WO1992008723A1 - Fully alkoxysilane-functionalized aliphatic polyamine compounds - Google Patents
Fully alkoxysilane-functionalized aliphatic polyamine compounds Download PDFInfo
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- WO1992008723A1 WO1992008723A1 PCT/US1991/008597 US9108597W WO9208723A1 WO 1992008723 A1 WO1992008723 A1 WO 1992008723A1 US 9108597 W US9108597 W US 9108597W WO 9208723 A1 WO9208723 A1 WO 9208723A1
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- Prior art keywords
- alkoxysilane
- functionalized
- aliphatic polyamine
- fully
- compound
- Prior art date
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Classifications
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic System
- C07F7/02—Silicon compounds
- C07F7/08—Compounds having one or more C—Si linkages
- C07F7/18—Compounds having one or more C—Si linkages as well as one or more C—O—Si linkages
- C07F7/1804—Compounds having Si-O-C linkages
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/31504—Composite [nonstructural laminate]
- Y10T428/31507—Of polycarbonate
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/31504—Composite [nonstructural laminate]
- Y10T428/31678—Of metal
- Y10T428/31714—Next to natural gum, natural oil, rosin, lac or wax
Definitions
- U.S. Patent No. 3,847,860 shows compounds in whioh the amino groups are not fully functionalized with alkoxysilane groups for use in relatively minor amount (0.02%-3%) in. a cold setting or thermosetting adhesive.
- U.S. Patent No. 4,448,694 also shows compounds in which less than all the amino groups are functionalized with alkoxysilane moieties. These compounds are described for use as chelants for metals after being immobilized on an inorganic solid.
- the present invention is directed to a novel class of fully alkoxysilane-functionalized aliphatic polyamine compounds that are useful, for example, as the predominant reagent in the aforementioned type of sol-gel reactible compositions as sources of the organic moieties (or domains) in organic/inorganic hybrid materials.
- This class of reagent can be cured, without the additional presence of a metal alkoxide, such as a tetralkylsilicate or zirconium alkoxide, to form hybrid organic/inorganic materials generally analogous to the previously described materials reported in the Huang et al. publications described before.
- a metal alkoxide such as a tetralkylsilicate or zirconium alkoxide
- Fig. 1 is a graphical representation of the wear resistance for a 30% zirconium isopropoxide-70% triethoxysilane-capped diethylenetriamine (DETA) material when cured at 145°C and when such a cured material is allowed to remain in water for forty-eight hours at 60°C then dried and tested;
- DETA triethoxysilane-capped diethylenetriamine
- Fig. 2 is a plot of the wear of a series of compositions, such as tested in Fig. 1, on polycarbonate resin showing the effect of different curing temperatures for the coating;
- Fig. 3. is a plot of the effect of triethoxysilane functionality for a coating derived from a series of alkoxy silane-functionalized aliphatic polyamine compounds.
- the term "fully alkoxysilane- functionalized” is intended to connote that the number of alkoxysilane moieties and reacted amine moieties in the functionalized product are substantially equal. In other words, substantially all the amine groups (-NH or -NH 2 if ⁇ » terminal) have been functionalized with alkoxysilane groups. 5
- the aliphatic polyamine compounds which are appropriately 10 functionalized by means of the present invention may have the formula:
- n can; be 2, 3 or 4 and m can vary from 1 to about 30.
- a particularly preferred compound has m and n both equal to 2 15 and is a triamine.
- Another aliphatic polyamine compound useful in accordance with the present invention has the formula:
- A is the amine-reactive function
- L is a linking group
- R is lower alkyl.
- One class of compound which can be used are the isocyanatoalkylalkoxysilanes wherein the isocyanato moiety reacts with the amine functions in the polyamine j 30 forming urethane bonds (e.g., compounds of the formula
- the functionalized aliphatic polyamine compounds described herein can be used to form coatings for wear- resistance applications in conjunction with metal alkoxides or, surprisingly, alone to form organic/inorganic hybrid materials.
- the aliphatic polyamine compounds are present in predominant amount in the compositions used to form the organic/inorganic hybrid materials previously described.
- the amount of aliphatic polyamine compound can constitute about 70% or more of such a composition, on a weight basis, and may constitute substantially the entire content of the composition.
