WO1982004015A1 - Primed inorganic substrates overcoated with curable protective compositions - Google Patents
Primed inorganic substrates overcoated with curable protective compositions Download PDFInfo
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- WO1982004015A1 WO1982004015A1 PCT/US1982/000518 US8200518W WO8204015A1 WO 1982004015 A1 WO1982004015 A1 WO 1982004015A1 US 8200518 W US8200518 W US 8200518W WO 8204015 A1 WO8204015 A1 WO 8204015A1
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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
- C09D4/00—Coating compositions, e.g. paints, varnishes or lacquers, based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; Coating compositions, based on monomers of macromolecular compounds of groups C09D183/00 - C09D183/16
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- 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
- Y10T428/26—Web or sheet containing structurally defined element or component, the element or component having a specified physical dimension
- Y10T428/263—Coating layer not in excess of 5 mils thick or equivalent
- Y10T428/264—Up to 3 mils
- Y10T428/265—1 mil or less
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- 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
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- 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.]
- Y10T428/31609—Particulate metal or metal compound-containing
- Y10T428/31612—As silicone, silane or siloxane
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- 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]
- Y10T428/31652—Of asbestos
- Y10T428/31663—As siloxane, silicone or silane
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- 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]
- Y10T428/31652—Of asbestos
- Y10T428/31667—Next to addition polymer from unsaturated monomers, or aldehyde or ketone condensation product
Definitions
- This invention relates to a composition and method for priming inorganic substrates. In another aspect, it relates to a method for overcoating such primed substrates with a protective organic layer and to the layered structure resulting therefrom. In a further aspect, it relates to articles primed and overcoated with the compositions of the present invention.
- Primers which are compositions that promote the adhesion of overcoatings onto substrates, are known in the art. They are particularly useful in articles requiring that organic materials be bonded onto inorganic substrates. The strength of the interfacial bond formed in such constructions often determines the ultimate strength and utility of the articles.
- U.S. Patent No. 3,321,350 teaches that adhesion of a cured polysiloxane onto a solid material, e.g., aluminum, is improved if a primer containing an organosilane and a hydrolyzable titanium compound is first applied. It is taught in U.S. Patent No. 3,794,556, that a fluorosilane-containing/ titanate primer composition can be used to improve the adhesion of silicone elastomers to titanium metal and to certain polymerized substrates. A composition and method for enhancing bonding and protection of aluminum surfaces is disclosed in U.S.
- Patent No. 3,687,882 wherein the adherent coating is derived from a cohydrolyzed composition of a diaminosubstituted silane and a titanate.
- compositions comprising silanes and metal esters some within the scope of the primer compositions of the present invention, have been disclosed in U.S. Pat. Nos.
- the present invention provides primer compositions for adhering coatings derived from JJI situ polymerizations of uncured monomers onto inorganic substrates.
- These primer compositions comprise at least one non-amino- or non-amido-containing silane and at least one of certain metal esters, and also preferably include acidic materials in these primer compositions.
- the priming compositions of the present invention provide for the adherence onto inorganic substrates, such as metals, metal oxides, and ceramics, of overcoatings derived from in situ polymerization of monomeric organic compositions that are known in the art to adhere poorly to such substrates.
- the overcoating compositions which contain, for example, epoxy or vinyl monomers, are cured in situ by heat or radiation.
- substrate is meant an underlying support layer which can be the base layer or it can be a thin coating on the base layer.
- the primed and overcoated substrates of the present invention provide articles having surfaces that are protected, for example, against weathering, or they may be painted or marked as desired.
- the present invention provides in one embodiment a primer composition
- a primer composition comprising: a. one part by weight of a non-amino- or non-amido- containing silane of the formula [R 1 ] m -Si-[R 2 ] n (1).
- R 1 is an alkyl or cycloalkyl group that can be unsubstituted or substituted by an ethenyl, methethenyl, acryloxy, methacryloxy, epoxy, mercapto, or an isocyanato group, said substituted group having a total of two to ten carbon atoms and said unsubstituted group having a total of one to ten carbon atoms;
- R 2 is a hydrolyzable group selected from alkoxy groups having one to eight carbon atoms and acyloxy groups having two to eight carbon atoms;
- m is an integer from 1 to 3;
- the present invention also provides .a layered structure on an inorganic substrate, e.g., metals, such as aluminum, steel or zinc, metal oxides of these metals, and ceramics, such as glass, but preferably on aluminum, which may be dead-soft (i.e., flexible, easily bent and which retains its shape) or vapor coated on another substrate, which preferably is primed with the above-mentioned acidic material-containing composition, although the above mentioned primer composition gives satisfactory results with no acidic component present, and overcoated with an organic monomer composition which is subsequently cured.
- the monomer which preferably is an epoxy or vinyl monomer or mixtures thereof, is blended with a suitable initiator or a latent polymerization agent.
- the monomer composition After being applied to the primed substrate, the monomer composition is then cured in situ by heat, radiation, or other appropriate means.
- the above-mentioned primer which is heat curable, can be cured simultaneously with the monomer composition if heat is used, or it can be separately cured by heat before application of the monomer layer.
- Preparation of the layered structure of the present invention involves two steps.
- the first step is the primer preparation and application. This involves the simple mixing or blending at ambient conditions of the following ingredients: a suitable silane, a hydrolyzable metal ester (also called an alkoxide), a suitable solvent, such as ethanol, butanol, 2-ethylhexanol, acetone, or methylethyl ketone, but preferably isopropyl alcohol.
- a suitable silane such as ethanol, butanol, 2-ethylhexanol, acetone, or methylethyl ketone, but preferably isopropyl alcohol.
- an acidic material is added (i.e., 0:1 to 10:1 moles by weight of an inorganic acidic material, or 0:1 to 20:1 moles by weight of an organic acidic material, compared to the total moles by weight of metal ester plus silane).
- the primer is then applied onto an inorganic substrate such as a metal.
- the cured primer coating be very thin, i.e., 0.02 to 0.5 microns in thickness.
- One method of achieving such a thin coating is to use an amount of organic solvent in the range of 50 to 99 weight percent of the composition, preferably at least 90 weight percent being present.
- this primer coating composition is then applied to an inorganic substrate. These primer coatings are preferably used shortly after they are prepared; however, they may be prepared and stored at room temperature or below for several weeks before application.
- Non-amino- or non-amido-containing silanes represented by formula (1) above are those wherein R 2 is a hydrolyzable group selected from alkoxy groups having 1 to
- R 1 can be an unsubstituted alkyl or cycloalkyl group, for example, methyltriethoxysilane, octyltriethoxy silane and cyclohexyltrimethoxysilane (all available from Petrarch Systems Inc., Levittown, PA).
- R 1 contains ethenyl and methethenyl functionality are vinyl triacetoxysilane (Union Carbide Corp.
- R 1 is a substituted epoxy, mercapto or isocyanato group
- gamma-glycidoxypropyltrimethoxysilane Union Carbide Corp.
- silanes and some of the other useful silanes as known in the art are given in Table IV.
- the silanes may be utilzed alone or as a mixture of silanes in the practice of the present invention.
- Gamma-methacryloxypropyl- trimethoxysilane is the preferred reactive silane.
- Metal esters which have been found useful in the practice of the present invention may be represented by the formula M[OR 3 ] x , where M is a metal selected from the group consisting of titanium, tantalum, antimony, aluminum, and zirconium, and R 3 is selected from the group consisting of lower alkyl groups containing from 1 to 8 carbon atoms which are bonded to the oxygen atom, and x is equal to the number of valence bonds of M.
- Representative metal esters (some of which are shown in Table V, below) which have been found useful in the practice of the present invention include tetraiso propyl titanate (E.I. duPont de Nemours & Co., Inc.), tetrabutyl titanate (duPont), tetraethyl titanate (Alfa
- Each of the metal esters may be utilized by itself, or in a mixture of metal esters, in the practice of the present invention.
- Other useful metal esters of the type described are known to the art.
- the preferred metal ester is tetraisopropy ⁇ titanate.
- the molar ratio of metal ester to silane can vary.
- TPT tetraisopropyl titanate
- GMPS gamma-methacryloxypropyltrimethoxysilane
- the preferred method of curing primer coatings of the present invention is exposure to heat.
- Acidic materials which can be added to the primer composition are such inorganic acids as nitric acid and sulfuric acid and such organic acidic materials as acetic acid, bis(perfluoromethylsulfonyl)methane (see U.S. Patent No. 2,732,398), higher homologs of fluorinated sulfonylmethanes (see U.S. Patent No. 3,281,472), and bis(perfluoromethylsulfonyl)phenylmethane (see U.S. Patent No. 3,632,843). These acidic materials can be present in various concentration levels.
- the ratio of moles of inorganic acid to the sum of the mole quantities of titanate plus silane is 0:1 to 10:1, and preferably 0.5:1 to 4:1, and for the organic acidic materials the mole ratios are 0:1 to 20:1, and preferably 0.5:1 to 8:1. Priming effects can be achieved without acidic materials in the composition, but incorporation of acid makes a priming composition less subject to attack by moisture and allows for greater variability in the thickness of the primer layer.
