CN1294219C - High strength organic / inorganic nano composite transparent film layer materials and method for preparing same - Google Patents
High strength organic / inorganic nano composite transparent film layer materials and method for preparing same Download PDFInfo
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Abstract
The present invention relates to wear-resistance scratch-resistance transparent thin film material with a high refractive index and a preparation method thereof, particularly relates to an organic/inorganic hybrid film layer material compounded on a nanometer scale and a preparation method thereof. The compound comprises 10% to 40% of titanate, 7% to 17% of silane coupling agent, 0% to 6% of silicate, 40% to 65% of alcohol solvent and 1% to 4% of water; the composition takes an inorganic acid as a catalyst, and the titanate, the silicate and the silane coupling agent are cohydrolyzed in isopropyl alcohol to obtain stable and uniform collosol. Obtained paint can be coated on the surface of a device by spin coating, dip coating or spray coating, and the paint can be cured at the temperature of 135 to 150D EGC for 1 to 3 hours to obtain a transparent optical coating layer with high refractive index and high strength. The compounded film layer material can be used as the protective layers of automobile lamps, optical disk surfaces and gas masks; the compounded film layer material can be used as surface antireflection wear-resistance coating layers of resin glasses, transparent optical devices, display devices and solar cells.
Description
Technical field
The present invention relates to a kind of high refractive index, transparent, wear-resisting damage resistant thin-film material and preparation method, be specifically related to a kind of on nanoscale compound hybrid film material and preparation method.This thin-film material can be used for the protective layer of automobile lamp, CD and smoke mask, also can be used for the surperficial antireflective wear-resistant coating of high refractivity resin lens, transparent optical device, display device and solar cell.
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.The inorganic-organic hybridization material then can have the advantage of above two kinds of materials concurrently, therefore people begin by the method for collosol and gel inorganic nano-particle to be introduced the nano combined hybrid material for preparing high refractive index in the optical coating in recent years, and this material can or be heating and curing through ultraviolet light polymerization and obtain compound transparent film layer materials on the nanoscale.This material can be used for the surface of glass or resin lens, smoke mask, automobile lamp and CD as the wear Protection coating, is also having broad application prospects aspect the antireflective coating of solar cell, material of infrared window and optical component.
The generally all lower (n of specific refractory power of the present wear-resisting optical coating of using of hybrid inorganic-organic
d＜1.60), still can not well satisfy the design requirements of the antireflection coatings of high refractive index optical material surface.Therefore the inorganics of high refractive index is incorporated in the hybrid coating preparation specific refractory power more than 1.65, and optically transparent wear-resisting hydridization compound coating is the current problem that solves of needing.
Summary of the invention
The present invention is incorporated into high-load titanium oxide the hybrid composite film material that has prepared high refractive index in the hybrid coating by sol-gel technique, the good film-forming property of this hybridized film layer material, the optical property homogeneous, it is high and adjustable continuously to have specific refractory power, wear resistance is good, therefore the transparency advantages of higher has actual using value aspect wear-resisting, the damage resistant of surface optical device, antireflection film layer.
The quality percentage composition of each component is in the organic/inorganic nano hydridization composite film material of the present invention:
A.10%～40% chemical formula is (I) titanic acid ester;
B.7%～17% chemical formula is (II) silane coupling agent;
C.0%～6% chemical formula is (III) silicon ester;
D.1%～4% water;
E.0～0.5% acid catalyst;
F.0～0.05% solidifying agent;
G.0～0.3% flow agent;
H.40%～65% alcoholic solvent;
R wherein
1For containing a alkyl to five carbon; R
2For containing a alkyl to two carbon; R
3For containing two alkyl (as KH570, SJ42) that two keys (as KH-151,171), epoxide group (as KH560), amino (as KH550, KH551, KH602, KH792), sulfydryl (as KH580, KH590), phenyl, carbonyl or above group occur with complex form that have to seven carbon.
The present invention adopts sol-gel method, titanic acid ester is hydrolyzed with the acid catalysis condition in Virahol, based on this solution, to wherein adding a certain amount of silicon ester and silane coupling agent, after stirring, continue moisturizing and carry out further hydrolysis, finally obtain settled solution transparent, homogeneous, high strength organic/inorganic nano hydridization composite film material promptly of the present invention.Preparation methods of the present invention comprises following two steps:
One, sol-gel method prepares the blend colloidal sol of titaniferous and silicon;
Two, obtain nano combined film material by applying and solidifying.
