US 3860525 A
An alkaline detergent composition containing a citrus fragrance stabilized by the inclusion of 1 to 15% by weight of a boron compound selected from the group consisting of boric oxide, boric acid and mixtures thereof, in the absence or presence of a chlorine bleaching agent.
Description (OCR text may contain errors)
252-99. AU 165 EX 12 g 1! l 1-14-75 OR 3.8609525 United States Patent [191 111 3,860,525
Bechtold Jan. 14, 1975 1 CLEANING COMPOSITION WITH 3,474,037 10/1969 Goldsmith 252/99 STABILIZED PERFUME 3,494,868 2/1970 Gray 252/99 Charles L. Bechtold, Edison, NJ.
Colgate-Palmolive Company, New York, NY.
Filed: Feb. 26, 1973 Appl. No.: 335,460
Related U.S. Application Data Continuation of Ser. No. 133,339, April 12, 1971, abandoned.
U.S. Cl 252/99, 252/89, 252/95,
260/601 R Int. Cl Clld 7/54 Field of Search 252/95. 99, 89; 260/601 R References Cited UNITED STATES PATENTS 6/1961 Baxter 260/601 R Primary Examiner-Mayer Weinblatt Attorney. Agent. or Firm- Herbert S. Sylvester; Murray M. Grill; John J. Tomaszewski 7 Claims, No Drawings I 133,339, filed Apr. 12, 1971, now abandoned.
The present invention relates in general to perfumed cleaning compositions and in particular to the provision of perfumed cleaning compositions adapted for use in connection with the cleaning of dishware and glassware.
The presence of perfumes in cleaning compositions has attained considerable importance in industry for improving a variety of commercial products. Perfumes have been utilized for both masking undesirable and offensive odors and for imparting a pleasant aroma thereto. The formulation of perfumes having a particular essence is a highly intricate art since it comprises a mixture of organic compounds including alcohols, aldehydes, ketones, esters and hydrocarbons combined in fixed proportions to impart a particular fragrance. The instability of one or more of aforesaid components per se or in the presence of bleaching agents and/or other ingredients normally found in cleaning compositions effects a rapid loss in fragrance. Thus, it is apparent that the fugitive behavior of perfume in detergent formulations renders its utilization therein commercially infeasible. This is especially true with citrus fragrance which has been found to be particularly desirable in compositions for dishwashers because of its fresh aroma. Remedial techniques heretofore provided for overcoming this difficulty were based on the development of specific synthetic aromatic compounds as perfume substitutes and/or stabilizers. However, the great alkalinity exhibited by dishwasher detergent products has aggravated the problem of fragrance stability. While some perfumes have been found to be substantially stable under neutral, mildly acidic and mildly alkaline conditions, said perfumes quickly lose their essence in the strongly alkaline dishwasher formulations.
It has now been found that this rapid loss of the citrus fragrance may be substantially avoided and the citrusy aroma prolonged by incorporating into said alkaline cleaning composition a stabilizing agent selected from the group consisting of boric oxide, boric acid and mixtures thereof.
Thus, a primary object of the present invention resides in the provision of perfumed cleaning compositions having a citrus fragrance of prolonged duration.
Another object of the instant invention resides in the provision of a perfumed dishwasher composition stabilized against loss of its fragrance.
A further object of the present invention resides in the provision of a commercially more desirable perfumed cleaning product.
Other objects and advantages of the present invention will become more apparent hereinafter as the description proceeds.
The attainment of the foregoing and related objects is made possible in accordance with the present invention which provides a cleaning composition containing a citrus fragrance stabilized against degradation and dissipation, containing as the essential ingredient about 1-15% by weight of a boron compound selected from the group consisting of boric oxide, boric acid, and mixtures thereof.
