CN111534248A - Pressure-sensitive adhesive, method for producing the same, surface protective film, and element - Google Patents
Pressure-sensitive adhesive, method for producing the same, surface protective film, and element Download PDFInfo
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- CN111534248A CN111534248A CN202010449622.8A CN202010449622A CN111534248A CN 111534248 A CN111534248 A CN 111534248A CN 202010449622 A CN202010449622 A CN 202010449622A CN 111534248 A CN111534248 A CN 111534248A
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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
- 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
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- 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
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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
- 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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- 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 protection film and a component. The pressure-sensitive adhesive contains a crosslinked graft copolymer which is crosslinked by a crosslinking agent and is formed by a main monomer, a comonomer and a grafting agent, wherein the main monomer comprises methacrylate, the comonomer comprises an acrylic derivative containing an epoxy group, the grafting agent comprises a polymeric polyol, and the monomer for forming the pressure-sensitive adhesive does not contain acrylic acid polyethylene glycol ester. 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 difficult to leave even under the condition 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 protection film and an element.
Background
At present, in optical elements or electronic elements, for example, the surfaces of display devices such as LCD and organic EL displays need to be attached with a surface protection 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 needs to be attached with another member, the surface protective film needs to be peeled off when the surface protective film is not to be reused. Therefore, in the steps of manufacturing, processing, inspecting, transporting, etc. of the above-described element, the surface protective film is often used, and it is inevitable to perform operations of attaching, peeling, reattaching, and re-peeling the surface protective film a plurality of times. However, on the one hand, a surface protective film is attached to the surface of the element for a long period of time, and the pressure-sensitive adhesive layer in the surface protective film may leave adhesive residue on the surface of the element after peeling due to temperature, humidity, and the like; on the other hand, when the surface protective film is first attached to the surface of the element, no bubble is generated, but when the surface protective film is peeled off and reattached, bubbles are easily generated, sometimes the bubbles are very small and difficult to distinguish, and after the attachment, the bubbles exist for a long time, and when the surface protective film is peeled off again, a mark is generated at the bubble position; on the other hand, when the surface protective film is peeled off from the surface of the element, static electricity is generated, which may cause a failure of a circuit in the element, and it is necessary to add an antistatic agent to the pressure-sensitive adhesive of the surface protective film, but since the antistatic agent is not well compatible 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 the pressure-sensitive adhesive in the existing surface protective film still remains to be improved.
Disclosure of Invention
The present invention is directed to solving, at least to some extent, one of the technical problems in the related art. To this end, an object of the present invention is to provide a pressure-sensitive adhesive having abundant chemical crosslinking sites, abundant physical crosslinking sites, high cohesive energy, low peeling force, good compatibility between components, low surface resistance, excellent antistatic properties when used as a surface protective film, or being 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 crosslinked via a crosslinking agent, formed from a main monomer, a comonomer and a grafting agent, wherein the main monomer includes 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 leave residues 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 ester 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, isocyanurate body of hexamethylene diisocyanate, isocyanurate body of isophorone diisocyanate, or an adduct of a polyol and an isocyanate.
According to an embodiment of the invention, the epoxy compound comprises at least one of N, N' -tetraglycidyl-m-xylylenediamine or 1, 3-bis (N, N-diglycidylaminomethyl) cyclohexane.
According to an embodiment of the present invention, the aziridine compound comprises at least one of a polyethylenimine crosslinking agent, SaC-100, or a nwaitc aqueous crosslinking agent.
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 invention, the comonomer further comprises at least one of a hydroxyl group-containing acrylic derivative or an amide group-containing acrylic derivative.
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 acrylic derivative having a hydroxyl group 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-methylol (meth) acrylamide, or N-hydroxyethyl (meth) acrylamide.
According to an embodiment of the present invention, the acryl-based derivative having an amide group includes at least one of acrylamide, methacrylamide, diethylacrylamide, N-vinylpyrrolidone, N ' -dimethylacrylamide, N ' -dimethylmethacrylamide, N ' -diethylacrylamide, N ' -diethylmethacrylamide, N ' -methylenebisacrylamide, N ' -dimethylaminopropylacrylamide, N ' -dimethylaminomethylpropylacrylamide, diacetoneacrylamide, N-methylolacrylamide, and N-hydroxyethyl acrylamide.
According to an embodiment of the present invention, the raw materials 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 the grafting agent; and 2.5 to 2.8 parts by weight of the crosslinking agent.
