An aerosol antimicrobial composition is provided with the following ingredients: a) an anionic polymer or prepolymer; (b) a quaternary ammonium compound, the components (a) and (b) combining to form an antimicrobially effective complex; (c) at least one water-soluble or dispersible organic solvent having a vapor pressure of at least 0.001 mm Hg at 25xc2x0 C., said at least one organic solvent present in a solubilizingxe2x80x94or dispersionxe2x80x94effective amount; (d) an effective amount of a propellant; and (e) the remainder, water. Further is provided a novel method of decontaminating a surface fouled with microorganisms and a dispenser for said aerosol composition. The novel composition advantageously has both disinfectancy (contact efficacy) and residual antimicrobial efficacy.

The present invention relates generally to dispensable antimicrobial compositions, and more particularly to an aerosol composition which has both disinfectancy (contact efficacy) and residual antimicrobial efficacy.
In the seemingly perpetual battle against infection by pathogenic microorganisms, a recent, alarming trend has been observed. Antibiotic medications and treatments long thought to have conquered, if not arrested, the invasive infection of humans by such pathogens (generally, prokaryotic organisms, such as bacteria), have recently begun to fail or lose effectiveness at stopping such infections. Terrifying, and seemingly increasingly frequent, news stories of either fatal or serious infection by such bacteria as the common intestinal inhabitant Escherichia coli 0.157 (especially affecting small children and those with a lesser, or challenged immune system), and by certain species of Staphylococcus sp. (colorfully, but somewhat inaccurately dubbed in news accounts as xe2x80x9cflesh eating bacteriaxe2x80x9d) have led to the conclusion that prevention, by decontamination of surfaces touched by humans, may indeed be a wiser remedy than cure by antibiotics. So, the search for appropriate antimicrobial treatments of surfaces is spurred by this new challenge by these old enemies of the human population.
The use of quaternary ammonium compounds as antimicrobial agents is well known in the art. See U.S. Pat. Nos. 2,746,928, 3,344,018, 3,719,711, and JP 01/046081. For instance, quaternary ammonium compounds have been incorporated into polymer and liquid compositions to protect the compositions themselves from microbial attack (i.e., used as preservatives). See U.S. Pat. Nos. 3,471,423, 5,028,619 and 5,399,343. Furthermore, quaternary ammonium compounds have also been employed as an additive in a variety of household products including detergents. See U.S. Pat. Nos. 3,093,591, 3,560,390, 4,272,395 and 4,576,729.
An effort to remedy the issues faced by prior antimicrobial compositions was posed in the commonly owned Zhou et al., S. U.S. Pat. No. 6,017,561, the disclosure of which is incorporated herein by reference. This Patent Application contemplated the formation of a novel mixed anionic/cationic polymer having residual antimicrobial efficacy. However, the application did not disclose, suggest or teach that an aerosol composition containing a mixture of an anionic polymer and a quaternary ammonium compound has both disinfectancy (contact efficacy) and residual antimicrobial efficacy. There are also various compositions, especially hard surface cleaners, which have been delivered as aerosols but which do not contain the inventive mixture of an anionic polymer and a quaternary ammonium compound having both disinfectancy (contact efficacy) and residual antimicrobial efficacy.
The invention is an antimicrobial dispensable composition comprising:
(a) an anionic polymer or prepolymer;
(b) a quaternary ammonium compound, the components (a) and (b) combining to form an antimicrobially effective complex;
(c) at least one water-soluble or dispersible organic solvent having a vapor pressure of at least 0.001 mm Hg at 25xc2x0 C., said at least one organic solvent present in a solubilizingxe2x80x94or dispersionxe2x80x94effective amount;
(d) an effective amount of a propellant; and
(e) the remainder, water.
In one aspect, the invention is directed to a dispensable composition for treating surfaces which contain microorganisms.
In another aspect, the invention is directed to a method for decontaminating a surface containing microorganisms by contacting the surface with the dispensable composition.
In a further aspect, the invention is directed to a device, for dispensing a composition for treating a surface containing microorganisms, which includes, a pressurized closed container containing the above antimicrobial composition and nozzle means for releasing said composition towards a contaminated surface.
It is therefore an object and an advantage of the present invention to provide antimicrobial composition which has both disinfectancy (contact efficacy) and residual antimicrobial efficacy.
It is another object and another advantage of the present invention to provide a convenient and easy to use product which has prolonged residual efficacy in a single treatment of surfaces, which thus reduces labor, time, effort and cost to treat such surfaces.
It is a further object and advantage of the present invention to provide a method for decontaminating a surface containing microorganisms, or which can be potentially contaminated thereafter.
It is a still further object and advantage of this invention to provide a dispensable antimicrobial composition which contacts a surface and forms thereon a film or residue which has prolonged antimicrobial efficacy.
It is yet another object and advantage of this invention to provide a dispensable antimicrobial composition which has up to 99.9% residual efficacy in a 24 hour period.
It is a final object and advantage of this invention to provide a dispensable antimicrobial composition which out performs commercially available products which claim to have antimicrobial efficacy.
The invention provides an aerosol formulation comprising a novel antimicrobial composition for treating one or more surfaces containing microorganisms. These surfaces include those which are typically contacted by human touch: bathroom surfaces, such as a bath tub, sink, commode, toilet, or shower stall, which may have glass doors, and include vertical wall surfaces typically made of tile, glass, or composite materials; kitchen surfaces, such as countertops, stove tops, sinks, table tops, chairs; and generally, any other surface, whether hard or soft, such as furniture, window ledges, window frames and other edges, door knobs, handles, tools, appliances, utility devices (such as telephone handsets and portable telephones), implements (such as pens, mechanical pencils and the like), wrist watches, clothing (such as stockings), shoes, outer garments, and other common and uncommon surfaces. Each of these types of surfaces can act to harbor microorganisms, including bacteria, fungi, molds, mildew and viruses. Thus, each such surface can communicate a potential infectious vector to the unwitting person (or, in the case of cross-species infection, household pets) unless treated with an appropriate antimicrobial composition. The inventive antimicrobial composition is intended to so treat and decontaminate such surfaces, and others, by aerosol application of a metered discrete amount of the composition via a dispenser onto the surface to be treated. The antimicrobial composition is generally merely applied as an aerosol composition to the surface in order to effect antimicrobial efficacy. The surface can additionally be spread or wiped, but this would then remove the composition and may lessen the efficacy thereof.
The antimicrobial composition is formulated with ingredients which themselves are found often in cleaners, such as hard surface and fabric cleaners. Thus, an additional benefit of the composition is that it can also act as a cleaner and soil remover. It is preferred that this benefit be achieved without detriment to its primary advantage as an antimicrobial composition.
The aerosol formulation comprises an antimicrobial composition that is mixed with a propellant. The composition has the following ingredients:
(a) an anionic polymer or prepolymer;
(b) a quaternary ammonium compound, the components (a) and (b) combining to form an antimicrobially effective complex;
(c) at least one water-soluble or dispersible organic solvent having a vapor pressure of at least 0.001 mm Hg at 25xc2x0 C., said at least one organic solvent present in a solubilizingxe2x80x94or dispersionxe2x80x94effective amount;
(d) an effective amount of a propellant; and
(e) the remainder, water.
Additional adjuncts in small amounts such as buffers, fragrances, dyes and the like can be included to provide desirable attributes of such adjuncts.
In the application, effective amounts are generally those amounts listed as the ranges or levels of ingredients in the descriptions which follow hereto. Unless otherwise stated, amounts listed in percentage (xe2x80x9c%""sxe2x80x9d) are in weight percent (based on 100% active) of the cleaning composition.
1. Anionic Polymer or Prepolymer
The anionic polymer or prepolymer (generally, component) generally has an acid number greater than 10. It is an essential part of the invention since it combines with the quaternary ammonium compound in a mechanism which, as yet, is not completely understood, and may or may not involve an ionic bonding, or pairing, mechanism. The anionic component is usually a polymer having an average molecular weight of about 100 to about 2,000,000 daltons, with an acid number preferably greater than about 10. As used herein, xe2x80x9cacid numberxe2x80x9d retains its conventional meaning and is determined by the number of milligrams of potassium hydroxide required for the neutralization of the corresponding acids of the anionic groups present in one gram of the polymer.
