WO1998054127A1 - Iminodiacetonitrile mirror back coating corrosion inhibitor - Google Patents
Iminodiacetonitrile mirror back coating corrosion inhibitor Download PDFInfo
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- WO1998054127A1 WO1998054127A1 PCT/US1998/001950 US9801950W WO9854127A1 WO 1998054127 A1 WO1998054127 A1 WO 1998054127A1 US 9801950 W US9801950 W US 9801950W WO 9854127 A1 WO9854127 A1 WO 9854127A1
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- Prior art keywords
- corrosion inhibitor
- composition
- organic resin
- resins
- coating system
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Classifications
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C255/00—Carboxylic acid nitriles
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/08—Anti-corrosive paints
- C09D5/082—Anti-corrosive paints characterised by the anti-corrosive pigment
- C09D5/086—Organic or non-macromolecular compounds
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B17/00—Layered products essentially comprising sheet glass, or glass, slag, or like fibres
- B32B17/06—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
-
- 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]
- Y10T428/31511—Of epoxy ether
- Y10T428/31529—Next to metal
-
- 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]
- Y10T428/31551—Of polyamidoester [polyurethane, polyisocyanate, polycarbamate, etc.]
- Y10T428/31605—Next to free metal
-
- 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
- Y10T428/31681—Next to polyester, polyamide or polyimide [e.g., alkyd, glue, or nylon, etc.]
-
- 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
- Y10T428/31688—Next to aldehyde or ketone condensation product
-
- 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
- Y10T428/31692—Next to addition polymer from unsaturated monomers
-
- 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
- This invention relates to a coating for use on mirror backs, and, in particular, to a lead-free organic coating containing a di- or tri- nitrile containing compound, preferably iminodiacetonitrile or nitrilotriacetonitrile, which coating is applied to the metallic film layer on the back of a mirror to protect the metallic layer and prevent corrosion thereof.
- Typical mirrors are made of a glass sheet and a thin layer of a metallic film applied to the back of the sheet.
- the metallic film layer adhered directly to the glass is usually a film of silver, although other metallic films may also be used, such as copper.
- silver is used as the primary reflective layer, it is commonly protected by a second metallic film layer of copper or some other metal.
- 5,389,301 to Fenzi discloses a lead-free anticorrosive resin formulation containing cyanoacetylurea for protecting mirror backs.
- Japanese patents 531 1485, 531 1492 and 531 1495 show processes for treating a noble metal, including silver, by electrolyzing the metal in an aqueous solution containing an organic compound such as an imino compound or other nitrogen containing compounds such as EDTA to increase the corrosion resistance of the noble metal.
- U.S. Patent No. 4,543,215 to Brunnmueller et al. discloses novel iminodiacetonitriles and their preparation. It is disclosed that the nitriles are useful as starting materials for the preparation of dyes, fungicides and other materials including anticorrosion agents.
- composition comprising a paint or other fluid organic resin coating system capable of being applied as a film and hardened to form a protective layer, the resin additionally containing a corrosion inhibitor containing a di- and/or tri- nitrile containing compound.
- Preferred compounds may be defined according to the formula:
- R', R 2 , R 3 and R 4 can be identical or different and are each hydrogen, an aliphatic, cycloaliphatic, araliphatic or aromatic radical, and can be substituted or unsubstituted;
- A is hydrogen or Cz-CR 5 R°CN;
- X, Y and Z are independently selected from 0-5; and
- R 5 and R 6 are as defined for R 1 , R 2 , R 3 and R 4 above.
- a preferred additive is iminodiacetonitrile (IDAN) where A is hydrogen; R 1 , R 2 , R 3 and R 4 are each hydrogen; and X and Y are 0.
- IDAN iminodiacetonitrile
- the term "hardened” is used to mean that the coating system can be cured if the resins are thermosetting or dried if the resins are thermoplastic.
- the organic resins employed in the coating system can be any thermoplastic or thermosetting resin suitable for coating a metallic layer such as that found on the back of a mirror.
