A method for a low temperature cure for a coating composition comprising: applying to a substrate a low temperature curing coating composition consisting essentially of a film forming component consisting essentially of a non-carbamate functional polymeric component selected from the group consisting of polyester, silicone modified polyester, polyurethane, acrylic, alkyd, epoxy, polyamide, phenolic and polysilane polymers and mixtures thereof; a crosslinking component to crosslink the non-carbamate functional polymeric component; a catalyst selected from the group consisting of Lewis acids, perflouracetic acid, methane sulfonic acid catalyst and mixtures thereof; and additives selected from the group consisting of solvents, flow control agents, pigments, flexibilizing resins, surfactants, waxes, wetting agents, plasticizers, anti-oxidants, UV light absorbers, and a mixture thereof, and subjecting the coated substrate to a cure temperature of between 280xc2x0 F. and 450xc2x0 F., for a time sufficient to cure the coating.

This invention relates to coating compositions having a low curing temperature and short cure time.
The present invention is directed to a method for decreasing the bake temperature and cure or dwell time of a coating process by utilizing a coating composition comprising a Lewis acid catalyst or a trifluoroacetic acid catalyst.
A method for coating over a cured coating with a coating containing Lewis acid catalysts is taught in U.S. Pat. No. 5,972,422 to Harmon et al., for a Method for Low Bake Repair of Composite Color Plus Clear Coatings and Compositions for Use Therein. These coatings however, are directed to low bake repair methods, where a coating comprising a carbamate functionality is applied over an area having a cured coating on it already. The repair coating requires a carbamate functional resin and is an automotive repair coating process for OEM.
Another references teaching the use of a Lewis Acid catalyst in a coating is U.S. Pat. NO. 6,045,872 to Harmon for a Method for Eliminating Wrinkling in Composite Color-Plus-Clear Coating and Compositions for Use Therein. This reference is also limited to a method using a coating containing a carbamate functional resin in a coating method for automotive coatings in an OEM coating process.
The coatings in both Harmon references are directed to carbamate coatings which cure for much longer times, and which provide a more brittle coating than those coatings contemplated by the present invention. Additionally, the coatings taught in Harmon are directed for use in processes for coating in OEM automotive applications.
The present invention is directed to industrial coating compositions that are used in a wide variety of coating applications, including application to primed metal and direct to metal coatings. These coatings include both liquid and powder coatings. The coatings are applied by a variety of methods including for liquids, electrodeposition, spraying, extruding, plate coating, dipping, and coil coating, and for powders, cloud chamber, plasma coating and electrostatic deposition. These coatings are applied to metal and plastic substrates.
Coatings applied by the above described methods employ forming a film of a liquid or powder coating composition at temperatures between about 280xc2x0 F. and 450xc2x0 F. (232xc2x0 C.) at a thickness of between 0.01 and 5 mils, for a period of between about 10 minutes and about 40 minutes.
In the coil coating operation, a coil of sheet metal is uncoiled as it is pulled through a series of rollers, one or more of which is a paint applicator roller, at up to about 600 feet per minute. It is then passed through a curing oven and coiled again for the market. The paint is picked up by a roller rotating in the paint pan and transferred to a reverse or direct applicator roller. The cure temperature in a coil coating operation is typically measured as a peak metal temperature (PMT). The peak metal temperature is generally between 425xc2x0 F. and 525xc2x0 F. using a conventional acid catalyst such as aromatic sulfonic acid catalysts, including napthalene disulfonic acid, dinonyl napthalene sulfonic acid, para-toluene sulfonic acid, and dececylbenzene sulfonic acid, other acids such as phosphate acid catalysts including phosphoric acid, and mono- and dibutyl acid phophate may also be used. The curing times range generally from 14 to 40 seconds.
The present invention provides an improvement over the known methods of coil coating by providing a low temperature curing composition by use of the Lewis Acid or perfluoroacetic acid, or methane sulfonic acid catalyst, or any mixture of these catalysts in the present invention provides a curing at lower temperatures than those of a coating using other catalysts. This results in savings on energy costs to the coater and increased line speeds which result in larger volumes of coated product and higher productivity to the coater.
The present invention is directed to a method for coating a metallic substrate comprising the steps of applying to a substrate a low temperature cure coating composition consisting essentially of a non-carbamate polymeric film forming component selected from the group consisting of polyester, polyurethane, acrylic, alkyd, epoxy, polyamide, and polysilane polymers and mixtures thereof, a crosslinking component to crosslink the polymeric component, and a catalyst selected from the group consisting of Lewis acids, trifluoroacetic acid, methane sulfonic acid and mixtures thereof, wherein the coated substrate is subjected to a low cure temperature for a time sufficient to cure the coating composition.
The present invention is directed to a method for coating a metallic or plastic substrate to minimize the cure temperature and cure or dwell time used in the coating process. The process comprises the steps of applying to a substrate a low temperature curing coating composition consisting essentially of a non-carbamate polymeric film forming component, a crosslinking component to crosslink the polymeric component, and a catalyst selected from the group consisting of Lewis acids, trifluoroacetic acid, methane sulfonic acid and mixtures thereof. It is believed that the specific catalysts utilized in the present invention lower the cure temperature and cure time of the coating. The coating is applied to a substrate, either directly or to a coated or uncoated substrate. When the uncoated substrate is metal, it is referred to as xe2x80x9cdirect to metalxe2x80x9d, or the coating may be applied to a substrate that has been coated with a first coating such as a primer or other coating. In processes such as spraying, electrodeposition, extruding, plate coating, dipping, powder coating, cloud chamber, plasma coating and electrostatic deposition, the typical,cure time ranges from 10 to 40 minutes, at temperatures between 250xc2x0 F. and 450xc2x0 F., contrasting with the method of the present invention, where the cure time is reduced to about 5 to 25 minutes, generally at reduced temperatures between 180xc2x0 F. and 350xc2x0 F. In coil coating, generally the cure time ranges from about 10 to about 60 seconds at temperatures between about 425xc2x0 F. to 525xc2x0 F., in contrast to the present invention, where the cure time ranges from about 5 to about 60 seconds and more preferably from about 7 to about 40 seconds and most preferably from about 7 to about 35 seconds, generally at a curing temperature of between about 300xc2x0 F.(135xc2x0) and about 450xc2x0 F.(232xc2x0 C.). In coil coating the cure temperature is referred to as the peak metal temperature. It is desirable to minimize the cure temperature and cure or dwell time used in all coating processes. Using the specific catalysts described in the present invention enables cure times and temperatures to be reduced to levels below that in coating compositions utilizing catalysts other than those defined in the present invention.
The non-carbamate functional film forming polymer component useful in the coatings of the present invention consists essentially of polymers selected from the group consisting of polyester, polyurethane, acrylic, alkyd, epoxy, polyamide, and polysilane polymers and mixtures thereof. Most preferably, the coating is a polyester, acrylic or polyurethane polymer or any combination thereof. Polymers useful in the present invention are described as follows. The non-carbamate functional polymer is present in the coating composition in an amount between 10% and 90% by weight, based on total coating composition weight. More preferably, the polymer is present in amount between 20% and 80% by weight and most preferably between 25% and 65% by weight, based on total coating composition weight.
Polyester compositions useful for solvent borne coatings in accordance with the invention are formed by polyesterification of organic polycarboxylic acids and polyhydric alcohols. Suitable acids include but are not limited to, phthalic acid, isophthalic acid, hexahydrophthalic acid, adipic acid, succinic acid, fumaric acid , maleic acid, isophthalic acid, cyclohexyl dicarboxylic acid, azeleic acid, sebacic acid, dimethylolpropionic acid, and ricinoleic acid and mixtures thereof, and hydroxy acids such as 12-hydroxystearic acid and mixtures thereof or the anhydrides of any of these acids and mixtures thereof, and mixtures of any of these acids and anhydrides.
Suitable polyhydric alcohols for reaction with the acid or anhydride to form the polyesters include but are not limited to 1,4-butanediol, 1,6-hexanediol, neopentyl glycol, ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, butylene glycol, glycerol, trimethylolpropane, pentaerythritol, sorbitol and 2,2,3,3,4,4-hexafluoro-1,5-pentanediol. Suitable alcohols include alcohols derived from fatty alcohols. Particularly preferred are dimer fatty alcohols. Other components of polyesters can include lactones or mixtures of lactones, such as epsilon.-caprolactone and delta.-butyrolactone.
Polyester compositions in accordance with the invention may form in a polycondensation reaction between polyols, predominantly diols, and carboxylic acids and/or anhydrides of carboxylic acids. The polyesters may be linear or branched. Substantially linear polyesters may be formed by reacting predominantly diols, carboxylic acids or anhydrides of carboxylic acids. A small amount of triol, e.g., trimethylol may also be included. The polyester resin preferably has a number average molecular weight, as determined by the GPC method using the polystyrene standard of between 2,000 and 15,000, more preferably between 3,000 and 6000 and most preferably between 3,000 and 4,000.
