KR880001845B1 - Liquid detergent compositions - Google Patents

Abstract

A fluid, non-sedimental aq.-based detergent comprises (i) the 1st mainly aq. liq. phase contg. at least 25 wt.% of payload and dissolved-surfactant to dissolve electrolytes and (ii) enough aliquots of water to supply payload, which is higher than the lowest limit of sedimentation rate and lower than the upper bound of fluidity and contains (a) at least one dispersed solid phase contg. builder, (b) enough concn. of dissolved electrolytes to supply at least one another phase and (c) up to 25 wt.% of dispersed effective ingredient, to separate by 800 centrifugations for 17 hrs at 25 deg.C on normal gravity, in the first phase.

Description

Liquid detergent composition

1-11 illustrate exemplary groups of neutron scattering spectra.

FIGS. 12-18 are electron micrographs made with Lancaster University cold scanning electron microscopy using freeze eroded samples.

The present invention relates to an aqueous-based liquid liquid detergent composition containing an effective amount of a detergent builder.

The term "builder" is sometimes vaguely used in the detergent art to include non-surfactants, where the presence of the above non-surfactant in the detergent formulation forms the cleaning effect of the detergent formulation. Promotes However, when the term is limited to the conventional "enhancer", the scope is first limited. First, such conventional enhancers are calcium and magnesium by chelation, metal ion sequestering, precipitation or adsorption. It is used as a meaning to prevent or improve the adverse effects during the washing action by the ions, and secondly, as a source of basicity and buffering action. In the present specification, "enhancer" is used in the latter sense and is also referred to as an additive for obtaining the above-described effect to a substantial degree.

These additives include sodium tripolyphosphate and other phosphates and concentrated phosphates such as sodium orthophosphate or potassium orthophosphate, pyrophosphate, metaphosphate or tetraphosphate, as well as acetodiphosphonates, aminotrimethylenephosphonates and ethylene diamine tetra Phosphonate salts such as methylene phosphonate salts and the like. Or polycarboxylic acid polymers, such as organometallic disintegrants such as alkali metal carbonates, nitrilotriacetic acid, citric acid and salts of ethylenediamine tetraacetic acid and copolymers based on zeolites, polyacrylates and maleic anhydrides; This includes.

More specifically, the term " enhancer " as used herein includes carboxymethyl cellulose which acts primarily as a soil-suspending agent or anti-sedimentation agent, although it includes silicates of water-soluble alkali metals such as sodium silicate. Excipients such as polyvinyl pyrrolidone and the like that act primarily as thickening agents are excluded.

As used herein, an "electrolyte" refers to a water-soluble ionic compound that is at least partially separated in an aqueous solution to provide ions and that tends to lower the micelle concentration or solubility of the surfactant in the solution by salting effect, such compounds These include water-soluble and separable inorganic salts other than sodium sulfate, such as chlorides, nitrates, phosphates, carbonates, silicates, perborates, and polyphosphates, and water-soluble organic salts that "rock" or de-solubilize surfactants. And salts of cations that form insoluble precipitates in water due to the presence of surfactants. Such compounds also cause undesirable crystallization upon storage.

By "hydrotrope" is meant a water-soluble compound that tends to increase the solubility of the surfactant in aqueous solution. Conventional hydrotropes include alkyls of lower alkylbenzenesulfonic acids such as sodium toluenesulfonic acid and sodium xylenesulfonic acid. Ly metal or ammonium salts and urea.

As used herein, the term "soap" refers to at least some water-soluble salts of natural or synthetic aliphatic monocarboxylic acids having the properties of a surfactant, including stearic acid, palmitic acid, oleic acid, linoleic acid, ricinoleic acid, Sodium, potassium, lithium and ammonium salts of C _8-22 natural fatty acids and synthetic fatty acids, including behenic acid, dodecanoic acid, resinic acid and side chain monocarboxylic acids.

"Normal trace ingredients" are ingredients other than water, active ingredients, enhancers, and electrolytes, which are usually included in the detergent composition at a rate of about 5% and can coexist in fluid and chemically stable non-precipitating compositions with appropriate formulations. Ingredients are included. Such components include reprecipitation inhibitors, fragrances, dyes, optical gloss agents, hydrotropes, solvents, buffers, bleaches, corrosion inhibitors, antioxidants, preservatives, scale inhibitors, humectants, enzymes and stabilizers thereof, bleach activators and the like.

"Functional Ingredients" as described herein are the ingredients necessary to produce a beneficial effect in the cleaning liquid and are surfactants, enhancers, bleaches, optical gloss agents, buffers, enzymes and anti-sedimentation inhibitors that may contribute to the cleaning effect. Stability, including ingredients such as, and also preservatives, to stabilize, fluidize, or impart other desirable properties to water, solvents, dyes, flavorings, hydrotropes, sodium chloride, sodium sulfate, solubilizers, and concentrated formulations. Topics do not include. "Payload (payload)" means the weight of the active ingredient in percentage of the total weight of the composition, the active ingredient (Active Ingredients) means the surface active materials.

Unless stated otherwise, the term "centrifugation" in this specification means centrifugation at a rotational speed of about 800 times under normal gravity for 17 hours at 25 ° C.

The term "Separble phase" refers to a phase that can be separated into a separate layer from the mixture by centrifugation in the case of a liquid phase or a liquid crystal phase. In the case of a solid phase, this is not necessary, but from the liquid phase by centrifugation. It is used herein to mean a phase that can be separated. Unless the context requires otherwise, all references to separate phases refer to compositions of the separated phase by centrifugation and reference to the structure of the composition relates to the composition that is not centrifuged. A single separation phase contains thermodynamically two or more distinct phases, which are in stable emulsion form and do not separate from each other in centrifugation.

The term "Dispersed" is used herein to describe a phase that is discontinuously separated into particles or droplets at least in different phases. The term "Co-continuous" refers to two or more interpenetrating phases that extend continuously through a common volume or to the matrix when the system is stable. Discrete elements are formed that interact to form a continuous matrix that tends to maintain the orientation and position of the element. The term "Interspersed" describes two or more phases in which one or more phases are dispersed or inter-continuous.

Reference to a solid phase refers to materials that are substantially present in the composition in a solid state at ambient temperature and includes crystallized or recovered water unless otherwise indicated. References to solids include those for microcrystals and thermophilic solids, ie, solids that can only be inferred without being directly observed by optical microscopy. "Solid layer" is a non-flowable gelatin layer or paste or solid form formed by centrifugation.

The term "Total Water" refers to water in the composition, i.e. water present in the composition, such as crystallized or hydrated water or water present in the main non-aqueous phase, and in liquid form in the main aqueous phase. It refers to all the water that exists as water. The term "dry weight" refers to the weight remaining after removal of the total water and the solvent having a boiling point below 110 ° C.

The term "Fomulation" refers to a combination of ingredients in the composition corresponding to the dry weight. Therefore, the same formulation may be exemplified for various compositions with different percentages of dry weight.

Unless stated otherwise, the viscosities used herein refer to flat cups with a diameter of 20 mm and a length of 92 mm, and cone ends and diameters having a diameter of 13.7 mm, a length of 44 mm, and a horizontal angle of about 45 °. Using a 4mm spindle with a bob (bob) was rotated for 2 minutes at a speed of 350rpm and then measured with a cup and a fluorometer at 25 ℃. The tip of the weight is 23mm above the bottom of the cup. This viscosity is consistent with the viscosity with a Contraves "Rheomat 50" viscometer using the measuring system C at a rate of sedimentation rate 30.

These conditions are not suitable for measuring viscosities greater than 12 Pascal Seconds, which can cause partial loss of the contact surface between the weight and the sample.

As used herein, "fluid" means having a viscosity less than 11.5 Pascal seconds.

The "L" phase refers to the micelle solution, the isotropic fluid of the surfactant in water, which is usually made at a concentration between the critical micelle concentration and the lyotropic mesophase of the first ion, with the surfactant molecule Form a globular or rod-shaped micelle.

The "G" phase describes a liquid crystal phase of a type well known in the literature, such as the "neat phase" or the "lamellar phase", in which case the surfactant molecules are separated by a layer of water or an aqueous solution. They are parallel to the separated infinitely enlarged layers. This layer may be a bilayer or interdigited layer of a surfactant. The "G" phase for a given surfactant or mixture of surfactants is usually present in a narrow range of concentrations.

The pure "G" phase can be identified by experimenting with the sample under a polarizing microscope, usually between the interfering polarizer plates. Resevear, JAOCS Vol. 31 p 628 (1954) or on J. Colloid and Interfacial Science, Vol. 30 No. A special structure is observed at 4, p.500.

Yield point described herein means that measured by RML Series 11 Deer Rheometer at 25 ℃.

Unless stated otherwise, all percentages are by weight ratio based on the total weight of the composition.

As used herein, "sedimentation" includes not only down-separation of solid particles but also up-separation.

The term "non-sedimentation" means that no sedimentation will occur under normal storage conditions unless otherwise indicated. Usually, "non-sedimentation" means that no sedimentation occurs after three months at room temperature under normal gravity at sea level. The term also includes compositions that indicate the degree of syneresis, so that some of the aqueous phase separates to form a clear layer that is the outer layer for the homogeneous gel or dispersion. These partially separated systems can usually be shaken and distributed. This results in substantially more problems in dispersing the product in contrast to the sedimentation system where the solid precipitate is separated from the dispersion.

Until now, liquid cleaners have been used mainly for light tasks such as dish washing. In detergent products used for heavy duty applications such as laundry detergents, powder form predominates because it is difficult to obtain a stable liquid formulation with an effective amount of sufficient surfactant and a particularly effective amount of enhancer. These liquid cleaners do not need to be dried and in many cases should be cheaper than powder cleaners because water is used instead of the sulfate fillers commonly used in powder cleaners. It is also possible that these cleaners dissolve faster and more readily in cleaning solutions than powders and provide more convenience. Attempts to prepare solutions of active ingredients have not been very successful commercially. One reason for this failure is that commonly used and well-valued active ingredients, such as sodium tripolyphosphate and sodium dodecylbenzenesulfonate, are not sufficiently dissolved in aqueous formulations. I also tried using amine salts and potassium pyrophosphate as the active ingredients better soluble in water, but found that the cost was not appropriate.

Unimproved liquid cleaners containing high purity surfactants commercially available for laundries are not suitable for hard water, but have only been able to succeed in a limited range.

Another approach is to suspend a sufficient amount of enhancer as a solid in the liquid surfactant solution. However, the problem here is to stabilize the condition so that the enhancer remains suspended and prevent sedimentation from occurring. In the past, such problems have required relatively impure formulations to prevent the potential cost savings from realizing and require relatively low concentrations of solid enhancers to exhibit limited cleaning effects. This attempt was conditioned by the following assumptions:

The detergent should be as solution as possible; The amount of suspended solids should be minimized to overcome the difficulties in stabilizing the suspension so that it does not precipitate; In addition, special acid thickeners or stabilizers should be used to prevent precipitation.

The products introduced so far are those that have certain serious drawbacks commercially. In particular, each formulation was proved to be very sensitive to relatively small changes in composition and production. Power generation from a particular composition that is optimal within a very narrow range becomes unstable, resulting in reduced storage levels. These formulations are therefore limited to special ingredients and proportions that do not include the most effective combination of surfactants for cleaning purposes.

Since no adequate theoretical explanation has been given for the stability of these systems, it was not possible to propose whether the formulations are stable or unstable, or how to stabilize surfactants that may be necessary for effective cleaning or cost reasons. However, each formulation was discovered by trial and error, and there was little flexibility for using each formulation according to particular needs.

