KR100525042B1 - Thickened aqueous cleaning composition - Google Patents

Abstract

This invention relates to a non-abrasive cleaning composition comprising an aqueous solution of bleach, colloidal thickener and divalent ionic calcium source. The composition comprises at least one surfactant which exhibits a cleaning action and which thickens with the colloidal thickener and an electrolyte / buffer effective to provide an atmosphere in which the above-mentioned thickeners and surfactants can moderately thicken. The composition of the present invention comprising ionic calcium has the required viscosity and viscoelasticity and exhibits excellent viscosity stability, flow stability, phase stability and bleaching stability. The cleaning composition retains the aforementioned properties even when stored for a long time and at high temperatures. The present invention also relates to a process for preparing the cleaning composition described above and a method for cleaning the substrate using the non-abrasive cleaning composition described above.

Description

Thickened Aqueous Cleaning Composition

FIELD OF THE INVENTION The present invention relates to non-abrasive thickened aqueous cleaning compositions and, in particular, to thickened aqueous cleaning compositions comprising colloidal thickeners and bleaching components. In particular, the present invention relates to compositions comprising an ionic calcium ion source and having the required viscosity, flowability, phase stability and bleaching stability. The invention also relates to a process for preparing the above-mentioned compositions and to the use of the above-mentioned compositions for cleaning.

Abrasive cleaning compositions comprising an abrasive component are already known. Such abrasive cleaners are used to clean or rub off hard surfaces.

The abrasive cleaner is formulated to stably disperse the abrasive such as calcium carbonate. In such a cleaning composition, in order to stably disperse the abrasives, problems of fluidity due to increase in viscosity over time and two-liquidity problems in which the solid and liquid components in the liquid are separated over time appear. When the abrasive composition as described above contains a bleaching component, a problem of bleaching instability may appear when the polishing components are stably dispersed.

Thickened aqueous cleaning compositions comprising a bleach component and a stable dispersion of abrasives are already known. U.S. Patent Nos. 4,599,186 (registered on July 08, 1986), 4,657,692 (registered on April 14, 1987), 4,695,394 (registered on September 22, 1987), and US Patent No. 5,346,641 to Argo et al. (1994. 09. Registration) describes a cleaning composition of the type described above. For example, the aforementioned U.S. patents describe hard surface cleaners containing abrasives and bleaching agents incorporating an inorganic colloidal thickener, alumina, in combination with a surfactant / electrolyte system to exhibit excellent physical stability. In addition, the above-mentioned US patent of Argo et al. Describes an abrasive hardening material comprising an alumina thickener, a surfactant for imparting required fluidity and detergency, an electrolyte / buffer, a halogen bleach, a granular abrasive, and a polyhydric salt in an amount capable of stabilizing the viscosity. Surface cleaners are described. The abrasive hard surface cleaners described in US patents of Argo et al. Have excellent abrasive dispersion capabilities and viscosity stability and exhibit plastic flow phenomena. Plastic flows have the advantage of not having to shear agitate the cleaning composition in order to improve flowability when used.

Non-abrasive cleaning compositions that do not contain abrasives are easier to manufacture than cleaning compositions containing abrasives because the problems associated with stable dispersion of the abrasives do not appear. An object of the present invention is to provide a non-abrasive cleaning composition containing no abrasive and a method for producing the same.

Liquid or gel cleaning compositions which contain a gelling or stabilizing agent and do not contain abrasives or bleaches are already known. The cleaning compositions of the foregoing types are described in WO94 / 16808 (published Aug. 04, 1994) by Vista Chemical Company, Beck, and WO94 / 05758 (published March 17, 1994) by The Procter & Gamble Company, Diet. It is. Beck et al. Patent describe alumina-thickening cleaning compositions comprising a gelling agent. The above-mentioned composition included alumina in an amount sufficient to make the composition reversible, and a gelling agent was included in an amount sufficient to aggregate or gel the alumina. The reversibility of the compositions described above is significantly different from the above-mentioned plastic flow characteristics required for thickening cleaning compositions.

Diet et al. Disclose a liquid or gel cleansing composition comprising a nonionic surfactant, anionic sulfate and / or anionic sulfonate surfactant, calcium and / or strontium ions, and a stabilizer selected from malic acid, maleic acid and / or acetic acid. It is described. According to the above-mentioned documents, calcium has been shown to be useful in detergent compositions containing polyhydroxy fatty acid amides for cleaning grease dirt. In practice, however, calcium is known to be inadequate for making stable liquid compositions. Therefore, the above patent uses stabilizers such as malic acid, maleic acid and / or acetic acid which are necessary to stabilize calcium or strontium ions contained in the composition. The above-mentioned patent states that the above-mentioned acids are useful as stabilizers in compositions that do not contain bleach, but these acids are detrimental to bleach stability when used in compositions containing bleach components, for example halogen bleach. Affect

Amed et al., US Pat. Nos. 4,970,016 (registered Nov. 13, 1990) and 5,089,161 (registered Feb. 18, 1992), disclose a thixotropic aqueous liquid automatic dish washing liquid comprising a bleach. The cleaning composition such as Amed described above contains a thixotropic thickener made of alumina or titanium dioxide and a film forming inhibitor in addition to the bleach component. Thixotropic thickeners include organic fatty acids or fatty acid polyvalent metal salts and / or inorganic clay materials for colloid formation. The anti-film forming component used in Amed's US patent serves to prevent the film from forming on the dish or glass container during dish washing. The aforementioned U. S. patent composition has thixotropic properties but does not exhibit the plastic flow properties required in thickened cleaning compositions.

