CN117467373A - Thin-coating high-viscosity polyacrylate pressure-sensitive adhesive and preparation method thereof - Google Patents
Thin-coating high-viscosity polyacrylate pressure-sensitive adhesive and preparation method thereof Download PDFInfo
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- 229920000058 polyacrylate Polymers 0.000 title claims abstract description 70
- 239000004820 Pressure-sensitive adhesive Substances 0.000 title claims abstract description 65
- 239000011248 coating agent Substances 0.000 title claims abstract description 47
- 238000000576 coating method Methods 0.000 title claims abstract description 47
- 238000002360 preparation method Methods 0.000 title claims abstract description 24
- 229920001971 elastomer Polymers 0.000 claims abstract description 82
- 239000005060 rubber Substances 0.000 claims abstract description 82
- 229920001195 polyisoprene Polymers 0.000 claims abstract description 66
- 229920002857 polybutadiene Polymers 0.000 claims abstract description 59
- 239000005062 Polybutadiene Substances 0.000 claims abstract description 57
- 239000012948 isocyanate Substances 0.000 claims abstract description 40
- 150000002513 isocyanates Chemical class 0.000 claims abstract description 40
- 239000011347 resin Substances 0.000 claims abstract description 27
- 229920005989 resin Polymers 0.000 claims abstract description 27
- 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 abstract description 19
- 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 abstract description 19
- 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 abstract description 19
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims abstract description 15
- 229920002799 BoPET Polymers 0.000 claims abstract description 11
- 238000002156 mixing Methods 0.000 claims abstract description 10
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 54
- 238000003756 stirring Methods 0.000 claims description 38
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 29
- 239000002904 solvent Substances 0.000 claims description 18
- 239000007788 liquid Substances 0.000 claims description 16
- 239000000178 monomer Substances 0.000 claims description 14
- 230000009477 glass transition Effects 0.000 claims description 13
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 claims description 11
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 11
- 238000000034 method Methods 0.000 claims description 10
- 239000004342 Benzoyl peroxide Substances 0.000 claims description 9
- 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 9
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 claims description 9
- 235000019400 benzoyl peroxide Nutrition 0.000 claims description 9
- 239000012975 dibutyltin dilaurate Substances 0.000 claims description 9
- 238000010438 heat treatment Methods 0.000 claims description 9
- 239000005057 Hexamethylene diisocyanate Substances 0.000 claims description 7
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 claims description 7
- 125000005442 diisocyanate group Chemical group 0.000 claims description 6
- WARQUFORVQESFF-UHFFFAOYSA-N isocyanatoethene Chemical compound C=CN=C=O WARQUFORVQESFF-UHFFFAOYSA-N 0.000 claims description 6
- RBQRWNWVPQDTJJ-UHFFFAOYSA-N methacryloyloxyethyl isocyanate Chemical compound CC(=C)C(=O)OCCN=C=O RBQRWNWVPQDTJJ-UHFFFAOYSA-N 0.000 claims description 6
- VPASWAQPISSKJP-UHFFFAOYSA-N ethyl prop-2-enoate;isocyanic acid Chemical compound N=C=O.CCOC(=O)C=C VPASWAQPISSKJP-UHFFFAOYSA-N 0.000 claims description 4
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 claims description 4
- RTJGBIGSNVJSDM-UHFFFAOYSA-N 1-(2-isocyanatopropan-2-yl)-3-propan-2-ylbenzene Chemical compound CC(C)C1=CC=CC(C(C)(C)N=C=O)=C1 RTJGBIGSNVJSDM-UHFFFAOYSA-N 0.000 claims description 3
- 229920002121 Hydroxyl-terminated polybutadiene Polymers 0.000 claims description 2
- 239000004925 Acrylic resin Substances 0.000 abstract description 7
- 238000012986 modification Methods 0.000 abstract description 6
- 230000004048 modification Effects 0.000 abstract description 6
- 239000003795 chemical substances by application Substances 0.000 abstract description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 28
- 239000000203 mixture Substances 0.000 description 16
- 230000001070 adhesive effect Effects 0.000 description 14
- 239000007795 chemical reaction product Substances 0.000 description 14
- 229910052757 nitrogen Inorganic materials 0.000 description 14
- 230000000052 comparative effect Effects 0.000 description 12
- 239000000853 adhesive Substances 0.000 description 9
- 238000006243 chemical reaction Methods 0.000 description 9
- 239000012299 nitrogen atmosphere Substances 0.000 description 7
- 238000004132 cross linking Methods 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- 230000007547 defect Effects 0.000 description 3
- 238000006116 polymerization reaction Methods 0.000 description 3
- 238000001556 precipitation Methods 0.000 description 3
- 238000010998 test method Methods 0.000 description 3
