CN115368856B - Photo-thermal response type adhesive with optical switch and preparation method thereof - Google Patents
Photo-thermal response type adhesive with optical switch and preparation method thereof Download PDFInfo
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- CN115368856B CN115368856B CN202210834087.7A CN202210834087A CN115368856B CN 115368856 B CN115368856 B CN 115368856B CN 202210834087 A CN202210834087 A CN 202210834087A CN 115368856 B CN115368856 B CN 115368856B
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- 239000000853 adhesive Substances 0.000 title claims abstract description 49
- 230000001070 adhesive effect Effects 0.000 title claims abstract description 49
- 230000003287 optical effect Effects 0.000 title claims abstract description 26
- 230000004044 response Effects 0.000 title claims abstract description 23
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- 239000002994 raw material Substances 0.000 claims abstract description 20
- 239000003999 initiator Substances 0.000 claims abstract description 18
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 11
- 239000000178 monomer Substances 0.000 claims abstract description 10
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 8
- 239000002518 antifoaming agent Substances 0.000 claims abstract description 5
- 239000004005 microsphere Substances 0.000 claims description 35
- 229920000089 Cyclic olefin copolymer Polymers 0.000 claims description 26
- 239000003822 epoxy resin Substances 0.000 claims description 20
- 229920000647 polyepoxide Polymers 0.000 claims description 20
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical class C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 claims description 18
- 229920003229 poly(methyl methacrylate) Polymers 0.000 claims description 18
- 239000004926 polymethyl methacrylate Substances 0.000 claims description 18
- 229910052582 BN Inorganic materials 0.000 claims description 13
- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical compound N#B PZNSFCLAULLKQX-UHFFFAOYSA-N 0.000 claims description 13
- 239000004841 bisphenol A epoxy resin Substances 0.000 claims description 13
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 12
- 239000013530 defoamer Substances 0.000 claims description 12
- 239000004593 Epoxy Substances 0.000 claims description 11
- -1 bis (4-tertiary butylphenyl) iodonium hexafluorophosphate Chemical group 0.000 claims description 11
- 239000002245 particle Substances 0.000 claims description 11
- 239000004814 polyurethane Substances 0.000 claims description 11
- 229920002635 polyurethane Polymers 0.000 claims description 11
- 125000002723 alicyclic group Chemical group 0.000 claims description 10
- UHESRSKEBRADOO-UHFFFAOYSA-N ethyl carbamate;prop-2-enoic acid Chemical compound OC(=O)C=C.CCOC(N)=O UHESRSKEBRADOO-UHFFFAOYSA-N 0.000 claims description 10
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical group C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 claims description 9
- 239000003211 polymerization photoinitiator Substances 0.000 claims description 9
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 8
- 238000010538 cationic polymerization reaction Methods 0.000 claims description 8
- 239000011353 cycloaliphatic epoxy resin Substances 0.000 claims description 8
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical group O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 8
- 239000006258 conductive agent Substances 0.000 claims description 7
- 125000005520 diaryliodonium group Chemical group 0.000 claims description 7
- 150000001451 organic peroxides Chemical group 0.000 claims description 7
- ZXHDVRATSGZISC-UHFFFAOYSA-N 1,2-bis(ethenoxy)ethane Chemical compound C=COCCOC=C ZXHDVRATSGZISC-UHFFFAOYSA-N 0.000 claims description 6
- 235000019400 benzoyl peroxide Nutrition 0.000 claims description 6
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 5
- 229920000298 Cellophane Polymers 0.000 claims description 3
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 3
- 239000010931 gold Substances 0.000 claims description 3
- 229910052737 gold Inorganic materials 0.000 claims description 3
- DMKSVUSAATWOCU-HROMYWEYSA-N loteprednol etabonate Chemical compound C1CC2=CC(=O)C=C[C@]2(C)[C@@H]2[C@@H]1[C@@H]1CC[C@@](C(=O)OCCl)(OC(=O)OCC)[C@@]1(C)C[C@@H]2O DMKSVUSAATWOCU-HROMYWEYSA-N 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- 238000012216 screening Methods 0.000 claims description 3
- 229910052710 silicon Inorganic materials 0.000 claims description 3
- 239000010703 silicon Substances 0.000 claims description 3
- 238000003756 stirring Methods 0.000 claims description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 2
- KUQWZSZYIQGTHT-UHFFFAOYSA-N hexa-1,5-diene-3,4-diol Chemical compound C=CC(O)C(O)C=C KUQWZSZYIQGTHT-UHFFFAOYSA-N 0.000 claims description 2
- 238000005516 engineering process Methods 0.000 abstract description 7
- 239000004065 semiconductor Substances 0.000 abstract description 7
- 230000000694 effects Effects 0.000 abstract description 3