The fragrance found particularly desirable in instant detergent composition is the citrus odor which may be found in essential oils, lemon oil, lime oil, orange oil,
etc. This fresh citrusy aroma is a function of the constituents therein which comprise mixtures of natural and- /or synthetic hydrocarbons, alcohols, phenols, ethers, aldehydes, ketones, acids and esters. Some of the components known to have the citrus fragrance include argeol, benzyl acetate, citral, citronella, citronellol, deodall, fleur delys, geraniol from citronella, heliotropine, linalool, peppermint oil. sandalwood oil, terpinyl acetate, glycidon, rhodinol, bergamot compound, lavindin abrial replacement compound, olibanum compound, etc. The perfume incorporated into instant cleaning compositions to effect a citrus fragrance may include one or more of aforesaid ingredients together with fixatives, modifiers, etc. The preferred perfume known as Lemon detergent perfume contains as the two main ingredients citral and deodall plus 30 other ingredients in minor amounts, some of which contribute the citrus character to the odor. Deodall is a trademarked perfume and comprises, among other: monoterpene hydrocarbons, e.g., alphapinene, camphene, beta-pinene, myrcene, terpinene, limonene, dipentene, paracymene, terpinolene, and others; cineole, fenchol (fenchyl alcohol), alphaterpineol, cinnamaldehyde and coumarin. The complex nature of the citrus perfume renders its classification into definite chemical types feasible. The degradation of some of the compounds destroys the delicate balance of said compounds in the perfume thereby materially altering and/or dissipating the original fragrance. Consequently, the need for stabilizing the citrus fragrance without adversely affecting the cleaning properties of the detergent composition is evident. The amount of perfume utilized depends on the specific nature of the perfume and the type of cleaning product. Generally, the perfume constitutes about 0.05 1.0% by weight of the total cleaning product.
It has been found that the addition of a boron compound selected from the group consisting of boric oxide, boric acid and mixtures thereof to a cleaning composition containing the citrus fragrance stabilizes said fragrance against dissipation with no deleterious action being attributed thereto. The specificity of boric oxide (B 0 and/or boric acid as stabilizers for those perfume components which contribute citrus character to the odor was clearly shown by testing each of thirty-two components of a lemon detergent perfume, with only the eighteen citrus components resulting in improved odor characteristics in the presence of boric oxide as opposed to odor degradation in the absence of boric oxide. The boric oxide had no effect on the rose compound, amyl cinnamic aldehyde, diethyl phthalate, diphenyl methane, methyl naphthyl ketone, dihydro mercenol, etc., some of the non-citrus ingredients which may be found in a lemon perfume. The two main ingredients, citral and deodall exhibited excellent odor quality in cleaning compositions containing boric oxide or boric acid and poor odor quality in samples not containing said boron compound. The protection afforded by the boric oxide or boric acid against odor degradation is specific to the citrus components and not to any particular chemical types. The amount of boric oxide and/or boric acid utilized herein must be sufficient to effect stabilization of the citrus fragrance. Although the amount can be varied, a desirable range is about 1-1 5% by weight of the total composition with a preferred range being about 5l2%.
The cleaning composition of this invention has particular utility as an automatic dishwasher product which customarily and preferably contains one or more bleaching agents capable of liberating hypochlorite chlorine and/r hypobromite bromine on contact with aqueous media. Particular examples of bleaching agents include the dry, particulate heterocyclic N- bromo and N-chloro imides such as trichlorocyanuric, tribromocyanuric acid, dibromoand dichlorocyanuric acid, the salts thereof with water-solubilizing cations such as potassium and sodium, and mixtures thereof. Particular compounds found useful are potassium dichloro-isocyanurate and trichloroisocyanuric acids.
