Patent Application
20060293202
1. Field of the Invention
The present invention relates generally to cleaning compositions for use on hard surfaces. The invention also relates to cleaning compositions for use with cleaning substrates, cleaning heads, cleaning pads, cleaning sponges and related systems for cleaning hard surfaces. The composition also relates to acidic cleaning compositions with low residue. The invention also relates to cleaning compositions suitable for use on food contact services and on surfaces in and around food preparation areas such as countertops, kitchen tables, stoves and the like.
2. Description of the Related Art
U.S. Pat. No. 6,699,825 to Rees et al. discloses low residue antimicrobial cleaners with low concentrations of organic acid, glycols, and solvents with less than 10% water solubility. U.S. Pat. No. 6,812,196 to Rees et al. discloses antimicrobial cleaners with solvents of low volatility. PCT Pat. App. WO2004/018599 to McCue et al. discloses antimicrobial cleaners with mixtures of anionic and nonionic surfactants.
Prior art compositions do not combine disinfection and low residue, and particularly low filming and streaking on surfaces, especially with food safe ingredients. It is therefore an object of the present invention to provide a cleaning composition that overcomes the disadvantages and shortcomings associated with prior art cleaning compositions.
In accordance with the above objects and those that will be mentioned and will become apparent below, one aspect of the present invention comprises a cleaning composition comprising:
In accordance with the above objects and those that will be mentioned and will become apparent below, one aspect of the present invention comprises a cleaning composition for use on food contact surfaces comprising:
In accordance with the above objects and those that will be mentioned and will become apparent below, one aspect of the present invention comprises a cleaning substrate impregnated with a cleaning composition comprising:
In accordance with the above objects and those that will be mentioned and will become apparent below, one aspect of the present invention comprises a method of treating a food contact surface to remove residues and render the surface suitable for contact with ingestible food items comprising:
Further features and advantages of the present invention will become apparent to those of ordinary skill in the art in view of the detailed description of preferred embodiments below, when considered together with the attached claims.
Before describing the present invention in detail, it is to be understood that this invention is not limited to particularly exemplified systems or process parameters that may, of course, vary. It is also to be understood that the terminology used herein is for the purpose of describing particular embodiments of the invention only, and is not intended to limit the scope of the invention in any manner.
All publications, patents and patent applications cited herein, whether supra or infra, are hereby incorporated by reference in their entirety to the same extent as if each individual publication, patent or patent application was specifically and individually indicated to be incorporated by reference.
It must be noted that, as used in this specification and the appended claims, the singular forms “a,” “an” and “the” include plural referents unless the content clearly dictates otherwise. Thus, for example, reference to a “surfactant” includes two or more such surfactants.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which the invention pertains. Although a number of methods and materials similar or equivalent to those described herein can be used in the practice of the present invention, the preferred materials and methods are described herein.
The cleaning composition can be used as a disinfectant, sanitizer, and/or sterilizer. As used herein, the term “disinfect” shall mean the elimination of many or all pathogenic microorganisms on surfaces with the exception of bacterial endospores. As used herein, the term “sanitize” shall mean the reduction of contaminants in the inanimate environment to levels considered safe according to public health ordinance, or that reduces the bacterial population by significant numbers where public health requirements have not been established. An at least 99% reduction in bacterial population within a 24 hour time period is deemed “significant.” As used herein, the term “sterilize” shall mean the complete elimination or destruction of all forms of microbial life and which is authorized under the applicable regulatory laws to make legal claims as a “Sterilant” or to have sterilizing properties or qualities.
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 (“%'s”) are in weight percent (based on 100% active) of the cleaning composition alone, not accounting for the substrate weight. Each of the noted cleaner composition components and substrates is discussed in detail below.
As used herein, the term “substrate” is intended to include any material that is used to clean an article or a surface. Examples of cleaning substrates include, but are not limited to nonwovens, sponges, films and similar materials which can be attached to a cleaning implement, such as a floor mop, handle, or a hand held cleaning tool, such as a toilet cleaning device.
As used herein, “film” refers to a polymer film including flat nonporous films, and porous films such as microporous, nanoporous, closed or open celled, breathable films, or aperatured films.
As used herein, “wiping” refers to any shearing action that the substrate undergoes while in contact with a target surface. This includes hand or body motion, substrate-implement motion over a surface, or any perturbation of the substrate via energy sources such as ultrasound, mechanical vibration, electromagnetism, and so forth.
As used herein, the term “fiber” includes both staple fibers, i. e., fibers which have a defined length between about 2 and about 20 mm, fibers longer than staple fiber but are not continuous, and continuous fibers, which are sometimes called “continuous filaments” or simply “filaments”. The method in which the fiber is prepared will determine if the fiber is a staple fiber or a continuous filament.
As used herein, the terms “nonwoven” or “nonwoven web” means a web having a structure of individual fibers or threads which are interlaid, but not in an identifiable manner as in a knitted web. Nonwoven webs have been formed from many processes, such as, for example, melt blowing processes, spun bonding processes, and bonded carded web processes.
As used herein, the term “polymer” generally includes, but is not limited to, homopolymers, copolymers, such as for example, block, graft, random and alternating copolymers, terpolymers, etc. and blends, modifications, addition products, condensates and derivatives thereof. Furthermore, unless otherwise specifically limited, the term “polymer” shall include all possible geometrical configurations of the molecule. These configurations include, but are not limited to isotactic, syndiotactic and random symmetries.
The term “sponge”, as used herein, is meant to mean an elastic, porous material, including, but not limited to, compressed sponges, cellulosic sponges, reconstituted cellulosic sponges, cellulosic materials, foams from high internal phase emulsions, such as those disclosed in U.S. Pat. No. 6,525,106, polyethylene, polypropylene, polyvinyl alcohol, polyurethane, polyether, and polyester sponges, foams and nonwoven materials, and mixtures thereof.
The term “cleaning composition”, as used herein, is meant to mean and include a cleaning formulation having at least one surfactant.
The term “surfactant”, as used herein, is meant to mean and include a substance or compound that reduces surface tension when dissolved in water or water solutions, or that reduces interfacial tension between two liquids, or between a liquid and a solid. The term “surfactant” thus includes anionic, nonionic and/or amphoteric agents.
Where appropriate for proper chemical identification as to substitution position and/or isomer configuration, Greek characters, including [alpha], [beta], [gamma], [delta] and so forth, are designated as terms between square brackets and have the meaning associated according to convention in the art as recognized by the IUPAC (International Union of Pure & Applied Chemistry) rules of chemical identification.
2-Hydroxycarboxylic Acids
One aspect of the invention is a 2-hydroxycarboxylic acid. Examples of 2-hydroxycarboxylic acids are given in Table I. 2-Hydroxycarboxylic acids also include polymeric forms of 2-hydroxycarboxylic acid, such as polylactic acid. Suitable compositions comprise 2-hydroxycarboxylic acids in concentrations of 1 to 50% by weight, or 1 to 20% by weight, or 1 to 10% by weight.
One suitable 2-hydroxyacid for use in compositions of the present invention is 2-hydroxy propionic acid, known as lactic acid. Without being bound by theory, it is believed that the low melting point (MP) of the organic acids enables use for cleaning and disinfecting surfaces combined with the beneficial property of leaving little or no visible residues on surfaces, particularly high gloss and reflective surfaces where residues from cleaning compositions are otherwise particularly visually noticeable by eye. Lactic acid, having the lowest MP of the preferred 2-hydroxyacids is particularly advantageous for providing disinfectancy and leaving little or no visible residue when combined with food safe nonionic surfactants for improved cleaning characteristics.
Food Safe Nonionic Surfactant
The food safe nonionic surfactant useful in the present invention may include those formed from a fatty alcohol, a fatty acid, a glyceride, a saccharide, an alkyl ether or derivative thereof having a C6 to C24 carbon chain, derivatized with a polymeric radical to yield a Hydrophilic-Lipophilic Balance (HLB) of at least 3. HLB is understood to mean the balance between the size and strength of the hydrophilic group and the size and strength of the lipophilic group of the surfactant. Such derivatives include radicals or reaction products being polymers such as ethoxylates, propoxylates, polyglucosides, polyglycerins, polylactates, polyglycolates, polysorbates, and others that would be apparent to one of ordinary skill in the art. Such derivatives may also be mixed polymers of the above, commonly designated as copolymer, such as ethoxylate/propoxylate species, where the total HLB is preferably greater than or equal to 3. Polymers include copolymers formed either by linear, random or block copolymerization prior to further derivatization as is common in the art.
Suitable for use in the present invention are food safe nonionic surfactants selected from polyoxyalkylene condensates derivatized with fatty alkyl ethers including those commonly designated under the trade name “BRIJ”, and available from ICI Surfactants. Examples include Brij® 30-polyoxyethylene (4) lauryl ether, Brij® 35-polyoxyethylene (23) lauryl ether, also known as an ethoxylated lauryl alcohol or lauryl polyethylene glycol ether, Brij® 52-polyoxyethylene (2) cetyl ether, Brij® 58-polyoxyethylene (20) cetyl ether, Brij® 76-polyoxyethylene (10) stearyl ether, Brij® 78-polyoxyethylene (20) stearyl ether, Brij® 93-polyoxyethylene (2) oleyl ether, Brij® 97-polyoxyethylene (10) oleyl ether, and Brij® 98-polyoxyethylene (20) oleyl ether. Other commercially available materials suitable for use include alkyl C-18 Steareth-10 available as Volpo S-10 from Croda Chemicals Ltd, and alkyl C-18 Steareth-16 available as Solulan-16 from Amerchol Corp.
Also suitable for use in the present invention are food safe nonionic surfactants based on block copolymers derived from polyethylene and polypropylene derivatized with glycol radical functionality sold under the “Pluronic® ” trade name available from BASF. Examples include, but are not limited to Pluronic® L44 (also known as Poloxamer 124), Pluronic® L61 (Poloxamer 181), Pluronic® L64 (Poloxamer 184), Pluronic® F68 (Poloxamer 188), Pluronic® F68 (Poloxamer 188), Pluronic® F87 (Poloxamer 237), Pluronic® L101 (Poloxamer 331), Pluroni® L108 (Poloxamer 338), and Pluronic® F127 (Poloxamer 407).
Also suitable for use in the present invention are food safe nonionic surfactants based on tetrafunctional block copolymers terminating in primary hydroxyl groups, such as poloxamines, being copolymers of ethylene oxide and propylene oxide block copolymers. Preferred are those having an HLB of at least about 3, so as to have partial water solubility to complete water miscibility. Examples includes those materials commercially available under the trade name “Tetronic” from the BASF Corporation, such as TETRONIC® 1107, TETRONIC® 1301, TETRONIC® 1304, TETRONIC® 1307, TETRONIC® 304, TETRONIC® 701, TETRONIC® 901 and TETRONIC® 908.
