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Publication numberUS3018251 A
Publication typeGrant
Publication dateJan 23, 1962
Filing dateJan 11, 1957
Priority dateJan 11, 1957
Publication numberUS 3018251 A, US 3018251A, US-A-3018251, US3018251 A, US3018251A
InventorsRaymond L Mayhew, Iii John P Miller, Kopp Marvin
Original AssigneeGen Aniline & Film Corp
Export CitationBiBTeX, EndNote, RefMan
External Links: USPTO, USPTO Assignment, Espacenet
Dry cleaning compositions
US 3018251 A
Abstract  available in
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Claims  available in
Description  (OCR text may contain errors)

3,018,251 DRY CLEANING COMPOSITIONS Raymond L. Mayhew, Phillipsburg, and John P. Miller III, Bloomfield, N.J., and Marvin Kopp, Lenox, Mass., assignors to General Aniline & Film Corporation, New York, N.Y., a corporation of Delaware No Drawing. Filed Jan. 11, 1957, Ser. No. 633,545 6 Claims. (Cl. 252-152) This invention relates to improvements in the dry cleaning of fibrous textiles and related materials and more particularly to new and improved compositions for use with dry cleaning solvents, and to processes of dry cleaning wherein said improved compositions are employed.

It is well known that many types of fabrics and materials cannot be cleaned by the ordinary means of soap or detergents and water, such as are employed in laundering type operations since the presence of water deleteriously affects such materials. To provide effective cleaning for such materials, a dry cleaning process must be used. Dry cleaning processes employ organic solvents which are effective in removing from the materials treated most of the undesirable dirt, grease, dust and the like. It is also a common expedient in dry cleaning processes to add a small amount of water which, sufficiently dis persed in the dry cleaning fluid, will be effective to remove water-soluble stains without adversely affecting the material treated.

It is therefore an object of this invention to provide new compositions, particularly suitable for use in dry cleaning operations.

It is a further object of this invention to provide new compositions suitable for use in all of the generally employed dry cleaning solvents.

It is a still further object of this invention to provide new compositions which give outstanding and improved cleaning ability by virtue of an outstanding detergency action coupled with an excellent ability to prevent soil redeposition on the materials treated.

It is another object of this invention to provide an improved process of dry cleaning in all types of dry cleaning solvents.

It is a further object of this invention to provide an improved process of dry cleaning wherein the usual dry cleaning solvents are employed in conjunction with minor amounts of water.

According to the present invention the new compositions thereof, hereinafter termed dry cleaning compositions, to be incorporated in the usual dry cleaning solvents contain as the essential components thereof a cationic surfactant derived from fatty amines and an alkylene oxide and at least one anionic surfactant. In addition thereto it is desirable to incorporate in the above described mixture an additional surfactant of the nonionic type.

Compositions as above described give particularly outstanding results in all types of dry cleaning solvents. In addition, they give excellent results where a small amount of water has been incorporated into the dry cleaning solvent for the purposes described above. Among the dry cleaning solvents one may use and which are normally employed in dry cleaning operations are the following:

Gasoline Kerosene Trichloroethylene Tetrachloroethylene Carbon tetrachloride Stoddard solvent, and the like The cationic agents which are contemplated in this invention are derived as described above from fatty amines reacted with alkylene oxides or their equivalent. The fatty amines which are employed herein are those amines which contain at least 75% unsaturated linkages therein,

3,018,251 Patented Jan. 23, 1962 "ice Percent Octadecadienyl amine 45 Octadecenyl amine 3S Octadccyl amine 10 Hexadecyl amin 10 It will be noted that this nixture contains 80% unsaturates of which 45% are of the diethenoid type. It is of course possible to employ in the preparation of the compositions of this invention synthetically prepared mixtures from the various amines within the scope of this invention and it is further possible to employ the pure unsaturated amines provided they come within the scope of the above limitations. In addition to soybean amine, numerous other fatty oils are suitable as precursors for the amines operable in this invention. Such fatty oils include cottonseed oil, corn oil, sesame oil, sunflower seed oil and the like. The approximate acid constituents of these oils are given below:

Cotton seed oil Amines derived from these oils in the manner of that described above for soybean amine will contain at least of the amine constituent as unsaturates of which amount at least 35% will represent doubly unsaturated compounds. In addition to the above mentioned fatty oils it is also possible to employ other naturally occurring materials which, upon suitable treatment by hydrolysis, ammonolysis and reduction, yield an amine or mixtures of amines coming within the scope of the limitations described above as to the unsaturate content thereof. The cationic agent suitable for use in the compositions of this invention are prepared from the above described amines or mixtures of amines by well known reactions with alkylene oxides or their equivalents. The polyoxyalkylated products resulting from such processes which are suitable for use in this invention are those products which contain from about 14 to about 53% alkylene oxide or its equivalent (l to 7 moles of alkylene oxide per mole of amine). Methods for the preparation of such condensation products are described in United States Patents 1,970,578 and 2,213,477.

