AU729225B2

AU729225B2 - Chemical linker compositions

Info

Publication number: AU729225B2
Application number: AU55989/98A
Authority: AU
Inventors: Guy Broze; Hoai-Chau Cao; Thomas Connors; Michele Davister; Patrick Durbut; John Labows; Anne-Marie Misselyn
Original assignee: Colgate Palmolive Co
Current assignee: Colgate Palmolive Co
Priority date: 1996-12-12
Filing date: 1997-12-10
Publication date: 2001-01-25
Anticipated expiration: 2017-12-10
Also published as: NZ336086A; HUP0000701A3; CA2274567A1; EP0951217A1; IL130213A0; PL333931A1; WO1998025455A1; IL130213A; HUP0000701A2; AU5598998A; BR9713911A

Description

WO 98/25455 PCT/US97/22672 CHEMICAL LINKER COMPOSITIONS Field of the Invention The present invention relates to a chemical linkers that can be added to an organic chemical such as a perfume, insect repellent, antibacterial agent, and/or an allergen agent in order to reduce the rate of vaporization of the chemical additive from the surface to which it has been applied.

The present invention also relates to a method for improving the retention time of an additive coated on a surface which comprises adding chemical linkers to an organic chemical such as a perfume, insect repellent, antibacterial agent, and/or an allergen agent in order to reduce the rate of vaporization of the organic chemical from the surface to which it has been applied.

Background of the Invention A major problem is how long a chemical additive such as a perfume, fabric softener, sunscreen agent, insect repellent, antibacterial agent and/or allergen agent will be effective on a surface on which the chemical has been deposited. For example, if the lasting effect of a perfume deposited on the human skin could be increased the necessity for repeat application of the perfume would be reduced. Alternatively, if the concentration of the perfume in a solution could be reduced while maintaining its effectiveness substantial cost savings could be achieved. The present invention relates to chemical linkers which can be added to the organic chemical whereby the chemical linker by chemical association links the organic chemical to the surface on which the organic chemical has been deposited thereby decreasing the rate of vaporization of the organic chemical. The requirement of the chemical linker is that when the chemical linker is added to a organic chemical that an exothermic interaction occurs between the chemical linker and the organic chemical which causes a reduction in the active vapor pressure of the organic chemical.

The instant invention further relates to the use of the chemical linkers and the organic chemical in a surfactant based cleaning compositions.

WO 98/25455 PCT/US97/22672 For example, Methylneodecanamide (MNDA) is an insect repellent agent which can be added to a hard surface cleaning composition. This is necessary to deposit micrograms of MNDA per cm2 to have one day efficacy. It is more than 500 molecular layers. To deliver this amount requires almost neat usage and is not compatible with consumers habits and practice. Unfortunately, one may not increase the MNDA concentration. It is desirable to increase the repellency duration without increase MNDA quantity.

On the other hand, it would be desirable to have more formulation flexibility with high oil uptake capacity perfumes. The increase of the substantivity of these perfumes ingredients would make possible to either increase performance of the perfume, or deliver the same cleaning and olfacting results with less perfume. This invention teaches that chemical linkers are a way to deliver more efficiently actives such as MNDA or perfumes to a surface to which it has been applied.

Summary of the Invention The present invention relates to chemical compositions which comprise by weight a complex of: an organic chemical having a chemical group with a dipole moment of at least 1.5 selected from the group consisting of a chemical compound containing an amide linkage such as an insect repellents, antibacterial agents containing a carbonhalogen bond such as triclosan, allergen agents, fabric softener or sunscreen agent containing an ester group or enzymes containing acid groups and a chemical compound containing an aldehyde group or alcohol group such as those type of compounds present in perfumes and mixtures thereof; and a chemical linker which undergoes an exothermic reaction with the organic chemical, wherein the chemical linker can be a polyvinyl pyrrolidone polymer, an ethoxylated polyhydric alcohol, carboxylic acid having 4 to 6 carbon atoms and a polyethylene glycol having a molecular weight of 600 to 10,000, preferably 1,000 to 8,000 wherein the mole ratio of the organic chemical to the chemical linker is 4:1 to 1:4.

WO 98/25455 PCT/US97/22672 3 The present invention also relates to a process for improving the retention time of an organic chemical on a surface and to chemical compositions which comprise applying to a substrate a complex of by weight: an organic chemical having a chemical group with a dipole moment of at least 1.5 selected from the group consisting of a chemical compound containing an amide linkage such as an insect repellents, antibacterial agents containing a carbonhalogen bond such as triclosan, allergen agents, fabric softener or sunscreen agent containing an ester group or enzymes containing acid groups and a chemical compound containing an aldehyde group or alcohol group such as those type of compounds present in perfumes and mixtures thereof; and a chemical linker composition which undergoes an exothermic reaction with the organic chemical, wherein the chemical linker composition which is an ethoxylated glycerol type compound and, optionally, a compound selected from the group consisting of a polyvinyl pyrrolidone polymer and a carboxylic acid having 4 to 6 carbon atoms and a polyethylene glycol having a molecular weight of 600 to 10,000, preferably 1,000 to 8,000 wherein the ratio of chemical additive to chemical linker composition is 4:1 to 1:4.

The instant compositions excluded the use of ethoxylated nonionic surfactants formed for the condensation product of primary or secondary alkanols and ethylene oxide or propylene oxides because the use of these ethoxylated nonionic would cause a weakening of the chemical association between the chemical linker and the organic chemical and/or anionic surfactant.

