US3697467A - Aqueous dispersion of polycarboxylic acid resin with silica - Google Patents

Aqueous dispersion of polycarboxylic acid resin with silica Download PDF

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US3697467A
US3697467A US873531A US3697467DA US3697467A US 3697467 A US3697467 A US 3697467A US 873531 A US873531 A US 873531A US 3697467D A US3697467D A US 3697467DA US 3697467 A US3697467 A US 3697467A
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resin
silica
bath
polycarboxylic acid
acid
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Joseph P Haughney
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Sherwin Williams Co
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Sherwin Williams Co
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/44—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes for electrophoretic applications
    • C09D5/4484—Anodic paints
    • 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
    • C09D167/00—Coating compositions based on polyesters obtained by reactions forming a carboxylic ester link in the main chain; Coating compositions based on derivatives of such polymers

Definitions

  • FIG. 1 A first figure.
  • Electrodeposition of a dielectric coating from a bath including an acidic polymer, a base, and a minor amount of such silica enables more nearly uniform electrocoating and when cured, as by thermal means, yields an improved product exhibiting higher dielectric breakdown voltages along edges and other contoured surfaces.
  • This invention relates to a new process, composition and article which when used as hereinafter disclosed give rise to a coated metal strip or foil having a high, relatively uniform dielectric coating on the broad surface, narrow edge and the surface defining the meeting of these edges, be it a line or the larger surface area available with some strip where it has been possible to provide a radius defining a larger connecting area.
  • an enamel is understood to mean a liquid vehicle capable of depositing a stet film containing sufiicient pigment to provide the final film with opacity in an amount insufiicient to materially impair the natural glass characteristic of the vehicle itself.
  • enamel In the electrical insulation field enamel is used to define a vehicle standardly devoid of pigmentation in the paint sense, though the color of the vehicle itself may be, and often is, dark due to the presence of colloidal or smaller particles of light absorbing material. Insulating varnishes in the electrical wire, strip and foil field, then, though called enamels are not commensurate with enamels as are used to finish major appliance surfaces. Pigmentation in the latter sense seriously impairs the quality of insulating varnish or enamel in a number of respects.
  • edges thereof may become conductive at from 0 to 200 volts, the higher end being improved to some extent by edge pretreatment to the order of 350 to 450 volts on the narrow edge.
  • an electrically conductive metal anode coated with an improved dielectric or insulating composition by the process of electrodeposition of the coating from an aqueous bath forming a part of an electrical circuit and containing a polyelectrolyte of an acidic polymer in water imparting a negative charge to inorganic particles originally dispersed in said polymer.
  • novel wire and strip or foil enamel comprising a synthetic polycarboxylic acid resin and containing dispersed therein an extremely finely divided form of silica in an amount sufiicient to increase the dielectric breakdown point on interconnecting surfaces between the broad surface and the thin edge to a level such that the final insulated metallic conductive body can be used more widely in areas where dielectric breakdown between adjacent surfaces or convolutions has heretofore limited practical use.
  • coated anodes including metallic foil and strip capable of withstanding up to about 3000 volts on the broad areas and up above 1500 volts across the areas intermediate thereof, e.g. edges, at 0.9 to 1.1 mils film thickness of the fiat surface.
  • 400 volts breakdown was standardly found at similar film thickness. In excess of 500 volts is essential to meet the minimum requirements for certain uses in the electrical industry.
  • the present invention is an improvement upon the electropainting process and paint binder concentrate composition therefor described in US. Pat. 3,230,162 and issued to A. E. Gilchrist on J an. 18, 1966.
  • a process for electrocoating an anode with a pigmented coating composition in an electrical circuit including a bath of an aqueous medium in electrical contact with an anode and a cathode.
  • a paint containing as the predominant fraction of the film-forming material a synthetic polycarboXylic acid resin at least partially neutralized with a sufficient quantity of a water soluble amino compound to maintain the resin as a dispersion of anionic polyelectrolyte in said bath.
  • the acidic resin has an electrical equivalent weight between about 1,000 and 20,000, an acid number between about 30 and about 300, and in the bath exhibits anionic polyelectr-olyte behavior.
  • a direct current is passed through a circuit at a potential between 50 and 500 volts thereby causing the coating composition film to electrodeposit on the anode, whereupon the anode is withdrawn from the bath.
  • micron to 3 microns desirably with less than about 0.05% retained upon a Standard 325 mesh screen.
  • silica materials are commercially available.
