CN114736634B - Adhesive for WDM encapsulation and manufacturing method - Google Patents
Adhesive for WDM encapsulation and manufacturing method Download PDFInfo
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- CN114736634B CN114736634B CN202210278742.5A CN202210278742A CN114736634B CN 114736634 B CN114736634 B CN 114736634B CN 202210278742 A CN202210278742 A CN 202210278742A CN 114736634 B CN114736634 B CN 114736634B
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- 239000000853 adhesive Substances 0.000 title claims abstract description 36
- 230000001070 adhesive effect Effects 0.000 title claims abstract description 36
- 238000005538 encapsulation Methods 0.000 title claims abstract description 18
- 238000004519 manufacturing process Methods 0.000 title claims description 20
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 166
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 82
- 239000003822 epoxy resin Substances 0.000 claims abstract description 69
- 229920000647 polyepoxide Polymers 0.000 claims abstract description 69
- 239000004593 Epoxy Substances 0.000 claims abstract description 49
- 239000003085 diluting agent Substances 0.000 claims abstract description 38
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 33
- 238000013007 heat curing Methods 0.000 claims abstract description 31
- 239000006087 Silane Coupling Agent Substances 0.000 claims abstract description 27
- 235000012239 silicon dioxide Nutrition 0.000 claims abstract description 26
- 238000010438 heat treatment Methods 0.000 claims abstract description 23
- 238000001816 cooling Methods 0.000 claims abstract description 20
- 239000007822 coupling agent Substances 0.000 claims abstract description 16
- 238000003860 storage Methods 0.000 claims abstract description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000008367 deionised water Substances 0.000 claims abstract description 7
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 7
- 238000002360 preparation method Methods 0.000 claims abstract description 5
- 229920005989 resin Polymers 0.000 claims description 25
- 239000011347 resin Substances 0.000 claims description 25
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 claims description 18
- 239000002245 particle Substances 0.000 claims description 14
- 239000006185 dispersion Substances 0.000 claims description 13
- 239000000243 solution Substances 0.000 claims description 13
- 229930185605 Bisphenol Natural products 0.000 claims description 12
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 claims description 12
- -1 aryl diazonium salt Chemical class 0.000 claims description 10
- 238000000034 method Methods 0.000 claims description 10
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical compound C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 claims description 9
- 238000002156 mixing Methods 0.000 claims description 9
- 238000004381 surface treatment Methods 0.000 claims description 9
- 238000012360 testing method Methods 0.000 claims description 9
- 239000005062 Polybutadiene Substances 0.000 claims description 8
- 239000011230 binding agent Substances 0.000 claims description 8
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 claims description 8
- 239000011256 inorganic filler Substances 0.000 claims description 8
- 229910003475 inorganic filler Inorganic materials 0.000 claims description 8
- 229920002857 polybutadiene Polymers 0.000 claims description 8
- 229920002521 macromolecule Polymers 0.000 claims description 7
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 6
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 claims description 6
- 238000013329 compounding Methods 0.000 claims description 6
- NIHNNTQXNPWCJQ-UHFFFAOYSA-N fluorene Chemical compound C1=CC=C2CC3=CC=CC=C3C2=C1 NIHNNTQXNPWCJQ-UHFFFAOYSA-N 0.000 claims description 6
- 239000003999 initiator Substances 0.000 claims description 6
- 238000012856 packing Methods 0.000 claims description 6
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 5
- 125000002723 alicyclic group Chemical group 0.000 claims description 5
- 125000005520 diaryliodonium group Chemical group 0.000 claims description 5
- 239000012954 diazonium Substances 0.000 claims description 5
- 238000009826 distribution Methods 0.000 claims description 5
- WJRBRSLFGCUECM-UHFFFAOYSA-N hydantoin Chemical compound O=C1CNC(=O)N1 WJRBRSLFGCUECM-UHFFFAOYSA-N 0.000 claims description 5
- 229940091173 hydantoin Drugs 0.000 claims description 5
- AHHWIHXENZJRFG-UHFFFAOYSA-N oxetane Chemical compound C1COC1 AHHWIHXENZJRFG-UHFFFAOYSA-N 0.000 claims description 5
- 125000005409 triarylsulfonium group Chemical group 0.000 claims description 5
- 238000001132 ultrasonic dispersion Methods 0.000 claims description 5
- HOZMLTCHTRHKRK-UHFFFAOYSA-N 2-methyl-1-silylprop-2-en-1-one Chemical compound CC(=C)C([SiH3])=O HOZMLTCHTRHKRK-UHFFFAOYSA-N 0.000 claims description 4
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims description 4
- NOKSMMGULAYSTD-UHFFFAOYSA-N [SiH4].N=C=O Chemical compound [SiH4].N=C=O NOKSMMGULAYSTD-UHFFFAOYSA-N 0.000 claims description 4
- 239000004305 biphenyl Substances 0.000 claims description 4
- 235000010290 biphenyl Nutrition 0.000 claims description 4
- 229910052796 boron Inorganic materials 0.000 claims description 4
- QGBSISYHAICWAH-UHFFFAOYSA-N dicyandiamide Chemical compound NC(N)=NC#N QGBSISYHAICWAH-UHFFFAOYSA-N 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 4
- 125000001624 naphthyl group Chemical group 0.000 claims description 4
- ACECBHHKGNTVPB-UHFFFAOYSA-N silylformic acid Chemical compound OC([SiH3])=O ACECBHHKGNTVPB-UHFFFAOYSA-N 0.000 claims description 4