- the primer coating compositions used in this invention can be applied to a variety of inorganic substrates, such as steel, zinc, ceramics, but preferably the substrate is aluminum.
- inorganic substrates such as steel, zinc, ceramics, but preferably the substrate is aluminum.
- metals used as substrates for the primer coatings are summarized in Table VI, below.
- the metal surfaces were first cleaned in a variety of ways (see Table VI), before the primer coatings were applied, to remove surface contamination.
- aluminum was precleaned by 1.5 minute immersion in hot (60-70°C) aqueous 2.5% Oakite 166 solution (Oakite Products, Berkeley Heights, New Jersey) followed by distilled water rinse, and air drying.
- the primer layer may be coated on a substrate by usual methods known in the art, e.g., bar, knife, reverse roll, knurled roll, or spin coating, or by dipping, spraying, or brushing.
- the cured primer coating is very thin, i.e., 0.02 to 0.5 micron in thickness.
- the second step is the organic overcoating preparation which involves the simple mixing or blending of the ingredients of a suitable organic monomer with an initiator or a latent polymerization agent.
- Other additives such as leveling agents, diluents, colorants, fillers, viscosity modifiers, etc. may be added to the above formulation by simple mixing.
- the method of preparation of the monomer overcoating composition involves the mixture of a suitable organic monomer, diluted or undiluted, a suitable solvent, such as acetone, fillers, colorants, additives, polymerization agents, initiators, and the like.
- a suitable solvent such as acetone
- fillers, colorants, additives, polymerization agents, initiators, and the like Preferably, the latent polymerization agent or initiator is added last.
- the overcoating composition is applied to the primer coating layer previously coated onto a suitable inorganic substrate, for example, aluminum.
- these overcoatings are used shortly after preparation; however, they may be stored if properly protected from heat and light for several months before application. More than one overcoating layer may be applied to the primed substrates.
- a variety of thicknesses for the overcoating layers is possible; the ultimate thickness allowable is determined by the properties of the cured overcoatings.
- Monomers for overcoatings which have been found useful in the practice of this invention include epoxy resins such as bis(3,4-epoxycyclohexylmethyl) adipate (union Carbide), and vinyl monomers such as trimethylolpropane triacrylate, hexanediol diacrylate, and pentaerythritol tetraacrylate (all are available from Sartomer Co.).
- epoxy resins such as bis(3,4-epoxycyclohexylmethyl) adipate (union Carbide)
- vinyl monomers such as trimethylolpropane triacrylate, hexanediol diacrylate, and pentaerythritol tetraacrylate (all are available from Sartomer Co.).
- vinyl monomers for overcoatings are 1,3-bis [3-(2,2,2-(triacryloxymethyl)ethoxy-2-hydroxy- propyl] -5,5-dimethyl-2,4-imidazolidinedione and 1,3-bis [3-(2-acryloxyethoxy)-2-hydroxypropyl]-5,5- dimethyl-2,4-imidazolidinedione, (as disclosed in assignee's copending patent applications, U.S.S.N. 051,876 and U.S.S.N. 051,877, both filed on June 25, 1979).
- These monomers are film-forming monomers or prepolymers with a molecular weight up to 5,000, preferably up to 2,000, perpolymerizable group.
- Leveling agents are also useful in the overcoating composition in the practice of the invention in that they improve coating uniformity.
- Leveling agents which have been found useful in the practice of the present invention include fluorocarbon-based surfactants, "FC-430” and FC-431” (3M). These agents are used in minor amounts, i.e., about 0.01% up to about 1% by weight.
- Epoxy monomers such as bis(3,4-epoxycyclohexylmethyl) adipate can be cured, for example, with a photoactivatable epoxy cure initiator.
- photoactivatable epoxy cure initiators are generally known in the art and are described in a number of U.S. Patents, e.g,, Nos. 4,219,377, 4,101,513, and 4,039,521.
- Triarylsulfoniumhexafluoroantimonate disclosed in U.S. Patent No.
- 4,173,476, is a particularly preferred photoactivatable epoxy cure initiator for use in the present invention, and it is usually present in an amount up to 2% by weight of the epoxy resin.
- Vinyl monomer-containing overcoatings typically with an appropriate latent polymerization agent present in the overcoating blend, can be cured by exposure to ultraviolet light or heat.
- Latent polymerization agents need not be present to effect curing of vinyl monomer- containing overcoatings via electron beam radiation. Free radical curing of vinyl monomers such as acrylates and methacrylates via utlraviolet light generally requires the presence of latent polymerization agents known as photoinitiators.
- acetophenone derivatives such as 2,2-dimethoxy-2-phenylacetophenone (Ciba-Geigy), and 2-hydroxy-2-methyl(3',4'-dimethyl)- propiophenone (E. Merck) and are usually present in the overcoating in minor amounts.
- Other acetophenone derivatives are known in the art (see U.S. Patent No. 3,715,293), e.g., 2-2-dimethoxyacetophenone,
- Vinyl overcoating compositions containing free radical photoinitiators will cure when exposed to ultraviolet light. However, it is preferable that curing be conducted in an inert atmosphere such as nitrogen since oxygen inhibits the reaction.
- Monomeric overcoatings whose cure can be photoinitiated in the absence or presence of oxygen are those containing 1,3-bis[3-(2,2,2-(triacryloxy- methyl)ethoxy-2-hydroxypropyl)] -5,5-dimethyl-2,4-imidazo- lidinedione and 1,3-bis[3-(2-acryloxyethoxy)-2-hydroxy- pro ⁇ yl]-5,5-dimetbyl-2,4-imidazolidinedione, mentioned above.
- any suitable source which emits ultraviolet light may be used to activate the photoinitiators in the practice of this invention.
- Suitable sources are mercury arcs, carbon arcs, low-, medium- and high-pressure mercury lamps, plasma arcs, ultraviolet light emitting diodes, and ultraviolet emitting lasers.
- Ultraviolet light activation of the latent curing agents used in the overcoatings of this invention can be brought about with the use of such commercially available ultraviolet light sources as the UVEXS model LCU 750 (UVEXS, Inc., Sunnyvale, California) and the RPC model QC 1202 ANIR (RPC Equipment, Plainfield, Illinois).
- Typical cure conditions with such ultraviolet light sources involve the conveying, or repeated conveying, of an overcoated substrate several centimeters from the source of a 200 watt per 2.54 cm medium pressure mercury lamp, at a suitable conveyor speed, for example, 15 meters/minute.
- the overcoatings of the present invention may be applied by methods known in the art, such as bar, knife, reverse roll, knurled roll, or spin coating, or by dipping, spraying, or brushing.
- the evaluation of adhesion of the overcoating onto a primed inorganic substrate such as aluminum and other metals was conducted using two test methods, both of which were modeled after ASTM tests. In the first test modeled after ASTM D3359 test method B, "Standard Methods for Measuring Adhesion by Tape Test", strips of Scotch ® Brand No. 250 Masking Tape or Scotch ® Brand No.
- the layered structures of the present invention find utility in articles that require adherent protective overcoatings, such as automotive trim, window frames, fireplace brick, or metal based tapes, and as pavement marking tapes wherein the overcoating layer has a top surface in which glass retroreflective raicrospheres and skid-resistant particles may be partially embedded in the surface.
- adherent protective overcoatings such as automotive trim, window frames, fireplace brick, or metal based tapes, and as pavement marking tapes wherein the overcoating layer has a top surface in which glass retroreflective raicrospheres and skid-resistant particles may be partially embedded in the surface.
- Other applications include applications which require decorative overcoatings.
- RDS bar coater No. 14 both coaters are available from
- a primer composition was prepared by adding two drops of concentrated nitric acid to a solution of 19.6 g of isopropyl alcohol containing 0.4 g of gamma-methacryl- oxypropyltrimethoxysilane (GMPS) with 0.04 g of tetraisopropyl titanate (TPT).
- GMPS gamma-methacryl- oxypropyltrimethoxysilane
- TPT tetraisopropyl titanate
- overcoating formulation A prepared by mixing 60 parts of 1,3-bis [3-(2,2,2-(triacryloxymethyl)ethoxy-2-hydroxy- propyl)3-5,5-dimethyl-2,4-imidazolidinedione to 40 parts of 1,3-bis[3-(2-acryloxyethoxy)-2-hydroxypropyl]-5,5- dimethyl-2,4-imidazolidinedione to 2 parts of 2,2-dimethoxy-2-phenylacetophenone (Ciba-Geigy Corp., Ardsley, N.Y.) to 0.1 part of FC-430 to 100 parts acetone.
- This overcoating was cured photochemically by exposure of the overcoated substrate to ultraviolet light.
- the ultraviolet light source was a model LCU 750 200 watt/2.54 cm medium pressure mercury lamp (UVEXS, Sunnyvale, CA) which emitted short wavelength (200-320 nra) and long wavelength (320-430 nm) ultraviolet light.