Thus, non-abrasive thickened cleaning compositions, including bleaches and colloidal thickeners, but without abrasives, need to have the required viscosity, plastic flow properties, phase safety, and bleach stability.

Summary of the Invention

It is an object of the present invention to provide a non-abrasive thickened aqueous cleaning composition exhibiting the required viscosity, plastic flow properties, phase stability and bleach stability. Another object of the present invention is to provide a method for preparing the cleaning composition described above and a method for cleaning the body using the composition described above.

The object of the present invention described above is achieved by the present invention providing a non-abrasive thickened aqueous cleaning composition comprising a bleach, a colloidal thickener and a divalent ionic calcium source in an aqueous solution. The composition of the present invention comprises at least one type of surfactant which exhibits a cleaning action and thickens in combination with a colloidal thickener. The compositions of the present invention also include electrolytes / buffers that are effective in providing an atmosphere in which the thickeners and surfactants have a moderate thickening effect.

It has been found that the cleaning compositions of the present invention comprising an ionic calcium source have in particular the properties required for thickened aqueous cleaning compositions. For example, the composition of the present invention exhibited the following advantageous properties. (1) The viscosity of the composition initially increased remains stable over time. (2) It shows the required fluidity, that is, the plastic flow characteristic, and this plastic flow characteristic is kept stable over time. (3) There is phase stability and does not show a liquefaction property. (4) It has bleach stability.

The beneficial properties as described above of the compositions according to the invention have been shown to be obtained by the presence of the ionic calcium component. Ionic calcium is considered ionic due to the fact that it has been conventionally recognized as a component that cannot be used in cleaning compositions because of the formation of undesirable precipitates, the formation of soap sediments, the adverse effects on the viscoelasticity of the composition and the adverse effects on stability. It is surprising to know that the presence of the calcium component results in the beneficial properties as described above in the cleaning composition.

The nonabrasive compositions of the present invention exhibit an initial viscosity greater than that shown by the co-action of thickeners and surfactants. The viscosity of the composition can be adjusted so as not to be too viscous or thin by controlling the content of ionic calcium. The viscosity of the composition according to the present invention thus adjusted is not only maintained stable over time but also stably at high temperatures. Moreover, the composition of the present invention exhibits fluidity of plastic flow in addition to maintaining the required viscosity as described above. In addition, the compositions of the present invention exhibit bleaching stability in addition to having flow stability and phase stability.

The above-mentioned advantages with the present invention can be obtained when traces or small amounts of ionic calcium are present. According to one aspect of the invention the ionic calcium concentration in the composition is maintained in the range of 0.0001 to 1.0%, in particular 0.0001 to 0.34% by weight of the composition by the water soluble divalent ionic calcium source. The most preferred concentration of ionic calcium is in the range of 0.0007 to 0.07%. Therefore, the bottoms of the present invention can be produced economically.

The composition of the present invention can be used for various cleaning applications. For example, the composition of the present invention may be used for washing by treating the fabric, and may be used to wipe hard surfaces such as tiles, porcelains, floors, bathtubs, walls, sinks, tubs, and toilets.

Hereinafter, the present invention will be described in detail with reference to the drawings.

1 is a plot showing viscosity stability at 70 ° F. for one composition without ionic calcium and two compositions according to the present invention with varying concentrations of ionic calcium, the ordinate being 1000 centimeters; The viscosity is expressed in units of (cp), and the abscissa is the storage period in days.

FIG. 2 is a plot showing viscosity stability at 120 ° F. for one composition without ionic calcium and two compositions according to the present invention with varying concentrations of ionic calcium. The viscosity is expressed in units of (cp), and the abscissa is the storage period in days.

FIG. 3 is a diagram showing the phase stability at 70 ° F. for one composition without ionic calcium and two compositions according to the invention with varying concentrations of ionic calcium, the ordinate being shown in% It is liquid, and the abscissa is the storage period in days.

FIG. 4 is a chart showing phase stability at 120 ° F. for one composition without ionic calcium and three compositions according to the invention with varying concentrations of ionic calcium, the ordinate being shown in% It is liquid, and the abscissa is the storage period in days.

FIG. 5 is a chart showing the bleaching stability at 120 ° F. for one composition without ionic calcium and three compositions according to the invention with varying concentrations of ionic calcium, the ordinate being expressed in weight percent The bleach (sodium hypochlorite) concentration, and the abscissa is the storage period in days.

The present invention provides a non-abrasive cleaning composition having good bleaching stability without exhibiting significant lipophilic properties and without excessive viscosity increase. All of the above characteristics are maintained over time and even at high temperatures.

