FI80473B - STABIL, HAELLBAR, FLYTANDE TVAETTMEDELSKOMPOSITION. - Google Patents

Description

1 80473

Stable, pourable, liquid detergent composition

The invention relates to a new stable, pourable liquid detergent composition as defined in the preamble of claim 1, comprising water, a surfactant, an electrolyte salt and a builder salt.

Unless otherwise indicated or otherwise indicated in the context, the following terms in quotation marks in the specification and claims are as defined in this specification.

The term "enhancer salt" or "enhancer" is sometimes widely used in the detergent art to mean any non-surfactant whose presence in a detergent composition improves cleaning performance. More generally, however, the term is limited to typical "enhancers" which are primarily used as a means of preventing or reversing the adverse effects of calcium or magnesium ions, e.g., by chelating, sequestering, doping, or absorbing ions, and secondarily as a source of alkalinity and buffering agents. The term "enhancer" or "enhancer salt" is used in this specification and claims in a more limited sense, and refers to additives that substantially inhibit the adverse effects of calcium. These include sodium and potassium tripolyphosphate and other phosphate and condensed phosphate salts, such as sodium and potassium orthophosphates, pyrophosphates, metaphosphates or tetraphosphates, as well as phosphonates, such as acetodiphosphonate ethanedis-triethylates, amino tris tris, amino tris tris They also include alkali metal carbonates, zeolites and organic sequestrants such as salts of nitrilotriacetic acid, citric acid and ethylenediaminetetraacetic acid, polymeric polycarboxylic acids such as polyacrylates and copolymers based on maleic anhydride.

For the sake of clarity, the term "enhancer" as used herein includes water-soluble alkali metal silicates, such as sodium silicate, but not additives such as carboxymethylcellulose or polyvinylpyrrolidone, which act primarily as dirt suspending or anti-redeposition agents.

"Electrolytes" as used herein means water-soluble ionic compounds which have an anhydrous solubility in water at 0 ° C of at least 5% by weight and which dissociate at least in part into ions in aqueous solution and which, at concentrations present in surfactant solutions, reduce their total solubility (including micelle concentration) by "salting out". These include water-soluble, dissociable inorganic salts, such as alkali metal or ammonium chlorides, nitrates, carbonates, silicates, perborates and polyphosphates, and certain water-soluble organic salts which desolubilize or "salt out" the surface. They do not include salts or cations which form insoluble precipitates with the surfactants present or which are sparingly soluble in the composition, such as calcium chloride or sodium sulfate.

When reference is made herein to electrolyte concentration or concentration, it is meant the total amount of dissolved electrolytes, including dissolved enhancer, if such enhancer is also an electrolyte, but does not include suspended solids.

"Hydrotrop" means any water-soluble compound that improves the solubility of a surfactant in aqueous solution. Typical hydrotropes include urea and alkali metal or ammonium salts of lower alkylbenzenesulfonic acids such as sodium toluenesulfonate and sodium xylene sulfonate.

Depending on the active substances present, a particular compound may sometimes be either an electrolyte or a hydrotrope. Sodium chloride is normally considered a typical-> 1 3 80473 electrolyte, but relative to sultons, it is a hydrotrope. As used herein, the terms "electrolyte" and "hydrotrope" must therefore be construed in accordance with the active ingredient in question.

As used herein, "soap" means a salt of natural or synthetic aliphatic monocarboxylic acid that is at least to some extent soluble in water and has surfactant properties. This term includes the sodium, potassium, lithium, ammonium, and alkanolamine salts of natural and synthetic Cg_22 fatty acids, such as stearic acid, palmitic acid, oleic acid, linoleic acid, castor oil acid, pericarboxylic acid, behenic acid, and dodecanoic acid.

15 The term "common minor ingredients" includes ingredients that are not water, active ingredients, synergists, or electrolytes that can typically be used in laundry detergent compositions, typically up to about 5%, and that are compatible with the relevant formulation of the pourable, chemically stable non-sedimenting composition. with. This term includes anti-redeposition agents, dispersants, antifoams, perfumes, dyes, optical brighteners, hydrotropes, solvents, buffers, bleaches, corrosion inhibitors, antioxidants, preservatives, anti-peeling agents, wetting agents, wetting agents, As used herein, the term "functional ingredients" means ingredients necessary to provide a beneficial effect in a washing liquid and includes substances that contribute to the washing performance of the composition, e.g., surfactants, enhancers, bleaches, optical brighteners, alkaline buffers, enzymes and anti-redeposition agents and also corrosion inhibitors and defoamers, but excluding water, 4 80473 solvents, dyes, perfumes, hydrotropes, sodium chloride, sodium sulphate, solubilizers and stabilizers, the function is to provide stability, flowability and other desirable properties to the concentrated formulation. "Payload" means the percentage of active ingredients by weight of the total composition. By "active ingredients" is meant surfactants.