According to an embodiment of the invention, the comonomers comprise: 0.001 to 0.15 parts by weight of an epoxy group-containing acrylic derivative; 0.01 to 0.5 parts by weight of an acrylic derivative containing a hydroxyl group; and 0.001 to 0.15 parts by weight of an acrylic derivative having an amide group.
According to an embodiment of the invention, the polymeric polyol has a weight average molecular weight of not more than 2000 Da.
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 present invention, theThe alkali metal ion includes Li+、Na+Or K+At least one of (1).
According to an embodiment of the invention, in the salt or ionic liquid, the anion comprises halide, CH3COO-、CF3SO3 -、(CF3SO2)2N-、(C2F5SO2)2N-、(C3F7SO2)2N-、(C4F9SO2)2N-、(FSO2)2N-Or (CF)3SO2)3C-At least one of (1).
According to an embodiment of the invention, the pressure sensitive adhesive further comprises an auxiliary agent.
According to an embodiment of the present invention, the auxiliary agent includes at least one of a catalyst, a catalyst promoter, a surfactant, a diluent, a plasticizer, a filler, a crosslinking inhibitor, an antioxidant, or an aging inhibitor.
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 above. According to an embodiment of the invention, the method comprises: polymerizing the main monomer and the comonomer to obtain a first polymer; carrying out grafting reaction on the first polymer and the grafting agent for 4-8 h at the temperature of 60-90 ℃ to obtain a second polymer; and (c) subjecting the second polymer to a crosslinking reaction with the crosslinking agent to obtain the pressure-sensitive adhesive. The inventor finds that the method is simple and convenient to operate, easy to implement, easy for 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, carrying out a first polymerization reaction on part of the main monomer and part of the comonomer for 15-75 min to obtain a prepolymer; and carrying out second polymerization reaction on the prepolymer and part of the main monomer and part of the comonomer for 3-10 h 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 (2-4): (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 (2-3): (2-3).
In yet another aspect of the present invention, the present 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 disposed on at least a portion of a surface of the substrate layer, wherein at least a portion of the pressure-sensitive adhesive layer is formed from or prepared by the pressure-sensitive adhesive described above. The inventors found that the surface protective film can realize excellent antistatic properties, is less likely to remain even when peeled under high temperature and high humidity conditions, and has all the features and advantages of the pressure sensitive adhesive described above, and thus, it will not be described in excessive detail herein.
In yet another aspect of the invention, an element is provided. 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 contacted with the body. The inventors found that the surface protective film of the element can realize excellent antistatic performance, is less likely to leave residues 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 previously, and will not be described in excessive detail herein.
Drawings
FIG. 1 shows a schematic flow diagram of a method of making a pressure sensitive adhesive according to one embodiment of the present invention.
FIG. 2 shows a schematic flow chart of the steps of forming a first polymer according to one embodiment of the present invention.
Fig. 3 is a schematic cross-sectional view of a surface protective film according to an embodiment of the present invention.
Fig. 4 shows a schematic cross-sectional structure of an element of an embodiment of the present invention.
Reference numerals:
10: element 100: a body 200: surface protective film 210: substrate 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 crosslinked via a crosslinking agent, formed from a main monomer, a comonomer and a grafting agent, wherein the main monomer includes 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 leave residues 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 and the cross-linking agent can form a relatively stable cross-linking structure; and the epoxy group can also form intramolecular crosslinking with hydroxyl in the polymerized polyol, so that the molecules of the pressure-sensitive adhesive have higher cohesive energy, the stripping force can be less 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 low-speed and high-speed conditions, and the stripping force is balanced under the low-speed and high-speed conditions, so that the pressure-sensitive adhesive is difficult to leave residues when being used as a surface protective film.
