US3628911A

US3628911A - Textile chemical cleaning processes

Info

Publication number: US3628911A
Application number: US776753A
Authority: US
Inventors: Werner Grunewalder
Original assignee: Henkel AG and Co KGaA
Current assignee: Henkel AG and Co KGaA
Priority date: 1967-12-08
Filing date: 1968-11-18
Publication date: 1971-12-21
Anticipated expiration: 1988-12-21
Also published as: GB1248757A; TR16758A; SE351244B; DK130421B; BE724984A; DK130421C; DE1617136B1; FR1590310A; CH481256A; DK130421A; NL6815957A; AT289713B

Abstract

In the chemical cleaning of textiles by subjecting the textiles to a chemical cleaning bath consisting of a major amount of an organic solvent, a minor amount of water and a surface-active cleaning intensifier, the improvement which comprises utilizing, as said cleaning intensifier, an addition product of 2 to 14 mols of propylene oxide to an alcohol selected from the group consisting of primary alkanols having from 10 to 20 carbon atoms, primary alkenols having from 10 to 20 carbon atoms and alkylphenols having from six to 12 carbon atoms in the alkyl. The invention also relates to the chemical cleaning bath and the preliminary emulsion containing the organic solvent, water and the propylene oxide adduct.

Description

United Mates atem [72] Inventor Werner Grunewalder Duesseldorl-Elolthausen, Germany [21] Appl. No. 776,753

[22] Filed Nov. 18, 1968 [45] Patented Dec. 21, 1971 [73] Assignee Henkel & Cle Gmbll Duesseldorf-Holthausen, Germany [32] Priority Dec. 8, 1967 [33] Germany [54] TEXTILE CHEMIHCAL CLEANING PROCESSES 2 Claims, No Drawings 5n lm.Cl D061 1/02 [50] Field of Search 8/142;

[56] References Cited UNITED STATES PATENTS 2,213,477 9/1940 Steindorffet a1. 252/89 X Primary ExaminerMayer Weinblatt Attorney-Hammond & Littell ABSTRACT: In the chemical cleaning of textiles by subjecting the textiles to a chemical cleaning bath consisting of a major amount of an organic solvent, a minor amount of water and a surface-active cleaning intensifier, the improvement which comprises utilizing, as said cleaning intensifier, an addition product of 2 to 14 mols of propylene oxide to an alcohol selected from the group consisting of primary alkanols having from 10 to 20 carbon atoms, primary alkenols having from 10 to 20 carbon atoms and alkylphenols having from six to 12 carbon atoms in the alkyl. The invention also relates to the chemical cleaning bath and the preliminary emulsion containing the organic solvent, water and the propylene oxide adduct.

TEXTILE CHEMICAL CLEANING PROCESSES THE PRIOR ART The chemical cleaning of textiles in organic solvents with the addition of surface-active cleaning intensifiers is known. In this case, a small addition of water to the cleaning baths has been found advantageous in order to be able to remove watersoluble dirt more easily. The surface-active cleaning intensifiers are incorporated in the cleaning bath in order to bring about a good emulsification and solubilizing of the water in the cleaning bath, in order to prevent clogging of the filter and damage to the textiles owing to an uneven absorption of water. It has been shown that, owing to their strong hydrophilic character, the surface-active cleaning intensifiers presently used are absorbed on the fibers to a considerable extent together with the water taken up by the textiles. The surfaceactive substances remaining absorbed on the fiber cannot be satisfactorily removed again, even by a subsequent rinsing with pure solvent.

After the chemical cleaning, the cleaned textiles are frequently subjected to a so-called dry hydrophobic treatment. In this treatment, the agent for the hydrophobic treatment is applied in the same solvents used for the chemical cleaning. This measure is for the purpose of making the textiles, for example poplin clothing, such as raincoats, parkas and the like, as water-repellent as possible. The result of the impregnation is often very detrimental, however, because the surface-active cleaning intensifiers adhering to the fiber have a more or less strongly hydrophilic action.

In order to avoid these disadvantages, it has already been proposed to use cleaning intensifiers which do not or reduce only to an insignificant extent, the surface tension of the water, as for example, wool fat, cholesterol, fatty acid esters, metal soaps, and the like. These cleaning intensifiers are added to the organic solvent together with the necessary amount of water in the form of a water-in-oil emulsion. The emulsions obtained, however, are relatively coarsely dispersed owing to the relatively small emulsifying action of such substances. This may lead to turbidity and separation of water in the cleaning bath as well as to damage of the goods to be cleaned on account of uneven wetting. The process can therefore only be used to a limited extent.

OBJECTS OF THE INVENTION An object of the present invention is to develop cleaning intensifiers which make possible a good dispersion of the water in the cleaning bath and which are not detrimental to a subsequent dry hydrophobic treatment.

Another object of the present invention is in the chemical cleaning of textiles by subjecting the textiles to a chemical cleaning bath consisting of a major amount of an organic solvent, a minor amount of water and a surface-active cleaning intensifier, the improvement which comprises utilizing, as said cleaning intensifier, an addition product of 2 to 14 mols of propylene oxide to an alcohol selected from the group consisting of primary alkanols having from to carbon atoms, primary alkenols having from 10 to 20 carbon atoms and alkylphenols having from six to 12 carbon atoms in the alkyl.

A further object of the present invention is the development of a preliminary emulsion for dilution with a chemical textile cleaning organic solvent consisting essentially of from about 20 to 50 parts by weight of an addition product of 2 to 14 mols of propylene oxide to an alcohol selected from the group consisting of primary alkanols having from 10 to 20 carbons atoms, primary alkenols having from 10 to 20 carbon atoms and alkylphenols having from six to 12 carbon atoms in the alkyl, and from about 80 to 50 parts by weight of water.

A yet further object of the present invention is the development of a preliminary emulsion for dilution with a chemical textile cleaning organic solvent consisting essentially of from 0.5 to 2 parts by weight of a chemical textile cleaning organic solvent and l part by weight of the above preliminary emul- SlOll.

A still further object of the present invention is the development of a cleaning bath for the chemical cleaning of textiles consisting essentially of a major amount of a chemical textile cleaning organic solvent, a minor amount of water and a minor amount of an addition product of 2 to 14 mols of propylene oxide to an alcohol selected from the group consisting of primary alkanols having from 10 to 20 carbon atoms, primary alkenols having from 10 to 20 carbon atoms and alkylphenols having from six to l2 carbon atoms in the alkyl.

These and other objects of the invention will become more apparent as the description thereof proceeds.

DESCRIPTION OF THE INVENTION The present invention therefore provides a cleaning liquor for use in a chemical cleaning process for the cleaning of textiles comprising a major amount of a chemical textile cleaning organic solvent usually utilized, a minor amount of water and a minor amount of a product of addition of 2 to 14 mols of propylene oxide to a primary alcohol with 10 to 20 carbon atoms and/or to an alkylphenol with six to 12 carbon atoms in the alkyl as a cleaning intensifier.

In a further aspect the invention provides a chemical cleaning process utilizing the liquor described above.

The cleaning intensifier products of the invention are prepared in known way by adding propylene oxide to suitable saturated or unsaturated primary alcohols or to alkylphenol. The alkyl chains of the alcohols or alkylphenols may be straight or branched. The addition of the propylene oxide is effected in known way, preferably under pressure and in the presence of alkaline catalysts. Suitable adducts are obtained, for example, by addition of 6 mols of propylene oxide to lauryl alcohol, 8 mols of propylene oxide to myristyl alcohol, 3 mols of propylene oxide to decyl alcohol, 14 mols of propylene oxide to a tallow alcohol mixture of chain lengths C to C 8 to 12 mols of propylene oxide to an alcohol mixture of chain lengths (I to C, obtained from coconut fats, 2 mols of propylene oxide to an alcohol mixture of chain lengths C to C obtained from coconut fats, 5 mols of propylene oxide to isotridecyl alcohol, 4 to 8 mols of propylene oxide to oleyl alcohol, 4 to 6 mols of propylene oxide to undecylenyl alcohol, and 6 or 12 mols of propylene oxide to technical nonylphenyl.

The cleaning intensifier compounds of the invention have surface-active properties that make possible a very finely divided and stable dispersion or solubilization of the water in the cleaning bath. On account of their great affinity with the organic solvent however, the propylene oxide adducts are not adsorbed by the textiles to an appreciable extent, but remain in the cleaning liquor. Any possibly adhering amounts of the cleaning intensifier of the invention may be easily and completely removed by a subsequent rinsing with pure solvent.

The application of the cleaning intensifier of the invention is effected suitably in the usual way by first preparing an emulsion of the cleaning intensifier and the necessary amount of water. This preliminary emulsion may also already contain more or less large amounts of the solvent to be used for the cleaning. Such preliminary emulsions have good stability and are able to be stored until they are finally used.

Suitable preliminary emulsions comprise about 20 to 50 parts by weight of the cleaning intensifier of the invention and to 50 parts by weight of water. To this may also be added half to twice the amount of an organic solvent such as is usually used in chemical cleaning, based on the quantity of cleaning intensifier. Such chemical textile cleaning organic solvents are, for example, carbon tetrachloride, perchloroethylene, trifluorotrichloroethane and other liquid halogenated hydrocarbons, as well as low boiling or higher boiling hydrocarbons, as for example, petroleum fractions of boiling range to 200, benzene or the like. Furthermore, small amounts of low molecular weight alcohols, for example ethanol, propanol or isopropanol, can also be coemployed in the preparation of the preliminary emulsions. The preparation of the emulsion is generally effected by stirring by hand though a mechanical homogenization may possibly be used.

The preliminary emulsion is added into the cleaning liquor in such amounts that the latter contains from 1 to 20 g. per liter, preferably from lg. per liter, of the cleaning intensifier of the invention and from 2-6 g. per liter, preferably about 4 g. per liter of water. in the undiluted state the preliminary emulsion can also be used as the preliminary spot cleaner, par ticularly if small amounts of solvent are present therein. The preliminary emulsion is generally added to the cleaning liquor by hand or by means of an automatic dosing device. When the liquor is circulated an extremely fine division and dispersion of the water in the cleaning liquor occurs. The cleaning liquor obtained is stable and possesses an excellent filterability.

For carrying out the cleaning process the so-called single bath-three stage process has proved particularly satisfactory. Loosely attached dirt and fat-containing contaminations are first detached from the articles being cleaned and removed by a treatment with pure solvent and a simultaneously occurring prefiltration. After disconnecting the filter circuit, the required amount of concentrated preliminary emulsion containing the cleaning intensifier and water is added to the liquor and cleaning is continued for a further 5 to minutes. The filter pump is then switched on again and the dissolved dirt is filtered off for 3 to 8 minutes. Then a further rinsing with pure solvent is carried out. The textiles cleaned by this process are also cleansed from water-soluble dirt and can be satisfactorily waterproofed.

The dry hydrophobic treatment of the cleaned textiles is carried out by using hydrophobic agents such as paraffins, waxes, fatty acid salts of polyvalent metals, aluminum alcoholates or alcoholates of other polyvalent metals, dissolved in organic solvents, possibly in conjunction with stabilizers such as acetoacetic ester, and the like. The quantities used are in general about 40 to 80 per liter of cleaning liquor. Excellent water-repellent effects can be obtained which are not adversely affected by the cleaning intensifiers according to the invention.

The following examples are illustrative of the practice of the invention. They are not, however, to be deemed limitative in any manner.

EXAMPLE I Three pieces of a cotton poplin fabric with a weight of 300 g. per square meter were impregnated for 50 minutes in a perchloroethylene solution which contained 40 g. of paraffin (solidifying point 5052) and a reaction product of 8 g. of aluminum isobutylate with 10 g. of acetoacetic ester per liter of solution.

The pieces of fabric were cleaned before the impregnation in a laboratory cleaning plant as follows:

The first piece of fabric was cleaned for minutes simply with pure solvent without addition ofa cleaning intensifier.

The second piece of fabric was cleaned according to the process of the invention with a cleaning liquor which contained 2 g. of the adduct of 2 mols of propylene oxide to a coconut fatty alcohol mixture of chain lengths C to C and 4 cc. of water per liter of perchloroethylene, for 15 minutes at a bath ratio of M0.

After cleaning, the pieces of fabric were each centrifuged and impregnated as indicated above. After drying and air conditioning in normal conditions, the three pieces were tested for their water-repelling properties by the Bundesmann rain test (DIN 53,888). The following values were obtained.

Rain Test Water passing through in cc Rain Test Absorption of water in percent Preliminary cleanlng The result shows that the impregnation, after cleaning using the cleaning intensifier according to the invention, is practically unimpaired.

EXAMPLE H In a cleaning plant of the Bowe R 9 maxima type, 6 kg. of cotton poplin coats were cleaned in liters of perchloroethylene for 5 minutes with simultaneous filtration of the bath. The filter pump was then disconnected and a preliminary emulsion was added to the liquor which consisted of 200 g. of the adduct of 8 mols of propylene oxide to nonylphenyl and 240 cc. of water and the cleaning was continued. After 8 minutes the filter pump was switched on again and the dissolved dirt was filtered off for 3 minutes. Then the liquor was pumped into the tank and the textiles were centrifuged. After centrifuging the coats were rinsed for 3 minutes with clean solvent, centrifuged again and impregnated.

The impregnation was effected with perchloroethylene, which contained 50 g. of paraffin (solidification point 50-52 and a reaction product from 10 g. of aluminum isopropylate and 12 g. of acetoacetic ester. After spin-drying off about 60 percent of the remaining impregnating liquor the coats were dried and finished. Both the cleaning and the waterproofing effects were very good.

in order to determine the water-repellent effect, under the conditions of the above experiment, cotton poplin samples with a weight of 300 g. per square meter were also cleaned, impregnated and after air conditioning under normal conditions, the water taken up after the Bundesmann rain test was determined.

In the same way a cotton poplin fabric was simply cleaned with pure solvent without addition of a cleaning intensifier and then, after impregnation and air conditioning, subjected in the same way to the rain test.

The following average values from 4 separate measurements were obtained:

In this case also it was found that the impregnating effect is not appreciably impaired on prior cleaning with the propylene oxide adduct according to the invention.

EXAMPLE III In the plant described in example 2, 6 kg. of waterproof clothing consisting of cotton/polyester mixed textile, were cleaned in 100 liters of perchloroethylene in the single baththree-stage process. In the second stage, cleaning without filtration, an addition of 200 g. of the adduct from l4 mols of propylene oxide to dodecylalcohol and 200 g. of water in the form of a preliminary emulsion was made. After the subsequent filtration until clear, the liquor was pumped off, and the clothing spin-dried and further dried as usual.

A further experiment with waterproof clothing was carried out in the same way, but instead of the propylene oxide adduct described, a commercial cleaning intensifier with the following composition was used:

30 percent of an adduct of 14 mols of ethylene oxide to nonylphenol 15 percent of sodium petroleum sulfonate with 63 percent of detergent substance, 5 percent of water and 32 percent of mineral oil 5 percent of water 5 percent of ethanol 45 percent of perchloroethylene The quantity of this product used amounted to 400 g. with an addition of water of 200 g. to 100 liters of perchloroethylene. To determine the cleaning and the greying effect, test fabrics of cotton from Testfabrics lnc., l3 Vandam Street, New York prepared according to Specification 5] S 47. were added to the two charges. The brightening of the soiled part and the greying of the unsoiled part of the fabric were determined with a reflectometer. The following values were obtained;

Preliminary Reflectometer measurement cleaning I: brightening k greying Adduct of l4 mols of propylene oxide to dodecyl alcohol 49.8 0.5 Commercial cleaning intensifier 50.3 0.4

The comparative example shows that the propylene oxide adduct according to the invention has practically the same good cleaning action as the commercial cleaning intensifier.

EXAMPLE IV In the cleaning plant described in example 2, 6 kg. of parkas and Windbreakers were cleaned in the single bath-three-stage process. After switching off the filter, a water-containing preliminary emulsion was added during the second stage with a fully automatic dosing device until the adjusted relative moisture of 88 percent was reached. The preliminary emulsion consisted of:

one part by weight of an adduct of IO mols of propylene oxide to nonylphenol one part by weight of an adduct of 12 mols of propylene oxide to a coconut fatty alcohol mixture of chain lengths C to C m six parts by weight of water.

The preliminary emulsion had a good stability and showed no troublesome separations during this stage of operation. The cleaning effect was good and the subsequent water-repellent application was excellent.

To test the filterability of the cleaning liquor the filter pressure was measured at the end of the first and third cleaning operations. The following result was obtained:

Filter pressure in atmospheres after the lst Cleaning stage 3rd cleaning ltage The measured values show that the cleaning intensifier of the invention possesses a very good filterability.

The preceding specific embodiments are illustrative of the practice of the invention. It is to be understood, however, that other expedients known to those skilled in the art may be employed without departing from the spirit of the invention.

1 claim:

1. [n the chemical cleaning of textiles by subjecting the textiles to a chemical cleaning bath consisting of a chemical textile dry cleaning organic solvent, from 2 to 6 g. per liter of water and a surface-active cleaning intensifier, the improvement which consists of utilizing, as said cleaning intensifier, from 1 to 20 g. per liter of an addition product of2 to 14 mols of propylene oxide to a mono-hydroxy alcohol selected from the group consisting of primary alkanols having from 10 to 20 carbon atoms, primary alkenols having from 10 to 20 carbon atoms and alkylphenols having from six to 12 carbon atoms in the alkyl.

2. The process as defined in claim 1 wherein said chemical cleaning bath contains from I to 5 g. per liter of said cleaning intensifier.

TWICATE 0F CQRREC'HON Patent No L-628 911 Dated Dec.21: 971

Inventofls) WERNER cRfiNEwKLDER It is certified that: erroreppears in the above-identified patent and that said Letters Patent are hereby corrected as shown below:

m m PATENT, Column 3, Line 61 m THE APPLICATION, Page 8, Lines 2 2 2., the roilowin I paragraph was omitted, "The third piece of fabric was cleaned a cleaning liquor contained 2 gin of sodium dodecylbenzene sulphonate and t c. c. of water per liter of pei-chioroethyl'ene, for 15 minutes at a bath retio of 1 10."

PATENT Colnmnfi, line 1 1 A APPLICATION, Page 12, line 29, underthe heading I. "3rd cleaning stage", the figure should fie 0.8 instead of 8.8.

Signed and sealed this 22nd day of August 1972.

(SEAL) Attest:

EDWARD M.FLETCHER, JR. ROBERT GOTTSGHALK Attesting Officer Commissioner of Patents :2 0 511: STATES PATENT OFFICE CTIiF-ICATE OF coRREcTmN ?at ent Nov V 3,628,911 Dated 5 .2 1971 Inventm-(s) WERNER oRiiNEwKmER It isacertified that error appears in the aboie-identifiedpatent and that said Letters Patent are hereby cor rected as shown below:

in m PATENT, Column 3, Line 61 w m THE APPLICATION, Page 8, Lines 2Q 2 the roilowin paragraph was omitted, "The third piece of fabric was cleaned a cleaning liquor which contained 2 gin of sodium dodecylbenzene- I sulphonete and t c. c. of water per liter of perchioi'oethylene, for 15 minutes at a bath ratio of 1 10." PATENT Co1nmn 6, line 1 1 I APPLICATION, Page 12, line 29, under the heading v "3rd cleaning sta efifihe figure should be 0.8 instead of 8.8.

Signed and sealed this 22nd day of August 1972.

(SEAL) Attest:

EDWARD M.FLETCHER, JR. ROBERT GOTTSGHALK Attesting Officer Commissioner of Patents

Claims

2. The process as defined in claim 1 wherein said chemical cleaning bath contains from 1 to 5 g. per liter of said cleaning intensifier.