- the alkoxysilane functionalized polyamine compounds are converted to the desired organic/inorganic hybrid materials by conventional sol-gel hydrolysis and condensation procedures in which the alkoxysilane functionalities are treated, usually in the presence of acidic catalysis to dehydrolytically cocondense such alkoxysilane groups into silica rich domains.
- the curing of the desired materials can be accelerated using microwave treatment.
- this substrate can be treated to a plasma pretreatment (e.g., 50W to 100W at times of from several seconds up to about 30 minutes) to- enhance the adhesion of such a coating.
- This Example illustrates preparation of a triethoxy ⁇ silane-capped diethylenetriamine (DETA) .
- This Example illustrates preparation of a Ti-DETA sol for use in forming a wear resistant coating.
- This Example illustrates preparation of a Zr-DETA sol for coatings.
- a sheet of isotactic poly (4-methyl-l-pentene) termed "PMP", which was 3.5 by 3.5 inches square and 1/16 inch in thickness was wiped with ethanol soaked KIMWIPE fabric. The sheets were then dried with the same dry fabric to insure that the surface was dry. Next, this sample was placed in a plasma chamber and pumping was commenced to reach a vacuum of less than 2 torr. Before turning on the plasma, the gas line was flushed for five minutes with oxygen. Then, the plasma source was turned on for five minutes.
- Example 3 illustrates formation of the Zr-DETA sol.
- This Example and Fig. 1 illustrate the results of a visible light measure transmission test on the wear area of a coated polycarbonate sample that had undergone a Taber abrasion test at a load of 250 gm on each wheel using ASTM Taber wheel. CS10.
- the light beam was 0.4 x 10 mm and the wavelength was 420 nm.
- the first coating was formed by curing, at 145°C, a 30 wt% zirconium isopropoxide-70% triethoxysilane-functionalized coating made by the procedure of Example 3, above.
- the second coating tested was the previously described cured coating which had been allowed to remain in hot (60°C) water for forty-eight hours followed by drying and testing.
- Fig. 2 illustrates the wear performance of a coating of the compositional type described in Example 6 which had been cured at 80°C, 100°C, and 146°C, respectively, for three hours.. Better wear performance was observed for higher curing temperatures with all being significantly better than an uncoated polycarbonate control.
- Fig. 3 shows the performance of the wear performance of three trialkoxysilane-functionalized monomers as set .forth below:
- Coatings containing all three as the sole component showed significantly better wear than a polycarbonate (pc) control.
Abstract
Fully alkoxysilane-functionalized aliphatic polyamine compounds (e.g., fully functionalized dialkylenetriamine compounds) can be formed by reacting a dialkylenetriamine (e.g., diethylenetriamine) with a compound comprising an amine-reactive group and an alkoxysilane group (e.g., an isocyanatoalkylalkoxysilane). These functionalized compounds find utility as the predominant component in forming organic/inorganic hybrid materials via sol-gel processing.
Description
FULLY ALKOXYSILANE-FUNCTIONALIZED ALIPHATIC POLYAMINE COMPOUNDS
BACKGROUND OF THE INVENTION
It is known to use sol-gel hydrolyzation/condensation procedures with a reaction mixture comprising one or more metal alkoxide(s) and a trialkoxysilane-functionalized organic reagent to form organic/inorganic hybrid materials having interesting properties. Some recent publications which are representative of work in this area include: Huang, H. et al., Macro olecules, 1987 20(6), 1322; Huang, H. et al., ACS
Symposium Series, 1987, 360, 354; and Huang, H. et al., Polym. Bull., 1987, 18, 455. There is interest in expanding' the area of known organic/inorganic hybrid systems to novel combinations. Certain disclosures also exist in the art regarding alkoxysilane-functionalized aliphatic polyamine compounds:
U.S. Patent No. 3,847,860 shows compounds in whioh the amino groups are not fully functionalized with alkoxysilane groups for use in relatively minor amount (0.02%-3%) in. a cold setting or thermosetting adhesive.
U.S. Patent No. 4,448,694 also shows compounds in which less than all the amino groups are functionalized with alkoxysilane moieties. These compounds are described for use as chelants for metals after being immobilized on an inorganic solid.