- 238000007711 solidification Methods 0.000 abstract description 3
- 230000008023 solidification Effects 0.000 abstract description 3
- 238000012546 transfer Methods 0.000 abstract description 2
- 238000005286 illumination Methods 0.000 abstract 1
- 238000001723 curing Methods 0.000 description 15
- 238000000034 method Methods 0.000 description 5
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 4
- 229910052782 aluminium Inorganic materials 0.000 description 4
- 239000003292 glue Substances 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 229920001187 thermosetting polymer Polymers 0.000 description 4
- 239000007788 liquid Substances 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 238000000016 photochemical curing Methods 0.000 description 3
- 229920005989 resin Polymers 0.000 description 3
- 239000011347 resin Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 238000000149 argon plasma sintering Methods 0.000 description 2
- 238000003776 cleavage reaction Methods 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 238000013007 heat curing Methods 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 238000004806 packaging method and process Methods 0.000 description 2
- 230000007017 scission Effects 0.000 description 2
- 238000007789 sealing Methods 0.000 description 2
- 239000012205 single-component adhesive Substances 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- FODCFYIWOJIZQL-UHFFFAOYSA-N 1-methylsulfanyl-3,5-bis(trifluoromethyl)benzene Chemical compound CSC1=CC(C(F)(F)F)=CC(C(F)(F)F)=C1 FODCFYIWOJIZQL-UHFFFAOYSA-N 0.000 description 1
- OLPZCIDHOZATMA-UHFFFAOYSA-N 2,2-dioxooxathiiran-3-one Chemical class O=C1OS1(=O)=O OLPZCIDHOZATMA-UHFFFAOYSA-N 0.000 description 1
- BQZJOQXSCSZQPS-UHFFFAOYSA-N 2-methoxy-1,2-diphenylethanone Chemical group C=1C=CC=CC=1C(OC)C(=O)C1=CC=CC=C1 BQZJOQXSCSZQPS-UHFFFAOYSA-N 0.000 description 1
- HMBNQNDUEFFFNZ-UHFFFAOYSA-N 4-ethenoxybutan-1-ol Chemical compound OCCCCOC=C HMBNQNDUEFFFNZ-UHFFFAOYSA-N 0.000 description 1
- 239000004925 Acrylic resin Substances 0.000 description 1
- 229920000178 Acrylic resin Polymers 0.000 description 1
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 description 1
- WHNWPMSKXPGLAX-UHFFFAOYSA-N N-Vinyl-2-pyrrolidone Chemical compound C=CN1CCCC1=O WHNWPMSKXPGLAX-UHFFFAOYSA-N 0.000 description 1
- 239000004809 Teflon Substances 0.000 description 1
- 229920006362 Teflon® Polymers 0.000 description 1
- QYKIQEUNHZKYBP-UHFFFAOYSA-N Vinyl ether Chemical group C=COC=C QYKIQEUNHZKYBP-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- VGZKCAUAQHHGDK-UHFFFAOYSA-M bis(4-tert-butylphenyl)iodanium;trifluoromethanesulfonate Chemical compound [O-]S(=O)(=O)C(F)(F)F.C1=CC(C(C)(C)C)=CC=C1[I+]C1=CC=C(C(C)(C)C)C=C1 VGZKCAUAQHHGDK-UHFFFAOYSA-M 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- PMHQVHHXPFUNSP-UHFFFAOYSA-M copper(1+);methylsulfanylmethane;bromide Chemical compound Br[Cu].CSC PMHQVHHXPFUNSP-UHFFFAOYSA-M 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 229910003460 diamond Inorganic materials 0.000 description 1
- 239000010432 diamond Substances 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 229940052303 ethers for general anesthesia Drugs 0.000 description 1
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 1
- 239000011551 heat transfer agent Substances 0.000 description 1
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical class I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 230000001678 irradiating effect Effects 0.000 description 1
- 238000002356 laser light scattering Methods 0.000 description 1
- 238000013008 moisture curing Methods 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- AHHWIHXENZJRFG-UHFFFAOYSA-N oxetane Chemical compound C1COC1 AHHWIHXENZJRFG-UHFFFAOYSA-N 0.000 description 1
- 125000003566 oxetanyl group Chemical group 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 238000010526 radical polymerization reaction Methods 0.000 description 1
- 238000011897 real-time detection Methods 0.000 description 1
- 238000007142 ring opening reaction Methods 0.000 description 1
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 1
- 229910010271 silicon carbide Inorganic materials 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 230000000930 thermomechanical effect Effects 0.000 description 1
- 239000012780 transparent material Substances 0.000 description 1
- 125000005409 triarylsulfonium group Chemical group 0.000 description 1
- 238000009281 ultraviolet germicidal irradiation Methods 0.000 description 1
- 229960000834 vinyl ether Drugs 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
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
- C09J163/00—Adhesives based on epoxy resins; Adhesives based on derivatives of epoxy resins
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/02—Non-macromolecular additives
- C09J11/04—Non-macromolecular additives inorganic
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/02—Non-macromolecular additives
- C09J11/06—Non-macromolecular additives organic
