Source: http://www.google.com/patents/US4904360?dq=7,134,016
Timestamp: 2015-08-04 13:53:54
Document Index: 791702997

Matched Legal Cases: ['arts 9', 'arts 2', 'arts 2', 'arts 9', 'arts 2', 'arts 2', 'arts 2', 'arts 9', 'arts 2', 'arts 2', 'arts 9', 'arts 2', 'arts 290', 'arts 9', 'arts 2', 'arts 450', 'arts 2', 'arts 2', 'arts 2', 'arts 2', 'arts 2', 'arts 2', 'arts 2', 'arts 2', 'arts 2', 'arts 2', 'arts 2', 'arts 2', 'arts 2']

Patent US4904360 - Water-compatible coating composition - Google PatentsSearch Images Maps Play YouTube News Gmail Drive More »Sign inAdvanced Patent SearchPatentsWater-compatible compositions containing resins that contain nitrogen but are substantially free of mercaptan groups, primary amino groups, and secondary amino groups. The compositions are heat-cured at low temperatures using bis-maleimides or sparingly-soluble corrosion-inhibiting chromate pigments....http://www.google.com/patents/US4904360?utm_source=gb-gplus-sharePatent US4904360 - Water-compatible coating compositionAdvanced Patent SearchPublication numberUS4904360 APublication typeGrantApplication numberUS 07/149,434Publication dateFeb 27, 1990Filing dateJan 29, 1988Priority dateSep 12, 1986Fee statusLapsedPublication number07149434, 149434, US 4904360 A, US 4904360A, US-A-4904360, US4904360 A, US4904360AInventorsThomas H. Wilson, Jr., Alphonsus V. PociusOriginal AssigneeMinnesota Mining And Manufacturing CompanyExport CitationBiBTeX, EndNote, RefManPatent Citations (25), Non-Patent Citations (10), Referenced by (35), Classifications (17), Legal Events (6) External Links: USPTO, USPTO Assignment, EspacenetWater-compatible coating composition
US 4904360 AAbstract
1. A process for coating a metallic substrate with cathodic electrophoretically depositable structural adhesive bonding primer, comprising the steps of:(A) placing said substrate in fluid contact with an anode and a coating composition comprising(i) water-compatible curable resin having a substantially linear structure of the formula: A31 30 C--E--(L--E)y --C+ A- wherein: each E is independently a residue of a diepoxide; each L is independently a residue of a linking compound having an average of two epoxide-reactive groups; each C is independently a cationic water-compatible ammonium, sulfonium or phosphonium group; each A is independently the conjugate base of a water-soluble acid HA having a pKa for use under cathodic electrodeposition conditions; and y has an average value of about 1 to about 20; (ii) crosslinking agent selected from the group consisting of bis-maleimide and sparingly-soluble chromate pigments; (iii) water; and (iv) resin solvent or coalescing solvent, said curable resin containing tertiary nitrogen before or after electrodeposition but being substantially free, before and after electrodeposition, of mercaptan groups, primary amino groups and secondary amino groups, with the proviso that said nitrogen comprises tertiary aromatic amine if said crosslinking agent consists of said pigment; (B) passing electrical current between said substrate and said anode for a time period sufficiently long to attain a continuous coating of said primer on said substrate; (C) removing excess primer from said substrate; and (D) heating said primer, in the absence of a UV photoinitiator or a UV curecycle, at a curing temperature and for a curing time sufficient to crosslink said primer to a solvent-resistance state. 2. A process according to claim 1, wherein said substrate comprises aluminum, said curing temperature is about 176� C. or less, and said curing time is about 2 hours or less.
3. A process according to claim 1, wherein said crosslinking agent is a sparingly-soluble chromate pigment.
4. A process according to claim 3, wherein said pigment is selected from the group consisting of barium chromate and lead chromate.
This application is a continuation-in-part of application Ser. No. 906,795, filed Sept. 12, 1986. now abandoned.
Several electrodepositable primers have been investigated for use on aircraft parts, to prepare such parts for the application of structural bonding adhesives and to inhibit corrosion. These primers include the anodic electrodepositable primers described in U.S. Pat. No. 4,405,427 and the cathodic electrodepositable primers described in Diener, S.L. "Exploratory Development of Corrosion Inhibiting Primers", Report No. AFML-TR-77-71 (May, 1977), Diener, S.L. "Development of Improved Electrodeposited Corrosion Inhibiting Primers", Report No. AFML-TR-79-4073 (June, 1978), Diener, S.L. and Mels, S. J., "Electrodeposited Corrosion Inhibiting Adhesive Primers", Proceedings of the 11th National SAMPE Technical Conference, Azusa, California, page 759 (1979), Beckwith, G.E., "Interfacial Bond Integrity (350� F Service)", Report No. AFWAL-TR-82-4171 (January, 1983) and Meade, L.E. and McBrayer, T.E., "Manufacturing Technology for Integration of Advanced Repair Bonding Techniques", Report No. IR-466-1(IX) (January 15, 1985).
The anodically-applied primer of the ,'427 patent would be expected to have only limited corrosion resistance. Adhesive bonds made with the primers of the other references cited above exhibit a loss in shear strength after exposure to elevated temperatures. For example, the best reported primer of the Beckwith reference was a composition identified as "MD-902". Using "AF-143" epoxy film adhesive (3M), this primer provided adhesive bonds that after exposure to 149� C. for only 200 hours exhibited an 18% drop in lap shear strength. In comparison, bonds made using state-of-the-art solvent-borne primers and the same epoxy film adhesive typically exhibit an increase in lap shear strength when exposed to similar conditions, since the cured film adhesive gains strength when first heated.
Improved retention of adhesive strength at temperatures of 149� C. and above and service times of 200 hours and longer is considered desirable, particularly for applications such as the manufacture or repair of aircraft, in order to insure that the bonded assembly will not fail in use. As indicated by the above references and data, current primers do not satisfy this need. In an effort to obtain primers that will satisfy it, the U.S. Air Force recently issued RFP No. F33615-86R-5009 for "Electrodeposited Primer Development".
The present invention provides, in one aspect, a water-compatible (i.e., water-soluble or water-dispersible) coating composition comprising a) water-compatible curable resin having a substantially linear structure and water-solubilizing groups (i.e., terminal, pendant or backbone groups that are cationic, anionic, amphoteric or nonionic), the backbone of such resin being derived from reaction between a polyepoxide and a linking compound having a plurality of (preferably two) epoxide-reactive groups, and (b) crosslinking agent selected from the group consisting of bis-maleimides and sparingly-soluble corrosion-inhibiting chromate pigments, the uncured resin containing tertiary nitrogen before or after electrodeposition but being substantially free, before and after electrodeposition, of mercaptan groups, primary amino groups and secondary amino groups, with the proviso that said nitrogen comprises tertiary aromatic amine if said crosslinking agent consists of said pigment, said composition being curable to form a solvent-resistant coating without the use of a UV photoinitiator or UV cure cycle.
