KR880001846B1 - Liquid detergent compositions - Google Patents

Abstract

Non-sedimenting, pourable, water-based detergent compsns. are claimed. One compsn. contains active ingredients and a builder, contains at least 25 wt.% of functional components, and is characterised in that it consists of a liq. phase contg. a dissolved electrolyte, at least one dispersed solid phase comprising the builder, and at least one other phase contg. the active ingredients. The compsn. is separable from the liq. phase by centrifuging at 800 G and 25≰C for 17 hr.. The compsns. are useful as laundry detergents.

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, flowable liquid detergent composition containing an effective amount of a detergent builder.

The term "builder" is sometimes used vaguely in the detergent art to include non-surfactants, which is a cleaning effect of the detergent formulation if the above non-surfactant is present in the detergent formulation. Promotes However, when the term is limited to the conventional "enhancer", the scope is first described. First, such conventional enhancers include chelation, metal ion sequestering, and precipitation. Or it is used as a means to prevent or improve the adverse effects during the cleaning action by calcium and magnesium ions by the adsorption method, secondly it is used as a source of basicity and buffering action.

As used herein, "enhancer" is used in the latter sense and is referred to as an additive to obtain a substantial degree of the effects described above.

These additives include sodium tripolyphosphate and other phosphates and concentrated phosphates such as sodium orrophosphate or potassium orrophosphate, pyrophosphate, metaphosphate or metrate, as well as acetodiphosphonates, aminotrimethyltenphosphonates and ethylene Phosphonates, such as diamine tetramethylene phosphonate, and the like. Or polycarboxylic acid polymers such as organometallic sequestrants such as alkali metal carbonates, nitrilotriacetic acid, citro acid and salts of ethylenediamine tetraacetic acid and copolymers based on zeolites, polyacrylates and maleic anhydride Etc. are included.

More specifically, the term " enhancer " used herein includes silicates of water-soluble alkali metals such as sodium silicate, and the like, but it can be used as a carboxymethyl cellulose which acts primarily as an oil-suspending agent or anti-sedimentation agent. 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, thereby lowering the micelle concentration or solubility of the surfactant in the solution by salting effect. 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 are not included. 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 alkali metals of lower alkylbenzenesulfonic acids such as sodium toluenesulfonic acid and sodium xylenesulfonic acid. And ammonium and urea and the like.

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.

"Typical trace ingredients" are components 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 ingredients include reprecipitation inhibitors, fragrances, dyes, optical brighteners, hydrotropes, solvents, buffers, bleaches, preservatives, antioxidants, preservatives, scale inhibitors, humectants, enzymes and their stabilizers, surfactants.

As described herein, "Functional Ingredient" is a component necessary to produce a beneficial effect in the cleaning liquid, and ingredients such as surfactants, enhancers, bleaches, optical gloss agents, buffers, enzymes and anti-sedimentation inhibitors, etc., which may contribute to the cleaning effect. And preservatives, but also include water, solvents, dyes, flavorings, hydrotropes, sodium chloride, sodium sulfate, solubilizers, and stabilizers that stabilize, fluidize, or otherwise impart desired properties to the concentrated formulation. I never do that.

“Payload” means payload of the active ingredient in percent of the total weight of the composition, and Active Ingredient means active surface material.

Unless stated otherwise, the term "centrifugal separation" in the present specification means centrifugation at about 800 rotational speeds 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. 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 two or more distinct phases thermodynamically, which are in stable emulsion form and are not separated from each other by 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 each element associated with the matrix when the system is stable. The discontinuous elements formed in the interaction are described to form a continuous matrix that tends to maintain the direction and position of.

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 silver crystalline solids, ie, solids whose crystals can only be inferred without being observed directly under an optical microscope. "Solid layer" is a non-flowable gelatin layer or paste or solid form formed by centrifugation.

The term "Total Water" refers to water present in the composition, such as water in the composition, that is, crystallized or hydrated water and present in the main non-aqueous phase, and water in liquid form in the main aqueous phase. As it refers to all the water that exists. 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. Thus, the same formulation can be exemplified by various compositions with different percentages of dry weight.

Unless stated otherwise, the viscosities used herein refer to a flat cup with a diameter of 20 mm and a length of 92 mm and a cone with a diameter of 13.7 mm and a length of 44 mm and a horizontal angle of about 45 ° C. Using a bob with a 4mm spindle (bob) was rotated for 2 minutes at a speed of 350rpm and then measured by 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 measurement system C at a rate of settling 30. These conditions are not suitable for measuring viscosities greater than 12 Pascal Seconds, which can cause partial loss of 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 imge micelle concentration and the lyotropic mesophase of the first ion. Molecules form globular or rod-shaped micelles.

The "G" phase describes a liquid crystal phase of a type well known in the literature, such as the "neat phase" or the "lamellalr 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. Pure "G" phases can be identified by experimenting with a sample under a polarizing microscope, usually between interfering polarizer plates.

Resevear, JAOCS Vo1. 31 on classic paper by p628 (1954) or in J, Colloid and Interfacial Science, Vo1. 30 No. 4, a special structure is observed in P.500.

Yield point described herein means that measured by RML Series 11 Deer Rheometer at 25 ℃. All percentages unless otherwise stated are by weight ratio based on the total weight of the composition. As used herein, “sedimentation” includes not only the downward separation of solid particles but also the upward separation.

The term "non-sedimentation" means that no precipitation occurs under normal storage conditions unless otherwise indicated. "Non-sedimentation" usually 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 a portion of the aqueous phase separates to form a clear layer that is the outer layer for a 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 primarily for light work, such as dishwashers. In detergent products used for heavy duty applications such as laundry detergents, powder form predominates because it is difficult to obtain a stabilizer 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 more quickly and more readily in powders 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 dodecylbenzelsulfonate 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. The problem here, however, is that the enhancer must be stabilized and prevented from settling so that it remains suspended.