In addition, food safe nonionic surfactants based on copolymers of ethylene oxide and propylene oxide block copolymers with terminal secondary hydroxyl groups. Commercial examples include those available from BASF, designated as TETRONIC® 90R4 and TETRONIC® 150R1, may be employed.
Also suitable for use in the present invention are food safe nonionic surfactant difunctional block copolymers of polyoxyethylene and polyoxypropylene with terminal secondary hydroxyl groups, including but not limited to those commercial materials available from BASF Corporation sold under the trade name Pluronic®® 10R5, Pluronic®® 17R2, Pluronic®® 17R4, Pluronic®® 25R2, Pluronic®® 25R4, and Pluronic®® 31R1.
Further suitable are the food safe nonionic surfactant difunctional block copolymers of polyoxyethylene and polyoxypropylene with terminal primary hydroxyl groups, including but not limited to those commercial materials available from BASF Corporation sold under the trade name “PLURONIC” and represented by “L,” “F”, and “P” series identifiers. Examples include Pluronic® F108, Pluronic® F127, Pluronic® F38, Pluronic® F77, Pluronic® F87, Pluronic® F88, Pluronic® F98, Pluronic® L10, Pluronic® L101, Pluronic® L121, Pluronic® L31, Pluronic® L35, Pluronic® L43, Pluronic® L44, Pluronic® L61, Pluronic® L62, Pluronic® L64, Pluronic® L81, Pluronic® L92, Pluronic® P103, Pluronic® P104, Pluronic® P105, Pluronic® P123, Pluronic® P65, Pluronic® P84, and Pluronic® P85.
Also suitable are food safe nonionic polymer condensates of polyethylene glycol and fatty acids, including such fatty acids as lauric, myristic, palmitic, stearic, oleic, linoleic, and other well known similar saturated, unsaturated (being either cis or trans isomers), as well as branched and/or unbranched fatty acids. Examples, include but are not limited to those materials approved for indirect food contact use, such as polyethylene glycol (400) monolaurate, polyethylene glycol (600) monolaurate, polyethylene glycol (400) monooleate, polyethylene glycol (600) monooleate, polyethylene glycol (400) monostearate and polyethylene glycol (600) monostearate.
Polysaccharide-polyalkylene Nonionic Surfactants
Also suitable for use in the present invention are polyalkylene oxide derivatives of a sorbitan or sorbitol aliphatic ester, where either sorbitol or sorbitan are derivatized with an alkylene oxide such as ethylene oxide or propylene oxide to produce nonionic surfactants. Suitable nonionics are those typically characterized by the presence of from 1 to 3 moles of a fatty acid, in ester form, per mole of surfactant and greater than about 5 moles of alkylene oxide, preferably 10 or more for good solubility. The composition of the resulting nonionic surfactant is a mixture of a large number of compounds characterized by the molar proportion of alkylene oxide and the molar proportion of fatty acid residues on the sorbitol or sorbitan molecules. Examples of particularly suitable food safe nonionic surfactants are Polysorbate 20®, also known as Tween 20® (Available from ICI), typically considered to be a mixture of laurate esters of sorbitol and sorbitan consisting predominantly of the mono fatty acid ester condensed with approximately 20 moles of ethylene oxide. Also suitable is Polysorbate 60®, a mixture of stearate esters of sorbitol and sorbitan consisting predominantly of the mono fatty acid ester condensed with approximately 20 moles of ethylene oxide, Tween 80® (also a available from ICI), which is a mixture of oleate esters of sorbitol and sorbitan consisting predominantly of the mono fatty acid ester condensed with approximately 20 moles of ethylene oxide.
Other suitable examples of food safe nonionic surfactants are sucrose esters, such as sucrose cocoate available from Croda, and sorbitan esters, such as polyoxyethylene(20) sorbitan monooleate available from Uniquema. Other examples of food safe nonionic surfactants are given in Generally Recognized As Safe (GRAS) lists, as described below.
Suitable food safe nonionic surfactants include those listed in Title 40 Code of Federal Regulations Part 180.940 (40 C.F.R. 180.940), which is hereby incorporated by reference. Examples include, but are not limited to [alpha]-alkyl(C10-C14)-[omega]-hydroxypoly(oxyethylene)-poly(oxypropylene) having an average molecular weight (in average molecular weight units of AMU) of 768 to 837, [alpha]-alkyl(C12-C18)-[omega]-hydroxypoly(oxyethylene)-poly(oxypropylene) 950 to 1120, [alpha]-(p-Nonylphenyl)-[omega]-hydroxypoly(oxyethylene) with average poly(oxyethylene) content of 11 moles, [alpha]-Lauroyl-[omega]-hydroxypoly(oxyethylene) with an average of 8-9 moles of ethylene oxide and average molecular weight (in AMU) of 400, [alpha]-alkyl(C11-C15)-[omega]-hydroxypoly(oxyethylene) with ethylene oxide content 9 to 13 moles, [alpha]-alkyl(C12-C15)-[omega]-hydroxypoly(oxyethylene)-polyoxypropylene with average molecular weight (in AMU) of 965, alkyl(C12-C15) monoether of mixed (ethylene-propylene)polyalkylene glycol with a cloud point of 70-77° C. in 1% aqueous solution and average molecular weight (in AMU) of 807, [alpha]-(p-Nonylphenyl)-[omega]-hydroxypoly(oxyethylene) with a maximum average molecular weight (in AMU) of 748, [alpha]-(p-Nonylphenyl)-[omega]-hydroxypoly(oxyethylene) produced by the condensation of 1 mole para-nonylphenol with 9 to 12 moles ethylene oxide, [alpha]-(p-Nonylphenyl)-[omega]-hydroxypoly(oxyethylene) with 9 to 13 moles ethylene oxide, Poly(oxy-1,2-ethanediyl)-[alpha]-[(1,1,3,3-tetramethylbutyl)phenyl]-[omega]-hydroxy-produced with one mole of the phenol and 4 to 14 moles ethylene oxide, and combinations thereof. Other listed food-safe materials may optionally be included in embodiments of the current invention as additional adjuncts.
Also preferred for use on food contact surfaces and surfaces coming into direct human contact include those selected nonionic polysorbate surfactant materials that are approved for direct use in food intended for human consumption under specified conditions and levels of use. Examples include alkoxylated sorbitan or sorbitol aliphatic esters employing ethylene oxide condensates with sorbitan or sorbitol fatty acid esters. Also suitable are the alkoxylated sorbitan or sorbitol fatty acid esters include mono-, di- and tri-esters and mixtures thereof. Sorbitan fatty acid esters may be derivatized by esterification of sorbitol or sorbitan with such fatty acids as lauric, myristic, palmitic, stearic, oleic, linoleic, and other well known similar saturated, unsaturated (being either cis or trans isomers), as well as branched and/or unbranched fatty acids. For use on food contact surfaces, those materials that employ GRAS fatty acids include the sorbitan esters approved as direct food additives, such as for example sorbitan monostearate, polyoxyethylene (20) sorbitan monolaurate, polyoxyethylene (20) sorbitan monostearate, polyoxyethylene (20) sorbitan monooleate, and mixtures thereof.
Most preferred for use in compositions of the present invention are those food safe nonionic surfactants specifically listed as GRAS according to any one of Title 21 Code of Federal Regulations (21 C.F.R.), Parts 172 to 582, specifically those listed in 21 C.F.R. 172, 21 C.F.R. 178, 21 C.F.R. 181, 21 C.F.R. 186, and 21 C.F.R. 582, which are hereby incorporated by reference.
Additional Surfactants
The cleaning composition may contain one or more additional surfactants selected from anionic, cationic, ampholytic, amphoteric and zwitterionic surfactants and mixtures thereof. A typical listing of anionic, ampholytic, and zwitterionic classes, and species of these surfactants, is given in U.S. Pat. No. 3,929,678 to Laughlin and Heuring. A list of suitable cationic surfactants is given in U.S. Pat. No. 4,259,217 to Murphy. Where present, anionic, ampholytic, amphoteric and zwitterionic surfactants are generally used in combination with one or more nonionic surfactants. The surfactants may be present at a level of from about 0% to 90%, or from about 0.001% to 50%, or from about 0.01% to 25% by weight.
The cleaning composition may comprise an anionic surfactant. Essentially any anionic surfactants useful for detersive purposes can be used in the cleaning composition. These can include salts (including, for example, sodium, potassium, ammonium, and substituted ammonium salts such as mono-, di- and tri-ethanolamine salts) of the anionic sulfate, sulfonate, carboxylate and sarcosinate surfactants. Anionic surfactants may comprise a sulfonate or a sulfate surfactant. Anionic surfactants may comprise an alkyl sulfate, a linear or branched alkyl benzene sulfonate, or an alkyldiphenyloxide disulfonate, as described herein.
Other anionic surfactants include the isethionates such as the acyl isethionates, N-acyl taurates, fatty acid amides of methyl tauride, alkyl succinates and sulfosuccinates, monoesters of sulfosuccinate (for instance, saturated and unsaturated C12-C18 monoesters) diesters of sulfosuccinate (for instance saturated and unsaturated C6-C14 diesters), N-acyl sarcosinates. Resin acids and hydrogenated resin acids are also suitable, such as rosin, hydrogenated rosin, and resin acids and hydrogenated resin acids present in or derived from tallow oil. Anionic sulfate surfactants suitable for use herein include the linear and branched primary and secondary alkyl sulfates, alkyl ethoxysulfates, fatty oleoyl glycerol sulfates, alkyl phenol ethylene oxide ether sulfates, the C5-C17acyl-N—(C1-C4 alkyl) and —N—(C1-C2 hydroxyalkyl) glucamine sulfates, and sulfates of alkylpolysaccharides such as the sulfates of alkylpolyglucoside (the nonionic nonsulfated compounds being described herein). alkyl sulfate surfactants may be selected from the linear and branched primary C10-C18 alkyl sulfates, the C11-C15 branched chain alkyl sulfates, or the C12-C14 linear chain alkyl sulfates.
Alkyl ethoxysulfate surfactants may be selected from the group consisting of the C10-C18 alkyl sulfates, which have been ethoxylated with from 0.5 to 20 moles of ethylene oxide per molecule. The alkyl ethoxysulfate surfactant may be a C11-C18, or a C1-C15 alkyl sulfate which has been ethoxylated with from 0.5 to 7, or from 1 to 5, moles of ethylene oxide per molecule. One aspect of the invention employs mixtures of the alkyl sulfate and/or sulfonate and alkyl ethoxysulfate surfactants. Such mixtures have been disclosed in PCT Patent Application No. WO 93/18124.
