CN1394900A - Preparation method of nano particles with high refractive index and polymer nano composite film material - Google Patents
Preparation method of nano particles with high refractive index and polymer nano composite film material Download PDFInfo
- Publication number
- CN1394900A CN1394900A CN 02132752 CN02132752A CN1394900A CN 1394900 A CN1394900 A CN 1394900A CN 02132752 CN02132752 CN 02132752 CN 02132752 A CN02132752 A CN 02132752A CN 1394900 A CN1394900 A CN 1394900A
- Authority
- CN
- China
- Prior art keywords
- refractive index
- high refractive
- composite film
- polymer
- nano
- 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
Landscapes
- Paints Or Removers (AREA)
- Polyurethanes Or Polyureas (AREA)
Abstract
The preparation method of nano composite film material by using nano microparticles with high refractive index and polymer includes the following three steps: preparing ZnS nano microparticles for surface modification, preparing organic polymer monomer and polymer with high refractive index and preparing nano composite film. In the organic solvent of zinc metal salt the organic small molecule surface modifier with function group is added, and the hydrogen sulfide gas is introduced to synthesize ZnS nano colloidal microparticles, and the polymer base material for combining ZnS nano microparticles can be polymethyl methacrylate, polybutyl methacrylate, polystyrene, epoxyresin, polymer large monomer, optimally can be polyurethane oligomer and polyurethane acrylate large monomer with high refractive index, finally the above-mentioned materials can be made into the invented nano composite film.
Description
Technical field:
The present invention relates to a kind of preparation method of high refractive index, thin film materials, relate to a kind of nanoparticle of high refractive index and the method that the compound back of polymkeric substance prepares nano composite film specifically.The synthetic thin-film material can be used to construct the surperficial antireflection coatings of optics, display device and solar cell in this way.
Technical background:
Current, the high refractive index optical coating mainly is divided into two big classes: polymkeric substance optical coating and inorganic optical coating.The polymkeric substance optical coating has advantages such as light weight, shock resistance, easy machine-shaping, however low, the poor heat resistance of polymer surfaces hardness, the narrower (n of change of refractive scope
dBetween 1.35～1.7).Although some specific polymers has higher specific refractory power (n=2.12) as poly-thiophene phenol, it has the coupling of intensive optical absorption at visible region, and this has just limited it at high refractive index (n
d＞1.7) application on the optical component.Inorganic materials generally has higher specific refractory power (n
d=2.0～5.0), bigger Abbe number, but its density is big, material is more crisp.When particularly using as antireflection coatings, the value of its specific refractory power can not be adjustable continuously, and having relatively high expectations to complete processing.
Traditional optical material comprises inorganic materials and organic materials two big classes.The inorganic-organic hybridization material then can have the advantage of above two kinds of materials concurrently, and therefore people begin inorganic nano-particle is incorporated into the nano composite material for preparing high refractive index in the polymkeric substance in recent years.This material is having broad application prospects aspect the antireflective coating of solar cell, material of infrared window and optical component.
At present aspect inorganic-organic hybridization high refractive index polymer optical material research more be PbS, Si nanoparticle simply to be entrained in the water miscible polymkeric substance (as polyoxyethylene, polyvinyl alcohol) improve specific refractory power.Yet owing to be water-soluble polymers, so the water tolerance of final matrix material is relatively poor, and physical strength is relatively poor.In addition, inorganic nano-particle is to be present in the polymkeric substance with simple adulterated form, does not have chemical bond between particulate and the polymer molecule, so nanoparticle assembles in polymeric substrate easily, and the less stable of material.Though TiO
2/ polymer hybrid material can overcome above shortcoming, but this class material shrinking percentage in solidification process is bigger, and film-forming properties is bad, influences the optics and the mechanical property of material the most at last.
Summary of the invention:
The present invention is by being incorporated into the ZnS nanoparticle in the oil-soluble polymers, thereby provides a kind of technology simply to prepare the novel method of high refractive index nano composite film material.The ZnS of body phase is as a kind of high refractive index (n
620nm=2.36) inorganic semiconductor material, because it has low-down uptake factor in the wider wavelength region of 400～14000nm, so it has many different application at optical field.This class high refractive index nano composite film material good film-forming property, the optical property homogeneous, the form with covalent linkage between nanoparticle and the polymkeric substance exists, and material has stability preferably, therefore has actual application value more aspect antireflection film layer.