One, the preparation of titanium, silicon blend colloidal sol:
1. titanic acid ester is dissolved in the alcoholic solution, add 80～200g titanic acid ester in every 100ml alcoholic solution, after stirring makes and mixes, alcoholic solution with water and acid under continuing stirring condition joins in the above-mentioned solution, be dissolved with the acid of water and the 0.5～1g of 5～10g in per 100 milliliters of alcoholic solutions, reacted 1～12 hour, wherein the mol ratio of water and titanic acid ester is 0.5～1.5: 1, add silicon ester and silane coupling agent then, the mol ratio of silicon ester and titanic acid ester is 0～1: 1; The mol ratio of silane coupling agent and titanic acid ester is 0.5～1: 1.Stir, again to the uniform mixing liquid that wherein adds a certain amount of alcohol, water and hydrochloric acid (being dissolved with the acid of water and the 0.5～1g of 5～10g in per 100 milliliters of Virahols) make it further hydrolysis (silane coupling agent that the amount that add entry this moment adds for the back and silicon ester mole number and two times, reach the theoretical amount that makes it hydrolysis; The amount of the acid that the amount of the acid that add this moment is added during with the titanic acid ester hydrolysis with should account for final coating total amount 0.5% in), reacted 10～12 hours, final adding accounts for the solidifying agent of total mass percentage composition 0～0.05% and accounts for the flow agent of total mass percentage composition 0～0.3%, obtains the vitreosol of proterties homogeneous.
The described titanic acid ester of top method is one or more in positive four butyl esters of metatitanic acid, titanium ethanolate, titanium propanolate, isopropyl titanate, the iso-butyl titanate; Alcoholic solution is the mixing solutions of ethanol, Virahol or ethanol and Virahol; Acid catalyst is one or more the mixing in hydrochloric acid, sulfuric acid, acetate, phosphoric acid, nitric acid, chlorsulfonic acid, tosic acid, hydroiodic acid HI, Hydrogen bromide, perchloric acid, the Periodic acid; Silicon ester is one or more in methyl silicate, tetraethoxy, silicic acid n-propyl, the isopropyl silicate; Silane coupling agent is γ-(2,3-epoxy third oxygen) propyl trimethoxy silicane (KH-560), Trimethoxy silane, triethoxyl silane, butyl trimethoxy silane, the butyl triethoxyl silane, γ-An Bingjisanyiyangjiguiwan (KH-550), γ-(methacryloxypropyl) propyl trimethoxy silicane (KH-570), γ-mercapto propyl group front three (second) TMOS (KH-580, KH-590), vinyl front three (second) TMOS (KH-151, KH-171), N-(β-aminoethyl)-γ-aminopropyl methyl dimethoxysilane (KH-602), N-(β-aminoethyl)-γ-An Bingjisanjiayangjiguiwan (KH-792), γ-An Bingjisanjiayangjiguiwan (KH-551), the mixture of one or more in γ-aminopropyl methyldiethoxysilane (DB-902); Solidifying agent is sodium acetate, cobalt naphthenate, Rinmann's green or acetylacetonate aluminium; Flow agent is polymethyl siloxane, polydimethylsiloxane, PSI or polyether-modified silicone oil.
Two, coating and curing molding:
The above-mentioned vitreosol that makes is coated onto device surface by methods such as spin coating, dip-coatings, placed at ambient temperature 10～20 minutes, treat that the surface forms even, smooth, transparent rete after, again it is transferred in the baking oven, be warming up to 135～150 ℃, kept 1～3 hour, reduce to room temperature then.So just, can obtain having optical coating certain physical strength, transparent.
The solid content of above-mentioned coating can be regulated between 10%～20%, and the quality percentage composition of titanic acid ester in coating can be regulated between 10～40%; The quality percentage composition of silane coupling agent can be regulated between 7%～17%; The quality percentage composition of silicon ester can be regulated between 0～6%; The consumption of inorganic acid catalyst accounts between total mass 0.3～0.5wt%.The consumption of solidifying agent and flow agent, can be according to the difference of raw material and the viscosity of final coating, between quality percentage composition 0%～0.05% and 0%～0.3%, regulate respectively, as use when titanic acid ester be titanium ethanolate the time, because its hydrolysis rate is than very fast, the consumption of solidifying agent will lack some when using butyl (tetra) titanate or not add; When the viscosity of coating is low or hope can not use flow agent, opposite its consumption that just suitably increases when obtaining thicker coating.For coating process, can adopt multiple coating method, the thickness of its floating coat can be regulated by the viscosity of spin speed, coating liquid.