- the coated substrate was placed on a conveyor and was passed under this ultraviolet light source three to four times at a- conveyor speed of 15.2 meters per minute and at a distance of about 15 cm from this source.
- EXAMPLES 13-25 The following is a model procedure for Examples 13-25. The results are summarized in Table III.
- a primer composition was prepared by adding one drop of concentrated nitric acid to a solution of 9.8 g isopropyl alcohol containing 0.2 g gamma-methacryloxy- propyltrimethoxysilane with 0.2 g tetraisopropyl titanate. As in Examples 1-12, this solution was coated onto a sample of cleaned aluminum alloy #3003 (cleaned as indicated in Examples 1-12) and cured for five minutes at 120°C.
- the primed aluminum was then overcoated with coating formulation B prepared by mixing of 100 parts of 1,3-bis [3-(2,2,2-(triacryloxymethyl)ethoxy-2-hydroxy- propyl)]-5,5-dimethyl-2,4-imidazolidinedione to 100 parts 2-butanone (methyl ethyl ketone) to 2 parts of 2-hydroxy- 2-methyl(3',4'-dimethyl)pro ⁇ ionphenone (E. Merck, Darmstadt, Germany) to 0.1 part FC-431 (3M).
- the cure of this overcoating composition was initiated photo- chemically, essentially following the procedure of
- the coated substrate was placed on a conveyor and was exposed to this ultraviolet light source at a distance of about 15 cm and at a conveyor speed of 24.4 meters per minute.
- compositions within the invention i.e., Ex. Nos. 19-273 generally show better adhesion than controls; especially good are those compositions with TPT:GMPS ratios within the preferred range of TABLE I, above.
- EXAMPLES 26-45 Examples 26-45 evaluate different silanes used in formulations for primers on aluminum substrates, which were then overcoated with formulations A and B of Examples 1-25. Results are summarized in Table IV using the following procedural model.
- a primer composition was prepared by adding one drop of concentrated nitric acid to a solution of 9.8 g isopropyl alcohol containing 0.15 g tetraisopropyl titanate and the corresponding weight of selected silane indicated in Table IV (the number of moles of silane was kept constant within limits of measurements).
- This composition was coated onto a sample of aluminum alloy #3003 (cleaned as described in Example 1) and then cured at 120 ⁇ C for five minutes.
- the primed aluminum panel was then overcoated with the overcoating formulation A, and photochemically cured as described in Examples 1-12. Adhesion of the overcoating was evaluated using the ASTM D3359 test method B using Scotch Brand tapes previously mentioned and results of two runs are shown in the Acrylate Formulation columns of Table IV.
- the primed aluminum panel primed as described above, was then overcoated with an epoxy formulation in place of the acrylate formulations used in Examples 1-25.
- the epoxy formulation which was made by adding 100 parts of epoxy resin, bis(3,4-epoxy- cyclohexylmethyl) adipate with 2 parts of photoactivatable epoxy cure initiator triarylsulfoniumhexafluoroantimonate (General Electric Co.) and 0.1 part of surfactant FC-430 in 100 parts of acetone, was overcoated onto the primed aluminum.
- the overcoating was cured via ultraviolet light photoinitiation as described above and adhesion of this epoxy overcoating was evaluated for two runs according to ASTM D3359 test method B using Scotch Brand tapes previously mentioned and summarized in the Epoxy Formulation columns of Table IV.
- Run 1 used formulation A see Ex. 1-12
- Run 2 used formulation B see Ex. 13-25
- Scotch Brand No. 810 Magic Mending Tape i n all adhesion tests
- a primer composition was prepared by adding one drop of concentrated nitric acid to a solution of 9.8 g isopropyl alcohol containing 0.05 g gamma-methacryloxy- propyltrimethoxysilane with the corresponding weight of selected metal ester indicated in Table V.
- the weight of metal ester was selected so that the mole ratio of the ester to silane was in a preferred ratio of about 2.6:1 (see Table I).
- This composition was coated onto two samples of aluminum alloy #3003 (cleaned as indicated in Examples 1-12) which were then cured at 120°C for five minutes.
- One of the primed panels was then overcoated with overcoating formulation A (see Examples 1-12) and one with overcoating formulation B (see Examples 13-25), and both were then photocheraically cured as described above.
- the effectiveness of the metal ester in the primer composition was then indirectly measured by evaluating the adhesion of the overcoating onto the respective primed aluminum panel.
- ASTM D3359 test method B used Scotch Brand tapes previously mentioned and the results are provided in Table V.
- TABLE V show a range of priming capabilities observable upon use of different metal esters (alkoxides). Preferred, due to performance, price, and availability is Ti(i-OC 3 H 7 )4.
- EXAMPLES 58-60 The application of three different acrylic monomer based overcoatings onto primed aluminum is illustrated by Examples 58-60 with details and adhesion results reported in Table VII.
- the most preferred (i.e. , Ti: Si ratio of 3 : 1 ) primer composition of Example 20 was coated onto panels of cleaned aluminum alloy #3003 and cured at 120 °C for five minutes.
- the panel was overcoated (see Table VII) with the respective acrylate formulation which contained one drop of 10% FC 431 surfactant in acetone plus the indicated amount of photoinitiator ( i .e. , 2-hydroxy-2-rae thyl (3 ' ,4 ' -dimethyl ) - propiophenone , HMDP.
- the overcoating was cured by the photo initiation technique and adhesion was evaluated according to ASTM D3359 test method B using Scotch Brand No . 810 Magic Mending Tape .
- a primer coating composition prepared by adding 0.03 g of acidic material to a solution of 9.8 g of isopropyl alcohol containing 0. 1 g of tetrapropyl titanate with 0.1 g of gamma-raethacryloxypropyltrimethoxysilane was coated onto aluminum as described in Example 1 and cured at 90°C for five minutes .
- the primed panel was then overcoated with the overcoating formulation A (see Example
- Example 1 1) and photochemically cured as described in Example 1.
- a primer coating composition prepared by adding the specified amount of acid, as indicated in the corresponding example of TABLE IX, to a solution of 9.8 g of isopropyl alcohol containing 0.15 g of tetraisopropyl titanate with 0.05 g gamma-methacryloxypropyltrimethoxy- silane, was coated onto cleaned aluminum as described in Examples 13-25 and cured at 120°C for five minutes. The primed panel was then overcoated with overcoating formulation B and photochemically cured as described in Examples 13-25. Adhesion was evaluated according to model ASTM D3359 test method B using Scotch Brand No. 810 Magic Mending Tape. The results are summarized in TABLE IX.
- EXAMPLE 88 Modified ASTM D 2197 Test Method B mentioned above was used in this example.
- Primed (as in Example 6) and non-primed aluminum panels were overcoated with formulation A (see Examples 1-12) modified to include about 0.05% of Brillant Yellow fluorescent indicator (Aldrich Chemical Co., Milwaukee, WI) for visual purposes.
- Each panel was placed under the tip of a carbide scribe to which a force of about 130 g was applied.
- Each panel was then mechanically moved beneath this scribe to provide a line through the overcoating.
- a second line, parallel to and 0.25 ram away from the first line, was similarly scribed.
- the overcoating between these two scribed lines remained intact on the primed panel but flaked off from the non-primed panel, indicating a failure of the overcoating to adhere to the non-primed substrate.
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Abstract
Primer compositions for adhering overcoatings derived from in situ polymerizations of uncured monomers onto inorganic substrates. These primer compositions when coated on a substrate and included in a layered structure comprise at least one non-amino- or non-amido-containing silane, at least one of certain metal esters, and preferably an acidic material. The overcoatings are derived from epoxy and vinyl monomers which require a superior level of adhesion. The primed and overcoated substrates of the present invention provide articles having protective or decorative surface layers.
Description
PRIMED INORGANIC SUBSTRATES OVERCOATED
WITH CURABLE PROTECTIVE COMPOSITIONS
Technical Field This invention relates to a composition and method for priming inorganic substrates. In another aspect, it relates to a method for overcoating such primed substrates with a protective organic layer and to the layered structure resulting therefrom. In a further aspect, it relates to articles primed and overcoated with the compositions of the present invention.
Background Art Primers, which are compositions that promote the adhesion of overcoatings onto substrates, are known in the art. They are particularly useful in articles requiring that organic materials be bonded onto inorganic substrates. The strength of the interfacial bond formed in such constructions often determines the ultimate strength and utility of the articles.
Previous attempts have been made to overcoat aluminum and other metals with various substances, but the resulting adhesion of the overcoating is frequently less than is necessary for the desired use. U.S. Patent No. 3,321,350 teaches that adhesion of a cured polysiloxane onto a solid material, e.g., aluminum, is improved if a primer containing an organosilane and a hydrolyzable titanium compound is first applied. It is taught in U.S. Patent No. 3,794,556, that a fluorosilane-containing/ titanate primer composition can be used to improve the adhesion of silicone elastomers to titanium metal and to certain polymerized substrates. A composition and method for enhancing bonding and protection of aluminum surfaces is disclosed in U.S. Patent No. 3,687,882, wherein the adherent coating is derived from a cohydrolyzed composition of a diaminosubstituted silane and a titanate.
