CN114836138B - Super elastic glue, preparation method and application - Google Patents
Super elastic glue, preparation method and application Download PDFInfo
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- CN114836138B CN114836138B CN202210313042.5A CN202210313042A CN114836138B CN 114836138 B CN114836138 B CN 114836138B CN 202210313042 A CN202210313042 A CN 202210313042A CN 114836138 B CN114836138 B CN 114836138B
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- elastic body
- monomer
- adhesive
- film layer
- acrylate
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- 239000003292 glue Substances 0.000 title claims description 55
- 238000002360 preparation method Methods 0.000 title abstract description 13
- 230000001070 adhesive effect Effects 0.000 claims abstract description 63
- 239000000853 adhesive Substances 0.000 claims abstract description 61
- 239000002313 adhesive film Substances 0.000 claims abstract description 55
- 238000004132 cross linking Methods 0.000 claims abstract description 32
- 239000000178 monomer Substances 0.000 claims description 74
- 229920000642 polymer Polymers 0.000 claims description 42
- 239000003431 cross linking reagent Substances 0.000 claims description 41
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 22
- 239000003999 initiator Substances 0.000 claims description 22
- -1 isooctyl Chemical group 0.000 claims description 21
- 239000000463 material Substances 0.000 claims description 18
- 238000000034 method Methods 0.000 claims description 16
- 229920001971 elastomer Polymers 0.000 claims description 15
- 238000011068 loading method Methods 0.000 claims description 15
- 238000006116 polymerization reaction 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
- 238000006356 dehydrogenation reaction Methods 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 7
- 238000003776 cleavage reaction Methods 0.000 claims description 7
- 230000007017 scission Effects 0.000 claims description 7
- 239000000758 substrate Substances 0.000 claims description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 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 6
- 238000001035 drying Methods 0.000 claims description 6
- 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
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 4
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 4
- 238000005520 cutting process 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
- 229920001223 polyethylene glycol Polymers 0.000 claims description 4
- 229920001296 polysiloxane Polymers 0.000 claims description 4
- CERQOIWHTDAKMF-UHFFFAOYSA-N alpha-methacrylic acid Natural products CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 3
- 150000001412 amines Chemical class 0.000 claims description 3
- 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
- 150000004056 anthraquinones Chemical class 0.000 claims description 3
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 3
- 238000007493 shaping process Methods 0.000 claims description 3
- 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
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 claims description 2
- 239000011159 matrix material Substances 0.000 claims description 2
- 239000012752 auxiliary agent Substances 0.000 claims 1
- 238000005336 cracking Methods 0.000 claims 1
- 230000000977 initiatory effect Effects 0.000 claims 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims 1
- 238000002791 soaking Methods 0.000 claims 1
- 239000004820 Pressure-sensitive adhesive Substances 0.000 abstract description 16
- 230000037303 wrinkles Effects 0.000 abstract description 5
- 230000002349 favourable effect Effects 0.000 abstract description 3
- 230000000087 stabilizing effect Effects 0.000 abstract description 3
- 229920002521 macromolecule Polymers 0.000 abstract 6
- 238000011084 recovery Methods 0.000 description 15
- 230000000052 comparative effect Effects 0.000 description 13
- 238000012360 testing method Methods 0.000 description 12
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 10
- 238000005452 bending Methods 0.000 description 10
- 239000000741 silica gel Substances 0.000 description 10
- 229910002027 silica gel Inorganic materials 0.000 description 10
- 229920002799 BoPET Polymers 0.000 description 9
- 125000004122 cyclic group Chemical group 0.000 description 9
- 238000011056 performance test Methods 0.000 description 9
- 238000006073 displacement reaction Methods 0.000 description 8
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 7
- 230000004044 response Effects 0.000 description 6
- 239000004205 dimethyl polysiloxane Substances 0.000 description 5
- 235000013870 dimethyl polysiloxane Nutrition 0.000 description 5
- 238000002474 experimental method Methods 0.000 description 5
- 239000011521 glass Substances 0.000 description 5
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 description 5
- 238000005303 weighing Methods 0.000 description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 4
- 238000011161 development Methods 0.000 description 4
- 239000000806 elastomer Substances 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
- 239000000203 mixture Substances 0.000 description 4
- 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 4
- 238000004987 plasma desorption mass spectroscopy Methods 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 150000003839 salts Chemical class 0.000 description 4
- 229920002379 silicone rubber Polymers 0.000 description 4
- 239000002998 adhesive polymer Substances 0.000 description 3
- 239000002390 adhesive tape Substances 0.000 description 3
- 125000004432 carbon atom Chemical group C* 0.000 description 3
- 230000007423 decrease Effects 0.000 description 3
- 230000009477 glass transition Effects 0.000 description 3
- 229910003473 lithium bis(trifluoromethanesulfonyl)imide Inorganic materials 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 239000004945 silicone rubber Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 230000002195 synergetic effect Effects 0.000 description 3
- 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
- 230000006399 behavior Effects 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 2
- 239000004020 conductor Substances 0.000 description 2
- 230000003111 delayed effect Effects 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 150000002009 diols Chemical class 0.000 description 2
- 238000009472 formulation Methods 0.000 description 2
- 239000000499 gel Substances 0.000 description 2
- 230000010354 integration Effects 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- 238000002834 transmittance Methods 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
- GJKGAPPUXSSCFI-UHFFFAOYSA-N 2-Hydroxy-4'-(2-hydroxyethoxy)-2-methylpropiophenone Chemical compound CC(C)(O)C(=O)C1=CC=C(OCCO)C=C1 GJKGAPPUXSSCFI-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
- GAWIXWVDTYZWAW-UHFFFAOYSA-N C[CH]O Chemical group C[CH]O GAWIXWVDTYZWAW-UHFFFAOYSA-N 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 125000005396 acrylic acid ester group Chemical group 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 230000008094 contradictory effect Effects 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000002354 daily effect Effects 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 230000003203 everyday effect Effects 0.000 description 1
- 239000002360 explosive Substances 0.000 description 1
- 238000009661 fatigue test Methods 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 238000004088 simulation Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- 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
Abstract
The application belongs to the technical field of superelastic adhesives, and particularly relates to a superelastic adhesive, a preparation method and application. The application provides a superelastic adhesive, which comprises an elastic body and an adhesive film layer formed on the surface of the elastic body, wherein the elastic body comprises first macromolecules, the adhesive film layer comprises second macromolecules, the length of a molecular chain between crosslinking points of the first macromolecules is larger than that between crosslinking points of the second macromolecules, and the number of crosslinking points of the first macromolecules is higher than that of the second macromolecules. The super elastic adhesive is a tape with low hysteresis and strong adhesion, is favorable for stabilizing the electric signal of a flexible electronic device, is more suitable for fatigue working conditions than the existing pressure-sensitive adhesive (viscoelastic adhesive) with high hysteresis and large residual strain, and can improve the bad phenomena of instability of the flexible electronic device and a folding screen, such as folds, wrinkles and the like caused by the viscoelastic adhesive.
