CN117467374A - Acrylic pressure-sensitive adhesive, preparation method thereof and pressure-sensitive adhesive product - Google Patents
Acrylic pressure-sensitive adhesive, preparation method thereof and pressure-sensitive adhesive product Download PDFInfo
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- CN117467374A CN117467374A CN202311520810.5A CN202311520810A CN117467374A CN 117467374 A CN117467374 A CN 117467374A CN 202311520810 A CN202311520810 A CN 202311520810A CN 117467374 A CN117467374 A CN 117467374A
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- Prior art keywords
- sensitive adhesive
- pressure
- acrylate
- percent
- solvent
- Prior art date
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- 239000004820 Pressure-sensitive adhesive Substances 0.000 title claims abstract description 114
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 title claims abstract description 21
- 238000002360 preparation method Methods 0.000 title abstract description 11
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims abstract description 67
- 239000005062 Polybutadiene Substances 0.000 claims abstract description 52
- 229920002857 polybutadiene Polymers 0.000 claims abstract description 52
- 239000000178 monomer Substances 0.000 claims abstract description 50
- 239000002904 solvent Substances 0.000 claims abstract description 38
- -1 acrylic ester Chemical class 0.000 claims abstract description 33
- 239000004814 polyurethane Substances 0.000 claims abstract description 30
- 229920002635 polyurethane Polymers 0.000 claims abstract description 30
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 29
- 229920000058 polyacrylate Polymers 0.000 claims abstract description 29
- 239000002994 raw material Substances 0.000 claims abstract description 24
- 229920005862 polyol Polymers 0.000 claims abstract description 23
- 150000003077 polyols Chemical class 0.000 claims abstract description 23
- 229920005989 resin Polymers 0.000 claims abstract description 23
- 239000011347 resin Substances 0.000 claims abstract description 23
- 239000001257 hydrogen Substances 0.000 claims abstract description 14
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 14
- 239000005056 polyisocyanate Substances 0.000 claims abstract description 13
- 229920001228 polyisocyanate Polymers 0.000 claims abstract description 13
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 11
- 239000003112 inhibitor Substances 0.000 claims abstract description 9
- 239000003999 initiator Substances 0.000 claims abstract description 9
- 239000000945 filler Substances 0.000 claims abstract description 8
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims abstract description 4
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 12
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 12
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 claims description 9
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 9
- 238000000034 method Methods 0.000 claims description 9
- 238000002156 mixing Methods 0.000 claims description 9
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 7
- 239000012948 isocyanate Substances 0.000 claims description 7
- 150000002513 isocyanates Chemical class 0.000 claims description 7
- 239000005011 phenolic resin Substances 0.000 claims description 7
- 150000003505 terpenes Chemical class 0.000 claims description 7
- 235000007586 terpenes Nutrition 0.000 claims description 7
- AZQWKYJCGOJGHM-UHFFFAOYSA-N 1,4-benzoquinone Chemical compound O=C1C=CC(=O)C=C1 AZQWKYJCGOJGHM-UHFFFAOYSA-N 0.000 claims description 6
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 claims description 6
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 6
- CERQOIWHTDAKMF-UHFFFAOYSA-N alpha-methacrylic acid Natural products CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 6
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 claims description 5
- 239000005058 Isophorone diisocyanate Substances 0.000 claims description 5
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 claims description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical group O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 4
- 229910021485 fumed silica Inorganic materials 0.000 claims description 4
- DXPPIEDUBFUSEZ-UHFFFAOYSA-N 6-methylheptyl prop-2-enoate Chemical compound CC(C)CCCCCOC(=O)C=C DXPPIEDUBFUSEZ-UHFFFAOYSA-N 0.000 claims description 3
- 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 3
- 239000004342 Benzoyl peroxide Substances 0.000 claims description 3
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 claims description 3
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 claims description 3
- 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 3
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 claims description 3
- 239000002313 adhesive film Substances 0.000 claims description 3
- 125000000217 alkyl group Chemical group 0.000 claims description 3
- 235000019400 benzoyl peroxide Nutrition 0.000 claims description 3
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 claims description 3
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 claims description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 3
- YPHQUSNPXDGUHL-UHFFFAOYSA-N n-methylprop-2-enamide Chemical compound CNC(=O)C=C YPHQUSNPXDGUHL-UHFFFAOYSA-N 0.000 claims description 3
- 239000003208 petroleum Substances 0.000 claims description 3
- 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 3
- 239000000463 material Substances 0.000 abstract description 41
- 230000009286 beneficial effect Effects 0.000 abstract description 9
- 239000004743 Polypropylene Substances 0.000 description 36
- 230000000052 comparative effect Effects 0.000 description 16
- 239000000853 adhesive Substances 0.000 description 14
- 230000001070 adhesive effect Effects 0.000 description 14
- 125000005396 acrylic acid ester group Chemical group 0.000 description 13
- 238000012360 testing method Methods 0.000 description 13
- 238000006243 chemical reaction Methods 0.000 description 11
- 229920001187 thermosetting polymer Polymers 0.000 description 9
- 239000004831 Hot glue Substances 0.000 description 8
- 229920000139 polyethylene terephthalate Polymers 0.000 description 8
- 239000005020 polyethylene terephthalate Substances 0.000 description 8
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 7
- 239000003365 glass fiber Substances 0.000 description 7
- 239000003292 glue Substances 0.000 description 7
- 229920002545 silicone oil Polymers 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 230000000903 blocking effect Effects 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 5