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 approach has been tidied by the following assumptions: The detergent should be as solution as possible; the amount of suspended solids should be minimal to overcome the difficulties in stabilizing the suspension so that it does not precipitate; In addition, special thickening agents or stabilizers should be used to prevent precipitation.

The products introduced so far are those that have certain serious drawbacks commercially. In particular, Gaga's formulation has proved to be very sensitive to relatively small changes in composition and production.

Power generation from a particular composition that is in optimal condition to a very good extent becomes unstable, resulting in reduced shelf life. 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 would be stable or unstable or how to stabilize surfactants that may be needed 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 was undesirably low, and the ratio of the enhancer to the active ingredient was generally lower than the ratio of the preferred active ingredient enhancer to the optimal cleaning agent, 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 with 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 marketed so far, the specific advantages of the present invention are as follows: The ratio of enhancer to surfactant was increased; Stability is increased; Easy to manufacture and low cost by using inexpensive components; Satisfactory mobility; Washing performance was increased; Has a "non-drip" property; 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, what the present invention has found is that the greater the amount of undissolved material, the more stable the composition becomes.

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, it is necessary to stabilize the composition without requiring all the methods for the formulation even without a special stabilizer. As a result, most surfactants that have been used in powder cleaners have been found to exhibit the effect of stabilizing an aqueous suspension of the active ingredients. It has also been found that the surfactant can be formed into an open three-dimensional structure that imparts stability to the aqueous suspension by controlling the mixing conditions or by preparing the electrolyte.

Applying the above principles provides advantages over conventional cleaners, and manufactures laundry detergents such as thixotropic gels having a matrix of hydrated solids or liquid crystalline surfactants that may contain suspended solid builder particles. I found it possible.

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 available from JAOCS (April 1981) P356A- "Heavy Duty Laundry Detergents" and the Sur-factant Scient Series, which contains a review of some of the most commercially available liquid formulations. 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 Patents 3235505, 3346503, 3351557, 3509059, 3574122, 3346503, 3328309 and Canadian Patent 917031.

In each of these patents, an aqueous solution of the water-soluble enhancer is sufficiently concentrated to salt the surfactant (usually in the form of an ionic liquid), and the surfactant is dispersed in an aqueous medium like a clade droplet by various oily agents.

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

The formulations described in this patent are separated by centrifugation into a solid phase containing mostly an enhancer slightly soluble in water and a liquid phase containing most of an active ingredient. 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, requiring expensive additives, most of which are not active ingredients.

Another attempt is to suspend the solid enhancer in a nonionic surfactant which is a liquid anhydride, as described in British Patent 1600981. 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 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 a surfactant in aqueous solution, such as in US Pat. Nos. 3281367 and 3813349.

U. S. Patent 3956158 describes suspensions in which the abrasive is suspended in an interlocking fiber gel state such as asbestos or soap. However, these patents, which generally contain low surfactants, do not contain enhancers, and contain high concentrations of abrasives, are of no help in the manufacture of 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 of the method and method of spray drying these slurry intermediates is described in US Pat. No. 3639288 and W.German OLS 1567656.

Australian patent 507431 describes suspensions in which the enhancer is suspended in an aqueous surfactant stabilized with a material such as sodium carboxymethyl cellulose 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. 3039971 describes a cleaner paste containing a solution enhancer.

French patent 2839651 describes a suspension in which a zeolite enhancer is suspended in a nonionic surfactant system, which composition is a hard paste rather than a fluid liquid. A.C.S Symposium series No.194

"Silicates in Detergents" describes the effects of silicates in liquid detergents.

It is to be understood that the above-mentioned patent references 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 in this field, who had no foresight in the present invention when the applicant first claimed its priority, would not have chosen the patent specification as a special meaning and would not be able to extract particular relevance.

Therefore, the above-mentioned summary does not usually describe the general part of the skilled people.

There are methods for preparing liquid cleaners by suspending the enhancer in a fully improved liquid detergent or in an aqueous solution of a surfactant that contains some soluble enhancer that is difficult to manufacture, although we generally believed that the latter view prevails. Attempts both failed.

The present invention provides a non-settling, fluid liquid detergent composition containing an active ingredient and a dispersed solid enhancer, which composition does not necessarily represent all active ingredients exhibiting (but not necessarily all) exhibiting at least some of the following properties: It is mainly composed of an aqueous separation phase containing 75% or less 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 separation phase containing a substantial proportion of the active ingredients interspersed with this aqueous phase and a dispersed solid phase consisting mainly of enhancers; 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 mm 3; One or more other phases are mainly non-aqueous phases; The composition usually has a high functional payload of at least 20%, i.e., about 25-75% (usually about 30%, preferably at least 35%, more preferably 40%) by weight; They contain an adjuvant and an active ingredient in a ratio of 1: 1 or more, preferably 1.2: 1-4: 1, and contain 5% or more, preferably 8% or more, by weight of the active ingredient; The main aqueous phase is contained in a concentration of 15% or less, preferably 8% or less, that is, 2% or less, and in the case of nonionic surfactants or alkylbenzenesulfonic acids, 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, and the at least one main aqueous liquid phase contains a sufficient amount of electrolyte 0.8, preferably 1: 2, i.e., a concentration containing about 2.0-4.5 g of ions per liter of total alkali metal and ammonium cation; 15% by weight, preferably 20% It contains more than one enhancer;

Enhancers are mainly sodium tripolyphosphate; This enhancer contains a small amount of alkali metal and silicate, preferably sodium silicate; The volumetric viscosity of the composition is on the order of 0.1-10 Pascal Seconds, preferably 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; Among the particle growth inhibitors, the room temperature particles containing the enhancer contain solid particles having a maximum particle size of less than or equal to the limit of sedimentation and the surface of these particles is sufficient to keep the particles below the limit of sedimentation. One of is adsorbed; The composition contains a direct inhibitor sufficient to prevent solid particles from solidifying.