The complex of the organic chemical and chemical linker can be applied neat to the surface which is being treated, wherein the chemical linker functions to bind the organic chemical to the treated surface. Alternatively, the complex of the organic chemical and the chemical linker can be dissolved at a concentration of 0.1 wt. to 99.9 wt. in a solvent which dissolves both the chemical linker and organic chemical.

Alternatively, the complex of the chemical linker and the organic chemical can be incorporated into a cleaning composition such as a body cleansing formulation, a fabric 4 softening composition, a body lotion, a shampoo, an oral cleaning composition, a light duty liquid composition, an all purpose or microemulsion hard surface cleaning composition and a fabric care cleaning composition.

The instant invention also relates to complexes of a chemical linker, an organic chemical having a dipole moment of at least 1.5 Debyes and an anionic sulfonate, carboxylate or sulfate containing surfactant which is mixed with either of a zwitterionic surfactant, an amine oxide or an alkylene carbonate and mixtures thereof.

Detailed Description of the Invention The present invention relates to a complex of: 10 an organic chemical having a chemical group having a dipole moment of *o at least 1.5 Debyes, more preferably at least 1.6 Debyes; and a chemical linker selected from the group consisting of carboxylic acids having 4 to 6 carbon atoms, polyethylene glycols having a molecular weight of 600 to 10,000, an ethoxylated polyhydric alcohol and a polyvinyl pyrrolidone, polymer wherein 15 the mole ratio of the organic chemical to chemical linker is 4:1 to 1:4. The present invention also relates to a solution of 0.25 wt. to 99.75 wt. of the complex of the organic chemical and chemical linker in a solvent which can solubilize the complex of *the organic chemical and chemical linker.

The present invention further relates to a composition which comprises: 0.1 to 10 wt. of an organic chemical having a chemical group with dipole moment of at least 1.5 Debyes, more preferably at least 1.6 Debyes; ito 30 Wt. of at least one anionic surfactant having a carboxylate, sulfate or sulfonate group: 0.1 to 20 wt. of a chemical linker compound selected from the group consisting of an ethoxylated polyhydric alcohol, a polyvinyl pyrrolidone polymer, a polyethylene glycol having a molecular weight of 600 to 10,000 and a carboxylic acid having 4 to 6 carbon atoms and mixtures thereof, wherein the chemical linker complexes both with the anionic surfactant and the additive; 1 to 15 wt of a second surfactant selected from the group consisting of an amine oxTde-urfactant, a zwitterionic surfactant and an alkylene carbonate surfactant and mixtures thereof, wherein the anionic surfactant complexes with the amine oxide, zwitterionic surfactant or alkylene carbonate; 0 to 20 wt. of a cosurfactant; and 50 to 99.8 wt. of water.

The present invention also relates to a complex comprising: an organic chemical having a chemical group having a dipole moment of at least 1.5, more preferably at least 1.6; and a chemical linker composition which comprises an ethoxylated glycrol type compound and, optionally a compound selected from the group consisting of carboxylic acids having 4 to 6 carbon atoms, polyethylene glycols having a molecular weight of 600 to 10,000, and a polyvinyl pyrrolidone, wherein the mole ratio of chemical additive to chemical linker composition is 4:1 to 1:4. The present invention also relates to a solution of 0.25 wt. to 99.75 wt. of the complex of the organic chemical and chemical linker composition in a solvent which can solubilize the complex of the organic chemical and chemical linker composition.

The present invention further relates to a composition which comprises: 0.1 to 10 wt. of an organic chemical having a chemical group with 20 dipole moment of at least 1.5, more preferably at least 1.6; 1 to 30 wf. of at least one anionic surfactant having a carboxylate, sulfate or sulfonate group; 0.1 to 30 wt. of a chemical linker composition which is an ethoxylated glycerol type compound and, optionally, a compound selected from the group consisting of a polyvinyl pyrrolidone polymer, a polyethylene glycol having a molecular weight of 600 to 10,000 and a carboxylic acid having 4 to 6 carbon atoms and mixtures thereof, wherein the chemical linker composition complexes both with the anionic Ssurfactant and the organic chemical; 1 to 15 wt'. of an amine oxide surfactant, a zwitterionic surfactant and an alkylene carbonate surfactant and mixtures thereof, wherein the anionic surfactant complexes with the amine oxide, zwitterionic surfactant or alkylene carbonate; and 15 to 99.8 wt. of water.

The compositions of the instant invention can be in the form of a solution, a microemulsion, a gel or a paste.

The complex of the organic chemical and chemical linker can be made by simple mixing with or without heat, if the chemical linker is a liquid. If the chemical linker is a solid, the chemical linker must be heat above its melting point and the organic chemical mixed into the melted chemical linker.

The organic chemicals used in the instant invention have chemical group having dipole moments of at least 1.5 Debyes, more preferably at least one 1.6 Debyes such as halogens affixed to a carbon atom, alcohol groups, aldehyde groups, ester groups, carboxylic acid groups, amine groups and amide groups. Typical chemical additives containing groups with high dipole moments are perfumes containing alcohol and aldehyde compounds, an insect repellent such as an N-lower alkyl neoalkanoamide wherein the alkyl group has 1 to 4 carbon atoms and the neodalkanoyl moiety has 7 to 14 carbon atoms, antibacterial agents such as triclosan, enzymes, proteins and allergen such as benzyl benzoate.

