US3748268A

US3748268A - Spot and stain removing composition

Info

Publication number: US3748268A
Application number: US00238475A
Authority: US
Inventors: B Loudas
Original assignee: Minnesota Mining and Manufacturing Co
Current assignee: 3M Co
Priority date: 1972-03-27
Filing date: 1972-03-27
Publication date: 1973-07-24
Anticipated expiration: 1990-07-24
Also published as: DE2323605A1; DE2323605B2; GB1397475A

Abstract

A STABLE, ONE-PHASE COMPOSITION WHICH IS USEFUL AS A SPOT AND STAIN REMOVER COMPRISING A HYDROCARBON SOLVENT OF LOW VOLATILITY, WATER, SURFACTANT, ORGANIC CO-SOLVENT AND ANTI-SOILING AGENT.

Description

United States Patent 3,748,268 SPOT AND STAIN REMOVING COMPOSITION Basil L. Loudas, St. Paul, Minn., assignor to Minnesota Mining and Manufacturing Company, St. Paul, Minn. No Drawing. Continuation-impart of abandoned applicatio Ser. No. 123,080, Mar. 10, 1971. This application Mar. 27, 1972, Ser. No. 238,475

Int. Cl. Clld 7/52 US. Cl. 252-90 17 Claims ABSTRACT OF THE DISCLOSURE A stable, one-phase composition which is useful as a spot and stain remover comprising a hydrocarbon solvent of low volatility, water, surfactant, organic co-solvent and anti-soiling agent.

This application is a continuation-in-part of my copending application Ser. No. 123,080, filed Mar. 10, 1971 now abandoned.

BACKGROUND OF THE INVENTION (1) Field of the invention This invention relates to cleaning compositions and, more specifically, to spot and stain removing compositions.

(2) Description of the prior art The need for removal of spots and stains from fabrics, upholstery, carpets and a variety of other substrate surfaces has been present from the very time that fabrics, upholstery, etc. came into existence. Obtaining complete and efiective removal of such spots and stains has always been one of mans desires. However, the existence of a tremendous 'variety of commonly used fabrics, carpets, etc. coupled with the existence of an equally tremendous variety of spotand stain-producing substances has made the magnitude of the stain removal problem staggering.

To combat this problem, man has used a variety of cleaning substances with some degree of success. Many of such cleaning compositions, however, are specific only to certain types of stains (e.g., the compositions of US. Pat. 3,093,592 are specific to oily stains), or they must be used in such large quantities as to be prohibitorily expensive unless commercialized (e.g., commercial dry cleaning of fabrics), or they cannot be used on all types of stained materials because they might damage the color or integrity of the delicate substrate, or they can only be used for surface stains because they cannot penetrate the fabric or other substrate.

Furthermore, many stains comprise both oleophilic constituents and hydrophilic constituents. To remove such stains many profesisonal spot remover kits recommend the use of successive washings, first with substances which dissolve water-dispersible substances, or vice versa. For example, US. Pat. 1,990,691, suggests Washing first with solvent and then with Water and alcohol. Even such techniques, however, are not always successful. For example, some types of stains are rendered more resistant to removal if they are initially contacted with the inappropriate agent.

Moreover, certain substrates, such as carpets or upholstery, cannot be soaked or washed in cleaning baths in the same manner as can be done with fabrics, clothes or the like. Thus, cleaning solvents or compositions which are effective for fabrics and clothes may be utterly useless for carpets and upholstery.

Although cleaning compositions have been proposed which contain water, solvent, and soap, such compositions do not provide the ability to clean or remove a wide range of stains nor do such compositions render the cleaned Patented July 24, 1973 ice substrate resistant to staining. For example, the compositions described in US. 1,748,999 and US. 3,549,545, which are directed to cleaning fluids for dry cleaners, contain only a minor amount of water and are not generally suitable for all types of stains, nor do the compositions render the cleaned substrate resistant to subsequent soiling. Similarly, the emulsion described in U.S. Pat. 1,786,249 does not render the cleaned substrate resistant to staining or soiling. Furthermore, compositions in the form of emulsions characteristically remove the oleophilic and hydrophilic constituents of a stain successively and therefore do not provide a simultaneous cleaning or removing action.

SUMMARY OF THE INVENTION The present invention provides a one-phase cleaning composition which overcomes the problems attendant with previously known and used spot and stain removing substances. The novel composition is a general purpose spot and stain remover which is capable of removing a very diverse variety of stains, including most of the common household stains, from fabrics, linen, clothes, carpets, upholstery, etc. Furthermore, the color or integrity of the substrate is not damaged by the use of this composition.

Because the composition penetrates the stain and the substrate very etfectively, it is possible to remove groundin stains in addition to stains which lie on the surface of the substrate. The penetrating ability of the composition also obviates the need to use excessive quantities of the novel composition. Because the composition contains solvents and detergents for both water-soluble and oil-soluble stains, it is especially useful for removing spots and stains from carpets and upholstery.