Anionic sulfonate surfactants suitable for use herein include the salts of C5-C20 linear alkylbenzene sulfonates, alkyl ester sulfonates, C6-C22 primary or secondary alkane sulfonates, C6-C24 olefin sulfonates, sulfonated polycarboxylic acids, alkyl glycerol sulfonates, fatty acyl glycerol sulfonates, fatty oleyl glycerol sulfonates, and any mixtures thereof. Suitable anionic carboxylate surfactants include the alkyl ethoxy carboxylates, the alkyl polyethoxy polycarboxylate surfactants and the soaps (‘alkyl carboxyls’), especially certain secondary soaps as described herein. Suitable alkyl ethoxy carboxylates include those with the formula RO(CH2CH2O)xCH2COO −M+ wherein R is a C6 to C18 alkyl group, x ranges from 0 to 10, and the ethoxylate distribution is such that, on a weight basis, the amount of material where x is 0 is less than 20% and M is a cation. Suitable alkyl polyethoxypolycarboxylate surfactants include those having the formula RO—(CHR1—CHR2—O)—R3 wherein R is a C6 to C18 alkyl group, x is from 1 to 25, R1 and R2 are selected from the group consisting of hydrogen, methyl acid radical, succinic acid radical, hydroxysuccinic acid radical, and mixtures thereof, and R3 is selected from the group consisting of hydrogen, substituted or unsubstituted hydrocarbon having between 1 and 8 carbon atoms, and mixtures thereof.
For use around food preparation areas, food safe anionic surfactants are generally preferred, and suitable examples for use in food safe cleaning compositions of the present invention include, but are not limited to, sodium lauryl sulfate, sodium dodecyl sulfate, linear alkyl sulfonate, linear alkylbenzene sulfonate, and mixtures thereof.
Suitable soap surfactants include the secondary soap surfactants, which contain a carboxyl unit connected to a secondary carbon. Suitable secondary soap surfactants for use herein are water-soluble members selected from the group consisting of the water-soluble salts of 2-methyl-1-undecanoic acid, 2-ethyl-1-decanoic acid, 2-propyl-1-nonanoic acid, 2-butyl-1-octanoic acid and 2-pentyl-1-heptanoic acid. Certain soaps may also be included as suds suppressors.
Other suitable anionic surfactants are the alkali metal sarcosinates of formula R—CON(R1)CH—)COOM, wherein R is a C5-C17 linear or branched alkyl or alkenyl group, R1 is a C1-C4 alkyl group and M is an alkali metal ion. Examples are the myristyl and oleoyl methyl sarcosinates in the form of their sodium salts.
Suitable amphoteric surfactants for use herein include the amine oxide surfactants and the alkyl amphocarboxylic acids. Suitable amine oxides include those compounds having the formula R3(OR4)XNO(R5)2 wherein R3 is selected from an alkyl, hydroxyalkyl, acylamidopropyl and alkylphenyl group, or mixtures thereof, containing from 8 to 26 carbon atoms; R4 is an alkylene or hydroxyalkylene group containing from 2 to 3 carbon atoms, or mixtures thereof, x is from 0 to 5, preferably from 0 to 3; and each R5 is an alkyl or hydroxyalkyl group containing from 1 to 3, or a polyethylene oxide group containing from 1 to 3 ethylene oxide groups. Suitable amine oxides are C10-C18 alkyl dimethylamine oxide, and C10-18 acylamido alkyl dimethylamine oxide. A suitable example of an alkyl amphodicarboxylic acid is Miranol™ C2M Conc. manufactured by Miranol, Inc., Dayton, N.J.
Zwitterionic surfactants can also be incorporated into the cleaning compositions. These surfactants can be broadly described as derivatives of secondary and tertiary amines, derivatives of heterocyclic secondary and tertiary amines, or derivatives of quaternary ammonium, quaternary phosphonium or tertiary sulfonium compounds. Betaine and sultaine surfactants are exemplary zwitterionic surfactants for use herein.
Suitable betaines are those compounds having the formula R(R1)2N+R2COO— wherein R is a C6-C18 hydrocarbyl group, each R1 is typically C1-C3 alkyl, and R2 is a C1-C5 hydrocarbyl group. Suitable betaines are C12-18 dimethyl-ammonio hexanoate and the C10-18 acylamidopropane (or ethane) dimethyl (or diethyl) betaines. Complex betaine surfactants are also suitable for use herein.
Suitable cationic surfactants to be used herein include the quaternary ammonium surfactants. The quaternary ammonium surfactant may be a mono C6-C16, or a C6-C10 N-alkyl or alkenyl ammonium surfactant wherein the remaining N positions are substituted by methyl, hydroxyethyl or hydroxypropyl groups. Suitable are also the mono-alkoxylated and bis-alkoxylated amine surfactants.
Another suitable group of cationic surfactants, which can be used in the cleaning compositions, are cationic ester surfactants. The cationic ester surfactant is a compound having surfactant properties comprising at least one ester (i.e. —COO—) linkage and at least one cationically charged group. Suitable cationic ester surfactants, including choline ester surfactants, have for example been disclosed in U.S. Pat. Nos. 4,228,042, 4,239,660 and 4,260,529. The ester linkage and cationically charged group may be separated from each other in the surfactant molecule by a spacer group consisting of a chain comprising at least three atoms (i.e. of three atoms chain length), or from three to eight atoms, or from three to five atoms, or three atoms. The atoms forming the spacer group chain are selected from the group consisting, of carbon, nitrogen and oxygen atoms and any mixtures thereof, with the proviso that any nitrogen or oxygen atom in said chain connects only with carbon atoms in the chain. Thus spacer groups having, for example, —O—O— (i.e. peroxide), —N—N—, and —N—O— linkages are excluded, whilst spacer groups having, for example —CH2—O—, CH2— and —CH2—NH—CH2— linkages are included. The spacer group chain may comprise only carbon atoms, or the chain is a hydrocarbyl chain.
The cleaning composition may comprise cationic mono-alkoxylated amine surfactants, for instance, of the general formula: R1R2R3N+ApR4X− wherein R1 is an alkyl or alkenyl moiety containing from about 6 to about 18 carbon atoms, or from 6 to about 16 carbon atoms, or from about 6 to about 14 carbon atoms; R2 and R3 are each independently alkyl groups containing from one to about three carbon atoms, for instance, methyl, for instance, both R2 and R3 are methyl groups; R4 is selected from hydrogen, methyl and ethyl; X− is an anion such as chloride, bromide, methylsulfate, sulfate, or the like, to provide electrical neutrality; A is a alkoxy group, especially a ethoxy, propoxy or butoxy group; and p is from 0 to about 30, or from 2 to about 15, or from 2 to about 8. The ApR4 group in the formula may have p=1 and is a hydroxyalkyl group, having no greater than 6 carbon atoms whereby the —OH group is separated from the quaternary ammonium nitrogen atom by no more than 3 carbon atoms. Suitable ApR4 groups are —CH2CH2—OH, —CH2CH2CH2—OH, —CH2CH(CH3)—OH and —CH(CH3)CH2—OH. Suitable R1 groups are linear alkyl groups, for instance, linear R1 groups having from 8 to 14 carbon atoms.
Suitable cationic mono-alkoxylated amine surfactants for use herein are of the formula R1(CH3)(CH3)N+(CH2CH2O)2-5H X− wherein R1 is C10-C18 hydrocarbyl and mixtures thereof, especially C10-C14 alkyl, or C10 and C12 alkyl, and X is any convenient anion to provide charge balance, for instance, chloride or bromide.
As noted, compounds of the foregoing type include those wherein the ethoxy (CH2CH2O) units (EO) are replaced by butoxy, isopropoxy [CH(CH3)CH2O] and [CH2CH(CH3)O] units (i-Pr) or n-propoxy units (Pr), or mixtures of EO and/or Pr and/or i-Pr units.
The cationic bis-alkoxylated amine surfactant may have the general formula: R1R2N+ApR3A′qR4X− wherein R1 is an alkyl or alkenyl moiety containing from about 8 to about 18 carbon atoms, or from 10 to about 16 carbon atoms, or from about 10 to about 14 carbon atoms; R2 is an alkyl group containing from one to three carbon atoms, for instance, methyl; R3 and R4 can vary independently and are selected from hydrogen, methyl and ethyl, X− is an anion such as chloride, bromide, methylsulfate, sulfate, or the like, sufficient to provide electrical neutrality. A and A′ can vary independently and are each selected from C1-C4 alkoxy, for instance, ethoxy, (i.e., —CH2CH2O—), propoxy, butoxy and mixtures thereof, p is from 1 to about 30, or from 1 to about 4 and q is from 1 to about 30, or from 1 to about 4, or both p and q are 1.
Suitable cationic bis-alkoxylated amine surfactants for use herein are of the formula R1CH3N+(CH2CH2OH)(CH2CH2OH)X−, wherein R1 is C10-C18 hydrocarbyl and mixtures thereof, or C10, C12, C14 alkyl and mixtures thereof, X− is any convenient anion to provide charge balance, for example, chloride. With reference to the general cationic bis-alkoxylated amine structure noted above, since in one example compound R1 is derived from (coconut) C12-C14 alkyl fraction fatty acids, R2 is methyl and ApR3 and A′qR4 are each monoethoxy.
Other cationic bis-alkoxylated amine surfactants useful herein include compounds of the formula: R1R2N+—(CH2CH2O)pH—(CH2CH2O)qH X31 wherein R1 is C10-C18 hydrocarbyl, or C10-C14 alkyl, independently p is 1 to about 3 and q is 1 to about 3, R2 is C1-C3 alkyl, for example, methyl, and X− is an anion, for example, chloride or bromide.
Other compounds of the foregoing type include those wherein the ethoxy (CH2CH2O) units (EO) are replaced by butoxy (Bu) isopropoxy [CH(CH3)CH2O] and [CH2CH(CH3)O] units (i-Pr) or n-propoxy units (Pr), or mixtures of EO and/or Pr and/or i-Pr units.