20 As used herein and in the appended claims one of the organic chemicals is a perfume which is used in its ordinary sense to refer to and include any non-water soluble fragrant substance or mixture of substances including natural obtained by extraction of flower, herb, blossom or plant), artificial 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 terpenes) such as from 0% to 80%, usually from 10% to 70% by weight. The Sessential oils themselves are volatile odoriferous compounds and also serve to ssolve the other components of the perfume. The analephotropic negatively charged anionic complex which is contained in the instant cleaning compositions such as a fabric cleaning composition, a light duty liquid composition, an all purpose or microemulsion composition, a body cleaning composition or a shampoo comprises a complex of: at least one anionic surfactant which is an alkali metal salt or an alkaline earth metal salt of a sulfonate or sulfate surfactant; and an amine oxide, zwitterionic surfactant or alkylene carbonate surfactant wherein the ratio of the anionic surfactant to the amine oxide surfactant, zwitterionic surfactant or alkylene carbonate surfactant is 7:1 to 0.2:1, more preferably 2:1 to 0.4:1.

The instant composition contains 3 to 40 wt. more preferably 5 to 20 wt. of the analephotropic negatively charged complex.

activ Suitable water-soluble non-soap, anionic surfactants include those surfaceactive or detergent compounds which contain an organic hydrophobic group containing o generally 8 to 26 carbon atoms and preferably 10 to 18 carbon atoms in their molecular structure and at least one water-solubilizing group selected from the group of sulfonate, sulfate and carboxylate so as to form a water-soluble detergent. Usually, the hydrophobic group will include or comprise a C8-C22 alkyl, alkyl or acyl group. Such surfactants are employed in the form of water-soluble salts and the salt-forming cation usually is selected from the group consisting of sodium, potassium, or magnesium, with 20' the sodium and magnesium cations again being preferred.

Examples of suitable sulfonated anionic surfactants are the well known higher alkyl mononuclear aromatic sulfonates such as the higher alkyl benzene sulfonates containing from 10 to 16 carbon atoms in the higher alkyl group in a straight or branched chain, C8-C15 alkyl toluene sulfonates and C8-C15 alkyl phenol sulfonates.

A preferred sulfonate is linear alkyl benzene sulfonate having a high content of 3- (or higher)'phenyl isomers and a correspondingly low content (well below 50%) of 2- (or lower) phenyl isomers, that is, wherein the benzene ring is preferably attached in c large part at the 3 or higher (for example, 4, 5, 6 or 7) position of the alkyl group and Z ^the content of the isomers in which the benzene ring is attached in the-2 or 1 position is WO 98/25455 PCT/US97/22672 correspondingly low. Particularly preferred materials are set forth in U.S. Patent 3,320,174.

Other suitable anionic surfactants are the olefin sulfonates, including long-chain alkene sulfonates, long-chain hydroxyalkane sulfonates or mixtures of alkene sulfonates and hydroxyalkane sulfonates. These olefin sulfonate detergents may be prepared in a known manner by the reaction of sulfur trioxide (SO 3 with long-chain olefins containing 8 to 25, preferably 12 to 21 carbon atoms and having the formula RCH=CHR1 where R is a higher alkyl group of 6 to 23 carbons and R1 is an alkyl group of 1 to 17 carbons or hydrogen to form a mixture of sultones and alkene sulfonic acids which is then treated to convert the sultones to sulfonates. Preferred olefin sulfonates contain from 14 to 16 carbon atoms in the R alkyl group and are obtained by sulfonating an a-olefin.

Other examples of suitable anionic sulfonate surfactants are the paraffin sulfonates containing 10 to 20, preferably 13 to 17, carbon atoms. Primary paraffin sulfonates are made by reacting long-chain alpha olefins and bisulfites and paraffin sulfonates having the sulfonate group distributed along the paraffin chain are shown in U.S. Patents Nos.. 2,503,280; 2,507,088; 3,260,744; 3,372,188; and German Patent 735,096.

Examples of satisfactory anionic sulfate surfactants are the C8-C18 alkyl sulfate salts and the ethoxylated C8-C18 alkyl sulfate salts and the ethoxylated C8-C1 8 alkyl ether sulfate salts having the formula R(OC2H4)n OSO3M wherein n is 1 to 12, preferably 1 to 5, and M is a metal cation selected from the group consisting of sodium, potassium, ammonium, magnesium and mono-, di- and triethanol ammonium ions.

The alkyl sulfates may be obtained by sulfating the alcohols obtained by reducing glycerides of coconut oil or tallow or mixtures thereof and neutralizing the resultant product.

On the other hand, the ethoxylated alkyl ether sulfates are obtained by sulfating the condensation product of ethylene oxide with a C8-C18 alkanol and neutralizing the resultant product. The alkyl sulfates may be obtained by sulfating the alcohols WO 98/25455 PCTIUS97/22672 9 obtained by reducing glycerides of coconut oil or tallow or mixtures thereof and neutralizing the resultant product. The ethoxylated alkyl ether sulfates differ from one another in the number of moles of ethylene oxide reacted with one mole of alkanol.

Preferred alkyl sulfates and preferred ethoxylated alkyl ether sulfates contain 10 to 16 carbon atoms in the alkyl group.

The ethoxylated C8-C1 2 alkylphenyl ether sulfates containing from 2 to 6 moles of ethylene oxide in the molecule also are suitable for use in the inventive compositions. These surfactants can be prepared by reacting an alkyl phenol with 2 to 6 moles of ethylene oxide and sulfating and neutralizing the resultant ethoxylated alkylphenol.