Waterborne polyester coating compositions comprise partially neutralized acidic functional polyesters dispersed in water as very fine particles may be utilized in the present invention. Such compositions form coating compositions which have low VOCs, i.e., about 1.5 lbs/gal. or below and even as low as about 0.5 lb/gal. or below. The polyesters may be formed for example, from between about 30 and about 60 mole percent polycarboxylic acids and the of which at least about 80 mole percent comprises cyclohexanedicarboxylic acids and the 1,2, 1,3 and 1,4 isomers thereof, or the anhydride thereof, and ring-alkylated derivatives of each, e.g., derivatives in which one or more alkyl group(s) of up to about seven carbon atoms is bound to the cycloaliphatic ring. Of the polycarboxylic acid content, at least about 80 mole percent comprises cyclohexanedicarboxylic acids, preferably at least about 90 mole percent and most preferably at least about 100 mole percent. The balance of the carboxylic acid content, if any, is preferably substantially all dicarboxylic acids and preferably substantially all aliphatic dicarboxylic acids. Carboxylic acids of functionality greater than 2 may be used to a minor extent if branching is desired, but generally linear polyester chains are preferred. The polyester may also contain some aromatic polycarboxylic content, but aromatic polycarboxylic acids are considered to be undesirable as they tend to detract from UV-stability.
The polyester preferably further comprises between about 35 and about 70 mole percent polyols, at least about 95 mole percent of the polyol content comprising diols, and between about 40 and about 100 mole percent of the polyol content comprising cycloaliphatic diols. Between about 40 and about 100 mole percent of the polyol content of the polyester comprises cycloaliphatic diols, such as 1,4-cyclohexanediol, 1,4-cyclohexanedimethanol, hydrogenated bisphenol A, 1,2-cyclopentanediol, 1,3-cyclopentanediol, 1,2, 1,3, 1,4, and 1,5-cyclooctanediol. Of the remaining up to about 60 mole percent of the polyol content, the major portion comprises diols, although up to about 15 mole percent may be higher number diols. Polyols having more than two hydroxy groups may be used to provide branching which imparts increased chemical resistance, durability and stain resistance, depending on the relative amounts used, but at the expense of flexibility and solution viscosity. Preferably, the content of polyols having hydroxyl functionality greater than two, e.g., three or four, is no greater than about 5 mole percent of polyol content, but may be advantageously employed at amounts greater than about 0.5 mole percent.
If desired, suitable non-cyclic polyols include, for example, 1,6 hexanediol, pentaerythritol, trimethylolpropane, 2-methyl-1,3-propanediol, neopentyl glycol, 2-butyl-2-ethyl-1,3-propanediol, ethylene glycol, 1,4-butanediol, 1,3-butanediol, 1,5-pentanediol and trimethylol ethane.
The polyester further comprises between about 5 and about 25 mole percent of a monomer having dihydroxy, monocarboxylic acid functionality. Examples of aliphatic acids which may be included include succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, diglycolic acid, 1,12-dodecanoic acid, tetrapropenyl succinic acid, maleic acid, fumaric acid, itaconic acid, malic acid, etc. Examples of aromatic dicarboxylic acids are phthalic acid, isophthalic acid, terephthalic acid, benzophenone dicarboxylic acid, diphenic acid, 4,4xe2x80x2dicarboxydiphenyl ether, 2,5-pyridine dicarboxylic acid, trimellitic acid, etc. Preferably at least about 95 mole percent and most preferably about 100% of the dicarboxylic acid content is cycloaliphatic or aliphatic.
The polyester may be formed by any of the conventional methods. It is preferred that the polyester be formed at a temperature no higher than about 2000 C. The use of a catalyst is preferred, as is the passage of an inert gas through the reaction mixture to protect against discoloration and to aid in the liberation of water from the mixture as it is produced by the condensation. The esterification takes place almost quantitatively and may be monitored by determining the acid and/or hydroxyl numbers or by monitoring the viscosity of the product.
The molar ratio of polyol +monomer/acid is between about 1.01 and about 1.30, whereby the polyester is hydroxyl-terminated having hydroxyl numbers of between about 20 and about 150. The polyester has an acid numbers between about 30 and about 100. Preferably, no more than about 5 mole percent of the monomers which form the polyester have aromatic groups. The polyesters have weight average molecular weights ranging from about 100 to about 20,000.
The acrylic resins useful in the present invention preferably have a molecular weight of 500 to 1,000,000, and more preferably of 1500 to 50,000. As used herein, xe2x80x9cmolecular weightxe2x80x9d refers to number average molecular weight, which may be determined by the GPC method using a polystyrene standard. Such polymers can be prepared from acrylic and methacrylic monomers such as methyl acrylate, acrylic acid, butyl acrylate, ethyl acrylate, methacrylic acid, methyl methacrylate, butyl methacrylate, cyclohexyl methacrylate, styrene and the like. A functional group can be incorporated into the ester portion of the acrylic monomer. For example, hydroxy-functional acrylic monomers that can be used to form such polymers include hydroxyethyl acrylate, hydroxybutyl acrylate, hydroxybutyl methacrylate, hydroxypropyl acrylate, and the like; amino-functional acrylic monomers may include t-butylaminoethyl methacrylate and t-butylamino-ethylacrylate; acid-functional monomers may include acrylic acid, methacrylic acid, and itaconic acid; epoxide-functional monomers may include glycidyl acrylate and glycidyl methacrylate.
Modified acrylics can also be used as the polymer according to the invention. Such acrylics may be polyester-modified acrylics or polyurethane-modified acrylics, as is well-known in the art. Polyester-modified acrylics modified with xcex5-caprolactone are described in U.S. Pat. No. 4,546,046 of Etzell et al., the disclosure of which is incorporated herein by reference. Polyurethane-modified acrylics are also well-known in the art. They are described, for example, in U.S. Pat. No. 4,584,354, the disclosure of which is incorporated herein by reference. Preferred acrylic resins have a glass transition temperature (Tg) in the range of about +10xc2x0 C. to +50xc2x0 C. It is necessary that the polymer provide a flexible coating for the substrate.
In general, polyurethanes are prepared by reaction of a polyisocyanate component with a polyol component. Preferably, the polyurethane is linear (that is, it is prepared by reacting one or more diisocyanates with one or more diols). Hydroxyl functional polyurethanes may be prepared by reaction of an excess of equivalents of diol with diisocyanate(s). Hydroxyl-functional or amine-functional polyurethanes may also be prepared by reacting an isocyanate-terminated polyurethane with an excess of equivalents of a diol, polyol, polyamine, or amino alcohol (such as diethanol amine) in a capping step. Acid-functional polyurethanes may be synthesized by including a monomer having acid functionality, for example, without limitation, dimethylolpropionic acid. The hydroxyl groups react to form the urethane linkages while the acid group remains unreacted in the polyurethane polymerization.
Preparation of polyurethanes for coating compositions are described in many publications. In general, monomeric polyisocyanates such as those mentioned already may be used in preparing the polyurethane. Aliphatic diisocyanates, particularly IPDI, are preferred. Useful active hydrogen-containing chain extension agents generally contain at least two active hydrogen groups, for example, diols, dithiols, diamines, or compounds having a mixture of hydroxyl, thiol, and amine groups, such as alkanolamines, aminoalkyl mercaptans, and hydroxyalkyl mercaptans, among others. For purposes of this aspect of the invention both primary and secondary amine groups are considered as having one active hydrogen. Active hydrogen-containing chain extension agents also include water, pentaerythritol, among other compounds. Polymeric chain extension agents can also be used, such as polyester polyols, polyether polyols, polyurethane polyols, or polymeric amino group-containing polymers, and it is often preferred to include these. Mixtures of any of the above chain extension agents can also be used.
The reaction of the polyisocyanate and chain extension agent is conducted by heating the components in a suitable reaction medium such as xylene or propylene glycol monoethylether acetate. The use of catalysts for this reaction, e.g., organotin catalysts such as dibutyltin diacetate, is well-known in the art. Polyurethanes useful as the polymeric component may have a number average molecular weight of from 600 to 6000. Various groups, such as nonionic polyether stabilizing groups, ionic stabilizing groups (e.g., carboxyl groups), unsaturated groups, and the like may be incorporated or appended to the material, as is known in the art. Active hydrogen or isocyanate terminal groups may be provided by adjusting the stoichiometry of the chain extension agent and polyisocyanate in the reaction mixture. A molar ratio of active hydrogen:NCO in the reaction mixture of less than 1 will tend to provide isocyanate-terminated polymers. Other terminal groups may be provided by the use of capping agents. For example, an acid terminal group can be provided by capping an isocyanate-terminated polymer with a hydroxyacid. Pendant functional groups may be provided by using chain extension agents having two active hydrogen groups and the desired functional group, e.g., dimethanol propionic acid, as noted above.
The phenolic resins useful in the present invention are commonly referred to as phenoplasts and are obtained by the condensation of phenol or alkyl substituted phenols with aldehydes. The monohydric phenols such as phenol, cresol and xylenol are the most typically utilized since they are readily available and relatively inexpensive. Phenol is the typically preferred monohydric phenol. Polyhydric phenols such as resorcinol can also be used herein. Formaldehyde is the preferred aldehyde used in the production of the phenolic resins. Other useful aldehydes include acetaldehyde, butyraldehyde and furfuraldehyde or mixtures thereof. The preferred phenolic resin is produced by the condensation of phenol and formaldehyde.