- 230000007423 decrease Effects 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- DXPPIEDUBFUSEZ-UHFFFAOYSA-N 6-methylheptyl prop-2-enoate Chemical compound CC(C)CCCCCOC(=O)C=C DXPPIEDUBFUSEZ-UHFFFAOYSA-N 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical group CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- 239000002390 adhesive tape Substances 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- PUSKHXMZPOMNTQ-UHFFFAOYSA-N ethyl 2,1,3-benzoselenadiazole-5-carboxylate Chemical group CCOC(=O)C1=CC=C2N=[Se]=NC2=C1 PUSKHXMZPOMNTQ-UHFFFAOYSA-N 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000007719 peel strength test Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 239000010959 steel Substances 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
- C09J133/08—Homopolymers or copolymers of acrylic acid esters
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Adhesives Or Adhesive Processes (AREA)
Abstract
The invention discloses a thin-coating high-viscosity polyacrylate pressure-sensitive adhesive and a preparation method thereof. The thin-coating high-viscosity polyacrylate pressure-sensitive adhesive consists of 40-60 parts by mass of carboxylated polyacrylate, 10-20 parts by mass of isocyanate-terminated polybutadiene, 5-10 parts by mass of isocyanate-modified polyisoprene rubber and 5-10 parts by mass of hydroxylated acrylic rosin tackifying resin. The preparation method comprises the following steps: introducing isocyanate into polyisoprene rubber through graft modification to obtain modified polyisoprene rubber, uniformly mixing carboxylated polyacrylate solution, isocyanate-terminated polybutadiene, isocyanate modified polyisoprene rubber and hydroxylated tackifying resin, and coating on a PET film to obtain the modified polyisoprene rubber. The invention uses the polybutadiene blocked by isocyanate and the polyisoprene rubber modified by isocyanate as curing agents, solves the problem that the traditional rubber system is incompatible with polyacrylate resin and tackifying resin, realizes the forced compatibility of polyacrylate and tackifying resin with the rubber system, and obtains the thin-coating high-viscosity polyacrylate pressure-sensitive adhesive with high initial adhesion and high stripping.
Description
Technical Field
The invention relates to the field of pressure-sensitive adhesives, in particular to a thin-coating high-viscosity polyacrylate pressure-sensitive adhesive and a preparation method thereof.
Background
In recent years, with the miniaturization of electronic products, the requirement on pressure-sensitive adhesives is higher and higher, and in particular, the miniaturization of electronic products puts a great application demand on ultrathin pressure-sensitive adhesives, which requires the pressure-sensitive adhesives to meet the high performance while being thin-coated. However, the adhesive properties of the pressure-sensitive adhesive depend on its thickness. As the thickness of the pressure-sensitive adhesive decreases, the adhesive strength thereof decreases greatly, and therefore, how to develop a thin-coating high-viscosity polyacrylate pressure-sensitive adhesive is a hot spot of current research.
The traditional method for improving the thin coating performance of the thin coating polyacrylate pressure-sensitive adhesive mainly comprises the steps of reducing the glass transition temperature of a system, reducing the crosslinking density, using tackifying resin with a low softening point and introducing rubber for modification. The glass transition temperature of the system is lowered by introducing a monomer with a low glass transition temperature such as isooctyl acrylate or reducing the amount of a hard monomer such as vinyl acetate monomer, which, although improving the adhesive property, can cause cohesive failure of the pressure-sensitive adhesive and lower the holding property thereof. This also occurs when the crosslink density is reduced. The use of a tackifying resin with a low softening point reduces the heat resistance of the pressure-sensitive adhesive, and at the same time, the adhesion performance of the tackifying resin with a low softening point to the thin-coated pressure-sensitive adhesive is not obviously improved, and the initial adhesion of the pressure-sensitive adhesive is reduced.
The introduction of rubber for modification is a common method for improving the thin coating of high-viscosity pressure-sensitive adhesive. By introducing polyisoprene or polybutadiene rubber into polyacrylate, the adhesive property of the polyacrylate can be effectively improved during thin coating, but the rubber is usually poor in compatibility with the polyacrylate system, so that the rubber system is separated out in the use process, and the stability and adhesive property of the polyacrylate are reduced. Even if the residual double bonds in the rubber system are utilized to participate in the polymerization of polyacrylate in the polymerization process, the polymerization still cannot be well carried out due to the polarity difference, so that how to improve the compatibility of the rubber and the polyacrylate resin is the key for preparing the thin-coating high-viscosity polyacrylate pressure-sensitive adhesive.
Disclosure of Invention
The invention aims at overcoming the defects of the existing thin-coating high-viscosity polyacrylate pressure-sensitive adhesive, and provides a thin-coating polyacrylate pressure-sensitive adhesive with high initial adhesion and high stripping and a preparation method thereof.