Other N-bromo and N-chloro imides may also be used, such as N-brominated and N-chlorinated succinimide, malonimide phthalimide and naphthalimide. Other compounds include the hydantoins, such as 1,3- dibromo and 1,3-dichloro-5, S-dimethylhydantoin; N- monochloro-S, S-dimethylhydantoin, methylene-bis (N-bromo-S, S-dimethylhydantoin); 1,3-dibromo and 1,3-dichloro -isobutylhydantoin; 1,3-dichloro 5, methyl-S-ethylhydantoin; l,3-dibromo and 1,3 dichloro 5,5-diisobutylhydantoin; 1,3-dibromo and 1,3- dichloro 5-methyl-5-n-amylhydantoin, and the like. Other useful hypohalite-liberating agents comprise tribromomelamine and trichloromelamine. Dry particulate, water soluble anhydrous inorganic salts are likewise suitable for use such as lithium hypochlorite and hypobromite. The hypohalite-liberating agent may, if desired, be provided in the form of a stable, solid com plex or hydrate, such as sodium p-toluene-sulfobromamine-trihydrate, sodium benzenesulfochloramine-dihydrate, calcium hypobromite tetrahydrate, calcium hypochlorite tetrahydrate, etc. Brominated and chlorinated trisodium phosphate formed by the reaction of the corresponding sodium hypohalite solution with trisodium phosphate (and water as necessary) likewise comprise efficacious materials. The present invention contemplates as an additional embodiment the use of bleaching agents capable of liberating hypochlorite as well as hypobromite such as, for example, the N-brominated, N'-chlorinated heterocyclic imides, as for example the N-bromo, N'chloro-cyanuric acids and salts thereof, e.g., N-monobromo-N, N- dichloro=cyanuric acid, N-mon-bromo-N- monochlorocyanuric acid, sodium-N-monobromo-N- monochloro-cyanurate, potassium-N-monobromo-N- monochlorocyanurate; and the N-brominated, N- chlorinated hydantoins, e.g., N-bromo-N-chloro-5, 5- dimethylhydantoin and N-bromo-N-chloro-S-ethyl-S- methyl hydantoin.
The hypohalite-liberating compound is employed in an amount of from 0.5 to 5% by weight of the composition, and preferably in an amount of from about 0.5% to 3% by weight thereof. In any event, the hypohalide material should preferably be employed in amounts sufficient to yield from about 0.5-3% available chlorine, bromine etc. in order to assure optimum results.
The instant cleaning compositions preferably comprise one or more water-soluble builder salt, including inorganic and organic; basic and neutral water soluble salts and mixtures thereof. The builder salts are employed in amounts ranging up to about 95% i.e., 40-95% by weight with a range of from about 60% to about 90% by weight of the composition being preferred. The alkali metal salts such as sodium, potassium and lithium; ammonium and substituted ammonium salts such as methylammonium, diethanolammonium and triethanolammonium; and amine salts such as mono, diand triethanolamine methylamine, octylamino diethylenetriamine, triethylenetetramine and ethylenediamine are efficacious. Suitable builders include without necessary limitation, trisodium phosphate, tetrasodium pyrophosphate, sodium acid pyrophosphate, sodium tripolyphosphate hexahydrate, so dium monobasic phosphate, sodium dibasic phosphate, sodium hexameta phosphate, sodium silicates, SiO,/- Na O of H1 to 3.2/1, e.g. (sodium metasilicate), sodium carbonate, sodium sulfate, borax, etc. Other organic builders include salts of organic acids and, in particular, the water soluble salts of amino polycarboxylic acids. The acid portion of the salt can be derived from acids such as nitrilodiacetic; N-(Z-hydroxyethyl) nitrilodiacetic acid, nitrilotriacetic acid(NTA), ethylenediamine tetracetic acid, (EDTA); N-(2-hydroxyethyl) ethylene diamine triacetic acid; 2-hydroxyethyl iminodiacetic acid; l,2-diaminocyclohexanediacetic acid; diethylenetriamine penta-acetic acid and the like. The builder salt is preferably employed in amounts sufficient to yield a pH in water of from 9.5 to 12, preferably from 10 to 11, in order to obtain optimum detergency performance.
Water soluble organic detergent, i.e., surface active components may be employed, such materials being well known in the prior art, the term detergent comprehending species of the anionic, cationic, amphoteric and zwitterionic, non-ionic, types. ln formulating an automatic dishwasher product, it is preferred to utilize a low-foaming detergent such as the nonionics.