Description
Technical Field
The application belongs to the technical field of superelastic adhesives, and particularly relates to a superelastic adhesive, a preparation method and application.
Background
An adhesive, a substance that can adhere materials together through a surface. With the progress of the age, the 20 th century has witnessed the rapid development of polymer-based adhesives. Polymer-based adhesives, which have excellent formulation adjustability, allow for rapid development of functionalized diverse adhesive products, such as flexible, tough engineering adhesives, rapid curing adhesives, high temperature and humidity resistant adhesives, and chemically resistant adhesives, etc., which are witnessed as "Adhesives touch our lives every day" ("adhesives are closely related"). In particular, the pressure-sensitive adhesive is capable of wetting and adhering to a substrate with very small force, and has unique excellent adhesive property, high transparent optical property, high tolerance and property formula controllability, so that the pressure-sensitive adhesive has been widely applied to industries such as display screens, mobile phones, flexible electronics, flexible folding screens and the like which are indispensable for daily use except for home use. However, the varying stack-up structure and functional requirements of flexible displays present unprecedented challenges for pressure sensitive adhesives, which are inherently significant viscoelasticity, large residual strains, and limit their explosive development.
It is difficult and contradictory to have both excellent elasticity and tackiness in terms of both mechanics and materials. Strongly bonded adhesives generally have long chain polymers between the cross-links, which means that there is more entanglement of the polymer chains to dissipate more energy, which is dominant in the material, and thus greater hysteresis and residual deformation, i.e. the strain energy is dissipated as heat. In contrast, elastomers/gums with good resilience require short chain polymers with many cross-links, have good entropy elasticity, less dissipation, exhibit dominant entropy elasticity in the material, but their weak interfacial bonding makes it even impossible to call it "adhesive". In recent years, scientists have optimized their elastic recovery based on adequate adhesive power for better application of pressure sensitive adhesives to flexible screens. For example, back et al skillfully cover the light source at the position of the adhesive part to adjust the crosslinking density at different positions of the adhesive tape by using an ultraviolet light mask method, so that the short-chain polymer formed at the position with high crosslinking density has good elastic recovery, and the long-chain polymer formed at the position with low crosslinking density has good bonding performance, thereby having certain elastic recovery under the condition of sufficient bonding.
Lee et al directly mix a long-chain styrene-isoprene-styrene elastomer into a pressure-sensitive adhesive in order to adjust the elastic recovery ability of 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 degree of improvement in the elastic recovery of the pressure-sensitive adhesive, and the addition of the styrene-isoprene-styrene makes the pressure-sensitive adhesive less transparent.
In addition, scientists adjust the high molecular matrix by a chemical method, lee et al adjust the proportion of flexible monomer isooctyl acrylate and functional monomer acrylic acid to adjust the elastic recovery capacity in flexibility and the specific gravity of functional bonding so as to improve the relaxation and creep properties brought by the rebound resilience of the pressure-sensitive adhesive, so that the pressure-sensitive adhesive can be better applied to flexible screens. The methods show balanced mechanical behaviors to us, and only on the basis of sacrificing the bonding performance, the rebound resilience of the adhesive can be weakly improved, so that the development of flexible display screens is greatly prevented. Thus, developing a flexible adhesive behavior with excellent tack and resilience is a "critical" and highly desirable task.
The existence of contradiction leads the common pressure-sensitive adhesive to be mainly sticky, has larger residual deformation during loading and unloading, is slow in relaxation and can not be recovered, and is unfavorable for flexible electronic stability, flexible electronic integrated laminated structure and production of folding screens. Thus, it is highly desirable and important to make superelastic adhesives that have good rebound resilience and strong adhesion.
Disclosure of Invention
Aiming at the prior art, the application aims to provide a superelastic adhesive, a preparation method and application thereof, and aims to solve the problem that the existing adhesive cannot balance elasticity and viscosity.
In order to achieve the purposes of the application, the technical scheme adopted by the application is as follows:
the application provides a superelastic adhesive, which comprises an elastic body and an adhesive film layer formed on the surface of the elastic body, wherein the elastic body comprises first polymers, the adhesive film layer comprises second polymers, the molecular chain length between the crosslinking points of the first polymers is longer than the molecular chain length between the crosslinking points of the second polymers, and the crosslinking points of the first polymers are higher than the crosslinking points of the second polymers.
