CN114836138A - Super elastic glue, preparation method and application - Google Patents
Super elastic glue, preparation method and application Download PDFInfo
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- CN114836138A CN114836138A CN202210313042.5A CN202210313042A CN114836138A CN 114836138 A CN114836138 A CN 114836138A CN 202210313042 A CN202210313042 A CN 202210313042A CN 114836138 A CN114836138 A CN 114836138A
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- elastic body
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- acrylate
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- 239000003292 glue Substances 0.000 title claims abstract description 32
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- 230000001070 adhesive effect Effects 0.000 claims abstract description 63
- 239000000853 adhesive Substances 0.000 claims abstract description 60
- 238000004132 cross linking Methods 0.000 claims abstract description 37
- 239000000178 monomer Substances 0.000 claims description 62
- 229920001971 elastomer Polymers 0.000 claims description 43
- 239000003431 cross linking reagent Substances 0.000 claims description 37
- 239000000806 elastomer Substances 0.000 claims description 33
- 239000002313 adhesive film Substances 0.000 claims description 32
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 24
- -1 isooctyl Chemical group 0.000 claims description 18
- 239000003999 initiator Substances 0.000 claims description 16
- 239000000463 material Substances 0.000 claims description 16
- 229920002521 macromolecule Polymers 0.000 claims description 13
- 238000005452 bending Methods 0.000 claims description 12
- 239000002994 raw material Substances 0.000 claims description 10
- LEJBBGNFPAFPKQ-UHFFFAOYSA-N 2-(2-prop-2-enoyloxyethoxy)ethyl prop-2-enoate Chemical compound C=CC(=O)OCCOCCOC(=O)C=C LEJBBGNFPAFPKQ-UHFFFAOYSA-N 0.000 claims description 8
- 150000001252 acrylic acid derivatives Chemical class 0.000 claims description 8
- WURBFLDFSFBTLW-UHFFFAOYSA-N benzil Chemical compound C=1C=CC=CC=1C(=O)C(=O)C1=CC=CC=C1 WURBFLDFSFBTLW-UHFFFAOYSA-N 0.000 claims description 8
- 238000006356 dehydrogenation reaction Methods 0.000 claims description 8
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 6
- 229910052744 lithium Inorganic materials 0.000 claims description 6
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 claims description 5
- 239000012965 benzophenone Substances 0.000 claims description 5
- FIHBHSQYSYVZQE-UHFFFAOYSA-N 6-prop-2-enoyloxyhexyl prop-2-enoate Chemical compound C=CC(=O)OCCCCCCOC(=O)C=C FIHBHSQYSYVZQE-UHFFFAOYSA-N 0.000 claims description 4
- 239000002202 Polyethylene glycol Substances 0.000 claims description 4
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- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 4
- 238000003776 cleavage reaction Methods 0.000 claims description 4
- 125000004386 diacrylate group Chemical group 0.000 claims description 4
- YDKNBNOOCSNPNS-UHFFFAOYSA-N methyl 1,3-benzoxazole-2-carboxylate Chemical compound C1=CC=C2OC(C(=O)OC)=NC2=C1 YDKNBNOOCSNPNS-UHFFFAOYSA-N 0.000 claims description 4
- 238000000465 moulding Methods 0.000 claims description 4
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- PYKYMHQGRFAEBM-UHFFFAOYSA-N anthraquinone Natural products CCC(=O)c1c(O)c2C(=O)C3C(C=CC=C3O)C(=O)c2cc1CC(=O)OC PYKYMHQGRFAEBM-UHFFFAOYSA-N 0.000 claims description 3
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- YRHRIQCWCFGUEQ-UHFFFAOYSA-N thioxanthen-9-one Chemical compound C1=CC=C2C(=O)C3=CC=CC=C3SC2=C1 YRHRIQCWCFGUEQ-UHFFFAOYSA-N 0.000 claims description 3
- DTGKSKDOIYIVQL-WEDXCCLWSA-N (+)-borneol Chemical group C1C[C@@]2(C)[C@@H](O)C[C@@H]1C2(C)C DTGKSKDOIYIVQL-WEDXCCLWSA-N 0.000 claims description 2
- JWYVGKFDLWWQJX-UHFFFAOYSA-N 1-ethenylazepan-2-one Chemical compound C=CN1CCCCCC1=O JWYVGKFDLWWQJX-UHFFFAOYSA-N 0.000 claims description 2
- WHNPOQXWAMXPTA-UHFFFAOYSA-N 3-methylbut-2-enamide Chemical compound CC(C)=CC(N)=O WHNPOQXWAMXPTA-UHFFFAOYSA-N 0.000 claims description 2
- GAWIXWVDTYZWAW-UHFFFAOYSA-N C[CH]O Chemical group C[CH]O GAWIXWVDTYZWAW-UHFFFAOYSA-N 0.000 claims description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 2
- 238000005336 cracking Methods 0.000 claims description 2
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 claims description 2
- 238000002791 soaking Methods 0.000 claims description 2
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims 4
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims 2
- HRNDFHCRWHCDNZ-UHFFFAOYSA-N C(C)O.C(C1=CC=CC=C1)(=O)C1=CC=CC=C1 Chemical compound C(C)O.C(C1=CC=CC=C1)(=O)C1=CC=CC=C1 HRNDFHCRWHCDNZ-UHFFFAOYSA-N 0.000 claims 1
- 239000012752 auxiliary agent Substances 0.000 claims 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims 1
- 229920000642 polymer Polymers 0.000 abstract description 36
- 239000004820 Pressure-sensitive adhesive Substances 0.000 abstract description 17
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- 238000002474 experimental method Methods 0.000 description 4
- 239000000499 gel Substances 0.000 description 4
- 229910003473 lithium bis(trifluoromethanesulfonyl)imide Inorganic materials 0.000 description 4
- QSZMZKBZAYQGRS-UHFFFAOYSA-N lithium;bis(trifluoromethylsulfonyl)azanide Chemical compound [Li+].FC(F)(F)S(=O)(=O)[N-]S(=O)(=O)C(F)(F)F QSZMZKBZAYQGRS-UHFFFAOYSA-N 0.000 description 4
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- VSKJLJHPAFKHBX-UHFFFAOYSA-N 2-methylbuta-1,3-diene;styrene Chemical compound CC(=C)C=C.C=CC1=CC=CC=C1.C=CC1=CC=CC=C1 VSKJLJHPAFKHBX-UHFFFAOYSA-N 0.000 description 2
- 239000004971 Cross linker Substances 0.000 description 2
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- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 2
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- CXQXSVUQTKDNFP-UHFFFAOYSA-N octamethyltrisiloxane Chemical compound C[Si](C)(C)O[Si](C)(C)O[Si](C)(C)C CXQXSVUQTKDNFP-UHFFFAOYSA-N 0.000 description 2
- 238000004987 plasma desorption mass spectroscopy Methods 0.000 description 2
- 238000007789 sealing Methods 0.000 description 2
- 239000000741 silica gel Substances 0.000 description 2
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- 230000002195 synergetic effect Effects 0.000 description 2
- PSGCQDPCAWOCSH-UHFFFAOYSA-N (4,7,7-trimethyl-3-bicyclo[2.2.1]heptanyl) prop-2-enoate Chemical compound C1CC2(C)C(OC(=O)C=C)CC1C2(C)C PSGCQDPCAWOCSH-UHFFFAOYSA-N 0.000 description 1
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- DXPPIEDUBFUSEZ-UHFFFAOYSA-N 6-methylheptyl prop-2-enoate Chemical compound CC(C)CCCCCOC(=O)C=C DXPPIEDUBFUSEZ-UHFFFAOYSA-N 0.000 description 1
- 241000251468 Actinopterygii Species 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
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Images
Classifications
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J7/00—Adhesives in the form of films or foils
- C09J7/20—Adhesives in the form of films or foils characterised by their carriers
- C09J7/22—Plastics; Metallised plastics
- C09J7/24—Plastics; Metallised plastics based on macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J7/00—Adhesives in the form of films or foils