Other suitable anionic surfactants are the C9-C15 alkyl ether polyethenoxyl carboxylates having the structural formula R(OC2H4)nOX COOH wherein n is a number from 4 to 12, preferably 5 to 10 and X is selected from the group consisting of CH2, (C(O)RI and 0 wherein R1 is a C1-C3 alkylene group. Preferred compounds include C9-Cl 1 alkyl ether polyethenoxy C(0) CH2CH2COOH, C1i 3-C1 5 alkyl ether polyethenoxy (7-9) 0

-C

and C10-C12 alkyl ether polyethenoxy CH2COOH. These compounds may be prepared by considering ethylene oxide with appropriate alkanol and reacting this reaction product with chloracetic acid to make the ether carboxylic acids as shown in US Pat. No. 3,741,911 or with succinic anhydride or phthalic anhydride. Obviously, these anionic surfactants will be present either in acid form or salt form depending upon the pH of the final composition, with salt forming cation being the same as for the other anionic surfactants.

Of the foregoing non-soap anionic surfactants used in forming the analephotropic complex, the preferred surfactants are the sodium or magnesium salts of the C8-C18 alkyl sulfates such as magnesium lauryl sulfate and sodium lauryl sulfate and mixtures thereof.

Generally, the proportion of the nonsoap-anionic surfactant will be in the range of 1 to 30%, preferably from 1% to 15%, by weight of the cleaning composition.

The instant composition contains as part of the analephotropic negatively charged complex 3% to 30%, preferably 4% to 15% of an amine oxide, alkylene carbonate or zwitterionic surfactant.

The amine oxides used in forming the analephotropic complex are depicted by the formula R2

-N

R3 wherein Ri is a C10-C18 a linear or branched chain alkyl group, R2 is a C1-C16 linear alkyl group and R3 is a C1-C16 linear alkyl group.

The zwitterionic surfactant used in forming the analephotropic complex is a water soluble betaine having the general formula: R2 I R1-N -R4-X R3 wherein X- is selected from the group consisting of COO- and S03- and R1 is an alkyl group having 10 to 20 carbon atoms, preferably 12 to 16 carbon atoms, or the amido radical: 0 H II I R- N (CH2)-a- WO 98/25455 PCT/US97/22672 11 wherein R is an alkyl group having 9 to 19 carbon atoms and a is the integer 1 to 4: R2 and R3 are each alkyl groups having 1 to 3 carbons and preferably 1 carbon; R4 is an alkylene or hydroxyalkylene group having from 1 to 4 carbon atoms and, optionally, one hydroxyl group. Typical alkyldimethyl betaines include decyl dimethyl betaine or 2- (N-decyl-N, N-dimethyl-ammonia) acetate, coco dimethyl betaine or 2-(N-coco N, Ndimethylammonia) acetate, myristyl dimethyl betaine, palmityl dimethyl betaine, lauryl dimethyl betaine, cetyl dimethyl betaine, stearyl dimethyl betaine, etc. The amidobetaines similarly include cocoamidoethylbetaine, cocoamidopropyl betaine and the like. A preferred betaine is coco (C8-C18) amidopropyl dimethyl betaine. Three preferred betaine surfactants are Genagen CAB and Rewoteric AMB 13 and Golmschmidt Betaine L7.

The alkylene carbonate surfactant is depicted by the following formula: 0

II

C

0 0 wherein R is an alkyl group having 4 to 14 carbon atoms, more preferably 6 to carbon atoms.

The instant compositions contain 0.5 wt. to 10 wt. more preferably 1 wt. to 7.0 wt. of a chemical linker which can be a carboxylic acid having 4 to 6 carbon atoms, a Lewis base, neutral polymer which is soluble in water and has either a nitrogen or oxygen atom with a pair of free electrons such that the Lewis base, neutral polymer can electronically associate with the anionic surfactant and an active organic chemical having a dipole moment of at least 1.5 Debyes such as an enzyme, protein, allergen agent, a perfume or an antimicrobial agent such as triclosan or an insect repellent such as MNDA wherein the Lewis base, neutral polymer is deposit and anchors onto the surface of the surface being treated thereby holding the organic chemical in close proximity to the surface thereby ensuring that the properties being 12 parted by the organic chemical last longer. The chemical linker also links with the anionic surfactant to hold the anionic surfactant in close proximity to the surface being .cleaned.

The Lewis base, neutral polymers are selected from the group consisting of an ethoxylated polyhydric alcohol, a polyvinyl pyrrolidone polymer and a polyethylene glycol.

The instant compositions contain 0.1 to 20 wt. more preferably 0.5 to 15 wt.

of the chemical linker composition which comprises an ethoxylated glycerol type compound and/or, optionally, a carboxylic acid and/or a Lewis base. The concentration of the ethoxylated glycerol type composition in the instant compositions is 0.1 to 20 wt.

more preferably 0.5 to 15 wt. The concentration of the carboxylic acid and/or the Lewis base is 0 to 15 wt. more preferably 0.25 to 10 wt. The ethoxylated polyhydric alcohol is depicted by the following formula:

R'

2 CHO) -H

R'

CH

2 0(CH2CHO) -H 15 z wherein w equals one to four and x, y and z have a value between 0 and 60, more preferably 0 to 40, provided that equals 2 to 100, preferably 4 to 24 and most preferably 4 to 19, and wherein R' is either hydrogen atom or methyl group. A preferred ethoxylated polyhydric alcohol is glycerol 6EO.