The elastic body of the super elastic glue provided by the application is composed of an entropy elastic polymer network which is stretchable, has high crosslinking points and short molecular chains, the surface of the adhesive film layer is composed of an adhesive polymer network viscoelasticity polymer which is soft, has low crosslinking points and has a chain length, and the interface between the two polymers is strongly adhered through covalent bonds and topological structures. The elasticity and the viscosity are decoupled through the compounding and the synergistic effect of the elastic body and the viscous film layer, so that the super elastic adhesive is effectively endowed with the balance characteristic of elasticity and viscosity. The super elastic adhesive has low hysteresis and strong adhesion, is favorable for stabilizing electric signals in flexible electronic, is higher than the existing hysteresis, is more suitable for fatigue working conditions, and can improve the instability phenomena of folds, wrinkles and the like caused by the hysteresis of the viscoelastic adhesive in the modern social flexible electronic integration.
The second aspect of the application provides a preparation method of super elastic glue, comprising the following steps:
preparing a first solution for forming an adhesive film layer and a second solution for forming an elastic body;
carrying out prepolymerization treatment on the first solution to obtain a third solution;
shaping the second solution to obtain an elastic body;
and (3) carrying out film forming treatment on the surface of the elastic body by the second solution, and drying and curing the second solution to form a viscous film layer on the surface of the elastic body so as to obtain the superelastic adhesive.
According to the preparation method of the super elastic adhesive, the first solution for forming the adhesive film layer and the second solution for forming the elastic body are prepared by blending the raw materials of the elastic body and the adhesive film layer, the first solution is subjected to pre-polymerization treatment to obtain the adhesive film layer formed by the adhesive polymer network viscoelasticity first polymer with soft surface, low crosslinking point and short molecular chain length, the second solution is subjected to forming treatment to obtain the elastic body formed by the entropy elasticity second polymer network with high tensile property, high crosslinking point and short molecular chain length, the elastic body is immersed into the first solution and then is subjected to drying treatment, and the interface between the adhesive film layer and the elastic body can be strongly adhered through covalent bonds and topological structures.
The third aspect of the application provides an application of the superelastic glue, which comprises the application of the superelastic glue provided by the embodiment of the application in folding or bending materials.
The super elastic glue provided by the embodiment of the application has good rebound resilience, so that the phenomenon that the traditional viscoelastic glue has poor line elasticity due to unmatched modulus between the middle layers in folding or bending, the viscoelastic glue is delayed due to sliding generated when the viscoelastic glue is bent, the layers recover in a non-uniform pace, and finally, after the force is released, wrinkles are generated at the interface is avoided.
Drawings
FIG. 1 is a schematic view of an elastic body according to an embodiment of the present application;
FIG. 2 is a schematic view of an adhesive film structure according to an embodiment of the present application;
FIG. 3 is a schematic diagram illustrating connection between an elastic body and an adhesive film layer according to an embodiment of the present application;
FIG. 4 is a graph showing stress-strain relationship of an adhesive film layer according to an embodiment of the present application;
FIG. 5 is a graph showing stress-strain relationship for an adhesive film layer with 100% strain loading and unloading according to an embodiment of the present application;
FIG. 6 is a graph showing hysteresis statistics for the adhesive film layer of FIG. 5 provided by an embodiment of the present application;
FIG. 7 is a graph of adhesive film layer force versus displacement provided by an embodiment of the present application;
FIG. 8 is a graph of stress-strain relationship of an elastomeric body according to an embodiment of the present application;
FIG. 9 is a graph showing stress-strain relationship for an elastomeric body with 100% strain loading and unloading according to an embodiment of the present application;
FIG. 10 is a graph of the hysteresis statistics of the elastomeric body of FIG. 9 provided by an embodiment of the present application;
FIG. 11 is a graph of elastic body force versus displacement provided by an embodiment of the present application;
FIG. 12 is a graph showing the stress-strain relationship of the superelastic adhesive according to the embodiment of the present application;
FIG. 13 is a graph showing stress-strain relationship for 100% strain for loading and unloading of a superelastic adhesive according to an embodiment of the present application;
FIG. 14 is a graph showing the relationship between superelastic force and displacement according to an embodiment of the present application;
FIG. 15 is a statistical chart of hysteresis performance provided by an embodiment of the present application;
FIG. 16 is a graph showing the statistics of adhesion performance provided by an embodiment of the present application;
FIG. 17 is a graph of the experimental results of transparency of the super elastic glue provided by the embodiment of the application under visible light;
FIG. 18 is a diagram of a method for testing the performance of cyclic bending according to an embodiment of the present application;
FIG. 19 is a graph showing the results of the cyclic bending performance test of the laminated structure according to the embodiment of the present application;
FIG. 20 is a graph showing the results of the cyclic bending performance test of the laminate structure provided in the comparative example of the present application.
Detailed Description
In order to make the technical problems, technical schemes and beneficial effects to be solved more clear, the application is further described in detail below with reference to the embodiments. It should be understood that the specific embodiments described herein are for purposes of illustration only and are not intended to limit the scope of the application.
In the present application, the term "and/or" describes an association relationship of an association object, which means that three relationships may exist, for example, a and/or B may mean: a alone, a and B together, and B alone. Wherein A, B may be singular or plural. The character "/" generally indicates that the context-dependent object is an "or" relationship.
In the present application, "at least one" means one or more, and "a plurality" means two or more. "at least one of" or the like means any combination of these items, including any combination of single item(s) or plural items(s). For example, "at least one (a), b, or c)", or "at least one (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, c may be single or multiple, respectively.
