CN115368856A - Photo-thermal response type adhesive with photo-switch and preparation method thereof - Google Patents
Photo-thermal response type adhesive with photo-switch and preparation method thereof Download PDFInfo
- Publication number
- CN115368856A CN115368856A CN202210834087.7A CN202210834087A CN115368856A CN 115368856 A CN115368856 A CN 115368856A CN 202210834087 A CN202210834087 A CN 202210834087A CN 115368856 A CN115368856 A CN 115368856A
- Authority
- CN
- China
- Prior art keywords
- photo
- thermal
- parts
- adhesive
- optical switch
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000000853 adhesive Substances 0.000 title claims abstract description 55
- 230000001070 adhesive effect Effects 0.000 title claims abstract description 55
- 238000002360 preparation method Methods 0.000 title abstract description 11
- 239000002994 raw material Substances 0.000 claims abstract description 23
- 239000003999 initiator Substances 0.000 claims abstract description 21
- 230000003287 optical effect Effects 0.000 claims abstract description 13
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 11
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 11
- 239000000178 monomer Substances 0.000 claims abstract description 11
- 239000002518 antifoaming agent Substances 0.000 claims abstract description 10
- 239000004005 microsphere Substances 0.000 claims description 29
- 229920000089 Cyclic olefin copolymer Polymers 0.000 claims description 23
- 239000003822 epoxy resin Substances 0.000 claims description 17
- 229920000647 polyepoxide Polymers 0.000 claims description 17
- 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 16
- 239000004841 bisphenol A epoxy resin Substances 0.000 claims description 14
- 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 13
- 229920003229 poly(methyl methacrylate) Polymers 0.000 claims description 13
- 239000004926 polymethyl methacrylate Substances 0.000 claims description 13
- 229910052582 BN Inorganic materials 0.000 claims description 10
- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical compound N#B PZNSFCLAULLKQX-UHFFFAOYSA-N 0.000 claims description 10
- 125000002723 alicyclic group Chemical group 0.000 claims description 8
- 239000003211 polymerization photoinitiator Substances 0.000 claims description 8
- 238000000034 method Methods 0.000 claims description 7
- 238000010538 cationic polymerization reaction Methods 0.000 claims description 6
- 150000001451 organic peroxides Chemical class 0.000 claims description 6
- QYKIQEUNHZKYBP-UHFFFAOYSA-N Vinyl ether Chemical compound C=COC=C QYKIQEUNHZKYBP-UHFFFAOYSA-N 0.000 claims description 5
- 239000004925 Acrylic resin Substances 0.000 claims description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 4
- -1 ethyl 2-vinyloxyethoxy acrylate Chemical compound 0.000 claims description 4
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 4
- 229960000834 vinyl ether Drugs 0.000 claims description 4
- 238000006243 chemical reaction Methods 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- 238000003756 stirring Methods 0.000 claims description 3
- HMBNQNDUEFFFNZ-UHFFFAOYSA-N 4-ethenoxybutan-1-ol Chemical compound OCCCCOC=C HMBNQNDUEFFFNZ-UHFFFAOYSA-N 0.000 claims description 2
- 229920000178 Acrylic resin Polymers 0.000 claims description 2
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 claims description 2
- WHNWPMSKXPGLAX-UHFFFAOYSA-N N-Vinyl-2-pyrrolidone Chemical compound C=CN1CCCC1=O WHNWPMSKXPGLAX-UHFFFAOYSA-N 0.000 claims description 2
- PMHQVHHXPFUNSP-UHFFFAOYSA-M copper(1+);methylsulfanylmethane;bromide Chemical compound Br[Cu].CSC PMHQVHHXPFUNSP-UHFFFAOYSA-M 0.000 claims description 2
- 229910003460 diamond Inorganic materials 0.000 claims description 2
- 239000010432 diamond Substances 0.000 claims description 2
- GTPROMYYPGDANE-UHFFFAOYSA-N ethenoxyethene;prop-2-enoic acid Chemical compound C=COC=C.OC(=O)C=C GTPROMYYPGDANE-UHFFFAOYSA-N 0.000 claims description 2
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 2
- AHHWIHXENZJRFG-UHFFFAOYSA-N oxetane Chemical compound C1COC1 AHHWIHXENZJRFG-UHFFFAOYSA-N 0.000 claims description 2
- 239000004417 polycarbonate Substances 0.000 claims description 2
- 229920000515 polycarbonate Polymers 0.000 claims description 2
- 229920001296 polysiloxane Polymers 0.000 claims description 2
- KCTAWXVAICEBSD-UHFFFAOYSA-N prop-2-enoyloxy prop-2-eneperoxoate Chemical compound C=CC(=O)OOOC(=O)C=C KCTAWXVAICEBSD-UHFFFAOYSA-N 0.000 claims description 2
- 238000010526 radical polymerization reaction Methods 0.000 claims description 2