- 229920001568 phenolic resin Polymers 0.000 description 5
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 4
- 229910052782 aluminium Inorganic materials 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- 238000007599 discharging Methods 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 230000002349 favourable effect Effects 0.000 description 4
- 238000010008 shearing Methods 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 3
- 238000009835 boiling Methods 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 238000004132 cross linking Methods 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 239000011094 fiberboard Substances 0.000 description 3
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 3
- 150000002431 hydrogen Chemical class 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 230000018044 dehydration Effects 0.000 description 2
- 238000006297 dehydration reaction Methods 0.000 description 2
- 125000005442 diisocyanate group Chemical group 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000000835 fiber Substances 0.000 description 2
- 230000009477 glass transition Effects 0.000 description 2
- 238000007731 hot pressing Methods 0.000 description 2
- 125000004356 hydroxy functional group Chemical group O* 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 238000004321 preservation Methods 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 150000003254 radicals Chemical class 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 229920001169 thermoplastic Polymers 0.000 description 2
- 239000004416 thermosoftening plastic Substances 0.000 description 2
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 description 2
- 229920002818 (Hydroxyethyl)methacrylate Polymers 0.000 description 1
- OALMZWNBNXQUAL-UHFFFAOYSA-N 2-[(1-amino-2-methyl-1-oxopropan-2-yl)diazenyl]-2-methylpropanamide Chemical compound NC(=O)C(C)(C)N=NC(C)(C)C(N)=O OALMZWNBNXQUAL-UHFFFAOYSA-N 0.000 description 1
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 description 1
- OZAIFHULBGXAKX-VAWYXSNFSA-N AIBN Substances N#CC(C)(C)\N=N\C(C)(C)C#N OZAIFHULBGXAKX-VAWYXSNFSA-N 0.000 description 1
- GAWIXWVDTYZWAW-UHFFFAOYSA-N C[CH]O Chemical group C[CH]O GAWIXWVDTYZWAW-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
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 239000012790 adhesive layer Substances 0.000 description 1
- 239000002390 adhesive tape Substances 0.000 description 1
- 239000003085 diluting agent Substances 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 239000000806 elastomer Substances 0.000 description 1
- 238000010292 electrical insulation Methods 0.000 description 1
- UHESRSKEBRADOO-UHFFFAOYSA-N ethyl carbamate;prop-2-enoic acid Chemical class OC(=O)C=C.CCOC(N)=O UHESRSKEBRADOO-UHFFFAOYSA-N 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000007719 peel strength test Methods 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000010526 radical polymerization reaction Methods 0.000 description 1
- 230000002787 reinforcement Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000003746 surface roughness Effects 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- 239000000057 synthetic resin Substances 0.000 description 1
- 210000000538 tail Anatomy 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 229920002725 thermoplastic elastomer Polymers 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
- C09J133/04—Homopolymers or copolymers of esters
- C09J133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
- C09J133/062—Copolymers with monomers not covered by C09J133/06
- C09J133/064—Copolymers with monomers not covered by C09J133/06 containing anhydride, COOH or COOM groups, with M being metal or onium-cation
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/08—Macromolecular additives
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
- C09J133/04—Homopolymers or copolymers of esters
- C09J133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
- C09J133/062—Copolymers with monomers not covered by C09J133/06
- C09J133/066—Copolymers with monomers not covered by C09J133/06 containing -OH groups
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J7/00—Adhesives in the form of films or foils
- C09J7/30—Adhesives in the form of films or foils characterised by the adhesive composition
- C09J7/38—Pressure-sensitive adhesives [PSA]
- C09J7/381—Pressure-sensitive adhesives [PSA] based on macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
- C09J7/385—Acrylic polymers
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- 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
- C09J2301/00—Additional features of adhesives in the form of films or foils
- C09J2301/40—Additional features of adhesives in the form of films or foils characterized by the presence of essential components
- C09J2301/408—Additional features of adhesives in the form of films or foils characterized by the presence of essential components additives as essential feature of the adhesive layer
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Adhesives Or Adhesive Processes (AREA)
Abstract
The invention relates to an acrylic pressure-sensitive adhesive, a preparation method thereof and a pressure-sensitive adhesive product. The raw materials for preparing the acrylic pressure-sensitive adhesive comprise the following components in percentage by mass: 40 to 50 percent of polyacrylate, 10 to 20 percent of tackifying resin, 0.1 to 1 percent of normal temperature curing agent, 1 to 10 percent of latent curing agent, 0.5 to 2 percent of filler and 30 to 40 percent of first solvent; the raw materials for preparing the polyacrylate comprise the following components: 25 to 35 percent of soft monomer, 10 to 20 percent of hard monomer, 0.5 to 5 percent of functional monomer, 0.5 to 5 percent of polybutadiene modified polyurethane acrylate, 0.01 to 1 percent of initiator and 45 to 55 percent of second solvent; the raw materials for preparing the polybutadiene modified polyurethane acrylate comprise the following components: 25 to 35 percent of polybutadiene polyol, 5 to 15 percent of polyisocyanate, 5 to 10 percent of acrylic ester with active hydrogen, 0.1 to 1 percent of polymerization inhibitor and 45 to 55 percent of third solvent. The combination and the mass percentage range enable the acrylic pressure-sensitive adhesive to have good adhesion to PP materials, and simultaneously can reduce the use temperature, thereby being beneficial to wide application.
