JPS6051800A - Foamable acidic detergent composition - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

DETAILED DESCRIPTION OF THE INVENTION (Field of the Invention) The present invention relates to a stone scum, a hardness component
The present invention relates to a liquid, foaming cleaning composition that can be used in a domestic or industrial environment to clean surfaces contaminated with organic and inorganic contaminants such as components, greases, and the like. More particularly, this invention relates to sprayable foaming acidic cleaning compositions.

BACKGROUND OF THE INVENTION Sprayable cleaning agents have been used for many years for domestic and industrial cleaning of a variety of organic and inorganic contaminants, such as food residue, soap scum, grease, hardening ingredients, etc. . Generally, these cleaning agents include a large amount of solvent, such as water or mixed aqueous organic solvents, and components such as chelating agents, such as EDTA.

Contains anionic, nonionic and cationic surfactants such as NTA, preservatives, fragrances, and dyes. These spray cleaners are generally formulated at approximately neutral pH (about 7) to alkaline pH (up to about 12). These cleaners work well against many contaminants; however, in some applications, neutral or basic cleaners may be effective against certain contaminants, such as hardening components (calcium salts that precipitate from hard water and They have the disadvantage that they can be very difficult to clean, as they are insoluble at basic pH as well as soap scum (precipitated calcium soap salts). Acidic cleaning agents are indicated to remove contaminants in such cases.

However, acidic detergents pose several problems in use and formulation. Many surfactants have an acidic pH
may be insoluble or hydrolyzed. Many fragrances are unstable at low pH. Strong inorganic acids, such as hydrochloric acid or sulfuric acid, strongly attack basic contaminants, but their use in water-based cleaning compositions can irritate or burn the user's skin, and Damages metal or coated surfaces. When sprayed, such cleaning agents can produce an acidic mist or spray that can cause eye irritation and damage, and can irritate the nose and throat if inhaled. May cause irritation and cough. If such irrigants are inhaled in sufficient quantities, lung damage will occur. For these reasons, sprayable acidic cleaning agents have not received the attention that has been given to sprayable neutral or basic cleaning compositions. However, there is a substantial need for acidic cleaning agents that can be used to effectively remove contaminants such as hard minerals, soap scum, dirt, grease and body oils found in home bathrooms and kitchens. It has arisen.

Inherent advantages of foaming acidic cleaning compositions, such as reduced aerosol dispersion, increased detergency and visibility
strong acids were considered necessary to obtain an effective cleaning action, despite the fact that the strong acids destabilize the foam and break down the surfactants necessary to foam the composition. ,To date, there has been little disclosure.

5chsrubal (U.S. Patent 11m4,235,73
No. 4] is an acid, a cationic or nonionic surfactant,
and alkanols or inert substituted alkanols, such as butylcarpitol, are generally disclosed. Alkanols are disclosed for foam stabilization.

The composition disclosed in the Cherubel patent comprises a solution of a strong acid, hydrochloric acid, and a surfactant mixture consisting primarily of a cationic "quaternary" surfactant.

Accordingly, there is a need for effective foaming cleaning compositions comprising one or more weak acids and compatible cleaning and foam-forming solvents and surfactant systems.

BRIEF DESCRIPTION OF THE INVENTION The inventors have discovered an acidic component comprising a majority of water, a mixture of a weak inorganic acid and a weak organic acid, having the following formula: (R4XR2XR3)
By combining an effective amount of an amine oxide surfactant, represented by It has been discovered that foaming acidic cleaning compositions can be produced.

The inventors have formulated many combinations of surfactants, solvents, acids, and water that provide low cleaning activity, whereas the acidic cleaning compositions of the present invention combine ease of application and safety. We have discovered that it has a surprisingly high level of cleaning power.

DETAILED DESCRIPTION OF THE INVENTION Briefly described, the sprayable foaming acidic cleaning composition of the present invention comprises an acidic component comprising a major portion of water, a mixture of weak inorganic acids and weak organic acids. , a uniquely high dipole mome/
and a co-solvent which is preferably an alkanol or an alkoxy-substituted alkanol.