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 claims description 2
- 229910010271 silicon carbide Inorganic materials 0.000 claims description 2
- 239000000126 substance Substances 0.000 claims description 2
- 239000006258 conductive agent Substances 0.000 claims 1
- 238000005215 recombination Methods 0.000 claims 1
- 230000006798 recombination Effects 0.000 claims 1
- 238000005516 engineering process Methods 0.000 abstract description 8
- 239000004065 semiconductor Substances 0.000 abstract description 7
- 230000000694 effects Effects 0.000 abstract description 3
- 238000005286 illumination Methods 0.000 abstract description 3
- 230000005540 biological transmission Effects 0.000 abstract description 2
- 238000001723 curing Methods 0.000 description 15
- 239000002245 particle Substances 0.000 description 10
- 239000004593 Epoxy Substances 0.000 description 8
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 8
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 7
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical group C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 6
- 239000003292 glue Substances 0.000 description 6
- 125000005520 diaryliodonium group Chemical group 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 229920001187 thermosetting polymer Polymers 0.000 description 5
- 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 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 4
- 229910052782 aluminium Inorganic materials 0.000 description 4
- 235000019400 benzoyl peroxide Nutrition 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 238000000016 photochemical curing Methods 0.000 description 4
- 239000004814 polyurethane Substances 0.000 description 4
- 229920002635 polyurethane Polymers 0.000 description 4
- CYIGRWUIQAVBFG-UHFFFAOYSA-N 1,2-bis(2-ethenoxyethoxy)ethane Chemical compound C=COCCOCCOCCOC=C CYIGRWUIQAVBFG-UHFFFAOYSA-N 0.000 description 3
- 239000013530 defoamer Substances 0.000 description 3
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 3
- 239000010931 gold Substances 0.000 description 3
- 229910052737 gold Inorganic materials 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 229920002160 Celluloid Polymers 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 2
- 238000000149 argon plasma sintering Methods 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 238000005336 cracking Methods 0.000 description 2
- 239000011353 cycloaliphatic epoxy resin Substances 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 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 2
- 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 description 2
- 238000004806 packaging method and process Methods 0.000 description 2
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 239000011347 resin Substances 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
- 238000003860 storage Methods 0.000 description 2
- 239000002470 thermal conductor Substances 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- OLPZCIDHOZATMA-UHFFFAOYSA-N 2,2-dioxooxathiiran-3-one Chemical compound 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
- 241000219310 Beta vulgaris subsp. vulgaris Species 0.000 description 1
- 235000021538 Chard Nutrition 0.000 description 1
- 241000764238 Isis Species 0.000 description 1
- 239000004809 Teflon Substances 0.000 description 1
- 229920006362 Teflon® Polymers 0.000 description 1
- 239000013543 active substance Substances 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
- 238000001816 cooling Methods 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- LWNLJVHOPWATFY-UHFFFAOYSA-N ethyl 2-(2-ethenoxyethoxy)prop-2-enoate Chemical compound CCOC(=O)C(=C)OCCOC=C LWNLJVHOPWATFY-UHFFFAOYSA-N 0.000 description 1
- 239000011551 heat transfer agent Substances 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
- 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
- 125000003566 oxetanyl group Chemical group 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 238000001029 thermal curing Methods 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
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 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