- Exemplary resins include alkyd resins, acrylic resins, acrylic and other modified alkyd resins, polyesters, urethane oils, vinyl halide polymers or copolymers, oleoresinous varnishes, nitrocellulose compositions, phenol-formaldehyde resins varnishes and epoxy resins.
- the resin is an alkyd or modified, e.g., short oil, alkyd resin or a phenolic alkyd resin system.
- the corrosion inhibitor compounds may be present in an amount, by weight, about 0.1 to 20%, preferably about 0.5 to 10%, based on the organic resin coating system (including resins, solvents and other additives).
- the organic resin coating system should be essentially free of lead and lead salts, either as corrosion inhibitors or other components.
- a mirror having a glass substrate layer and a metallic film layer thereover should be obtained, after which the fluid organic resin coating system containing one or more of the aforementioned corrosion inhibitors is applied over the metallic film layer.
- the organic resin coating system is then hardened to produce a protective coating layer over the metallic layer.
- the preferred mirror article contains, in sequence, the glass substrate, the metallic film layer(s) which may be silver and/or copper or some other metal, and the hardened organic resin system as described above.
- the mirror has a thin layer of silver film attached directly to the glass layer as the reflective layer, a thin protective layer of a copper film over the silver layer, and the hardened coating system described above directly over the copper film layer as the primary corrosion inhibitor layer.
- Other articles having metallic surfaces may be protected by the non-lead corrosion inhibitor-containing resin systems described above as well.
- the mirrors and metallic film layers on which the coating of the present invention has been found to be particularly useful are those in which one or more layers of silver and/or copper films have been applied to a glass substrate, although the coating may also be useful over film layers of other metals as well.
- the mirror consists of a substrate layer of glass and a layer of reflective silver or copper film applied to the rear surface of the glass. If a silver film is applied directly to the glass, it is common to apply a second film layer of copper over the silver to provide protection against corrosion and physical damage to the silver layer.
- Such metallic film layers are relatively thin and on the order of approximately 700 angstroms for the silver layer and approximately 210 angstroms for the copper layer.
- Such mirrors may be made by any of the known processes in the prior art.
- the glass surface to which the metallic film layer is to be applied is usually lightly polished and cleaned and thereafter sensitized with an aqueous stannous chloride solution.
- the silver film layer may be deposited on the sensitized glass surface by one of many methods such as that described in U.S. Pat. No. 4,737,188 to Bahls, the disclosure of which is hereby incorporated by reference, in which an N- methylglucamine reducer is utilized with ammoniacal silver nitrate and a strong base such as sodium hydroxide in aqueous solution which solution is sprayed on and combined at the sensitized glass surface to deposit the silver film.
- a copper film may be applied to and over the silver film by any one of a variety of prior art procedures such as a galvanic process which utilizes aqueous suspensions of iron and copper powder or by the disproportionation of cuprous ions on the silver surface.
- a galvanic process which utilizes aqueous suspensions of iron and copper powder or by the disproportionation of cuprous ions on the silver surface.
- the latter process is described in U.S. Pat. No. 3,963,842 to Sivertz et al., the disclosure of which is hereby incorporated by reference.
- a cupric tetraammonium sulfate solution is reduced by combination with hydroxylamine sulfate and thereafter reacted with an activator-modifier such as a mixture of citric acid or ethylene diamine and H S0 4 to form a copper film on the silvered surface.
- an activator-modifier such as a mixture of citric acid or ethylene diamine and H S0 4
- thermosetting resins contemplated in use in the present invention are those that require heat to effect curing, such as by infrared heating, although room temperature air drying resins are also included.
- Suitable resins include alkyd resins, acrylic resins, polyesters, urethane oils, vinyl halide polymers or copolymers, oleoresinous varnishes, nitrocellulose compositions, phenol-formaldehyde resin varnishes, epoxy resins, or combinations of such resins.
- the resins employed in the present invention are alkyd or modified alkyd resins such as acrylic-alkyd copolymers in combination with a solvent, and other additives such as a pigment, if desired, to produce a resin coating system.
- Such alkyd resin systems may be modified with acrylics, urethanes and polyurethanes, phenolics, and combinations of the above.
- the resins may be acrylic-alkyd copolymers and phenolic resins in combination.