The polyvinyl pyrrolidone polymer is depicted by the formula:

-CH-CH

2 1 'm CH2 0 I I CH2-CH2 in m is 20 to 350 more preferably 70 to 110.

13 The polyethylene glycol is depicted by the formula HO-(CH2-CH20G-rH wherein ii is 8 to 225, more preferably 10 to 100, wherein PEG1000 is preferred which is a polyethylene glycol having a molecular weight of 1000.

The ethoxylated polyhydric (glycerol) type compound is a nonesterified ethoxylated polyhydric alcohol, wherein the preferred polyhydric alcohol is glycerol, and the compound is: CH2-O-(CH2CH-O-)-B H-G-CH2CH-O-yB w Formula S* 2- CH2H-O-* Iz-B 15 and .CH2- -(CH2 H-0-)x-H wCH-G H2CH--)y Formula I (1I) CH2-G-(CH2 H-O -i-H wherein w equals one to four, most preferably one, and B is selected from the group consisting of hydrogen or a group represented by:

R

wherein R is selected from the group consisting of alkyl group having 6 to 22 carbon atoms, more preferably 11 to 15 carbon atoms and alkenyl groups having 6 to 22 S carbon atoms, more preferably 11 to 15 carbon atoms, wherein a hydrogenated tallow WO 98/25455 PCTIUS97/22672 14 alkyl chain or a coco alkyl chain is most preferred, wherein at least one of the B groups is represented by said /0 and R' is selected from the group consisting of hydrogen and methyl groups; x, y and z have a value between 0 and 60, more preferably 0 to 40, provided that equals 2 to 100, preferably 4 to 24 and most preferably 4 to 19, wherein in Formula the weight ratio of monoester diester triester is 40 to 90 5 to 35 1 to 20, more preferably 50 to 90 9 to 32 1 to 12, wherein the weight ratio of Formula to Formula (11) is a value between 3 to 0.02, preferably 3 to 0.1, most preferably 1.5 to 0.2, wherein it is most preferred that there is more of Formula (II) than Formula in the mixture that forms the compound.

The ethoxylated glycerol type compound used in the instant composition is manufactured by the Kao Corporation and sold under the trade name Levenol such as Levenol F-200 which has an average EO of 6 and a molar ratio of coco fatty acid to glycerol of 0.55 or Levenol V501/2 which has an average EO of 17 and a molar ratio of tallow fatty acid to glycerol of 1.0. It is preferred that the molar ratio of the fatty acid to glycerol is less than 1.7, more preferably less than 1.5 and most preferably less than The ethoxylated glycerol type compound has a molecular weight of 400 to 1600, and a pH (50 grams liter of water) of 5-7. The Levenol compounds are substantially non irritant to human skin and have a primary biodegradabillity higher than 90% as measured by the Wickbold method Bias-7d.

Two examples of the Levenol compounds are Levenol V-501/2 which has 17 ethoxylated groups and is derived from tallow fatty acid with a fatty acid to glycerol ratio of 1.0 and a molecular weight of 1465 and Levenol F-200 has 6 ethoxylated groups and is derived from coco fatty acid with a fatty acid to glycerol ratio of 0.55. Both Levenol F-200 and Levenol V-501/2 are composed of a mixture of Formula and Formula The Levenol compounds has ecoxicity values of algae growth inhibition 100 mg/liter; acute toxicity for Daphniae 100 mg/liter and acute fish toxicity 100 WO 98/25455 PCT1US97/22672 mg/liter. The Levenol compounds have a ready biodegradability higher than 60% which is the minimum required value according to OECD 301 B measurement to be acceptably biodegradable.

A cosurfactant can be optionally used in forming the cleaning compositions of the instant invention. Suitable cosurfactants over temperature ranges extending from 4°C to 43°C are: water-soluble C3-C4 alkanols, polypropylene glycol of the formula HO(CH3CHCH20)nH wherein n is a number from 2 to 18 and copolymers of ethylene oxide and propylene oxide and mono C1-C6 alkyl ethers and esters of ethylene glycol and propylene glycol having the structural formulas R(X)nOH and Ri (X)nOH wherein R is C1-C6 alkyl, R1 is C2-C4 acyl group, X is (OCH2CH2) or (OCH2 (CH3)CH) and n is a number from 1 to 4.

Representative members of the polypropylene glycol include dipropylene glycol and polypropylene glycol having a molecular weight of 200 to 1000, polypropylene glycol 400. Other satisfactory glycol ethers are ethylene glycol monobutyl ether (butyl cellosolve), diethylene glycol monobutyl ether (butyl carbitol), triethylene glycol monobutyl ether, mono, di, tri propylene glycol monobutyl ether, tetraethylene glycol monobutyl ether, mono, di, tripropylene glycol monomethyl ether, propylene glycol monomethyl ether, ethylene glycol monohexyl ether, diethylene glycol monohexyl ether, propylene glycol tertiary butyl ether, ethylene glycol monoethyl ether, ethylene glycol monomethyl ether, ethylene glycol monopropyl ether, ethylene glycol monopentyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monopropyl ether, diethylene glycol monopentyl ether, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, triethylene glycol monopropyl ether, triethylene glycol monopentyl ether, triethylene glycol monohexyl ether, mono, di, tripropylene glycol monoethyl ether, mono, di tripropylene glycol monopropyl ether, mono, di, tripropylene glycol monopentyl ether, mono, di, tripropylene glycol monohexyl ether, mono, di, tributylene glycol mono methyl ether, mono, di, tributylene glycol monoethyl ether, mono, di, tributylene glycol monopropyl ether, mono, di, tributylene glycol monobutyl ether, mono, di, tributylene glycol WO 98/25455 PCT/US97/22672 16 monopentyl ether and mono, di, tributylene glycol monohexyl ether, ethylene glycol monoacetate and dipropylene glycol propionate. Representative members of the aliphatic carboxylic acids include C3-C6 alkyl and alkenyl monobasic acids such as acrylic acid and propionic acid and dibasic acids such as glutaric acid and mixtures of glutaric acid with adipic acid and succinic acid, as well as mixtures of the foregoing acids.