It should be understood that, in various embodiments of the present application, the sequence number of each process does not mean that the sequence of execution is sequential, and some or all of the steps may be executed in parallel or sequentially, where the execution sequence of each process should be determined by its functions and internal logic, and should not constitute any limitation on the implementation process of the embodiments of the present application.
The terminology used in the embodiments of the application is for the purpose of describing particular embodiments only and is not intended to be limiting of the application. As used in the present specification 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 weights of the relevant components mentioned in the description of the embodiments of the present application may refer not only to the specific contents of the components, but also to the proportional relationship between the weights of the components, so long as the contents of the relevant components in the description of the embodiments of the present application are scaled up or down within the scope of the disclosure of the embodiments of the present application. Specifically, the mass described in the specification of the embodiment of the application can be mass units known in the chemical industry field such as mu g, mg, g, kg.
The terms first and second are used for descriptive purposes only and are not to be construed as indicating or implying any relative importance or number of features indicated in order to distinguish one object from another. 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 the inventive embodiments. Thus, a feature defining "a first" or "a second" may explicitly or implicitly include one or more such feature.
The first aspect of the embodiment of the application provides a superelastic adhesive, which comprises an elastic body and an adhesive film layer formed on the surface of the elastic body, wherein the thickness of the elastic body is larger than that of the adhesive film layer, the elastic body comprises a first polymer, the adhesive film layer comprises a second polymer, the molecular chain length of the first polymer is longer than that of the second polymer, and the number of crosslinking points of the first polymer is higher than that of the second polymer.
The superelastic glue provided by the embodiment of the application decouples elasticity and viscosity through the combination and synergistic effect of the elastic body and the viscous film layer, so that the superelastic glue is effectively endowed with the characteristic of elasticity and viscosity balance, the elastic body comprises a first polymer, the elastic body is composed of an entropy elastic first polymer network which can be stretched and has high crosslinking points and short molecular chains, the adhesive film layer comprises a second polymer, the surface of the viscous film layer is composed of a viscous polymer network viscoelasticity second polymer which is soft and has low crosslinking points and chain length, the crosslinking points are represented by the number of cross-linking points among the polymers, the crosslinking points of the first polymer in the embodiment of the application are higher than the crosslinking points of the second polymer, and the number of the crosslinking points among the first polymer is larger than that among the second polymer, as shown in the embodiment of the application. Referring to fig. 3, the interface between the two is strongly bonded by covalent bonds and topology. The superelastic adhesive provided by the embodiment of the application is an adhesive tape with low hysteresis and strong adhesion, is favorable for stabilizing the electric signal of a flexible electronic device, is higher than the existing hysteresis, is more suitable for fatigue working conditions, and can be used for improving the bad phenomenon of instability such as crease, fold and the like caused by hysteresis in the current social flexible electronic integration.
The elastic body is used as a substrate for loading the adhesive film layer, and the thickness of the elastic body is larger than that of the adhesive film layer and is different by at least one order of magnitude. Illustratively, the elastomeric body has a thickness of 1 millimeter and the adhesive film layer has a thickness of 50 to 200 microns. In some embodiments, the raw materials forming the elastic body include a first monomer, a 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 to 10:1 to 5. The first monomer, the cross-linking agent and the first initiator provided by the embodiment of the application can be subjected to 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 (meth) acrylates such as isooctyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, alkoxy acrylates, and the like, 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 having a low glass transition temperature, and the wettability and viscosity of the soft monomer can be further controlled so as to meet the actual requirements.
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 crosslinking agent provided by the embodiment of the application can promote the crosslinking 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, acyl phosphine oxide. In some embodiments, the class II hydrogen abstraction type photoinitiator comprises at least one of benzophenone, thioxanthone, anthraquinone, and an organic amine in combination with an initiator aid. The class I cleavage type photoinitiator or the class II hydrogen abstraction type photoinitiator provided by the embodiment of the application can promote the polymerization of the embodiment of the application. Further, there are benzil groups including at least one of DCP and BPO, benzil ketal groups including at least one of I-907 and I-369, alpha-hydroxy ketones including at least one of I-1173, I-184 and I-2959, and acylphosphine oxides including at least one of I-819 and TPO.
In some embodiments, the adhesive for forming the adhesive film layer in the thermosensitive adhesive according to the embodiment of the present application includes a second monomer, a secondary monomer, a functional monomer, a crosslinking agent and a second initiator, and the mass ratio of the second monomer, the secondary monomer, the functional monomer, the second crosslinking agent and the second initiator is 50-90: 10 to 50:1 to 10:0.01 to 1:0.01 to 1. The second monomer, the secondary monomer, the functional monomer, the cross-linking agent and the second initiator provided by the embodiment of the application can be subjected to polymerization reaction under certain conditions, the adhesive film layer can be obtained by polymerizing the second monomer, the secondary monomer and the functional monomer, and the cohesive energy of the adhesive film layer is improved by controlling the dosage of the second cross-linking agent, so that the adhesive film layer is beneficial to adhesion.
In some embodiments, the second monomer comprises a soft monomer having a carbon chain containing 4 to 7 carbon atoms and having a low glass transition temperature, further the second monomer comprises at least one of isooctyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, alkoxy acrylates, and the like (meth) acrylates, hexafluorobutyl (meth) acrylate, silicone modified (meth) acrylates. The second monomers may further control their wettability and tackiness.