- Amino crosslinking agents such as melamine-formaldehyde resins and/or urea- formaldehyde resins may be included in the modified alkyd or other resin system to make the system heat-curable
- metal dryers can be employed in the system to make it air drying.
- the resin system of the present invention should employ a binder resin which casts a suitable film and provides good adhesion to and over the aforementioned metallic film layer(s).
- the system may employ a suitable solvent of the type normally employed in the particular resin system.
- an ester such as propylene glycol monomethyl ether acetate, butyl acetate or isobutyl acetate may be employed.
- the alkyd or modified alkyd resins comprise 20 to 50 percent by weight of the system, more preferably 20 to 35 weight percent.
- the solvents or solvent blends employed in this system are preferably 20 to 35 percent by weight of the system.
- Additives normally employed in resin coating systems for this type of application may also be added in addition to the resins and solvent, for example, pigments (where it is desired to impart a color) and inert fillers or extenders such as barytes or calcium carbonate; flow additives; anti- settling agents to support any dense pigment particles; catalysts such as blocked or unblocked acids (where a thermosetting resin is employed); surface active agents; antiskinning agents such as methyl ethyl ketoxime; and additives for other purposes.
- the aforementioned resin systems are by themselves fully hardenable to form a film over a metallic film layer.
- the present invention specifically contemplates the use of a non-lead compound represented by the following formula:
- R', R 2 , R 3 and R 4 can be identical or different and are each hydrogen, an aliphatic, cycloaliphatic, araliphatic or aromatic radical, and can be substituted or unsubstituted;
- A is hydrogen or Cz-CR 5 R 6 CN;
- X, Y and Z are independently selected from 0-5; and
- R 5 and R 6 are as defined for R', R 2 , R 3 and R 4 above.
- a preferred additive is iminodiacetonitrile wherein A is hydrogen; R 1 , R 2 , R 3 and R 4 are each hydrogen; and X and Y are 0.
- nitrilotriacetonitrile NTAN
- A is Cz- CR 5 R 6 CN
- X, Y and Z are 0
- R'-R 6 are all hydrogen.
- the nitrile corrosion inhibitors of the invention are well-known compounds and their method of preparation are likewise well-known to those skilled in the art.
- U.S. Patent No. 4,543,215, supra discloses, -iminodiacetonitriles and their method of preparation. Methods of preparation include reacting an aldehyde-cyanohydrin with an aminonitrile.
- the corrosion inhibitor additives may be employed in an amount, by weight, of about 0.01 to about 25% of the resin coating system, although about 0.1 to about 10% is preferred. More preferably, a range of about 0.1 % to about 5% is employed, e.g., .5% to 1.5%. At the higher amounts, particularly above 10%, the corrosion inhibitor becomes particularly susceptible to reaction with water, for example, any moisture present in the environment. If such higher amounts of the nitrile compound are employed in the resin coating system of the present invention, it is preferred that an additional water or moisture proof coating be applied over the hardened resin coating.
- the corrosion inhibitors of the present invention may be blended with the resin system by comminuting them into fine particles, generally up to about 50 microns, preferably from 10 to 40 microns and most preferably about 1 to 10 micron, e.g., 5 microns in size. It has been found that when the small size particles are employed, a lower overall weight percentage of the inhibitor is needed to achieve a desired level of corrosion protection, since the smaller particle size can be dispersed throughout the resin to a greater extent to provide the necessary protection.
- the corrosion inhibitor may be dissolved in a suitable solvent and dispersed and blended into the resin system. The corrosion inhibitors are believed to be substantially unreacted in the blended, fluid resin system and available for corrosion inhibition during or after application to the metallic surface.
- the non-lead corrosion inhibitor compounds disclosed herein react in the present system to: 1 ) passivate the metallic film on which it is applied, for example, a copper film, and create a complex with the metal to reduce corrosion; 2) increase the adhesion of the metal film, such as copper, to the cured resin; or 3) a combination of 1 and 2 above.
- the corrosion inhibitors are incorporated instead of utilizing conventional lead based pigments, such as lead salts, employed in the past.