As requested prepared coating spin coating or dip-coating being arrived on the surface-treated substrate (as silicon chip, sheet glass or plastics sheet), is example with the dip-coating sheet glass: sheet glass soaked 5～15 minutes with washing lotion earlier, and is clean with distilled water flushing then, oven dry.Sheet glass vertically is inserted in the coating, at the uniform velocity lifts lentamente, at room temperature placed 20 minutes, it is transferred in the baking oven, be warming up to 135～150 ℃, kept 1～3 hour, reduce to room temperature again, obtain the nano combined optical coating of water white homogeneous at last.
Description of drawings
Fig. 1: the transmission electron microscope photo of compound coating;
Fig. 2: the transmittance curve figure of coating;
Fig. 3: the atomic power photo of film surface.
The optical coating that obtains like this, we test and characterize its some structures and performance, are example with embodiment 3, and the transmission electron microscope of composite film characterizes as shown in Figure 1; The specific refractory power of solidifying the back rete can reach 1.6; The transmitance T% of 550nm place be 86.35% (rete is coated on the PC) as shown in Figure 2; Hardness reaches 2-3H; The AFM of film surface characterizes as Fig. 3, and nanophase is distinguished and loose evenly the surface finish height.
Below in conjunction with embodiment the present invention is further set forth.
Embodiment
Embodiment 1:
The preparation of titanium colloidal sol is dissolved in positive four butyl esters of 24g metatitanic acid in the Virahol of 6.28g, stirs, and note is done solution A; 1.28g water and 0.15g hydrochloric acid are dissolved in the 15.71g Virahol, mix, note is done solution B; Under stirring condition, B solution is poured among the A, reacted 12 hours.The mol ratio that obtains titanium and water like this is 1: 1 a titanium colloidal sol, and can store the long period.
Embodiment 2:
Experimental technique just replaces positive four butyl esters of 24g metatitanic acid with the 16g titanium ethanolate with embodiment 1, and the mol ratio that obtains titanic acid ester and water equally is 1: 1 a titanium colloidal sol, and can store the long period.
Embodiment 3: the preparation method one of titanium, silicon blend colloidal sol
Positive four butyl esters of 223.70g metatitanic acid are dissolved in the Virahol of 87.85g, stir; The 175.69g aqueous isopropanol that is dissolved with 11.75g water and 1.12g hydrochloric acid is added in the above-mentioned solution, reacted 10 hours; Again to wherein adding 119.58g γ-(2,3-epoxy third oxygen) propyl trimethoxy silicane, stirring makes it to mix, add the 363.75g aqueous isopropanol that is dissolved with 13.73g water and 1.67g hydrochloric acid at last, continue reaction 10 hours, to wherein adding 4g sodium acetate and 2g polydimethylsiloxane, obtain homogeneous, stable clear solution, wherein the quality percentage composition of each component is: positive four butyl esters 22.26% of metatitanic acid; γ-(2,3-epoxy third oxygen) propyl trimethoxy silicane 11.90%; Water 2.54%; Hydrochloric acid 0.28%; Sodium acetate 0.4%; Polydimethylsiloxane 0.2%; Virahol 62.43%.
Embodiment 4:
Experimental technique is with embodiment 2, just replace 119.58g γ-(2 with 116.90g γ-(methacryloxypropyl) propyl trimethoxy silicane, 3-epoxy third oxygen) propyl trimethoxy silicane, obtain homogeneous, stable clear solution, wherein the quality percentage composition of each component is: positive four butyl esters 22.32% of metatitanic acid; γ-(methacryloxypropyl) propyl trimethoxy silicane 11.66%; Water 2.54%; Hydrochloric acid 0.28%; Sodium acetate 0.4%; Polydimethylsiloxane 0.2%; Virahol 62.59%.
