US 3859225 A
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United States Patent [191 McKnight et a1.
1 3,859,225 1 Jan.7, 1975 1 DRYCLEANING DETERGENT COMPOSITION  Inventors: Eugene Audrey McKnight; Clyde Davis Kishbaugh, both of Stamford, Conn.
 Assignee: Stamford Chemical Industries, Inc.,
Cincinnati, Ohio  Filed: Sept. 7, 1971  Appl. No.: 178,409
Related U.S. Application Data  Continuation of Ser. No. 745,683, July 18, 1968,
 U.S. Cl 252/153, 8/142, 252/117, 252/118, 252/171, 252/542, 252/545, 252/546  Int. Cl. Clld 1/84, C1 1d 3/30, D061 1/04  Field of Search 252/117, 118, 526,527, 252/524, 542, 545,546, 153, 171; 8/142  References Cited UNITED STATES PATENTS 3,280,179 10/1966 Ernst 252/117 X Knaggs 252/153 3,600,318 8/1971 Mast 252/99 3,635,656 1/1972 Piepmeyer 8/142 3,697,452 10/1972 Olson et a1 252/545 3,715,186 2/1973 Anninos 8/142 FOREIGN PATENTS OR APPLICATIONS 705,862 3/1965 Canada 252/171 Primary ExaminerMayer Weinblatt Assistant Examiner-Dennis L. Albrecht Attorney, Agent, or Firm-Wood, Herron & Evans  ABSTRACT 4 Claims, No Drawings 1 DRYCLEANING DETERGENT COMPOSITION This is a continuation of application Ser. No. 745,683, filed July 18, 1968, now abandoned.
BACKGROUND OF THE INVENTION It has become a common practice to use a dry cleaning detergent in an. organic dry cleaning solvent to remove and suspend soil when cleaning soiled garments. It has also been proposed to substantively treat the garment during the dry cleaning process with an agent which tends to reduce soil redeposition and also contributes to fabric softness, as described in U.S. application Ser. No. 539,675 directed to Dry Cleaning Method and Detergents Therefor, filed Apr. 4, 1966. While the detergent compositions described in that application have provided new 1 improvements in dry cleaning garments, those compositions like other heretofore known compositions have only been capable to a limited extent in satisfactorily cleaning the garment while simultaneously providing the garment with softness and lint control.
Specifically, known detergents of the type described in the above mentioned application are not capable of providing sufficient anti-static protection in the dry cleaned garment along with equally desirable and important properties such as fabric softness. Various efforts heretofore have been made in an attempt to derive a detergent composition which not only provides detergency but also which substantively treats the garment during cleaning. These efforts have met with limited success. Also, heretofore garments have been antistaticly treated after being dry cleaned, usually by separate methods of coating or otherwise depositing antistatic agents upon the surface of the garment. These separate coating methods are not completely satisfactory because of the coatings tendency to render the dry cleaned garment harsh or stiff-like thereby destroying to some extent any garment softness which was imparted during the cleaning cycle. In short, known detergent compositions which have been proposed for sub stantive and detersive treatment of garments in methods of dry cleaning have achieved only limited improvements.
SUMMARY OF THE INVENTION This invention is directed to a new concept in detergent compositions. This concept involves the provision of a dry cleaning detergent composition which has a bundle of synergistically novel characteristics which are delicately balanced to supply detergency, soil suspension and soil redeposition prevention during the dry cleaning process and, moreover, which substantively treats the garment during the cleaning cycle to render it static-free and soft to the touch.
The detergent composition of this invention contains as essential ingredients a detergent, a garment softening agent and a garment anti-static agent. The detergent is a substance or a mixture of substances which provides a cleansing action to the surface of the garment being cleaned by a combination of properties including lowering of surface tension, wetting action,
emulsifying and dispersing action. The garment softening agent is characterized by its substantivity for the garment, Le, a specific or preferential affinity for the fabric or fibers even in the presence of the dry cleaning solvent and other detergent ingredients such that, when the cleaning solvent is removed, the softening agent remains substantively associated with the garment to supply it with a soft feel. The anti-static agent ofthis invention is also characterized by its substantivity for the garment in the same sense of preferential association mentioned for the softening agent. This anti-static agent will neutralize very rapidly any build-up of electrostatic charge on the garment either during the tumbling action of the cleaning cycle or thereafter in normal wear.