The acidic component used in making the sprayable foaming acidic compositions of this invention is a weakly inorganic acidic component that can be dissolved in the aqueous organic cosolvent system of this invention and provides an acidic pH in the range of about 1-5. It will comprise a mixture of acids and weak organic acids.

Practical pHs lower than about 1 may result in substantial corrosion of metals and other surfaces in the cleaning environment, while pHs higher than about 5 may unacceptably reduce the cleaning efficiency of the composition. There is.

The term "weak" as used with respect to acidic components means that when the acid is dissolved in water at ambient temperature at an acidity within the range useful for forming the compositions of this invention, the first dissociation step is substantially Used for acids that do not go to completion. Such inorganic and organic acids are also referred to as weak electrolytes, and this term
xtL+ook ofQuantitative In
organic analysis, 1. M.

Kolthoff et al., Macmillan Publishing, pp. 34-37. This disclosure is incorporated herein by reference.

In this invention, most commonly commercially available weak inorganic acids and weak organic acids can be used. Examples of weak inorganic acids include phosphoric acid and sulfamino acid. Useful weak organic acids include acetic acid, hydroxyacetic acid, citric acid, benzoic acid,
Includes tartaric acid and the like. The inventors have found that in many applications, a mixture of weak organic acids and inorganic acids in the composition can provide a surprising increase in cleaning effectiveness. Preferred cleaning systems comprise a combination of sulfamino or phosphoric acid and an organic acid such as citric acid, acetic acid or hydroxyacetic acid (glycolic acid). The most preferred acid wash system comprises sulfamino or phosphoric acid and hydroxyacetic acid.

In the case of a phosphoric acid-hydroxyacetic acid system, the weight ratio of phosphoric acid to hydroxyacetic acid is preferably about 15:1 to 1:1, most preferably about 5 to 1.5:1.

The inventors have found that one type of contamination that is difficult to remove from surfaces is CaHPOa. This component is part of many contaminants and may be the result of interactions between the curing component and acid-containing cleaners that use phosphoric acid as the acidic component.

The inventors believe that a mixture of hydroxyacetic acid and phosphoric acid in an acidic cleaner may optimize cleaning performance. However, in some regions, the phosphoric acid content allowed in cleaning compositions is or must be limited to negligible amounts. Surprisingly, the inventors have discovered that using a sulfamino acid-hydroxyacetic acid system, the amount of hydroxyacetic acid can be greater than the amount of sulfamino/rRO to form a phosphate-free composition. In such systems, the weight ratio of 1 hydroxyacetic acid to sulfamic acid is preferably about 5 to 1:11, most preferably about 3 to 1:1.

The inventors have discovered that the surfactants that work in conjunction with the other ingredients of this invention to provide the highly effective cleaning properties of this invention are commonly used in sprayable cleaning products. and is the most commonly used surfactant as a foam stabilizer in shampoos or other cosmetic products. The surfactants used in the sprayable foaming acidic cleaners of this invention have the following formula:
C2o-alkylamide-C2-C5-alkyl group; and R2 and R6 are each independently C1-C4-
or hydroxy-C5-C4-lower alkyl). Preferably, R2 and t3 are both methyl, ethyl, or 2-hydroxyethyl. Preferred members of this class include:
Lauryl(dimethyl)amine oxide (N1nox (
(registered trademark) L, Stephen Chemical
Cor Northfield, IL], cocodimethylamine oxide [N1nox C], myristyl (ester) amine oxide [:N1nox M], stearyl (dimethyl) amine/oxide (Schercam
ox (registered trademark) DMS * ScherChem
Coco(bis-hydroxyethyl)amine oxide (5cherc, amox CMS), Mellow(bis-hydroxyethyl)amine oxide, and Cocoamidopropyl(ester)amine oxide (NlnoxCA)
) is included. These surfactants are nonionic in alkaline solutions, but cationic in acidic solutions. Preferably, the amine oxide surfactant accounts for about 1 to 15 liters of the composition of this invention, most preferably about 2 to 1 liters.
Configure.