In general, the payload is undesirably low, and the ratio of the enhancer to the active ingredient is generally lower than the ratio of the active ingredient and the enhancer to the optimal detergent, which is not usually needed in powdered formulations. Expensive ingredients were often needed to prevent precipitation of suspended solids and to increase the amount of active ingredients in solution.

We have a new structure up to now, containing the optimal proportions of commonly used cleaning enhancers, and non-settling and fluidity that can actually use any surfactant or combination of surfactants useful for cleaning as a surfactant. Conditions appropriate for preparing the detergent composition based on the phosphorus aqueous aqueous base were observed.

In general, the compositions according to the present invention contain substantially more payload by using the enhancer and the surfactant at a higher ratio than the ratio of the enhancer and the surfactant used to date.

Compared with the products sold so far, the specific advantages of the present invention are as follows; Payload is high; The ratio of enhancer to surfactant was increased; Increased stability: easy to manufacture, lower cost by using cheaper components; Satisfactory mobility; Washing performance was increased; Has a "non-drip" characteristic; It is formulated not to break down too quickly in a washing machine designed to use a powder cleaner; At a suitable concentration so as to disperse automatically; In any particular use, there is fluidity to select the optimum surfactant composition.

Contrary to what was assumed in the art, the present invention found that the greater the amount of undissolved material, the more stable the composition.

In particular, the present invention is that the lower the ratio of the active ingredient dissolved in the aqueous solution state, the higher the ratio of the present in the scattered structure of the solid or lamellae phase, the easier it is possible to obtain a non-precipitable and fluid product of the payload Found. Furthermore, when the payload is high, when a sufficient amount of surfactant is present in a particular form of new structure in the composition, without the need for a special stabilizer and without requiring other methods for the formulation, it is usually It has been found that most surfactants used in powder cleaners have the effect of stabilizing an aqueous suspension of the active ingredients.

It has also been found that the surfactant may be formed into an open three-dimensional structure that imparts stability to the aqueous suspension by controlling the mixing conditions or the presence of an electrolyte. By applying the above principles, it is possible to produce laundry detergents such as thixotropic gels having a matrix of hydrated solids or liquid crystalline surfactants which may provide advantages over conventional detergents and may contain suspended solid enhancer particles. I found out.

There are many conventional inventions for liquid detergents. However, for the purposes of the present invention, an immense number of references to laundry detergents with all components present in solution and cleaning solutions for light work may be ignored. This is because in each case the content of the enhancer is generally less than the desired amount.

An overview of recent general technology flows is provided by JAOCS (April 1981) P 356A-"Heavy Duty Laundry Detergents" and the Sur-factant Scient Series, which contains a review of some of the most commercially available liquid formulations. By Marcel Dekker Inc. It is described in Rutkowski's "Recent Changes in Laundry Detergents", published in 1981.

The problem of making fully improved liquid detergents can be approached by two principles: adding surfactants to the aqueous solution of the enhancer to make them oily or suspending the solid enhancer in the aqueous solution or emulsion of the surfactant.

Attempts by the former are exemplified in US Pat. Nos. 3,235,505, 33,6503, 33,51557, 3,530,059, 3,574,122, 33,6503, 33,28,309, and Canadian patent, 9,7031. In each of these patents, an aqueous solution of a water-soluble enhancer is sufficiently concentrated to salt the surfactant (usually in the form of a non-ionic liquid), and the surfactant is dispersed in an aqueous medium like a clade droplet by various oils. . In each case a clear emulsion is formed, which contains relatively low levels of enhancer and tends to be undesirably expensive by using solubility enhancers.

Another attempt is exemplified in British Patents 948617, 943171, 2028365, European Patent 38101, Australian Patent 522983, US Patents 4018720, 3232878, 3075922 and 2920045. have.

The formulations described in these patents are separated by centrifugation into a liquid phase that contains mostly an enhancer that is slightly soluble in water and that contains mostly solids and active ingredients. Commercially manufactured products according to embodiments of two of these patent specifications have recently been marketed in Australia and Europe. In general, the stability of such compositions is very sensitive to small changes in formulation form and therefore requires expensive additives, most of which are not active ingredients.

Another attempt is to suspend the solid builder in a nonionic surfactant which is a liquid anhydride, as described in British Patent 160981. Such systems, however, are expensive, have limited choice of surfactants, and have insufficient rinsing properties.

Some patents describe the emulsions in which the enhancer is in a dispersed state of the emulsion rather than in suspension. U.S. Patent No. 4057506 describes the preparation of a clear emulsion of sodium tripolyphosphate, and U.S. Patent No. 4007067 describes an inverted emulsion in which an aqueous solution enhancer is dispersed in a liquid crystalline surfactant system.

There are a number of patent specifications that will refer to hard surface cleaners in which an abrasive is suspended in an aqueous surfactant, as in US Pat. Nos. 3,328,673 and 3813349.

US Pat. No. 3,56,158 describes suspensions in which the abrasive is suspended in an interlocking fiber gel such as asbestos or soap. However, these patents, which generally contain low surfactant concentrations, do not contain enhancers, and contain high concentrations of abrasives, are of no help when producing laundry detergents.

Powder cleaners are usually made by spray drying an aqueous slurry. Slurry solutions have in common appearance with the formulation of liquid detergents, but do not need to be stabilized upon storage and are prepared and handled at high temperatures.

Usually these slurries are not fluid at ambient temperatures. A description and method of spray drying these slurry intermediates are described in US Pat. No. 3,339,288 and in W. German OLS 1567656. Australian patent 507431 describes suspensions in which the enhancer is suspended in an aqueous surfactant stabilized with a substance such as sodium carboxymethylcellulose or clay as a thickening agent. However, in the formulation form exemplified, the content of the active ingredient, in particular the enhancer, is not sufficient to be accepted as a commercial product.

U.S. Patent No. 30,999,71 discloses a detergent paste containing a solution enhancer.

French patent 2839651 describes a suspension in which a zeolite enhancer is suspended in a nonionic surfactant system which is a hard paste rather than a fluid liquid.

A. C. S. Symposium series No. 194 "Silicates in Detergents" describes the effect of silicates in liquid detergents.

It will be appreciated that the patent references described above are taken from a very wide range of prior art and have utilized the knowledge of the present invention as a criterion for selection and emphasis of the literature. Ordinary people working in this field that had no foresight in the present invention when the applicant first claimed priority would not have chosen the patent specification in a particular sense and would not be able to extract particular relevance.

Therefore, the summaries described earlier do not usually describe the overall portion of the skill that experienced people have. There are methods for preparing liquid cleaners by suspending the enhancer in an aqueous solution of a fully improved liquid detergent or surfactant that contains only a slightly soluble enhancer that is difficult to manufacture. We generally believed that the latter view prevailed but this approach was attempted. Both failed.

The present invention provides a non-settling, flowable liquid detergent composition containing an active ingredient and a dispersed solid enhancer, which composition (not necessarily all) exhibits at least some of the following properties: It is mainly composed of an aqueous separated phase containing less than 75% by weight.

Enumerating the characteristics is as follows; The composition is thixotropic and the composition consists of at least one main liquid aqueous phase and one or more phases that can be separated from the main liquid aqueous phase by centrifugation and contained in at least one of the one or more other phases mentioned. Active ingredients are present, at least one of the one or more other phases mentioned is an enhancer, and the one or more other phases are interspersed in the main aqueous phase. They are gel; They contain, in succession, a main aqueous separation phase containing a dissolved electrolyte and a solid or liquid crystal separation phase containing a substantial proportion of the active ingredients interspersed with this aqueous phase and a dispersed solid phase consisting mainly of an enhancer; They have an organic lamellar component; This lamellar component consists of surfactant layer and aqueous solution; This layer is repeated at intervals of 20-65 A °; One or more other phases are mainly non-aqueous phases; The composition usually has a high active ingredient payload of at least 20% by weight, that is, about 25-75% (usually about 30%, preferably at least 35%, more preferably 40%); They contain an adjuvant and an active ingredient in a ratio of 1: 1 or more, preferably 1.2: 1-4: 1; The active ingredient is contained in an amount of at least 5% by weight, preferably at least 8%; The main aqueous phase is contained in a concentration of 15% or less, preferably 8% or less, or 2% or less, and in the case of nonionic surfactants or alkylbenzenesulfonic acid, the dissolved active ingredient is contained in a weight ratio of 0.5% or less. have ;

The ratio of the total active ingredient in the composition to the active ingredient in the main aqueous phase is 1: 1.5 or less, preferably 1: 2 or less, ie, 1: 4 or less; The at least one main aqueous liquid phase contains a sufficient amount of electrolyte and is provided at a concentration of 0.8, preferably 1.2, i.e. 2.0-4.5 g of ions per liter of the total alkali metal and ammonium cation; The composition contains 15% by weight, preferably 20% or more, by weight ratio; The enhancer is mainly sodium tripolyphosphate and this enhancer contains small amounts of alkali metal silicates, preferably sodium silicate; The volumetric viscosity of the present composition is about 0.1-10 pascal seconds, preferably about 0.5-5 pascal seconds; The yield point of the composition is 2, i.e. about 5, preferably 200 dynes / cm ² or less, i.e. 10-150 dynes / cm ² ; The phase containing the enhancer contains solid particles having a maximum particle size below the limit size at which the particles can settle; One of the particles growth inhibitors is adsorbed on the surface of these particles enough to keep them below the threshold size at which they can settle; The composition contains a direct inhibitor sufficient to prevent solid particles from solidifying.

Specifically, the non-precipitable and flowable aqueous base detergent composition has a payload of at least 25% by weight and comprises the first major aqueous liquid phase and solid enhancer containing dissolved electrolyte. It comprises at least one dispersed solid phase and at least one other phase which can be separated from the first phase above by centrifugation at 800 times under normal gravity for 17 hours at 25 ° C.

Specifically, the present invention provides a detergent composition comprising a flowable, non-settling aqueous base consisting of at least 5% surfactant, 16% enhancer and water by weight, the composition for 17 hours at 25 degrees Celsius. Centrifugation 800 times under normal gravity provides a primarily aqueous liquid layer containing dissolved electrolyte and one or more other layers comprising at least a portion of the enhancer as a solid dispersed with most of the surfactant.

Third, and specifically, the present invention provides a non-precipitable and flowable liquid detergent composition having at least 25% payload and having an organic component of lamellar structure. This detergent composition is intended for use as an enhancer for solid particles dispersed in a predominantly aqueous liquid phase containing dissolved electrolytes, in separate phases containing significant amounts of surfactants interspersed in the aqueous phase and in other phases. It is composed of at least one solid mainly composed.

Fourth specifically, it provides a non-settling, flowable liquid detergent composition having a payload of 25% by weight, wherein the detergent composition comprises at least one predominantly aqueous liquid separation phase, at least one phase of which is predominantly. It consists of suspended particles of one or more other phases and solid enhancers consisting of a matrix of solid surfactant hydrates that form a thixotropic gel with an aqueous liquid phase or other phases.

Fifthly specifically, the present invention provides a liquid detergent composition which is non-settling and fluid, wherein the detergent composition is suspended in at least one liquid crystal separation phase and composition comprising a primarily aqueous liquid separation phase and a surfactant. It consists of at least one predominantly nonaqueous separation phase consisting of solid enhancer particles. It is preferable that a liquid crystal is a "G" phase at this time.