The preparation method of nano particles with high refractive index and polymer nano composite film material of the present invention comprises following three steps:
1, synthetic surface modified ZnS colloidal nanoparticles;
2, synthetic high refractive index organic polymer monomer and polymkeric substance;
3, the nanometer film layer material of the compound preparation high refractive index by nanoparticle and polymeric substrate;
At last the nano composite material performance is tested.One, the ZnS colloidal nanoparticles of finishing is synthetic:
Described colloidal nano particulate can synthesize in second cyanogen, methyl alcohol, dimethyl formamide organic solvent, with synthetic effect the best in the dimethyl formamide organic solvent, and through the modification of organic molecule coating materials, coating materials can be for having the modifier of functional group; The molar ratio of the coating materials of nanoparticle and metal-salt (as acetate, perchlorate or vitriol) is 0.2～1.0: 1, and the feeding amount of hydrogen sulfide is normal 6～10 times an of metal-salt; Feed speed-controllable built in 0.1 milliliter～5 ml/min.The coating materials of ZnS particulate can be thiophenol, to the methylbenzene thiophenol, to ethyl thiophenol, to the methylol thiophenol, to hydroxyethylbenzene thiophenol, thiopurine methyltransferase vinylbenzene, mercaptoethanol, mercaprol, thioglycerol etc., can mix with one or both of above compound and modify the ZnS nanoparticle, total coating materials and metal-salt equivalence ratio are 0.2～1.0: 1.
Certainly above method is not limited only to the synthetic of ZnS nanoparticle, is suitable for synthesizing of other semi-conductor nano particles such as CdS too, and these nanoparticles all can be compound in the following polymkeric substance.Two, high refractive index organic polymer monomer and polymkeric substance is synthetic:
When top synthetic ZnS nanoparticle was mixed with polymkeric substance or the big monomer of polymkeric substance, polymeric substrate can be polymethylmethacrylate (PMMA), poly-n-butyl methacrylate, polystyrene (PS), urethane and Resins, epoxy etc.; Also can be the big monomer of polymkeric substance, as the big monomer of acrylate, polyurethane oligomer etc.These polymkeric substance can be synthetic from the corresponding polymer monomer, for preparation high refractive index nano matrix material, the polymer-based carbon bottom material of high refractive index is even more ideal, and the polymkeric substance or the polymer monomer that therefore design the synthesizing new high refractive index are very important.Provide the preparation embodiment of several high refractive index polymer monomers and polymkeric substance below, wherein big monomeric urethane segment of urethane acrylate and polyurethane oligomer can be prepared through polyaddition by dibasic alcohol or binary mercaptan and vulcabond.Here, binary (sulphur) alcohol can be ethylene glycol, propylene glycol, dihydroxyethylsulfide, mercaptoethanol, 2,2 '-dimercapto ethyl-sulfide, dithioglycol etc.; Vulcabond can be 2,4 '-tolylene diisocyanate, isophorone diisocyanate, '-diphenylmethane diisocyanate etc.Binary (sulphur) alcohol is 1: 1.1～2 with the equivalence ratio of vulcabond, and reaction solvent can be benzene, toluene, tetrahydrofuran (THF), dimethyl formamide etc., and temperature of reaction can be controlled at 45～85 ℃, and the reaction times can be at 2～10 hours.
The big monomer of top synthetic urethane acrylate can pass through uv-light polymerization, also available initiator thermopolymerization.Three, the preparation of ZnS nanoparticle/polymer nano composite film material:
Prepare ZnS nanoparticle/polymer nano composite film by shifting diffuse-aggregate method, wherein polymer materials can be a polymeric linear polymer in advance, as polymethylmethacrylate (PMMA), polystyrene (PS), urethane etc. mix the direct dried coating film in back with it and can obtain composite material film with nanoparticle colloidal sol; Also can be that polymerization on the throne forms, film earlier with after nanoparticle colloidal sol mixes that repolymerization forms polymkeric substance-nanoparticle composite film material as polymer monomer.Nanoparticle is to be present in the polymkeric substance with simple adulterated form in preceding a kind of method; Then a kind of method then has certain advantage, because the ZnS microparticle surfaces has functional group's (two keys, hydroxyl), can react with the acrylate or the polyurethane oligomer of polyfunctionality, nanoparticle is fixed in the polymer network by covalent linkage, formed polymkeric substance is a cross-linked form, and therefore the composite film material that finally obtains has mechanical property and thermal stability preferably.
The performance test of nano compound film: the specific refractory power of measuring 632.8nm place film with ellipsometer; Measure the thermal characteristics and the content of actual ZnS in film of film with thermogravimetric analyzer; With the transmitance of uv-vis spectra MEASUREMENTS OF THIN at the 550nm place.
