CN117801730A - Reversible thermal viscosity-reducing pressure-sensitive adhesive, double-sided adhesive tape and preparation method thereof - Google Patents
Reversible thermal viscosity-reducing pressure-sensitive adhesive, double-sided adhesive tape and preparation method thereof Download PDFInfo
- Publication number
- CN117801730A CN117801730A CN202311806071.6A CN202311806071A CN117801730A CN 117801730 A CN117801730 A CN 117801730A CN 202311806071 A CN202311806071 A CN 202311806071A CN 117801730 A CN117801730 A CN 117801730A
- Authority
- CN
- China
- Prior art keywords
- acrylic acid
- sensitive adhesive
- acrylate
- chain alkyl
- polymer solution
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000004820 Pressure-sensitive adhesive Substances 0.000 title claims abstract description 106
- 230000002441 reversible effect Effects 0.000 title claims abstract description 73
- 239000002390 adhesive tape Substances 0.000 title claims abstract description 39
- 238000002360 preparation method Methods 0.000 title abstract description 17
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims abstract description 91
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims abstract description 87
- 239000000178 monomer Substances 0.000 claims abstract description 68
- 239000003999 initiator Substances 0.000 claims abstract description 64
- 239000011347 resin Substances 0.000 claims abstract description 54
- 229920005989 resin Polymers 0.000 claims abstract description 54
- 229920000058 polyacrylate Polymers 0.000 claims abstract description 50
- 239000002904 solvent Substances 0.000 claims abstract description 44
- 125000005907 alkyl ester group Chemical group 0.000 claims abstract description 40
- 150000002148 esters Chemical class 0.000 claims abstract description 33
- 239000002994 raw material Substances 0.000 claims abstract description 26
- 239000000463 material Substances 0.000 claims abstract description 20
- 229920006222 acrylic ester polymer Polymers 0.000 claims abstract description 16
- 238000004519 manufacturing process Methods 0.000 claims abstract description 9
- 239000004971 Cross linker Substances 0.000 claims abstract description 8
- 229920002125 Sokalan® Polymers 0.000 claims abstract description 8
- 239000004584 polyacrylic acid Substances 0.000 claims abstract description 8
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 69
- 238000006243 chemical reaction Methods 0.000 claims description 59
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 claims description 44
- 239000003431 cross linking reagent Substances 0.000 claims description 41
- 239000010410 layer Substances 0.000 claims description 41
- 239000012790 adhesive layer Substances 0.000 claims description 35
- 238000001035 drying Methods 0.000 claims description 29
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 24
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 claims description 24
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 claims description 22
- DXPPIEDUBFUSEZ-UHFFFAOYSA-N 6-methylheptyl prop-2-enoate Chemical compound CC(C)CCCCCOC(=O)C=C DXPPIEDUBFUSEZ-UHFFFAOYSA-N 0.000 claims description 22
- 239000006260 foam Substances 0.000 claims description 17
- 238000002156 mixing Methods 0.000 claims description 17
- 239000004342 Benzoyl peroxide Substances 0.000 claims description 15
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 15
- 235000019400 benzoyl peroxide Nutrition 0.000 claims description 15
- 239000011248 coating agent Substances 0.000 claims description 15
- 238000000576 coating method Methods 0.000 claims description 15
- 238000000034 method Methods 0.000 claims description 14
- 239000011241 protective layer Substances 0.000 claims description 14
- 125000005396 acrylic acid ester group Chemical group 0.000 claims description 13
- 230000003014 reinforcing effect Effects 0.000 claims description 13
- 229910052757 nitrogen Inorganic materials 0.000 claims description 12
- 238000010992 reflux Methods 0.000 claims description 11
- 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 10
- 239000003085 diluting agent Substances 0.000 claims description 10
- 229920000642 polymer Polymers 0.000 claims description 10
- 238000010438 heat treatment Methods 0.000 claims description 8
- 239000007787 solid Substances 0.000 claims description 8
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 claims description 7
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 claims description 7
- 239000002131 composite material Substances 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 6
- 230000035484 reaction time Effects 0.000 claims description 6
- KHAYCTOSKLIHEP-UHFFFAOYSA-N docosyl prop-2-enoate Chemical compound CCCCCCCCCCCCCCCCCCCCCCOC(=O)C=C KHAYCTOSKLIHEP-UHFFFAOYSA-N 0.000 claims description 4
- FSAJWMJJORKPKS-UHFFFAOYSA-N octadecyl prop-2-enoate Chemical compound CCCCCCCCCCCCCCCCCCOC(=O)C=C FSAJWMJJORKPKS-UHFFFAOYSA-N 0.000 claims description 4
- 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
- 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
- 239000004593 Epoxy Substances 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
- PZDUWXKXFAIFOR-UHFFFAOYSA-N hexadecyl prop-2-enoate Chemical compound CCCCCCCCCCCCCCCCOC(=O)C=C PZDUWXKXFAIFOR-UHFFFAOYSA-N 0.000 claims description 3
- 239000012948 isocyanate Substances 0.000 claims description 3
- 150000002513 isocyanates Chemical class 0.000 claims description 3
- 150000003505 terpenes Chemical class 0.000 claims description 3
- 235000007586 terpenes Nutrition 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
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 2
- 230000002829 reductive effect Effects 0.000 abstract description 8
- 238000012360 testing method Methods 0.000 description 17
- 125000005250 alkyl acrylate group Chemical group 0.000 description 14
- 230000000694 effects Effects 0.000 description 12
- 125000000217 alkyl group Chemical group 0.000 description 10
- 238000003756 stirring Methods 0.000 description 10
- 230000009467 reduction Effects 0.000 description 9
- 230000001070 adhesive effect Effects 0.000 description 8
- 230000008569 process Effects 0.000 description 8
- VEPKQEUBKLEPRA-UHFFFAOYSA-N VX-745 Chemical compound FC1=CC(F)=CC=C1SC1=NN2C=NC(=O)C(C=3C(=CC=CC=3Cl)Cl)=C2C=C1 VEPKQEUBKLEPRA-UHFFFAOYSA-N 0.000 description 7
- 239000000853 adhesive Substances 0.000 description 6
- 239000002313 adhesive film Substances 0.000 description 6
- 238000001816 cooling Methods 0.000 description 6
- 229920001577 copolymer Polymers 0.000 description 6
- OZAIFHULBGXAKX-VAWYXSNFSA-N AIBN Substances N#CC(C)(C)\N=N\C(C)(C)C#N OZAIFHULBGXAKX-VAWYXSNFSA-N 0.000 description 5
- 239000007788 liquid Substances 0.000 description 5
- 238000006116 polymerization reaction Methods 0.000 description 5
- 238000002844 melting Methods 0.000 description 4
- 230000008018 melting Effects 0.000 description 4
- 230000002787 reinforcement Effects 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- JTHZUSWLNCPZLX-UHFFFAOYSA-N 6-fluoro-3-methyl-2h-indazole Chemical compound FC1=CC=C2C(C)=NNC2=C1 JTHZUSWLNCPZLX-UHFFFAOYSA-N 0.000 description 2
- 230000000977 initiatory effect Effects 0.000 description 2
- 230000002427 irreversible effect Effects 0.000 description 2
- 230000007704 transition Effects 0.000 description 2
- XFMDETLOLBGJAX-UHFFFAOYSA-N 2-methylideneicosanoic acid Chemical compound CCCCCCCCCCCCCCCCCCC(=C)C(O)=O XFMDETLOLBGJAX-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 1
- 239000004974 Thermotropic liquid crystal Substances 0.000 description 1
- 150000001253 acrylic acids Chemical class 0.000 description 1
- 239000002518 antifoaming agent Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 230000005284 excitation Effects 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000004973 liquid crystal related substance Substances 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000004005 microsphere Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000036961 partial effect Effects 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 230000001603 reducing effect Effects 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
Abstract
The invention relates to a reversible thermal visbreaking pressure-sensitive adhesive, a double-sided tape and a preparation method thereof, wherein the reversible thermal visbreaking pressure-sensitive adhesive comprises the following raw materials: an acrylate polymer solution, a tackifying resin, and a crosslinker; the acrylic ester polymer solution comprises the following raw materials in parts by mass: 60-120 parts of acrylic acid long-chain alkyl ester monomer, 100-150 parts of acrylic acid and ester monomer thereof, 0.1-1 part of initiator and a proper amount of solvent; in the acrylic ester polymer solution, the acrylic acid long-chain alkyl ester monomer is polymerized to obtain the polyacrylic acid long-chain alkyl ester, and the polyacrylic acid long-chain alkyl ester is polymerized with the acrylic acid long-chain alkyl ester monomer. The reversible thermal visbreaking pressure-sensitive adhesive has reversible thermal visbreaking property, and the prepared double-sided adhesive tape can be reused, so that the production efficiency is improved, and the material loss is reduced.
