Process for coating of lead-batterygrids with an electrically conductive glycidyl-acryl-polymer.

BACKGROUND OF THE INVENTION

0001This invention relates to an electrically conductive coating composition which forms a chemical and temperature resistant coating.

0002The prior art shows coating compositions of acrylic silicone copolymers which are crosslinked by heat or radiation after application to a substrate. Patents showing such compositions are as follows: Sekmakas, U.S. Patent 3,468,836, issued September 23, 1969, Kincheloe et al., U.S. Patent 3,644,566 issued February 22, 1972, Nordstrom et al., U.S. Patent 3,650,813 issued March 21, 1972 and Sekmakas U.S. Patent 3,655,602 issued April 11, 1972. Vasta U.S. Patent 4,446,259 issued May 1, 1984 shows a coating composition of an acrylic polymer and a polysiloxane.

0003The life of conventional lead-acid storage batteries can be increased, the power of these batteries can be increased without an increase in battery size or size of the batteries can be decreased without a decrease in power of the battery by coating lead grids used to make the electrodes of the batteries with a conductive acid resistant coating. To be useful, the coating must adhere to the lead grid, be impervious to the sulfuric acid used in the battery, be electrically conductive and have a low electrical resistance.

0004None of the above prior art patents suggest or show coatings that are useful to coat grids used in lead acid storage batteries. The unique coating composition of this invention is designed for such use and batteries made with grids coated with the composition have longer life, increased power without an increase in battery size or can be made smaller and lighter without a decrease in power output in comparison to conventional lead acid batteries.

SUMMARY OF THE INVENTION

0005The coating composition contains about 10-80% by weight of a film-forming binder and 20-90% by weight of a liquid carrier; wherein the binder is a blend of about <ul id="ul0001" list-style="none"><li>a. 20-90% by weight, based on the weight of the binder, of an acrylic polymer of about 10-50% by weight, based on the weight of the acrylic polymer,of polymerized glycidyl methacrylate or glycidyl acrylate and 50-90% by weight of other polymerized ethylenically unsaturated monomers such as alkyl methacrylates, alkyl acrylates, styrene or alkyl substituted styrenes or mixtures thereof; wherein the acrylic polymer has a weight average molecular weight of about 10,000 - 100,000 determined by gel permeation chromatography using polymethylmethacrylate as a standard and</li><li>b. 10-80% by weight, based on the weight of the binder, of a crosslinkable polysiloxane having attached to silicone atoms of its backbone alkyl groups with 1-6 carbon atoms, phenyl groups and hydroxyl groups and containing sufficient hydroxyl groups to provide a silanol content of about 0.5-7% by weight, based on the weight of the polysiloxane;</li></ul> wherein the coating composition contains electrically conductive pigments in a pigment to binder weight ratio of about 50/100 to 300/100 and a dry film of the coating composition 25 microns thick has an electrical resistance of 1-50 ohms.

DETAILED DESCRIPTION OF THE INVENTION

0006The coating composition contains about 10-80% by weight of a film forming binder and 20-90% by weight of a liquid carrier. Preferably, the composition contains 40-70% by weight of the film-forming binder and 30-60% by weight of the liquid carrier. Generally, the liquid carrier is an organic solvent for the binder. The carrier can be aqueous to form a dispersion or a blend of a nonsolvent and solvent for the binder to form a nonaqueous dispersion.

0007The binder of the composition is a blend of 20-90% by weight of an acrylic polymer and 10-80% by weight of a polysiloxane. Preferably, the composition contains about 50-75% by weight of the acrylic polymer and 25-50% by weight of the polysiloxane.

0008To be an effective coating for the grids of electric storage batteries, the composition must be electrically conductive and have a low resistance. The composition contains electrically conductive pigments such as carbon black, graphite and the like in a pigment to binder weight ratio of about 50/100 to 300/100 to provide an electrically conductive film. A 25 micron thick film of the composition in its dried state has an electrical resistance of about 1-50 ohms and preferably, 5-20 ohms.

0009Typical conductive pigments are carbon black pigments such as furnace black, acetylene black and graphite. One preferred carbon black pigment is Gulf acetylene black. Preferably, a mixture of carbon black pigments and finely divided graphite is used. Transition metal oxides also are useful conductive pigments,such as lead oxide, magnetite, titanium-suboxides having the formula TiOx where x is less than 2, ruthenium oxide, mixtures of ruthenium oxide and titanium suboxides and the like.

