JP2987817B2 - Concentrated detergent aqueous solution that can be dropped and has abrasive properties - Google Patents

Abstract

This invention provides a thickened aqueous hard surface abrasive scouring cleanser having improved cleaning efficacy due to the presence of an organic solvent in the composition. It has surprisingly been found that an organic solvent can be included in an abrasive, surfactant, electrolyte/buffer, soap and colloidal alumina thickened composition without causing the system to become unstable. The abrasive cleanser of this invention has a smoothly flowable or plastic, preferably pourable, consistency and has stable abrasive-suspension characteristics over long periods of time.

Description

DETAILED DESCRIPTION OF THE INVENTION (Industrial application field) The present invention relates to a concentrated detergent aqueous solution having abrasiveness and rub-cleaning properties for hard surfaces, and more particularly, capable of dropping at room temperature.
The present invention relates to the above-mentioned detergent, which exhibits little or no syneresis even after a lapse of time and has an improved cleaning effect.

(Prior Art) In the current state of the art, various concentrated detergent aqueous solutions having frictional detergency are known, and these detergents have various characteristics. For example, U.S. Pat.
186 and 4,657,692 and 4,695,394, and January 21, 1988
Roboa et al. Concurrent U.S. Application Serial No. 0
7 / 146,519 discloses an aqueous abrasive detergent solution that uses a colloidal alumina concentrate to produce an abrasive detergent that exhibits little or no syneresis over time. U.S. Patent No. 4,676,920 to Culshaw and Published Patent Application EP 126545 and Idin for Buzzaccarini
g, EP 216416, discloses abrasive detergents containing clay-type concentrates. Although these detergents contain a hydrocarbon solvent, clay-type condensing agents do not provide desirable properties in terms of dripping and resistance to syneresis. Id
The disclosure of ing indicates that the inclusion of a solvent in the abrasive detergent component contributes to detergent instability and syneresis.

Other abrasive detergents are disclosed in U.S. Patent No. 4,158,5 to Chapman.
No. 53 and No. 4,240,919, No. 4,396,525 for Rubin
No. 4,129,423, Hartman No. 4,005,027
No. 4,457,856 to Mitchell and Japanese Patent Application No. 60-108499 to Watanabe et al. None of the detergents disclosed in these references have the desired cleaning efficacy for a particular application, and the excellent resistance to syneresis as demonstrated by the Choy et al. Detergents also provides desirable fluidity and plasticity. It does not have the consistency shown. Elepan
U.S. Pat. No. 4,508,634 to O et al. discloses that components of emulsion-type coating special detergents for removing paint stabilize emulsions capable of converting colloidal alumina into surfactants, solvents, selectable mild abrasives, and colloidal alumina. It is disclosed as a protective colloid concentrate.

The disclosure content of the above cited references is cited in this document with reference to the source.

(Problems to be Solved by the Invention) From the above viewpoints, it has been found that there is a need for a concentrated aqueous detergent solution having the following characteristics: (a) a consistency exhibiting smooth fluidity or plasticity; With
It is possible to drip as much as possible and maintain these properties for a long period of time. (B) The feature of stably suspending the abrasive, that is, resuspending the abrasive after standing for a long time. Thus, the ability to suspend the abrasive so that it can be used without the need for prior shaking or agitation, and (c) improved cleaning efficacy for certain applications.

The term "plastic" in the context of the present invention means that the detergent has a continuously deformable consistency, and that the consistency does not break or attenuate. The term "droppable" also means that the detergent has a consistency that allows it to be dropped from an open container without the need to apply a force other than gravity. The term "stable suspension of the abrasive" also refers to the fact that the abrasive in the detergent is totally completely suspended in the detergent system for a long time, thus re-suspending the abrasive mixture. This means that there is no need to shake or agitate the detergent before use. In this regard, liquid separation, in other words syneresis may occur with the detergent, but the detergent is considered to be stable in terms of abrasive suspension as long as the abrasive is completely suspended. You need to be careful. In addition, the liquid separation is not harmful to the dispensing and use of the detergent as long as the abrasive is completely suspended.

It has been determined by the present invention that it is desirable to add an organic solvent to a concentrated aqueous detergent solution to enhance the cleaning efficacy of the detergent for a particular application. Contrary to the expectation that the addition of an organic solvent to the detergent will promote syneresis, surprisingly, the above-mentioned desirable cleaning efficiency is improved and the abrasive aqueous concentrated detergent solution is used in a hydrocarbon solvent. In addition, it can be manufactured and has a smooth fluidity or plasticity when using hydrocarbon solvents in combination with fatty acid soaps and colloidal alumina with conventional electrolytes or buffers and surfactants, preferably dripping. It has been found that a detergent of the above-mentioned desirable properties, having a consistency of potential and having a stable abrasive suspension, is obtained. The improved detergent may also include a bleach if necessary. The improved detergent is described in detail below.

It is a first object of the present invention to obtain an aqueous abrasive concentrate solution characterized by flowability and consistency that maintains smooth flowability or plasticity for a long period of time.

A second object of the present invention is to obtain an abrasive concentrated aqueous detergent solution characterized by having a stable abrasive suspension for a long period of time.

A third object of the present invention is to obtain an aqueous abrasive concentrate solution characterized by improved detergent efficacy.