First, specifically, the non-precipitable and flowable aqueous based detergent composition has a payload of at least 25% by weight and comprises the first primarily 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 of the Sanging by centrifugation at 800 times under normal gravity for 17 hours at 25 ° C.

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

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 consists mainly of a predominantly aqueous liquid separation phase containing a dissolved electrolyte, a separation phase containing a significant amount of surfactant interspersed with said aqueous liquid separation phase and an enhancer of other normally dispersed solid particles. At least one solid form.

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.

Fifth, specifically, the present invention provides a liquid detergent composition which is non-precipitable and flowable, wherein the detergent composition is suspended in at least one liquid crystal separation phase and composition comprising primarily an 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 non-precipitable, flowable, and improved liquid detergent composition, which is composed primarily 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.

Seventh specifically, a non-precipitable and flowable liquid detergent composition is provided which comprises a predominantly aqueous liquid phase, anion and / or non-sediment in which up to 60% of the total weight of the active ingredients in the detergent composition is dissolved. It consists of at least one phase containing an ionic active ingredient and one or more other separate 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 per liter, i.e. at least 0.8 g, preferably 1-4 g ions. A non-invasive and flowable improved liquid detergent composition comprising at least one predominantly aqueous liquid phase separated surfactant and comprising one or more other phases interspersed with suspended solid enhancers, the composition comprising at least one 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. This composition has payloads that fall 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. It contains an inhibitor to prevent coagulation and aggregation of inhibitors and 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, the liquid detergent for washing the aqueous base in which the 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.

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.

Usually the formulation form of the group exhibits some typical properties as follows.

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 composition generally has a yield point of 4 dyne / cm 2 or less, often 1 dyne / cm 2 or less. This is a relatively unstructured composition and confirmed by neutron scattering, X-ray diffraction studies and electron microscopy. Under high shear rolls, 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 detergent compositions of the invention prepared from nonionic surfactants or surfactants mixed with nonionics and anionics 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 (less than 0.1 Pascal seconds, but usually 0.02 Pascal, which contains an electrolyte but little or no 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 becomes gel like with 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 rotation experiments and electron microscopy.

Most Group II compositions that are centrifuged have a liquid or liquid crystal interfacial agent layer at the top, but an aqueous electrolyte layer appears at the top or at least one layer is associated with two liquid layers or one of them by centrifugation. It is not possible to exclude compositions in which two or more solid layers can be distinguished from one another, where sedimentation may occur.

The essential difference from other groups and group III is that most of the surfactant is centrifuged into the 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 mixtures of minimal nonionic surfactants and the following anionic surfactants, are surfactants that are slightly soluble in the aqueous state, especially sodium alkylbenzene sulfonates, alkylsulfates, 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., viscosity) containing dissolved electrolyte and an extremely small (sometimes not included) surfactant. 0.1 pascal second or less, usually 0.02 pascal second 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 / ㎠, the recovery time after applying a shear force above the yield point is very short, usually 20 to 100 minutes.

Most of the 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.

The composition at the borderline of group I and group II is 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 by 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 Method and Microscope]

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 neutral asset spectrometer. In addition, both deuterium oxide based samples and aqueous samples were tested with a small angle X-ray diffractometer.

The aqueous sample is coated with gold or an alloy of gold and palladium and frozen in corroded pieces. Observed by electron microscope irradiated at low temperature of 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, in which the three categories of suspensions are described in Groups I, II, In connection with the composition of III.

The first category of compositions includes compositions belonging to the group, which have no discontinuous advantages and are similarly characterized by regularity, repeatability and structural properties by neutrons and X-ray analysis with high levels of scattering at small angles, etc. Built.

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. In addition, the show rates or humps observed in group I formulations 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 are relatively unstructured and have fewer detectable lamellar shapes. However, some of Group I can be clearly observed by electron microscopy, having a spherical structure of approximately 5 microns in diameter.

Very different forms are obtained from typical Group II formulations. The formulation now exhibits relatively low levels of scattering at small angles near the incident light and their peaks are typical peaks of concentrated micelle solution (L ₁ phase) and peaks by 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. Lamellar structures can be observed by electron microscopy. In some cases, spherical structures of approximately 1 micron in diameter may be observed.

Typical Group III formulations are relatively very narrow, have strong small angle scattering and have distinct peaks that represent lamellar structures. These vertices appear wider than in the typical Group II case and do not always distinguish between 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). Electron microscopy can clearly observe the lamellar structure.

[PROPOSED STRUCTURE]

Based on the assumption that the above-described properties are specifically expressed in the new structure in which the solid enhancer is deposited on the solid surfactant hydrate or the arrangement structure of the "G" surfactant combined with the micelle solution of the L ₁ phase, I believe it can be explained most easily.

Compositions of Group III which specifically express the present invention consist 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 powdered into a relatively non-viscous aqueous phase which contains a dissolved electrolyte with little or no crab surfactant. It consists of a relatively weak three-dimensional network of surfactant hydrates. This network prevents suspended discrete particles from forming and resembling networks. The solids that form the network may be in the form of platelets, 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 net shape interspersed with liquids. . This structure is a very stable structure that prevents sedimentation during storage, prevents sedimentation, and limits the horizontal expansion of the gel. However, this structure is weak enough to cause the composition to flow or unfold.

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 matrix of flat crystals arranged randomly around the gap between the enhancer particles. Solid surfactants may be immediately bound or at least partially replaced by surfactants on the "G".