Description
Technical Field
The invention relates to the technical field of pressure-sensitive adhesives, in particular to an acrylic pressure-sensitive adhesive, a preparation method thereof and a pressure-sensitive adhesive product.
Background
The PP material, namely the polypropylene material, is thermoplastic synthetic resin with excellent performance, is thermoplastic light general plastic, and has chemical resistance, heat resistance, electrical insulation, high strength mechanical performance and good high wear resistance processing performance. Because the excellent performance of the PP glass fiber material has very important effect in production or life of people, the PP glass fiber material commonly used for people is obtained by adding glass fibers in order to increase heat resistance, and the PP is a nonpolar material, so that the PP glass fiber material is difficult to bond even though the surface roughness of the PP glass fiber material can be increased by physical means. However, prior art adhesives such as solvent-based pressure sensitive adhesives or hot melt adhesives have been used for bonding.
The solvent-based pressure-sensitive adhesive has good adhesion to the PP material, because the solvent contained in the solvent-based pressure-sensitive adhesive erodes the surface of the PP material, namely damages the surface of the PP material, and the solvent is volatilized and then external force is applied for adhesion, effective adhesion can be achieved, but the surface of the substrate is often limited due to the solvent and damage, and the solvent-based pressure-sensitive adhesive is not environment-friendly.
The hot melt adhesive is heated to reduce the viscosity so as to enable the hot melt adhesive to have fluidity, then the base material is bonded, and the bonding can be completed after the hot melt adhesive is cooled. However, since the hot melt adhesive contains various elastomers and tackifying resins, the hot melt adhesive with high bonding strength generally contains thermoplastic elastomers and tackifying resins with high melting points, so that the hot melt adhesive is heated to 140 ℃ or higher to have better fluidity and better adhesion on the surface of a substrate, and the bonding purpose can be achieved after the hot melt adhesive is cooled.
Disclosure of Invention
Based on this, it is necessary to provide an acrylic pressure-sensitive adhesive having good adhesion to PP materials while being capable of reducing the use temperature, a method for preparing the same, and a pressure-sensitive adhesive article.
The acrylate pressure-sensitive adhesive comprises the following raw materials in percentage by mass:
wherein, the raw materials for preparing the polyacrylate comprise the following components in percentage by mass:
wherein, the raw materials for preparing the polybutadiene modified polyurethane acrylic ester comprise the following components in percentage by mass:
in the acrylic acid ester pressure-sensitive adhesive, polybutadiene polyol and polyisocyanate can react, acrylic acid ester with active hydrogen is used for blocking, and polybutadiene modified polyurethane acrylic acid ester has a nonpolar molecular structure, so that the adhesive force of the pressure-sensitive adhesive to a PP material can be improved, and the peeling force of the pressure-sensitive adhesive to the PP material is improved; the soft monomer, the hard monomer and the functional monomer are used together as monomers, which is favorable for the excellent balance of mechanical properties such as initial adhesion, 180-degree peel strength, holding adhesion and the like of the acrylate pressure-sensitive adhesive; tackifying resins are beneficial for improving material adhesion. The combination of the components and the percentage ranges of the components are determined through a large number of experiments, and the combination and the percentage ranges of the mass percent ensure that the acrylic pressure-sensitive adhesive has good adhesion to PP materials, can reduce the use temperature and is beneficial to wide application.
In one possible implementation, the polyisocyanate is selected from at least one of MDI, TDI and IPDI.
In one possible implementation, the active hydrogen-bearing acrylate is a hydroxy (meth) acrylate.
In one possible implementation, the soft monomer is selected from at least one of n-butyl acrylate and isooctyl acrylate;
the hard monomer is at least one selected from styrene, vinyl acetate and methyl (meth) acrylate;
the functional monomer is at least one selected from (methyl) acrylic acid, (methyl) acrylamide and hydroxyethyl (methyl) acrylate.
In one possible implementation, the tackifying resin is selected from at least one of rosin resins, petroleum resins, terpene resins, alkyl phenolic resins, and terpene phenolic resins.
In one possible implementation, the polymerization inhibitor is selected from at least one of hydroquinone and p-benzoquinone;
the normal temperature curing agent is a polyfunctional isocyanate curing agent;
the latent curing agent is a shielding isocyanate curing agent;
the initiator is at least one selected from azodiisobutyronitrile and benzoyl peroxide.
In one possible implementation, the filler is fumed silica;
the first solvent, the second solvent and the third solvent are independently selected from at least one of ethyl acetate, toluene, butyl acetate, acetone and methyl ethyl ketone.
The preparation method of the acrylic pressure-sensitive adhesive comprises the following steps:
uniformly mixing polybutadiene polyol, polyisocyanate, a polymerization inhibitor and a third solvent, then fully reacting at the temperature of 75-80 ℃ until the mass fraction of NCO is 4.5-5.5%, adding acrylic ester with active hydrogen, and then fully reacting at the temperature of 75-80 ℃ until the NCO content is less than 0.5%, thus obtaining polybutadiene modified polyurethane acrylic ester;
uniformly mixing the polybutadiene modified polyurethane acrylic ester, a soft monomer, a hard monomer, a functional monomer, an initiator and a second solvent, and fully reacting at 70-75 ℃ to obtain polyacrylate; and
and uniformly mixing the polyacrylate, the tackifying resin, the normal-temperature curing agent, the latent curing agent, the filler and the first solvent, and defoaming to obtain the acrylate pressure-sensitive adhesive.