In some embodiments, the secondary monomer comprises at least one of styrene, isobornyl (meth) acrylate, such a short carbon chain of 1-3 carbon atoms, or a hard monomer with a high glass transition temperature of cyclic, aromatic hydrocarbons. The secondary monomer and the second monomer provided by the embodiment of the application have synergistic effect, so that the wettability and the viscosity of the superelastic glue can be further balanced.
In some embodiments, the functional monomer includes at least one of (meth) acrylic acid, hydroxyethyl (meth) acrylate, N-vinylcaprolactam, dimethylacrylamide, glycidyl methacrylate. The functional monomer provided by the embodiment of the application can further control the adhesiveness thereof so as to meet the actual requirements.
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 monomer, further improve the cohesive force of the adhesive film layer and reduce the residual glue 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, acyl phosphine oxide. In some embodiments, the class II hydrogen abstraction type photoinitiator comprises at least one of benzophenone, thioxanthone, anthraquinone, and an organic amine in combination with an initiator aid. The class I cleavage type photoinitiator or the class II hydrogen abstraction type 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 tacky film layer, the raw material forming the elastomeric body, further comprises lithium bis (trifluoromethanesulfonyl) imide, which may be present in an amount of 0.5 to 2M (mol/l). The super elastic glue provided by the embodiment of the application is selectively added with the conductive ionic salt to realize the application of the conductive flexible electronic electrode, and the conductive elastic body P (BA-co-IBA) -0.1% with remarkable viscoelasticity is subjected to high comparison hysteresis under cyclic loading, so that the super elastic glue after each circle of external force release has a stable resistance value, a baseline signal is kept at a level, and the super elastic glue has a rapid average response time of 10ms and an average recovery time of 10ms. While P (BA-co-IBA) -0.1%, its resistance signal is drifting all the time due to its large viscoelasticity and residual stress, the recovery time is approximately an order of magnitude 82ms slower, although there is a faster average response time of 10ms. It should be noted that, the super-elastic conductor can be prepared by adding lithium bis (trifluoromethanesulfonyl) imide into the independent elastic body, and the viscoelastic conductor can be prepared by adding lithium bis (trifluoromethanesulfonyl) imide into the independent adhesive film layer.
In some embodiments, a release film is also included disposed on the surface of the adhesive film layer. The release film provided by the embodiment of the application can protect the superelastic glue and is convenient for transportation of the superelastic glue. In the use process, the stripping type film is required to be adhered to the substrate through the adhesive film layer.
In some embodiments, the bonding energy of the superelastic adhesive is 113-605J/m 2 . The superelastic adhesive provided by the embodiment of the application directly characterizes rebound resilience and viscoelasticity through hysteresis magnitude under loading and unloading, characterizes adhesion by using a peeling adhesion test, has rebound resilience and low hysteresis of 4%, can be firmly adhered to the surfaces of various engineering substrates, and has the highest adhesion energy of 600J/m of plastics 2 。
The second aspect of the embodiment of the application provides a preparation method of super elastic glue, which comprises 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: carrying out prepolymerization treatment on the first solution to obtain a third solution;
step 30: shaping the second solution to obtain an elastic body;
step 40: and (3) carrying out film forming treatment on the surface of the elastic body by the second solution, drying and curing treatment, and forming a viscous film layer on the surface of the elastic body to obtain the superelastic adhesive.
According to the preparation method of the superelastic adhesive, the first solution for forming the adhesive film layer and the second solution for forming the elastic body are prepared, the first solution is subjected to pre-polymerization treatment, the adhesive film layer formed by the non-uniform adhesive polymer network viscoelasticity second polymer with soft surface, low crosslinking point and short molecular chain length can be obtained, the second solution is subjected to forming treatment, the elastic body formed by the uniform entropy elastic first polymer network with high tensile property, high crosslinking point and short molecular chain length can be obtained, the elastic body is immersed into the first solution and then subjected to drying treatment, and the interface between the adhesive film layer and the elastic body can be strongly adhered through covalent bonds and topological structures.
In the step S10, the overall performance of the superelastic rubber is regulated and controlled by blending the proportions of the raw materials of the elastic body and the adhesive film layer, and the mass ratio of the two monomers, the secondary monomer, the functional monomer, the second crosslinking agent and the second initiator is 50-90: 10 to 50:1 to 10:0.01 to 1, and preparing a first solution for forming an adhesive film layer. The mass ratio of the first monomer to the first cross-linking agent to the photoinitiator is 90-100: 1 to 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 two monomers, the secondary monomer, the functional monomer, the second crosslinking agent, and the second initiator is 50 to 90:10 to 50:1 to 10:0.01 to 1 weight each raw material, and prepare a first solution forming an adhesive film layer, and 0.5 to 2M (mol/l) of lithium bistrifluoromethane sulfonyl imide with the mass fraction of 14.3 to 57.1 percent is added into the first solution based on 100 percent of the mass of the first solution. The mass ratio of the first monomer to the first cross-linking agent to the photoinitiator is 90-100: 1 to 10: 1-5, weighing raw materials, preparing a second solution for forming an elastic body, and adding 0.5-2M (mol/l) into the first solution by taking the mass of the second solution as 100%, wherein the second solution is converted into lithium bistrifluoromethane sulfonyl imide with the mass fraction of 14.3-57.1%. The superelastic rubber provided by the embodiment of the application is selectively added with the conductive ionic salt, 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 pre-polymerization process specifically includes the following steps: the first solution was 1w/cm at room temperature under nitrogen atmosphere 2 The second monomer can be polymerized by the pre-polymerization treatment, the pre-polymerization time is controlled, and the polymerization degree of the second monomer, the secondary monomer and the functional monomer is regulated and controlled. The wettability and viscosity of the super elastic glue can be balanced.