As used herein, "centrifugation" means centrifugation-10 from 25 ° C for 17 hours at 800 times the force of gravity, unless otherwise indicated.

The term "high G centrifugation" means centrifugation at 20,000 G at 25 ° C. High G-centrifugation is performed for 5 minutes unless otherwise indicated.

The term "separating phase" is used herein to refer to the components or component mixtures of a detergent composition to be poured, each of which can be separated from the composition into a separate layer by centrifugation. Unless otherwise indicated in connection 20, all references to the composition of the separating phases refer to the compositions of the separated phases by centrifugation, and references to the structure of the composition refer to the non-centrifuged composition. One separable phase may comprise two or more thermodynamically separate phases which cannot be separated by interleaving; examples are stable emulsion or flock.

The term "dispersed" is used herein to describe a phase that is discontinuously distributed as discrete particles or droplets in at least one other phase. "Continuous" describes two or more interpenetrating phases, each extending as a continuous or cohesive network through a common space, or otherwise composed of discrete or dispersed elements that interact to form a matrix of a continuous image and tend to hold each matrix with respect to the matrix. in place when the system is at rest. "Scattered" describes two or more phases that are either continuous or one or more of which are dispersed in one or other of the following.

5 References to "solid phases" are substances which are actually present in the composition in a solid state at room temperature, this term also including water of crystallization or water of hydration, unless the context otherwise requires. Solids also include micro-10 crystalline and crystalline solids, i. solids whose crystals cannot be directly detected by optical microscopy but whose presence can be inferred. A "solid layer" is a solid, pasty or non-pourable gel-like layer formed during centrifugation.

"Total water" means water present as a liquid in the predominantly aqueous phase, as well as other water containing the composition, e.g., water of crystallization or hydration, or water that is dissolved or otherwise present in the predominantly anhydrous phase. "Dry weight" 20 means the weight of the residue after drying at 140 ° C to constant weight.

The term "formulation" is used herein to refer to the combination of substances that make up the dry weight of the composition. Thus, there may be several composition examples of the same formulation that differ in% by dry weight.

"Stable" means that the composition mass is separated at room temperature under normal gravity in 3 months by only a layer of up to 2% of the total volume.

30 "Shear test" means a test in which a specimen is pressed at a pressure of 3.45 MPa through a straight pipe 40 mm long with an inside diameter of 0.5 mm. The shear test was performed on all the measurements described in this application by drawing the sample into a 500 ml pressure vessel through a wide-open tube, replacing the wide-open tube with a 0.5 mm 6 80473 diameter tube and compressing nitrogen at 3.45 MPa into the pressure vessel until the vessel is empty. The 0.5 mm diameter tube is then replaced with a wide bore tube, and the cycle was repeated. Typically, this method provides a shear rate of about 127,000 sec. "Shear stable" means that the specimen is stable after three rounds of shear testing. "Shear unstable" means that after three (or less) three rounds of shear test or 10 tests at a lower shear rate, the specimen is not stable. "Non-shear sensitive" means that the composition does not lose its stability after exposure to moderate shear stress or that the viscosity of the composition does not substantially increase. Shear sensitivity was determined using a Contraves 15 "Rheomat 30" viscometer cone and plate measurement system at 20 ° C, increasing the shear force linearly within 1 minute from 0 to 280 sec 1 ("up sweep") and immediately decreasing it linearly to 0 sec ^ 1 minute ( "alaspyyhkäisv"). A composition is considered non-shear sensitive if it is stable after this cycle and if its viscosity at 150 rpm is no more than 10% higher in the down sweep than in the up sweep.

"Thermally stable" means that a maximum of 5% of the composition is separated from the composition in 24 hours by volume 25, after treatment in which 20 g of a composition sample is heated in a 90 ° C water bath for 110 minutes and then immediately kept in a 100 ° C water bath for 10 minutes. .

"PH" of a detergent composition means pH 30 as measured by a Pye Unicam 401 meter with a glass / calomel electrode.

"Electrical conductivity" refers to the specific conductivity measured at 25 ° C at 50 kHz. The reported measurements were performed on a CDM3 "Radiometer" conductivity bridge using 35 CDC314 flow and pipette cells.

7 80473

When referring to the "first electrical conductivity names", reference is made to a graph showing electrical conductivity as a function of dissolved electrolyte concentration in a liquid detergent composition in which the ratio of active agent-5 to water is determined. By this expression is meant the concentration of electrolyte corresponding to the minimum value or, when there are several minima, one of the lowest concentrations of dissolved electrolyte corresponding to such minimum.

All percentages are by weight of the total weight of the composition, unless otherwise indicated.