In the case of group II, the formulation form consists of four thermodynamically distinct phases where only three are separate phases under the conditions defined herein. The phase detected by diffraction consists of a "G" phase, a lamellar phase, but in some cases an aqueous "L ₁ " micelle solution with a surfactant hydrate or a mixture of the "G" phase and a surfactant and a solid enhancer It may be configured as.

Also mainly aqueous solutions are 75%, in particular 50% or less, generally 40% or less, more typically 20% or less, preferably 10% or less, more preferably 5% or less, by weight of the total active ingredients It contains less than 2% electrolyte.

Enhancers are suspended in a system consisting of a "G" phase or a globular or follicular network, which may have the same structure or shell as onions formed from a continuous layer of surfactant such as the "G" phase. It may also contain an electrolyte solution or more preferably at least one predominantly aqueous phase, such as a "L ₁ " micelle solution. At least one mainly aqueous phase 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% of a surfactant by weight ratio. It is also preferable that the surfactant is contained in an amount of about 7% -35%, that is, about 10-20% by weight of the composition. For example, the surfactant may be substantially at least slightly water soluble sulfonate or monoesterified sulfonate, ie alkylbenzenesulfonate, alkylsulfate, alkylethersulfate, olefinsulfonate, alkanesulfonate, alkylphenylsulfate, alkylphenylether Sulfates, alkylethanolamide sulfates, alkylethanolamide ether sulfates or esters of α-sulfofatty 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 that it contains an oxyalkylene group. For example, sulfonated or sulfated surfactants include sodium dodecylbenzenesulfonate, potassium hexadecylbenzenesulfonate, sodium dodecyldimethylbenzenesulfonate, sodium lauryl sulfate, sodium industrial sulfate, potassium oleyl sulfate, lauryl monoe 10 mol of ammonium sulfate or monoethanolamine cetyl is ethoxylated sulfate, etc.

Other anionic surfactants useful according to the present invention include fatty alkylsulfosuccinates, fatty alkylethersulfosuccinates, fatty alkylsulfosuccinates, fatty alkylethersulfosuccinates, acylsarcosinates, acyllaurates, Isethionates and stearates, palmitates, lecinates, oleates, soaps such as linoleates and alkyl ester 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 glyceryl and / or 1-20 Ethyleneoxy groups and / or propyleneoxy groups.

Anionic surfactants such as olefins sulfonates and paraffinsulfonates are commercially available only if they are disulfonic acids containing 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 form a stable composition in which only a small amount of the total surfactant is contained in the aqueous phase. These compositions thus constitute a special aspect of the present invention as new laundry detergents of value.

Preferred anionic surfactants are sodium salts. Other commercially available salts include salts such as potassium salts, magnesium salts, ammonium 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 Propoxylated or ethoxylated and propoxylated analogs of esters, ethoxylated phosphate esters and all of the aforementioned ethoxylated nonionics, alkyl groups of C _8-22 or alkenyl and up to 20 ethylene groups Everything having a propyleneoxy group or another nonionic surfactant that has been mixed in a detergent composition in powder or liquid form, such as amine oxide, 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 three carbon atoms (ie, C _1-4 , preferably C _1-2 ). 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 ilkenyl groups, amidoamines and two long chain alkyl groups or alkenyl groups. Tea amidoamines and the like. Quaternary emollients are usually anionic salts, which can measure solubility in water, such as formate, acetate, lactate, tartarate, chloride, methosulfate, 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; There are imidazolines having one or two long chain alkyl or alkenyl groups and amidoamines having one or two long chain alkyl or alkenyl groups.

Detergents"에 기술되어 있다.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 important forms of commercially available surfactants is given by Schwartz Perry and Berch, "Surface Acteive Agents."

Detergents ".

[Enhancer]

In a preferred composition according to the invention, the enhancer is present as discrete solid crystals suspended in the composition. Crystals typically range up to 60 microns, ie 5-50 microns.

The present invention relates to a formulation that contains sodium tripolyphosphate as an enhancer or that contains sodium tripolyphosphate in a mixture with other enhancers in a major proportion, rather than a formulation containing other enhancers. It was found to have fluidity. Therefore such formulations are preferred for the present invention.

However, the present invention also provides compositions containing other enhancers such as potassium tripolyphosphate, carbonate, zeolite, nitrilotriacetate, citrate, metaphosphate, pyrophosphate, phosphate, DETA and / or polycarboxylates, etc., on the other side. Although possible, it is preferred, however, to contain a mixture with tripolyphosphate. Orthophosphate, an alkali metal silicate, etc. can also be contained in a mixture with a tripolyphosphate 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 electrolytes to make active ingredients stand out from primarily aqueous liquid phases, thereby reducing the proportion of active ingredients contained in the solution and improving the stability and flowability 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 Sio2 by weight.

Typically, the silicate used to prepare the composition described above has a Na ₂ o: Sio ₂ ratio of 1: 1-1: 2 or 1: 1.5-1: 1.8. However, silicates or silicic acids in which Na ₂ O (or other bases) 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 find out. Formulation forms that are not intended for washing machines do not require silicates to be supplied to the 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 in the predominantly aqueous phase at a low level, which is to select surfactants that are slightly soluble 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 the specific examples 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 fairow 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 consequences of increasing the transition temperature of these phases is that the surfactant has raised the minimum temperature beyond that of forming a liquid or liquid crystalline phase. In the presence of water, the surfactant, which is usually a liquid crystal phase or an 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 the at least one main aqueous phase is about 0.8, preferably about 1.2 concentrations (i.e., about 2.0-4.5 g added per liter of alkali metal, alkylolitometal or ammonium cation). It is preferable to contain in the ratio of. The degree of stabilization of such a system can be improved even further 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, preferred anionic surfactants include sodium sulfate salts or sulfonated anionic surfactants, carboxymethylcellulose, silicates or carbonates which are preferably present as sodium salts. There are reprecipitation inhibitors, 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 a surfactant such as olefin sulfonate or nonionic material irrelevant to the presence of alkaline earth metals.