In accordance with the invention, there is provided a stable, one-phase composition useful as a spot and stain remover consisting essentially of:

(a) About 40 to percent by weight of water;

(b) About 4 to 25 percent by weight of liquid hydrocarbon solvent having a boiling point higher than about 70 C. and having a vapor pressure not less than 2 mm. Hg at 20 C.;

(0) About 4 to 20 percent by weight of surfactant;

((1) About 3 to 25 percent by weight of organic co-solvent; and

(e) About 1 to 10 percent by weight of solid, nontacky, water-dispersible anti-soiling agent which, upon drying of the composition, is capable of rendering the residue of the surfactant nontacky and resistant to soiling.

Because the composition consists of a single phase (i.e., is clear and homogeneous) it cleans or removes all of the constituents of a stain simultaneously. Consequently, the novel composition has exhibited emphatic superiority over spot and stain removers heretofore available.

To remove spots and stains from a substrate, the composition is spread over the soiled areas and is allowed to penetrate the stain. Gentle rubbing action may be used to help work the composition into the stain. The composition first acts upon the stain to soften it.

After the composition has penetrated and softened the stain, loosened stain material is removed from the substrate by blotting with a dry, absorbent cloth. The remaining composition is then contacted with a small amount of water (applied by means of a swab, sponge, brush or cloth wetted with water) and then is scrubbed to effect sudsing and completion of the cleaning operation.

The substrate can then be blotted with water-soaked, absorbent material to remove the soil and composition remnants. Vacuuming the substrate may follow in the same manner as is done after cleaning with conventional compositions.

3 DETAILED DESCRIPTION OF THE INVENTION Useful hydrocarbons for the novel compositions are those which are normally solvents for oleaginous materials and which are liquid under ambient conditions but are of low volatility, i.e., they have a boiling point of not less than about 70 C. and vapor pressure not less than 2 mm. Hg at 20 C. Those hydrocarbons having boiling points below 70 C. are not desirable because they tend to evaporate too quickly when the composition is applied to a soiled area; when this occurs, the hydrocarbon solvent may evaporate before the oleophilic portion of the stain is dissolved or softened. By using hydrocarbons which have boiling points about 70 C. and vapor pressures not less than 2 mm. Hg at 20 C., the composition will remain stable on the soiled surface for 20 minutes or more, which is ample time for cleaning.

Useful hydrocarbon solvents are those which are normally liquid, Water-immiscible, and substantially free of functional groups (e.g., amino, hydroxyl, mercapto, or carboxyl groups). Thus, useful hydrocarbon solvents include saturated and unsaturated aliphatics containing 7 or more carbon atoms; cyclo-aliphatics containing 6 or more carbon atoms; and halogen-substituted aliphatics, e.g., trichloroethylene, perchloroethylene, diand trichloroethane, chloropropane and carbon tetrachloride. Useful aromatic hydrocarbon solvents include benzene, toluene, xylene, and chlorobenzene. Mixtures of these aliphatic and aromatic solvents, e.g., low boiling kerosene fractions and V. M. & P. naphtha, are also quite useful.

The amount of hydrocarbon solvent present in the novel compositions can range from about 4 weight percent to about 25 weight percent. Preferably, the hydrocarbon solvent present is in the range of 5 to 20 weight percent. The amount of water present can range from about 40 to about 85 percent by weight of the composition, and preferably the water is in the range of 50 to 75 weight percent.

Surfactants which are useful in the novel compositions are water-dispersible. The term water-dispersible means that the surfactant is either soluble, or otherwise stably dispersible in water at the desired concentration. The amount of the surfactant used in the composition is generally in the range of 4 to 20 percent of the total weight of the composition, and 5 to 15 weight percent is preferred for good composition stability and cleaning power.

Useful anionic surfactants include alkali metal or ammonium salts of fatty acids (i.e., 8 carbons or more), alcohol sulfates (or sulfonates), polyoxyalkylene alkyl carboxylates, and polyoxyalkylene alcohol phosphates (or phosphonates). Useful nonionic surfactants, which can be used by themselves or in conjunction with anionic surfactants, include polyethoxylated alcohols, polyethoxylated alkyl phenols, polyethoxylated fatty acids, polyethoxylated amines, and polyethoxylated amides.