A- + C--E--(L--E)y --C+ A-         II
y has an average value of about 1 to about 20. The water-compatible coating compositions containing a resin of Formula II are particularly useful as cathodic electrophoretically-depositable structural adhesive bonding primers ("CEDSABPs").
Tertiary amino groups, if present in the resin, are believed to be unaffected by electrodeposition. Quaternary ammonium groups and tertiary amine acid salt groups, if present in the resin, are believed to form tertiary amino groups upon electrodeposition. When dissolved or dispersed in water, the resin is free of secondary amine acid salt groups (which are believed to form secondary amine groups upon electrodeposition) and primary amine acid salt groups (which are believed to form
The water-compatible resins preferably have terminal water-solubilizing groups, although such groups can be pendant or, if desired, bound within the backbone of the resin. The preferred resins have terminal water-solubilizing groups, and the discussion that follows will deal primarily with such resins. These resins can be synthesized by reacting a polyepoxide with a linking compound having a plurality of epoxide-reactive groups, using a stoichiometric excess of epoxide groups to epoxide-reactive groups, to provide a substantially linear reaction product having terminal epoxide groups. For brevity, this reaction product will sometimes be referred to herein as the "EL" reaction product. The polyepoxide preferably is a diepoxide, and the epoxide-reactive linking compound preferably contains two epoxide-reactive groups. If desired, limited quantities of tri- or higher-functional epoxides (e.g., tetraepoxides) or tri- or higher-functional epoxide-reactive linking compounds (e.g., di(primary)amines) can be combined with the above-described reactants to form the EL reaction product, although this may decrease the linearity and increase the brittleness of cured coatings made from the resulting resin. The EL reaction product is made water-compatible by reacting it with an epoxide-reactive water-compatibilizing compound. For brevity, the reaction product formed by reacting this water-compatibilizing compound with the EL reaction product will sometimes be referred to herein as the "ELT" reaction product.
Suitable polyepoxide reactants (for brevity, such reactants will sometimes be referred to herein as "E precursors") include 1,2-, 1,3-, or 1,4-aromatic diepoxides such as those described in Frisch and Reegan, "Ring-Opening Polymerizations", Vol. 2, Marcel Dekker, Inc. (1969). Particularly useful are mono- or poly-nuclear aromatic diepoxides, for example, phenol-based 1,2-epoxides such as resorcinol diglycidyl ether (e.g., "Kopoxite"), bisphenol-based 1,2-epoxides such as the diglycidyl ether of bisphenol A ("DGEBA") (e.g., "EPON 828" and "DER 331"), and polynuclear diepoxides such as 2,2-bis[4-(2,3epoxyproxy)phenyl]norcamphane, 2,2-bis[4-(2,3-epoxypropoxy)phenyl]decahydro-1,4,5,8-dimethanonaphthalene and 9,9-bis[4-(2,3-epoxypropoxy)phenyl]fluorene. Mixtures of aromatic diepoxides can be used if desired.
Cycloaliphatic, heterocyclic or aliphatic diepoxides also can be used as E precursors. However, they are less preferred, and are believed to be less stable against oxidation than aromatic diepoxides. Examples of such less preferred diepoxides include vinylcyclohexene dioxide (e.g., "ERL-4206"), 3,4-epoxycyclohexylmethyl3,4-epoxycyclohexanecarboxylate (e.g., "ERL-4221"), 3,4-epoxy-6-methylcyclohexylmethyl-3,4-epoxy-6-methylcyclohexanecarboxylate (e.g., "ERL-4201"), bis(3,4-epoxy6-methylcyclohexylmethyl)-adipate (e.g., "ERL-4289"), aliphatic epoxy modified with polypropylene glycol (e.g., "ERL-4050" and "ERL-4052"), dipentene dioxide (e.g., "ERL-4269"), 1,4-butanediol diglycidyl ether (e.g., "Araldite RD-2"), polyglycol diepoxide (e.g., "DER 736"), urethane modified epoxide (e.g., "QX3599"), polyfunctional flexible epoxides (e.g., "Flexibilizer 151"), and mixtures thereof.
The diglycidyl ether of bisphenol A ("DGEBA") is a particularly preferred diepoxide for use in the present invention. This and many other suitable epoxy resins are commercially available, e.g., as listed in Lee and Neville, "Handbook of Epoxy Resins", McGraw-Hill Book Company, New York (1967) and in Bruins, P.F., "Epoxy Resin Technology", John Wiley & Sons, New York (1968).
The epoxide-reactive linking compound has a plurality of (preferably two) epoxide-reactive groups. For brevity, such linking compounds will sometimes be referred to herein as "L precursors". Preferred epoxide-reactive groups are selected from amine, phenol, mercaptan, and carboxyl groups, as well as mixtures thereof. For example, the L precursor can be a diphenol, aliphatic glycol, secondary amine, dimercaptan, dicarboxylic acid, or other compound containing a combination of amine, phenol, mercaptan, or carboxyl groups. Preferably, the L precursor is an aromatic diamine e.g., a di(methylaryl(amine)), diphenol, or di(arylthiol). Most preferably, the L precursor has a bulky, Tg -enhancing structure. Such bulky L precursors are described in copending U.S. Pat. application Ser. No. 906,830, "Water-Compatible Coating Resin", filed on Sept. 12, 1986 in the name of Alphonsus V. Pocius. The disclosure of that application is incorporated herein by reference.
The coating compositions of the invention are crosslinked using a crosslinking agent selected from bis-maleimides and sparingly soluble corrosion-inhibiting chromate pigments. Suitable bis-maleimides are described in U.S. Pat. Nos. 3,925,181, 4,225,409, 4,029,561, 4,035,272, 4,037,018, 4,066,523, 4,094,843, 4,130,469, and 4,140,816. Bis-maleimides can be made using conventional methods, e.g. by reaction of maleic anhydride and a di(primary)amine as described in U.S. Pat. No. 2,444,536. Since most bis-maleimides are insoluble in water and common organic solvents, they usually are employed in particulate form.
Preferred bis-maleimides have the formula: ##STR1## wherein R is an alkylene, arylene, alkarylene or cycloalkylene group, or a polymeric linkage with a molecular weight sufficiently low to provide a cured coating resin having the desired physical properties. Bis-maleimides of Formula III can be prepared from di(primary)amines of the formula H2 NRNH2. Preferably, R is --(CH2)6 --, --C6 H4 SO2 C6 H4 --, --C6 H4 CH2 C6 H4-- or --C6 H10 CH2 C6 H10 --. If a crosslinking pigment is used as the sole crosslinking agent, the cured coating film may tend toward roughness. Accordingly, sufficient bis-maleimide or other crosslinking film-former preferably is included to provide a solvent-resistant cured coating and discourage roughness.