- C09J7/30—Adhesives in the form of films or foils characterised by the adhesive composition
- C09J7/38—Pressure-sensitive adhesives [PSA]
- C09J7/381—Pressure-sensitive adhesives [PSA] based on macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
- C09J7/385—Acrylic polymers
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J9/00—Adhesives characterised by their physical nature or the effects produced, e.g. glue sticks
- C09J9/02—Electrically-conducting adhesives
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J2301/00—Additional features of adhesives in the form of films or foils
- C09J2301/10—Additional features of adhesives in the form of films or foils characterized by the structural features of the adhesive tape or sheet
- C09J2301/12—Additional features of adhesives in the form of films or foils characterized by the structural features of the adhesive tape or sheet by the arrangement of layers
- C09J2301/124—Additional features of adhesives in the form of films or foils characterized by the structural features of the adhesive tape or sheet by the arrangement of layers the adhesive layer being present on both sides of the carrier, e.g. double-sided adhesive tape
-
- 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
- C09J2433/00—Presence of (meth)acrylic polymer
- C09J2433/006—Presence of (meth)acrylic polymer in the substrate
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Adhesives Or Adhesive Processes (AREA)
Abstract
The application belongs to the technical field of super elastic glue, and particularly relates to super elastic glue, a preparation method and application. Wherein, the application provides a super elastic glue, including elastic body and the viscidity rete that forms on the elastic body surface, elastic body includes first polymer, and the viscidity rete includes the second polymer, and the molecular chain length between the first polymer cross-linking point is greater than the molecular chain length between the second polymer cross-linking point, and the cross-linking point number of first polymer is higher than the cross-linking point quantity of second polymer. The application of the super elastic adhesive is a low-hysteresis adhesive tape which is strongly bonded, is favorable for the stability of electric signals of a flexible electronic device, is more suitable for fatigue working conditions than the pressure-sensitive adhesive (viscoelastic adhesive) with high hysteresis and large residual strain in the prior art, can improve the poor phenomena of instability of the flexible electronic device, a folding screen, creases, folds and the like caused by the viscoelastic adhesive.
Description
Technical Field
The application belongs to the technical field of super elastic glue, and particularly relates to super elastic glue, a preparation method and application.
Background
An adhesive, a substance that can hold materials together by surface. With the progress of the era, the 20 th century and the 40 th century witnessed the rapid development of polymer-based adhesives. The polymer-based adhesive has excellent formula adjustability, so that functionalized adhesive products with different types can be rapidly developed, such as engineering Adhesives with good flexibility and toughness, fast-curing Adhesives, high-temperature and high-humidity resistant Adhesives, chemically resistant Adhesives and the like, and the adhesive proves ' Adhesives ' in relation to our information '. In particular, the pressure-sensitive adhesive, which can wet a bonding substrate with a very slight force, has unique excellent adhesive property, high transparent optical property, high tolerance and property formulation controllability, so that it has been widely used in industries such as daily indispensable display screens, mobile phones, flexible electronics, flexible folding screens and the like, in addition to household use. However, the versatile laminate structure and functional requirements of flexible displays present unprecedented challenges for pressure sensitive adhesives, which inherently possess significant viscoelastic properties, large residual strains, and limit their explosive development.
Having both excellent elasticity and viscosity is difficult and contradictory in both mechanical and material aspects. Strongly bonding adhesives, which generally have long chain macromolecules between the cross-linking points, mean that more polymer chain entanglements are available for dissipating more energy, and that the tack predominates in the material, and thus greater hysteresis and residual deformation, i.e. strain energy dissipation in the form of heat, results. On the contrary, the elastomer/adhesive with good resilience needs short-chain macromolecules with a plurality of crosslinking points, has good entropy elasticity and less dissipation, shows that the entropy elasticity is dominant in the material, but the weak interfacial bonding of the elastomer/adhesive makes the elastomer/adhesive not even called as an adhesive. In recent years, scientists have optimized elastic recovery based on sufficient adhesive energy for better application of pressure sensitive adhesives to flexible panels. For example, Back et al skillfully covers the light source at the position of the adhesive part by using an ultraviolet light mask method to adjust the crosslinking density at different positions of the adhesive tape, so that short-chain macromolecules formed at a place with high crosslinking density have good elastic recovery, and long-chain macromolecules formed at a place with low crosslinking density have good bonding performance, and thus have certain elastic recovery based on sufficient bonding.
Lee et al, in order to adjust the elastic recovery ability of a pressure-sensitive adhesive, directly mix a long-chain styrene-isoprene-styrene elastomer into the pressure-sensitive adhesive, although the elastic recovery of the pressure-sensitive adhesive is improved, the weak interface between the added carbon skeleton elastomer and the pressure-sensitive adhesive results in a limited improvement in the elastic recovery of the pressure-sensitive adhesive, and the addition of styrene-isoprene-styrene makes the pressure-sensitive adhesive less transparent.
In addition, scientists adjust the high molecular skeleton by a chemical method, and Lee et al adjust the proportion of the flexible monomer isooctyl acrylate and the functional monomer acrylic acid to adjust the elastic recovery capability in flexibility and the specific gravity of functional bonding so as to improve the relaxation and creep property caused by the resilience of the pressure-sensitive adhesive and better apply the pressure-sensitive adhesive to the flexible screen. These methods all show the balanced mechanical behavior to us, and can only weakly improve the resilience of the adhesive on the basis of sacrificing the bonding performance, thereby greatly preventing the development of flexible display screens. Therefore, developing a flexible adhesive behavior with excellent tack and resilience is a "critical" and demanding task.