According to an embodiment of the present invention, the number of carbon atoms in the methacrylate ester 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, or 10, etc. Therefore, more chemical crosslinking points and physical crosslinking points can be present in the main monomer and the comonomer, so that the peel force of the pressure-sensitive adhesive can 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. Therefore, more chemical crosslinking points and physical crosslinking points can be present in the main monomer and the comonomer, so that the peel force of the pressure-sensitive adhesive can 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, isocyanurate body of hexamethylene diisocyanate, isocyanurate body of isophorone diisocyanate, or adduct of polyol and isocyanate, etc.; in other embodiments of the present invention, the epoxy compound may include N, N' -tetraglycidyl-m-xylylenediamine or 1, 3-bis (N, N-diglycidylaminomethyl) cyclohexane, or the like; in still other embodiments of the present invention, the aziridine compound may include a polyethylenimine crosslinking agent, SaC-100, or nwaitc aqueous crosslinking agent, or the like; in still other embodiments of the present invention, the metal chelate may include metal aluminum chelate, metal iron chelate, metal tin chelate, metal titanium chelate, metal nickel chelate, etc.; in addition, in the metal chelate compound, the ligand may include acetylene, methyl acetoacetate, ethyl lactate, or the like. Therefore, the material source is wide and easy to obtain, the cost is low, the pressure-sensitive adhesive is easy to prepare, in the obtained pressure-sensitive adhesive, the crosslinking among the components is more sufficient, the components are mutually wound and crosslinked, and the formed pressure-sensitive adhesive has more chemical crosslinking points and physical crosslinking points, so that the internal energy accumulation is higher, and the stripping force is further reduced.
According to an embodiment of the present invention, specifically, the comonomer, i.e., the acrylic derivative containing an epoxy group according to the present invention 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, and more chemical crosslinking points and physical crosslinking points exist in the pressure-sensitive adhesive, so that the components in the pressure-sensitive adhesive are crosslinked more tightly, the stripping force of the pressure-sensitive adhesive is further reduced, and the pressure-sensitive adhesive is less prone to residue when being used as a surface protective film during stripping.
According to an embodiment of the present invention, further, the comonomer may further include an acrylic derivative containing a hydroxyl group or an acrylic derivative containing an amide group, etc. in other embodiments of the present invention, in addition to the aforementioned acrylic derivative containing an epoxy group. Therefore, in the pressure-sensitive adhesive, a plurality of types of comonomers exist, and hydroxyl can react with a cross-linking agent to form a cross-linked network of polymers, so that the wettability and the stripping force of the composition are controlled; in addition, the pressure-sensitive adhesive is different from groups with higher polarity such as carboxyl, sulfonic acid group and the like, and the hydroxyl and the antistatic agent have interaction, so that the pressure-sensitive adhesive can realize better antistatic performance; in addition, multiple comonomers can be matched with each other to play a synergistic effect, the epoxy group can also react with the hydroxyl group and the amide group to form intramolecular crosslinking, and the amide group can also be used as a physical crosslinking point, so that the cohesive energy of the pressure-sensitive adhesive is high.
According to an embodiment of the present invention, further, the acrylic derivative having a hydroxyl group 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-methylol (meth) acrylamide, or N-hydroxyethyl (meth) acrylamide. Therefore, in the pressure-sensitive adhesive, a plurality of kinds of comonomers exist, and the plurality of comonomers can be matched with each other to play a synergistic effect, so that the cohesive energy of the pressure-sensitive adhesive is high.
According to an embodiment of the present invention, the amide group-containing acrylic derivative further includes at least one of acrylamide, methacrylamide, diethylacrylamide, N-vinylpyrrolidone, N ' -dimethylacrylamide, N ' -dimethylmethacrylamide, N ' -diethylacrylamide, N ' -diethylmethacrylamide, N ' -methylenebisacrylamide, N ' -dimethylaminopropylacrylamide, N ' -dimethylaminomethylpropylacrylamide, diacetoneacrylamide, N-methylolacrylamide, and N-hydroxyethyl acrylamide. Therefore, in the pressure-sensitive adhesive, a plurality of kinds of comonomers exist, and the plurality of comonomers can be matched with each other to play a synergistic effect, 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 having a carboxyl group, for example, at least one of compounds consisting of methacrylic acid, carboxyethyl (meth) acrylic acid, carboxypentyl (meth) acrylic acid, 2- (meth) acryloyloxyethylphthalic acid, 2- (meth) acryloyloxyethylsuccinic acid, 2- (meth) acryloyloxyethylmaleic acid, carboxypolycaprolactone mono (meth) acrylate, 2- (meth) acryloyloxyethyltetrahydrophthalic acid; in still other embodiments of the present invention, the comonomer may further include other monomers, such as at least one of a cyano-containing monomer, a vinyl monomer, an aromatic vinyl monomer, an imide-based monomer, an epoxy-based monomer, a vinyl monomer, or an amino-based monomer. Specifically, the cyano group-containing monomer may include acrylonitrile, methacrylonitrile, and the like; the vinyl monomer may include vinyl acetate, vinyl propionate, vinyl laurate, and the like; the aromatic vinyl monomer may include styrene, chlorostyrene, chloromethylstyrene, α -methylstyrene, etc.; the imide group monomers 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. Therefore, multiple comonomers can be matched with each other to play a synergistic effect, and the cohesive energy of the pressure-sensitive adhesive is high.