- 241000252506 Characiformes Species 0.000 claims description 3
- 150000008064 anhydrides Chemical class 0.000 claims description 3
- 125000002091 cationic group Chemical group 0.000 claims description 3
- 239000012986 chain transfer agent Substances 0.000 claims description 3
- OTARVPUIYXHRRB-UHFFFAOYSA-N diethoxy-methyl-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical group CCO[Si](C)(OCC)CCCOCC1CO1 OTARVPUIYXHRRB-UHFFFAOYSA-N 0.000 claims description 3
- 239000011259 mixed solution Substances 0.000 claims description 3
- 239000003504 photosensitizing agent Substances 0.000 claims description 3
- 238000005507 spraying Methods 0.000 claims description 3
- 238000003756 stirring Methods 0.000 claims description 3
- BPSIOYPQMFLKFR-UHFFFAOYSA-N trimethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[Si](OC)(OC)CCCOCC1CO1 BPSIOYPQMFLKFR-UHFFFAOYSA-N 0.000 claims description 3
- 238000011282 treatment Methods 0.000 claims description 2
- 238000001723 curing Methods 0.000 abstract description 16
- 239000000945 filler Substances 0.000 abstract description 12
- 238000004806 packaging method and process Methods 0.000 abstract description 4
- 230000003287 optical effect Effects 0.000 description 10
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 239000003292 glue Substances 0.000 description 5
- 239000013307 optical fiber Substances 0.000 description 5
- 238000005119 centrifugation Methods 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 229910020175 SiOH Inorganic materials 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- 230000035699 permeability Effects 0.000 description 3
- 238000011049 filling Methods 0.000 description 2
- 238000009472 formulation Methods 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
- 230000000977 initiatory effect Effects 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000004382 potting Methods 0.000 description 2
- 238000002604 ultrasonography Methods 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 238000003848 UV Light-Curing Methods 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 239000011324 bead Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 150000001989 diazonium salts Chemical class 0.000 description 1
- 229920006332 epoxy adhesive Polymers 0.000 description 1
- 125000003700 epoxy group Chemical group 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 230000020169 heat generation Effects 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 239000012948 isocyanate Substances 0.000 description 1
- 150000002513 isocyanates Chemical class 0.000 description 1
- 125000005641 methacryl group Chemical group 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 239000012766 organic filler Substances 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 239000011342 resin composition Substances 0.000 description 1
- 238000007151 ring opening polymerisation reaction Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- UDUKMRHNZZLJRB-UHFFFAOYSA-N triethoxy-[2-(7-oxabicyclo[4.1.0]heptan-4-yl)ethyl]silane Chemical compound C1C(CC[Si](OCC)(OCC)OCC)CCC2OC21 UDUKMRHNZZLJRB-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
- 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
- C08K2201/002—Physical properties
- C08K2201/005—Additives being defined by their particle size in general
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Adhesives Or Adhesive Processes (AREA)
- Epoxy Resins (AREA)
Abstract
The invention provides an adhesive for WDM encapsulation and a preparation method thereof, and step 1. An epoxy silane coupling agent, deionized water and absolute ethyl alcohol are prepared into a solution according to the proportion of 1:8:91, and the solution is fully stirred and mixed for standby. And 2, pre-dispersing spherical silicon dioxide. S1, adding commercial micron-sized spherical silicon dioxide into a muffle furnace, heating at 600 ℃ for 1 hour, and then cooling for standby. The invention uses the components of component A (low molecular epoxy oligomer), component B (high molecular epoxy resin is not added in proportion), component C (epoxy diluent), component D (coupling agent), component F (photoinitiator), component E (filler (spherical silica)), component G (latent heat curing agent) and the like to realize UV/heat dual-curing, and can realize the characteristics of ultralow curing shrinkage rate/ultralow thermal expansion coefficient/excellent high-temperature high-humidity performance and the like so as to meet the packaging requirement of WDM devices. Meanwhile, the adhesive can realize the storage validity period of 23 ℃ at normal temperature for one year.
Description
Technical Field
The invention belongs to the technical field of materials, and particularly relates to an adhesive for WDM packaging and a manufacturing method thereof.
Background
WDM all-wavelength division multiplexer is an optical device used in optical networks. The optical fiber can multiplex light with multiple wavelengths into one optical fiber, can demodulate light with multiple wavelengths from one optical fiber into light with multiple independent wavelengths to propagate in multiple optical fibers, and is widely applied to 5G networks.
Because WDM devices need to be used outdoors, international and national standards have strict requirements on the reliability of the WDM devices in consideration of factors such as different time points of different regions. For example, high and low temperature cycles of at least 2000 hours, high temperature and high humidity for 2000 hours, PCT168 hours test (autoclave test) is also required, and a series of mechanical reliability tests are required.