Therefore, the contradiction exists, so that the common pressure-sensitive adhesive has dominant viscosity, has larger residual deformation during loading and unloading, is slowly loosened and cannot be recovered, and is not favorable for the production of flexible electronic stability, flexible electronic integrated laminated structures and folding screens. Therefore, the manufacture of the super elastic glue with good resilience and strong bonding is urgently needed and is urgently important.
Disclosure of Invention
The application aims to provide a super elastomer, a preparation method and application in the prior art, and aims to solve the problem that the elasticity and the viscosity of the existing adhesive cannot be balanced.
In order to achieve the purpose of the application, the technical scheme adopted by the application is as follows:
this application first aspect provides a super elastic glue, including the elastic body with the viscidity rete that the elastic body surface formed, wherein, the elastic body includes first polymer, and the viscidity rete includes the second polymer, and the molecular chain length between the first polymer cross-linking point is greater than the molecular chain length between the second polymer cross-linking point, and the cross-linking point number of first polymer is higher than the cross-linking point number of second polymer.
The elastic body of the super elastic adhesive provided by the application is composed of an entropy elastic polymer network which is stretchable, high in cross-linking point and short in molecular chain, the surface of the viscous film layer is composed of a viscous polymer network viscoelastic polymer which is soft, low in cross-linking point and long in molecular chain length, and the interface between the two is strongly bonded through a covalent bond and a topological structure. Through the compounding and synergistic effect of the elastic body and the viscous film layer, the elasticity and the viscosity are decoupled, and the super elastic adhesive is effectively endowed with the balance characteristic of elasticity and viscosity. And make the superelastic glue of this application have the hysteresis low, and bond strongly, be favorable to the electrical signal stability among the flexible electron, it is high than current hysteresis, the pressure-sensitive adhesive that the residual strain is big more adapts to the fatigue operating mode to and can improve in the flexible electronic integration of modern society because the destabilizing bad phenomenon such as crease, fold appears in the viscous elastomer hysteresis quality.
The second aspect of the application provides a preparation method of a super elastomer, which comprises the following steps:
preparing a first solution for forming an adhesive film layer and a second solution for forming an elastic body;
performing prepolymerization treatment on the first solution to obtain a third solution;
molding the second solution to obtain an elastic body;
and performing film forming treatment on the surface of the elastic body by using the second solution, and performing drying and curing treatment to form a viscous film layer on the surface of the elastic body to obtain the super elastomer.
The preparation method of the super elastomer comprises the steps of preparing a first solution for forming the viscous film layer and a second solution for forming the elastic body by blending raw materials of the elastic body and the viscous film layer, performing prepolymerization treatment on the first solution by a first party, obtaining the viscous film layer formed by the viscous polymer network viscoelastic first polymer with soft surface selection, low crosslinking point and long molecular chain length, performing molding treatment on the second solution by a second party, obtaining the elastic body formed by the entropy elastic second polymer network with stretching property, high crosslinking point and short molecular chain, immersing the elastic body into the first solution, and performing drying treatment, wherein the interface between the viscous film layer and the elastic body can be strongly bonded through a covalent bond and a topological structure.
In a third aspect, the present application provides a use of a superelastic adhesive, including the use of a superelastic adhesive provided in an embodiment of the present application in folding or bending a material.
Just because the super-elastic adhesive provided by the embodiment of the application has good resilience, the linear elasticity attributed to the unmatched modulus between the layers in folding or bending of the traditional viscoelastic adhesive is avoided, the slippage of the viscoelastic adhesive during bending causes the hysteresis of the viscoelastic adhesive, the layers recover from the inconsistent pace, and finally the bad phenomenon that wrinkles are generated at the interface after the force is released is avoided.
Drawings
Fig. 1 is a schematic structural diagram of an elastic body according to an embodiment of the present invention;
FIG. 2 is a schematic structural view of an adhesive film layer according to an embodiment of the present invention;
FIG. 3 is a schematic view of an embodiment of an elastomeric body bonded to an adhesive film layer;
FIG. 4 is a graph of stress-strain relationship for an adhesive film layer provided in accordance with an embodiment of the present invention;
FIG. 5 is a graph of stress-strain relationship for an adhesive film layer with 100% strain applied and removed in accordance with an embodiment of the present invention;
FIG. 6 is a hysteresis statistical chart for the adhesive film layer of FIG. 5 provided in accordance with an embodiment of the present invention;
FIG. 7 is a force-displacement relationship diagram for an adhesive film layer provided in accordance with an embodiment of the present invention;
FIG. 8 is a graph of stress-strain relationship for an elastic body according to an embodiment of the present invention;
FIG. 9 is a graph of stress-strain relationship for an elastomeric body with 100% strain applied and removed;
FIG. 10 is a hysteresis statistical chart for the elastic body of FIG. 9 according to an embodiment of the present invention;
FIG. 11 is a graph of elastic body force versus displacement according to an embodiment of the present invention;
FIG. 12 is a graph of the stress-strain relationship of a super elastic adhesive according to an embodiment of the present invention;
FIG. 13 is a graph showing the relationship between stress and strain for 100% strain when the super elastic rubber is loaded and unloaded in accordance with the embodiment of the present invention;
FIG. 14 is a graph of super-elastic-gel force versus displacement provided by an embodiment of the present invention;
FIG. 15 is a hysteresis performance statistical chart provided by an embodiment of the present invention;
FIG. 16 is a statistical chart of the bonding performance provided by the embodiment of the present invention;
FIG. 17 is a graph showing the results of an experiment on the transparency of the super elastic adhesive under visible light according to the embodiment of the present invention;
FIG. 18 is a diagram of a method for testing the bending cycle performance of the test device according to an embodiment of the present invention;
FIG. 19 is a graph showing the results of testing the cyclic bending performance of the stacked structure according to the embodiment of the present invention;
FIG. 20 is a graph showing the results of the test of the cyclic bending properties of the laminated structure according to the comparative example of the present invention.
Detailed Description
In order to make the technical problems, technical solutions and beneficial effects to be solved by the present application more clearly apparent, the present application is further described in detail below with reference to the embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the present application and are not intended to limit the present application.
In this application, the term "and/or" describes an association relationship of associated objects, meaning that there may be three relationships, e.g., a and/or B, which may mean: a is present alone, A and B are present simultaneously, and B is present alone. Wherein A and B can be singular or plural. The character "/" generally indicates that the former and latter associated objects are in an "or" relationship.