The invention aims at realizing the following technical scheme:
the thin-coating high-viscosity polyacrylate pressure-sensitive adhesive consists of the following components:
40-60 parts by mass of carboxylated polyacrylate;
10 to 20 parts by mass of an isocyanate-terminated polybutadiene;
5-10 parts by mass of isocyanate modified polyisoprene rubber;
5-10 parts by mass of hydroxylated acrylic rosin tackifying resin;
the isocyanate modified polyisoprene rubber consists of 2-5 parts by mass of vinyl isocyanate monomer, 3-8 parts by mass of butyl acrylate and 80-100 parts by mass of polyisoprene liquid rubber;
the isocyanate-terminated polybutadiene is formed by condensing diisocyanate monomers and hydroxyl-terminated polybutadiene;
the number average molecular weight of the carboxylated polyacrylate is 135000 ～ 325000, the glass transition temperature is-55 to-35 ℃, and the carboxyl content is 0.5 to 1.5 weight percent;
the hydroxyl content of the hydroxylated acrylic rosin tackifying resin is 0.5-1.2 wt% and the softening point is 60-100 ℃.
A preparation method of a thin-coating high-viscosity polyacrylate pressure-sensitive adhesive comprises the steps of uniformly mixing 40-60 parts by mass of carboxylated polyacrylate, 10-20 parts by mass of isocyanate-terminated polybutadiene, 5-10 parts by mass of isocyanate modified polyisoprene rubber and 5-10 parts by mass of hydroxylated acrylic rosin tackifying resin, coating the mixture on a PET film, controlling the thickness of a dry adhesive to be 5-15 mu m, drying, and transferring the mixture into an oven for curing.
The preparation method of the isocyanate-terminated polybutadiene comprises the following steps: uniformly mixing 5-25 parts by mass of diisocyanate monomer, 30-60 parts by mass of hydroxy polybutadiene, 0.01-0.02 part by mass of dibutyltin dilaurate and 60-80 parts by mass of toluene, stirring at room temperature for 4-8 hours, and removing the solvent to obtain isocyanate-terminated polybutadiene;
the hydroxyl value content of the hydroxyl polybutadiene is 0.5-1.5 wt% and the relative molecular weight is 500-3200;
the diisocyanate monomer is one of toluene diisocyanate and hexamethylene diisocyanate;
the preparation method of the isocyanate modified polyisoprene rubber comprises the following steps: dissolving 80-100 parts by mass of polyisoprene liquid rubber in 100-200 parts by mass of toluene solution, adding 0.4-0.8 part by mass of benzoyl peroxide, 2-5 parts by mass of vinyl isocyanate monomer and 3-8 parts by mass of butyl acrylate, uniformly stirring, heating to 85-110 ℃ for reacting for 3-6 hours, and removing solvent to obtain isocyanate modified polyisoprene rubber;
the vinyl isocyanate monomer is one of isocyanoethyl methacrylate, 3-isopropyl-dimethylbenzyl isocyanate, isocyanate ethyl acrylate and derivatives thereof.
The modified polyacrylate pressure-sensitive adhesive is prepared by introducing a rubber system into polyacrylate, so that the adhesive property of the pressure-sensitive adhesive in the process of thin coating can be effectively improved; introducing isocyanate into polyisoprene rubber through graft modification to obtain modified polyisoprene rubber, compounding the modified polyisoprene rubber with isocyanate-terminated polybutadiene, taking the isocyanate-terminated polybutadiene and the isocyanate-modified polyisoprene rubber as curing agents, and improving the compatibility of the polyisoprene rubber, the polybutadiene rubber, the polyacrylate resin and the tackifying resin by utilizing the cross-linking reaction of carboxyl, hydroxyl and isocyanate; meanwhile, the polyisoprene rubber and the polybutadiene are compounded, so that the initial adhesion of the pressure-sensitive adhesive is improved, and meanwhile, the bonding strength of a system is kept, and therefore, the functional groups are introduced into the rubber modification, the reaction between the groups is utilized, the polybutadiene blocked by isocyanate and the polyisoprene rubber modified by isocyanate are used as curing agents, the rubber can be directly grafted onto the polyacrylate resin, the compatibility of a rubber system and the polyacrylate resin is improved, and the thin-coating high-viscosity pressure-sensitive adhesive with excellent performance is obtained. Compared with the prior art, the invention solves the defects of low primary adhesion and adhesive strength of the traditional thin-coating pressure-sensitive adhesive, and the prepared thin-coating pressure-sensitive adhesive has good primary adhesion, holding adhesion and stripping performance.
Detailed Description
For a better understanding of the present invention, the present invention will be further described with reference to examples, but the embodiments of the present invention are not limited thereto.