In the antimicrobial composition, the anionic component may or may not be partially or completely neutralized by the quaternary ammonium compound to form a polymer complex. The actual manner of combining of the two key components of the inventive antimicrobial compositions has not been fully determined at this time. Thus, instead of ionic bonding , as in the classic sense of anionic and cationic materials forming an ion pair (See Cationic Surfactants, Physical Chemistry, in: Surfactant Science Series Vol. 37, p. 93 (Marcel Dekker, 1983)), when the liquid, dispensable compositions of this invention are delivered from the dispenser to a surface, physical association may actually be taking place, such as occlusion, where the quaternary ammonium compound is evenly dispersed in the resulting polymer matrix or film. It is also speculated that, in the dispenser, the components may also form another state in which ion pairing does take place. However, all of the foregoing is by way of non-binding theory.
The antimicrobial composition is preferably prepared by mixing effective amounts of the anionic component and the quaternary ammonium compound in water with agitation. A water miscible solvent and/or dispersing/emulsifying/wetting agent is preferably added before the two main. components are mixed together. The xe2x80x9cdispersing/emulsifying/wetting agentxe2x80x9d comprises any suitable agent which will cause the admixture of anionic component and the quaternary ammonium compound to be stably distributed substantially homogeneously in the liquid composition. Depending on the particular anionic components and quaternary ammonium compounds used to make the composition, the presence of cross-linkers, stabilizers and other variables, the antimicrobial compositions of the invention may exist as emulsions, suspensions, dispersions, solutions, or possibly, as other forms of liquids, such as microemulsions and liquid crystals.
The anionic component, which can be a polymer or prepolymer, is preferably derived from monomers having anionic groups attached thereto. Preferably, the polymer has an average molecular weight of about 200 to 2,000,000, more preferably, about 2,000 to 1,000,000, and most preferably, about 5,000 to 150,000 daltons, with an acid number greater than about 10 and preferably from about 60 to 700.
Preferred anionic polymers are selected from the group consisting of: (1) a homopolymer that is selected from the group consisting of vinyl sulfonates, acrylates, methacrylates, styrene sulfonates, maleates, vinyl sulfates and mixtures thereof; (2) a copolymer that is derived from (i) one or more anionic monomers selected from the group consisting of vinyl sulfonates, acrylates, methacrylates, styrene sulfonates, maleates, vinyl sulfates; and (ii) one or more nonionic monomers selected from vinyl esters, vinyl alcohols, vinyl ethers, acrylamides, methacrylamides, alkyl or aryl acrylates, alkyl or aryl methacrylates, alkyl or aryl maleates, acrylonitriles, vinyl pyrrolidones, alkenes, such as, for example, styrene, ethylene and propylene, multifunctional acids, polyols, multifunctional amines, multifunctional isocyanates and multifunctional epoxy compounds; and (3) methylcarboxycellulose.
As is apparent, copolymers may include nonionic monomers. A preferred copolymer comprising nonionic and anionic monomers is formed from acrylic acid esters, such as methacrylate or acrylate. The anionic polymers can be in their salt, acid, or partially protonated forms.
The solubility/dispersability of the polymer will depend, in part, on its molecular weight, acid number, and the solvent and/or wetting/dispersing/emulsifying agent involved. Optionally, the anionic polymer or component may be cross-linked with common cross-linkers such as, for example, carbodimide, aziridine, polyols, glyoxal, epoxy compounds, transition metal ions, and ionene polymers to reduce solubility. Typically, in formulating a liquid, dispensable antimicrobial composition, the anionic polymer is present in an amount of about 0.01 to 15%, more preferably about 0.1 to 10$, and most preferably, about 0.5 to 5% by weight of the composition. Important examples of the preferred anionic polymers include the acrylate copolymers produced by B.F. Goodrich under the trademark Carboset. Preferred is Carboset GA 2123, which appears to be an acrylic acid/acrylate ester copolymer. Especially preferred are two different copolymers, namely, Omnirez 2000, which is a monoethylester of poly(methylvinylether/maleic) acid, from ISP, and Dermacryl 79, which is an acrylate/octylacrylamide copolymer, from National Starch. These particular latter copolymers resulted in optimal films in the inventive compositions hereof. There further appears to be a preferential ratio of the anionic component to the quaternary ammonium compound. This ratio may be from about 1:100 to about 100:1, more preferably about 1:10 to about 10:1, and most preferably, about 5:1 to about 1:5. In balancing the ratio of anionic component to quaternary ammonium compound, one must keep in mind the desirable characteristics in the dispenser (i.e., xe2x80x9ccan stabilityxe2x80x9d) versus that of the dispensed liquid versus that of the cured or dried film/residue (when the liquids/solvents volatilize or xe2x80x9cflash offxe2x80x9d). The more anionic polymer, the smoother, glassier appearing of the resulting film, and the more water soluble. The more quaternary ammonium compound, the less water soluble the resulting film, but, aesthetics of the film appear to become less pleasing, however, such less attractive forms are still part of the invention. The most preferred range of 5:1 to 1:5 appears to result in an aesthetically pleasing film which has excellent residual antimicrobial efficacy, as well as disinfectancy. This also seems to imply that, in the cured film/residue, there may actually not be complete ion pairing between the quaternary ammonium compound and the anionic sites in the anionic polymer, since the quaternary ammonium active sites are available for residual microbial kill, although there is clearly an interaction between the two components. Again, the mechanism of the film/residue is not completely understood, so these latter observations are made by way of non-binding theory. Further, it is preferred to obtain a transparent to translucent, smooth, homogeneous, tack-free film. So, other additives can be added to improve the film""s characteristics, such as the use of various water soluble polymers, and by neutralizing some of the acid groups of the anionic polymers by various buffers, such as alkali metal (Na+, K+) and ammonium buffers, although organic buffers, such as alkanolamines may be used. Additionally, some wetting/dispersing/emulsifying agents as described below in 4. help to enable the formation of effective films or residues, by placing the ingredients into dispersion. By xe2x80x9ceffectivexe2x80x9d is meant that the films achieve consistent residual efficacy throughout the film.
2. Quaternary Ammonium Compound
A critical second component of the invention is a quaternary ammonium compound, or surfactant. These types of surfactants are typically used in bathroom cleaners because they are generally considered xe2x80x9cbroad spectrumxe2x80x9d antimicrobial compounds, having efficacy against both gram positive (e.g., Staphylococcus so) and gram negative (e.g., Escherichia coli or Klebsiella s) microorganisms. Thus, the quaternary ammonium surfactant, or compounds, are incorporated for bacteriostatic/disinfectant purposes and should be present in amounts effective for such purposes.
The quaternary ammonium compounds are selected from mono-long-chain, tri-short-chain, tetraalkyl ammonium compounds, di-long-chain, di-short-chain tetraalkyl ammonium compounds, trialkyl, mono-benzyl ammonium compounds, and mixtures thereof. By xe2x80x9clongxe2x80x9d chain is meant about C6-30 alkyl. By xe2x80x9cshortxe2x80x9d chain is meant about C1-5 alkyl, preferably C1-3. Suitable counterions for such quaternary ammonium compounds include halides (chlorides, bromides, iodides), hydroxides, saccharinates, carbonates, phosphates, phosphonates, sulfates, bisulfates, alkylsulfates, carboxylates, other negatively charged counterions, and mixtures thereof. Preferred materials include the BTC 885xe2x80x94which comprises a mixture of C12-16 alkyl dimethylbenzyl ammonium chloride, C8/C10 alkyl dimethyl ammonium chloride, di-C8 alkyl dimethyl ammonium chloride, and di-C10 alkyl dimethyl ammonium chloridexe2x80x94and 2125 series from Stepan, which comprises di-C24-dialkyl ammonium chloride, and the Barquat and Bardac series, such as Bardac MB 2050, from Lonza Chemical. Also preferred appears to be a mixed quaternary ammonium surfactant in which there is a combination of di-long-chain, di-short-chain tetraalkyl ammonium compounds, and trialkyl, mono-benzyl ammonium compounds. Most preferred appears to be quaternary ammonium compounds (or xe2x80x9cquatsxe2x80x9d) which contain either chloride or saccharinate counterions, or, especially, a mixture thereof. The saccharinate quat is Onyxide 3300, from Stepan Company. Both the chloride quats and the saccharinate quats when combined, provide excellent residual antimicrobial kill performance (referred to herein as xe2x80x9c99.99% Efficacyxe2x80x9d). The ratio of these counterions should be 1:100 to 100:1, most preferably 1:10 to 10:1. These particularly preferred quaternary ammonium surfactants form both smooth films with the anionic polymers listed above, but also are the most effective at broad spectrum contact and residual antimicrobial efficacy (both gram negative and gram positive microorganisms), antifungal and antiviral efficacy. Typical amounts of the quaternary ammonium compound range from preferably about 0.01-5%, more preferably about 0.01-2%.