- other corrosion inhibitors may be used in conjunction with the nitrile compounds such as zinc oxide, to provide a desired degree of protection in a specific application.
- low amounts of leaded materials which comply with environmental laws and regulations may be added to the resin system.
- the blended resin system to be applied over the aforementioned metallic films is completely free of lead to comply more easily with environmental laws and regulations in its manufacturing and use.
- the blended resin system employing the non-lead corrosion inhibitors of the present invention is applied to the metallic layers on the mirror backs by conventional processes, such as air or airless spraying (preferably the latter), roller coating, curtain coating, screen printing or electrostatically.
- Thermosetting resin systems such as the aforementioned preferred alkyd or modified alkyd resin systems may be dried by infrared heating, typical conditions being five minutes heating time with an exit film temperature of about 250°F (120°C).
- the thickness of the dried resin film layer may be up to 0.002 in. (51 microns) thick, or higher although it is preferred that the film thickness be from about 0.001 to 0.0015 in. (25 to 38 microns) in thickness. Where thicker coatings are desired, multiple layers of the coating may be applied.
- the use of the thin layers described above enables the applied resin system to be quickly dried to a hardened layer without causing bubbles or other defects.
- the resin system incorporating the corrosion inhibitors of the present invention provide good protection to the edges of the mirror metallic film layers, at which location corrosion usually commences.
- Mirror edge corrosion also known as "black edge” can occur because of moisture present in bathrooms or other high humidity environments.
- Other causes include the use of certain adhesives in which a component (for example, acetic acid in silicone based adhesives) can attack the resin coating layer and metallic film.
- abrasive coolant having a high pH level can remain on the edge and attack the paint and metallic film layers of the mirror.
- the resin coating system employing the corrosion inhibitors of the present invention should be able to provide a smooth finish having a good appearance, and, if the mirror is later cut or otherwise handled, should prevent chipping of the resin paint at the mirror edges.
- a series of glass panels were cleaned, sensitized, and coated with successive layers of a silver film and a copper film according to the processes described above.
- the resulting silver film layer was approximately 700 angstroms thick and the resulting copper film top layer was approximately 220 angstroms thick.
- the silver was applied to the glass panels by a conventional spray system and the copper was applied to the silver layer on a comparative basis by either a galvanic system or cuprous disproportionation system.
- a commercial short oil alkyd based liquid resin coating system used as a base for preventing corrosion of the metal layer of mirrors was modified as shown below in Table I by adding to the system the noted additives at a concentration of 15-20 lb/100 gal (about 1.4-1.9% wt/wt).
- the density of the resin is about 1 1 lb/gal.
- the liquid resin coating systems were applied to the copper layer on the backs of the aforementioned mirrored glass samples using a draw down bar and thereafter subjected to infrared drying at about 250°F. (120°C.) for approximately five (5) minutes until cured to a hardened film layer of approximately 0.001 in. (25 microns) thickness.
- the coated mirror samples were then subjected to a corrosion test in a 20% salt spray environment for 300 hours pursuant to Federal specification DD-M-441 1 B and ASTM B-1 17-73. All the additives were added to the resin coating system as commercially available powders.
- the resin coating system of EXAMPLE 1 was used to show the effect of concentration on the effectiveness of the additive of the invention.
- IDAN was pulverized to approximately 5 micron particle size and added to the system in the concentration as shown in Table 2.
- a control using DCDA at 1 5lb/gal. showed 0 black edge (mm) and had density of spots of 8.
- the following example shows the effect of particle size on the corrosion inhibiting effectiveness of IDAN.
- the resin coating system of EXAMPLE 1 was used and the IDAN added to each sample at a level of 10 Ibs./I OO gallon. The results are shown in Table 3.
- the lab grind is about 40 micron, the pebble mill grind about 25 micron and the pulverized about 5 micron.
- EXAMPLE 4 The following example shows the effect of both additive level and the type copper surface being protected when using IDAN in the resin formulation of Example 1 .
- the IDAN had a particle size of about 5 micron. The results are shown in Table 4. TABLE 4
- Lead in the form of lead cyanamide was used at a level of 4 0 lb/100 gal.