Description
Technical Field
The invention relates to the technical field of adhesives, in particular to a reversible thermal viscosity-reducing pressure-sensitive adhesive, a double-sided adhesive tape and a preparation method thereof.
Background
In the processing process of some products, the raw materials need to be fixed by using the adhesive tape so as to be convenient to process, and the products need to be conveniently taken down after the processing is finished, so that the quality of the products is not affected. For example, in the process of processing a semiconductor chip, the wafer material needs to be bonded and fixed to play a protective role when being cut and ground; when the processing is finished, the wafer slice is required to be easily and completely taken off from the fixed position, and the wafer is not influenced. Meanwhile, when tiny components such as plastic parts, glass, metal plates and the like are processed, the tiny components are usually fixed by adopting adhesive tapes, so that damage caused by movement of the components in a cutting process is avoided. The adhesive tape for fixing can provide better adhesive strength at normal temperature, and can be easily taken down when processing is finished, so that the processed parts are not damaged. The prior art generally adopts the visbreaking double-sided adhesive tape to process, and the adhesive tape keeps high adhesive force during fixing, so that the fixed stability of a stuck object is ensured, and the adhesive tape viscosity is reduced in a heating or UV mode after the processing is finished, so that the fixed object can be easily removed.
Some visbreaking double-sided tapes are known in the art. For example, patent CN210012792U discloses a UV-reducing film, but the film can only be removed under specific UV conditions, and at the same time the crosslinking reaction under UV excitation is irreversible, and the double-sided tape can only be used once. For another example, the techniques disclosed in patent CN109749672a and patent CN113817423a utilize the volume expansion of thermally expanded microspheres under heating to achieve a thermal viscosity reduction effect, which is also single-pass and irreversible. For another example, patent CN113845849a discloses a technology for doping thermotropic liquid crystal to achieve the effect of thermal viscosity reduction, but the preparation process of the liquid crystal monomer is cumbersome and time-consuming, and is not suitable for industrial production.
Disclosure of Invention
Aiming at the defects of the prior art, the first aim of the invention is to provide a reversible thermal visbreaking pressure-sensitive adhesive which has higher bonding strength at normal temperature and can play a better role in fixation; the adhesive property is rapidly reduced when heating, and the adhered object can be easily removed; meanwhile, the pressure-sensitive adhesive can restore a stronger bonding effect when the pressure-sensitive adhesive is cooled to normal temperature.
The second object of the invention is to provide a preparation method of the reversible thermal visbreaking pressure-sensitive adhesive, which has the advantages of simple steps and high production efficiency.
The third object of the invention is to provide a reversible thermal visbreaking double-sided adhesive tape, which has a reversible visbreaking effect, can be reused in the application process, improves the production efficiency and reduces the material loss.
The fourth object of the invention is to provide a preparation method of the reversible thermal visbreaking double-sided adhesive tape, which has the advantages of simple steps and high production efficiency.
In order to achieve the first object of the invention, the invention provides a reversible thermal visbreaking pressure-sensitive adhesive, which comprises the following raw materials: an acrylate polymer solution, a tackifying resin, and a crosslinker; the mass ratio of the solid matters, the tackifying resin and the crosslinking agent in the acrylic acid ester polymer solution is 100: (5-20): (0.2-1.2); the acrylic ester polymer solution comprises the following raw materials in parts by mass: 60-120 parts of acrylic acid long-chain alkyl ester monomer, 100-150 parts of acrylic acid and ester monomer thereof, 0.1-1 part of initiator and a proper amount of solvent; in the acrylic ester polymer solution, the acrylic acid long-chain alkyl ester monomer is polymerized to obtain the polyacrylic acid long-chain alkyl ester, and the polyacrylic acid long-chain alkyl ester is polymerized with the acrylic acid and the ester monomer thereof.
In some embodiments of the invention, the mass ratio of solids in the acrylate polymer solution, the tackifying resin, and the crosslinker is 100: (9-13): (0.6-1.1).
In some embodiments of the invention, the acrylate polymer solution comprises the following raw materials in parts by mass: 70-110 parts of acrylic acid long-chain alkyl ester monomer, 105-148 parts of acrylic acid and ester monomer thereof, 0.5-0.7 part of initiator and 200-250 parts of solvent.
In some embodiments of the present invention, the acrylic acid and its ester monomers are a mixture of isooctyl acrylate, butyl acrylate, acrylic acid, hydroxyethyl acrylate, and methyl acrylate, the mass ratio of isooctyl acrylate, butyl acrylate, acrylic acid, hydroxyethyl acrylate, and methyl acrylate being (10-60): (30-80): (2-6): (1-3): (5-25).
In some embodiments of the present invention, the acrylic acid and its ester monomers are a mixture of isooctyl acrylate, butyl acrylate, acrylic acid, hydroxyethyl acrylate, and methyl acrylate, the mass ratio of isooctyl acrylate, butyl acrylate, acrylic acid, hydroxyethyl acrylate, and methyl acrylate being (20-60): (50-80): (5-6): (2-3): (15-25).
In some embodiments of the invention, the long chain alkyl acrylate monomer is at least one of cetyl acrylate, stearyl acrylate, and behenyl acrylate.
In some embodiments of the invention, the solvent is at least one of ethyl acetate, butyl acetate, toluene.
In some embodiments of the invention, the initiator comprises: at least one of benzoyl peroxide, azobisisobutyronitrile and azobisisoheptonitrile.
In some embodiments of the invention, the crosslinking agent comprises at least one of an isocyanate-based crosslinking agent, an epoxy-based crosslinking agent.
In some embodiments of the invention, the tackifying resin is at least one of a terpene and its derivative resin, rosin and its derivative resin.
In some embodiments of the invention, the tackifying resin has a softening point of 120 to 150 ℃.
In order to achieve the second object of the present invention, the present invention provides a method for preparing a reversible thermal-viscosity-reducing pressure-sensitive adhesive according to any one of the above-mentioned aspects, comprising the steps of:
step one: carrying out a first-step reaction on acrylic acid long-chain alkyl ester monomers, a first part of solvents and a first part of initiators in a reaction container, and then adding acrylic acid and ester monomers thereof, a second part of solvents and a second part of initiators to carry out a second-step reaction to obtain acrylic ester polymer solution;
step two: and uniformly mixing the acrylic polymer solution, the tackifying resin and the cross-linking agent to obtain the pressure-sensitive adhesive solution.