U.S. Patent No. 4,791,214 and British Patent No. 1,458,533 show "hybrid" compounds containing an alkoxysilane- functionalized amine group and either a glycidyl group or an N-substituted amino group. These compounds are used as bonding agents or adhesion promoters in resin compositions or organic adhesives.
SUMMARY OF THE INVENTION
The present invention is directed to a novel class of fully alkoxysilane-functionalized aliphatic polyamine compounds that are useful, for example, as the predominant reagent in the aforementioned type of sol-gel reactible compositions as sources of the organic moieties (or domains) in organic/inorganic hybrid materials.
This class of reagent can be cured, without the additional presence of a metal alkoxide, such as a tetralkylsilicate or zirconium alkoxide, to form hybrid organic/inorganic materials generally analogous to the previously described materials reported in the Huang et al. publications described before.
DESCRIPTION OF THE DRAWINGS
The Drawings enclosed herewith as part of the present invention illustrate certain embodiments of the invention wherein:
Fig. 1 is a graphical representation of the wear resistance for a 30% zirconium isopropoxide-70% triethoxysilane-capped diethylenetriamine (DETA) material when cured at 145°C and when such a cured material is allowed to remain in water for forty-eight hours at 60°C then dried and tested;
Fig. 2 is a plot of the wear of a series of compositions, such as tested in Fig. 1, on polycarbonate resin showing the effect of different curing temperatures for the coating; and
Fig. 3. is a plot of the effect of triethoxysilane functionality for a coating derived from a series of alkoxy silane-functionalized aliphatic polyamine compounds.
DETAILED DESCRIPTION OF THE INVENTION
As used herein the term "fully alkoxysilane- functionalized" is intended to connote that the number of
alkoxysilane moieties and reacted amine moieties in the functionalized product are substantially equal. In other words, substantially all the amine groups (-NH or -NH2 if ■» terminal) have been functionalized with alkoxysilane groups. 5 The term "aliphatic" as used herein is intended to cover moieties which include alkylene groups (CH2) , and, in the case of the diamine compound shown in Example 8, below, the group >C=0.
The aliphatic polyamine compounds which are appropriately 10 functionalized by means of the present invention may have the formula:
where n can; be 2, 3 or 4 and m can vary from 1 to about 30. A particularly preferred compound has m and n both equal to 2 15 and is a triamine. Another aliphatic polyamine compound useful in accordance with the present invention has the formula:
H2N-C(0)-NH2.
The foregoing type of compounds are functionalized by 20 reaction with a compound having an amine-reactive group ("A") at one end (such as an isocyanate group) and an alkoxysilane group at the other. In the case of trialkoxysilane-containing compounds, which are preferred, this compound for use in functionalizing the polyamine will have the general structure:
25 A - L - Si(OR)3
where A is the amine-reactive function, L is a linking group, and R is lower alkyl. One class of compound which can be used are the isocyanatoalkylalkoxysilanes wherein the isocyanato moiety reacts with the amine functions in the polyamine j30 forming urethane bonds (e.g., compounds of the formula
(RO)3Si(CH2)mN=C=0, where R is a lower alkyl and can vary from 1 to 4) .
The functionalized aliphatic polyamine compounds described herein can be used to form coatings for wear- resistance applications in conjunction with metal alkoxides or, surprisingly, alone to form organic/inorganic hybrid materials. In accordance with the present invention, the aliphatic polyamine compounds are present in predominant amount in the compositions used to form the organic/inorganic hybrid materials previously described. Generally, the amount of aliphatic polyamine compound can constitute about 70% or more of such a composition, on a weight basis, and may constitute substantially the entire content of the composition. The alkoxysilane functionalized polyamine compounds are converted to the desired organic/inorganic hybrid materials by conventional sol-gel hydrolysis and condensation procedures in which the alkoxysilane functionalities are treated, usually in the presence of acidic catalysis to dehydrolytically cocondense such alkoxysilane groups into silica rich domains.
If desired, the curing of the desired materials can be accelerated using microwave treatment. In addition, if the cured coating of the alkoxysilane-functionalized aliphatic polyamine is to be placed on a polymeric substrate, this substrate can be treated to a plasma pretreatment (e.g., 50W to 100W at times of from several seconds up to about 30 minutes) to- enhance the adhesion of such a coating.
