, is less likely to remain after peeling even under high temperature and high humidity conditions, and has all the features and advantages of the pressure-sensitive adhesive described above, and will not be described in detail herein.
The specific material for forming the base material layer according to the embodiment of the present invention is not particularly limited, and those skilled in the art can flexibly select according to actual needs, and may include, for example, polyesters such as polyethylene terephthalate, polyethylene naphthalate, polybutylene terephthalate, cellulose-based polymers such as diacetyl cellulose and triacetyl cellulose, polycarbonate-based polymers, and the like. Thus, the transparent, mechanical strength, thermal stability, water resistance, isotropy, flexibility, dimensional stability and other properties are all better.
In other embodiments of the present invention, the surface protective film may further include a release film, and the release film used in the present invention is not particularly limited, and a polyester film, preferably a film material with a small surface tension after surface treatment, may be used.
In yet another aspect of the invention, the invention provides an element. According to an embodiment of the invention, referring to fig. 4, the element 10 comprises: a body 100; and the aforementioned surface protective film attached to at least part of the surface of the body 100, the pressure-sensitive adhesive layer 220 being in contact with the body 100. The inventors found that the surface protective film of the element 10 can achieve excellent antistatic properties, is less likely to remain after peeling even under high temperature and high humidity conditions, and has all the features and advantages of the pressure-sensitive adhesive and the surface protective film described above, and will not be described in detail herein.
According to an embodiment of the invention, the element may particularly comprise at least one of an optical element or an electronic element. Therefore, the pressure-sensitive adhesive disclosed by the invention has a wider application range.
It will be appreciated by those skilled in the art that the element may include other structures of conventional elements in the related art in addition to the surface protective film described above, and will not be described in detail herein.
Embodiments of the present invention are described in detail below. The following examples are illustrative only and are not to be construed as limiting the invention. The examples are not to be construed as limiting the specific techniques or conditions described in the literature in this field or as per the specifications of the product. The reagents or apparatus used were conventional products commercially available without the manufacturer's attention.
The performance test method comprises the following steps:
peel force: test method 1 for peel strength of adhesive tape according to standard GB/T2792-2014 test method 1 for 180 DEG peel strength of adhesive tape and stainless steel.
Antistatic: the surface resistance of the protective film was measured using a ZC36 type resistance meter.
Residue: the protective film was attached to a steel plate, and the steel plate was aged at 60℃in 90% RH for 12 hours, and then the steel plate was observed to remain.
Example 1
Preparation of mixed solution M1: the monomer, initiator and 15 g solvent were uniformly mixed and sufficiently dissolved as described in the following table to obtain a mixed solution M1.
Preparation of mixed solution M2: the monomer, initiator and 15 g solvent were uniformly mixed and sufficiently dissolved as described in the following table to obtain a mixed solution M2.
Preparation of polyacrylate Compound: introducing nitrogen into a four-mouth bottle provided with a stirrer, a reflux condenser, a thermometer, a constant-pressure dropping funnel and a nitrogen inlet pipe until the air in the system is replaced by the nitrogen, adding the mixed solution M1, introducing the nitrogen, removing oxygen in the mixture, heating to 80 ℃, preserving heat for 0.5 hour, slowly dropwise adding the mixed solution M2, and dropwise adding for 3 hours.
Preparation of polyethylene glycol grafted polyacrylate resin: 15 g of butanone and polyethylene glycol are added into the reaction system, the temperature is kept for 4 hours, the heating is stopped, and the natural cooling is carried out, thus obtaining the polyethylene glycol grafted modified polyacrylate resin.
Preparation of coating liquid (pressure-sensitive adhesive): 30 g of the polyethylene glycol grafted polyacrylate is weighed, added with 0.75 g of curing agent, 0.75 g of antistatic agent and 7.5 g of ethyl acetate, and fully mixed. Further, examples 2 to 6 were prepared in the same manner as in example 1; comparative example 1 was prepared as in example 1, except that no polyethylene glycol was added; comparative example 2 was prepared as in example 1, except that polyethylene glycol acrylate monomer was added to the substrate and polyethylene glycol acrylate monomer was added to the drop.
And (3) coating and curing: the coating liquid is coated on a PET substrate layer with surface treatment, the coating liquid is dried for 2min at 100 ℃, the solvent is removed, a release film is covered by a film covering machine, and the release film is put into an oven for curing at 80 ℃ for 5 hours, so that a surface protection film is obtained, and the performance is tested.