If desired, crosslinking film-formers other than bis-maleimides, or noncrosslinking pigments can be added to the coating compositions. Such other crosslinking film-formers include blocked isocyanates, aminoplasts and phenolplasts e.g., as described in U.S Pat. Nos. 3,894,922, 3,959,106, 4,064,090, 4,134,864, 4,198,331, 4,248,753, 4,256,560, 4,339,369 and 4,376,848. Such noncrosslinking pigments include sparingly-soluble molybdates, phosphates (e.g., zinc phosphate), and phospho-molybdates, and insoluble pigments such as carbon black, titania, and talc. Use of such pigments can provide additional corrosion inhibition, alter color, modify flow characteristics, or reduce cost.
The CEDSABP can be applied to metallic substrates using methods familiar to those skilled in the art. The CEDSABP preferably is placed in a nonconductive vessel equipped with a stirrer and a metallic (e.g., stainless steel) anode. The vessel itself, if metallic, can serve as the anode. The substrate to be coated is placed in fluid contact with the CEDSABP bath. The substrate and anode are connected to a power supply so that the substrate serves as the cathode. Although voltages as high as 300 volts or more can be used, lower voltages (e.g., about 5 to 80 volts) preferably are used. Current is permitted to flow for a sufficiently long time period to attain the desired coating thickness (e.g., typically a thickness of about 0.002 to about 0.008 millimeters) at the chosen voltage. Such time period preferably is less than about 1 minute and more preferably is less than about 20 seconds. After the substrate has been disconnected from the voltage, excess CEDSABP is removed from the substrate (e.g., by draining and rinsing with water). The coated substrate preferably is allowed to air dry for a short period of time (e.g., about 1/2 hour), followed by heating in an oven at a temperature and for a time sufficient to crosslink the CEDSABP coating. On aluminum, curing temperatures of about 176� C. or less and curing times of about 2 hours or less preferably are employed. Higher cure or post-cure temperatures (e.g., 232� C.) and shorter or longer curing times can be used if desired, especially on heat-resistant substrates such as titanium or steel. Higher cure temperatures and shorter curing times are particularly useful for curing CEDSABPs made from coating resins in which the E precursor is longer than DGEBA.
Panels of bare or clad 2024-T3 aluminum were prepared for testing in accordance with ASTM D-1002 and cleaned in accordance with ASTM D-2651-79, Method G, but using a 10 minute etch. The etched panels were rinsed in tap water, then phosphoric acid anodized in accordance with Boeing specification BAC-5555. The anodized panels were primed by placing them in a stirred CEDSABP bath in a glass tank equipped with a stainless steel anode and applying a potential of 40 Volts DC for 10 seconds. The primed panels were air dried, then placed in an air circulating oven at 176� C. for 1 to 2 hours. The primed panels were bonded to one another in an overlap relationship along their long dimension using a 12.7 mm wide strip of epoxy film adhesive ("AF-143", 0.366 kg/m2, 3M). The resulting assembly was fastened together using tape and cured in a "Bros" autoclave. The temperature of the autoclave was increased by 2 to 3� C./min to a maximum temperature of 177� C., held at that temperature for 1 hour, air-cooled to 79� C., then water-cooled to 25� C.. The bonded panels were sawn into strips and evaluated for overlap shear strength in accordance with ASTM D-1002 using four different test temperatures (-55� C., 25� C., 149� C. and 176� C.). Sawn strips were also exposed to elevated temperatures for extended periods of time, then evaluated for overlap shear strength in order to assess retention of coating properties after heat aging.
Panels of bare or clad 2024-T3 aluminum were prepared for testing in accordance with ASTM D-3167-76, then cleaned, anodized and primed using the same procedure employed for overlap shear samples. The primed panels were bonded together using the same film adhesive and cure cycle employed for overlap shear samples, then evaluated for floating roller peel strength in accordance with ASTM D-3167-76, but using 25.4 mm wide strips and an "Instron" tensile tester operated at a peel rate of 305 mm/min.
209 Parts DGEBA resin with an epoxy equivalent weight of 185 to 192 ("EPON 828", Shell Chemical Co.) and 100 Parts 9,9-bis(4-methylaminophenyl)fluorene were combined in a heated reaction vessel and stirred at 150� C. for 2 hours. 109 Parts mixed xylenes were added to the reaction mixture to dissolve it. 105 Parts of the resulting light-brown EL reaction product solution were placed in a heated reaction vessel maintained at a temperature of 50� C.. A mixture of 10 parts diethylamine, 10 parts 2-butoxyethanol and 5 parts distilled water was added dropwise to the reaction vessel over a period of 5 minutes. The resulting opalescent reaction mixture was allowed to react for 1.5 hours, then allowed to react for an additional 1.5 hours at a temperature of 92� C.. The reaction vessel was opened to the air for 15 minutes and then closed. A mixture of 14.5 parts of an 85% aqueous solution of lactic acid, and 5 parts distilled water was added dropwise to the reaction vessel over a period of 5 minutes. The mixture was allowed to react for 45 minutes at 80� C.. A solution of 18 parts 2-butoxyethanol and 5 parts distilled water was added to the reaction vessel. The resulting viscous, light-brown mixture was stirred for 15 minutes, then removed from the vessel and identified as "Coating Resin A". This resin contained tertiary amine groups within the backbone, and terminal tertiary amine acid salt groups.
The procedure employed for making Coating Resin A was repeated, with the following differences. The EL reaction product was heated to 90� C. instead of 50� C.. 14.4 Parts of diethanolamine were used in place of 10 parts of diethylamine. Following addition of the diethanolamine:2-butoxyethanol:water mixture the reaction mixture was allowed to react for 3 hours at 90� C.. Following addition of the lactic acid:water mixture the reaction mixture was heated to 90� C. instead of 80� C.. Following addition of the 2-butoxyethanol:water solution, the reaction mixture was stirred for 5 minutes rather than 15 minutes. The final product was identified as "Coating Resin B". This resin contained tertiary amine groups within the backbone, and terminal tertiary amine acid salt groups.