The anionic synthetic surfactant to be employed as the second component of the compositions of this invention include the alkyl aryl sulfonates such as sodium keryl benzene sulfonate, diisobutyl naphthalene sulfonic acid and the like, the N-fatty acid acyl-N-alkyl taurates, such as sodium-N-oleoyl-N-methyl taurate, sodium-N-lauryl- N-cyclohexyl taurate, and the like, alkyl aryl-polyoxyalkylene salts such as those derived from alkylated aromatic hydroxy compounds of the benzene and naphthalene series reacted with 3 to 7 moles of an alkylene oxide or its equivalent and subsequently esterified with a strong acid such as sulfonic, phosphoric or the like. Additionally, anionic salts from the nonionic alkyl aryl polyoxyalkylene glycols described below may be employed.

In addition to the two classes of ingredients described above, that is, the cationic and anionic surfactants, there may be employed in the composition a nonionic surfactant of the alkyl aryl polyoxyalkylene glycol type. These glycol ethers may be derived in the known manner from alkylated aromatic hydroxy compounds of the benzene and naphthalene series such as p-n-butylphenol, amylcresol, diisobutylphenol, diamylphenol, isohexylphenol, oleylphenol, isododecylphenol, tetradecylphenol, isooctylresorcinol, nonylphenol, dinonylphenol, isooctylphenol, isooctyl-fi-naphthol, isohexylxylenol, n-octadecylphenol, and the like. In general, these alkylated aromatic hydroxy compounds should contain at least one alkyl radical of at least 4 carbon atoms as a ring substituent. It will be understood that such compounds may contain up to 3 alkyl substituents which may be straight or branched, which substituents may contain a total of or more carbon atoms.

These alkylaryl hydroxy compounds are polyoxyalkylenated by reaction under proper conditions, preferably in the presence of an alkaline catalyst such as potassium hydroxide or sodium hydroxide, and heat and pressure, with from 3 to 7 moles of an alkylene oxide such as ethylene oxide, propylene oxide, or the like, or mixtures thereof.

The anionic polyoxyalkylene salts described above are readily prepared from these nonionic compounds by subjecting said nonionic glycol ether to esterification with a strong acid such as chlorosulfonic, sulfamic, sulfuric, or phosphoric or with an inorganic acid anhydride such as sulfur trioxide or phosphorus pentoxide or with acid halides such as sulfuryl chloride, phosphorus oxychloride or phosphorus pentachloride or the like. When a properly substituted acid mixture is employed in the esterification such as aminosulfonic acids, sulfamic acid, ammonium bisulfate, and the like, a. water-soluble or dispersible salt is directly produced without the necessity of subsequent neutralization with a basic substance. In such cases, subsequent treatment with basic materials is only for the purpose of neutralizing excess acid, and the like. Excellent results are also obtained when complexes of some of the above acids and anhydrides are employed. For example, a combination of sulfur trioxide or chlorosulfonic acid with an ether such as dioxane, thioxane or [3,,8' dichlorodiethylether, or with a tertiary nitrogen base such as pyridine or triethylamine may be used. The resulting esters may be neutralized with a basic material such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium acetate, ammonium hydroxide, ammonia, calcium oxide and hydroxide, magnesium oxide and hydroxide, strontium hydroxide, cthanolaminc, diethanolamine, triethanolamine, methylamine, dimethylamine, trimethylamine, ethylamine, triethylamine, diethylamine, butylamine, propylamine, cyclohexylarnine, morpholine, pyridine, octanolamine, octylamine, and the like.