In the WDM fabrication process, an adhesive is required to bond the optical devices together. In view of the precise positioning and the later use environment of each device in the manufacturing process, the adhesive is required to meet the requirements of ultra-low curing shrinkage (usually lower than 0.3%), ultra-low thermal expansion coefficient (usually lower than 20 ppm), ultra-low moisture permeability and extremely high temperature and high humidity. Meanwhile, considering the gaps among the WDM optical components and the manufacturing efficiency, extremely high requirements are also put on the viscosity of the adhesive: the rotational viscosity is required to be 60000-120000cps. Meanwhile, the adhesive for WDM packaging needs to be UV cured in view of process efficiency and tooling specificity.
CN103497723 shows a precision adhesive and a method of making. The adhesive is composed of epoxy resin, reactive diluent, filler and additive, and can be used for manufacturing the BOSA of the optical device. Unfortunately, the cure shrinkage of the invention is greater than 1% and the coefficient of thermal expansion is relatively high, which is not substantially satisfactory for WDM optical device fabrication.
Patent CN103087664a shows an adhesive for relay potting. The relay potting adhesive is prepared by adding common commercial spherical alumina filler into resin. Since alumina is not properly surface-treated, when the added amount is more than 70% by weight, the binder becomes paste, and no fluidity is observed at ordinary temperature. Further, since alumina has a large thermal expansion coefficient, it is impossible to reduce the thermal expansion coefficient of the system to 50ppm or less by adding it to the binder. And, since alumina is opaque, it cannot be used in UV curing systems.
Patent CN107216613a shows a photocurable resin composition. The adhesive is prepared from resin, an initiator, a coupling agent, a filler and the like. Since it uses ordinary commercial spherical silica, its addition amount cannot exceed 70%, and if not it is very thick, its cure shrinkage hardly breaks through 0.5%. Moreover, the common spherical silica cannot be crosslinked with the system, and the moisture permeability cannot be effectively improved, so that the high-temperature and high-humidity performance of the spherical silica is affected.
To achieve low cure shrinkage/low coefficient of thermal expansion for epoxy resin systems, silica must be added in proportions exceeding 50%. However, silica is a hydrophilic material and is very easily absorbed by water vapor in the air, and SiOH is produced by hydrolysis of the surface. Conventional silica surface treatments, particularly epoxy treatments, are not effective in capping the SiOH of the silica surface. When silica which does not effectively seal SiOH is added into epoxy system resin, the storage stability of glue is affected, and the storage time at normal temperature of 23 ℃ is usually not longer than one month, so that many commercial epoxy adhesives added with silica are stored at low temperature.
Disclosure of Invention
The invention aims to solve the defects of the prior art, and provides an adhesive for WDM encapsulation and a manufacturing method thereof, wherein the adhesive is composed of a component A (low molecular epoxy oligomer), a component B (high molecular epoxy resin), a component C (epoxy diluent), a component D (coupling agent), a component F (photoinitiator), a component E (filler (spherical silica)), a component G (latent heat curing agent) and the like, and the components are used for realizing UV/heat dual-curing, and simultaneously can realize the characteristics of ultralow curing shrinkage rate, ultralow thermal expansion coefficient, excellent high-temperature high-humidity performance and the like so as to meet the encapsulation requirements of WDM devices. Meanwhile, the adhesive can realize the storage validity period of 23 ℃ at normal temperature for one year.
The invention adopts the following technical scheme:
the surface treatment method of the spherical silicon dioxide comprises the following steps:
step 1, preparing an epoxy silane coupling agent, deionized water and absolute ethyl alcohol into a solution according to the proportion of 1:8:91, and fully stirring and mixing for later use;
step 2, pre-dispersing spherical silicon dioxide:
s1, adding commercial micron-sized spherical silicon dioxide into a muffle furnace, heating at 600 ℃ for 1 hour, and then cooling for standby;
s2, dissolving the micron-sized spherical silicon dioxide processed in the S1 into acetone for high-power ultrasonic dispersion, and then centrifuging to separate the spherical silicon dioxide. The separated spherical silica was then treated for 5 minutes by adding it to piranha solution. The separated spherical silica is then dissolved in absolute ethanol and dispersed with high power by ultrasonic waves, and then the spherical silica is separated off again by centrifugation. The separated spherical silica is then dissolved in deionized water and dispersed with high power by ultrasound, followed by centrifugation again to separate the spherical silica. Finally, the separated spherical silicon dioxide is put into a vacuum double-planetary disperser to rotate 1000 rpm and revolve 2000 rpm for 2 minutes. The heating temperature in the cavity was set to 100 degrees celsius during dispersion. The vacuum was set to 10 for the first 2 minutes at dispersion -1 -10 2 Pa low vacuum state, along withThe vacuum pump is then turned off.
S3, atomizing the mixed solution in the step 1, spraying the atomized solution into a dispersion tank of a double-planetary dispersion machine, starting the double-planetary dispersion machine again to disperse for 2 minutes, standing for 5 minutes, setting the heating temperature to 105 ℃ to disperse for 10 minutes, standing for 5 minutes again, and repeating 2 cycles of dispersing for 10 minutes and standing for 5 minutes again to finish the surface treatment of the spherical silicon dioxide, so as to obtain the spherical silicon dioxide.