312 Parts EPON 828 epoxy resin and 150 parts 9,9-bis(4-methylaminophenyl)fluorene were combined in a heated reaction vessel and stirred at 150� C. for 3 hours. The temperature of the reaction mixture was reduced to 20� C. and 160 parts MIBK added to the reaction mixture to dissolve it. The temperature of the reaction mixture was reduced to 90� C.. A mixture of 100 parts thiodiethanol, 86.7 parts of an 85% percent aqueous solution of lactic acid, and 62 parts distilled water was added dropwise to the reaction vessel over a period of 15 minutes. The reaction mixture was allowed to react for 30 minutes, resulting in formation of a cloudy yellow ELT reaction product. A solution of 55 parts 2-butoxyethanol and 32 parts distilled water was added to the reaction vessel. The resulting solution was stirred for a few minutes, followed by addition of 55 parts 2-butoxyethanol. The solution was stirred for an additional 15 minutes, becoming more transparent. 200 Parts of the resulting yellowish solution were transferred to a flask to which was added with stirring 34.8 parts MIBK and 52.2 parts 2-butoxyethanol. The speed of the stirrer was increased and 600 parts distilled water were slowly added to the reaction vessel, resulting in formation of a brown-white emulsion. The emulsion was removed from the vessel and identified as "Coating Resin C". This resin contained tertiary amine groups within the backbone, and terminal sulfonium salt groups.
112 Parts EPON 829 epoxy resin (a precatalyzed version of EPON 828 epoxy resin) and 50 parts 9,9-bis(4-hydroxyphenyl)fluorene were combined in a heated reaction vessel and stirred at 150� C. for 2 hours. 57 Parts mixed xylenes were added to the reaction mixture to dissolve it. The temperature of the reaction mixture was reduced to 55� C.. A mixture of 21.9 parts diethylamine, 20 parts 2-butoxyethanol and 10 parts distilled water was added dropwise to the reaction vessel over a period of about one-half hour. The reaction mixture became cloudy. The reaction was permitted to proceed overnight, then the temperature of the reaction mixture was increased to 90� C.. A solution of 31.8 parts of an 85% aqueous of lactic acid, and 10.5 parts of distilled water was added dropwise to the reaction vessel over a period of about one-half hour. The mixture was allowed to react for 45 minutes at 90� C. A solution of 38 parts 2-butoxyethanol and 11 parts distilled water was added to the reaction vessel. The resulting amber, translucent mixture was stirred for a few minutes, then removed from the vessel and identified as "Coating Resin D". This resin contained no nitrogen atoms within the backbone, but contained terminal tertiary amine acid salt groups.
83.6 Parts EPON 828 epoxy resin and 40 parts 9,9-bis(4-methylaminophenyl)fluorene were combined in a heated reaction vessel and stirred at 150� C. for 2 hours. 40 Parts MIBK were added to the reaction mixture to dissolve it. The temperature of the reaction mixture was reduced to 90� C.. A mixture of 28.1 parts thiodiethanol, 46.8 parts of an 85% aqueous solution of lactic acid, and 25.3 parts of distilled water was added dropwise to the reaction vessel over a period of about one-half hour. The resulting mixture was allowed to react for 4 hours. The reaction mixture was initially cloudy but began to clear after the first hour of the reaction. A solution of 29 parts 2-butoxyethanol and 8.4 parts distilled water was added dropwise to the reaction mixture over a period of about one-half hour. The mixture was stirred about three-quarters of an hour, then removed from the vessel and identified as "Coating Resin E". This resin contained tertiary amine groups within the backbone, and terminal sulfonium salt groups.
262.5 Parts 290 to 335 epoxy equivalent weight DGEBA resin ("EPON 836", Shell Chemical Co.) and 75.6 parts 9,9-bis(4-methylaminophenyl)fluorene were combined in a heated reaction vessel and stirred at 150� C. for 2.5 hours. 200 Parts MIBK were added to the reaction vessel and the temperature of the reaction mixture was reduced to 90� C.. A mixture of 55 parts thiodiethanol, 48.2 parts of an 85% aqueous solution of lactic acid, and 35 parts distilled water was added dropwise to the reaction mixture over a period of about one-half hour. The resulting mixture was allowed to react for 40 minutes. A solution of 100 parts 2-butoxyethanol and 62 parts distilled water was added dropwise to the reaction mixture over a period of about one-half hour. The resulting translucent, brown mixture was stirred until it became homogeneous, then removed from the vessel and identified as "Coating Resin F". This resin contained tertiary amine groups within the backbone (separated by a longer E residue than in Coating Resin E), and terminal sulfonium salt groups.
employed for making Coating Resin F
The procedure was repeated, with the following differences. 420 Parts 450 to 550 epoxy equivalent weight DGEBA resin ("EPON 1001", Shell Chemical Co.) were used in place of 262.5 parts EPON 836 epoxy resin. The amount of MIBK was increased to 271 parts. The 2-butoxyethanol:water solution contained 135.3 parts 2-butoxyethanol and 100.5 parts water. The final product was identified as "Coating Resin G". This resin contained tertiary amine groups within the backbone (separated by a longer E residue than in Coating Resin E and Coating Resin F), and terminal sulfonium salt groups.
174 Parts EPON 828 and 50 parts bis(N-methyl-p-phenyl)methane were combined in a heated reaction vessel and stirred at 150� C. or more for 2 hours. The temperature of the reaction mixture was reduced to 115� C.. 80 Parts MIBK were added to the reaction mixture to dissolve it, resulting in a formation of a red-amber solution. The temperature of the solution was reduced to 90� C. A mixture of 56.3 parts thiodiethanol, 46.9 parts of 85% aqueous solution of lactic acid, and 85 parts distilled water was added dropwise to the reaction mixture over a period of about one-half hour. The reaction mixture was stirred for 45 minutes at a temperature of 85� to 90� C.. A solution of 25 parts 2-butoxyethanol and 15.5 parts distilled water was added to the reaction vessel over a period of about one-half hour. The resulting red-amber mixture was stirred for 15 minutes at 90� C., then an additional 27 parts 2-butoxyethanol was added with stirring. The mixture was removed from the vessel and identified as "Coating Resin I". This resin contained tertiary amine groups within the backbone, and terminal sulfonium salt groups.
A coating resin with a non-cross planar linking compound was prepared by mixing 300 parts EPON 1001 epoxy resin and 100 parts mixed xylenes in a reaction vessel heated to 90� C.. The epoxy resin was allowed to dissolve. 63.1 Parts diethanolamine were mixed with 63.1 parts 2-butoxyethanol and 31.5 parts distilled water, then added dropwise to the reaction vessel over a period of 30 minutes with stirring. The reaction was allowed to proceed for 3 hours at 90-95� C., then heated to reflux, (99� C.) for 15 minutes and cooled to 90� C.. 63.5 Parts of an 85% aqueous solution of lactic acid was diluted with 20 parts distilled water, then added dropwise to the reaction vessel over a period of 5 minutes with stirring. The reaction mixture was maintained at 90� C. for 45 minutes. 67.7 Parts 2-butoxyethanol and 18.8 parts distilled water were added to the reaction vessel with stirring until a homogeneous mixture was obtained. The resulting solution was removed from the vessel and identified as "Coating Resin J". The linking compound in such resin was derived from bisphenol A, that being a linking compound from which EPON 1001 epoxy resin is believed to be manufactured. This resin contained no nitrogen atoms within the backbone, but contained terminal tertiary amine acid salt groups.