The polyepoxides useful for the present invention are those materials having a 1,2 epoxide group present in the molecule. Hydroxyl groups may also be present and often are. Polyepoxides contain more than one 1,2-epoxy group per molecule. In general, the epoxide equivalent weight can range from about 280 to about 4,000. These polyepoxides are saturated or unsaturated, cyclic or acyclic, aliphatic, alicyclic, aromatic or heterocyclic. They can contain substituents such as halogen, hydroxyl and ether groups. One useful class of polyepoxides comprises the epoxy polyethers obtained by reacting an epihalohydrin (such as epichlorohydrin or epibromohydrin) with a polyphenol in the presence of an alkali. Suitable polyphenols include resorcinol, catechol, hydroquinone, bis(4-hydroxyphenyl)-2,2-propane, i.e., bisphenol A; bis(4-hydroxyphenyl)- 1,1-isobutane; 4,4-dihydroxybenzophenone; bis(4-hydroxyphenyl)- 1,1-ethane; bis(2-hydroxynaphenyl)-methane; and 1,5-hydroxynaphthalene. One very common polyepoxide is a polyglycidyl ether of a polyphenol, such as bisphenol A.
Another class of epoxy resins are the polyglycidyl ethers of polyhydric alcohols. These compounds may be derived from such polyhydric alcohols as ethylene glycol, diethylene glycol, triethylene glycol, 1,2-propylene glycol, 1,4-butylene glycol, 1,5-pentanediol, 1,2,6-hexanetriol, glycerol, trimethylolpropane, and bis(4-hydroxycyclohexyl)-2,2-propane.
Another class of epoxide resins are the polyglycidyl esters of polycarboxylic acids. These compounds are produced by the reaction of epichlorohydrin or a similar epoxy compound with an aliphatic or aromatic polycarboxylic acid such as oxalic acid, succinic acid, glutaric acid, terephthalic acid, 2,6-naphthalene dicarboxylic acid and dimerized linoleic acid.
Still another class of polyepoxides are derived from the epoxidation of an olefinically unsaturated alicyclic compound. These polyepoxides are non-phenolic and are obtained by epoxidation of alicyclic olefins, for example, by oxygen and selected metal catalysts, by perbenzoic acid, by acid-aldehyde monoperacetate or by peracetic acid. Among such polyepoxides are the epoxy alicyclic ethers and esters well known in the art.
Useful epoxides can be prepared from alcohols, e.g., butanol, trimethylol propane, by reaction with an epihalohydrin (e.g., epichlorohydrin), or by reaction of an allyl group with peroxide. The epoxide may be monofunctional or polyfunctional, which can be controlled by selection of the starting material. For example, a monoepoxide can be prepared by reacting a mono-alcohol or mono-acid with an epihalohydrin or a monounsaturate with peroxide, and a polyepoxide can be prepared by reacting a polyol (including diols, triols, and higher-functionality polyols) with an epihalohydrin or a polyunsaturate compound with peroxide. Oligomeric or polymeric polyepoxides, such as acrylic polymers or oligomers containing glycidyl methacrylate or epoxy-terminated polyglycidyl ethers such as the diglycidyl ether of bisphenol A (DGEBPA), can also be used. Epoxidized polyurethane resins or polyester resins can be prepared by reacting OH group-containing polyurethanes or polyesters, as are known in the art, with an epihalohydrin. Epoxides can also be prepared by reacting an isocyanate-terminated component such as a monomeric polyisocyanate (including isocyanurates, e.g., the isocyanurate of isophorone diisocyanate) or polymer or oligomer with glycidol. Other known polyepoxides, e.g., epoxy-novolacs, may also be used.
The alkyd resins useful in the present invention are produced by reacting the polycarboxylic acid and the polyhydric alcohol together with a drying, semi-drying or non-drying oil in proportions depending upon the properties desired. The oils are coupled into the resin molecule by esterification during the manufacturing and become an integral part of the polymer. The oil is fully saturated or predominantly unsaturated. When cast into films, the fully saturated oils tend to give a plasticizing effect to the film, whereas the predominantly unsaturated oils tend to crosslink and dry rapidly with oxidation to give more tough and solvent resistant films. Suitable oils include coconut oil, fish oil, linseed oil, tung oil, castor oil, cottonseed oil, safflower oil, soybean oil, and tall oil. Various proportions of the polycarboxylic acid, polyhydric alcohol and oil are used to obtain alkyd resins of various properties as is well know in the art.
To form a curable composition, such as a coating composition, the polymeric resin compositions, as described above, are combined with a cross-linking agent. The cross-linking agent is one which is capable of reacting with the active hydrogens (normally, but not always provided byxe2x80x94OH hydrogens and sometimesxe2x80x94COOH hydrogens) in the polyester to give a thermoset composition upon curing. Examples of suitable cross-linking agents are aminoplasts and polyisocyanates including blocked polyisocyanates.
Aminoplasts are obtained by the condensation reaction of formaldehyde with an amine or an amide. The most common amines or amides are melamine, urea, benzoguanamine or glycourils. However, condensation with other amines or amides can be employed. While the aldehyde employed is most often formaldehyde, other aldehydes such as acetaldehyde, crotonaldehyde, benzaldehyde and furfural may be used. The aminoplast contains methylol or similar alkylol groups, and preferably, at least a portion of these alkylol groups are etherified by reaction with alcohol to provide organic solvent-soluble resins. Any monohydric alcohol can be employed for this purpose including such alcohols as methanol, ethanol, butanol and hexanol. Preferably, the aminoplasts which are used are melamine-, urea- or benzoguanamine-formaldehyde condensates etherfied with an alcohol containing 1 to 4 carbon atoms such as methanol, ethanol, butanol or mixtures thereof. Suitable commercially available products include Resimene products available from Solutia or Cymel products available from Cytec.
Polyisocyanates and blocked polyisocyanates may also be used as curing agents. Examples of suitable polyisocyanates include monomeric polyisocyanates such as toluene disocyanate and 4,4xe2x80x2-methylene-bis(cyclohexyl isocyanate), isophorone diisocyanate and NCO-prepolymers such as the reaction products of monomeric polyisocyanate such as those mentioned above with polyester or polyether polyols. A particularly useful isocyanate is the biuret from 1,6-hexamethylene diisocyanate commercially available from Bayer.RTM. AG as Desmodur.RTM. N.
The polyisocyanate may optionally be blocked. Examples of suitable blocking agents are those materials that would unblock at elevated temperatures such as caprolactam, methyl ethyl ketoxime, or dimethylpyrozole. Blocked isocyanates can be used to form stable one-package systems. Polyfunctional isocyanates with free isocyanate groups can be used to form two-package room temperature curable systems. In these systems, the polyester and isocyanate curing agent are mixed just prior to their application.
The amount of curing agent which is used from about 1 to 70 percent by weight, preferably 5 to 50 percent by weight, based on total weight of the total coating composition.
Critical to the present invention is the addition of a catalyst such as a Lewis Acid catalyst, methane sulfonic acid or perflouroacetic acid or mixtures of these catalysts. It is believed that the catalyst provides a lowered bake temperature and a shortened bake time. Preferred Lewis acid catalysts include aluminum nitrate, iron nitrate, zinc nitrate, zirconium perchlorate, barium nitrate, aluminum sulfate, and aluminum perchlorate and mixtures thereof. Most preferred catalysts for purposes of the present invention include perflouroacetic acid, aluminum nitrate, zinc nitrate, iron nitrate, barium nitrate, aluminum sulfate, and aluminum perchlorate, methane sulfonic acid and mixtures thereof. The catalyst is utilized in an amount between 0.01% and 5.0% by weight based on total coating composition weight. More preferably the catalyst is utilized in an amount between 0.01% to 2.0 % by weight, and most preferably between 0.05 and 1.0% by weight, based on total weight of the coating composition.
Solvent is utilized in the coating composition to adjust the viscosity of the coating composition to that desired for a coil coating process. Solvents are utilized in an amount between 1 and 50% by weight, more preferably between 1 and 40% by weight and most preferably between 1 and 35% by weight based on total coating composition weight. Low boiling solvents, such as aromatic, esters or ketone solvents or mixtures of aromatic ester or ketone solvents are preferred, as quick solvent evaporation is necessary in the method of the present invention. In the case of waterborne coatings, water alone or in mixture with organic solvent or diluent may be used.
In addition to the polymeric component, crosslinking agent and catalyst, the high solids coating composition can optionally contain other hydroxyl functional polymers, pigments, liquid diluents, plasticizers, anti-oxidants, UV light absorbers, surfactants, flow control agents, as are well known in the art.
Substrates coated according to the method of the present invention may be used for a variety of purposes including, but not limited to, automotive parts, appliance parts, and architectural building materials.