According to an embodiment of the present invention, the raw materials 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 the 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 parts by weight, 0.002 parts by weight, 0.005 parts by weight, 0.01 parts by weight, 0.02 parts by weight, 0.05 parts by weight, 0.1 parts by weight, 0.2 parts by weight, 0.4 parts by weight, 0.6 parts by weight, or 0.8 parts by weight, etc.; the weight portion of the grafting agent may be 0.1, 0.2, 0.5, 1, 2, 4, 6, 8, or 10 parts by weight, etc.; the weight portion of the crosslinking agent may be 2.5 parts by weight, 2.6 parts by weight, 2.7 parts by weight, 2.8 parts by weight, or the like. Therefore, in the pressure-sensitive adhesive, the ratio of each component is proper, multiple comonomers can be matched with each other to play a synergistic effect, the cohesive energy of the pressure-sensitive adhesive is high, the stripping 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 after being stripped under the high-temperature and high-humidity condition.
According to an embodiment of the present invention, further, the comonomer may include: 0.001 to 0.15 parts by weight of an epoxy group-containing acrylic derivative; 0.01 to 0.5 parts by weight of an acrylic 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 derivative having a carboxyl group. Specifically, the weight part of the epoxy group-containing acrylic derivative may be 0.001 parts by weight, 0.002 parts by weight, 0.005 parts by weight, 0.01 parts by weight, 0.02 parts by weight, 0.05 parts by weight, 0.1 parts by weight, 0.12 parts by weight, or 0.15 parts by weight. Therefore, in the pressure-sensitive adhesive, multiple comonomers can be matched with each other to play a synergistic effect, so that the cohesive energy of the pressure-sensitive adhesive is high, the stripping force of the pressure-sensitive adhesive is further reduced, the compatibility among the components is better, the surface resistance is lower, and residues are less prone to being generated in stripping under the conditions of high temperature and high humidity; in addition, the amount of the carboxyl group-containing acrylic derivative is not too large, and since the carboxyl group is reactive and has a weak catalytic action, a small amount of the carboxyl group-containing acrylic derivative does not result in a short shelf life of the composition solution, which is disadvantageous for the application.
According to an embodiment of the present invention, in particular, the polymeric polyol has a weight average molecular weight not greater than 2000 Da. In some embodiments of the invention, the polymeric polyol may have a weight average molecular weight of 1000Da, 1200Da, 1400Da, 1600Da, 1800Da, 2000Da, or the like. Therefore, the condition that polyethylene glycol forms a phase by itself to cause micro-phase separation or phase separation of the polymer can be avoided due to the fact that the weight average molecular weight of the grafting agent is not too high, and the grafting agent can be grafted with the main monomer and the comonomer better so as to form the pressure-sensitive adhesive with higher cohesive energy.
According to an embodiment of the present invention, in particular, the polymeric polyol may be in particular polyethylene glycol. The 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 source is wide and easy to obtain, the cost is low, and meanwhile, the material can be well grafted with the main monomer and the comonomer so as to form the pressure-sensitive adhesive with higher cohesive energy, so that the stripping force is further reduced; meanwhile, the polyethylene glycol can better react with the epoxy group to form a chemical bond between the polyethylene glycol and the epoxy group, so that the compatibility among the components is better, the surface resistance is lower, and the polyethylene glycol is less prone to residue after being stripped 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. Therefore, the antistatic performance of the pressure-sensitive adhesive can be better, and meanwhile, because the compatibility of the resin of each component in the pressure-sensitive adhesive and the antistatic agent is better, the cohesive energy of the pressure-sensitive adhesive can not be influenced even if a certain amount of the antistatic agent is added into the pressure-sensitive adhesive, so that the pressure-sensitive adhesive can have lower stripping force and can also realize more excellent antistatic performance when being used as a surface protective film.