(Means for Solving the Problems) The present invention is characterized in that it has a smooth fluidity or plasticity and has a stable abrasive suspending property, and is a concentrated detergent exhibiting abrasiveness and friction cleaning properties on hard surfaces. An aqueous solution is obtained whose constituents are: (a) a content of from about 5% to about 70% by weight of the detergent;
%, A particulate abrasive having an average particle size of greater than about 1 micron and exhibiting a friction-cleaning effect; (b) one or more anions which are effective in detergency and are contained in an amount which suspends the abrasive; Anionic, nonionic, zwitterionic or zwitterionic surfactants, (c) having a content of about 0.1% to about 1% by weight of the detergent
0% electrolyte or buffer; (d) content from about 1% to about 15% by weight of the detergent
% Colloidal alumina condensate having an average particle size of less than about 1 micron in a dispersed state, and (e) a content of an effective amount or about 5% by weight of the detergent.
% Fatty acid soap and (f) content is an effective amount or about 10% by weight of the detergent.
% Organic solvent.

(Embodiment) One aspect of the present invention is characterized by having a viscosity that allows dropping and exhibits smooth fluidity, and provides an abrasive aqueous detergent solution that maintains these characteristics even for a long period of time. More particularly, according to the present invention, it has the above-mentioned properties and has a stable abrasive suspending property, and the latter property makes it possible to stably suspend a solid abrasive for a long period of time, A detergent having abrasiveness and friction cleaning properties is obtained.

Accordingly, in at least one or more embodiments of the present invention, the components of a concentrated aqueous detergent solution having the desirable characteristics of a droppable and smooth fluidity and a stable abrasive suspension are as follows: About 10% to about 70% of the above-mentioned detergent and having an average particle size of more than about 1 micron and exhibiting a friction-cleaning action, and (b) a content of about 0.1% by weight of the above-mentioned detergent. Or about 1
0%, one or more anionic, nonionic, zwitterionic or zwitterionic surfactants, (c) an electrolyte or buffer having a content of about 0.1% to about 10%, (d) a content of About 1% to about 15% by weight of the detergent
%, A colloidal alumina condensate having an average particle size of less than about 1 micron in a dispersed state; (e) a fatty acid soap having a content of about 0.1% to about 5% by weight of the detergent; (F) a content of about 0.1% to about 1% by weight of the detergent;
0% organic solvent.

The essential components of the abrasive component of the present invention summarized above are the above colloidal alumina concentrates, surfactants, soaps and solvents, especially where the colloidal alumina concentrates are the above surfactants, abrasives , Soap and organic solvents tend to exhibit smooth fluidity or plasticity (especially droppability) but not thixotropic properties.

For a more complete understanding of the invention, a summary of each component in the construction of the invention is set forth in more detail below.

Abrasives In the case of using the detergents of the present invention on hard surfaces, abrasives are used in the present invention in order to improve the cleaning effect by imparting frictional detergency. Preferred abrasives include silica sand but other hard abrasives such as perlite, which is one type of expanded silica, and various insoluble particulate abrasives such as quartz, pumice, calcium carbonate, feldspar, talc, tripoly and calcium phosphate. Can be used. The abrasive is present in an amount ranging from about 5% to about 70%, preferably from about 10% to about 60%, more preferably from about 20% to about 40%, based on the total weight of the detergent. Add.

Useful abrasives are generally sold according to grades based on "American sieve mesh units.""American sieve mesh unit" is inversely related to the measured value in microns, for example an 80 mesh sieve is equivalent to about 180 microns and a 325 mesh sieve is equivalent to about 45 microns. The average size of the particles should be at least about 10 microns, preferably from about 20 to about 200 microns, more preferably from about 30 to about 100 microns,
Usually the average size of useful abrasive particles is about
45 microns. The hardness of the abrasive particles is in the range of about 1 to 10, more preferably 3 to 8, Mohs hardness. Organic abrasives, such as melamine granules, urea formaldehyde, corn cobs, rice pulp, etc., but generally the abrasives useful in the detergents of the present invention are insoluble inorganic materials.

Some concentrates are also insoluble inorganic materials, for example, the present invention uses colloidal aluminum oxide concentrates. However, the colloidal alumina concentrating agent used in the present invention differs from the above-described aluminum oxide in many respects. That is, the colloidal alumina concentrate is dispersible in an aqueous system, and the average size of the particles in the dispersed state is less than 1 micron, usually even smaller. Aluminum oxide abrasives, on the other hand, are much larger, eg, up to 500 microns, and do not concentrate the detergents of the present invention even when dispersed in aqueous systems. As described below, the colloidal thickener must first be dispersed in an acidic solvent to provide concentrating properties. When the colloidal concentrating agent of the present invention is not used, even an abrasive such as an aluminum oxide abrasive cannot be stably suspended.

Surfactants As mentioned above, surfactants suitable for use in the present invention include anionic, nonionic, amphoteric or zwitterionic surfactants, generally non-soap surfactants, and these. From the mixture. It is particularly desirable to use a combination of an anionic surfactant and a bleach-stable nonionic surfactant, which is usually more saturated and retains stability in the presence of the bleach. However, when the detergent of the present invention is used in a formulation containing no bleach, the non-saturation of the selected surfactant can be increased. The anionic surfactant useful in the present invention is an alkali metal salt of alkyl sulfate,
It can be selected from surfactants such as secondary alkane sulfonic acids and linear alkyl benzene sulfonic acids, and mixtures thereof. The alkyl chain of these anionic surfactants desirably has an average of about 8 to about 20 carbon atoms. In practice, it is often desirable to add a bleach to the detergent. If a bleaching agent is included, the surfactant may be another anionic surfactant that does not chemically degrade when contacted with a hypohalite bleach, such as hypochlorite.