In the present application, "at least one" means one or more, "a plurality" means two or more. "at least one of the following" or similar expressions refer to any combination of these items, including any combination of the singular or plural items. For example, "at least one item(s) of a, b, or c," or "at least one item(s) of a, b, and c," may each represent: a, b, c, a-b (i.e., a and b), a-c, b-c, or a-b-c, wherein a, b, and c may be single or plural, respectively.
It should be understood that, in various embodiments of the present application, the sequence numbers of the above-mentioned processes do not mean the execution sequence, some or all of the steps may be executed in parallel or executed sequentially, and the execution sequence of each process should be determined by its function and inherent logic, and should not constitute any limitation to the implementation process of the embodiments of the present application.
The terminology used in the embodiments of the present application is for the purpose of describing particular embodiments only and is not intended to be limiting of the application. As used in the specification of the present application and the appended claims, the singular forms "a," "an," and "the" are intended to include the plural forms as well, unless the context clearly indicates otherwise.
The weight of the related components mentioned in the specification of the embodiments of the present application may not only refer to the specific content of each component, but also refer to the proportional relationship of the weight of each component, and therefore, the proportional enlargement or reduction of the content of the related components according to the specification of the embodiments of the present application is within the scope disclosed in the specification of the embodiments of the present application. Specifically, the mass described in the specification of the embodiments of the present application may be a mass unit known in the chemical industry field such as μ g, mg, g, kg, etc.
The terms first, second, etc. are used for descriptive purposes only and are used for distinguishing purposes such as substances from one another and are not to be construed as indicating or implying relative importance or implying any number of technical features indicated. For example, a first XX may also be referred to as a second XX, and similarly, a second XX may also be referred to as a first XX, without departing from the scope of regulations of this application. Thus, a feature defined as "first" or "second" may explicitly or implicitly include one or more of that feature.
The first aspect of the embodiment of this application provides a super elastic glue, including the elastic body with the viscidity rete that the elastic body surface formed, and the thickness of elastic body is greater than the thickness of viscidity rete, and the elastic body includes first polymer, and the viscidity rete includes the second polymer, and the molecular chain length of first polymer is greater than the molecular chain of second polymer, and the crosslinking point number of first polymer is higher than the crosslinking point of second polymer.
The superelastic adhesive provided by the embodiment of the application decouples elasticity and viscosity through the compounding and synergistic effect of the elastic body and the viscous film layer, so that the superelastic adhesive is effectively endowed with the characteristics of elasticity and viscosity balance, as shown in figure 1, the elastic body comprises a first macromolecule, the elastic body is composed of a stretchable entropy elastic first macromolecule network with a high crosslinking point and a short molecular chain, as shown in figure 2, the viscous film layer comprises a second macromolecule, the surface of the adhesive film layer is formed by a viscoelastic second polymer of an adhesive polymer network with softness, low cross-linking point and a long molecular chain, as shown in fig. 1 and fig. 2, the cross-linking point represents the number of cross-linking points between the polymers, and in the embodiment of the present application, the cross-linking point of the first polymer is higher than the cross-linking point of the second polymer, which represents that the number of cross-linking points between the first polymers is greater than the number of cross-linking points between the second polymers. Referring to fig. 3, the interface between the two is strongly bonded by covalent bonds and topological structures. The super-elastic adhesive provided by the embodiment of the application is an adhesive tape with low hysteresis and strong adhesion, is favorable for the stability of electric signals of a flexible electronic device, is higher than the existing hysteresis, is more suitable for fatigue working conditions due to a pressure-sensitive adhesive with large residual strain, and can improve the instability phenomena such as crease marks and wrinkles caused by the hysteresis in the flexible electronic integration of the modern society.
The elastic body contained in the super elastic adhesive is used as a substrate for loading the viscous film layer, and the thickness of the elastic body is larger than that of the viscous film layer and has a difference of at least one order of magnitude. Illustratively, the thickness of the elastic body is 1 millimeter, and the thickness of the adhesive film layer is 50-200 micrometers. In some embodiments, the raw material for forming the elastic body comprises a first monomer, a cross-linking agent and a first initiator, and the mass ratio of the first monomer to the first cross-linking agent to the first initiator is 90-100: 1-10: 1 to 5. The first monomer, the cross-linking agent and the first initiator provided by the embodiment of the application can perform polymerization reaction under certain conditions, and a body with good elasticity can be obtained after polymerization.
In some embodiments, the first monomer includes at least one of isooctyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, alkoxy acrylates, and like (meth) acrylates, hexafluorobutyl (meth) acrylate, silicone modified (meth) acrylates. The first monomer provided by the embodiment of the application comprises a soft monomer with a carbon chain containing 4-7 carbon atoms and a low glass transition temperature, and the wettability and viscosity of the soft monomer can be further controlled to meet the actual requirement.
In some embodiments, the first crosslinker comprises at least one of diethylene glycol diacrylate, polyethylene glycol (diol) diacrylate, propoxylated neopentyl glycol diacrylate, 1, 6-hexanediol diacrylate. The first cross-linking agent provided by the embodiment of the application can promote the cross-linking of the first monomer, further improve the cohesive force of the elastic body, and improve the entropy elasticity of the elastic body.
In some embodiments, the first initiator comprises a class i cleavage type photoinitiator or a class ii hydrogen abstraction type photoinitiator. In some embodiments, the class I cleavage-type photoinitiator comprises at least one of benzil, benzil ketal, alpha-hydroxy ketone, and acylphosphine oxide. In some embodiments, the class II hydrogen abstraction photoinitiator includes at least one of benzophenone, thioxanthone, anthraquinone, and an organic amine in combination with an initiation aid. The type i cleavage type photoinitiators or type ii hydrogen abstraction photoinitiators provided in the embodiments herein can promote the polymerization described above in the embodiments herein. Further, the benzil comprises at least one of DCP and BPO, the benzil ketal comprises at least one of I-907 and I-369, the alpha-hydroxyketone comprises at least one of I-1173, I-184 and I-2959, and the acylphosphine oxide comprises at least one of I-819 and TPO.
In some embodiments, the adhesive for forming the adhesive film layer in the thermal sensitive adhesive of the embodiments of the present application includes a second monomer, a functional monomer, a cross-linking agent, and a second initiator, and a mass ratio of the second monomer, the functional monomer, the second cross-linking agent, and the second initiator is 50 to 90: 10-50: 1-10: 0.01-1: 0.01 to 1. The second monomer, the sub-monomer, the functional monomer, the cross-linking agent and the second initiator provided by the embodiment of the application can generate polymerization reaction under certain conditions, the second monomer, the sub-monomer and the functional monomer can be polymerized to obtain the viscous film layer, and the cohesive energy of the viscous film layer is improved by controlling the using amount of the second cross-linking agent, so that the adhesion is facilitated.