An adhesive for WDM encapsulation consists of 1-10 parts of low molecular epoxy oligomer, 0.5-5 parts of high molecular epoxy resin, 0.5-10 parts of reactive epoxy diluent, 0.5-5 parts of coupling agent, 0.5-8 parts of photoinitiator, 0.1-1 part of latent heat curing agent and spherical silica treated by a surface treatment method, wherein the curing shrinkage rate is <0.3%, the viscosity is 60000-120000cps, the thermal expansion coefficient is <20ppm, the change amount of WDM device parameters is <0.1dB before and after the CWDM device is manufactured, and the storage stability is one year after the high temperature and high humidity reliability test is carried out for 2000 hours.
A method of making an adhesive for WDM encapsulation comprising:
and step 1, mixing 1-10 parts of the component A and 0.5-5 parts of the component B together, heating to 120 ℃, dispersing by a high-speed dispersing machine for 5 minutes, and cooling for later use.
And 2, adding 0.5-10 parts of component C and 0.5-5 parts of component D into the resin mixed in the step 1, heating to 60 ℃, dispersing at a high speed for 20 minutes, and cooling for later use.
And 3, adding 0.5-8 parts of component E into the resin mixed in the step 2, dispersing for 5 minutes at a high speed, and cooling for standby.
And 4, heating the resin mixed in the step 3 to 30 ℃, adding 50-90 parts of component F into the step 3 twice, dispersing at a high speed for 20 minutes, and cooling for later use.
And 5, adding 0.1-1 part of component G into the resin prepared in the step 4, and dispersing at a low speed for 30 minutes to finish the preparation of the adhesive.
Component a is one or more of bisphenol type epoxy resin, alicyclic epoxy resin, low molecular epoxy oligomer of hydantoin epoxy resin. Wherein the bisphenol type epoxy resin is bisphenol A type glycidyl ether, bisphenol F type glycidyl ether, hydrogenated bisphenol type glycidyl ether, low molecular fluorinated epoxy resin.
The component B is formed by mixing one or more of polybutadiene modified epoxy resin, hydrogenated polybutadiene modified epoxy resin, bisphenol fluorene epoxy resin, biphenyl epoxy resin, naphthalene ring epoxy resin, organosilicon modified epoxy resin, macromolecule fluorinated epoxy resin and macromolecule epoxy resin of POSS modified epoxy resin.
Component C is one or more of monofunctional reactive epoxy diluents, difunctional reactive epoxy diluents, polyfunctional reactive epoxy diluents, cycloaliphatic reactive diluents, oxetane reactive diluents, hybrid reactive diluents.
When the component A is selected from the low viscosity epoxy resin and the epoxy resin combination, the component C may be omitted.
The component D is an epoxy silane coupling agent, a carboxyl silane coupling agent, a methacryloyl silane coupling agent, an isocyanate silane coupling agent and a titanate coupling agent. Wherein the epoxy silane coupling agent is 3-glycidoxypropyl methyl diethoxy silane, beta- (3, 4-epoxy cyclohexyl) hexyl triethoxy silane, 3- (2, 3-epoxy propoxy) propyl trimethoxy silane.
The component E is one or more of aryl diazonium salt photoinitiator, diaryl iodonium salt photoinitiator, triarylsulfonium salt photoinitiator, aromatic ferrocenium salt photoinitiator, macromolecular photoinitiator and polymerizable photoinitiator. Component E also includes a photosensitizer or chain transfer agent and a cationic initiator.
The component F is spherical silica, and when the component F is an inorganic filler, the particle size range is 0.001-25um, and the spherical silica with different center particle sizes is compounded according to the Horsfield closest packing theory.
Preferably, spherical silica with a central particle size of 5-8um and spherical silica with a central particle size of 1-2um are selected, wherein the two spherical silica accords with normal distribution, and the compounding ratio is 4:1.
The component G is dicyandiamide latent heat curing agent, organic hydrazide latent heat curing agent, organic anhydride latent heat curing agent, imidazole latent heat curing agent and boron trifluoride-amine complex latent heat curing agent.
The invention has the beneficial effects that:
the invention can realize the characteristics of ultralow solidification shrinkage, ultralow thermal expansion coefficient, excellent high-temperature high-humidity performance and the like so as to meet the packaging requirement of WDM devices. Meanwhile, the adhesive can realize the storage validity period of 23 ℃ at normal temperature for one year.
Drawings
Fig. 1 is a schematic structural view of the present invention.
Detailed Description
For the purpose of making the objects, technical solutions and advantages of the present invention more apparent, the technical solutions in the present invention will be clearly and completely described below, and it is apparent that the described embodiments are some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention. The adhesive for WDM encapsulation is prepared by mixing 1-10 parts of low molecular epoxy oligomer, 0.5-5 parts of high molecular epoxy resin, 0.5-10 parts of active epoxy diluent, 0.5-5 parts of coupling agent, 0.5-8 parts of photoinitiator, 0.1-1 part of latent heat curing agent and spherical silica treated by a surface treatment method, wherein the curing shrinkage rate is <0.3%, the viscosity is 60000-120000cps, the thermal expansion coefficient is <20ppm, the variation of WDM device parameters before and after a CWDM device is manufactured at a high temperature and high humidity reliability test of 2000 hours is <0.1dB, and the storage stability is one year.