In the step S30, the method further includes performing directional cutting processing on the elastic body to obtain the super elastic rubber with mechanical directional design. The super elastic glue prepared by the embodiment of the application is a super elastic glue with low hysteresis and strong adhesion and mechanical orientation design.
In some embodiments, the method further comprises immersing the elastomeric body in an ethanol solution of 1-10 wt% benzophenone for a period of 1-10 minutes. The elastic body is soaked to facilitate the adhesion of the elastic body and the adhesive film layer.
In the step S40, leveling treatment is further included, and the time of the leveling treatment is 30S-5 min, so that 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 applying release PET films on the surfaces of the two layers of the super elastic adhesives, placing the release PET films under 30w,365nm UV-Vis ultraviolet lamps for curing for 20min, and adhering the release PET films on the surfaces of the adhesive film layers, so that the super elastic adhesives are protected, and transportation is facilitated.
The third aspect of the application provides an application of the super elastic glue, which comprises the application of the super elastic glue provided by the embodiment of the application in a flexible screen.
The super elastic glue provided by the embodiment of the application has good rebound resilience, so that the phenomenon that the traditional viscoelastic glue has poor line elasticity due to unmatched modulus between the middle layers in folding or bending, the viscoelastic glue is delayed due to sliding generated when the viscoelastic glue is bent, the layers recover in a non-uniform pace, and finally, after the force is released, wrinkles are generated at the interface is avoided.
In order that the details and operations of the present application may be clearly understood by those skilled in the art, and that the advanced performance of the superelastic glue, the preparation method and the application of the embodiments of the present application may be significantly embodied, the following examples are given to illustrate the above technical solutions.
Example 1
The embodiment provides a preparation method of super elastic glue, which comprises the following steps:
step 101, weighing 100wt% of monomer butyl acrylate, 1wt% of cross-linking agent PEGDA-600, 2wt%,3wt% (relative to the mass fraction of the monomer) and 1wt% of photoinitiator I-1173 (relative to the mass fraction of the monomer) respectively to prepare a first solution.
Step 102, weighing 80wt% of monomer butyl acrylate, 20wt% of isobornyl acrylate, 0.1wt% of crosslinking agent PEGDA-600, 0.5wt%,1wt% (relative to the mass fraction of the monomer) and 0.1wt% of photoinitiator I-1173 (relative to the mass fraction of the monomer), weighing the corresponding masses, and mixing and stirring to prepare a second solution.
Step 201, placing the first solution into a nitrogen atmosphere, prepolymerizing for 1min in a 30W and 365nm ultraviolet lamp, transferring the beaker into a cold water bath, and cooling to room temperature to serve as a third solution for standby.
Step 202, respectively injecting first solutions with the content of the cross-linking agent of 1 weight percent, 2 weight percent and 3 weight percent into prepared glass molds: the middle is provided with a silica gel gasket with the interval of 1mm, both ends of the silica gel gasket are transparent, glass with release films is adhered on the two ends of the silica gel gasket, the silica gel gasket is sealed, and the silica gel gasket is placed into a 30W ultraviolet lamp with the wavelength of 365nm for curing for 30min, so that three groups of adhesive film layers are obtained, and mechanical test and standby are carried out.
Step 301. Injecting second solutions with the cross-linking agent content of 0.1wt% and 0.5wt% respectively into prepared glass moulds: the middle is provided with a 1mm silica gel gasket, two ends of the silica gel gasket are transparent, glass with release films is adhered on the two ends of the silica gel gasket, the silica gel gasket is sealed, and the silica gel gasket is placed into a 30W ultraviolet lamp and a 365nm ultraviolet lamp to be cured for 30min, so that three groups of elastic bodies are obtained, and mechanical test and standby are carried out.
Step 302, directionally cutting the elastic body with the mass percent of the cross-linking agent being 2%.
And 303, immersing the oriented cutting elastic body in ethanol solution of 2wt% of benzophenone for 2min, and drying the elastic body in a 6 ℃ oven 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 percent, immediately lifting, leveling for 1min at room temperature in air, and applying release films on the upper surface and the lower surface.
And 402, placing the mixture into a 30W 365nm ultraviolet lamp for curing for 20 minutes, and then performing mechanical test.
Comparative example 1
Acrylic pressure sensitive adhesive 3MVHB4905.
Comparative example 2
Flexible electronics frequently used are silicone rubber polydimethylsiloxane PDMS Sylgard 184 (10:1).
Performance test 1
The elastic body, the adhesive film layer, the super elastic glue and the common silicone rubber PDMS Sylgard 184 (10:1) of the flexible electronic (comparative example 2) and the acrylic pressure-sensitive adhesive 3MVHB4905 (comparative example 1) prepared in example 1 are respectively subjected to a loading and unloading hysteresis test, a 180 DEG peeling test and a PET film test of which the two sides of the adhesive tape are adhered with a hard back plate with the thickness of 25 mu m, and the hysteresis and the adhesive energy are recorded. The results are shown in Table 1. The mass percentage of the crosslinking agent contained in the adhesive film layer in the superelastic adhesive (HEA) was 0.1%, and the mass percentage of the crosslinking agent contained in the elastic body in the superelastic adhesive (HEA) was 2%.
Table 1 test results
Name | Hysteresis | Adhesion energy(J/m 2 ) |
PBA-1% (body) | 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 |
VHB 4905 | 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 the crosslinking agent and materials contained in comparative example 1, and the results show that as the content of the crosslinking agent decreases, the adhesion performance increases, but at the same time, the hysteresis increases, and the hysteresis of three sets of adhesive film layers contained in example 1 is more serious and the adhesion is stronger than that of comparative example 1. As the content of the crosslinking agent decreases, the longer the molecular chain between the crosslinking points, the interaction force with the interface increases, but at the same time, the hysteresis phenomenon is serious.