The doping of ZnS in polymkeric substance can change between 0～97wt% as requested.For coating process, spin speed can be regulated between 500～4000 rev/mins according to the viscosity of coating liquid and the thickness of final coating; For curing process, can adopt uv-light polymerization, AIBN or BPO etc. to cause radical polymerization and thermopolymerization.Certainly also can adopt first uv photopolymerization, the method that thermal-initiated polymerizations such as back AIBN combine.The time of uv photopolymerization was generally 20 seconds～5 minutes, and generally between 60～180 ℃, the time was generally 3～10 hours the temperature of thermal-initiated polymerizations such as AIBN.
Below in conjunction with embodiment the present invention is further set forth.
Embodiment:
Embodiment 1: synthetic (1) of the ZnS colloidal nanoparticles of finishing
On ice bath, under the vigorous stirring, in 100ml contains the solution of Glacial acetic acid zinc/dimethyl formamide (DMF) of 0.2M thiophenol and the cinnamic 0.5M of 0.1M thiopurine methyltransferase, feed excessive 6 times to the normal dry hydrogen sulfide of zinc acetate, control feeding speed is 0.5 ml/min, remove excessive hydrogen sulfide with nitrogen at last, obtain water white ZnS Nano sol.
Utilize transmission electron microscope (TEM) that surperficial modified ZnS nanoparticle is observed and show that the particle diameter of particulate is in 2～5 nanometers, electron diffraction and X-ray diffraction show that the ZnS particle is a cubic structure.With the ZnS Nano sol vacuum-drying that obtains above, the ZnS nanoparticle powder that obtains finishing is through Infrared Characterization result following (KBr): ν (cm
-1): 3404,2920,2855,1647,1629,1603,1577,1508,1406～1477cm
-1, 690～990.Characterize discovery by ultimate analysis and plasma body linking atom emmission spectrum: C, 30.5; H, 2.66; S, 25.30; Zn, 42.90. according to the chemical constitution that feed ratio calculates the ZnS nanoparticle that can release finishing is: Zn
2+: S
2-: RS
-=1: 0.6: 0.6, show that most coating materials all is coated on the surface of ZnS particulate.
Embodiment 2: synthetic (2) of the ZnS colloidal nanoparticles of finishing
Except replacing the thiopurine methyltransferase vinylbenzene with mercaptoethanol, other condition is with embodiment 1.
The particle diameter of analysis revealed ZnS particulate is also in 2～5 nanometers, and crystal formation is a cubic structure.The chemical constitution of the ZnS nanoparticle of finishing is Zn
2+: S
2-: RS
-=1: 0.78: 0.6.
Equally, among the top embodiment, coating materials can be simple thiophenol, thiopurine methyltransferase vinylbenzene or mercaptoethanol etc., and their concentration separately can change between 0.1～0.5M.
Preparing the nanometer ZnS colloid with the coating materials of other kind can be with method same as described above.
Embodiment 3: the big monomeric synthetic and polymerization of urethane acrylate
With 2 of 2,2 of 15.4g '-dimercapto ethyl-sulfide (MES) and 26.1g, 4 '-tolylene diisocyanate (TDI) is dissolved in 100ml anhydrous dimethyl formamide (DMF) solution, adds a spot of dibutyl tin laurate and makes catalyzer.This reaction mixture 55 ℃ of reactions 4 hours, drips the 6.5g hydroxyethyl methylacrylate then under nitrogen protection, continue reaction 2 hours, obtains the big monomeric DMF solution of urethane acrylate of 23wt% at last.IR spectrum (KBr): ν (cm
-1) 3292,3047,2930,2924,2857,1726,1654,1639,1618,1602,1540,1454,1448,1418,1300,1215,1194,1031,878,815,768.IR spectroscopic analysis result shows 1639cm
-1The place is the characteristic peak of the two keys of methacrylic ester, 1654,3239cm
-1Be the eigen vibration peak of urethane bonds, and the characteristic peak of sulfydryl and isocyanic ester disappears, so the gained compound is the big monomer of urethane acrylate.
The big monomer of top synthetic urethane acrylate can pass through uv-light polymerization, also available initiator thermopolymerization.As through 2,2-dimethyl-2-hydroxy acetophenone (1173) light initiation polymerization and azo-bis-isobutyl cyanide (AIBN) thermal-initiated polymerization, the polymeric film that obtains has higher specific refractory power, and specific refractory power is 1.64.
