CN113930196B - High-temperature-resistant residue-free aqueous pressure-sensitive adhesive and preparation method thereof - Google Patents
High-temperature-resistant residue-free aqueous pressure-sensitive adhesive and preparation method thereof Download PDFInfo
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- CN113930196B CN113930196B CN202111199083.8A CN202111199083A CN113930196B CN 113930196 B CN113930196 B CN 113930196B CN 202111199083 A CN202111199083 A CN 202111199083A CN 113930196 B CN113930196 B CN 113930196B
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- 239000004820 Pressure-sensitive adhesive Substances 0.000 title claims abstract description 71
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- 239000000839 emulsion Substances 0.000 claims abstract description 81
- 229920000359 diblock copolymer Polymers 0.000 claims abstract description 40
- 238000003756 stirring Methods 0.000 claims abstract description 40
- 229920000428 triblock copolymer Polymers 0.000 claims abstract description 40
- 239000011347 resin Substances 0.000 claims abstract description 28
- 229920005989 resin Polymers 0.000 claims abstract description 28
- 239000000080 wetting agent Substances 0.000 claims abstract description 24
- 239000003242 anti bacterial agent Substances 0.000 claims abstract description 23
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 22
- 238000002156 mixing Methods 0.000 claims abstract description 19
- 239000000203 mixture Substances 0.000 claims abstract description 15
- 239000002994 raw material Substances 0.000 claims abstract description 13
- 229920001400 block copolymer Polymers 0.000 claims description 34
- 239000000178 monomer Substances 0.000 claims description 32
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 22
- -1 acrylic ester Chemical class 0.000 claims description 21
- RSWGJHLUYNHPMX-UHFFFAOYSA-N Abietic-Saeure Natural products C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C(O)=O RSWGJHLUYNHPMX-UHFFFAOYSA-N 0.000 claims description 17
- KHPCPRHQVVSZAH-HUOMCSJISA-N Rosin Natural products O(C/C=C/c1ccccc1)[C@H]1[C@H](O)[C@@H](O)[C@@H](O)[C@@H](CO)O1 KHPCPRHQVVSZAH-HUOMCSJISA-N 0.000 claims description 17
- 239000003153 chemical reaction reagent Substances 0.000 claims description 17
- KHPCPRHQVVSZAH-UHFFFAOYSA-N trans-cinnamyl beta-D-glucopyranoside Natural products OC1C(O)C(O)C(CO)OC1OCC=CC1=CC=CC=C1 KHPCPRHQVVSZAH-UHFFFAOYSA-N 0.000 claims description 17
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 14
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims description 9
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 claims description 8
- DXPPIEDUBFUSEZ-UHFFFAOYSA-N 6-methylheptyl prop-2-enoate Chemical compound CC(C)CCCCCOC(=O)C=C DXPPIEDUBFUSEZ-UHFFFAOYSA-N 0.000 claims description 8
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 claims description 8
- 229920001577 copolymer Polymers 0.000 claims description 7
- 238000010438 heat treatment Methods 0.000 claims description 7
- 229910052757 nitrogen Inorganic materials 0.000 claims description 7
- 238000012546 transfer Methods 0.000 claims description 7
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 6
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 6
- 238000006243 chemical reaction Methods 0.000 claims description 6
- 238000001816 cooling Methods 0.000 claims description 6
- 229940088644 n,n-dimethylacrylamide Drugs 0.000 claims description 6
- YLGYACDQVQQZSW-UHFFFAOYSA-N n,n-dimethylprop-2-enamide Chemical compound CN(C)C(=O)C=C YLGYACDQVQQZSW-UHFFFAOYSA-N 0.000 claims description 6
- 238000013467 fragmentation Methods 0.000 claims description 5
- 238000006062 fragmentation reaction Methods 0.000 claims description 5
- 239000003999 initiator Substances 0.000 claims description 5
- 229920002521 macromolecule Polymers 0.000 claims description 5
- 230000002441 reversible effect Effects 0.000 claims description 5
- 238000000034 method Methods 0.000 claims description 4
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 3
- 239000003945 anionic surfactant Substances 0.000 claims description 3
- 238000010556 emulsion polymerization method Methods 0.000 claims description 3
- 239000002736 nonionic surfactant Substances 0.000 claims description 3
- 239000007787 solid Substances 0.000 claims description 3
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 claims description 2
- 150000002148 esters Chemical class 0.000 claims description 2
- 229920005862 polyol Polymers 0.000 claims description 2
- 239000003002 pH adjusting agent Substances 0.000 claims 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims 1
- 239000002904 solvent Substances 0.000 abstract description 7
- 239000002390 adhesive tape Substances 0.000 abstract description 6
- 230000001681 protective effect Effects 0.000 abstract description 4
- 238000009826 distribution Methods 0.000 abstract description 3
- 238000004519 manufacturing process Methods 0.000 abstract description 2
- 230000007613 environmental effect Effects 0.000 abstract 1
- 239000000758 substrate Substances 0.000 description 15
- 239000006185 dispersion Substances 0.000 description 10
- 239000000853 adhesive Substances 0.000 description 8
- 230000001070 adhesive effect Effects 0.000 description 8
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 7
- 238000007792 addition Methods 0.000 description 7
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 6
- 238000009736 wetting Methods 0.000 description 6
- 238000004132 cross linking Methods 0.000 description 5
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- 238000001914 filtration Methods 0.000 description 4
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 239000004816 latex Substances 0.000 description 3
- 229920000126 latex Polymers 0.000 description 3
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 2
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 2
- 229910000831 Steel Inorganic materials 0.000 description 2
- 230000032683 aging Effects 0.000 description 2
- 235000011114 ammonium hydroxide Nutrition 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 235000014113 dietary fatty acids Nutrition 0.000 description 2