- 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 09J7, and more particularly relates to a photo-thermal response type adhesive with an optical switch and a preparation method thereof. The photo-thermal response adhesive with the photo-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 photo-thermal response adhesive with the photo-switch, prepared by the invention, aims at the shadow area which cannot be illuminated, achieves the effect of thorough curing by light guiding and heat conducting transmission, has no obvious difference with the performance of 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 09J7, 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 foundation of modern industry and have also evolved as a relatively independent high-tech industry. Electronic products often use thermosetting epoxy resin in the assembling process, but the thermosetting time is long, and often can add a certain amount of curing agent in the raw materials of thermosetting, lead to the poor reliability, and present industry mostly adopts intelligent manufacturing assembly line's mode to produce electronic products, and the thermosetting material required time is long, and solidification efficiency is low, does not accord with present intelligent manufacturing assembly line's control mode. And the electronic product obtained by thermosetting can not meet the curing requirement at low temperature, while the curing speed can be improved at an excessively high temperature, but the storage stability of the electronic product is greatly reduced, even the electronic product can be stored for only 1 day or less at 25 ℃, the product is continuously tackified in the using process, and great trouble is caused to the production line management of customers, so that the development of a single-component adhesive with high curing speed and good storage stability is urgently required.
In the prior art, patent application publication No. CN113980582A discloses a photo-, thermal-, and moisture-curable adhesive and a preparation method thereof, which is improved by adding oxetanyl, acrylate, and alkoxysilane groups to branches, and the prepared adhesive has photo-, thermal-, and moisture-curing functions at the same time, but the curing speed and curing temperature are not improved.
The patent document with the granted publication number of CN104212391B discloses an epoxy resin-acrylate copolymer adhesive formula and a preparation process thereof, and the prepared adhesive is non-toxic and harmless, strong in water resistance and high in bonding strength, but the curing speed and the curing temperature are not improved.
Photocuring is a new technology with high efficiency, energy conservation and environmental protection, and is increasingly popular in the business industry. 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 mode, can be cured within several seconds once being illuminated, is high in curing speed and yield, and is particularly suitable for a production line assembly process of electronic products. But the defect is also obvious, the method is only suitable for surface coating and bonding and sealing of transparent materials, and cannot be used for bonding and sealing of opaque materials, and most electronic products are made of opaque materials, so that the application range is limited.
Therefore, the industry is urgently required to develop a new technology with good storability at normal temperature, high curing speed and low curing temperature to meet the increasing demand of the fast assembly process of electronic products.
Disclosure of Invention
In order to solve the above problems, according to a first aspect of the present invention, a photo-thermal responsive adhesive with a photo-switch is provided, in which UV light is irradiated on the surface of the adhesive, a portion of main raw materials and active monomers on the surface of the adhesive generate a photo-reaction to generate heat, the reaction at least including the rest of main raw materials is activated, and the photo-thermal responsive adhesive with the photo-switch is prepared according to a photo-thermal 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 epoxy resin, vinyl ether acrylate prepolymer and the like, polyurethane acrylate oligomer, alicyclic epoxy resin, epoxy acrylate resin and pure acrylic resin; further preferred are hydrogenated bisphenol a type epoxy resins, alicyclic epoxy resins and urethane acrylate oligomers.
Preferably, the weight ratio of the hydrogenated bisphenol a epoxy resin, the cycloaliphatic epoxy resin and the urethane acrylate oligomer is 1:2:1.
preferably, the hydrogenated bisphenol A epoxy resin has an epoxy equivalent of 150 to 300g/eq and a viscosity of 1000 to 5000cps at 25 ℃; 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 EP-4080E, a hydrogenated epoxy resin manufactured by Ediko, japan.