3. Solvents
The solvent is a water soluble or dispersible organic solvent having a vapor pressure of at least 0.001 mm Hg at 25xc2x0 C. It is preferably selected from C1-6 alkanols, C1-6 diols, C1-6 alkyl ethers of alkylene glycols and polyalkylene glycols, and mixtures thereof. The alkanol can be selected from methanol, ethanol, n-propanol, xe2x80x9cisopropanol,xe2x80x9d the various positional isomers of butanol, pentanol, and hexanol, and mixtures of the foregoing. It may also be possible to utilize in addition to, or in place of, said alkanols, the diols such as methylene, ethylene, propylene and butylene glycols, and mixtures thereof, and including polyalkylene glycols.
It is preferred to use a C1-4 alkanol solvent in this invention. One preferred alkanol is ethanol, which advantageously acts as both a solvent, to maintain the ingredients in the liquid composition in dispersion, as well as a disinfectant. If mixtures of solvents are used, the amounts and ratios of such solvents used are important to determine the optimum performances of the inventive composition. One further preferred solvent which may be either added in addition to ethanol or in place thereof is ethylene glycol. It is preferred to have the total amount of solvent to at least 20%, more preferably least 30%, and most preferably, at least 50%, of the composition. A preferred range is about 20-99.9%. These amounts of solvents are generally referred to as dispersion effective or solubilizing effective amounts, since the other components, such as surfactants, are materials which are assisted into solution by the solvents. As in the case of ethanol, the solvent can also have disinfectancy capacity itself. Finally, the solvent is also important as a cleaning materials itself, helping to loosen and solubilize certain soils for easy removal from the surface treated.
4. Wetting/Emulsifying/Dispersing Agent
The wetting/emulsifying/dispersing agent may be preferably a surfactant (preferably, anionic, cationic nonionic, amphoteric, or zwitterionic surfactant; but the quaternary ammonium surfactant of 2., above, is not considered as one of the wetting agents herein), or possibly, a hydrotrope (which is also treated below, in 5.). The surfactant may be an nonionic, amphoteric or zwitterionic surfactant, or mixtures thereof. The following is a nonlimiting description of surfactants which might be employed in the present invention. The description is intended to exemplify that a wide variety of surfactants can be used according to the present invention.
a. Anionic, Nonionic, Amphoteric and Zwitterionic Surfactants
The anionic surfactants may include a negatively charged water solubilizing group.
The nonionic surfactants may be selected from modified polysiloxanes, alkoxylated alcohols, alkoxylated phenol ethers, glycosides, and the like. Trialkyl amine oxides, and other surfactants often referred to as xe2x80x9csemi-polarxe2x80x9d nonionics, may also be employed.
Most preferred are modified polysiloxanes. The modified polysiloxane can be an alkoxylated dimethylsiloxane, such as those available from Byk Chemie, such as BYK-345 and Dow Corning 5103 and Q2-5247, both from Dow Corning.
The alkoxylated alcohols may include, for example, ethoxylated, and ethoxylated and propoxylated C6-16 alcohols, with about 2-10 moles of ethylene oxide, or 1-10 and 1-10 moles of ethylene and propylene oxide per mole of alcohol, respectively. Exemplary surfactants are available from Shell Chemical under the trademarks Neodol and Alfonic, and from Huntsman Chemicals under the trademark Surfonic (e.g., Surfonic L12-6, a C10-12 ethoxylated alcohol with 6 moles of ethylene oxide, and Surfonic L12-8, a C10-12 ethoxylated alcohol with 8 moles of ethylene oxide).
The alkoxylated phenol ethers may include, for example, octyl- and nonylphenol ethers, with varying degrees of alkoxylation, such as 1-10 moles of ethylene oxide per mole of phenol. The alkyl group may vary, for example, from C6-16, with octyl- and nonyl chain lengths being readily available. Various suitable products are available from Rohm and Haas under the trademark Triton, such as Triton N-57, N-101, N-111, X45, X-100, X-102, from Mazer Chemicals under the trademark Macol, from GAF Corporation under the trademark Igepal, and from Huntsman under the trademark Surfonic.
The glycosides, particularly the alkyl polyglycosides, may also be used as a surfactant for purposes of the aerosol formulation of the present invention. These glycosides include those of the formula:
RO(CnH2nO)y(Z)x
wherein R is a hydrophobic group (e.g., alkyl, aryl, alkylaryl etc., including branched or unbranched, saturated and unsaturated, and hydroxylated or alkoxylated members of the foregoing, among other possibilities) containing from about 6 to about 30 carbon atoms, preferably from about 8 to about 15 carbon atoms, and more preferably from about 9 to about 13 carbon atoms; n is a number from 2 to about 4, preferably 2 (thereby giving corresponding units such as ethylene, propylene and butylene oxide); y is a number having an average value of from 0 to about 12, preferably 0; Z is a moiety derived from a reducing saccharide containing 5 or 6 carbon atoms (e.g., a glucose, fructose, mannose, galactose, talose, gulose, allose, altrose, idose, arabinose, xylose, lyxose, or ribose unit, etc., but most preferably a glucose unit); and x is a number having an average value of from 1 to about 10, preferably from 1 to about 5, and more preferably from 1 to about 3.
It would be apparent that a number of variations with respect to the makeup of the glycosides are possible. For example, mixtures of saccharide moieties (Z) may be incorporated into polyglycosides. Also, the hydrophobic group (R) can be attached at the 2-, 3-, or 4-positions of a saccharide moiety rather than at the 1-position (thus giving, for example, a glucosyl as opposed to a glucoside). In addition, normally free hydroxyl groups of the saccharide moiety may be alkoxylated or polyalkoxylated. Further, the (CnH2nO)y group may include ethylene oxide and propylene oxide in random or block combinations, among a number of other possible variations.
An exemplary glycoside surfactant is APG 325n, which is manufactured by the Henkel Corporation. APG 325n is a nonionic alkyl polyglycoside in which R is a mixture of C9, C10 and C11 chains in a weight ratio respectively of 20:40:40 (equivalent to an average of C10.2), with x of 1.6, and an HLB of 13.1.
Compositions containing other surfactants, such as some amine oxides, may be less compatible with the tin-plated steel can environment (or even with steel cans that are lined with, e.g., an epoxy phenolic coating). Tin-plated steel cans are desirable as containers for aerosol compositions because they are more readily available and are less expensive than aluminum or specially lined steel cans.
The amine oxides, referred to as mono-long chain, di-short chain, trialkyl amine oxides, have the general configuration:
wherein R1 is C6-24 alkyl, and R2 and R3 are both C1-4 alkyl, or C1-4 hydroxyalkyl, although R2 and R3 do not have to be equal. These amine oxides can also be ethoxylated or propoxylated. The preferred amine oxide is lauryl amine oxide. The commercial sources for such amine oxides are Barlox 10, 12, 14 and 16 from Lonza Chemical Company, Varox by Witco and Ammonyx by Stepan Company.
A further semi-polar nonionic surfactant is alkylamidoalkylenedialkyl-amine oxide. Its structure is shown below:
wherein R1 is C5-20 alkyl, R2 and R3 are C1-4 alkyl,
although R2 and R3 do not have to be equal or the same substituent, and n is 1-5, preferably 3, and p is 1-6, preferably 2-3. Additionally, the surfactant could be ethoxylated (1-10 moles of EO/mole) or propoxylated (1-10 moles of PO/mole). This surfactant is available from various sources as a cocoamidopropyldimethyl amine oxide; it is sold by Lonza Chemical Company under the brand name Barlox C. Additional semi-polar surfactants may include phosphine oxides and sulfoxides.
A preferred cationic surfactant is morpholinium ethosulfate, such as Forestall (Atlas) G-271.
The amphoteric surfactant is typically an alkylbetaine, an amidobetaine, or a sulfobetaine. One group of preferred amphoterics are alkylamidoalkyl-dialkylbetaines. These have the structure:
wherein R1 is C6-20 alkyl, R2 and R3 are both C4 alkyl, although R2 and R3 do not have to be equal, and m can be 1-5, preferably 3, and n can be 1-5, preferably 1. These alkylbetaines can also be ethoxylated or propoxylated. The preferred amidobetaine is cocoamidopropyldimethyl betaine, available from Lonza Chemical Co. as Lonzaine CO. Other vendors are Henkel KGaA, which provides Velvetex AB, and Witco Chemical Co., which offers Rewoteric AMB-15, both of which products are cocobetaines.