Table 1 formulations of examples and comparative examples
Table 2 results of performance testing of examples and comparative examples
| - | Example 1 | Example 2 | Example 3 | Example 4 |
| Stripping force (N/25 mm) | 0.085 | 0.146 | 0.190 | 0.213 |
| Surface resistance (omega) | 1.5×10 10 | 5×10 9 | 5×10 10 | 7×10 9 |
| Residual steel plate | ○ | ○ | ○ | ○ |
| - | Example 5 | Example 6 | Comparative example 1 | Comparative example 2 |
| Stripping force (N/25 mm) | 0.159 | 0.076 | 0.151 | 0.132 |
| Surface resistance (omega) | 7×10 9 | 5×10 9 | 7×10 10 | 2×10 10 |
| Residual steel plate | ○ | ○ | Δ | × |
Note that: "Δ" represents a slight residue; "good" indicates no residue; "×" indicates residue.
As shown by the experimental data, the stripping force of the pressure-sensitive adhesive disclosed by the invention is below 0.1N/25 mm; the residue is reduced; the polymer has no residue, and the ether bond existing in the polymer is complexed with the cation of the antistatic agent, so that the compatibility between the antistatic agents is improved, and the surface resistance is reduced.
In the description of the present invention, it should be understood that the terms "first," "second," and the like are used for descriptive purposes only and are not to be construed as indicating or implying a relative importance or number of technical features indicated. Thus, a feature defining "a first" or "a second" may explicitly or implicitly include one or more such feature. In the description of the present invention, the meaning of "a plurality" is two or more, unless explicitly defined otherwise.
In the description of the present specification, a description referring to terms "one embodiment," "some embodiments," "examples," "specific examples," or "some examples," etc., means that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the present invention. In this specification, schematic representations of the above terms are not necessarily directed to the same embodiment or example. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples. Furthermore, the different embodiments or examples described in this specification and the features of the different embodiments or examples may be combined and combined by those skilled in the art without contradiction.
While embodiments of the present invention have been shown and described above, it will be understood that the above embodiments are illustrative and not to be construed as limiting the invention, and that variations, modifications, alternatives and variations may be made to the above embodiments by one of ordinary skill in the art within the scope of the invention.
Claims (24)
1. A method of making a pressure sensitive adhesive comprising:
polymerizing the main monomer and the comonomer to obtain a first polymer;
under the condition of 60-90 ℃, the first polymer and the grafting agent are subjected to grafting reaction for 4-8 hours to obtain a second polymer;
crosslinking the second polymer with the crosslinking agent to obtain the pressure-sensitive adhesive,
the step of polymerizing the primary monomer and the comonomer to obtain a first polymer further comprises:
under the conditions of 60-90 ℃ and inert gas, partial main monomers and partial comonomers are subjected to a first polymerization reaction for 15-75 min to obtain prepolymer;
causing the prepolymer to undergo a second polymerization reaction with a part of the main monomer and a part of the comonomer at 60-90 ℃ for 3-10 hours so as to obtain the first polymer,
The mass ratio of the main monomer in which the first polymerization reaction occurs to the main monomer in which the second polymerization reaction occurs is 0.4 to (44/95),
the pressure-sensitive adhesive contains a crosslinked graft copolymer formed from a main monomer, a comonomer and a grafting agent, wherein the main monomer comprises (meth) acrylic acid ester, the comonomer comprises an acrylic derivative containing an epoxy group, an acrylic derivative containing a hydroxyl group and an acrylic derivative containing an amide group, the grafting agent comprises a polymeric polyol, and the monomer forming the pressure-sensitive adhesive does not contain polyethylene glycol acrylate.
2. The method according to claim 1, wherein the mass ratio of the comonomer in which the first polymerization reaction occurs to the comonomer in which the second polymerization reaction occurs is (2 to 3): (2-3).
3. The method according to claim 1, wherein the number of carbon atoms in the methacrylate is 4 to 10.
4. The method of claim 1, wherein the (meth) acrylate comprises at least one of hexyl (meth) acrylate, isobutyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, n-octyl (meth) acrylate, isooctyl (meth) acrylate, n-nonyl (meth) acrylate, isononyl (meth) acrylate, n-decyl (meth) acrylate, or isodecyl (meth) acrylate.