Embodiment 5: the preparation method two of titanium, silicon blend colloidal sol
74.57g positive four butyl esters of metatitanic acid are dissolved in the 48.80g Virahol, make it to mix, and 3.90g water and 0.66g hydrochloric acid are dissolved in the 48.80g Virahol, together add behind the mixing in the above-mentioned solution, react 12 hours; Again 36.67g γ-(2,3-epoxy third oxygen) propyl trimethoxy silicane and 8.58g tetraethoxy are added wherein, stir evenly; To wherein adding the 102.50g aqueous isopropanol that is dissolved with 5.67g water and 0.93g hydrochloric acid, reaction is 12 hours under the room temperature at last.The adding tetraethoxy has certain benefit to the raising of final film hardness, but along with the increase of add-on can make the shelf lives of coating descend to some extent, takes all factors into consideration, and the optimum mole ratio of silicon ester and titanic acid ester should be controlled at 0～0.6: 1.The quality percentage composition of each component is in this system: positive four butyl esters 22.52% of metatitanic acid; γ-(2,3-epoxy third oxygen) propyl trimethoxy silicane 11.08%; Tetraethoxy 2.59%; Water 2.89%; Hydrochloric acid 0.48%; Virahol 60.44%.
Embodiment 6: the preparation method three of titanium, silicon blend colloidal sol
Above-mentioned titanium, silicon blend colloidal sol all are to have prepared titanium colloidal sol earlier, and then based on it, again to wherein adding silane coupling agent and tetraethoxy, further again hydrolysis obtains.Here also can in preparation titanium colloidal sol, prepare silicon sol, then two components are mixed, obtain the coating of blend, promptly at first positive four butyl esters of 74.57g metatitanic acid are dissolved in the 48.40g Virahol, after mixing, will be dissolved with the 48.40g aqueous isopropanol of 3.90g water and 0.66g hydrochloric acid, add wherein, reacted 12 hours, and obtained titanium colloidal sol; Simultaneously 36.67g γ-(2,3-epoxy third oxygen) propyl trimethoxy silicane, 8.58g tetraethoxy, 5.67g water, 0.93g hydrochloric acid and 102.50g Virahol are mixed, reaction is 2 hours under the room temperature, obtains silicon sol.At last two colloidal sols were mixed, stir evenly in 10: 9 by volume～10: 27 and promptly get titanium, silicon blend colloidal sol.When above-mentioned two colloidal sols mixed in 1: 1 by volume, the quality percentage composition of each component was: positive four butyl esters 21.19% of metatitanic acid; γ-(2,3-epoxy third oxygen) propyl trimethoxy silicane 11.88%; Tetraethoxy 2.78%; Water 2.95%; Hydrochloric acid 0.49%; Virahol 60.71%.
Its viscosity of the coating that makes like this is generally at tens to tens centipoises, and along with the increase of time, viscosity also increases accordingly; Be not quite similar with amount different that silicon ester add according to titanic acid ester the storage period of coating, is example with embodiment 1, and under the situation that does not add silicon ester, can reach five months its storage period.
Claims (8)
1, a kind of high strength organic/inorganic nano composite transparent film layer material, the quality percentage composition of its component is:
A.10%～40% chemical formula is (I) titanic acid ester;
B.7%～17% chemical formula is (II) silane coupling agent;
C.0%～6% chemical formula is (III) silicon ester;
D.1%～4% water;
E.0～0.5% acid catalyst;
F.0～0.05% sodium acetate, cobalt naphthenate, Rinmann's green or acetylacetonate aluminium solidifying agent;
G.0～0.3% polymethyl siloxane, polydimethylsiloxane, PSI or polyether-modified silicone oil flow agent;
H.40%～65% alcoholic solvent;
R wherein
1For containing a alkyl to five carbon; R
2For containing a alkyl to two carbon; R
3For containing two alkyl that two keys, epoxide group, amino, sulfydryl, phenyl, carbonyl or above group occur with complex form that have to seven carbon.