In general, coating thicknesses will vary depending upon the application desired. In general, coatings from about 0.01 to 5 mils have been found to be useful in most applications, and coatings from about 0.1 to 1.5 mils have been found to be more useful.

Low temperature cure coating composition and method therefore


A method of treating or preventing oral fungal infection includes applying a polymerizable monomer adhesive composition to an area afflicted with or susceptible to oral fungal infection, optionally with at least one of an additional anti-fungal agent, and allowing the polymerizable monomer composition to polymerize to form a polymer film over the area.

1. Field of Invention
According to the present invention, any suitable application can be used to apply the composition to the affected areas of. Suitable applicators and pack again systems are disclosed in, for example, U.S. Pat. No. 5,928,611 and U.S. patent applications Ser. Nos. 09/430,177, 09/430,176, 09/430,289, 09/430,290, and 09/430,180 filed Oct. 29, 1999; Ser. No. 09/343,914 filed Jun. 30, 1999; Ser. No. 09/385,030 filed Aug. 30, 1999; and Ser. No. 09/176,889 filed Oct. 22, 1998; the entire disclosures of which are incorporated herein by reference. A further further suitable application is described in co-pending U.S. patent application Ser. No. 09/898,006, filed concurrently herewith, the entire disclosures of which are incorporated herein by reference.
2. Description of Related Art
Monomer and polymer adhesives are used in both industrial (including household) and medical applications. Included among these adhesives are the 1,1-disubstituted ethylene monomers and polymers, such as the xcex1-cyanoacrylates. Since the discovery of the adhesive properties of such monomers and polymers, they have found wide use due to the speed with which they cure, the strength of the resulting bond formed, and their relative ease of use. These characteristics have made the xcex1-cyanoacrylate adhesives the primary choice for numerous applications such as bonding plastics, rubbers, glass, metals, wood, and, more recently, biological tissues.
It is known that monomeric forms of xcex1-cyanoacrylates are extremely reactive, polymerizing rapidly in the presence of even minute amounts of an initiator, including moisture present in the air or on moist surfaces such as animal (including human) tissue. Monomers of xcex1-cyanoacrylates are anionically polymerizable or free radical polymerizable, or polymerizable by zwitterion or ion pairs to form polymers. Once polymerization has been initiated, the cure rate can be very rapid.
Medical applications of 1,1-disubstituted ethylene adhesive compositions include use as an alternate or an adjunct to surgical sutures and/or staples in wound closure, as well as for covering and protecting surface wounds such as lacerations, abrasions, burns, stomatitis, sores, minor cuts and scrapes, and other wounds. When an adhesive is applied to surfaces to be joined, it is usually applied in its monomeric form, and the resultant polymerization gives rise to the desired adhesive bond.
U.S. Pat. Nos. 5,514,371, 5,514,372, 5,575,997, 5,624,669, and 5,582,834 to Leung et al. disclose the addition of a therapeutic agent in a cyanoacrylate composition. The cyanoacrylate adhesive forms a matrix for the therapeutic agent, with the therapeutic agent being released in vivo over time from the matrix during biodegradation of the polymer.
U.S. Pat. No. 5,762,955 to Smith discloses a treatment for healthy, damaged, diseased, or infected biological tissue by applying a bioadhesive coating in conjunction with a medication. The treatment is directed, in part, to treating external biological tissue that may be affected by harmful afflictions such as bruises, burns, dermatological afflictions, infections, gashes, wounds, herpes sores, canker sores, or intra-oral lesions, and skin cancers such as leukemia. Smith further discloses several medications that may be used including corticosteroids, fluoroouracil, obtundants, anesthetics, antibiotics, fungicides, anti-inflammatory agents, antibacterial agents, antiseptic agents, and other medications or combinations of medications used in processes for healing tissue, promoting or preventing blood clotting, destroying cancer cells, palliative treatments and killing of bacteria or viruses.
U.S. Pat. No. 4,880,416 to Horiuchi et al., discloses a dermal bandage of a pre-formed film-like adhesive material for preventing dermally applied ointments, creams, solutions, powders, etc. from falling off, and for delivering drugs, such as anti-fungal agents, to affected parts of the skin. U.S. Pat. Nos. 5,716,607 and 5,716,608, both to Byram et al., disclose the use of cyanoacrylate adhesives to prevent ionization radiation damage to skin. Such damage is prevented by applying the cyanoacrylate polymer to the skin to be protected. U.S. Pat. No. 5,653,769 to Barkey, Jr., et al., discloses protecting skin areas from irritation due to contact with artificial devices such as prosthetics, bandages and casts by applying a cyanoacrylate polymer to the desired skin areas that otherwise would be prone to ulceration or irritation by the devices.
U.S. Pat. No. 4,287,177 to Nakashima et al. discloses a protective covering material for forming a film or coat on the skin or wound surface, wherein the film may contain an anti-fungal agent that is controllably released when the composition is placed in contact with the skin. U.S. Pat. Nos. 5,684,042; 5,753,699; 5,762,919; 5,783,177; and 5,811,091 to Greff et al. disclose a cyanoacrylate composition with a compatible anti-fungal agent to form an anti-fungal polymeric cyanoacrylate film to be applied on mammalian skin as wound dressings, wound bandages, surgical incise drapes, wound closure materials and the like.
Oral candidiasis is a yeast infection of the mouth, especially of the mucous membranes of the mouth and tongue, generally caused by fungal species of Candida albicans. This fungal species, or similar species, also cause similar and related fungal infections in the mouth. The condition generally includes the appearance of whitish velvety plaques on the mucous membranes of the mouth and/or tongue. If the whitish plaques are scraped away, the underlying base may be red (erythematous) with pinpoint bleeding. Oral candidiasis, sometimes referred to as adult oral thrush, and related or similar oral fungal infections, are common occurrences in infants where they do not pose a serious concern. However, the occurrence of such oral infections in adults is considered abnormal, and generally occurs only when conditions that depress the immune system are present. That is, the presence of the fungal species in healthy individuals is kept in balance by the presence of other bacteria in the mouth. However, when this balance is upset, the fungal species may grow out of control. For example, such oral infections are common in patients that are infected with the AIDS virus, in patients under immunosuppression for organ transplant, individuals undergoing chemotherapy, patients with diabetes, patients of advanced age or general poor health, and individuals having inherited abnormalities of the immune system. The occurrence of such oral infections may also occur in individuals where the balance of normal microorganisms is upset, such as by the use of antibiotics, excessive use of mouthwash or mouth sprays, long-term use of corticosteroids or immunosuppressive medications, uncontrolled diabetes mellitus, or with normal hormone changes associated with pregnancy or the use of birth control pills.
In the case of immunocompromised people, the infection may be massive, coating much of the surface of the mouth and tongue. In addition, it may spread to the esophagus, producing esophagitis candida with resulting painful difficult swallowing.
Because the conditions oral candidiasis and esophagitis candida are related in terms of their origins, xe2x80x9coralxe2x80x9d infections, as used herein, is intended to cover infections not only of the oral cavity (such as the mouth and tongue) but also of the esophagus. However, xe2x80x9coralxe2x80x9d infections in the context of the present invention is not intended to cover infections of other bodily areas caused by the same or similar microorganisms, such as candidal vulvovaginitis or vaginal yeast infections.
Furthermore, based on the similarity between fungal infections and yeast infections, particularly in terms of their causes, xe2x80x9cfungal infectionxe2x80x9d as used herein is intended to mean fungal and/or yeast infections, unless noted otherwise.
The incidence of oral candidiasis in adults has increased dramatically with the spread of AIDS. HIV infected people are at high risk for oral candidiasis, which often may be one of the first signs of AIDS infection. In extreme cases, oral candidiasis may also spread further, including throughout the body, as a condition known as disseminated candidiasis. The death rate from disseminated candidiasis may reach as high as 70%.
Physicians commonly prescribe medications in the form of powders, aerosols, liquids or creams for the treatment of oral fungal infections. Such medications are also commonly obtained by individuals xe2x80x9cover-the-counterxe2x80x9d for treatment of the same condition.
Because the infection occurs in the mouth, topically applied medications are often easily removed from the affected areas. Moreover, topically applied medications are more prone to the affects of moisture and saliva that is present in the area of the infection. These difficulties mean that treatment is significantly reduced, because the medication is not held in place for a sufficient time. As a result, the efficacy of the treatment is significantly reduced, and patients must frequently reapply medications so that the affected area receives proper treatment. Furthermore, the inconvenience of bandages due to the location of the infection and the constant or frequent movement and flexing of the mouth, the small surface area usually involved, and the presence of moisture and saliva, make bandages impractical as a means to hold the medication in place for longer periods of time.
In addition, conventional treatment regimens for oral fungal infections continue to pose significant public health and safety concerns. Because conventional treatments have the above-described problems of being easily removed from the afflicted area and being susceptible to moisture, there is a much greater chance that the fungal infection can be spread. This spread of the fungus can be either to other parts of the same patient""s body, ultimately leading to disseminated candidas, or to other individuals.