  • the improvements of. the present invention are obtained with all of the resinous compositions described in the Pat. 3,230,162, but excluding pigments and other solid particulate matter except as herein noted.
  • the alkali metal bases, the water soluble amino and hydroxy amino compounds, and ammonia may be utilized to effect neutralization of the polycarboxylic acid resin to an extent suflicient to maintain the resin as a vdispersion of anionic polyelectrolyte in the bath.
  • the disclosure of Pat. 3,230,162 is included herein in its entirety by reference thereto with the modifications indicated herein.
  • FIG. x1 is a photomicrograph of a cross-section of aluminum foil of the type used in making electrical coils, and showing the nature of a coating obtained from a pigment-free. electrocoating bath including a polyacrylic acid resinbut without silica present.
  • FIG. 2 is a photomicrograph of a cross-section of aluminum foil coated with the same electrocoating bath to which has been added about 3% by weight of the resin solids of fumed'silica having an average particle diameter of 0.012 micron.
  • FIG. 3 is a photomicrograph of a cross-section of a contoured aluminum foil having an electrodeposited coating of the same composition as used in FIG. 2.
  • FIG. 4 is a diagrammatic andschematic illustration of an apparatus suitable for use in carrying out the process of the invention on metallic foil or strip.
  • the polycarboxylic acid resins of the present invention are of a wide variety seemingly unlimited by anything but their ability to be put into aqueous solution, or apparent solution,or in ultrafine aqueous dispersion in a bath by at least partial neutralization with abasic material in which condition they can. be typified as polyelectrolytes in aqueous dispersion.
  • the dispersed or solubilized resins show migration in the bath with respect to the electric current characteristic of current-carrying anions in an aqueous solution and other solution properties.
  • the especially useful polycarboxylic acid resins useful as insulative film forming materials in the present compositions have an electrical equivalent weight between about 1000 and about 20,000 and preferably between about 1,000 and about 2,000 for ease of dispersion and efiiciency of operation. These resins disperse efiectively in the electrocoating.
  • the resin solids content of the electrocoating bath is generally between 5% and 20% by weight of the bath.
  • electrical equivalent weight resin is defined in Pat. 3,230,162 and is used hereinin the same sense.
  • the resin is made in a typical resin reactor.
  • the butyl Cellosolve is added to the reactor and heated to 250 P.
  • All the ethylenically unsaturated monomers, i.e. butyl acrylate, acrylic acid, styrene, and 2-hydroxypropyl acrylate are added together with a suitable catalyst to form an interpolymerizable monomer mix.
  • the ratio of catalyst to the monomer mix is in the range of from 10 to 13 parts of the catalyst to each parts of the monomer mix.
  • the polymerizable monomers and solvents are heated at 250 F. for about 5 to 7 hours at which time the acid value of the acrylic acid resin or polymer is between about 70 and 75.
  • the resin is completed and cooled to room temperature.
  • a suitable catalyst is azo-bis-isobutyro-nitrile. Near the end of the cook, cumene hydroperoxide or other free radical polymerization catalyst is added at about 1% to 3% by weight of the resin solids.
  • the ethylenically unsaturated monomers useful herein generally have a molecular weight below about and contain less than 10 carbon atoms. They may be hydrocarbons, halogen-containing hydrocarbons or acids or esters, or hydroxyl-containing materials.
  • acrylic acid andits homologues acrylic acid esters and their homologues, acrylonitrile, vinyl alcohol, vinyl chloride, vinylidene chloride, vinyl benzene (styrene), etc.
  • acrylic acid may be used in addition to acrylic acid as secondary, tertiary and quaternary monomers to yield the acidic polymers hereof.
  • the monomer mix may contain 2, 3, 4 or more monomers to form the acidic interpolymers.
  • the resin of this example is then solubilized for electrocoating. However, before solubilizing, 20 parts per 1000 parts of resin solution as produced above of fumed silica having an average particle diameter of 0.012 micron with no more than 0.05% retained on a Standard 325 mesh screen is added to the resin. Thereafter, 213 parts of a 10% solution of lithium. hydroxide monohydrate in water and 1237 parts of deionized water are added, and the dispersion thoroughly mixed, e.g. in a Cowles unit.
  • metal hydroxides including sodium hydroxide, potassium hydroxide, ammonium hydroxide, triethanolamine, diethanolamine, monoethanolamine, morpholine, and the like may be used as the solubilizing agent.
  • the material resulting has a solids content of about 30%, and for electrocoating purposes, it is further reduced with deionized water to a solids content of from. 10% to 12%.