The present invention is illustrated by the Examples which follow.
EXAMPLE 1
This Example illustrates preparation of a triethoxy¬ silane-capped diethylenetriamine (DETA) .
First, 5 gm of DETA was mixed with.20 g of isopropanol, Then, 40 gm of 3-isocyanatopropyltriethoxysilane was slowly added to this solution and was stirred for three hours to yield the desired product which was of the formula:
O C IINH(CH2)3Si(OC2H5)3
(H5C20)3Si(CH2)3NHC(0)NH(CH2)2N(CH2)2NHC(0)NH(CH2)3Si(OC2H5)3
EXAMPLE 2
This Example illustrates preparation of a Ti-DETA sol for use in forming a wear resistant coating.
First, 0.1 ml of HC1 (ION), 0.6 ml of H20, and 5 gm of isopropanol" were mixed together in a flask. Then the alcohol solution was transferred to an addition funnel. Next, the HCl-containing isopropanol was slowly added to a polypropylene flask which contained 5 gm of titanium tetraisopropoxide'. In order to avoid local inhomogeneity, a slow addition rate of the HCl-containing isopropanol solution and a fast stirring rate were utilized. This procedure developed a clear titania sol (pH = 2.2). Then, a solution containing an appropriate amount of triethoxysilane-capped DETA was mixed with the titanium sol and stirring was continued for twenty-seven hours to obtain a viscous homogeneous system for coating on polymeric surfaces (e.g. polycarbonate, polyi ide, etc.) by either a dip or spin coating procedure. After drying in an oven at 60°C for four hours, these coated samples were annealed
(cured) at a minimum of 120°C.
EXAMPLE 3
This Example illustrates preparation of a Zr-DETA sol for coatings.
First, 0.1 ml of HC1 (ION), and 5 gm of isopropanol were mixed together in a flask. Then the solution was transferred to an addition funnel. Next, the HCl-containing isopropanol was slowly added to a polypropylene flask which contained 5 gm of zirconium tetraisopropoxide. In order to avoid local inhomogeneity, a slow addition rate of the HCl-containing isopropanol solution was maintained and a fast stirring rate was utilized. This procedure developed a clear zirconia sol (pH = 2.2). Then, a solution containing an appropriate amount of triethoxysilane-capped DETA was mixed with the zirconium sol and stirring was continued for twenty-seven hours to obtain a viscous homogeneous system for coatings on polymeric surfaces (e g. polycarbonate, polyimide, etc.) by either a dip or spin coating procedure. After drying in an oven at 60°C for four hours, these coated samples were annealed (cured) at a minimum of 120°C.
EXAMPLE 4
A sheet of isotactic poly (4-methyl-l-pentene) , termed "PMP", which was 3.5 by 3.5 inches square and 1/16 inch in thickness was wiped with ethanol soaked KIMWIPE fabric. The sheets were then dried with the same dry fabric to insure that the surface was dry. Next, this sample was placed in a plasma chamber and pumping was commenced to reach a vacuum of less than 2 torr. Before turning on the plasma, the gas line was flushed for five minutes with oxygen. Then, the plasma source was turned on for five minutes. Following the plasma treatment, the polymer substrate was coated with a zirconium- containing organic/inorganic based sol which also contained moieties derived from the triethoxysilane-functionalized diethylenetriamine of Example 1. Example 3 illustrates formation of the Zr-DETA sol.
The following results were obtained in regard to abrasion resistance using the type of test described in Example 6 for a 30 wt% zirconium isopropoxide-70% functionalized DETA-derived coating which was cured at 145°C on plasma pretreated PMP:
Wheel PMP PMP with
Cycles Alone Cured Coating
10 76.1 + 3.3 98.3 ± 0.3
50 67.6 + 2.5 96.3 + 0.5
EXAMPLE 5
This Example reports data analogous to that of Example 6 for a hybrid coating formed from 30 wt% zirconium isopropoxide and 70 wt% trialkoxysilane-functionalized diethylene triamine on polycarbonate using a peel adhesion tape test using 3M-610 brand tape,* the tape being applied to the substrate with finger pressure to insure good contact with essentially no dwell time, at a 1 cm/ in peeling rate with the adhesion (W) being calculated by the formula W = P(l-cos θ) with P being the peeling force per unit width and θ the peeling angle (180°) . — Adhesion (N/m)
Pretreatment/Cure Temp High Low
None/ 145°C . 128 122
O2-l'00W-5 min. /145°C . 139 131
EXAMPLE 6
This Example and Fig. 1 illustrate the results of a visible light measure transmission test on the wear area of a coated polycarbonate sample that had undergone a Taber abrasion test at a load of 250 gm on each wheel using ASTM Taber wheel. CS10. The light beam was 0.4 x 10 mm and the wavelength was 420 nm. The first coating was formed by curing, at 145°C, a 30 wt% zirconium isopropoxide-70% triethoxysilane-functionalized coating made by the procedure of Example 3, above. The second coating tested was the previously described cured coating which had been allowed to remain in hot (60°C) water for forty-eight hours followed by drying and testing.