The preparation method of the acrylic ester pressure-sensitive adhesive comprises the steps of reacting polybutadiene polyol with polyisocyanate, and then blocking by using acrylic ester with active hydrogen to obtain polybutadiene modified polyurethane acrylic ester with a nonpolar molecular structure; and then obtaining polyacrylate through solution polymerization, and obtaining the acrylate pressure-sensitive adhesive. By applying the preparation method of the acrylic acid ester pressure-sensitive adhesive, the adhesive force of the pressure-sensitive adhesive to the PP material can be improved, so that the peeling force of the pressure-sensitive adhesive to the PP material is improved, the prepared acrylic acid ester pressure-sensitive adhesive has good adhesive force to the PP material, and meanwhile, the use temperature can be reduced, thereby being beneficial to wide application.
A pressure sensitive adhesive article comprising any of the acrylate pressure sensitive adhesives described above.
In the pressure-sensitive adhesive product of the technical scheme, the acrylic acid ester pressure-sensitive adhesive has good adhesion to the PP material and can reduce the use temperature, so that the 180-degree peel strength and the shear strength of the pressure-sensitive adhesive product of the invention are higher, and the wide application is facilitated.
In one possible implementation, the pressure-sensitive adhesive article is a pressure-sensitive adhesive tape or film.
Drawings
Fig. 1 is a flowchart of a method for preparing an acrylate pressure sensitive adhesive according to an embodiment of the present invention.
Detailed Description
In order that the above objects, features and advantages of the invention will be readily understood, a more particular description of the invention will be rendered by reference to the appended drawings. In the following description, numerous specific details are set forth in order to provide a thorough understanding of the present invention. The present invention may be embodied in many other forms than described herein and similarly modified by those skilled in the art without departing from the spirit of the invention, whereby the invention is not limited to the specific embodiments disclosed below.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used herein in the description of the invention is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. The term "and/or" as used herein includes any and all combinations of one or more of the associated listed items.
The acrylic pressure-sensitive adhesive of an embodiment comprises the following raw materials in percentage by mass:
wherein, the raw materials for preparing the polyacrylate comprise the following components in percentage by mass:
wherein, the raw materials for preparing the polybutadiene modified polyurethane acrylic ester comprise the following components in percentage by mass:
in the raw materials for preparing the polybutadiene modified polyurethane acrylic ester, the polybutadiene polyol and the polyisocyanate can react, the acrylic ester with active hydrogen is used for blocking, and the prepared polybutadiene modified polyurethane acrylic ester has a nonpolar molecular structure, so that the adhesive force of the pressure-sensitive adhesive to the PP material can be improved, and the stripping force of the pressure-sensitive adhesive to the PP material is improved.
Furthermore, the polybutadiene chain segments in polybutadiene polyols or hydrogenated polybutadiene polyols with different molecular weights can be used as nonpolar molecular structures to introduce an acrylic ester structure, and simultaneously, hydroxyl groups in the polybutadiene polyols can react with isocyanate to achieve the purpose of modification. Further preferred are hydrogenated polybutadiene polyols, i.e., nonpolar segments having no unsaturation, which can reduce viscosity during free radical polymerization.
In the raw materials for preparing the polyacrylate, the soft monomer, the hard monomer and the functional monomer are used together as the monomers, so that the excellent balance of mechanical properties such as initial adhesion, 180-degree peel strength and holding adhesion of the acrylate pressure-sensitive adhesive is facilitated.
In the raw materials for preparing the acrylic pressure-sensitive adhesive, the tackifying resin is beneficial to improving the material viscosity; the normal temperature curing agent can react with carboxyl or hydroxyl in the polyacrylate; the latent curing agent does not react at normal temperature, and can react after being heated in the using process, in particular, NCO groups can generate crosslinking reaction when contacting with active hydrogen in the pressure-sensitive adhesive.
In the acrylate pressure-sensitive adhesive of the embodiment, the combination of the components and the percentage range of each component are determined through a large number of experiments, and the combination and the percentage range of the mass percent ensure that the acrylate pressure-sensitive adhesive has good adhesion to PP materials, can reduce the use temperature, has good adhesion performance only by heating to 120 ℃ for 10-30 min, is not degummed after boiling, and is favorable for wide application.
The polyisocyanate is preferably a diisocyanate based on the above embodiment, and specifically may be at least one selected from MDI (chinese name diphenylmethane diisocyanate, foreign name 4, 4' -diphenylmethane diisocyanate), TDI (chinese name toluene diisocyanate, foreign name Toluene diisocyanate) and IPDI (chinese name isophorone diisocyanate, foreign name isophorone diisocyanate).
In addition to the above embodiments, the active hydrogen-containing acrylate is a hydroxy (meth) acrylate. The hydroxyl (meth) acrylate may be, but is not limited to, hydroxyl-containing acrylates such as hydroxyethyl (meth) acrylate or hydroxypropyl (meth) acrylate.