In some embodiments, the second monomer includes a soft monomer having a carbon chain containing 4 to 7 carbon atoms and a low glass transition temperature, and further includes at least one of isooctyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, alkoxy acrylate and other (meth) acrylate esters, hexafluorobutyl (meth) acrylate, and silicone-modified (meth) acrylate. These second monomers can further control their wettability and viscosity.
In some embodiments, the secondary monomer comprises at least one of styrene, isobornyl (meth) acrylate, such short carbon chains of 1-3 carbon atoms, or hard monomers with high glass transition temperatures of cyclic, aromatic hydrocarbons. The sub-monomer and the second monomer provided by the embodiment of the application act synergistically, and the wettability and the viscosity of the super elastomer can be further balanced.
In some embodiments, the functional monomer comprises at least one of (meth) acrylic acid, hydroxyethyl (meth) acrylate, N-vinyl caprolactam, dimethyl acrylamide, glycidyl methacrylate. The functional monomer provided by the embodiment of the application can further control the adhesiveness of the functional monomer so as to meet the actual requirement.
In some embodiments, the second crosslinker comprises at least one of diethylene glycol diacrylate, polyethylene glycol (diol) diacrylate, propoxylated neopentyl glycol diacrylate, 1, 6-hexanediol diacrylate. The second cross-linking agent provided by the embodiment of the application can promote the cross-linking of the monomers, further improve the cohesive force of the adhesive film layer and reduce the residual adhesive amount.
In some embodiments, the second initiator comprises a class i cleavage type photoinitiator or a class ii hydrogen abstraction type photoinitiator. In some embodiments, the class I cleavage-type photoinitiator comprises at least one of benzil, benzil ketal, alpha-hydroxy ketone, and acylphosphine oxide. In some embodiments, the class II hydrogen abstraction photoinitiator includes at least one of benzophenone, thioxanthone, anthraquinone, and an organic amine in combination with an initiation aid. The type I cracking photoinitiator or the type II hydrogen abstraction photoinitiator provided by the embodiment of the application can promote the polymerization of the second monomer, the secondary monomer and the functional monomer provided by the embodiment of the application.
In some embodiments, the adhesive forming the adhesive film layer and the raw material forming the elastic body further include lithium bis (trifluoromethanesulfonyl) imide, and the content of the lithium bis (trifluoromethanesulfonyl) imide may be 0.5-2M (mol/l). The super-elastic gel provided by the embodiment of the application is selectively added with conductive ionic salts to realize the application of the conductive flexible electronic electrode, through cyclic loading, the conductive elastomer P (BA-co-IBA) -with high contrast delay and remarkable viscoelastic behavior is 0.1%, the super-elastic gel after each circle of external force is released has stable resistance value, a base line signal is kept at a level, and the super-elastic gel has quick average response time of 10ms and average recovery time of 10 ms. And P (BA-co-IBA) -0.1 percent, because of large viscoelasticity and residual stress, the resistance signal of the P (BA-co-IBA) -is always drifting, and although the P (BA-co-IBA) -has a relatively fast average response time of 10ms, the recovery time is about an order of magnitude of 82 ms. It should be noted that the superelastic conductor can be prepared by adding the lithium bistrifluoromethanesulfonylimide to the single elastic body, the viscoelastic conductor can be prepared by adding the lithium bistrifluoromethanesulfonylimide to the single viscous film layer, and the superelastic rubber provided by the embodiment of the present application can include both structures of the superelastic conductor and the viscoelastic conductor, and the superelastic conductor and the viscoelastic conductor can be applied to a conductive material.
In some embodiments, the adhesive film further comprises a release film disposed on the surface of the adhesive film layer. The release film provided by the embodiment of the application can protect the super elastomer and facilitate the transportation of the super elastomer. In the using process, the release film is required to be stripped and is adhered to the substrate through the adhesive film layer.
In some embodiments, the bonding energy of the superelastic rubber ranges from 113J/m to 605J/m 2 . The superelastic adhesive provided by the embodiment of the application directly represents resilience and viscoelasticity through hysteresis size under loading and unloading, represents adhesion by a peeling adhesion test, has resilience and 4% low hysteresis, can be firmly adhered to the surfaces of various engineering base materials, and has the highest adhesion energy of plastic as high as 600J/m 2 。
The second aspect of the embodiment of the present application provides a method for preparing a superelastic rubber, comprising the following steps:
step 10: preparing a first solution for forming an adhesive film layer and a second solution for forming an elastic body;
step 20: performing prepolymerization treatment on the first solution to obtain a third solution;
step 30: molding the second solution to obtain an elastic body;
step 40: and performing film forming treatment on the surface of the elastic body by using the second solution, and performing drying and curing treatment to form a viscous film layer on the surface of the elastic body to obtain the super elastomer.
According to the preparation method of the super elastic glue, the first solution for forming the viscous film layer and the second solution for forming the elastic body are prepared, prepolymerization treatment is carried out on the first solution, the viscous film layer formed by the viscoelastic second high polymer of the heterogeneous viscous high polymer network with soft surface, low cross-linking point and long molecular chain length can be obtained, the elastic body formed by the elastic first high polymer network with uniform entropy and high cross-linking point and short molecular chain can be obtained by shaping the second solution, the elastic body is immersed into the first solution and then dried, and the interface between the viscous film layer and the elastic body can be strongly adhered through a covalent bond and a topological structure.
In the step S10, the method further includes adjusting and controlling the overall performance of the super-elastomer by adjusting the ratio of the raw materials of the elastic body to the viscous film layer, wherein the mass ratio of the two monomers, the secondary monomer, the functional monomer, the second cross-linking agent and the second initiator is 50-90: 10-50: 1-10: 0.01-1, weighing each raw material, and preparing a first solution for forming the adhesive film layer. According to the mass ratio of the first monomer, the first cross-linking agent and the photoinitiator being 90-100: 1-10: 1-5, weighing the raw materials, and preparing a second solution for forming the elastic body. In some embodiments, the mass ratio of the second monomer, the second sub-monomer, the functional monomer, the second cross-linking agent and the second initiator is 50-90: 10-50: 1-10: 0.01-1 of each raw material is weighed, a first solution for forming the adhesive film layer is prepared, and 0.5-2M (mol/l) of lithium bistrifluoromethanesulfonylimide is added into the first solution, wherein the mass fraction of the lithium bistrifluoromethanesulfonylimide is 14.3% -57.1% based on 100% of the mass of the first solution. According to the mass ratio of the first monomer, the first cross-linking agent and the photoinitiator being 90-100: 1-10: 1-5, weighing the raw materials, preparing a second solution for forming the elastic body, and adding 0.5-2M (mol/l) of lithium bis (trifluoromethanesulfonyl) imide with the mass fraction of 14.3% -57.1% into the first solution by taking the mass of the second solution as 100%. The super elastic glue provided by the embodiment of the application is selectively added with conductive ionic salts, so that the application of the conductive flexible electronic electrode is realized, and the contrast hysteresis is high under cyclic loading.