In some embodiments of the invention, in the first step, the reaction vessel is provided with a stirrer, a thermometer, a reflux condenser, a nitrogen inlet pipe and a dropping funnel; firstly, heating a solution of acrylic long-chain alkyl ester monomers, and then adding a first part of solution of an initiator; the first step reaction is carried out under the nitrogen atmosphere; the reaction temperature of the first step reaction is 60-90 ℃ and the reaction time is 60-90 minutes; the acrylic acid and the ester monomer thereof, the second part of solvent and the second part of initiator are uniformly mixed and then are added into the reaction container in a dropwise manner; the reaction temperature of the second step is 60-90 ℃ and the reaction time is 4-6 hours; the total amount of the first part of solvent and the second part of solvent is the dosage of the solvent; the total amount of the first portion of initiator and the second portion of initiator is the amount of the initiator.
In some embodiments of the present invention, in the second step, the acrylic polymer solution, the tackifying resin, and the crosslinking agent are stirred and mixed uniformly; and a diluent or no diluent is added to the acrylate polymer solution, the tackifying resin and the crosslinking agent.
In order to achieve the third object of the invention, the invention provides a reversible thermal visbreaking double-sided adhesive tape, which comprises a tape body, wherein the tape body comprises a first adhesive layer, a reinforcing body layer, a second adhesive layer and a release protective layer which are sequentially laminated, and at least one of the first adhesive layer and the second adhesive layer is the reversible thermal visbreaking pressure-sensitive adhesive according to any one of the schemes.
In order to achieve the fourth object of the present invention, the present invention provides a method for preparing a reversible thermal-viscosity-reducing double-sided tape according to any one of the above embodiments, comprising the steps of:
step one: carrying out a first-step reaction on acrylic acid long-chain alkyl ester monomers, a first part of solvents and a first part of initiators in a reaction container, and then adding acrylic acid and ester monomers thereof, a second part of solvents and a second part of initiators to carry out a second-step reaction to obtain acrylic ester polymer solution;
step two: uniformly mixing an acrylic polymer solution, tackifying resin and a cross-linking agent to obtain a pressure-sensitive adhesive solution;
step three: and coating the pressure-sensitive adhesive solution on the release protective layer, drying to form a composite layer of the second adhesive layer and the release protective layer, bonding the composite layer on the first surface of the reinforcing body layer, coating or transferring the first adhesive layer on the second surface of the reinforcing body layer, and curing in a drying room to obtain the double-sided adhesive tape.
In some embodiments of the invention, in the third step, the release protective layer is release paper; the reinforced body layer is a PE foam base material; the curing temperature of the drying room is 35-45 ℃ and the curing time is 2-4 days.
In some embodiments of the invention, the reinforcing body layer has a thickness of 50 to 200 μm.
In some embodiments of the invention, the first adhesive layer has a thickness of 20 to 100 μm and the second adhesive layer has a thickness of 20 to 100 μm.
Compared with the prior art, the invention has the following beneficial effects:
the reversible thermal visbreaking pressure-sensitive adhesive of the invention utilizes acrylic acid long-chain alkyl ester monomer to polymerize to obtain polyacrylic acid long-chain alkyl ester, and then carries out polymerization reaction of acrylic acid and ester monomer thereof to obtain the acrylic acid long-chain alkyl ester doped acrylic acid ester pressure-sensitive adhesive. The acrylic acid ester pressure-sensitive adhesive has higher bonding strength at normal temperature, can play a better fixing effect, and can easily remove an adherend due to the solid-liquid transition of the long-chain alkyl polyacrylate as the long-chain alkyl polyacrylate has high-temperature melting characteristic when the temperature rises, so that the pressure-sensitive adhesive has increased fluidity and reduced peel strength. And the solid-liquid conversion of the long alkyl polyacrylate is reversible, so that the thermal viscosity reduction effect of the obtained pressure-sensitive adhesive is reversible, and the pressure-sensitive adhesive can be repeatedly used in application. The pressure-sensitive adhesive and the double-sided tape prepared by the pressure-sensitive adhesive can be applied to the adhesion of parts needing temporary fixation in the production process, can be reused, improves the production efficiency and reduces the loss.
Drawings
FIG. 1 is a schematic structural view of an embodiment of the reversible thermal-adhesive double-sided tape of the present invention.
In the figure, 1-a first adhesive layer; 2-a bulk reinforcement layer; 3-a second adhesive layer; 4-release protective layer.
The invention is described in further detail below with reference to the drawings and detailed description.
Detailed Description
The embodiment of the invention provides a reversible thermal viscosity-reducing pressure-sensitive adhesive which has reversible thermal viscosity-reducing property, and is particularly suitable for the situation that the raw materials are fixed by using adhesive tapes in the processing process of products so as to be convenient to process and the products are required to be conveniently removed after the processing is finished.
Specifically, the reversible thermal visbreaking pressure-sensitive adhesive comprises the following raw materials: an acrylate polymer solution, a tackifying resin and a crosslinking agent. The acrylic acid and the ester copolymer thereof are provided by the acrylic acid ester polymer solution, are main substances for playing roles of adhesion and thermal viscosity reduction, and the viscosity and mechanical strength of the pressure-sensitive adhesive can be improved by the tackifying resin and the crosslinking agent. The mass ratio of the solid matters, the tackifying resin and the crosslinking agent in the acrylic acid ester polymer solution is 100: (5-20): (0.2-1.2), and the reversible thermal visbreaking pressure-sensitive adhesive with excellent performance can be obtained by mixing the three components according to the proportion.
Wherein the acrylic ester polymer solution comprises the following raw materials in parts by mass: 60-120 parts of acrylic acid long-chain alkyl ester monomer, 100-150 parts of acrylic acid and ester monomer thereof, 0.1-1 part of initiator and a proper amount of solvent. The raw materials are matched according to the proportion, so that better bonding and thermal viscosity reduction effects can be obtained. The solid matter in the acrylate polymer solution may be acrylic acid long chain alkyl ester monomer, acrylic acid and its ester monomer and initiator. In the acrylic ester polymer solution, the acrylic acid long-chain alkyl ester monomer is polymerized to obtain the acrylic acid long-chain alkyl ester, and the acrylic acid long-chain alkyl ester is polymerized with the acrylic acid and the ester monomer thereof to obtain the acrylic acid and the ester copolymer thereof doped with the acrylic acid long-chain alkyl ester chain segment.
From the above, the acrylic acid ester polymer solution in the pressure-sensitive adhesive of this embodiment adopts acrylic acid and its ester copolymer doped with long-chain alkyl acrylate chain segments, and in the first stage of polymerization, the long-chain alkyl acrylate monomer is polymerized to obtain long-chain alkyl acrylate, and on the basis, polymerization reaction of acrylic acid and its ester monomer is performed to obtain the acrylic acid long-chain alkyl acrylate pressure-sensitive adhesive doped with long-chain alkyl acrylate chain segments. The long-chain alkyl polyacrylate has high-temperature melting characteristic, and when the temperature is increased to be higher than the melting point, the long-chain alkyl polyacrylate is subjected to solid-liquid conversion, so that the fluidity of the pressure-sensitive adhesive is increased, and the peel strength of the pressure-sensitive adhesive is reduced. Since the solid-liquid transition of the long alkyl polyacrylate is reversible, the long alkyl polyacrylate can still maintain the original bonding and thermal visbreaking properties after multiple heating visbreaking. The pressure-sensitive adhesive prepared by the embodiment has higher bonding strength at normal temperature, the bonding strength is reduced along with the temperature rise, and the bonding strength is increased along with the temperature rise again when the temperature is reduced, namely the pressure-sensitive adhesive of the embodiment has reversibility in thermal viscosity reduction effect and can be repeatedly used in application.