The inventive compositions may include at least one fluorosurfactant selected from nonionic fluorosurfactants, cationic fluorosurfactants, and mixtures thereof which are soluble or dispersible in the aqueous compositions being taught herein, sometimes compositions which do not include further detersive surfactants, or further organic solvents, or both. Suitable nonionic fluorosurfactant compounds are found among the materials presently commercially marketed under the trade name Fluorad® (ex. 3M Corp.) Exemplary fluorosurfactants include those sold as Fluorad® FC-740, generally described to be fluorinated alkyl esters; Fluorad® FC-430, generally described to be fluorinated alkyl esters; Fluorad® FC-431, generally described to be fluorinated alkyl esters; and, Fluorad® FC-170-C, which is generally described as being fluorinated alkyl polyoxyethylene ethanols.
An example of a suitable cationic fluorosurfactant compound has the following structure: CnF2n+1SO2NHC3H6N+(CH3)3I31 where n˜8. This cationic fluorosurfactant is available under the trade name Fluorad® FC-135 from 3M. Another example of a suitable cationic fluorosurfactant is F3—(CF2)n—(CH2)mSCH2CHOH—CH2—N+R1R2R3Cl− wherein: n is 5-9 and m is 2, and R1, R2 and R3 are —CH3. This cationic fluorosurfactant is available under the trade name ZONYL® FSD (available from DuPont, described as 2-hydroxy-3-((gamma-omega-perfluoro-C6-20-alkyl)thio)-N,N,N-trimethyl-1-propyl ammonium chloride). Other cationic fluorosurfactants suitable for use in the present invention are also described in EP 866,115 to Leach and Niwata.
The fluorosurfactant selected from the group of nonionic fluorosurfactant, cationic fluorosurfactant, and mixtures thereof may be present in amounts of from 0.001 to 5% wt., preferably from 0.01 to 1% wt., and more preferably from 0.01 to 0.5% wt.
Most preferred for use in compositions of the present invention are those food safe surfactants specifically listed as GRAS according to any one of Title 21 Code of Federal Regulations (21 C.F.R.), Parts 172 to 582, specifically those listed in 21 C.F.R. 172, 21 C.F.R. 178, 21 C.F.R. 181, 21 C.F.R. 186, and 21 C.F.R. 582.
Solvents with Less than 20% Water Solubility
One aspect of the invention is an optional solvent with less than 20% solubility in water. Solvents with less than 20% solubility in water include the glycol ether solvents; propylene glycol n-butyl ether, dipropylene glycol n-butyl ether, dipropylene glycol n-propyl ether, and ethylene glycol n-hexyl ether. Also, included are essentially water insoluble solvents such as hydrocarbons and terpenes. Suitable solvents with less than 20% solubility in water can be present in from 0.1 to 10% by weight, or from 1 to 10% by weight.
Volatile Solvents Miscible in Water
One aspect of the invention is an optional volatile solvent that is miscible in water. These solvents tend to volatilize off after application and not form multiple phases that can lead to enhanced filming and streaking. The volatile solvent can have a vapor pressure greater than 10 mm Hg at 20° C. The volatile solvent can have a vapor pressure greater than 1 mm Hg at 20° C. The solvent should be completely miscible in water. Examples of solvents that have a vapor pressure greater than 1 mm Hg at 20° C. and that are completely miscible in water are listed in Table II. Compositions can contain 0.1 to 10% by weight of volatile solvents that are miscible in water.
Solvent
Suitable organic solvents include, but are not limited to, C1-6 alkanols, C1-6 diols, C1-10 alkyl ethers of alkylene glycols, C3-24 alkylene glycol ethers, polyalkylene glycols, short chain carboxylic acids, short chain esters, isoparafinic hydrocarbons, mineral spirits, alkylaromatics, terpenes, terpene derivatives, terpenoids, terpenoid derivatives, formaldehyde, and pyrrolidones. Alkanols include, but are not limited to, methanol, ethanol, n-propanol, isopropanol, butanol, pentanol, and hexanol, and isomers thereof. Diols include, but are not limited to, methylene, ethylene, propylene and butylene glycols. alkylene glycol ethers include, but are not limited to, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, ethylene glycol monohexyl ether, diethylene glycol monopropyl ether, diethylene glycol monobutyl ether, diethylene glycol monohexyl ether, propylene glycol methyl ether, propylene glycol ethyl ether, propylene glycol n-propyl ether, propylene glycol monobutyl ether, propylene glycol t-butyl ether, di- or tri-polypropylene glycol methyl or ethyl or propyl or butyl ether, acetate and propionate esters of glycol ethers. Short chain carboxylic acids include, but are not limited to, acetic acid, glycolic acid, lactic acid and propionic acid. Short chain esters include, but are not limited to, glycol acetate, and cyclic or linear volatile methylsiloxanes. Water insoluble solvents such as isoparafinic hydrocarbons, mineral spirits, alkylaromatics, terpenoids, terpenoid derivatives, terpenes, and terpenes derivatives can be mixed with a water-soluble solvent when employed. The solvents can be present at a level of from 0.001% to 10%, or from 0.01% to 10%, or from 1% to 4% by weight.
Additional Adjuncts
The cleaning compositions optionally contain one or more of the following adjuncts: stain and soil repellants, lubricants, odor control agents, perfumes, fragrances and fragrance release agents, and bleaching agents. Other adjuncts include, but are not limited to, acids, electrolytes, dyes and/or colorants, solubilizing materials, stabilizers, thickeners, defoamers, hydrotropes, cloud point modifiers, preservatives, and other polymers. The solubilizing materials, when used, include, but are not limited to, hydrotropes (e.g. water soluble salts of low molecular weight organic acids such as the sodium and/or potassium salts of toluene, cumene, and xylene sulfonic acid). The acids, when used, include, but are not limited to, organic hydroxy acids, citric acids, keto acid, and the like. Electrolytes, when used, include, calcium, sodium and potassium chloride. Thickeners, when used, include, but are not limited to, polyacrylic acid, xanthan gum, calcium carbonate, aluminum oxide, alginates, guar gum, methyl, ethyl, clays, and/or propyl hydroxycelluloses. Defoamers, when used, include, but are not limited to, silicones, aminosilicones, silicone blends, and/or silicone/hydrocarbon blends. Bleaching agents, when used, include, but are not limited to, peracids, hypohalite sources, hydrogen peroxide, and/or sources of hydrogen peroxide.
Preservatives, when used, include, but are not limited to, mildewstat or bacteriostat, methyl, ethyl and propyl parabens, short chain organic acids (e.g. acetic, lactic and/or glycolic acids), bisguanidine compounds (e.g. Dantagard and/or Glydant) and/or short chain alcohols (e.g. ethanol and/or IPA). The mildewstat or bacteriostat includes, but is not limited to, mildewstats (including non-isothiazolone compounds) include Kathon GC, a 5-chloro-2-methyl-4-isothiazolin-3-one, KATHON ICP, a 2-methyl-4-isothiazolin-3-one, and a blend thereof, and KATHON 886, a 5-chloro-2-methyl-4-isothiazolin-3-one, all available from Rohm and Haas Company; BRONOPOL, a 2-bromo-2-nitropropane 1,3 diol, from Boots Company Ltd., PROXEL CRL, a propyl-p-hydroxybenzoate, from ICI PLC; NIPASOL M, an o-phenyl-phenol, Na30 salt, from Nipa Laboratories Ltd., DOWICIDE A, a 1,2-Benzoisothiazolin-3-one, from Dow Chemical Co., and IRGASAN DP 200, a 2,4,4′-trichloro-2-hydroxydiphenylether, from Ciba-Geigy A.G.
Antimicrobial Agent
Antimicrobial agents, in addition to 2-hydroxycarboxylic acids and other ingredients, include quaternary ammonium compounds and phenolics. Non-limiting examples of these quaternary compounds include benzalkonium chlorides and/or substituted benzalkonium chlorides, di(C6-C14)alkyl di short chain (C1-4 alkyl and/or hydroxyalkl) quaternary ammonium salts, N-(3-chloroallyl) hexaminium chlorides, benzethonium chloride, methylbenzethonium chloride, and cetylpyridinium chloride. Other quaternary compounds include the group consisting of dialkyldimethyl ammonium chlorides, alkyl dimethylbenzylammonium chlorides, dialkylmethyl-benzylammonium chlorides, and mixtures thereof. Biguanide antimicrobial actives including, but not limited to polyhexamethylene biguanide hydrochloride, p-chlorophenyl biguanide; 4-chlorobenzhydryl biguanide, halogenated hexidine such as, but not limited to, chlorhexidine (1,1′-hexamethylene-bis-5-(4-chlorophenyl biguanide) and its salts are also in this class. Additional antimicrobial agents include those employed in the art for use in oral, topical and mucous membrane treating solutions and compositions in applications suitable for incidental human ingestion owing to their extremely low toxicities and low irritancy characteristics. These are sometimes denoted as “acceptable oral antimicrobials” in the art.
Representative oral antimicrobials suitable for use in the present invention include, but are not limited to phenolics, such as phenol and thymol; carboxylic acids and alkali metal salts thereof, such as benzoic acid, sodium benzoate, sorbic acid, sodium sorbate and potassium sorbate; p-hydroxybenzoic acid and methyl, ethyl or propyl ester derivatives thereof, quaternary ammonium halides having antimicrobial properties such as cetylpyridinium chloride, domiphen bromide, benzalkonium chloride, cetalkonium chloride and benzethonium chloride; chlorhexidine; triclosan, peroxides, notably hydrogen peroxide; zinc compounds, such as zinc chloride, zinc oxychloride, zinc hydroxide, zinc oxide, sodium zincate, zinc citrate, sodium zinc citrate and zinc fluoride; sodium salicylate; silver citrate, silver dihydrogen citrate, and compatible combinations thereof. Also suitable is octenidine dihydrochloride.
Builder/Buffer
The cleaning composition may include a builder or buffer, which increase the effectiveness of the surfactant. The builder or buffer can also function as a softener and/or a sequestering agent in the cleaning composition. A variety of builders or buffers can be used and they include, but are not limited to, phosphate-silicate compounds, zeolites, alkali metal, ammonium and substituted ammonium poly-acetates, trialkali salts of nitrilotriacetic acid, carboxylates, polycarboxylates, carbonates, bicarbonates, polyphosphates, aminopolycarboxylates, polyhydroxy-sulfonates, and starch derivatives.
Builders or buffers can also include polyacetates and polycarboxylates. The polyacetate and polycarboxylate compounds include, but are not limited to, sodium, potassium, lithium, ammonium, and substituted ammonium salts of ethylenediamine tetraacetic acid, ethylenediamine triacetic acid, ethylenediamine tetrapropionic acid, diethylenetriamine pentaacetic acid, nitrilotriacetic acid, oxydisuccinic acid, iminodisuccinic acid, mellitic acid, polyacrylic acid or polymethacrylic acid and copolymers, benzene polycarboxylic acids, gluconic acid, sulfamic acid, oxalic acid, phosphoric acid, phosphonic acid, organic phosphonic acids, acetic acid, and citric acid. These builders or buffers can also exist either partially or totally in the hydrogen ion form.