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/08—Macromolecular additives
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/38—Boron-containing compounds
- C08K2003/382—Boron-containing compounds and nitrogen
- C08K2003/385—Binary compounds of nitrogen with boron
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2203/00—Applications
- C08L2203/20—Applications use in electrical or conductive gadgets
- C08L2203/206—Applications use in electrical or conductive gadgets use in coating or encapsulating of electronic parts
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/14—Polymer mixtures characterised by other features containing polymeric additives characterised by shape
- C08L2205/18—Spheres
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Adhesives Or Adhesive Processes (AREA)
Abstract
The invention relates to the technical field of adhesives, in particular to the field of IPC C09J7, and more particularly relates to a photo-thermal response type adhesive with an optical switch and a preparation method thereof. The photo-thermal response type adhesive with the optical switch comprises the following preparation raw materials in parts by weight: 30-60 parts of main raw materials, 15-35 parts of active monomers, 5-20 parts of light guide auxiliary agents, 1-10 parts of photoinitiators, 1-10 parts of thermal initiators, 5-20 parts of heat conducting agents and 0.1-0.3 part of defoaming agents. The prepared photo-thermal response adhesive with the optical switch achieves the effect of thorough solidification by light guide and heat conduction transfer aiming at the shadow area incapable of illuminating, has no obvious difference in performance from direct illumination, and can be applied to the modern industrial fields of semiconductor industry, semiconductor technology and the like.
Description
Technical Field
The invention relates to the technical field of adhesives, in particular to the field of IPC C09J7, and more particularly relates to a photo-thermal response type adhesive with an optical switch and a preparation method thereof.
Background
The semiconductor industry and semiconductor technology are known as the basis of modern industry and have also evolved into a relatively independent high-tech industry. The electronic product often uses thermosetting epoxy resin in the assembly process, but the thermosetting time is long, and a certain amount of curing agent is often added into the thermosetting raw materials, so that the reliability is poor, but the electronic product is produced in an intelligent manufacturing assembly line mode in the industry at present, the time required for thermosetting the material is long, the curing efficiency is low, and the control mode of the intelligent manufacturing assembly line at present is not met. The electronic product obtained by heat curing can not meet the curing requirement at low temperature, and the curing speed can be improved at too high temperature, but the preservability of the electronic product can be greatly reduced, even the electronic product can be preserved for 1 day or less at 25 ℃, the product is continuously thickened in the use process, and great trouble is caused to the line management of customers, so that the development of a single-component adhesive with high curing speed and good preservability is urgently required.
In the prior art, the application publication No. CN113980582A discloses an adhesive capable of being cured by light, heat and moisture and a preparation method thereof, wherein oxetane groups, acrylate groups and alkoxysilane groups are added to branches to improve the adhesive, and the prepared adhesive has the functions of light curing, heat curing and moisture curing, but has no improvement on curing speed and curing temperature.
The patent document with the publication number of CN104212391B discloses an epoxy resin-acrylic ester copolymer adhesive formula and a preparation process thereof, and the prepared adhesive is nontoxic and harmless, has strong water resistance and high bonding strength, but has no improvement on the curing speed and curing temperature.
Photocuring is a novel technology with high efficiency, energy conservation and environmental protection, and is increasingly popular with enterprises and industries. The photo-curing adhesive is a single-component adhesive, can have a shelf life of 1 year or even several years at normal temperature as long as the photo-curing adhesive is stored in a shading way, can be cured within a few seconds once being illuminated, has high curing speed and high yield, and is particularly suitable for a production line assembly process of electronic products. However, the defects are also obvious, and the adhesive is only suitable for surface coating and adhesive sealing of transparent materials, and cannot be used for adhesive sealing of opaque materials, and most electronic products are made of opaque materials, so that the application range of the adhesive is limited.