In some embodiments, the reversible thermal-reduction pressure-sensitive adhesive is made from the following raw materials: an acrylate polymer solution, a tackifying resin and a crosslinking agent. The reversible thermal visbreaking pressure sensitive adhesive contains no other substances except the raw materials.
In other embodiments, the reversible thermal-viscosity-reducing pressure-sensitive adhesive is made primarily from the following raw materials: an acrylate polymer solution, a tackifying resin and a crosslinking agent. The reversible thermal visbreaking pressure-sensitive adhesive can contain other raw materials besides the raw materials, such as a diluent, a pigment, a filler, a leveling agent, a defoaming agent and the like, wherein the diluent can be an active diluent or an inactive diluent.
In some embodiments, the acrylate polymer solution is prepared from the following raw materials in parts by mass: 60-120 parts of acrylic acid long-chain alkyl ester monomer, 100-150 parts of acrylic acid and ester monomer thereof, 0.1-1 part of initiator and a proper amount of solvent. The raw materials of the acrylic ester polymer solution do not contain other raw materials except acrylic acid long-chain alkyl ester monomers, acrylic acid and ester monomers thereof, an initiator and a solvent.
In some embodiments, the acrylate polymer solution consists essentially of the following raw materials in parts by mass: 60-120 parts of acrylic acid long-chain alkyl ester monomer, 100-150 parts of acrylic acid and ester monomer thereof, 0.1-1 part of initiator and a proper amount of solvent. The acrylate polymer solution may also contain other raw materials, such as some functional aids, etc.
In some embodiments, in addition to the presence of acrylic acid and its ester copolymers doped with long chain alkyl acrylate segments, the presence of polymers of some long chain alkyl acrylate monomers, polymers of acrylic acid and its ester monomers is also allowed in the acrylate polymer solution.
In some embodiments, the reversible thermal-viscosity-reducing pressure-sensitive adhesive is formed after at least partial evaporation of the solvent.
In some embodiments, the mass ratio of solids, tackifying resin, and crosslinker in the acrylate polymer solution is 100: (9-13): (0.6-1.1). When the mass ratio of the solid matters, the tackifying resin and the crosslinking agent in the acrylic acid ester polymer solution is in the above range, the obtained pressure-sensitive adhesive has better bonding and reversible thermal viscosity reduction effects.
In some embodiments, the acrylate polymer solution comprises the following raw materials in parts by mass: 70-110 parts of acrylic acid long-chain alkyl ester monomer, 105-148 parts of acrylic acid and ester monomer thereof, 0.5-0.7 part of initiator and 200-250 parts of solvent. When the mass ratio of the acrylic polymer solution is within the above range, the obtained pressure-sensitive adhesive has better bonding and reversible thermal viscosity reduction effects.
In some embodiments, the acrylic acid and its ester monomers are a mixture of isooctyl acrylate, butyl acrylate, acrylic acid, hydroxyethyl acrylate, and methyl acrylate, and the tackiness of the pressure-sensitive adhesive is tuned by a variety of acrylic acids and their esters. Wherein, the mass ratio of the isooctyl acrylate to the butyl acrylate to the acrylic acid to the hydroxyethyl acrylate to the methyl acrylate is (10-60): (30-80): (2-6): (1-3): (5-25). When the mass ratio of each component is in the range, the obtained pressure-sensitive adhesive can have proper adhesiveness, and is suitable for the processing requirement of products.
In some embodiments, the mass ratio of isooctyl acrylate, butyl acrylate, acrylic acid, hydroxyethyl acrylate, and methyl acrylate is (20-60): (50-80): (5-6): (2-3): (15-25). When the mass ratio of each component is in the above range, the pressure-sensitive adhesive obtained can have better adhesiveness.
In some embodiments, the long chain alkyl acrylate monomer is at least one of cetyl acrylate, stearyl acrylate, and behenyl acrylate. These acrylate monomers all have a longer alkyl chain, and reversible thermal visbreaking effect can be obtained by utilizing the reversible melting characteristic of the alkyl chain.
In some embodiments, the solvent is at least one of ethyl acetate, butyl acetate, toluene. The solvent has low toxicity, is easy to recycle and is environment-friendly.
In some embodiments, the initiator comprises: at least one of benzoyl peroxide, azodiisobutyronitrile and azodiisoheptonitrile can well initiate the polymerization of acrylic acid and ester monomers thereof by adopting the initiator.
In some embodiments, the crosslinker comprises at least one of an isocyanate-based crosslinker, an epoxy-based crosslinker. The cross-linking agent can enable polymers to be cross-linked, and the mechanical strength of the pressure-sensitive adhesive is improved.
In some embodiments, the tackifying resin is at least one of a terpene and its derivative resin, rosin and its derivative resin. The tackifying resin has the advantages of easily available raw materials and good tackifying effect.
In some embodiments, the tackifying resin has a softening point of 120 to 150 ℃ and can improve the heat resistance of the pressure sensitive adhesive.
In some embodiments, the preparation method of the reversible thermal visbreaking pressure-sensitive adhesive comprises the following steps:
step one: carrying out a first-step reaction on acrylic acid long-chain alkyl ester monomers, a first part of solvents and a first part of initiators in a reaction container, and then adding acrylic acid and ester monomers thereof, a second part of solvents and a second part of initiators to carry out a second-step reaction to obtain acrylic ester polymer solution;
step two: and uniformly mixing the acrylic polymer solution, the tackifying resin and the cross-linking agent to obtain the pressure-sensitive adhesive solution.
Therefore, the pressure-sensitive adhesive of the embodiment is obtained by adopting two-step polymerization to obtain the acrylic polymer doped with the polyacrylic acid long-chain alkyl ester chain segment, and then mixing the acrylic polymer with the tackifying resin and the crosslinking agent, so that the pressure-sensitive adhesive of the embodiment can be obtained, and the preparation method is simple.
In some embodiments, in the first step, the reaction vessel is provided with a stirrer, a thermometer, a reflux condenser, a nitrogen inlet pipe and a dropping funnel, wherein the stirrer is used for uniformly mixing materials through stirring, the thermometer is used for obtaining temperature to realize temperature control, the reflux condenser is used for refluxing a solvent, the nitrogen inlet pipe is used for introducing nitrogen to realize nitrogen protection, and the dropping funnel is used for adding materials.
In some embodiments, in step one, the solution of long chain alkyl acrylate monomers is heated prior to the addition of the first portion of the solution of initiator to better control the progress of the reaction.
In some embodiments, the reaction temperature of the first reaction step is 60-90 ℃ and the reaction time is 60-90 minutes, so that the long-chain alkyl acrylate monomer can be fully reacted to obtain the long-chain alkyl polyacrylate.
In some embodiments, in step one, the acrylic acid and its ester monomers, the second portion of solvent, and the second portion of initiator are mixed uniformly and then added dropwise to the reaction vessel so that the reaction is uniform and does not proceed vigorously.