"Viscosity" as used herein, unless otherwise indicated, means the viscosity measured with a cup-hanger-15 viscometer at 25 ° C after draining for 2 minutes using a 20 mm ID flat-bottomed cup, 92 mm long and 13.7 mm diameter hanging bullet with 44 mm ends. long cones (angle 45 ° from the horizontal), and a spindle 4 mm in diameter. The end of the hanging bullet is 23 mm from the bottom 20 of the cup. This corresponds to a Contraves "Rheomat 30" viscometer with measuring system C.

"Pourable" as used herein means that the viscosity of the composition at a shear rate of 136 seconds is less than 2 Pa seconds.

"Viscosity reduction" means the difference in viscosities reduced by the shear force of a composition as measured at speeds of 21 sec and 136 sec.

"Yield strength" as used herein means the yield strength measured at 25 ° C with an RML Series II Deer Rheometer.

"L 2" phase means a clear, liquid, optically isotropic micelle solution of a surfactant in water, obtained at concentrations above the critical micelle concentration, and in which the surfactant molecules are believed to be aggregated as spherical, wafer (plate) ) or prolate (rod) micelles.

80473 A "bilayer" comprises a surfactant layer approximately two molecules thick, consisting of two parallel layers, each of which consists of surfactant molecules 5 arranged so that the hydrophobic portions of the molecule are on the inner surface of the bilayer and the hydrophilic portions on the outer surface. "Layer" herein also includes overlapping layers that are less than two molecules thick. The overlapping layers can also be considered as a double layer, where both layers have penetrated each other so that the hydrophobic parts of the molecules of both layers overlap to some extent.

"Spherulite" means a spherical or spheroidal body having dimensions of 0.1 to 50 μm. Sfe-15 rolls can sometimes be deformed in the form of a prolate, wafer, pear or hand weight. "Blister" means a spherulite with a liquid phase surrounded by a bilayer. "Multiple vesicle" means a vesicle containing one or more small vesicles.

"Lamellar phase" means a hydrated solid or liquid crystal phase having a plurality of bilayers arranged in substantially parallel directions, separated by aqueous or aqueous solution layers, and having a sufficiently regular lattice spacing of 2.5 to 7.0 nm (25 to 70 Å). , readily detectable by neutron diffraction when the lamellar phase is present in the composition to a substantial extent. As used herein, this term does not include concentric multiple vesicles.

The "G" phase refers to a liquid crystal lamellar phase, the types of which are known in the literature as the "pure" phase or the "lamellar phase". The "G" phase of a given surfactant or mixture of surfactants normally occurs in a narrow concentration range. Pure "G" phases can normally be identified by examining the sample with a polarizing microscope between cross-polarizers. According to the classic publication of Rosevear (JAOCS vol. 31, p. 628 (1954) or J. Colloid and Interfacial Science, vol. 30 No. 4, p. 500 (1969)), characteristic structures can then be observed.

"Spherical G-phase" means shells formed of substantially concentric, two layers of surfactant alternately with the aqueous phase and having a "G" phase interval. Typically, a conventional G-phase may contain small amounts of spherical G-phase.

"Liquid" means an aqueous liquid phase containing an electrolyte, which phase is separated from another liquid phase containing more active ingredient and less electrolyte, or having such a phase scattered.

"Lamellar composition" means a composition in which the majority of the surfactant is in the lamellar phase or in which the lamellar phase is the major factor preventing sedimentation. "Spherulitic composition" means a composition in which the majority of the surfactant is in the form of spherulites or which is stabilized against sedimentation by a spherulitic surfactant phase.

Liquid detergents have heretofore been used, usually as light detergents, such as dishwashing detergents.

Detergent powders have prevailed in the market for detergents for heavier detergents, e.g. laundry detergents due to the difficulty in obtaining an effective amount of surfactant and in particular a builder in a stable liquid formulation. In theory, such liquids should be less expensive than powder detergents because they do not need to be dried and in many cases the sulphate filler normally used in washing powders could be replaced by water. The use of liquids would also be more comfortable and dissolution in 10 80473 wash water faster than when using powders. Attempts to prepare solutions of functional ingredients have been relatively unsuccessful commercially. One reason for this failure has been that the most economically effective enhancers used, e.g., sodium tripolyphosphate, are not sufficiently soluble in aqueous compositions. In addition, salting out appears to increase the amount of surfactant that can be dissolved in the composition as the amount of enhancer present in the solution tends to decrease, and vice versa. As alternatives to sodium salts, potassium pyrophosphate has been tried as an adjuvant in combination with the more soluble amine salts of the active ingredients, but the effect obtained does not correspond to the cost.

15 Non-adjuvant-free liquid detergents have been marketed for laundry use which contain a high concentration of surfactant but are not suitable for hard water areas and have had only limited success, mainly in markets where the use of effective adjuvants is legally restricted and competition with powders equivalent to-- roughly less severe.