- 125000003700 epoxy group Chemical group 0.000 description 2
- 229930195729 fatty acid Natural products 0.000 description 2
- 239000000194 fatty acid Substances 0.000 description 2
- 238000011031 large-scale manufacturing process Methods 0.000 description 2
- 230000014759 maintenance of location Effects 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- JPMIIZHYYWMHDT-UHFFFAOYSA-N octhilinone Chemical group CCCCCCCCN1SC=CC1=O JPMIIZHYYWMHDT-UHFFFAOYSA-N 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- 239000010959 steel Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 229920002818 (Hydroxyethyl)methacrylate Polymers 0.000 description 1
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- GNSFRPWPOGYVLO-UHFFFAOYSA-N 3-hydroxypropyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCCO GNSFRPWPOGYVLO-UHFFFAOYSA-N 0.000 description 1
- QZPSOSOOLFHYRR-UHFFFAOYSA-N 3-hydroxypropyl prop-2-enoate Chemical compound OCCCOC(=O)C=C QZPSOSOOLFHYRR-UHFFFAOYSA-N 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 1
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- WHNWPMSKXPGLAX-UHFFFAOYSA-N N-Vinyl-2-pyrrolidone Chemical compound C=CN1CCCC1=O WHNWPMSKXPGLAX-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- 239000002313 adhesive film Substances 0.000 description 1
- 150000008051 alkyl sulfates Chemical class 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 125000002843 carboxylic acid group Chemical group 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 239000003431 cross linking reagent Substances 0.000 description 1
- 238000007405 data analysis Methods 0.000 description 1
- 239000002612 dispersion medium Substances 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- 150000002191 fatty alcohols Chemical class 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 238000005191 phase separation Methods 0.000 description 1
- 235000021317 phosphate Nutrition 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920002503 polyoxyethylene-polyoxypropylene Polymers 0.000 description 1
- 239000012429 reaction media Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000000344 soap Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 150000003871 sulfonates Chemical class 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 239000012855 volatile organic compound Substances 0.000 description 1
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Classifications
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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
- C09J153/00—Adhesives based on block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Adhesives based on derivatives of such 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
- C08F293/00—Macromolecular compounds obtained by polymerisation on to a macromolecule having groups capable of inducing the formation of new polymer chains bound exclusively at one or both ends of the starting macromolecule
- C08F293/005—Macromolecular compounds obtained by polymerisation on to a macromolecule having groups capable of inducing the formation of new polymer chains bound exclusively at one or both ends of the starting macromolecule using free radical "living" or "controlled" polymerisation, e.g. using a complexing agent
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J7/00—Adhesives in the form of films or foils
- C09J7/20—Adhesives in the form of films or foils characterised by their carriers
- C09J7/22—Plastics; Metallised plastics
- C09J7/25—Plastics; Metallised plastics based on macromolecular compounds obtained otherwise than by reactions involving only carbon-to-carbon unsaturated bonds
- C09J7/255—Polyesters
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- 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
- C09J7/387—Block-copolymers
-
- 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
- C08F2438/00—Living radical polymerisation
- C08F2438/03—Use of a di- or tri-thiocarbonylthio compound, e.g. di- or tri-thioester, di- or tri-thiocarbamate, or a xanthate as chain transfer agent, e.g . Reversible Addition Fragmentation chain Transfer [RAFT] or Macromolecular Design via Interchange of Xanthates [MADIX]
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J2301/00—Additional features of adhesives in the form of films or foils
- C09J2301/30—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier
- C09J2301/302—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier the adhesive being pressure-sensitive, i.e. tacky at temperatures inferior to 30°C
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J2467/00—Presence of polyester
- C09J2467/006—Presence of polyester in the substrate
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Adhesives Or Adhesive Processes (AREA)
Abstract
The invention discloses a high-temperature-resistant residue-free aqueous pressure-sensitive adhesive and a preparation method thereof, wherein the preparation method comprises the following steps: the water-based pressure-sensitive adhesive is prepared by taking diblock copolymer emulsion as a raw material, or triblock copolymer emulsion as a raw material, or taking a uniform mixture of at least two of diblock copolymer emulsion, triblock copolymer emulsion and tackifying resin as a raw material, adding a pH regulator to adjust the pH value of a system to 6-10, dropwise adding a wetting agent and an antibacterial agent after the pH value is stable, and stirring and mixing. The prepared water-based pressure-sensitive adhesive has the temperature resistance of 120-150 ℃, high cohesive force, high adhesion property, water resistance, wide peeling force distribution range and no residue, and in addition, the pressure-sensitive adhesive has the advantages of simple preparation method, convenient mass production, environmental protection compared with solvent-based pressure-sensitive adhesive, and wide application in the fields of medium-low adhesion protective film adhesive tapes, medium-high adhesion protective adhesive tapes and industrial adhesive tapes.