In some embodiments, the reaction temperature of the second reaction step is 60-90 ℃ and the reaction time is 4-6 hours, so that the acrylic acid and the ester monomer thereof can be fully reacted to obtain the copolymer doped with the poly (long chain alkyl acrylate).
In some embodiments, the total amount of the first portion of solvent and the second portion of solvent is the total amount of solvent. The solvent of the first part is used for mixing with the acrylic long-chain alkyl ester monomer, and the solvent of the second part is used for mixing with the initiator of the second part, so that the solution of the initiator of the second part can be added into the preheated acrylic long-chain alkyl ester monomer solution in a dropwise manner for reaction. The mass ratio of the first portion of solvent to the second portion of solvent may be 1: (0.5-2).
In some embodiments, the total amount of the first portion of initiator and the second portion of initiator is the amount of the initiator. The mass ratio of the first portion of initiator to the second portion of initiator may be 1: (0.5-2).
In some embodiments, in step two, the acrylic polymer solution, tackifying resin, and crosslinking agent are mixed uniformly by stirring.
In some embodiments, in the second step, a diluent is further added to the acrylic polymer solution, the tackifying resin and the crosslinking agent to adjust the viscosity of the pressure-sensitive adhesive solution. In other embodiments, no diluent may be added.
In some embodiments, the present embodiment further provides a reversible thermal-adhesion-reducing double-sided tape, including a tape body, as shown in fig. 1, which includes a first adhesive layer 1, a reinforcing body layer 2, a second adhesive layer 3, and a release protective layer 4 laminated in this order. Wherein, the first adhesive layer 1 and the second adhesive layer 3 play a role in adhesion, the reinforcing body layer 2 plays a role in reinforcement, and the release protection layer 4 provides protection and support for the adhesive tape. The reversible thermal visbreaking double-sided adhesive tape can be in a form that a first adhesive layer 1 of one layer of double-sided adhesive tape is adhered to the back surface of a release protection layer 4 of the other layer of double-sided adhesive tape, so that the double-sided adhesive tape can be wound or laminated, and the double-sided adhesive tape is convenient to store and transport. Wherein at least one of the first adhesive layer 1 and the second adhesive layer 3 is the reversible thermal-reduction pressure-sensitive adhesive in the above embodiment. For example, one of the first adhesive layer 1 and the second adhesive layer 3 is a reversible thermal-viscosity-reducing pressure-sensitive adhesive for bonding products, and the other is a general adhesive for bonding in a fixed position. For another example, both the first adhesive layer 1 and the second adhesive layer 3 are reversible thermal visbreaking pressure sensitive adhesives, which not only can bond and peel products, but also can adhere and separate the adhesive tape from the equipment, thereby facilitating the movement of the adhesive tape.
In some embodiments, the preparation method of the reversible thermal visbreaking double-sided tape comprises the following steps:
step one: carrying out a first-step reaction on acrylic acid long-chain alkyl ester monomers, a first part of solvents and a first part of initiators in a reaction container, and then adding acrylic acid and ester monomers thereof, a second part of solvents and a second part of initiators to carry out a second-step reaction to obtain acrylic ester polymer solution;
step two: uniformly mixing an acrylic polymer solution, tackifying resin and a cross-linking agent to obtain a pressure-sensitive adhesive solution;
step three: and coating the pressure-sensitive adhesive solution on the release protective layer, drying to form a composite layer of the second adhesive layer and the release protective layer, connecting the composite layer to the first surface of the reinforced body layer, coating or transferring the first adhesive layer on the second surface of the reinforced body layer, and curing in a drying room to obtain the double-sided adhesive tape.
Wherein, the first step and the second step are the preparation method of the pressure-sensitive adhesive. And thirdly, preparing the pressure-sensitive adhesive into a layered adhesive tape, wherein the preparation steps are simple.
In some embodiments, in the third step, the release protective layer is release paper, and the reinforcing body layer is a PE foam substrate, which may be all commonly used raw materials. The curing temperature in the drying room is 35-45 ℃ and the curing time is 2-4 days.
In some embodiments, the specific operations of step three are: fixing the release protective layer on special coating equipment, coating a certain amount of reversible thermal visbreaking pressure-sensitive adhesive as a second adhesive layer, drying to form a film, and compounding with a body reinforcing layer (PE foam) to roll for later use. The coiled material is spread on special coating equipment, a certain amount of reversible thermal viscosity-reducing pressure-sensitive adhesive is coated on the other surface of the body reinforcing layer (PE foam) as a first adhesive layer, and the double-sided adhesive tape can be obtained by drying and film forming and coiling.
In some embodiments, the reinforcing body layer has a thickness of 50 to 200 μm, which may provide good reinforcement.
In some embodiments, the first adhesive layer has a thickness of 20 to 100 μm and the second adhesive layer has a thickness of 20 to 100 μm.
The reversible thermal visbreaking pressure-sensitive adhesive tape of the present invention will be described in further detail by way of specific examples, but the present invention is not limited to the contents included in the examples. In the following examples, unless otherwise specified, the same species and quality are indicated by the same names of substances, and the same process steps are indicated by the same described processes.
Example 1
The formula of the reversible thermal visbreaking pressure-sensitive adhesive of the embodiment is as follows: 100g of hexadecyl acrylate, 30g of isooctyl acrylate, 50g of butyl acrylate, 5g of acrylic acid, 2g of hydroxyethyl acrylate, 20g of methyl acrylate, 220g of ethyl acetate, 0.6g of initiator BPO, 20g of resin D-125 g and 2g of cross-linking agent L-75 g.
The manufacturing method of the reversible thermal visbreaking double-sided tape of the embodiment comprises the following steps:
(1) 100g of hexadecyl acrylate and 120g of ethyl acetate are added into a four-neck flask equipped with a stirrer, a thermometer, a reflux condenser, a nitrogen inlet pipe and a dropping funnel, heated to 80 ℃, 0.3g of initiator BPO (dissolved by 10g of ethyl acetate) is added to initiate reaction, and the reaction is carried out for 90 minutes at 80-82 ℃; uniformly mixing 30g of isooctyl acrylate, 50g of butyl acrylate, 5g of acrylic acid, 2g of hydroxyethyl acrylate, 20g of methyl acrylate, 90g of ethyl acetate and 0.3g of initiator BPO, adding into a dropping funnel, dropping into a reaction system at a uniform speed within 90 minutes, and keeping the temperature at 80-82 ℃; and (3) preserving heat for 270 minutes after the dripping is finished, and cooling to below 50 ℃ to obtain polyacrylate solution for later use.
(2) And (3) adding 20g of resin D-125 and 2g of cross-linking agent L-75 into the polyacrylate solution obtained in the step (1), and uniformly stirring to obtain the reversible thermal visbreaking pressure-sensitive adhesive capable of being coated on a machine.
(3) And (3) coating the pressure-sensitive adhesive obtained in the step (2) on release paper, drying to form a pressure-sensitive adhesive layer (controlling the thickness of a dry adhesive film to be 70 mu m), transferring to a PE foam base material with the thickness of 150 mu m, transferring the same other part of pressure-sensitive adhesive layer formed by drying to the other side of the foam base material, and curing for 3 days at the temperature of 40 ℃ in a drying room to obtain the double-sided adhesive tape.