Comparative Coating Resin
A coating resin without nitrogen was prepared by combining 250 parts EPON 1001 epoxy resin and 83.3 parts MIBK at 90� C. in a heated reaction vessel, and adding dropwise to the reaction vessel over a period of about one-half hour a mixture of 61.1 parts thiodiethanol, 53 parts of an 85% aqueous solution of lactic acid, and 38 parts distilled water. The resulting mixture was allowed to react for 30 minutes. Next, a solution of 51 parts 2-butoxyethanol and 34.5 parts distilled water was added to the reaction vessel. The resulting translucent, yellow mixture was stirred until it was homogeneous, then an additional 63.4 parts 2-butoxyethanol was added with stirring. The solution was stirred for a few minutes, allowed to cool, removed from the vessel and identified as "Comparative Coating Resin A".
A coating resin without nitrogen or a linking compound was prepared by heating 150 parts EPON 828 epoxy resin and 50 parts MIBK to a temperature of 90� C. in a reaction vessel equipped with a stirrer, and adding dropwise to the reaction vessel over a period of 15 minutes a mixture of 90 parts thiodiethanol, 85.9 parts of an 85% percent aqueous solution of lactic acid, and 62 parts distilled water. The reaction mixture was allowed to react at 85 to 90� C. for 30 minutes. A solution of 51 parts 2-butoxyethanol and 32 parts distilled water was added to the reaction vessel, stirred for a few minutes, and followed by the addition of 55 parts 2-butoxyethanol. 200 Parts of the resulting yellowish solution were transferred to a flask to which was added with stirring 34.8 parts MIBK and 52.2 parts 2-butoxyethanol. The speed of the stirrer was increased and 600 parts distilled water were slowly added to the reaction vessel, resulting in formation of an emulsion. The emulsion was removed from the vessel and identified as "Comparative Coating Resin B".
250 Parts EPON 1001 epoxy resin and 83 Parts MIBK were combined at 90� C. in a heated reaction vessel. A mixture of 61.1 parts thiodiethanol, 53 parts of an 85% aqueous solution of lactic acid and 38 parts distilled water was added dropwise to the reaction vessel over a period of less than 1/2 hour. The resulting mixture was allowed to react for 30 minutes. Next, 32 parts distilled water and 51 parts 2-butoxyethanol were added to the reaction vessel with stirring. The mixture was stirred until it was homogeneous, then an additional 55 parts 2-butoxyethanol were added with stirring. The resulting solution was allowed to cool, removed from the vessel and labeled as "Comparative Coating Resin C". This resin contained no nitrogen atoms.
The above-described ingredients were used to prepare a varity of CEDSABPs, as described in the following examples:
CEDSABP 1 was cathodically electrophoretically applied to bare aluminum and cured at 176� C. for 1 hour. An orange, MEK-resistant coating was obtained. The coating levelled well and had excellent throwing power. The following lap shear strength and floating roller peel strength values were obtained:
______________________________________Lap shear:-55� C., initial                 257 kg/cm225� C., initial                 253 kg/cm225� C., aged 500 hours at 149� C.                 234 kg/cm225� C., aged 1,000 hours at 149� C.                 250 kg/cm2149� C., initial                 232 kg/cm2149� C., aged 500 hours at 149� C.                 215 kg/cm2149� C., aged 1,000 hours at 149� C.                 236 kg/cm2176� C., initial                 184 kg/cm2176� C., aged 500 hours at 149� C.                 188 kg/cm2176� C., aged 1,000 hours at 149� C.                 185 kg/cm2Floating roller peel: 710 g/cm of width______________________________________
The above overlap shear strength results can be compared with CEDSABP "MD-902" of the Beckwith reference. Its 201 kg/cm2 initial lap shear strength at 149� C. decreased significantly after heat aging, reaching a value of 171 kg/cm2 at 149� C after only 200 hours aging at 149� C.. In contrast, the overlap shear strength of the CEDSABP of this EXAMPLE 1 remained above that of MD-902 even after much longer aging times, and increased in strength after aging for 1000 hours.
CEDSABP 2 was cathodically electrophoretically applied to bare aluminum and cured at 176� C. for 2 hours. A tan, MEK-resistant coating was obtained. The coating levelled well and exhibited excellent throwing power. The following lap shear strength and floating roller peel strength values were obtained:
______________________________________Lap shear:-55� C., initial                 287 kg/cm225� C., initial                 253 kg/cm225� C., aged 500 hours at 149� C.                 246 kg/cm225� C., aged 1,000 hours at 149� C.                 239 kg/cm2149� C., initial                 229 kg/cm2149� C., aged 500 hours at 149� C.                 220 kg/cm2149� C., aged 1,000 hours at 149� C.                 239 kg/cm2176� C., initial                 192 kg/cm2176� C., aged 500 hours at 149� C.                 195 kg/cm2176� C., aged 1,000 hours at 149� C.                 207 kg/cm2Floating roller peel: 890 g/cm of width______________________________________
______________________________________Lap shear:______________________________________-55� C.       246 kg/cm225� C.        266 kg/cm2149� C.       213 kg/cm2176� C.       178 kg/cm2Floating roller peel 1800 g/cm of width(0.003 mm thick primer film):______________________________________
In order to evaluate the resistance of the cured CEDSABP 3 coating to heat aging, bonded samples were stored at 149� C. for various periods of time, then evaluated for lap shear strength at three test temperatures. The lap shear strengths at 25� C., 149� C. and 171� C. were as follows:
______________________________________        Hours at 149� C.Lap shear, Kg/cm2 :          0          500    1000______________________________________ 25� C. 266        224    248149� C. 213        247    229176� C. 178        202    227______________________________________
TABLE I__________________________________________________________________________                                           Bis-maleimide    Coating Resin           Resin solvent                   Coalescing solvent                             Water                                 Pigment Dispersion                                           DispersionEx.   CEDSABP    Type       Parts           Type Parts                   Type Parts                             Parts                                 Type                                     Parts Type                                              Parts__________________________________________________________________________4  4     B  100                   68.5                                 A   17.75  5     B  100 MX.sup.(1)                15.2                   BE.sup.(2)                        25.6 592.7                                 A   76.86  6     B  100                   68.5                                 C   17.77  7     B  100                   68.5                                 D   17.78  8     B  100                   76.7                                 E   9.59  9     C  100 MIBK.sup.(3)                17.4                   BE   26.1 430.510 10    C  100 MIBK 17.4                   BE   26.1 705.4                                 B   123.411 11    C  100 MIBK 17.4                   BE   26.1 430.5         A  102.912 12    D  100 MX   6.5                   BE   23.7 548 A   71.013 13    E  100 MIBK 0.2                   BE   22.3 367.514 14    E  100 MIBK 0.2                   BE   22.3 515.7                                 A   66.815 15    E  100 MIBK 0.2                   BE   22.3 595.3                                 B   105.316 16    E  100 MIBK 0.2                   BE   22.3 367.5         A  87.8__________________________________________________________________________ Notes to entries in Table I .sup.(1) MX = Mixed xylenes. .sup.(2) BE = Butoxyethanol. .sup.(3) MIBK = Methyl isobutyl ketone.