Description
Technical Field
The invention relates to the technical field of adhesives, in particular to a high-temperature-resistant residue-free aqueous pressure-sensitive adhesive and a preparation method thereof.
Background
Pressure sensitive adhesives refer to adhesives that bond to an adherend under external pressure. The peel strength of a pressure-sensitive adhesive is mainly determined by the adhesive force of its constituent components and the adhesive force of the colloid to the adhesive surface, and the holding power is mainly determined by the cohesive force, which are mutually affected.
The pressure-sensitive adhesive may be classified into a solvent-type pressure-sensitive adhesive and an aqueous pressure-sensitive adhesive according to the dispersion medium. The solvent pressure-sensitive adhesive adopts toluene, ethyl acetate and other organic solvents as reaction media, has the advantages of excellent pressure-sensitive property and cohesiveness, aging resistance, light resistance, water resistance, oil resistance, peelability and the like, and the water-based pressure-sensitive adhesive adopts water as the solvent, has the advantages of low price, high production rate, no pollution and the like, but has low cohesiveness.
Patent CN105482748A discloses a high temperature resistant solvent type acrylate pressure-sensitive adhesive, a preparation method and a pressure-sensitive adhesive tape, and the cohesive strength and the temperature resistance of the solvent type acrylate pressure-sensitive adhesive are improved through researches on polymerization technology and monomer composition, but the solvent type pressure-sensitive adhesive is gradually replaced by a water-based pressure-sensitive adhesive due to the fact that the solvent type pressure-sensitive adhesive contains a large amount of volatile organic compounds, pollutes the environment and has high cost.
Patent CN111187585a discloses a high temperature resistant aqueous acrylate pressure sensitive adhesive and a preparation method thereof, the method is to synthesize two kinds of acrylate emulsion respectively, one kind of acrylate emulsion contains carboxylic acid group and the other kind of acrylate emulsion contains epoxy group, then the two kinds of acrylate emulsion are blended according to a certain proportion, the carboxyl group and the epoxy group in the emulsion are crosslinked under the condition of high temperature, and the crosslinking all occur between latex particles, thus bringing high crosslinking degree for the adhesive film, and simultaneously reducing less stripping force, however, the curing is performed by using a crosslinking agent, the process is difficult to control, and the required crosslinking density and crosslinking condition are harsh.
Therefore, there is a need to develop a pressure-sensitive adhesive preparation method which is easy to operate, low in cost and capable of achieving high temperature resistance and residue-free excellent performance.
Disclosure of Invention
The invention provides a high-temperature-resistant residue-free aqueous pressure-sensitive adhesive, which has good high-temperature resistance, high cohesive force, high adhesion retention property, water resistance property, wide stripping force distribution range and no residue, and the pressure-sensitive adhesive is simple in preparation method, convenient for large-scale production and more environment-friendly than solvent-type pressure-sensitive adhesive.
The technical scheme adopted is as follows:
the invention provides a high-temperature-resistant residue-free aqueous pressure-sensitive adhesive, which comprises the following components in parts by mass:
0 to 100 parts of diblock copolymer emulsion, 0 to 100 parts of triblock copolymer emulsion, 0.5 to 2 parts of wetting agent, 0.5 to 2 parts of pH regulator and 0.05 to 1 part of antibacterial agent, wherein the mass parts of the diblock copolymer emulsion and the triblock copolymer emulsion are not 0 at the same time;
or, the mass portion includes:
60 to 95 parts of diblock copolymer emulsion or triblock copolymer emulsion, 5 to 40 parts of tackifying resin, 0.5 to 2 parts of wetting agent, 0.5 to 2 parts of pH regulator and 0.05 to 1 part of antibacterial agent;
or, the mass portion includes:
10 to 85 parts of diblock copolymer emulsion, 10 to 85 parts of triblock copolymer emulsion, 5 to 30 parts of tackifying resin, 0.5 to 2 parts of wetting agent, 0.5 to 2 parts of pH regulator and 0.05 to 1 part of antibacterial agent;
the diblock copolymer emulsion and the triblock copolymer emulsion are prepared by a RAFT active emulsion polymerization method, wherein the diblock copolymer is an AB type acrylic ester block copolymer, and the triblock copolymer is an ABA type acrylic ester block copolymer;
in the two-block copolymer and the three-block copolymer, A is a hard block of the block copolymer and consists of at least one monomer of styrene, vinyl acetate, methyl methacrylate and acrylonitrile; b is a soft block copolymer and is a copolymer taking butyl acrylate and/or isooctyl acrylate as main monomers;
the tackifying resin is aqueous rosin tackifying resin.
The aqueous pressure-sensitive adhesive provided by the invention takes the acrylic ester diblock copolymer emulsion or acrylic ester triblock copolymer emulsion with a nano-scale microphase separation structure prepared by a RAFT active emulsion polymerization method as a raw material, and the acrylic ester diblock copolymer or acrylic ester triblock copolymer has high cohesive strength and double glass transition temperature, so that the prepared aqueous pressure-sensitive adhesive has excellent performances of high temperature resistance and no residue, and in addition, the addition of tackifying resin can improve the initial adhesion and peeling performance of the aqueous pressure-sensitive adhesive.
In the two-block copolymer and the three-block copolymer, the weight ratio of A is 5-30 percent; the weight ratio of B is 70-95%.