This invention is predicated in part upon the discovery that an anti-static agent can be incorporated directly into a dry cleaning detergent system along with a garment softening agent without upsetting the balance of detergency necessary to adequately remove, suspend, clean and soften the fabric. Moreover, in another of this invention s aspects, it has been determined that the anti-static agent not only is made to prevent build-up of static electricity during the cleaning and drying cycle of the dry cleaning method but also gives the garment a built-in conductor to rapidly dissipate static electricity when the garment is worn.
The detergent composition of this invention also eliminates the need to further treat garments with antistatic agents after they have been dry cleaned according to the mentioned known techniques. By eliminating separate techniques of anti-static treatment, this invention also eliminates the deleterious effects of such treatment as the harsh stiff-like fabric surface which is objectionable to the wearer.
In another of its aspects, this invention provides a balanced system of detergent ingredients which can be premixed and ready for introduction into any commercial dry cleaning unit without the necessity of separately charging and controlling ingredients at the dry cleaning installation site. As a practical matter, this feature is important because it permits the operation of equipment with minimummaterial control procedures. All that is necessary for use of the detergent composition according to this invention is to merely add the pre-mixed ingredients to the dry cleaning solvent. In other words, the detergent composition can be prepacked with all its synergistic properties ready for use.
Another significant aspect of this invention is the concept of economically providing a single'charge detergent system which can be supplied in very small amounts to the dry cleaning solvent of a commercial unit and which is virtually entirely consumed in the process of cleaning and substantively treating the fabric. Any amount of detergent ingredient remaining in the solvent is so insignificant that it can be disposed of. Moreover, such disposal eliminates the guess-work usually involved in accounting for amounts of left-over detergent in solvent for reuse according to prior art techniques. Thus, this invention also embodies a disposable dry cleaning detergent for use in a single charge system which does not require the detergent control in reuse of solvent which has heretofore been an economical necessity in commercial establishments.
The detergents for use in the composition according to this invention are of the conventional type comprising a substance or a mixture of substances that has a cleansing action due to a combination of properties including lowering of surface tension, wetting action, emulsifying and dispersing action. These conventional detergents are preferably of the synthetic type and generally fall into three main catagories: anionic, non-ionic and cationic or mixtures thereof. The anionic and nonionic type detergents have been found preferred because of their tendency to better suspend the soil in the dry cleaning solvent without becoming substantively associated as most cationic detergents would do thereby decreasing the cationic detergents soil suspension ability. Suitable examples of anionic detergents include soaps, and more preferably synthetic detergents of the class of alkali and alkaline salts of organic sulphonates or sulphates, particularly alkylaryl sulphonates (sulphonates of dodecylbenzene) usually formed by neutralization of dodecylbenzene sulphonic acid with an alkali material such as an alkaline earth metal salt or an alkylor alkanolamine. Also in this class of anionic detergents are alkaline earth metal salts of neutral phosphoric acid esters of oxyalkyated (e.g., oxyethylated) higher alkyl phenols or aliphatic monohydric alcohols. specific members of this latter class of metal salts of neutral phosphoric acid esters and methods of producing them are fully described in U.S. application Ser. No. 576,814, by Wetmore, et al., entitled Novel Detergent Compositions And Methods For Preparing Same" and that disclosure is incorporated herein by reference. Suitable examples of non-ionic detergents include the alkylphenoxy polyoxyethylene glycols, for example, ethylene oxide adducts of either octyl-, nonylor tri decyl-phenol and the like. These mentioned non-ionic detergents are usually prepared by the reaction of an alkylphenol with an ethylene oxide and commercial products are sold underthe trademark Triton X-35 by Rohm and Hass Company or the trademark TergitoP by Union Carbide and Carbon Corporation. Of course, the detergents selected from the general class of anionic, non-ionic and cationic groups of compounds can be used as mixtures.