Compositions comprising silanes and metal esters, some within the scope of the primer compositions of the present invention, have been disclosed in U.S. Pat. Nos.
4,042,749, 4,073,967, and 4,084,021 as useful abrasion or corrosion resistant coatings for soft surfaces, including aluminum. These are relatively thick coatings and they are not taught as useful primer compositions.
The prior art, however, does not teach the promotion of adhesion of polymerizable monomeric organic materials, such as epoxy or acrylic monomers, onto primed inorganic surfaces such as aluminum metal, preferably where the primer composition contains acidic material in addition to silanes and metal esters, nor does it teach the curing of monomeric organic coatings by in situ polymerization of the monomers coated onto the primed surfaces with a superior level of adhesion needed in certain applications.
Disclosure of Invention Briefly the present invention provides primer compositions for adhering coatings derived from JJI situ polymerizations of uncured monomers onto inorganic substrates. These primer compositions comprise at least one non-amino- or non-amido-containing silane and at least one of certain metal esters, and also preferably include acidic materials in these primer compositions. The priming compositions of the present invention provide for the adherence onto inorganic substrates, such as metals, metal oxides, and ceramics, of overcoatings derived from in situ polymerization of monomeric organic compositions that are known in the art to adhere poorly to such substrates. The overcoating compositions which contain, for example, epoxy or vinyl monomers, are cured in situ by heat or radiation.
By "substrate" is meant an underlying support layer which can be the base layer or it can be a thin coating on the base layer.
The primed and overcoated substrates of the present invention provide articles having surfaces that are protected, for example, against weathering, or they may be painted or marked as desired.
Detailed Description
The present invention provides in one embodiment a primer composition comprising: a. one part by weight of a non-amino- or non-amido- containing silane of the formula [R1]m-Si-[R2]n (1). in which R1 is an alkyl or cycloalkyl group that can be unsubstituted or substituted by an ethenyl, methethenyl, acryloxy, methacryloxy, epoxy, mercapto, or an isocyanato group, said substituted group having a total of two to ten carbon atoms and said unsubstituted group having a total of one to ten carbon atoms; R2 is a hydrolyzable group selected from alkoxy groups having one to eight carbon atoms and acyloxy groups having two to eight carbon atoms; m is an integer from 1 to 3; n is an integer from 1 to 3, with the proviso that m + n = 4; b. 1 to 50 parts by weight of metal ester of the formula
M[OR3]x (2) in which M is a metal selected from a group consisting of titanium, tantalum, zirconium, aluminum, and antimony; R3 is an alkyl group having from one to eight carbon atoms; and x is equal to the number of valence bonds of M; c. an acidic material; and d. an amount of organic solvent sufficient to provide blending for the components of the primer composition.
The present invention also provides .a layered structure on an inorganic substrate, e.g., metals, such as aluminum, steel or zinc, metal oxides of these metals, and ceramics, such as glass, but preferably on aluminum, which may be dead-soft (i.e., flexible, easily bent and which retains its shape) or vapor coated on another substrate,
which preferably is primed with the above-mentioned acidic material-containing composition, although the above mentioned primer composition gives satisfactory results with no acidic component present, and overcoated with an organic monomer composition which is subsequently cured. The monomer, which preferably is an epoxy or vinyl monomer or mixtures thereof, is blended with a suitable initiator or a latent polymerization agent. After being applied to the primed substrate, the monomer composition is then cured in situ by heat, radiation, or other appropriate means. The above-mentioned primer, which is heat curable, can be cured simultaneously with the monomer composition if heat is used, or it can be separately cured by heat before application of the monomer layer. Preparation of the layered structure of the present invention involves two steps.
The first step is the primer preparation and application. This involves the simple mixing or blending at ambient conditions of the following ingredients: a suitable silane, a hydrolyzable metal ester (also called an alkoxide), a suitable solvent, such as ethanol, butanol, 2-ethylhexanol, acetone, or methylethyl ketone, but preferably isopropyl alcohol. Optionally, an acidic material is added (i.e., 0:1 to 10:1 moles by weight of an inorganic acidic material, or 0:1 to 20:1 moles by weight of an organic acidic material, compared to the total moles by weight of metal ester plus silane). The primer is then applied onto an inorganic substrate such as a metal. It is desirable that the cured primer coating be very thin, i.e., 0.02 to 0.5 microns in thickness. One method of achieving such a thin coating is to use an amount of organic solvent in the range of 50 to 99 weight percent of the composition, preferably at least 90 weight percent being present. Typically, after admixing or blending, this primer coating composition is then applied to an inorganic substrate. These primer coatings are preferably used shortly after they are prepared; however, they may be
prepared and stored at room temperature or below for several weeks before application.
Non-amino- or non-amido-containing silanes represented by formula (1) above are those wherein R2 is a hydrolyzable group selected from alkoxy groups having 1 to
8 carbon atoms and acyloxy groups having 2 to 8 carbon atoms and R1 can be an unsubstituted alkyl or cycloalkyl group, for example, methyltriethoxysilane, octyltriethoxy silane and cyclohexyltrimethoxysilane (all available from Petrarch Systems Inc., Levittown, PA). Examples where R1 contains ethenyl and methethenyl functionality are vinyl triacetoxysilane (Union Carbide Corp. ), methylvinyl diethoxysilane (Petrarch Systems, Inc.), divinyldiethoxy silane (Petrarch Systems, Inc.), and gamma-methacryloxy- propyltriraethoxysilane (Union Carbide Corp.). Examples where R1 is a substituted epoxy, mercapto or isocyanato group are gamma-glycidoxypropyltrimethoxysilane (Union
Carbide Corp.), beta-(3,4-epoxycyclohexyl)ethyltriraethoxy silane (Union Carbide Corp.), gamma-mercaptopropyltri- methoxysilane (Union Carbide Corp.), and gamma-isocyanato- propyltriethoxysilane (Petrarch Systems, Inc.). These silanes and some of the other useful silanes as known in the art, are given in Table IV. The silanes may be utilzed alone or as a mixture of silanes in the practice of the present invention. Gamma-methacryloxypropyl- trimethoxysilane is the preferred reactive silane.
Metal esters which have been found useful in the practice of the present invention may be represented by the formula M[OR3]x, where M is a metal selected from the group consisting of titanium, tantalum, antimony, aluminum, and zirconium, and R3 is selected from the group consisting of lower alkyl groups containing from 1 to 8 carbon atoms which are bonded to the oxygen atom, and x is equal to the number of valence bonds of M. Representative metal esters (some of which are shown in Table V, below) which have been found useful in the practice of the present invention include tetraiso
propyl titanate (E.I. duPont de Nemours & Co., Inc.), tetrabutyl titanate (duPont), tetraethyl titanate (Alfa
Products, Thiokol/Ventron Div., Danvers, MA.), tetra-2- ethylhexyl titanate (duPont); and pentaethyl tantalate, aluminum isopropoxide, aluminum-s-butoxide, and tetra-n-propyl zirconate, (all available from Alfa
Products). Each of the metal esters may be utilized by itself, or in a mixture of metal esters, in the practice of the present invention. Other useful metal esters of the type described are known to the art. The preferred metal ester is tetraisopropyϊ titanate.
It has been found that the molar ratio of metal ester to silane can vary. For example, in the primer compositions containing tetraisopropyl titanate (TPT) and gamma-methacryloxypropyltrimethoxysilane (GMPS), the useful, preferred, and most preferred ratios are summarized in Table I.
Energy is usually required to cure the primer coatings of the present invention. The preferred method of curing primer coatings of the present invention is exposure to heat.
While it is not necessary to incorporate an acidic material in the primer composition, it is desirable to do so. Acidic materials which can be added to the primer composition are such inorganic acids as nitric acid
and sulfuric acid and such organic acidic materials as acetic acid, bis(perfluoromethylsulfonyl)methane (see U.S. Patent No. 2,732,398), higher homologs of fluorinated sulfonylmethanes (see U.S. Patent No. 3,281,472), and bis(perfluoromethylsulfonyl)phenylmethane (see U.S. Patent No. 3,632,843). These acidic materials can be present in various concentration levels. The ratio of moles of inorganic acid to the sum of the mole quantities of titanate plus silane is 0:1 to 10:1, and preferably 0.5:1 to 4:1, and for the organic acidic materials the mole ratios are 0:1 to 20:1, and preferably 0.5:1 to 8:1. Priming effects can be achieved without acidic materials in the composition, but incorporation of acid makes a priming composition less subject to attack by moisture and allows for greater variability in the thickness of the primer layer.
The primer coating compositions used in this invention can be applied to a variety of inorganic substrates, such as steel, zinc, ceramics, but preferably the substrate is aluminum. Studies of metals used as substrates for the primer coatings are summarized in Table VI, below. The metal surfaces were first cleaned in a variety of ways (see Table VI), before the primer coatings were applied, to remove surface contamination. For example, aluminum was precleaned by 1.5 minute immersion in hot (60-70°C) aqueous 2.5% Oakite 166 solution (Oakite Products, Berkeley Heights, New Jersey) followed by distilled water rinse, and air drying. The primer layer may be coated on a substrate by usual methods known in the art, e.g., bar, knife, reverse roll, knurled roll, or spin coating, or by dipping, spraying, or brushing. The cured primer coating is very thin, i.e., 0.02 to 0.5 micron in thickness.