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, hysteresis decreases, and hysteresis of the three elastic bodies contained in example 2 is reduced as compared with comparative example 1, which is equivalent to that of comparative example 2. As the content of the crosslinking agent increases, the chain length of molecules between crosslinking points becomes shorter, hysteresis is improved, but the acting force between the crosslinking agent and the interface is reduced.
Fig. 12 to 14 are graphs showing the performance test results of the superelastic adhesive 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 result shows that the superelastic adhesive provided in example 1 can effectively balance the elasticity and the adhesiveness of the material.
In addition, as shown in FIGS. 15 to 16, the superelastic tape prepared by the experiment was directly loaded and unloadedThe following hysteresis sizes characterize rebound and viscoelasticity, peel adhesion tests characterize adhesion, and the superelastic adhesives of the examples have 4% better rebound, lower hysteresis than the industry and academically accepted superelastic and weak adhesion silicone rubber PDMS Sylgard 184 (10:1), and higher average adhesion energy 270J/m 2 Is higher than the common flexible glue VHB4905 of 3M company.
Example 2
The preparation of the conductive superelastic rubber material in this embodiment follows the preparation flow of the superelastic rubber in embodiment 1, and the only difference between the superelastic material in the original formula and the first solution is that 0.5-2M of lithium bistrifluoromethane sulfonyl imide 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 final prepared conductive superelastic adhesive has hysteresis of 9% and adhesive energy of 300J/m 2 Both the average response time and the average recovery time were 10ms. While the viscoelastic gel P (BA-co-IBA) -0.1%, the surface gel formulation of example 1 was followed with an additional 0.5-2M (mol/l) of lithium bistrifluoromethane sulphonimide, all other conditions and steps remaining unchanged. The average response time of the finally prepared conductive viscoelastic was 10ms, but the average recovery time was 81.5ms.
The super elastic glue provided by the embodiment of the application is selectively added with the conductive ionic salt to realize the application of the conductive flexible electronic electrode, and has the advantages of high contrast hysteresis under cyclic loading, and conductive elastomer P (BA-co-IBA) -0.1% with remarkable viscoelasticity, stable resistance value of the super elastic glue after each circle of external force release, and a baseline signal kept at a level, and quick average response time of 10ms and average recovery time of 10ms. While P (BA-co-IBA) -0.1%, its resistance signal is drifting all the time due to its large viscoelasticity and residual stress, the average recovery time is approximately an order of magnitude 82ms slower, although there is a faster average response time of 10ms. The elastic rubber has excellent rebound resilience and ultra-fast recovery, avoids the line elasticity attributed to the unmatched modulus between layers in the laminated structure, hysteresis of the viscoelastic rubber caused by slippage generated when the rubber is bent, non-uniform pace of recovery between layers, and finally, after force is released, the bad phenomenon of wrinkling at an interface is avoided.
Performance test 2
And (3) evaluating the bonding energy of the super elastic glue to various base materials, wherein one surface of the super elastic glue is polymerized and bonded on the base materials in situ, a hard back plate 25 mu m PET film is attached to the other surface of the super elastic glue, a preset crack is glued on the surface of the base materials in advance by a blade, and the bonding energy of the super elastic glue to the lattice base materials is measured and recorded by adopting a test method of 90-degree peeling. As a result, please refer to fig. 2:
TABLE 2 Performance test results
Substrate name | Adhesive energy (J/m) 2 ) |
Acrylic plate (Plastic) | 605 |
Wood | 595 |
Steel (Metal) | 594 |
Glass | 400 |
Ceramic (alumina ceramic) | 320 |
Rubber (silicon rubber) | 113 |
Example 2 simulation of a laminate junction common in flexible screensStress working conditions are constructed, the super elastic glue is applied to the laminated structure, and a cyclic bending experiment is carried out on the laminated structure, wherein the bonding energy is 113-605J/m 2 Has good adhesive property with most materials on the market, can be firmly adhered on the surfaces of various engineering substrates, and has the highest average adhesive energy of 600J/m 2 。
Example 3
The embodiment provides an application of super elastic glue in a laminated structure. The superelastic adhesive in example 1 was set in the middle of two PET films, one PET film had a thickness of 25. Mu.m, and the other PET film had a thickness of 200. Mu.m, and the superelastic adhesive had a thickness of 1000. Mu.m, 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 P (BA-co-IBA) -0.1% acrylic viscoelastic.
Performance test 3
The head transmittance test was performed on the 1mm superelastic glue in example 1 and the P (BA-co-IBA) -0.1% acrylic acid ester type viscoelastic glue in comparative example 3 by using the ultraviolet-visible light spectrum scanning method in the visible light wavelength range, and as a result of the experiment, please refer to fig. 17, the penetration rate of the superelastic glue provided in example 1 is 89%, and the superelastic glue has good light transmittance and can be used as a material of a display screen.
Taking rectangular strips with the dimensions of 60mm long and 20mm wide of the laminated structure in the embodiment 3, referring to fig. 18, firstly, respectively clamping two acrylic plates on a clamp of an Instron 3000 of a fatigue testing machine, then vertically fixing two ends of the laminated structure on the central line of the two acrylic plates along the clamp, performing downward cyclic bending test on the laminated structure, circularly loading for 1000 circles, applying downward displacement to the laminated structure by a displacement control method for each circle, circularly loading and unloading, wherein the downward maximum displacement in the experiment is 20mm, the minimum displacement is 0mm, and the loading rate is 1Hz by adopting triangular wave control displacement. As a result of the experiment, referring to fig. 19, after the bending portion of the laminated structure provided in example 3 was recovered, no wrinkles were generated, and after the bending portion of the laminated structure provided in comparative example 3 was recovered, indicating that the laminated structure provided in example 3 did not have hysteresis.