TABLE II______________________________________          CEDSABP   CEDSABP   CEDSABPIngredient     17        18        19______________________________________"XU-292" bis-maleimide          39.8      39.8      39.8BaCrO4    48        48        48Coating Resin F          114.4Coating Resin G          141.8Coating Resin H                    145.1Distilled water          570.4     597.8     566.4______________________________________
These CEDSABPs were individually cathodically electrophoretically applied to aluminum using the method of EXAMPLE 2. All three coatings levelled well and displayed good throwing power. Set out below in Table III are the characteristics of the cured coatings. The entry "--" indicates that the CEDSABP was not evaluated at the indicated test condition.
TABLE III______________________________________          CEDSABP   CEDSABP   CEDSABPProperty       17        18        19______________________________________Lap shear, kg/cm2 :25� C., initial          256       226       24825� C., aged 2,500 hours          --        --        221at 149� C.25� C., aged 2,500 hours          --        --        187at 176� C.149� C., initial          225       209       238149� C., aged 2,500 hours          --        --        251at 149� C.149� C., aged 2,500 hours          --        --        204at 176� C.Floating roller peel,          1070      1750      1390g/cm of width at 25� C.:______________________________________
An MEK rub test on coatings made from the above CEDSABPs, cured at 176� C. for 2 hours, indicated that CEDSABP 19 had excellent solvent resistance, whereas CEDSAPBs 17 and 18 had marginal solvent resistance. All three CEDSABPs had excellent solvent resistance when cured for one hour at 176� C. followed by 20 minutes at 232� C..
TABLE IV______________________________________          CEDSABP   CEDSABP   CEDSABPIngredient     20        21        22______________________________________Coating Resin C          84.3      84.3      84.3Bis-maleimide  77.6Dispersion BBis-maleimide            77.6Dispersion CBis-maleimide                      77.6Dispersion DPigment Dispersion A          93.2      93.2      93.2Distilled Water (total)          745       745       745______________________________________
TABLE V______________________________________          CEDSABP   CEDSABP   CEDSABPProperty       20        21        22______________________________________Lap shear, kg/cm2 :-55� C., initial          251       254       27525� C., initial          256       281       28525� C., aged 500 hours          245       232       240at 149� C.149� C., initial          200       193       210149� C., aged 500 hours          224       226       233at 149� C.176� C., initial          182       171       188176� C., aged 500 hours          212       184       215at 176� C.Floating roller peel,          2320      1790      1607g/cm of width, 25� C.:Pencil hardness:Initial        9H        9H        9HAged 7 days in phosphate          9H        9H        9Hester hydraulic fluidAged 7 days in jet fuel          9H        9H        9HMEK resistance:          excellent excellent excellentCorrosion resistance:          excellent excellent excellentBath stability, aged          excellent hard to   good, but6 weeks at 25� C.:                    redisperse                              rough                              coating______________________________________
This example illustrates the use of a coating resin having a non-cross-planar L moiety. CEDSABP 23 was prepared by slowly adding a solution of 12 parts MIBK and 52.5 parts 2-butyoxyethanol to a rapidly stirred portion (222 parts) of Coating Resin I. 600 Parts distilled water were added slowly with rapid stirring to form an emulsion. 502.5 Parts of the emulsion were combined with 139.8 parts Pigment Dispersion A, 116.5 parts Bis-maleimide Dispersion A and 741.3 parts distilled water, and stirred until homogeneous.
______________________________________Lap shear:-55� C., initial                 239 kg/cm225� C., initial                 271 kg/cm225� C., aged 500 hours at 149� C.                 247 kg/cm2149� C., initial                 204 kg/cm2149� C., aged 500 hours at 149� C.                 234 kg/cm2176� C., initial                 183 kg/cm2176� C., aged 500 hours at 149� C.                 191 kg/cm2Floating roller peel, 25� C.:                 1700 g/cm of widthPencil hardness:Initial               9HAged 7 days in phosphate ester                 9Hhydraulic fluidAged 7 days in jet fuel                 9HMEK resistance:       excellentCorrosion resistance: excellentBath stability, aged 4 weeks at 25� C.:                 excellent______________________________________
TABLE VI______________________________________                             Comparative         CEDSABP   CEDSABP   CEDSABPIngredient    24        25        1______________________________________Let down resin, parts:Coating Resin J         176.6     176.6Comparative Coating               200Resin CDistilled Water         541.3     541.3     600Xylene        35        352-Butoxyethanol         47.1      47.1Let down resin         170.3     170.3     398.2Bis-maleimide A         39.1      39.4      77.6Pigment dispersion A    47.4      93.2Distilled water         137.5     242.9     431______________________________________
TABLE VII______________________________________          Compar.   Compar.   Compar.          CEDSABP   CEDSABP   CEDSABPIngredient     2         3         4______________________________________Coating Resin C          84.26     84.26     84.26"Cymel 300".sup.(1)          51"Mondur XB749".sup.(2)   55.7"Desmocap 11A".sup.(3)             55.7Distilled water          772       772       772Pigment Dispersion A          93.2      93.2      93.2______________________________________ Notes to entries in TABLE VI: .sup.(1) Methoxylated melamine resin, commercially available from America Cyanamid Corp. .sup.(2) Blocked isocyanate, commercially available from Mobay Chemical Corp. .sup.(3) Blocked isocyanate, commercially available from Mobay Chemical Corp.