Example 1
Preparation of isocyanate-terminated polybutadiene:
placing 16 parts by mass of hexamethylene diisocyanate, 45 parts by mass of hydroxy polybutadiene (the hydroxyl value content is 1.2wt%, and the relative molecular weight is 1600), 0.01 part by mass of dibutyltin dilaurate and 80 parts by mass of toluene in a three-port bottle provided with a thermometer, a condenser tube and a stirring paddle, uniformly mixing, introducing nitrogen to replace air for three times, stirring at room temperature for 6 hours under the nitrogen atmosphere, then transferring the reaction product into a single-port bottle, and removing the solvent by adopting a rotary evaporator to obtain isocyanate-terminated polybutadiene;
preparation of isocyanate modified polyisoprene rubber:
dissolving 90 parts by mass of polyisoprene liquid rubber in 160 parts by mass of toluene solution, adding 0.6 part by mass of benzoyl peroxide, 4.5 parts by mass of isocyanoethyl methacrylate and 6 parts by mass of butyl acrylate, uniformly stirring, then, moving into a three-port bottle provided with a thermometer, a condenser tube and a stirring paddle, introducing nitrogen to replace air for three times, stirring and heating to 100 ℃ for 4.5 hours, then, moving a reaction product into a single-port bottle, and removing a solvent by adopting a rotary evaporator to obtain isocyanate modified polyisoprene rubber;
preparing a thin coating high-viscosity polyacrylate pressure-sensitive adhesive:
50 parts by mass of carboxylated polyacrylate (having a number average molecular weight of 225000, a glass transition temperature of-45 ℃ and a carboxyl content of 1.2 wt%), 15 parts by mass of isocyanate-terminated polybutadiene, 6 parts by mass of isocyanate-modified polyisoprene rubber and 6 parts by mass of hydroxylated acrylic rosin tackifying resin are uniformly mixed, and then placed until no obvious bubbles are generated, uniformly coated on a PET film by using a coating machine, and the thickness of the dry adhesive is controlled to be 10 mu m, then the dry adhesive is transferred to a 150 ℃ oven for 8min, and then transferred to a 70 ℃ oven for curing for 48h, thereby obtaining the thin-coated high-viscosity polyacrylate pressure-sensitive adhesive.
Example 2
Preparation of isocyanate-terminated polybutadiene:
placing 5 parts by mass of hexamethylene diisocyanate, 30 parts by mass of hydroxy polybutadiene (the hydroxyl value content is 0.5wt%, and the relative molecular weight is 1800), 0.01 part by mass of dibutyltin dilaurate and 60 parts by mass of toluene in a three-port bottle provided with a thermometer, a condenser tube and a stirring paddle, uniformly mixing, introducing nitrogen to replace air for three times, stirring for 4 hours at room temperature in a nitrogen atmosphere, then transferring the reaction product into a single-port bottle, and removing the solvent by adopting a rotary evaporator to obtain isocyanate-terminated polybutadiene;
preparation of isocyanate modified polyisoprene rubber:
dissolving 80 parts by mass of polyisoprene liquid rubber in 120 parts by mass of toluene solution, adding 0.4 part by mass of benzoyl peroxide, 2 parts by mass of 3-isopropyl-dimethylbenzyl isocyanate and 3 parts by mass of butyl acrylate, uniformly stirring, then, moving to a three-mouth bottle provided with a thermometer, a condenser tube and a stirring paddle, introducing nitrogen to replace air for three times, stirring and heating to 85 ℃ for reaction for 6 hours, moving a reaction product to a single-mouth bottle, and removing a solvent by adopting a rotary evaporator to obtain isocyanate modified polyisoprene rubber;
preparing a thin coating high-viscosity polyacrylate pressure-sensitive adhesive:
after 40 parts by mass of carboxylated polyacrylate (number average molecular weight: 135000, glass transition temperature: minus 35 ℃, carboxyl content: 0.5 wt%), 10 parts by mass of isocyanate-terminated polybutadiene, 5 parts by mass of isocyanate-modified polyisoprene rubber and 5 parts by mass of hydroxylated acrylic rosin tackifying resin were uniformly mixed, left until no significant air bubbles were generated, uniformly coated on a PET film by using a coater, controlled to a dry gel thickness of 5 μm, then transferred to an oven at 140 ℃ for 10min, and then transferred to an oven at 80 ℃ for curing for 36 hours, to obtain a thin-coated high-viscosity polyacrylate pressure-sensitive adhesive.