The builder agent can include sodium and/or potassium salts of EDTA and substituted ammonium salts. The substituted ammonium salts include, but are not limited to, ammonium salts of methylamine, dimethylamine, butylamine, butylenediamine, propylamine, triethylamine, trimethylamine, monoethanolamine, diethanolamine, triethanolamine, isopropanolamine, ethylenediamine tetraacetic acid and propanolamine.
Buffering and pH adjusting agents, when used, include, but are not limited to, organic acids, mineral acids, alkali metal and alkaline earth salts of silicate, metasilicate, polysilicate, borate, hydroxide, carbonate, carbamate, phosphate, polyphosphate, pyrophosphates, triphosphates, tetraphosphates, ammonia, hydroxide, monoethanolamine, monopropanolamine, diethanolamine, dipropanolamine, triethanolamine, and 2-amino-2methylpropanol. Preferred buffering agents for compositions of this invention are nitrogen-containing materials. Some examples are amino acids such as lysine or lower alcohol amines like mono-, di-, and tri-ethanolamine. Other preferred nitrogen-containing buffering agents are tri(hydroxymethyl)amino methane (TRIS), 2-amino-2-ethyl-1,3-propanediol, 2-amino-2-methyl-propanol, 2-amino-2-methyl-1,3-propanol, disodium glutamate, N-methyl diethanolamide, 2-dimethylamino-2-methylpropanol (DMAMP), 1,3-bis(methylamine)-cyclohexane, 1,3-diamino-propanol N,N′-tetra-methyl-1,3-diamino-2-propanol, N,N-bis(2-hydroxyethyl)glycine (bicine) and N-tris(hydroxymethyl)methyl glycine (tricine). Other suitable buffers include ammonium carbamate, citric acid, acetic acid. Mixtures of any of the above are also acceptable. Useful inorganic buffers/alkalinity sources include ammonia, the alkali metal carbonates and alkali metal phosphates, e.g., sodium carbonate, sodium polyphosphate. For additional buffers see WO 95/07971, which is incorporated herein by reference. Other preferred pH adjusting agents include sodium or potassium hydroxide.
When employed, the builder, buffer, or pH adjusting agent comprises at least about 0.001% and typically about 0.01-5% of the cleaning composition. Preferably, the builder or buffer content is about 0.01-2%.
Pine Oil, Terpene Derivatives and Essential Oils
Compositions according to the invention may comprise pine oil, terpene derivatives and/or essential oils. Pine oil, terpene derivatives and essential oils are used primarily for cleaning efficacy. They may also provide some antimicrobial efficacy and deodorizing properties. Pine oil, terpene derivatives and essential oils may be present in the compositions in amounts of up to about 1% by weight, preferably in amounts of 0.01% to 0.5% by weight.
Pine oil is a complex blend of oils, alcohols, acids, esters, aldehydes and other organic compounds. These include terpenes that include a large number of related alcohols or ketones. Some important constituents include terpineol. One type of pine oil, synthetic pine oil, will generally contain a higher content of turpentine alcohols than the two other grades of pine oil, namely steam distilled and sulfate pine oils. Other important compounds include alpha- and beta-pinene (turpentine), abietic acid (rosin), and other isoprene derivatives. Particularly effective pine oils are commercially available from Millennium Chemicals, under the Glidco trade name. These pine oils vary in the amount of terpene alcohols and alpha-terpineol.
Terpene derivatives appropriate for use in the inventive composition include terpene hydrocarbons having a functional group, such as terpene alcohols, terpene ethers, terpene esters, terpene aldehydes and terpene ketones. Examples of suitable terpene alcohols include verbenol, transpinocarveol, cis-2-pinanol, nopol, isobomeol, carbeol, piperitol, thymol, alpha-terpineol, terpinen-4-ol, menthol, 1,8-terpin, dihydro-terpineol, nerol, geraniol, linalool, citronellol, hydroxycitronellol, 3,7-dimethyl octanol, dihydro-myrcenol, tetrahydro-alloocimenol, perillalcohol, and falcarindiol. Examples of suitable terpene ether and terpene ester solvents include 1,8-cineole, 1,4-cineole, isobomyl methylether, rose pyran, menthofuran, trans-anethole, methyl chavicol, allocimene diepoxide, limonene mono-epoxide, isobornyl acetate, nonyl acetate, terpinyl acetate, linalyl acetate, geranyl acetate, citronellyl acetate, dihydro-terpinyl acetate and meryl acetate. Further, examples of suitable terpene aldehyde and terpene ketone solvents include myrtenal, campholenic aldehyde, perillaldehyde, citronellal, citral, hydroxy citronellal, camphor, verbenone, carvenone, dihydro-carvone, carvone, piperitone, menthone, geranyl acetone, pseudo-ionone, ionine, iso-pseudo-methyl ionone, n-pseudo-methyl ionone, iso-methyl ionone and n-methyl ionone.
Essential oils include, but are not limited to, those obtained from thyme, lemongrass, citrus, lemons, oranges, anise, clove, aniseed, pine, cinnamon, geranium, roses, mint, lavender, citronella, eucalyptus, peppermint, camphor, sandalwood, rosmarin, vervain, fleagrass, lemongrass, ratanhiae, cedar and mixtures thereof. Preferred essential oils to be used herein are thyme oil, clove oil, cinnamon oil, geranium oil, eucalyptus oil, peppermint oil, mint oil or mixtures thereof.
Actives of essential oils to be used herein include, but are not limited to, thymol (present for example in thyme), eugenol (present for example in cinnamon and clove), menthol (present for example in mint), geraniol (present for example in geranium and rose), verbenone (present for example in vervain), eucalyptol and pinocarvone (present in eucalyptus), cedrol (present for example in cedar), anethol (present for example in anise), carvacrol, hinokitiol, berberine, ferulic acid, cinnamic acid, methyl salycilic acid, methyl salycilate, terpineol and mixtures thereof. Preferred actives of essential oils to be used herein are thymol, eugenol, verbenone, eucalyptol, terpineol, cinnamic acid, methyl salycilic acid, and/or geraniol.
Other essential oils include Anethole 20/21 natural, Aniseed oil china star, Aniseed oil globe brand, Balsam (Peru), Basil oil (India), Black pepper oil, Black pepper oleoresin 40/20, Bois de Rose (Brazil) FOB, Borneol Flakes (China), Camphor oil, White, Camphor powder synthetic technical, Canaga oil (Java), Cardamom oil, Cassia oil (China), Cedarwood oil (China) BP, Cinnamon bark oil, Cinnamon leaf oil, Citronella oil, Clove bud oil, Clove leaf, Coriander (Russia), Coumarin (China), Cyclamen Aldehyde, Diphenyl oxide, Ethyl vanilin, Eucalyptol, Eucalyptus oil, Eucalyptus citriodora, Fennel oil, Geranium oil, Ginger oil, Ginger oleoresin (India), White grapefruit oil, Guaiacwood oil, Gurjun balsam, Heliotropin, Isobomyl acetate, Isolongifolene, Juniper berry oil, L-methhyl acetate, Lavender oil, Lemon oil, Lemongrass oil, Lime oil distilled, Litsea Cubeba oil, Longifolene, Menthol crystals, Methyl cedryl ketone, Methyl chavicol, Methyl salicylate, Musk ambrette, Musk ketone, Musk xylol, Nutmeg oil, Orange oil, Patchouli oil, Peppermint oil, Phenyl ethyl alcohol, Pimento berry oil, Pimento leaf oil, Rosalin, Sandalwood oil, Sandenol, Sage oil, Clary sage, Sassafras oil, Spearmint oil, Spike lavender, Tagetes, Tea tree oil, Vanilin, Vetyver oil (Java), Wintergreen. Each of these botanical oils is commercially available.
Particularly preferred oils include peppermint oil, lavender oil, bergamot oil (Italian), rosemary oil (Tunisian), and sweet orange oil. These may be commercially obtained from a variety of suppliers including: Givadan Roure Corp. (Clifton, N.J.); Berje Inc. (Bloomfield, N.J.); BBA Aroma Chemical Div. of Union Camp Corp. (Wayne, N.J.); Firmenich Inc. (Plainsboro N.J.); Quest International Fragrances Inc. (Mt. Olive Township, N.J.); Robertet Fragrances Inc. (Oakland, N.J.).
Particularly useful lemon oil and d-limonene compositions which are useful in the invention include mixtures of terpene hydrocarbons obtained from the essence of oranges, e.g., cold-pressed orange terpenes and orange terpene oil phase ex fruit juice, and the mixture of terpene hydrocarbons expressed from lemons and grapefruit.
Polymers
In preferred embodiments of the invention, polymeric material that improves the hydrophilicity of the surface being treated is incorporated into the present compositions. The increase in hydrophilicity provides improved final appearance by providing “sheeting” of the water from the surface and/or spreading of the water on the surface, and this effect is preferably seen when the surface is rewetted and even when subsequently dried after the rewetting. Polymer substantivity is beneficial as it prolongs the sheeting and cleaning benefits. Another important feature of preferred polymers is lack of visible residue upon drying. In preferred embodiments, the polymer comprises 0.001 to 5%, preferably 0.01 to 1%, and most preferably 0.1 to 0.5% of the cleaning composition.
Nanoparticles
Nanoparticles, defined as particles with diameters of about 400 nm or less, are technologically significant, since they are utilized to fabricate structures, coatings, and devices that have novel and useful properties due to the very small dimensions of their particulate constituents. “Non-photoactive” nanoparticles do not use UV or visible light to produce the desired effects. Nanoparticles can have many different particle shapes. Shapes of nanoparticles can include, but are not limited to spherical, parallelepiped-shaped, tube shaped, and disc or plate shaped. Nanoparticles can be present from 0.01 to 1%.
Inorganic nanoparticles generally exist as oxides, silicates, carbonates and hydroxides. These nanoparticles are generally hydrophilic. Some layered clay minerals and inorganic metal oxides can be examples of nanoparticles. The layered clay minerals suitable for use in the coating composition include those in the geological classes of the smectites, the kaolins, the illites, the chlorites, the attapulgites and the mixed layer clays. Smectites include montmorillonite, bentonite, pyrophyllite, hectorite, saponite, sauconite, nontronite, talc, beidellite, volchonskoite and vermiculite. Kaolins include kaolinite, dickite, nacrite, antigorite, anauxite, halloysite, indellite and chrysotile. Illites include bravaisite, muscovite, paragonite, phlogopite and biotite. Chlorites include corrensite, penninite, donbassite, sudoite, pennine and clinochlore. Attapulgites include sepiolite and polygorskyte. Mixed layer clays include allevardite and vermiculitebiotite. Variants and isomorphic substitutions of these layered clay minerals offer unique applications.