Nonionic surface active agents include those surface active or detergent compounds which contain an organic hydrophobic group anad a hydrophilic group which is a reaction product of a solubilizing group such as carboxylate, hydroxyl, amido or amino with ethylene oxide or with the polyhydration product thereof, polyethylene glycol.
As examples of nonionic surface active agents which may be used there may be noted the condensation products of alkyl phenols with ethylene oxide, e.g., the reaction product of isooctyl phenol with about 6 to 30 ethylene oxide units; condensation products of alkyl thiophenols with 10 to 15 ethylene oxide units; condensation products of higher fatty alcohols of monoesters of hexahydric alcohols and inner ethers thereof such as sorbitan monolaurate, sorbitol mono-oleate and mannitan monopalmitate, and the condensation products of polypropylene glycol with ethylene oxide.
Further suitable detergents are polyoxyalkene esters of organic acids, such as the higher fatty acids, rosin acids, tall oil, or acids from the oxidation of petroleum, and the like. The polyglycol esters will usually contain from about 8 to about 30 moles of ethylene oxide or its equivalent and about 8 to 22 carbon atoms in the acyl group. Suitable products are refined tall oil condensed with 16 to 20 ethylene oxide groups, or similar polyglycol esters of lauric, stearic, oleic and like acids.
Additional suitable non-ionic detergents are the polyalkylene oxide condensates with higher fatty acid amides, such as the higher fatty acid primary amides and higher fatty acid monoand di-ethanol-amides. Suitable agents are coconut fatty acid amide condensed with about 10 to 30 moles of ethylene oxide. The fatty acyl group will similarly have about 8 to 22 carbon atoms, and usually about 10 to 18 carbon atoms in each product. The corresponding sulphonamides may also be used if desired.
Other suitable polyether non-ionic detergents are the polyalkylene oxide ethers of higher aliphatic alcohols. Suitable alcohols are those having a hydrophobic character, and preferably 8 to 22 carbon atoms. Examples thereof are iso-octyl, nonyl, decyl, dodecyl, tridecyl, tetradecyl, hexadecyl, octadecyl and oleyl alcohols which may be condensed with an appropriate amount of ethylene oxide, such as at least about 6, and preferably about -30 moles. A typical product is tridecyl alcohol, produced by the 0x0 process, condensed with about l2, l5 or moles of ethylene oxide. The corresponding higher alkyl mercaptans or thioalcohols condensed with ethylene oxide are also suitable for use in compositions of the present invention.
Examples of other suitable wetting agents include low foaming anionic materials such as dodecyl hydrogen phosphate, methyl naphthalene sulfonate, sodium 2-acetamido-hexadecane-l-sulfonate, and mixtures thereof. Mixtures of the foregoing wetting agents may also be employed, and, if desired, foamreducing additive may be added as appropriate to minimize undesirable foaming tendencies of these wetting agents under conditions of use.
The detergent material is employed in concentrations ranging from about 0.5% to about 5% by weight of total compositions with a range of l to 3% being particularly preferred.
Thus, a relatively minor amount of nonionic type detergent, that is, about 2 4% is especially beneficial inasmuch as it acts as a foam depressant as well as a detersive agent in an automatic dishwashing solution.
The preferred cleaning compositions of this invention can contain any of the usual additives such as fillers, extenders, pigments, dyes, anti-tamishing agents, suds depressors, suds builders, anti-redeposition agents, overglaze protectors including alkali metal aluminum phosphates, aluminum acetate, aluminum formate, alkali aluminate, zincate, berylliate, etc., which do not interfere with the detergency properties not the citrus fragrance thereof.
The following examples are given for purposes of iilustration only and are not to be considered as constituting a limitation on the present invention. All parts and percentages given are by weight unless otherwise indicated. The products are prepared by dry-blending the specified ingredients to form a dry particulate composition.