It is also less preferred, but may also be used to select from inflammation 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 main aqueous liquid phase to form a phase, preferably at least 75% or at least about 80% 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 booklet sample, that is, centrifuging to form a clear aqueous liquid phase, and then evaporating the separated layer at a temperature of 110 ° C. to leave only the content.

[Stabilization of Suspended Solids]

The solid particle size was made smaller than the particle size where sedimentation occurs. The critical limit 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 crystal of suspended slightly dissolved soluble solids to prevent further solids from settling in the saturated aqueous phase of the main aqueous liquid. Typical particle growth inhibitors include sulfonated aromatic compounds. For example, alkylbenzenesulfonates such as sodium dodecylbenzenesulfonate, which are present as surfactants, are themselves particle growth 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 can be added to the liquid detergent as a hydrotrop, as well as to stabilize. In the present invention, however, the addition of lower alkylbenzenesulfonates is less preferred.

Sulfonated naphthalenes, especially methylnaphthalenesulfonate, are effective particle growth 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 detergent compositions 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 help stabilize the suspension, but insufficient to significantly increase the viscosity of the main aqueous liquid phase to reduce the fluidity of the composition.

Still other particle growth inhibitors which may optionally be included in the compositions according to the invention include 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'-ratio. Phenyldisulfonates, etc. These particle growth inhibitors may be added instead of the sulfonated surfactants, and other effective particle growth inhibitors include ligrosulfonates and alkanesulfonate surfactants. This sulfonic acid surfactant compound 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 inhibitors that may be used are polyacrylic acid and polycarboxylates thereof, polyvinylpyrrolidone, carboxymethyl starch and lignosulfonate salts and the like. 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 alkyl benzene sulfonate is preferably contained in the ratio described above in consideration of the ratio of the surfactant.

If a relatively high proportion of up to 3 or 5% is not excluded if it matches a particular formulation with the flowable composition, the preferred proportion of sodium carboxymethyl cellulose is about 2.5% by weight of the composition and more preferably 0.5 by weight. About -2%, or about 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.

[Alkylideo]

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 wash containing a composition diluted to a dry weight of 0.5%. Although higher alkalinity compositions 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 amounts of organic hydroxy solvents or hydrotropes that can combine methanol, isopropane with water such as 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 requiring 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 flow. It is therefore advisable to ensure that only the minimum amount necessary to ensure proper fluidity is present without totally excluding them in the overall composition according to the invention. If not necessary, it is better not to add them.

[Farrowwood]

The choice of appropriate payload is generally important to achieve the desired stability and flow.

The optimal payows vary considerably with the form of the formulation. Although some forms of formulations add up to 30% payload, sometimes up to 25% and a non-settled form of the composition can be obtained, generally when payload is added up to 35% by weight, Not sure that the composition would not settle.

In particular, soap-based formulations were obtained with up to 25% payload, i.e. 24% concentrate. Lowering the payload by 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 that the suspension is prepared using the minimum amount of water necessary to keep the composition in a confused state, followed by progressive dilution of several samples, followed by It can be measured by observing the degree of sedimentation that appears in each sample.

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

If the method described above is unable to 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 usually increased as the payload 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 are not fully stabilized without further stirring the composition longer. In some extreme cases it is necessary to break up the solids contained in the product in the 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 when 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, other components containing the anti-reprecipitation agent, the optical gloss agent, and the foaming agent may be added, and finally, the enhancer may be added when it is not necessary to add the initial electrolyte solution. Sufficient amount of water is added to maintain the composition evenly into 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 coconet 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.

[Formation 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) a soap-based cleaner, consisting of an active ingredient in which a substantial portion is a soap, more preferably a majority soap, 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 a complete description of a list of formulation forms according to the invention that also contain forms that are not described separately as described above.

Considering other forms of the preparation form according to the present invention in more detail, even in the "A" form, it is possible to distinguish between a high foaming sulfate form or a sulfonate form and a low foaming form "A" form. Formulations of the "A" form with high foaming are prepared with C _10-14 linear or branched alkylbenzene sulfonates themselves or mixtures with C _10-18 alkyl sulfates or alkyl C _10-20 mol ether sulfates. can do.

A small amount of soap (approximately 1% by weight of the composition) can be added to aid the fabric in aidrinsing.

Nonionic and effervescent boosters and stabilizers, ethoxylated alkylphenols, fatty alcohols or theirs, such as C _12-18 acyl (ie coconut) monoethanolamide or diethanolamide or ethoxylates thereof. Ethoxydes can be used as effervescent boostina stabilizers, which 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 that are salted with toluenesulfonates, such as sulfosuccinates, sulfosuccinates and 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 surfactant contained in the composition is the composition dryness. 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. When no effervescent booster is present, it is preferred that the proportion of alkylbenzenesulfonate salt 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 and preferably 1: 1.5-1.5. It may also consist of a mixture of 1, ie, 1: 1 or so. In the latter case, in the absence of a foamable 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 the acid salt. In another "A" formulation form, the anionic surfactant comprises essentially alkyl sulfates or alkyl ether sulfates.

In the absence of a foamable booster, the total concentration of the active ingredient is preferably 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 C _10-20, and the longer the chain, the higher the ethylene-oxy content.