Despite the known use of adhesives, such as described above, such adhesives have not been used in the treatment of oral fungal infections. Instead, the majority of oral fungal infection treatments currently on the market include topically applied medications that have the problems of being easily removed from the application site, being prone to moisture effects, and resulting in higher spread or transmission rates, or orally administered anti-fungal agents. Therefore, there is a need for an alternative oral fungal infection treatment that remains at the application site for longer periods, that reduces the spread or transmission of the fungal infection, and that provides fast, effective relief from the symptoms of.
The present invention provides methods for preventing and/or treating oral fungal infections by applying a monomeric adhesive composition to the affected area, or to areas that are prone to infection. The monomeric adhesive composition of the present invention preferably comprises a polymerizable 1,1-disubstituted ethylene monomer such as a cyanoacrylate monomer, that may include or be accompanied by an additional anti-fungal agent. The composition reduces moisture contact with the affected area, keeps any active ingredients in contact with the affected area for a longer time, provides fast and effective treatment of oral fungal infection, and can act to prevent infection in the first instance, or prevent the spread of an infection to other areas.
The present invention provides an unexpected treatment or prevention composition and method for oral fungal infection, because polymerizable monomers such as 1,1-disubstitutyed ethylene monomers and cyanoacrylates have not previously been used to treat or prevent such conditions. Moreover, while such polymerizable monomers have been variously used on other parts of the body, such as for sealing open wounds, their use for treating or preventing oral fungal infection is an entirely and new and unexpected use of the materials.
The present treatment for or prevention of oral fungal infection is advantageous for several reasons. First, because oral fungal infection affects the patient""s mouth, it is often very difficult for the patient to keep a treatment agent in contact with the affected area for an extended period of time. This is generally because higher levels of moisture present in the area tend to affect or likewise disturb the applied agent. Furthermore, because the treatment and prevention methods of the present invention provide a stronger physical barrier at the affected area, the risks of spread or transmission of the fungal infection, either to other areas of the patient""s body or to other individuals, is significantly decreased. The present invention thus provides significant public health benefits.
Because cyanoacrylates tend to polymerize rapidly to form a relatively robust polymerized film, cyanoacrylates applied to an affected area (or to an area prone or susceptible to infection) can provide fast, effective protection over the affected area and other surfaces. By protecting the affected area from moisture and frictional contact, the cyanoacrylate compound can hold any applied active agents in place for a longer period of time and can accordingly significantly increase the time of exposure of an applied medication to the affected area, ensure more effective treatment, and minimize the possibility of re-infection or transmission of the fungal infection to other areas of the patient""s body or to other individuals. Likewise, the same benefits can be obtained by applying the composition of the present invention to an area prone or susceptible to infection, which in turn aids in preventing spread or transmission of the infection.
In addition to forming a stronger barrier to keep moisture away from the affected area while maintaining active agents in contact with the area, cyanoacrylate compounds are also desirable for the treatment or prevention of oral fungal infections because of their inherent anti-fungal properties. In laboratory tests, it has been discovered that at least some cyanoacrylate compounds or formulations, even in the absence of an added anti-fungal agent, appears to inhibit fungal infections. Because of this anti-fungal property, such cyanoacrylate compounds and formulations may be especially desirable for treating or preventing oral fungal infections, even without the introduction or pre-application of other anti-fungal agents. Moreover, the anti-fungal properties of such cyanoacrylate compounds and formulations may also be beneficial in instances where an anti-fungal agent is applied before, or together with, the cyanoacrylate, because the cyanoacrylate can continue to provide its anti-fungal effect even after the applied anti-fungal agent has been completely absorbed or used up.
In addition, cyanoacrylate compounds are also useful as anti-fungal agent carriers or delivery agents. In this capacity, the cyanoacrylate compound provides the same protective and anti-fungal benefits, but also offers the added benefit of enhancing the treatment of the affected area by controllably releasing an anti-fungal agent to the affected area, or providing prolonged preventative benefits to an applied area by controllably releasing an anti-fungal agent to the area.
The present invention also provides various applicators that are suitable for applying the adhesive composition.
This invention is directed to methods of treating oral fungal infection, such as oral candidiasis or oral thrush, by applying a monomeric adhesive composition to an afflicted area of a patient""s mouth. This invention is also directed to methods of preventing oral fungal infection by applying a monomeric adhesive composition to an area of a patient""s mouth that is prone or susceptible to such infection.
According to embodiments of the present invention, the adhesive composition can be applied alone, or it can be applied subsequent to or concurrent with the application of a separate anti-fungal agent. Furthermore, in embodiments, the cyanoacrylate composition can itself include an anti-fungal agent in addition to polymerizable monomer.
According to the present invention, xe2x80x9ctreatxe2x80x9d (or other forms of the word such as xe2x80x9ctreatingxe2x80x9d and xe2x80x9ctreatmentxe2x80x9d) refers to employment of the methods against an established fungal infection. xe2x80x9cTreatxe2x80x9d thus encompasses both amelioration of effects of the fungal infection, such as by reducing swelling, irritation, pain and the like, and active reduction of the infection such as by killing the fungus and preventing re-growth of the fungus at an infected area.
According to the present invention, xe2x80x9cpreventxe2x80x9d (or other forms of the word such as xe2x80x9cpreventingxe2x80x9d and xe2x80x9cpreventionxe2x80x9d) refers to employment of the methods against a subsequent fungal infection, such as at areas that are prone or susceptible to fungal infection. xe2x80x9cPreventxe2x80x9d thus encompasses both prevention of spread of an established fungal infection, as well as prevention of infection in the first instance on the particular patient.
In embodiments of the invention, an adhesive composition can be used alone for treating or preventing oral fungal infection. In such embodiments, a patient or care-provider simply applies the composition to an area of the mouth afflicted with an oral fungal infection, or to an area where prevention of infection is desired. The composition then is permitted to polymerize to form a robust polymeric coating that effectively covers and protects the affected or applied area. Anti-fungal properties of the composition may inhibit or kill microbes, and the robust polymeric coating that the composition forms protects the area from frictional contact with other surfaces so that prolonged treatment or prevention can be achieved.
Preferably, the composition is applied in a sufficient amount to entirely cover the desired area, which generally would correspond to an affected area where an oral fungal infection is present, or to an areas that is prone or susceptible to infection. In embodiments, the composition covers an additional area around the desired area, for example to prevent further infection.
According to the present invention, the adhesive composition is preferably permitted to substantially or fully polymerize to form a polymer film before the treated area is permitted to contact other surfaces. Thus, for example, when the composition is applied to the tongue, the tongue is preferably kept separated from other surfaces in the mouth until the composition has substantially or fully polymerized, to prevent bonding the tongue and other surfaces together.
In further embodiments of the present invention, the adhesive composition can be applied over a medicament for treating or preventing oral fungal infections. The medicament in this embodiment is not particularly limited, and can include any of the available medicaments for the condition. The medicament can also be, or comprise, any suitable anti-fungal agent, as described below. In this embodiment, the medicament can be first applied to the affected or desired area, followed by application of a polymerizable adhesive composition. The medicament can be in any suitable form, including liquid, solid, powder, cream or the like, and can include only a medicament or can include other suitable additives such as diluents, carriers or the like. Where the medicament is in a liquid or a semi-liquid form, it is preferred that the medicament be permitted to dry, substantially or completely, prior to application of the adhesive composition. However, the adhesive composition can also be immediately applied over the applied medicament, or can be applied prior to drying of the medicament, if desired.
In embodiments of the present invention, an appropriate, preferably monomer-compatible, anti-fungal agent can be mixed with the polymerizable adhesive composition and a resultant composition applied to the affected or desired area. In this embodiment, the anti-fungal agent can be mixed with the polymerizable adhesive composition during manufacture (i.e. prior to packaging the materials), or immediately prior to use. However, the present invention is not limited to such embodiments. Thus, for example, the anti-fungal agent need not be monomer-compatible. In these embodiments, the anti-fungal agent can be mixed or combined with the polymerizable adhesive composition, usually just prior to application, and a resultant composition applied to the affected or desired area
In further embodiments of the present invention the anti-fungal agent may also serve as a polymerization initiator or a stabilizer. Thus, the anti-fungal agent can provide not only a biological activity, but a chemical one as well.
Anti-fungal agents that also serve as polymerization initiators can initiate and/or accelerate the polymerization of the composition when applied to an affected or desired area. Accelerated polymerization reduces the waiting time necessary after application, and makes the composition more convenient to apply. Suitable anti-fungal agents that can also serve as initiators include, but are not limited to, certain acidic and quaternary ammonium compounds. In embodiments where the anti-fungal agent also acts as a polymerization initiator or rate modifier, the present invention provides the additional advantage of not requiring that a further, separate polymerization initiator or rate modifier be used. Furthermore, in these embodiments, the anti-fungal agent is preferably located in a non-contacting relationship with the adhesive composition prior to use, so that premature polymerization of the adhesive composition does not occur.
Anti-fungal agents that also serve as stabilizers can extend the useful life of the composition. By increasing the useful life of the composition, the composition can be stored and packaged for longer periods of time without the risk of premature polymerization. Suitable anti-fungal agents that can also serve as stabilizers can include, but are not limited to, certain acidic and phenolic compounds. In embodiments where the anti-fungal agent also acts as a stabilizer for the adhesive composition, the present invention provides the additional advantage of not requiring that a further, separate stabilizer be used. Furthermore, in these embodiments, the anti-fungal agent is preferably located in a contacting relationship with the adhesive composition, such as being mixed with the adhesive composition, prior to use.
Although a mixture of anti-fungal agent and cyanoacrylate, according to the present invention, is not limited to a specific ratio of anti-fungal agent to cyanoacrylate, the anti-fungal agent is preferably present in an effective amount, preferably a therapeutically effective amount for treating or preventing the oral fungal infection.
When mixed or combined immediately prior to use, the anti-fungal agent can be mixed with the polymerizable cyanoacrylate composition in a suitable container and thereafter applied. Alternatively, mixing can be conducted during the application process, for example by using an applicator that is loaded with anti-fungal agent, which thereby mixes the agent with the adhesive composition during application.
Suitable anti-fungal agents include, but are not limited to, known agents such as parabens, cresols, azoles, allylamines, pollyenes, acidics, mercurials, quaternary ammonium compounds, other agents, non-polymer-stabilized compounds, i.e., that are not complexed with or otherwise part of a polymer species, mixtures thereof, and the like. Such anti-fungal agents should preferably be present in a therapeutically effective amount, particularly in cases where higher amounts may otherwise be toxic to the patient.
For example, suitable parabens include, but are not limited to, alkyl parabens and salts thereof, such as methylparaben, methylparaben sodium, ethylparaben, propylparaben, propylparaben sodium, butylparaben, and the like. Butyl-paraben is especially preferred as it can also act as a stabilizer for certain polymerizable monomers, such as cyanoacrylate monomers, in the adhesive composition. Suitable cresols include, but are not limited to, cresol, chlorocresol, and the like. Suitable azoles include, but are not limited to, voriconazole, ketoconazole, fluconazole, itraconazole, miconazole, clotrimazole, saperconazole, neticonazole, oxiconazole, isoconazole, sulconazole, tercanazole, tioconazole, and the like. Suitable allylamines include, but are not limited to, naftifine, SF86-327, and the like. Suitable polyenes include, but are not limited to, nyastatin, amphotericin B, pimaricin, and the like. Suitable acidics include, but are not limited to, benzoic acid and salts thereof, sorbic acid and salts thereof, propionic acids and salts thereof, boric acid and salts thereof, dehydroacetic acid, sulphurous and vanillic acids, and alkyl esters of pararhydrobenzoic acid. Suitable mercurials include but are not limited to, thiomersal, phenylmercuric acetate and nitrate, nitromersol and sodium ethylmercurithiosalicylate. Suitable quaternary ammonium compounds include, but are not limited to, benzalkonium chloride, cetylpyridinium chloride, benzethonium chloride, and cetyltrimethyl ammonium bromide. Other known agents that can be used include, but are not limited to, hydroquinone, pyrocatechol, resorcinol, 4-n-hexyl resorcinol, captan (i.e., 3a,4,7,7a-tetrahydro-2-((trichloromethyl)thio)-1H-isoindole-1,3(2H)-dione), benzalkonium chloride, benzalkonium chloride solution, benzethonium chloride, benzoic acid, benzyl alcohol, cetylpyridinium chloride, chlorobutanol, dehydroacetic acid, o-phenylphenol, phenol, phenylethyl alcohol, potassium benzoate, potassium sorbate, sodium benzoate, sodium dehydroacetate, sodium propionate, sorbic acid, thimerosal, thymol, chlorothymol, alcohols, chlorobutanol, phenoxy-2-ethanol, benzyl alcohol, xcex2-phenylethyl alcohol, chlorhexidine, 6-acetoxy-2,4-dimethyl-m-dioxane 2,4,4xe2x80x2trichloro-2xe2x80x2-hydroxy-diphenylether, imidizoldinylether urea compound, bromo-2-nitropropanediol-1,3 5-bromo-5-nitrol-1,3 dioxane 2-methyl 1-4-isothiazolin-3-one and 5 chloro derivative 1-(3-chloroallyl)-3,5,7-triazo 1-azoniaadamantane chloride (Dowicil 200), phenylmercuric compounds such as phenylmercuric borate, phenylmercuric nitrate and phenylmercuric acetate, formaldehyde, formaldehyde generators such as the preservatives Germall II(copyright) and Germall 115(copyright) (imidazolidinyl urea, available from Sutton Laboratories, Charthan, N.J.), morpholines, salicylic and benzoic acids, sodium and potassium iodides, flucytosine, 5-flucytosine, griseofulvin, terbinafine, cidofovir, famicoclovir, valacyclovir, echinocandins, pneumocandins, pradimicins, benanomicins, nikkomycins, amorolfine, polyoxins, duanorubicin citrate, doxorubicin hydrocholride, tolnaftate, ciclopirox, butenafine, ergestrol biosynthesis inhibitors, miconazole nitrate, povidone iodine complex, cliquinol, haloprogin, undecylenic acid, mixtures thereof, and the like.
Non-polymer-stabilized compounds, i.e., that are not complexed with or otherwise part of a polymer species, which can be either soluble or insoluble in the monomeric composition, can also be used. Where the compounds are insoluble in the monomeric composition, they must generally be capable of releasing species, such as ions, which are soluble in the monomer composition and provide the anti-fungal effect. Thus such compounds either themselves are, or provide, the anti-fungal agent. Such suitable non-polymer-complexed materials include, but are not limited to, metals and metal compounds. Examples of such metal compounds or elemental metals include, but not limited to, mercurial compounds, such as phenolmercuric chloride, phenolmercuric acetate, acetomeroctol, nitromersol, thimerosal, mercurochrome, mercuric chloride, and mercuric iodide; elemental metals, such as silver and copper; and metal compounds, such as copper chloride, copper sulfate, copper peptides, zinc chloride, zinc sulfate, zinc salts of cyanoacrylic acid, zinc salts of cyanoacetic acid, zinc salts of dicyanoglutaric acid, zinc salts of rosin, zinc oxide, zinc salts of polycyanoacrylic acid, zinc salts of polyacrylic acid, zinc bacitracin, zinc salicylate, zinc stearate, zinc citrate, zinc lactate, silver nitrate, silver iodide, silver acetate, silver benzoate, silver carbonate, silver chloride, silver citrate, silver oxide, silver sulfate, and tincture of iodine; as well as mixtures thereof and the like. Copper peptides are discussed, for example, in xe2x80x9cCopper: An Essential Element for Life,xe2x80x9d ProCyte Corporation, available at
http://www.humatech.com/technology.html (Oct. 28, 1999), the entire disclosure of which is incorporated herein by reference. Further information on anti-fungal activities of metals can be found, for example, in S. Seymour Block, Disinfection, Sterilization and Preservation, 3rd Ed., Philadelphia: Lea and Febiger, 1983, the entire disclosure of which is incorporated herein by reference. The ions from the metal, which constitute the anti-fungal agent, diffuse into and through the adhesive composition.
Other suitable anti-fungal agents include the various compounds identified as such in The Merck Index, 12th Ed. (1996), incorporated herein by reference. Such agents include acrisorein, 3-amino-4-hydroxybutyric acid, ammonium mercuric chloride, amorolfine, amphotericin B, anthralin, azaserine, benzoic acid, bifonazole, biphenamine, boric acid, bromosalicylchloranilide, buclosamide, butenafine, butoconazole, calcium propionate, candicidin, chlordantoin, chlormidazole, chlorphenesin, chlorquinaldol, ciclopirox, cloconazole, clotrimazole, cloxyquin, coparaffinate, m-cresyl acetate, cupric sulfate, dermostatin, diamthazole dihydrochloride, econazole, enilconazole, etisazol, exalamide, fenticonazole, filipin, fluconazole, flucytosine, flutrimazole, fungichromin, griseofulvin, hachimycin, halethazole, hamycin, hexetidine, isoconazole, itraconazole, ketoconazole, lanoconazole, loflucarban, lucensomycin, Magenta I, mepartricin, 2-(methoxymethyl)-5-nitrofuran, miconazole, monensin, myxin, naftifine, natamycin, neomycin undecylenate, nifuratel, nystatin, oligomycins, omoconazole, ontianil, oxiconazole nitrate, pecilocin, perimycin, phenylmurcuric nitrate (basic), potassium iodide, propionic acid, pyrithione, pyrrolnitrin, rubijervine, salicylanilide, salicylic acid, saperconazole, sertaconzole, siccanin, sodium propionate, sulbentine, sulconazole, tenonitrozole, terbinafine, terconazole, thimerosal, tioconazole, tolciclate, tolindate, tolnaftate, triacetin, 2,4,6-tribromo-m-cresol, tubercidin, ujothion, undecylenic acid, viridin, zinc propionate, mixtures thereof, and the like.
In addition, in embodiments where monomer additives including, but not limited to those listed above, are insoluble with the monomer composition, the additive can be applied to a desired area before applying the monomer composition. In such embodiments, the additive and the monomer composition can be provided, for example, in separate packages in a kit.
In other embodiments, where such additives are soluble with the monomer composition, the additives can be combined with the monomer composition during manufacture of the composition. Moreover, in cases where the additive is soluble with the monomer composition, the additive can be applied before the monomer composition is applied, it can be pre-mixed with and applied together with the monomer composition, it can be mixed together with the monomer composition immediately before application, or it can even be applied after the monomer composition has been applied. As a result, in cases where a soluble additive is to be applied, the additive and the composition can be provided in a kit where the additive and the monomer composition are pre-mixed, or the additive and the monomer composition can be provided separately to be applied separately or mixed together immediately prior to, during, or after application.
Although a mixture of additive and cyanoacrylate, according to the present invention is not limited to a specific ratio of additive to cyanoacrylate, the additive is preferably present in an effective amount, and preferably in a therapeutically effective amount.
When mixed immediately prior to use, the additive can be mixed with the polymerized cyanoacrylate composition in a suitable container and thereafter applied. Alternatively, mixing can be conducted during the application process, for example by using an applicator loaded with anti-fungal agent, which thereby mixes the additive with the adhesive composition during application.
In addition, as discussed above with respect to suitable anti-fungal agents, various additives may also serve as polymerization initiators or rate modifiers. Also, suitable additives may serve as stabilizers for the adhesive composition.
In embodiments, the monomer composition and/or its packaging can be sterilized. However, sterilization is by no means required, particularly in view of the fact that most commercially available products for the treatment of oral fungal infection are not sterilized. Furthermore, whether or not the composition and container is sterilized, the composition can further include one or more suitable preservative, as described below.
Sterilization of the monomer composition and/or its packaging can be accomplished by techniques known to the skilled artisan, and is preferably accomplished by methods including, but not limited to, chemical, physical, and/or irradiation methods. Examples of chemical methods include, but are not limited to, exposure to ethylene oxide or hydrogen peroxide vapor. Examples of physical methods include, but are not limited to, sterilization by heat (dry or moist) or retort canning. Examples of irradiation methods include, but are not limited to, gamma irradiation, electron beam irradiation, and microwave irradiation. A preferred method is electron beam irradiation, as described in U.S. patent application Ser. No. 09/025,472, filed on Feb. 18, 1998, the entire disclosure of which is incorporated herein by reference. The composition should also show low levels of toxicity to living tissue during its useful life. In preferred embodiments of the present invention, the composition is sterilized to provide a Sterility Assurance Level (SAL) of at least 10xe2x88x923. In embodiments, the Sterility Assurance Level may be at least 10xe2x88x924, or may be at least 10xe2x88x925, or may be at least 10xe2x88x926.
The monomer (including prepolymeric) adhesive composition may include one or more polymerizable monomers. Preferred monomers that may be used in this invention are readily polymerizable, e.g. anionically polymerizable or free radical polymerizable, or polymerizable by zwitterion or ion pairs to form polymers. Such monomers include those that form polymers, that may, but do not need to, biodegrade. Such monomers are disclosed in, for example, U.S. Pat. Nos. 5,328,687 and 5,928,611 to Leung et al., U.S. patent application Ser. No. 09/430,177, filed on Oct. 29, 1999, and U.S. patent application Ser. No. 09/471,392 filed Dec. 23, 1999, which are hereby incorporated in their entirety by reference herein.
The xcex1-cyanoacrylates of the present invention can be prepared according to several methods known in the art. U.S. Pat. Nos. 2,721,858, 3,254,111, 3,995,641, and 4,364,876, each of which is hereby incorporated in its entirety by reference herein, disclose methods for preparing xcex1-cyanoacrylates.
The composition may optionally also include at least one other plasticizing agent that assists in imparting flexibility to the polymer formed from the monomer. The plasticizing agent preferably contains little or no moisture and should not significantly affect the stability or polymerization of the monomer. Examples of suitable plasticizers include but are not limited to tributyl citrate, acetyl tri-n-butyl citrate (ATBC), polymethylmethacrylate, polydimethylsiloxane, hexadimethylsilazane and others as listed in U.S. patent application Ser. No. 09/471,392 filed Dec. 23, 1999, the disclosure of which is incorporated in its entirety by reference herein.
The composition may also optionally include at least one thixotropic agent. Suitable thixotropic agents are known to the skilled artisan and include, but are not limited to, silica gels such as those treated with a silyl isocyanate, and optionally surface treated titanium dioxide. Examples of suitable thixotropic agents and thickeners are disclosed in, for example, U.S. Pat. No. 4,720,513, and U.S. patent application Ser. No. 09/374,207 filed Aug. 12, 1999, the disclosures of which are hereby incorporated in their entireties by reference herein.
The composition may optionally also include thickeners. Suitable thickeners may include poly (2-ethylhexy methacrylate), poly(2-ethylhexyl acrylate) and others as listed in U.S. patent application Ser. No. 09/472,392 filed Dec. 23, 1999, the disclosure of which is incorporated by reference herein in its entirety.
The composition may also optionally include at least one natural or synthetic rubber to impart impact resistance. Suitable rubbers are known to the skilled artisan. Such rubbers include, but are not limited to, dienes, styrenes, acrylonitriles, and mixtures thereof. Examples of suitable rubbers are disclosed in, for example, U.S. Pat. Nos. 4,313,865 and 4,560,723, the disclosures of which are hereby incorporated in their entireties by reference herein.
The composition may optionally also include one or more stabilizers, preferably both at least one anionic vapor phase stabilizer and at least one anionic liquid phase stabilizer. These stabilizing agents may inhibit premature polymerization. Suitable stabilizers may include those listed in U.S. patent application Ser. No. 09/471,392 filed on Dec. 23, 1999, the disclosure of which is incorporated by reference herein in its entirety. Furthermore, certain stabilizers may also function as anti-fungal agents, such as, for example, various acidic anti-fungals, as identified above.
The stability, and thus the shelf-life, of some monomeric adhesive compositions can be further enhanced and extended through careful regulation of the packaging. Treated (e.g., fluorinated polymer) packaging such as that disclosed in copending U.S. patent application Ser. No. 09/430,289, filed Oct. 29, 1999, which is hereby incorporated by reference herein in its entirety, is preferred and may reduce the amount of stabilizer that is combined into the composition. As mentioned above, certain stabilizers including, but not limited to, certain acidics can also function as anti-fungal agents. In this case, the amount of the anti-fungal/stabilizer material is either not reduced below a level to provide the desired anti-fungal effect, or a further anti-fungal/non-stabilizing agent is added to ensure that the desired anti-fungal effect is provided.
The compositions may also include pH modifiers to control the rate of degradation of the resulting polymer, as disclosed in U.S. patent application Ser. No. 08/714,288, filed Sep. 18, 1996, the entire disclosure of which is hereby incorporated by reference herein in its entirety.
Compositions of the present invention may also include at least one biocompatible agent effective to reduce active formaldehyde concentration levels produced during in vivo biodegradation of the polymer (also referred to herein as xe2x80x9cformaldehyde concentration reducing agentsxe2x80x9d). Preferably, this component is a formaldehyde scavenger compound. Examples of formaldehyde scavenger compounds useful in this invention include sulfites; bisulfites; mixtures of sulfites and bisulfites, etc. Additional examples of formaldehyde scavenger compounds useful in this invention and methods for their implementation can be found in U.S. Pat. Nos. 5,328,687, 5,514,371, 5,514,372, 5,575,997, 5,582,834 and 5,624,669, all to Leung et al., which are hereby incorporated herein by reference in their entireties.
To improve the cohesive strength of adhesives formed from the compositions of this invention, difunctional monomeric cross-linking agents may be added to the monomer compositions of this invention. Such crosslinking agents are known. U.S. Pat. No. 3,940,362 to Overhults, which is hereby incorporated herein in its entirety by reference, discloses exemplary cross-linking agents.
The compositions of this invention may further contain fibrous reinforcement and colorants such as dyes, pigments, and pigment dyes. Examples of suitable fibrous reinforcement include PGA microfibrils, collagen microfibrils, and others as described in U.S. patent application Ser. No. 09/471,392 filed on Dec. 23, 1999, the disclosure of which is incorporated by reference herein in its entirety.
The polymerizable compositions useful in the present invention may also further contain one or more preservatives, for prolonging the storage life of the composition. Suitable preservatives, and methods for selecting them and incorporating them into adhesive compositions, are disclosed in U.S. patent application Ser. No. 09/430,180, the entire disclosure of which is incorporated herein by reference. Such preservatives can be in addition to any anti-fungal agent that may or may not be added to the composition, as described above. Such preservatives can be included irrespective of whether the composition and containers are sterilized.
In embodiments of the present invention, the composition and/or its applicator may contain materials such as a polymerization initiator, accelerator, rate-modifier, and/or cross-linking agent for initiating polymerization and/or cross-linking of the polymerizable monomer material. Suitable materials and applicators and packaging systems are disclosed in U.S. Pat. No. 5,928,611 and U.S. patent application Ser. Nos. 09/430,177, 09/430,176, 09/430,289, 09/430,290, and 09/430,180 filed Oct. 29, 1999; 09/343,914 filed Jun. 30, 1999; 09/385,030 filed Aug. 30, 1999; and 09/176,889 filed Oct. 22, 1998; the entire disclosures of which are incorporated herein by reference.
According to the present invention, any suitable applicator can be used to apply the composition to the affected areas of. Suitable applicators and packaging systems are disclosed in, for example, U.S. Pat. No. 5,928,611 and U.S. patent application Ser. Nos. 09/430,177, 09/430,176, 09/430,289, 09/430,290, and 09/430,180 filed Oct. 29, 1999; 09/343,914 filed Jun. 30, 1999; 09/385,030 filed Aug. 30, 1999; and 09/176,889 filed Oct. 22, 1998; the entire disclosures of which are incorporated herein by reference. A further suitable application is described in co-pending U.S. patent application Ser. No. 09/898,006, filed concurrently herewith, the entire disclosures of which are incorporated herein by reference.

Adhesive treatment for oral fungal infection


A method and apparatus for laser making a moving object may be used to decorate the surfaces of sealing caps. The sealing caps are transported past a first and second sensor for detecting the transport speed and the position of the sealing cap to be decorated to a laser station having at least one laser for decorating the sealing cap using the laser beam. The first and second sensors communicate with a laser beam control device and the information of the sensors is linked with the control information for the laser beam.

This application claims Paris Convention priority of DE 101 46 820.2 filed Sep. 19, 2001 the complete disclosure of which is hereby incorporated by reference.
The invention concerns a device for decorating sealing cap surfaces, in particular, the sealing caps of beverage bottles, comprising a transport means for the sealing caps, a sensor for detecting the position of the sealing cap to be treated, and a laser station comprising a laser for processing the sealing cap by means of the laser beam.
Lasers have been conventionally used to mark sealing caps, i.e. by irradiating a high-energy laser beam through a mask onto the sealing cap for an extremely short period of time. The mask defines the information to be marked. The laser beam does not produce information or an image but merely illuminates the mask. The mask can be compared with a diapositive containing information which is irradiated by a radiation source onto the object to be treated and is burned into the surface by the high-energy laser beam.
Since the high-energy laser beam is required for only a very short time, the objects to be treated can be marked during transport if their transport speed is low. Although the information applied through the mask is not of high quality with regard to sharpness and accuracy, it is nevertheless possible to apply the production date, production location, production information etc. to the moving object.
In contrast to this marking process, decoration of objects without using a mask is also known, with the decoration being produced through deflection of the laser beam. The laser beam therefore forms the image. Advantageously, the quality of the decoration is considerably improved with regard to sharpness and fineness compared to the above-mentioned marking procedure. Moreover, different (personalized) information can be provided, since the information content is not defined and limited by a rigid mask. Disadvantageously, however, the construction of an image for decorating objects takes a relatively long time and can therefore not be effected during transport of the sealing caps. Transport must therefore be interrupted.
It is therefore the underlying purpose of the present invention to provide a device for decorating surfaces of sealing caps and/or a method for decorating surfaces of sealing caps with which the time period between entry of the sealing cap into and exit of the sealing cap out of the decorating device is shortened.
This object is achieved in accordance with the invention with a decorating device for the surfaces of sealing caps in that the decorating device has a transport means for the sealing caps, a first sensor for detecting the transport speed of the sealing caps, a second sensor for detecting the position of the sealing cap to be decorated, and a laser station with at least one laser for decorating the sealing cap by means of the laser beam, wherein the control means of the laser beam is connected to the first and second sensor, and the information of the sensors is linked with the control information for the laser beam.
In the inventive decorating device, the transport of the sealing caps to be decorated is not interrupted. The sealing caps are decorated in the laser station during transport. A first sensor detects the transport speed of the sealing cap to be decorated, and a second sensor determines the position of the sealing cap to be decorated, wherein the data of these two sensors is linked with the information for controlling the laser beam such that the laser beam is transported at the same speed to prevent a relative speed shift between the object to be decorated and the image to be produced. The movement coordinates of the sealing cap to be decorated overlie the control coordinates of the laser beam.
The inventive decorating device is advantageous in that the sealing caps to be decorated remain in the laser station for a considerably shorter time, permitting easy integration of the decorating device in a system for producing such sealing caps or in a filling system. The production flow is not impaired or slowed down by the decorating device.
In accordance with the invention, the laser is stationary. This produces a considerably sharper contour, since the laser is mounted in a shock-free manner, together with the deflecting mirrors and the focusing objective.
Preferably, the laser is a solid state laser, e.g. a YAG laser, a gas laser, e.g. a CO2 or HeNe laser, a liquid laser or a semiconductor laser. The use of the appropriate laser produces optimum decoration results for the sealing cap. Selection of the laser can also be matched to the sealing cap material or to the design to be provided.
In a preferred embodiment, the transport means has switches, disposed upstream of the laser station, for multi-path transport of the sealing caps through the laser station. This multi-path transport has the considerable advantage that the transport speed of the sealing caps is reduced to increase the quality of the decoration and to increase the total throughput of sealing caps. This permits adaptation of the laser station to almost any transport speed.
In case of sealing cap transport along several paths, each transport path is associated with one laser. In addition to an increase in performance of the laser station, this is further advantageous since the sealing caps can be provided with different decorations without having to change the laser control data.
In a further development, the decorating device has its own transport means for the sealing caps and, in particular, all sealing caps are transported through the decorating device uniformly and at the same speed.
The above-mentioned object is also achieved in accordance with the invention with a method for decorating the surfaces of sealing caps, in particular of the sealing caps of beverage bottles, wherein the sealing caps are transported by a transport means, the speed and the position of the sealing cap to be decorated are detected and the sealing cap is decorated in a laser station during transport and by means of a laser.
This inventive method has the above-mentioned advantages, i.e. that the production process of the sealing caps is not disturbed and that the inventive method can be directly integrated in the production device or in a filling station. Precise decoration can be applied to the sealing caps at a high speed.
The inventive method produces decoration by means of a laser beam moving over the surface to be decorated. In contrast to marking of a surface using a high-energy laser beam directed through a mask, onto the surface to be decorated, decoration with the inventive method is carried out via the laser beam without using a mask: the laser beam is moved over the surface to be decorated.
In the inventive method, the information corresponding to the transport speed overlies the information of the control means for the laser beam. The information concerning the transport speed as well as the information concerning the position of the sealing cap is determined by sensors.
Further advantages, features and details can be extracted from the following detailed description of two particularly preferred embodiments with reference to the drawing. The features shown in the drawing, in the description, and in the claims may be essential to the invention either individually or collectively in any arbitrary combination.

Method and apparatus for laser marking a moving object


An apparatus for winding a flexible web continuously moving in a longitudinal travel direction as rolls onto sleeves has a winding station for holding a sleeve and rotating it about an axis for winding the web onto the sleeve. Upstream of the winding station at a changeover station a fresh sleeve is held adjacent the continuously moving web. A shell juxtaposed with the fresh sleeve in the changeover station forms therewith a gap. A cross-cutter for the web is provided adjacent an end of the gap and can form on the web a trailing end and a leading end so that the trailing end travels to the winding station for winding on the sleeve therein. Air is drawn air into the end of the gap to aspirate the leading end into the gap. This leading end is electrostatically adhered to the fresh sleeve in the changeover station.

After a web is manufactured it is normally wound up onto rolls each holding a considerable length of the freshly made web, for instance a plastic sheet. Since the manufacturing process is a continuous one, the rolls must be produced without interrupting the movement of the web, that is in a quick operation the web must be cross cut, the full roll must be moved out of the way, and the fresh leading end created by the cross cut must be applied to and wound on a fresh sleeve.
An apparatus of the type described above has been disclosed in DE 195 42 906. Here the sleeve onto which the web is to be wound is partially surrounded by a guide shell during the roll-changeover operation. At the beginning of a roll-changeover operation, a continuously fed plastic foil is cross-cut by means of a separate cutter. In the region of this cross-cutting action, air is blown at high speed into the flow gap through a slot nozzle. The result is that a partial vacuum is created below the plastic foil and the end of the web is sucked into the flow gap and pressed against the sleeve onto which material is to be wound. While this known device has fundamentally proven to be successful, it nevertheless is characterized by certain disadvantages. The known device has a relatively high number of parts and is consequently of relatively complex design, thereby necessitating correspondingly expensive servicing and maintenance measures. In addition, the cross-cutting and roll-changeover operation in this known device takes a relatively long time. Another disadvantage consists in the fact that it is not possible to do a fold-free winding of the end of the web onto the sleeve.
Another aspect known from use in practice is to specially prepare the sleeves for the roll changeover, in particular, to provide them with an adhesive. However, an apparatus that is breakdown-prone and of costly design is required for this purpose.

Cross-cutting and roll-changeover apparatus for continuous moving web

Reifenhauser GmbH & Co., KG Maschinenfabrik