- the following example shows the effectiveness of different levels of IDAN in another commercial resin formulation which is a phenolic-alkyd resin based resin coating system used for preventing corrosion of mirrors.
- the results are shown in Table 5.
- Lead in the form of lead cyanamide was used al a level of 40lb/100gal.
- resin systems including the corrosion inhibitors of the present invention may be further modified, for example, by including other pigments such as zinc oxide or titanium dioxide in part replacement for the talc, or by using additional resin in part replacement for the pigments to achieve better corrosion resistance.
- the resins containing the corrosion inhibitors of the present invention may be applied to and over metallic surface layers, such as copper, copper-based alloys, silver, or silver based alloys of other articles to provide enhanced corrosion protection.
Abstract
Description
Claims
Priority Applications (10)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE1998629859 DE69829859T2 (en) | 1997-05-27 | 1998-02-03 | IMINODIACETONITRILE AS CORROSION INHIBITORS IN COATINGS FOR MIRROR BACKPAGES |
AT98904831T ATE293593T1 (en) | 1997-05-27 | 1998-02-03 | IMINODIACETONITRILES AS CORROSION INHIBITORS IN COATINGS FOR THE BACKS OF MIRRORS |
CA 2281771 CA2281771A1 (en) | 1997-05-27 | 1998-02-03 | Iminodiacetonitrile mirror back coating corrosion inhibitor |
AU62615/98A AU728727B2 (en) | 1997-05-27 | 1998-02-03 | Iminodiacetonitrile mirror back coating corrosion inhibitor |
HU0004180A HUP0004180A3 (en) | 1997-05-27 | 1998-02-03 | A composition for inhibiting corrosion for coating mirror back and metal plated products coated by these compositions and process for the prevention of the corrosion of the thin metal layer being on the back of the mirror |
JP50062899A JP3786430B2 (en) | 1997-05-27 | 1998-02-03 | Iminodiacetonitrile-based mirror back coating corrosion inhibitor |
PL33698698A PL336986A1 (en) | 1997-05-27 | 1998-02-03 | Iminodiacetonitrile qas a corrosion inhibitor for use on backside of reflective mirror coatings |
KR1019997010970A KR20010012998A (en) | 1997-05-27 | 1998-02-03 | Iminodiacetonitrile mirror back coating corrosion inhibitor |
EP98904831A EP1012135B1 (en) | 1997-05-27 | 1998-02-03 | Iminodiacetonitrile mirror back coating corrosion inhibitor |
BR9808228A BR9808228A (en) | 1997-05-27 | 1998-02-03 | Corrosion of iminodiacetonitrile rear mirror coating |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US08/863,219 | 1997-05-27 | ||
US08/863,219 US5863611A (en) | 1997-05-27 | 1997-05-27 | Iminodiacetonitrile mirror back coating corrosion inhibitor |
Publications (1)
Publication Number | Publication Date |
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WO1998054127A1 true WO1998054127A1 (en) | 1998-12-03 |
Family
ID=25340600
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
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PCT/US1998/001950 WO1998054127A1 (en) | 1997-05-27 | 1998-02-03 | Iminodiacetonitrile mirror back coating corrosion inhibitor |
Country Status (19)
Country | Link |
---|---|
US (1) | US5863611A (en) |
EP (1) | EP1012135B1 (en) |
JP (1) | JP3786430B2 (en) |
KR (1) | KR20010012998A (en) |
CN (1) | CN1140502C (en) |
AR (1) | AR015693A1 (en) |
AT (1) | ATE293593T1 (en) |
AU (1) | AU728727B2 (en) |
BR (1) | BR9808228A (en) |