Example 3
Preparation of isocyanate-terminated polybutadiene:
placing 25 parts by mass of toluene diisocyanate, 60 parts by mass of hydroxy polybutadiene (the hydroxyl value content is 1.5wt%, and the relative molecular weight is 500), 0.02 part by mass of dibutyltin dilaurate and 60 parts by mass of toluene in a three-port bottle provided with a thermometer, a condenser tube and a stirring paddle, uniformly mixing, introducing nitrogen to replace air for three times, stirring at room temperature for 8 hours under the nitrogen atmosphere, then transferring the reaction product into a single-port bottle, and removing the solvent by adopting a rotary evaporator to obtain isocyanate-terminated polybutadiene;
preparation of isocyanate modified polyisoprene rubber:
dissolving 100 parts by mass of polyisoprene liquid rubber in 100 parts by mass of toluene solution, adding 0.8 part by mass of benzoyl peroxide, 5 parts by mass of isocyanate ethyl acrylate and 8 parts by mass of butyl acrylate, uniformly stirring, then transferring to a three-port bottle provided with a thermometer, a condenser tube and a stirring paddle, introducing nitrogen to replace air for three times, stirring and heating to 110 ℃ for reaction for 3 hours, transferring a reaction product to a single-port bottle, and removing a solvent by adopting a rotary evaporator to obtain isocyanate modified polyisoprene rubber;
preparing a thin coating high-viscosity polyacrylate pressure-sensitive adhesive:
after 60 parts by mass of carboxylated polyacrylate (number average molecular weight: 325000, glass transition temperature: -55 ℃ C., carboxyl content: 1.5 wt%), 20 parts by mass of isocyanate-terminated polybutadiene, 10 parts by mass of isocyanate-modified polyisoprene rubber and 10 parts by mass of hydroxylated acrylic rosin tackifying resin were uniformly mixed, left until no significant air bubbles were generated, uniformly coated on a PET film by a coater, controlled to a dry gel thickness of 15 μm, then transferred to a 160 ℃ oven for 5min, and then transferred to a 70 ℃ oven for curing for 36h, to obtain a thin-coated high-viscosity polyacrylate pressure-sensitive adhesive.
Example 4
Preparation of isocyanate-terminated polybutadiene:
placing 15 parts by mass of hexamethylene diisocyanate, 52 parts by mass of hydroxy polybutadiene (the hydroxyl value content is 1.0wt%, and the relative molecular weight is 3200), 0.01 parts by mass of dibutyltin dilaurate and 80 parts by mass of toluene in a three-port bottle provided with a thermometer, a condenser tube and a stirring paddle, uniformly mixing, introducing nitrogen to replace air for three times, stirring at room temperature for 5 hours under the nitrogen atmosphere, transferring the reaction product into a single-port bottle, and removing the solvent by adopting a rotary evaporator to obtain isocyanate-terminated polybutadiene;
preparation of isocyanate modified polyisoprene rubber:
dissolving 85 parts by mass of polyisoprene liquid rubber in 160 parts by mass of toluene solution, adding 0.6 part by mass of benzoyl peroxide, 3.6 parts by mass of isocyanoethyl methacrylate and 4.8 parts by mass of butyl acrylate, uniformly stirring, then, moving to a three-port bottle provided with a thermometer, a condenser tube and a stirring paddle, introducing nitrogen to replace air for three times, stirring and heating to 100 ℃ for reaction for 6 hours, moving a reaction product to a single-port bottle, and removing a solvent by adopting a rotary evaporator to obtain isocyanate modified polyisoprene rubber;
preparing a thin coating high-viscosity polyacrylate pressure-sensitive adhesive:
after 48 parts by mass of carboxylated polyacrylate (number average molecular weight: 272000, glass transition temperature: -43 ℃ C., carboxyl content: 0.7 wt%), 16 parts by mass of isocyanate-terminated polybutadiene, 7 parts by mass of isocyanate-modified polyisoprene rubber and 9 parts by mass of hydroxylated acrylic rosin tackifying resin were uniformly mixed, left until no significant air bubbles were generated, uniformly coated on a PET film by a coater, controlled in dry gel thickness to 12 μm, then transferred to a 130 ℃ oven for 12 minutes, and then transferred to a 60 ℃ oven for curing for 72 hours, to obtain a thin-coated high-viscosity polyacrylate pressure-sensitive adhesive.
Example 5
Preparation of isocyanate-terminated polybutadiene:
21 parts by mass of toluene diisocyanate, 50 parts by mass of hydroxy polybutadiene (the hydroxyl value content is 1.3wt%, relative molecular weight is 2200), 0.01 part by mass of dibutyltin dilaurate and 75 parts by mass of toluene are placed in a three-port bottle provided with a thermometer, a condenser tube and a stirring paddle, after being uniformly mixed, nitrogen is introduced to replace air for three times, and the mixture is stirred for 5 hours at room temperature under the nitrogen atmosphere, then the reaction product is moved into a single-port bottle, and the solvent is removed by adopting a rotary evaporator to obtain isocyanate-terminated polybutadiene;
preparation of isocyanate modified polyisoprene rubber:
dissolving 88 parts by mass of polyisoprene liquid rubber in 200 parts by mass of toluene solution, adding 0.5 part by mass of benzoyl peroxide, 3.5 parts by mass of isocyanate ethyl acrylate and 3 parts by mass of butyl acrylate, uniformly stirring, then transferring to a three-port bottle provided with a thermometer, a condenser tube and a stirring paddle, introducing nitrogen to replace air for three times, stirring and heating to 110 ℃ for reaction for 3 hours, transferring a reaction product to a single-port bottle, and removing a solvent by adopting a rotary evaporator to obtain isocyanate modified polyisoprene rubber;
preparing a thin coating high-viscosity polyacrylate pressure-sensitive adhesive:
45 parts by mass of carboxylated polyacrylate (the number average molecular weight is 174000, the glass transition temperature is-42 ℃, the carboxyl content is 1.0 wt%), 16 parts by mass of isocyanate-terminated polybutadiene, 7 parts by mass of isocyanate-modified polyisoprene rubber and 6 parts by mass of hydroxylated acrylic rosin tackifying resin are uniformly mixed, and then the mixture is placed until no obvious bubbles are generated, uniformly coated on a PET film by using a coating machine, the dry adhesive thickness is controlled to be 8 mu m, then the mixture is transferred to a 150 ℃ oven for 10min, and then transferred to a 80 ℃ oven for curing for 48h, so that the thin-coated high-viscosity polyacrylate pressure-sensitive adhesive is obtained.