Sixth specifically, the present invention provides a liquid detergent composition which is non-precipitable, flowable and improved, wherein the detergent composition consists mainly of an aqueous liquid separation phase and one or more other separation phases, and one or more other separation phases. One of the phases consists of an oval or vesicle formed from one or more shells of the surfactant. The cell of the aforementioned surfactant may optionally be separated by a cell of water or an aqueous solution which gives a lamellae having a "G" phase structure. The aforementioned vesicle form may contain primarily aqueous liquid phase and / or one or more oval or rod-shaped surfactant micelles and / or one or more solid enhancer particles.

Specifically, a non-precipitable and flowable liquid detergent composition is provided, which comprises a predominantly aqueous liquid separation phase, anion and / or in which up to 60% of the total weight of the active ingredients in the composition is dissolved. Or at least one phase containing a nonionic active ingredient and one or more other separation phases interspersed with at least one phase containing a solid enhancer.

Eighth specifically, the present invention includes a sufficient amount of electrolyte in which the total alkali metal and alkaline earth metal and / or ammonium cation are dissolved at least 0.5 g, i.e. at least 0.8 g, preferably 1-4 g, per liter. A non-settling, flowable improved liquid detergent composition comprising at least one predominantly aqueous liquid separation phase and one or more other phases containing a surfactant and interspersed with suspended solid enhancers, the composition comprising at least It has a payload of at least 25% by weight, and the electrolyte is present in an amount sufficient to allow a large proportion of the composition in one or more other phases to maintain the total active ingredient and thus inhibit the settling of the enhancer.

Ninth specifically, the present invention relates to a non-settling, fluid liquid consisting of a predominantly aqueous liquid separation phase containing a dissolved electrolyte and at least one other separation phase and suspended solid enhancer containing an active ingredient. It provides a detergent composition. Such compositions have a payload that falls between the minimum concentration for making the composition free of sedimentation and the maximum concentration for making the composition flowable.

More specifically, the present invention provides a non-settling, flowable liquid detergent composition consisting of a substantially aqueous mainly separated phase substantially saturated with a surfactant that can form a solid hydrate or liquid crystalline phase and an enhancer. .

The surfactant, which is a matrix of solid hydrates or liquid crystals, is interspersed in the main aqueous phase in which the enhancer particles are suspended in sub-minimum size at which sedimentation occurs. Growth inhibitors and aggregators are included to prevent the coagulation and aggregation of particles. In the foregoing description, the dry weight content is more than 35% by weight of the detergent, the ratio of the enhancer and the active ingredient is greater than 1: 1.

Classification by Centrifugation

In general, a liquid-based detergent for washing an aqueous base in which a solid enhancer is suspended can be classified simply by centrifugation as defined herein. Three important forms of detergents containing a continuous aqueous phase and dispersed solids can be distinguished into suspensions of group I, group II and group III.

The detergent suspensions of group I are characterized by the prior art described above with regard to suspensions in which solid enhancers are suspended in aqueous solutions or emulsions of surfactants. Centrifugation as defined herein separates the composition of Group I into a solid phase consisting of an enhancer and a viscous liquid phase consisting of water and a surfactant. The composition of group I is separated into a solid phase consisting of an enhancer and a viscous liquid phase consisting of water and a surfactant. Factors of the formulation to attempt to form the composition of Group I include water-soluble surfactants such as alkylether sulfates, solubilizers such as hydrotropes and organic solvents that can be mixed with water, relatively low concentrations of electrolytes and relatively low concentrations of pay. Use of wood is included.

Formulation forms of group I usually exhibit some typical properties, such as: The volumetric viscosity of the composition is determined by the viscosity of the aqueous liquid layer and is about the same as the viscosity of the aqueous liquid layer. The aqueous layer typically has a viscosity of 0.1-1.0 Pascal seconds. In general, the viscosity of the composition is less than one pascal second, which is on the order of 0.3-0.6 pascal seconds. The present composition generally has a yield point of 4dyne / cm ² or less, often 1dyne / cm ² or less. This suggests a relatively unstructured composition and has been confirmed by neutron scattering, X-ray diffraction studies and electron microscopy. Under high shear rates, most Group I formulations become unstable.

In essence, Group II is distinguished from Group I because at least most surfactants exist in a separate phase from the predominantly aqueous liquid phase containing the electrolyte. This group is distinguished from Group III in that most surfactants are centrifuged into a liquid or liquid crystal layer by centrifugation.

Group II is typical of the cleaning composition of the present invention prepared from nonionic surfactants or surfactants mixed with nonionic and anionic as the main component of the active ingredient, although not represented in the prior art. Typically, the composition of group II is separated into three layers by centrifugation, the first layer being non-viscous (0.1 Pascal or less, usually 0.02 Pascal, which contains electrolyte but little or little surfactant). The second layer is a viscous liquid layer containing most of the active ingredient, and the third layer consists of a solid layer composed mainly of an enhancer. The composition of group II has a very low yield point at the time of its initial preparation but it becomes gel like time. The viscosity of this composition is usually between 1 and 1.5 pascal seconds.

The composition of this type was confirmed to form a lamellar structure by X-rays, neutron diffraction experiments and electron microscopy. Most Group II compositions that are centrifuged have a liquid or liquid crystalline surfactant layer at the top, but an aqueous electrolyte layer appears at the top or at least one layer is directed upwards in relation to the two liquid layers or one of them by centrifugation. It is not possible to exclude compositions in which two or more solid layers distinguishable from one another in which sedimentation may occur.

Intrinsic differences from other groups and group III may be that most of the surfactant may be centrifuged into a solid bed. Group III formulations may be centrifuged into one or more solid layers. Usually, if both surfactant and enhancer are precipitated downward by centrifugation, these two solid layers cannot be distinguished. However, the formulation of Group III provides an upwardly precipitated surfactant layer or at least one surfactant layer provides one or more surfactant layers that settle upwards. In addition, some or all of the enhancer may settle upwards.

The third group of detergent solutions, like the mixture of the minimum nonionic surfactants and the following anionic surfactants, are surfactants that are slightly soluble in the aqueous state, in particular sodium alkylbenzenesulfonates, alkylsulphates, carboxyestersulfonates and many soaps. A composition according to the invention prepared with anionic surfactants such as. Typically, Group III formulations are separated into two layers by centrifugation, where the first layer is a non-viscous aqueous layer (i.e. a viscosity of 0.1) that contains a dissolved electrolyte and an extremely small (sometimes not included) surfactant. Pascal seconds or less, usually 0.02 Pascal seconds or less), and the second layer is solid, consisting of an enhancer and a surfactant.

The rheological properties of Group III represent the strongest evidence for structure. The viscosity of the suspension is 1.2 to 2 pascal seconds, which is much greater than the viscosity of the aqueous layer. In general, the composition has a higher yield point than 10 dyne / cm ² , the recovery time after applying a shear force above the yield point is usually very short, 20 to 100 minutes. Most Group III formulations recovered after very high shear forces were found to have increased viscosity and greater stability.

Group I was gradually changed to Group III using a formulation with one group of characteristics and another group of characteristics. For example, centrifugation of the soap based formulations according to the invention results in a small amount of the third phase, but has the lyologic properties of group III.

Compositions at the borderline of Group I and Group II are sometimes unstable, but can also be converted to a stable Group II formulation according to the present invention by adding a sufficient amount of electrolyte or increasing the payload. Most Group I formulations can be converted to Group II by adding a sufficient amount of electrolyte. Similarly, the addition of higher amounts of electrolytes tends to convert Group II formulations to Group III. Conversely, by adding hydrotrope, group III can be converted to group II and group II can be converted to group I. Formulations of Group III can be directly converted to Group I by adding hydrotropes and vice versa directly from Group I to Group III by adding electrolyte.

Classification by Diffraction and Microscopy

The formulation form according to the invention and the formulation form according to the prior art were compared by X-ray, neutron diffraction and electron microscopy.

Samples for neutron diffraction studies were prepared using deuterium oxide instead of water. Although aqueous solutions such as sodium silicate or components such as hydrates were not possible in deuterated form, water was kept to a minimum.

Formulations based on deuterium oxide were tested with a small angle Howell neutron scattering spectrometer. In addition, both deuterium oxide based samples and aqueous samples were tested with a small angle X-ray diffractometer. Aqueous samples were coated with gold or a combination of gold and palladium, frozen into corroded pieces, cut into pieces, and observed by electron microscopy at low temperatures at Lancaster University. Of course, competitive commercial formulations that cannot be used in deuterated form cannot be tested by neutron scattering.

In the case of centrifugation, the three techniques described above provide three categories of liquid detergent suspensions, three of which are group I, II and III described under "Sorting by Centrifugation". In connection with the composition of.

The first category of compositions includes those belonging to group I, which have no discontinuous advantages and similarity in regularity, repeatability and structural properties by neutrons and X-ray analysis burns due to high levels of scattering at small angles, etc. Is specified. Some formulations come in the form of inconspicuous wide shoulders, hump smooth continuums and the like.

Scattering at a small angle scatters very close to the line of incident light, which usually occurs in dispersions that are unevenly diluted in composition. The shoulders or humps observed in the group I formulations also show typical angular displacements and morphologies of the concentrated micelle solution (phase L ₁ ) of the surfactant. Observation of typical Group I formulations by electron microscopy reveals multidirectionally dispersed enhancer crystals with large granular structures without features.

These results are consistent with the assumptions based on the rheology properties that typical Group I formulations have less detectable lamellae shape unless relatively organized. However, some of Group I can be clearly observed by electron microscopy, which has a spherical structure of approximately 5 microns in diameter.

A very different form is obtained from a typical group II formulation. This formulation exhibits relatively low levels of scattering at small angles near the incident light, with their peaks representing typical peaks of concentrated micelle solution (L ₁ phase) and peaks due to well-defined peaks or lamellar structures. . The position of the latter vertices is usually distinguished from the third vertex because it is represented by a simple numerical ratio with the first and second. These vertices prove that they exist as lamellar layers (36-60 microns) occupying a relatively large space. The lamellar structure can be observed by an electron microscope. In some cases, spherical structures of approximately 1 micron in diameter may be observed.

Typical Group III formulations have relatively very narrow and strong small angle scattering and have distinct peaks that represent lamellar structures. These vertices appear wider than those of the typical group II formulation and are not capable of improving and separating the second and third vertices. In general, the displacement of the vertices shows a more dense lamellar structure than in the typical group II formulation (ie (26-36 mm 3). The lamellar structure can be clearly observed by electron microscopy.

PROPOSED STRUCTURE

The present inventors assume that the above-described characteristics are specifically expressed by the assumption that the solid enhancer is a solid surfactant hydrate or a new structure in which the "G" phase surfactant is suspended in combination with a micellar solution of L ₁ . I believe it can be explained most easily.

The present invention in particular expresses the composition of Group III consisting of a flowable gel system formed of two or more inter-continuous or interspersed phases. The properties of the composition of Group III can be explained on the basis of being thixotropic gels, which are interspersed with a relatively non-viscous aqueous phase containing a dissolved electrolyte with little or no surfactant. It consists of a relatively weak three-dimensional network of surfactant hydrates. This network prevents suspended discrete particles from forming and forming meshes with each other. The solids that form the network may be in the form of platelets or in the form of wide or infinitely wide sheets or fabrics, or in the form of symmetrical particles that interact or combine to provide a sparse, sparse net shape of liquid or interspersed. . This structure is a very stable structure that prevents sedimentation during storage, prevents sedimentation and limits the expansion of the gel's horizontal surface. However, this structure is weak enough to cause the composition to flow down or to pour out.