The garment softening agent of the detergent composition according to this invention has, as mentioned, the essential requirement of substantivity for the fabric or garment to provide a soft hand and feel in the finished dry cleaned garment. Detergents of the cationic type which have been found to possess this desirable substantivity include cation-active agents of the type disclosed in U.S. application Ser. No. 539,675 directed to Dry Cleaning Method and Detergents Therefor, filed Apr. 4, 1966. These cation-active agents have been fully described in that application along with their methods of preparation and that disclosure is incorporated herein by reference. Briefly, cation-agents of this invention include betaines and quaternary ammonium compounds. Specific examples of betaines include the following:
Imidazoline betaines having the structural formula:
wherein R is a hydrocarbyl radical containing from 8 to 21 carbon atoms and R, is a lower alkyl or hydroxyalkyl radical and x is 2 or 3, such as l-hydroxyethyl, lcarboxyethyl, 2-pelargonyl (nonyl) imidazoline; 1- hydroxypropyl, l-carboxyethyl, 2-lauryl imidazoline,
pyridine betaines, such as N-dodecyl pyridinyl acetic acid; piperidine betaines, such as N-hexadecylpiperidinopropionic acid; aliphatic and carbocyclic betaines, such as N-dodecyl N, N-bisBhydroxyethylamino-acetic acid; N-octadecyl-N-fl-hydrocyethyl- N-carboxymethylaminoacetic acid; N-hexadec'yl-N, N- bis-carboxymethylaminopropionic acid; N-dodecyl-N- B,a-bis-hydroxypropyl-N-carboxylpropylaminoacetic acid; N-heptadecyl-N, N-hydroethoxyethyl-N-carboxymethylaminoacetic acid; N-decyl-N-B-hydroxyethyl- N-methyl-a-aminosuccinic acid; N-heptadecyl-N, N-bis-hydroxyethylaminoacetic acid; N- dodecylphenyl-N, N-bis-hydroxyethylaminopropionic acid; N, N-bis dodecyl-N-Bhydroxyethylaminoacetic acid; and betaines with hetero atoms in the hydrophobic chains such as dodecyloxypropyldimethyl aminoacetic acid, and mixed C to C alkoxyethyldimethyl aminopropionic acid.
Typical of the quaternary ammonium compounds may be mentioned cetyl pyridinium acetate; methyl cetyl piperidinium propionate, hydroxyethyl octadecyl morpholinium methosulfate, octyltrimethyl ammonium phosphate, N-oleylamidopropyl N, N, trimethyl ammonium dimethophosphate, p-stearamidophenyl trimethyl ammonium ethosulfate, N, N dilauryl, N, N dimethyl ammonium diethophosphate.
It is to be understood that other compounds can demonstrate a substantivity for the fabric to provide softness, the essential requirement being that they achieve the advantages of this invention. However, the specific mentioned betaines and quaternary compounds have been found essentially preferred because this invention provides for effective use of their known soil redeposition prevention and detersive properties even though combined with the detergent and anti-static agents of this invention.
The garment anti-static agent which has been found to synergistically behave with the detergent and garment softening agent according to the principles of this invention is a humectant, i.e., a substance that promotes the retention of moisture during the dry cleaning cycle and in the garment after it is dried and ready for wear. The term humectant is used herein to denote a substance having an affinity for water and a stabilizing action on the water content of the garment or fabric to provide an electrically conductive surface which neutralizes any build-up of electrical charge very rapidly from the surface of the fabric thereby rendering the surface static-free. Humectants for use in accordance with this invention include hydratable solids or liquids which demonstrate substantivity for the fabric during the cleaning process in the presence of the other detergent ingredients and also remain substantively associated with the fabric after the garment has been cleaned and dried. More particularly, the anti-static agents according to this invention are selected from the group consisting of mineral acid salts, water soluble salts of organic acids and polyols. Of those mineral acid salts, specific examples include either the mono-, diand tri-enthanolamine salts of hydrochlorid acid, phosphoric acid, sulphuric acid, and mixtures thereof. Suitable examples of the organic acids include either the mono-, diand tri-ethanolamine salts of acetic acid, propionic acid, formic acid and mixtures thereof. Suitable examples of polyols are ethylene glycol, propylene glycol, butylene glycol, glycerin, sorbitol, mannitol and the like. Of course, mixtures of the mentioned antistatic agents or other equivalent agents can be used.