The second step is the organic overcoating preparation which involves the simple mixing or blending of the ingredients of a suitable organic monomer with an initiator or a latent polymerization agent. Other
additives such as leveling agents, diluents, colorants, fillers, viscosity modifiers, etc. may be added to the above formulation by simple mixing.
The method of preparation of the monomer overcoating composition involves the mixture of a suitable organic monomer, diluted or undiluted, a suitable solvent, such as acetone, fillers, colorants, additives, polymerization agents, initiators, and the like. Preferably, the latent polymerization agent or initiator is added last. After blending, the overcoating composition is applied to the primer coating layer previously coated onto a suitable inorganic substrate, for example, aluminum. Preferably these overcoatings are used shortly after preparation; however, they may be stored if properly protected from heat and light for several months before application. More than one overcoating layer may be applied to the primed substrates. A variety of thicknesses for the overcoating layers is possible; the ultimate thickness allowable is determined by the properties of the cured overcoatings.
Monomers for overcoatings which have been found useful in the practice of this invention include epoxy resins such as bis(3,4-epoxycyclohexylmethyl) adipate (union Carbide), and vinyl monomers such as trimethylolpropane triacrylate, hexanediol diacrylate, and pentaerythritol tetraacrylate (all are available from Sartomer Co.). Other vinyl monomers for overcoatings are 1,3-bis [3-(2,2,2-(triacryloxymethyl)ethoxy-2-hydroxy- propyl] -5,5-dimethyl-2,4-imidazolidinedione and 1,3-bis [3-(2-acryloxyethoxy)-2-hydroxypropyl]-5,5- dimethyl-2,4-imidazolidinedione, (as disclosed in assignee's copending patent applications, U.S.S.N. 051,876 and U.S.S.N. 051,877, both filed on June 25, 1979). These monomers are film-forming monomers or prepolymers with a molecular weight up to 5,000, preferably up to 2,000, perpolymerizable group.
Leveling agents are also useful in the overcoating composition in the practice of the invention in that they improve coating uniformity. Leveling agents which have been found useful in the practice of the present invention include fluorocarbon-based surfactants, "FC-430" and FC-431" (3M). These agents are used in minor amounts, i.e., about 0.01% up to about 1% by weight.
Various methods may be employed to cure the overcoatings of the present invention. Epoxy monomers, such as bis(3,4-epoxycyclohexylmethyl) adipate can be cured, for example, with a photoactivatable epoxy cure initiator. Such photoactivatable epoxy cure initiators are generally known in the art and are described in a number of U.S. Patents, e.g,, Nos. 4,219,377, 4,101,513, and 4,039,521. Triarylsulfoniumhexafluoroantimonate, disclosed in U.S. Patent No. 4,173,476, is a particularly preferred photoactivatable epoxy cure initiator for use in the present invention, and it is usually present in an amount up to 2% by weight of the epoxy resin. Vinyl monomer-containing overcoatings, typically with an appropriate latent polymerization agent present in the overcoating blend, can be cured by exposure to ultraviolet light or heat. Latent polymerization agents need not be present to effect curing of vinyl monomer- containing overcoatings via electron beam radiation. Free radical curing of vinyl monomers such as acrylates and methacrylates via utlraviolet light generally requires the presence of latent polymerization agents known as photoinitiators. One class of photoinitiators is acetophenone derivatives such as 2,2-dimethoxy-2-phenylacetophenone (Ciba-Geigy), and 2-hydroxy-2-methyl(3',4'-dimethyl)- propiophenone (E. Merck) and are usually present in the overcoating in minor amounts. Other acetophenone derivatives are known in the art (see U.S. Patent No. 3,715,293), e.g., 2-2-dimethoxyacetophenone,
2,2-diethoxyacetophenone, 2,2-dibutoxyacetophenone, 2,2-dihexoxyacetophenone, 2,2-diphenoxyacetophenone,
2,2-diphenoxy-2-ethylacetophenone, 2,2-diphenoxy-2-cyclo- pentylacetophenone.
Vinyl overcoating compositions containing free radical photoinitiators will cure when exposed to ultraviolet light. However, it is preferable that curing be conducted in an inert atmosphere such as nitrogen since oxygen inhibits the reaction. Monomeric overcoatings whose cure can be photoinitiated in the absence or presence of oxygen are those containing 1,3-bis[3-(2,2,2-(triacryloxy- methyl)ethoxy-2-hydroxypropyl)] -5,5-dimethyl-2,4-imidazo- lidinedione and 1,3-bis[3-(2-acryloxyethoxy)-2-hydroxy- proρyl]-5,5-dimetbyl-2,4-imidazolidinedione, mentioned above.
Any suitable source which emits ultraviolet light may be used to activate the photoinitiators in the practice of this invention. Suitable sources are mercury arcs, carbon arcs, low-, medium- and high-pressure mercury lamps, plasma arcs, ultraviolet light emitting diodes, and ultraviolet emitting lasers. Ultraviolet light activation of the latent curing agents used in the overcoatings of this invention can be brought about with the use of such commercially available ultraviolet light sources as the UVEXS model LCU 750 (UVEXS, Inc., Sunnyvale, California) and the RPC model QC 1202 ANIR (RPC Equipment, Plainfield, Illinois). Typical cure conditions with such ultraviolet light sources involve the conveying, or repeated conveying, of an overcoated substrate several centimeters from the source of a 200 watt per 2.54 cm medium pressure mercury lamp, at a suitable conveyor speed, for example, 15 meters/minute.
The overcoatings of the present invention, of which there may be one or more on the primed substrate, may be applied by methods known in the art, such as bar, knife, reverse roll, knurled roll, or spin coating, or by dipping, spraying, or brushing.
The evaluation of adhesion of the overcoating onto a primed inorganic substrate such as aluminum and other metals was conducted using two test methods, both of which were modeled after ASTM tests. In the first test modeled after ASTM D3359 test method B, "Standard Methods for Measuring Adhesion by Tape Test", strips of Scotch® Brand No. 250 Masking Tape or Scotch® Brand No. 810 Magic Mending Tape (3M) were applied to a cross-cut section previously made in the overcoated substrate and the tape was then removed. The percent adhesion, that is, the amount (area) of coating remaining on the substrate was assessed on a 0-100 scale (see U.S. Patent No. 4,042,749, col. 8, lines 23-40).
In a second test, modeled after ASTM D2197 test method B, "Standard Test Methods for Adhesion of Organic Coatings", using the parallel groove adhesion test, a point force of approximately 130 grams at the tip of a fixed carbide scribe was applied to a suitably coated substrate. The substrate was then moved beneath the scribe to produce a lined pattern through the coating. Adhesion was evaluated in terms of the closeness with which parallel scribed grooves could be cut through the coating before the film flakes or chips from the substrate. The better the adhesion, the closer together the grooves were cut before film failure (flaking or chipping) occurred.
The layered structures of the present invention find utility in articles that require adherent protective overcoatings, such as automotive trim, window frames, fireplace brick, or metal based tapes, and as pavement marking tapes wherein the overcoating layer has a top surface in which glass retroreflective raicrospheres and skid-resistant particles may be partially embedded in the surface. Other applications include applications which require decorative overcoatings.
The present invention will be more readily understood from a consideration of the following examples
which are meant to illustrate, but not limit this invention. Parts and percentages are by weight unless otherwise indicated and temperatures are in degrees centigrade. In the following examples, primer coatings were applied to substrates using an ROS bar coater No. 3 and overcoatings were applied to primed surfaces using an
RDS bar coater No. 14 (both coaters are available from
R.D. Specialties Inc., Webster, N.Y.) unless indicated otherwise. Percent adhesion was measured using as a model ASTM D3359 test method B, unless indicated otherwise. In the examples using acids, i.e., cone, nitric acid (70%), acetic acid (glacial), cone, sulfuric acid (96%), each drop of acid contains 0.02 to 0.04 g acid.
EXAMPLES 1-12 The following is a model procedure for Examples
1-12. The results are summarized in Table II.