According to one aspect of the present invention, the alkaline nonabrasive cleaning composition comprises a colloidal aluminum oxide thickener; At least one kind of surfactant which exhibits a washing action and exhibits a thickening effect in combination with alumina; Electrolytes / buffers that create an atmosphere that causes the alumina thickener to thicken with the surfactant; Halogen bleach; And water soluble divalent ionic calcium sources. The divalent ionic calcium source provides the flow viscosity and phase stability and provides the amount of ionic calcium required to maintain bleaching stability while providing an initial viscosity that is greater than the viscosity exhibited by the combination of alumina thickener and surfactant. The present invention therefore provides a non-abrasive bleach containing detergent that is very stable both physically and in bleaching efficacy.

According to yet another aspect of the present invention, there is provided an alkaline non-abrasive cleaning composition, which comprises a colloidal aluminum oxide thickener, at least one surfactant, electrolyte or buffer, and halogen bleach, as described above, the weight of the composition and the weight of the composition. And a soluble divalent ionic calcium source providing 0.0001 to 1.0% by weight of ionic calcium based. In particular, the aforementioned ionic calcium source is preferably included in an amount such that 0.0001 to 0.34% by weight, in particular 0.0007 to 0.07% by weight, of ionic calcium is included in the composition. Thus, the non-abrasive bleach-containing cleaning composition of the present invention contains only trace amounts of ionic calcium and thus can be economically produced.

Hereinafter, each component of the cleaning composition according to the present invention will be described in detail. In the following description, "effective amount" means a sufficient amount required to fulfill the desired purpose, for example thickening, bleaching or other purposes, and "half-life" is present in the composition when used for the bleaching component. Means the time required for the bleach to degrade to 50% of the initial amount.

Colloidal thickener

Thickener components according to the invention include alumina or hydrated aluminum oxide, which range from 0.1 to 25%, in particular from 0.1 to 10% by weight of the composition. Representative alumina is disfural manufactured by Condia Chemie in Bruns-Betel, Germany, and sold by Remet Chemical Corporation in Chadwick, New York, USA. This disfural is an aluminum oxide monohydrate that forms a stable colloidal aqueous dispersion.

The special form of alumina described above is a dry powder that forms thixotropic gel, which is bound to silica and other ceramic materials and has a positive charge when dissolved in an acidic medium. Disfural contains 90% alpha-aluminum oxide monohydrate (biomite), 9% water, 0.5% carbon (as primari alcohol), 0.008% silicon dioxide, 0.005% ferric oxide, 0.004% sodium silicate and 0.05% sulfur. It has the representative chemical composition to include. Disfural has a surface area (BET) of about 320 m ² / gm, an average particle size (determined by sifting) of 15% above 45 microns and 85% below 45 microns, X-ray refractive index of 0.0048 microns and a rough bulk 45 lbs./ft . ³ and dense bulk 50 lbs./ft. ^It has a bulk density of ^three .

Another alumina source suitable for use in the present invention is catapal alumina, manufactured by Vista Chemical Company, Houston, Texas. Catapal esbi was composed of 74.2% aluminum oxide (biomite), 25.8% water, 0.36% carbon, 0.008% silicon dioxide, 0.005% ferric oxide, 0.004% sodium oxide and up to 0.01% sulfur. Catapal SB has a surface area (BET) of 280 m ² / gm, an average particle size (determined separately) of 38% below 45 microns and 19% above 90 microns. Catapal di was composed of about 73% alumina, 0.15% carbon, 0.01% silicon dioxide, 0.01% ferric oxide, 0,03% titanium dioxide and 26.8% water. Catapal di exhibits a BET surface area of about 220 m ² / gm and an average particle size distribution of 35% below 45 microns and 17% above 90 microns.

Such colloidal alumina thickeners generally have an extremely small average particle size (eg, 90% of the total is 50 microns or less). Preferred average particle sizes are 40 microns or less, in particular 30 microns or less, but most preferably have an average particle size of 25 microns or less. The measured average particle size of these thickeners currently on sale is 1 to 10 microns. However, the average particle size of the alumina described above in the dispersion is 1 micron or less.

Although the alumina particles of the type described above are inorganic and chemically insoluble, they exhibit little polishing due to their small particle size. Preferred hydrated alumina is obtained from biomite (found in the oxite light precipitate) having about 3 degree of polishing showing a low Mohs hardness showing relatively ductility.

The advantage of hydrated alumina is that it does not dissolve in acidic, basic and neutral media, so it exhibits effective thickening as well as stability. It is necessary to neutralize the acidified colloid in order to have the required fluidity of the product. In particular, since the halogen bleaching component contained in the cleaning composition is unstable under acidic conditions, it is necessary to neutralize the acidified colloid in the cleaning composition of the present invention including the halogen bleaching component. The acidified dilute colloid can be neutralized using sodium hydroxide (eg 50% solution). If sodium carbonate or sodium silicate is used as the electrolyte / buffer, sodium hydroxide may be added as a separate component. Moreover, when an alkali neutralizing agent is added separately, you may use anionic surfactant as a carrier.

Various types of inorganic and organic thickeners are known as thickeners, but not all thickeners provide the plastic flow, ie fluidity, required by the present invention. For example, conventional clays induce undesirable body fluidity, making them very viscous when standing. Thixotropic fluidity is undesirable in the present invention because the liquid thickens in the thixotropic state. Thixotropes have the same yield stress values as those found in clay thickening liquid media, so stationary fluids may not return to flow unless shaken or agitated. Although colloidal alumina alone can be used as a thickener, thixotropes with high yield stress values will appear.

The cleaning composition of the present invention plays an important role in making the creamy plastic fluidity required by the surfactant component described below. Compositions of the present invention having such plastic flow properties do not need to be sheared to improve flowability. Thus, the cleaning composition of the present invention does not need to be squeezed, shaken or stirred in order to be discharged out of the container or injector.

Surfactants

Suitable surfactants for use in the present invention are selected from anionic, nonionic, amphoteric, zwitteric surfactants and mixtures thereof. Preferred surfactants, however, are anionic surfactants and bleaching stable nonionic surfactants.

Anionic surfactants include alkali metal alkylsulfonates, secondary alkanesulfonates (also called paraffin sulfonates), alkyldiphenylether disulfonates, fatty acid soaps and mixtures thereof. These anionic surfactants have alkyl groups containing 8 to 20 carbon atoms. However, other anionic surfactants that do not chemically decompose upon contact with bleach hypohalite, such as hypochlorite, may also be used.

Examples of preferred secondary alkanesulfonates include Parberg Hoechst A.C., Frankfurt, Germany. There is Hostarpur manufactured by. Representative alkali metal salts of alkylbenzenesulfonic acids are those sold under the name Calsoft under Pilot Chemical Company. An example of a typical alkali metal alkylsulfate is a concosulfate WU having an alkyl group containing about 16 carbon atoms sold by Continental Chemical Company. If the electrolyte used is an alkali metal silicate, it is most preferred to use soluble alkali metal soaps of fatty acids such as C _6-14 fatty acid soaps. Preferred are sodium or potassium soaps of lauric acid and myristic acid. In the compositions of the present invention, alkali metal soaps of fatty acids are used in the range of 0 to 10% by weight of the composition.

Examples of bleaching stable nonionic surfactants are amine oxides, in particular trialkylamine oxides represented by the formula:

[Formula]

    R '

R-N → O

    R "

In the foregoing formulae, R 'and R "may each be an alkyl group having 1-3 carbon atoms, in particular a methyl group, and R is an alkyl group having 10 to 20 carbon atoms. R' and R" are both methyl groups and R Compounds having about 12 carbon atoms include dimethyldodecylamine oxide, which is the most preferred amine oxide. A representative example of this type of bleach stable nonionic surfactant is dimethyldodecylamine oxide, sold under the Ammonics Eloran trade name from Stefan Chemical. Other suitable amine oxides include Barox sold by Lonza, Conco XA sold by Continental Chemical Company, Aromax sold by Akzo and Cermokox sold by Ser Brothers Incorporated. These amine oxides have a main alkyl group containing on average 10-20 carbon atoms.

Other examples of suitable surfactants that may be used in the present invention include amphoteric surfactants such as betaine, imidazoline and some quaternary phosphonium and tertiary sulfonium compounds.

Preferably, a mixture of anionic surfactants and bleaching stable nonionic surfactants is used. When the two types of surfactants are mixed and used, the half-life of hypochlorite is increased because the hypochlorite is stably maintained for a long time at high temperature. The composition of the present invention is preferably such that the content of the total surfactant is in the range of 0.1 to 20% based on the weight of the composition.

In the present invention, it is very important to use a mixture of alumina and a surfactant. The use of alumina alone reduces the half life of the bleach when the composition is two-part and the surfactant is used alone, especially in large quantities. Theoretically, 0.1-25% of alumina and total surfactants (anionic surfactants, bleaching stability nonionics), based on the weight of the composition, in order to obtain a composition with improved flowability (plastic flow) and improved bleaching stability and reduced lipophilic properties. Surfactants and mixtures thereof) from 0.1 to 20%. In practice, however, it is preferable to use alumina and a minimum amount of surfactant. The amount normally used is an amount which shows a cleaning effect.

According to the invention alumina and surfactant are used in the following ranges: Alumina is used in an amount of 0.1 to 10%, in particular 0.5 to 6%, based on the weight of the composition, and total surfactant is 0.1 to 20, based on the weight of the composition %, In particular 0.5 to 5%. The use range of the alumina and the surfactant described above is to have the liquefaction and the optimum bleaching stability required by the composition, resulting in a reduction in the overall manufacturing cost according to the reduced amount of the active ingredient.

Electrolyte / Buffer

The electrolyte / buffer component of the cleaning composition according to the present invention has been shown to create an environment in which alumina and surfactant are combined. The electrolyte serves to provide ions (usually anions) to the aqueous solution. The electrolyte provides a charged liquid medium that combines the alumina thickener and the surfactant to exhibit the desired plastic flowability. The buffer serves to keep the pH constant. In the present invention, it is preferable to maintain the alkaline pH in order to maintain the required fluidity and halogen bleach stability.

Some compounds act as electrolytes and buffers. Such special electrolyte / buffer compounds include various inorganic acid salts, for example alkali metal salts of inorganic acids such as polyphosphates, pyrophosphates, triphosphates, tetraphosphates, silicates, metasilicates, polysilicates, carbonates and alkali metal hydroxides and mixtures thereof. There is this. Some divalent metal salts, such as phosphates, carbonates and hydroxides of alkaline earth metals, act only as buffers. When such a divalent metal salt compound is used as a buffer, at least one of the above-described electrolyte / buffer compounds should be additionally used to maintain a proper pH. As the buffer, inorganic materials such as aluminosilicate (zeolite), borate and aluminate, or bleaching stable organic materials such as gluconate, succinate and maleate may be used. Sodium chloride or sodium sulfate can be used as an electrolyte but not as a buffer to maintain the ionic strength necessary to achieve the required fluidity.

Particularly preferred electrolytes / buffers are alkali metal silicates, which are preferably used with alkali metal fatty acid soaps in order to obtain the plastic flowability required by the present invention. Preferred silicates are sodium silicates having the formula NaO: SiO ₂ . The ratio of silicon oxide and sodium oxide is preferably 1: 4 to 1: 1, in particular 1: 2. Such silicates can be purchased from Picue Corporation. The electrolyte / buffer compounds serve to keep the pH of the cleaning composition according to the invention at least 7.0, in particular in the range of 10-14. The amount of electrolyte / buffer may vary from 0.1 to 25%, in particular from 0.1 to 10%, based on the weight of the composition, but the preferred concentration range is from 0.5 to 5% by weight.

Halogen bleach

Suitable bleach sources for use in the present invention can be selected from a variety of halogen bleaches. For example, the bleach is selected from alkali metals or alkaline earth metals of hypohalite, hypohalite adducts, haloamines, halomines, haloimides and haloamides. These bleaches produce hypohalus bleach.

Preferred halogen bleaches are substances which produce hypochlorite in hypochlorite and in aqueous solution. But bromite is also an excellent halogen bleach. Representative hypochlorite compounds include sodium, potassium, lithium and calcium hypochlorite; Chlorinated trisodium phosphate tetrahydrate (hypohalite adduct); Potassium and sodium dichloroisocyanurate; Trichlorocyanuric acid; Dichlorodimethylhydantoin; Chlorobromohydantoin; N-chlorosulfamide (haloamide) and chloramine (haloamine). Halogen bleaching agents comprise from 0 to 15%, in particular from 0.5 to 5% by weight of the composition. Halogen bleach suitable for use in the compositions of the present invention is sodium hypotolite, represented by the formula NaOCl, and comprises from 0.1 to 15%, in particular from 0.1 to 10% by weight of the composition. More preferred amount of sodium hypochlorite is 0.25 to 5% by weight of the composition, the most preferred amount is 0.5 to 2% by weight.

The aforementioned bleaches are known as oxidative bleaches and their purpose is to remove contaminants that can be oxidized, such as organic pollutants. Oxidative bleaches of the type described above have a problem in that oxidation occurs when contacted with active substances in an aqueous system, thereby decreasing the bleaching efficacy. From a commercial point of view, bleaching stability is an important variable in maintaining its efficacy during storage or display of the cleaning composition. In the case of the hypochlorite bleach, when the hypochlorite is decomposed, oxygen is generated to increase the pressure in the packaging container and there is a problem in that bubbles are generated therein.

According to the invention, the bleach half-life appears to be superior. The bleaching stability of the cleaning composition according to the invention is believed to be represented by the ionic calcium source as described above.

Ionic Calcium Source

It has been shown in the present invention that the ionic calcium source acts to increase the initial viscosity of the cleaning composition. Moreover, addition of an ionic calcium source to the cleaning composition results in the desired composition properties such as viscosity stability, plastic flow, flow stability, phase stability and bleaching stability.

The composition of the present invention comprises a water soluble source of divalent ionic calcium. The solubility of the water soluble calcium source, ie K _sp , is preferably at least 10 ^-30 , in particular about 10 ^-10 . Most preferred solubility is from 10 ⁻¹ to 10 ⁻² . Ionic calcium sources include calcium in ionic or salt form. For example, a representative source of ionic calcium is calcium chloride.

According to one aspect of the present invention, the ionic calcium source can be such that the cleaning composition has an initial viscosity that is greater than the initial viscosity exhibited by the alumina thickener and surfactant, and maintains bleaching stability while exhibiting flow and phase stability. Use is made such that the ionic calcium of is included in the composition. For example, the ionic calcium source provides the cleaning composition with 0.0001 to 1.0% of the composition weight, in particular 0.0001 to 0.34% of the ionic calcium. The most preferred amount of ionic calcium is used to provide 0.0007 to 0.07% of ionic calcium in the composition.

Contrary to theory, calcium ions are supposed to react with alumina, surfactants and / or electrolytes / buffers without reacting with anions such as hydroxide ions (OH ⁻ ) present in the composition. The positively charged calcium ions are thus believed to stabilize the alumina, surfactant and / or buffer components in the composition. Unlike calcium ions, magnesium ions and aluminum ions have been shown to have more affinity for negative ions than alumina, surfactants and / or electrolytes / buffers present in the composition. It is believed that magnesium ions and aluminum ions form ion pairs with hydroxide ions in the composition, lowering the pH of the composition and adversely affecting the bleaching stability of the composition. Magnesium ions and aluminum ions do not serve to increase the initial viscosity of the composition exhibited by the ionic calcium according to the present invention.

As mentioned above, relatively small amounts of ionic calcium provide the desired properties related to initial viscosity and viscosity stability, plastic flow and flowability, phase stability and bleaching stability. Moreover, according to the present invention, since a small amount to a small amount of ionic calcium is used, the cleaning composition can be produced at low cost.

Other additives

Compositions of the present invention may include perfumes, colorants, pigments (eg, ultramarine blue), bleaching stability dyes (eg, anthraquinone dyes), fluorescent agents, solvents, keys to improve the performance, stability, or appearance of the composition. And other additives such as ratings and bilda. Generally such additives may comprise an extremely small amount, eg 0.001 to 5.0% by weight of each composition.

For example, fragrances sold by International Flavors and Fragrances, Inc. are included from 0.01 to 0.5% by weight of the composition. Small amounts of dyes and pigments may also be used, and representative examples of the pigments that can be used in the present invention include ultramarine blue (UMB) and copper phthalocyanine. Buffers such as carbonates, silicates and polyacrylates may also be added, but such buffers should be used to such an extent that they do not increase the ionic strength of the composition. Water may be added to the composition of the present invention for the balance of the compositional components.

The composition of the present invention may also include a solvent. For example, a solvent may be added that does not dissolve well in water, which is advantageously stable to hypochlorite bleach. Bleach stability solvents are used as flavoring ingredients such as terpene derivatives.

Terpene derivatives suitable for use in the present invention include terpene hydrocarbons having functional groups. Terpene derivatives having functional groups include, but are not limited to, alcohols, ethers, esters and ketones. Representative examples of the above-mentioned terpenes include the following: (1) verbenol, transpinocarbiol, cis-2-pinanol, nopol, iso-borniol, carviol, piperitol, thymol, a-ter Pininiol, terpinene-4-ol, menthol, 1,8-terpin, dihydroterpineol, nerol, geraniol, linalool, citronellol, hydroxycitronellol, 3,7-dimethyl Terpene alcohols such as octanol, dihydromirsenol, β-terpineol, tetrahydro- allooxymenol and peryl alcohol; (2) 1,8-Synol, 1,4-Synol, Iso-Bornylmethyl Ether, Rosepyran, α-terpinylmethyl Ether, Mentofuran, Trans-Anithol, Methylcarbicol, Alloxymen diepoxy Terpene ethers and esters, such as sides, limonene mono-epoxide, iso-bornyl acetate, nofil acetate, α-terpinyl acetate, linaryl acetate, geranyl acetate, citronellol acetate, dihydroterpinyl acetate, and neryl acetate ; And (3) mirtenal, camphoric aldehyde, perylaldehyde, citronellal, citral, hydroxycitronellal, camphor, verbenone, carbenone, dihydrocarbon, carbon, piperitone, menton, geranyl acetone Terpene aldehydes and ketones such as pseudo-ionone, α-ionone, β-ionone, iso- pseudo-methylionone, normal- pseudo-methylionone, iso-methylionone and normal-methylionone. Suitable terpene hydrocarbons for use in the compositions of the present invention include Simon and Rose, "The Terpenes", Vol. I-V, 2nd edition, 1947, Cambridge University Press. It is also described in US Pat. No. 5,279,758 to J. et al.

Manufacturing method

In order to prepare the composition of the present invention, the composition ingredients are injected and mixed in a suitable mixer. The order of addition is not important when mixing the components but the divalent ionic calcium source should be added after the addition of the alumina but before the addition of the surfactant. In practice, the alumina is mixed with an acid to be activated, and then the activated alumina is neutralized with sodium hydroxide. Halogen bleach is added after the alumina is neutralized. The order of addition of the other components, such as divalent ionic calcium sources, surfactants and optional additives, is not fixed, but the electrolyte / buffer component is preferably added after the addition of the halogen bleach and surfactant. Mixing the electrolyte / buffer results in a uniform composition that is slightly opaque.

Washing method

When washing the body with the composition of the present invention, the composition of the present invention is brought into contact with the body that needs to be contaminated and cleaned. The composition of the present invention is treated as a pretreatment step before washing the contaminated material, for example before washing the contaminated fabric to be washed with water. The contact of the composition with the body according to the invention may also occur during substantial laundering.

The composition according to the present invention comprises the components described in Table 1 below. The amount of each component used is expressed in weight percent based on the weight of the composition. The cleaning composition of Example 1 shows the advantages of the composition according to the invention.

Example 1

¹ : CAPATAL D manufactured by Vista Chemical Company.

² : L / CO sold by Stephan Chemical.

³ : Egg oil (RU) sold by PICQ Corporation, Valley Forge, PA.

1 and 2 show the viscosity stability at 70 and 120 ° F. for three compositions A, B, C comprising the conventional ingredients listed in Table 1 below. The amount of these components used is expressed in weight percent of the composition.

TABLE 1

¹ : CAPATAL D manufactured by Vista Chemical Company.

² : L / CO sold by Stephan Chemical.

³ : Egg oil (RU) sold by PICQ Corporation, Valley Forge, PA.

Composition A is a conventional composition containing only the ingredients listed in Table 1 and free of ionic calcium, and forms a decontamination gel suitable for prewashing treatment. This decontamination gel does not contain ionic calcium. Composition B is a composition according to the invention comprising 0.0007% by weight of ionic calcium, and composition C is a composition according to the invention containing 0.07% by weight of ionic calcium.

Each composition was stored at 70 ° F. and 120 ° F. and measured at 5 ° F. at 70 ° F. using a Brookfield model dbu 2-albu viscometer. Compositions stored at 120 ° F were measured to lower the temperature to 70 ° F to measure the viscosity. As can be seen in Figures 1 and 2, the viscosity of the compositions B, C according to the present invention showed a higher initial viscosity than the conventional composition at 70 ° F considered realistic display conditions and 120 ° F considered high temperature. The viscosity of the compositions B, C according to the present invention was stable over time as can be seen in Figure 1 showing the viscosity after storage for 250 days at 70 ° F. In addition, the viscosity of the compositions B, C of the present invention was stable even at high temperatures as can be seen in Figure 2 showing the viscosity after storage for 27 days at 120 ° F.

3 and 4 show phase stability at 70 ° F and 120 ° F for conventional Composition A and Compositions B and C according to the present invention. The two graphs described above also show phase stability at 70 ° F and 120 ° F for the conventional ingredients listed in Table 1 used in Compositions A, B, and C and Composition D comprising 0.35% of the ionic calcium according to the present invention. Is showing.

The term "phase stability" in the description relating to Figures 3 and 4 is intended to describe the lipophilic properties of the composition over time. The aliquots for each composition are determined by visual observation of the height of the separated layer in a transparent container such as a plastic container (not a glass container) such as high density polyethylene.

3 and 4, it can be seen that compositions C and D show extremely weak two-part liquidity, and composition B shows a weak two-part liquidity, while composition A shows a high two-part liquidity. For example, according to FIG. 3, which shows a two-liquidity after about 250 days at 70 ° F., the phase stability data for compositions B, C, and D according to the present invention was found to be stable over time. In addition, according to Fig. 4 showing the two-liquidity after the elapse of 27 days at 120 ° F., the compositions B, C and D according to the present invention is shown to be stable over time at high temperature.

5 shows the bleaching stability at 120 ° F. for conventional Composition A and Compositions B, C and D according to the present invention. The four compositions described above comprise a halogen bleach, for example sodium hypochlorite as described in Table 1. Compositions A, B, C, and D were added sodium hydroxide to adjust the pH of the composition to an appropriate level, such as alkalinity (eg to increase the pH) before adding ionic calcium.

In the description of FIG. 5, the term “bleaching stability” is used to describe a phenomenon in which the decomposition of sodium hypochlorite does not occur over time, that is, a phenomenon in which the concentration of sodium hypochlorite does not appear. After about 40 days at 120 ° F., bleaching stability data was collected. Bleaching stability for each composition was determined by iodine titration.

According to FIG. 5, Compositions A, B and C had similar levels of bleaching stability. These levels indicate a bleaching stability suitable for the present invention. Composition D showed that the concentration of sodium hypochlorite decreased more over time than Compositions A, B and C. This phenomenon is thought to be due to the higher concentration of sodium hypochlorite over time as the ionic calcium reacts with bleach at the ionic calcium concentration of composition D, resulting in a higher ionic strength of the composition. . However, even when a large decrease in the concentration of sodium hypochlorite associated with composition D as described above appears, such a decrease in concentration has a bleaching stability suitable for the present invention.

The three compositions comprising ionic magnesium at concentrations of 0.007, 0.07 and 0.28% based on the components and composition weights in Table 1, did not differ significantly from conventional Composition A after 63 days at 70 ° F. As can be seen in FIG. 1, the initial viscosity of the conventional composition A, measured at 70 ° F., was not higher than the composition according to the invention comprising ionic calcium. However, compositions comprising ionic magnesium did not increase the initial viscosity as required by the present invention.

Compositions containing 0.007% and 0.7% ionic magnesium had a bleaching stability after about 40 days at 120 ° F., although the composition did not differ significantly from the bleaching stability of conventional Composition A, but with 0.28% ionic magnesium. After storage for the same temperature and for the same period of time, the bleaching stability became unacceptably low.

For all compositions comprising ionic magnesium described above, to adjust the pH to an appropriate level, for example alkaline, before adding ionic magnesium as in the experiments for ionic calcium (e.g. to raise the pH). ) Sodium hydroxide was added. In the first experiment on compositions containing individual ionic magnesium, the pH of the composition was immediately lowered by the addition of ionic magnesium, resulting in loss of bleaching stability. The stoichiometry to equilibrate with the ionic magnesium to be added following the composition containing ionic magnesium to determine whether the aforementioned decrease in pH and lowering of the bleaching stability are due to ionic magnesium or insufficient use of sodium hydroxide. A second experiment was conducted with the addition of a theoretical amount of sodium hydroxide. In the second experiment, the addition of ionic magnesium did not affect the bleaching stability and flowability of the composition. As a result of these first and second experiments, it is believed that ionic magnesium forms ion-pairs with anions such as hydroxide ions present in the composition, lowering the pH and consequently adversely affecting the bleaching stability. Thus, compositions comprising ionic magnesium do not exhibit the same bleaching stability as in the compositions according to the invention comprising ionic calcium.