On the basis of the foregoing embodiment, the soft monomer is selected from at least one of n-butyl acrylate and isooctyl acrylate; the hard monomer is at least one selected from styrene, vinyl acetate and methyl (meth) acrylate; the functional monomer is at least one selected from (methyl) acrylic acid, (methyl) acrylamide and (methyl) hydroxyethyl acrylate. Among them, the soft monomer is the most important monomer among the acrylic esters, and its function is to produce a polymer having a low glass transition temperature (Tg) and an initial tackiness. The hard monomer in turn can give a higher glass transition temperature and can copolymerize with the soft monomer. After the hard monomer and the soft monomer are copolymerized according to the proper proportion, the pressure-sensitive adhesive with higher cohesive strength and better service temperature performance can be prepared. The functional monomer is an vinyl monomer with various functional groups and can be copolymerized with soft monomers and hard monomers, so that the pressure-sensitive adhesive can generate a certain degree of crosslinking, and the cohesive strength, the heat resistance and the better holding power are improved.
In addition to the foregoing embodiments, the tackifying resin is selected from at least one of rosin resins, petroleum resins, terpene resins, alkyl phenolic resins, and terpene phenolic resins.
In addition to the foregoing embodiments, the polymerization inhibitor is at least one selected from hydroquinone and p-benzoquinone. These types of polymerization inhibitors have a good effect of preventing self-polymerization.
In addition to the above embodiments, the room temperature curing agent is a polyfunctional isocyanate curing agent. The room temperature curing agent may be, but is not limited to, colorginal L-75, etc., with the aim of increasing the crosslinking density and increasing the cohesive strength.
In addition to the foregoing embodiments, the latent curing agent is a masked isocyanate curing agent. The latent curing agent may be, but not limited to, bastinon Trixene-BI7982, but may also be other latent curing agents with activation temperatures of 110℃to 120 ℃.
On the basis of the foregoing embodiment, the initiator is selected from at least one of azobisisobutyronitrile (AIBN, foreign name 2,2' -Azobis (2-methylpropionamide)) and benzoyl peroxide. These types of radical initiators are capable of generating radicals by thermal decomposition to initiate polymerization of the monomers.
In addition to the foregoing embodiments, the filler is fumed silica. Fumed silica serves as reinforcement.
In addition to the foregoing embodiments, the first solvent, the second solvent, and the third solvent are independently selected from at least one of ethyl acetate, toluene, butyl acetate, acetone, and methyl ethyl ketone. The types of the first solvent, the second solvent and the third solvent may be the same or different. The first solvent is used as a diluent for controlling viscosity, and the solvents of the types are selected to facilitate coating; the second solvent and the third solvent are preferably ethyl acetate or toluene, which is favorable for the synthesis of polybutadiene modified polyurethane acrylate or polyacrylate.
In the acrylic acid ester pressure-sensitive adhesive, polybutadiene polyol and polyisocyanate can react, acrylic acid ester with active hydrogen is used for blocking, and polybutadiene modified polyurethane acrylic acid ester has a nonpolar molecular structure, so that the adhesive force of the pressure-sensitive adhesive to a PP material can be improved, and the peeling force of the pressure-sensitive adhesive to the PP material is improved; the soft monomer, the hard monomer and the functional monomer are used together as monomers, which is favorable for the excellent balance of mechanical properties such as initial adhesion, 180-degree peel strength, holding adhesion and the like of the acrylate pressure-sensitive adhesive; the tackifying resin is beneficial to improving the adhesive force of the material. The combination of the components and the percentage ranges of the components are determined through a large number of experiments, and the combination and the percentage ranges of the mass percent ensure that the acrylic pressure-sensitive adhesive has good adhesion to PP materials, can reduce the use temperature and is beneficial to wide application.
Referring to fig. 1, the preparation method of the acrylate pressure-sensitive adhesive according to an embodiment of the invention includes the following steps:
s10, uniformly mixing polybutadiene polyol, polyisocyanate, a polymerization inhibitor and a third solvent, fully reacting at the temperature of 75-80 ℃ until the mass fraction of NCO is 4.5-5.5%, adding acrylic ester with active hydrogen, and fully reacting at the temperature of 75-80 ℃ until the NCO content is less than 0.5%, thus obtaining the polybutadiene modified polyurethane acrylic ester.
In step S10, the polybutadiene polyol may be dehydrated before use, and the dehydration of the polybutadiene polyol is performed as follows: adding hydrogenated polybutadiene polyol into a dry and impurity-free reaction bottle, heating the material to 120 ℃ while stirring, vacuumizing and stirring for 2 hours under the pressure of-0.1 MPa, discharging, and placing in a drying room for standby.
In step S10, polybutadiene polyol and polyisocyanate are reacted, and then the end-capped is reacted by acrylic ester with active hydrogen, so as to obtain polybutadiene modified polyurethane acrylic ester with a nonpolar molecular structure. The specific reaction equation is as follows:
a. the polyurethane intermediate reaction equation is as follows:
wherein R1 represents other chain segments of the polybutadiene polyol except the end group, namely hydroxyl, taking hydrogenated polybutadiene polyol as an example, the structural formula is as follows:
b. taking hydroxyethyl methacrylate as an example to block the polyurethane intermediate, the reaction equation is as follows:
in the polybutadiene modified urethane acrylate obtained in the step S10, N (NCO)/n (OH) =0.8 to 0.9.
And S20, uniformly mixing the polybutadiene modified polyurethane acrylic ester, the soft monomer, the hard monomer, the functional monomer, the initiator and the second solvent, and fully reacting at the temperature of 70-75 ℃ to obtain the polyacrylate.