The greatest values to be derived from this invention lie not only in the superior detergent action of the dry cleaning compositions thereof but further, in the outstanding characteristics of soil rcdeposition prevention and whiteness retention which are evident in all types of dry cleaning solvents. This is in contrast to the usual detergent compositions which are suitable for use in only one of the two major types of dry cleaning solvent systems. In order to achieve the excellent and superior effects to be derived from the use of the compositions of this invention, the proportions of the various ingredients thereof must be employed within certain critical limits. The cationic surfactant which, as described above, is of the polyoxyalkylated unsaturated amine type, should comprise at least 25% on a volume basis of the total surfactants present, and no more than about 55%. The above described anionic agents should be employed within the range of 30 to 75% on a volume basis based on the total surfactants present. The nonionic compounds when present should not exceed on a volume basis 30% of the total surfactants. While it is not essential in order to achieve outstanding results with the compositions of this invention to incorporate a nonionic agent in the majority of formulations, the addition thereto of nonionics results in compositions of exceptionally outstanding properties. The formulations hereinafter described where specific data is indicated for detergency action and whiteness retention characteristics were tested as follows:

Into each of 8 pint Mason jars there were introduced- 50 /2 in. steel balls 50 ml. of solvent 1 3 /2 in. diameter circular swatch of acetate jersey or Botany wool flannel, soiled or unsoiled, as indicated below. The 8 jars contained the following:

TABLE 1 Launder-Ometer test components Test Acetate jersey solled swatch Detergency. Wool flannel soiled swatch Do. Acetatie jersey soiled swatch, detergent wet Do.

stoc Wool lflannel soiled swatch, detergent wet Do.

stoc Unsoiled acetate jersey swatch, 5 mg. syn- Itedeposltlon.

thetic dry soil. Unsoiled acetate wool flannel swatch, 5 mg. Do.

synthetic dry soil. Unsoiled acetate jersey swatch, 5 mg. syn- Do.

thetic dry soil, detergent wet stock. Unsolled wool flannel swatch, 5 mg. syn- Do.

thetlc dry soil, detergent wet stock.

The synthetic dry soil used in the above tests has the following composition:


Synthetic soil composition Ingredients mixed as follows:

The above were mixed in a ball mill until heterogeneous. The oils listed below were melted and blended by hand into the powdered mixture. They were:

Components Percent Grams stenric acid 1. 6 16.0 olelc acid 1. ti 16. 0 palm oil fatty acid (lInrsborn) 3. .5 32. o lnuryl alcohol t). 5 5.1) lanolin unltydride (Merck) 1.0 10.0 m-mrtmlccznn: (Conn. llnrtl ltnbhcr). 1.1 ll." l-oetadccenc (Humphrey \l'ilkinuon) 1.1 11. (t

1500 ml. H O were added. The above were mixed in a ball mill for 16 hours and dried. The dried soil was then pulverized in a hammer mill to approximately 200 mesh.

The cloth used for detergcncy tests was soiled by padding in the Butterworth three-roll padder, giving 3 passes 6 reacted with 33% ethylene oxide are added to 10 parts of Stoddard solvent (3. petroleum solvent). The elficiency of the above formulation is set forth in Table 3 and a comparison with other commercial dry cleaning dethrough a suspension of the synthetic dry soil in 5 tergents and a control containing no detergent is also Stoddard solvent and air drying the cloth. All cloth was given. stored in a constant humidity chamber prior to use at a In the following table, column 1 indicates the detergent relatively humid ty of 50 to 63%. tested, column 2 the fabric, which is prepared for the The test conditions were as follows: detergency tests as described above. Column 3 lists Apparatus employed: Atlas Launder-Ometer (42 rpm.) g sPlvents i 3 1 3 thedeergency gl with water bath drain to avoid excess moisture F a i Dye age or} re q i g' Temperature: Temperature maintained at room temperae S ta en as a magneslum e :10 ture The unsoiled rayon and wool have varying degrees of Medium: Stoddard solvent or perchlorethylene5l) cc. (hltemss and f f the mgmficam values are the cleaningcycle. min 15 differences appearing in columns 5 and 7. Thus the Rinse cycle: 15 min., in 50 cc. clean solvent larger g izl .93 1S g g q Control: Appropriate solvent with no detergent added acne 0 t e e H t e gum.m column 7 the better is the composition for preventing In the hQ E examples which W111 serve to mplify soil redeposition. The figures in column 6(a) are the the compositions and processes of this invention, it will values obtained for unsoiled, untreated fabrics, those of be understood that such exemplification is not deemed to column 6(b) the values for the same swatches put through be limitative of the invention herein covered. In the a cleaning cycle as indicated in Table 1 for jars 5-8.

TABLE 3 Reflectance Readings Detergency whiteness Retentlon 1 2 3 Detergent Fabric Solvent 4 5 6 7 Soiled Cleaned Before After Cleaning Cleaning rayon L. 51.0 53. 0 2 77.1 57. 5 19.6 32. 0 35. 0 3 63. 0 47. 0 16. o 52.3 66.0 14.6 77.1 70.0 7.1 34.0 53.3 19.3 62.8 61.0 1.8 40. 7 60. 5 10. s 77.3 66. 0 11.3 44.5 50.5 6.0 63.5 60.8 12.7 51. 4 66. 7 15. 3 77.3 71. 0 6. 3 42.0 60.0 12.0 63.2 61.0 2.2 30. 6 34. 0 3. 4 78.8 58. 3 20. 5 24. 0 23. 3 (a) 62. 0 47. 1 14.9 36.0 45.0 0.9 78.0 53.0 20.0 23. 9 31.1 7. 2 63. 6 55. 5 8.1 34.0 43.0 0.0 77.0 49.6 27.4 24.1 26.0 1.0 63.9 40.2 14.7 34. 5 1 57.2 22. 7 77. 0 64.0 13. 0 24.6 46.0 22.0 63.4 57.1 6.3 34.0 43.0 9.0 77.8 70.0 7.0 24.1 26.0 1.9 64.5 56.0 8.5 34.5 47.2 12.7 77.0 72.1 7.8 24.6 36.0 12.6 64.5 56.1 2.4 34.3 64.0 20.7 77.4 72.5 4.0 24. 7 37. 0 13. 7 64. 5 57. 5 7. 0 36.2 65.6 20.4 77.7 67.3 9.0 24.4 48.4 24.0 64.4 57.0 6.5 36. 0 54. 0 l8. 0 70.5 56. 7 13. 8 23. 7 24. s 1.1 61. 0 40. 0 12.0 36. 7 61. 7 25. 0 70. 3 66. 1 5. 2 22.4 31.7 0.3 61.0 55.0 6.0 3-1. 1 50. 1 16. 0 77. s 53. 0 24. s 25. 5 32. 2 6. 7 64. 0 52. 0 12. 0 34. 2 36. 3 1.5 76. 0 50. 0 10.0 25. 3 35. 7 10. 4 64. 5 50.9 13. 6

1 Acetate jersey.

2 Wool flannel.

a Stoddard solvent. Perchloroethylene.

5 Useful only in solvent tested. 6 The cleaned wool was not cleaned ln this test.

7 Fabric badly streaked.

w '1li0seagenls useful only in the solvents tested.

said examples, parts indicates parts on a volume basis unless otherwise indicated.

EXAMPLE 1 A mixture of 7 parts diisobutyl naphthalene sulfonic acid and 2 parts of a cationic surfactant prepared from refined soybean amine having the following composition:

' Percent Octadecadienyl amine Octadecenyl amine 35 Octadecyl amine l0 Hexadecyl amine 10 Example 1 when tested in Stoddard solvent on rayon 001207605902485220000552 6 LZZZOKLA QL 8 4-4L3 &L MMG66H665766576H4756576 oooozvuu n 221 varying pro- Whlteness Retention Before Cleaning Cleaning 805293565765901207 033004 &&3 7 Z5 Q&4 0 &lomomidflqwomflinhid 1221321112 111 321 32 Percent EXAMPLE 3 EXAMPLE 4 Table 4.

Reflectance Readings Cleaned Anionic Agent Parts iven in TABLE 4 Detergency Solled TABLE 5 ti parts D 0 Alkylaryl polyoxyethylene glycol 3.0 Reaction product of refined soybean amine containing 33% ethylene oxide 4.0 Sodium keryl benzene sulfonate 3.0

Sodium N-oleoyl-N-methyltaurate. 5 Reaction product of refined soybean amine containing ethylene oxide (33%).. 6 n-Butanol 1 Petroleum solvent 4 Solvent A composition comprising the following ingredients is prepared:


10 idNgnyl phenoxy polyoxyethylene ethanol (58% ethylene The results are given in Table 4.

A composition comprising the following ingredients is 5 prepared:

Components The results are g In the following Examples 5 through 12 portions of cationic, anionic and nonionic surfactants are Cationic Agent Parts Parts by volume 4.0 1 Diisobutyl naphthalene sulfonic acid 1.5

Commercial agent D'with rayon,

EXAMPLE 2 A composition comprising the following ingredients is prepared gives a value of 14.6 in column 5 as opposed to a value of 2.0 for the control. on the other hand, gives a value of 29.4 but this must be compared to the control value of 29.7 which indicates that here the detergent impaired the normal action of the 5 solvent.


Alkylaryl polyoxyethylene glycol 3.0 Reaction product of refined soybean amine containing 33% ethylene oxide Alkylaryl polyoxyethylene sulfate 1.5 Petroleum solvent"--- 5.0

:Nonyl phenoxy polyoxyethylene ethanol (58% ethylene ox e).

Ammonium salt of the sulfate ester of nonyl phenoxy (58% ethylene oxide).

Example Table 4.

l A is rcactionprotluot showing refined soybean ainine containing 33% ethelene oxide.

1 ll isrmtolion product showing refined soybean amine containing 14% ethylene oxide.

3 is react ion nroduot showing refined soyhcanainino containing 53% ethylene oxide.

l) is diisohntyl nuphtlmlonv sulfouic aeidi 5 E is sodium laoryl hem no sullouate.

7 (l is nouyl phon xy polyoxyothylcnc ethanol.

employed. In each instance the results are outstanding in so far as detergency action is concerned and further, there is excellent soil redeposition prevention.

This invention has been disclosed with respect to certain preferred embodiments. Various modifications and variations of these embodiments will become apparent to those skilled in the art, and it is to be understood that such modifications and variations are to be included within the spirit and purview of this application and the scope of the appended claims.

We claim:

1., A composition adapted for use in the dry cleaning of textile and fibrous materials consisting essentially of a surface active agent mixture for each 100 parts of which there are present at least 25 parts of a polyoxyalkylated dialkenoid fatty amine containing from about 14 to about 53% alkylene oxide and 30 to 75 parts of an anionic surface active agent.

2. A composition adapted for use in the dry cleaning of textile and fibrous materials consisting essentially of a surface active agent mixture for each 100 parts of which there are present at least 25 parts of a polyoxyalkylated dialkenoid fatty amine containing from about 14 to about 53% ethylene oxide and 30 to 75 parts of an anionic surface active agent selected from the group consisting of alkylaryl sulfonate surface active agents, N-fatty acid acyl-N-alkyl taurate surface active agents and alkylaryl polyoxyalkylated salt surface active agents and mixtures thereof.

3. A composition adapted for use in the dry cleaning anionic surface active agent is diisobutyl naphthalene sulfonic acid.

5. A composition as defined in claim 3 wherein the anionic surface active agent is a mixture of diisobutyl naphthalene sulfonic acid and an alkylaryl polyoxyethylene sulfate.

6. A composition as defined in claim 3 wherein the anionic surface active agent is sodium N-oleoyl-N-methyl taurate.

References Cited in the file of this patent UNITED STATES PATENTS 2,271,635 Flett Feb. 3, 1942 2,619,467 'Isbell Nov. 25, 1952 2,677,700 Jackson et al. May 4, 1954 2,697,075 Echols Dec. 14, 1954 2,721,847 Gebhart et a1 Oct. 25, 1955 2,733,212 Epstein et a1. Jan. 31, 1956 2,778,814 Behrens et al. Jan. 22, 1957

Patent Citations
Cited PatentFiling datePublication dateApplicantTitle
US2271635 *Sep 25, 1935Feb 3, 1942Allied Chem & Dye CorpDry cleaning composition and method
US2619467 *Apr 16, 1949Nov 25, 1952 Detergent mixtures containing
US2677700 *May 31, 1951May 4, 1954Wyandotte Chemicals CorpPolyoxyalkylene surface active agents
US2697075 *Dec 21, 1951Dec 14, 1954California Research CorpDry-cleaning compositions
US2721847 *Mar 28, 1950Oct 25, 1955Colgate Palmolive CoSynthetic detergent composition
US2733212 *Jan 2, 1952Jan 31, 1956 Hair shampoo
US2778814 *Nov 7, 1952Jan 22, 1957 Alkyl aryl sulfonic acid amine salt
Referenced by
Citing PatentFiling datePublication dateApplicantTitle
US3162604 *May 10, 1960Dec 22, 1964Stamford Chemical Ind IncDry cleaning solvent compositions
US3190836 *Jul 3, 1962Jun 22, 1965Atlantic Refining CoWater-soluble liquid detergent compositions
US3222286 *Oct 19, 1962Dec 7, 1965Shell Oil CoDry cleaning composition
US3226331 *Jul 3, 1962Dec 28, 1965Atlantic Refining CoOil-soluble liquid detergent compositions
US3345300 *Dec 10, 1952Oct 3, 1967 Ohj-ohi
US3378496 *May 8, 1964Apr 16, 1968Kuhlmann EtsDetergent compositions useful for dry cleaning
US3962151 *Aug 6, 1973Jun 8, 1976Lever Brothers CompanySolvent type cleaners
U.S. Classification510/289, 510/537, 510/499, 510/413, 516/DIG.500, 510/496, 510/494
International ClassificationD06L1/04
Cooperative ClassificationY10S516/05, D06L1/04
European ClassificationD06L1/04