One example of a particularly desirable secondary alkanesulfonic acid is Farbwe.
HOSTAPUR manufactured by rke Hoeschst (Frankfurt, West Germany)
SAS. Another example of an alkanesulfonic acid is Mobay Chemical, which has an alkyl group of about 13 to 15 carbon atoms.
Mersolat sold by al. A typical example of an alkali metal salt of alkyl sulfate is Conco Sulfate having an alkyl group having about 16 carbon atoms and sold by Continental Chemical Company.
ate WR. If the electrolyte used is an alkali metal silicate, add a water soluble alkali metal soap of a fatty acid such as a C _6-18 , more preferably a C _10-16 fatty acid soap, with a surfactant. Is more desirable. Particularly desirable are the sodium and potassium soaps of lauric and myristic acids.

A preferred example of a bleach-stable nonionic surfactant is an amine oxide, especially a trialkylamine oxide. Representative structures are shown below.

In the above structure, R 'and R "are alkyl groups having 1 to 3 carbon atoms, most preferably a methyl group, and R is an alkyl group having about 10 to about 20 carbon atoms. there .R 'and R "are both CH ₃ - a, a structure of dimethyldodecylamine oxide is particularly desirable amine oxide when R is the average number of carbon atoms is from about 12 alkyl group. These amine oxides can be linear or branched (U.S. Pat.
If necessary, various substituents, such as a hydroxyethyl group and an ethoxylate group, which can coexist with the above-mentioned detergent system to obtain desired properties can be added. A representative example of these special, bleach-stable, nonionic surfactants is dimethyldodecylamine oxide sold under the trademark Ammonyx LO by Stepan Chemical Company (Chicago, IL). Another preferred amine oxide is Baid Chemical Industries, Inc.
There are amine oxides sold under the trademark rlox, and the Conco XA series, Armour Industrial C, sold by Continental Chemical as another amine oxide.
Aromax series, sold by hemical, Scher Brothe
Schercamox, ICI Americas Inc. sold by rs, Inc.
Synprolam series and Ethyl Corpora sold by
There are special amine oxides sold by tion. The primary alkyl chain of these amine oxides preferably has an average of about 10 to 20 carbon atoms. Another class of suitable surfactants is zwitterionic surfactants, typical of betaines, imidazolines and certain quaternary phosphonium and tertiary sulfonium compounds. Particularly desirable is N-carboxymethyl-N-dimethyl-
N- (9-octadecenyl) ammonium hydroxide and N-carboxymethyl-N-cocoalkyl-N-dimethylammonium hydroxide, the latter being Lonza Corporatio.
n sold under the Lonzaine trademark. Jone, whose disclosure has been signed in this document as another desirable surfactant
There are zwitterionic surfactants exemplified in U.S. Patent No. 4,005,029 to s (see columns 11-15).
In some cases, it may be desirable to use a combination of two or more of the above surfactants, most preferably a combination of an anionic surfactant and a bleach-stable nonionic surfactant. If the bleach is included in the above detergents and the temperature is high,
It may be particularly desirable to use surfactants of the above type in combination to maintain the half-life stability of hypochlorite for long periods of time. Furthermore, when a special combination of such surfactants is used in combination with an alumina condensing agent, the resulting formulation liquid hardly causes syneresis.

The surfactant may range from about 0.1% to about 15%, more preferably from about 0.5% to about 10%, based on the total weight of the detergent.
More preferably, it is added in the range of about 1% to about 5%.

Electrolyte or Buffer The electrolyte or buffer used in the present invention is a combination of a surfactant and a colloidal alumina condensing agent so as to have a viscosity that exhibits a desirable dripability and smooth fluidity in the composition of the present invention. The choice must be made with consideration. In a broad sense,
The electrolyte or buffer used in the present invention is generally an alkali metal phosphate, polyphosphate, pyrophosphate, triphosphate, tetrapyrophosphate, silicate, metasilicate, polysilicate, carbonate, Various inorganic acid salts such as hydroxides, chlorides, sulfates and mixtures thereof.
Certain divalent salts, such as, for example, alkaline earth metal phosphates, carbonates, hydroxides, etc., alone function as buffers. When such compounds are used, they are usually used in combination with one or more of the above-mentioned electrolytes or buffers in order to properly adjust the pH. Bleaching-stable organic substances such as aluminosilicates (zeolites), borates, aluminates and gluconates, succinates, maleates and their alkali metal salts may also be used as buffers. Deemed desirable. These electrolytes or buffers should be used to control the pH range of the inventive detergent compounds as much as possible.
It has the ability to maintain at least 7.0, more preferably at least 8.0 or 9.0, and most preferably between about 10.0 and 13.0. The amount of electrolyte or buffer used in the construction of the present invention is from about 0.1% to about 15%, preferably from about 0.5% to about 10%, more preferably from about 1%, by weight of the detergent. To about 5%. Silicate electrolytes or buffers useful in the present invention are formed by combining sodium oxide and silicon dioxide, wherein the weight ratio of silicon dioxide to sodium oxide is from about 3.75 / 1 to about 1/1, and possibly about
3/1 to about 1.5 / 1 sodium silicate. More preferably, the electrolyte or buffer is sodium silicate with a weight ratio of silicon dioxide to sodium oxide of about 2.4 / 1.

The above silicates are commercially available, for example, from PQ Corporation (Philadelphia, PA).

Colloidal Alumina Concentrator The colloidal alumina concentrator component of the present invention is desirably an aluminum oxide hydrate having suitable characteristics such as particle size that functions as a colloidal concentrator. In this sense, the colloidal alumina concentrate used in the present invention must be in contrast to the relatively large abrasive alumina material having a particle size of, for example, 1 micron or more. Thus, the particle size of the colloidal alumina concentrate is a particularly important feature for this component of the present invention. Although the discussion in this section relates to colloidal alumina as a thickener, the very important function of the colloidal alumina is that when combined with the surfactant and soap in the detergent components of the present invention, It must act as a suspension or suspending agent, and in particular must stably suspend the abrasive so that it does not settle or separate during prolonged storage.