In the step S20, the polybutadiene modified polyurethane acrylic ester, the soft monomer, the hard monomer and the functional monomer are subjected to solution polymerization to obtain the polyacrylate.
And S30, uniformly mixing the polyacrylate, the tackifying resin, the normal-temperature curing agent, the latent curing agent, the filler and the first solvent obtained in the step S20, and defoaming to obtain the acrylate pressure-sensitive adhesive.
In step S30, the tackifying resin is beneficial to improving the material viscosity; the normal temperature curing agent can react with carboxyl or hydroxyl in the polyacrylate; the latent curing agent does not react at normal temperature, and can react after being heated in the using process.
The preparation method of the acrylic ester pressure-sensitive adhesive comprises the steps of reacting polybutadiene polyol with polyisocyanate, and then blocking by using acrylic ester with active hydrogen to obtain polybutadiene modified polyurethane acrylic ester with a nonpolar molecular structure; and then obtaining polyacrylate through solution polymerization, and obtaining the acrylate pressure-sensitive adhesive. By applying the preparation method of the acrylic acid ester pressure-sensitive adhesive, the adhesive force of the pressure-sensitive adhesive to the PP material can be improved, so that the peeling force of the pressure-sensitive adhesive to the PP material is improved, the prepared acrylic acid ester pressure-sensitive adhesive has good adhesive force to the PP material, and meanwhile, the use temperature can be reduced, thereby being beneficial to wide application.
An embodiment of the pressure sensitive adhesive article comprises any of the acrylate pressure sensitive adhesives described above.
On the basis of the foregoing embodiment, the pressure-sensitive adhesive article is a pressure-sensitive adhesive tape or film.
The pressure-sensitive adhesive tape can be prepared by the following steps: coating the prepared acrylic pressure-sensitive adhesive on a base film such as PET (polyethylene terephthalate), controlling the thickness of the coated dry adhesive to be 10-120 micrometers, drying at 95-125 ℃ for 5-10 min, covering a silicone oil release film, and curing at 40 ℃ for 72h to obtain the pressure-sensitive adhesive tape.
The pressure-sensitive adhesive film can be prepared by the following steps: coating the prepared acrylic acid ester pressure-sensitive adhesive on a silicone oil release film, controlling the thickness of the coated dry adhesive to be 10-120 micrometers, drying at 95-125 ℃ for 5-10 min, covering another silicone oil release film with different release forces, and curing at 40 ℃ for 72h to obtain the pressure-sensitive adhesive film.
In the pressure-sensitive adhesive product of the technical scheme, the acrylic acid ester pressure-sensitive adhesive has good adhesion to the PP material and can reduce the use temperature, so that the 180-degree peel strength and the shear strength of the pressure-sensitive adhesive product of the invention are higher, and the wide application is facilitated.
With reference to the foregoing embodiments, the technical solutions of the present invention will be described by way of example, but it should be noted that the present invention is not limited to the following embodiments 1 to 3.
The raw materials used in the following examples include: MDI-100, the manufacturer is Wanhua chemistry; MDI-50, the manufacturer is Wanhua chemistry; hydrogenated polybutadiene polyol, manufacturer is Japanese Cauda; terpene phenolic resin 803L, the manufacturer is Japanese waste; TDI 80/20, the manufacturer is a scientific innovation; h20, manufacturer is German Wake.
Example 1
Example 1 provides an acrylic pressure-sensitive adhesive, and the components and mass of each raw material are shown in table 1 (a), table 1 (b) and table 1 (c).
Table 1 (a) polybutadiene modified polyurethane acrylate (A1)
In Table 1 (a), the first NCO content theoretical value was 5.25% and was found to be 4.85%; the second NCO content was 0% by theory and 0.38% by actual measurement.
TABLE 1 (B) polyacrylate (B1)
TABLE 1 (C) acrylic pressure sensitive adhesive (C1)
Example 2
Example 2 provides an acrylate pressure sensitive adhesive, and the components and mass of each raw material are shown in table 2 (a), table 2 (b) and table 2 (c).
Table 2 (a) polybutadiene modified polyurethane acrylate (A2)
In Table 2 (a), the first NCO content was 5.03% of theory and 4.70% was actually measured; the second NCO content was 0% by theory and 0.42% by actual measurement.
TABLE 2 (B) polyacrylate (B2)
TABLE 2 (C) acrylate pressure sensitive adhesive (C2)
Example 3
Example 3 provides an acrylate pressure sensitive adhesive, the raw material components and mass are shown in table 3 (a), table 3 (b) and table 3 (c).
Table 3 (a) polybutadiene modified polyurethane acrylate (A3)
In Table 3 (a), the first NCO content was 5.53% of theory, and 5.12% was actually measured; the second NCO content was 0% by theory and was measured practically at 0.44%.
TABLE 3 (B) polyacrylate (B3)
TABLE 3 (C) acrylate pressure sensitive adhesive (C3)
Comparative example 1
Comparative example 1 provides a non-thermosetting acrylate pressure-sensitive adhesive without non-polar segments, the raw material components and mass are detailed in tables 4 (b) and 4 (c).
Table 4 (B) polyacrylate (B4)
TABLE 4 (C) acrylic pressure sensitive adhesive (C4)
Comparative example 2
Comparative example 2 provides a thermosetting acrylate pressure sensitive adhesive without non-polar segments, the raw material components and mass are detailed in tables 5 (b) and 5 (c).