The solid structure usually consists of surfactant hydrates such as sodium alkylbenzenesulfonate or alkylsulfonate salts, eliminating the need to use stabilizers required for the formulation of the end use. These gels have a mud-like structure and are sometimes described as a "house of cards" structure with a flat, crystalline substrate arranged randomly around the gaps between the enhancer particles. Solid surfactants may be bound immediately or at least partially solid by surfactants on the "G" phase.

In the case of group II, the formulation form consists of four thermodynamically distinct phases in which only three are separate phases under the conditions defined herein. The phase detected by diffraction consists of a lamellar phase consisting of the "G" phase but in some cases is mainly an aqueous "L ₁ " with a surfactant hydrate or a mixture of the "G" phase and a surfactant and a solid enhancer. It may be composed of a micelle solution. Also mainly aqueous solutions are 75, in particular 50% or less, generally 40% or less, more generally 20% or less, preferably 10% or less, more preferably 5% or less, that is 2 Contains less than% electrolyte.

Enhancers are suspended in a system consisting of a "G" phase or a spherical or follicular network, which may have onion-like structures or shells formed from successive layers of surfactant such as the "G" phase. And at least one predominantly aqueous phase, such as an electrolyte solution or more preferably a "L ₁ " micelle solution, is a continuous phase. In the case of compositions containing olefins and paraffin sulfonates, the presence of vesicle morphology can be confirmed under a microscope.

Surfactants

It is preferable that the composition of this invention contains 5% or more of surfactant by weight. In addition, the surfactant is preferably contained in the weight ratio of the composition 7-35%, that is, about 10-20%.

For example, the surfactant may be substantially at least slightly water soluble sulfonate or monoesterified sulfonate, ie alkylbenzene sulfonate, alkalsulfate, alkylethersulfate, olefinsulfonate, alkalsulfonate, alkylphenylsulfate, alkylphenylether Sulphates, alkylethanolamide sulfates, alkethanolamide ether sulfates or esters of α-sulfon fatty acids or α-sulfofatty acids having 8-22, usually at least one alkenyl or alkyl group having 10-20 aliphatic carbon atoms It consists of. The alkyl group or alkenyl group mentioned above may be a linear primary chain group, or optionally a secondary or branched chain group. The term "ether" mentioned above refers to polyoxyethylene, polyoxypropylene, glyceryl and mixed polyoxyethylene-oxypropylene or mixed glyceryl-oxyethylene or glyceryl-oxypropylene groups, typically 1-20 It shows what contains an oxyalkylene group. For example, sulfonated or sulfurized surfactants include sodium dodecylbenzenesulfonate, potassium hexadecylbenzenesulfonate, sodium dodecyldimethylbenzenesulfonate, sodium lauryl sulfate, sodium industrial sulfate, potassium oleyl sulfate, lauryl monoethoxysulfate And 10 moles of ammonium or monoethanolamine cetyl ethoxylated.

Other anionic surfactants useful in accordance with the present invention include fatty alkylsulfosuccinates, fatty alkyl ether sulfosuccinates, fatty alkyl sulfosuccinates, fatty alkyl ether sulfosuccinates, acyl sarcosinates, acyltaurates, ises Ionsthionate and stearates, palmitates, lecinates, oleates, soaps such as linoleates and alkylester carboxylates.

Anionic phosphate esters are also used.

Anionic surfactants contain at least one aliphatic hydrocarbon chain having 8 to 22 carbon atoms, preferably 10 to 20 carbon atoms, and for ethers one or more glycerol and / or 1-20 Ethyleneoxy groups and / or propyleneoxy groups.

Anionic surfactants, such as olefins sulfonates and paraffinsulfonates, are commercially available only when the disulfonates contain disulfonates formed as by-products of industrial manufacturing in the normal way. The latter tends to stabilize the surfactant by the method of hydrotropes.

However, olefins and paraffinsulfonic acid salts have a spherical structure and are centrifuged to easily form a stabilizing composition in which only a small amount of the total surfactant is contained in the aqueous phase. Therefore, such a composition forms a special aspect of the present invention as a new laundry detergent with use.

Preferred anionic surfactants are sodium.

Other commercially available salts thereof include potassium salts, magnesium salts, amonium salts, monoethanolamine salts, diethanolamine salts, triethanolamine salts, and alkylamines having up to seven aliphatic carbon atoms. .

The surfactant may comprise or consist of a nonionic surfactant. Nonionic surfactants include mono- or di-lower alkanolamines of C _10-22 alkanolamides, such as coconut monoethanolamide.

Other nonionic surfactants in common use include ethoxylated alcohols, ethoxylated carboxylic acids, ethoxylated amines, ethoxylated alkylolamides, ethoxylated alkylphenols, ethoxylated glyceryl esters, ethoxylated sorbitan Propoxy or ethoxylated and propoxylated analogues of esters, ethoxylated phosphate esters and all of the aforementioned ethoxylated nonionics with alkyl groups or alkenyls of C _8-22 and up to 20 ethylene or propylene Everything that has an oxy group or another nonionic surfactant that has been mixed in a detergent composition in powder or liquid form so far, such as amine oxides and the like.

The latter usually contains at least C _8-22 , preferably C _10-20 alkyl or alkenyl groups, and lower alkyl groups containing up to 3 carbon atoms (ie, C _1-4 , preferably C _1-2 ), and the like. I have more than one

More preferred nonionic groups according to the invention have an HLB of 7-18, i.e. 12-15.

The detergents of the present invention may include cationic surfactants, in particular cationic fabric softeners, which make up a very small amount of the total active material. Cationic fabric softeners effective in the present invention include C _12-22 , in particular an alkyl or alkenyl group consisting of two long chains of C _16-20 and an alkyl group consisting of two short chains of C _1-4 , or one short chain; Quaternary amines having one benzyl group are included. In addition, cationic fabric softeners include quaternary amidazolines having imidazolines and two long chain alkyl groups or alkenyl groups, and amidoamines and two long chain alkyl or alkenyl groups. Tea imidoamines and the like. Quaternary emollients are usually anionic salts, which can measure solubility in water, such as formate, acetate, lactate, tartarate, chloride, matosulfate, ethosulfate, sulfate or nitrate. Compositions of the present invention having fabric softener properties may also include small clays.

The composition according to the present invention may contain amphoteric surfactants which may be included in typical surfactants containing cationic fabric softeners but may also be included as a minimum component of the active ingredients in the other detergents mentioned above.

Amphoteric surfactants are sulfobetaines, phosphate betaines and other betaines formed by reacting an appropriate reagent such as chloroacetic acid or propane sultone with an appropriate tertiary nitrogen compound with a long chain alkyl or alkenyl group. And the like.

Examples of tertiary nitrogen compounds are as follows:

Tertiary amines which may contain one or two long chain alkyl groups alkenyl groups or benzyl groups or short chain alkyl groups substituted with other substituents; Amidazolines having one or two long chain alkyl or alkenyl groups and amidoamines having one or two long chain alkyl or alkenyl groups. Those skilled in the detergent field will appreciate that the particular type of surfactants described above are merely examples of common surfactants suitable for use in the present invention. Any surfactant may be included that can perform useful functions in the cleaning liquid.

A detailed description of the critical forms of commercially available surfactants is described in "Surface Active Agents & Detergents" by Schwartz Perry and Berch.

Enhancer

In a preferred composition according to the invention, the enhancer is present as discrete solid crystals suspended in the composition.

The size of the crystals is typically up to 60 microns, ie 5-50 microns.

The present invention is directed to formulations containing sodium tripolyphosphate as an enhancer or containing sodium tripolyphosphate in a mixture with other enhancers in a predominant proportion, with stability over a wider range of dry weight than formulations containing other enhancers. It was found to have fluidity. Therefore, this formulation is preferred for the present invention.

However, the present invention also provides compositions comprising other components such as potassium tripolyphosphate, carbonates, zeolites, nitrilotriacetates, citrates, metaphosphates, pyrophosphates, phosphates, DETA and / or polycarboxylates, and the like. Although provided, it is preferred, however, to contain a mixture with tripolyphosphate. The mixture with tripolyphosphate can also contain orthophosphate or an alkali metal silicate as a trace component.

The last thing to mention is that it is preferable to be configured in the preferred form according to the invention because it performs some valuable functions. They provide the desired free alkalinity for saponifying fatty acids when stained, which prevents corrosion of the aluminum surface in the washing machine and has an effect as an enhancer. They are also effective as an electrolyte that salts active ingredients from primarily aqueous liquid phases, thus reducing the proportion of active ingredients contained in the solution and improving the stability and flow of the composition. The composition according to the invention thus comprises about 1-12.3%, preferably 2-10%, most preferably 3-6.5%, ie 3.5-5%, alkali metal silicate, more preferably the composition as a whole by weight of the composition It may contain sodium silicate measured as SiO ₂ by weight. Typically the silicates used to prepare the compositions described above are Na ₂ O; The ratio of SiO ₂ 1: 1-1: ₂ or 1: 1.5 to 1: 1.8.

However, silicates or silicic acids in which Na ₂ O (or other base) and SiO ₂ are mixed in any ratio may be used to provide silicates in the composition, and other bases such as sodium carbonate or hydroxide may be added to provide additional base groups. You will see that it may. Formulation forms that are not intended for washing machines do not require silicates to be supplied as an alternative source of alkalinity.

Enhancers usually contain up to about 15%, preferably up to about 20% by weight of the composition. The ratio of the enhancer to the surfactant is preferably 1: 1 or more, preferably 1.2: 1-5: 1.

Electrolyte

It is advisable to keep the concentrations of dissolved organics and active ingredients contained in the predominantly aqueous liquid phase at low levels, which is to select surfactants which are slightly dissolved in the main aqueous phase as much as possible, and the more required for the particular end use. This can be done by keeping the amount of surfactant that is highly soluble to a minimum. It has been found by way of specific example according to the present invention that by adding a sufficient amount of electrolyte to at least one main aqueous phase, the selected surfactant system and payload can be stabilized.

The effect of the electrolyte is to limit the solubility of the active ingredient in the at least one main aqueous phase, thereby increasing the proportion of surfactants capable of providing a solid or liquid crystalline matrix which stabilizes the composition of the present invention.

Another effect of the electrolyte is to increase the transition temperature of the "G" phase to the extent that the surfactant becomes a solid. One of the results of increasing the transition temperature of these phases is to increase the minimum temperature beyond that of the surfactants forming a liquid or liquid crystalline phase. When water is present, the surfactant, which is usually a liquid crystal phase or aqueous micelle solution at ambient temperature, can be pressed to form a "G" phase with the solid matrix by the presence of the electrolyte.

The amount of electrolyte contained in at least one main aqueous phase is about 0.8, preferably about 1.2 (ie about 2.0-4.5 g added per liter of alkali metal, alkaline earth metal or ammonium cation). It is preferable to contain in a ratio. The degree of stabilization of such a system can be further improved by providing the anions needed for the composition by salts with the usual cations (preferably sodium ions) as possible. For example, preferred enhancers include sodium tripolyphosphate, and preferred anionic surfactants include sodium sulfate salts or sulfonated anionic surfactants and carbonates present as carboxymethylcellulose, silicates or preferably nat salts. There are anti-sedimentation agents such as alkalis. In order to minimize the concentration of the active ingredient contained in the aqueous liquid phase and increase the electrolyte concentration, sodium chloride or soluble inorganic sodium salt may be added.

However, the preferred electrolyte is sodium silicate. Alkaline earth metals are normally present when the active ingredient contains an olefin sulfonate irrelevant to the presence of alkaline earth metals but a surfactant such as a nonionic material.