As shown in fig. 1, a method for manufacturing an adhesive for WDM encapsulation includes:
1. surface treatment of spherical silica:
1.1 firstly, preparing an epoxy silane coupling agent, deionized water and absolute ethyl alcohol into a solution according to the proportion of 1:8:91, and fully stirring and mixing for standby.
1.2 Pre-dispersion of spherical silica:
1.2.1 commercial micron-sized spherical silica was added to a muffle furnace at 600 degrees celsius for 1 hour and then cooled for later use.
1.2.2 dissolving the micron-sized spherical silica treated in the previous step in acetone for high-power ultrasonic dispersion, and then centrifuging to separate the spherical silica. The separated spherical silica was then treated for 5 minutes by adding it to piranha solution. The separated spherical silica is then dissolved in absolute ethanol and dispersed with high power by ultrasonic waves, and then the spherical silica is separated off again by centrifugation. The separated spherical silica is then dissolved in deionized water and dispersed with high power by ultrasound, followed by centrifugation again to separate the spherical silica. Finally, the separated spherical silicon dioxide is put into a vacuum double-planetary disperser to rotate 1000 rpm and revolve 2000 rpm for 2 minutes. The heating temperature in the cavity was set to 100 degrees celsius during dispersion. The vacuum was set to 10 for the first 2 minutes at dispersion -1 Pa-10 2 Pa low vacuum state, followed by turning off the vacuum pump.
1.3 atomizing the mixed solution of 1.1, spraying the atomized solution into a dispersing tank of a double planetary dispersing machine, starting the double planetary dispersing machine again for dispersing for 2 minutes, standing for 5 minutes, setting the heating temperature to 105 ℃ for dispersing for 10 minutes, standing for 5 minutes again, and repeating 2 dispersing for 10 minutes and standing for 5 minutes again to finish the surface treatment of the spherical silicon dioxide.
1.4 adhesive formulation:
1.4.1 mixing 1-10 parts of component A and 0.5-5 parts of component B together, heating to 120 ℃ and dispersing for 5 minutes by a high-speed dispersing machine for later use.
1.4.2 adding 0.5-10 parts of component C and 0.5-5 parts of component D into the resin mixed with 1.4.1, heating to 60 ℃, dispersing at high speed for 20 minutes, and cooling for later use.
1.4.3 adding 0.5-8 parts of component E into the resin mixed with 1.4.2, dispersing for 5 minutes at high speed, and cooling for standby.
1.4.4 the resin mixed with 1.4.3 is heated to 30 ℃, then 50-90 parts of component F is added into 1.4.3 in two times, dispersed for 20 minutes at high speed and cooled for standby.
1.4.5 adding 0.1-1 part of component G into the resin prepared by 1.4.4, and dispersing at a low speed for 30 minutes to complete the preparation of the adhesive.
The components of the invention include:
component A: low molecular epoxy oligomers. It may be: bisphenol type epoxy resin, alicyclic epoxy resin and hydantoin epoxy resin. Wherein the bisphenol type epoxy resin can be bisphenol A type glycidyl ether, bisphenol F type glycidyl ether, and also comprises hydrogenated bisphenol type glycidyl ether and low molecular fluorinated epoxy resin. It should be noted that the component a may be a mixture of one or more of the low molecular epoxy oligomers listed above.
Component B: a high molecular epoxy resin. It may be: polybutadiene modified epoxy resin, hydrogenated polybutadiene modified epoxy resin, bisphenol fluorene ring resin, biphenyl type epoxy resin, naphthalene ring epoxy resin, organosilicon modified epoxy resin, macromolecule fluorinated epoxy resin and POSS modified epoxy resin. The component B may be one or more of the above-listed high molecular epoxy resins.
Component C: reactive epoxy diluents. It may be: monofunctional reactive epoxy diluents, difunctional epoxy diluents, polyfunctional epoxy reactive diluents, cycloaliphatic reactive diluents, oxetane reactive diluents, hybrid reactive diluents. Component C may be a combination of one or more of the reactive diluents listed above. If component A is selected from the group consisting of low viscosity epoxy resins and epoxy resin combinations, component C may also be absent.
Component D-coupling agent: the optical components used in WDM are generally made of quartz, so that it is necessary to add a proper coupling agent to the system to enhance the adhesion and water resistance. As the coupling agent, an epoxy-based silane coupling agent, a carboxyl-based silane coupling agent, a methacryl-based silane coupling agent, an isocyanate-based silane coupling agent, a titanate coupling agent, and the like can be selected. In view of crosslinking of the epoxy system, an epoxy-based coupling agent is preferable. As the epoxy silane coupling agent, 3-glycidoxypropyl methyl diethoxysilane, beta- (3, 4-epoxycyclohexyl) ethyl triethoxysilane, 3- (2, 3-epoxypropoxy) propyl trimethoxysilane can be used. Component C may be a combination of one or more of the above coupling agents.