In the step S10, the prepolymerization process specifically includes the following steps: the first solution was 1w/cm at room temperature under nitrogen atmosphere 2 The ultraviolet light is used for processing for 40-120 s, wherein the second monomer can be polymerized by prepolymerization, the prepolymerization time is controlled, and the polymerization degree of the second monomer, the secondary monomer and the functional monomer is further regulated and controlled. The wettability and viscosity of the superelastic glue can be balanced.
In step S30, the method further includes performing directional clipping processing on the elastic body to obtain the mechanically-oriented super elastomer. The super-elastic glue prepared by the embodiment of the application is a mechanical oriented design super-elastic glue with low hysteresis and strong bonding.
In some embodiments, the method further comprises soaking the elastic body in an ethanol solution of 1-10 wt% benzophenone for 1-10 min. The elastic body is soaked so as to facilitate the bonding of the elastic body and the adhesive film layer.
In the step S40, the method further includes leveling treatment, and the time of the leveling treatment is 30S to 5min, and the leveling treatment can further improve the uniformity of the super-elastic glue performance and reduce the number of fish eyes.
In some embodiments, the method further comprises the steps of coating release PET films on two surfaces of the super elastomer, placing the release PET films under a 30w,365nm UV-Vis ultraviolet lamp for curing for 20min, and adhering the release PET films on the surface of the adhesive film layer, so that the super elastomer is protected, and the transportation is facilitated.
The third aspect of the present application provides an application of a super elastomer, including the application of the super elastomer provided in the embodiment of the present application in a flexible screen.
Just because the super-elastic adhesive provided by the embodiment of the application has good resilience, the linear elasticity attributed to the unmatched modulus between the layers in folding or bending of the traditional viscoelastic adhesive is avoided, the slippage of the viscoelastic adhesive during bending causes the hysteresis of the viscoelastic adhesive, the layers recover from the inconsistent pace, and finally the bad phenomenon that wrinkles are generated at the interface after the force is released is avoided.
In order to clearly understand the details and operation of the above-mentioned embodiments of the present application and to significantly show the advanced performance of the super elastomers, the preparation methods and the applications thereof, the above-mentioned technical solutions are illustrated by a plurality of examples below.
Example 1
The embodiment provides a preparation method of a super elastic glue, which comprises the following steps:
step 101, weighing 100 wt% of monomer butyl acrylate, 1 wt% of cross-linking agent PEGDA-600, 2 wt% of cross-linking agent PEGDA-3 wt% (relative to the mass fraction of the monomer), and 1-11731 wt% (relative to the mass fraction of the monomer) of photoinitiator to prepare a first solution.
Step 102, weighing 80 wt% of monomer butyl acrylate, 20 wt% of isobornyl acrylate and 80 wt% of cross-linking agent PEGDA-6000.1 wt%, 0.5 wt%, 1 wt% (relative to the mass fraction of the monomer) and I-11730.1 wt% (relative to the mass fraction of the monomer), weighing corresponding masses, mixing and stirring to prepare a second solution.
Step 201, placing the first solution into a nitrogen atmosphere, pre-polymerizing for 1min in a 30W 365nm ultraviolet lamp, transferring the beaker into a cold water bath, cooling to room temperature, and using the beaker as a third solution for later use.
Step 202, injecting first solutions respectively containing 1 wt%, 2 wt% and 3 wt% of cross-linking agents into the prepared glass mold: and (3) spacing silica gel gaskets with a distance of 1mm in the middle, sealing the two ends of the transparent glass with release films, placing the glass into a 30W and 365nm ultraviolet lamp for curing for 30min to obtain three groups of adhesive film layers, and performing mechanical test for standby.
Step 301, injecting second solutions with the cross-linking agent content of 0.1 wt%, 0.5 wt% and 1 wt% into the prepared glass mold respectively: spacing silica gel gaskets with 1mm in the middle, sealing the two ends of the glass which is transparent and is adhered with release films, placing the glass in an ultraviolet lamp with the wavelength of 30W and 365nm for curing for 30min to obtain three groups of elastic bodies, and carrying out mechanical test and standby application.
And 302, directionally cutting the elastic body containing the cross-linking agent with the mass percentage of 2%.
And 303, immersing the directional cutting elastic body in an ethanol solution of 2 wt% of benzophenone for 2min, and drying the elastic body in a drying oven at the temperature of 6 ℃ for 1min to obtain the pretreated elastic body.
Step 401, immersing the pretreated elastic body into a first solution containing 0.1% of cross-linking agent by mass, lifting immediately, leveling for 1min in air at room temperature, and coating release films on the upper and lower surfaces.
And step 402, placing the glass substrate into a 30W 365nm ultraviolet lamp for curing for 20min, and then carrying out mechanical test.
Comparative example 1
Acrylate pressure-sensitive adhesive 3MVHB 4905.
Comparative example 2
Flexible electronics commonly used silicone rubber polydimethylsiloxane PDMSSylgard 184(10: 1).
The elastic body, the adhesive film layer, the super elastic adhesive and the flexible electronic common silicone rubber PDMSSylgard 184(10:1) (comparative example 2) prepared in example 1 and the acrylate pressure-sensitive adhesive 3MVHB4905 (comparative example 1) are subjected to loading and unloading hysteresis test, 180-degree peeling test and test of attaching a PET film with a thickness of 25 μm on both sides of the adhesive tape, and the hysteresis size and the bonding energy size are recorded. The results are shown in Table 1. The mass percentage of the crosslinking agent contained in the adhesive film layer in the super elastomer (HEA) was 0.1%, and the mass percentage of the crosslinking agent contained in the elastic body in the super elastomer (HEA) was 2%.