According to an embodiment of the present invention, further, the antistatic agent may specifically include at least one of a salt containing an alkali metal ion or an ionic liquid containing an alkali metal ion. In particular, in some embodiments of the present invention, the alkali metal ion may specifically include Li+、Na+Or K+At least one of; in other embodiments of the present invention, in the salt or the ionic liquid, the anion may specifically include halide, CH3COO-、CF3SO3 -、(CF3SO2)2N-、(C2F5SO2)2N-、(C3F7SO2)2N-、(C4F9SO2)2N-、(FSO2)2N-Or (CF)3SO2)3C-At least one of (1). Therefore, the material source is wide and easy to obtain, the cost is low, and the antistatic agents are all ionic compounds, have high dissociation property and low costThe pressure sensitive adhesive has high melting point and molecular motion capability, so that the pressure sensitive adhesive has better antistatic property, and cations in the pressure sensitive adhesive can be complexed with ether bonds, so that the compatibility of resin and the antistatic agent is further improved, and further, the excellent antistatic property can be realized, and the surface resistance of the pressure sensitive adhesive is favorably reduced.
In other embodiments of the present invention, the pressure sensitive adhesive may further comprise an auxiliary agent. Specifically, the auxiliary 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-based catalyst, or an amine-based catalyst. In addition, specific types of the catalyst promoter, the surfactant, the diluent, the plasticizer, the filler, the crosslinking inhibitor, the antioxidant or the anti-aging agent, and more specific types of the catalyst can be selected from auxiliary agents in the related art, and are not described in detail herein; in addition, the catalyst therein may promote the reaction, but an excessive amount of the catalyst or a catalyst having 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., relative 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 above. According to an embodiment of the invention, referring to fig. 1, the method comprises the steps of:
s100: and carrying out polymerization reaction on 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 include the sub-steps of:
s110: and under the conditions of 60-90 ℃ and inert gas, carrying out a first polymerization reaction on part of the main monomer and part of the comonomer for 15-75 min to obtain the prepolymer.
According to the embodiment of the present invention, the reaction temperature may be 60 ℃, 70 ℃, 80 ℃ or 90 ℃, the inert gas may be helium, argon or the like, and the reaction time may be 15min, 25min, 35min, 45min, 55min, 65min or 75min or the like. Therefore, before all the main monomers and all the comonomers are reacted to obtain the 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 monomer supplementing method can enable the reaction to be carried out smoothly because a large amount of heat is generated in the reaction process.
S120: and carrying out second polymerization reaction on the prepolymer and part of the main monomer and part of the comonomer for 3-10 h at the temperature of 60-90 ℃ so as to obtain the first polymer.
According to the embodiment of the present invention, the reaction temperature may be 60 ℃, 70 ℃, 80 ℃ or 90 ℃, the inert gas may be helium, argon or the like, and the reaction time may be 3h, 4h, 5h, 6h, 7h, 8h, 9h or 10 h. Therefore, the polymerization degree of the first polymer is higher, and the pressure-sensitive adhesive with higher internal performance can be prepared finally.
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, and the like. Therefore, the main monomer in which the first polymerization reaction occurs is better in quality than the main monomer in which the second polymerization reaction occurs, and a pressure-sensitive adhesive having better performance in various 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. Therefore, the comonomer subjected to the first polymerization reaction and the comonomer subjected to the second polymerization reaction are better in quality, and a pressure-sensitive adhesive with better performance in all aspects can be formed.
S200: and carrying out grafting reaction on the first polymer and the grafting agent for 4-8 h at the temperature of 60-90 ℃ to obtain a second polymer.
According to the embodiment of the present invention, the reaction temperature may be 60 ℃, 70 ℃, 80 ℃ or 90 ℃, the inert gas may be helium, argon or the like, and the reaction time may be 4h, 5h, 6h, 7h, 8h or the like. Therefore, the polymerization degree of the second polymer is higher, the pressure-sensitive adhesive with higher internal homoenergetic can be prepared finally, and the preparation method is simple and convenient to operate, easy to realize and easy for industrial production.
S300: and (c) subjecting the second polymer to a crosslinking reaction with the crosslinking agent 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 those skilled in the art can flexibly select the conditions according to actual needs, which are not described herein in detail.