In order to achieve both mechanical properties and pressure-sensitive properties, it is further preferred that the weight ratio of A in the two-block copolymer and the three-block copolymer is 10% -25%; the weight ratio of the B is 75-90%.
And B is a copolymer of the main monomer, the auxiliary monomer and the functional monomer, and the addition of the auxiliary monomer and the functional monomer can improve the crosslinking property, stability and the like of emulsion, so that the prepared aqueous pressure-sensitive adhesive has initial adhesion and stripping performance, mechanical strength, substrate adsorption performance and the like.
Preferably, the auxiliary monomer comprises at least one of ethyl acrylate, methyl acrylate, glycidyl methacrylate, vinyl pyrrolidone and N, N-dimethylacrylamide.
The functional monomer comprises at least one of hydroxyethyl acrylate, hydroxypropyl acrylate, hydroxyethyl methacrylate, hydroxypropyl methacrylate, methacrylic acid or acrylic acid.
Preferably, in the B, the weight of the main monomer accounts for 60-100%, the weight of the auxiliary monomer accounts for 0-40%, and the weight of the functional monomer accounts for 0-15%.
Further preferably, in the step B, the weight of the main monomer accounts for 80-100%, the weight of the auxiliary monomer accounts for 0-20%, and the weight of the functional monomer accounts for 0-10%.
Further preferably, A is styrene or a copolymer of styrene and methyl methacrylate; and B is a copolymer of butyl acrylate, isooctyl acrylate, N-dimethylacrylamide and hydroxyethyl acrylate.
Preferably, the weight average relative molecular weight of the two-block copolymer and the three-block copolymer is 5-50 ten thousand.
It is further preferred that the weight average relative molecular weight of the two-block copolymer and the three-block copolymer is 15 to 30 ten thousand in order to balance the relationship between the mechanical properties of the latex film and the stability of the latex particles.
The preparation method of the diblock copolymer emulsion comprises the following steps:
mixing and stirring 0.25-2.5 parts by weight of amphiphilic macromolecule reversible addition fragmentation chain transfer reagent and 50-117 parts by weight of water, adding 35-47.5 parts by weight of mixed monomer of block copolymer soft segment B, mixing and stirring, heating the reaction temperature to 60-90 ℃, introducing nitrogen into a reactor, adding 0.0054-0.054 part by weight of water-soluble initiator, reacting for 1-5 h, adding 2.5-15 parts by weight of mixed monomer of block copolymer hard segment A, continuing to react for 2-8 h, and cooling to normal temperature to obtain the diblock copolymer emulsion.
The preparation method of the triblock copolymer emulsion comprises the following steps:
mixing and stirring 0.22-2.2 parts by weight of amphiphilic macromolecule reversible addition fragmentation chain transfer reagent and 44-103 parts by weight of water, adding 1.1-6.6 parts by weight of mixed monomer of block copolymer hard segment A, mixing and stirring, heating the reaction temperature to 60-90 ℃, introducing nitrogen into a reactor, adding 0.0048-0.048 part by weight of water-soluble initiator, reacting for 1-4 h, adding 30.8-41.8 parts by weight of mixed monomer of block copolymer soft segment B, continuing to react for 2-8 h, adding 1.1-6.6 parts by weight of mixed monomer of block copolymer hard segment A again, continuing to react for 1-4 h, and cooling to normal temperature to obtain the triblock copolymer emulsion.
The amphiphilic macromolecule reversible addition fragmentation chain transfer reagent (DR reagent) is a chain transfer reagent published in CN 101591405A.
The water-soluble initiator comprises potassium persulfate and the like.
Preferably, the wetting agent comprises an anionic surfactant and/or a nonionic surfactant.
The anionic surfactants include, but are not limited to, alkyl sulfates, sulfonates, fatty acid or fatty acid ester sulfates, carboxylic soaps, phosphates, and the like.
The nonionic surfactant comprises polyoxyethylene alkylphenol ether, polyoxyethylene fatty alcohol ether, polyoxyethylene polyoxypropylene segmented copolymer and the like.
Preferably, the aqueous rosin tackifying resin comprises at least one of rosin ester, rosin polyol ester, rosin glycerol/pentaerythritol ester and polymerized rosin.
Preferably, the pH regulator comprises at least one of sodium hydroxide aqueous solution, potassium hydroxide aqueous solution, ammonia water and triethanolamine, and the solid content of the pH regulator is 15-30%. To ensure the stability of the system, it is necessary to control the pH of the system to between 6 and 10 by adding a pH adjustor.
In order to ensure that the high-temperature-resistant residue-free aqueous pressure-sensitive adhesive has good emulsion mildew-proof effect, the antibacterial agent is preferably 2 octyl-4 isothiazolin-3-ketone solution.
The invention also provides a preparation method of the high-temperature-resistant residue-free aqueous pressure-sensitive adhesive, which comprises the following steps:
the water-based pressure-sensitive adhesive is prepared by taking diblock copolymer emulsion as a raw material, or triblock copolymer emulsion as a raw material, or taking a uniform mixture of at least two of diblock copolymer emulsion, triblock copolymer emulsion and tackifying resin as a raw material, adding a pH regulator to adjust the pH value of a system to 6-10, dropwise adding a wetting agent and an antibacterial agent after the pH value is stable, and stirring and mixing.