CA (1) | CA2281771A1 (en) |
DE (1) | DE69829859T2 (en) |
ES (1) | ES2241116T3 (en) |
HU (1) | HUP0004180A3 (en) |
ID (1) | ID26521A (en) |
MY (1) | MY118713A (en) |
PL (1) | PL336986A1 (en) |
TW (1) | TW460553B (en) |
WO (1) | WO1998054127A1 (en) |
ZA (1) | ZA983605B (en) |
Families Citing this family (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
ES2199496T3 (en) * | 1998-06-02 | 2004-02-16 | Crompton Vinyl Additives Gmbh | CIANACETILURES FOR THE STABILIZATION OF POLYMERS WITH A HALOGEN CONTENT. |
US6979478B1 (en) | 2002-08-01 | 2005-12-27 | Hilemn, Llc | Paint for silver film protection and method |
US20110261473A1 (en) | 2008-04-15 | 2011-10-27 | Valspar Sourcing, Inc. | Articles Having Improved Corrosion Resistance |
FR2936240B1 (en) * | 2008-09-22 | 2012-08-03 | Saint Gobain | CORROSION RESISTANT MIRROR |
CN101392139B (en) * | 2008-11-05 | 2011-09-21 | 天津市新丽华色材有限责任公司 | Super fast curing silver mirror back priming paint coating |
CN101392140B (en) * | 2008-11-05 | 2011-08-03 | 天津市新丽华色材有限责任公司 | Super fast curing silver mirror back top coating |
CN106318159B (en) * | 2016-08-22 | 2019-04-05 | 东莞莱姆森科技建材有限公司 | A kind of scratch-resistant mirror and preparation method thereof |
Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4196233A (en) * | 1974-02-07 | 1980-04-01 | Ciba-Geigy Corporation | Process for coating inorganic substrates with carbides, nitrides and/or carbonitrides |
US4543215A (en) * | 1982-11-15 | 1985-09-24 | Basf Aktiengesellschaft | α-iminodiacetonitriles and their preparation |
US5248331A (en) * | 1990-01-11 | 1993-09-28 | Lilly Industries, Inc. | Mirror back coating |
US5252402A (en) * | 1990-01-11 | 1993-10-12 | Lilly Industries, Inc. | Mirrorback coating |
JPH05311492A (en) * | 1991-12-25 | 1993-11-22 | Nikko Kinzoku Kk | Hole sealing treatment of noble metal plated material |
Family Cites Families (15)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2790778A (en) * | 1953-07-27 | 1957-04-30 | Geigy Chem Corp | Rust preventive compositions containing amidodicarboxylic acids |
US2867538A (en) * | 1955-06-27 | 1959-01-06 | Bienenfeld Arthur | Protective backing compositions for mirrors |
US3262791A (en) * | 1960-08-04 | 1966-07-26 | Petrolite Corp | Corrosion preventing method and composition |
US3668137A (en) * | 1969-04-01 | 1972-06-06 | Amchem Prod | Composition and method for inhibiting acid attack of metals |
US3776950A (en) * | 1971-11-26 | 1973-12-04 | Minnesota Mining & Mfg | N-cyanophosphinimides |
GB1417555A (en) * | 1972-03-08 | 1975-12-10 | Ici Ltd | Inhibition of corrosion |
US4255214A (en) * | 1977-11-21 | 1981-03-10 | Falconer Plate Glass Corporation | Methods of manufacturing and protecting mirrors |
US4556110A (en) * | 1984-08-30 | 1985-12-03 | Phillips Petroleum Company | Corrosion inhibition |
US4707405A (en) * | 1985-01-02 | 1987-11-17 | Ppg Industries, Inc. | Cyanamide salts of non-lead metals as corrosion inhibitive pigments in mirror back coatings |
US5226956A (en) * | 1987-03-24 | 1993-07-13 | Alcan International, Inc. | Surface coating compositions |
US5094881A (en) * | 1990-01-11 | 1992-03-10 | Lilly Industrial Coatings, Inc. | Mirrorback coating |
US5314532A (en) * | 1991-09-04 | 1994-05-24 | Sureguard, Inc. | Soluble salt-free contaminant-free pigmented mirror coatings |