0010In general, the acrylic polymer must be compatible with the polysiloxane and contain a sufficient number of reactive groups, primarily glycidyl groups, to crosslink with the polysiloxane under ambient temperatures after the coating compositions has been applied to a substrate. The acrylic polymer should have a glass transition temperature of about 20°C to 50°C. A number average molecular weight of about 2,000 to 20,000, a weight average molecular weight of about 10,000 to 100,000 and a molecular weight distribution of about 2 to 5.

0011The molecular weight of the acrylic polymer is determined by gel permeation chromatography using polymethylmethacrylate as a standard.

0012The glass transition temperature of the polymer is determined by differential scanning colorimetry or is calculated.

0013The acrylic polymer is prepared by conventional polymerization procedure in which monomers, catalyst and solvent are charged into a conventional polymerization vessel and reacted at about 60 to 175°C for about 1-6 hours to form the polymer.

0014Typical solvents which are used to prepare the acrylic polymer are the following: toluene, ethyl acetate, acetone, methyl isobutyl ketone, methylethyl ketone, ethyl alcohol, mineral spirits, ethylene glycol monoethyl ether acetate, and other aliphatic, cycloaliphatic and aromatic hydrocarbon, esters, ethers, ketones and alcohols which are conveniently used.

0015About 0.1-4% by weight, based on the weight of the monomers, of the polymerization catalyst is used to prepare the acrylic polymer. Typical catalysts are: azobis-isobutyronitrile, azo-bis(gamma dimethyl valeronitrile), benzoyl peroxide, t-butyl pivalate and the like.

0016The acrylic polymer contains about 10-50% by weight of glycidyl methacrylate or glycidyl acrylate and 50-90% by weight of other ethylenically unsaturated monomers. Preferably, the acrylic polymer contains about 10-30% by weight of glycidyl methacrylate or glycidyl acrylate and 70-90% by weight of other ethylenically unsaturated monomers.

0017Typical ethylenically unsaturated monomers that are used to form the acrylic polymer are as follows: alkyl methacrylates having 1-12 carbon atoms such as methyl methacrylate, ethyl methacrylate, butyl methacrylate, hexyl methacrylate, 2-ethylhexyl methacrylate, nonyl methacrylate, lauryl methacrylate, cyclohexyl methacrylate, isodecyl methacrylate, propyl methacrylate, phenyl methacrylate, isobornyl methacrylate and the like; alkyl acrylates having 1-12 carbon atoms in the alkyl group such as methyl acrylate, ethyl acrylate, propyl acrylate, isopropyl acrylate, butyl acrylate, isobutyl acrylate, hexyl acrylate, 2-ethvlhexyl acrylate, nonyl acrylate, lauryl acrylate, cyclohexyl acrylate, isodecyl acrylate, phenyl acrylate, isobornyl acrylate and the like; styrene, alkyl substituted styrene such as α-methyl styrene, t-butyl. styrene, vinyl toluene.'

0018One preferred acrylic polymer contains about 10-30% by weight of glycidyl methacrylate, 10-20% by weight of styrene, 50-60% by weight of butyl methacrylate and 5-20% by weight butyl acrylate. One particularly preferred acrylic polymer contains 20% by weight glycidyl methacrylate, 15_% by weight styrene, 55% by weight butyl methacrylate and 10% by weight butyl acrylate.

0019The polysiloxane contains the following units <chemistry id="chem0001" num="0001"><img file="EP0189653A2_D0001.tif" /></chemistry>where R and R1 are alkyl group having 1-6 carbon atom, phenyl group or hydroxyl group and contains sufficient number of hydroxyl groups to provide a silanol content of about 0.5-7% by weight. One preferred resin is Dow Corning's D.C. 840 silicone resin which formed by hydrolyzing selected amounts of mono, di and tri methyl chlorosilicone, mono, di and tri phenyl chloro- silicone, mono, di and tri propyl chlorosilicone and mono, di and tri amyl chloro-silicone and the resulting products are condensed to form a resin blend having a silanol content of about 1.9-3% by weight. Other polysiloxanes which give similar results are Bayer's "Baysilone" Resin P150K, Rhone-Poulenc's "Rhodorsil" 6406 X and General Electric's SR-165. These polysiloxanes are proprietary products but are believed to be formed as described above.