TABLE VIII______________________________________          Compar    Compar.   Compar.          CEDSABP   CEDSABP   CEDSABPProperty       2         3         4______________________________________Lap shear, kg/cm2 :-55� C., initial          238       102       12325� C., initial          268       77        9325� C., aged 500 hours          207       39        36at 149� C.149� C., initial          200       36        38149� C., aged 500 hours          236       29        27at 149� C.176� C., initial          174       37        43176� C., aged 500 hours          268       25        27at 149� C.Floating roller peel,          1780      360       360g/cm of width, 25� C.:Pencil Hardness:Initial        --        4H        5-6HAged 7 days in phosphate          --        dissolved dissolvedester hydraulic fluidAged 7 days in jet fuel          --        &lt;2H       tacky                    (tacky)MEK resistance:          good      marginal  marginalCorrosion resistance:          slight    good      good          corrosion          and stainingBath stability, aged          powdery,  tacky     hard to6 weeks at 25� C.          nonad-    cured     redisperse,          herent    coating   tacky cured          coating             coating______________________________________
Comparative CEDSABP 6 was cathodically electrophoretically applied to phosphoric acid-anodized bare aluminum. When heated for 2 hours at 171� C., the coating was not MEK-resistant. This is believed to have been due to the absence of a nitrogen atom in the L or T moiety. The coating could be cured to an MEK-resistant state by heating for two hours at 176� C. followed by 0.5 hour at 232� C.. However, a 232� C. cure cycle typically is regarded as unsuitable for aluminum, particularly in aircraft applications.
Patent CitationsCited PatentFiling datePublication dateApplicantTitleUS2444536 *May 14, 1946Jul 6, 1948Du PontSynthesis of nu-aryl-maleimidesUS3477990 *Dec 7, 1967Nov 11, 1969Shell Oil CoProcess for reacting a phenol with an epoxy compound and resulting productsUS3663389 *Apr 17, 1970May 16, 1972American Cyanamid CoMethod of electrodepositing novel coatingUS3894922 *Apr 3, 1974Jul 15, 1975Ppg Industries IncElectrodeposition method utilizing quaternary phosphonium group-containing resinsUS3925181 *Oct 31, 1974Dec 9, 1975Scm CorpCathodic electrocoating processUS3935087 *Dec 23, 1974Jan 27, 1976Ppg Industries, Inc.Method for electrodeposition of self-crosslinking cationic compositionsUS3959106 *Jan 8, 1975May 25, 1976Ppg Industries, Inc.Method of electrodepositing quaternary sulfonium group-containing resinsUS3962165 *Apr 4, 1974Jun 8, 1976Ppg Industries, Inc.Quaternary ammonium salt-containing resin compositionsUS4025409 *Feb 17, 1976May 24, 1977Scm CorporationDual cure cathodic electrocoating processUS4029561 *Jan 22, 1976Jun 14, 1977Scm CorporationPhotocurable cathodic electrocoatingUS4035272 *Jul 23, 1976Jul 12, 1977Scm CorporationCathodic electrocoating processUS4037018 *Jul 2, 1976Jul 19, 1977Scm CorporationCationic aqueous compositions of polymer having amine groups, acid neutralized, and abis-maleimide cross-linker, coatings and processUS4064090 *Jan 23, 1976Dec 20, 1977Dulux Australia Ltd.Aqueous coating composition of epoxy-amine adduct and an acid with cross-linkerUS4066523 *Mar 28, 1977Jan 3, 1978Scm CorporationDual cure cathodic electrocoating compositionUS4094843 *Mar 28, 1977Jun 13, 1978Scm CorporationAqueous coating composition and process from a mercaptan containing polymer and a bis-maleimideUS4130469 *Feb 13, 1978Dec 19, 1978Scm CorporationAqueous coating composition from a mercaptan containing polymer and a bis-maleimideUS4134864 *Jan 23, 1978Jan 16, 1979Celanese Polymer Specialties CompanyCathodic electrocoating resin system comprising the reaction product of polyepoxide, a polyamine and a monocarboxylic acidUS4140816 *Feb 13, 1978Feb 20, 1979Scm CorporationAqueous coating composition and processUS4198331 *Aug 28, 1978Apr 15, 1980Ppg Industries, Inc.Resinous coating compositions curable by Michael adduct exchangeUS4248753 *Aug 28, 1978Feb 3, 1981Ppg Industries, Inc.Michael adducts of polymeric materials useful in coating applicationsUS4256560 *Sep 19, 1979Mar 17, 1981Ppg Industries, Inc.Curable resinous compositions useful in coating applicationsUS4339369 *Apr 23, 1981Jul 13, 1982Celanese CorporationCationic epoxide-amine reaction productsUS4376848 *Apr 3, 1981Mar 15, 1983Lackwerke Wulfing Gmbh & Co.Water dilutable cathodic depositable resinous binder production and useUS4405427 *Nov 2, 1981Sep 20, 1983Mcdonnell Douglas CorporationElectrodeposition of coatings on metals to enhance adhesive bondingUS4684678 *Feb 18, 1986Aug 4, 1987Minnesota Mining And Manufacturing CompanyEpoxy resin curing agent, process, and composition* Cited by examinerNon-Patent CitationsReference1Beckwith, G. E., "Interfacial Bond Integrity (350� F. Service)", Report No. AFWAL-TR-82-4171, (Jan. 1983).2 *Beckwith, G. E., Interfacial Bond Integrity (350 F. Service) , Report No. AFWAL TR 82 4171, (Jan. 1983).3Diener, S. L., "Development of Improved Electrodeposited Corrosion Inhibiting Adhesive Primers", Proceedings of the 11th National SAMPE Technical Conference, Azusa, Calif., p. 759, (1979).4Diener, S. L., "Exploratory Development of Corrosion Inhibiting Primers", Report No. AFML-TR-77-71, (May, 1977).5 *Diener, S. L., Development of Improved Electrodeposited Corrosion Inhibiting Adhesive Primers , Proceedings of the 11th National SAMPE Technical Conference, Azusa, Calif., p. 759, (1979).6 *Diener, S. L., Exploratory Development of Corrosion Inhibiting Primers , Report No. AFML TR 77 71, (May, 1977).7Meade, L. E. and McBrayer, T. E., "Manufacturing Technology for Integration of Advanced Repair Bonding Techniques", Report No. IR-466-1(IX), (Jan. 15, 1985).8 *Meade, L. E. and McBrayer, T. E., Manufacturing Technology for Integration of Advanced Repair Bonding Techniques , Report No. IR 466 1(IX), (Jan. 15, 1985).9 *RFP No. F33615 86R 5009, U.S. Air Force, Air Force Systems Command Aeronautical Systems Division/PMR RB, Mar. 26, 1986.10RFP No. F33615-86R-5009, U.S. Air Force, Air Force Systems Command Aeronautical Systems Division/PMR RB, Mar. 26, 1986.