JPH05311495A (en) * | 1991-12-25 | 1993-11-22 | Nikko Kinzoku Kk | Hole sealing treatment of noble metal plated material |
JPH05311485A (en) * | 1991-12-25 | 1993-11-22 | Nikko Kinzoku Kk | Hole sealing treatment of noble metal plate material |
IT1254545B (en) * | 1992-03-23 | 1995-09-25 | FORMULATION FOR THE CORROSION PROTECTION OF METAL FILMS OF MIRRORS AND SIMILAR AND PRODUCTION PROCESS OF THE SAME |
-
1997
- 1997-05-27 US US08/863,219 patent/US5863611A/en not_active Expired - Lifetime
-
1998
- 1998-02-03 EP EP98904831A patent/EP1012135B1/en not_active Expired - Lifetime
- 1998-02-03 DE DE1998629859 patent/DE69829859T2/en not_active Expired - Fee Related
- 1998-02-03 CA CA 2281771 patent/CA2281771A1/en not_active Abandoned
- 1998-02-03 ID ID990928D patent/ID26521A/en unknown
- 1998-02-03 PL PL33698698A patent/PL336986A1/en not_active IP Right Cessation
- 1998-02-03 AT AT98904831T patent/ATE293593T1/en not_active IP Right Cessation
- 1998-02-03 ES ES98904831T patent/ES2241116T3/en not_active Expired - Lifetime
- 1998-02-03 JP JP50062899A patent/JP3786430B2/en not_active Expired - Fee Related
- 1998-02-03 HU HU0004180A patent/HUP0004180A3/en unknown
- 1998-02-03 KR KR1019997010970A patent/KR20010012998A/en active IP Right Grant
- 1998-02-03 CN CNB988055120A patent/CN1140502C/en not_active Expired - Fee Related
- 1998-02-03 AU AU62615/98A patent/AU728727B2/en not_active Ceased
- 1998-02-03 BR BR9808228A patent/BR9808228A/en not_active Application Discontinuation
- 1998-02-03 WO PCT/US1998/001950 patent/WO1998054127A1/en not_active Application Discontinuation
- 1998-03-30 TW TW87104722A patent/TW460553B/en not_active IP Right Cessation
- 1998-04-29 ZA ZA983605A patent/ZA983605B/en unknown
- 1998-05-20 AR ARP980102345 patent/AR015693A1/en active IP Right Grant
- 1998-05-22 MY MYPI98002286A patent/MY118713A/en unknown
Patent Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4196233A (en) * | 1974-02-07 | 1980-04-01 | Ciba-Geigy Corporation | Process for coating inorganic substrates with carbides, nitrides and/or carbonitrides |
US4543215A (en) * | 1982-11-15 | 1985-09-24 | Basf Aktiengesellschaft | α-iminodiacetonitriles and their preparation |
US5248331A (en) * | 1990-01-11 | 1993-09-28 | Lilly Industries, Inc. | Mirror back coating |
US5252402A (en) * | 1990-01-11 | 1993-10-12 | Lilly Industries, Inc. | Mirrorback coating |
JPH05311492A (en) * | 1991-12-25 | 1993-11-22 | Nikko Kinzoku Kk | Hole sealing treatment of noble metal plated material |
Also Published As
Publication number | Publication date |
---|---|
AU6261598A (en) | 1998-12-30 |
BR9808228A (en) | 2000-05-16 |
ES2241116T3 (en) | 2005-10-16 |
DE69829859T2 (en) | 2006-03-02 |
HUP0004180A2 (en) | 2001-04-28 |
KR20010012998A (en) | 2001-02-26 |
HUP0004180A3 (en) | 2001-06-28 |
MY118713A (en) | 2005-01-31 |
CN1140502C (en) | 2004-03-03 |
EP1012135B1 (en) | 2005-04-20 |
ATE293593T1 (en) | 2005-05-15 |
AU728727B2 (en) | 2001-01-18 |
ID26521A (en) | 2001-01-11 |
ZA983605B (en) | 1998-11-02 |
AR015693A1 (en) | 2001-05-16 |
JP3786430B2 (en) | 2006-06-14 |
CA2281771A1 (en) | 1998-12-03 |
TW460553B (en) | 2001-10-21 |
EP1012135A4 (en) | 2003-05-28 |
JP2002500695A (en) | 2002-01-08 |
PL336986A1 (en) | 2000-07-31 |
CN1258272A (en) | 2000-06-28 |
US5863611A (en) | 1999-01-26 |
DE69829859D1 (en) | 2005-05-25 |
EP1012135A1 (en) | 2000-06-28 |
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