Example 2
The formula of the reversible thermal visbreaking pressure-sensitive adhesive of the embodiment is as follows: 85g of octadecyl acrylate, 20g of isooctyl acrylate, 80g of butyl acrylate, 6g of acrylic acid, 2g of hydroxyethyl acrylate, 20g of methyl acrylate, 220g of ethyl acetate, 0.7g of initiator BPO, 25g of resin D-125 g and 1.5g of cross-linking agent L-75.
The preparation method of the reversible thermal visbreaking double-sided adhesive tape comprises the following steps:
(1) 85g of octadecyl acrylate and 120g of ethyl acetate are added into a four-necked flask equipped with a stirrer, a thermometer, a reflux condenser, a nitrogen inlet pipe and a dropping funnel, heated to 80 ℃, 0.3g of initiator BPO (dissolved by 10g of ethyl acetate) is added to initiate reaction, and the reaction is carried out for 90 minutes at 80-82 ℃; uniformly mixing 20g of isooctyl acrylate, 80g of butyl acrylate, 6g of acrylic acid, 2g of hydroxyethyl acrylate, 20g of methyl acrylate, 90g of ethyl acetate and 0.4g of initiator BPO, adding into a dropping funnel, dropping into a reaction system at a uniform speed within 90 minutes, and keeping the temperature at 80-82 ℃; and (3) preserving heat for 270 minutes after the dripping is finished, and cooling to below 50 ℃ to obtain polyacrylate solution for later use.
(2) And (3) adding 25g of resin D-125 and 1.5g of cross-linking agent L-75 into the polyacrylate solution obtained in the step (1), and uniformly stirring to obtain the reversible thermal visbreaking pressure-sensitive adhesive capable of being coated on a machine.
(3) And (3) coating the pressure-sensitive adhesive obtained in the step (2) on release paper, drying to form a pressure-sensitive adhesive layer (controlling the thickness of a dry adhesive film to be 70 mu m), transferring to a PE foam base material with the thickness of 150 mu m, transferring the same other part of pressure-sensitive adhesive layer formed by drying to the other side of the foam base material, and curing for 3 days at the temperature of 40 ℃ in a drying room to obtain the double-sided adhesive tape.
Example 3
The formula of the reversible thermal visbreaking pressure-sensitive adhesive of the embodiment is as follows: sixteen acrylic acid ester 50g, twenty-two acrylic acid ester 40g, isooctyl acrylate 25g, butyl acrylate 80g, acrylic acid 5g, hydroxyethyl acrylate 3g, methyl acrylate 25g, butyl acetate 250g, initiator BPO 0.6g, resin D-125 g and cross-linking agent L-75.5 g.
The preparation method of the reversible thermal visbreaking double-sided adhesive tape comprises the following steps:
(1) 50g of hexadecyl acrylate, 40g of behenyl acrylate and 120g of butyl acetate were added to a four-necked flask equipped with a stirrer, a thermometer, a reflux condenser, a nitrogen inlet tube and a dropping funnel, heated to 80℃and 0.3g of BPO (dissolved in 10g of butyl acetate) as an initiator was added to initiate the reaction, and the reaction was carried out at 80 to 82℃for 90 minutes; uniformly mixing 25g of isooctyl acrylate, 80g of butyl acrylate, 5g of acrylic acid, 3g of hydroxyethyl acrylate, 25g of methyl acrylate, 120g of butyl acetate and 0.3g of initiator BPO, adding into a dropping funnel, dropping into a reaction system at a uniform speed within 90 minutes, and keeping the temperature at 80-82 ℃; and (3) preserving heat for 270 minutes after the dripping is finished, and cooling to below 50 ℃ to obtain polyacrylate solution for later use.
(2) And (3) adding 28g of resin D-125 and 2.5g of cross-linking agent L-75 into the polyacrylate solution obtained in the step (1), and uniformly stirring to obtain the reversible thermal visbreaking pressure-sensitive adhesive capable of being coated on a machine.
(3) And (3) coating the pressure-sensitive adhesive obtained in the step (2) on release paper, drying to form a pressure-sensitive adhesive layer (controlling the thickness of a dry adhesive film to be 70 mu m), transferring to a PE foam base material with the thickness of 150 mu m, transferring the same other part of pressure-sensitive adhesive layer formed by drying to the other side of the foam base material, and curing for 3 days at the temperature of 40 ℃ in a drying room to obtain the double-sided adhesive tape.
Example 4
The formula of the reversible thermal visbreaking pressure-sensitive adhesive of the embodiment is as follows: sixteen acrylic acid ester 70g, isooctyl acrylate 60g, butyl acrylate 60g, acrylic acid 6g, hydroxyethyl acrylate 2g, methyl acrylate 20g, ethyl acetate 220g, initiator AIBN 0.5g, resin D-135 20g and cross-linking agent XM-100X2g.
The preparation method of the reversible thermal visbreaking double-sided adhesive tape comprises the following steps:
(1) 70g of hexadecyl acrylate and 100g of ethyl acetate were charged into a four-necked flask equipped with a stirrer, a thermometer, a reflux condenser, a nitrogen inlet tube and a dropping funnel, and N was introduced 2 Heating to 65 ℃ with stirring, adding 0.2g of initiator AIBN (dissolved by 10g of ethyl acetate), initiating the reaction, and reacting for 75 minutes at 65+/-2 ℃; uniformly mixing 60g of isooctyl acrylate, 60g of butyl acrylate, 6g of acrylic acid, 2g of hydroxyethyl acrylate, 20g of methyl acrylate, 110g of ethyl acetate and 0.3g of initiator AIBN, adding the mixture into a dropping funnel, dropping the mixture into a reaction system at a uniform speed within 90 minutes, and keeping the temperature at 65+/-2 ℃; and (3) preserving heat for 270 minutes after the dripping is finished, and cooling to below 50 ℃ to obtain polyacrylate solution for later use.
(2) And (3) adding 20g of resin D-135 and 2g of cross-linking agent XM-100X into the polyacrylate solution obtained in the step (1), and uniformly stirring to obtain the reversible thermal visbreaking pressure-sensitive adhesive capable of being coated on a machine.
(3) And (3) coating the pressure-sensitive adhesive obtained in the step (2) on release paper, drying to form a pressure-sensitive adhesive layer (controlling the thickness of a dry adhesive film to be 70 mu m), transferring to a PE foam base material with the thickness of 200 mu m, transferring the same other part of pressure-sensitive adhesive layer formed by drying to the other side of the foam base material, and curing for 3 days at the temperature of 40 ℃ in a drying room to obtain the double-sided adhesive tape.
Example 5
The formula of the reversible thermal visbreaking pressure-sensitive adhesive of the embodiment is as follows: sixteen acrylic acid ester 50g, octadecyl acrylic acid ester 60g, isooctyl acrylate 20g, butyl acrylate 80g, acrylic acid 6g, hydroxyethyl acrylate 2g, methyl acrylate 15g, ethyl acetate 180g, toluene 70g, initiator AIBN 0.5g, resin D-125 20g, resin SYLVARES-1150 10g, and cross-linking agent L-90.5 g.
The preparation method of the reversible thermal visbreaking double-sided adhesive tape comprises the following steps:
(1) Into a four-necked flask equipped with a stirrer, a thermometer, a reflux condenser, a nitrogen inlet tube and a dropping funnel, 50g of hexadecyl acrylate, 60g of octadecyl acrylate and 130g of ethyl acetate were charged with N 2 Heating to 65 ℃ with stirring, adding 0.25g of initiator AI BN (dissolved by 10g of ethyl acetate), initiating the reaction, and reacting for 90 minutes at 65+/-2 ℃; uniformly mixing 20g of isooctyl acrylate, 80g of butyl acrylate, 6g of acrylic acid, 2g of hydroxyethyl acrylate, 15g of methyl acrylate, 40g of ethyl acetate, 70g of toluene and 0.25g of initiator AIBN, adding into a dropping funnel, uniformly dropping into a reaction system within 90 minutes, and keeping the temperature at 65+/-2 ℃; and after the dripping is finished, preserving the heat for 300 minutes, and cooling to below 50 ℃ to obtain polyacrylate solution for standby.