In another attempt to solve the problem, the excess enhancer is suspended as a solid in a liquid micelle solution or emulsion of the surfactant. However, the difficulty has been to stabilize the system so that the enhancer remains in suspension and does not sediment. Numerous relatively artificial formulations have been reported in the literature, for example those using expensive potassium salts instead of cheaper sodium salts and solubilizing agents such as hydrotropes, dispersants or solvents, all of which are likely to increase costs. Even with the use of these non-essential additives, it was considered necessary to use a relatively low concentration of solid enhancer, which limited the washing performance. This attempt is subject to certain assumptions: the active ingredient should be as dissolved as possible; the amount of active ingredient should be relatively large; the amount of suspended solid 5 should be as small as possible in order to avoid difficulties in stabilizing the suspension to prevent sedimentation; the use of special thickeners or stabilizers to prevent sedimentation would be essential; surfactant insolubilizing electrolytes should not be used or should be very low.

So far, solutions of an empirical nature have been presented. No acceptable general theory has been proposed to explain why some compositions are permanent while others are not. Thus, there is no way to predict which composition is permanent and no general method for designing a new permanent liquid detergent. No generally applicable guidelines are known in the art, moreover, the compositions according to the embodiments of most known liquid detergent patents differ! layers within a few weeks. Relatively few exceptions have apparently been invented by chance, and extrapolation has not been possible.

25 Products of this type have been commercially manufactured in Europe and Australia, but have suffered serious disadvantages. The products are relatively poor in washing due to either the low weight ratio of the enhancer to the active ingredients or the low alkalinity. They have also proven to be less desirably sensitive to mechanical and / or thermal stress, for example when subjected to shear stress or stored under very difficult temperature conditions. Some compositions are distinguished by shear forces, others become too viscous and most are distinguished when stored at either 0 ° C or 40 ° C. However, no way has been put forward to overcome these weaknesses.

In addition, the payload has generally been undesirably low. Likewise, the ratio of enhancer to active ingredient has generally been lower than desirable for optimum washing performance, and it has often been necessary to use expensive ingredients not normally required in powders to make the amount of active ingredient in solution large enough to prevent sedimentation of suspended solids. As a result, the best available commercial liquid detergents are less favorable in terms of washing performance and price than the best powders.

In addition to compositions developed into commercial products 15, many compositions have been proposed in the literature which are in practice unsuitable for commercial use. Typically, these compositions are unstable or not stable enough to withstand normal storage without sedimentation, or are too expensive relative to washing performance to be commercially viable.

Recently, it has been proposed to prepare compositions in which the active ingredients form a lamellar phase network that can be separated from the aqueous phase by leaching, which compositions have a gel structure capable of supporting suspended particles of a solid enhancer. The gel structure is obtained by adding sufficient electrolyte to out-salt the active ingredient to form an aqueous lye phase and a separable lamellar phase, and to keep the solids content above the stability threshold and below the concentration at which the product loses its pourability. The amount of electrolyte depends on the hydrophilicity and melting point of the surfactant and whether solubilization additives such as hydrotropes or solvents have been added. The payload and active ingredient / active ingredient ratio of the above-mentioned 13 80473 compositions are higher and the cost-effectiveness ratio of the compositions is more advantageous than with known commercial liquid compositions. The best of the above-mentioned lamellar gel-5 compositions are in fact more cost-effective as soil release agents than the best washing powders.

However, the lamellar compositions disclosed so far have lower mobility than the optimal mobility required for some purposes.

A new class of compositions has now been invented which contain an electrolyte, active ingredients and water and which are capable of suspending solids such as synergists so as to obtain a stable composition having both good washing performance and satisfactory flowability.

15 The stability of the new compositions is probably due to a spherulitic structure not previously reported in the literature. A general process has also been invented for preparing stable, flowable compositions with very good p-20 performance from a wide variety of active ingredients.

Preferred embodiments of the invention provide at least some of the following advantages over previously marketed products: high payload; high - enhancer / surfactant ratio; improved stability; lower prices due to the use of cheaper raw materials and ease of manufacture; good fluidity; better washing performance; high pH and / or alkalinity; good stability at high and / or low storage temperatures; and satisfactory resistance to shear.

It has been found that when the active ingredients, dissolved electrolyte and water are present in a certain ratio, depending on the active ingredients and electrolytes used, a stable spherulitic composition capable of suspending solid particles such as a builder is obtained.

35 It has also been discovered how such compositions are obtained ____ · 1. _ i4 80473 and how they are identified by various physical methods. In addition, it has been discovered how to optimize the ratio of active ingredients to electrolyte in order to obtain compositions which can withstand shear stress 5 and thermal fluctuations which occur during storage under different climatic conditions, as well as high pH, i.e. alkalinity, and which are very flowable. In contrast to the recently disclosed lamellar compositions, the stability of the novel compositions of the invention appears to be due to the surfactant in the spherulitic phase and not in the lamellar phase.