While all of the aforementioned glycol ether compounds and acid compounds provide the described stability, the most preferred cosurfactant compounds of each type, on the basis of cost and cosmetic appearance (particularly odor), are diethylene glycol monobutyl ether and a mixture of adipic, glutaric and succinic acids, respectively.

The ratio of acids in the foregoing mixture is not particularly critical and can be modified to provide the desired odor. Generally, to maximize water solubility of the acid mixture glutaric acid, the most water-soluble of these three saturated aliphatic dibasic acids, will be used as the major component.

Still other classes of cosurfactant compounds providing stable cleaning compositions at low and elevated temperatures are the mono-, di- and triethyl esters of phosphoric acid such as triethyl phosphate.

The amount of cosurfactant which might be required to stabilize the cleaning compositions will, of course, depend on such factors as the surface tension characteristics of the cosurfactant, the type and amounts of the analephotropic complex and perfumes, and the type and amounts of any other additional ingredients which may be present in the composition and which have an influence on the thermodynamic factors enumerated above. Generally, amounts of cosurfactant in the range of from 0 to 50 wt. preferably from 0.1 wt. to 25 wt. especially preferably from 0.5 wt. to 15 wt. by weight provide stable microemulsions for the abovedescribed levels of primary surfactants and perfume and any other additional ingredients as described below.

The present invention also relates to a stable concentrated microemulsion or acidic microemulsion composition comprising by weight: WO 98/25455 PCT/US97/22672 17 3 to 40% of an analephotropic negatively charged complex as previously herein defined; 2 to 30% of a cosurfactant; 0.4% to 10% of a water insoluble perfume and/or an insect repellent containing amide linkages; 0 to 18% of at least one dicarboxylic acid; 0 to 1% of phosphoric acid; 0 to 0.2% of an aminoalkylene phosphoric acid; 0 to 15% of magnesium sulfate heptahydrate; 0.1% to 10% of a Lewis base, neutral polymer being complexed with the perfume and/or insect repellent containing amide linkages; and the balance being water.

The present invention also relates to a light duty liquid composition or light duty liquid microemulsion composition which comprises by weight: 3% to 40% of the previously defined analephotropic negative charged complex; 0 to 10% of a perfume, allergen agent and/or antibacterial agent; 0 to 25% of a cosurfactant: 0.1% to 10% of a Lewis base, neutral polymer being complexed with said perfume and/or antibacterial; and the balance being water.

A typical shampoo formula utilizing linker chemicals comprises by weight: 10% to 30% of an ammonium or alkali metal salt of an ethoxylated C8-C16 alkyl ether sulfate, a C8-C16 alkyl benzene sulfonate or a C8-C16 alkyl sulfate; 0.1% to 4% of a dimethyl polysiloxane; 0 to 3% of a C12-16 alkyl diethanol amide; 0.1% to 3% of a C20-C40 alcohol; 0 to 1.5% of a distearyldimonium chloride; 0.1% to 2.0% of perfume; WO 98/25455 PCT/US97/22672 18 0.1% to 6% of a chemical linker; 0 to 4% of a zwitterionic surfactant which is complexed with said anionic surfactant; and the balance being water.

A typical body cleaning composition comprises by weight: 6% to 30% of an ethoxylated C8-C16 alkyl ether sulfate; 2% to 16% of a C8-C1 6 alkyl sulfate or a C8-C16 alkyl benzene sulfonate; 1 to 8% of a zwitterionic surfactant being complexed with said sulfate and said sulfonate surfactant; 1% to 8% of a C12-16 alkyl diethanol amide; 0.1% to 2% of a perfume; 0.5% to 6% of a chemical linker; and the balance being water.

A typical fabric care cleaning composition comprises by weight: 5% to 40% of a sulfate or sulfonate surfactant; 0.1% to 5% of a chemical linker; 0.05% to 5% of at least one enzyme; and the balance being water.

In addition to the above-described essential ingredients required for the formation of the cleaning compositions, the compositions of this invention may often and preferably do contain one or more additional ingredients which serve to improve overall product performance.

One such ingredient is an inorganic or organic salt of oxide of a multivalent metal cation, particularly The metal salt or oxide provides several benefits including improved cleaning performance in dilute usage, particularly in soft water areas, and minimized amounts of perfume required to obtain the microemulsion state.

Magnesium sulfate, either anhydrous or hydrated heptahydrate), is especially preferred as the magnesium salt. Good results also have been obtained with WO 98/25455 PCT/US97/22672 19 magnesium oxide, magnesium chloride, magnesium acetate, magnesium propionate and magnesium hydroxide. These magnesium salts can be used with formulations at neutral or acidic pH since magnesium hydroxide will not precipitate at these pH levels.

Although magnesium is the preferred multivalent metal from which the salts (inclusive of the oxide and hydroxide) are formed, other polyvalent metal ions also can be used provided that their salts are nontoxic and are soluble in the aqueous phase of the system at the desired pH level.