Embodiment 4: polyurethane oligomer synthetic
The isophorone diisocyanate (IPDI) of 2,2 of 15.4g '-dimercapto ethyl-sulfide (MES) and 33.4g is dissolved in about 100ml exsiccant toluene, adds a spot of dibutyl tin laurate again and make catalyzer.75～80 ℃ of reactions 9 hours, a part of toluene was removed in decompression at last to this reaction mixture, obtains the toluene solution of the polyurethane oligomer of the water white 61wt% of containing under nitrogen protection.IR spectrum (KBr): ν (cm
-1) 3290 (N-H), 2268 (N=C=O), 1667 (COS-), 1254,1530 (is polyurethane oligomer from the visible institute of ir data synthetic N-H).The specific refractory power of the pure polyurethane oligomer film of gained is 1.57.
Embodiment 5:
Prepare nano compound film with thiophenol (PhSH)/big monomer of thiopurine methyltransferase vinylbenzene (TMSt) modified ZnS nanoparticle (1) composite polyurethane acrylate.
By desired doping ZnS colloidal nanoparticles, the big monomer of urethane acrylate and initiator (comprise 1173 and AIBN) are mixed in DMF, the big monomeric ratio of ZnS colloidal particle and urethane acrylate is pressed table 1 and is calculated, TCZnS in the table 1
aRepresent the percentage composition of thiophenol (PhSH)/thiopurine methyltransferase vinylbenzene (TMSt) modified ZnS nanoparticle, and the big monomeric consumption of urethane acrylate is 100%-TCZnS%, the consumption of initiator is 3/1000ths of a big monomer weight, and the vacuum concentration mixing solutions is to certain viscosity under 40 ℃ of conditions.The gained mixed solution is spin-coated on (as silicon chip, sheet glass or plastics sheet) on the surface-treated substrate, spin speed can be regulated (promptly between 500～4000 rev/mins according to the viscosity of coating liquid and the thickness of final coating, the less solution of viscosity will obtain thicker coating and need adopt the low speed spin coating, and the coating that the bigger solution of viscosity will obtain approaching need adopt the high speed spin coating).The coating that spin coating is good 40 ℃ of dryings 20 minutes under vacuum, ultraviolet light polymerization 3 minutes under the medium pressure mercury lamp of 1KW then solidified 4 hours at 70 ℃ then, and 100 ℃ solidified 2 hours, 160 ℃ of thermal treatment 0.5 hour.Obtain the optical coating of water white homogeneous at last.Show the actual content of ZnS particulate in the film and Theoretical Calculation amount (seeing Table 1) in full accord through thermogravimetric analysis (TGA).The specific refractory power of the pure urethane acrylic acid ester polymer of doped ZnS is not 1.645, and the specific refractory power of the laminated film of doping 57wt%ZnS is near 1.8.Table 1 has been listed the performance of PhSH/TMSt modified ZnS-urethane acrylate polymer nano composite film.
The performance of table 1.PhSH/TMSt modified ZnS-urethane acrylate polymer nano composite film.
| ?TCZnS a | ?ZnS b | ?h() c | ?n(632.8nm) d | ??T d(℃) e | 750℃?residue f | ??T％ g |
| ????0 | ?0 | ??1795 | ??1.645 | ???200 | ????0 | ???96 |
| ????16 | ?11 | ??1463 | ??1.672 | ???201 | ????12 | ???96 |
| ????32 | ?21 | ??1386 | ??1.706 | ???205 | ????22 | ???95 |
| ????48 | ?31 | ??1508 | ??1.728 | ???204 | ????32 | ???95 |
| ????63 | ?46 | ??1614 | ??1.749 | ???202 | ????44 | ???95 |
| ????79 | ?52 | ??1370 | ??1.766 | ???206 | ????53 | ???95 |
| ????86 | ??57 | ??1162 | ??1.796 | ???203 | ????57 | ???95 |
aThe theoretical weight mark of the ZnS particulate that mercaptan coats in the film;
bThe theoretical weight mark of pure ZnS particulate in the film;
cThe thickness of nano compound film;
dNano compound film is in the specific refractory power at 632.8nm place;
eThe initial decomposition temperature of nano compound film;
fInorganics is at 750 ℃ residual rate (thermogravimetic analysis (TGA) result) in the film;
gThe thick nano compound film of about 1 μ m is in the transmitance at 550nm place.
Embodiment 6:
Prepare nano compound film with thiophenol (PhSH)/mercaptoethanol (ME) modified ZnS nanoparticle (2) composite polyurethane oligopolymer.