Compared with the prior art, the invention has the beneficial effects that:
(1) The aqueous pressure-sensitive adhesive takes the acrylic ester diblock copolymer or acrylic ester triblock copolymer as a raw material, and the block copolymer has a micro-phase separation structure with nanometer scale, can provide high elasticity and fatigue resistance for the pressure-sensitive adhesive, and has good high temperature resistance, high cohesion, high adhesion retention property and water resistance, and wide stripping force distribution range and no residue.
(2) The acrylic ester diblock copolymer or acrylic ester triblock copolymer adopted by the invention has excellent weather resistance, and can ensure long service life and weather resistance of the aqueous pressure-sensitive adhesive.
(3) The preparation method of the aqueous pressure-sensitive adhesive is simple, does not need large-scale equipment, has lower cost, is more environment-friendly than oily pressure-sensitive adhesives, and is convenient for large-scale production.
Drawings
Fig. 1 is a hot-peeled and cold-peeled picture of the high temperature resistant residue-free aqueous pressure sensitive adhesive prepared in example 9, wherein a is a hot-peeled picture and b is a cold-peeled picture.
Detailed Description
The invention is further illustrated by the following examples. It is to be understood that these examples are for illustration of the invention only and are not intended to limit the scope of the invention.
In the following examples, the performance test method of the aqueous pressure-sensitive adhesive comprises the following steps:
(1) The annular initial tack is tested according to GB/T31125-2014, the hold tack is tested according to GB/T4851-2014, and the peel strength is tested according to GB/T2792-2014.
(2) The high temperature resistance and no residue characteristic test method comprises the following steps: and (3) attaching the pressure-sensitive adhesive tape prepared by the high-temperature-resistant residue-free aqueous pressure-sensitive adhesive to a standard metal steel plate, transferring to an oven at 120-150 ℃ for 2-6 h, taking out to test cold and hot peeling strength (hot peeling, namely 180-degree peeling strength in 1min after taking out from the oven; cold peeling, namely standing for not less than 30min, and measuring peeling strength), and observing the residue adhesive condition on the surface of the standard steel plate.
(3) The high-temperature and high-humidity aging resistance testing method comprises the following steps: in an environment with 85 ℃ and 85% humidity, the adhesive holding performance is tested, the weight is 1kg, and the final dropping time is tested.
In the following examples, rosin pentaerythritol ester is used as the tackifying resin, and the antibacterial agent is
M210 (2 octyl-4 isothiazolin-3-ketone solution), wetting agent is Dynol 604 (alkyne diol) which is a gas chemistry in the United states, amphiphilic macromolecule reversible addition fragmentation chain transfer reagent (DR reagent) is a chain transfer reagent published in CN101591405A, monomer source drug groups in the block copolymer are synthesized, water-soluble initiator adopts potassium persulfate, and pH regulator adopts ammonia water with solid content of 20%.
The parameters of the monomers, other raw materials, etc. used to prepare the BC-1 emulsion of the diblock copolymer are shown in Table 1 below.
TABLE 1 preparation of the starting materials for the BC-1 emulsion of the diblock copolymer
Adding 0.42 weight part of DR reagent and 61 weight parts of water into a reactor, mixing and stirring for 30min until the DR reagent and the 61 weight parts of water are completely dissolved, adding 17.4 weight parts of butyl acrylate, 26.1 weight parts of isooctyl acrylate, 0.45 weight parts of N, N-dimethylacrylamide and 1 weight part of hydroxyethyl acrylate, heating to 70 ℃, introducing nitrogen, adding 0.012 weight part of potassium persulfate, reacting for 5h, adding 4 weight parts of styrene and 1 weight part of methyl methacrylate into the reactor for reacting for 2h after the reaction is finished, cooling, and filtering to obtain the diblock copolymer BC-1 emulsion.
The parameters of the monomers, other raw materials, etc. used to prepare the triblock copolymer BC-2 emulsion are shown in Table 2 below.
TABLE 2 preparation of triblock copolymer BC-2 emulsion
Adding 0.52 weight part of DR reagent and 61 weight parts of water into a reactor, mixing and stirring for 30min until the DR reagent and the 61 weight parts of water are completely dissolved, adding 4 weight parts of styrene and 1 weight part of methyl methacrylate, heating to 80 ℃, introducing nitrogen, adding 0.015 weight part of potassium persulfate, reacting for 2h, and then adding 27.1 weight parts of butyl acrylate, 11.6 weight parts of isooctyl acrylate, 0.40 weight parts of N, N-dimethylacrylamide and 0.88 weight parts of hydroxyethyl acrylate, and reacting for 5h. And after the reaction is finished, adding 4 parts by weight of styrene and 1 part by weight of methyl methacrylate into a reactor for reacting for 2 hours, cooling, and filtering to obtain the triblock copolymer BC-2 emulsion.
The parameters of the monomers, other materials, etc. used to prepare the BC-3 emulsion of the diblock copolymer are shown in Table 3 below.