Preferably, the functionality of the urethane acrylate oligomer is 15 to 20; more preferably, it is 18.
Preferably, the urethane acrylate oligomer is a star urethane acrylate oligomer.
In some preferred embodiments, the urethane acrylate oligomer is purchased from sanbish, sabioskitechnology ltd.
Preferably, the viscosity of the ring family epoxy resin at 25 ℃ is 150-350cps, and the epoxy equivalent is 100-200g/eq; further preferably, the ring family epoxy resin has a viscosity of 200 to 280cps at 25 ℃ and an epoxy equivalent of 128 to 145g/eq.
In some preferred embodiments, the ring family epoxy resin is purchased from cycloaliphatic epoxy resin 2021P, manufactured by the firm xylonite, japan.
Preferably, the active monomer is selected from one or more of oxetane, 4-hydroxybutyl vinyl ether, triethylene glycol divinyl ether, N-vinyl pyrrolidone and ethyl 2-ethyleneoxyethoxy acrylate; further preferred are ethyl 2-vinyloxyethoxyacrylate and trivinylglycol divinyl ether.
Preferably, the weight ratio of the 2-ethyleneoxyethoxy ethyl acrylate to the triethylene glycol divinyl ether is (1-2): (1-2); further preferably, it is 2.
Preferably, the light guide auxiliary agent is selected from one or more of polymethyl methacrylate microspheres, polycarbonate microspheres, organosilicon microspheres and Cyclic Olefin Polymer (COP) microspheres; further preferred are polymethyl methacrylate microspheres and Cyclic Olefin Polymer (COP) microspheres.
Preferably, the weight ratio of the polymethyl methacrylate microspheres to the cycloolefin polymer (COP) microspheres is (1-2): (1-3); further preferably, the ratio is 1.
Preferably, the particle size of the polymethyl methacrylate microsphere is 0.025-10 μm; more preferably, it is 1 μm.
In some preferred embodiments, the polymethylmethacrylate microsphere is purchased from ZZS-MMA1000, a product of Shanghai Yan Biotech Ltd.
Preferably, the particle size of the cycloolefin polymer (COP) microspheres is 1-5 μm; more preferably, it is 3 μm.
In some preferred embodiments, the Cyclic Olefin Polymer (COP) microspheres are purchased from the japanese swiss chard.
Preferably, the photoinitiator is selected from one or more of free radical polymerization photoinitiator and cationic polymerization photoinitiator; further preferred are cationic polymerization photoinitiators.
Preferably, the cationic polymerization photoinitiator is selected from one or more of triarylsulfonium salt, alkyl sulfonium salt, diaryl iodonium salt, iron arene salt, sulfonyloxy ketone and triarylsiloxy ether; further preferred are diaryl iodonium salts.
Preferably, the diaryl iodonium salt is one or more of bis (4-tert-butylphenyl) iodonium hexafluorophosphate, bis (4-tert-butylphenyl) iodonium trifluoromethanesulfonate; further preferred is bis (4-t-butylphenyl) iodonium hexafluorophosphate.
Preferably, the bis (4-tert-butylphenyl) iodonium hexafluorophosphate has a CAS number of 61358-25-6.
Preferably, the thermal initiator is selected from one or more of azo thermal initiators, organic peroxide thermal initiators, redox thermal initiators and borate thermal initiators; more preferably, the thermal initiator is an organic peroxide thermal initiator.
Preferably, the organic peroxide thermal initiator is dibenzoyl peroxide.
Preferably, the CAS number of 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.
Preferably, the median particle diameter D of the alumina 50 Is 2-50 μm; more preferably, it is 8 to 12 μm.
Preferably, the boron nitride has a median particle diameter D 50 Is 2-600nm; further preferred isIs 50nm.