In a specific embodiment of the present invention, the method may comprise: uniformly mixing and fully dissolving at least 20 to 40 parts by weight of methacrylate containing 4 to 10 carbon atoms, 0 to 5 parts by weight of acrylic derivative containing epoxy group, 0 to 5 parts by weight of acrylic derivative containing amido group, 0.075 to 1 part by weight of initiator and 40 to 60 parts by weight of solvent, heating the mixture as a substrate to 60 to 90 ℃ under the protection of inert gas, and keeping the temperature for 15 to 75min to obtain the prepolymer; slowly adding a dropwise mixture of at least 20 to 50 parts by weight of 20 to 40 parts by weight of methacrylate containing 4 to 10 carbon atoms, 0.5 to 5 parts by weight of acrylic derivative containing epoxy group, 0 to 5 parts by weight of acrylic derivative containing amide group, 0.1 to 1 part by weight of initiator and 0 to 20 parts by weight of solvent into the prepolymer, adding the mixture for 2 to 4 hours, and keeping the temperature for 3 to 10 hours; adding 0.5-8 parts by weight of polyethylene glycol, continuing to react for 4-8 hours, and finally crosslinking through 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 accounts for 0 to 10 parts by weight in the prepolymer, and accounts for 0.01 to 10 parts by weight in the dropping mixture; the methacrylate monomer having more than two ether bonds is present in an amount of 0 to 10 parts by weight in the prepolymer and 0.01 to 10 parts by weight in the dropping mixture.
According to the embodiment of the present 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 of the solvents may be selected. Because of the solubility difference of polyacrylate and polyethylene glycol in the solvent, as the preferable solvent, two or more solvents can be selected for use, for example, ethyl acetate, toluene, ethyl acetate and butanone are used 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 in the other solvent.
According to embodiments of the present invention, the polymerization method of the present invention, including but not limited to bulk polymerization, solution polymerization, emulsion polymerization and suspension polymerization, is preferably solution polymerization.
In yet another aspect of the present invention, the present invention provides a surface protective film. According to an embodiment of the present invention, referring to fig. 3, the surface protective film 200 includes: a base material 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 substrate layer 210, wherein at least a portion of the pressure-sensitive adhesive layer 220 is formed from 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 even when peeled under high temperature and high humidity conditions, and has all the features and advantages of the pressure sensitive adhesive described above, and thus, it will not be described in excessive detail herein.
According to the embodiment of the present invention, the specific material forming the substrate layer is not particularly limited, and those skilled in the art can flexibly select the material according to actual needs, and examples thereof include polyesters such as polyethylene terephthalate, polyethylene naphthalate, and polybutylene terephthalate, cellulose polymers such as diacetyl cellulose and triacetyl cellulose, and polycarbonate polymers. Thus, the properties such as transparency, mechanical strength, thermal stability, water resistance, isotropy, flexibility, dimensional stability, and the like are all preferable.
In other embodiments of the present invention, the surface protection 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 surface-treated film material with a low surface tension, may be used.
In yet another aspect of the invention, an element is provided. According to an embodiment of the invention, with reference to fig. 4, the element 10 comprises: a body 100; and the aforementioned surface protective film attached to at least a 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 this element 10 can realize excellent antistatic properties, is less likely to cause residue even under high-temperature and high-humidity conditions upon peeling, and has all the features and advantages of the pressure-sensitive adhesive and the surface protective film described previously, and will not be described in excessive 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 has wider application range.
According to the embodiments of the present invention, it can be understood by those skilled in the art that the element may include other structures of the conventional elements in the related art, in addition to the surface protective film described above, and thus, redundant description is not repeated herein.
The following describes embodiments of the present invention in detail. The following examples are illustrative only and are not to be construed as limiting the invention. The examples, where specific techniques or conditions are not indicated, are to be construed according to the techniques or conditions described in the literature in the art or according to the product specifications. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products commercially available.
The performance test method comprises the following steps:
peeling force: the test was performed according to test method for peel strength of adhesive tape of standard GB/T2792-2014, test method 1 for 180 ° peel strength of adhesive tape and stainless steel.
Antistatic: the surface resistance of the protective film was measured using a resistance meter model ZC 36.
And (4) residual: the protective film was attached to a steel plate, aged at 60 ℃ in a 90% RH atmosphere for 12 hours, and then the steel plate was observed to remain.
Example 1
Preparation of mixed solution M1: the monomers, initiator and 15 g of solvent were mixed uniformly and dissolved sufficiently as described in the following table to obtain a mixed solution M1.
Preparation of mixed solution M2: the monomers, initiator and 15 g of solvent were mixed uniformly and dissolved sufficiently as described in the following table to obtain a mixed solution M2.