Little- difference was noted in the wear behavior of the two samples as shown in Fig. 1.
EXAMPLE 7
Fig. 2 illustrates the wear performance of a coating of the compositional type described in Example 6 which had been cured at 80°C, 100°C, and 146°C, respectively, for three hours.. Better wear performance was observed for higher curing temperatures with all being significantly better than an uncoated polycarbonate control.
EXAMPLE 8
Fig. 3 shows the performance of the wear performance of three trialkoxysilane-functionalized monomers as set .forth below:
0
II f -= 2: X-NH-C-NH-X
f = 3: X-NH-(CH2)2-NX-(CH2)2-NH-X
f = 4: X-NH-(CH2)3-NX-CH2-CH2-NX-(CH2)3-NH-X
0
II where X = -C-NH-(CH2)3-Si(OC2H5)3
Coatings containing all three as the sole component (no metal alkoxide was present) showed significantly better wear than a polycarbonate (pc) control.
The foregoing are intended to illustrate certain., embodiments of the invention and should not therefore be construed in a limiting sense. The scope of protection sought is set forth in the claims which follow.
Claims
1. A fully alkoxysilane-functionalized aliphatic polyamine compound.
2. A compound as claimed in Claim 1 formed by reaction of an aliphatic polyamine with a compound comprising an amine- reactive group and an alkoxysilane group.
3. A compound as claimed in Claim 2 wherein the aliphatic polyamine is of the formula:
^-[(CH^NE^-H where m can range from 1 to about 30 and n can be 2, *3 or 4.
4. A compound as claimed in Claim 3 wherein the aliphatic polyamine is a dialkylenetriamine and is reacted with an isocyanatoalkylalkoxysilane.
5. A compound as claimed in Claim 4 wherein the dialkylenetriamine is diethylenetriamine.
6. A fully alkoxysilane-functionalized dialkylene¬ triamine formed by reaction of diethylenetriamine and 3- isocyanatopropyltriethoxysilane.