It is also less preferred, but may be selected from among salts of potassium, ammonium, lower amines, alkanolamines or mixed cations. Sodium sulfate at concentrations above 3% causes undesirable crystallization upon storage. It is preferred that at least two-thirds of the total weight of the active ingredients are separated in at least one major aqueous liquid phase to form a phase and at least 75%, i.e. at least 80%, is separated. The concentration of the active ingredient contained in the main aqueous liquid phase is generally 10% by weight or less, preferably 7%, more preferably 5% or less by weight ratio, that is, about 2% or less.

Most of the most effective compositions of the present invention have a concentration of the active ingredient dissolved in the main aqueous phase of 1% or less, that is 0.5 or less. The concentration of solids dissolved in the main aqueous liquid can be measured by separating the aqueous liquid sample, i.e., centrifuging to form a clear aqueous liquid phase, and then evaporating the separated layer at a temperature of 110 ° C. to leave only a constant amount.

Stabilization of Suspended Solids

The solid particle size was made smaller than the particle size where sedimentation occurs. The critical maximum of the particle size varies depending on the density of the particles and the density of the continuous phase and the yield point of the composition.

The composition according to the present invention preferably contains a particle growth inhibitor.

This particle growth inhibitor is attached to the surface of the crystalline solid phase of suspended slightly soluble solids and prevents further solids from settling in the saturated solution of the main aqueous liquid. Typical particle growth inhibitors include sulfonated aromatic compounds. For example, alkylbenzene sulfonates, such as sodium dodecylbenzene sulfonate, which are present as surfactants, are themselves particulate inhibitors and can sufficiently maintain the particle size of the enhancer within the desired size range without the addition of stabilizers. In addition, lower alkyl benzene sulfonates such as sodium xylene sulfonate and sodium toluene sulfonate may be added to the liquid detergent as a hydrotrop, and may also stabilize.

However, in the present invention, the addition of lower alkylbenzene sulfonates is less preferred. Sulfonated naphthalenes, in particular methylnatalenesulfonate, are effective particulate spermatide inhibitors. However, this is not desirable in terms of cost since it is not a normal component of the cleaning composition.

Another particle growth inhibitor is a water-soluble polysaccharide derivative such as sodium carboxymethyl cellulose, which is often included in the cleaning composition as a soy anti-redeposition agent.

It is present in the composition of the present invention in a small amount sufficient to perform its normal function in the detergent composition and to aid in stabilization of the suspension, but insufficient to significantly increase the viscosity of the main aqueous liquid phase to reduce the fluidity of the composition.

Another particulate inhibitor which may optionally be included in the composition according to the invention includes sulfonated aromatic dyes, in particular sulfonated optical aromatic brighteners which are sometimes included in powder formulations. Typical examples include 4, 4'-bis (4-phenyl-1, 2, 3-triazol-2-yl-2, 2'-styrenebendisulfonate and 4, 4'-diphenylvinylene-2, 2'-biphenyldisulfonate etc. These particle growth inhibitors can be added instead of adding sulfonated surfactant.

Other effective particle growth inhibitors include _{lignosulfonate} and C _6-18 alkanesulfonate surfactants, which may also be present as part of the amount of surfactant contained in the composition. .

It is also desirable to add agglomeration inhibitors. Sodium carboxymethyl cellulose may be used as an inhibitor for use in accordance with the present invention. For example, sodium carboxymethyl cellulose preferably contains an effective accumulation inhibitor chemically distinguishable from the particle growth inhibitor, despite performing both functions of particle growth inhibition and accumulation inhibition.

It is preferable to add a particle growth inhibitor to the cleaning composition, and then add an accumulation inhibitor to prevent the particle growth inhibitor from first adhering to the solid particles, thereby increasing them, and then adding an accumulation inhibitor to prevent the particles from being deposited. . Less preferred, but other antidepressants that may be used include polyacrylates and other polycarboxylates, polyvinylpyrrolidone, carboxymethyl starch and lignosulfon trisalts.

The concentration of the particle growth inhibitor and the anti-inhibitor can vary greatly depending on the nature of the compound used as the inhibitor, the nature of the dispersed solids and the proportion of solid particles and whether the compound is additive in the composition. For example, the alkylbenzene sulfonate is preferably contained in the ratio of the above-mentioned degree in consideration of the ratio of surfactant.

If a certain formulation with a flowable composition is to be matched, although a fairly high proportion of up to 3 or 5% is not excluded, the preferred proportion of sodium carboxymethyl cellulose is preferably 2.5% by weight of the composition, more preferably by weight. 0.5-2%, or 1-2.

Sulfonated optical brighteners can usually be present in the weight ratio of about 0.05-1%, i.e. on the order of 0.1-0.3% and, although less preferred, even higher proportions, i.e. up to 5%, may be present in the appropriate composition.

Alkalinity

The composition according to the invention is preferably alkaline, preferably buffered with an alkaline buffer selected to be at least pH8, i.e. at least 9 and most preferably at least 10 in a cleaning solution containing a composition diluted to a dry weight of 0.5%. Although compositions with higher alkalinity are commercially acceptable, they reduce the pH of 100 mls of diluted composition solutions containing 0.5% dry weight to 9 N / 10 HCl 0.4-12 mls, preferably 3-10 mls. It is desirable to have a sufficient amount of free alkalinity that requires. Although generally not excluded from the scope of the present invention, low basicity is less desirable for commercial use. It is preferable to use sodium tripolyphosphate as the alkaline buffer, and the alkalinity is preferably provided at least in part by sodium silicate. Other less preferred alkaline buffers include sodium carbonate.

Solubilizer

To date, liquid detergent compositions usually contain significant concentrations of organic hydroxy solvents or hydrotropes that are compatible with water such as methanol, ethanol, isopropanol, glycols, polyethylene glycols and polypropylene glycols. Such additives are often needed to stabilize the formulation of Group I.

However, in Group II and III formulations of the present invention, they may have destabilizing effects, often to maintain stability, and often require the addition of an additional amount of electrolyte to maintain stability. In addition, they are expensive and are not active ingredients. However, in some circumstances they may increase the concentration of oil.

It is therefore advisable to ensure that only the minimum amount necessary to ensure proper fluidity is present without total exclusion of these in the overall composition according to the invention. If you don't need it, don't add it.

Paywood

Selection of the appropriate payload is generally important to achieve the desired stability and flow. The optimal payows vary considerably with the form of the formulation. Some forms of formulation can be added with up to 30% payload, sometimes up to 25%, to obtain a composition in non-settled form. However, in general, if the payload is added below 35% by weight, it is not certain that the composition will not settle. In particular, soap-based formulations were obtained in up to 25% payload, i.e. 24% concentrate.

Lowering the payload to around 20% does not mean that such formulations will not be produced. Referring to the prior art of forming stable compositions at low payloads, it has not been possible to provide sufficiently stable suspensions that have been limited to particular formulations with specific stabilizers or that meet normal commercial standards.

The range of payload in the formulation given by the present invention may be defined within the range that allows the composition to stabilize and fluidize. Generally, sedimentation occurs below this range and too much viscosity occurs above this range. The acceptable range of payload for a given formulation is to prepare a suspension with the minimum amount of water necessary to keep the composition in a confused state, then gradually dilute several samples and then, for an appropriate period of time, It can be measured by observing the degree of sedimentation that appears in each sample.

The range of acceptable payloads in some formulations may extend by 30 or 35% -60 or 70% with respect to the weight of the other composition, and may be as narrow as 40-45% (by weight).

If the method described above cannot determine a stable and fluid range, the formulation can be modified by adding sodium silicate solution or other electrolyte.

In the formulation of group III, the yield point is usually increased as the payload is increased. For these Group III formulations the minimum stable paylow generally coincides with a yield point of about 10-12 dyne / cm ² .

quite

The compositions according to the invention can be easily prepared by stirring together all the components. However, some types of formulations according to the present invention do not fully stabilize without stirring the composition longer or harder. In some extreme cases it is necessary to grind the solids contained in the product in the presence of a liquid phase. In this case, a colloid mill is used, but this is not usually necessary.

In some cases, high viscosity products are produced only by mixing at high sheer rates. The order and conditions of mixing the components sometimes play an important role in preparing a stable mixture in accordance with the present invention. Water, sodium dodecylbenzene sulfonate, coconut monoethanolamide, sodium tripolyphosphate, sodium silicate, sodium carboxymethyl cellulose and optical brightener were not stabilized in the above-described order so that the dry weight was about 45%. After mixing, when the last step is added by mixing coconut monoethanolamide and sodium tripolyphosphate, a stabilized composition is formed.

A general and suitable method for preparing a stable mixture from a formulation that can provide a stable mixture is concentrated (ie 30-60%, preferably 45-50%) aqueous silicate solution or the non-interface required for the formulation. The active ingredients or their hydrates are mixed in concentrated form with a concentrated solution of the non-surfactant electrolyte. After mixing as described above, the reprecipitation inhibitor, the optical gloss agent, and other components containing the foaming agent may be added, and then, when it is not necessary to add the initial electrolyte solution, the last enhancer may be added. Sufficient amount of water is added to keep the composition uniform in the fluid during mixing. If all active ingredients are present, the mixture is diluted to provide the required payload. Usually mixing is carried out at ambient temperature to ensure proper dispersion. Certain components, such as non-ionic surfactants such as coconut monoethanolamide, require a warm temperature of about 40 ° C. for proper dispersion. This warmth can generally be obtained by the heat of hydration of sodium tripolyphosphate. Allowing it to warm sufficiently causes a transformation called phase I by adding tripolyphosphate salts in the form of anhydrides contained at sufficiently high proportions at high temperatures.

The method described above describes only one method among the various ways in which most of the compositions according to the invention can be used satisfactorily. Some formulations are more sensitive to the mixing temperature and the order of mixing than others.

Formulation Form

Formulation forms according to the invention usually belong to one of the following forms; (A) an anionic form, not a soap, in which the active ingredient may contain small amounts of non-ionic surfactants, preferably consisting primarily of sulfated or sulfonated anionic surfactants; (B) Soap-based cleaner, consisting of an active ingredient in which a substantial portion of the soap, more preferably most of the soap, together with any nonionic or sulfated or sulfonated anionic surfactant. (C) Non-ionic surfactants comprise a major proportion of the active ingredient and may contain small amounts of anionic surfactants, soaps, cationic fabric softeners or amphoteric surfactants (surfactants having both acidic and alkaline properties). Non-ionic form.

The above described forms are not exhaustive descriptions of the list of formulation forms according to the invention which also contain other forms which are not separately described as above.

Considering another form of the preparation form according to the present invention in more detail, even in the "A" form, it is possible to distinguish between the form of the sulfate form or sulfonate form having a high foaming form and the form of the form "A" form having low foamability. Formulations of the "A" form with high foaming properties are either C _10-14 linear or branched alkylbenzenesulfonate itself or C _10-18 alkyl sulfate or C _10-20 alkyl 1-10 mole ether sulfate. It can be prepared as a mixture. A small amount of soap (approximately 1% by weight of the composition) can be added to allow the fabric to be aidrinsing. Nonionic and effervescent boosters and stabilizers, ethoxylated alkylphenols, fatty alcohols or the like, such as C _12-18 acyl (ie coconut) monoethanolamide or diethanolamide or ethoxylates thereof. Ethoxylates and the like can be used as effervescent boosters or stabilizers that account for up to about 6% of the dry weight in the composition.