TABLE 3 preparation of the starting materials for the BC-3 emulsions of the diblock copolymers
Adding 0.50 weight part of DR reagent and 61 weight parts of water into a reactor, mixing and stirring for 30min until the DR reagent and the 61 weight parts of water are completely dissolved, adding 16.5 weight parts of butyl acrylate, 24.7 weight parts of isooctyl acrylate, 0.43 weight part of N, N-dimethylacrylamide and 1 weight part of hydroxyethyl acrylate, heating to 70 ℃, introducing nitrogen, adding 0.014 weight part of potassium persulfate, reacting for 5h, adding 6 weight parts of styrene and 1.5 weight parts of methyl methacrylate into the reactor for reacting for 2h after the reaction is finished, cooling, and filtering to obtain the diblock copolymer BC-3 emulsion.
The parameters of the monomers, other materials, etc. used to prepare the triblock copolymer BC-4 emulsion are shown in Table 4 below.
TABLE 4 preparation of triblock copolymer BC-4 emulsion
Adding 0.46 weight part of DR reagent and 54 weight parts of water into a reactor, mixing and stirring for 30min until the DR reagent and the 54 weight parts of water are completely dissolved, adding 2.64 weight parts of styrene and 0.66 weight part of methyl methacrylate, heating to 80 ℃, introducing nitrogen, adding 0.013 weight part of potassium persulfate, reacting for 2h, and then adding 25.3 weight parts of butyl acrylate, 10.9 weight parts of isooctyl acrylate, 0.37 weight parts of N, N-dimethylacrylamide and 0.82 weight part of hydroxyethyl acrylate, and reacting for 5h. After the completion, 2.64 parts by weight of styrene and 0.66 parts by weight of methyl methacrylate are put into a reactor to react for 2 hours, the temperature is reduced, and the triblock copolymer BC-4 emulsion is obtained by filtration.
Example 1
At room temperature, 100 parts by weight of the diblock copolymer BC-1 emulsion is uniformly stirred for 20min, a pH regulator is added to regulate the pH value of the system to 6, the mixture is stirred until the pH value is stable, then a wetting agent and an antibacterial agent are added dropwise, and after stirring for 15min, the pressure-sensitive adhesive is ensured to be completely wetted on the PET substrate.
Example 2
At room temperature, 100 parts by weight of triblock copolymer BC-2 emulsion is uniformly stirred for 20min, a pH regulator is added to regulate the pH value of the system to 6, the mixture is stirred until the pH value is stable, then a wetting agent and an antibacterial agent are added dropwise, and after stirring for 15min, the pressure-sensitive adhesive is ensured to be completely wetted on a PET substrate.
Example 3
At room temperature, 50 parts by weight of the diblock copolymer BC-1 emulsion and 50 parts by weight of the triblock copolymer BC-2 emulsion are stirred and mixed uniformly for 20min, a pH regulator is added to adjust the pH value of the system to 6, stirring is carried out until the pH value is stable, then a wetting agent and an antibacterial agent are added dropwise, and after stirring is carried out for 15min, the pressure-sensitive adhesive can be completely wetted on the PET substrate.
Example 4
At room temperature, 60 parts by weight of the diblock copolymer BC-1 emulsion is stirred for 15min, 40 parts by weight of tackifying resin is added, mixing and stirring are carried out for 20min, complete and uniform dispersion is ensured, a pH regulator is continuously added to regulate the pH value of a system to 8, stirring is carried out until the pH value is stable, then a wetting agent and an antibacterial agent are added dropwise, and after stirring for 18min, complete wetting of the pressure-sensitive adhesive on the PET substrate is ensured.
Example 5
At room temperature, 95 parts by weight of the diblock copolymer BC-1 emulsion is stirred for 20min, then 5 parts by weight of tackifying resin is added, mixing and stirring are carried out for 10min, complete and uniform dispersion is ensured, a pH regulator is continuously added to adjust the pH value of a system to 8, stirring is carried out until the pH value is stable, then a wetting agent and an antibacterial agent are added dropwise, and stirring is carried out for 18min, so that the pressure-sensitive adhesive can be completely wetted on a PET substrate.
Example 6
At room temperature, 60 parts by weight of triblock copolymer BC-2 emulsion is stirred for 15min, 40 parts by weight of tackifying resin is added, mixing and stirring are carried out for 20min, complete and uniform dispersion is ensured, a pH regulator is continuously added to adjust the pH value of a system to 8, stirring is carried out until the pH value is stable, then a wetting agent and an antibacterial agent are added dropwise, and after stirring for 18min, complete wetting of the pressure-sensitive adhesive on the PET substrate is ensured.
Example 7
At room temperature, 95 parts by weight of triblock copolymer BC-2 emulsion is stirred for 20min, then 5 parts by weight of tackifying resin is added, mixing and stirring are carried out for 10min, complete and uniform dispersion is ensured, a pH regulator is continuously added to regulate the pH value of a system to be 6-10, stirring is carried out until the pH value is stable, then a wetting agent and an antibacterial agent are added dropwise, and after stirring for 18min, complete wetting of the pressure-sensitive adhesive on the PET substrate is ensured.
Example 8
At room temperature, 57 parts by weight of the diblock copolymer BC-1 emulsion and 38 parts by weight of the triblock copolymer BC-2 emulsion are stirred and mixed uniformly for 20min, then 5 parts by weight of tackifying resin is added, the mixture is stirred for 15min to ensure complete uniform dispersion, a pH regulator is continuously added to regulate the pH value of a system to 10, the mixture is stirred until the pH value is stable, then a wetting agent and an antibacterial agent are added dropwise, and the pressure-sensitive adhesive is ensured to be completely wetted on a PET substrate after stirring for 20 min.
Example 9
At room temperature, 50 parts by weight of the diblock copolymer BC-1 emulsion and 30 parts by weight of the triblock copolymer BC-2 emulsion are stirred and mixed uniformly for 20min, then 20 parts by weight of tackifying resin is added, the mixture is stirred for 15min to ensure complete uniform dispersion, a pH regulator is continuously added to regulate the pH value of a system to 10, the mixture is stirred until the pH value is stable, then a wetting agent and an antibacterial agent are added dropwise, and the pressure-sensitive adhesive can be completely wetted on a PET substrate after stirring for 20 min.
The hot stripping and cold stripping pictures of the high-temperature-resistant residue-free aqueous pressure-sensitive adhesive prepared by the implementation are shown in figure 1, wherein A is a hot stripping picture, B is a cold stripping picture, and the aqueous pressure-sensitive adhesive has good stripping performance and no residue.
Example 10
At room temperature, 50 parts by weight of the diblock copolymer BC-1 emulsion and 20 parts by weight of the triblock copolymer BC-2 emulsion are stirred for 20min, then 30 parts by weight of tackifying resin is added, the mixture is stirred for 15min to ensure complete and uniform dispersion, a pH regulator is continuously added to regulate the pH value of the system to 10, the mixture is stirred until the pH value is stable, then a wetting agent and an antibacterial agent are added dropwise, and the mixture is stirred for 20min to ensure complete wetting of the pressure-sensitive adhesive on the PET substrate.
Example 11
At room temperature, 50 parts by weight of the diblock copolymer BC-3 emulsion and 30 parts by weight of the triblock copolymer BC-4 emulsion are stirred for 20min, then 20 parts by weight of tackifying resin is added, the mixture is stirred for 15min to ensure complete and uniform dispersion, the pH regulator is continuously added to regulate the pH value of the system to 10, the mixture is stirred until the pH value is stable, then the wetting agent and the antibacterial agent are added dropwise, and the pressure-sensitive adhesive can be completely wetted on the PET substrate after stirring for 20 min.
Example 12
At room temperature, 50 parts by weight of the diblock copolymer BC-3 emulsion and 50 parts by weight of the triblock copolymer BC-4 emulsion are stirred and mixed uniformly for 20min, a pH regulator is added to adjust the pH value of the system to 6, stirring is carried out until the pH value is stable, then a wetting agent and an antibacterial agent are added dropwise, and after stirring is carried out for 15min, the pressure-sensitive adhesive can be completely wetted on the PET substrate.
Example 13
At room temperature, 60 parts by weight of the diblock copolymer BC-3 emulsion is stirred for 20min, 40 parts by weight of tackifying resin is added, mixing and stirring are carried out for 10min, complete and uniform dispersion is ensured, a pH regulator is continuously added to adjust the pH value of a system to 8, stirring is carried out until the pH value is stable, then a wetting agent and an antibacterial agent are added dropwise, and after stirring for 18min, complete wetting of the pressure-sensitive adhesive on the PET substrate is ensured.
Example 14
At room temperature, 60 parts by weight of triblock copolymer BC-4 emulsion is stirred for 20min, 40 parts by weight of tackifying resin is added, mixing and stirring are carried out for 10min, complete and uniform dispersion is ensured, a pH regulator is continuously added to adjust the pH value of a system to 8, stirring is carried out until the pH value is stable, then a wetting agent and an antibacterial agent are added dropwise, and after stirring for 18min, complete wetting of the pressure-sensitive adhesive on the PET substrate is ensured.
Sample analysis
The performance indexes of the high temperature resistant residue free aqueous pressure sensitive adhesives prepared in examples 1 to 10 are shown in Table 5.
TABLE 5 Performance index of pressure sensitive adhesive
As can be seen from the data analysis in the table, the following results were obtained by adjusting the proportions of the diblock copolymer emulsion, triblock copolymer emulsion, and aqueous rosin-based tackifying resin:
the data of examples 1 to 3 show that when the mass parts of the two-block copolymer emulsion and the three-block copolymer emulsion are 0 to 100 and 0 to 100, the initial adhesion peeling is small, the temperature resistance is 120 to 150 ℃ within 6N, the room temperature adhesion is more than 1000h, the 80 ℃ adhesion is more than 500h, the 85 ℃ RH adhesion is more than 200h, and the cold and hot peeling is free.
The data of examples 4 to 5 show that when the mass part of the two-block copolymer emulsion is 60 to 95 and the mass part of the rosin tackifying resin is 5 to 40, the initial adhesion range is 7.0 to 9.0N, the peeling range is 5.0 to 7.0N/25mm, the temperature resistance temperature is 120 to 130 ℃, the room temperature adhesion is more than 200 hours, the 80 ℃ adhesion is more than 100 hours, the 85 ℃ RH adhesion is more than 24 hours, and the cold and hot peeling is free.
The data of examples 6 to 7 show that when the mass portion of the triblock copolymer emulsion is 60 to 95 and the mass portion of the rosin tackifying resin is 5 to 40, the initial adhesion range is 5.0 to 8.0N, the peeling range is 7.0 to 10.0N/25mm, the temperature resistance temperature is 120 to 130 ℃, the room temperature adhesion is greater than 400 hours, the 80 ℃ adhesion is greater than 200 hours, the 85 ℃ RH adhesion is greater than 24 hours, and the cold and hot peeling is free of residues.