A primer composition was prepared by adding two drops of concentrated nitric acid to a solution of 19.6 g of isopropyl alcohol containing 0.4 g of gamma-methacryl- oxypropyltrimethoxysilane (GMPS) with 0.04 g of tetraisopropyl titanate (TPT). The resulting primer solution was coated onto a sample of #3003 aluminum alloy [precleaned by 1.5 minute immersion in hot (60-70°C) aqueous 2.5% Oakite 166 solution followed by distilled water rinse, then air dried]. The primer coating was cured for five minutes at 120°C. The primed aluminum was then overcoated with overcoating formulation A prepared by mixing 60 parts of 1,3-bis [3-(2,2,2-(triacryloxymethyl)ethoxy-2-hydroxy- propyl)3-5,5-dimethyl-2,4-imidazolidinedione to 40 parts of 1,3-bis[3-(2-acryloxyethoxy)-2-hydroxypropyl]-5,5- dimethyl-2,4-imidazolidinedione to 2 parts of 2,2-dimethoxy-2-phenylacetophenone (Ciba-Geigy Corp., Ardsley, N.Y.) to 0.1 part of FC-430 to 100 parts acetone. This overcoating was cured photochemically by exposure of the overcoated substrate to ultraviolet light. The ultraviolet light source was a model LCU 750 200 watt/2.54 cm
medium pressure mercury lamp (UVEXS, Sunnyvale, CA) which emitted short wavelength (200-320 nra) and long wavelength (320-430 nm) ultraviolet light. The coated substrate was placed on a conveyor and was passed under this ultraviolet light source three to four times at a- conveyor speed of 15.2 meters per minute and at a distance of about 15 cm from this source.
The cured overcoating was then tested for adhesion using the ASTM D3359 test (cross hatch/tape pull test) using Scotch Brand No. 250 Masking Tape. The results using various ratios of GMPS to TPT for Examples 1-12 are given in Table II, and the range of utility was summarized in Table I, above.
The data show that adhesion of overcoating A onto primed aluminum was commercially useful when the weight ratio of TPT to GMPS was 1:1 to 50:1, the preferred ratio being 1:1 to 20:1, and the most preferred ratio being 3:1 to 10:1. These results were presented in
TABLE I, above.
EXAMPLES 13-25 The following is a model procedure for Examples 13-25. The results are summarized in Table III. A primer composition was prepared by adding one drop of concentrated nitric acid to a solution of 9.8 g isopropyl alcohol containing 0.2 g gamma-methacryloxy- propyltrimethoxysilane with 0.2 g tetraisopropyl titanate. As in Examples 1-12, this solution was coated onto a sample of cleaned aluminum alloy #3003 (cleaned as indicated in Examples 1-12) and cured for five minutes at 120°C. The primed aluminum was then overcoated with coating formulation B prepared by mixing of 100 parts of 1,3-bis [3-(2,2,2-(triacryloxymethyl)ethoxy-2-hydroxy- propyl)]-5,5-dimethyl-2,4-imidazolidinedione to 100 parts 2-butanone (methyl ethyl ketone) to 2 parts of 2-hydroxy- 2-methyl(3',4'-dimethyl)proρionphenone (E. Merck, Darmstadt, Germany) to 0.1 part FC-431 (3M). The cure of this overcoating composition was initiated photo- chemically, essentially following the procedure of
Examples 1-12 wherein the ultraviolet light source was a 300 watt/2.54 cm mercury lamp (Model QC 1202 ANIR, RPC Equipment, Plainfield, IL). The coated substrate was placed on a conveyor and was exposed to this ultraviolet light source at a distance of about 15 cm and at a conveyor speed of 24.4 meters per minute.
The cured overcoating was then tested for adhesion using ASTM D3359 test B described above (cross hatch/tape pull test) using No. 810 Scotch Brand Magic Mending Tape. Results for Examples 13-25 are shown in Table III.
(b) Example Nos. 13-18 and 24 and 25 are controls.
The data of TABLE III show results similar to those of TABLE II. Compositions within the invention (i.e., Ex. Nos. 19-23) generally show better adhesion than controls; especially good are those compositions with TPT:GMPS ratios within the preferred range of TABLE I, above.
EXAMPLES 26-45 Examples 26-45 evaluate different silanes used in formulations for primers on aluminum substrates, which were then overcoated with formulations A and B of Examples 1-25. Results are summarized in Table IV using the following procedural model.
A primer composition was prepared by adding one drop of concentrated nitric acid to a solution of 9.8 g isopropyl alcohol containing 0.15 g tetraisopropyl titanate
and the corresponding weight of selected silane indicated in Table IV (the number of moles of silane was kept constant within limits of measurements). This composition was coated onto a sample of aluminum alloy #3003 (cleaned as described in Example 1) and then cured at 120οC for five minutes. In one set of examples, the primed aluminum panel was then overcoated with the overcoating formulation A, and photochemically cured as described in Examples 1-12. Adhesion of the overcoating was evaluated using the ASTM D3359 test method B using Scotch Brand tapes previously mentioned and results of two runs are shown in the Acrylate Formulation columns of Table IV.
In a second set of examples, the primed aluminum panel, primed as described above, was then overcoated with an epoxy formulation in place of the acrylate formulations used in Examples 1-25. The epoxy formulation, which was made by adding 100 parts of epoxy resin, bis(3,4-epoxy- cyclohexylmethyl) adipate with 2 parts of photoactivatable epoxy cure initiator triarylsulfoniumhexafluoroantimonate (General Electric Co.) and 0.1 part of surfactant FC-430 in 100 parts of acetone, was overcoated onto the primed aluminum. The overcoating was cured via ultraviolet light photoinitiation as described above and adhesion of this epoxy overcoating was evaluated for two runs according to ASTM D3359 test method B using Scotch Brand tapes previously mentioned and summarized in the Epoxy Formulation columns of Table IV.
Ex. o n
No. (g) Silane Chemical Structure n 2
39 OCN(CH2 ) 3Si (OC2H5 ) 3
40 HS(CH2)3Si(OCH3)3
41 CH2=CHCONH(CH2)3Si(OC2H5)3
42 CH2=C(CH3)CONH(CH2)3Si(OC2H5)3
43 HO2CCH=CHCONH(CH2)3Si(OC2H5)3
44 H2N(CH2)3Si(OC2H5)3
(c) Run 1 used formulation A (see Ex. 1-12) and Scotch Brand No. 250 Masking Tape in all adhes i o n tests; Run 2 used formulation B (see Ex. 13-25) and Scotch Brand No. 810 Magic Mending Tape i n all adhesion tests
(d) See U.S. Patent No. 3,687,882
(e) Nitric acid omitted
(f) Replicate runs
(g) Ex. Nos. 41-45 were controls
The results of TABLE IV show that the control formulations of Examples 41-45, wherein the silanes contain amino or amido groups, do not perform as well as primers within the present invention. The formulation of Ex. No. 26 gave superior results.
EXAMPLES 46-52 Examples 46-52 illustrate some of the metal esters which have been evaluated as a constituent in the primer formulation. Results are given in Table V using the following procedural model.
A primer composition was prepared by adding one drop of concentrated nitric acid to a solution of 9.8 g isopropyl alcohol containing 0.05 g gamma-methacryloxy- propyltrimethoxysilane with the corresponding weight of selected metal ester indicated in Table V. The weight of metal ester was selected so that the mole ratio of the ester to silane was in a preferred ratio of about 2.6:1 (see Table I). This composition was coated onto two samples of aluminum alloy #3003 (cleaned as indicated in Examples 1-12) which were then cured at 120°C for five minutes. One of the primed panels was then overcoated with overcoating formulation A (see Examples 1-12) and one with overcoating formulation B (see Examples 13-25), and both were then photocheraically cured as described above. The effectiveness of the metal ester in the primer composition was then indirectly measured by evaluating the adhesion of the overcoating onto the respective primed aluminum panel. ASTM D3359 test method B used Scotch Brand tapes previously mentioned and the results are provided in Table V.
(g) control
(h) nitric acid omitted
The data of TABLE V show a range of priming capabilities observable upon use of different metal esters (alkoxides). Preferred, due to performance, price, and availability is Ti(i-OC3H7)4.
EXAMPLES 53-57
Various metal substrates for the primer coatings and the organic overcoatings were evaluated and the results are summarized in Table VI. The following is a model for the procedure used. Each pair of primer solutions in Examples 54-57 was coated onto clean sample panels of copper, steel, and zinc, and cured at 120°C for five minutes. Primer solutions in corresponding overcoatings as prepared in Examples 1, 4, 6, 11, 13, 18, 20, and 25 refer to Examples 54, 55, 56, and 57 as described in TABLE VI. The adhesion of the overcoatings to the panels was evaluated in accordance with ASTM D3359 test B using Scotch Brand No. 250 Masking Tape for Run 1 and Scotch Brand No. 810 Magic Mending Tape for Run 2.
(i) Cleaned using ASIM method B281A 1.5
(j) Cleaned by acetone rinse, then wiped, then acetone rinsed, and air dried (k) Cleaned by 1 rain, immersion in 0.3% hydrochloric acid followed by distilled water rinse, then air dried (l) Ex. Nos. 53, 54, 55, and 57 were controls
Results of TABLE VI show that the formulation of Ex. No. 56 , within the present invention , gave better to superior results to controls on all substrates evaluated , except copper.