Organic co-solvent is included in the composition to assist in obtaining a single-phase system. Thus, useful organic co-solvents are those which are soluble in the water/hydrocarbon mixture and which have a vapor pressure of at least 0.1 mm. Hg at 20 C. The organic co-solvent is a polar liquid and is generally a monofunctional alcohol of 1 to 5 carbons, a ketone of up to 6 carbons (e.g., acetone, methyl ethyl ketone, myethyl isobutyl ketoue, diethyl ketone), a water-miscible ether (e.g., dioxane, tetrahydrofuran, diethylene glycol diethyl ether), monoalkyl ether of ethylene glycol, or lower ester such as ethyl acetate or lower ester of monoalkyl ethers of ethylene glycol (e.g., Cellosolve acetate, Methyl Cellosolve Acetate, Carbitol acetate, all commercially available from Union Carbide). Mixtures of organic co-solvent can also be used. The organic co-solvent is normally present in the composition in amounts of 3 to 25 weight percent (and preferably 10 to percent by weight).

Representative co-solvents include monobutyl ether of ethylene glycol, ethylene glycol monoalkyl ether acetate, dioxane, etc.

Anti-soiling agents are included in the spot-removing composition so that resoiling of a cleaned substrate is retarded or inhibited. Useful anti-soiling agents are defined as those materials which are solid, nontacky, and Water-dispersible and which, upon drying of the spotremoving composition, are capable of rendering the surfactant residue nontacky and resistant to soiling.

Useful anti-soiling agents include brittle polymeric resins, such as styrene-maleic anhydride copolymers; colloidal alumina; colloidal suspensions of silica; polyvinylpyrollidone; polyacrylate/acrylic acid copolymers (e.g., Roplex resins available from Rohm and Haas); vinyl acetate/maleic anhydride copolymers (e.g., VAMA resins available from Monsanto); carboxymethylcellulose; carboxyl-containing resins (e.g., Carboset from B. F. Goodrich); and water-soluble melamineformaldehyde condensates. The anti-soiling agent is normally used in amounts ranging from about 1 percent to about 10 percent by weight of the total composition, and amounts of about 5 percent by weight are preferred.

Various additives such as germicides, perfume, brightening agents, and the like, may be included in the compositions in minor amounts, if desired.

The viscosity of the novel compositions varies widely depending upon the particular amounts of ingredients used. Generally speaking, the compositions may vary from low viscosity liquids to much higher viscosity, jellylike fluids. For aerosol formulations, the lower viscosity compositions are preferred. Other means for packaging the compositions include conventional dispensing tubes, bottles, jars, etc. Various common thickeners such as carboxymethyl cellulose, hydroxy propyl methyl cellulose, and Cab-O-Sil M-S (trade name of Godfrey L. Cabot, Inc.) can be used to adjust the viscosity to the desired range, if necessary.

The novel compositions will be more particularly described by means of the following examples wherein the term parts refers to parts by weight unless otherwise indicated.

EXAMPLE 1 Into a Silo-milliliter glass flask equipped with a mechanical stirrer, the following materials are added in order:

Parts Hi-flash Naththa 1 (boiling point l6(l180 C.) 22 Richinol A 2 (30% in water) 50 SMA 3000 A 3 (15% solution in water) 50 Mono-butyl ether of ethylene glycol 18 Ht-Flash Naphtha 1s a mixture of saturated hydrocarbon (commercially available from Amsco Company).

2 "Richinol A is sodium lauryl sulfate (commercially available from Richardson Company).

3 SMA 3000 A is a trade name of ARGO Chemical C0- for styrene maleic anhydrlde copolymer.

The resulting one-phase composition is a clear, homogeneous low viscosity liquid which is very stable. This composition can be packaged in bottles and jars and, preferably, in an aerosol-type container using any conventional propellant (e.g., fluorinated hydrocarbons).

The composition of Example 1 was used to very effectively and easily remove the following three-Week-old stains from polyester and nylon carpets: coffee, syrupy soft drinks, catsup, salad dressing, lipstick, ice cream, molten cheese, cooking oil, shoe polish, marker ink, pet stains, acrylic enamel spray paint, dried blood and rust. Similar types of stains are also effectively removed from various other substrates such as upholstery, fabrics, clothes, etc.

EXAMPLES 2-17 In the same manner as described in Example 1 several other spot removing composition were prepared. The formulations are shown in Table I below.

TABLE I.BPO'1 REMOVING COMPOSITIONS Ingredients (parts by weight) 2 3 4 6 6 7 8 9 10 11 12 13 14 15 16 17 l ,Hi-fiash naphtha 145 35 Richinol 8-1300 1 (60% in water) 60 32 Alipal -430" Additional water. 11. "Riehinol A (30% in water)- "Tergitol 8-12 30 Ethylene glycol monobutyl ether 15 3. 5 SMA 3000 A" (15% solution in water) 60 18 Kerosene Methylisobutyl lmfnnn Triehloroethylene "Ludox HS 40 4 Total l Richinol 8-1300 is a trade name of Richardson Company for ammonium dodecanoxy-polyethylenoxy ethyl sulfate.