Although the compositions of this invention can contain small amounts of nonionic surfactants to enhance the contaminant dispersing power of the amine oxide, such surfactants generally subtract from the total surfactant present. Do not exceed 25% of the drug. Useful nonionic surfactants include polyethyleneoxy condensates of C7-C1o-alkyl substituted phenols, such as the condensation product of 8-10 mol D ethylene oxide with nonylphenol [respectively, Igepal® GIO163
0, and 710, available from GAF].

Other useful nonionic surfactants include hydrophobic polyoxyalkylev pastes formed by condensation of zolobile/oxide with propylene glycol and condensation products of ethylene oxide (Pluronlc® series, BASF Wyandotte], C8-C22-alkyl alcohols, condensation products of 1 mole of alcohol with 2 to 50 moles of ethylene oxide, ethylene oxide esters of alkyl mercaptans, ethylene oxide esters of fatty acids, ethylene oxide ethers of fatty acid amides, and other similar Nonionic surfactants, if present, preferably constitute about 0.25-3% of the total composition, most preferably about 0.25% to 3% of the total composition.
It constitutes 5-1.5%.

Co-solvents used to maintain the stability of the foaming acidic cleaners of this invention include those that are miscible with water and maintain a stable solution of the amine oxide surfactant and acid in the aqueous medium. Any solvent that can be used is included. Preferred co-solvents are alcohols and alkylene/glycols,
Mono- and di-alkyl ethers such as dialkylene glycols and trialkylene glycols. Alcohols useful as cosolvents in this invention include methanol, ethanol, pronocentol, and isopro/gnol. Mono- and dialkyl ethers of ethylene glycol and diethylene glycol (these have common names such as polyglym, eelloiolve, and carpitol)
bltol) are particularly useful in this invention. Representative examples of this type of co-solvent include methylcellosolve, butylcarpitol, dibutylcarpitol,
Includes diglyme, triglyme, etc. C2-C6 alkyl carbitols are preferred from the standpoint of low cost, commercial availability, and solvent strength. The most preferred cosolvent of this invention is butylcarpitol. These preferred cosolvents help reduce surface tension and solubilize grease and soap scum, and maintain the foaming acidic cleaner as a stable single phase system.

Generally, the acid component of this invention is present in the cleaning agent in a total amount of about 5-25% by weight of the cleaning agent. The preferred sulfamic/acid or phosphoric acid and droxyacetic acid systems are generally present in an amount of about 5 to about 15 weight percent of the detergent. At this concentration, the preferred acidic components of the detergent are highly effective in removing hardened components at low component cost with substantial user safety.

The total surfactants of the foaming sprayable acidic cleaners of this invention may be present in a concentration of about 2 to about 15 weight percent of the composition. Preferably, because of their activity and low cost, the surfactants of this invention are present in detergents in an amount of about 3 to about 12
% by weight, most preferably at a concentration of about 2.5-6.5% by weight. The amine oxide surfactant accounts for a large portion of the amount, preferably about 50 to 50% of the total surfactant system.
100 inches, most preferably about 75-100 inches.

The co-solvent detergent stabilizer component of the foaming acidic detergents of this invention may be present in an amount ranging from about 1 to about 15% by weight of the composition. Preferably, the co-solvent comprising an ethylene glycol mono- or dialkyl ether to aid in soap scum removal and surface tension reduction is from about 2.5 to
It is used at a concentration of 10% by weight. The most preferred cosolvent for use in the pumpable foaming acidic cleaner of this invention comprises a C2-C5 alkylcarpitol and is used at a concentration of about 2.5-5 wt. Ru. If desired, a small but effective amount of an acid stable thickener can be added to improve the stability and adhesion of the foamed composition. Useful thickeners include xantano gum (Kelz
an(R) Merck]-1 and polyvinylpyrrolid/. When used, these thickeners are generally present at about 0.1-5% by weight of the composition.