TABLE 1 test results
| Name | Hysteresis | Adhesion energy(J/m 2 ) |
| PBA-1% (ontology) | 5.6％ | 23.40 |
| PBA-2％ | 0.9％ | 6.44 |
| PBA-3％ | 0.3％ | 3.00 |
| P (BA-co-IBA) -0.1% (surface) | 35.4％ | 2028 |
| P(BA-co-IBA)-0.5％ | 6.93 | 151 |
| P(BA-co-IBA)-1％ | 3.7％ | 97 |
| HEA (super elastic glue) | 4％ | 270 |
| PDMS Sylgard 184(10:1) | 7％ | 0.2 |
| |
51.63％ | 205 |
Among them, fig. 4 to 7 are graphs showing the results of performance tests of adhesive film layers containing 0.1%, 0.5% and 1% by mass of a crosslinking agent and materials contained in comparative example 1, and show that as the content of the crosslinking agent decreases, the adhesive properties increase, but at the same time, the hysteresis increases, and the hysteresis of the three adhesive film layers contained in example 1 is all worse and the adhesion is all stronger than that of comparative example 1. As the content of the crosslinking agent decreases, the interaction force with the interface increases as the molecular chain between the crosslinking points becomes longer, but the hysteresis phenomenon becomes severe.
Fig. 8 to 11 are graphs showing the results of performance tests of the elastic bodies containing 1%, 2% and 3% by mass of the crosslinking agent and the material contained in comparative example 2, and the results show that as the content of the crosslinking agent increases, the hysteresis decreases, and the hysteresis of the three elastic bodies contained in example 2 is reduced as compared with comparative example 1, and is comparable to the elastomer specific hysteresis of comparative example 2. As the content of the crosslinking agent increases, the molecular chain length between the crosslinking points becomes shorter, and the hysteresis is improved, but the force acting on the interface is reduced.
Fig. 12 to 14 are graphs showing the performance test results of the super elastomer formed by the adhesive film layer containing 0.1% by mass of the crosslinking agent, the elastic body containing 2% by mass of the crosslinking agent, and the adhesive film layer containing 0.1% by mass of the crosslinking agent, and the results show that the super elastomer provided in example 1 can effectively balance the elasticity and the viscosity of the material.
In addition, as shown in fig. 15 to 16, the ultra-elastic adhesive tape prepared through experiments directly represents the resilience and viscoelasticity through the hysteresis size under loading and unloading, and represents the adhesion by using the peel adhesion test, the ultra-elastic adhesive in the embodiment has the advantages of good resilience, 4 percent of low hysteresis, lower than that of the silicone rubber PDMS Sylgard 184(10:1) with super-elasticity and weak adhesion recognized by industry and academia, and higher average adhesion energy of 270J/m 2 And is higher than the common flexible adhesive VHB4905 of market 3M company.
Example 2
The preparation of the conductive superelastic material of the embodiment follows the preparation process of the superelastic rubber in embodiment 1, the only difference between the superelastic material in the original formula and the first solution is that 0.5-2M lithium bistrifluoromethanesulfonylimide is additionally added, the prepolymerization time of the first solution is prolonged to 3-5 min due to the influence of salt, and other conditions and steps are kept unchanged. The hysteresis of the finally prepared conductive super elastomer is 9 percent, and the bonding energy is 300J/m 2 The average response time and the average recovery time are both 10 ms. 0.1% of viscoelastic glue P (BA-co-IBA) -is added with 0.5-2M (mol/l) of lithium bis (trifluoromethanesulfonyl) imide according to the formula of the surface glue in the example 1, and other conditions and steps are kept unchanged. The finally prepared conductive viscoelastic glue has an average response time of 10ms, but an average recovery time of 81.5 ms.
The super-elastic glue provided by the embodiment of the application is selectively added with conductive ionic salts to realize the application of the conductive flexible electronic electrode, through cyclic loading, the conductive elastomer P (BA-co-IBA) -with high contrast hysteresis and obvious viscoelastic behavior is 0.1%, the super-elastic glue after each circle of external force is released has stable resistance value, a base line signal is kept at a level, and the super-elastic glue has quick average response time of 10ms and average recovery time of 10 ms. And P (BA-co-IBA) -0.1 percent, because of large viscoelasticity and residual stress, the resistance signal of the P (BA-co-IBA) -is always drifting, although the P (BA-co-IBA) -has a relatively fast average response time of 10ms, but the average recovery time is about an order of magnitude of 82 ms. The super elastic glue has excellent rebound resilience and ultrafast recovery, avoids the bad phenomena that the slippage of the glue generated during bending causes the hysteresis of the viscoelastic glue, the non-uniform and irregular recovery between layers occurs, and finally wrinkles are generated at an interface after force is released due to the linear elasticity attributed by the unmatched modulus between the layers in the laminated structure.
And (3) evaluating the bonding energy of the super elastic adhesive to various substrates, wherein one surface of the super elastic adhesive is polymerized and bonded on the substrate in situ, the other surface of the super elastic adhesive is bonded with a 25-micrometer PET film of a hard back plate, a preset crack is bonded on the surface of the substrate by a blade in advance, and the bonding energy of the super elastic adhesive to the lattice substrate is measured and recorded by adopting a 90-degree stripping test method. As a result, please refer to fig. 2:
table 2 results of performance testing
| Name of substrate | Adhesive energy (J/m) 2 ) |
| Acrylic plate (Plastic) | 605 |
| Wood (Woods) | 595 |
| Steel (Metal) | 594 |
| |
400 |
| Ceramic (alumina ceramic) | 320 |
| Rubber (Silicone rubber) | 113 |
Example 3
The embodiment provides application of the super elastic glue in a laminated structure. The super elastomer in example 1 was disposed between two PET films, one of which had a thickness of 25 μm, the other of which had a thickness of 200 μm, and the super elastomer had a thickness of 1000 μm, to obtain a laminated structure.
Comparative example 3
The difference from example 3 is that the material disposed between the two PET films is a viscoelastic glue of the P (BA-co-IBA) -0.1% acrylic ester type.
As a result of performing a head transmittance test on the 1mm superelastic rubber in example 1 and the viscoelastic rubber of P (BA-co-IBA) -0.1% acrylates in comparative example 3 in a visible light wavelength range by using an ultraviolet-visible spectrum scanning method, please refer to fig. 17, which shows that the superelastic rubber provided in example 1 has a transmittance of 89%, has a good transmittance, and can be used as a material for a display screen.
Taking a rectangular strip with the dimension of 60mm in length and 20mm in width of the laminated structure in example 3, please refer to fig. 18, first clamping two acrylic plates on a fixture of a fatigue testing machine Instron 3000, then vertically fixing two ends of the laminated structure on a center line of the two acrylic plates along the fixture, performing a downward cyclic bending test on the laminated structure, after 1000 cycles of cyclic loading, applying downward displacement to the laminated structure by a displacement control method for each cycle, and performing cyclic loading and unloading, wherein the downward maximum displacement in the test is 20mm, the minimum displacement is 0mm, the displacement is controlled by a triangular wave, and the loading rate is 1 Hz. As a result of the experiment, referring to fig. 19, no wrinkle occurred after the bent portion of the laminated structure provided in example 3 was restored, and a wrinkle occurred after the bent portion of the laminated structure provided in comparative example 3 was restored, which indicates that no hysteresis occurred in the laminated structure provided in example 3.