I "Alipal 00-436 is a tradename of General Aniline and Film Co fgithelamrnonium salt of a sulfate of an alkylphenoxypoly(ethyleneoxy e ano The compositions of Examples 2-17 are efiiective in removing a wide variety of common household stains from carpets, upholstery and fabrics. The compositions of Examples 2-11 and 13 are jelly-like in consistency; the compositions of Examples 12 and 15-17 are liquids; and the compositions of Example 14 is a very fluid gel.

What is claimed is:

1. A stable, one-phase composition useful as a spot and stain remover consisting essentially of:

(a) about 40 to 85 percent by weight of water;

(c) about 4 to 20 percent by weight of water-dispersible anionic or nonionic surfactant;

(d) about 3 to 25 percent by weight of organic co-solvent which is a polar liquid having a vapor pressure of at least 0.1 mm. Hg at 20 C.; and

(e) about 1 to percent by weight of solid, non-tacky,

water-dispersible anti-soiling agent which, upon drying of said composition, is capable of rendering the residue of said surfactant nontacky and resistant to soiling.

2. The composition of claim 1, wherein water is present in an amount of about 50 to 75 percent by weight of said composition.

3. The composition of claim 1, wherein said surfactant is present in an amount of about 5 to percent by weight of said composition.

4. The composition of claim 1, wherein said organic cosolvent is selected from the group consisting of ethylene glycol monobutyl ether and ethylene glycol lower monoalkyl ether acetate.

5. The composition of claim 1, wherein said anti-soiling agent is a styrene/maleic anhydride copolymer.

6. The composition of claim 5, wherein said hydrocarbon solvent comprises naphtha and said organic co-solvent comprises ethylene glycol mono-butyl ether.

7. The composition of claim 1, wherein said hydrocarbon solvent comprises trichloroethyleue.

8. A stable, one-phase composition useful as a spot and stain remover consisting essentially of:

(a) about 50 to 75 percent by weight of water;

(b) about 5 to percent by weight of liquid hydrocarbon solvent having a boiling point higher than about 70 C. and having a vapor pressure not less than 2 mm. Hg at 20 C.;

(c) about 5 to 15 percent by weight of water-dispersible surfactant;

(d) about 10 to 15 percent by weight of organic cosolvent which is a polar liquid having a vapor pressure of at least 0.1 mm. Hg at 20 C.; and

(e) about 1 to '10 percent by weight of solid, nontacky, water-dispersible anti-soiling agent which,

Terg'ltol 8-12" is a trade name 01 Union Carbide for secondary pentadecanoxy-undecaethylenoxy ethanol. S; Ludox HS 40" is a trade name of DuPont ior dispersed colliodal upon drying of said composition, is capable of rendering the residue of said surfactant nontacky and resistant to soiling.

9. The composition of claim 8, wherein said organic co-solvent is selected from the group consisting of ethylene glycol mono-butyl ether and ethylene glycol lower monoalkyl ether acetate.

10. The composition of claim 8, wherein said anti-soiling agent is a styrene/maleic anhydride copolymer.

11. A process for removing spots and stains from textile substrates such as carpets, upholstery and the like, comprising the steps of:

(a) contacting the stained portion of said substrate with an effective amount of the one-phase composition of claim 1;

(b) effecting penetration of said stained portion of said substrate by said composition; and

(c) effecting substantially complete removal of said composition and the stain from said substrate.

12. A process in accordance with claim 11, wherein step (c) comprises the steps of:

(1) eifecting substantially complete removal of stain material which has been loosened by said composition;

(2) contacting any remaining composition with a small amount of water; and

(3) scrubbing any remaining stain with said remaining composition.

13. A process for removing spots and stains from textile substrates such as carpets, upholstery, and the like, comprising the steps of:

(a) contacting the stained portion of said substrate with an eifective amount of the one-phase composition of claim 8;

14. An aerosol-type container charged with the composition of claim 1 and a propellant.

15. An aerosol-type container in accordance with claim 14, wherein water represents 50 to 75 percent by weight of said composition and wherein said organic co-solvent is selected from the group consisting of ethylene glycol monobutyl ether and methyl isobutyl ketone.

16. An aerosol-type container charged with the composition of claim 8 and a propellant.

17. An aerosol-type container in accordance with claim 16, wherein water represents 50 to 75 percent by weight of said composition and wherein said organic co-solvent is selected from the group consisting of ethylene glycol monobutyl ether and ethylene glycol lower mono-alkyl ether acetate.

(References on following page) References Cited UNITED STATES PATENTS Stolmeijer 8142 Rudzenia 252163 Hatfield 252163 Hollub et a1. 252-163 Porcaro 2S2163 8 3,619,830 11/1971 Harris et a1 14-142 3,642,644 2/1972 Grote et a1 s 142 WILLIAM E. SCHULZ, Primary Examiner us. 01. X.R,