Automatic Dishwasher Detergent S e dium tripolyphosphatefiexahydtate, 6l.40%
Anhydrous Sodium Metasilicate 20.00 Boric Oxide (8,0,) 6.00 mot -jett qfists sm. l 50 Lemon Detergent Perfume 0.10 Potassium Trichloroisocyanurate [.60 Sodium Sulfate 4.00 Color. pigment 0.13 Sodium Chloride 2.95 Propylene Glycol 0.02 Magnesium Silicate 2.00 Water 0.30
The non-ionic detergent is the product obtained by the condensation of about three mols of propylene oxide with the condensation product of one mol of a mixture of essentially straight chain. primary, fatty alcohols in the C r-C range with about six mols of ethylene oxide.
The lemon fragrance of this product is preserved for the life of the product, whereas the elimination of boric oxide therefrom yields a product which lost its lemon fragrance after one day's aging.
EXAMPLE 2 10 which persists for the life of the product.
EXAMPLE 3 Example 1 is repeated except that 11.055% boric acid is substituted for the 6% boric oxide and the phosl5 phate content is reduced 5.055%. This product also exhibits a stabilized lemon fragrance of long duration.
EXAMPLE 4 di h te Hexah drate 4l.098% 2 Sodium Tripolyphosphate Granular Anhydrous 10.870 Anhydrous Sodium Metasilicate 9.000 Boric Oxide (8,0,) [.000 Boric Acid (H,B0,) 1.786 Sodium Acid Aluminum Phosphate 3.000 Nonionic deter ent Ex. I 2.750 Eemon fietergent Perfume 0.l50 Sodium Chloride 24.868 Pro lene Glycol 0.033 L Color solult!5ll"""' 0.445 t 3... Magnesium Silicate 2.000 Potassium dichloroisocyanurate 3.000
EXAMPLE 5 odium Tri l hos hate H exahydrate 59.9% Anhy runs 0 turn Metasilicafe gnfit'tlar 20.0 Boric Oxide (8,0,) 6.0 ,flon-ionic deter ent Ex. I L5 80 turn u fate 4.0 Sodium Chloride 4.4 Magnesium Silicate 2.0 Potassium Dichloroisocyanurate granular L6 40 Color solution 0.45 Lemon Detergent Perfume 0.l5 l00.00
The granular dishwasher product has a pronounced lemon fragrance which persisted for the shelf life of the product.
The screening test used to determine the perfume stabilization effect of boric oxide and/or boric acid comprises the addition of four drops of the perfume, oil or compound to be tested to approximately ninety grams of unperfumed base with and without the boron compound. After simple tumble mixing, the samples are aged at room temperature for at least a day for the effect to develop. The results are then checked by a perfumer. The lemon detergent perfume as well as eighteen citrus components of said perfume exhibits improved odor characteristics in the base with the boric oxide. Citral from lemongrass, citronella, citronellol and deodall tested in accordance with the above procedure, exhibits odor enhancement in the presence of either boric oxide or boric acid. in the absence of said boron stabilizer, aforesaid compounds lose their citrus fragrance after one day's aging.
While the detergent composition of the present invention finds most efficacious utilization in connection with the washing of the dishes and the like in automatic dishwashers, naturally, the detergent may be utilized in other fashions as desired. Usually, howwever, the best mode of use will be in connection with automatic dishwashers which have the ability of dispensing the detergent of the present invention in one or more separate wash cycles. Accordingly, the detergent composition of the present invention is added to the two receptacles, if such are present, in an automatic dishwasher. When the dishwasher is set into operation, after the dishes have been suitably positioned therein, the automatic devices of the dishwasher permit the addition of sufficient water to produce a concentration of the detergent composition of approximately 0.3% by weight. The operation of the dishwasher results in treating, that is, washing of the dishes with the aqueous solution of the detergent composition. Usually, the sequence of operation in utilizing an automatic dishwasher results in one or more rinsing steps following the one or more washing cycles. in utilizing the detergent composition of the present invention it will be noted that even after use for a considerable number of washings so that there is substantial air-space in the carton, there will be substantially no degradation of the citrus fragrance during the lifetime of the detergent composition in the carton or package.