Therefore, the industry is urgent to develop a new technology with good preservability at normal temperature, fast curing speed and low curing temperature to meet the increasing requirements of rapid assembly technology of electronic products.
Disclosure of Invention
In order to solve the above problems, according to a first aspect of the present invention, there is provided an adhesive having an optical switch, wherein UV light is irradiated on the surface of the adhesive, and a part of main raw materials and an active monomer on the surface of the adhesive generate photoreaction to generate heat, so that a reaction including at least the rest of main raw materials is excited, and the adhesive having an optical switch is prepared by a photothermal response principle.
The preparation raw materials comprise the following components in parts by weight: 30-60 parts of main raw materials, 15-35 parts of active monomers, 5-20 parts of light guide auxiliary agents, 1-10 parts of photoinitiators, 1-10 parts of thermal initiators, 5-20 parts of heat conducting agents and 0.1-0.3 part of defoaming agents.
Preferably, the main raw material is selected from one or more of hydrogenated bisphenol A type epoxy resin, vinyl ether acrylic ester prepolymer, polyurethane acrylic ester oligomer, alicyclic epoxy resin, epoxy acrylic ester resin and pure acrylic resin; further preferred are hydrogenated bisphenol a type epoxy resins, cycloaliphatic epoxy resins and urethane acrylate oligomers.
Preferably, the weight ratio of the hydrogenated bisphenol A epoxy resin, the alicyclic epoxy resin and the urethane acrylate oligomer is 1:2:1.
preferably, the hydrogenated bisphenol A epoxy resin has an epoxy equivalent of 150-300g/eq and a viscosity of 1000-5000cps at 25deg.C; further preferably, the hydrogenated bisphenol A epoxy resin has an epoxy equivalent of 200 to 230g/eq and a viscosity of 1500 to 3000cps at 25 ℃.
In some preferred embodiments, the hydrogenated bisphenol A epoxy resin is purchased from Japanese Ai Dike company, hydrogenated epoxy resin EP-4080E.
Preferably, the urethane acrylate oligomer has a functionality of 15 to 20; further preferably 18.
Preferably, the urethane acrylate oligomer is a star urethane acrylate oligomer.
In some preferred embodiments, the urethane acrylate oligomer is purchased from the company Sorbiscott, shenzhen.
Preferably, the viscosity of the cycloaliphatic epoxy resin is 150-350cps at 25 ℃ and the epoxy equivalent is 100-200g/eq; further preferably, the cycloaliphatic epoxy resin has a viscosity of 200-280cps at 25 ℃ and an epoxy equivalent weight of 128-145g/eq.
In some preferred embodiments, the cycloaliphatic epoxy resin is purchased from cycloaliphatic epoxy resin 2021P, manufactured by japanese cellophane corporation.
Preferably, the reactive monomer is selected from one or more of oxetane, 4-hydroxybutyl vinyl ether, trivinyl ethylene glycol divinyl ether, N-vinyl pyrrolidone and ethyl 2-ethyleneoxy ethoxy acrylate; further preferred are ethyl 2-ethyleneoxyethoxy acrylate and trivinyl ethylene glycol divinyl ether.
Preferably, the weight ratio of the 2-ethyleneoxy ethoxy ethyl acrylate to the trivinyl ethylene glycol divinyl ether is (1-2): (1-2); further preferably, it is 2:3.
Preferably, the light guide auxiliary agent is selected from one or more of polymethyl methacrylate microsphere, polycarbonate microsphere, organosilicon microsphere and cycloolefin polymer (COP) microsphere; further preferred are polymethyl methacrylate microspheres and Cyclic Olefin Polymer (COP) microspheres.
Preferably, the weight ratio of the polymethyl methacrylate microsphere to the cycloolefin polymer (COP) microsphere is (1-2): (1-3); further preferably, the ratio is 1:1.
Preferably, the polymethyl methacrylate microsphere has a particle size of 0.025-10 μm; further preferably, it is 1. Mu.m.
In some preferred embodiments, the polymethyl methacrylate microspheres are purchased from polymethyl methacrylate microsphere ZZS-MMA1000, manufactured by Shanghai screening quasi-biotechnology Co.
Preferably, the particle size of the cycloolefin polymer (COP) microspheres is 1-5 μm; further preferably, it is 3. Mu.m.
In some preferred embodiments, the Cyclic Olefin Polymer (COP) microspheres are purchased from japan rayleigh.
Preferably, the photoinitiator is selected from one or more of a free radical polymerization photoinitiator and a cationic polymerization photoinitiator; further preferred is a cationic polymerization photoinitiator.