The form described above can be changed by replacing part or all of the anionic active ingredient, wherein the sulfated or sulfonated anionic surfactant is described above, and the sulfated or sulfonated anionic surfactant is described above. Are classified together. 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 0-6%, preferably 0.1-4%, that is, about 0.5-2%. Soap should be used in an amount of 25% or less, usually 10% or less of the total sulfated and sulfonated surfactant 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 monoethanolamide or diethanolamide or their ethoxylates, alkyl phenol ethoxylates, fatty alcohols or their ethoxylates or fatty acid ethoxides Phosphorus is C _10-18 alkyl. Effervescent boosters or stabilizers can be added up to about 20% of the dry weight in the composition, i.e. 0.1-6%, preferably about 0.5-4%, and are highly foamable by adding an effervescent booster or stabilizer. It can reduce the total concentration of the active ingredient contained in.

Compositions comprising effervescent boosters or stabilizers and alkyl benzenesulfonates may contain 25% alkylbenzene sulfate with 15-40%, preferably 20-36%, or 4%, nonionic surfactant 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 above, other formulations of sulfated or sulfonated anionic surfactants can similarly reduce the concentration of the active ingredient by containing a foamable booster and a stabilizer.

The enhancer is preferably sodium polypolyphosphate, optionally but preferably used with trace amounts of soluble silicates, although another enhancer as 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%, i.e. 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, that is, 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 mild silicones or foam inhibitors.

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

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 It is preferable to select from _16-20 alkyl phosphate esters and silicone antifoaming agents.

The action of soap as a foam inhibitor depends on the ratio of soap to sulfated or sulfonated anionic surfactants. A ratio of 10% or less is not effective as a foam inhibitor but is useful for aiding rinsing in highly foaming detergent compositions. The minimum proportion of soap needed to act as a foam inhibitor is about 20% of the sulfated or sulfonated surfactants. 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, the ratio of soap to the weight of the sulfated or sulfonated surfactant is preferably 25-50% or 30-45%.

The less foamable "A" type surfactants may contain nonionic foam inhibitors instead of soaps, such as, for example, C _16-20 acyl monoethanolamide (ie rape monoethanol-damide). , 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 ethers, are present in the formulation up to about 10% based on dry weight, preferably about 2-8%, ie 3-4%.

Silicone foam inhibitors may also be used as foam inhibitors or as part of foam inhibitors. The effective amount of this silicone foam inhibitor can be contained in the formulation form is generally less than when using the other types of foam inhibitors 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 of the "A" form of the formulation, and may include fabric softeners such as clays, 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 "A" is usually less than the dry weight of form "A". Ie 25-60%, preferably 29-45%. The overall proportion of active ingredient is usually 10-60%, preferably 15-40%, ie 20-30% of the dry weight of the composition and the proportion of the enhancer is usually 30-80% of the dry weight.

In general, the addition of a sufficient amount of a water soluble inorganic electrolyte, in particular sodium silicate, to the formulation can improve the mobility of the formulation in the form of "B".

Highly foamable soap formulations usually contain small amounts of nonionic foamable boosters or stabilizers or anionic sulfate boosters, such as alkylethersulfates or alkylether sulfonesuccinates, as described with respect to the "A" form. It may also contain an active ingredient substantially composed of soap. The low foaming "B" type formulations may contain small amounts of sulfated or sulfonated anionic surfactants, nonionic phosphate ester foam inhibitors or silicone foam inhibitors, together with low concentrations of soap.

In the less foamable formulation, the relationship between sulfated or sulfonated anionic surfactants and soaps is contrary to the relationship contained in the "A" form of foams with low foamability. In the "B" form of formulation, sulfated or sulfonated anionic surfactants act as antifoam when present at a rate of about 20-60% of the weight of the soap.

Nonionic phosphate esters and silicone foam inhibitors are substantially as described with reference to the "A" type of cleaner.

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 be included.

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

Powder cleaners also limit 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 a detergent, even a powder, of potentially desired nonionic gases. 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 should be limited to less than the optimum proportion 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 fluid aqueous base composed of at least one main liquid aqueous phase and at least one other phase containing a surfactant enhancer according to a particular preferred embodiment. , The composition is composed of 10-50% active ingredient and 30-80% enhancer based on dry weight, in which case the active ingredient is a nonionic interface having at least 10-18 HLB by weight of the active ingredient. It consists of an active agent. 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 axial or unsaturated hydrocarbon groups are not excluded, it is preferred that the surfactant consists 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 form of a highly foamed C form, anions with C _12-16 alkyl anions having 8-20 ethylene oxy groups, alkylphenolethoxydes having 6-12 aliphatic carbons and 8-20 ethyleneoxy groups Surfactants, preferably sulfated or sulfonated anionic surfactants such as alkylbenzenesulfonates, alkyl sulfates, alkylethersulfates, paraffinsulfonates, olefinsulfonates or other sulfated or sulfonated compounds described above It is preferable to contain a small amount of surfactant, i.e., 0-20% by dry weight ratio of the composition, but no substantial amount of antifoaming agent. However, in this formulation, stabilizing agents 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 12-15 HLB.

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 10-40 C _12-18 alkyl 5-20 mole ethyleneoxy nonionic surfactants such as fatty alcohol ethoxylates, fatty acid ethoxides or alkylphenol ethoxylates. It is preferable to contain in about% (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" A foam inhibitor such as mono-, di- or trialkyl phosphate ester or silicone foam inhibitor is described as described above for the "type of cleaner.

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

In particular, the cleaning agent as a nonionic base according to the present invention may be mixed with a cationic fabric softener. Cationic fabric softeners may also 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 groups or alkyl or alkenyl groups, preferably two tallowyl groups. For example, di C _12-20 alkyl di (lower, ie C _1-3 , alkyl) ammonium salt, ie di tallowyldimethyl ammonium chloride, di (C _16-20 alkyl) benzalkonium salt, ie dityloylmethyl Benzylammonium chloride, di C _16-20 alkylamido imidazolines and di C _16-20 acylamidoamines or quaternary aminoamines, ie bis (tallow amido ethyl) ammonium salts.

It is preferred that formulations containing cationic fabric softeners do not contain 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 optionally contain small amounts of amphoteric surfactants such as betaine and sulfonbetaine in weight ratios of about 3%, preferably 1-2%, and also smectic clay and It may contain a conventional fluke component.

[Trace component]

The composition according to the present invention may contain conventional trace components. Important among them are anti-deposition agents, optical gloss agents and bleaches.

The most commonly used re-deposition inhibitors in the preparation of detergents are carboxymethyl cellulose sodium (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.

Anti-deposition agents or stain removers include methyl cellulose, polyvinyl pyrrolidone, carboxymethyl starch and similar polyelectrolytes, all of which may be used in place of SCMS, as are other water soluble salts of carboxymethyl cellulose.

Optical brighteners (OBA'S) are optional but are preferred components of the compositions 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 an OBA that is convenient and cost-effective or omitting them entirely 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 for some liquid cleaners (ie, C form formulations), OBA tends to be slightly less effective than in powder cleaners.

Therefore, it is preferable to add them at a slightly higher concentration as compared to the powder formulation. Typical OBA concentrations 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 [1,2di-] 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 "-stilbene disulfonate; 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-dimethyl aminocoumarin; and alkoxylated 4,4'-bis (benz imidazoline 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 bleach peroxide in the composition 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 pralocyanine 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.

Proteolytic enzymes and starch enzymes, along with enzyme stabilizers and carriers, can also be added in conventional amounts. Enveloped enzymes may also be suspended.

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

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 low foaming compositions are particularly useful in automatic washing machines. The composition can also be used for washing dishes, or for cleaning hard surfaces, and less foaming living organisms 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 garments in boiled 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 at a dry weight of 0.05-3%, preferably 0.1-2%, more preferably 0.3-1% (ie 0.4-0.8%). 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 10-14} Linear Alkyl Benzene Sulfonate

Alkylbenzene sulfonates used in all formulations are the sodium salts of the polymeric para-sulfonated "dobane" JN materials (dovan 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).

In said formula, R is as follows.

C ₅ 0.5% C ₁₅ 8.5%

C ₇ 6.5% Stearin C ₁₇ 2.0%

C ₉ 6.0% Olein C ₁₇ 6.0%

C ₁₁ 49.5% Lenolein C ₁₇ 1.5%

C ₁₃ 19.5%

3. Sodium alpa olefin sulphonate

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

55.0% C ₁₆ Terminal Olefin

45.0% C ₁₈ terminal olefin

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

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

C ₁₀ 3.0% C ₁₆ 9.0%

C ₁₂ 57.0% C ₁₈ 11.0%

C ₁₄ 20.0%

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 - ₁₈ Sodium sulfate

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

C ₁₀ 3.0% C ₁₆ 9.0%

C ₁₂ 57.0% C ₁₈ 11.0%

C ₁₄ 20.0%

7. Sodium tripoly phoshate

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

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

week

All alcohols mentioned and their ethylene oxides are linear in their primary form. All examples were prepared by adding surfactant as a hydrated solid to 47% solution of silicate. The 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 the ambient temperature as possible to ensure proper dispersion of the components.

For Examples 25, 26, 27 and 28, concentrated aqueous solutions of electrolytes (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 substantial 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 gloss, and 5 (a), (b) and (c) represent different forms of the world. Formulations in the form of payloads, 6 and 7 demonstrate that SCMC or optical varnishes are not essential to obtain a non-settling formulation and 8 contains anticorrosive and flavoring agents. 9 (a) and (b) represent the ratio of the active ingredient (3: 1) to the formulation-type high enhancer in the two payloads, and 10 (a) and (b) represent the two payloads Shows that the content of the enhancer is relatively low for the active ingredient in Formulation, and 11 represents the non-settling formulation obtained by centrifuging the formulation of Example 9 for only 3 hours at low payload and then decanting the supernatant. 12 indicates a relatively high SCMC level effect, and 13-19 indicates various effects. Formulations of form A containing ionic surfactants, 20-24 describe various electrolytes, 25 is a formulation in which sodium tripolyphosphate is a single electrolyte, and 26-31 represents 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 olefin sulfonates and 39-42 show the formulation of paraffin sulfonates (each with a continuously increased electrolyte). 43-46 describe Form B formulations, 43 depict Form B formulations in three different payloads, and 44-46 describe Form B formulations with increasing electrolyte. 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 cationic fabric softener, 56 represents a branched alkylbenzene sulfonate, 57 represents 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 prepared 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. The example is substantially the same as Example 1 of Australian Patent 522983. Example A is close to Example 1 of the European Patent, and a sample for neutron dispersion was prepared 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.

Example Polyester / Cotton Condition

31 95% 100%) Temperature 50 ℃

55 90% 70%) 300 ppm calcium carbonate

16 100% 100% Time 30 minutes

33 95% 110% Concentration of effective detergent

Standard powder 100% 100% solids

정도로 사용하였으며, 이들 실시예를 세제액에서 동일한 %의 유효세제 고형물질이 제공되도록 조절하였다.By "effective detergent solids" is meant the sum of the active ingredient and the enhancer. Standard powder is 6g /

Used to the extent that these examples were adjusted to provide the same percent effective detergent solids in the detergent solution.

Step 2

The test was carried out at the same (wt) temperature at three types of representative formulations of the high foamability and the low release property.

Condition: temperature; 40 °, 60 ° and 85 ° C., water; Hardness, time of 300 ppm; 30 minutes, concentration; 6g / 1 (approved)

Step 3

In this step, examples based on non-ionic substrates with low foaming properties were tested against standard powders.