(2) And (2) adding 20g of resin D-125, 10g of resin SYLVARES-1150 and 1.5g of cross-linking agent L-90 into the polyacrylate solution obtained in the step (1), and uniformly stirring to obtain the reversible thermal visbreaking pressure-sensitive adhesive capable of being coated on a machine.
(3) And (3) coating the pressure-sensitive adhesive obtained in the step (2) on release paper, drying to form a pressure-sensitive adhesive layer (controlling the thickness of a dry adhesive film to be 70 mu m), transferring to a PE foam base material with the thickness of 200 mu m, transferring the same other part of pressure-sensitive adhesive layer formed by drying to the other side of the foam base material, and curing for 3 days at the temperature of 40 ℃ in a drying room to obtain the double-sided adhesive tape.
Example 6
The formula of the reversible thermal visbreaking pressure-sensitive adhesive of the embodiment is as follows: 40g of hexadecyl acrylate, 25g of isooctyl acrylate, 130g of butyl acrylate, 5g of acrylic acid, 3g of hydroxyethyl acrylate, 25g of methyl acrylate, 250g of ethyl acetate, 0.6g of initiator BPO, 28g of resin D-125 g and 2.5g of cross-linking agent L-75.
The preparation method of the reversible thermal visbreaking double-sided adhesive tape comprises the following steps:
(1) 40g of hexadecyl acrylate, 50g of butyl acrylate and 120g of ethyl acetate are added into a four-neck flask equipped with a stirrer, a thermometer, a reflux condenser, a nitrogen inlet pipe and a dropping funnel, heated to 80 ℃, 0.3g of initiator BPO (dissolved by 10g of ethyl acetate) is added to initiate reaction, and the reaction is carried out for 90 minutes at 80-82 ℃; uniformly mixing 25g of isooctyl acrylate, 80g of butyl acrylate, 5g of acrylic acid, 3g of hydroxyethyl acrylate, 25g of methyl acrylate, 120g of ethyl acetate and 0.3g of initiator BPO, adding into a dropping funnel, dropping into a reaction system at a uniform speed within 90 minutes, and keeping the temperature at 80-82 ℃; and (3) preserving heat for 270 minutes after the dripping is finished, and cooling to below 50 ℃ to obtain polyacrylate solution for later use.
(2) And (3) adding 28g of resin D-125 and 2.5g of cross-linking agent L-75 into the polyacrylate solution obtained in the step (1), and uniformly stirring to obtain the reversible thermal visbreaking pressure-sensitive adhesive capable of being coated on a machine.
(3) And (3) coating the pressure-sensitive adhesive obtained in the step (2) on release paper, drying to form a pressure-sensitive adhesive layer (controlling the thickness of a dry adhesive film to be 70 mu m), transferring to a PE foam base material with the thickness of 150 mu m, transferring the same other pressure-sensitive adhesive layer formed by drying to the other side of the foam base material, and curing for 3 days at the temperature of 40 ℃ in a drying room to obtain the double-sided adhesive tape.
The double-sided tape obtained in each of the examples and comparative examples was subjected to a normal temperature peel force test and a high temperature peel force test. The test method is as follows:
(1) The normal temperature peeling force testing method comprises the following steps:
| test board | SUS-A |
| Width of adhesive tape | 25mm |
| Pressure conditions | 2kg,600mm/min, rolling back and forth 2 times |
| Reinforced film | 25μm PET |
| Time of immersion | RT 30min |
| Peeling speed | 300mm/min |
| Test environment | Temperature 23+ -1deg.C, humidity (50+ -5%) RH |
| Test unit | N/25cm |
(2) The high-temperature stripping force testing method comprises the following steps:
the high temperature peeling force test is carried out at normal temperature except for the soaking time and the test environment.
The test results are shown in table 1 below.
TABLE 1 results of the normal temperature peel force test and the high temperature peel force test
The samples of the respective examples after the above-mentioned heat-thinning test were subjected to the peeling force test again by sticking SUS-A and repeating the peeling force test at 23℃C/60℃C/80℃C, and the results are shown in Table 2 below.
Table 2 results of the room temperature peel force test and the high temperature peel force test for re-adhesion of examples
/>
From the above, the pressure-sensitive adhesive and the double-sided tape of examples 1 to 5 within the scope of the present invention have high adhesive strength at normal temperature, the adhesive property is drastically reduced when heated, and the pressure-sensitive adhesive can recover a strong adhesive effect, i.e., has good reversible thermal visbreaking property when cooled to normal temperature. In the pressure-sensitive adhesive and the double-sided tape of example 6, the long-chain segment of the long-chain alkyl acrylate is not formed, and the copolymer of the long-chain alkyl acrylate and the butyl acrylate formed in the first stage has a higher solid-liquid conversion temperature point, so that the pressure-sensitive adhesive has no obvious viscosity reducing effect at a specific temperature. Pressure sensitive adhesives and double sided tapes have poor thermal tack reduction.
Finally, it should be emphasized that the above description is merely of a preferred embodiment of the invention, and is not intended to limit the invention. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (10)
1. The reversible thermal visbreaking pressure sensitive adhesive is characterized by comprising the following raw materials: an acrylate polymer solution, a tackifying resin, and a crosslinker; the mass ratio of the solid matters, the tackifying resin and the crosslinking agent in the acrylic acid ester polymer solution is 100: (5-20): (0.2-1.2);
the acrylic ester polymer solution comprises the following raw materials in parts by mass: 60-120 parts of acrylic acid long-chain alkyl ester monomer, 100-150 parts of acrylic acid and ester monomer thereof, 0.1-1 part of initiator and a proper amount of solvent;
in the acrylic ester polymer solution, the acrylic acid long-chain alkyl ester monomer is polymerized to obtain the polyacrylic acid long-chain alkyl ester, and the polyacrylic acid long-chain alkyl ester is polymerized with the acrylic acid and the ester monomer thereof.
2. The reversible thermal visbreaking pressure sensitive adhesive of claim 1, wherein:
the mass ratio of the solid matters, the tackifying resin and the crosslinking agent in the acrylic acid ester polymer solution is 100: (9-13): (0.6-1.1); and/or
The acrylic ester polymer solution comprises the following raw materials in parts by mass: 70-110 parts of acrylic acid long-chain alkyl ester monomer, 105-148 parts of acrylic acid and ester monomer thereof, 0.5-0.7 part of initiator and 200-250 parts of solvent.
3. The reversible thermal visbreaking pressure sensitive adhesive of claim 1 or 2, wherein:
the acrylic acid and the ester monomer thereof are a mixture of isooctyl acrylate, butyl acrylate, acrylic acid, hydroxyethyl acrylate and methyl acrylate, and the mass ratio of isooctyl acrylate to butyl acrylate to acrylic acid to hydroxyethyl acrylate to methyl acrylate is (10-60): (30-80): (2-6): (1-3): (5-25).