Effective industrial bottle cleaning compositions may be provided in accordance with the present invention by merely admixing the perfumed detergent formulation with suitable active ingredients, e.g., caustic alkali whereby to provide a highly alkaline composition preferably having a pH of approximately l2. Such compositions may be readily formulated in accordance with the parameters hereinbefore described.
Results similar to those described in the foregoing examples are obtained when the procedures delineated therein are repeated but employing in lieu of the specific non-ionic detergent identified a variety of materials selected from nonionic, anionic, cationic, ampho- -teric and zwitterionic types. Moreover, various bleaching agents hereinbefore recommended for such purposes may be readily employed to advantage. Similarly, and citrus fragrance per se or in combination can advantageously be utilized in the formation ofa stabilized perfumed cleaning composition.
It will be apparent that many changes and modifications of the several features described herein may be made without departing from the spirit and scope of the invention. It is therefore apparent that the foregoing description is by way of illustration of the invention rather than limitation of the invention.
What is claimed is:
l. A stable. perfumed, alkaline detergent composition consisting essentially of from 0.05 to 1.0% by weight of citrus fragrance selected from the group consisting of argeol, benzyl acetate, citral, citronellal, citronellol, fleur delys, geraniol, heliotropine, linalool, peppermint oil, sandalwood oil, terpinyl acetate, glycidon, rhodinol, bergamot compound, lavindin abrial replacement compound, olibanum compound, and the composition consisting of mono-terpene hydrocarbons, cineole, fenchol, alpha-terpineol, cinnamaldehyde and coumarin, from about 40-95% by weight of water soluble organic and/or inorganic builder salts sufficient to yield a pH in water of from 9.5 to 12, from about 0.5 to 5% by weight of water soluble organic anionic and nonionic detergent and from 1 to 15% by weight of boron compound selected from the group consisting of boric oxide, boric acid and mixtures thereof.
2. A dishwasher product in accordance with claim 1, which contains about 0.5 to 5% by weight of a bleaching agent capable of liberating hypohalite on contact with aqueous media.
3. A composition in accordance with claim 1, wherein the surface-active agent is a low-foaming anionic agent.
4. A composition in accordance with claim 1, wherein the surface-active agent is non-ionic.
5. A composition in accordance with claim 1, wherein the citrus fragrance is citral.
6. A composition in accordance with claim 4, wherein the bleaching agent is chlorine-liberating.
7. A composition in accordance with claim 5,
wherein the boron compound is boric oxide.
UNITED STATES PATENT OFFICE CERTIFICATE OF CORI'iECTION PATENT NO. I 3,860,525 DATED January 1 1975 INVENTOR(S) Charles L. Bechtold It is certified that error appears In the 8bOVG--ldlltlfld patent and that said Letters Patent are hereby corrected as shown below:
Column 5, in the table beginning after line 50, delete "Trichloroisocyanurate" and insert --Dichloroisocyanurate-.
Column 6, line 7, delete "tri" and insert --di--.
Claim line 9,, after "composition consisting",
insert --essentially-- Signed and Sealed this twelfth Day of August 1975 [SEAL] Arrest:
RUTH C. MASON C. MARSHALL DANN .-llrcsring ()Ifr'm'r ('rmlmisximu'r u! Iuh'llls uml l'rmlumurkx UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION PATENT NO. 3,860,525 DATED January 1 1975 !NVENTOR(S) Charles L. Bechtold It is certified that error appears to the above--rdent1fieo patent and that sold Letters Patent are hereby corrected as shown below:
Column 5, in the table beginning after line 50, delete Trichloroisoeyanurate" and insert --Dichloroisocyanurate--.
Column 6, line 7, delete "tri" and insert -di.
Claim f line 9, after 'compositior: consisting",
insert --essentially-- Signed and Scaled this twelfth Day Of August1975 [SEAL] Arrest:
RUTH C. MASON C. MARSHALL DANN :UH'SII X ffiu' (nmmixsr'um'r n] Iulunlx uml 'lrut/cmurkx