0020Trace amounts of multivalent metal ions of iron, aluminum, zinc and tin from the above pigments are present in the composition and co-ordinate with the silanol groups of the polysiloxane and catalyze the crosslinking reaction between the acrylic polymer and polysiloxane to provide ambient temperature curing of the coating composition after application to a substrate. If the metal ions complexed with the silanol groups are not present, elevated temperatures are required to cure the composition.

0021To insure stability of the coating composition during storage, compounds such as acetyl acetone are added in amounts of about 0.75-3% by weight. The acetyl acetone complexes with metal ions in the composition and prevents catalyzation of the crosslinking reaction during storage. Upon application the acetyl acetone volatilizes and allows the metal ions to complex with the silanol groups as described above and catalyze curing of the finish. Other auxiliary stabilizers can also be added such as glycidyloxy alkoxy silanes such as gamma-glycidoxy propyl trimethoxy silane.

0022The coating composition can be applied using conventional techniques such as spraying, dipping, brushing, roller coating, flow coating and the like and dried at ambient temperatures or baked at temperatures of 50-250°C to give a coating about 10-200 microns thick, preferably about 20-100 microns thick.

0023Typically, the grids of lead acid storage batteries are made from antimony lead alloys or calcium lead alloys. Preferably, a thin coat of an amino silane such as gamma amino propyl trimethoxy silane is applied and then the above composition is applied. Other amino silanes that can be used are N-(2-amimethyl)-3-amino-propyltrimethoxy silane and 3[2(vinyl benzylamino)ethylamino)propyltrimethcocy silane. The composition has excellent adhesion to the amino silane coated alloy grids. Coatings of about 10-200 microns, preferably 20-50 microns, are applied to the grid usually by spray application and baked at about 125-175°C.

0024Batteries made-from such coated grids have a life 2-3 times that of batteries made with uncoated grids. Alternatively, thinner grids coated with the composition of this invention can be used which reduces battery size and weight by half to a third without decreasing the life of the battery in comparison to a battery made with uncoated grids. By maintaining the size and weight of the battery to that of a conventional battery but using 2-3 times the number of the thinner coated grids, the power output of the battery can be increased by 2-3 times in comparison to a conventional battery made with uncoated grids.

0025The following examples illustrate the invention. All parts and percentages are on a weight basis. Molecular weights are determined by gel permeation chromatography using polymethyl methacrylate as a standard.

EXAMPLE

0026A conductive paint was prepared by blending the following constituents together and charging the resulting blend into a sand mill and grinding 4 passes through the mill: <tables id="tabl0001" num="0001"><img file="EP0189653A2_D0002.tif" /></tables><tables id="tabl0002" num="0002"><img file="EP0189653A2_D0003.tif" /></tables>

0027The resulting paint has a weight solids of 30% and a pigment to binder weight ratio of 100/100. The paint was reduced to a 25 second spray viscosity measured with a No. 2 Zahn cup with a 80/20 mixture of propylene glycol methyl ether acetate. The paint was sprayed onto a glass panel to a 25 micron dry film thickness and the electrical resistance was measured and was about 5-7 ohms.

0028A calcium alloy lead grid and an antimony alloy lead grid used in storage batteries were first coated with a 2% solution of gamma-amino propyl trimethoxy silane and dried and then sprayed with the above paint and baked at about 65°C for about 1 hour. The resulting film was about 40 microns thick and had excellent adhesion to the lead substrate.

0029The coated lead grids were immersed in sulfuric acid solution and held at 2.3 volts potential for 4 weeks. The coating did not blister or deteriorate and no corrosion of the substrate was noted. In comparison, uncoated lead grids exposed under the same conditions corroded severely.

0030Lead acid storage batteries made with the coated lead grids are expected to have a life of about 2-3 times that of batteries made with uncoated lead grids. Lead acid storage batteries can be made with grids that are 1/3-1/2 of the weight of conventional uncoated grids and can be expected to have a life equivalent to that of a conventional battery. Also, lead acid storage batteries can be made of the same size as conventional batteries but with substantially more power since the grids can be made thinner and more grids can be used in the battery; hence, increasing power of the battery.