Component E-photoinitiator: considering that the whole system is an epoxy system, a photoinitiator which can initiate ring-opening polymerization of epoxy groups under illumination can be used. Generally, photo-cationic initiators are preferred. As the photo cation initiator, square base diazonium salt photoinitiator, diaryl iodonium salt photoinitiator, triarylsulfonium salt photoinitiator, arylferrocenium salt photoinitiator, macromolecular photoinitiator, polymerizable photoinitiator may be selected. Considering the initiation efficiency of the photoinitiator wavelength agent, a photosensitizer or a chain transfer agent and a cationic initiator can be selected to be compounded to improve the initiation efficiency. Component E may be a combination of one or more of the above photoinitiators. Component F-filler: the proper filler is added in the adhesive compounding process, so that the curing shrinkage rate and CTE can be effectively reduced, and the moisture permeability can be reduced and the curing local internal stress can be improved. As the filler, an inorganic filler and an organic filler can be selected. In the present invention, the inorganic filler is preferably in the range of 0.001 to 25. Mu.m. These inorganic fillers may be in the form of flakes, spheres, etc., and spherical inorganic fillers are preferable in view of the fact that the amount added is most likely to be more than 80% at all. The inorganic spherical filler can be spherical silica, hollow glass beads, spherical alumina and spherical graphite particles. The spherical silica is preferred in view of the requirement of the present invention to achieve an ultra low coefficient of thermal expansion. To achieve maximum packing of spherical silica in the binder, spherical silica of different center particle sizes must also be compounded according to Horsfield's closest packing theory. The present invention preferably has spherical silica with a center particle diameter of 5-8um and spherical silica with a center particle diameter of 1-2um, both of which are in conformity with normal distribution, and the compounding ratio is 4:1 while considering a high filling rate.
Component G-latent heat curing agent: since a large amount of filler is incorporated in the resin system of the present invention. The filler may scatter UV light, potentially allowing the deep glue to cure for up to several days. Also, some fillers are inherently opaque, resulting in a very slow or inefficient curing of the deep glue. The invention can effectively solve the problem of deep curing of the glue by adding the latent heat curing agent. Latent heat curing agents are curing agents which are stable at room temperature and which react with the epoxy resin only when the temperature exceeds the decomposition temperature. As the latent heat curing agent, dicyandiamide latent heat curing agent, organic hydrazide latent heat curing agent, organic acid anhydride latent heat curing agent, imidazole latent heat curing agent, boron trifluoride-amine complex latent heat curing agent, and the like may be selected, and a proper amount of accelerator may be added to increase the curing speed. Considering the heat generation during dispersion of the inorganic highly filled system and the temperature resistance requirement of the optical fiber for making the WDM optical device, it is necessary to select a latent heat curing agent having a curing temperature of 80 to 110 ℃ from the above-mentioned latent heat curing agents.
The invention is verified:
the experimental evaluation was performed according to the following method
The binders were formulated according to the examples and comparative examples in the following tables and then tested for viscosity/cure shrinkage/CTE according to the corresponding national standards. For testing high temperature and high humidity performance, the prepared adhesive is used for bonding quartz glass sheets with the thickness of 10mm multiplied by 10mm for high temperature and high humidity testing, and then the high temperature and high humidity performance is qualified by checking no water seepage and no air bubble under a 100x microscope. Storage stability judgment criteria: and testing the rotational viscosity after being stored for one year at the normal temperature of 23 ℃, and judging to be qualified if the change is less than 5%.
Examples:
comparative example:
it can be seen from examples 1, 2, 6 and comparative examples 1, 2, 6 that if the general commercial spherical silica is not subjected to a suitable surface treatment, the viscosity of the binder will increase and the storage stability will decrease; as can be seen from example 3, example 4 and comparative examples 3, 4: if the spherical silica filling ratio is reduced, the CTE is raised and the curing shrinkage rate is increased; examples 7, 8 and comparative examples 7, 8, good high temperature and high humidity performance could not be obtained without proper resin formulation.
The compound adhesive is used for manufacturing 6 CWDM optical devices, and then the process availability and the optical parameter evaluation are respectively carried out, and the evaluation results are as follows:
* Judgment standard
1. The parameter change before and after the curing of the glue is less than 0.05dB
2.2000h high-temperature and high-humidity less than 0.1dB
Finally, it should be noted that: the above embodiments are only for illustrating the technical solution of the present invention, and are not limiting; although the invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical scheme described in the foregoing embodiments can be modified or some technical features thereof can be replaced by equivalents; such modifications and substitutions do not depart from the spirit and scope of the technical solutions of the embodiments of the present invention.
Claims (8)
1. A method for treating a spherical silica surface, comprising:
step 1, preparing an epoxy silane coupling agent, deionized water and absolute ethyl alcohol into a solution according to the proportion of 1:8:91, and fully stirring and mixing for later use;
step 2, pre-dispersing spherical silicon dioxide:
s1, adding commercial micron-sized spherical silicon dioxide into a muffle furnace, heating at 600 ℃ for 1 hour, and then cooling for standby;
s2, dissolving the micron-sized spherical silica treated in S1 into acetone for high-power ultrasonic dispersion, then centrifuging to separate the spherical silica, then adding the separated spherical silica into piranha solution for treatment for 5 minutes, then dissolving the separated spherical silica into absolute ethyl alcohol for high-power ultrasonic dispersion, then centrifuging again to separate the spherical silica, then dissolving the separated spherical silica into deionized water for high-power ultrasonic dispersion, centrifuging again to separate the spherical silica, finally placing the separated spherical silica into a vacuum double-planetary dispersing machine for autorotation 1000 rpm and revolution 2000 rpm parameters, dispersing again for 2 minutes, setting the heating temperature in a cavity to 100 ℃, and setting the vacuum to 10 ℃ for 2 minutes before dispersing -1 -10 2 Pa low vacuum state, then turning off the vacuum pump;
s3, atomizing the mixed solution in the step 1, spraying the atomized solution into a dispersion tank of a double-planetary dispersion machine, starting the double-planetary dispersion machine again to disperse for 2 minutes, standing for 5 minutes, setting the heating temperature to 105 ℃ to disperse for 10 minutes, standing for 5 minutes again, and repeating 2 cycles of dispersing for 10 minutes and standing for 5 minutes again to finish the surface treatment of the spherical silicon dioxide, so as to obtain the spherical silicon dioxide.
2. A binder for WDM encapsulation characterized by a composition of 1-10 parts of low molecular epoxy oligomer, 0.5-5 parts of high molecular epoxy resin, 0.5-10 parts of reactive epoxy diluent, 0.5-5 parts of coupling agent, 0.5-8 parts of photoinitiator, 0.1-1 part of latent heat curing agent, and spherical silica according to claim 1, which has a cure shrinkage of <0.3%, a viscosity of 60000-120000cps, a thermal expansion coefficient of <20ppm, a WDM device parameter variation of <0.1dB after 2000 hours of high temperature and humidity reliability test after manufacturing into CWDM devices, and a storage stability of one year.
3. A method of making an adhesive for WDM encapsulation comprising:
step 1, heating 1-10 parts of component A to 120 ℃ and dispersing for 5 minutes by a high-speed dispersing machine for later use;
step 2, adding 0.5-10 parts of component C and 0.5-5 parts of component D into the resin mixed in the step 1, heating to 60 ℃, dispersing at a high speed for 20 minutes, and cooling for later use;
step 3, adding 0.5-8 parts of component E into the resin mixed in the step 2, dispersing for 5 minutes at a high speed, and cooling for later use;
step 4, heating the resin mixed in the step 3 to 30 ℃, then adding 50-90 parts of component F into the step 3 for two times, dispersing at a high speed for 20 minutes, and cooling for later use;
step 5, adding 0.1-1 part of component G into the resin prepared in the step 4, and dispersing at a low speed for 30 minutes to finish the preparation of the adhesive, so as to prepare the adhesive with lower viscosity and suitable for WDM encapsulation;
component A is one or more of bisphenol epoxy resin, alicyclic epoxy resin and low molecular epoxy oligomer of hydantoin epoxy resin;
the component C is one or more of a monofunctional reactive epoxy diluent, a difunctional reactive epoxy diluent, a polyfunctional reactive epoxy diluent, a cycloaliphatic reactive diluent, an oxetane reactive diluent and a hybrid reactive diluent;
the component D is an epoxy silane coupling agent, a carboxyl silane coupling agent, a methacryloyl silane coupling agent, an isocyanate silane coupling agent and a titanate coupling agent;
the component E is one or more of aryl diazonium salt photoinitiator, diaryl iodonium salt photoinitiator, triarylsulfonium salt photoinitiator, aromatic ferrocenium salt photoinitiator, macromolecular photoinitiator and polymerizable photoinitiator;
component F is spherical silica as prepared in claim 1;
the component G is dicyandiamide latent heat curing agent, organic hydrazide latent heat curing agent, organic anhydride latent heat curing agent, imidazole latent heat curing agent and boron trifluoride-amine complex latent heat curing agent;
when the component F is an inorganic filler, the particle size range is 0.001-25um, and spherical silica with different center particle sizes is compounded according to the Horsfield closest packing theory;
spherical silicon dioxide with the center grain diameter of 5-8um and spherical silicon dioxide with the center grain diameter of 1-2um are selected, and the two spherical silicon dioxide are in normal distribution, and the compounding ratio is 4:1.
4. A method of making an adhesive for WDM encapsulation comprising:
step 1, mixing 1-10 parts of component A and 0.5-5 parts of component B together, heating to 120 ℃, dispersing by a high-speed dispersing machine for 5 minutes, and cooling for later use;
step 2, adding 0.5-10 parts of component C and 0.5-5 parts of component D into the resin mixed in the step 1, heating to 60 ℃, dispersing at a high speed for 20 minutes, and cooling for later use;
step 3, adding 0.5-8 parts of component E into the resin mixed in the step 2, dispersing for 5 minutes at a high speed, and cooling for later use;
step 4, heating the resin mixed in the step 3 to 30 ℃, then adding 50-90 parts of component F into the step 3 for high-speed dispersion for 20 minutes twice, and cooling for standby to prepare a single UV cured adhesive suitable for WDM encapsulation;
component A is one or more of bisphenol epoxy resin, alicyclic epoxy resin and low molecular epoxy oligomer of hydantoin epoxy resin;
the component B is one or more of polybutadiene modified epoxy resin, hydrogenated polybutadiene modified epoxy resin, bisphenol fluorene epoxy resin, biphenyl epoxy resin, naphthalene ring epoxy resin, organosilicon modified epoxy resin, macromolecule fluorinated epoxy resin and macromolecule epoxy resin of POSS modified epoxy resin;
the component C is one or more of a monofunctional reactive epoxy diluent, a difunctional reactive epoxy diluent, a polyfunctional reactive epoxy diluent, a cycloaliphatic reactive diluent, an oxetane reactive diluent and a hybrid reactive diluent;
the component D is an epoxy silane coupling agent, a carboxyl silane coupling agent, a methacryloyl silane coupling agent, an isocyanate silane coupling agent and a titanate coupling agent;
the component E is one or more of aryl diazonium salt photoinitiator, diaryl iodonium salt photoinitiator, triarylsulfonium salt photoinitiator, aromatic ferrocenium salt photoinitiator, macromolecular photoinitiator and polymerizable photoinitiator;
component F is spherical silica as prepared in claim 1;
when the component F is an inorganic filler, the particle size range is 0.001-25um, and spherical silica with different center particle sizes is compounded according to the Horsfield closest packing theory;
spherical silicon dioxide with the center grain diameter of 5-8um and spherical silicon dioxide with the center grain diameter of 1-2um are selected, and the two spherical silicon dioxide are in normal distribution, and the compounding ratio is 4:1.