* Cited by examinerReferenced byCiting PatentFiling datePublication dateApplicantTitleUS5143650 *Nov 13, 1990Sep 1, 1992Aster, Inc.Electrophoretic coatable sealant compositions comprising polyvinyl chloride and furnace carbon blackUS5223106 *Apr 23, 1992Jun 29, 1993Aster, Inc.Method of using an electrophoretic coatable sealant composition in assembling automobile bodiesUS5616796 *Apr 14, 1995Apr 1, 1997Minnesota Mining And Manufacturing CompanyOrganoborane polyamine complexes and adhesive composition made therewithUS5684102 *Dec 16, 1996Nov 4, 1997Minnesota Mining And Manufacturing CompanyOrganoborane polyamine complexes and adhesive compositions made therewithUS5795657 *Dec 16, 1996Aug 18, 1998Minnesota Mining And Manufaturing CompanyOrganoborane polyamine complexes and adhesive compositions made therewithUS5872197 *Jun 23, 1997Feb 16, 1999Minnesota Mining & Manufacturing CompanyInitiator system and adhesive composition made therewithUS5883208 *Nov 8, 1996Mar 16, 1999Minnesota Mining And Manufacutring CompanyInitiator system and adhesive composition made therewithUS5935711 *Oct 23, 1996Aug 10, 19993M Innovative Properties CompanyOrganoborane amine complex initiator systems and polymerizable compositions made therewithUS5952409 *Jan 31, 1996Sep 14, 19993M Innovative Properties CompanyCompositions and methods for imparting stain resistance and stain resistant articlesUS5990036 *Oct 7, 1997Nov 23, 19993M Innovative Properties CompanyInitiator system and adhesive composition made therewithUS6027813 *Dec 23, 1998Feb 22, 20003M Innovative Properties CompanyInitiator system and adhesive composition made therewithUS6034194 *Sep 2, 1994Mar 7, 2000Quantum Materials/Dexter CorporationBismaleimide-divinyl adhesive compositions and uses thereforUS6034195 *Jun 2, 1995Mar 7, 2000Dexter CorporationThermosetting resin compositions containing maleimide and/or vinyl compoundsUS6252023Mar 19, 1999Jun 26, 20013M Innovative Properties CompanyOrganoborane amine complex inatator systems and polymerizable compositions made therewithUS6383655Jun 12, 1998May 7, 20023M Innovative Properties CompanyLow odor polymerizable compositions useful for bonding low surface energy substratesUS6384165Feb 15, 2001May 7, 20023M Innovative Properties Co.Organoborane amine complex initiator systems and polymerizable compositions made therewithUS6479602Mar 15, 2000Nov 12, 20023M Innovative PropertiesPolymerization initiator systems and bonding compositions comprising vinyl aromatic compoundsUS6624213Nov 8, 2001Sep 23, 20033M Innovative Properties CompanyHigh temperature epoxy adhesive filmsUS6646082 *Sep 4, 2002Nov 11, 2003Rohm And Haas CompanyCorrosion inhibiting compositionsUS6746778Apr 13, 1998Jun 8, 2004Daimlerchrysler AgMetal substrate for a vehicle bodyUS6790597Aug 1, 2002Sep 14, 2004Henkel CorporationThermosetting resin compositions containing maleimide and/or vinyl compoundsUS6803092Jun 26, 2001Oct 12, 20043M Innovative Properties CompanySelective deposition of circuit-protective polymersUS6812308Jan 21, 2003Nov 2, 20043M Innovative Properties CompanyInitiator systems and adhesive compositions made therewithUS6825245Aug 1, 2002Nov 30, 2004Henkel CorporationThermosetting resin compositions containing maleimide and/or vinyl compoundsUS6916856Jul 3, 2002Jul 12, 2005Henkel CorporationThermosetting resin compositions containing maleimide and/or vinyl compoundsUS6960636Jan 13, 2003Nov 1, 2005Henkel CorporationThermosetting resin compositions containing maleimide and/or vinyl compoundsUS7189303Aug 31, 2004Mar 13, 20073M Innovative Properties CompanyInitiator systems and adhesive compositions made therewithUS7387740 *Nov 7, 2005Jun 17, 2008Sutech Trading LimitedMethod of manufacturing metal cover with blind holes thereinUS7601280Jul 8, 2008Oct 13, 2009Lumimove, Inc. A Missouri CorporationCorrosion-responsive coating formulations for protection of metal surfacesUS7645899Sep 5, 2006Jan 12, 2010Henkel CorporationVinyl compoundsUS20050027087 *Aug 31, 2004Feb 3, 20053M Innovative Properties CompanyInitiator systems and adhesive compositions made therewithDE19715062A1 *Apr 11, 1997Oct 15, 1998Daimler Benz AgMetallisches Substrat, insbesondere eine Fahrzeugkarosserie, mit einer korrosionssch�tzenden HaftschichtDE19715062C2 *Apr 11, 1997Nov 23, 2000Daimler Chrysler AgVerfahren zur Applikation einer korrosionssch�tzenden Haftschicht auf ein metallisches SubstratWO2003002675A1 *Mar 21, 2002Jan 9, 20033M Innovative Properties CoSelective deposition of circuit-protective polymersWO2003102034A1 *Jun 4, 2003Dec 11, 2003Patrick J KinlenCorrosion-responsive coating formulations for protection of metal surfaces* Cited by examinerClassifications U.S. Classification204/501, 523/514International ClassificationC08G59/10, C09D163/00, C08G59/14, C08G59/40, C09D5/44Cooperative ClassificationC08G59/1433, C09D163/00, C09D5/4453, C08G59/10, C08G59/4042European ClassificationC08G59/40B2D, C08G59/10, C09D5/44D4C, C08G59/14K, C09D163/00Legal EventsDateCodeEventDescriptionJan 29, 1988ASAssignmentOwner name: MINNESOTA MINING & MANUFACTURING COMPANY, SAINT PAFree format text: ASSIGNMENT OF ASSIGNORS INTEREST.;ASSIGNORS:WILSON, THOMAS H. JR.;POCIUS, ALPHONSUS V.;REEL/FRAME:004844/0625Effective date: 19880129Owner name: MINNESOTA MINING & MANUFACTURING COMPANY, A CORP.Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNORS:WILSON, THOMAS H. JR.;POCIUS, ALPHONSUS V.;REEL/FRAME:004844/0625Effective date: 19880129Apr 28, 1992CCCertificate of correctionJun 23, 1993FPAYFee paymentYear of fee payment: 4Oct 7, 1997REMIMaintenance fee reminder mailedMar 1, 1998LAPSLapse for failure to pay maintenance feesMay 12, 1998FPExpired due to failure to pay maintenance feeEffective date: 19980304RotateOriginal ImageGoogle Home - Sitemap - USPTO Bulk Downloads - Privacy Policy - Terms of Service - About Google Patents - Send FeedbackData provided by IFI CLAIMS Patent Services