Example Detergent Solids (%) Cotton Polyester / Cotton

52 70 110% 110%)

53 66 105% 90%)

54 61 115% 120%

Condition: temperature; 50 ° C., water; 300 ppm hardness, time; 30 minutes, concentration; 6 g / l powder, 11 g / l example

Step 4

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

Condition: temperature; 50 ° C., water; 300 ppm hardness (wash and rinse), wash time; 30 minutes, textile; White polyester: cotton (65: 35), concentration; Equal 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 scattering spectra illustrating 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 grids expressed in Å units. I is the intensity expressed in neutron coefficients. Each drawing corresponds to the following embodiment.

Drawing Example Drawing Example

1 5 (a) 7 50 (b)

2 18 8 53

3 21 9 52

4 25 10 A (comparative example)

5 39 11 B (comparative example)

6 26

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 (17)

Essentially less than 75 weight percent water, 5 to 35 weight percent surfactant, at least a portion of the enhancer particles suspended in excess of solubility so as to remain solid in the composition, and the composition becomes stable and elevated after shearing the composition A liquid, liquid, non-settling, aqueous based detergent composition consisting of a dissolved electrolyte present at a concentration above a lower limit that can exhibit viscosity. 2. The detergent composition of claim 1, wherein the proportion of surfactant is from about 5% to 35% by weight of the composition by weight of the composition, fluid, liquid and non-settling. 3. The aqueous based detergent composition of claim 2, wherein the payload is from about 25% to about 75% flowable, liquid, and non-settling. 2. The surfactant of claim 1, wherein the surfactant is a fluid, liquid, non-flowable, consisting of a mixture of substantially linear alkyl benzene sulfonic acid salts with at least one other surfactant selected from alkyl polyalkyleneoxy sulfates and non-ionic surfactants. -Cleaning composition of aqueous base which is settled. 5. The aqueous mechanical cleaning composition of claim 4, wherein said particulate enhancer is a fluid, liquid, and non-settling composition consisting essentially of at least one component selected from sodium tripolyphosphate, zeolite, and sodium carbonate. 2. A liquid, liquid, and non-settling, aqueous based detergent composition according to claim 1, wherein said electrolyte consists essentially of at least one component selected from a functional component and a water soluble organic salt dissolving said surfactant, chloride and nitrate. 7. The electrolyte of claim 6, wherein the electrolyte is essentially at least one component selected from dissolved tripolyphosphate, sodium orthophosphate, sodium phosphate, sodium citrate, sodium nitrilotriacetate, sodium ethylene diamine tetraacetate, sodium carbonate and sodium silicate A flowable, liquid, non-settling, aqueous based detergent composition consisting of: 7. The aqueous based detergent composition of claim 6, wherein the payows are at least 35% by weight of the composition, fluid, liquid and non-settling. 7. The aqueous based detergent composition of claim 6, wherein the surfactant is comprised of 10% to 20% by weight of the composition. 10. The aqueous based detergent composition of claim 9, wherein the surfactant is at least partially ellipsoidal fluid, liquid and non-settling. At least one surfactant and non-ionic surfactant selected from essentially water and (1) a generally straight alkyl benzene sulfonate having 10 to 20 aliphatic carbon atoms and an alkyl epoxy sulfate having an alkyl group of 10 to 20 carbon atoms And 10 to 20% of the weight ratio of the main product composed of a mixture of soap; (2) partially solid, selected from concentrated phosphates, carbonates, zeolites, citrates, nitrilotriacetates, ethylenediaminetetraacetates, orthophosphates, silicates and mixtures thereof, and stable to shear forces At least 15% by weight enhancer sufficiently present in solution to provide the composition; (3) 0 to 2.5% by weight of carboxymethyl cellulose; (4) 0 to 0.5% by weight of an optical brightener and (5) a fluid and non-settling composition consisting of a small amount of components selected from enzymes, chemically compatible bleaches, antifoams, cationic fiber softeners, cosmetic clays, perfumes, dyes and sodium chloride Phosphorus Liquid Detergent Composition. 12. The liquid detergent composition of claim 11, wherein the liquid and non-settling liquid composition comprises at least 5.6% sodium carbonate based on the composition weight ratio. Essentially about 12 wt% sodium alkyl benzene sulfonate, about 3 wt% C _12-15 primary _alcoholepoxy sulfate, about 15 wt% sodium tripolyphosphate, about 2.5 wt% sodium carbonate, about 0.5 wt% optical brightener, Improved fluidity, which consists of an effective amount of sodium carboxymethyl cellulose, fragrances, dyes, and a solid blue color and ballast water, after application of shear force to the composition to increase the carbonate component above the minimum concentration exhibiting elevated viscosity upon recovery And non-settling liquid detergent composition. The liquid detergent composition of claim 13, wherein the carbonate is at least 5.6% by weight flowable and non-settling. Flowable, non-settling suspense consisting of water, about 5% to 35% of surfactant by weight, and an electrolyte dissolved in the medium above the lowest concentration exhibiting elevated viscosity upon recovery after shearing of the composition Sufficient stable aqueous liquid detergent vehicle capable of suspending solid enhancer particles to form a warp. 16. The sufficiently stable aqueous liquid detergent vehicle according to claim 15, wherein the surfactant consists essentially of one component selected from straight chain alkylbenzene sulfonic acid sodium salts and alkylepoxy sodium sulfate, non-ionic surfactants and soaps. 17. The electrolyte of claim 16, wherein the electrolyte is essentially at least one selected from sodium carbonate, sodium silicate, sodium citrate, ethylenediamine, sodium tetraacetate, sodium nitrilotriacetate, sodium orthophosphate, sodium sodium phosphate and sodium phosphonate. A sufficiently stable aqueous liquid detergent medium consisting of the components.

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