The experimental results described by the composition comprising ionic magnesium described above are different from the experimental results described by the composition comprising ionic calcium. For example, adding ionic calcium to a composition to which sodium hydroxide was added to adjust the pH did not immediately result in a drop in pH and a decrease in bleaching stability. Thus, a composition containing ionic calcium does not need to be additionally added sodium hydroxide as in a composition containing ionic magnesium. In compositions comprising ionic calcium, it is believed that ionic calcium stabilizes these compositions by reacting with alumina, surfactants and / or electrolytes / buffers in the composition in preference to sodium hydroxide present in solution. It is thought that a composition comprising ionic calcium uniquely imparts the viscosity and viscoelasticity necessary for the present invention without lowering the pH of the composition and without compromising the bleaching stability. Thus, the compositions of the present invention comprising ionic calcium have viscosity stability, flow stability, phase stability and bleaching stability, as expected.

The present invention provides a cleaning composition having the required elasticity in addition to the properties as described above. In general, the elasticity required in the thickened cleaning composition means that the ratio of storage modulus (G ') to loss modulus (G ") is high, and the higher ratio of G' to G" increases phase stability. do. Increasing the G ': G "ratio of the composition at a given viscosity means improved elasticity and phase stability of the composition. In the compositions of the present invention the ratio of G' to G" increases with increasing concentration of ionic calcium. Thus, compositions of the present invention with increased calcium concentrations exhibit increased phase stability.

Moreover, in the composition of the present invention, the yield stress value, the stress applied to the system to induce flow, increases with increasing ionic calcium concentration. In general, low yielding in thickened aqueous cleaning compositions means that less force is required to induce the flow of the composition. For proper dispersion of the thickened cleaning composition, the composition must not be flow resistant or too large. The yield stress value of the composition according to the present invention is maintained at the level required for the thickened composition together with the amount of ionic calcium required for viscosity stability and phase stability. Accordingly, the present invention provides a cleaning composition having the required viscosity, phase stability and dispersibility.

Compositions B, C and D of the present invention exhibit the required shear-dilution properties as determined by a shear-dilution profile, ie, a plot (not shown) showing viscosity versus shear rate. In general, the shear-dilution profile provides an index for the degree of dilution as the composition passes through the small pores under pressure, while at the same time providing an index indicating dispersibility. Shear-dilution profiles for compositions B, C and D according to the present invention are not sufficient for the dispersibility required for thickened aqueous cleaning compositions but are higher than conventional compositions A. Shear-dilution profiles of compositions B and C according to the invention are lower than other compositions D according to the invention. This indicates that Compositions B and C have better dispersibility than Composition D, which has a relatively low shear-dilution profile. However, the dispersibility of the composition D according to the present invention is also less than that of the compositions B and C, but to the extent required. The present invention therefore provides a cleaning composition having good dispersibility.

Experimental data show that the compositions according to the invention have good viscosity and flowability with viscosity stability, flow stability, phase stability and bleaching stability. These beneficial properties of the compositions of the present invention are maintained under representative storage conditions as well as when stored for long periods of time and under high temperature.

The foregoing embodiments are described by way of example so that the present invention can be easily understood, and the scope of the present invention is not limited to the above description.

Claims (13)

0.1 to 10% by weight of a colloidal aluminum oxide thickener component; 0.1 to 20% by weight of at least one surfactant which exhibits a washing action and shows a thickening action with an alumina thickener; 0.1 to 25% by weight of an electrolyte / buffer effective to create an atmosphere in which the aforementioned alumina thickener and the aforementioned surfactant act to thicken; 0.1-15% by weight of halogen bleach; And An alkaline non-abrasive cleaning composition comprising an aqueous solution of a water-soluble divalent ionic calcium source that provides 0.0001 to 1.5% by weight of ionic calcium based on the weight of the composition. 2. A composition according to claim 1, wherein the halogen bleach is selected from alkali metals or alkaline earth metals of hypohalite, hypohalite adducts, haloamines, haloimines, haloamides and haloimides. The method of claim 1, wherein the electrolyte / buffer is selected from phosphates, polyphosphates, pyrophosphates, triphosphates, tetraphosphates, silicates, metasilicates, polysilicates, carbonates, hydroxides; Composition selected from alkali metal salts and mixtures thereof The composition of claim 1 wherein the divalent ionic calcium source is calcium chloride.  The composition of claim 1, wherein the amount of ionic calcium ranges from 0.0007 to 0.07% by weight of the composition. The composition of claim 1 wherein the surfactant is selected from anionic, nonionic positive, amphoteric and zwitterionic surfactants and mixtures thereof. 7. The composition of claim 6 wherein the surfactant is an anionic surfactant selected from alkali metal alkylsulfates, secondary alkanesulfonates, alkyldiphenyletherel disulfonates and mixtures thereof. 7. The composition of claim 6 wherein the surfactant is an amine oxide. 7. The composition of claim 6, wherein the surfactant is a mixture of anionic surfactant and bleaching stable nonionic surfactant. 10. The composition of claim 9, wherein the anionic surfactant is secondary alkanesulfonate and the bleaching stable nonionic surfactant is an amine oxide. 2. The composition of claim 1, wherein the composition comprises C _6-14 soap as an additional component. 12. The composition of claim 11 wherein the C _6-14 soap is an alkali metal soap of lauric acid. 2. The composition of claim 1, wherein the composition further comprises an additive selected from dyes, pigments, colorants, fluorescent agents, flavorings, solvents, chelating agents, bilders and mixtures thereof.