The foregoing description of the preferred embodiments of the application is not intended to be limiting, but rather is intended to cover all modifications, equivalents, and alternatives falling within the spirit and principles of the application.
Claims (5)
1. The super elastic glue is characterized by comprising an elastic body and a viscous film layer formed on the surface of the elastic body, wherein the elastic body comprises a first polymer, the viscous film layer comprises a second polymer, the length of a molecular chain between crosslinking points of the first polymer is longer than that of a molecular chain between crosslinking points of the second polymer, and the number of crosslinking points of the first polymer is higher than that of the crosslinking points of the second polymer;
the raw materials for forming the elastic body comprise a first monomer, a first crosslinking agent and a first initiator, wherein the mass ratio of the first monomer to the first crosslinking agent to the first initiator is 90-100: 1-10: 1-5;
the adhesive for forming the adhesive film layer comprises a second monomer, a secondary monomer, a functional monomer, a second crosslinking agent and a second initiator, wherein the mass ratio of the second monomer to the secondary monomer to the functional monomer to the second crosslinking agent to the second initiator is 50-90: 10-50: 1-10: 0.01-1: 0.001-1;
the elastic body contained in the super elastic glue is used as a matrix for loading the adhesive film layer, the thickness of the elastic body is 1 millimeter, and the thickness of the adhesive film layer is 50-200 microns;
when imparting electrical conductivity to the superelastic gel, the raw material forming the elastic body and the adhesive forming the adhesive film layer further include lithium bistrifluoromethane sulfonyl imide;
the first monomer comprises at least one of isooctyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, alkoxy acrylate, hexafluorobutyl (meth) acrylate and silicone modified (meth) acrylate;
the first crosslinking agent comprises at least one of diethylene glycol diacrylate, polyethylene glycol diacrylate, propoxylated neopentyl glycol diacrylate and 1, 6-hexanediol diacrylate;
the first initiator and the second initiator independently comprise a type I cleavage type photoinitiator or a type II hydrogen abstraction type photoinitiator;
the I-type cracking photoinitiator comprises at least one of benzil, alpha-hydroxy ketone and acyl phosphine oxide;
the II type hydrogen abstraction photoinitiator comprises at least one of diphenyl ketone, thioxanthone, anthraquinone and organic amine matched with an initiation auxiliary agent;
the second monomer comprises at least one of isooctyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, alkoxy acrylate, hexafluorobutyl (meth) acrylate, and silicone modified (meth) acrylate;
the secondary monomer comprises at least one of styrene, isobornyl (meth) acrylate and methyl (meth) acrylate;
the functional monomer comprises at least one of (methyl) acrylic acid, hydroxyethyl (methyl) acrylate, N-vinyl caprolactam, dimethyl acrylamide and glycidyl methacrylate;
the second crosslinking agent comprises at least one of diethylene glycol diacrylate, polyethylene glycol diacrylate, propoxylated neopentyl glycol diacrylate and 1, 6-hexanediol diacrylate.
2. The superelastic glue according to claim 1, wherein the bonding energy of the superelastic glue is 113-605J/m 2 。
3. A method for preparing the superelastic glue according to claim 1 or 2, comprising the following steps:
preparing a first solution for forming an adhesive film layer and a second solution for forming an elastic body;
carrying out prepolymerization treatment on the first solution to obtain a third solution;
shaping the second solution to obtain an elastic body;
forming a film on the surface of the elastic body by the third solution, drying and curing to form a viscous film layer on the surface of the elastic body, thereby obtaining the superelastic rubber;
the raw materials for forming the elastic body comprise a first monomer, a first crosslinking agent and a first initiator, wherein the mass ratio of the first monomer to the first crosslinking agent to the first initiator is 90-100: 1-10: 1-5;
the adhesive for forming the adhesive film layer comprises a second monomer, a secondary monomer, a functional monomer, a second crosslinking agent and a second initiator, wherein the mass ratio of the second monomer to the secondary monomer to the functional monomer to the second crosslinking agent to the second initiator is 50-90: 10-50: 1-10: 0.01-1: 0.001-1;
the elastic body contained in the super elastic glue is used as a substrate for loading the adhesive film layer, the thickness of the elastic body is 1 millimeter, and the thickness of the adhesive film layer is 50-200 microns.
4. The method for preparing the superelastic rubber according to claim 3, wherein the pre-polymerization treatment comprises the following steps:
the first solution was 1w/cm at room temperature under nitrogen atmosphere 2 Is processed for 40-120 s under ultraviolet light;
or/and, the method further comprises the step of carrying out directional cutting treatment on the elastic body;
or/and, before the third solution is subjected to film forming treatment on the surface of the elastic body, soaking the elastic body in an ethanol solution of 1-10wt% of benzophenone for 1-10 min.
5. Use of a superelastic glue according to claim 1 or 2 in folded or bent materials.
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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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CN1912038A (en) * | 2005-08-11 | 2007-02-14 | 日东电工株式会社 | Adhesive sheet and process for preparing it and method for processing the product |
CN104937059A (en) * | 2013-02-12 | 2015-09-23 | 三菱树脂株式会社 | Transparent double-sided adhesive sheet, laminate obtained using same for constituting image display device, process for producing said laminate, and image display device obtained using said laminate |
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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