In desired doping ZnS colloidal nanoparticles, polyurethane oligomer are mixed back (the big monomeric ratio of ZnS colloidal particle and urethane acrylate is pressed table 2 and calculated) in dry DMF, the vacuum concentration mixing solutions is to certain viscosity (can regulate according to film-forming properties and thicknesses of layers) under 40 ℃ of conditions.The gained mixed solution is spin-coated on surface-treated substrate (on silicon chip, sheet glass or plastics sheet), and spin speed can be regulated between 500～4000 rev/mins according to the viscosity of coating liquid and the thickness of final coating.The coating that spin coating is good was solidified 4 hours at 70 ℃, and 100 ℃ solidified 2 hours, and 120 ℃ solidified 1 hour, 160 ℃ of thermal treatment 0.5 hour.Obtain water white optical coating at last.Show also basically identical (seeing Table 2) of the actual content of ZnS particulate in the film and Theoretical Calculation amount through thermogravimetric analysis (TGA).The specific refractory power of the pure polyether polyols with reduced unsaturation of doped ZnS is not 1.574, and the specific refractory power of the laminated film of doping 63wt%ZnS is near 1.85.Table 2 has been listed the performance of PhSH/ME modified ZnS-polyether polyols with reduced unsaturation nano compound film.
The performance of table 2.PhSH/ME modified ZnS-polyurethane nano laminated film.
| ?TCZnS a | ?ZnS b | ?h() c | ??n(632.8nm) d | ??Td(℃) e | ?750℃reisdue f |
| ????0 | ??0 | ??1760 | ????1.574 | ????202 | ????0 |
| ????16 | ??10 | ??1282 | ????1.592 | ????207 | ????11 |
| ????32 | ??20 | ??1551 | ????1.635 | ????209 | ????21 |
| ????47 | ??31 | ??1311 | ????1.70 | ????204 | ????30 |
| ????63 | ??41 | ??1586 | ????1.754 | ????203 | ????43 |
| ????80 | ??52 | ??1542 | ????1.789 | ????198 | ????52 |
| ????88 | ??58 | ??1601 | ????1.821 | ????206 | ????57 |
| ????97 | ??63 | ??1477 | ????1.848 | ????208 | ????61 |
*The meaning of footmark is with table 1.
Claims (7)
1, a kind of preparation method of nano particles with high refractive index and polymer nano composite film material comprises three steps of ZnS nanoparticle, high refractive index organic polymer monomer and polymkeric substance, nano compound film that prepare finishing, it is characterized in that:
(1) in the organic solvent of zinc metal-salt, adding can have the organic molecule coating materials of functional group, and feeding hydrogen sulfide, the molar ratio of coating materials and metal-salt is 0.2～1.0: 1, the feeding amount of hydrogen sulfide is normal 6～10 times an of metal-salt, feeding speed 0.1 milliliter～5 ml/min;
(2) polymeric substrate that is used for compound ZnS nanoparticle can be polymethylmethacrylate, poly-n-butyl methacrylate, polystyrene, urethane and Resins, epoxy, it also can be the big monomer of polymkeric substance, as the big monomer of acrylate, polyurethane oligomer, be the best with the polyurethane oligomer and the big monomer effect of urethane acrylate of high refractive index; Polyurethane oligomer can be prepared through polyaddition by dibasic alcohol or binary mercaptan and vulcabond, binary (sulphur) alcohol is 1: 1.1～2 with the equivalence ratio of vulcabond, temperature of reaction is 45～85 ℃ in the solvent, reaction times is 2～10 hours, the big monomer of urethane acrylate can be obtained with the hydroxyethyl methylacrylate end-blocking by polyurethane oligomer, it can pass through uv-light polymerization, also available initiator thermopolymerization;
(3) nano compound film is by shifting diffuse-aggregate method preparation, and the nanoparticle colloidal sol before the spin-coating film can contain polymkeric substance, direct then film forming; Also can contain the big monomer of polymkeric substance, repolymerization after the film forming; The doping of ZnS in polymkeric substance is 0～97wt%, is 500～4000 rev/mins in on-chip spin speed, gets the high refractive index nano composite film material.
2, the preparation method of nano particles with high refractive index and polymer nano composite film material as claimed in claim 1 is characterized in that: the zinc metal-salt can be a kind of in zinc acetate, zinc perchlorate or the zinc sulfate.