In a presently preferred mode and to achieve the mentioned advantages of having a pre-packed detergent composition according to this invention, with all of the essential synergistic ingredients ready for introduction into a dry cleaning solvent system, the-essential ingredients are pre-mixed with or without suitable carrier or diluent. The use of a carrier or diluent is preferred to facilitate handling and storage. The quantities of detergent, garment softening agent and garment anti-static agent in the dry cleaning detergent composition will vary depending upon the specific chemical compounds utilized. The detergent in this mixture of ingredients is generally in an amount in the range of about 25% to about 75% by weight based upon total weight of the three essential ingredients and usually is an amount of about 50% by weight of the total. Correspondingly, the total amount of the garment softening agent and anti-static agent in the dry cleaning detergent mixture is in the range of about 75% to about 25% by weight based upon total weight of the three essential ingredients. The ratio of the garment softening agent to the anti-static agent is suitably from about 1:9 to about 9:1 and normally is of about a 1:1 ratio. As may be seen, the ratios of the essential ingredients may vary over a relatively wide range.
As mentioned, the essential ingredients of the detergent composition of this invention can be pre-mixed with carrier fluids or diluents to facilitate their handling and storage. The use of a diluent in the pre-mix is, however, not essential to this invention in its broader aspects. Suitable pre-mix diluents include organic solvents such as kerosene, alcohols, Stoddard, perchloroethylene and other hydrocarbon solvents which are compatible with dry cleaning solvents.
As mentioned, only small amounts of the essential ingredients need to be present in the dry cleaning solvent during the dry cleaning cycle to achieve the advantageous synergism of detergency, soil suspension, soil redeposition prevention, fabric softness and anti-static control according to the principles of this invention. In general, the concentration of active ingredients in the dry cleaning solvent mixture is at a level which may range from about 0.01% up to about 12% of the dry cleaning solvent (expressed as percent by volume). Of course, it is to be understood that this mentioned lower level of 0.01% is approximated and may vary depending upon the garments, detergent composition, etc. Above about 1-2%, it has been found that garments may tend to get sticky, harsh or stiff, thereby tending to lack the desired degree of comfort when worn. This upper limit is not precise and varies from garment to garment, depending upon the chemical nature of the ingredients being used in the detergent composition and their relationship to the nature of the fiber of the fabric.
The detergent compositions according to this invention can be used in all types of dry cleaning solvents, i.e., polar or non-polar organic solvents. The dry cleaning solvents suitable for use in this invention include hydrocarbon and chlorinated hydrocarbon solvents, e.g., Stoddard solvent and perchloroethylene or trichloroethylene or mixtures of these solvents. Also, the dry cleaning solvents conventionally used can be moisturized, i.e., where water is added in a minor amount to facilitate the suspension and the removal of water soluble soil in the garment to be dry cleaned. The exact amount of water present in a moisturized-solvent system depends upon a number of factors such as the type of garment being cleaned, water soluble or dispersible soil load, tendencies of fiber shrinkage, and the like, but normally water is in an amount of about 0.003% 0.05% by volume in the dry cleaning solvent. A unique feature of the detergent composition of this invention is its ability to contain water for use is moisturized dry cleaning without adverse effects.
The following examples will further illustrate the practice of this invention and the advantages secured thereby.
EXAMPLE I A conventional dry cleaning machine of the rotary drum type was charged with about gal. of perchloroethylene as the dry cleaning solvent and about 60 lbs. soiled garments were introduced into the solvent-filled drum. The following detergent composition was then added to the solvent-clothes charged drum in an amount of about 0.1% by volume based upon gallons of perchloroethylene present (0.2 ounces detergent composition per 100 gallons of solvent). All percents are by weight.
15% l-hydroxyethyl, l-carboxyethyl, 2-oleyl imidazoline, as a 66.7% solution in triethylene glycol.
10% Diethanolamine hydrochloride solution containing about 35% by weight of water.
35% Anionic detergent mixture containing: 12.1% magnesium phosphate ester of Triton X-35, defined below; 1% coconut oil alkanolamide, Monamid AD by Mona Industries; 4% of a free acid of a complex organic phosphate ester, Gafac RE 610 by General Aniline and Film; 0.4% of a 50% aqueous solution of NaOH and 82.5% deodorized kerosene.
10% Non-ionic detergent containing ethylene oxide adduct of octylphenol having an average of about 3.5 moles of ethylene oxide to about 1 mole of octylphenol, sold under the trademark Triton X-35" by Rohm and Hass Company.