7. Hybrid organic/inorganic materials formed by curing a predominant' amount of any of the compounds of Claim 1.
8. Materials as claimed in Claim 7 wherein microwave curing is used.
9. Materials as claimed in Claim 7 formed by curing a fully alkoxysilane-functionalized dialkylenetriamine formed by reaction of a diethylenetriamine and an isocyanatoalkyl¬ alkoxysilane.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
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US08/050,377 US5371261A (en) | 1990-11-19 | 1991-11-18 | Fully alkoxysilane-functionalized aliphatic polyamine compounds |
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US615,569 | 1984-05-31 | ||
US61553990A | 1990-11-19 | 1990-11-19 | |
US07/615,569 US5316855A (en) | 1990-07-13 | 1990-11-19 | High abrasion resistance coating materials from organic/inorganic hybrid materials produced by the sol-gel method |
US615,539 | 1990-11-19 |
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WO1992008723A1 true WO1992008723A1 (en) | 1992-05-29 |
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PCT/US1991/008597 WO1992008723A1 (en) | 1990-11-19 | 1991-11-18 | Fully alkoxysilane-functionalized aliphatic polyamine compounds |
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Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE19910876A1 (en) * | 1999-03-11 | 2000-10-05 | Fraunhofer Ges Forschung | Process for the production of a weather-resistant coating |
JP2010030993A (en) * | 2008-06-24 | 2010-02-12 | Hoya Corp | Functional silane compound, coating liquid and manufacturing method of plastic lens |
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US5266715A (en) * | 1991-03-06 | 1993-11-30 | Ciba-Geigy Corporation | Glass coating with improved adhesion and weather resistance |
KR19990022348A (en) * | 1995-06-05 | 1999-03-25 | 미리암 디. 메코너헤이 | Coating Composition Containing Silane Functional Group |
US6072018A (en) * | 1996-09-30 | 2000-06-06 | Virginia Tech Intellectual Properties, Inc. | High abrasion resistant coating material |
US5750596A (en) * | 1996-12-23 | 1998-05-12 | E. I. Du Pont De Nemours And Company | Cathodic electrocoating compositions containing an anticrater agent |
US5948927A (en) * | 1998-04-01 | 1999-09-07 | Witco Corporation | Bis-silyl tertiary amines |
DE19846099C2 (en) * | 1998-10-07 | 2000-08-24 | Bayer Ag | Amine functional urea alkoxy silanes, a process for their preparation and their use |
KR100649511B1 (en) * | 1999-04-23 | 2006-11-24 | 위트코 코포레이션 | Bis-Silyl Tertiary Amines |
US6506921B1 (en) * | 2001-06-29 | 2003-01-14 | Virginia Tech Intellectual Properties, Inc. | Amine compounds and curable compositions derived therefrom |
GB2431173B (en) * | 2005-09-15 | 2010-01-13 | Alexium Ltd | Method for attachment of silicon-containing compounds to a surface |
US20100305289A1 (en) * | 2009-05-29 | 2010-12-02 | Jiang Dayue D | Hybrid composition and membrane based on silylated hydrophilic polymer |
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US3856756A (en) * | 1971-11-06 | 1974-12-24 | Bayer Ag | Silyl substituted urea derivatives and a process for their preparation |
US3940370A (en) * | 1975-03-31 | 1976-02-24 | The United States Of America As Represented By The Secretary Of The Army | Method of making polyureas |
US4448694A (en) * | 1981-09-04 | 1984-05-15 | Dow Corning Corporation | Metal extraction from solution and immobilized chelating agents used therefor |
US4719262A (en) * | 1986-03-26 | 1988-01-12 | Dow Corning Corporation | Organosilicon primer compositions |
US4746366A (en) * | 1984-02-27 | 1988-05-24 | Fraunhofer-Gesellschaft Zur Forderung Der Angewandten Forschung E.V. | Process and lacquer for the production of scratch-resistant coatings |
-
1991
- 1991-11-18 WO PCT/US1991/008597 patent/WO1992008723A1/en active Application Filing
- 1991-11-18 US US08/050,377 patent/US5371261A/en not_active Expired - Fee Related
Patent Citations (5)
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US3856756A (en) * | 1971-11-06 | 1974-12-24 | Bayer Ag | Silyl substituted urea derivatives and a process for their preparation |
US3940370A (en) * | 1975-03-31 | 1976-02-24 | The United States Of America As Represented By The Secretary Of The Army | Method of making polyureas |
US4448694A (en) * | 1981-09-04 | 1984-05-15 | Dow Corning Corporation | Metal extraction from solution and immobilized chelating agents used therefor |
US4746366A (en) * | 1984-02-27 | 1988-05-24 | Fraunhofer-Gesellschaft Zur Forderung Der Angewandten Forschung E.V. | Process and lacquer for the production of scratch-resistant coatings |
US4719262A (en) * | 1986-03-26 | 1988-01-12 | Dow Corning Corporation | Organosilicon primer compositions |
Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
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DE19910876A1 (en) * | 1999-03-11 | 2000-10-05 | Fraunhofer Ges Forschung | Process for the production of a weather-resistant coating |
DE19910876C2 (en) * | 1999-03-11 | 2003-07-17 | Fraunhofer Ges Forschung | Process for producing a weather-resistant coating |
JP2010030993A (en) * | 2008-06-24 | 2010-02-12 | Hoya Corp | Functional silane compound, coating liquid and manufacturing method of plastic lens |
EP2138501A3 (en) * | 2008-06-24 | 2010-03-03 | Hoya Corporation | Functional silane compound, coating solution, and method for manufacturing plastic lens |
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US5371261A (en) | 1994-12-06 |
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