Thus, depending on such factors as the pH of the system, the nature of the analephotropic complex or anionic surfactant and cosurfactant, as well as the availability and cost factors, other suitable polyvalent metal ions include aluminum, copper, nickel, iron, calcium, etc. It should be noted, for example, that with the preferred paraffin sulfonate anionic detergent calcium salts will precipitate and should not be used. It has also been found that the aluminum salts work best at pH below 5 or when a low level, for example 1 weight percent, of citric acid is added to the composition which is designed to have a neutral pH. Alternatively, the aluminum salt can be directly added as the citrate in such case. As the salt, the same general classes of anions as mentioned for the magnesium salts can be used, such as halide bromide, chloride), sulfate, nitrate, hydroxide, oxide, acetate, propionate, etc.

The cleaning compositions can optionally include from 0 to 2.5 wt. preferably from 0.1 wt. to 2.0 wt. of the composition of a C8-C22 fatty acid or fatty acid soap as a foam suppressant. The addition of fatty acid or fatty acid soap provides an improvement in the rinseability of the composition whether applied in neat or diluted form. Generally, however, it is necessary to increase the level of cosurfactant to maintain product stability when the fatty acid or soap is present. If more than 2.5 wt. of a fatty acid is used in the instant compositions, the composition will become unstable at low temperatures as well as having an objectionable smell.

As example of the fatty acids which can be used as such or in the form of soap, mention can be made of distilled coconut oil fatty acids, "mixed vegetable" type fatty acids high percent of saturated, mono-and/or polyunsaturated C18 chains); oleic WO 98/25455 PCT/US97/22672 acid, stearic acid, palmitic acid, eiocosanoic acid, and the like, generally those fatty acids having from 8 to 22 carbon atoms being acceptable.

The liquid cleaning compositions 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 formalin, 5-chloro-2-methyl-4isothaliazolin-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.

In final form, the cleaning compositions exhibit stability at reduced and increased temperatures. More specifically, such compositions remain clear and stable in the range of 40C to 500C, especially 10OC to 430C. Such compositions exhibit a pH in the acid or neutral range depending on intended end use. The liquids are readily pourable and exhibit a viscosity in the range of 6 to 60 milliPascal- Second (mPas.) as measured at 25°C. with a Brookfield RVT Viscometer using a #1 spindle rotating at 20 RPM.

Preferably, the viscosity is maintained in the range of 10 to 40 mPas.

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. When intended for use in the neat form, the liquid compositions can be packaged under pressure in an aerosol container or in a pump-type sprayer for the so-called spray-and-wipe type of application.

Because the compositions as prepared are aqueous liquid formulations and since no particular mixing is required to form the all purpose cleaning or microemulsion composition, the compositions are easily prepared simply by combining all the ingredients in a suitable vessel or container. The order of mixing the ingredients is not particularly important and generally the various ingredients can be added sequentially or all at once or in the form of aqueous solutions of each or all of the primary WO 98/25455 PCTfUS97/22672 21 detergents and cosurfactants can be separately prepared and combined with each other and with the perfume. The magnesium salt, or other multivalent metal compound, when present, can be added as an aqueous solution thereof or can be added directly. It is not necessary to use elevated temperatures in the formation step and room temperature is sufficient.

The following examples illustrate the complexes of additives and chemical linker and liquid cleaning compositions containing complexes of the chemical linker with the additive and/or surfactant invention. Unless otherwise specified, all percentages are by weight. The exemplified compositions are illustrative only and do not limit the scope of the invention. Unless otherwise specified, the proportions in the examples and elsewhere in the specification are by weight.

Example I The following complexes of chemical additive and chemical linker were made: Tests were run with a microcalorimeter CALVET. A cell contains 0.5 g of the chemical additive and 0.5 g of a chemical linker such as polyethylene glycol in two separated parts. A semi circular cup disposed with in the cell allows the mixing of the two components in the cell. The heat flow generated by the mixing is measured. If the components interact together, their mixing releases heat. The table hereafter gives the components of the mixture, the time and the microwatt value to the maximum of the exothermic peak.

WO 98/25455 WO 9825455PCT/US97/22672 A B C D E F G H I J hemical additives uat ester 0.5 enzyl benzoate Dihdramyrcenol Perfume Idehyde C9 Perfume 0.5 -F0.5 riclosan 0.5 MNDA 0.5 n-dimethyl para-amine octyl benzoate -0.5 BSA -Protein PEG 200 0.5

J

PEG 600 0.5 0.5 0.5 0.5 PEG 6000 0.5 0.5 0.5 Exothermic reaction Microwatte to exothermic energy peak 107013240 115 15550d 327 171 98 700 39700 1934' Tine (seconds) to energy peak 80 10 30 40 120 130 140 820 380 670 Levenol F-200 Isobutyric Acid -0.3 Example 11 The following formulas were made by simple mixing at 2500 and tested for roach repelling.