EXAMPLES 58-60 The application of three different acrylic monomer based overcoatings onto primed aluminum is illustrated by Examples 58-60 with details and adhesion results reported in Table VII. In each case , the most preferred (i.e. , Ti: Si ratio of 3 : 1 ) primer composition of Example 20 was coated onto panels of cleaned aluminum alloy #3003 and cured at 120 °C for five minutes. The panel was overcoated (see Table VII) with the respective acrylate formulation which contained one drop of 10% FC 431 surfactant in acetone plus the indicated amount of photoinitiator ( i .e. , 2-hydroxy-2-rae thyl (3 ' ,4 ' -dimethyl ) - propiophenone , HMDP. The overcoating was cured by the
photo initiation technique and adhesion was evaluated according to ASTM D3359 test method B using Scotch Brand No . 810 Magic Mending Tape .
The results of TABLE VII show that all three cured monomer coatings adhered very well to the primed aluminum.
EXAMPLES 61-76 The percent adhesion of primed , overcoated aluminum wherein no acidic material was incorporated into the primer formulation is shown in the data of Examples 61-64 of Table VIII , while the percent adhesion using various acid ic materials incorporated into the primer formulation is given in the data of Examples 65-76 of Table VIII . Two curing temperatures ( 90°C and 150°C) and two curing times ( 5 minutes and 10 minutes) are reported . The following procedure was the model for the examples in Table VIII.
A primer coating composition , prepared by adding 0.03 g of acidic material to a solution of 9.8 g of isopropyl alcohol containing 0. 1 g of tetrapropyl titanate with 0.1 g of gamma-raethacryloxypropyltrimethoxysilane was coated onto aluminum as described in Example 1 and cured at 90°C for five minutes . The primed panel was then
overcoated with the overcoating formulation A (see Example
1) and photochemically cured as described in Example 1.
Adhesion was evaluated according to model ASTM D3359 test method B using Scotch Brand No. 810 Magic Mending Tape. Results are shown in Table VIII.
n
(m) PDS = bis(ρerfluoromethylsulfonyl)phenylmethane (see
U.S. Patent No. 3 ,632,843)
The data of TABLE VIII show that acidic material is not required in the primer compositions of the present invention; however, it is preferred and more consistent results are obtainable when acid is used.
EXAMPLES 77-87
The percent adhesion of unpriraed and primed overcoated aluminum wherein different concentrations of nitric acid and acetic acid were used in the primer formulation is summarized in TABLE IX. The following procedure is a model for Examples 77-87.
A primer coating composition, prepared by adding the specified amount of acid, as indicated in the corresponding example of TABLE IX, to a solution of 9.8 g of isopropyl alcohol containing 0.15 g of tetraisopropyl titanate with 0.05 g gamma-methacryloxypropyltrimethoxy- silane, was coated onto cleaned aluminum as described in Examples 13-25 and cured at 120°C for five minutes. The primed panel was then overcoated with overcoating formulation B and photochemically cured as described in Examples 13-25. Adhesion was evaluated according to model ASTM D3359 test method B using Scotch Brand No. 810 Magic Mending Tape. The results are summarized in TABLE IX.
The results of TABLE IX show that, within limits, varying the amount of acidic material in the primer composition does not deleteriously affect adhesion.
It was useful to have a ratio of moles of inorganic acid to the sum of mole quantities of titanate plus silane that were 0:1 to 10:1, and preferably 0.5:1 to 4:1, and for the organic acidic materials, the useful mole ratios were 0:1 to 20:1, and preferably 0.5:1 to 8:1.
EXAMPLE 88 Modified ASTM D 2197 Test Method B mentioned above was used in this example. Primed (as in Example 6) and non-primed aluminum panels were overcoated with formulation A (see Examples 1-12) modified to include about 0.05% of Brillant Yellow fluorescent indicator (Aldrich Chemical Co., Milwaukee, WI) for visual purposes. Each panel was placed under the tip of a carbide scribe to which a force of about 130 g was applied. Each panel was then mechanically moved beneath this scribe to provide a line through the overcoating. A second line, parallel to and 0.25 ram away from the first line, was similarly scribed. The overcoating between these two scribed lines remained intact on the primed panel but flaked off from the non-primed panel, indicating a failure of the overcoating to adhere to the non-primed substrate.
Various modifications and alterations of this invention will become apparent to those skilled in the art without departing from the scope and spirit of this invention, and it should be understood that this invention is not to be unduly limited to the illustrative embodiments set forth herein.
Claims
1. A layered structure comprising an inorganic substrate selected from metals, metal oxides, and ceramics, said layered structure characterized by: a. a primer composition having a thickness in the range of 0.02 to 0.5 microns, coated upon said substrate, said priming composition comprising: 1) one part by weight of a non-amino- or non-amido-containing silane of the formula
[R1]m-Si-[R2]n (1)
in which R1 is an alkyl or cycloalkyl group that can be unsubstituted or substituted by an ethenyl, methethenyl, acryloxy, methacryloxy, epoxy, mercapto, or an isocyanato group, said substituted group having a total of two to ten carbon atoms and said unsubstituted group having a total of one to eight carbon atoms; R2 is a hydrolyzable group selected from alkoxy groups having one to eight carbon atoms, and acyloxy groups having two to eight carbon atoms; m is an integer from 1 to 3; n is an integer from 1 to 3, with the proviso that m + n = 4; 2) 1 to 50 parts by weight of metal ester of the formula
M[OR3]x (2)
in which M is a metal selected from the group comprising titanium, tantalum, zirconium, aluminum, and antimony; R3 is an alkyl group having from one to eight carbon atoms; and x is equal to the number of valence bonds of M, and 3) 0:1 to 10:1 moles by weight of an inorganic acidic material, or 0:1 to 20:1 moles by weight of an organic acidic material, compared to the total moles by weight of metal ester plus silane,
4) 50 to 99 weight percent of solvent consisting essentially of organic solvent compared to the total composition weight, and b. at least one layer of an overcoating composition polymerized in situ and comprising at least one organic monomer selected from epoxy and vinyl monomers.
2. The layered structure according to Claim 1 wherein said silane is selected from methyltriethoxysilane, octyltriethoxysilane, cyclohexyltrimethoxysilane, vinyltriacetoxysilane, methyl vinyldiethoxysilane, divinyldiethoxysilane, gamma-methacryloxypropyltrimethoxysilane, garama-glycidoxypropyltrimethoxysilane, beta-(3,4-epoxy- cyclohexyl)ethyltrimethoxysilane, gamma-mercaptopropyl- trimethoxysilane, and gamma-isocyanatopropyltriethoxy- silane, wherein said metal ester is selected from tetraisopropyl titanate, tetrabutyl titanate, tetraethyl titanate, tetra-2-ethylhexyl titanate, pentaethyl tantalate, aluminum isopropoxide, aluminum-s-butoxide, and tetra-n-propyl zirconate, and wherein said inorganic substrate is selected from the group consisting of steel, zinc, aluminum, and ceramics.
3. The layered structure according to Claims 1 or 2 wherein said silane is gamma-methacryloxypropyl- trimethoxysilane, wherein said metal ester is tetraisopropyl titanate, and wherein said substrate is aluminum.
4. The layered structure according to any of the foregoing Claims wherein said metal ester and said silane are in a weight ratio in the range of 3:1 to 10:1.
5. The layered structure according to any of the foregoing Claims wherein said primer composition is cured.
6. The layered structure according to any of the foregoing Claims wherein said monomer in said overcoating composition is selected from bis(3,4-epoxycyclohexylmethyl) adipate, trimethylolpropane triacrylate, hexanediol diacrylate, pentaerythritol tetraacrylate, 1,3-bis[3- (2,2,2-triacryloxymethyl)ethoxy-2-hydroxy-propyl]-5,5- dimethyl-2,4-imidazolidinedione, and 1,3-bis[3-(2-acryloxy- ethoxy)-2-hydroxypropyl]-5,5-dimethyl-2,4-imidazolidine- dione.
7. The layered structure according to any of the foregoing Claims wherein said mole ratio of acidic material to metal ester plus silane is 0.5:1 to 4:1 moles by weight of an inorganic acidic material, or 0.5:1 to 8:1 moles by weight of an organic acidic material.
8. The layered structure according to any of the foregoing Claims wherein said overcoating composition further comprises leveling agents, diluents, colorants, fillers, or viscosity modifiers.