Preferably, the cationic polymerization photoinitiator is selected from one or more of triarylsulfonium salts, alkyl sulfonium salts, diaryl iodonium salts, iron arene salts, sulfonyloxy ketones and triarylsiloxane ethers; further preferred is a diaryliodonium salt.
Preferably, the diaryl iodonium salt is one or more of bis (4-tert-butylphenyl) iodonium hexafluorophosphate and bis (4-tert-butylphenyl) iodonium triflate; further preferred is bis (4-t-butylphenyl) iodonium hexafluorophosphate.
Preferably, the bis (4-t-butylphenyl) iodonium hexafluorophosphate has a CAS number of 61358-25-6.
Preferably, the thermal initiator is selected from one or more of azo thermal initiator, organic peroxide thermal initiator, redox thermal initiator and borate thermal initiator; further preferred is an organic peroxide-based thermal initiator.
Preferably, the organic peroxide thermal initiator is dibenzoyl peroxide.
Preferably, the CAS number for dibenzoyl peroxide is 94-36-0.
Preferably, the heat conducting agent is selected from one or more of diamond, boron nitride, silicon carbide, aluminum oxide and aluminum nitride; further preferred are alumina and boron nitride.
The weight ratio of the aluminum oxide to the boron nitride is (1-2): (1-2); further preferably, the ratio is 1:1.
Preferably, the median particle diameter D of the alumina 50 2-50 μm; further preferably, it is 8-12. Mu.m.
Preferably, the median diameter D of the boron nitride 50 2-600nm; further preferably, it is 50nm.
In some preferred embodiments, the alumina is purchased from GD-S spherical alumina series heat transfer agent GD-S010Q, manufactured by New Material Co., ltd. Of Buddha Jin Ge.
In some preferred embodiments, the boron nitride is purchased from nano heat conductor DK-BN-001, manufactured by Beijing, island gold technologies, inc.
Preferably, the weight ratio of the light guide auxiliary agent to the heat conductive agent is (1-2): (1-2); further preferably, the ratio is 1:1.
Preferably, the defoamer does not contain organic silicon.
Preferably, the active content in the defoamer is 100%.
In some preferred embodiments, the defoamer may be commercially available, such as the vendor di-high chemistry defoamer Airex 920.
The invention provides a preparation method of a photo-thermal response type adhesive with an optical switch, which comprises the following steps:
mixing the raw materials, and stirring uniformly at room temperature in dark.
The beneficial effects are that:
1. by selecting hydrogenated bisphenol A epoxy resin with the epoxy equivalent of 150-300g/eq and the viscosity of 1000-5000cps at 25 ℃ as the main resin, the adhesive strength of the prepared adhesive can be improved, and the hardness after film formation can be improved.
2. The weight ratio of the components is 1:2:1, the hydrogenated bisphenol A epoxy resin, the alicyclic epoxy resin and the polyurethane acrylate oligomer are used as main resin, so that the mechanical property and the bonding strength of the adhesive can be improved, the shrinkage rate of a system can be improved, the curing speed can be increased, the cost is lower, and in addition, the ring-opening efficiency of the specific alicyclic epoxy resin under the action of an iodonium salt cationic polymerization photoinitiator is higher, and the heat release amount is large.
3. By adding the following components in weight ratio (1-2): the 2-ethyleneoxy ethoxy ethyl acrylate and the trivinyl ethylene glycol divinyl ether of (1-2) are used as active monomers, have both acrylate double bonds and vinyl ether functional groups, and can react to emit continuous heat while being rapidly cured.
4. Polymethyl methacrylate microsphere with the particle size of 0.025-10 mu m and cycloolefin polymer (COP) microsphere with the particle size of 1-5 mu m are selected as light guiding auxiliary agents, and the weight ratio of the polymethyl methacrylate microsphere to the cycloolefin polymer (COP) microsphere is (1-2): in the process (1-3), light can be guided into a narrow part which cannot be irradiated at the moment of initial irradiation, so that the effect of thorough solidification is achieved, and the prepared adhesive has low expansion coefficient, high TG, low shrinkage rate, high breaking strength and high bonding strength.
5. The weight ratio of the components is (1-2): the light guide auxiliary agent and the heat conductive agent in the (1-2) have a synergistic effect, so that the subsequent curing efficiency can be improved.
6. The prepared photo-thermal response adhesive with the optical switch achieves the effect of thorough solidification by light guide and heat conduction transfer aiming at the shadow area which cannot be irradiated by light, and the performance is not obviously different from that of direct irradiation.