3, the preparation method of nano particles with high refractive index and polymer nano composite film material as claimed in claim 1 is characterized in that: organic solvent can be second cyanogen, methyl alcohol or dimethyl formamide, with dimethyl formamide organic solvent best results.
4, the preparation method of nano particles with high refractive index and polymer nano composite film material as claimed in claim 1 is characterized in that: coating materials can be thiophenol, to the methylbenzene thiophenol, to ethyl thiophenol, to the methylol thiophenol, to one or both mixing in hydroxyethylbenzene thiophenol, thiopurine methyltransferase vinylbenzene, mercaptoethanol, mercaprol or the thioglycerol.
5, the preparation method of nano particles with high refractive index and polymer nano composite film material as claimed in claim 1, it is characterized in that: binary (sulphur) alcohol of preparation big monomer of polymkeric substance or polyurethane oligomer can be ethylene glycol, propylene glycol, dihydroxyethylsulfide, mercaptoethanol, 2,2 '-dimercapto ethyl-sulfide or 7 two mercaptan; Vulcabond can be 2,4 '-tolylene diisocyanate, isophorone diisocyanate or '-diphenylmethane diisocyanate, and reaction solvent can be benzene, toluene, tetrahydrofuran (THF), dimethyl formamide.
6, the preparation method of nano particles with high refractive index and polymer nano composite film material as claimed in claim 1, it is characterized in that: polymerization can adopt uv-light polymerization, AIBN or BPO etc. to cause radical polymerization and thermopolymerization, also can adopt first uv photopolymerization, the method that thermal-initiated polymerizations such as back AIBN combine, the time of uv photopolymerization is 20 seconds～5 minutes, the temperature of thermal-initiated polymerizations such as AIBN is between 60～180 ℃, and the time is 3～10 hours.
7, as the prepared nano particles with high refractive index and polymer nano composite film material of the method in the claim 1 in the application that is used to construct aspect the surperficial antireflection coatings of optics, display device and solar cell.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 02132752 CN1204170C (en) | 2002-08-08 | 2002-08-08 | Preparation method of nano particles with high refractive index and polymer nano composite film material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 02132752 CN1204170C (en) | 2002-08-08 | 2002-08-08 | Preparation method of nano particles with high refractive index and polymer nano composite film material |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1394900A true CN1394900A (en) | 2003-02-05 |
| CN1204170C CN1204170C (en) | 2005-06-01 |
Family
ID=4746916
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 02132752 Expired - Fee Related CN1204170C (en) | 2002-08-08 | 2002-08-08 | Preparation method of nano particles with high refractive index and polymer nano composite film material |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1204170C (en) |
Cited By (17)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102061079A (en) * | 2010-11-12 | 2011-05-18 | 吉林大学 | Method for preparing transparent high-refractive-index nano composite bulk phase optical material |
| CN102173155A (en) * | 2011-01-14 | 2011-09-07 | 北京化工大学 | Polymer-base ceramic composite dielectric material and preparation method thereof |
| CN101611080B (en) * | 2007-02-26 | 2011-12-28 | 贝卡尔特股份有限公司 | A layered structure comprising nanoparticles |
| CN101803016B (en) * | 2007-07-19 | 2012-04-25 | 弗赖斯金属有限公司 | Methods for attachment and devices produced using the methods |
| CN102959716A (en) * | 2010-03-23 | 2013-03-06 | 保利瑞斯公司 | Photovoltaic devices comprising an anti-reflective layer containing dispersed objects having areas with different refractive indices |
| CN102993644A (en) * | 2012-10-30 | 2013-03-27 | 无锡三幸高膜科技有限公司 | Transparent organic polymer material with high index of refraction and preparation method thereof |
| CN103360746A (en) * | 2013-07-24 | 2013-10-23 | 上海冠旗电子新材料股份有限公司 | Method for preparing nano-ZnS / polycarbonate composite film |
| WO2014001404A3 (en) * | 2012-06-26 | 2014-07-03 | Nikon Corporation | Liquid polymerizable composition comprising mineral nanoparticles and its use to manufacture an optical article |
| CN104031525A (en) * | 2014-06-04 | 2014-09-10 | 绍兴京华激光制品有限公司 | Coating liquid with high refractive index for transparent holographic film and preparation method thereof |