The layered clay minerals suitable for use in the coating composition may be either naturally occurring or synthetic. An example of one embodiment of the coating composition uses natural or synthetic hectorites, montmorillonites and bentonites. Another embodiment uses the hectorites clays commercially available. Typical sources of commercial hectorites are LAPONITE® from Southern Clay Products, Inc., U.S.A; Veegum Pro and Veegum F from R. T. Vanderbilt, U.S.A.; and the Barasyms, Macaloids and Propaloids from Baroid Division, National Read Comp., U.S.A.
The inorganic metal oxides used in the coating composition may be silica- or alumina-based nanoparticles that are naturally occurring or synthetic. Aluminum can be found in many naturally occurring sources, such as kaolinite and bauxite. The naturally occurring sources of alumina are processed by the Hall process or the Bayer process to yield the desired alumina type required. Various forms of alumina are commercially available in the form of Gibbsite, Diaspore, and Boehmite from manufacturers such as Condea.
In some preferred embodiments, the nanoparticles will have a net excess charge on one of their dimensions. For instance, flat plate-shaped nanoparticles may have a positive charge on their flat surfaces, and a negative charge on their edges. Alternatively, such flat plate-shaped nanoparticles may have a negative charge on their flat surfaces and a positive charge on their edges. Preferably, the nanoparticles have an overall net negative charge. This is believed to aid in hydrophilizing the surface coated with the nanoparticles. The amount of charge, or “charge density”, on the nanoparticles can be measured in terms of the mole ratio of magnesium oxide to lithium oxide in the nanoparticles. In preferred embodiments, the nanoparticles have a mole ratio of magnesium oxide to lithium oxide of less than or equal to about 11%.
Substances Generally Recognized as Safe
Compositions according to the invention may comprise substances generally recognized as safe (GRAS), including essential oils, oleoresins (solvent-free) and natural extractives (including distillates), and synthetic flavoring materials and adjuvants. Compositions may also comprise GRAS materials commonly found in cotton, cotton textiles, paper and paperboard stock dry food packaging materials (referred herein as substrates) that have been found to migrate to dry food and, by inference may migrate into the inventive compositions when these packaging materials are used as substrates for the inventive compositions.
Suitable GRAS materials are listed in the Code of Federal Regulations (C.F.R.) Title 21 of the United States Food and Drug Administration, Department of Health and Human Services, Parts 180.20, 180.40 and 180.50, which are hereby incorporated by reference. These suitable GRAS materials include essential oils, oleoresins (solvent-free), and natural extractives (including distillates). The GRAS materials may be present in the compositions in amounts of up to about 10% by weight, preferably in amounts of 0.01 and 5% by weight.
Also suitable are materials considered safe as an indirect or direct food additive. The FDA provides a GRAS list for indirect food additives are defined by Title 21 C.F.R. Parts 178, 181, and 186 and direct food additives by 21 C.F.R. Parts 172 and 582, which are hereby incorporated by reference. The indirect and direct food additive GRAS materials may be present in the compositions in amounts of up to about 10% by weight, preferably in amounts of 0.01 and 5% by weight. Also suitable for use are those materials that the United States Environmental Protection Agency (U.S.E.P.A.) allows for use in and around foods, including those specific food-safe ingredients and surfactants that may not be considered GRAS but are approved for use, including those materials listed in either 40 C.F.R. Parts 180.940 and 180.960, both of which are hereby incorporated by reference.
Preferred GRAS materials include oils and oleoresins (solvent-free) and natural extractives (including distillates) derived from alfalfa, allspice, almond bitter (free from prussic acid), ambergris, ambrette seed, angelica, angostura (cusparia bark), anise, apricot kernel (persic oil), asafetida, balm (lemon balm), balsam (of Peru), basil, bay leave, bay (myrcia oil), bergamot (bergamot orange), bois de rose (Aniba rosaeodora Ducke), cacao, camomile (chamomile) flowers, cananga, capsicum, caraway, cardamom seed (cardamon), carob bean, carrot, cascarilla bark, cassia bark, Castoreum, celery seed, cheery (wild bark), chervil, cinnamon bark, Civet (zibeth, zibet, zibetum), ceylon (Cinnamomum zeylanicum Nees), cinnamon (bark and leaf), citronella, citrus peels, clary (clary sage), clover, coca (decocainized), coffee, cognac oil (white and green), cola nut (kola nut), coriander, cumin (cummin), curacao orange peel, cusparia bark, dandelion, dog grass (quackgrass, triticum), elder flowers, estragole (esdragol, esdragon, estragon, tarragon), fennel (sweet), fenugreek, galanga (galangal), geranium, ginger, grapefruit, guava, hickory bark, horehound (hoarhound), hops, horsemint, hyssop, immortelle (Helichrysum augustifolium DC), jasmine, juniper (berries), laurel berry and leaf, lavender, lemon, lemon grass, lemon peel, lime, linden flowers, locust bean, lupulin, mace, mandarin (Citrus reticulata Blanco), marjoram, mate, menthol (including menthyl acetate), molasses (extract), musk (Tonquin musk), mustard, naringin, neroli (bigarade), nutmeg, onion, orange (bitter, flowers, leaf, flowers, peel), origanum, palmarosa, paprika, parsley, peach kernel (persic oil, pepper (black, white), peanut (stearine), peppermint, Peruvian balsam, petitgrain lemon, petitgrain mandarin (or tangerine), pimenta, pimenta leaf, pipsissewa leaves, pomegranate, prickly ash bark, quince seed, rose (absolute, attar, buds, flowers, fruit, hip, leaf), rose geranium, rosemary, safron, sage, St. John's bread, savory, schinus molle (Schinus molle L), sloe berriers, spearmint, spike lavender, tamarind, tangerine, tarragon, tea (Thea sinensis L.), thyme, tuberose, turmeric, vanilla, violet (flowers, leaves), wild cherry bark, ylang-ylang and zedoary bark.
Suitable synthetic flavoring substances and adjuvants are listed in the Code of Federal Regulations (C.F.R.) Title 21 of the United States Food and Drug Administration, Department of Health and Human Services, Part 180.60, which is hereby incorporated by reference. These GRAS materials may be present in the compositions in amounts of up to about 1% by weight, preferably in amounts of 0.01 and 0.5% by weight.
Suitable synthetic flavoring substances and adjuvants that are generally recognized as safe for their intended use, include acetaldehyde (ethanal), acetoin (acetyl methylcarbinol), anethole (parapropenyl anisole), benzaldehyde (benzoic aldehyde), n-Butyric acid (butanoic acid), d- or 1-carvone (carvol), cinnamaldehyde (cinnamic aldehyde), citral (2,6-dimethyloctadien-2,6-al-8, gera-nial, neral), decanal (N-decylaldehyde, capraldehyde, capric aldehyde, caprinaldehyde, aldehyde C-10), ethyl acetate, ethyl butyrate, 3-Methyl-3-phenyl glycidic acid ethyl ester (ethyl-methyl-phenyl-glycidate, so-called strawberry aldehyde, C-16 aldehyde), ethyl vanillin, geraniol (3,7-dimethyl-2,6 and 3,6-octadien-1-ol), geranyl acetate (geraniol acetate), limonene (d-, 1-, and d1-), linalool (linalol, 3,7-dimethyl-1,6-octadien-3-ol), linalyl acetate (bergamol), methyl anthranilate (methyl-2-aminobenzoate), piperonal (3,4-methylenedioxy-benzaldehyde, heliotropin) and vanillin.
Suitable GRAS substances that may be present in the inventive compositions that have been identified as possibly migrating to food from cotton, cotton textiles, paper and paperboard materials used in dry food packaging materials are listed in the Code of Federal Regulations (C.F.R.) Title 21 of the United States Food and Drug Administration, Department of Health and Human Services, Parts 180.70 and 180.90, which are hereby incorporated by reference. The GRAS materials may be present in the compositions either by addition or incidentally owing to migration from the substrates to the compositions employed in the invention, or present owing to both mechanisms.
Suitable GRAS materials that are suitable for use in the invention, identified as originating from either cotton or cotton textile materials used as substrates in the invention, include beef tallow, carboxymethylcellulose, coconut oil (refined), cornstarch, gelatin, lard, lard oil, oleic acid, peanut oil, potato starch, sodium acetate, sodium chloride, sodium silicate, sodium tripolyphosphate, soybean oil (hydrogenated), talc, tallow (hydrogenated), tallow flakes, tapioca starch, tetrasodium pyrophosphate, wheat starch and zinc chloride.
Suitable GRAS materials that are suitable for use in the invention, identified as originating from either paper or paperboard stock materials used as substrates in the invention, include alum (double sulfate of aluminum and ammonium potassium, or sodium), aluminum hydroxide, aluminum oleate, aluminum palmitate, casein, cellulose acetate, cornstarch, diatomaceous earth filler, ethyl cellulose, ethyl vanillin, glycerin, oleic acid, potassium sorbate, silicon dioxides, sodium aluminate, sodium chloride, sodium hexametaphosphate, sodium hydrosulfite, sodium phospho-aluminate, sodium silicate, sodium sorbate, sodium tripolyphosphate, sorbitol, soy protein (isolated), starch (acid modified, pregelatinized and unmodified), talc, vanillin, zinc hydrosulfite and zinc sulfate.
Fragrance
Compositions of the present invention may comprise from about 0.001% to about 5% by weight of the fragrance oil. Compositions of the present invention may comprise from about 0.002% to about 2.5% by weight of the fragrance oil. Compositions of the present invention may comprise from about 0.01% to about 1.0% by weight of the fragrance oil.
As used herein the term “fragrance oil” relates to the mixture of perfume raw materials that are used to impart an overall pleasant odor profile to a composition. As used herein the term “perfume raw material” relates to any chemical compound which is odiferous when in an un-entrapped state, for example in the case of pro-perfumes, the perfume component is considered, for the purposes of this invention, to be a perfume raw material, and the pro-chemistry anchor is considered to be the entrapment material. In addition “perfume raw materials” are defined by materials with a ClogP value preferably greater than about 0.1, more preferably greater than about 0.5, even more preferably greater than about 1.0. As used herein the term “ClogP” means the logarithm to base 10 of the octanol/water partition coefficient. This can be readily calculated from a program called “CLOGP” which is available from Daylight Chemical Information Systems Inc., Irvine Calif., U.S.A. Octanol/water partition coefficients are described in more detail in U.S. Pat. No. 5,578,563.