Comparative example 1
Preparation of isocyanate-terminated polybutadiene:
placing 16 parts by mass of hexamethylene diisocyanate, 45 parts by mass of hydroxy polybutadiene (the hydroxyl value content is 1.2wt%, and the relative molecular weight is 1600), 0.01 part by mass of dibutyltin dilaurate and 80 parts by mass of toluene in a three-port bottle provided with a thermometer, a condenser tube and a stirring paddle, uniformly mixing, introducing nitrogen to replace air for three times, stirring at room temperature for 6 hours under the nitrogen atmosphere, then transferring the reaction product into a single-port bottle, and removing the solvent by adopting a rotary evaporator to obtain isocyanate-terminated polybutadiene;
preparing a thin coating high-viscosity polyacrylate pressure-sensitive adhesive:
50 parts by mass of carboxylated polyacrylate (the number average molecular weight is 225000, the glass transition temperature is-45 ℃, the carboxyl content is 1.2 wt%), 15 parts by mass of isocyanate-terminated polybutadiene, 6 parts by mass of polyisoprene liquid rubber and 6 parts by mass of hydroxylated acrylic rosin tackifying resin are uniformly mixed, and then the mixture is placed until no obvious bubbles are generated, the mixture is uniformly coated on a PET film by using a coating machine, the thickness of dry adhesive is controlled to be 10 mu m, then the mixture is transferred to a 150 ℃ oven for 8min, and then the mixture is transferred to a 70 ℃ oven for curing for 48h, so that the thin-coating high-viscosity polyacrylate pressure-sensitive adhesive is obtained.
Comparative example 2
Preparation of isocyanate modified polyisoprene rubber:
dissolving 90 parts by mass of polyisoprene liquid rubber in 160 parts by mass of toluene solution, adding 0.6 part by mass of benzoyl peroxide, 4.5 parts by mass of isocyanoethyl methacrylate and 6 parts by mass of butyl acrylate, uniformly stirring, then, moving into a three-port bottle provided with a thermometer, a condenser tube and a stirring paddle, introducing nitrogen to replace air for three times, stirring and heating to 100 ℃ for 4.5 hours, then, moving a reaction product into a single-port bottle, and removing a solvent by adopting a rotary evaporator to obtain isocyanate modified polyisoprene rubber;
preparing a thin coating high-viscosity polyacrylate pressure-sensitive adhesive:
50 parts by mass of carboxylated polyacrylate (the number average molecular weight is 225000, the glass transition temperature is-45 ℃, the carboxyl content is 1.2 wt%), 15 parts by mass of hydroxy polybutadiene (the hydroxyl value content is 1.2wt%, the relative molecular weight is 1600), 6 parts by mass of isocyanate modified polyisoprene rubber and 6 parts by mass of hydroxylated acrylic rosin tackifying resin are uniformly mixed, and then the mixture is placed until no obvious bubbles are generated, and the mixture is uniformly coated on a PET film by using a coating machine, wherein the dry adhesive thickness is controlled to be 10 mu m, and then the mixture is transferred to an oven at 150 ℃ for 8min, and then transferred to an oven at 70 ℃ for curing for 48 hours, so that the thin-coating high-viscosity polyacrylate pressure-sensitive adhesive is obtained.