| CN106653875A (en) * | 2017-02-20 | 2017-05-10 | 江苏欧耐尔新型材料股份有限公司 | Nano light absorption composite material and preparation method thereof, and coated film preparation method |
| CN106833406A (en) * | 2017-02-22 | 2017-06-13 | 杭州福斯特光伏材料股份有限公司 | A kind of high refractive index nano inorganic matter hydridization photovoltaic encapsulation material |
| CN110627981A (en) * | 2018-06-22 | 2019-12-31 | 万华化学集团股份有限公司 | Optical resin composition, optical resin material, preparation method and application thereof |
| CN112397659A (en) * | 2019-08-19 | 2021-02-23 | Tcl集团股份有限公司 | Composite material, preparation method thereof and quantum dot light-emitting diode |
| CN112959781A (en) * | 2020-10-09 | 2021-06-15 | 江苏双星彩塑新材料股份有限公司 | Optical film substrate and preparation method thereof |
| CN113637198A (en) * | 2021-08-18 | 2021-11-12 | 中国科学院光电技术研究所 | High-refractive-index near-infrared high-transmittance polyimide film material and preparation method thereof |
| CN114383514A (en) * | 2021-12-30 | 2022-04-22 | 广州市合熠智能科技股份有限公司 | CMOS contact displacement sensor and measuring method |
| CN115124837A (en) * | 2021-12-28 | 2022-09-30 | 苏州太湖电工新材料股份有限公司 | Polyimide composite film |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106497499B (en) * | 2016-10-28 | 2019-07-12 | 南京汇鑫光电材料有限公司 | A kind of UV solidification optical cement |
-
2002
- 2002-08-08 CN CN 02132752 patent/CN1204170C/en not_active Expired - Fee Related
Cited By (25)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101611080B (en) * | 2007-02-26 | 2011-12-28 | 贝卡尔特股份有限公司 | A layered structure comprising nanoparticles |
| CN101803016B (en) * | 2007-07-19 | 2012-04-25 | 弗赖斯金属有限公司 | Methods for attachment and devices produced using the methods |
| CN102959716A (en) * | 2010-03-23 | 2013-03-06 | 保利瑞斯公司 | Photovoltaic devices comprising an anti-reflective layer containing dispersed objects having areas with different refractive indices |
| CN102061079A (en) * | 2010-11-12 | 2011-05-18 | 吉林大学 | Method for preparing transparent high-refractive-index nano composite bulk phase optical material |
| CN102173155A (en) * | 2011-01-14 | 2011-09-07 | 北京化工大学 | Polymer-base ceramic composite dielectric material and preparation method thereof |
| CN102173155B (en) * | 2011-01-14 | 2013-11-20 | 北京化工大学 | Polymer-base ceramic composite dielectric material and preparation method thereof |
| CN104411745B (en) * | 2012-06-26 | 2017-08-25 | 株式会社尼康 | Liquid polymerizable composition comprising mineral nano particle and its purposes for producing optical article |
| WO2014001404A3 (en) * | 2012-06-26 | 2014-07-03 | Nikon Corporation | Liquid polymerizable composition comprising mineral nanoparticles and its use to manufacture an optical article |
| US10934451B2 (en) | 2012-06-26 | 2021-03-02 | Nikon Corporation | Liquid polymerizable composition comprising mineral nanoparticles and its use to manufacture an optical article |
| CN104411745A (en) * | 2012-06-26 | 2015-03-11 | 株式会社尼康 | Liquid polymerizable composition comprising mineral nanoparticles and its use to manufacture an optical article |
| CN102993644A (en) * | 2012-10-30 | 2013-03-27 | 无锡三幸高膜科技有限公司 | Transparent organic polymer material with high index of refraction and preparation method thereof |
| CN103360746A (en) * | 2013-07-24 | 2013-10-23 | 上海冠旗电子新材料股份有限公司 | Method for preparing nano-ZnS / polycarbonate composite film |
| CN103360746B (en) * | 2013-07-24 | 2016-02-10 | 上海冠旗电子新材料股份有限公司 | Nano-zinc sulfide/polycarbonate compound film preparation method |
| CN104031525A (en) * | 2014-06-04 | 2014-09-10 | 绍兴京华激光制品有限公司 | Coating liquid with high refractive index for transparent holographic film and preparation method thereof |
| CN106653875A (en) * | 2017-02-20 | 2017-05-10 | 江苏欧耐尔新型材料股份有限公司 | Nano light absorption composite material and preparation method thereof, and coated film preparation method |
| CN106833406A (en) * | 2017-02-22 | 2017-06-13 | 杭州福斯特光伏材料股份有限公司 | A kind of high refractive index nano inorganic matter hydridization photovoltaic encapsulation material |
| CN110627981A (en) * | 2018-06-22 | 2019-12-31 | 万华化学集团股份有限公司 | Optical resin composition, optical resin material, preparation method and application thereof |
| CN110627981B (en) * | 2018-06-22 | 2022-01-07 | 万华化学集团股份有限公司 | Optical resin composition, optical resin material, preparation method and application thereof |