Table 5 (B) polyacrylate (B4)
TABLE 5 (C) acrylate pressure sensitive adhesive (C5)
Comparative example 3
Comparative example 3 provides a non-thermosetting acrylate pressure-sensitive adhesive with non-polar segments, the raw material components and mass are shown in Table 6 (a), table 6 (b) and Table 6 (c).
Table 6 (a) polybutadiene modified polyurethane acrylate (A1)
In Table 6 (a), the first NCO content theoretical value was 5.25% and was found to be 4.85%; the second NCO content was 0% by theory and 0.38% by actual measurement.
TABLE 6 (B) polyacrylate (B1)
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TABLE 6 (C) acrylate pressure sensitive adhesive (C6)
The acrylate pressure-sensitive adhesives of examples 1 to 3 and comparative examples 1 to 3 were prepared as follows:
weighing the raw materials according to the raw material formulation tables of examples 1-3 and comparative examples 1-3, and sequentially synthesizing polybutadiene modified polyurethane acrylate, polyacrylate and acrylate pressure-sensitive adhesive according to the following steps;
(1) synthesis of polybutadiene modified polyurethane acrylate
a. Dehydration of hydrogenated polybutadiene polyol
Adding hydrogenated polybutadiene polyol into a dry and impurity-free reaction bottle, heating the material to 120 ℃ while stirring, vacuumizing and stirring for 2 hours under the pressure of-0.1 MPa, discharging, and placing in a drying room for standby.
b. Adding a third solvent into a dry impurity-free reaction bottle provided with a thermometer, a stirrer and a condenser tube, adding diisocyanate and a polymerization inhibitor into the reaction bottle, starting condensed water, and heating the materials to 75 ℃; adding hydrogenated polybutadiene polyol into a reaction bottle, controlling the temperature of the material at 75-80 ℃, carrying out heat preservation reaction for 3h, directly adding (methyl) hydroxyl acrylate after the NCO content is detected to be close to a theoretical value (the theoretical value at the moment is marked as a first NCO content theoretical value), carrying out heat preservation for 3h at 75-80 ℃, detecting the NCO content to be less than 0.5% (the theoretical value at the moment is marked as a second NCO content theoretical value), then stirring the material, cooling to be less than 35 ℃, and discharging for standby, thus obtaining the polybutadiene modified polyurethane acrylate A.
(2) Synthesis of polyacrylates
Adding soft monomer, hard monomer, functional monomer, polyurethane acrylic ester, initiator and second solvent into a dry impurity-free reaction bottle provided with a thermometer, a stirrer, a condenser and a dropwise adding device, starting stirring and condensing water, gradually heating the material to 70 ℃, preserving heat at 70-75 ℃, reacting for 5h, measuring the solid content, cooling to 35 ℃ after the solid content is qualified (the solid content is more than 48%), discharging for standby, and marking as polyacrylate B.
(3) Preparation of acrylate pressure sensitive adhesive
And adding polyacrylate, tackifying resin, a normal-temperature curing agent, a latent curing agent, filler and a first solvent into a planetary stirrer, uniformly dispersing, and defoaming to obtain the polyacrylate pressure-sensitive adhesive C.
Performance test:
(1) 180 degree peel strength test
The acrylic pressure-sensitive adhesive synthesized in examples 1-3 and comparative examples 1-3 was coated on a 50 micron thick PET base film to prepare a 50 micron dry adhesive thickness adhesive tape, which was cured and then covered with a PET silicone oil release film (release force 8 g-15 g) to be tested.
a. Pretreating according to the method of GB/T2792-1998, bonding on a PP glass fiber plate, making a group (5 sheets each, the same applies below), hot-pressing (2 kg iron block) test pieces on a 120-DEG C hot table for 20min, cooling to normal temperature, and measuring the peel strength in N/25mm on the PP glass fiber plate.
b. After two groups of test pieces are prepared by the method a, the test pieces are put into 80 ℃ water for boiling for 1h, the phenomena of glue opening, water seepage and the like are observed, one group is used for measuring the thermal peeling strength at 80 ℃, and the other group is used for measuring the peeling strength after being cooled to normal temperature, wherein the unit is N/25mm.
(2) Shear Strength test
The acrylic pressure-sensitive adhesive synthesized in examples 1-3 and comparative examples 1-3 is coated on a PET silicone oil release film with the thickness of 50 microns (release force 8 g-15 g) to prepare a glue film with the thickness of 50 microns, and the glue film is dried and covered with the PET silicone oil release film (1 g-3 g) to be cured and tested.
a. Pretreating according to the method in GB/T7124-2008, tearing off a light release film of a pressure-sensitive adhesive film, attaching the light release film to an aluminum plate, tearing off a heavy release film, adhering a PP fiber plate to the aluminum plate, making a group of test pieces, placing the aluminum plate surface on a 120-DEG C hot table, hot-pressing (2 kg iron block) the test pieces for 20min, cooling to normal temperature, and measuring the shear strength of the PP fiber plate and the aluminum plate in MPa.
b. And b, preparing a shearing test piece according to the method of a, putting the shearing test piece into water with the temperature of 80 ℃ for boiling for 1h, observing the phenomena of glue opening, water seepage and the like, wherein one group is subjected to a thermal shearing test at the temperature of 80 ℃, and the other group is subjected to a shearing test after being cooled to the normal temperature, wherein the unit is MPa.