Comparative example 3
Preparation of isocyanate-terminated polybutadiene:
placing 16 parts by mass of hexamethylene diisocyanate, 45 parts by mass of hydroxy polybutadiene (the hydroxyl value content is 1.2wt%, and the relative molecular weight is 1600), 0.01 part by mass of dibutyltin dilaurate and 80 parts by mass of toluene in a three-port bottle provided with a thermometer, a condenser tube and a stirring paddle, uniformly mixing, introducing nitrogen to replace air for three times, stirring at room temperature for 6 hours under the nitrogen atmosphere, then transferring the reaction product into a single-port bottle, and removing the solvent by adopting a rotary evaporator to obtain isocyanate-terminated polybutadiene;
preparation of isocyanate modified polyisoprene rubber:
dissolving 90 parts by mass of polyisoprene liquid rubber in 160 parts by mass of toluene solution, adding 0.6 part by mass of benzoyl peroxide, 4.5 parts by mass of isocyanoethyl methacrylate and 6 parts by mass of butyl acrylate, uniformly stirring, then, moving into a three-port bottle provided with a thermometer, a condenser tube and a stirring paddle, introducing nitrogen to replace air for three times, stirring and heating to 100 ℃ for 4.5 hours, then, moving a reaction product into a single-port bottle, and removing a solvent by adopting a rotary evaporator to obtain isocyanate modified polyisoprene rubber;
preparing a thin coating high-viscosity polyacrylate pressure-sensitive adhesive:
50 parts by mass of carboxylated polyacrylate (the number average molecular weight is 225000, the glass transition temperature is-45 ℃, the carboxyl content is 1.2 wt%), 15 parts by mass of isocyanate-terminated polybutadiene, 6 parts by mass of isocyanate-modified polyisoprene rubber and 6 parts by mass of rosin tackifying resin are uniformly mixed, and then the mixture is placed until no obvious bubbles are generated, the mixture is uniformly coated on a PET film by using a coating machine, the thickness of dry adhesive is controlled to be 10 mu m, then the mixture is transferred to a baking oven at 150 ℃ for 8min, and then the mixture is transferred to a baking oven at 70 ℃ for curing for 48h, so that the thin-coated high-viscosity polyacrylate pressure-sensitive adhesive is obtained.
Test method
Peel strength test: reference is made to GB/T2792-1998 (180℃peel strength test method for pressure-sensitive adhesive tape). SUS304 stainless steel plate with specially treated surface is selected as the adherend.
And (3) testing the holding power: the tape holding test is determined with reference to GB/T4851-2014, and the time to failure of the tape under load is tested.
Initial tack test: the initial tackiness of the adhesive tape was measured by the ball initial tackiness method (J.DOW method) with reference to GB/T4852-2002 (pressure sensitive adhesive tape initial tackiness test method), and the measurement result was expressed as the ball number of the largest steel ball that the pressure sensitive adhesive tape could stick.
Table 1 results of performance tests of examples and comparative examples
| Peel force/gf | Holding time/h | Initial adhesion/# | |
| Example 1 | 1534 | ＞72 | 7 |
| Example 2 | 1312 | ＞72 | 5 |
| Example 3 | 1629 | ＞72 | 11 |
| Example 4 | 1477 | ＞72 | 5 |
| Example 5 | 1415 | ＞72 | 6 |
| Comparative example 1 | 1178 | 37 | 8 |
| Comparative example 2 | 1241 | 63 | 8 |
| Comparative example 3 | 1337 | ＞72 | 5 |
As can be seen from the performance tests of the examples and the comparative examples in Table 1, the thin-coated high-viscosity polyacrylate pressure-sensitive adhesives obtained in examples 1 to 5 not only have higher peel strength, but also have better holding power and high initial adhesion.
In contrast to example 1, the liquid polyisoprene rubber used in comparative example 1 replaced the isocyanate modified polyisoprene rubber of example 1. Because of lack of reactive crosslinking, the polyisoprene liquid rubber has poor compatibility with polyacrylate, which results in precipitation of the polyisoprene liquid rubber, which has low pressure-sensitive adhesive stripping force of 1178gf, short holding time, and falling after 37 hours of holding test, while example 1 still does not fall after 72 hours of holding test. The pressure-sensitive adhesive prepared in comparative example 1 had slightly higher initial adhesion due to precipitation of polyisoprene liquid rubber. Therefore, the polyisoprene rubber can be crosslinked with the polyacrylate resin by modifying and introducing the isocyanate, so that the compatibility of the polyisoprene rubber and the polyacrylate resin is improved, and the thin-coating high-viscosity pressure-sensitive adhesive with excellent performance is obtained.
In contrast to example 1, comparative example 2 directly adds unmodified hydroxy polybutadiene instead of isocyanate-terminated polybutadiene. Although the hydroxy polybutadiene can be crosslinked with isocyanate, it is not directly crosslinked with polyacrylate, resulting in poor compatibility and low peel strength, the pressure-sensitive adhesive has a peel force of only 1241gf, and drops after 63 hours of tack time test, compared with the peel force 1534gf of example 1. In addition, the precipitation of the hydroxyl polybutadiene contributes to the improvement of the initial adhesion, which is 8#. It can be seen that even though the hydroxy polybutadiene can be crosslinked with isocyanate to some extent, it is not directly crosslinked with polyacrylate, so that there is still a problem of poor compatibility, and the polybutadiene blocked by isocyanate can be crosslinked with polyacrylate, thereby obtaining a thin-coated high-viscosity pressure-sensitive adhesive with excellent performance.