The state of the art for liquid detergents is very extensive. However, for the purposes of the present invention, it is not necessary to take into account the numerous references in the literature to liquid laundry detergents for light washing (not laundry) and clear laundry detergents containing no builder or builder in which all the ingredients are dissolved. The proportion of enhancer in them is substantially lower than expected.

Recent general industry summaries include: JAOCS (April 1981) p. 356A - "Heavy Duty Laundry Detergents" with an overview of typical commercially available liquid formulations, and 25 Rutkowsky: "Recent Changes in Laundry Detergents", published by Marcel Dekker Inc ., 1981, Surfactant Science Series.

The problem of formulating liquid detergents containing the required amount of enhancer has in principle been approached in three main ways: the surfactant is emulsified in an aqueous solution of the enhancer, the solid enhancer is suspended in an aqueous solution or emulsion of the surfactant, or the solid enhancer is suspended in a gelling agent. is a lamellar structure.

Examples of the first solution are U.S. Patent Nos. 3,235,505, 3,346,503, 3,351,557, 80473, 3,509,059, 3,574,122, 3,328,309, and CA Patent 917,031. In all of these patents, the aqueous solution of the water-soluble enhancer is so concentrated. that it salt-out a surfactant (usually a liquid nonionic) which is dispersed in the aqueous medium as colloidal droplets by various emulsifiers. In all cases, the system is a clear emulsion which usually contains a small amount of enhancer and is disadvantageously expensive due to the use of soluble excipients.

Examples of another solution are GB Patent Publications 855,893, 948,617, 943,271, 1,468,181, 1,506,427, 2,028,365, EP Patent Publication 38,101, AU Patent Publication No. 522,983, U.S. Patent Publication Nos. 4,018,720, 3 232,878, 15,075,922 and 2,920,045. The compositions described in these patents are not stable or are not thermally stable or shear stable. Commercial products corresponding to the two examples of these patents have recently been launched in Australia and Europe. In particular, the composition of AU Patent Publication No. 522,983 has achieved commercial success, but has proven to be shear sensitive.

A third solution is described in EP 86 614. The matrix of the described compositions consists of 25 lamellar, solid or liquid crystalline surfactants. The viscosity of such compositions may be higher than desired for certain uses.

A different solution is disclosed in GB Patent Publication 30 1,600,981, in which a solid enhancer is suspended in an anhydrous liquid nonionic surfactant. Such systems are expensive, limited in surfactant selection, and provide unsatisfactory rinsing properties. Although the level of the enhancer 35 is high with respect to the whole composition, it is low with respect to the active ingredients, and the cost-effective effect is thus very low.

Several patents describe emulsions in which the enhancer is present as a dispersed phase in the form of an emulsion rather than a suspension. U.S. Patent No. 4,057,506 describes the preparation of a clear emulsion of sodium tripolyphosphate, and U.S. Patent No. 4,107,067 describes an inverse emulsion in which an aqueous solution of an enhancer is dispersed in a liquid crystalline surfactant system. Reference should also be made to numerous patents relating to hard surface cleaners in which the abrasive is usually suspended in an aqueous solution of a surfactant, e.g. GB Patent 2,031,455, U.S. Patents 3,281,367, 3,813,349, 3,956,158 and 4,302,347. However, the low amount of surfactant, the absence of a builder, and the high concentration of abrasive generally preclude the use of these patents to aid in the design of laundry detergent compositions.

Other publications of potential interest include: AU Patent Publication No. 507,431, which describes a suspension of a builder in an aqueous surfactant with sodium carboxymethylcellulose or clay used as a stabilized thickener. However, the level of the active ingredients, in particular the level of the active ingredient in the exemplary formulations, is not sufficient for a fully acceptable commercial product, and the stability of the product is not good enough for storage.

U.S. Patent 3,039,971 describes a surfactant paste containing a builder as a solution.

FR patent publication 2,283,951 describes zeolite builders in nonionic surfactant systems; however, the compositions are essentially rigid pastes and not sensitive liquids.

U.S. Pat. Nos. 3,346,504 and 3,346,873,355 describe the solubilization of sultons by hydrotropes, referred to in these publications as "electrolytes".

Il i7 80473 A.C.S Symposium Series No. 194 "Silicates in Detergents" describes the effect of silicates on liquid surfactants.

It is to be understood that each of the above 5 references was selected from a very extensive literature in the art, and that relevant aspects were considered and the selection made with the aid of hindsight and knowledge of the invention. At the time of the first priority of the present application, and without knowledge of the present invention, one of ordinary skill in the art would not necessarily have chosen the same patents as particularly significant or the same aspects as interesting or relevant.

The above summary therefore does not represent a complete picture of the field by an ordinary expert in the field.