In some preferred embodiments, the alumina is purchased from GD-S spherical alumina series thermal conductor GD-S010Q manufactured by Fushan gold Gorgo New materials, inc.
In some preferred embodiments, the boron nitride is purchased from DK-BN-001, a nano thermal conductor manufactured by Takaki technologies, inc. of Beijing Dekko.
Preferably, the weight ratio of the light guide auxiliary agent to the heat conducting agent is (1-2): (1-2); further preferably, the ratio is 1.
Preferably, the defoamer contains no silicone.
Preferably, the content of active substances in the defoaming agent is 100%.
In some preferred embodiments, the anti-foaming agent can be commercially available, for example, the anti-foaming agent Airex 920 of the supplier Digaku Chemicals.
The second aspect of 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 room temperature in dark.
Has the advantages 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 main resin, the adhesive strength of the prepared adhesive can be improved, and the hardness of the adhesive after film forming can be improved.
2. Selecting the weight ratio of 1:2: the hydrogenated bisphenol A epoxy resin, the alicyclic epoxy resin and the polyurethane acrylate oligomer as the main resin can improve the mechanical property and the bonding strength of the adhesive, improve the shrinkage rate of a system, accelerate the curing speed, and have low cost.
3. Adding the following components in a weight ratio of (1-2): and (1-2) the 2-ethyleneoxyethoxy ethyl acrylate and the trivinyl glycol divinyl ether are used as active monomers, have both acrylate double bonds and vinyl ether functional groups, can be quickly cured and can react to generate continuous heat.
4. The light guide auxiliary agent is prepared by selecting polymethyl methacrylate microspheres with the particle size of 0.025-10 mu m and cycloolefin polymer (COP) microspheres with the particle size of 1-5 mu m, wherein the weight ratio of the polymethyl methacrylate microspheres to the cycloolefin polymer (COP) microspheres is (1-2): (1-3), the light can be guided into a narrow part which cannot be illuminated at the moment of initial illumination, so that the effect of thorough curing is achieved, and the prepared adhesive has high bonding strength while having low expansion coefficient, high TG, low shrinkage and high breaking strength.
5. Selecting the components in the weight ratio of (1-2): and (1-2) the light guide auxiliary agent and the heat conducting agent have a synergistic effect, so that the subsequent curing efficiency can be improved.
6. The photo-thermal response adhesive with the photo-switch, which is prepared by the invention, can achieve the effect of complete curing by light guiding and heat conducting transmission aiming at the shadow area which cannot be irradiated by light, and the performance of the photo-thermal response adhesive is not obviously different from that of direct illumination.
7. The photo-thermal response adhesive with the photo-switch prepared by the invention can be applied to the modern industrial fields of semiconductor industry, semiconductor technology, semiconductor packaging, 3D stacked packaging and the like, and especially can be applied to assembling electronic products.
Detailed Description
Examples
Example 1
Embodiment 1 provides a photo-thermal responsive adhesive with a photoswitch, which is prepared from the following 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 urethane acrylate oligomer.
The weight ratio of the hydrogenated bisphenol A epoxy resin to the alicyclic epoxy resin to the urethane acrylate oligomer is 1:2:1.
the hydrogenated bisphenol A epoxy resin has an epoxy equivalent of 200 to 230g/eq and a viscosity of 1500 to 3000cps at 25 ℃.
The hydrogenated bisphenol A epoxy resin was purchased from EP-4080E, a hydrogenated epoxy resin produced by Ediko, japan.
The functionality of the urethane acrylate oligomer is 18.
The polyurethane acrylate oligomer is star polyurethane acrylate oligomer.
The urethane acrylate oligomer was purchased from Spanish technologies, inc., shenzhen.
The ring family epoxy resin has the viscosity of 200-280cps at 25 ℃ and the epoxy equivalent of 128-145g/eq.
The epoxy resin of the alicyclic group was purchased from 2021P manufactured by the firm of xylonite, japan.
The active monomers are 2-ethyleneoxy ethoxy ethyl acrylate and triethylene glycol divinyl ether.
The weight ratio of the ethyl 2-ethyleneoxyethoxy acrylate to the divinyl ether of the triethylene glycol is 2.
The light guide auxiliary agent is polymethyl methacrylate microspheres and cycloolefin polymer (COP) microspheres.
The weight ratio of the polymethyl methacrylate microspheres to the cycloolefin polymer (COP) microspheres is 1.
The particle size of the polymethyl methacrylate microsphere is 1 mu m.
The polymethyl methacrylate microsphere is purchased from a polymethyl methacrylate microsphere ZZS-MMA1000 manufactured by Shanghai Yan Biotech Co.
The particle size of the cycloolefin polymer (COP) microspheres is 3 μm.
The cycloolefin polymer (COP) microspheres were purchased from the Japanese Ralski company.
The photoinitiator is a cationic polymerization photoinitiator.
The cationic polymerization photoinitiator is diaryl iodonium salt.
The diaryl iodonium salt is bis (4-tert-butylphenyl) iodonium hexafluorophosphate.
The CAS number of the bis (4-tert-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 alumina to the boron nitride is 1.
The median particle diameter D of the alumina 50 Is 8-12 μm.
The alumina was purchased from GD-S spherical alumina series heat transfer agent GD-S010Q manufactured by Fushan gold Ge New materials GmbH.
The median particle diameter D of the boron nitride 50 Is 50nm.
The boron nitride is purchased from DK-BN-001 which is a nano heat-conducting agent and is produced by Beijing German island gold technology and Co.
The defoaming agent does not contain organic silicon.
The active matter content in the defoaming agent is 100%.
The defoamer was purchased from a supplier digaku defoamer Airex 920.
The invention provides a preparation method of a photo-thermal response adhesive with a photoswitch, which comprises the following steps:
mixing the raw materials, and stirring at 25 deg.C in dark.
Example 2
Example 2 provides a photo-thermal responsive adhesive with an optical switch, and the specific implementation manner is the same as that of example 1, except that: the main raw material is hydrogenated bisphenol A type epoxy resin.
Example 3
Embodiment 3 provides a photo-thermal responsive adhesive with a photo switch, and the specific implementation manner is the same as that of embodiment 1, except that: the weight ratio of the hydrogenated bisphenol A epoxy resin to the urethane acrylate oligomer is 1.
Example 4
Embodiment 4 provides a photo-thermal responsive adhesive with a photo switch, and the specific implementation manner is the same as that of embodiment 1, except that: the preparation raw materials comprise: 45 parts of main raw material, 25 parts of active monomer, 2 parts of light guide auxiliary agent, 5 parts of photoinitiator, 5 parts of thermal initiator, 1 part of heat conducting agent and 0.1 part of defoaming agent.
Example 5
Example 5 provides a photo-thermal responsive adhesive with a photo switch, and the specific implementation manner is the same as that of example 1, except that: the photoinitiator is a cracking photoinitiator.
The cracking type photoinitiator is benzoin methyl ether.
Performance test method
1. Initial heat release temperature of light irradiation
The photo-thermal responsive adhesives prepared in examples 1 to 5 and having the photo-switch were measured for the exothermic temperature during 5 seconds of UV light irradiation by an infrared thermometer in real time, and the results are shown in table 1.
2. Coefficient of thermal conductivity
The photo-thermal responsive adhesives prepared in examples 1 to 5 and having the photo switch were measured for thermal conductivity using a rapid thermal conductivity meter, and the results are shown in table 1.
3. Coefficient of light scattering
The photo-thermal responsive adhesives prepared in examples 1 to 5 with a photo switch were measured for their light scattering coefficient by a wide-angle laser light scattering instrument, and the results are shown in table 1.
4. Determination of light intensity
In a long strip-shaped die with the length of 50mm, the width of 10mm and the thickness of 1mm, which is manufactured by an adhesive by utilizing a Teflon die, the head and the tail of an AB end of a long strip-shaped sample strip are taken as limits, an A end is irradiated by a UV light source with fixed light intensity, light intensity is measured by a light intensity meter at the two ends of the AB simultaneously, light intensity values at the two ends of the AB are recorded, and a light intensity attenuation rate is calculated, wherein the light intensity attenuation rate (%) = (the light intensity at the A end-the light intensity at the B end)/the light intensity at the A end is multiplied by 100%. The light intensity meter is a big-FZ-A type radiometer from north teachers. The measured values are shown in Table 2.
5. Coefficient of expansion
The photo-thermo-responsive adhesives with optical switches prepared in examples 1 to 5 were tested for their expansion coefficient by a static thermo-mechanical analyzer, and the results are shown in table 1.
6. Shrinkage rate
Weighing a certain mass of glue solution, testing the density of the glue solution by using a densitometer, and calculating the liquid volume of the glue solution, wherein the glue solution is prepared in the examples 1-5 and has the photo-thermal response type with the photo-switch; weighing the glue solution with the same mass, solidifying, cooling, testing the density of the solidified glue block by using a densimeter, and calculating the solid volume and the shrinkage (%) = (V) (liquid state) -V (solid state) )/V (liquid state) * The results are shown in Table 1 at 100%.
7. Breaking strength
For the photo-thermo-responsive adhesives with photoswitch prepared in examples 1-5, the maximum load when the test piece was pulled off was measured with reference to ASTM D5034-95, and the results are shown in Table 1.
8. Adhesive strength
The photo-thermo-responsive adhesives with photoswitch prepared in examples 1-5 were adhered to two aluminum sheets, wherein the area of the adhered surface was 75mm × 75mm, the amount of single-sided coating was 140 g/m, the mixed adhesive was irradiated with UV light (365 nm) for 4min, a load was hung on one aluminum sheet, the weight of the load was increased until the two aluminum sheets were separated, the weight when the two aluminum sheets were separated was recorded, and the results are shown in table 1.
TABLE 1
TABLE 2
Claims (10)
1. A photo-thermal response adhesive with a photo-switch is characterized in that UV light is irradiated on the surface of the adhesive, main body raw materials and active monomers on the surface of the adhesive partially react with each other to generate a large amount of heat, thermal reaction active centers at least comprising the rest main body raw materials are excited, and continuous fracture and recombination of chemical bonds are initiated by the photo-thermal response principle to prepare a photo-thermal response curing adhesive with the photo-switch.
2. The photo-thermal responsive adhesive with the optical switch according to claim 1, which is prepared from the following 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.
3. An optothermal responsive adhesive with an optical switch according to claim 2, wherein the main raw material is selected from one or more of hydrogenated bisphenol a epoxy resin, vinyl ether acrylate prepolymer, urethane acrylate oligomer, alicyclic epoxy resin, epoxy acrylate resin and pure acrylic resin.
4. An optothermal responsive adhesive with optical switch according to claim 3, wherein the reactive monomer is selected from one or more of oxetane, 4-hydroxybutyl vinyl ether, trivinyl glycol divinyl ether, N-vinyl pyrrolidone, and ethyl 2-vinyloxyethoxy acrylate.
5. The photo-thermal responsive adhesive with optical switch according to claim 3, wherein the light guide auxiliary agent is selected from one or more of polymethyl methacrylate microspheres, polycarbonate microspheres, silicone microspheres, and cyclic olefin polymer microspheres.
6. A photo-thermal responsive adhesive with photoswitch according to any one of claims 3-5, wherein the photoinitiator is selected from one or more of radical polymerization photoinitiators and cationic polymerization photoinitiators.
7. An optical switch photo-thermal response adhesive according to claim 6, wherein the thermal initiator is selected from one or more of azo thermal initiators, organic peroxide thermal initiators, redox thermal initiators and borate thermal initiators.
8. An optothermal responsive adhesive with an optical switch according to claim 2, wherein the thermal conductive agent is selected from one or more of diamond, boron nitride, silicon carbide, aluminum oxide and aluminum nitride.
9. The photo-thermal responsive adhesive with optical switch according to claim 3, wherein the main raw material is hydrogenated bisphenol A epoxy resin, alicyclic epoxy resin and urethane acrylate oligomer.
10. A method for preparing a photo-thermal responsive adhesive with an optical switch according to any one of claims 1 to 9, comprising the steps of: mixing the raw materials in parts by weight, and stirring uniformly at room temperature to obtain the product.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210834087.7A CN115368856B (en) | 2022-07-14 | 2022-07-14 | Photo-thermal response type adhesive with optical switch and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210834087.7A CN115368856B (en) | 2022-07-14 | 2022-07-14 | Photo-thermal response type adhesive with optical switch and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN115368856A true CN115368856A (en) | 2022-11-22 |
| CN115368856B CN115368856B (en) | 2024-03-26 |
Family
ID=84060980
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202210834087.7A Active CN115368856B (en) | 2022-07-14 | 2022-07-14 | Photo-thermal response type adhesive with optical switch and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN115368856B (en) |
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 |
-
2022
- 2022-07-14 CN CN202210834087.7A patent/CN115368856B/en active Active
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 |
Also Published As
| Publication number | Publication date |
|---|---|
| CN115368856B (en) | 2024-03-26 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US11248144B2 (en) | UV-curable silsesquioxane-containing write-through optical fiber coatings for fabrication of optical fiber Bragg gratings, and fibers made therefrom | |
| CN101479104B (en) | Rigid optical laminates and methods of forming the same | |
| JP6188716B2 (en) | Adhesive tape composition and adhesive tape produced from the composition | |
| CN105985749B (en) | UV solidifies liquid optical cement and the preparation method and application thereof | |
| CN102952503B (en) | High temperature resistant pressure sensitive adhesive composition and high temperature resistant pressure sensitive adhesive band | |
| CN108034395B (en) | LED lens fixing UV glue and preparation method and application thereof | |
| CN103725245B (en) | A kind of optical clear adhesive tape solvent-free UV solidified glue and Synthesis and applications thereof | |
| JP5401767B2 (en) | Curable composition and optical device | |
| CN105802517B (en) | A kind of optical lens UV glue and preparation method | |
| CN106047184A (en) | Liquid optical adhesive and 3D image structure with liquid optical adhesive | |
| CN109593497B (en) | UV-cured acrylate pressure-sensitive adhesive suitable for plastic material and preparation method and application thereof | |
| CN109716172A (en) | High refractive index nano compound | |
| CN106398554A (en) | Ultraviolet-cured pressure-sensitive adhesive and preparation method therefor | |
| CN105131849A (en) | Production method of ultraviolet light curing pressure-sensitive adhesive film | |
| Weaver et al. | Preparation and properties of optically transparent, pressure‐cured poly (methacrylate) composites | |
| CN112812596A (en) | Brightness enhancement film coating and application thereof | |
| CN115368856A (en) | Photo-thermal response type adhesive with photo-switch and preparation method thereof | |
| CN102482423A (en) | Curable resins and articles made therefrom | |
| CN115433537A (en) | High-cohesiveness ultraviolet-curing adhesive and preparation method and application thereof | |
| JP4142981B2 (en) | UV-curable epoxy resin composition and process for producing the same | |
| CN111253883B (en) | Ultrafast photon curing conductive adhesive and preparation method thereof | |
| CN114702932A (en) | High-transmittance glass UV transfer adhesive and transfer process | |
| CN112852306B (en) | Preparation method of UV laminating adhesive | |
| JP2006008740A (en) | Ultraviolet curable resin composition | |
| CN114989730A (en) | Expansion type UV cross-linking low-stress adhesive and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |