US3733277A - Cleaning and sanitizing concentrate containing lemon-lime fragrance - Google Patents

Abstract

THIS INVENTION IS BASED UPON THE DISCOVERY THAT A SUBLIMINIAL QUANTITY OF A LEMON-LIME FRAGRANCE CAN BE EMPLOYED EFFECTIVELY WITHOUT DEGRADATION IN A LIQUID, LOW PH, SANITIZING AND CLEANING SOLUTION CONTAINING QUATERNARY AMMONIUM HALIDES TO PRODUCE A FRESH, CLEAN FRAGRANCE SENSATION WITHOUT PRODUCING AN AWARENESS OF THE SPECIFIC LEMON-LIME ODOR. A CLEANING AND SANITIZING CONCENTRATE IS DISCLOSED CONSISTING ESSENTIALLY OF (A) PHOSPHORIC OR HYDROXYACETIC ACID, (B) A NONIONIC SYNTHETIC DETERGENT,

(C) A QUATERNARY AMMONIUM HALIDE, (D) WATER, AND (E) LEMON-LIME FRAGRANCE.

Description

CLEAN ODOR PREFERENCE May 15, 1973 3,733,277

R. P. WOODEN ET AL CLEANING AND SANITIZING CONCENTRATE CONTAINING LEMON-LIME FRAGRANCE Filed Dec. 6, i971 FRAGRANCE AS PER CENT OF QUATERNARY CPD.

United States Patent Oflice 3,733,277 Patented May 15, 1973 US. Cl. 252-106 8 Claims ABSTRACT OF THE DISCLOSURE This invention is based upon the discovery that a subliminal quantity of a lemon-lime fragrance can be employed effectively without degradation in a liquid, low pH, sanitizing and cleaning solution containing quaternary ammonium halides to produce a fresh, clean fragrance sensation without producing an awareness of the specific lemon-lime odor. A cleaning and sanitizing concentrate is disclosed consisting essentially of (a) phosphoric or hydroxyacetic acid, (b) a nonionic synthetic detergent, (c) a quaternary ammonium halide, (d) water, and (e) lemon-lime fragrance.

CROSS REFERENCE TO RELATED APPLICATION This application is a continuation-in-part of applicants copending application, Ser. No. 887,529, filed Dec. 25, 1969, and now abandoned, entitled Fragrance for Sanitizing and Cleaning Solutions.

BACKGROUND OF THE INVENTION A fragrance or perfume is used in conjunction with many cleaning and sanitizing solutions now being marketed. However, these fragrances are often damaged or incompatible with certain components of these solutions such as acids and quaternary ammonium halide sanitizers. Even if the fragrance is not degraded by these components, the fragrance will generally produce the specific odor characteristics of that fragrance in the room that is cleaned.

In contrast to the prior art, this invention has the following objects:

(a) The provision of an improved sanitizing and cleaning solution together with a specific amount of a lemonlime fragrance adapted to produce a clean, fresh odor without imparting a distinguishable lemon-lime aroma of is own; and,

(b) The provision of a cleaner containing a suitable nonionic detergent, phosphoric acid or hydroxyacetic acid, a quaternary ammonium halide sanitizer and a subliminal amount of a lemon-lime fragrance adapted to produce a clean, fresh odor in a freshly cleaned room in which the fragrance Will not be damaged or otherwise deodorized by the sanitizer.

SUMMARY OF THE INVENTION The product of this invention is a cleaning and sanitizing concentrate comprising, by weight, from to 50% phosphoric or hydroxyacetic acid; from 5% to nonionic detergent; from 10% to quaternary ammonium halides having the following formula:

wherein R and R are ethyl or methyl and R is an alkyl chain containing from 6 to 20 carbon atoms, n equals 0, 1 or 2, and X is selected from the group consisting of chloride ion, bromide ion and iodide ion; from 15% to 65% water; and from 0.5 to 2 parts lemon-lime fragrance for each parts by weight of quaternary ammonium halide. The lemon-lime fragrance is used is such amounts that when the concentrate is diluted with from 250 to 1500 parts water per part of concentrate, a clean, fresh fragrance is provided in a freshly cleaned room without producing a perceptible lemon-lime fragrance.

DESCRIPTION OF THE DRAWING The drawing is a graph of preference versus lemon-lime fragrance as a percentage of the quaternary ammonium halide and demonstrates the critical amount of lemonlime fragrance required herein.

DESCRIPTION OF THE PREFERRED EMBODIMENT Briefly, the present invention is based upon the discovery that a subliminal quantity of a lemon-lime fragrance can be employed effectively in a sanitizing and cleaning solution to produce fresh, clean fragrance sensation proximate cleaned surfaces without producing a perceptible lemon-lime odor or fragrance.

In a preferred aspect of this invention, the cleaning and sanitizing composition is first manufactured in concentrate form and subsequently diluted with water by the ultimate user. The concentrate, as described hereinafter, is preferably diluted with from 250 parts to 1500 parts water per part of concentrate. The amount of Water used in diluting the concentrate is specifically related to the desired cleaning function. For cleaning bathroom bowls, shower tile, etc., a relatively small amount of water is used to dilute the concentrate. For less stringent cleaning, e.g., cleaning mirrors and less soiled hard surfaces, more water is used to dilute the concentrate. The concentrate will be specifically described in the following paragraphs.

From 20% to 50% of the concentrate is comprised of phosphoric or hydroxyacetic acid. Both of these acids are sufiiciently strong to provide a concentrate pH ranging from about 0.3 to 0.75 and a use dilution pH of 0.5 to 2.0. Both of these acids are compatible with the quaternary ammonium halides and nonionic detergents used herein. The acids are utilized in this formula to remove mineral deposits, e.g., carbonates, stearates, blood stains, iron salts and water spots.

Nonionic synthetic detergents comprise from 5% to 25%, preferably from 10% to 20%, of the concentrate. Nonionic synthetic detergents can be broadly defined as compounds produced by the condensation of alkylen oxide groups (hydrophilic in nature with an organic hydrophobic compound, which may be aliphatic or alkyl aromatic in nature. The length of the hydrophilic or polyoxyalkylene radical which is condensed with any particular hydrophobic groups can be readily adjusted to yield a water-soluble compound having the desired degree of balance between hydrophilic and hydrophobic elements. The following nonionic synthetic detergents can be successfully used herein:

(1) The polyethylene oxide condensates of alkyl phenols, e.g., the condensation products of alkyl phenols having an alkyl group containing from about 6 to 12 carbon atoms in either a straight chain or branched chain configuration, with ethylene oxide, the ethylene oxide being present in amounts equal to 5 to 25 moles of ethylene oxide per mole of alkyl phenol. The alkyl substituent in such compounds may be derived from polymerized propylene, diisobutylene, octene, or nonene, for example. One suitable member of this class is octyl phenoxy polyethoxy ethanol wherein 7 to 8 moles of ethylene oxide are condensed with one mole of octyl phenol. This compound is a water-soluble liquid with excellent wetting and detergent properties. It is a clear, pale, straw-colored liquid with a mild odor typical of detergents. It is compatible with low pH systems and with quaternary ammonium compounds.

(2) The condensation product of aliphatic alcohols having from 8 to 22 carbon atoms, in either straight chain or branched chain configuration, with ethylene oxide, for example, a coconut alcohol-ethylene oxide condensate having from to 30 moles of ethylene oxide per mole of coconut alcohol, the coconut alcohol fraction having from to 14 carbon atoms.

(3) The condensation product of ethylene oxide with a hydrophobic base formed by the condensation of propylene oxide with propylene glycol. The hydrophobic portion of the molecule, which exhibits water in solubility has a molecular weight of from about 1500 to 1800. The liquid character of this product is retained up to the point where the ethylene oxide content is about 50% of the total weight of the condensation product.

(4) Those nonionic synthetic detergents derived from the condensation of ethylene oxide with the product resulting from the reaction of propylene oxide and ethylene diamine. For example, compounds containing from about 40% to about 80% ethylene oxide by weight and having a molecular weight of from about 5,000 to about 11,000 resulting from the reaction of ethylene oxide groups with a hydrophobic base constituted of the reaction product of ethylene diamine and excess propylene oxide, said base having a molecular weight of the order of 2500 to 3000, are satisfactory. The nonionics are used herein primarily for their detergency effects.

From 10 to 30%, preferably to of the concentrate is comprised of quaternary ammonium halides having the following formula:

wherein R and R are ethyl or methyl and R is an alkyl chain containing from 6 to 20 carbon atoms, 12 equals 0, 1 or 2, and X is selected from the group consisting of chloride ions, bromide ions and iodide ions. The quaternary ammonium halide is utilized in this concentrate because of its excellent bactericidal activity. Specially preferred for use herein is a mixture of quaternary ammonium halides containing n-alkyl C14 30% C16, 5% C and 5% C dimethyl benzyl ammonium chlorine and 50% n-alkyl (50% C 30% C 17% C and 3% C dimethyl ethylbenzyl ammonium chloride.

In manufacturing quaternary ammonium halides, a significant amount of water is introduced into the quaternary product. Generally, the product comprises about 50% active and 50% water. Herein, the total weight of the product including the active and the Water is used in computing the amount of fragrance to be added and the relative weight of the various other components.

From 15% to of the concentrate is comprised of Water. This water, in addition to that added with the quaternary ammonium halide, is required to adequately solubilize the nonionic and to prevent precipitation of components prior to dilution by the ultimate consumer. The upper limit of 65% is not critical but only represents a practical limit from a transportation standpoint.

Because the quaternary ammonium halides are particularly good biological deodorizers, it was necessary to find a fragrance that would not be deodon'zed or otherwise degraded by them while at the same time providing a clean, fresh fragrance in a cleaned room without adding an identifiable odor of its own. It was discovered that this could be accomplished by using a lemon-lime fragrance including both natural and artificial fragrances. While the composition of the lemon-lime fragrance may be varied considerably, it generally includes most of the following and preferably all of the following components: terpineol, linalool, aldehyde C aldehyde C geranyl acetate, citral, oil of lemon (cold pressed), cymene, dipentene, oil of lime (distilled), citronellol, amyl cinnamic aldehyde, oil of jasmin, methyl anthranilate, yara yara, indole, cinnamic alcohol, linalyl acetate, benzyl butyrate, benzyl acetate, citronellyl acetate and orange terpenes.

A typical formulation for lemon-lime of the type used in accordance with the invention is the following:

TABLE I Component: Parts by weight Terpineol 1.00 Linalool 1.00 Aldehyde C10 tAldehyde C 1.25 Geranyl acetate 1.75 Citral 60.00 Oil of lemon (cold pressed) 100.00 Cymene .10 Dipentene .10 Oil of lime (distilled) .30 Citronellol .25 Amyl cinnamic aldehyde .35 Oil of jasmin .80 Methyl anthraniliate .50 Yara yara .50 Indole .50 Cinnamic alcohol 2.00 Linalyl acetate .05 Benzyl butyrate .05 Benzyl acetate .05 Citronellyl acetate .06 Orange terpenes 828.14

The amount of lemon-lime fragrance is critical as can be seen by reference to the drawing which illustrates the responses of a panel of eight persons. Scores run from 1 to 4 with higher numbers indicating increased preference.

The tests used in constructing the curve shown in the figure were performed as follows. Cleaning solutions comprising phosphoric acid, a nonionic synthetic detergent, a quaternary ammonium chloride sanitizer, water (in amounts specified hereinbefore) and various concentrations of lemon-lime fragrance were used for cleaning a bathroom in the use dilutions hereinbefore specified. The curve represents a preference for the clean smell left in the room after the cleaner was used. Specifically, it was discovered that the preferred fragrance concentration of the lemon-lime composition must be between about one-half and 2% of the amount of quaternary ammonium halide (50% active, 50% water) used to produce the desired result when used in use dilutions ranging from 250 parts water per part of concentrate to 1500 parts water per part of concentrate. When the concentration of fragrance was increased beyond about 2%, as above specified, the fragrance of lemon-lime gradually became discernible in the above use dilution. The invention is therefore the provision of a sanitizing and cleaning solution which provides a fresh, clean smell in a freshly cleaned room by utilizing a subliminal quantity of a lemon-lime fragrance. The preferred amount of fragrance is between about one-half and 2% by weight of the total quaternary ammonium halide (50% active, 50% water) present.

The concentrate form, above described, is the preferred embodiment of this invention. The concentrate can be readily shipped at low cost and the ultimate consumer can add the bulkiest ingredient, water. By supplying the cleaning and sanitizing product in concentrate form, the ultimate consumer can also tailor the product for specific jobs by increasing or decreasing the use dilution.

The following example is illustrative of the present invention:

EXAMPLE I A cleaning and sanitizing concentrate was prepared from 40 parts phosphoric acid, 20 parts of a mixture of quaternary ammonium chlorides comprising 50% n-alkyl 5 (60% C 30% C 5% C 5% C dimethyl benzyl ammonium chloride and 50 n-alkyl (50% C 30% C 17% C 3% C dimethyl ethylbenzyl ammonium chloride, 10 parts octyl phenoxy polyethoxy ethanol and 29.7 parts water. The concentrate was divided into 9 aliquots and to each aliquot was added 0.033 part of the fragrances listed below (0.033 parts fragrance divided by 2.22 parts quaternary equals 1.5 parts fragrance per 100 parts quaternary):

Aliquot 1 Fritzsche D&O Inc. No. 42149 (Lemon-Lime) Aliquot 2 Fritzsche D&O Inc. No. 41994 (Pine) Aliquot 3 Fritzsche D&O No. 42249 (Pine) Aliquot 4 (Fritzsche D&O Inc. No. 47314 (Woody Amber) Aliquot 5 Fritzsche D&O Inc. No. 41985 (Musk) Aliquot 6 Fritzsche D& Inc. No. 54566 (Woody Amber) Aliquot 7 Fritzsche D&O Inc. No. 43798 (Musk) Aliquot 8 Fritzsche D&O Inc. No. 49745 (Orange) Aliquot 9 Fritzsche D&O Inc. No. 42193 (Orange) Bathroom testing was simulated by diluting each concentrate with 250 parts water per part of concentrate. One ml. of the diluted concentrate was placed in a 500 ml. jar. After about 15 minutes, fragrance experts odor tested these fragrances and found no degradation in the fragrance of aliquots 1, 8 and 9 and significant degradation in aliquots 2 through 7.

After 12 hours, the fragrance of aliquots 2 through 7 and 9 had significantly degraded and were not desirable odors for this product. Concentrate 8 had a sweet, heavy orange odor which was unpleasant in the context of a bathroom.

The lemon-lime fragrance in aliquot 1 above did not degrade over a 30-day period. When used in the manner described above, a clean, fresh odor sensation was recognizable with no noticeable lemon-lime fragrance. This product, diluted as stated above, was used to clean a bathroom and left a clean, fresh odor sensation in the bathroom with no noticeable lemon-lime fragrance.

What is claimed is:

1. A cleaning and sanitizing concentrate consisting essentially of:

(a) from 20% to 50% of an acid selected from the group consisting of phosphoric and hydroxyacetic acid;

(b) from to 25% of a nonionic synthetic detergent;

(c) from 10% to 30% of quaternary ammonium halide having the following formula:

wherein R and R are ethyl or methyl and R is an alkyl chain containing from 6 to 20 carbon atoms, n equals 0, 1 or 2, and X is selected from the group consisting of chloride ion, bromide ion and iodide ion;

(d) at least 15% water; and,

(e) from 0.5 parts to 2 parts lemon-lime fragrance for each parts by weight of said quaternary ammonium halide.

2. The cleaning and sensitizing concentrate of claim 1 wherein the pH of said composition is between 0.3 and 0.75.

3. The cleaning and sanitizing concentrate of claim 2 wherein the nonionic synthetic detergent comprises from 10% to 20% of the composition.

4. The cleaning and sanitizing concentrate of claim 3 wherein the concentrate contains from 20% to 30% of said quaternary ammonium halide.

5. The cleaning and sanitizing concentrate of claim 4 wherein the quaternary ammonium halide salt is a chloride salt.

6. The cleaning and sanitizing concentrate of claim 4 wherein the nonionic synthetic detergent is octyl phenoxy polyethoxy ethanol.

7. The cleaning and sanitizing concentrate of claim 4 wherein the quaternary ammonium halide is a mixture of n-alkyl C14, C16, C12, 5% C13) d] methyl benzyl ammonium chloride and 50% n-alkyl (50% C12, 30% C 17% C 3% C dimethyl ethylbenzyl ammonium chloride.

8. The cleaning and sanitizing concentrate of claim 4 wherein the acid is phosphoric acid.

References Cited UNITED STATES PATENTS 2,702,774 2/ 1955 Stayner 252-l06 X 2,998,390 8/1961 Hamilton 252106 X 3,223,643 12/1965 Law 252-106 3,373,208 3/ 1968 -Blumenthal 252-522 X 3,382,285 5/1968 Egan et a1 252--- X RICHARD D. LOVERIN G, Primary Examiner US. Cl. X.R.

252-136, 522, DIG. 1, DIG. 10, DIG. 14

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