In each of the above tests, 5 pieces of each group were averaged to obtain the data in table 7.
TABLE 7 test results of acrylate pressure sensitive adhesives synthesized in examples 1-3 and comparative examples 1-3
Remarks: (1) "-" represents a minimum shear strength of less than 0.1MPa;
(2) the 'tearing' represents that the adhesive layer is torn, so that even residual adhesive exists on the PP fiber board and the PET base film, which indicates that the adhesive has poor temperature resistance, is soft and is easy to tear after being heated;
(3) the "release film" represents that the glue layer is completely separated from the PET base film, and the glue is completely on the PP fiber board, which means that the glue has great bonding force on the PP fiber board, and the release film is caused.
As can be seen from the test results of Table 7, comparative example 1 is a non-thermosetting acrylate pressure-sensitive adhesive without a nonpolar segment, which is inferior in heat resistance and has a low peel strength; comparative example 2 is a thermoset acrylate pressure sensitive adhesive without a non-polar segment, which has higher peel strength and better shear strength because of the presence of a non-polar segment while being thermoset; comparative example 3 is a non-thermosetting acrylate pressure-sensitive adhesive with a non-polar segment, and has slightly higher peel strength than comparative example 1 because of the non-polar segment, but also has poor heat resistance because of its non-thermosetting acrylate; examples 1, 2 and 3 are thermosetting acrylate pressure-sensitive adhesives with non-polar segments, which have not only excellent peel strength but also excellent heat resistance, which are superior to comparative example 2, showing that the acrylate pressure-sensitive adhesives of examples 1 to 3 have good adhesion to PP materials, and at the same time, can reduce the use temperature.
The technical features of the above-described embodiments may be arbitrarily combined, and all possible combinations of the technical features in the above-described embodiments are not described for brevity of description, however, as long as there is no contradiction between the combinations of the technical features, they should be considered as the scope of the description.
The above examples illustrate only a few embodiments of the invention, which are described in detail and are not to be construed as limiting the scope of the invention. It should be noted that it will be apparent to those skilled in the art that several variations and modifications can be made without departing from the spirit of the invention, which are all within the scope of the invention. Accordingly, the scope of protection of the present invention is to be determined by the appended claims.
Claims (10)
1. The acrylic pressure-sensitive adhesive is characterized by comprising the following raw materials in percentage by mass:
wherein, the raw materials for preparing the polyacrylate comprise the following components in percentage by mass:
wherein, the raw materials for preparing the polybutadiene modified polyurethane acrylic ester comprise the following components in percentage by mass:
2. the acrylate pressure sensitive adhesive of claim 1 wherein the polyisocyanate is selected from at least one of MDI, TDI and IPDI.
3. The acrylate pressure sensitive adhesive of claim 1 wherein the active hydrogen bearing acrylate is hydroxy (meth) acrylate.
4. The acrylate pressure sensitive adhesive according to claim 1, wherein the soft monomer is selected from at least one of n-butyl acrylate and isooctyl acrylate;
the hard monomer is at least one selected from styrene, vinyl acetate and methyl (meth) acrylate;
the functional monomer is at least one selected from (methyl) acrylic acid, (methyl) acrylamide and hydroxyethyl (methyl) acrylate.
5. The acrylate pressure sensitive adhesive according to claim 1, wherein the tackifying resin is selected from at least one of rosin resin, petroleum resin, terpene resin, alkyl phenol resin and terpene phenol resin.
6. The acrylate pressure sensitive adhesive according to claim 1, wherein the polymerization inhibitor is selected from at least one of hydroquinone and p-benzoquinone;
the normal temperature curing agent is a polyfunctional isocyanate curing agent;
the latent curing agent is a shielding isocyanate curing agent;
the initiator is at least one selected from azodiisobutyronitrile and benzoyl peroxide.
7. The acrylate pressure sensitive adhesive of claim 1 wherein the filler is fumed silica;
the first solvent, the second solvent and the third solvent are independently selected from at least one of ethyl acetate, toluene, butyl acetate, acetone and methyl ethyl ketone.
8. A method for preparing the acrylic pressure-sensitive adhesive according to any one of claims 1 to 7, comprising the steps of:
uniformly mixing polybutadiene polyol, polyisocyanate, a polymerization inhibitor and a third solvent, then fully reacting at the temperature of 75-80 ℃ until the mass fraction of NCO is 4.5-5.5%, adding acrylic ester with active hydrogen, and then fully reacting at the temperature of 75-80 ℃ until the NCO content is less than 0.5%, thus obtaining polybutadiene modified polyurethane acrylic ester;
uniformly mixing the polybutadiene modified polyurethane acrylic ester, a soft monomer, a hard monomer, a functional monomer, an initiator and a second solvent, and fully reacting at 70-75 ℃ to obtain polyacrylate; and
and uniformly mixing the polyacrylate, the tackifying resin, the normal-temperature curing agent, the latent curing agent, the filler and the first solvent, and defoaming to obtain the acrylate pressure-sensitive adhesive.
9. A pressure sensitive adhesive article comprising the acrylate pressure sensitive adhesive of any one of claims 1 to 7.
10. The pressure-sensitive adhesive article according to claim 9, wherein the pressure-sensitive adhesive article is a pressure-sensitive adhesive tape or film.
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