  • vinyl aromatic hydrocarbons may be used including vinyl toluene, a-ChlOIO styrene, amethyl styrene, etc.
  • the extremely finely divided silica additions are also useful in improving the electrocoatability of epoxy ester carboxylic acid resins.
  • a typical example of such a resin is produced as follows:
  • EXAMPLE 2 P.b.w. Bisphenol A/epichlorohydrin epoxy resin (epoxy equivalent weight 130-145) 457 Linseed oil fatty acid 439 Succinic acid anhydride 104 These ingredients are cooked in an alkyd kettle equipped with a condenser, and heating or cooling coils. The epoxy resin and the linseed oil fatty acid are heated with a few percentages (4-'6%) of xylene for solvent cooking process and a conventional catalyst, e.g. 250-500 ppm. of sodium carbonate based on the weight of the epoxy resin. The temperature of the cook is raised slowly to about 450 F. over 3 to 4 hours time. Foaming from the interaction of the materials occurs at a temperature in the range of from 300 to 400 F.
  • the input of heat to the kettle will control the foaming.
  • the reaction is continued at 450 F. for 1 to 2 hours. At this point, the acid value is about to 15.
  • the material is then cooled to 300-325 F. and the succinic acid anhydride is added.
  • the resin is cooked at 300 F. for an additional 2 to 4 hours at which time the acid value is in the range of from 60 to 66. This resin is then cooled, thinned, and filtered.
  • the foregoing polycarboxylic acid resin is solubilized in the following manner:
  • the epoxy resin may vary widely in epoxy content from 130 grams per epoxide group to 1100 grams per epoxide group.
  • the fatty acid used to modify the epoxy resin can be any of those drying oil acids or semidrying oil acids typically used in alkyd resin formulations, such as soya fatty acid, tall oil fatty acid, safllower fatty acids, castor oil fatty acids, and the like.
  • the amount of fatty acid used is based upon the amount of epoxy resin used. Considering the total weight of epoxy resins and fatty acid as 100 parts, the amount of fatty acid utilized may vary from about 35% to about 65% while the amount of the epoxy resin varies from 65% to 35%. Many of these resins are available in the trade. Many different anhydrides may be used to carboxylate the epoxy resin esters including maleic anhydride, succinic anhydride, phthalic anhydride, trirnellitic anhydride, pyromellitic anhydride, and the like.
  • a typical polyester polycarboxylic acid resin may be produced as follows:
  • Trimethylol ethane diol 313 Trimethylol ethane 106 Isophthalic acid (95%) 100 Trimellitic anhydride -116 Azelaic acid 228 to 350 F. The trimellitic anhydride and the azelaic acid are then added and the temperature held at 335 F. for a period of from 8 to 10 hours. At this point, the acid value is about 50 to 60. The resin is the cooled, thinned with a material, such as butyl Cellosolve, to solids and filtered. The resin is then solubilized as follows:
  • Polyester polycarboxylic acid resin as above prepared 1000 Furned silica (0.012 micron average particles diameter) 20 10% aqueous solution of sodium hydroxide 264 Deionized water 2330 This produces a 30% total solids solution which is then reduced to 10% to 12% total solids with deionized water for electrocoating purposes.
  • ethylene glycol propylene glycol, neopentyl glycol. glycerol, pentaerythritol and the like.
  • Dibasic acids may be phthalic acid, tetrahydrophthalic acid, adipic acid, succinic acid, fumeric acid, maleic acid, and the like.
  • EXAMPLE 4 Another example of a polyester is as follows:
  • silica Prior to neutralization and formation of the polyelectrolyte containing electrocoating bath, 423 parts of the above polymer are combined with eight parts of fumed silica having a particle size between 3 and millimicrons average particle diameter. The silica is blended by highspeed agitation (for example in a Cowles unit). Thereafter 572 parts of deionized water are incorporated along with sufiicient base (lithium hydroxide monohydrate) to increase the pH of the system above 7 but not in excess of about 8.5. These pH limits are preferred for the compositions of the present invention to yield best results although deviations therefrom may be followed with decreased efliciency of operation.
  • sufiicient base lithium hydroxide monohydrate
  • Cross-linking agents in amounts ranging from to 15% by weight of the resin solids may also be included at the time the silica is added.
  • Such cross-linking agents include melamine formalidehyde, hexamethylol melamine formaldehyde, epoxy and epoxy ester resins, etc., for control of the hardness of the cured film. While these materials have not been found to be essential, such further modification is often advantageous.