Potentially suitable zwitterionic surfactants can be found described in Jones, U.S. Pat. No. 4,005,029, at columns 11-15, which are incorporated herein by reference.
The amounts of surfactants present are to be somewhat minimized, for purposes of cost-savings and to generally restrict the dissolved actives which could contribute to leaving behind residues when the aerosol is applied to a surface. However, the amounts added are generally about 0.001-5%, more preferably 0.002-3.00% surfactant. These are generally considered to be dispersion-effective amounts.
5. Water and Miscellaneous
Since the composition is an aqueous composition, water can be, along with the solvent, be a predominant ingredient. The water should be present at a level of less than 70%, more preferably less than about 65%, and most preferably, less than about 50%. Deionized water is preferred.
Small amounts of adjuncts can be added for improving performance, stability or aesthetic qualities of the composition. For example, buffers can be added to maintain a constant pH (which for the invention is between about 5-14, more preferably between about 8-13; formulations containing the tripotassiui and/or triammonium salts will naturally be at a lower end of the range as compared to the corresponding tetra salts). These buffers include, for example, NaOH, KOH, Na2CO3, and K2CO3 as alkaline buffers, and phosphoric, hydrochloric, sulfuric, and citric acids as acidic buffers, among others. It may be desirable to add chelating agents, such as polycarboxylates (e.g., EDTA and its alkali metal and ammonium salts, especially K4EDTA, see commonly assigned Robbins et al., U.S. Pat. No. 5,972,876, which is incorporated herein by reference), aminopolyphosphonates, and polyphosphonates, metasilicates and organic amines. Chelating agents may help to potentiate antimicrobial efficacy or have other functional uses.
Further solubilizing materials, such as hydrotropes (e.g., water soluble salts of low molecular weight organic acids such as the sodium or potassium salts of cumene-, toluene-, benzene-, and xylene sulfonic acid), may also be desirable. Adjuncts for cleaning include additional surfactants, such as those described in Kirk-Othmer, Encyclopedia of Chemical Technology, 3rd Ed., Volume 22, pp. 332-432 (Marcel-Dekker, 1983), and McCutcheon""s Soaps and Detergents (N. Amer. 1984), which are incorporated herein by reference. Aesthetic adjuncts include fragrances or perfumes, such as those available from Givaudan, IFF, Quest, Sozio, Firmenich, Dragoco and others, and dyes or colorants which can be solubilized or suspended in the formulation, such as diaminoanthraquinones. Enhancing ingredients, such as nerolidol, may be present to perform in multiple capacities, both aesthetic and finctional, the composition (See commonly owned U.S. patent application Ser. No. 09/085,340, of Blum et al., filed May 27, 1998, and incorporated herein by reference). Water-insoluble solvents may sometimes be desirable as added grease-or oily soil-cutting agents. These types of solvents include tertiary alcohols, hydrocarbons (e.g., alkanes), pine-oil, d-limonene and other terpenes and terpene derivatives, and benzyl alcohols. Thickeners, such as calcium carbonate, sodium bicarbonate, aluminum oxide, and polymers, such as polyacrylate, starch, xanthan gum, alginates, guar gum, cellulose, and the like, may be desired additives, although care must be taken since the inventive compositions are meant to be relatively thin liquids for effective dispensation from a pressurized canister. The use of some of these thickeners (e.g., CaCO3 or NaHCO3) is to be distinguished from their potential use as builders, generally by particle size or amount used. Additional additives may include further antimicrobial compounds, such as phenols (See, Moseman, U.S. Pat. No. 4,985,945, incorporated herein by reference), pine oil (See Spaulding et al., U.S. Pat. No. 4,867,898, incorporated herein by reference) and liposome-like microemulsions such as mentioned in the paper by T. Hamouda et al., xe2x80x9cMicrobiocidal Effects of Liposomes-Like Microemulsions on Pathogenic Gram Negative Bacteria,xe2x80x9d in: Poster Session 251/A Antimicrobial Therapy and Charactertization of Pathogens, American Society of Microbiology 98th Annual Meeting, May 17-21, 1998, p. 152, said paper incorporated herein by reference.
As already noted above, the preferred container for dispensing of the present composition in aerosol form is a tin-plated steel can, but other aerosol packages may be suitable for use. Therefore, it is advantageous to add one or more corrosion inhibitors to prevent or at least reduce the rate of expected corrosion of such a metallic dispenser. Chloride salts, if present, may cause corrosion. Preferred corrosion inhibitors include, for example, sodium nitrite, potassium nitrite, sodium benzoate, potassium benzoate, amine neutralized alkyl acid phosphates and nitroalkanes, amine neutralized alkyl acid phosphates and volatile amines, diethanolamides, amine borates, hydroxylamines, alkanolamines, amine carboxylates, esters, volatile silicones, amines and mixtures thereof. Specific inhibitors include, for example, sodium lauroyl sarcosinate, available from Stepan Company under the trademark Maprosyl 30, sodium meta silicate, sodium or potassium benzoate, triethanolamine, and morpholine. When employed, the corrosion inhibitor preferably comprises about 0.01% to 5% of the aerosol formulation.
6. Propellant
The antimicrobial composition is delivered in the form of an aerosol. The propellant comprises, for example, a hydrocarbon, of from 1 to 10 carbon atoms, such as methane, ethane, n-propane, n-butane, isobutane, n-pentane, isopentane, and mixtures thereof. The propellant may also be selected from halogenated hydrocarbons including, for example, fluorocarbons, chlorocarbons, chlorofluorocarbons, and mixtures thereof. (Besides of concerns about the destruction of the stratosphere""s ozone layer, the use of fluorocarbons and chlorofluorocarbons is less preferred.) Examples of other suitable propellants are found in P. A. Sanders Handbook of Aerosol Technology (Van Nostrand Reinhold Co.) (1979) 2nd Ed., pgs. 348-353 and 364-367, which are incorporated by reference herein. Further, non-hydrocarbon propellants may be possible, such as carbon dioxide, nitrogen, compressed air, and, possibly, dense or supercritical fluids.
A liquefied gas propellant mixture comprising about 85% isobutane and 15% propane is preferred because it provides sufficient pressure to expel the cleaning composition from the container and provides good control over the nature of the spray upon discharge of the aerosol formulation. Preferably, the propellants comprises about 1% to 50%, more preferably about 2% to 25%, and most preferably about 5% to 15% of the aerosol formulation.
The aerosol formulation is preferably stored in and dispensed from a pressurized can that is equipped with a nozzle so that an aerosol of the formulation can be readily sprayed onto a surface. Dispensers are known in the art and are described, for example, in U.S. Pat. Nos. 4,780,100, 4,652,389, and 3,541,581 which are incorporated by reference herein. Although pressure within the dispenser, i.e., can pressure, does not appear to be critical, it may be preferred to range from about 10 to 100 psiq. at 70xc2x0 F. (21.1xc2x0 C.).
In loading the dispenser, the non-propellant components of the aerosol formulation are mixed into a concentrate and loaded into the dispenser first. Thereafter, the liquefied gaseous propellant is inserted before the dispenser is fitted with a nozzle.


The subject of the invention is an effect pigment which is coated with surface-modifying agents, wherein the initial pigment has a layer with at least one reactive surface-modifying agent, wherein the surface-modifying agent is a compound which has at least two functional groups which are different from each other and which are spaced by a spacer, chemically bound to the initial pigment. Also described is a process for the production of an effect pigment of that kind.

The present invention concerns effect or fancy pigments whose service is modified with orientation aids.
The literature (EP 0 634 459 A2) describes coating pearl shine pigments with alkyl silanes to improve orientation of the pigments in the ambient medium (paint or lacquer, casting resin etc). The modification process used in that case controls the wetting characteristics of the pearl shine pigments by the introduction of hydrophobing alkyl silanes and results in a leafing effect, as is also known in relation to metal effect pigments.