The data of examples 8 to 10 show that when the mass parts of the two-block copolymer emulsion are 10 to 85, the mass parts of the three-block copolymer emulsion are 10 to 85, and the mass parts of the rosin tackifying resin are 5 to 30, the initial adhesion range is 8.0 to 15.0N, the peeling range is 8.0 to 15.0N/25mm, the temperature resistance temperature is 120 to 130 ℃, the room temperature adhesion is more than 500 hours, the 80 ℃ adhesion is more than 200 hours, the 85 ℃ RH adhesion is more than 24 hours, and the cold and hot peeling is free from residues.
The aqueous pressure-sensitive adhesive prepared by the formulas of examples 1-3 has small initial adhesion and peeling, and the temperature resistance range is 120-150 ℃ within 6N; the adhesive is suitable for the field of medium-low viscosity protective adhesive tapes; the aqueous pressure-sensitive adhesive prepared by the formulas of examples 4-7 has initial adhesion and peeling of 6-10N and temperature resistance of 120-130 ℃; can be applied to the field of medium-high viscosity protective adhesive tapes; the aqueous pressure-sensitive adhesive prepared by the formulas of examples 8-10 can reach 10-15N in initial adhesion, has the temperature resistance of 120 ℃, and can be applied to industrial adhesive tapes.
While the foregoing embodiments have been described in detail in connection with the embodiments of the invention, it should be understood that the foregoing embodiments are merely illustrative of the invention and are not intended to limit the invention, and any modifications, additions, substitutions and the like made within the principles of the invention are intended to be included within the scope of the invention.
Claims (6)
1. The high-temperature-resistant residue-free aqueous pressure-sensitive adhesive is characterized by comprising the following components in parts by weight: 10 to 85 parts of diblock copolymer emulsion, 10 to 85 parts of triblock copolymer emulsion, 5 to 30 parts of tackifying resin, 0.5 to 2 parts of wetting agent, 0.5 to 2 parts of pH regulator and 0.05 to 1 part of antibacterial agent;
the diblock copolymer emulsion and the triblock copolymer emulsion are prepared by a RAFT active emulsion polymerization method, wherein the diblock copolymer is an AB type acrylic ester block copolymer, and the triblock copolymer is an ABA type acrylic ester block copolymer; in the two-block copolymer and the three-block copolymer, the weight ratio of A is 10-25%; the weight ratio of the B is 75-90%;
in the two-block copolymer and the three-block copolymer, A is styrene or a copolymer of styrene and methyl methacrylate; b is a copolymer of butyl acrylate, isooctyl acrylate, N-dimethylacrylamide and hydroxyethyl acrylate, and the main monomers are butyl acrylate and isooctyl acrylate; in the B, the weight ratio of the main monomer is 60-100%, the weight ratio of the auxiliary monomer N, N-dimethylacrylamide is more than 0% and less than 40%, and the weight ratio of the functional monomer hydroxyethyl acrylate is more than 0% and less than 15%;
the tackifying resin is aqueous rosin tackifying resin;
the preparation method of the diblock copolymer emulsion comprises the following steps:
mixing and stirring 0.25-2.5 parts by weight of amphiphilic macromolecule reversible addition fragmentation chain transfer reagent and 50-117 parts by weight of water, adding 35-47.5 parts by weight of mixed monomer of block copolymer soft segment B, mixing and stirring, heating the reaction temperature to 60-90 ℃, introducing nitrogen into a reactor, adding 0.0054-0.054 part by weight of water-soluble initiator, reacting for 1-5 h, adding 2.5-15 parts by weight of mixed monomer of block copolymer hard segment A, continuing to react for 2-8 h, and cooling to normal temperature to obtain the diblock copolymer emulsion.
2. The high temperature resistant residue free aqueous pressure sensitive adhesive of claim 1 wherein the weight average relative molecular weight of the two and three block copolymers is from 5 to 50 ten thousand.
3. The high temperature resistant residue free aqueous pressure sensitive adhesive of claim 1 wherein the wetting agent comprises an anionic surfactant and/or a nonionic surfactant.
4. The high temperature resistant residue free aqueous pressure sensitive adhesive of claim 1 wherein said aqueous rosin based tackifying resin comprises at least one of rosin ester, rosin polyol ester, rosin glycerol/pentaerythritol ester, polymerized rosin.
5. The high temperature resistant residue free aqueous pressure sensitive adhesive of claim 1, wherein the pH adjuster comprises at least one of aqueous sodium hydroxide, aqueous potassium hydroxide, aqueous ammonia, and triethanolamine, and the solid content of the pH adjuster is 15% -30%.
6. The method for preparing the high-temperature-resistant residue-free aqueous pressure-sensitive adhesive according to any one of claims 1 to 5, comprising the steps of:
the water-based pressure-sensitive adhesive is prepared by taking diblock copolymer emulsion as a raw material, or triblock copolymer emulsion as a raw material, or taking a uniform mixture of at least two of diblock copolymer emulsion, triblock copolymer emulsion and tackifying resin as a raw material, adding a pH regulator to adjust the pH value of a system to 6-10, dropwise adding a wetting agent and an antibacterial agent after the pH value is stable, and stirring and mixing.
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