The above description is only exemplary of the present application and should not be taken as limiting the present application, as any modification, equivalent replacement, or improvement made within the spirit and principle of the present application should be included in the protection scope of the present application.
Claims (10)
1. The super elastic glue is characterized by comprising an elastic body and an adhesive film layer formed on the surface of the elastic body, wherein the elastic body comprises a first macromolecule, the adhesive film layer comprises a second macromolecule, the chain length of molecules between cross-linking points of the first macromolecule is larger than that between cross-linking points of the second macromolecule, and the number of cross-linking points of the first macromolecule is larger than that of cross-linking points of the second macromolecule.
2. The super elastomer as claimed in claim 1, wherein the raw material for forming the elastic body comprises a first monomer, a first cross-linking agent and a first initiator, and the mass ratio of the first monomer, the first cross-linking agent and the first initiator is 90-100: 1-10: 1-5;
or/and the adhesive for forming the adhesive film layer comprises a second monomer, a functional monomer, a second cross-linking agent and a second initiator, wherein the mass ratio of the second monomer to the functional monomer to the second cross-linking agent to the second initiator is 50-90: 10-50: 1-10: 0.01-1: 0.001 to 1.
3. The superelastomer of claim 2, wherein the raw material forming the elastomeric body and the adhesive forming the adhesive film layer further comprise lithium bis (trifluoromethanesulfonylimide) when the superelastomer is rendered electrically conductive.
4. The superelastomer of claim 2 or 3, wherein the first monomer comprises at least one of (meth) acrylates such as isooctyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, alkoxy acrylates, hexafluorobutyl (meth) acrylate, silicone-modified (meth) acrylates;
or/and the first cross-linking agent comprises at least one of diethylene glycol diacrylate, polyethylene glycol (glycol) diacrylate, propoxylated neopentyl glycol diacrylate and 1, 6-hexanediol diacrylate;
and/or the first initiator and the second initiator respectively comprise a type I cracking type photoinitiator or a type II hydrogen abstraction type photoinitiator.
5. The superelastomer of claim 4, wherein the class I cleavage type photoinitiator comprises at least one of benzil, benzil ketal, α -hydroxy ketone, acylphosphine oxide;
or/and the II type hydrogen abstraction photoinitiator comprises at least one of benzophenone, thioxanthone, anthraquinone and organic amine matched with an initiation auxiliary agent.
6. The superelastomer of claim 2 or 3, wherein the second monomer comprises at least one of (meth) acrylates such as isooctyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, alkoxy acrylates, hexafluorobutyl (meth) acrylate, silicone-modified (meth) acrylates;
or/and the secondary monomer comprises at least one of styrene, isobornyl (meth) acrylate and methyl (meth) acrylate;
or/and the functional monomer comprises at least one of (meth) acrylic acid, hydroxyethyl (meth) acrylate, N-vinyl caprolactam, dimethyl acrylamide and glycidyl methacrylate;
and/or the second cross-linking agent comprises at least one of diethylene glycol diacrylate, polyethylene glycol (glycol) diacrylate, propoxylated neopentyl glycol diacrylate and 1, 6-hexanediol diacrylate.
7. The superelastic adhesive according to any one of claims 1 to 3 wherein said superelastic adhesive has a bond energy of from 113 to 605J/m 2 。
8. The preparation method of the super elastomer is characterized by comprising the following steps:
preparing a first solution for forming an adhesive film layer and a second solution for forming an elastic body;
performing prepolymerization treatment on the first solution to obtain a third solution;
molding the second solution to obtain an elastic body;
and performing film forming treatment on the surface of the elastic body by using the second solution, and performing drying and curing treatment to form a viscous film layer on the surface of the elastic body to obtain the super-elastic glue.
9. The process for preparing a superelastic rubber according to claim 8, wherein said prepolymerization step comprises the steps of:
the first solution is 1w/cm at room temperature under nitrogen atmosphere 2 Treating for 40-120 s under ultraviolet light;
or/and further comprises the step of carrying out directional cutting processing on the elastic body;
and/or before the second solution is subjected to film forming treatment on the surface of the elastic body, soaking the elastic body in 1-10 wt% of benzophenone ethanol solution for 1-10 min.
10. Use of a superelastomer comprising any one of claims 1-7 in folding or bending materials.
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210313042.5A CN114836138B (en) | 2022-03-28 | 2022-03-28 | Super elastic glue, preparation method and application |
| PCT/CN2022/111469 WO2023184815A1 (en) | 2022-03-28 | 2022-08-10 | Super-elastic adhesive, preparation method and use |
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| Application Number | Priority Date | Filing Date | Title |
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| CN202210313042.5A CN114836138B (en) | 2022-03-28 | 2022-03-28 | Super elastic glue, preparation method and application |
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| CN114836138A true CN114836138A (en) | 2022-08-02 |
| CN114836138B CN114836138B (en) | 2023-11-10 |
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| WO (1) | WO2023184815A1 (en) |
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|---|---|---|---|---|
| WO2023184815A1 (en) * | 2022-03-28 | 2023-10-05 | 南方科技大学 | Super-elastic adhesive, preparation method and use |
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| CN113667410A (en) * | 2020-05-14 | 2021-11-19 | 德莎欧洲股份公司 | Pressure sensitive adhesive electrolyte |
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| CN106397657A (en) * | 2016-09-10 | 2017-02-15 | 东莞市富印胶粘科技有限公司 | Optical double-side adhesive tape composition and method for preparing optical double-side adhesive tape by using same |
| CN109096929B (en) * | 2018-06-29 | 2021-07-16 | 新纶科技（常州）有限公司 | Incompletely cured OCA optical cement with multilayer structure and preparation method thereof |
| CN112384587B (en) * | 2018-08-06 | 2023-04-14 | 三菱化学株式会社 | Photocurable adhesive sheet, adhesive sheet laminate, laminate for image display device, and image display device |
| CN111019543B (en) * | 2019-12-24 | 2021-12-07 | 苏州赛伍应用技术股份有限公司 | High-strength foam adhesive tape and preparation method thereof |
| CN114836138B (en) * | 2022-03-28 | 2023-11-10 | 南方科技大学 | Super elastic glue, preparation method and application |
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| WO2023184815A1 (en) * | 2022-03-28 | 2023-10-05 | 南方科技大学 | Super-elastic adhesive, preparation method and use |
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| CN114836138B (en) | 2023-11-10 |
| WO2023184815A1 (en) | 2023-10-05 |
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