The alumina hydrate desired in the present invention is obtained from synthetic boehmite. More importantly, the colloidal alumina concentrates of the present invention are chemically insoluble, that is, must not dissolve in common acidic, basic and neutral solvents. However, colloidal alumina is a strongly acidic solvent such as 50% NaOH
Note that it dissolves in water.

Typical alumina is DISPERAL (formally DISPUR) from Remet Chemical Corp. (Cadwick, NY).
AL) and manufactured by Condea Chemie (Brunsvetter, West Germany). DISPERAL is an aluminum oxide monohydrate that generally forms a stable aqueous colloidal dispersion. Alumina products of this type are dry powders that form thixotropic gels and bind silica and other ceramic product substrates, while having a positive charge and binding to various surfaces.

The typical chemical composition of DISPERAL is α-aluminum oxide monohydrate (boehmite) 90%, water 9%, carbon (as primary alcohol) 0.5%, silicon dioxide 0.008%, ferric oxide 0.005%, silica 0.004% sodium acid and 0.05 sulfur
%. DISPERAL has a surface area (BET) of about 320 m ² / gm, and the average size of particles in non-dispersed state (measured by sieving) is greater than 45 microns and 85% by weight at 15% by weight. In this case, the average size of the particles in the dispersed state is 0.0048 microns as measured by X-ray analysis, and the bulk density is 0.718 in the coarse state and 0.798 in the dense state. In addition, another type of alumina, particularly less desirable but suitable for use in the present invention, is manufactured by Vista Chemicals (Houston, TX) and sold under the trademark CATAPAL Alumina. The typical chemical composition of CATAPAL is aluminum oxide (boehmite) 74.2%, water 25.8%, carbon 0.36%, silicon dioxide 0.008%, ferric oxide 0.005%, sodium oxide 0.
004% and less than 0.01% sulfur. The surface area (BET) of CATAPAL is 280 m ² / gm, and the average size of particles in a non-dispersed state (measured with a sieve) is 4% when the weight ratio is 38%.
Less than 5 microns, weight ratio of 19%, greater than 90 microns.

The colloidal alumina concentrates described above are used in a dispersed state in the present invention, but the average size of the particles in the dispersed state is very small (ie, generally less than 1 micron). In practice, the average diameter of the particles when the above-mentioned concentrating agent is dispersed is often about 0.0048 microns. Thus, the desired average size of the particles in the dispersed state is preferably less than 1 micron, more preferably less than about 0.5 micron, and most preferably less than 0.1 micron. Although the above types of concentrates are inorganic particles that are chemically insoluble, they have little or substantially no abrasive action due to the small size of the particles. Further, the colloidal alumina is chemically very different from aluminum oxide abrasives such as corundum. Colloidal alumina is made from synthetic boehmite. Generally, synthetic boehmite is synthesized by hydrolyzing aluminum alcoholate. In this case, two reaction products obtained are aluminum hydrate (colloidal alumina) and three molecules of fatty acid alcohol.

(Cited from Cadea Chemic's booklet "PURAL PURALOX DISPERAL High-Purity Alumina", the contents of which are referenced in this document.) The above aluminum oxide hydrate is considered to be similar in crystal structure to natural boehmite simply. It is called synthetic boehmite only for reasons. Boehmite is actually inorganic and has a Mohs hardness of about 3. Therefore, the hardness of synthetic boehmite is not expected to be higher than natural boehmite. On the other hand, the Mohs hardness of corundum is at least 8, and probably higher. Since the colloidal aluminum oxide is relatively soft, its polishing effect is considered to be extremely low. An important aspect of the hydrated alumina used in the present invention is that it must be chemically insoluble, ie, must not dissolve in acidic, basic and neutral solvents, in order to have effective concentrating action as well as stability. However, colloidal boehmite alumina is a strong basic solvent such as 50% NaOH
Dissolve in

More importantly, the colloidal alumina concentrate must first be dispersed in an aqueous dispersion with a strong acid in order to be useful as a concentrate in the detergents of the present invention. The preferred acids used to disperse the colloidal alumina are acetic acid, nitric acid and hydrochloric acid,
Sulfuric and phosphoric acids, which are not limited to these acids, are undesirable.

In some cases, the effective content of colloidal alumina is 10
Calculate as 0% (ie, as if it were in a non-dispersed state), but generally 1-50%, and more preferably about 5%
Prepare a dispersion of from 40% to 40%, most preferably about 10% to 35%. In practice, the colloidal alumina is added to enough water to prepare the desired proportion of the dispersion, and then the acid is added to the dispersion. Alternatively, the acid is first added to water and then the colloidal alumina is dispersed in the dilute acid solution. In each case, considerable shear (i.e., mixing in a large liquid storage tank) is required to obtain adequate fluidity.

Usually, a relatively small amount of concentrated acid is added. For example, for a 25% by weight dispersing material, 25% alumina monohydrate is added to 1.75% concentrated hydrochloric acid (12M) and then dispersed in 73.75% water. The colloidal alumina concentrate itself is generally present in the above detergents in the range of about 1% to about 15% based on the total weight of the detergent,
More preferably about 1% to 6%, most preferably about 1%
% To about 4.7%. According to the present invention, the colloidal amina content in many useful formulations is about 2.
5% to about 3.5%.

It is necessary to neutralize the acidic dispersion of the colloid to make the final product flowable (i.e., the dispersion will concentrate). Such an acidic thin colloid is preferably neutralized with sodium hydroxide (eg, a 50% solution). However, if the electrolyte or buffer is sodium carbonate or sodium silicate, it can be added before sodium hydroxide as a separate component. Second, if necessary, a halogen bleach may be added to the detergents of the present invention, which are unstable under acid and need to be neutralized when bleach is used.

Although there are many types of inorganic and organic thickeners for concentration, not all concentrates provide the plastic, flowable rheological properties required for the present invention, especially the desired droppable consistency. Not always. US Patent No.
The common clays used in 3,985,668 and U.S. Pat. No. 3,558,496 can result in inadequate overall rheological properties. The inadequacy of the overall rheological properties is seen with liquids that are very viscous on standing, ie gel-forming.

What is difficult to solve due to the inadequacy of such a whole liquid is that the liquid will condense very quickly and harden or precipitate, which may result in flow problems. The liquid upon standing in a thixotropic state also condenses dramatically, but theoretically becomes fluid by shearing, so that thixotropic rheological properties are not particularly desirable in the present invention. If thixotropicity has a high stress value, as is typically found in clay-concentrated liquids, the fluidity of the liquid on standing must be returned by shaking or stirring. In fact, when only colloidal alumina is used in concentrating the liquid detergent of the present invention, it is considered that thixotropicity with a high stress value occurs. This type of product is undesirable and therefore the surfactants included in the formulations of the present invention are important for obtaining the desired rheological properties of creamy, flowable and plastic, especially the desired droppable consistency. is there. Normally, thixotropic liquids exit the dispenser only when shaken or squeezed. An example of a typical thixotropic liquid is ketchup, which requires vigorous shaking and tapping the bottom of the ketchup bottle to promote flow.

The rheological properties desired in the present invention are plasticity and flowability. With such rheological properties, shearing to improve flowability is unnecessary. Products made in accordance with the present invention in this manner require, in a desired condition, squeezing (assuming the bottle is deformable, plastic and squeezable), shaking and stirring to drain from the container or dispenser. It has a droppable consistency. Although the detergent of the present invention may not be dripped from a special container in an undesirable state,
However, it has a consistency showing smooth flowability and plasticity and does not show thixotropic.

It is expected that the addition of an organic solvent to the detergent component in which the abrasive is suspended will normally have a different effect on the rheological properties, promote syneresis and cause the abrasive suspension to be unstable. It is very surprising that the detergents according to the invention containing organic solvents have the above-mentioned rheological properties as well as the stability of suspending the abrasive. Detergents concentrated and stabilized with colloidal alumina as in U.S. Pat. No. 4,695,394 to Choy et al. Have the plasticity described above as well as the stability of suspending abrasives, and according to the present invention, It was surprising that it did not become unstable when the organic solvent was added. There is no previous disclosure in the state of the art that organic solvents can be added to household detergents on hard surfaces with concentrated abrasives and suspended abrasives to improve detergency in certain applications. It is believed that the organic solvent was expected to have a deleterious effect on the consistency that provides plasticity to the detergent or the stabilizing properties of the abrasive. One patent, U.S. Pat. No. 3,558,496, suggested combining aluminum oxide and ordinary clay to concentrate hypochlorite, but using a surfactant instead of clay would be desirable as in the present invention. It did not show that a plasticity, in particular a desirable droppable consistency was obtained. Another patent, US Pat. No. 4,508, to Elepano et al.
No. 634 discloses the possibility of using colloidal alumina as a protective colloid thickener to stabilize emulsions of surfactants, solvents and selectable mild abrasives, but the use of stable abrasives The suspension is a surfactant,
No recognition or disclosure was made of a combination of soap and an organic solvent.

Fatty acid soaps Soaps useful in the present invention have mono- or polyvalent kaotin that renders the soap soluble or dispersible in the aqueous detergents described above, with linear or branched fatty acids having 6 to 24 carbon atoms. I do. The soap is an alkali metal salt of the fatty acid, for example, Li, Na or K, or an ammonium or alkyl ammonium salt. Soaps conventionally used as foam control agents are generally useful in the present invention. Soaps have been selected in prior art detergents for foam control or bleach stability, but the soaps coexist with and solubilize with the organic solvents in the detergents of the present invention, and the colloids in the detergents of the present invention. Coexistence with the alumina concentrating agent is also important in the present invention. The above-mentioned soaps may be saturated or unsaturated. In any case, the combination of the present invention with a colloidal alumina concentrating agent and a hydrocarbon solvent provides the characteristics of improved detergency and resistance to syneresis. Maintain the characteristic of plastic viscous or dripping flowability of the detergents. In order to maintain the stability of the bleaching agent when a bleaching agent is included, as previously indicated for surfactants, a saturated soap is usually preferred, but some bleaching agents are not included in the detergents of the present invention. In some instances, unsaturated soaps are desirable.

Soaps useful in the present invention are generally limited to a range of molecular weights characterized in that they are either straight-chain or branched and have from about 8 to about 20 carbon atoms. More preferably, the soap is of the type having about 10 to about 14 carbon atoms, and even more preferably of the type having about 12 to about 14 carbon atoms. The amount of soap used in the detergent according to the invention can be an effective amount or about 5%, preferably about 0.1% to about 5%, more preferably about 0.5%, based on the weight of the detergent.
Or about 4%, most preferably up to about 3%.

Fatty acid soaps useful and suitable for the present invention are potassium laurate, sodium laurate, sodium stearate,
Select from fatty acids such as potassium stearate and sodium oleate. The same soap containing an ammonium salt as a cation can also be used, particularly when the detergent does not contain a bleaching agent. Soaps suitable for use in the present invention are Ch
emical Publishing Co. Inc.'s Encyclopedia Of Surface
−Active Agents, Vol I (1952), p. 39, Kirk-Othme
r, Encyclopedia of Chemical Technology, 3rd Edition, Vol. 21, pp. 162-181, for "Soap" and Vol. 22, Vol. Therefore, these documents are fully incorporated by reference in this document.

The mechanism by which fatty acid anionic surfactants or soaps function in combination with a colloidal alumina concentrate and a hydrocarbon solvent according to the present invention is not completely understood.
The above soaps are considered useful for the following reasons. However, the present invention is not limited by the following theory.

First, tests were conducted on other anionic surfactants, but the same advantages were not obtained. Therefore, it is not only the anionic state that makes the above soap useful in the present invention. It is believed that the soaps described in this document are generally more hydrophobic than other anionic surfactants. The stronger hydrophobicity of the above soaps is not completely understood, but is surprisingly thought to contribute to maintaining the feature of uniform and smooth flowability in the systems containing organic solvents of the present invention. The advantages of the rheological properties which result in the smooth flow and plasticity of the inventive detergents, as well as the improved consistency which results in the desired dripping properties.

It should be further noted that the soap is particularly effective in combination with a colloidal alumina concentrate if the detergent also contains silicate-based materials as electrolytes or buffers. In this regard, it is theoretically possible for silicates and alumina to act to form a network, probably due to the formation of bridging oxygen, resulting in a very thixotropic structure similar to the use of clay as a thickener. Conceivable.

The above-mentioned soap having a carbonyl group having hydrophilicity in combination with a hydrophobic alkali chain acts to destroy a network structure formed between silicate and alumina, and as described in the present invention, a detergent. It is considered that the structure of the present invention provides smooth flowability.

In addition, the above-mentioned soap is presumed to promote the mixing or emulsification of the organic solvent in the detergent of the present invention, so that it is considered that the soap also contributes to dissolving the above-mentioned solvent.

Organic Solvents The organic solvents useful in the present invention are alkyl or allyl hydrocarbons having at least 2 carbon atoms, preferably from about 4 to about 18 carbon atoms, and fatty acids contained in the components of the detergents of the present invention. Ethers, alcohols, esters, ketones and other hydrocarbons coexisting with soap surfactants and colloidal aluminum. D- limonene Examples of the organic solvent, terpinolene, pine oil, glycol ethers such as butoxyethanol (butyl "Cellosolve"), straight or branched C ₄ glycol ether, glycols such as polyethylene glycol, phenol, ethyl alcohol Benzyl alcohol, geraniol, citronellol, santalol, menthol, borneol, carveol, ethylhexylcarbonyl, vetiverol, linalool, terpineol, myrcenol,
There are esters such as cellulose and linalyl acetate, benzyl acetate, isobornyl acetate, ethyl acetoacetate, isoamyl acetate. Other examples of organic solvents that may be useful in the detergents of the present invention are terpenes, isoprene, petroleum spirits such as the Isopar and Norpar series of petroleum spirits, mineral oil sold by Exxon Corporation, P
Mineral oil sold by enreco. of course,
Mixtures of each organic solvent are useful in the detergents of the present invention.

As is understood with respect to the above surfactants and soaps, when a bleaching agent is included in the detergent of the present invention, a saturated organic solvent is added to improve the stability of the bleaching agent as recognized in the state of the art. Must be used. Conversely, to use the detergent of the present invention in a bleach-free formulation, an unsaturated organic solvent is selected. It is further understood that, as already mentioned, the organic solvent is selected to be compatible with the soaps and surfactants useful in the present invention. The amount of organic solvent used in the detergent according to the present invention is from an effective amount to about 10%, preferably from about 0.1% to about 8%, more preferably from about 0.1% to about 6% by weight of the detergent. %, Most likely about 4
%. Furthermore, in the most practical formulations, it is generally considered desirable in the present invention that the ratio of the amount of organic solvent to the total amount of soap and surfactant be within a certain range. Generally, the weight ratio of organic solvent to the total amount of soap and surfactant is about 1:40, usually from about 10: 1 to about 1:20, and preferably about 2:
1 to about 1:10, more preferably from about 1: 1.5 to about 1: 9, even more preferably from about 1: 2 to about 1: 8, and most preferably about 1: 3 Or about 1: 7.

Other Components As described above, a bleaching agent can be added to the detergent of the present invention, if necessary. The bleach is selected from various halogen bleaches. Halogen bleaches are particularly suitable for the present invention. As an example of a halogen bleach, the bleach is essentially selected from the group consisting of hypohalous acid, hypohalous acid-added products, alkali metal and alkaline earth metal salts of haloamines, haloimines, haloimides and haloamides. Can be. These materials form hypohalous bleach in their original state, of which hypochlorite is the preferred bleach. Typical compounds that form hypochlorite are sodium hypochlorite, potassium hypochlorite, lithium hypochlorite and calcium hypochlorite, chlorin
ated trisodium phosphate dodecahyrate, potassium and sodium dichloroisocyanurate, trichloroisocyanuric acid, dichlorodimethylhydantoin, chlorobromodimethylhydantoin, N-chlorosulfamide and chloramine.

As noted above, bleaching agents preferred for use in the present invention have a content of about 0.1% to about 5%, more preferably about 0.25% to 4%, and most preferably 0.5% to 2.0%. The chemical formula is sodium hypochlorite of NaOCl. The purpose of bleach is evident in forming a very effective oxidizing detergent against oxidizable stains such as organic stains.

The main problem with using bleach in the above components is that bleach is unstable and, if present in significant amounts, may cause destabilization of other components, especially certain surfactants. That is the tendency. In any case, in the present invention, colloidal alumina is used as a thickener together with a fatty acid soap and a surfactant, and an organic solvent is used together with a small amount of an additional surfactant component. (Expressed in terms of initial stability) is surprisingly good, so that the product can maintain excellent flow characteristics and bleaching power even after prolonged storage.

In addition to the components of the detergent composition of the present invention described above, dyes for stabilizing bleach (eg, anthraquinone dyes) and pigments (eg, phthalocyanine, TiO.
₂ , ultramarine blue), colorants and fragrances can be added in relatively small amounts, for example from about 0.001% to 5.0% by weight of the detergent.

Water Water is a solvent used as a continuous layer in which each component of the detergent of the present invention is dissolved, dispersed and suspended. Some of the detergent components are added to the detergent on a water basis and thus contribute to the total amount of water contained in the detergent. Water and various minor components or additives are constituents other than the detergent components, and water is generally included in amounts ranging from 10% to 80% by weight of the detergent.

Preparation As already mentioned, the preparation of the liquid detergents according to the invention consists of a mixture of: (a) an initial part of the total amount of water with the colloidal aluminum oxide concentrate, (b) a final part of the total amount of water. And (c) a selectable halogen bleach (d) a fatty acid soap (e) a surfactant (a bleach-stable nonionic surfactant if a bleach is used) ), (F) an electrolyte or buffer which interacts with the surfactants mentioned in steps (d) and (e) and the thickeners mentioned in step (a) to provide plastic rheological properties; g) Organic solvents.

To make detergents, see U.S. Pat.
Alumina, as described in US Patent Application No. 2005/02/027, the disclosure of which is hereby incorporated by reference, also incorporates alumina into a suitable mixing which is always agitated at a suitable sharp speed such as an impeller. Fill a large liquid storage tank with means or a suitable mixing container. Dilute the alumina with about 50% of the total water used as acid. At this time, an alkylbenzenesulfonic acid phase stabilizer is optionally added. Then 50%
A neutralizing agent such as NaOH is added along with the remaining amount of water. Next, a halogen bleach and an abrasive are added. Thereafter, an anionic surfactant is added. When silicates are used as electrolytes or buffers, fatty acid soaps have a network structure that can form between silicates and colloidal alumina, as described in U.S. Patent No. 4,695,394. It is necessary to use a fatty acid soap as one of the anionic surfactants, as it is thought to be surprisingly destructive.
Next, a stable nonionic surfactant is added to the bleaching agent. The nonionic surfactant (generally is a trialkylamine oxide (although betaine and other surfactants are also deemed suitable), at which point the alkylbenzene sulfonic acid is optional but most desirable.
Next, an electrolyte or a buffer is added, and finally an organic solvent is added. Alternatively, an organic solvent may be pre-mixed with the surfactant, if necessary, in some methods of making the detergents of the present invention. Note that selectable minor components such as fragrances and pigments can be added at almost every stage of the process. However, it is desirable to add the fragrance last because fragrances may be susceptible to oxidation by halogen bleaches. The present invention is further defined by the examples and the following results.

Examples 1-9 The following detergents were prepared and tested for the indicated properties.

The present invention also considers a method for preparing a detergent containing the components described above and in each of the examples. Generally, the above method comprises the steps of combining the various ingredients to form a detergent composition.

The present invention also contemplates a method for cleaning hard surfaces and removing dirt in a manner that is apparent from the foregoing. However, in order to ensure a complete understanding of the invention, the above method is practiced by contacting the components according to the invention with hard surfaces, stains or soils. After contact, it is desirable to remove the detergent components together with the suspended soil from the surface by washing with water.

Some specific examples of aqueous abrasive detergent solutions, which are characterized by a consistency exhibiting smooth fluidity or plasticity, while exhibiting the effect of suspending dirt as much as possible in the form of an abrasive. And examples have been disclosed above. While preferred embodiments and embodiments of the present invention have been described above, these embodiments can be further modified and improved, and the invention is not limited to only the precise details of the above embodiments, but is intended to It should be understood that changes and variations in the range should be considered.

EFFECTS OF THE INVENTION An excellent suspension of abrasive particles can be obtained by the abrasives of the present invention summarized above, which have abrasive and rub cleaning properties. Furthermore, it has been found that it is surprisingly evident that the detergents of the invention show little phase separation of the abrasive. It has also been recognized that detergents which stably suspend the abrasive obtained according to the present invention are stable for long periods and at relatively high temperatures. The detergents obtained according to the invention are physically stable and do not require shaking before use to resuspend or remix the formulation containing the abrasive. In practice, the detergents of the present invention maintain a uniform flowability even when stored for a long period of time and have a consistency exhibiting smooth flowability or plasticity, and more desirably a dripping consistency. Therefore, the detergents of the present invention are attractive enough in aesthetic sense, while being easy to dispense, to maintain solid abrasives and other components in a uniform suspension and to adhere to vertical surfaces. It is useful in the sense that proper run-off is sufficient for the application range.

In another aspect, the present invention provides a fluidity or plasticity consistency that is smooth, and desirably a droppable consistency, stably suspends the abrasive and provides abrasiveness and friction cleaning to hard surfaces. An aqueous concentrated detergent solution having properties is obtained. The constituent steps are: (a) the content is about 5% to about 70% based on the weight of the detergent, and the average particle size is more than about 1 micron; (B) one or more anionic, nonionic, zwitterionic or zwitterionic surfactants whose content is effective for cleaning and suspends the abrasive, (c) The content is about 0.1% to about 1% by weight of the detergent.
0% electrolyte or buffer; (d) content from about 1% to about 15% by weight of the detergent
% Colloidal alumina concentrating agent having a particle size of about 1 micron or less in dispersed state, and (e) a content of an effective amount or about 5% by weight of the detergent.
% Fatty acid soap and (f) content is an effective amount or about 10% by weight of the detergent.
% Organic solvent.