The stable, pourable liquid detergent composition according to the invention, comprising water, a surfactant, an electrolyte salt and an enhancer salt, is characterized by what is stated in the characterizing parts of the claims.

In the detergent composition of the invention, which contains substantially active ingredients, an electrolyte and water, and has solids suspending properties, the relative proportion of electrolyte is such that the composition is temperature stable, non-shear sensitive and substantially non-lamellar.

In the detergent composition of the invention having solids suspending properties and containing water, active ingredient and electrolyte, the relative proportion of electrolyte is such that a space-filling spherulite floc is formed which is temperature stable and non-shear sensitive.

The detergent composition of the invention having solids suspending properties contains water, the active ingredient and an amount of electro-SO 473 lysate to form a dispersed stable Ease containing at least a portion of the active ingredients corresponding to the electrolyte concentration-electrolyte concentration of the electrolyte concentration curve. "a waveguide containing a first minimum electrical conductivity, wherein the relative amount of electrolyte is in a range where the composition is temperature stable and non-shear sensitive.

Preferably, in all of the above embodiments, the electrolyte concentration is such that a shear stable composition is obtained.

Preferably, the composition in all of the above embodiments contains suspended solids, such as builders and / or abrasives. The suspended solids may be insoluble in the aqueous liquid medium, already present in a saturation concentration, or as an encapsulated material, thereby preventing their dissolution in the medium.

The yield strength of the detergent composition of the invention containing water, active ingredients, electrolyte and suspended solids, and wherein the relative proportion of electrolyte is such that a shear-stable spherulite composition is formed, is 0.1 to 1.5 N m 15 dyne.cm- ^).

The yield strength of the composition is preferably greater than 0.15, more preferably greater than 0.20, most preferably greater than 0.25, e.g. greater than 0.2 3, and more preferably less than 1.0 N m. The viscosity at 136 s-1 is preferably less than 1.5, more preferably less than 1, e.g. 0.2 to 0.6 Pa.s.

In the detergent composition of the invention containing substantially water, 5-25% by weight of the composition of the active ingredients, electrolyte and suspended solid enhancer, the total weight ratio of enhancer salt or enhancer to active ingredient is 1.4: 1 to 4: 1, and the relative electrolyte the amount is such that ti 19 80473 to obtain a shear stable, non-lamellar composition.

In addition, the composition may contain the usual minor ingredients. Preferably the active ingredients are present in the composition in an amount of 10 to 20% by weight, more preferably 10 to 14% by weight, and preferably the total weight ratio of the enhancing salt to the active ingredient is 1.5: 1 to 3: 1, e.g. 1.9: 1 - 2.5: 1.

In the detergent composition of the invention containing water, 5-25% by weight of the composition of active ingredients, an electrolyte and a suspended solid enhancer, and having a payload of at least 35% by weight, the relative amount of electrolyte is such as to obtain a shear stable, spherulitic composition .

In the detergent composition of the invention containing water, 5 to 25% by weight of active ingredients, electrolyte and suspended solid builder, and wherein the total weight ratio of builder salt to active ingredients is 1.5: 1 to 4: 1, the relative amount of electrolyte is such that a spherulitic composition is obtained which is stable when stored at 40 ° C. Preferably, the relative amount of electro-20 lysate is such that a temperature stable composition is obtained.

In the detergent composition of the invention containing water, 5-20% by weight of active ingredients, electrolyte and suspended solid enhancer, and wherein the total weight ratio of enhancer salt to active ingredient is 1: 1 to 4: 1, the relative amount of electrolyte is such that a temperature-stable, non-shear-sensitive composition which, on centrifugation, separates into an aqueous layer containing more than 50% by weight of the total weight of the active substances and a solid layer.

The detergent composition of the invention, comprising substantially water, dissolved electrolyte and 8 to 14% by weight of the active ingredients of the composition, as well as a suspended solid enhancer and optionally 20,4473 common minor ingredients, separates on centrifugation into a solid layer and a single liquid layer greater than 0. , 15 N m

The detergent composition of the invention, which essentially contains water, active ingredients and an electrolyte, and which has solids suspending properties, and in which the active ingredients are capable of forming a stable composition at the first electrical conductivity, has an amount of electrolyte to give a composition which yield strength greater than 0.15 N m and viscosity measured at 136 s- · * "is less than 0.28 Pa.s.

A detergent composition according to the invention comprising essentially water, electrolyte, active ingredient 15 and a builder comprises a first, substantially aqueous, liquid, separable phase containing at least a portion of the electrolyte in solution and at least 50-80% by weight of the total active ingredients, at least one dispersed solid. a separable phase containing at least a portion of the enhancer as a solid.

Preferably, the substantially aqueous separating phase contains at least 40%, usually at least 50%, e.g. at least 60% of the total water.