Weight A B C D E Deionized Water 82.2260 83.2260 82.9260 84.9260 83.9260 MqS04Y7H20 1.0000 1 .0000 1 .0000 1.0000 1.0000 C14-17 Paraffin Sulfonate 60% 6.6700 6.6700 6.6700 6.6700 6.6700 No C13-15 Fatty Alcohol EQ 7:1 /PO 3.0000 3.0000 0.0000 0.0000 0.0000 4:1 Esterified Polyethoxyether Levanol 0.0000 0.0000 2.3000 2.3000 2.3000 F200 PEG-600 0.0000 1.0000 0.0000 0.0000 1.0000 Diethylene Glycol Monobutyl Ether 3.5000 2.5000 3.5000 2.5000 2.5000 Sodium Hydroxide (38% Na2O) 0.0500 0.00 0.0500 0.0500 0.0500 Dist. Coco Fatty Acid 0.5000 0.5000 0.5000 0.5000 0.5000 Stabilisant B 30% 0.1540 0.1540 0.1540 0.1540 0.1540 FD&C Green 3 C142053 0.0700 0.0700 0.0700 0.0700 0.0700 FD&C Yellow 10 01 47005 0.0300 0.0300 0.0300 0.0300 0.0300 Repellent Perfume Mizgui 0.8000 0.8000 0.8000 0.8000 0.8000 Methyl Neodecanamide 2.0000 1.0000 2.0000 1.0000 1.0000 Days Roach Repellency, Probit 7.1000 1.7000 10.9000 8.8000 7.3000 The testing for roach repellency was done by a tile cup test procedure which was as follows: WO 98/25455 PCTIUS97/22672 23 German cockroaches (Blattella germancia) were maintained at 270C on a 12 hour light/12 hour dark photo period. Vinyl floors were cleaned and cut into 3 x 3 inch squares (58.1 cm 2 with an electric saw. A 1.5 cm square notch was cut out of half of the resulting squares to provide the roaches access to the shelter. The tiles were washed with water before treatment. Each of six cut tiles (two with access openings) were treated with 0.62 ml of test product (Formula L) diluted 4:1. Similarly six control tiles were treated with 0.62 ml of an identical formulation which did not contain MNDA (Formula M) diluted 4:1. The tiles were allowed to dry 4-6 hours before the cup, a six sided cube was assembled. The cut tiles were held together firmly with strips of clear tape on the outside edges, except the floor of the shelter was left unattached. The control and product treated shelter were placed in the cage and the bioassay started.

Forty-eight hours prior to initiation of the assay, 50 male German cockroaches were allowed to acclimate to the pastic test cages (51 x 28 x 20 cm) with food and water available in the center, outside of the cups. A thin film of Teflon emulsion on the sides of the cages restricted the insects to the floor of the cage.

The number of insects resting on the inner walls of each cup were recorded in the middle of the photophase daily for 14 days or until equal numbers were found in treated and control cups. After counting, all roaches were removed from each cup.

The position of the cups were reversed each day.

Repellency was calculated as: Nt Repellency Nt+Nc where Nt is the number of insects on the treated surface and Nc is the number on the control surface. Any insect found outside of either shelter was not counted. Generally, less than 5 of the 50 insects were found outside of the shelters.

WO 98/25455 PCT/US97/22672 24 Example 3 The following compositions were made by simple mixing at 250C.

A B C D E F Sodium lauryl sulfate (Empicol LX-28 21.43 21.43 21.43 21.43 21.43 21.43 Hoechst) Lauryl alkyldimethyl betaine (Genaga 6.67 6.67 6.67 6.67 6.67 6.67 LAB-Hoechst) Formalin 0.1 0.1 0.1 0.1 0.1 0.1 PEG MW400 1.0 1.0 Limonene fragrance 0.1 0.1 D-citronellol fragrance 0.31 0.30 Aubepine fragrance 0.33 0.32 Water Bal. Bal. Bal. Bal. Bal.

Static headscape/GP measurements 1,366,797 1,538,430 44,086 46.335 18,171 18,832 Static headspace/GC measurements were made 5 gm samples of formulas (A- F) were placed into 22 ml. headspace vials. The samples were analyzed on a Perkin- Elmer HS-100 attached to a Signma GC. Samples were thermostated at 60 0 C for minutes and following transfer (transfer line temperature: 1400°C) to the GC, the volatiles were separated on a Supelcowax (30M x 0.32 mm, 0.25 m coating) column.

The GC was equipped with an FID (detector temperature: 225°C), helium was used as the carrier gas (7.2 ml/min.), and the oven temperature program began with an initial oven temperature of 50°C for 2 min., then ramped to 1750°C at 6 0 C/min. and held for 2 minutes. All peaks were automatically integrated by the Turbochrom 3 data acquisition and analysis software, version 3.3, loaded on a Gateway 386/33 computer.

Claims

1. A composition comprising by weight: 0.1% to 10% of an organic chemical having a chemical group having a dipole moment of at least 1.5 Debyes, said organic chemical containing a halogen, alcohol, aldehyde, ester, carboxylic acid, amine or amide group; 0.1% to 20% of a chemical linker selected from the group consisting of carboxylic acids having 4 to 6 carbon atoms, a non-esterified ethoxylated polyhydric alcohol, a polyvinyl pyrrolidone polymer and a polyethylene glycol having the formula HO(CHCH 2 zO)H wherein n is 8 to 225 having a molecular weight of 600 to 10,000, wherein the molar ratio of the chemical linker to the organic chemical is 4:1 to 1:4; 1 to 30% of at least one anionic surfactant having a carboxylate, 15 sulfate or sulfonate group; 0.25 to 10% of a second surfactant selected from the group consisting of amine oxide surfactants, zwitterionic surfactants and alkylene carbonate surfactants; and 50% to 99.8% water.

2. A composition according to Claim 1, further including 0 to 20 wt% of a cosurfactant. Dated this 3rd day of November 2000 Colgate-Palmolive Company Patent Attorneys for the Applicant: F BRICE&CGO