10% An anionic detergent mixture containing: 1 1.7% dodecylbenzene sulfonic acid; 0.5% water; 30.6% petroleum sulfonates; 44.4% deodorized kerosene; 6.6% Triton X-35, defined above; 0.7% monoisopropanolamine; 4.1% triethanolamine and 1.4% methylamyl alcohol.
20% Deodorized kerosene.
After the detergent composition was charged, the drum was agitated for about 10 to about 15 minutes to dry clean the clothes after which the solvent was drained. The clothes were centrifuged to remove excess solvent and dried by heating.
The detergent composition of this example was found to provide excellent detergency, soil suspension and soil redeposition prevention during the dry cleaning process as measured by the detergency and soil removal tests commonly adopted in the industry. Moreover, the cleaned garments were found to possess an excellent soft hand and feel in addition to having an anti-static surface.
EXAMPLE I] The procedures of Example 1 were repeated except .that the detergent composition which was added to the dry cleaning solvent contained the following ingredients:
50% Anionic detergent mixture containing: 12.1% magnesium phosphate ester of Triton X-35, defined above; 1% coconut oil alkanolamide, Monamid 150 AD by Mona Industries; 4% of a free acid of a complex organic phosphate ester, Gafac RE 610 by General Aniline and Film; 0.4% of a 50% aqueous solution of NaOH and 82.5% deodorized kerosene.
20% l-hydroxyethyl, l-carboxyethyl, 2-olelyl imidazoline.
10% Anionic detergent mixture containing: 11.7% dodecylbenzene sulfonic acid; 0.5% water; 30.6% petroleum sulfonates; 44.4% deodorized kerosene; 6.6% Triton X-35 defined above; 0.7% monoisopropanolamine; 4.1% triethanolamine and 1.4% methylamyl alcohol.
% Diethanolamine hydrochloride.
The dry cleaned garments according to this example were found to have properties similar to those of the garments cleaned according to the procedure in Example I.
There are many substitutions or modifications which can be made in the above examples in accordance with NCH2 wherein R is a hydrocarbyl radical containing from 8 to 21 carbon atoms, and R is a lower alkyl or hydroxyalkyl radical and x is 2 or 3,
N-dodecyl pyridinyl acetic acid,
N-dodecyl-N, N-bis-B-hydroxyethylaminoacetic acid,
N-octadecyl-N-B-hydroxyethyl-N-carboxyme thylaminoacetic acid,
N-hexadecyl-N, N-bis-carboxymethylaminopropionic 'acid,
N-heptadecyl-N, N-hydroethoxyethyl-N-carboxymethylaminoacetic acid,
N-dodecylphenyl-N, N-bis-hydroxyethylaminopropionic acid,
Dodecyl-oxypropyl-dimethyl aminoacetic acid,
and mixed C to C alkoxyethyl-dimethyl aminopropionic acid,
and a humectant as a garment anti-static agent selected from the group consisting of (a) a mineral acid salt selected from the group consisting of mono-, diand triethanolamine salts of hydrochloric acid, phosphoric acid, sulfuric acid and mixtures thereof and (b) a water soluble salt of an organic acid selected from the group consisting of mono-, diand tri-ethanolamine salts of acetic acid, propionic acid, formic acid and mixtures thereof, wherein said detergent is present in an amount of about 25% to about by total weight of said ingredients and the remaining amount of said ingredients being constituted by said garment softening agent and said anti-static agent in a ratio in the range of about 1:9 to about 9:1.
2. A dry cleaning composition consisting essentially of the dry cleaning detergent composition according to claim 1 and an hydrocarbon dry cleaning solvent wherein said detergent composition is present in said dry cleaning solvent in an amount in the range of about 0.01 up to about 2% by volume of the dry cleaning solvent.
3. The dry cleaning composition of claim 2 which additionally contains water in an amount of about 0.003% to about 0.05% by volume of said dry cleaning solvent.
4. The detergent composition of claim 1 wherein said betaine is selected from the group consisting of lhydroxyethyl, l-carboxyethyl, 2-pelargonyl imidazoline, l-hydroxypropyl, l-carboxyethyl, 2-lauryl imidazoline and l-hydroxyethyl, l-carboxyethyl, 2-oleyl imid-- azoline.