7. The photo-thermal response type adhesive with the optical switch prepared by the invention can be applied to the modern industrial fields of semiconductor industry, semiconductor technology, semiconductor packaging, 3D stack packaging and the like, and particularly can be applied to assembly of electronic products.
Detailed Description
Examples
Example 1
The embodiment 1 provides a photo-thermal response type adhesive with an optical switch, which comprises the following preparation raw materials in parts by weight: 40 parts of main raw materials, 20 parts of active monomers, 15 parts of light guide auxiliary agents, 5 parts of photoinitiators, 5 parts of thermal initiators, 15 parts of heat conducting agents and 0.1 part of defoaming agents.
The main raw materials are hydrogenated bisphenol A epoxy resin, alicyclic epoxy resin and polyurethane acrylate oligomer.
The weight ratio of the hydrogenated bisphenol A epoxy resin to the cycloaliphatic epoxy resin to the polyurethane acrylate oligomer is 1:2:1.
the epoxy equivalent of the hydrogenated bisphenol A epoxy resin is 200-230g/eq, and the viscosity at 25 ℃ is 1500-3000cps.
The hydrogenated bisphenol A type epoxy resin was purchased from the hydrogenated epoxy resin EP-4080E produced by Japanese Ai Dike company.
The urethane acrylate oligomer has a functionality of 18.
The polyurethane acrylate oligomer is a star polyurethane acrylate oligomer.
The urethane acrylate oligomer is purchased from Shenzhen, sapiscow, inc.
The viscosity of the cycloaliphatic epoxy resin is 200-280cps at 25 ℃ and the epoxy equivalent is 128-145g/eq.
The finger ring epoxy resin is purchased from alicyclic epoxy resin 2021P manufactured by japanese cellophane corporation.
The active monomers are ethyl 2-ethyleneoxy ethoxy acrylate and trivinyl ethylene glycol divinyl ether.
The weight ratio of the ethyl 2-ethyleneoxy ethoxy acrylate to the divinyl glycol ether is 2:3.
The light guide auxiliary agent is polymethyl methacrylate microsphere and cycloolefin polymer (COP) microsphere.
The weight ratio of the polymethyl methacrylate microsphere to the cycloolefin polymer (COP) microsphere is 1:1.
The particle size of the polymethyl methacrylate microsphere is 1 mu m.
The polymethyl methacrylate microsphere is purchased from polymethyl methacrylate microsphere ZZS-MMA1000 manufactured by Shanghai screening quasi-biotechnology Co.
The particle size of the cycloolefin polymer (COP) microspheres was 3. Mu.m.
The cycloolefin polymer (COP) microspheres were purchased from japan rayleigh company.
The photoinitiator is a cationic polymerization photoinitiator.
The cationic polymerization photoinitiator is diaryl iodonium salt.
The diaryliodonium salt is bis (4-t-butylphenyl) iodonium hexafluorophosphate.
The CAS number of the bis (4-tertiary butylphenyl) iodonium hexafluorophosphate is 61358-25-6.
The thermal initiator is an organic peroxide thermal initiator.
The organic peroxide thermal initiator is dibenzoyl peroxide.
The CAS number of the dibenzoyl peroxide is 94-36-0.
The heat conductive agent is aluminum oxide and boron nitride.
The weight ratio of the aluminum oxide to the boron nitride is 1:1.
Median particle diameter D of the alumina 50 8-12 μm.
The aluminum oxide is purchased from GD-S spherical aluminum oxide series heat conductive agent GD-S010Q manufactured by Buddha Jin Ge New Material Co., ltd.
The median diameter D of the boron nitride 50 50nm.
The boron nitride is purchased from nano heat conductive agent DK-BN-001 manufactured by Beijing De island gold technology Co.
The defoamer does not contain organic silicon.
The active matter content in the defoamer is 100%.
The defoamer was purchased from vendor di-high chemistry defoamer Airex 920.
The invention provides a preparation method of a photo-thermal response type adhesive with an optical switch, which comprises the following steps:
mixing the raw materials, and stirring at 25deg.C in dark.
Example 2
Embodiment 2 provides a photo-thermal response type adhesive with an optical switch, and the specific embodiment is the same as embodiment 1, in that: the main raw material is hydrogenated bisphenol A type epoxy resin.
Example 3
Embodiment 3 provides a photo-thermal response type adhesive with an optical switch, and the specific embodiment is the same as embodiment 1, in that: the weight ratio of the hydrogenated bisphenol A epoxy resin to the polyurethane acrylate oligomer is 1:2.