Preparation of polyacrylate compound: introducing nitrogen into a four-neck flask provided with a stirrer, a reflux condenser tube, a thermometer, a constant-pressure dropping funnel and a nitrogen inlet tube 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 the temperature for 0.5 hour, slowly dropwise adding the mixed solution M2, and dropwise adding for 3 hours.
Preparation of polyethylene glycol grafted polyacrylate resin: adding 15 g of butanone and polyethylene glycol into the reaction system, keeping the temperature for 4 hours, stopping heating, and naturally cooling to obtain the polyethylene glycol grafted and modified polyacrylate resin.
Preparation of coating liquid (pressure-sensitive adhesive): 30 g of the polyethylene glycol grafted polyacrylate is weighed, 0.75 g of curing agent, 0.75 g of antistatic agent and 7.5 g of ethyl acetate are added, and the mixture is fully mixed. Additionally, examples 2-6 were prepared according to the method of example 1; comparative example 1 was prepared according to the method of example 1 except that no polyethylene glycol was added; comparative example 2 was prepared according to the method of example 1, except that the polyethylene glycol acrylate monomer was added to the substrate and the polyethylene glycol acrylate monomer was added to the drop.
Coating and curing: coating the coating liquid on a PET substrate layer subjected to surface treatment, drying at 100 ℃ for 2min, removing the solvent, covering a release film by using a film covering machine, placing the release film in an oven at 80 ℃ for 5 hours for curing to obtain a surface protective film, and testing the performance.
TABLE 1 formulation of examples and comparative examples
TABLE 2 results of performance test of examples and comparative examples
| - | Example 1 | Example 2 | Example 3 | Example 4 |
| Peel force (N/25mm) | 0.085 | 0.146 | 0.190 | 0.213 |
| Surface resistance (omega) | 1.5×1010 | 5×109 | 5×1010 | 7×109 |
| Steel plate residue | ○ | ○ | ○ | ○ |
| - | Example 5 | Example 6 | Comparative example 1 | Comparative example 2 |
| Peel force (N/25mm) | 0.159 | 0.076 | 0.151 | 0.132 |
| Surface resistance (omega) | 7×109 | 5×109 | 7×1010 | 2×1010 |
| Steel plate residue | ○ | ○ | Δ | × |
Note: ". indicates slight residue; ". o" means no residue; "×" indicates residue.
As can be seen from the above experimental data, the peel force of the pressure-sensitive adhesive of the present invention is 0.1N/25mm or less; the residue is reduced; 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 increased, and the surface resistance is reduced.
In the description of the present invention, it is to 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 relative importance or implying any number of technical features indicated. Thus, a feature defined as "first" or "second" may explicitly or implicitly include one or more of that feature. In the description of the present invention, "a plurality" means two or more unless specifically defined otherwise.
In the description herein, references to the description of the term "one embodiment," "some embodiments," "an example," "a specific example," or "some examples," etc., mean 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 invention. In this specification, the schematic representations of the terms used above are not necessarily intended to refer 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, various embodiments or examples and features of different embodiments or examples described in this specification can be combined and combined by one skilled in the art without contradiction.
Although embodiments of the present invention have been shown and described above, it is understood that the above embodiments are exemplary and should not be construed as limiting the present invention, and that variations, modifications, substitutions and alterations can be made to the above embodiments by those of ordinary skill in the art within the scope of the present invention.
Claims (10)
1. A pressure-sensitive adhesive comprising a crosslinked graft copolymer crosslinked via a crosslinking agent and formed from a main monomer, a comonomer and a grafting agent, wherein the main monomer comprises a methacrylate, the comonomer comprises an epoxy-containing acrylic derivative, the grafting agent comprises a polymeric polyol, and the monomers forming the pressure-sensitive adhesive do not contain polyethylene glycol acrylate.
2. The pressure-sensitive adhesive according to claim 1, wherein the number of carbon atoms in the methacrylate ester is 4 to 10,
optionally, the methacrylate 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.
3. The pressure sensitive adhesive of claim 1 wherein the crosslinker comprises at least one of an isocyanate compound, an epoxy compound, an aziridine compound or a metal chelate,
optionally, 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 adduct of a polyol and an isocyanate,
optionally, the epoxy compound comprises at least one of N, N, N ', N' -tetraglycidyl-m-xylylenediamine or 1, 3-bis (N, N-diglycidylaminomethyl) cyclohexane,
optionally, the aziridine compound includes at least one of a polyethylenimine crosslinker, Sac-100, or an NWIITC aqueous crosslinker,
optionally, the metal chelate comprises at least one of metal aluminum chelate, metal iron chelate, metal tin chelate, metal titanium chelate and metal nickel chelate, preferably, in the metal chelate, the ligand comprises at least one of acetylene, methyl acetoacetate or ethyl lactate.