Water
When the composition is an aqueous composition, water can be, along with the solvent, a predominant ingredient. The water should be present at a level of less than 99.9%, more preferably less than about 99%, and most preferably, less than about 98%. Deionized water is preferred. Where the cleaning composition is concentrated, the water may be present in the composition at a concentration of less than about 85 wt. %.
Cleaning Substrate
The cleaning composition may be part of a cleaning substrate. A wide variety of materials can be used as the cleaning substrate. The substrate should have sufficient wet strength, abrasivity, loft and porosity. Examples of suitable substrates include, nonwoven substrates, wovens substrates, hydroentangled substrates, foams and sponges. Any of these substrates may be water-insoluble, water-dispersible, or water-soluble.
In one embodiment, the cleaning pad of the present invention comprises a nonwoven substrate or web. The substrate is composed of nonwoven fibers or paper. The term nonwoven is to be defined according to the commonly known definition provided by the “Nonwoven Fabrics Handbook” published by the Association of the Nonwoven Fabric Industry. A paper substrate is defined by EDANA (note 1 of ISO 9092-EN 29092) as a substrate comprising more than 50% by mass of its fibrous content is made up of fibers (excluding chemically digested vegetable fibers) with a length to diameter ratio of greater than 300, and more preferably also has density of less than 0.040 g/cm3. The definitions of both nonwoven and paper substrates do not include woven fabric or cloth or sponge. The substrate can be partially or fully permeable to water. The substrate can be flexible and the substrate can be resilient, meaning that once applied external pressure has been removed the substrate regains its original shape.
Methods of making nonwovens are well known in the art. Generally, these nonwovens can be made by air-laying, water-laying, melt blowing, coforming, spun bonding, or carding processes in which the fibers or filaments are first cut to desired lengths from long strands, passed into a water or air stream, and then deposited onto a screen through which the fiber-laden air or water is passed. The air-laying process is described in U.S. Pat. App. 2003/0036741 to Abba et al. and U.S. Pat. App. 2003/0118825 to Melius et al. The resulting layer, regardless of its method of production or composition, is then subjected to at least one of several types of bonding operations to anchor the individual fibers together to form a self-sustaining substrate. In the present invention the nonwoven substrate can be prepared by a variety of processes including, but not limited to, air-entanglement, hydroentanglement, thermal bonding, and combinations of these processes.
Additionally, the first layer and the second layer, as well as additional layers, when present, can be bonded to one another in order to maintain the integrity of the article. The layers can be heat spot bonded together or using heat generated by ultrasonic sound waves. The bonding may be arranged such that geometric shapes and patterns, e.g. diamonds, circles, squares, etc. are created on the exterior surfaces of the layers and the resulting article.
The cleaning substrates can be provided dry, pre-moistened, or impregnated with cleaning composition, but dry-to-the-touch. In one aspect, dry cleaning substrates can be provided with dry or substantially dry cleaning or disinfecting agents coated on or in the multicomponent multilobal fiber layer. In addition, the cleaning substrates can be provided in a pre-moistened and/or saturated condition. The wet cleaning substrates can be maintained over time in a sealable container such as, for example, within a bucket with an attachable lid, sealable plastic pouches or bags, canisters, jars, tubs and so forth. Desirably the wet, stacked cleaning substrates are maintained in a resealable container. The use of a resealable container is particularly desirable when using volatile liquid compositions since substantial amounts of liquid can evaporate while using the first substrates thereby leaving the remaining substrates with little or no liquid. Exemplary resealable containers and dispensers include, but are not limited to, those described in U.S. Pat. No. 4,171,047 to Doyle et al., U.S. Pat. No. 4,353,480 to McFadyen, U.S. Pat. No. 4,778,048 to Kaspar et al., U.S. Pat. No. 4,741,944 to Jackson et al., U.S. Pat. No. 5,595,786 to McBride et al.; the entire contents of each of the aforesaid references are incorporated herein by reference. The cleaning substrates can be incorporated or oriented in the container as desired and/or folded as desired in order to improve ease of use or removal as is known in the art. The cleaning substrates of the present invention can be provided in a kit form, wherein a plurality of cleaning substrates and a cleaning tool are provided in a single package.
The substrate can include both natural and synthetic fibers. The substrate can also include water-soluble fibers or water-dispersible fibers, from polymers described herein. The substrate can be composed of suitable unmodified and/or modified naturally occurring fibers including cotton, Esparto grass, bagasse, hemp, flax, silk, wool, wood pulp, chemically modified wood pulp, jute, ethyl cellulose, and/or cellulose acetate. Various pulp fibers can be utilized including, but not limited to, thermomechanical pulp fibers, chemi-thermomechanical pulp fibers, chemi-mechanical pulp fibers, refiner mechanical pulp fibers, stone groundwood pulp fibers, peroxide mechanical pulp fibers and so forth.
Suitable synthetic fibers can comprise fibers of one, or more, of polyvinyl chloride, polyvinyl fluoride, polytetrafluoroethylene, polyvinylidene chloride, polyacrylics such as ORLON®, polyvinyl acetate, Rayon®, polyethylvinyl acetate, non-soluble or soluble polyvinyl alcohol, polyolefins such as polyethylene (e.g., PULPEX®) and polypropylene, polyamides such as nylon, polyesters such as DACRON® or KODEL®, polyurethanes, polystyrenes, and the like, including fibers comprising polymers containing more than one monomer.
The cleaning substrate of this invention may be a multilayer laminate and may be formed by a number of different techniques including but not limited to using adhesive, needle punching, ultrasonic bonding, thermal calendering and through-air bonding. Such a multilayer laminate may be an embodiment wherein some of the layers are spunbond and some meltblown such as a spunbond/meltblown/spunbond (SMS) laminate as disclosed in U.S. Pat. No. 4,041,203 to Brock et al. and U.S. Pat. No. 5,169,706 to Collier, et al., each hereby incorporated by reference. The SMS laminate may be made by sequentially depositing onto a moving conveyor belt or forming wire first a spunbond web layer, then a meltblown web layer and last another spunbond layer and then bonding the laminate in a manner described above. Alternatively, the three web layers may be made individually, collected in rolls and combined in a separate bonding step.
The substrate may also contain superabsorbent materials. A wide variety of high absorbency materials (also known as superabsorbent materials) are known to those skilled in the art. See, for example, U.S. Pat. No. 4,076,663 issued Feb. 28, 1978 to Masuda et al, U.S. Pat. No. 4,286,082 issued Aug. 25, 1981 to Tsubakimoto et al., U.S. Pat. No. 4,062,817 issued Dec. 13, 1977 to Westerman, and U.S. Pat. No. 4,340,706 issued Jul. 20, 1982 to Obayashi et al. The absorbent capacity of such high-absorbency materials is generally many times greater than the absorbent capacity of fibrous materials. For example, a fibrous matrix of wood pulp fluff can absorb about 7-9 grams of a liquid, (such as 0.9 weight percent saline) per gram of wood pulp fluff, while the high-absorbency materials can absorb at least about 15, preferably at least about 20, and often at least about 25 grams of liquid, such as 0.9 weight percent saline, per gram of the high-absorbency material. U.S. Pat. No. 5,601,542, issued to Melius et al., discloses an absorbent article in which superabsorbent material is contained in layers of discrete pouches. Alternately, the superabsorbent material may be within one layer or dispersed throughout the substrate.
Cleaning Implement
In an embodiment of the invention, the cleaning composition may be used with a cleaning implement. In an embodiment of the invention, the cleaning implement comprises the tool assembly disclosed in Co-pending application Ser. No. 10/678,033, entitled “Cleaning Tool with Gripping Assembly for a Disposable Scrubbing Head”, filed Sept. 30, 2003. In another embodiment of the invention, the cleaning implement comprises the tool assembly disclosed in Co-pending application Ser. No. 10/602,478, entitled “Cleaning Tool with Gripping Assembly for a Disposable Scrubbing Head”, filed Jun. 23, 2003. In another embodiment of the invention, the cleaning implement comprises the tool assembly disclosed in Co-pending application Ser. No. 10/766,179, entitled “Interchangeable Tool Heads”, filed Jan. 27, 2004. In another embodiment of the invention, the cleaning implement comprises the tool assembly disclosed in Co-pending application Ser. No. 10/817,606, entitled “Ergonomic Cleaning Pad”, filed Apr. 1, 2004. In another embodiment of the invention, the cleaning implement comprises the tool assembly disclosed in Co-pending application Ser. No. 10/850,213, entitled “Locking, Segmented Cleaning Implement Handle”, filed May 19, 2004.
In another embodiment of the invention, the cleaning implement comprises an elongated shaft having a handle portion on one end thereof. The tool assembly may further include a gripping mechanism that is mounted to the shaft to engage the removable cleaning pad. Examples of suitable cleaning implements are found in US2003/0070246 to Cavalheiro; U.S. Pat. No. 4,455,705 to Graham; U.S. Pat. No. 5,003,659 to Paepke; U.S. Pat. No. 6,485,212 to Bomgaars et al.; U.S. Pat. No. 6,290,781 to Brouillet, Jr.; U.S. Pat. No. 5,862,565 to Lundstedt; U.S. Pat. No. 5,419,015 to Garcia; U.S. Pat. No. 5,140,717 to Castagliola; U.S. Pat. No. 6,611,986 to Seals; US2002/0007527 to Hart; and U.S. Pat. No. 6,094,771 to Egolf et al. The cleaning implement may have a hook, hole, magnetic means, canister or other means to allow the cleaning implement to be conveniently stored when not in use.
Compositions were evaluated for their cleaning performance, foaming characteristics, filming and streaking tendency and residue formation when used on high gloss black enamel tiles. Compositions in the following tables below are shown with all ingredients given in % active by weight, the balance being deionized water present to 100 wt %.