Example 4
Embodiment 4 provides a photo-thermal response type adhesive with an optical switch, and the specific embodiment is the same as embodiment 1, in that: the preparation raw materials comprise: 45 parts of main raw materials, 25 parts of active monomers, 2 parts of light guide auxiliary agents, 5 parts of photoinitiators, 5 parts of thermal initiators, 1 part of heat conducting agents and 0.1 part of defoaming agents.
Example 5
Embodiment 5 provides a photo-thermal response type adhesive with an optical switch, and the specific embodiment is the same as embodiment 1, in that: the photoinitiator is a cleavage type photoinitiator.
The cleavage type photoinitiator is benzoin methyl ether.
Performance test method
1. Light initiation exothermic temperature
The exothermic temperature of the photo-thermal response type adhesives with optical switches prepared in examples 1 to 5 was measured by real-time detection using an infrared thermometer during 5 seconds of UV irradiation, and the results are shown in Table 1.
2. Coefficient of thermal conductivity
The thermal conductivity of the photo-thermal responsive adhesive with optical switch prepared in examples 1 to 5 was measured by a rapid thermal conductivity meter, and the results are shown in Table 1.
3. Light scattering coefficient
The photo-thermal response type adhesives with optical switches prepared in examples 1 to 5 were measured for their light scattering coefficients by using a wide angle laser light scattering meter, and the results are shown in Table 1.
4. Determination of light intensity
Using Teflon mold, making adhesive into 50mm long, 10mm wide and 1mm thick strip mold, using the ends of the AB head and tail of the strip sample strip as boundary, irradiating the A end with UV light source with fixed light intensity, measuring light intensity with light intensity meter at the two ends of the AB, recording light intensity value at the two ends of the AB, and calculating light intensity attenuation rate, wherein light intensity attenuation rate (%) = (A end light intensity-B end light intensity)/A end light intensity is multiplied by 100%. The light intensity meter is a North Master and DaFZ-A type irradiator. The measured values are shown in Table 2.
5. Coefficient of expansion
The coefficients of expansion of the photo-thermal response adhesives with optical switches prepared in examples 1 to 5 were measured by a static thermo-mechanical analyzer, and the results are shown in Table 1.
6. Shrinkage rate
For the photo-thermal response type adhesive with the optical switch prepared in the examples 1-5, weighing a certain mass of glue solution, testing the density of the glue solution by using a densitometer, and calculating the liquid volume; then weighing the glue solution with the same quality, solidifying, testing the density of the solidified glue block by using a densimeter after solidifying and cooling, calculating the solid volume, and calculating the shrinkage (%) = (V) (liquid state) -V (solid state) )/V (liquid state) *100% and the results are reported in Table 1.
7. Breaking strength
For the photo-thermal responsive adhesives with optical switch prepared in examples 1-5, referring to ASTM D5034-95, the maximum load when the test specimens were pulled apart was reported in Table 1.
8. Adhesive strength
The photo-thermal response type adhesive with an optical switch prepared in examples 1 to 5 was adhered to two aluminum sheets, wherein the area of the adhered surface was 75mm×75mm, the single-sided adhesive coating amount was 140 g/square meter of the mixed adhesive, after UV light (365 nm) was irradiated for 4min, a weight was hung on one side of the aluminum sheet, the weight of the weight was increased until the two aluminum sheets were separated, and the weight when the two aluminum sheets were separated was recorded, and the results are recorded in table 1.