| CN112397659A (en) * | 2019-08-19 | 2021-02-23 | Tcl集团股份有限公司 | Composite material, preparation method thereof and quantum dot light-emitting diode |
| CN112397659B (en) * | 2019-08-19 | 2023-02-07 | Tcl科技集团股份有限公司 | Composite material, preparation method thereof and quantum dot light-emitting diode |
| CN112959781A (en) * | 2020-10-09 | 2021-06-15 | 江苏双星彩塑新材料股份有限公司 | Optical film substrate and preparation method thereof |
| CN112959781B (en) * | 2020-10-09 | 2022-01-11 | 江苏双星彩塑新材料股份有限公司 | Optical film substrate and preparation method thereof |
| CN113637198A (en) * | 2021-08-18 | 2021-11-12 | 中国科学院光电技术研究所 | High-refractive-index near-infrared high-transmittance polyimide film material and preparation method thereof |
| CN115124837A (en) * | 2021-12-28 | 2022-09-30 | 苏州太湖电工新材料股份有限公司 | Polyimide composite film |
| CN114383514A (en) * | 2021-12-30 | 2022-04-22 | 广州市合熠智能科技股份有限公司 | CMOS contact displacement sensor and measuring method |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1204170C (en) | 2005-06-01 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN1204170C (en) | Preparation method of nano particles with high refractive index and polymer nano composite film material | |
| Yu et al. | Transparent organic–inorganic hybrid thin films prepared from acrylic polymer and aqueous monodispersed colloidal silica | |
| CN1320051C (en) | Method for preparing transparent optical material of polymer in high nano phase | |
| US7648645B2 (en) | Pre-polymer formulations for liquid crystal displays | |
| KR101273097B1 (en) | Anti-reflection and anti-glare coating composition, anti-reflection and anti-glare film, and method for preparation of the same | |
| KR101497409B1 (en) | Resin composition | |
| Ding et al. | Formation of supra-amphiphilic self-cleaning surface through sun-illumination of titania-based nanocomposite coatings | |
| CN102149667B (en) | Fluorine-based compounds and coating compositions comprising the same | |
| TW200920802A (en) | Hardcoats having low surface energy and low lint attraction | |
| Xiong et al. | Sol–gel derived organic–inorganic hybrid from trialkoxysilane-capped acrylic resin and titania: effects of preparation conditions on the structure and properties | |
| CN101069109A (en) | Optical component comprising an organic-inorganic hybrid material for producing refractive index gradient layers with rapid kinetics and method for its production | |
| CN101343536A (en) | Surface functionalized nano-particle and method for preparing its polymer nanometre composite material | |
| TWI784116B (en) | Photocurable composition for imprint | |
| Chang et al. | Preparation and characterization of TiO 2 hybrid sol for UV-curable high-refractive-index organic–inorganic hybrid thin films | |
| Yu et al. | Preparation and optical properties of organic/inorganic nanocomposite materials by UV curing process | |
| Shankar et al. | Design and fabrication of a transparent, tough and UVC screening material as a substitute for glass substrate in display devices | |
| Yao et al. | Synthesis of acrylate-based UV/thermal dual-cure coatings for antifogging | |
| CN109929130B (en) | High-water-drop contact angle easy-to-adhere hardened film and preparation method thereof | |
| CN113105766B (en) | Superhard wear-resistant transparent film material with silicon-doped carbonized polymer dots as construction elements and preparation method thereof | |
| CN104418958A (en) | Preparation method of organic mineral complex, curable composition, cured product of curable composition, hard coating material, hard coating film and silane coupling agent | |
| Tian et al. | Renewable UV-curable polyester methacrylate/cellulose nanocrystals composite resin for wood waterproof coating | |
| Tsai et al. | Novel solution-processable optically isotropic colorless polyimidothioethers–TiO 2 hybrids with tunable refractive index | |
| KR100541316B1 (en) | Organic-inorganic hybrid ultraviolet curable hard coating composition and method for preparing same, and hard coat film manufactured by using same | |
| KR20130061683A (en) | High refractive index composition | |
| CN112457455B (en) | Preparation method of fluorocarbon resin, fluorocarbon resin and application |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| C19 | Lapse of patent right due to non-payment of the annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |