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Publication numberUS3737386 A
Publication typeGrant
Publication dateJun 5, 1973
Filing dateAug 4, 1970
Priority dateAug 6, 1969
Also published asDE1940018A1, US3856695
Publication numberUS 3737386 A, US 3737386A, US-A-3737386, US3737386 A, US3737386A
InventorsGeiss R, Quarch R
Original AssigneeGeiss R, Quarch R
Export CitationBiBTeX, EndNote, RefMan
External Links: USPTO, USPTO Assignment, Espacenet
Solvent based detergent
US 3737386 A
Abstract
A solvent based detergent composition consisting essentially of (A) 10-80% liquid aliphatic chlorinated hydrocarbon solvents, (B) 10-40% liquid aliphatic ketones and/or liquid aliphatic esters, (C) 6 to 50% water soluble liquid alkanols having two to five carbon atoms and (D) 1-10% surface active agents.
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Description  (OCR text may contain errors)

United States Patent 3,737,386 SOLVENT BASED DETERGENT Richard Geiss, 8875 Lnsshof, Olfingen (Danube), Germany, and Rolf Quarch, St. Johannisstrasse 37, Weissenhorn, Germany No Drawing. Filed Aug. 4, 1970, Ser. No. 60,924 Int. Cl. C09d 9/04; C11d 7/22, 7/50 US. Cl. 252-162 12 Claims ABSTRACT OF THE DISCLOSURE The invention relates to a detergent used particularly in industry on the base of a combination of different organic solvents in admixture with cleansing intensifiers.

It has long been known to utilize a number of different mixtures of solvents for industrial use, in particular combinations of trichloroethylene or perchloroethylene in admixture with benzines or aromatics such as benzene, toluene and xylene. In general these substances are used for removing fat and varnish.

For several cleaning processes, however, detergents of the known prior art have proved to be insufficient, particularly for cleaning construction units e.g. tiles in service-stations, tunnels, railway stations and similar buildings, soiled concrete areas and other cemented surfaces.

The dirt on walls and floors of such buildings consists of tars, greases, oils, rosins, resins, asphaltenes, set paints and varnishes as well as of mechanical impurities.

It is impossible to solve such dirt accumulations and wash them away with water immediately without a long residence time and without applying mechanical power such as scrubbing and rubbing. The same is true with soiled tools, eg brushes.

Accordingly, it is an aim of the present invention to provide a detergent composition comprising in combination several solvents which can be applied even at high levels of impurity, i.e. which exhibit good solving properties and which make it possible to wash away the lubricants composed of dirt (tars, greases, oils, rosins, resins, etc.).

The new detergents are liquid mixtures which can be mixed with water and consist of:

(A) 10 to 25% by weight liquid aliphatic chlorinated hydrocarbons,

(B) 25 to 40% by weight liquid lower aliphatic ketones and/or lower aliphatic esters,

(C) 40 to 50% by weight water-soluble alkanols 2 to carbon atoms and (D) 1 to by weight surface active agents.

Preferred use is made of mixtures of components of the groups consisting of (A) methylene chloride, trichloroethylene, and perchloroethylene,

(B) methyl ethyl ketone and ethyl acetate,

(C) isopropanol, propanol and butanol and (D) an anionic surface active agent.

Additionally, the following substances individually or in admixture with other representatives of the same groups may be used as components of the groups consisting of (A) as chlorinated hydrocarbons: monochloromethane,

trichloromethane and tetrachloromethane, 1,1- and l,

Z-dichloroethanes, 1,1,1- and 1,1,2-trichloroethanes,

and 1,1,1,2- and l,l,2,2-tetrachloroethanes;

(B) as esters: methyl acetate, propyl acetates and butyl acetates, as well as the corresponding propionates and butyrates including ethyl esters; as ketones: diethyl, methyl propyl and isomeric ethyl butyl ketones;

Patented June 5, 1973 (C) as alkanols: ethanol and amyl alcohols;

(D) as anionic surface active agents: sulphates and ether sulphates of fatty alcohols, acyl sulphonates, aryl alkyl sulphonates and alkyl aryl sulphonates, ethylene oxide adducts, e.g. sodium lauryl sulphates, lauryl alcohol sulfuric acid ester and triethanolamine salts of ether sulphates of fat alcohols.

Test l.-Test composition without a surface active substance The test composition had the following ingredients:

Percent Methylene chloride 10 Methyl ethyl ketone 20 Ethyl acetate 20 Isopropanol 50 In the absence of a surface active substance the lubricants formed by dirt and solvent from the test composition could not be washed away with water from the soiled areas or could not be washed away completely. Dirtstripes remained which could be removed only after various applications of the solvent while rubbing or by means of other mechanical powers.

Test 2.-Test composition without chlorinated hydrocarbon The mixture had the following ingredients:

Percent Methyl ethyl ketone 25 Ethyl acetate 25 Isopropanol 40 Surface active substance 10 In the absence of a chlorinated hydrocarbon the mixture of solvents required a prolonged residence time to remove the dirt lubricant, ie the total cleaning of l m? of soiled area required more than 3 minutes time and the application of mechanical power. Thus, it can be stated that the detergency power is rather high but that the dirt lubricant solving time is far too long, especially in view of the great areas to be cleaned.

Further tests showed that aliphatic, lower ketones, from which acetone is known as a solvent for certain resins, exhibit a much stronger and quicker solving efliciency for resins in admixture with the other ingredients (A), (B), and (D) than individual ketones. This synergetic effect was very much surprising and unpresumable.

EXAMPLE 1 The tiles to be cleaned were soiled with the above mentioned lubricant forming dirt composition and submitted to an ageing process of one year. -By means of a cleaning cloth soaked with the above mentioned detergent an area of tiles of 1 m? was cleaned and rinsed with water in '30 sec. time. This detergency power 30 seconds could be considered as very good.

A similar very good detergency power was exhibited by the following combinations according to Examples 2 to 5.

Ammonium salt of the sulphuric acid ester of lauryl alcohol 10 EXAMPLE 3 Percent Methylene chloride 25 Diethyl ketone 12.5 Ethyl acetate 12.5 Butanol 40 Monoethanolamine salt of the sulphonated coconut fatty alcohols ether 10 EXAMPLE 4 Percent Methylene chloride 10 Methyl ethyl ketone 20 Propyl acetate 20 Ethanol 40 Triethanolamine salt of the lauryl alcohol sulphuric acid ester 10 EXAMPLE 5 Percent Methylene chloride l Methyl ethyl ketone 20 Ethyl acetate 20 Isopropanol 40 Sodium lauryl sulphate 10 The results obtained in Examples 1 to could be considered as very good: the joints of the cleaned tiles did not show any changes and the lustre of the tiles remained unchanged. The maximum allowable vapour concentration (in p.p.m. or g./m. of the detergent according to the invention is so high that they can be used without any risk for the operating safety.

In the following Examples 6 and 7 the detergency power of combinations including perchloroethylene or trichloroethylene was examined. For this end methylene chloride from the composition according to Example 5 was substituted by perchloroethylene or trichloroethylene. This composition required a longer residence time, the detergency power of the mixture, however, can be considered as good.

showed a good detergency power, required, however, a much longer residence time than the compositions including methylene chloride according to the Examples 1 to 5.

EXAMPLE 7 A similar composition which had the following ingredients showed the same results:

Percent Perchloroethylene 10 Methyl ethyl ketone 20 Ethyl acetate 20 Isopropanol 40 Sodium lauryl sulphate 10 Finally compositions with considerably changing concentrations of the ingredients were examined, i.e. compositions with a considerably higher or lower amount of methylene chloride, methyl ethyl ketone, ethyl acetate, surface active substances and alcohols according to Examples .1 to 5. It was observed that within a great range dirt lubricant solubility is to be called good or very good, but that theresidence time of the lubricants soaked by the solvent increases with a decreasing amount of methylene chloride, whereas the Wettability of the dirty places increases with a rising amount of surface active substances.

TEST COMPARISON REPORT (a) varnish of a polyacrylic resin (b) a mixed styrene butadiene polymer (c) a dispersion of polyvinyl acetate (d) lignite tar (e) motor oil recovered from waste oils and fat and submitted to an ageing process, comprising the following steps: for 12 hours the tiles were dryed by infrared light and aerated and then for 12 hours submitted to a relative humidity of 65% at 20 C. The prepared tiles were then treated with each 250 g. of the detergent in the composition of the invention and of the fluid detergent known from the German published patent application 1,200,460. In the examples which follow, after 5 minutes time we tried to remove the impurities with water. Out of the known detergents were applied those of Examples 1 (with perchloroethylene), 2 and 6 of the German published patent 1,200,460.

The composition of Example 1 of the German patent contains parts by weight of carbon tetrachloride or percholorethylene and 20 parts by weight of a 80% technical alkyl benzene sulfonic acid, neutralized with 15 parts by weight of crude pyridine.

The composition of. Example 2 of the German patent contains 2320 parts by weight of perchloroethylene, parts by Weight of a sulfated polyglycol ether of fat alcohol and 660 parts by weight of the above mentioned alkylbenzene sulfonic acid neutralized with 330 parts by weight of crude pyridine and parts by weight of morpholine.

The composition of Example -6 of the German patent contains 2600 parts by weight of decylphenolepolyglycolether and 390 parts by Weight of a 80% dibutylnaphthalenesulfonic acid, which was neutralized with 100 parts by Weight of pyridine.

These compositions were capable of solving only oils (e) and tars (d); only these tars and fats could be removed in the form of aqueous emulsions; varnishes i.e. resins (a), (b) and (c) remained, however, unchanged and could not be removed. For comparison the following mixtures in the composition of the invention were applied:

G. Penchloroethylene 800 Methylene chloride 80 Methyl ethyl ketone 40 Isopropanol 30 Sodium lauryl sulphate 200 Percent by weight Methylene chloride 25 Ethyl acetate 25 Isopropanol 40 Sodium lauryl sulphate l Percent by weight Methylene chloride 15.5 Butanone 37.5 Isopropanol 40 Sodium lauryl sulphate 7 Percent by weight Methylene chloride 12 Methyl ethyl ketone 25 Isopropanol 50 Sodium lauryl sulphate 13 In the four cases all impurities spread on the tiles could be solved quickly and removed easily with water.

The same results were obtained when cleaning spatulas, brushes etc. soiled with oil, tar, paint and varnish. In most of the cases there was required a residence time of only 1 minute; set residues of resin, varnish and paint required depending on the hardening rate a longer residence time. The detergents of the German patent 1,200,460 and liquid hydrocarbon-based cleansing agents proved to be insufficient.

Therefore it can be seen that in general the known detergents which were used for comparison are effective at solving oil and fat but have no or only minor solving efficiency to solve varnish, paint and resin. In contrast the detergents of the present invention removed varnish, paint and resin easily. Thus, the detergents of the present invention are universal cleansing agents.

What is claimed is:

1. A solvent based detergent composition that is miscible with water consisting essentially of (A) 10 to 25% by weight of liquid lower aliphatic chlorinated hydrocarbons,

(B) 25 to 40% by weight lower aliphatic ketones and/ or lower aliphatic esters,

(C) 40 to 50% by weight water-soluble alkanols having 2 to carbon atoms and (D) 1 to by weight anionic surface active agents.

2. A detergent composition of claim 1 wherein said component (A) is methylene chloride, tn'chloroethylene or perchloroethylene,

(B) is methyl ethyl ketone or ethyl acetate,

(C) is isopropanol, propanol or butanol and (D) is an anionic surface active agent.

3. A detergent composition of claim 1 wherein said chlorinated hydrocarbons are selected from the group consisting of monochloromethane, trichloromethane, tetrachloromethane, dichloroethane, trichloroethaue and tetrachloroethane.

4. A detergent composition of claim 1, wherein said ketone (B) is selected from the group consisting of diethyl ketone, methyl propyl ketone and isomeric ethyl butyl ketones.

5. A detergent composition of claim 1, wherein said esters (B) are selected from the group consisting of methyl acetate, propyl acetates, butyl acetates, methyl propionates, ethyl propionates, propyl propionates, butyl propionates, methyl butyrates, ethyl butyrates, propyl butyrates and butyl butyrates.

6. A detergent composition of claim 1, wherein said alkanols (C) are selected from the group consisting of. ethanol and amyl alcohols.

7. Cleaning surfaces soiled with oils, fats, tars, resins, asphaltenes, pitches, varnishes, paints or mechanical impurities with the composition of claim 1.

8. A detergent composition of claim 1, wherein (A) is methylene chloride, (B) is ethyl acetate, (C) is isopropanol and (D) is a sulphonate of coconut fat alcohols.

9. A detergent composition of claim 1 wherein (A) is methylene chloride, (B) is methyl propyl ketone, (C) is propanol and (D) is ammonium salt of sulphuric acid ester of lauryl alcohol.

10. A detergent composition of claim 1 wherein (A) is methylene chloride, (B) is diethyl ketone and ethyl acetate, (C) is butanol and (D) is monoethanolamine salt of the sulphonated coconut fatty alcohols ether.

11. A detergent composition of claim 1, wherein (A) is methylene chloride, (B) is methyl ethyl ketone and propyl acetate, (C) is ethanol and (D) is triethanolamine salt of the lauryl alcohol sulphuric acid ester.

12. A detergent composition of claim 1, wherein (A) is methylene chloride, (B) is methyl ethyl ketone and ethyl acetate, (C) is isopropanol and (D) is sodium lauryl sulphate.

References Cited UNITED STATES PATENTS 3,338,756 8/1967 Leon 252171 2,371,647 3/ 1945 Petering et a1 252171 2,630,409 3/ 1953 Bruner 252l7l 3,179,609 4/ 1965 Morison 252-171 3,423,323 1/1969 Hunter et a1 252162 3,475,343 10/1969 Kusawa et al. 252-162 3,535,392 10/ 1970 Cormany et a1 252-171 WILLIAM E. SCHULZ, Primary Examiner US. Cl. X.R.

134-38; 252-171, Dig. 8, Dig. 10

Referenced by
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US3988256 *Apr 3, 1974Oct 26, 1976Allied Chemical CorporationPhotoresist stripper rinse
US4085059 *Mar 4, 1976Apr 18, 1978Bunker Ramo CorporationFoam type coating remover
US4220549 *May 4, 1978Sep 2, 1980Ronnie J. MooreMethod for removing reflective decal
US4271214 *Aug 29, 1979Jun 2, 1981Nippon Paint Co., Ltd.Method for recovering acrylic resin from excess of sprayed powder coating composition by using aromatic solvents
US4309300 *May 4, 1979Jan 5, 1982Mcdonnell Douglas CorporationCleaning solvent and method of cleaning a metal surface
US4333845 *Sep 8, 1980Jun 8, 1982Grow Group, Inc.Coating composition thinner for decreasing pollution resulting from the application of a coating composition
US4336024 *Feb 13, 1981Jun 22, 1982Airwick Industries, Inc.Process for cleaning clothes at home
US4421665 *Jan 19, 1981Dec 20, 1983Lloyd Eugene AContact lens cleaning composition containing lipid solvent and method of using
US4518518 *Feb 14, 1984May 21, 1985Amchem Products, Inc.Cold paint stripping composition
US4664721 *Dec 11, 1985May 12, 1987Intercontinental Chemical CorporationPrinting screen cleaning and reclaiming compositions
US4810411 *Jul 23, 1987Mar 7, 1989E. I. Du Pont De Nemours And CompanySolvent-based fabric protector
US4965010 *Oct 27, 1988Oct 23, 1990Swett Ralph RPaint stripping composition containing ketones, methanol, and aromatic hydrocarbon
US5045224 *Jan 11, 1989Sep 3, 1991Toyota Jidosha Kabushiki KaishaColor-change washing solution, suitable for spray coating devices
US5102573 *May 18, 1990Apr 7, 1992Colgate Palmolive Co.Detergent composition
US5676764 *Mar 7, 1996Oct 14, 1997Mcdonnell Douglas CorporationLow vapor pressure solvent
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US6200945May 20, 1999Mar 13, 2001Mcdonnell Douglas CorporationEnvironmentally safe solvent composition
EP0139560A1 *Sep 11, 1984May 2, 1985Societe Nationale Elf AquitaineAqueous composition for dispersing hydrophobic substances,in particular suitable for cleaning objects soiled by paint or the like
EP0320394A2 *Dec 9, 1988Jun 14, 1989Gérard GrandryLiquid aid for pulverisation and cleaning of pulverizers
EP0698118A1 *Mar 7, 1995Feb 28, 1996Biogenex LaboratoriesDeparaffinization compositions and methods for their use
EP1179041A1Mar 13, 2000Feb 13, 2002The Boeing CompanyEnvironmentally safe solvent composition
Classifications
U.S. Classification510/204, 510/365, 510/412, 510/240, 134/38, 510/366, 510/238
International ClassificationC23G5/032, C09D9/00, C23G5/00, C11D3/43, C11D3/48
Cooperative ClassificationC11D3/48, C11D3/43, C09D9/005, C23G5/032
European ClassificationC11D3/48, C11D3/43, C23G5/032, C09D9/00B