5. The method of claim 1, wherein the cross-linking agent comprises at least one of an isocyanate compound, an epoxy compound, an aziridine compound, or a metal chelate.
6. The method according to claim 5, wherein the isocyanate compound comprises at least one of hexamethylene diisocyanate, isophorone diisocyanate, toluene diisocyanate, an isocyanurate body of hexamethylene diisocyanate, an isocyanurate body of isophorone diisocyanate, or an addition product of a polyol and an isocyanate.
7. The method of claim 5, wherein the epoxy compound comprises at least one of N, N' -tetraglycidyl-m-xylylenediamine or 1, 3-bis (N, N-diglycidyl aminomethyl) cyclohexane.
8. The method of claim 5, wherein the aziridine compound comprises at least one of a polyethylenimine crosslinker, saC-100, or an NWIITC aqueous crosslinker.
9. The method of claim 5, wherein the metal chelate comprises at least one of a metal aluminum chelate, a metal iron chelate, a metal tin chelate, a metal titanium chelate, a metal nickel chelate.
10. The method of claim 9, wherein in the metal chelate, the ligand comprises at least one of acetylene, methyl acetoacetate, or ethyl lactate.
11. The method of claim 1, wherein the acrylic derivative containing an epoxy group comprises at least one of glycidyl methacrylate, methyl glycidyl methacrylate, or allyl glycidyl ether.
12. The method of claim 1, wherein the hydroxyl-containing acrylic derivative comprises at least one of 8-hydroxyoctyl (meth) acrylate, 6-hydroxyhexyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, N-hydroxy (meth) acrylamide, N-hydroxymethyl (meth) acrylamide, or N-hydroxyethyl (meth) acrylamide.
13. The method according to claim 1, wherein the amide group-containing acrylic acid derivatives include acrylamide, methacrylamide, diethylacrylamide, N-vinylpyrrolidone, N ' -dimethylacrylamide, N ' -dimethylmethacrylamide, N, at least one of N ' -diethyl acrylamide, N ' -diethyl methacrylamide, N ' -methylenebisacrylamide, N ' -dimethylaminopropyl acrylamide, N ' -dimethylaminomethyl propyl acrylamide, diacetone acrylamide, N-methylolacrylamide and N-hydroxyethyl acrylamide.
14. The method of claim 1, wherein the polymeric polyol has a weight average molecular weight of no greater than 2000Da.
15. The method of claim 1, wherein the polymeric polyol is polyethylene glycol.
16. The method of claim 1, wherein the pressure sensitive adhesive further comprises an antistatic agent.
17. The method of claim 16, wherein the antistatic agent comprises at least one of a salt comprising an alkali metal ion or an ionic liquid comprising an alkali metal ion.
18. The method of claim 16, wherein the alkali metal ions comprise Li + 、Na + Or K + At least one of them.
19. The method according to claim 18, wherein in the salt or ionic liquid, the anion comprises a halide ion, CH 3 COO - 、CF 3 SO 3 - 、(CF 3 SO 2 ) 2 N - 、(C 2 F 5 SO 2 ) 2 N - 、(C 3 F 7 SO 2 ) 2 N - 、(C 4 F 9 SO 2 ) 2 N - 、(FSO 2 ) 2 N - Or (CF) 3 SO 2 ) 3 C - At least one of them.
20. The method of claim 1 wherein the pressure sensitive adhesive further comprises an auxiliary agent.
21. The method of claim 20, wherein the adjunct comprises at least one of a catalyst, a catalyst promoter, a surfactant, a diluent, a plasticizer, a filler, a crosslinking inhibitor, an antioxidant, or an anti-aging agent.
22. The method of claim 21, wherein the catalyst comprises at least one of a tin-based catalyst, an iron-based catalyst, a copper-based catalyst, a phosphorous-containing catalyst, or an amine-based catalyst.
23. A surface protective film, comprising:
a substrate layer; and
a pressure-sensitive adhesive layer provided on at least a part of the surface of the base material layer,
wherein at least a portion of the pressure sensitive adhesive layer is prepared by the method of any one of claims 1 to 22.
24. An element, comprising:
a body; and
the surface protective film of claim 23, which is attached to at least a portion of a surface of the body, the pressure sensitive adhesive layer being in contact with the body.
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