  • the aqueous acrylic acid polymer is further reduced in total solids to from about 6% to about 12% to provide a solution having an electrical resistance of the order of from 500 to 1500 ohm centimeters.
  • the dip tank 1 is filled with the electrocoating bath prepared in accordance with Example above, and ribbon stock 3 is fed from the spool 2 downward into the tank 1 under immersed idler rolls 4 and 5, and upward between confronting flat surface cathode plates 6 and 7 and end cathode plates such as end cathode plate. 8 the opposing end cathode plate not being shown in FIG. 4.
  • Suitable means such as direct current battery 9 are provided and arranged to render the raw stock strip material 3 positive with respect to the cathode plates 6,7 and 8.
  • the bath in the dip tank 1 is water thin.
  • the metal ribbon e.g. an aluminum foil
  • the metal ribbon is advanced from the reel 2 downward through the bath, and as it is drawn between the cathode plates, the acid form of the dispersed resin plus the silica particles, which may be either mechanically entrained with the resin or may possiblycarry a negative charge, are deposited out uniformly over the surfaces of the ribbon 3.
  • a voltage of from 125 to 150 volts DC and a coating time of about 30 seconds at a current rate of from 0.9 to 2.0 amperes yield film deposits of the order of from 1 to 1.5 mils after drying.
  • the metal ribbon is passed into a slit oven 10 where the temperature interiorly thereof is maintained on the order of 500 to 510 F., heating the stock at a rate of about 1 foot per minute to a stock temperature of from 125 F. to 500 F. at the exit and during a residence time in the heated zone 12 of about 5 minutes.
  • the completed cured coated ribbon is rewound on takeup reel 14 which serves to supply tension to the stock 3 as it traverses through the electrocoating steps.
  • the electrocoating characteristics for example the near uniformity of deposition even on edges and contoured surfaces as well as the flat surfaces, available with the electrocoating bath compositions hereof are greatly improved and yield a product having improved dielectric properties.
  • composition and processes of the present invention are particularly useful with respect to the coating of aluminum foils and strips, and wire useful in forming electrical components such as condensers or coils, and in the production of wire enamels for coating wire.
  • Conventional electrocoating apparatus utilizing a circular cathode may be used for wire coating.
  • compositions produced in accordance with the specific examples above set forth have been tested for dielectric breakdown voltages when coated upon both metallicribbons and upon wire.
  • the dielectric breakdown voltage of the coated film varies from .1000 to 3000 volts per mil of thickness on fiat surfaces, and from 400 to 2000- volts on the edges. Tests are run in accordance with ASTM D-149-6l, Tests for Dielectric Breakdown Voltage and Dielectric Strength of Electrical Insulating Materials at Commercial Power Frequencies.
  • the aluminum industry designates the metal ribbon as strip when its thickness is 10 mils or greater, and as foil when its thickness is less than 10 mils. These compositions have also been found to be successful as wire enamels on both copper and aluminum wire.
  • the dielectric breakdown voltages for these coated films on wire varies from 1000 to 2000 volts per mil of thickness.
  • the following table gives comparative values for dielectric breakdown voltages for various polycarboxylic acid resins for both the edges and fiat surfaces of aluminum foil with extremely finely divided silica and without extremely finely divided silica.
  • an improved electrocoating bath having improved electrocoatability characteristics and an improved electrocoated product, as well as a method for obtaining a more nearly uniform coating on an anode, particularly an elongated or continuous metallic anode which is characterized by edges defined by intersecting planes or surfaces.
  • Such portions of metallic anodes are difficult to coat uniformly by conventional electrodeposition means with conventional electrocoating baths and as shown above, the inclusion of a small amount of an extremely finely divided silica in the electrocoating bath greatly improves the character of the deposition and the nature of the product obtained thereby.
  • a bath composition for electrodepositing on an anode for forming an organic insulative coating film thereon consisting essentially of an aqueous dispersion of:
  • a synthetic preformed polycarboxylic acid resin having an electrical equivalent weight between about 1000 and about 20,000 and an acid number between about 30 and about 300, the concentration of said resin in said aqueous dispersion being between about 5% and about 20% by weight, said polycarboxylic acid being maintained in said aqueous dispersion with (b) a suflicient quantity of a water-soluble base selected from the group consisting of water-soluble alkali metal bases, water-soluble amino compounds, water-soluble hydroxy amino compounds, and ammonia to maintain said polycarboxylic acid resin as anionic polyelectrolyte;
  • CH1 CCOOH wherein R is hydrogen or a C -C alkyl group, and the second monomer is ethylenically unsaturated.