The sprayable effervescent acidic compositions of this invention can be formulated by any conventional means. Dissolve the ingredients in water,
Alternatively, it can be suspended in water and stirred until a solution is obtained. In general, the order of addition of the ingredients is not critical; however, for ease of manufacture and initial detergent stability, the acidic ingredients can be dissolved in the aqueous phase and then the co-solvent added; Finally, the surfactant composition comprising the amine oxide is added to the stirred homogeneous mixture. The ingredients are then formulated into an aqueous system and at a concentration of about 1% to about 5% in soft water, or tap water or potable water detergent.
to provide a final pH in the range of . Preferably, the pH of the final solution will be in the range of about 5 to 3, and most preferably the pH of the final solution will be in the range of about 2 to 3 at a concentration of cleaning agent in tap water or potable water. do it like this. At this pH the detergent is stable and provides surprisingly high cleaning power.

The foamable pumpable acidic cleaning composition of this invention is intended to be applied to contaminated surfaces in a manner other than spraying.

Spraying means that use nozzles to disperse substantial amounts of fine mist or flying droplets of cleaning agent into the air, such as pump sprayers or aerosol sprayers, are not preferred. This is because such dispersions of cleaning agents are extremely hazardous and can damage the user's eyes and respiratory tract. The cleaning agent of the invention can be applied as a liquid, as a sticky liquid or as a foam powder. Liquid applicators can have push-pull tops, toggles tops, or sponge applicators. Preferably, foam application means are preferred that are capable of applying at least one layer of foam to a surface without substantial fog formation. Foaming containers with pump action or means of using an aerosol propellant are known to those skilled in the art.

When filled or loaded with the acidic composition of the invention, these containers constitute the foam generator of the invention. 1
One preferred foam generator is U.S. Pat. No. 4,350,29
No. 8, No. 4,230,277, and No. 4,153,2
No. 03, the disclosures of which are incorporated herein by reference. This foam application means can be applied to horizontally and vertically fixed surfaces from about 1 m to about 30 m.
A layer of foam 1 m thick can be applied. However, from the viewpoint of cleaning efficiency and economy, a foam layer of about 2 to 10 m is preferred. After applying the foam to the contaminated surface, the foam is left to act on the contaminant and is then rinsed off.
or wiped off with clean absorbent material.

If very stubborn soiling is present, applying a cleaning agent to the surface and dispersing the contaminant using brushing or scraping means capable of breaking up the soiled surface;
The activity of the cleaning agent can be brought into contact with the finely divided particles of contaminants. However, the most aggressive contaminants may require a single application of a modest amount of the pumpable foaming acid cleaner of this invention without substantial brushing or scrubbing of the contaminant. removed by A substantial advantage of the invention is that it removes water from scratch-prone fiberglass, glass, and plastic appliances in home bathrooms.
rdener) and soap scum can be removed and brightened by a single application of the cleaning agent, which is then rinsed off or removed by an absorbent material.

The invention will now be explained in more detail by way of specific examples. However, this does not limit the scope of the invention. In these examples, parts by weight or type treatments are used without regard to percentages.

Example 1. 65.4 parts of soft water in a 500m/beaker, and 23.
Two parts of 75 thiphosphoric acid aqueous solution were charged. The mixture was stirred until homogeneous and 9.6 parts of 70% aqueous hydroxyacetic acid was added and stirred until homogeneous. To this homogeneous mixture was added 1.0 part of ethoxylated nonylphenol surfactant [IGEPAL Co-630].
), and 0.07 parts of methylsalicylic acid flavor were added.

This mixture was mixed until homogeneous and placed in a pump foam generator.

Example 2 500mA! 74.3 parts of water and 11.6 parts of 75% phosphoric acid aqueous solution were placed in a glass beaker. The mixture was stirred until homogeneous and 4.8 parts of 70-thihydroxyacetic acid aqueous solution was added. The mixture was stirred until homogeneous and 4.0 parts of butyl cellosolve was mixed with 1.0 part of polyethyloxynonylphenol surfactant (IC
EPAL® CO-630), 0.20 parts methylsalicylic acid flavor, traces of blue dye, and 4 parts lauryl(dimethyl)amine oxide surfactant [:
N1nox® L] was added to the mixture.

The mixture was mixed until homogeneous and placed in a plastic foam bottle.

Example 3 - Example 2 was repeated. However, 4 parts of methyl cellosolve was used instead of 4 parts of butyl cellosolve.

Example 4 Example 2 was repeated. However, 4 parts of butyl carpitol was used instead of 4 parts of butyl cellosolve.

Example 5 77.3 parts of soft water was added to a stainless steel stirring vessel equipped with a heating device, a cooling device and a propeller stirrer, and stirring was started. To the stirred water was added 3.5 parts of sulfamino acid along with 10 parts of technical grade (70%) hydroxyacetic acid. After stirring the mixture until homogeneous, 4 parts diethylene glycol monobutyl ether, 0.2 parts fragrance, traces of blue dye, and 4 parts lauryl (dimethyl) amine oxide (lauramine oxide) were added to the homogeneous solution. It was blended into the patch until it became . The liquid was drained and placed into a 16 oz/s spray container.

Example 6 A 500° glass beaker was charged with 76 parts deionized water. To this water was added 10 parts of a 75% aqueous phosphoric acid solution. The mixture was stirred until homogeneous and 10 parts of a 50% active aqueous solution of citric acid were added - after uniform mixing, 2 parts of diethylene glycol monobutyl ether were added to the mixture with continuous stirring. After homogenizing, add 2 parts of Turami/Oxide and blend the mixture until homogeneous, IJ? Take it out into a polyethylene vinyl,
Then I put the lid on.

Example 7 64.4 parts of soft water, 11.6 parts of a 75-thiphosphoric acid aqueous solution, and 4.8 parts of a 70-thihydroxyacetic acid aqueous solution were placed in a 500 m/○ beaker. The solution was mixed until homogeneous and 4.0 parts of diethylene glycol monobutyl ether was mixed with 4 parts of cocamidopropyl (dimethyl) amide/diethylene glycol monobutyl ether.
Added with oxide.

The mixture was blended until homogeneous and poured into a bottle of polyethylene.

Example 8 75.5 parts of deionized water were added to a suitable mixing apparatus at a diopter of 25°C. Add 11.6 to this water while stirring.
75 parts of an aqueous phosphoric acid solution was added. The mixture was stirred until homogeneous and 4.81 parts of 70% aqueous hydroxyacetic acid was added. The resulting mixture was stirred until homogeneous and 4 parts of lauryl(dimethyl)amine oxide were added to the solution along with 4 parts by weight of butylcarpitol. Stir the mixture until homogeneous, remove from the mixing device,
And 1. Stored in fron plastic bottles. A 1% solution of the μ parabolite in deionized water had a pH of 2.3.

The products of Examples 1-4 were treated with a surface containing soap scum, body oils, and water hardness.
Tested on shower stalls and sinks contaminated with nitrate. The product of Example 2 was found to be better in terms of commercially available detergents and substantially better than the product of Example 1 without amine oxide surfactants or cosolvents. Ta. The product of Example 2 was found to be substantially better than commercially available bathroom cleaners, and substantially better than the product of Example 1. The product of Example 3 was found to be substantially better than the commercially available bathroom cleaner and the product of Example 1. The products of Examples 2 and 4 were approximately equivalent in cleaning effectiveness and were better in practice than the product containing methyl cellosolve, indicating that higher alkyl ethers are preferred.

The product of Example 5 is approximately equivalent in effectiveness to the product of Example 4.

The descriptions, examples, and data set forth above are illustrative of the invention and are not intended to limit the scope of the invention or the claims. Many embodiments and modifications may be made within the spirit and scope of the invention.

patent applicant Engineering economics? Latry.

I/Corporate patent application agent Patent attorney Akira Aoki Patent attorney Kazuyuki Nishidate Patent Attorney Letter of Fortune Patent attorney Akira Yamaguchi Patent attorney Masaya Nishiyama

Claims (1)