In another aspect, the invention relates to a concentrated detergent having a consistency exhibiting smooth flowability or plasticity, and more desirably, a consistency exhibiting dripability, and a feature of stably suspending an abrasive. There is provided a method for cleaning a surface with an aqueous solution, in which the concentrated detergent aqueous solution is brought into contact with a soiled surface. The components of the concentrated detergent aqueous solution are as follows: (a) the content is from about 5% to about 70% by weight of the detergent;
% Abrasive particles having an average particle size greater than about 1 micron and exhibiting a friction-cleaning effect, and (b) one or more anionic or nonionic particles having a content effective for cleaning and suspending the abrasive. Amphoteric, zwitterionic or zwitterionic surfactants, (c) content of from about 0.1% to about 1% by weight of the detergent
0% electrolyte or buffer; (d) content from about 1% to about 15% by weight of the detergent
% Colloidal alumina condensate having an average particle size of less than about 1 micron in a dispersed state, and (e) a content of an effective amount or about 5% by weight of the detergent.
% Fatty acid soap and (f) content is an effective amount or about 10% by weight of the detergent.
% Organic solvent.

The present invention relates to the above-mentioned surfactant, colloidal alumina which not only stably suspends the abrasive, but also provides an abrasive detergent having excellent detergency. The effects of soap and organic solvents were surprisingly clearly demonstrated.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁶ Identification code FI C11D 3:43) (72) Inventor Frederick I. Keene Meadow Way 770, Manteca, California, United States of America (56) References JP-A-56-145996 (JP, A) JP-A-60-1006898 (JP, A) US Patent 4,956,394 (US, A)

Claims (12)

(57) [Claims] 1. A water-soluble concentrated detergent having a smooth fluidity or plasticity and capable of stably suspending an abrasive, and having abrasiveness and frictional detergency on hard surfaces. A) a particle abrasive whose content accounts for 5% to 70% by weight of the detergent and whose average particle size is greater than 1 micron and which exhibits frictional detergency; b) an abrasive which exhibits effective detergency and One or more anionic, nonionic, zwitterionic or zwitterionic surfactants, contained in suspending amounts; c) an amount whose content constitutes from 0.1% to 10% by weight of the detergent. An electrolyte or buffer; d) a colloidal alumina concentrating agent having a content of 1% to 15% by weight of the detergent and having an average particle size of 1 micron or less in a dispersed state; 5% by weight or weight of detergent Fatty acid soap; from f) content effective amount of 10% by weight of the detergent,
Organic solvents that are hydrocarbon solvents. 2. The detergent of claim 1 wherein the particle size of the colloidal alumina concentrate is less than 0.1 micron in a dispersed state. 3. The detergent according to claim 1, wherein the surfactant is an anionic surfactant. 4. The detergent according to claim 1, wherein the fatty acid soap is a fatty acid alkali metal salt soap. 5. The detergent according to claim 4, wherein the anionic surfactant is monovalent. 6. The hydrocarbon solvent is at least one of d-limonene, terpinolene, pine oil, glycol ether, alcohol or a mixture of these solvents.
Detergent. 7. The detergent according to claim 1, wherein the content of the fatty acid soap is 0.1% to 4% based on the weight of the detergent. 8. The detergent according to claim 1, wherein the content of the hydrocarbon solvent is 0.1% to 7% based on the weight of the detergent. 9. The detergent according to claim 1, further comprising hypochlorite. 10. Detergent according to claim 1, characterized in that it can be dripped. 11. A method for preparing a water-soluble concentrated detergent having a viscous property exhibiting smooth fluidity and plasticity, and having abrasiveness and frictional detergency on a hard surface, wherein: Particle abrasive having an average particle size of greater than 1 micron and exhibiting detergency; b) effective detergency and contained in an amount to suspend the abrasive; One or more anionic, nonionic, zwitterionic or zwitterionic surfactants; c) an electrolyte or buffer in an amount whose content constitutes 0.1% to 10% by weight of the detergent; d. A) a colloidal alumina concentrate having a content of from 1% to 15% by weight of the detergent and an average particle size of less than 1 micron in a dispersed state; e) a content of from an effective amount to the weight of the detergent. Fatty acid soaps present at 5% in comparison to Fine f) from content effective amount of 10% by weight of the detergent,
Mixing an organic solvent which is a hydrocarbon solvent. 12. A method of washing a surface with a water-soluble concentrated detergent having a viscous property exhibiting smooth fluidity and plasticity and having an abrasive property and a friction-cleaning property for a hard surface. A) abrasive having a content of from 5% to 70% by weight of the detergent and having an average particle size of more than 1 micron and abrasion-detergent; b) an effective detergency; One or more anionic, nonionic, zwitterionic or zwitterionic surfactants, contained in an amount to suspend the abrasive; c) content of 0.1% to 10% by weight of the detergent An amount of electrolyte or buffering agent; d) a colloidal alumina concentrating agent whose content is from 1% to 15% by weight of the detergent and whose average particle size in dispersion is less than 1 micron; e) Content is an effective amount or the weight of the above detergent 5% of fatty acid soap Te; and f) from content effective amount of 10% by weight of the detergent,
Contacting a concentrated detergent comprising: an organic solvent which is a hydrocarbon solvent.