The detergent composition of the invention having a payload of more than 35% by weight and a pH of more than 9 and containing water, dissolved electrolyte and at least 5% by weight of active ingredients and at least 16% by weight of enhancer salt has such a relative amount of electrolyte , 30 that the composition is shear stable but insufficient to form a substantial amount of lamellar phase of the active ingredients.

A detergent composition according to the invention contains an amount of active ingredients sufficient to form a surfactant-filled nourishment containing spherulites with a dispersed water phase and an amount of electrolyte corresponding to at least the first electrical conductivity names in the curve in which the electrical -5 conductivity is a function of electrolyte concentration, but less than the amount corresponding to lamellar phase formation, and sufficient to make the composition non-shear sensitive.

A detergent composition according to the invention comprising water, an electrolyte, an active ingredient and 10 enhancing salts is separated as defined above by centrifugation into at least two layers, namely: a predominantly aqueous layer containing dissolved electrolyte, at least 10% by weight of the total water and 80-50% by weight. % of the total amount of active ingredients, and a solid layer containing at least a portion of the enhancer.

The invention further relates to a stable, spherulitic composition containing the active ingredients, an electrolyte and water, from which a clear aqueous phase does not separate after high G-centrifugation at 20,000 G for 90 minutes.

In addition, listed in detail, the stable, pourable, liquid detergent compositions of the invention containing water, pin-25 active ingredients, an electrolyte, and a boiling salt have at least some, but not necessarily all, of the following properties: they contain a spherulitic phase with a dispersed a lye or L 2 phase, and preferably co-continuous with the lye or L 2 phase; they are substantially non-lamellar; they include a flock system, which is preferably space-filling; they comprise a flocculation system formed of particles containing active ingredients, which are preferably surfactant-containing spherulites, typically formed of concentric surfactant shells with alternating aqueous phases, e.g. lye phase, and with repeated intervals 6.0 to 10.0 nm, preferably 7.0 to 9.0 nm, often 7.5 to 8.5 nm, e.g. 8.0 nm; 5 they contain spherulites with a diameter of 0.5-5 μm, preferably 0.6-5 μm, which, when viewed at a suitable magnification between the cross-polarizers, show the structure of the so-called "The Cross of Malta"; they are thinning under shear; their viscosity reduction 10 is more than 0.35, usually more than 0.4, often more than 0.45 Pa.s, but preferably less than 2 Pa.s, e.g. 0.475 to 1.5, especially 0.48 to 1.1 Pa. s; they have a high payload of the functional ingredients, typically more than 20% by weight, e.g. 25 to 75% by weight, more usually at least 30% to 15% by weight, preferably at least 35% by weight, most preferably at least 40% by weight; their enhancer / active ingredient ratio is e.g. greater than 1: 1, preferably 1.2: 1 to 4: 1, more preferably 1.4: 1 to 4: 1, most preferably 1.5: 1 to 3.5: 1 ; they contain more than 5% by weight, preferably more than 8% by weight, based on the weight of the composition of the active ingredients; they contain less than 25% by weight, preferably less than 20% by weight, usually less than 15% by weight, more preferably less than 14.5% by weight most preferably less than 14% by weight, e.g. 10-13.5% by weight of the composition active ingredients; when centrifuged, they form a single aqueous layer and a solid layer, the yield strength of the aqueous layer being usually at least 1, preferably at least 0.15 N m 2, e.g. 0.2 to 1.0 N m, and the viscosity at 136 s ^ typically less than 1.5 Pa.s; the ratio of the weight of the active ingredient of the predominantly aqueous layer formed after centrifugation to the weight of the total active ingredient of the composition is more than 50%, preferably more than 55%, e.g. more than 60% but less than 90%, preferably less than 85%, e.g. less than 80 %, such as 75-65%; high G-centrifugation of 23 80 473 kee for 90 minutes no clear lye layer was observed; the pH of the composition is above 8.5, preferably 9 to 13, e.g.