The application of stearic acid to the pigment surface means that aluminium pigments can also be strongly hydrophobed, which then results in poorer wetting of the pigments by the individual components of the paint or lacquer. The content of the pigments is then increased at the interfaces (or the surface) of the liquid film of paint or lacquer. As after hardening of the film of paint or lacquer that results in coatings with a high level of brilliance, this is referred to as good orientation characteristics in respect of the pigments (xe2x80x98leafing effectxe2x80x99). The aluminium pigments which are oriented at the surface are however not particularly resistant to weathering as they are not enclosed in the film of paint or lacquer and thus protected from corrosion. In the case of metallic paints for automobiles, which must satisfy particularly high levels of weathering stability, therefore only aluminium pigments which are non-leafing (which can be well wetted) are used. Paints in the automobile sector involve a layer structure which in the case of metallic paints generally consists of five layers. Disposed on the metallic substrate is a phosphate layer, followed by a cathodic dip lacquering (CDL), a filler layer (to compensate for irregularities and unevenness etc), the base lacquer and finally the clear lacquer. The actual layer which affords the effect is the base lacquer which generally contains a mixture of metal pigments and pearl shine pigments and which nowadays is already used in many cases in the form of a water-based lacquer. The clear lacquer serves to protect the base lacquer and to xe2x80x98smooth outxe2x80x99 the surface.
An important check in terms of the resistance of metallic lacquers is the so-called condensed water test. In that case the complete coating is exposed to a condensed water testing climate (DIN 50 017) and then checked in terms of its mechanical strength and visual considerations. In the ideal case the properties of the coating should not change before and after the test. In a worse scenario, there is a loss of adhesion between the base lacquer and the clear lacquer or a loss of adhesion between the effect pigments and the base lacquer. Such changes can be seen in the cross-cutting adhesion test or the stone impact test. A negative test result involves partial detachment of the clear lacquer from the base lacquer or even involves the base lacquer layer completely breaking away. In addition, under some circumstances optical changes are also to be observed due to the action of water vapour on the coating (a greying effect, swelling, etc).
A disadvantage of coating effect pigments with hydrophobing alkyl silanes (for example EP 0 634 459 A2) are the weak bonding forces at the pigment/binding agent interface (van der Waals forces, hydrogen bridges). Because of those weak bonding forces the pigments are incompletely wetted, in particular in aqueous lacquer systems, which results in the pigments being poorly bound into the coating. As a result, both the adhesion of the pigments in the base lacquer layer and also the adhesion between the base lacquer and the clear lacquer are adversely affected. That impaired adhesion then results in worse results in the condensed water test.
The diffusion of water vapour through the clear lacquer into the base lacquer has a severely adverse effect on adhesion between the two layers in the condensed water test if condensation of water occurs between the base lacquer and the clear lacquer. That is the case in particular if the coated pigments cannot be wetted or can be only poorly wetted by the binding agents or solvents of the paint or lacquer (organic solvent and/or water) because the pigments are then at the surface of the base lacquer and are in direct contact with respect to the clear lacquer. In that case the reduced level of resistance to condensed water results under some circumstances in the lacquer layers completely breaking away under the action of shearing forces (cross-cut test, stone impact test, etc).
Therefore the object of the present invention is to provide effect pigments which on the one hand are easily wetted by the binding agent or solvent of the paint or lacquer and which can be well oriented in the liquid film of lacquer and which on the other hand involve an intimate bond with the surrounding binding agent matrix and therefore do not suffer from the above-described disadvantages involved in use thereof.
That object is attained in that the initial pigment has a layer comprising at least one reactive surface-modifying agent, wherein the surface-modifying agent is a compound which has at least two functional groups which are different from each other and which are spaced by a spacer and of which at least one functional group is chemically bound to the initial pigment.
At least one functional group which is directed outwardly, that is to say towards the binding agent, of the effect pigment according to the invention can react chemically with the binding agent in that case in a kind of cross-linking reaction. By virtue of the resulting strongly covalent bonding forces at the pigment/binding agent interface, water vapour in the finished coating can only diffuse with difficulty into the pigmented binding agent matrix. The strong linkage of the pigments to the binding agent of the base lacquer, which is caused by the relatively good wettability of the metal pigments coated with the reactive orientation agent means that there cannot be condensation and thus inclusion of water between the clear lacquer and the base lacquer. Therefore even coatings which are soaked with solvent (for example water) are highly stable in respect of shearing and impact-resistant. An effect pigment which is treated in that way has accordingly become a xe2x80x98chemical constituentxe2x80x99 of the ambient medium.
The effect pigments according to the invention involve either metal pigments such as aluminium, copper, zinc, gold-bronze, titanium (EP 0 796 688), zirconium, tin, iron (EP 0 673 980) and steel pigments or pigments of alloys of the above-mentioned metals. The effect pigments can also comprise flake-form glass, Al2O3, SiO2 (EP 0 803 550 A2), TiO2 or mica. Multi-layer pigments (DE 44 05 492 A1, EP 0 708 154; DE 196 18 569) or pearl shine pigments or mixtures thereof can also be coated in accordance with the invention. The pigments may carry a coating of metal oxides such as SiO2 (for example: U.S. Pat. No. 2,885,366, U.S. Pat. No. 3,954,496, EP 0 678 561, DE 195 01 307, EP 0 708 155), TiO2 (for example: 0 338 428), Al2O3 (for example: DE 195 20 312, EP 0 560 144) and Fe2O3 (for example: EP 0 033 457, EP 0 806 457) or organic polymers such as acrylate, methacrylate etc (for example: DE 40 30 727, EP 0 416 369). The particle size is between 1 and 200 xcexcm.
The described demands on an orientation aid are satisfied in accordance with the invention by a bonding agent which carries two or more functional groups. One group of the bonding agent reacts with the surface of the effect pigment, which surface is possibly occupied by oxides. Alkoxysilyl groups (for example methoxy and ethoxy silanes), halosilanes (for example chlorosilanes) or acid groups of phosphoric acid esters or phosphonic acids and phosphonic acid esters are considered here. The described groups are linked by way of spacers of greater or lesser length to a second, lacquer-friendly group. The spacer involves unreactive alkyl chains, siloxanes, polyethers, thioethers or urethanes or combinations of those groupings of the general formula (C, Si)nHm(N,O,S)x with n=1-50, m=2-100 and x=0-50. The lacquer-friendly group preferably involves acrylates, methacrylates, vinyl compounds, amino or cyano groups, isocyanates, epoxy, carboxy or hydroxy groups. Upon baking or hardening of the coating those groups chemically react with the ambient medium in a cross-linking reaction in accordance with the known chemical reaction mechanisms.
The effect pigments according to the invention are produced by agitating and heating the initial pigments in an organic solvent, mixing with a solution of a base in water or another solvent, adding the surface-modifying agent, cooling after 15 minutes to 24 hours of reaction time, and suction removal. The filter cake obtained can be dried in a vacuum at about 60xc2x0-130xc2x0 C.
Silane-based surface-modifying agents are described for example in DE 40 11 044 C2. Phosphoric acid-based surface-modifying agents can be obtained inter alia as Lubrizol(copyright) 2061 and 2063 from LUBRIZOL (Langer and Co).
The surface-modifying agent can also be produced directly on the pigment by chemical reaction from suitable starting substances. In that case the effect pigments are also agitated and heated in an organic solvent. They are then mixed with the solution of a base. Preferably organic amines are used for the metal effect pigments which react with water, while predominantly mineral bases are used for the mineral effect pigments. There is then added a bonding agent which chemically reacts with the effect pigments and which is firmly bound to the pigment surface. That bonding agent is then reacted by way of a further functional group, possibly in the presence of an initiator (radical-forming agent, acids, bases etc) with a cross-linking agent, in which case however only a part of the functional groups of the cross-linking agent reacts with the bonding agent and another part remains free, that is to say it remains further capable of reaction. After about 1-6 hours of reaction time the pigment suspension is cooled and subjected to suction removal. The filter cake obtained in that way can be dried in a vacuum at 60xc2x0-130xc2x0 C.