2, high strength organic/inorganic nano composite transparent film layer preparation methods comprises that sol-gel method prepares the blend colloidal sol of titaniferous and silicon and obtains two steps of nano composite membrane layer material by coating and curing, is characterized in that:
(1) titanic acid ester is dissolved in the alcoholic solution, add 80～200g titanic acid ester in every 100ml alcoholic solution, after stirring makes and mixes, alcoholic solution with water and acid under continuing stirring condition joins in the above-mentioned solution, be dissolved with the acid of water and the 0.5～1g of 5～10g in per 100 milliliters of alcoholic solutions, reacted 1～12 hour, wherein the mol ratio of water and titanic acid ester is 0.5～1.5: 1, add silicon ester and silane coupling agent then, the mol ratio of silicon ester and titanic acid ester is 0～1: 1; The mol ratio of silane coupling agent and titanic acid ester is 0.5～1: 1; Stir, again to wherein adding alcohol, the uniform mixing liquid of water and hydrochloric acid, the amount that adds entry be silane coupling agent and silicon ester mole number and 2 times, the amount of the acid that the amount that adds acid is added during with the titanic acid ester hydrolysis with account for final coating total amount 0.5% in, reacted 10～12 hours, the final sodium acetate that accounts for total mass percentage composition 0～0.05% that adds, cobalt naphthenate, Rinmann's green or acetylacetonate aluminium solidifying agent and the polymethyl siloxane that accounts for total mass percentage composition 0～0.3%, polydimethylsiloxane, PSI or polyether-modified silicone oil flow agent obtain the vitreosol of proterties homogeneous;
(2) method of the above-mentioned vitreosol that makes by spin coating, dip-coating is coated onto device surface, placed at ambient temperature 10～20 minutes, after treating that the surface forms even, smooth, transparent rete, again it is transferred in the baking oven, be warming up to 135～150 ℃, kept 1～3 hour, and reduced to room temperature then, obtain having optical coating certain physical strength, transparent at device surface.
3, high strength organic/inorganic nano composite transparent film layer preparation methods as claimed in claim 2 is characterized in that: titanic acid ester is one or more in positive four butyl esters of metatitanic acid, titanium ethanolate, titanium propanolate, isopropyl titanate, the iso-butyl titanate.
4, high strength organic/inorganic nano composite transparent film layer preparation methods as claimed in claim 2, it is characterized in that: silane coupling agent is γ-(2,3-epoxy third oxygen) propyl trimethoxy silicane, Trimethoxy silane, triethoxyl silane, butyl trimethoxy silane, the butyl triethoxyl silane, γ-An Bingjisanyiyangjiguiwan, γ-(methacryloxypropyl) propyl trimethoxy silicane, γ-mercaptopropyl trimethoxysilane, gamma-mercaptopropyltriethoxysilane, vinyltrimethoxy silane, vinyltriethoxysilane, N-(β-aminoethyl)-γ-aminopropyl methyl dimethoxysilane, N-(β-aminoethyl)-γ-An Bingjisanjiayangjiguiwan, γ-An Bingjisanjiayangjiguiwan, the mixture of one or more in γ-aminopropyl methyldiethoxysilane.
5, high strength organic/inorganic nano composite transparent film layer preparation methods as claimed in claim 2 is characterized in that: silicon ester is one or more in methyl silicate, tetraethoxy, silicic acid n-propyl, the isopropyl silicate.
6, high strength organic/inorganic nano composite transparent film layer preparation methods as claimed in claim 2 is characterized in that: acid catalyst is one or more the mixing in hydrochloric acid, sulfuric acid, acetate, phosphoric acid, nitric acid, chlorsulfonic acid, tosic acid, hydroiodic acid HI, Hydrogen bromide, perchloric acid, the Periodic acid.
7, high strength organic/inorganic nano composite transparent film layer preparation methods as claimed in claim 2 is characterized in that: alcoholic solution is the mixing solutions of ethanol, Virahol or ethanol and Virahol.
8, the high strength organic/inorganic nano composite transparent film layer material that any one described method prepares in the claim 2～7 is in the application of optical material surface.
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| JPH08134152A (en) * | 1994-11-08 | 1996-05-28 | Toyobo Co Ltd | Cationic modified polyester-based resin |
| CN1341542A (en) * | 2001-10-18 | 2002-03-27 | 郑秀娣 | Medicine bottle block isolation film |
| CN1358791A (en) * | 2000-12-12 | 2002-07-17 | 海尔科化工程塑料国家工程研究中心有限公司 | Polymer organic nano composite ocmposition for making agriculture greenhouse film and preparation process thereof |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| JPH08134152A (en) * | 1994-11-08 | 1996-05-28 | Toyobo Co Ltd | Cationic modified polyester-based resin |
| CN1358791A (en) * | 2000-12-12 | 2002-07-17 | 海尔科化工程塑料国家工程研究中心有限公司 | Polymer organic nano composite ocmposition for making agriculture greenhouse film and preparation process thereof |
| CN1341542A (en) * | 2001-10-18 | 2002-03-27 | 郑秀娣 | Medicine bottle block isolation film |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106366906A (en) * | 2016-08-23 | 2017-02-01 | 杭州国为光伏技术有限公司 | Solar photovoltaic glass antireflection coating and preparation method thereof |
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| CN1699488A (en) | 2005-11-23 |
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