5. A method of making an adhesive for WDM encapsulation comprising:
step 1, mixing 1-10 parts of component A and 0.5-5 parts of component B together, heating to 120 ℃, dispersing by a high-speed dispersing machine for 5 minutes, and cooling for later use;
step 2, adding 0.5-10 parts of component C and 0.5-5 parts of component D into the resin mixed in the step 1, heating to 60 ℃, dispersing at a high speed for 20 minutes, and cooling for later use;
step 3, adding 0.5-8 parts of component E into the resin mixed in the step 2, dispersing for 5 minutes at a high speed, and cooling for later use;
step 4, heating the resin mixed in the step 3 to 30 ℃, then adding 50-90 parts of component F into the step 3 for two times, dispersing at a high speed for 20 minutes, and cooling for later use;
step 5, adding 0.1-1 part of component G into the resin prepared in the step 4, and dispersing at a low speed for 30 minutes to finish the preparation of the binder;
component A is one or more of bisphenol epoxy resin, alicyclic epoxy resin and low molecular epoxy oligomer of hydantoin epoxy resin;
the component B is one or more of polybutadiene modified epoxy resin, hydrogenated polybutadiene modified epoxy resin, bisphenol fluorene epoxy resin, biphenyl epoxy resin, naphthalene ring epoxy resin, organosilicon modified epoxy resin, macromolecule fluorinated epoxy resin and macromolecule epoxy resin of POSS modified epoxy resin;
the component C is one or more of a monofunctional reactive epoxy diluent, a difunctional reactive epoxy diluent, a polyfunctional reactive epoxy diluent, a cycloaliphatic reactive diluent, an oxetane reactive diluent and a hybrid reactive diluent;
the component D is an epoxy silane coupling agent, a carboxyl silane coupling agent, a methacryloyl silane coupling agent, an isocyanate silane coupling agent and a titanate coupling agent;
the component E is one or more of aryl diazonium salt photoinitiator, diaryl iodonium salt photoinitiator, triarylsulfonium salt photoinitiator, aromatic ferrocenium salt photoinitiator, macromolecular photoinitiator and polymerizable photoinitiator;
component F is spherical silica as prepared in claim 1;
the component G is dicyandiamide latent heat curing agent, organic hydrazide latent heat curing agent, organic anhydride latent heat curing agent, imidazole latent heat curing agent and boron trifluoride-amine complex latent heat curing agent;
when the component F is an inorganic filler, the particle size range is 0.001-25um, and spherical silica with different center particle sizes is compounded according to the Horsfield closest packing theory;
spherical silicon dioxide with the center grain diameter of 5-8um and spherical silicon dioxide with the center grain diameter of 1-2um are selected, and the two spherical silicon dioxide are in normal distribution, and the compounding ratio is 4:1.
6. A method of making an adhesive for WDM encapsulation according to claim 3,4 or 5, wherein the bisphenol type epoxy resin is bisphenol a type glycidyl ether, bisphenol F type glycidyl ether, hydrogenated bisphenol type glycidyl ether, low molecular fluorinated epoxy resin.
7. A method for producing an adhesive for WDM encapsulation according to claim 3,4 or 5, wherein the epoxy silane coupling agent is 3-glycidoxypropyl methyldiethoxysilane, β - (3, 4-epoxycyclohexyl) hexyltriethoxysilane, or 3- (2, 3-epoxypropoxy) propyltrimethoxysilane.
8. A method of making a binder for WDM encapsulation according to claim 3,4 or 5, wherein component E further comprises a photosensitizer or chain transfer agent and a cationic initiator.
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| CN113652188A (en) * | 2021-09-24 | 2021-11-16 | 苏州艾迪亨斯新材料科技有限公司 | Single-component thermosetting packaging adhesive and preparation method thereof |
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| CN113652188A (en) * | 2021-09-24 | 2021-11-16 | 苏州艾迪亨斯新材料科技有限公司 | Single-component thermosetting packaging adhesive and preparation method thereof |
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| 东南大学MEMS教育部重点实验室著.《MEMS可靠性》.东南大学出版社,2009,(第一版),第224页. * |
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