The reaction can also be conducted in a solvent in which the coated effect pigments are later formed as a paste and used. That renders a drying step redundant. Specific examples of bonding agents that can be mentioned are for instance cross-linkable organo-functional silanes which after the hydrolysis operation are anchored with their reactive Sixe2x80x94OH units on the (partially oxidic) surface of the effect pigments. The potentially cross-linkable organic groups can later react with the lacquer binding agents. Examples of cross-linkable organo-functional silanes are as follows:
Vinyl trimethoxy silane, aminopropyl triethyoxy silane, N-ethylamino-N-propyl dimethoxy silane, isocyanatopropyl triethoxy silane, mercaptopropyl trimethoxy silane, vinyl triethoxy silane, vinyl ethyl dichlorosilane, vinyl methyl diacetoxy silane, vinyl methoyl dichlorosilane, vinyl methyl diethoxy silane, vinyl triacetoxy silane, vinyl trichlorosilane, phenyl vinyl diethoxy silane, phenyl allyl dichlorosilane, 3-isocyanatopropoxyl triethoxy silane, methacryloxy propenyl trimethoxy silane, 3-methacryloxy propyl trimethoxy silane, 3-glycidyloxypropyl trimethoxy silane, 1,2-epoxy-4-(ethyl triethoxysilyl)-cyclohexane, 3-acryloxypropyl trimethoxy silane, 2-methacryl-oxyethyl trimethoxy silane, 2-acryloxyethyl trimethoxy silane, 3-methacryloxypropyl triethoxy silane, 3-acryloxypropyl trimethoxy silane, 2-methacryloxyethyl triethoxy silane, 2-acryloxyethyl triethoxy silane, 3-methacryloxypropyl tris(methoxyethoxy)silane, 3-methacryloxypropyl tris(butoxyethoxy)silane, 3-methacryloxypropyl tris(propoxy)silane, 3-methacryloxypropyl tris(butoxy)silane, 3-acryloxypropyl tris(methoxyethoxy)silane, 3-acryloxypropyl tris(butoxyethoxy)silane, 3-acryloxypropyl tris(propoxy)silane, 3-acryloxypropyl tris(butoxy)silane. 3-Methacryloxypropyl trimethoxy silane is particularly preferred.
These and other silanes are commercially available for example from ABCR GmbH and Co, D-76151 Karlsruhe, or Sivento Chemie GmbH, D-40468 Dxc3xcssseldorf.
Vinyl phosphonic acid or vinyl phosphonic acid diethyl ester can also be listed here as bonding agents (manufacturer: Hoechst AG, Frankfurt am Main).
If acrylate/methacrylate silanes are used as bonding agents, it is possible to use the following multi-functional acrylates or methacrylates as cross-linking agents:
Tetraethylene glycol diacrylate (TTEGDA), triethylene glycol diacrylate (TIEGDA), polyethylene glycol-400-diacrylate (PEG400DA), 2,2xe2x80x2-bis(4-acryloxyethoxyphenyl)propane, ethylene glycol dimethacrylate (EGDMA), diethylene glycol dimethacrylate (DEGDMA), triethylene glycol dimethacrylate (TRGDMA), tetraethylene glycol dimethacrylate (TEGDMA), butane-1,3-diol dimethacryiate (1,3-BDDMA), butane-1,4-diol dimethacrylate (1,4-BDDMA), hexane-1,6-diol dimethacrylate (1,6-HDMA), dodecane-1,12-diol dimethacrylate (1,12-DDDMA), neopentyl glycol dimethacrylate (NPGDMA), trimethylol propane trimethacrylate (TMPTMA) and hexane-1,6-diol diacrylate (1,6-HDDA). Trimethylol propane trimethacrylate (TMPTMA) is particularly preferred.
When using epoxy silanes as bonding agents for example it is possible to use the following multi-functional amines as cross-linking agents: 3,3-dimethyl-4,4-diaminodicyclohexyl methane, ethylene diamine, triethylene tetramine, meta-xylylene diamine, N-aminoethyl piperazine, 2-methyl- 1,5-pentamethylene diamine, 1,2-diaminocyclohexane and isophorone diamine.
If amino silanes are used as bonding agents it is possible to use for example the following multi-functional epoxy compounds as cross-linking agents: butane-1,4-diol diglycidyl ether, glycerine triglycidether, neopentylglycol diglycidyl ether, pentaerythritol polyglycidether, hexane-1,6-diol diglycidether, polypropylene glycol diglycidyl ether and trimethylol propane triglycidether.
The specified acrylates and methacrylates can be obtained for example from Elf Atochem, D-40401 Dusseldorf, Rxc3x6hm, Darmstadt and Servo, 7490 AA Delden (Netherlands). All the mentioned multi-functional amine and epoxy compounds are commercially available, thus for example from UPPC, D-88487 Mietringen-Baltringen.
Commercially available organic peroxides but also inorganic peroxides and diazo compounds can be used as thermal initiators. Examples of such peroxides are diacetyl peroxides such as acetyl-cyclohexane-sulphonyl peroxide, bis(2,4-dichlorobenzoyl) peroxide, diisononanoyl peroxide, dioctanoyl peroxide, diacetyl peroxide and dibenzoyl peroxide; peroxydicarbonates (for example diisopropyl peroxydicarbonate, di-n-butylperoxydicarbonate, di-2-ethylhexyl-peroxydicarbonate, dicyclohexyl-peroxydicarbonate), alkyl peresters (for example cumyl perneodecanoate, t-butyl-perneodecanoate, t-amyl-perpivalate, t-butyl-per-2-ethylhexanoate, t-butyl-perisobutyrate, t-butyl perbenzoate), dialkyl peroxides (for example dicumyl peroxide, t-butylcumyl peroxide, 2,5-dimethylhexane-2,5-di-t-butyl peroxide, di(t-butylperoxyisopropyl)benzene, di-t-butylperoxide or 2,5-dimethylhexine-3-2,5-di-t-butyl peroxide), perketals (for example 1,1xe2x80x2-bis(t-butylperoxy)-3,3,5-trimethylcyclohexanone peroxide, methylisobutyl ketone peroxide, methyl ethyl ketone peroxide or acetyl acetone peroxide), alkyl hydroperoxides (for example pinane hydroperoxide, cumol hydroperoxide, 2,5-dimethyl hexane-2,5-dihydroperoxide or t-butylhydroperoxide), azo compounds (for example 4,4xe2x80x2-azo-bis(4-cyanovaleric acid), 1,1xe2x80x2-azo-bis(cyclohexane carboxylic acid nitrile), 2,2xe2x80x2-azo-bis(isobutyric acid amidine) dihydrochloride, 2,2xe2x80x2-azo-bis(isobutyric acid nitrile)) or persulphates such as sodium peroxydisulphate and potassium peroxodisulphate. Particularly preferred is 2,2xe2x80x2-azo-bis(isobutyric acid nitrile).
The specified compounds are commercially available from Aldrich Chemie, D-89552 Steinheim.
The sectors of use of the described invention are primarily aqueous paints and lacquers and printing inks. Here the described process provides for a brilliant shiny appearance of the effect pigments with at the same time good adhesion (cross-cutting test, Tesa test) and mechanical stability (stone impact test). The good adhesion of the coating is maintained even under the action of aggressive and corrosive media such as condensed water (for example the condensed water test in accordance with DIN 50 017). Even in powder lacquers and plastic materials the invention improves the bond of the pigments to the ambient medium and thus the mechanical and chemical properties of the coating system.
In accordance with the invention it is also possible to provide on the initial pigment a layer which includes side by side one or more of the above-mentioned hydrophobing alkyl silanes (for example described in EP 0 634 459 A2) and at least one of the reactive orientation aids described herein. Depending on the specific demands made on the pigment, the proportion of the surface-modifying agent described herein in that layer can basically be between 10% and 100%. It is particularly preferred however if the proportion is 10, 30, 50, 75 or 100%, as that provides for graduation of the operative bonding forces, such as to do justice to the most frequently occurring demands in a practical context. That provides for both improved orientation of the pigments in the lacquer, which is greater in accordance with the content of reactive orientation aids, and also strengthened binding in the hardened film of lacquer.
It is to be mentioned in general terms that the aluminium pigments according to the invention which are coated with a layer comprising a reactive surface-modifying agent can be dispersed markedly more easily than for example chromated aluminium types (for example Hydrolux types, Eckart-Werke). The dispersion of Al-pigments is a critical step as the Al-flakes can be mechanically damaged by the application of high levels of shearing energy. Lacquer films with such damaged pigments exhibit an unwanted xe2x80x98greyedxe2x80x99 appearance (the metallic shine of such coatings is markedly reduced).
Paints and printing inks which contain pigments in flake form cause problems in terms of handling insofar as, because of their size and density in comparison with the medium surrounding them, the pigments can easily settle and then cake together to form a solid sediment cake. That applies primarily in regard to mineral and oxidic effect pigments. The pigments according to the invention described herein do not settle in a lacquer so easily as a bottom sediment in comparison with the non-coated initial material, or after sedimentation they can be re-dispersed again markedly more easily.
Surface-modified flake pigments with improved settlement and sediment-agitation characteristics have already been described. EP 0 515 928 refers to coating pigments with a polyacrylate or polymethacrylate or salts thereof. There is no disclosure of more detailed information regarding the polyacrylates used so that the structural configuration of the coating is also unknown. This coating also does not contribute to improving orientation and thus the optical properties of the pigments; this coating also cannot make any contribution to controlling the wetting characteristics or improved adhesion.
EP 0 523 357 describes flake substrates which are coated with a modifying reagent comprising binding agent and particles in fibre form, to improve the settlement and sediment-agitation characteristics. The fibres prevent the coated substrates resting on each other by virtue of steric repulsion and thus being able to entail strong adhesion to each other. The fibres however are not/do not become chemically firmly anchored on the pigment surface or in the binding agent medium so that the fibres can become detached and can adversely influence the rheology of the lacquer or the printing ink.
PCT WO 96/32446 describes various compounds having epoxy groups, which together are intended to improve the settlement characteristics and also the weathering of pigments in flake form. As only similar reactive groups are present, a specifically targeted and oriented construction of a reactive orientation aid on the pigment surface is not possible.
Passivated Al-pigments for use in aqueous base lacquers (EP 0 259 592) are produced inter alia in the form of aqueous pigment pastes. Stability in terms of storage of such pastes which are produced in accordance with EP 0 259 592 is severely limited in terms of time as, in spite of passivation, the highly exothermic reaction of water with aluminium, with the formation of hydrogen, cannot be entirely stopped. The described modified new types of pigment on an aluminium basis have markedly prolonged stability in terms of storage, in comparison with passivated chromated aluminium types (Hydrolux types, Eckart-Werke).
Table 1 compares the properties in terms of use of various coated aluminium pigments (fineness D50=18-20 mm) in a commercially available aqueous lacquer system. It can be clearly seen that the SiO2-coated pigment quality V2521 which is surface-modified with the described bonding agents at least achieves and in part even exceeds the properties profile of commercially available chromated types (Hydrolux 8154, Eckart-Werke). Type V2421 involves SiO2-coated pigments which are modified with alkyl silanes while PCR 8154 (Eckart-Werke) which is available on the market is coated with pure SiO2.
Table 1:
ME-values, condensed water test and stone impact test on coated aluminium pigments.
Layer structure: phosphated steel sheet, KTL, filler, commercially available water-based lacquer on a polyurethane/polyacrylate base, 1K-High-Solid clear lacquer.

Effect pigments coated with reactive orientation aids

Eckart-Werke Standard Bronzepulver-Werker Carl-Eckart GmbH and Co.


The present invention relates to a toilet bowl cleaning composition containing a nonionic surfactant, perfume, disinfecting agent, polymeric viscosity modifier and water.

The present invention relates to a toilet bowl cleaner which contains a nonionic surfactant, a disinfecting agent, a polymeric viscosity modifier and water.
1. Background of the Invention
Numerous compositions and apparatus have been previously disclosed for cleaning toilet bowls. These compositions are designed to impede irritable smells and bacteria build up.
U.S. Pat. No. 4,852,201 teaches a cleaning composition containing a surfactant, alkali metal carbonate and acid.
U.S. Pat. No. 5,977,050 teaches a sprayable toilet bowl cleaning composition which is in a gel form which comprises a surfactant, crosslinked polyacrylic acid, a glycol ether solvent and water.
2. Summary of the Invention
The instant invention relates to a toilet bowl cleaning composition which contains an ethoxylated nonionic surfactant, a disinfecting agent, a polymeric thickening agent and water.
An object of the instant invention is to provide a thickened toilet bowl cleaner which permits easy cleaning of the vertical surfaces of the toilet bowl.
A further object of the instant invention is to provide a toilet bowl cleaner which is effective in killing germs.
A still further object of the instant invention is to provide a toilet bowl cleaner which is sprayable.
The present invention relates to a liquid toilet bowl cleaning composition which comprises approximately by weight:
(a) 0.1% to 12%, more preferably 1% to 10% of a nonionic surfactant;
(b) 0.05% to 5%, more preferably 0.1% to 4% of a disinfecting agent;
(c) 0.05% to 2%, more preferably 0.1% to 1% of a perfume;
(d) 0.1% to 3%, more preferably 0.2% to 2% of a polymeric viscosity modifier; and
(e) the balance being water, wherein the composition does not contain an anionic surfactant, a cationic surfactant, an amphoteric surfactant, a zwitterionic surfactant, an ethylene glycol ether, a propylene glycol ether, a fluorosurfactant, a thickener such as silica, methyl cellulose, clay, xanthan gum, polysaccharide or magnesium aluminum silicate, a polyglucoside or glucoside surfactant, sodium hydroxide, a halogen donating compound such as halohydantoins such as 1,3-dichloro-5,5-dimethyl hydantoin, 1,3-dichloro-5-ethyl-5methyl hydantoin and 1-bromo-3-3-chloro-5,5-dimethyl hydantoin and calcium hypochlorite, an abrasive, a suspending agent such as a hydrophilic silica, calcium carbonate, sodium bicarbonate, aluminum oxide, polyacrylate, alignates, guar gum, cellulosics, or a propellant such as a hydrocarbon having 1 to 10 carbon atoms such as propane or isobutane.
Also excluded from the instant compositions are insoluble particles selected from the group consisting of polybutylene, polyethene, polyisobutylene, polymethyl styrene, polypropylene, polystyrene, polyurethane, nylon and teflon and mixtures thereof.
The water soluble nonionic surfactants utilized in this invention are commercially well known and include the primary aliphatic alcohol ethoxylates, secondary aliphatic alcohol ethoxylates, alkylphenol ethoxylates and ethylene-oxide-propylene oxide condensates of primary alkanols, such a Plurafacs (BASF) and condensates of ethylene oxide with sorbitan fatty acid esters such as the Tweens (ICI). The nonionic synthetic organic detergents generally are the condensation products of an organic aliphatic or alkyl aromatic hydrophobic compound and hydrophilic ethylene oxide groups. Practically any hydrophobic compound having a carboxy, hydroxy, amido, or amino group with a free hydrogen attached to the nitrogen can be condensed with ethylene oxide or with the polyhydration product thereof, polyethylene glycol, to form a water soluble nonionic detergent.
The nonionic detergent class includes the condensation products of a higher alcohol (e.g., an alkanol containing about 8 to 18 carbon atoms in a straight or branched chain configuration) condensed with about 5 to 30 moles of ethylene oxide, for example, lauryl or myristyl alcohol condensed with about 16 moles of ethylene oxide (EO), tridecanol condensed with about 6 to moles of EO, myristyl alcohol condensed with about 10 moles of EO per mole of myristyl alcohol, the condensation product of EO with a cut of coconut fatty alcohol containing a mixture of fatty alcohols with alkyl chains varying from 10 to about 14 carbon atoms in length and wherein the condensate contains either about 6 moles of EO per mole of total alcohol or about 9 moles of EO per mole of alcohol and tallow alcohol ethoxylates containing 6 EO to 11 EO per mole of alcohol.
A preferred group of the foregoing nonionic surfactants are the Neodol ethoxylates (Shell Co.), which are higher aliphatic, primary alcohol containing about 9-15 carbon atoms, such as C9-C11 alkanol condensed with 8 moles of ethylene oxide (Neodol 91-8), C12-13 alkanol condensed with 6.5 moles ethylene oxide (Neodol 23-6.5), C12-15 alkanol condensed with 12 moles ethylene oxide (Neodol 25-12), C14-15 alkanol condensed with 13 moles ethylene oxide (Neodol 45-13), and the like. Such ethoxamers have an HLB (hydrophobic lipophilic balance) value of about 8 to 15 and give good O/W emulsification, whereas ethoxamers with HLB values below 8 contain less than 5 ethyleneoxide groups and tend to be poor emulsifiers and poor detergents.
Additional satisfactory water soluble alcohol ethylene oxide condensates are the condensation products of a secondary aliphatic alcohol containing 8 to 18 carbon atoms in a straight or branched chain configuration condensed with 5 to 30 moles of ethylene oxide. Examples of commercially available nonionic detergents of the foregoing type are C11-C15 secondary alkanol condensed with either 9 EO (Tergitol 15-S-9) or 12 EO (Tergitol 15-S-12) marketed by Union Carbide.
Other suitable nonionic detergents include the polyethylene oxide condensates of one mole of alkyl phenol containing from about 8 to 18 carbon atoms in a straight- or branched chain alkyl group with about 5 to 30 moles of ethylene oxide. Specific examples of alkyl phenol ethoxylates include nonyl phenol condensed with about 9.5 moles of EO per mole of nonyl phenol, dinonyl phenol condensed with about 12 moles of EO per mole of dinonyl phenol, dinonyl phenol condensed with about 15 moles of EO per mole of phenol and di-isoctylphenol condensed with about 15 moles of EO per mole of phenol. Commercially available nonionic surfactants of this type include Igepal CO-630 (nonyl phenol ethoxylate) marketed by GAF Corporation.
Condensates of 2 to 30 moles of ethylene oxide with sorbitan mono- and tri-C10-C20 alkanoic acid esters having a HLB of 8 to 15 also may be employed as the nonionic detergent ingredient in the described shampoo. These surfactants are well known and are available from Imperial Chemical Industries under the Tween trade name. Suitable surfactants include polyoxyethylene (4) sorbitan monolaurate, polyoxyethylene (4) sorbitan monostearate, polyoxyethylene (20) sorbitan trioleate and polyoxyethylene (20) sorbitan tristearate.
The disinfectant agent is selected from the group consisting of C8-C16 alkyl benzyl dimethyl ammonium chlorides, C8-C16 dialkyl dimethyl ammonium chlorides, C8-C16 alkyl, C8-C14 alkyl, dimethyl ammonium chloride and chlorohexidine and mixtures thereof. Some typical disinfectant agents useful in the instant compositions are manufactured by Lonza, S. A. They are: Bardac 2180 (or 2170) which is N-decyl-N-isonoxyl-N, N-dimethyl ammonium chloride; Bardac 22 which is didecyl dimethyl ammonium chloride; Bardac LF which is N,Ndioctyl-N, N-dimethyl ammonium chloride; Bardac 114 which is a mixture in a ratio of 1:1:1 of N-alkyl-N, N-didecyl-N, N-dimethyl ammonium chloride/N-alkyl-N, N-dimethyl-N-ethyl ammonium chloride; and Barquat MB-50 which is N-alkyl-N, N-dimethyl-N-benzyl ammonium chloride. The preferred disinfecting agent is a C8-C16 alkyl benzyl dimethyl ammonium chloride.
The polymeric viscosity modifier which permits the toilet bowl cleaning composition to have a Brookfield viscosity RVDV, 25xc2x0 C., cps about 150 to 400 cps, more preferably 175 to 250 cps. The polymeric viscosity modifier agent is a noncrosslinked quaternary acrylic acid homopolymer having a molecular weight of about 30,000 to about 2,000,000 such as Polygel K200 manufactured by 3V Inc. of Georgetown, S.C. The Polygel K200 is N,N,N,-Trimethyl-2-[Methyl-1-OXO-Propenyl)Oxy]-chloride homopolymer.
As used herein the term xe2x80x9cperfumexe2x80x9d is used in its ordinary sense to refer to and include any non-water soluble fragrant substance or mixture of substances including natural (i.e., obtained by extraction of flower, herb, blossom or plant), artificial (i.e., mixture of natural oils or oil constituents) and synthetically produced substance odoriferous substances. Typically, perfumes are complex mixtures of blends of various organic compounds such as alcohols, aldehydes, ethers, aromatic compounds and varying amounts of essential oils (e.g., terpenes) such as from 0 to 80%, usually from 10% to 70% by weight, the essential oils themselves being volatile odoriferous compounds and also serving to dissolve the other components of the perfume.
In the present invention the precise composition of the perfume is of no particular consequence to cleaning performance so long as it meets the criteria of water immiscibility and having a pleasing odor. Naturally, of course, especially for cleaning compositions intended for use in the home, the perfume, as well as all other ingredients, should be cosmetically acceptable, i.e., non-toxic, hypoallergenic, etc. The instant compositions show a marked improvement in ecotoxocity as compared to existing commercial products.
The final essential ingredient in the inventive toilet bowl cleaning compositions is water. The proportion of water in the toilet bowl cleaning composition compositions generally is in the range of 20% to 97%, preferably 70% to 97% by weight.
The liquid cleaning composition of this invention may, if desired, also contain other components either to provide additional effect or to make the product more attractive to the consumer. The following are mentioned by way of example: Colors or dyes in amounts up to 0.5% by weight; bactericides in amounts up to 1% by weight; preservatives or antioxidizing agents, such as EDTA, formalin, 5-bromo-5-nitro-dioxan-1,3; 5-chloro-2-methyl-4-isothaliazolin-3-one, 2,6-di-tert.butyl-p-cresol, etc., in amounts up to 2% by weight; and pH adjusting agents, such as sulfuric acid or sodium hydroxide, as needed. Furthermore, if opaque compositions are desired, up to 4% by weight of an opacifier may be added.
The toilet bowl cleaning composition can optionally including at a concentration of 0 to 2.5 wt. %, more preferably 0.1 to 1.5 wt. % a proton donating agent selected from the group consisting of nonhydroxy containing organic acids such as succinic acid, glutaric acid, adipic acid, hydroxy containing organic acids such as ortho hydroxy benzoic acid, citric acid and lactic acid and inorganic acids such as sulfuric acid, hydrochloric acid and phosphoric acid and mixtures thereof.
In final form, the compositions exhibit stability at reduced and increased temperatures. More specifically, such compositions remain clear and stable in the range of 4xc2x0 C. to 50xc2x0 C., especially 2xc2x0 C. to 43xc2x0 C. Such compositions exhibit a pH in the neutral range.
The compositions are directly ready for use or can be diluted as desired and in either case no or only minimal rinsing is required and substantially no residue or streaks are left behind. Furthermore, because the compositions are free of detergent builders such as alkali metal polyphosphates they are environmentally acceptable.
Addition of Polygel K200 requires special procedures to assure complete and timely hydration. As soon as Polygel K200 contacts an aqueous medium, it begins to hydrate. Large particles of Polygel K200 results in large lumps once in contact with aqueous medium and swell. The Polygel K200 should be added to non-aqueous medium to assure good dispersion, smallest particles size, before adding to aqueous medium to minimize lumps and have timely batch times. An acceptable practice is to add Polygel K200 to the fragrance and or nonionic surfactant with minimal mixing before adding to the aqueous medium. It is not necessary to use elevated temperatures in the formation step and room temperature is sufficient.
The instant compositions formulas explicitly exclude alkali metal sulfates, alkali metal silicates and alkali metal builders such as alkali metal polyphosphates, alkali metal carbonates, alkali metal phosphonates and alkali metal citrates because these materials, if used in the instant composition, would cause the composition to have a high pH as well as leaving residue on the surface being cleaned.
The following examples illustrate liquid cleaning compositions of the described invention. Unless otherwise specified, all percentages are by weight. The exemplified compositions are illustrative only and do not limit the scope of the invention.

Toilet bowl cleaning compositions containing a polymeric viscosity modifier


Reactive hotmelt adhesives based on copolyamide can be used in hybrid components. These hybrid components find application in, for example, vehicle construction and aircraft construction.

1. Field of the Invention
The present invention describes the use of reactive hotmelt adhesives in hybrid components (structural components).
2. Discussion of the Background
Structural components are components with subordinate aesthetic requirements which are employed in the construction both of vehicles and of aircraft in the area of load-bearing parts and of force-accommodating parts.
The structural components of the present invention are notable in particular for the local reinforcements they have, which give the component particular mechanical properties. The increase in torsional rigidity with additional weight reduction is particularly noteworthy in the present invention as compared with existing components.
The hybrid components described in the present invention are notable in particular for the fact that they consist of an assembly of principally metals with polymers. A polymer structure is inserted by means of injection moulding techniques into a metal component, and gives the component the appropriate torsional rigidity and crash rigidity in addition to comparatively low weight.
The weak point in conventional hybrid components to date has been the attachment of the polymer to the metallic material. Here, as a result of contraction and different expansion coefficients in the various materials, disbonding of the constituents occurs, leading to deterioration in the mechanical properties. At the present time, conventional structure-forming hybrid components are produced by injection-moulding a polymeric material into a metallic material. The problem with this physical join is the transition between the polymer and the metal, since the materials have different mechanical properties, leading to an adverse effect on the strength of the assembly, as a result of shrinking of the polymer, for example, and hence likewise adversely affecting the torsional rigidity of the components.

Hybrid components containing reactive hotmelt adhesives