4. A reversible thermal visbreaking pressure sensitive adhesive as claimed in claim 3, wherein:
the mass ratio of the isooctyl acrylate to the butyl acrylate to the acrylic acid to the hydroxyethyl acrylate to the methyl acrylate is (20-60): (50-80): (5-6): (2-3): (15-25).
5. The reversible thermal visbreaking pressure sensitive adhesive of claim 1 or 2, wherein:
the acrylic acid long-chain alkyl ester monomer is at least one of acrylic acid hexadecyl ester, acrylic acid octadecyl ester and acrylic acid docosyl ester; and/or
The solvent is at least one of ethyl acetate, butyl acetate and toluene; and/or
The initiator comprises: at least one of benzoyl peroxide, azobisisobutyronitrile and azobisisoheptonitrile; and/or
The cross-linking agent comprises at least one of isocyanate cross-linking agent and epoxy cross-linking agent; and/or
The tackifying resin is at least one of terpene and derivative resin thereof, rosin and derivative resin thereof; and/or
The softening point of the tackifying resin is 120-150 ℃.
6. The method for preparing a reversible thermal-viscosity-reducing pressure-sensitive adhesive according to any one of claims 1 to 5, characterized by comprising the steps of:
step one: carrying out a first-step reaction on acrylic acid long-chain alkyl ester monomers, a first part of solvents and a first part of initiators in a reaction container, and then adding acrylic acid and ester monomers thereof, a second part of solvents and a second part of initiators to carry out a second-step reaction to obtain acrylic ester polymer solution;
step two: and uniformly mixing the acrylic polymer solution, the tackifying resin and the cross-linking agent to obtain the pressure-sensitive adhesive solution.
7. The method of manufacturing according to claim 6, wherein:
in the first step, the reaction vessel is provided with a stirrer, a thermometer, a reflux condenser, a nitrogen inlet pipe and a dropping funnel; firstly, heating a solution of acrylic long-chain alkyl ester monomers, and then adding a first part of solution of an initiator; the first step reaction is carried out under the nitrogen atmosphere; the reaction temperature of the first step reaction is 60-90 ℃ and the reaction time is 60-90 minutes; the acrylic acid and the ester monomer thereof, the second part of solvent and the second part of initiator are uniformly mixed and then are added into the reaction container in a dropwise manner; the reaction temperature of the second step is 60-90 ℃ and the reaction time is 4-6 hours; the total amount of the first part of solvent and the second part of solvent is the dosage of the solvent; the total amount of the first part of initiator and the second part of initiator is the amount of the initiator;
in the second step, the acrylic polymer solution, the tackifying resin and the cross-linking agent are stirred and mixed uniformly; and a diluent or no diluent is added into the acrylic polymer solution, the tackifying resin and the crosslinking agent.
8. A reversible thermal visbreaking double-sided tape characterized by comprising a tape body, wherein the tape body comprises a first adhesive layer, a reinforcing body layer, a second adhesive layer and a release protective layer which are sequentially laminated, and at least one of the first adhesive layer and the second adhesive layer is the reversible thermal visbreaking pressure-sensitive adhesive of any one of claims 1 to 5.
9. The method for preparing the reversible thermal visbreaking double-sided tape according to claim 8, which is characterized by comprising the following steps:
step one: carrying out a first-step reaction on acrylic acid long-chain alkyl ester monomers, a first part of solvents and a first part of initiators in a reaction container, and then adding acrylic acid and ester monomers thereof, a second part of solvents and a second part of initiators to carry out a second-step reaction to obtain acrylic ester polymer solution;
step two: uniformly mixing an acrylic polymer solution, tackifying resin and a cross-linking agent to obtain a pressure-sensitive adhesive solution;
step three: and coating the pressure-sensitive adhesive solution on the release protective layer, drying to form a composite layer of the second adhesive layer and the release protective layer, bonding the composite layer on the first surface of the reinforcing body layer, coating or transferring the first adhesive layer on the second surface of the reinforcing body layer, and curing in a drying room to obtain the double-sided adhesive tape.
10. The method of manufacturing according to claim 9, wherein:
in the third step, the release protective layer is release paper; the reinforced body layer is a PE foam base material; the curing temperature of the drying room is 35-45 ℃ and the curing time is 2-4 days;
the thickness of the reinforced body layer is 50-200 mu m;
the thickness of the first adhesive layer is 20-100 mu m, and the thickness of the second adhesive layer is 20-100 mu m.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202311806071.6A CN117801730A (en) | 2023-12-25 | 2023-12-25 | Reversible thermal viscosity-reducing pressure-sensitive adhesive, double-sided adhesive tape and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202311806071.6A CN117801730A (en) | 2023-12-25 | 2023-12-25 | Reversible thermal viscosity-reducing pressure-sensitive adhesive, double-sided adhesive tape and preparation method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN117801730A true CN117801730A (en) | 2024-04-02 |
Family
ID=90426206
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202311806071.6A Pending CN117801730A (en) | 2023-12-25 | 2023-12-25 | Reversible thermal viscosity-reducing pressure-sensitive adhesive, double-sided adhesive tape and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN117801730A (en) |
-
2023
- 2023-12-25 CN CN202311806071.6A patent/CN117801730A/en active Pending
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP4623485B2 (en) | Adhesive composition and surface protective film | |
| US9109142B2 (en) | Photocurable adhesive composition, photocurable adhesive layer, and photocurable adhesive sheet | |
| US8242185B2 (en) | Adhesive compositions for easy application and improved durability | |
| WO2001046328A1 (en) | Acrylic polymer compositions, acrylic pressure-sensitive adhesion tapes and process for producing the same | |
| CN111133070B (en) | Adhesive sheet | |
| EP2439246B1 (en) | Photocurable adhesive composition, photocurable adhesive layer, and photocurable adhesive sheet | |
| EP0902071B1 (en) | Thermosetting pressure-sensitive adhesive and adhesive sheets made by using the same | |
| CN111492007A (en) | Resin composition, resin layer, and laminate sheet | |
| EP2508583B1 (en) | Photocurable pressure-sensitive adhesive composition, photocurable pressure-sensitive adhesive layer, and photocurable pressure-sensitive adhesive sheet | |
| JPH11293222A (en) | Pressure-sensitive adhesive composition | |
| JP4516632B2 (en) | Acrylic pressure-sensitive adhesive composition and its adhesive sheets | |
| JPH08120248A (en) | Pressure-sensitive acrylic adhesive composition | |
| JP3849889B2 (en) | Acrylic adhesive composition | |
| JP2000230161A (en) | Adhesive composition and adhesive film | |
| US9562173B2 (en) | Preparation method for porous pressure sensitive adhesive article | |
| CN117801730A (en) | Reversible thermal viscosity-reducing pressure-sensitive adhesive, double-sided adhesive tape and preparation method thereof | |
| JP2002012842A (en) | Acrylic thermoset adhesive and adhesive sheets | |
| JPH08143847A (en) | Acrylic adhesive composition | |
| JP2000265137A (en) | Pressure-sensitive adhesive composition and its bonding sheets | |
| US6312799B1 (en) | Pressure-sensitive acrylic adhesive composition for adhesion of polyester film and adhesive sheets thereof | |
| JP2008038103A (en) | Heat-resistant pressure-sensitive adhesive composition | |
| CN112210325B (en) | Adhesive composition | |
| JP2002012841A (en) | Acrylic thermoset adhesive composition and adhesive sheets | |
| JP3052062B2 (en) | Pressure sensitive adhesive composition and surface protection sheet | |
| JP2004217740A (en) | Adhesive composition and adhesive sheet using the same |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination |