JP5543490B2 - High viscosity detergent emulsion - Google Patents

Description

  The present invention relates to high viscosity, phase stable alkaline cleaning concentrates or compositions characterized by reduced water concentrations (high concentrations of active materials and surfactants such as alkalinity), and their use and their preparation. Regarding the method. In industrial or corporate applications, this material is phase stable and has a very high viscosity, but can be automatically or programmed to the point of use (which is easily mixed with water at the point of use to produce an aqueous cleaner) Can still be dispensed from a simple dispenser. This thickened emulsion is easy to make and is effective in soil removal in laundry, dishwashing, stationary cleaning and dairy applications. The composition provides improved or enhanced soil removal properties due to high alkalinity and surfactant contact.

  Cleaning compositions have been formulated in solid block, particulate and liquid forms. The solid form provides a high concentration of actives but needs to be dissolved in water to produce a cleaning liquid. Recent substantial trials have been directed to liquid detergent concentrates and, in particular, liquid detergents in the form of emulsions. Such detergent concentrates are typically not as active as solids and are often more than 50% water. Detergent emulsion concentrates have been used as general purpose cleaners, dishwashing detergents and in formulations for cleaning hard surfaces by diluting the concentrate with water.

  A typical emulsion liquid is less than 60% active agent, less than 10% surfactant, less than 30-40% alkalinity agent. Many of the prior art emulsions are not sufficiently phase stable, which means that many of the prior art emulsions do not remain totally homogeneous for storage and use in a variety of applications, and reduced activity It has an agent concentration (including more than 50% water), or exhibits reduced properties compared to other useful forms of detergent, or is difficult to manufacture, dispense or store. Many prior art emulsions contain a relatively low caustic content and a relatively low sequestering and surfactant content.

  Substantial attention has been directed to concentrate materials having a substantially increased active agent content that can be produced as a stable liquid. In order to provide solid effectiveness and performance, it was necessary to push the active concentrate of the detergent ingredients in the emulsion to 60-65%. These liquids preferably have a stable viscosity and a handleable viscosity so that the liquid can be reliably discharged from a material supplier to a place of use such as a washing machine. We have found that if the prior art material is simply increased in concentration without the introduction of new technology, the resulting material does not produce a simple solution and does not produce a phase stable emulsion. The prior art discloses a variety of liquid emulsion detergent compositions that can be used in a variety of forms, but in a highly alkaline, highly viscous, stable composition that is easy to manufacture and is suitable for laundry, dishwashing and other uses. Prior art highly active cleaning compositions that have acceptable cleaning properties and are capable of being dispensed by its shear thinning characteristic in dedicated detergent dispensers and are compatible with typical industrial or commercial cleaning equipment Does not provide. We have met substantial needs in improving the stability of compositions having desirable cleaning properties by improving the formulation and manufacturing process. A substantially improved thickened emulsion detergent composition, methods of use and preparation thereof have been found and are disclosed below.

  We have found an improved highly viscous, highly alkaline detergent composition having a high activator content. The composition includes a thickening system that is compatible with a highly alkaline formulation resulting in a high viscosity composition exhibiting shear thinning. The compositions of the present invention are particularly novel in that their rheology is unique. The composition can be defined as a solid if no shear is applied, but once the shear is applied, the composition begins to flow. The composition comprises a thickening system comprising an alkali source, a nonionic surfactant, a water conditioning or sequestering agent, an optional alkyl polyglucoside surfactant, and a fatty acid and a polycarboxylic acid. The resulting stable composition has a low water content, high activator concentration (greater than 60 wt% based on the concentrated composition), high alkalinity, and 0.2 / sec using a Bohlin CVO rheometer at 20 ° C. Characterized by a viscosity greater than about 250,000 centipoise, measured in the rotational shear mode of shear rate. This improved detergent can be used for a variety of applications, but is preferably used in laundry applications. We have achieved cleaner formulations containing more than 30 wt% mixed alkali source and surfactant formulation.

  In laundry applications, the soiled article is contacted with an aqueous liquid cleaning solution containing a major ratio of water and about 0.5-3.0 ppm of an emulsion detergent. The garment is contacted with the cleaning solution at a high temperature of about 25 ° C. to about 80 ° C. for a period of time to remove the soil. The soil and used solution is then rinsed from the garment in a rinse cycle. The improved detergent of the present invention is made by a process comprising the step of mixing a nonionic surfactant or surfactant mixture with an anionic surfactant, a chelating component, and various other textile detergent components. The To this mixture is added an alkali source followed by polyacrylic acid. Using a standard mixing tank, all ingredients are mixed briefly until the product is homogeneous and can be filled at that time to achieve its final viscosity as described above. In applications other than laundry, minor adjustments can be made to the formulation, such as selecting a suitable surfactant system to make it suitable for dishwashing or hard surface cleaning.

  For the purposes of this patent application, the term “thickened emulsion” means a substance that behaves as a solid until a load or stress is applied that is sufficiently high that the emulsion flows like a fluid. Rheologically, a thickened emulsion is a viscoplastic material that behaves as a rigid body at low stresses but flows as a viscous fluid at high stresses. The thickened emulsion of the present invention contains two immiscible liquids. For the purposes of the present invention, the continuous phase consists essentially of components dissolved in caustic salts and other aqueous media. However, since no additional water is added to the composition of the present invention, the thickened emulsion of the present invention will be a composition having a substantially low aqueous phase or low water content. For the purposes of the present invention, “emulsion” and “thickened emulsion” are used alternately. However, it is noted that as generally used in the art, the term “emulsion” refers to a composition having a substantially lower viscosity than that of the present invention.

  While not being bound by theory, it is believed that the thickened emulsion of the present invention consists of two limitedly miscible liquid phases, as mentioned above. When either is used to formulate the thickened emulsion of the present invention, the composition of the present invention may comprise third solid particles consisting essentially of carboxymethylcellulose or an optical brightener. it can. If a third phase is present, this discrete phase is believed to contain particles ranging from about 1 micrometer to about 100 μm, however, the composition of the present invention is substantially more than about 100 μm. Can contain large particles.

  Insoluble or water-insoluble portions, typically liquid nonionic surfactants, form dispersed droplets having a particle size of less than about 10 μm, less than about 5 μm, preferably about 0.5-8 μm. To do. Phase stability substantially reduces the finely divided and separated form from the aqueous phase to the extent that the dispersed phase is not useful for laundry or other cleaning purposes under typical manufacturing, storage and use conditions. Means not to lose. As long as the thickened emulsion retains a discontinuous phase (mainly organic material) in a small emulsified form of more than 98% and provides cleaning activity, some minor separation is acceptable.

  The aqueous material of the present invention typically comprises an emulsification of a relatively insoluble phase, typically an organic phase and an aqueous phase. The organic phase can contain one or more components such as surfactants, water conditioning agents, bleaching agents, etc., while the aqueous phase contains sodium hydroxide, water conditioning agents, bleaching in an aqueous medium. Aqueous solution components such as agents, dyes and other components can be included. The material is typically made by dispersing a relatively “oily” organic insoluble phase using shearing application in an aqueous phase stabilized by an emulsion stabilizer composition. In the present invention, the emulsion stabilizer typically comprises a polycarboxylic acid combined with a fatty acid in an amount that can promote a stable thickened emulsion. We have found that alkyl polyglucoside (APG) surfactants can be added to enhance emulsion stabilization. In another embodiment, the emulsion stabilizer is anionic that is sufficiently soluble in sodium hydroxide and promotes the formation of small particle sizes in the typical organic phase used in the thickened emulsions of the present invention. We have found that it is a polyacrylic acid combined with a surfactant. We have found that a simple mixture of aqueous sodium hydroxide, such as an alkyl ethoxylate without emulsion stabilizer, and a nonionic surfactant will rapidly separate into two separate phases. Such surfactants have a low solubility in sodium hydroxide, while sodium hydroxide is insoluble in this organic compound. A useful procedure for producing the dispersions of the present invention is to combine a fatty alcohol ethoxylate with an alkyl polyglucoside, carboxymethyl cellulose and tall oil. APG can be added at this time and the contents of the container can be stirred vigorously. Optional optical brightener is added to the described combination, followed by aqueous caustic, typically 50 wt% aqueous caustic, in a large metal container containing a stirrer. Monoethanolamine is added to this combination, followed by the polycarboxylic acid as the final component.

The main thing is laundry detergents, but this emulsion concept is equally applicable everywhere. This will include dishwashing, stationary cleaning cleaners and disinfectants, food and dairy formulations. Typically, this emulsion concept is where a relatively insoluble nonionic surfactant is mixed with a caustic solution to produce a thickened emulsion with properties balanced for the chosen end use. Could be used in any formulation. Low foaming surfactants include linear alcohol ethoxylates (Lutwigol ™ available from BASF located in Ludwigshafen, Germany), in particular fatty alcohols C _{13 to} C ₁₅ ethoxy with 2 to 10 polyethylene oxide groups. Nonionic substances such as rates can be included. Thickeners useful in the present invention include a combination of a linear polycarboxylic acid such as Acusol ™ (Rohm & Haas) and a fatty acid such as tall oil.

1-2 each have an x-axis and a y-axis. It is the x-axis shear rate in FIG. 1, and in FIG. 2 is the concentration deviation from the standard mixture. The y-axis is the viscosity in any case.
FIG. 1 is a plot that specifically describes the viscosity of a composition of the present invention that decreases with increasing shear rate. FIG. 2 is a plot that specifically describes the effect of some concentration change of the components on the viscosity.

  The term “surfactant” or “surfactant” refers to an organic chemical that, when added to a liquid, changes the properties of the liquid at the surface.

  The terms EO, PO, or EO / PO, as used herein, refer to ethylene oxide and propylene oxide, respectively. EO / PO refers to an ethylene oxide group and a propylene oxide group.

  The term “substantially free” refers to any ingredient that is absent or nearly absent from the compositions of the present invention. Reference to “substantially free” intends ingredients that are not intentionally added to the compositions of the present invention. The use of the term “substantially free” for an ingredient allows for trace amounts of that ingredient in the compositions of the present invention because they are present in another ingredient. However, it is recognized that if the composition is said to be “substantially free” of the component, only trace or de minimus components will be tolerated.

  In this specification, all numerical values are assumed to be modified by the term “about”, whether or not explicitly indicated. The term “about” usually refers to a range of numbers that one of ordinary skill in the art would consider equivalent to the recited value (ie, having the same function or result). In many instances, the term “about” can include numbers that are rounded to the nearest significant figure.

  % By weight,% by mass, wt%, and the like are synonymous with the substance concentration divided by the weight of the composition divided by the weight of the composition and multiplied by 100.

  Unless otherwise specified, all weight percentages herein reflect the weight percentage of the raw material provided by the manufacturer. The active weight percent of each component is readily determined from the information provided by use of a product data sheet provided by the manufacturer.

  Traditionally, emulsions have a system involving two isotropic, substantially Newtonian liquids, one dispersed in the other in the form of small droplets. . This system is stabilized by an absorbed parent medium that modifies the properties of the interface. However, we have found that many emulsions play a role in more than two phases. The description of emulsion and emulsion stability begins with a conventional two-phase system. An emulsion is formed such that when two immiscible liquids, usually water and oil, are stirred, for example, one liquid forms droplets dispersed in the other liquid. The emulsion is stabilized by adsorption of the compound at the interface. This compound is called an “emulsifier”. These are molecules that have both polar and non-polar regions and act to bridge the gap between two immiscible liquids. For example, in oil and water emulsions, the polar part of the emulsifier is soluble in the aqueous phase, while the nonpolar region is soluble in the oil phase. Usually, the formation of an emulsion or emulsification involves breaking large droplets into smaller droplets by shear forces.

  In order to describe the stability of an emulsion, it is necessary to first describe how the emulsion will fail. The initial step where the emulsion is lost is known as agglomeration, where individual droplets adhere to each other, but are still separated by a thin film of continuous phase. The next step is coalescence, allowing the thin liquid film between individual droplets to become unstable and allow large droplets to be formed. As the coalescence continues, the emulsion separates into an oil layer and an aqueous layer. Usually, emulsions are stabilized by slowing the destabilization or aggregation process. This can be done either by reducing the mobility of the droplets, by increasing the viscosity, or by inserting an energy barrier between the droplets. In the present invention, the size of the dispersed phase droplets or particles is less than 10 μm in diameter, preferably less than 5 μm.

Rheological features The compositions of the present invention are particularly unique in their rheological characteristics. Despite the fact that the compositions of the present invention behave differently from any currently known emulsion, the inventors have characterized their inventions as “thickened emulsions”. The composition is characterized as an emulsion because it consists of at least two immiscible phases as generally known in the emulsion art. However, the thickened emulsions of the present invention exhibit solid character when they are not under shear. The thickened emulsion of the present invention exhibits a viscosity of greater than 1,000,000 centipoise at zero shear. As the shear increases, the rheology of the compositions of the invention changes substantially until they exhibit liquid properties when the compositions of the invention are at high shear.

  The composition of the present invention exhibits a markedly high viscosity. In one embodiment, the thickened emulsion of the present invention has a viscosity of greater than 100,000 centipoise at 20 ° C. as measured using a Bohlin CVO rheometer in a rotational shear mode of 0.2 / sec shear rate. Indicates. In other embodiments, the thickened emulsion of the present invention is more than 300,000, 500 at 20 ° C. as measured using a Bohlin CVO rheometer in a rotational shear mode with a shear rate of 0.2 / sec. Viscosity up to over 1,000, 700,000, over 900,000, over 1,100,000, over 1,300,000, over 1.5 million centipoise. The viscosity of the composition of the present invention can be designed to suit a particular use or dispensing system. Usually, as the amount of thickening agent such as fatty acids and polycarboxylic acids increases, the viscosity of the composition increases.

  It has been found that fatty acids and polyacrylates positively affect the viscosity of the present invention. Compositions prepared differently in accordance with the present invention except for the absence of fatty acids are viscous fluids having a viscosity of about 10 Pa · s when measured at 0.2 / sec. Increasing the fatty acid content from 0% to 1% results in a continuous increase in shear viscosity up to several hundred Pa · s, along with an appearance change from a fluidized liquid to a solid gel or paste. Similar observations are made when the polycarboxylic acid concentration is changed. As stated earlier, without a polycarboxylic acid, the composition looks like a viscous liquid with a shear viscosity of less than 10 Pa · s (0.2 / sec). At a concentration of 5 to 8% by weight of polycarboxylic acid, the composition turns into a paste and produces a viscosity in the range of 100 to 1000 Pa · s (0.2 / sec).

Alkali Source An alkali source is necessary to control the pH of the detergent solution used. The alkali source is selected from the group consisting of alkali metal hydroxides such as sodium hydroxide, potassium hydroxide, or mixtures thereof; alkali metal silicates such as sodium metasilicate, and carbonates can also be used. The most cost-effective preferred supplier is commercially available sodium hydroxide that can be obtained in various solid forms of aqueous solutions and different particle sizes at a concentration of about 50 wt%. Sodium hydroxide can be used in the present invention in either liquid or solid form or a mixture of both. Other alkalinity sources include, but are not limited to, alkali metal carbonates, alkali metal bicarbonates, alkali metal sesquicarbonates, alkali metal borates, and alkali metal silicates. In some embodiments, about 40 to about 80 wt%, about 45 to about 75 wt%, and about 50 to about 70 wt% sodium hydroxide (50% active agent) are included in the compositions of the present invention.

Nonionic Surfactants Conventional, nonionic detergent surfactants that can be used with the present invention include alcohol ethoxylates. A combination of nonionic surfactants is preferred. These include linear and branched alcohol ethoxylates. Suitable alcohol ethoxylates include those having about 5 to about 10 EO, about 6 to about 8 EO, and linear alcohol ethoxylates having about 1 to 6 EO, about 2 to 5 EO. Examples of these are fatty alcohols C13-C15 ethoxylate (7EO) marketed as Lutensol ™ AO7, both available from BASF and fatty alcohols C13-C15 ethoxy sold as Lutensol ™ AO3. Includes rate (3EO). Dehydol ™ surfactants available from Cognis and Maripal ™ surfactants available from Sasol are also useful in the present invention. Lutensol ™ surfactant is an ethoxylate of oxo alcohol, which is a synthetic alcohol. Still other examples of nonionic surfactants suitable for use in the present invention are (available from BASF under Pluronics mark and Pluronics R, surfactants sold under BASF from Plurafacs mark Including, but not limited to, ethylene oxide / propylene oxide copolymers, ethylene oxide / propylene oxide / ethylene oxide copolymers, propylene oxide / ethylene oxide / propylene oxide copolymers (such as those sold from the agents and BASF and under the Polymarkers mark). I can't.

  In some embodiments, the compositions of the present invention comprise from about 5 to about 35 wt%, from about 10 to about 30 wt%, and from about 15 to about 25 wt% nonionic surfactant or nonionic surfactant mixture. Including. In another aspect, the composition comprises from about 2 to about 25 wt%, from about 5 to about 20 wt%, and from about 8 to about 17 wt% of the first nonionic surfactant; and from about 0.5 to About 15%, about 2 to about 13%, and about 5 to about 10% by weight of a second nonionic surfactant.

Stabilizer
Alkyl polyglucoside surfactants The thickened emulsions of the present invention are stabilized using soaps and polycarboxylic acids and alkyl polyglucosides, and optionally the consistency, stability of the thickened emulsions of the present invention We have found that, and improve the homogeneity. Such surfactants have a strong hydrophobic alkyl group with a strong hydrophilic glycoside group that can have a modified hydrophilicity by the presence of ethylene oxide groups. We have found that these materials are effective emulsion stabilizers if they are soluble in the aqueous phase and can promote small particle size emulsions. The alkyl polyglucoside, Glucopon ™ 215, contains a hydrophobic group with a C8-C10 alkyl straight chain. This material has good solubility in sodium hydroxide solution. There are other commercially available alkyl polyglucosides with different alkyl groups and DP. A general class of alkyl polyglucosides produces a low interfacial tension between mineral oil and water. The low interfacial tension is probably responsible for the success of these surfactants in stabilizing the thickened emulsion. The system used is different from typical emulsions. The oil phase is a surfactant (fatty alcohol ethoxylate), while the aqueous phase is a sodium hydroxide solution with other materials. Without being bound by theory, it is believed that surfactant droplets are stabilized by the presence of surfactant at the interface and the significantly high viscosity of the system. Surfactants (fatty alcohol ethoxylates) have essentially no solubility in sodium hydroxide solution, and sodium hydroxide has essentially no solubility in the surfactant phase.

  Alkyl polyglucoside is a surfactant useful as an emulsifier and it is known from the literature that it reduces the interfacial tension between the sodium hydroxide solution phase and the surfactant phase. This general concept allows other surfactants to be used and stabilizes the thickened emulsion in these systems if they are used to reduce the interfacial tension of the sodium hydroxide solution. Can be assumed. In some embodiments, the compositions of the present invention optionally comprise about 0.01 to about 10%, about 0.5 to about 8%, and about 1 to about 5% (50% active) alkyl. Contains polyglucoside.

  We have found that alkylpolyglucoside ("APG") has a synergistic thickening, stabilizing and homogenizing effect when used in combination with certain other thickening agents. In one aspect, APG is used in combination with fatty acids and / or polycarboxylic acids. In another embodiment, APG is used in combination with a polyacrylate copolymer. In another embodiment, APG is used in combination with alcohol ethoxylates and / or acrylic acid polymers and / or polycarboxylic acids. Each of these thickeners is described in further detail below.

Thickener
Fatty acids In this formulation, the combination of fatty acids, polycarboxylic acids and optionally alkylpolyglucosides has sufficient high viscosity, improved homogeneity and stability, even at the required high alkalinity It was surprisingly found to provide a composition. At the high pH and high caustic content provided in the formulations of the present invention, other thickeners commonly known in the industry such as CMC, guar gum, xanthan gum, polyethylene glycol, etc. will decompose to name a new break down. Therefore, it has been found to be ineffective in making high viscosity formulations. It is unusual for a composition with such a high caustic content and alkalinity to achieve the high viscosity exhibited by the compositions of the present invention.

  The fatty acid selected in the composition of the present invention comprises tall oil. Tall oil, also called liquid resin, is a resinous yellow-black oily liquid consisting of a mixture of pine, fatty acids, sterols, polymeric alcohols, and other alkyl chain materials. Crude tall oil is distilled into tall oil pine (having a content of 10-35% pine cone), and the oil refinery plant further converts to tall oil fatty acid (1-10% pine nut content). Tall oil fatty acids are particularly preferred in the compositions of the present invention due to their low cost and fluidity. Unlike many other fatty acids, tall oil remains liquid at ambient temperatures and is easier to handle than other fatty acids. Tall oil is an unsaturated fatty acid that contains primarily oleic and linoleic acids and, inter alia, smaller amounts of palmitic and stearic acid combinations. In embodiments of the invention, the tall oil fatty acid comprises about 0.01 to about 5% by weight, about 0.1 to about 4% by weight, and about 0.2 to about 3% by weight.

Polycarboxylic acids Polycarboxylic acids are also useful as thickeners in the compositions of the present invention. ACUSOL ™ 445 is a partially neutralized liquid detergent polymer. In the presently most preferred embodiment of the present invention, the polyacrylate comprises ACUSOL ™ 445, a polyacrylic acid having a molecular weight of 4500, manufactured by Rohm and Haas, Philadelphia, Pennsylvania. Other polyacrylic acids with molecular weights of 4500 (CRITERION ™ 2005) and 8000 (CRITERION ™ 2108) can be purchased from Kemira Chemicals, Kennesaw, Georgia. Other suitable examples would include Soakalan ™ CP5, Coatex ™ DE185, or Isol Dispersant ™ HN44 available from BASF.

  In embodiments of the present invention, the polycarboxylic acid comprises about 1 to about 30%, about 5 to about 20%, and about 10 to about 15% by weight.

Alcohol ethoxylates and acrylic acid polymer alcohol ethoxylates are also useful thickeners in the compositions of the present invention. Isotridecanol ethoxylate has been found to be effective in providing thickening, stabilization, and homogeneity in the compositions of the present invention as BA Lutenol ™ TO 8 It is a nonionic surfactant that is available. Alcohol ethoxylates such as isotridecanol ethoxylate can be any of the polycarboxylic acids such as Accusol ™ 445 described above and / or acrylic acid polymers such as Carbopol ™ ETD2691 available from Lubrizol Corporation. When combined with cocoon, it has improved performance as a thickener. Carbopol ™ is a lightly crosslinked polyacrylic acid polymer.

  In some embodiments of the invention, the alcohol ethoxylate is present in an amount of about 0.5 to about 10%, about 0.75 to about 9.5%, and about 0.9 to about 9.0% by weight. To do.

Polyacrylate Copolymers When incorporated into the compositions of the present invention, polyacrylate copolymers are also useful thickening, stabilizing, and homogenizing agents. An example of such a copolymer is Cosmedia ™ available from Cognis. Cosmedia® is an emulsified copolymer consisting of methacrylic acid and ethyl acrylate and butyl ester.

  In some embodiments of the present invention, the polyacrylate copolymer is present in an amount of about 0.5 to about 10%, about 0.75 to about 9.5%, and about 0.9 to about 9.0% by weight. To do.

Water Conditioner The composition of the present invention preferably comprises a water conditioner. The thickened emulsion composition of the present invention comprises a polyvalent metal complexing agent, sequestering agent or chelating agent that helps reduce the detrimental effects of soil removal and hardness components in tap water in metal compounds. Can be included. Typically, multivalent metal cations or compounds such as calcium, magnesium, iron, manganese, molybdenum cations or compounds, or mixtures thereof may be present in tap water and complex soils. Such compounds or cations may contain stubborn stains or may interfere with the action of either the cleaning composition or the rinsing composition during the cleaning regimen. Chelating agents can be effectively complexed and removed with such compounds or cations from the soiled surface and with active ingredients including the nonionic and anionic surfactants of the present invention. Inappropriate interactions can be reduced or eliminated. Both organic and inorganic chelators are common and can be used. Inorganic chelating agents can include compounds such as sodium tripolyphosphate and other higher order linear and cyclic polyphosphate species. Organic chelators include both polymeric chelators and small molecule chelators. The organic small molecule chelator is typically an organic carboxylate compound or an organic phosphate chelator. Polymeric chelating agents typically include polyanionic compositions such as polyacrylic acid compounds. Small molecule organic chelators include sodium gluconate, sodium glucoheptonate, N-hydroxyethylenediamine triacetic acid (HEDTA), ethylenediaminetetraacetic acid (EDTA), nitrilotriacetic acid (NTA), diethylenetriaminepentaacetic acid (DTPA), ethylenediamine Tetrapropionic acid, triethylenetetraamine hexaacetic acid (TTHA), and their respective alkali metals, ammonium and substituted ammonium salts, ethylenediaminetetraacetic acid tetrasodium salt (EDTA), nitrilotriacetic acid trisodium salt (NTA), ethanoldi Glycine disodium salt (EDG), diethanol glycine sodium salt (DEG), and 1,3-propylenediaminetetraacetic acid (PDTA), dicarboxymethyl glutamic acid 4 sodium Umushio (GLDA), including methylglycine -N-N-2 acetate trisodium salt (MGDA), and imino disuccinate sodium salt (IDS). All these are known and are commercially available. Small molecule organic chelators also include biodegradable sequestering agents that have a combination of chelating and hydrotrope functionality from EDG, MGDA and GLDA-type molecules. Preferred sequestering agents are ethanol diglycine disodium salt (EDG), dicarboxymethyl glutamic acid because of their biodegradability and their ability to easily combine with hydrotropes to produce ultra-compact concentrates. Tetrasodium salt (GLDA) and methylglycine-N-N-2 acetic acid trisodium salt (MGDA). Other sequestering agents that are suitable for inclusion in the compositions of the present invention include anionic polyelectrolytes such as polyacrylates and itaconic acid copolymers such as acrylic acid copolymers, acrylic / itaconic acid copolymers, maleates, sulfonates. And copolymers thereof, alkali metal gluconates. Also suitable chelating agents are 1-hydroxyethylidene-1, 1-diphosphonic acid, aminotri (methylenephosphonic acid), hexamethylenediaminetetra (methylenephosphonic acid), diethylenetriaminepenta (methylenephosphonic acid), and 2-phosphonobutane-1 Organic phosphonates such as 2,4-tricarboxylic acid and other commercially available organic phosphonate water regulators. Most conventional reagents appear to work because they are compatible in either the continuous phase or the droplet phase.

  In some embodiments, the chelating agent is present in the composition concentrate in an amount of about 0.05 to about 15 wt%, more preferably about 1 to about 10 wt%, and most preferably 3 to about 8 wt%.

  Quest ™ 2010 can be included in the compositions of the present invention as a sequestering or chelating agent. Dequest ™ 2010 is 1-hydroxyethylidene-1,1-diphosphonic acid, functions as a sequestering agent in the present invention and is available from ClearTech Industries, Inc., Saskatoon, Saskatchewan, Canada. . In certain embodiments, the compositions of the present invention comprise from about 0.01 to about 10%, from about 0.5 to about 8%, and from about 1 and about 5% (60% active) sequestering agent. Including.

  Baypure ™ CX100 can be included in the composition of the present invention as a chelating agent. Baypure ™ CX100 is a medium strength complexing agent with low heavy metal remigration. It is effective in complexed iron, copper and calcium ions and is biodegradable. When Baypure ™ CX100 is included in the composition of the present invention, Baypure ™ 34% active agent solution, from about 1 to about 30%, from about 2 to about 20%, and from about 3 Up to about 10% by weight.

  As one skilled in the art will appreciate, either one or a combination of sequestering agents can be included in the present invention.

The composition of the water present invention, does not normally contain additional water. Although certain ingredients are provided as a solution in water, it is recognized that they contain some amount of water, but additional water is usually not added to the compositions of the present invention. This is particularly important in order to maintain the necessary high viscosity of the composition of the present invention. The composition of the present invention can be formulated without any additional water or provided with a relatively small amount of water to reduce the transportation costs of the composition.

  The dilution water that can be used to dilute the composition to produce a use composition is preferably soft water. That is, it is preferable that the dilution water has substantially no hardness. Water is characterized as hard water if it contains at least one grain hardness.

Microcomponent detergents typically contain many conventional, but important, minor components. These include optical brighteners, soil anti-redeposition agents, antifoaming agents, low foaming surfactants, antifoaming surfactants, pigments and dyes used in these formulations. The compositions can also include chlorine and oxygen bleaches that are not currently used in these formulations. Such materials can be formulated with other ingredients or added during a cleaning operation.

Color Stabilizer The compositions of the present invention include ingredients to prevent discoloration or browning of the formulation, optionally or referred to as a color stabilizer. Such color stabilizers are optional. However, due to the unpleasant nature of discolored laundry detergents, it is a desirable option to include them. In the composition of the present invention, the color stabilizer is monoethanolamine. In certain embodiments of the invention, the color stabilizer comprises about 0.01 to about 5% by weight, about 0.05 to about 3% by weight, and about 0.10 to about 2% by weight.

Optical brighteners Optical brighteners can also optionally be added to the compositions of the present invention. Bleach is usually added to laundry detergent to replace the brightener removed during the wash and make the garment look cleaner. Optical brighteners are dyes that absorb light in the ultraviolet and violet regions of the electromagnetic spectrum (usually 340-370 nm) and emit light in the blue region (typically 420-470 nm). These additives often produce a discernible “whitening” effect and increase the overall amount of blue light reflected, thereby preventing the material from appearing more yellow. Often used to enhance the appearance.

  Optical brighteners may or may not be desirable additives to the compositions of the present invention. Whether it is desirable to include an optical brightener is up to the user. For example, a side effect of optical gloss is to make a treated fabric more visible with night vision equipment than an untreated fabric. In military or other applications, such an effect may not be desirable.

  Examples of optical brightener type classes include (di, tetra or hexasulfonated) triazine stilbenes, coumarins, imidazolines, diazoles, triazoles, benzoxazolines and biphenyl stilbenes, to name a few. A single optical brightener or a combination of optical brighteners can be useful in the compositions of the present invention. In certain embodiments of the compositions of the present invention, the optical brightener comprises about 0.1 to about 5% by weight, about 0.15 to about 3% by weight, and about 0.2 to about 2% by weight. Examples of commercially available optical brighteners suitable for use in the compositions of the present invention include DMS-X ™ and CBS-X ™, distyryl, both available from Vesta-Intracon BV Including but not limited to biphenyl derivatives.

Soil anti-redeposition agent The composition of the present invention may further comprise an anti-redeposition agent. Anti-redeposition agents can be made from complex cellulose materials such as carboxymethylcellulose (CMC) or synthetic materials such as polyethylene glycols and polyacrylates. These help prevent loose dirt from sticking onto the cleaned fabric. Polyphosphate builders also help reduce redeposition.