4. The pressure-sensitive adhesive of claim 1 wherein the comonomer further comprises at least one of an acrylic derivative containing a hydroxyl group or an acrylic derivative containing an amide group,
optionally, the acrylic derivative containing an epoxy group includes at least one of glycidyl methacrylate, methyl glycidyl methacrylate, or allyl glycidyl ether,
optionally, 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-methylol (meth) acrylamide, or N-hydroxyethyl (meth) acrylamide,
optionally, the amide group-containing acrylic derivative includes at least one of acrylamide, methacrylamide, diethylacrylamide, N-vinylpyrrolidone, N ' -dimethylacrylamide, N ' -dimethylmethacrylamide, N ' -diethylacrylamide, N ' -diethylmethacrylamide, N ' -methylenebisacrylamide, N ' -dimethylaminopropylacrylamide, N ' -dimethylaminomethylpropylacrylamide, diacetone acrylamide, N-methylolacrylamide, N-hydroxyethylacrylamide.
5. The pressure-sensitive adhesive of claim 4 wherein the raw materials from which the pressure-sensitive adhesive is formed comprise:
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 the grafting agent; and
2.5 to 2.8 parts by weight of the crosslinking agent,
optionally, the comonomers comprise:
0.001 to 0.15 parts by weight of an epoxy group-containing acrylic derivative;
0.01 to 0.5 parts by weight of an acrylic derivative containing a hydroxyl group; and
0.001 to 0.15 parts by weight of an acrylic derivative containing an amide group.
6. The pressure-sensitive adhesive of claim 1 wherein the polymeric polyol has a weight average molecular weight of no greater than 2000Da,
optionally, the polymeric polyol is polyethylene glycol,
optionally, the pressure sensitive adhesive further comprises an antistatic agent,
optionally, the antistatic agent comprises at least one of a salt containing an alkali metal ion or an ionic liquid containing an alkali metal ion,
optionally, the alkali metal ion comprises Li+、Na+Or K+Preferably, in the salt or ionic liquid, the anion comprises halide, CH3COO-、CF3SO3 -、(CF3SO2)2N-、(C2F5SO2)2N-、(C3F7SO2)2N-、(C4F9SO2)2N-、(FSO2)2N-Or (CF)3SO2)3C-At least one of (a) and (b),
optionally, the pressure-sensitive adhesive further comprises an auxiliary agent,
optionally, 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,
optionally, 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.
7. A method of making the pressure sensitive adhesive of any of claims 1-6 comprising:
polymerizing the main monomer and the comonomer to obtain a first polymer;
carrying out grafting reaction on the first polymer and the grafting agent for 4-8 h at the temperature of 60-90 ℃ to obtain a second polymer;
and (c) subjecting the second polymer to a crosslinking reaction with the crosslinking agent to obtain the pressure-sensitive adhesive.
8. The method of claim 7, wherein polymerizing the primary monomer and the comonomer to obtain the first polymer further comprises:
under the conditions of 60-90 ℃ and inert gas, carrying out a first polymerization reaction on part of the main monomer and part of the comonomer for 15-75 min to obtain a prepolymer;
carrying out a second polymerization reaction of the prepolymer with a part of the main monomer and a part of the comonomer for 3-10 h at 60-90 ℃ so as to obtain the first polymer,
optionally, the mass ratio of the main monomer for the first polymerization reaction to the main monomer for the second polymerization reaction is (2-4): (2-5) of a first step,
optionally, the mass ratio of the comonomer subjected to the first polymerization reaction to the comonomer subjected to the second polymerization reaction is (2-3): (2-3).
9. A surface protective film, comprising:
a substrate layer; and
a pressure-sensitive adhesive layer disposed on at least a portion of a surface of the substrate layer,
wherein at least a part of the pressure-sensitive adhesive layer is formed of the pressure-sensitive adhesive of any one of claims 1 to 6, or is prepared by the method of claim 7 or 8.
10. An element, comprising:
a body; and
the surface protective film of claim 9, which is attached to at least a part of the surface of the body, the pressure-sensitive adhesive layer being in contact with the body.
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