[Scope of Claims] 1. A foam generating device having a container having a foaming means and containing an acidic cleaning composition, wherein the acidic cleaning composition comprises mostly water; 1% of the cleaning composition in water; An effective amount of an acidic component comprising a mixture of weak inorganic and organic acids to provide a pH of about 1 to 5 in solution; C2o-alkyl, or C8-C
2o-alkylamide-C2-C5-alkyl)
: R2 and R3 are each independently C1-C4-lower alkyl or hydroxy-C2-C4-lower alkyl); and an effective amount of a surfactant capable of lowering the surface tension. and an effective amount of a co-solvent capable of maintaining the cleaning ingredients in a stable mixture; A device that generates a layer of adhesive foam approximately 30 cm deep. 2. The apparatus of claim 1, wherein said foaming means is an aerosol foam generating means having an acidic cleaning composition combined with a propellant. 3. The device according to claim 1, wherein the foaming means is a manual de/so foamer. 4. The apparatus of claim 1, wherein the inorganic acid comprises phosphoric acid or sulfamic acid, and the organic acid comprises acetic acid, citric acid, hydroxyacetic acid, or a mixture thereof. 5. The acidic component is present in a concentration of about 5 to 15% by weight of the effervescent pumpable acidic composition and comprises a mixture of phosphoric acid and hydroxyacetic acid, with 1 part hydroxyacetic acid being present in the effervescent pumpable acidic composition. 2. The device of claim 1, wherein the phosphoric acid is about 1.5 to 5 parts. 6. The acidic component comprises a mixture of sulfamino acid and hydroxyacetic acid, and contains about 5 to 1 part of hydroxyacetic acid to 1 part of sulfamino acid, and the acid mixture is foamed to be pumpable. About 5 to 15 parts of the acidic composition
A device according to claim 1, wherein the device is present in a concentration of %. 7. The surfactant has a surfactant represented by the following formula: (R,XR2)(R3)N→0 (wherein R2 and R5 are both methyl, ethyl, or 2-hydroxyethyl) from about 1% to about 10% by weight of the foaming acidic composition.
A device according to claim 1 comprising a mono- or diether of alkylene glycol, sialkylene/glycol or trialkylene glycol present in a concentration of . 9. The apparatus of claim 8, wherein the co-solvent comprises an alkyl calpitol present in a concentration of about 1 to about 15% by weight of the effervescent, pumpable acidic detergent. A pumpable foaming acidic cleaning composition comprising mostly water; a mixture of weak inorganic and organic acids that provides a pH of about 1 to 5 in a solution of the cleaning composition in water. an effective amount of an acidic component comprising:
2o-alkylamide-02-C5-alkyl;
And R2 and R3 are each independently methyl, ethyl,
or 2-hydroxyethyl)
an effective amount of a surfactant mixture comprising about 50-ioo% oxide; and an effective amount of a co-solvent capable of lowering the surface tension and maintaining the cleaning components in a stable mixture. A composition consisting of. 11. The composition of claim 1, wherein the inorganic acid comprises phosphoric acid or sulfamino acid, and the organic acid comprises acetic acid, citric acid, hydroxyacetic acid, or a mixture thereof. 12. The acid component is present at a concentration of about 5-15% by weight of the pumpable effervescent acidic composition and comprises a mixture of phosphoric acid and hydroxyacetic acid, 1 part hydroxyacetic acid. 11. The composition of claim 10 containing about 1.5 to 5 parts of phosphoric acid. 13. the acid component is present in a concentration of about 5 to 15% by weight of the pumpable effervescent acidic composition and comprises a mixture of sulfamino acids and hydroxyacetic acids;
11. The composition of claim 10 containing about 5 to 1 part hydroxyacetic acid per part sulfamino acid. 14. The surfactant mixture has the following formula, (R1XR2X
R,)N→0 (wherein both R2 and R3 are methyl, ethyl, or 2
- hydroxyethyl)
11. The composition of claim 10, comprising from about 75 to 1001 s of amide/oxide, and wherein said amide/oxide is present at a concentration of from about 1 to about 10% by weight of said foaming acidic composition. 15. The composition of claim 10, wherein said co-solvent comprises a water-miscible alcohol, or a mono- or diether of an alkylene glycol, dialkylene glycol or trialkylene/glycol. 16. The composition of claim 15, wherein said co-solvent comprises an alkylcarpitol present in a concentration of about 1 to about 15% by weight of said pumpable effervescent acidic composition. . 17. The composition of claim 15, further comprising about 0.1 to 5 hours of an acid-stable thickening agent. 18. The composition of claim 10, wherein the surfactant mixture further contains a nonionic surfactant.