TABLE 1
TABLE 2
Claims (1)
1. The photo-thermal response type adhesive with the optical switch is characterized by comprising the following preparation raw materials in parts by weight: 40 parts of main raw materials, 20 parts of active monomers, 15 parts of light guide auxiliary agents, 5 parts of photoinitiators, 5 parts of thermal initiators, 15 parts of heat conducting agents and 0.1 part of defoaming agents;
the main raw materials are hydrogenated bisphenol A epoxy resin, alicyclic epoxy resin and polyurethane acrylate oligomer;
the weight ratio of the hydrogenated bisphenol A epoxy resin to the cycloaliphatic epoxy resin to the polyurethane acrylate oligomer is 1:2:1, a step of;
the epoxy equivalent of the hydrogenated bisphenol A epoxy resin is 200-230g/eq, and the viscosity at 25 ℃ is 1500-3000cps;
the hydrogenated bisphenol A type epoxy resin is purchased from hydrogenated epoxy resin EP-4080E produced by Japanese Ai Dike company;
the urethane acrylate oligomer has a functionality of 18;
the polyurethane acrylate oligomer is a star-shaped polyurethane acrylate oligomer;
the urethane acrylate oligomer is purchased from Shenzhen, sapiscow, inc.;
the viscosity of the alicyclic epoxy resin is 200-280cps at 25 ℃, and the epoxy equivalent is 128-145g/eq;
the alicyclic epoxy resin is purchased from alicyclic epoxy resin 2021P manufactured by japanese cellophane corporation;
the active monomers are 2-ethyleneoxy ethoxy ethyl acrylate and trivinyl ethylene glycol divinyl ether;
the weight ratio of the ethyl 2-ethyleneoxy ethoxy acrylate to the divinyl glycol ether is 2:3;
the light guide auxiliary agent is polymethyl methacrylate microsphere and cycloolefin polymer microsphere;
the weight ratio of the polymethyl methacrylate microspheres to the cycloolefin polymer microspheres is 1:1;
the particle size of the polymethyl methacrylate microsphere is 1 mu m;
the polymethyl methacrylate microsphere is purchased from polymethyl methacrylate microsphere ZZS-MMA1000 manufactured by Shanghai screening quasi-biotechnology Co., ltd;
the particle size of the cycloolefin polymer microsphere is 3 mu m;
the cycloolefin polymer microsphere is purchased from Japanese rayleigh company;
the photoinitiator is a cationic polymerization photoinitiator;
the cationic polymerization photoinitiator is diaryl iodonium salt;
the diaryl iodonium salt is bis (4-tertiary butylphenyl) iodonium hexafluorophosphate;
the CAS number of the bis (4-tertiary butylphenyl) iodonium hexafluorophosphate is 61358-25-6;
the thermal initiator is an organic peroxide thermal initiator;
the organic peroxide thermal initiator is dibenzoyl peroxide;
the CAS number of the dibenzoyl peroxide is 94-36-0;
the heat conducting agent is aluminum oxide and boron nitride;
the weight ratio of the aluminum oxide to the boron nitride is 1:1;
median particle diameter D of the alumina 50 8-12 μm;
the aluminum oxide is purchased from GD-S spherical aluminum oxide series heat conductive agent GD-S010Q produced by Buddha Jin Ge New Material Co., ltd;
the median diameter D of the boron nitride 50 50nm;
the boron nitride is purchased from a nanometer heat conductive agent DK-BN-001 produced by Beijing De island gold technology Co., ltd;
the defoamer does not contain organic silicon;
the content of active matters in the defoamer is 100%;
the defoamer was purchased from vendor di-high chemistry defoamer Airex 920;
the preparation method of the photo-thermal response type adhesive with the optical switch comprises the following steps: mixing the raw materials, and stirring at 25deg.C in dark.
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| CN103917619A (en) * | 2011-11-08 | 2014-07-09 | 汉高股份有限公司 | Dual-curable adhesive composition, use thereof, and process for bonding substrates |
| WO2018092463A1 (en) * | 2016-11-18 | 2018-05-24 | 株式会社スリーボンド | Cationically curable adhesive composition for camera modules, cured product, and assembly |
| CN109232831A (en) * | 2018-04-03 | 2019-01-18 | 浙江国能密封材料科技有限公司 | A kind of hybrid UV-curing resin and preparation method thereof for 3D printing stereolithography rapid shaping |
| CN111117552A (en) * | 2019-12-31 | 2020-05-08 | 河南省中凌煜新材料科技有限公司 | Dual-responsiveness composite adhesive and preparation method thereof |
| CN112724605A (en) * | 2020-12-25 | 2021-04-30 | 中山大学 | Photosensitive resin composition for photocuring rapid prototyping and preparation method and application thereof |
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Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103917619A (en) * | 2011-11-08 | 2014-07-09 | 汉高股份有限公司 | Dual-curable adhesive composition, use thereof, and process for bonding substrates |
| WO2018092463A1 (en) * | 2016-11-18 | 2018-05-24 | 株式会社スリーボンド | Cationically curable adhesive composition for camera modules, cured product, and assembly |
| CN109232831A (en) * | 2018-04-03 | 2019-01-18 | 浙江国能密封材料科技有限公司 | A kind of hybrid UV-curing resin and preparation method thereof for 3D printing stereolithography rapid shaping |
| CN111117552A (en) * | 2019-12-31 | 2020-05-08 | 河南省中凌煜新材料科技有限公司 | Dual-responsiveness composite adhesive and preparation method thereof |
| CN112724605A (en) * | 2020-12-25 | 2021-04-30 | 中山大学 | Photosensitive resin composition for photocuring rapid prototyping and preparation method and application thereof |
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