Colorant Colorant is optionally added to the composition of the present invention. Coloring agents can be in the form of pigments or dyes and can be added to provide a color to the composition. In addition, blue colorants can be added to provide the blue that gives the white fabric the desired blue / white color.

Perfumes are optionally added to the compositions of the present invention. Perfumes usually provide three functions regardless of the scent used. These cover the chemical and soiling odors of the detergent in the cleaning solution and they give the fabric a pleasant scent and thus reinforce the cleaning performance. Furthermore, the fragrance can contribute to the characteristics of the product. In another aspect, the composition of the present invention provides a scented version to appeal to consumers who prefer a low scent or no scent when laundered, or to people with skin sensitive to fragrance ingredients. Can be removed.

  The following table includes exemplary ingredients and amounts for preparing the compositions of the present invention.

Preparation of the Composition of the Invention The composition of the invention is prepared by combining a nonionic surfactant, an alkyl polyglucoside composition, CMC and tall oil. APG can be added at this time with vigorous stirring. Optional optical brightener is added to this combination followed by an aqueous base containing 50 wt% active aqueous sodium hydroxide to produce an alkaline surfactant blend. Monoethanolamine is added in this combination, followed by the polycarboxylic acid as the final component. Stable thickening characterized by subjecting this final mixture to high shear and having a viscosity of greater than about 250,000 centipoise at 20 ° C. using a Bohlin CVO ™ rheometer with air bearing and thermostat Of the resulting emulsion. Measurements were made using two parallel plates, each having a 20 mm diameter and a distance of 2 mm between the plates. Under a constant temperature of 20 ° C., the sample is confined in the gap between the two plates. The measurements are made in a manner that the upper plate rotates at a certain speed (shear rate) and the lower plate is fixed thereby shearing the sample between the plates. Measure the torque required to maintain a certain shear rate. The shear stress on the sample is calculated from the torque and becomes the viscosity as the ratio of shear stress to shear rate.

Methods of Use of the Compositions of the Invention The present invention also includes methods of use. Such a method involves contacting a soiled laundry item with a cleaning solution comprising a liquid cleaner concentrate composition in the form of an aqueous emulsion having a major ratio of water and a continuous and dispersed phase of about 0.5-3.0 ppm. The thickened emulsion has a stable viscosity and a dispersed phase particle size and the composition comprises a continuous phase; an effective soil removal amount of alkali source comprising about 15 to about 50 wt%; An effective soil removal amount of a nonionic surfactant comprising about 10 to about 30 wt%; about 0.1 to about 20 wt% of a water conditioning agent or metal ion with an effective water conditioning or sequestering amount Sequestering agent; effective soil removal and emulsion stabilizing amount of alkyl polyglucoside surfactant, including up to about 5 wt%; effective thickening amount of polycarboxylic acid including about 1-20 wt%; and about 0 Comprising a phase stable thickened emulsion comprising an effective thickening amount of fatty acid comprising 1-5 wt%; wherein the dispersed phase comprises at least a portion of a nonionic surfactant; and The thickened emulsion concentrate has a viscosity of greater than 250,000 cps as measured in a rotational shear mode at a shear rate of 0.2 / sec using a Bohlin CVO rheometer at 20 ° C. and shear Shows thinning, thereby allowing discharge during manufacture and use, producing a washed laundry; and rinsing the washed laundry with an aqueous rinse.

Example I
Compositions were prepared according to the present invention except that there were no fatty acids. These comparative compositions have about 10 Pa.s when measured at 0.2 / sec. It was a viscous fluid having a viscosity of s. Increasing the fatty acid content from 0% to 1% continuously increased the shear viscosity while changing the appearance from a fluid liquid to a solid gel or paste.

  A composition was prepared according to the present invention except that there was no polycarboxylic acid. In the absence of polycarboxylic acid, the composition looks like a viscous liquid with a shear viscosity of less than 10 Pa · s (0.2 / sec). When the concentration of the polycarboxylic acid is 5 to 8% by weight, the composition becomes a paste and has a viscosity in the range of 100 to 1000 Pa · s (0.2 / second).

Viscosity was measured using a parallel plate system with each plate having a diameter of 20 mm and a gap distance of 2 mm between the plates. The measurement was performed at 20 ° C. Each sample is confined in the gap between the two plates, and the measurement is performed in a manner that the upper plate rotates at a certain speed (shear rate) and the lower plate is fixed thereby shearing the sample between the plates. went. The torque required to maintain a certain shear rate was measured. The shear stress on the sample is calculated from the torque and becomes the viscosity as the ratio of shear stress to shear rate.
The results are shown in the following table.

  The results show that the viscosity increases with increasing tall oil concentration and increasing polycarboxylic acid concentration.

Example II
This comparative example shows that not all thickening polymers are useful in the present invention. The composition was prepared using Sokalan AT ™ 10 from BASF, Carbopol ™ EZ3 and EZ 4 from Noveon and Acusol ™ 805S from Rohm & Haas, but the resulting mixture was stable Rather, it separated into two viscous liquid phases. Compositions were prepared according to the following table.

  Viscosity was measured at a shear rate of 0.1 / second. Since all these systems separated quickly, the values given are only approximations.

Example III
Samples prepared with the sample 6A formulation were subjected to increased shear. FIG. 1 shows the shear thinning of sample 6A of the present invention. As shear increased, the viscosity decreased by about 5 orders of magnitude. As specifically shown in the graph of FIG. 1, the viscosity changed by 5 digits or more at the shear rate in the range of 0.01 to 500 / second.

Example IV
This example shows that both tall oil and polycarboxylic acid have a positive effect on the viscosity of the composition of the present invention. Compositions were prepared according to the following table.

  Experiments were performed based on a statistical method called DOE (Design of Experiment) -Mixture Design. Some ingredients were kept at a constant concentration, while other contents were varied within the limits given in the table above. An evaluation of the viscosity measured using statistical methods is shown in the graph shown in FIG. 2, which shows the effect on viscosity of various components AF as their concentration increases. .

  The viscosity of each composition from the table above was measured according to the procedure provided in Example I. The graph of FIG. 2 shows the results specifically. As shown in the figure, both tall oil and polycarboxylic acid (Rheosolve or Acusol) have a strong positive effect on viscosity, and NaOH and Lutensol ™ AO3 (fatty alcohol ethoxylate) have a negative effect. And Lutensol ™ AO7 (fatty alcohol ethoxylate) and CMC generally do not affect viscosity.

Example V
This example shows that the thickened emulsion of the present invention has successfully cleaned various stains. The compositions of the present invention were prepared according to the following table.

  The pH of the 1% solution of the formulation identified above was in the range of 12.2 to 12.9.

  Standard test stains commercially available from WFK (Krefeld / Germany) were used for this example. Test spots were generated in a standardized manner and placed on the test strip. These were placed in a washer along with 6.5 kg of polyester fiber product. Each procedure was repeated 4 times in 4 different washers and the values in the table below are an average of the 4 results of each procedure. The above prepared composition was included in a dosage of 1.5 g / l and simultaneously 1 ml / l of bleach (Ozonit super ™ available from Ecolab, Inc.) was added in each test. The washing time was 10 minutes, the temperature was 70 ° C., and the bath ratio was 1: 5; soft water was used. After finishing the cleaning test, stain removal from the test strip was measured using optical methods, and light transmission at a fixed wavelength was measured with the stain before and after cleaning. This result is a relaxed value as shown in the table.

  The lab wash results of commercially available detergents and the thickened emulsions of the present invention are compared in the table below. The top two tables show the cleaning performance results using fat / pigment stains, and the bottom table shows the cleaning performance results using enzyme stains. This result indicates that the thickened emulsions of the present invention worked better or better than commercially available detergents in most cases.

The invention has been described with reference to various specific and preferred embodiments and techniques. However, it will be appreciated that many changes and variations can be made while remaining within the spirit and scope of the invention. Modifications of the ratios, elements, materials, and components used in the present invention or other implementations that are specifically adapted to specific environmental and operational requirements are envisioned by this application without departing from these principles. The appended claims are intended to cover and encompass any and all such modifications.
(Aspect)
(Aspect 1)
A liquid cleaner concentrate composition in the form of an aqueous thickened emulsion having an aqueous phase and a dispersed phase, the composition comprising:
(A) a continuous aqueous phase;
(B) an effective soil removal amount of alkali source comprising about 15 to about 50 wt%;
(C) an effective soil removal amount of a nonionic surfactant comprising from about 2 to about 30 wt%;
(D) an effective water conditioning amount or sequestering amount of water conditioning agent or sequestering agent comprising about 0.1 to about 10 wt%;
An effective thickening amount of polycarboxylic acid comprising about 1-25 wt%;
(E) an effective stabilizing and thickening amount of fatty acid comprising about 0.25 to about 5 wt%;
Including a phase stable thickened emulsion comprising
The dispersed phase contains at least a portion of the nonionic surfactant and the emulsion concentrate exhibits shear thinning that allows ejection during manufacture and use, and uses a Bohlin CVO rheometer at 20 ° C. A composition comprising greater than about 100,000 centipoise, measured in a rotational shear mode with a shear rate of 0.2 / sec.
(Aspect 2)
The composition of embodiment 1, wherein the viscosity comprises greater than about 300,000 viscosity centipoise as measured in a rotational shear mode at a shear rate of 0.2 / sec using a Bohlin CVO rheometer at 20 ° C. .
(Aspect 3)
The composition of embodiment 1, wherein the viscosity comprises greater than about 500,000 viscosity centipoise as measured in a rotational shear mode at a shear rate of 0.2 / sec using a Bohlin CVO rheometer at 20 ° C. .
(Aspect 4)
The composition of embodiment 1, wherein the viscosity comprises greater than about 700,000 viscosity centipoise as measured in a rotational shear mode at a shear rate of 0.2 / sec using a Bohlin CVO rheometer at 20 ° C. .
(Aspect 5)
The composition of embodiment 1, wherein the viscosity comprises greater than about 900,000 viscosity centipoise as measured in a rotational shear mode at a shear rate of 0.2 / sec using a Bohlin CVO rheometer at 20 ° C. .
(Aspect 6)
The composition of embodiment 1, wherein the nonionic surfactant comprises a fatty alcohol C _13-15 ethoxylate having from about 4 to about 10 moles of ethylene oxide .
(Aspect 7)
The composition of embodiment 1, wherein the nonionic surfactant comprises a fatty alcohol C _13-15 ethoxylate having 1 to 5 moles of ethylene oxide .
(Aspect 8)
The composition of embodiment 1, wherein the water conditioner comprises phosphonic acid.
(Aspect 9)
The composition of embodiment 1, wherein the water conditioner comprises hydroxyethylidene diphosphonic acid.
(Aspect 10)
The composition according to embodiment 1, wherein the polycarboxylic acid consists of a linear polyacrylic chain.
(Aspect 11)
The composition according to aspect 1, wherein the fatty acid comprises tall oil.
(Aspect 12)
The composition of embodiment 1, further comprising an optical brightener, a colorant, a fragrance, an antifoam, an antifoam, a bleach, an anti-redeposition agent, or a combination thereof.
(Aspect 13)
The composition of embodiment 1, further comprising a color stabilizing amount of monoethanolamine comprising about 0.01 wt% to 5 wt%.
(Aspect 14)
The composition of embodiment 1, wherein the composition further exhibits a viscosity of greater than 1,000,000 centipoise at zero shear.
(Aspect 15)
The composition of embodiment 1, further comprising an effective soil removal and emulsion stabilizing amount of the alkyl polyglucoside surfactant comprising about 0.1 to about 10 wt%.
(Aspect 16)
A liquid cleaner concentrate composition in the form of an aqueous thickened emulsion having an aqueous phase and a dispersed phase, the composition comprising:
(A) a continuous aqueous phase;
(B) an effective soil removal amount of alkali source comprising about 15 to about 50 wt%;
(C) an effective soil removal amount of a nonionic surfactant comprising from about 2 to about 30 wt%;
(D) an effective water conditioning amount or sequestering amount of water conditioning agent or sequestering agent comprising about 0.1 to about 15 wt%;
(E) an effective amount of a thickening agent comprising from about 1 to about 25 wt% selected from the group consisting of polycarboxylic acids, fatty acids, polyacrylate copolymers, acrylic acid polymers, alcohol ethoxylates, and combinations thereof;
Including a phase stable thickened emulsion comprising
The dispersed phase includes at least a portion of the nonionic surfactant and the emulsion concentrate exhibits shear thinning that allows ejection during manufacture and use, and the viscosity is 20 ° C. at Bohlin CVO A composition comprising greater than about 100,000 centipoise, measured using a rheometer in a rotational shear mode at a shear rate of 0.2 / sec.
(Aspect 17)
Embodiment 18. The composition of embodiment 16, comprising at least two nonionic surfactants.
(Aspect 18)
Embodiment 17. The composition of embodiment 16, comprising from about 0.5 to about 5 wt% of the water conditioning composition.
(Aspect 19)
Embodiment 17. The composition of embodiment 16, further comprising an effective soil removal and emulsion stabilizing amount of an alkyl polyglucoside surfactant comprising about 0.1 to about 10 wt%.
(Aspect 20)
Embodiment 18. The composition of embodiment 17, wherein the first nonionic surfactant comprises a fatty alcohol C13-C15 ethoxylate.
(Aspect 21)
The composition according to aspect 17, wherein the second nonionic surfactant comprises a fatty alcohol C13-C15 ethoxylate.
(Aspect 22)
The composition according to embodiment 16, wherein the polycarboxylic acid consists of a linear polyacrylic chain.
(Aspect 23)
The composition according to embodiment 16, wherein the fatty acid comprises tall oil.
(Aspect 24)
Embodiment 17. The composition of embodiment 16, wherein the composition further exhibits a viscosity of greater than 1,000,000 centipoise at zero shear.
(Aspect 25)
(I) Cleaning comprising a soiled laundry item and a major ratio of water and about 0.5 to about 3.0 ppm of a liquid cleaner concentrate composition in the form of an aqueous thickened emulsion having a continuous phase and a dispersed phase. Contacting the solution, wherein the thickened emulsion has a stable viscosity and dispersed phase particle size, and the composition comprises:
(A) a continuous phase;
(B) an effective soil removal amount of alkali source comprising about 15 to about 50 wt%;
(C) an effective soil removal amount of a nonionic surfactant comprising from about 10 to about 30 wt%;
(D) a water conditioning agent or sequestering agent of about 0.1 to about 20 wt% of an effective water conditioning amount or sequestering amount;
(E) an effective thickening amount of polycarboxylic acid comprising about 1-20 wt%;
(F) an effective thickening amount of fatty acid comprising about 0.1 to about 5 wt%;
Including a phase stable thickened emulsion comprising
The dispersed phase comprises at least a portion of the nonionic surfactant and the thickened emulsion concentrate is rotated at a shear rate of 0.2 / sec using a Bohlin CVO rheometer at 20 ° C. Producing a washed laundry having a viscosity of greater than 250,000 centipoise, measured in shear mode, and exhibiting shear thinning, thereby enabling dispensing during manufacture and use;
(Ii) rinsing the washed laundry with an aqueous rinse;
A method for cleaning dirty laundry items, comprising:
(Claim 26)
Embodiment 26. The method of embodiment 25, wherein the temperature of the wash solution is from about 25 to about 80 ° C.
(Aspect 27)
26. The method of embodiment 25, wherein the cleaning solution comprises about 1.0 to about 2.5 ppm of the liquid cleaner.
(Aspect 28)
Embodiment 26. The composition of embodiment 25, wherein the composition further exhibits a viscosity of greater than 1,000,000 centipoise at zero shear.
(Aspect 29)
26. The composition of embodiment 25, further comprising an effective soil removal and emulsion stabilizing amount of an alkyl polyglucoside surfactant comprising about 0.1 to about 5 wt%.

Claims (10)

A liquid cleaner concentrate composition in the form of an aqueous thickened emulsion having an aqueous phase and a dispersed phase, the composition comprising:
(A) a continuous aqueous phase;
(B) 15-50 wt% alkali source;
(C) 2-30 wt% nonionic surfactant;
(D) 0.1-10 wt% of water adjusting agent or sequestering agent;
5 and to 25 wt% of a polycarboxylic acid,
(E) 0. 6 5-5 wt% fatty acid,
An emulsion containing
The dispersed phase comprises at least a portion of the nonionic surfactant, the water conditioner comprises phosphonic acid, and the emulsion has a viscosity of 0.2 / sec shear using a Bohlin CVO rheometer at 20 ° C. 100 Pa., Measured in rotational shear mode of speed. A composition that is greater than s.   The viscosity was measured at 300 Pa. Using a Bohlin CVO rheometer at 20 ° C. in a rotational shear mode with a shear rate of 0.2 / sec. 2. The composition of claim 1, wherein the composition is greater than s. The composition of claim 1, wherein the nonionic surfactant comprises a fatty alcohol C _13-15 ethoxylate having 4-10 moles of ethylene oxide. The composition of claim 1 wherein the nonionic surfactant comprises a fatty alcohol C _13-15 ethoxylate having 1 to 5 moles of ethylene oxide.   The composition according to claim 1, wherein the polycarboxylic acid comprises a linear polyacrylic chain.   The composition of claim 1, wherein the fatty acid comprises tall oil.   The composition of claim 1, further comprising an optical brightener, a colorant, a fragrance, an antifoam, an antifoam, a bleach, an anti-redeposition agent, or a combination thereof. The composition has 1,000 Pa.s without further shear stress . The composition of claim 1, exhibiting a viscosity greater than s. A liquid cleaner concentrate composition in the form of an aqueous thickened emulsion having an aqueous phase and a dispersed phase, the composition comprising:
(A) a continuous aqueous phase;
(B) 15-50 wt% alkali source;
(C) 2-30 wt% nonionic surfactant;
(D) 0.1 to 15 wt% of water adjusting agent or sequestering agent;
(E) the polycarboxylic acid and fatty acid, or polycarboxylic acids and the fatty acid and polyacrylate copolymer, acrylic acid polymer, and at least one alcohol ethoxylate, and 5.65 to 25 wt% of a thickener,
An emulsion containing
The dispersed phase comprises at least a portion of the nonionic surfactant, the water conditioner comprises phosphonic acid, and the viscosity of the emulsion is 0.2 / 20 using a Bohlin CVO rheometer at 20 ° C. Measured in rotational shear mode with a shear rate of seconds, 100 Pa. A composition that is greater than s. The composition of claim 9 comprising at least two nonionic surfactants.

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