Residue and Foaming Activity
Compositions shown in Table III were tested to evaluate the amount of visual residue remaining on a high gloss black enamel tile to which a small amount of cooking grease was applied. For test purposes, a set of uniformly treated tiles were prepared and coated with a thin uniform film of bacon grease. Cleaning was performed by applying a small amount of the cleaning composition to a standard kitchen sponge and wiping the entire surface of the tile uniformly a set number of times, followed by reversing the sponge and wiping again the same number of times with the clean side, and allowing the tile to dry without further rinsing or wiping. Foaming activity was also noted for some example embodiments, evaluated by looking at the amount of foam generated during the wiping motion of the sponge during tile cleaning. The high gloss tile exhibits a high shine and contrast providing a convenient means to visually determine the presence of any significant residue from either the product, remaining soil, or the overall combined cleaning residue remaining on the surface following treatment. A clean, untreated tile is usually positioned adjacent to the test tile to aid evaluation and provide a comparison for assigning visual ratings. Inventive embodiments corresponding to Examples 1-6 show good foaming and low residue characteristics. Some foaming is a desirable attribute, as the perception of foam relates to perceived cleaning ability, particularly amongst users of cleaning products, although foaming itself is not strictly necessary for acceptable cleaning performance. Foaming activity generally increases with higher surfactant levels. In Table III, comparative Examples A-E, in which the level of food safe nonionic in the compositions is present above about 0.5% by weight, exhibit unacceptable residue levels compared to the inventive compositions.
Filming and Streaking
The compositions of the invention were tested for their filming and streaking characteristics by visually evaluating the amount of residual cleaner remaining on a four by four inch black ceramic tile. First, 0.6 g of solution was placed on the tile, and the tile was wiped across four times with a paper towel. The tile was then evaluated visually for filming and streaking on a scale indicated in Table III, in comparison to a clean, unsoiled tile. Visually, a rating of either N (no visible filming & streaking) or L (low, barely detectable filming & streaking) corresponds to an acceptable performance by a cleaning product, higher ratings being unacceptable in that they correspond to readily observable residue that denotes poor cleaning performance. The inventive embodiments of the present invention containing no more than about 0.5% weight actives of the food safe nonionic surfactants exhibit acceptable foaming, cleaning and filming & streaking characteristics.
aBIO-SOFT ® LAS 40S, a sodium (C10-16) benzene sulfonate obtained from Stepan Chemical Co.
bBrij ® series available from Uniquema.
cDetermined using visible appearance evaluated on scale.
dScale: 0 = No Foam, 5 = Moderate Foam, 10 = High Foam
eScale: N = No visible grease residue (equivalent to clean tile), L = Low, barely detectable residue (acceptable), M = Moderate residue (unacceptable), H = High Residue.
fScale: N = No or L = Low, barely detectable filming/streaking, M = Moderate filming/streaking (unacceptable), H = High filming/streaking.
Additional embodiments of cleaning compositions according to the present invention are given in Table IV below, corresponding to Examples 7-15. Additional optional ingredients are illustrated that may be formulated into the inventive compositions to provide additional performance benefits and aesthetic properties.
aDowanol PnB ® available from Dow Chemical.
bDowanol DPnB ® available from Dow Chemical.
cTween ® 20 available from Uniquema.
dAll available from ICI Surfactants.
eAll available from the BASF Corporation.
fAn alkyl C-18 Steareth-25 available from Amerchol Corp.
gSodium dodecyl diphenyloxide disulfonate, Dowfax 2A1 ® from Dow Chemical.
hCetyl betaine from Stepan.
iBarquat 4250Z ® from Lonza Chemical.
jLemon Scented Tea Tree Oil from Down Under Enterprises
kClay, LAPONITE ® RDS from Southern Clay Products.
lSodium bicarbonate.
Additional examples of suitable embodiments for cleaning and disinfecting food contact surfaces, and which may also be incorporated onto a cleaning substrate to treat food preparation surfaces before and after food contact are given in Table V below, corresponding to Examples 16-24.
aTween 20 ® available from Uniquema.
bPEG-12 Laurate available from Spectrum Chemicals.
cPEG-8 Oleate available from Spectrum Chemicals.
dAvailable from JLK Industries.
eNonionic C12-18 aliphatic alcohol ethylene oxide/propylene oxide copolymer from BASF Corporation.
fBarquat 4250Z ® from Lonza Chemical.
gLemon Scented Tea Tree Oil from Down Under Enterprises.
hSodium bicarbonate.
Cleaning Performance
In addition to leaving a low self residue on surfaces treated with the inventive compositions, superior cleaning performance on soils normally associated with food use and preparation areas is a desirable attribute of a cleaning composition. Typical soils include food residue, food oils, cooking oils, grease, and the like that are commonly present on food preparation areas, include stovetops and countertops. These soils are usually removed using a heavy duty surface cleaner, which require rinsing after use, particularly for food preparation areas, in order to remove excess cleaner from the surface. When used on highly glossy surfaces, such as glass and glazed tiles, such cleaners generally exhibit high filming and streaking, requiring additional wiping steps or wiping with a paper towel to leave surfaces with an acceptable appearance free of visual residue and without filming & streaking. Lighter duty cleaners, while providing little or no filming & streaking are generally less effective in removing heavy greasy soils.
Surprisingly, it has been found that selected food safe nonionic surfactants provide significantly better performance in overall cleaning efficacy when employed at low levels in the acidic cleaning formulas of the present invention. It has been found that at higher active levels, all else being equal, overall cleaning efficacy exhibited by representative compositions actually decreases. Without being bound by theory, it is believed that the preferred food safe nonionic surfactants effect cleaning of greasy soils by an emulsification process rather than by solubilization, so that beyond a critical level, found to be around 0.5% by weight, any increased soil removal benefit owing to increased levels of the nonionic surfactant is dramatically countered by an increased self residue of the nonionic surfactant itself that results in a significant decrease in overall cleaning efficacy.
Accordingly, by means of a visual assessment of total residue, owing to both non-removed soil and self-residue contributed by the cleaning compositions themselves, it has been discovered that selected food safe nonionic surfactants may be employed in the inventive acidic cleaning compositions exhibiting acceptable cleaning and appearance properties provided that their levels in the compositions do not exceed around 0.5% by weight on an active basis.
In evaluating cleaning performance, either the cleaning efficacy, being the ability of a cleaner to remove a soil from the test tile surface, or the total residue, being the amount of soil and cleaner remaining on the test tile following a cleaning operation can be evaluated visibly by eye and/or determined instrumentally. For improved consistency and reproducibility, instrumental means are generally preferred. Instrumental values may then be correlated to an acceptable visual appearance following cleaning of a soiled surface that a user of the cleaning product will experience, so that an “acceptable” cleaning performance benchmark can be established. This benchmark then corresponds to a particular instrumental value, so that measured performance can be evaluated to determine whether the tested composition performance is acceptable or unacceptable, or assigned consistent rankings.
Performance characteristics are determined instrumentally, following the soiling and cleaning protocol described above using black tiles soiled with bacon grease. Image analysis provides a reading of between 25 units corresponding to a clean and unsoiled tile, and a reading of 255 units corresponding to a soiled and uncleaned tile, for determination of relative product residue (product self-residue) and grease cleaning residue, respectively. The overall cleaning residue value is determined in a similar manner, but normalized to correspond to a scale from 0 to 100 units, a value of “0” being clean and a value of “100” being soiled. A value of about 40 units for the overall cleaning residue value has been found to correspond to an acceptable visual threshold value: above a value of 40, overall cleaning residue remaining on treated tiles is distinctly noticeable to the eye and therefore visually unacceptable; values at and below 40 represent visually acceptable overall cleaning performance.
Various embodiment compositions corresponding to the present invention are presented in Table VI as Examples 25-31, together with measurements of the three characteristic performance attributes. Inventive compositions all exhibit low overall cleaning residue values, while still providing excellent cleaning performance on greasy soil.
A comparison test composition, containing 2% by weight lactic acid and 1% by weight ethanol, but with no surfactant present, exhibited a product residue value of around 30.8, attributable to the baseline contribution of the lactic acid to product self-residue. Addition of up to about 0.5% by weight as active of a selected food safe nonionic surfactant according to the present invention, results in only a slight increase in product residue, demonstrated by the inventive Examples 28 and 31 having 0.3, and 0.5% by weight of the indicated food safe nonionic surfactant present. When compositions containing the same nonionic surfactants at levels above 0.5% by weight are tested, corresponding to comparative Examples F, G and H, product residue increases significantly while actual cleaning performance decreases. This results in poor overall cleaning efficacy compared to the inventive compositions.
Accordingly, in the present inventive acidic cleaning compositions, low levels of the food safe nonionic surfactants may be employed, provided that the total weight % level of the nonionic does not exceed greater than 0.5% on an active basis in cleaning compositions containing lactic acid.
aA linear alkylbenzene sulfonic acid available from Stepan Chemical Co.
bA visual threshold occurs at an overall cleaning residue value of around 40.0 units, cleaned tiles receiving a passing score at or below this value, and a failing score at values about this, when overall cleaning residue becomes visibly unacceptable.
Wetting Characteristics
The ability of the inventive compositions to wet and spread across a surface during cleaning and treatment may be improved by use of an additional surfactant. Preferred for use on food contact and food preparation areas are those anionic surfactants approved for food usage applications. Addition of a small amount with respect to the food safe nonionic is sufficient, so that levels wherein the ratio of the additional anionic surfactant to the nonionic surfactant is less than about 0.5. Wetting ability can be readily determined by measuring the equilibrium contact angle formed by a drop of a liquid cleaner placed onto the surface, and measuring the receding angle of the droplet at the interface of the cleaner and surface of a selected substrate, such as glass or plastic. Drop shape analysis, whereby a magnified image of the droplet on the surface is captured and fitted provides the most accurate measurement of equilibrium contact angle. Table VII presents contact angles for some selected embodiments of the present invention, Examples 32-36, compared to a control Example I free of any food safe nonionic surfactant.
Results show that addition of a selected anionic surfactant provides significantly improved wetting, owing to a large decrease in equilibrium contact angle, on both glass and plastic (PVC) substrates, for inventive compositions containing additional anionic surfactant. In the absence of the food safe nonionic surfactant, Example I, poor wetting characteristics are observed as well as poor cleaning performance.
aSynperonic ® PE-L62, a polyoxyethylene-polyoxypropylene block copolymer, having a MW of about 2500, available from Uniquema.
bEquilibrium contact angle on clean glass or polyvinylchloride (PVC) substrate.
cWetting acceptable (Pass) if both Glass <10° and Plastic <50°.
Without departing from the spirit and scope of this invention, one of ordinary skill can make various changes and modifications to the invention to adapt it to various usages and conditions. As such, these changes and modifications are properly, equitably, and intended to be, within the full range of equivalence of the following claims.
The present application is a continuation-in-part of Co-pending application Ser. No. 11/168,106, filed Jun. 28, 2005, which is hereby incorporated by reference.
| Number | Date | Country | |
|---|---|---|---|
| Parent | 11168106 | Jun 2005 | US |
| Child | 11424667 | Jun 2006 | US |