9. An article comprising the cured layered structure according to any of the foregoing Claims.
10. A primer composition useful for forming the layered structure of Claim 1, comprising: a. one part by weight of a non-amino- or non-amido- containing silane of the formula
[R1]m-Si-[R2]n (1)
in which R! is an alkyl or cycloalkyl group that can be unsubstituted or substituted by an ethenyl, methethenyl, acryloxy, methacryloxy, epoxy, mer capto, or an isocyanato group, said substituted group having a total of two to ten carbon atoms and said unsubstituted group having a total of one to eight carbon atoms; R2 is a hydrolyzable group selected from alkoxy groups having one to eight carbon atoms and acyloxy groups having two to eight carbon atoms; m is an integer from 1 to 3; n is an integer from 1 to 3, with the proviso that m + n = 4; b. 1 to 50 parts by weight of metal ester of the formula
M[OR3]x (2)
in which M is a metal selected from a group comprising titanium, tantalum, zirconium, aluminum, and antimony; R3 is an alkyl group having from one to eight carbon atoms; and x is equal to the number of valence bonds of M, c. 0.5:1 to 4:1 moles by weight of an inorganic acidic material, or 0.5:1 to 8:1 moles by weight of an organic acidic material, compared to the total moles by weight of metal ester plus silane, and d. an amount of solvent consisting essentially of organic solvent sufficient to provide for blending of the components of said primer composition.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE8282901753T DE3273618D1 (en) | 1981-05-20 | 1982-04-22 | Primed inorganic substrates overcoated with curable protective compositions |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US265467810520 | 1981-05-20 | ||
US06/265,467 US4356233A (en) | 1981-05-20 | 1981-05-20 | Primed inorganic substrates overcoated with curable protective compositions |
Publications (1)
Publication Number | Publication Date |
---|---|
WO1982004015A1 true WO1982004015A1 (en) | 1982-11-25 |
Family
ID=23010565
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/US1982/000518 WO1982004015A1 (en) | 1981-05-20 | 1982-04-22 | Primed inorganic substrates overcoated with curable protective compositions |
Country Status (6)
Country | Link |
---|---|
US (1) | US4356233A (en) |
EP (1) | EP0079372B1 (en) |
JP (1) | JPS58500752A (en) |
CA (1) | CA1170926A (en) |
DE (1) | DE3273618D1 (en) |
WO (1) | WO1982004015A1 (en) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0280423A2 (en) * | 1987-02-26 | 1988-08-31 | Lord Corporation | Heat activated silicon-based adhesive |
Families Citing this family (24)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4525422A (en) * | 1982-11-22 | 1985-06-25 | Olin Corporation | Adhesion primers for encapsulating epoxies |
US4521469A (en) * | 1982-11-22 | 1985-06-04 | Olin Corporation | Casing for electronic components |
US4692044A (en) * | 1985-04-30 | 1987-09-08 | International Business Machines Corporation | Interface resistance and knee voltage enhancement in resistive ribbon printing |
US4673354A (en) * | 1985-10-01 | 1987-06-16 | Minnesota Mining And Manufacturing Company | Stable silanol priming solution for use in dentistry |
US5204404A (en) * | 1989-03-21 | 1993-04-20 | E. I. Du Pont De Nemours And Company | Waterbased acrylic silane and polyurethane containing coating composition |
EP0601219B1 (en) * | 1990-08-16 | 1997-09-10 | E.I. Du Pont De Nemours And Company | Waterbased acrylic silane and polyurethane containing coating composition |
US5139601A (en) * | 1990-04-11 | 1992-08-18 | Lord Corporation | Method for metal bonding |
DE69219465T2 (en) * | 1991-05-08 | 1997-10-09 | Minnesota Mining And Mfg. Co., Saint Paul, Minn. | WASHABLE RETRORE-REFLECTIVE APPLICATION WORK |
CA2061708C (en) * | 1991-05-08 | 2002-04-23 | Wu-Shyong Li | Launderable retroreflective applique with colorant |
US5200262A (en) * | 1992-04-01 | 1993-04-06 | Minnesota Mining And Manufacturing Company | Launderable retroreflective applique with improved retention of retroreflective elements |
US5578347A (en) * | 1994-05-24 | 1996-11-26 | E. I. Du Pont De Nemours And Company | Process for applying a finish to a metal substrate |
GB9501287D0 (en) * | 1995-01-24 | 1995-03-15 | Ciba Geigy Ag | Surface treatment |
US5691402A (en) * | 1996-09-13 | 1997-11-25 | Composite Technology Group, Llc | Composite tooling material having vinyl ester resins and fillers |
US6136382A (en) * | 1997-12-29 | 2000-10-24 | Deco Patents, Inc. | Method and compositions for decorating vitreous articles with radiation curable inks having improved adhesion and durability |
US6413588B1 (en) | 1999-01-11 | 2002-07-02 | E. I. Du Pont De Nemours And Company | Method of producing durable layered coatings |
US6309587B1 (en) | 1999-08-13 | 2001-10-30 | Jeffrey L. Gniatczyk | Composite molding tools and parts and processes of forming molding tools |
US6475329B1 (en) | 1999-10-04 | 2002-11-05 | Tyco Electronics Corporation | Primer for silicone compositions |
US6709755B2 (en) | 2001-10-18 | 2004-03-23 | E. I. Du Pont De Nemours And Company | Method of priming inorganic substrates with a silane-based primer composition |
KR101012950B1 (en) * | 2003-10-15 | 2011-02-08 | 삼성전자주식회사 | Composition for Preparing Organic Insulator and the Organic Insulator |
US20060257555A1 (en) * | 2005-05-12 | 2006-11-16 | Brady Brian K | Sub-layer for adhesion promotion of fuel cell bipolar plate coatings |
US8133591B2 (en) * | 2006-06-27 | 2012-03-13 | GM Global Technology Operations LLC | Adhesion of polymeric coatings to bipolar plate surfaces using silane coupling agents |
DE102007030196A1 (en) * | 2006-11-03 | 2008-05-08 | Tesa Ag | Solution, in particular, for the pretreatment of a hydrophilic substrate to improve bonding in wet and moist conditions |
DE102018109102A1 (en) * | 2018-04-17 | 2019-10-17 | Schott Ag | Printed device component |
CN110643045A (en) * | 2019-08-30 | 2020-01-03 | 武汉华星光电半导体显示技术有限公司 | Hard material, method for producing the same, and cover plate and display device using the same |
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US3321350A (en) * | 1962-02-19 | 1967-05-23 | Union Carbide Corp | Organofunctional silane-hydrolyzable titanate primer compositions |
US3687882A (en) * | 1971-04-29 | 1972-08-29 | Nexcel Corp | Silane-titanate dispersions for coating aluminum |
US3794556A (en) * | 1970-12-30 | 1974-02-26 | Dow Corning | Primer composition for adhering silicone elastomer to substrates |
US4042749A (en) * | 1974-10-08 | 1977-08-16 | Minnesota Mining And Manufacturing Company | Article having abrasion resistant surface formed from the reaction product of a silane and a metal ester |
US4073967A (en) * | 1974-10-08 | 1978-02-14 | Minnesota Mining And Manufacturing Company | Method for rendering substrates resistant to abrasion |
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US2721855A (en) * | 1953-03-16 | 1955-10-25 | Dow Corning | Air-drying organosilicon compositions containing a titanic acid ester |
US3779991A (en) * | 1970-07-24 | 1973-12-18 | Essex International Inc | Silicon-hydantoin-ester resins |
BE793557A (en) * | 1971-12-30 | 1973-06-29 | Stauffer Chemical Co | COATING COMPOSITIONS PROVIDING GALVANIC PROTECTION |
JPS51126298A (en) * | 1975-03-25 | 1976-11-04 | Minnesota Mining & Mfg | Abrasionnresistant coat |
-
1981
- 1981-05-20 US US06/265,467 patent/US4356233A/en not_active Expired - Lifetime
-
1982
- 1982-04-22 JP JP57501776A patent/JPS58500752A/en active Pending
- 1982-04-22 WO PCT/US1982/000518 patent/WO1982004015A1/en active IP Right Grant
- 1982-04-22 DE DE8282901753T patent/DE3273618D1/en not_active Expired
- 1982-04-22 EP EP82901753A patent/EP0079372B1/en not_active Expired
- 1982-05-19 CA CA000403318A patent/CA1170926A/en not_active Expired
Patent Citations (6)
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US3321350A (en) * | 1962-02-19 | 1967-05-23 | Union Carbide Corp | Organofunctional silane-hydrolyzable titanate primer compositions |
US3794556A (en) * | 1970-12-30 | 1974-02-26 | Dow Corning | Primer composition for adhering silicone elastomer to substrates |
US3687882A (en) * | 1971-04-29 | 1972-08-29 | Nexcel Corp | Silane-titanate dispersions for coating aluminum |
US4042749A (en) * | 1974-10-08 | 1977-08-16 | Minnesota Mining And Manufacturing Company | Article having abrasion resistant surface formed from the reaction product of a silane and a metal ester |
US4073967A (en) * | 1974-10-08 | 1978-02-14 | Minnesota Mining And Manufacturing Company | Method for rendering substrates resistant to abrasion |
US4084021A (en) * | 1974-10-08 | 1978-04-11 | Minnesota Mining And Manufacturing Company | Method for rendering substrates resistant to abrasion |
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Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0280423A2 (en) * | 1987-02-26 | 1988-08-31 | Lord Corporation | Heat activated silicon-based adhesive |
EP0280423A3 (en) * | 1987-02-26 | 1989-12-06 | Lord Corporation | Heat activated silicon-based adhesive |
Also Published As
Publication number | Publication date |
---|---|
EP0079372A1 (en) | 1983-05-25 |
CA1170926A (en) | 1984-07-17 |
JPS58500752A (en) | 1983-05-12 |
EP0079372A4 (en) | 1983-08-17 |
DE3273618D1 (en) | 1986-11-13 |
EP0079372B1 (en) | 1986-10-08 |
US4356233A (en) | 1982-10-26 |
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