In contrast to example 1, comparative example 3 adds a conventional rosin tackifying resin in place of the hydroxylated acrylic rosin tackifying resin. Because of the existence of the rubber and polyacrylate system in the system, the direct addition of the rosin tackifying resin can lead to the existence of three systems in the system, which cannot undergo a crosslinking reaction with the rubber or polyacrylate, and the compatibility of each component in the system is relatively poorer than that of the example 1, but because the rubber and the polyacrylate in the system undergo a crosslinking reaction, the system still has better peel strength of 1337gf which is lower than 1534gf of the example 1, and the initial adhesion is also lower, namely 5# and the initial adhesion of the example 1 is higher and reaches 7#. Therefore, the compatibility of the rosin tackifying resin, polyacrylate and rubber also has a great influence on the performance of the pressure-sensitive adhesive, and the thin-coating high-viscosity pressure-sensitive adhesive with excellent performance can be obtained only if the tackifying resin, the rubber and the polyacrylate have good crosslinking reaction.
Therefore, the thin-coating high-viscosity pressure-sensitive adhesive prepared by using the polybutadiene blocked by isocyanate and the isocyanate modified polyisoprene rubber as curing agents has higher peel strength, good holding power and high initial adhesion, and overcomes the defects of low peel strength and poor holding power of common thin-coating polyacrylate pressure-sensitive adhesives.
The foregoing examples illustrate only a few embodiments of the invention and are described in detail herein without thereby 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 (6)
1. The thin-coating high-viscosity polyacrylate pressure-sensitive adhesive is characterized by comprising the following components:
40-60 parts by mass of carboxylated polyacrylate;
10 to 20 parts by mass of an isocyanate-terminated polybutadiene;
5-10 parts by mass of isocyanate modified polyisoprene rubber;
5-10 parts by mass of hydroxylated acrylic rosin tackifying resin;
the isocyanate modified polyisoprene rubber consists of 2-5 parts by mass of vinyl isocyanate monomer, 3-8 parts by mass of butyl acrylate and 80-100 parts by mass of polyisoprene liquid rubber;
the isocyanate-terminated polybutadiene is formed by condensing diisocyanate monomers and hydroxyl-terminated polybutadiene.
2. The thin-coating high-viscosity polyacrylate pressure-sensitive adhesive according to claim 1, wherein the carboxylated polyacrylate has a number average molecular weight of 135000 ～ 325000, a glass transition temperature of-55 to-35 ℃ and a carboxyl content of 0.5 to 1.5wt%.
3. The thin-coating high-viscosity polyacrylate pressure-sensitive adhesive according to claim 1, wherein the hydroxyl content of the hydroxylated acrylic rosin tackifying resin is 0.5-1.2 wt% and the softening point is 60-100 ℃.
4. A preparation method of a thin-coating high-viscosity polyacrylate pressure-sensitive adhesive is characterized by comprising the following steps of: 40-60 parts by mass of carboxylated polyacrylate, 10-20 parts by mass of isocyanate-terminated polybutadiene, 5-10 parts by mass of isocyanate modified polyisoprene rubber and 5-10 parts by mass of hydroxylated acrylic rosin tackifying resin are uniformly mixed, coated on a PET film, dried, transferred into an oven for curing to obtain the modified polyisoprene rubber.
5. The method for preparing a thin-coating high-viscosity polyacrylate pressure-sensitive adhesive according to claim 4, wherein the method for preparing the isocyanate-terminated polybutadiene comprises the following steps: uniformly mixing 5-25 parts by mass of diisocyanate monomer, 30-60 parts by mass of hydroxy polybutadiene, 0.01-0.02 part by mass of dibutyltin dilaurate and 60-80 parts by mass of toluene, stirring at room temperature for 4-8 hours, and removing the solvent to obtain isocyanate-terminated polybutadiene;
the hydroxyl value content of the hydroxyl polybutadiene is 0.5-1.5 wt% and the relative molecular weight is 500-3200;
the diisocyanate monomer is one of toluene diisocyanate and hexamethylene diisocyanate.
6. The method for preparing the thin-coating high-viscosity polyacrylate pressure-sensitive adhesive according to claim 4, wherein the method for preparing the isocyanate modified polyisoprene rubber is as follows: dissolving 80-100 parts by mass of polyisoprene liquid rubber in 100-200 parts by mass of toluene solution, adding 0.4-0.8 part by mass of benzoyl peroxide, 2-5 parts by mass of vinyl isocyanate monomer and 3-8 parts by mass of butyl acrylate, uniformly stirring, heating to 85-110 ℃ for reacting for 3-6 hours, and removing solvent to obtain isocyanate modified polyisoprene rubber;
the vinyl isocyanate monomer is one of isocyanoethyl methacrylate, 3-isopropyl-dimethylbenzyl isocyanate, isocyanate ethyl acrylate and derivatives thereof.
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