The sodium alkylbenzenesulfonates contained in the formulations described above may be substituted with fatty alkyl xylenes or other sulfonated surfactants containing toluenesulfonates, ie sulfonesuccinates and sulfosuccinates, alkyls. Alkyl ether sulfates (preferably) containing phenyl ether sulfates, fatty acyl monoethanolamide ether sulfates or mixtures thereof, alkyl sulfates, paraffin sulfonates and olefin sulfonates, sulfocarboxylates and their esters and amides, etc. Can be replaced in whole or in part.

Therefore, according to a particular embodiment the present invention is water; Surfactants accounting for about 15-60% of the dry weight in the composition, at least partially present as a lamellar separated phase; A non-settling, flowable detergent composition comprising suspended solids, an enhancer or the like comprising at least partly 20-80% of the dry weight, present in the composition, wherein the surfactants contained in the composition are composition dry. It consists of sulfated or sulfonated anionic surfactants optionally containing a small proportion of nonionic blowing agents, foam stabilizers, and soaps, accounting for up to 6% of the dry weight of the composition.

Sulfated or sulfonated anionic surfactants preferably consist of alkylbenzenesulfonates, more preferably sodium alkylbenzenesulfonates, ie C _10-14 alkylbenzenesulfonates. In the absence of effervescent boosters, it is preferred that the proportion of alkylbenzenesulfonate is about 20-60%, ie 30-35% of the dry weight of the composition. Other anionic surfactants include alkylbenzenesulfonates and alkyl sulfates, alkyl ether sulfates or alkylphenyl ether sulfates in a weight ratio of 1: 5-5: 1, usually 1: 2-2: 1 preferably 1: 1.5-1.5 ; It may consist of a mixture of 1, that is, about 1: 1. In the latter case, in the absence of an expandable booster, the total anionic surfactant preferably accounts for 15-50%, or 20-40%, of the dry weight of the composition.

Alkyl sulfates and alkyl ether sulfates used for mixing with alkylbenzenesulfonates usually have an average of 0-5, or 1-2 ethyleneoxy groups per molecule of sulfate. In another "A" form, the anionic surfactant consists essentially of alkyl sulfates or alkyl ether sulfates. In the absence of an expandable booster, the total concentration of the active ingredient may be about 15-50% of the dry weight of the composition. Active ingredients usually contain an average of 0-5, ie 0.5-3, ethyleneoxy groups per molecule of sulfated surfactant. The fatty alkyl chain is preferably about _10-20 C. The longer the chain is, the higher the ethylene-oxy content is.

The form described above can be changed by replacing part or all of the anionic active ingredient, and sulfated or sulfonated anionic surfactants are classified as described above. Soap may also be added to the detergent formulation described above to help rinse the fabric. Soap used for this purpose is preferably contained in a dry weight ratio of the composition in a concentration of about 0-6%, preferably 0.1-4%, that is 0.5-2%. Soap is preferably used in an amount of 25% or less of sulphated and sulfonated total surfactant of 10% or less to prevent foaming.

Effervescent boosters and stabilizers can be combined with any of the above highly effervescent anionic cleaners. Effervescent boosters or stabilizers are usually nonionic surfactants such as coconut monoethanol amides or diethanolamides or their ethoxylates, alkyl phenol ethoxylates, fatty alcohols or their ethoxylates or fatty acid ethoxylates. C _10-18 alkyl. Effervescent boosters or stabilizers can be added up to 20% of the dry weight in the composition, i.e. 0.1-6%, preferably 0.5-4%, and are highly foamable by adding an expandable booster or stabilizer. It can reduce the total concentration of the active ingredient contained in. Compositions comprising effervescent boosters or stabilizers and alkyl benzenesulfonates contain 25% alkylbenzene sulfate with a nonionic surfactant of 15-40%, preferably 20-36%, i.e., 4% by weight of the composition. It may also contain low proportions of anionic surfactants and high proportions of non-ionic surfactants and vice versa. As described previously, other formulations of sulfated or sulfonated anionic surfactants can similarly reduce the concentration of active ingredients by containing foamable boosters and stabilizers.

The enhancer is preferably sodium tripolyphosphate, optionally but preferably used with trace amounts of soluble silicates, although another enhancer described above may be used instead as a mixed enhancer. The proportion of enhancer contained in the formulation of form "A" is at least about 30%, preferably about 35-85%, ie about 40-80% of the DM weight of the composition. Particular preference is given to the proportion of enhancers which comprise about 50-70% of the dry weight.

The ratio between the enhancer and the active ingredient is preferably 1: 1 or more, preferably 1.2: 1-4: 1, or 1.5: 1-3: 1.

Formulations of the less foamable "A" form generally differ from the presence of sulfated or sulfonated anionic surfactants, which are contained in lesser proportions than those contained in the more foamable form, and the presence of many but still small amounts of soap. It depends on the addition of phosphate esters, which are crystalline silicones or foam inhibitors.

The present invention therefore provides, according to a second specific embodiment, a non-settling, flowable, aqueous based detergent composition containing an electrolyte solution and suspended enhancer particles, consisting primarily of an aqueous phase, which composition is based on dry weight. 15-50% active ingredient, at least 30% enhancer (the ratio of enhancer to active ingredient is at least 1: 1) and conventional minor ingredients, wherein the surfactant is 15-50% of the dry weight of the composition And a sulfated or sulfonated non-ionic surfactant which comprises% and an effective amount of at least one antifoam.

Antifoaming agents are soaps that are 20-60% of the weight of sulfated or sulfonated anionic surfactants, C _16-20 alkyl nonionic antifoams, 10% of the composition dry weight, C Preference is given to selecting among _16-20 alkyl phosphate esters and silicone antifoams.

The action of soap as an antifoaming agent depends on the ratio of soap to sulfated or sulfonated anionic surfactants. A ratio of 10% or less is not effective as an antifoaming agent but is useful for aiding in rinsing in highly foamable cleaning compositions. The minimum ratio required for the soap to act as an antifoam is about 20% of the sulfated or sulfonated surfactant. If the ratio of soap to sulfated or sulfonated surfactant in the "A" type of detergent is 60% or more by weight, its function as an antifoaming agent is reduced. Therefore, it is desirable that the ratio of soap to the weight of the sulfated or sulfonated surfactant is 25-50% or 30-45%.

The less foamable "A" type surfactant may contain a nonionic foam inhibitor instead of a soap, such as C _16-20 acyl monoethanolamide (ie, rape monoeth -anolamide). , C _16-22 alkyl phenol _ethoxylates , C _16-22 alcohol _ethoxylates or C _16-22 fatty acid _ethoxylates .

The composition may also contain mono or di C _16-22 alkyl phosphate esters of alkali metals. Foam inhibitors, which are nonionic or phosphate esters, are present in the formulation up to about 10% based on dry weight, preferably about 2-8%, ie 3-4%.

It is also possible to use a silicone foam inhibitor as part of the foam inhibitor or foam inhibitor. The effective amount of this silicone antifoam can be contained in the formulation is generally less than when using the other forms of antifoam described above. It is usually in an amount of 2% or less, preferably 0.1% or less, usually about 0.01-0.05%, that is, about 0.02% of the dry weight of the formulation.

It is preferable to include conventional trace ingredients in the "A" form of the formulation, and may also include fabric softeners such as clay, but such cationic fabric softeners are not effective for formulations based on anionic bases. However, sometimes it may be included in a specially formulated system.

Formulation form "B" according to the present invention contains soap as the main active ingredient. In addition to this, a small amount of nonionic or anionic surfactant may be contained.

The percentage of dry weight contained in the formulation of form B "is usually less than the dry weight of form" A ", ie, 25-60%, preferably about 29-45%. The overall proportion of active ingredient is usually 10-60%, preferably 15-40%, or 20-30% of the dry weight of the composition and the proportion of the enhancer is usually about 30-80% of the dry weight. The addition of an electrolyte, in particular sodium silicate, can improve the mobility of the formulation in the form of "B".

Highly effervescent soap formulations usually contain small amounts of nonionic effervescent boosters or stabilizers or anionic sulfate boosters, such as alkylether sulfates or alkyl ether sulfonesuccinates, as described with respect to the "A" form. It may also contain an active ingredient substantially composed of a soap which can be contained. The low form of the B-form formulation may contain a small amount of sulfated or sulfonated anionic surfactant, non-ionic phosphate ester antifoaming agent or silicone antifoaming agent together with low concentration of soap. The relationship between sulfated or sulfonated anionic surfactants and soaps in the less foamable "B" type formulations is contrary to the relationship contained in the less foamable formulations in the "A" form. In the "B" form of formulation, sulfated or sulfonated anionic surfactants act as inhibitors when present in a proportion of about 20-60% by weight of soap.

Nonionic phosphate esters and silicone antifoam agents are substantially as described with respect to the "A" type of detergent.

The detergent of type "B" may contain conventional trace components. As in the case of the formulation of Form A, cationic fabric softeners are usually not included, but other fabric softeners may also be included.

Detergents based on nonionic bases of the "C" form are an important part of the present invention. There is a tendency to use non-ionic surfactants in laundry detergents because of the increased proportion of man-made fibers in normal washing. Nonionic detergents are particularly suitable for washing artificial fibers. However, non-ionic liquid cleaners are not yet commercially available because they are not commercially acceptable.

The field of powder cleaners also limits the selection and level of nonionic surfactants. Most of the detergent formulations according to the invention described earlier in this specification are designed to provide a stable, flowable liquid detergent composition having the same washing ability as that seen in the form of a powder formulation. It can be easily formulated into a powder. To date, however, it has not been satisfactorily formulated as a specific form of even a desired nonionic base cleaning agent, even as a powder. The reason for this is that "solid" compositions containing significantly higher proportions of the required nonionic surfactants sometimes form sticky powders that do not flow freely and can cause problems in packaging and storage. Therefore, such surfactants had to be limited to less than the optimum ratio of detergent powder, or to low paywood or dilute or liquid formulations.

Accordingly, the present invention provides a liquid detergent composition with a non-settling and flowable aqueous base composed of at least one main liquid aqueous phase, at least one other phase containing a surfactant and an enhancer, according to a particular preferred embodiment. , The composition consists of 10-50% active ingredient and 30-80% enhancer based on dry weight, in which case the active ingredient is nonionic surfactant with at least 10-18 HLB by weight of the majority Consists of

The surfactant is preferably present in a separable hydrated solid or liquid crystalline phase.

Nonionic surfactants or mixtures thereof described earlier in this specification can be used in accordance with the specific description of the present invention. Although the branched or unsaturated hydrocarbon group is not excluded, the surfactant is preferably composed of C _12-18 alkyl groups (usually straight chain). It is preferred that the nonionic surfactant has an average HLB of 12-15.

Preferred nonionic surfactants contained in C form formulations are fatty alcohol ethoxides. In the highly foamed C-form formulation, an anion with C _12-16 alkylanions having 8-20 ethyleneoxy groups, alkylphenol ethoxylates having 6-12 aliphatic carbons and 8-20 ethyleneoxy groups Surfactants, preferably sulfated or sulfonated anionic surfactants, such as alkyl benzene sulfonates, alkyl sulfates, alkylethersulfates, paraffin sulfonates, olefin sulfonates or other sulfated or sulfonated compounds described above A small amount of surfactant, i.e., about 0-20% by the dry weight ratio of the composition, is preferably contained without a significant amount of the antifoaming agent. However, in this formulation, stabilizers such as nonionic foam boosters or C _10-18 acyl monoethanolamide may be contained in the proportions described above for the formulation of Form A. It is preferable that all nonionic active ingredients have 12-15HLB.

Particularly preferred is a non-ionic composition having low foamability according to the present invention. These compositions have a preferred HLB of 12-15, and 10-C _12-18 alkyl 5-20 mole ethyleneoxy nonionic surfactants such as fatty alcohol ethoxides, fatty acid ethoxides or alkylphenol ethoxides. It is preferable to contain about 40% (based on the dry weight of a composition). These compositions may contain up to 10% by weight of the composition of sulfated or sulfonated anionic surfactants, as described above with respect to the "A" type of cleaning agent, and these compositions also contain low foaming "A It contains foam inhibitors such as mono-, di- or trialkyl phosphate esters or silicone foam inhibitors as described above for the "type of cleaner.

Formulation forms of the “C” form may also contain customary minor ingredients.

In particular, the nonionic base cleaning agents of the present invention may be mixed with cationic fabric softeners. Cationic fabric softeners may be added to the formulation in the form of “C” in a weight ratio of 1: 1.5 to 1: 4, preferably 1: 2 to 1: 3, based on the nonionic surfactant. Cationic fabric softeners are cationic surfactants having two long chain alkyl or alkenyl groups, usually two C _16-20 alkyl or alkenyl groups, preferably two tallowyl groups. For example, di C _12-20 alkyl di (lower, ie C _1-3 , alkyl) ammonium salts, ie ditallowyl dimethylammonium chloride, di (C _16-20 alkyl) benzalkonium salts, ie di tallowyl methyl Benzyl ammonium chloride, di C _16-20 alkylamidoimidazolines and di C _16-20 acyl amido amines or quaternary aminoamines, ie bis (tallow amido ethyl) ammonium salts.

It is preferred that formulations containing cationic fabric chlorides contain no sulfated or sulfonated anionic surfactants or soaps. However, this formulation can contain up to 3%, preferably up to 2%, of anionic phosphate ester surfactants, based on the weight of the composition. The formulation may additionally or alternatively contain small amounts of amphoteric surfactants such as betaine and sulfonbetaine in weight ratios of about 3%, preferably 1-2%, and also smectic clays and Ordinary minor components may be contained.

Trace ingredients

The composition according to the present invention may contain conventional trace components. Important among them are antideposition agents, optical varnishes, and bleaches.

The most commonly used de-deposition agent in the preparation of cleaning agents is sodium carboxymethyl cellulose (SCMC), which is a conventional amount in the compositions of the invention, not less than 0.1% but not more than 5%, ie 0.2-4%, in particular 0.5-2% Preferably in an amount of about 0.7-1.5%. In general, SCMC is effective at a concentration of about 1%, and it is preferable not to exceed much of the usual effective concentration because a large amount of SCMC significantly increases the viscosity of the liquid composition. In the high ranges described above, such as on the order of 4-5%, most formulations cannot be obtained in flowable form at high payloads. Re-deposition inhibitors and stain removers include methyl cellulose, polyvinylpyrrolidone, carboxymethyl starch, and similar polyelectrolytes, all of which may be used in place of SCMC, like other water-soluble salts of carboxymethyl cellulose.

Optical varnish (OBA'S) is optional but is a preferred component of the composition according to the invention. Unlike some prior art formulations, the compositions of the present invention do not rely on OBA for stability. Therefore, the choice between choosing a convenient and cost-effective OBA or simply omitting them is free. It has been found that the fluorescent dyes recommended so far for use as OBAs in liquid detergents can be used like many dyes suitable for use in powder cleaners. OBA may be present in conventional amounts. However, it has been found that in some liquid cleaners (ie, C form formulations), OBA tends to be slightly less effective than in powder cleaners. Therefore, it is desirable to add these at slightly higher concentrations compared to powder formulations. Typical concentrations of OBA are 0.05-0.5%, ie 0.075-0.3%, especially 0.1-0.2%. Low concentrations may also be used but are not effective, while high concentrations may also be used but may not be effective in terms of cost and in some cases may cause compatibility issues.

Representative examples of OBAs that can be used in the present invention are as follows. Ethoxylated 1,2- (benzimidazolyl) ethylene; 2-stynylnaph [1,2 di-] oxazole; 1,2-bis (5'-methyl-2 benzoxazolyl) ethylene; Disodium-4,4'-bis (6-methylethanolamine-3-anilino-1,3,5-triazine-2 "-yl) -2,2'-stilbenesulfonate; N- (2 Hydroxyethyl-4,4'bis (benzimidazolyl) stilbene; tetrasodium 4,4'-bis [4 "-bis (2" -hydroxyethyl) -amino-6 "(3" -sulfo Phenyl) amino-1 ", 3", 5 "-triazine-2" -yl amino] -2,2'-stilbenedsulfonate; disodium-4- (6 "-sulfonapto [1 ', 2 '-Di] triazol-2-yl) -2-stilbenesulfonate; disodium 4,4'-bis [4 "-(2"'-hydroxyethoxy) -6 "-amino-1", 3 ", 5" -triazine-2 "-ylamino] -2,2'-stilbendisulfonate; 4-methyl-7-dimethylaminocoumarin; and alkoxylated 4,4'-bis (benzimida) Sleepy) steelbene.

Bleaches may be optionally mixed with the liquid detergent compositions according to the invention subject to chemical stability and compatibility. Encapsulated bleach may be formed as part of suspended solids.

The action of the peroxide bleach in the compositions of the present invention can be improved by adding an effective amount of a bleach activator such as tetraacetyl ethylenediamine.

Photoactive bleach such as zinc or sulfonated phthalocyanine aluminum can also be added.

Perfumes and dyes are usually added to laundry detergents in amounts of up to 1 or 2%, and similarly may be added to the compositions of the present invention. If additives are selected with normal care and compatible with the formulation, these additives do not affect the effects of the present invention.

In addition to enzyme stabilizers and carriers, proteases and starches may be added in conventional amounts. Enveloped enzymes may also be suspended.

Other trace ingredients include fungicides such as formaldehyde, milky ones such as vinyl latex emulsions, and anticorrosive agents such as benzotriazole.

In general, the composition according to the present invention is suitable for washing, and the present invention provides a method for washing clothes by stirring the clothes in the cleaning solution containing the composition of the present invention described above. The above-mentioned compositions having low foaming properties are particularly useful for automatic washing machines. The composition can also be used for washing dishes or for washing hard surfaces, and less foamy products are particularly suitable for use in dishwashers. These uses constitute another feature of the present invention.

In general, the compositions according to the invention can be used for washing clothes in suspended water or for washing at intermediate temperatures such as 50-80 ° C, in particular 55-68 ° C or at cooling temperatures such as 20-50 ° C and especially 30-40 ° C. Can be. Typically, the composition may be added to the wash water such that its dry weight is 0.05-3%, preferably 0.1-2%, more preferably 0.3-1% (ie 0.4-0.8%), based on the wash water. Can be.

The invention will be explained in more detail in the following examples. All figures described in the examples are given in weight percent based on the weight of the entire composition, unless otherwise noted.

Composition of various feedstocks

1.C ₁₀ -C ₁₄ Linear Alkyl Benzene Sulfonate

Alkylbenzene sulfonates used in all formulations are the sodium salts of the polymeric para-sulfonated "dobane" JN materials (Dovane is a registered trademark).

The composition is as follows.

C ₁₀ C ₁₁ C ₁₂ C ₁₃ C ₁₄ C ₁₅

13.0 27.0 27.0 19.0 11.0 1.0

This composition only relates to the alkyl chain length.

2. Coconut Monoethanolamide

It consists of RCO (NHCH ₂ CH ₂ OH).

R in the formula is as follows.

3. Sodium alpa olefin sulphonate

This material is a sulfonated C ₁₆ / C ₁₈ olefin sodium salt having approximately the following composition.

55.0% C ₁₆ Terminal Olefin

45.0% C ₁₈ terminal olefin

4. C ₁₂ -C ₁₈ +8 moles of ethylene oxide

This material is an average of 8 moles of ethylene oxide condensate with an alcohol having the following composition:

C ₁₀ 3.0%

C ₁₂ 57.0%

C ₁₄ 20.0%

C ₁₆ 9.0%

C ₁₈ 11.0%

5.C ₁₄ -C ₁₇ n-alkane sulfonate sodium

This material was prepared by neutralizing sulfonated C ₁₄ -C ₁₇ normal paraffin with sodium hydroxide and contained about 10% disulfonate based on the total active ingredient.

6.C ₁₂ -C ₁₈ Sodium Sulfate

This substance is the sodium salt of fatty alcohol sulfuric acid with the following composition:

C ₁₀ 3.0%

C ₁₂ 57.0%

C ₁₄ 20.0%

C ₁₆ 9.0%

C ₁₈ 11.0%

7. Sodium tripolyphosphate

This material was added as anhydrous Na ₅ P ₃ O ₁₀ containing 30% phase I but crystallized as hexahydrate.

8. Sodium Silicate

This material was added to the formulation as a viscous aqueous solution containing Na ₂ O: SiO ₂ = 1: 1.6 and containing 47% solids.

9. Optical polish

Optical brighteners for Examples 51-54 are the disodium salts of 4, 4 '[di (styryl-2-sulfonic acid) binenyl, sold under the trademark "TINOPAL CBS-X", and are optical for Examples 1-50 The brightener is a mixture of disodium salt of 4.4 '-[di (4-dichlorostyryl-3-sulfonic acid] biphenyl sold under the trademark "TINOPAL ATS-X" with the above optical brightener.

week

All alcohols mentioned and their ethylene oxides are linear in their primary form.

All examples were prepared by adding a surfactant as a hydrated solid to 47% solution of silicate. The other ingredients were then added in the order indicated from the top to the bottom of the table. Only major enhancers are added last. A small amount of water was added as needed to maintain a fluid homogeneous system at each stage. Finally, the composition was diluted to the desired dry weight percentage. All processes were carried out at temperatures as close to atmospheric as possible to ensure that the components were properly dispersed. For Examples 25, 26, 27 and 28, concentrated aqueous solutions of the electrolyte (ie sodium sulfate, sodium chloride and potassium carbonate, respectively) were used in place of the silicate solution in the process. In some cases, especially when using relatively high melting point nonionic surfactants such as coconut monoethanol amide, it is necessary to slowly heat up to 40 ° C. to achieve complete dispersion. In all examples in which sodium tripolyphosphate is used in practical amounts, the temperature is achieved by heat of hydration without external heating.

In Examples 1 and 2 represent Aa formulations of the basic form, 3 and 4 represent Form A formulations with SCMC and optical brightener, and 5 (a), (b) and (c) are three different Represents Form A formulation in payload, 6 and 7 demonstrate that SCMC or optical brighteners are not essential to obtain a non-settling formulation and 8 represents anticorrosive and fragrance. 9 (a) and (b) represent the ratio of the active ingredient (3: 1) to the formulation-enhanced high-enhancer in the two payloads, and 10 (a) and (b) represent the two payloads. Non-precipitating formulations obtained by centrifuging the formulation of Example 9 for only 3 hours at low paywood and then decanting the supernatant in the low paywood Type, with 12 representing a relatively high SCMC level effect, and 13-19 for each Form A forms containing anionic surfactants, 20-24 describe various electrolytes, 25 form a formulation in which sodium tripolyphosphate is a single electrolyte, and 26-31 represent various enhancers and mixtures thereof. As described above, 32 denotes a time when there are a lot of enhancers in the active form, 33 denotes an enzyme-type formulation, 34 contains a hydrotrop, 35 denotes a triethanolamine salt as a surfactant, , 36-38 show the inclusion of olefinsulfonates and 39-42 show the formulation of paraffin sulfonates (each with a continuously increased electrolyte).

43-46 describe Form B formulations, and 43 describe Form B formulations in three different payloads. 47 corresponds to Form B formulation obtained after centrifugation of 43 for 3 hours in low paywood, 48-49 represents Form A and Form C with less foaming, respectively, A type C formulation, 55 is a Form C formulation with a cationic fabric softener, 56 represents a branched alkylbenzene sulfonate, 57 represents a coconut diethanolamide, and 58 represents a nonionic glass formulation. 59 and 60 describe the use of phosphate enhancers, and 61-62 relate to particularly suitable formulations marketed in various parts of the North American market, each with a phosphate free formulation and a high phosphate formulation. , 63-66 are formulations suitable for the needs of specific Asian markets.

Comparative Examples A and B show two commercial formulations currently available on the Australian and European markets, respectively. The former corresponds to Australian patent 522983 and the latter corresponds to European patent 38101. The materials used in each comparative example are commercially available, with the exception of samples produced according to the examples of the appropriate patents conforming to the commercial formulation as analyzed and neutron dispersion results using deuterium oxide instead of water. Is the same substance. Example A is substantially the same as Example 1 of Australian Patent 522983. Example B is close to Example 1 of the European patent, and samples were prepared for neutron dispersion according to this European patent example. According to the analysis, the composition was as follows.

3. Test result of Example

Various tests were carried out in the above-described examples, and the results are described in the following table.

Note: The phases separated from the centrifugation test were numbered from the bottom (ie close layer) upwards.

Several of the above-described examples were used to test the washing ability as follows.

Step 1

Machine wash tests on two different stained standard fabric samples were used to compare representative foam formulations with standard foam formulations.

By "effective detergent solids" is meant the sum of the active ingredient and the enhancer. Standard powder was used at about 6 g / l, these examples were adjusted so that the same percentage of the effective detergent solids in the detergent solution.

Step 2

Representative formulations of high foamability and low foamability were tested in equal amounts (wt) at three temperatures.

Conditions: Temperature, 40 °, 60 ° and 85 ° C. +

Water: 300ppm hardness

Time: 30 minutes

Concentration: 6 g / l (approved)

Step 3

In this step, examples of non-ionic bases with low foamability were tested against standard powders.

Condition: temperature; 50 ℃

Water; 300 ppm hardness

time ; 30 minutes

Concentration; Powder 6g / l

Example 11 g / l

Step 4

Naturally stained fabrics were tested using two non-ionic formulations with low foaming (naturally stained 15 consecutive washes).

Condition: temperature; 50 ℃

Water; 300 ppm hardness (wash and hem)

Washing time; 30 minutes

Textile; White polyester: cotton (65: 35)

Concentration; Equivalent weight (ie 6 g / l)

result :

Example

52 = 100% Std)

54 = 75% Std) optical white efficiency

52 = 95-100%)

54 = 95-100%) Stain removal and deposition efficiency

Two examples were also compared to the three liquid laundry products most commonly used in this test among those commercially available in Europe at the time of this test.

Both examples gave good washing efficacy for all three commercial products.

1 through 11 are neutron shot spectra illustrating the different groups described above. All were prepared using Howell's Incinerator Neutron Scattering Spectrometer at a wavelength of 6.00 kHz using homologs based on the deuterium oxide base of certain examples of the invention and two comparative examples.

Q is the reciprocal Angstorm unit and is equal to 2TT / d, where d is the distance between the grids expressed in Å units. I is the intensity expressed in neutron coefficients. Each drawing corresponds to the following embodiment.

Drawing Example

1 5 (a)

2 18

3 21

4 25

5 39

6 36

7 50 (b)

8 53

9 52

10 A (comparative example)

11 B (comparative example)

Figures 12-18 are electron micrographs taken with a Lancaster University cold scanning electron microscope using a freeze crushed corrosion sample as follows.

17 and 18 relate to the actual commercial product as purchased.

Claims (31)

At least one dispersed solid phase containing at least 25% by weight of payload and primarily an aqueous first liquid phase containing a dissolved surfactant that dissolves the electrolyte and an enhancer, wherein the dissolved electrolyte is at least one Containing at least 25% by weight in the first phase of a dispersed effective ingredient which comprises a concentration sufficient to provide a different phase of and which can be separated by centrifugation 800 times at 25 ° C. for 17 hours under normal gravity and is non-settling A flowable, non-settling, aqueous based detergent composition comprising a sufficient amount of water to supply a payload higher than the lower limit and lower than the upper limit of the flowability. When centrifuged 800 times at 25 ° C. for 17 hours under normal gravity, the solution was composed of a predominantly aqueous liquid layer containing dissolved electrolyte, at least a certain amount of solid enhancer and at least one other layer containing a large amount of the active ingredient. A flowable, non-settling, aqueous based detergent composition, characterized in that it is separated and consists of water, at least 5% by weight active ingredient and at least 16% by weight enhancer. Consisting primarily of an aqueous first liquid separation phase containing a dissolved electrolyte and a significant amount of surfactant, the second separation phase interspersed with the first phase, the second separation phase interspersed with the first and second phases, and the first and second phases. Fluid and non-settling, characterized in that it comprises an organic lamellae structural component and at least 25% by weight of payloads, consisting of at least three separate phases comprising a third separate phase consisting of an enhancer of dispersed solid particles. An aqueous base cleaning composition. At least one mainly aqueous liquid separation phase; At least 25% by weight of payload consisting of at least one other phase consisting of a matrix of solid surfactant hydrates forming a thixopropy gel with the predominantly aqueous liquid separation phase and at least one other phase consisting of suspended solid enhancer particles A non-settling, flowable liquid detergent composition comprising a lowwood. (a) 25 to 75% by weight of water; (b) 5-35% by weight of surfactant; (c) an enhancer dissolved in the composition in excess of solubility so that at least a portion is present as solid particles suspended in the aqueous phase; (d) comprises some dissolved enhancer and an alkali metal ion dissolved in the aqueous phase at a concentration of 0.8 to 4.5 gm ions per liter, the concentration consisting of an electrolyte at least above the lower limit at which the surfactant is sufficiently present in the lamellae liquid crystal phase; A liquid detergent composition, characterized in that the composition comprises more than the lowest level of fluidity and less than the maximum level of composition that is non-settling. A predominantly aqueous separable first phase comprising less than 60 wt. A non-settling, flowable liquid detergent composition comprising a separable phase and consisting of water, an electrolyte, a solid enhancer, an active ingredient separated from an amino acid, a nonionic surfactant, and a mixture thereof. When centrifuged, a single liquid layer containing water and dissolved electrolyte can be separated into a solid layer comprising an enhancer and at least 25% active ingredient, essentially water, electrolyte, active ingredient, and at least 25% by weight of A non-settling, flowable liquid detergent composition, characterized in that it consists of an enhancer containing a lowwood. The liquid detergent composition according to claim 7, wherein the ratio of the total active ingredients contained in the solid layer is 90% or more by weight. 8. The liquid detergent composition of claim 7, wherein the viscosity of the liquid layer is less than 0.1 Pascal seconds. (a) 25% to 75% by weight of water; (b) 5% to 35% by weight of surfactant; (c) an enhancer suspended in the composition in excess of solubility so that at least a portion is present as solid particles; (d) containing a certain amount of dissolved enhancer and, when centrifuged at 800 ° C. for 25 hours at 25 ° C., containing an aqueous layer containing dissolved electrolyte, a liquid crystal layer containing a 'G' phase surfactant, and an enhancer. A liquid detergent composition comprising water below the upper limit at which the composition is fluid and at least below the upper limit at which the composition is non-settling, consisting of an electrolyte at a concentration above the lower limit at which the composition can be separated into a solid layer. The cleaning composition of claim 1 comprising components of an organic lamellae structure, repeated at intervals of 20-65 mm 3. The cleaning composition of claim 1, comprising at least 30% by weight of payload. The detergent composition according to claim 1, wherein the weight ratio of the enhancer to the active ingredient is 1: 1 or more. The composition of claim 1 wherein the builder comprises sodium tripolyphosphate or potassium tripolyphosphate. The detergent composition of claim 1, wherein the enhancer consists of zeolite. The method of claim 1, wherein Si

₂ of sodium silicate, based on the weight of the composition, detergent composition, characterized by containing 2-10%. The cleaning composition according to claim 1, wherein the active ingredient contains 8% or more by weight of the composition. The detergent composition according to claim 1, wherein the concentration of the surfactant contained in the mainly aqueous liquid phase is less than 25% by weight. The composition of claim 1 wherein the pH is at least 10 when dissolved in a dry weight ratio of 0.5% in the wash solution. The cleaning composition of claim 1, wherein the active ingredient consists of at least a large amount of sulfated or sulfonated anionic surfactant. 21. The detergent composition of claim 20, wherein the active ingredient accounts for 15-60% of the dry weight of the composition. A composition comprising 30-75% by weight of payload and consisting of anionic surfactants selected from sulfated or sulfonated surfactants, based on dry weight of 15-60% active weight; An electrolyte sufficient to maintain at least a large amount of active ingredient in the lamellae separation phase; And 20-80% of an enhancer based on the dry weight of the composition, at least partially present as solid particles suspended in the composition, at least a lower limit that renders the composition non-settling and also an upper limit that makes the composition fluid. A non-settling, flowable liquid detergent composition comprising a payload of. 23. The detergent composition of claim 22, comprising from 0.1% to 20% of non-ionic blowing agent based on the composition dry weight and from 0.1% to 60% soap based on the weight of the anionic surfactant. . 23. The detergent composition of claim 22, further comprising a foam inhibitor selected from non-ionic epoxidized phosphate esters or organopolysiloxanes. The cleaning composition of claim 1, wherein the active ingredient comprises at least a large amount of soap in a weight ratio thereof. Having payload of 20-60%, water; 10-55% of the active ingredient by dry weight ratio of the composition (this component mainly consists of soap); Sufficient amount of electrolyte to maintain at least a substantial amount of said active ingredient in a lamellar separation phase; A composition comprising 20% to 80% by weight dry weight of the composition, at least a portion of which is present as solid particles suspended in the composition, wherein the composition is at or above the minimum concentration at which the composition may be non-settling, and the maximum concentration at which the composition may be flowable. A non-settling, flowable liquid detergent composition characterized by containing the following payload: The method of claim 22, wherein the anionic surfactant is C 10-14 alkyl benzene sulfonate, C 10-18 alkyl sulfate, C 10-20 alkyl, 1-10 mole ethylene oxysulfate, paraffin and olefin sulfonate, sulfocarboxylate Or an ester or amide, sulfosuccinate or sulfosuccinate, alkyl phenyl ether sulfate or acyl mono ethanolamide ether sulfate thereof. 23. The detergent composition of claim 22, wherein the enhancer consists of a large amount of tripolyphosphate and a small amount of sodium silicate. The cleaning composition of claim 1, wherein the active ingredient consists mainly of a nonionic surfactant. Having payload of 30-75%, water; An active ingredient having a dry weight of 10-50% based on the composition dry weight and composed of at least most nonionic surfactants; An amount of electrolyte sufficient to maintain at least a significant amount of the active ingredient in the lamellar separation phase; At least partially suspended solid particles comprising 30-80% of an enhancer based on the dry weight of the composition, wherein the composition comprises a payload that is above the minimum concentration at which the composition is non-settling and below the maximum concentration at which the composition is fluid Non-settling and flowable liquid detergent composition. The cleaning composition of claim 1 comprising 0.5-2% of an alkali metal or ammonium carboxymethyl cellulose and an effective amount of optical varnish based on the weight of the composition.

Images