  • R is hydrogen or a C -C alkyl group and R is a C -C alkyl group.
  • polycarboxylic acid resin is formed from at least three monomers, the first of which has the general formula:

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Cited By (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3844834A (en) * 1972-04-17 1974-10-29 Westinghouse Electric Corp High temperature-stable abrasion-resistant coatings for conductors
US3846356A (en) * 1973-06-08 1974-11-05 Celanese Corp Trialkylsilyl-treated fumed silicon dioxide pigments for electro-deposition
US3951882A (en) * 1973-03-08 1976-04-20 Monsanto Company Dielectric coating compositions
US3953391A (en) * 1970-06-19 1976-04-27 Ppg Industries, Inc. Cationic acrylic electrodepositable compositions
US3984608A (en) * 1974-04-17 1976-10-05 Kerr Glass Manufacturing Corporation Glassware having improved resistance to abrasion
US3988281A (en) * 1972-05-19 1976-10-26 Shinto Paint Co., Ltd. Water-dispersible thermosetting coating composition
US4078518A (en) * 1975-02-11 1978-03-14 Veb Textilkombinat Cottbus Arrangement for the treatment of high-polymer articles with boiling acrylic acid
US4216106A (en) * 1978-12-18 1980-08-05 The Sherwin-Williams Co. Calcined clay containing dielectric coating composition
US4351922A (en) * 1979-02-19 1982-09-28 Showa Denko Kabushiki Kaisha Process for the production of highly water-absorbing but less water-soluble hydrogels
US4760296A (en) * 1979-07-30 1988-07-26 General Electric Company Corona-resistant insulation, electrical conductors covered therewith and dynamoelectric machines and transformers incorporating components of such insulated conductors
WO2007045633A1 (en) * 2005-10-18 2007-04-26 Altana Electrical Insulation Gmbh Use of nanomaterials in secondary electrical insulation coatings
US20140202731A1 (en) * 2010-01-08 2014-07-24 Hitachi Metals, Ltd. Enameled flat wire

Cited By (16)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3953391A (en) * 1970-06-19 1976-04-27 Ppg Industries, Inc. Cationic acrylic electrodepositable compositions
US3844834A (en) * 1972-04-17 1974-10-29 Westinghouse Electric Corp High temperature-stable abrasion-resistant coatings for conductors
US3988281A (en) * 1972-05-19 1976-10-26 Shinto Paint Co., Ltd. Water-dispersible thermosetting coating composition
US3951882A (en) * 1973-03-08 1976-04-20 Monsanto Company Dielectric coating compositions
US3846356A (en) * 1973-06-08 1974-11-05 Celanese Corp Trialkylsilyl-treated fumed silicon dioxide pigments for electro-deposition
US3984608A (en) * 1974-04-17 1976-10-05 Kerr Glass Manufacturing Corporation Glassware having improved resistance to abrasion
US4078518A (en) * 1975-02-11 1978-03-14 Veb Textilkombinat Cottbus Arrangement for the treatment of high-polymer articles with boiling acrylic acid
US4216106A (en) * 1978-12-18 1980-08-05 The Sherwin-Williams Co. Calcined clay containing dielectric coating composition
US4351922A (en) * 1979-02-19 1982-09-28 Showa Denko Kabushiki Kaisha Process for the production of highly water-absorbing but less water-soluble hydrogels
US4760296A (en) * 1979-07-30 1988-07-26 General Electric Company Corona-resistant insulation, electrical conductors covered therewith and dynamoelectric machines and transformers incorporating components of such insulated conductors
WO2007045633A1 (en) * 2005-10-18 2007-04-26 Altana Electrical Insulation Gmbh Use of nanomaterials in secondary electrical insulation coatings
US20070142526A1 (en) * 2005-10-18 2007-06-21 The P. D. George Company Secondary Electrical Insulation Coatings Containing Nanomaterials
CN101305039B (zh) * 2005-10-18 2011-11-09 阿尔特纳电绝缘有限公司 纳米材料在次级电绝缘涂料中的应用
AU2006303341B2 (en) * 2005-10-18 2011-12-01 Elantas Pdg, Inc. Use of nanomaterials in secondary electrical insulation coatings
US20140202731A1 (en) * 2010-01-08 2014-07-24 Hitachi Metals, Ltd. Enameled flat wire
US9330817B2 (en) * 2010-01-08 2016-05-03 Hitachi Metals, Ltd. Enameled flat wire

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DE2053258A1 (de) 1971-05-13

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