9.5 - 12; the composition produces, when diluted with 0.5% by weight of water, a washing liquid having a pH above 9.7, preferably above 10, e.g. 10.9 to 11.1; the alkalinity of the composition is such that 100 ml of a washing liquid containing 0.5% by dry weight of the composition requires at least 0.8 ml of 0.1 M HCl solution to lower the pH to 9, preferably 1 ml, e.g. 4.7 to 8.6 ml of 0.1 M HCl solution; the predominantly aqueous liquid phase (of which there is at least one) contains an amount of electrolyte such that the total amount of alkali metal and / or ammonium cations per liter is at least 0.3, preferably at least 0.5, more preferably at least 1.2, e.g. 4.5 gram ions; the concentration of electrolyte 15 is greater than the concentration corresponding to the first electrical conductivity minima of the electrolyte concentration versus electrical conductivity curve; the electrical conductivity is not more than 2 mS greater than the electrical conductivity of the first minimum electrical conductivity; the concentration of electrolyte-20 is less than the concentration with substantial lamellar phase formation; an electrolyte concentration greater than the minimum to obtain a stable composition, and preferably greater than the minimum to obtain a shear stable composition; the composition is non-shear-25 sensitive; the composition is temperature stable; the composition is stable at 40 ° C; the electrical conductivity of the composition is less than 15 mS / cm; the composition contains at least 15% by weight, preferably more than 20% by weight of enhancer; the enhancer is at least predominantly sodium tripolyphosphate; enhancers contain alkali metal silicate and / or carbonate, preferably sodium silicate and / or sodium carbonate; the viscosity of the composition at a shear rate of 136 s ~ * is 0.1-2 Pa.s, preferably 0.2-1 Pa.s, e.g. 0.3-0.6 Pa.s; the yield strength of the composition is preferably at least 24 80473 0.10, preferably at least 0.15, e.g. at least 0.20, preferably less than 3.0, e.g. less than 2.0, most preferably less than -2 1.5, usually less than 1.0 N m; the enhancer-containing phase consists of solid particles with a maximum particle size below the limit at which the particles tend to sediment; the composition is shear stable; the active ingredients include at least two components, one a non-ethoxylated anionic surfactant and the other a surfactant that forms stable foams such as ether sulfate, alkanolamide or amine oxide.

Interaction of electrolyte and surfactants

When the concentration of dissolved electrolyte in a suitable aqueous surfactant mixture is gradually increased from 0, the composition typically undergoes a series of easily identifiable steps, which are as follows:

Phase I

Initially, the conductivity increases to a maximum, during which the viscosity increases, and initially the clear, optically isotropic L 2 phase shows signs of spherulite formation. These can be seen in a polarizing microscope, where they appear between the cross-Nicolies in the so-called As a "Mal-25 tan cross" structure normally in combination with a spherulitic "G" phase. However, neutron diffraction does not indicate the presence of a "G" phase or any other liquid crystal phase, and is substantially equivalent to a micellar composition.

Phase I compositions are generally clear and stable, but lack the ability to suspend solid particles.

25 80473

Phase II

In the second stage, the conductivity decreases as the electrolyte concentration increases, and the composition becomes cloudy. With high G-centrifugation, the composition separates into a clear water-5 phase and a cloudy "emulsion phase", the volume of the latter phase increasing as the electrolyte concentration increases. Under the microscope, the number of spherulites is continuously increased and the size of the spherulites is reduced, and they are observed to aggregate into loose flocs separated by optically isotropic regions, with more and more flocs being formed as the electrolyte concentration increases.

Neutron diffraction studies show a decreased micelle concentration and an increased proportion of larger bodies, but not a significant amount of "G" phase. Phase II compositions are cloudy and unstable and rapidly form sediment.

Phase III

Conductivity drops to a minimum and then begins to rise. 20 The spaces between the spherulite flocs disappear and the spherulites form a space-filling floc extending through the entire liquid phase. High G-centrifugation does not separate the aqueous phase even if centrifugation is continued for 90 minutes. A yield point is observed which increases to its maximum and the composition becomes more fluid under shear, it has a clear decrease in viscosity.

According to neutron diffraction, there is essentially no lamellar phase at all. Also, according to nuclear magnetic resonance, the "G" phase is essentially absent at all, whereas micelle surfactants are present at low concentrations. Electron microscopy reveals that at least some of the spherulites are multiple lozenges with substantially concentric or partially overlapping shells possibly farther apart than in the normal G phase.

26 80473

The Phase III compositions are stable and capable of suspending solid particles and forming a stable suspension. Such Phase III compositions are the basis of the invention.

5 Phase IV

With further addition of dissolved electrolyte, the size of the spherulites gradually decreases and "The Maltese cross structure becomes more visible. The spherulites are no longer space-filling but form discrete flocs with optically isotropic regions between them. The yield strength and viscosity decrease decrease Neutron diffraction indicates a substantial amount of "G" phase High G-centrifugation separates the clear lye phase from the cloudy layer The composition is not permanent, it tends to form sediment and cannot suspend solid particles.

Step V

A lamellar composition of the type described in EP 86 614 is formed. When water is added in the amount required to obtain a stable composition, the viscosity is relatively high.

The above typically describes electrolytes and a wide variety of aqueous surfactants; the interaction of mixtures of substances. When the composition already contains some dissolved electrolyte, such as active substance-containing compositions suspended in tripolyphosphate, or when the initial mixture of surfactants is not completely water-soluble, the first step can be omitted. Similarly, when the solubility of the electrolyte is limited, as in the case of sodium tripolyphosphate or sodium carbonate, for example, adding the electrolyte above the saturation limit does not cause the composition to proceed to the next steps in the series.

Preferred compositions of the invention are in the third step of the series described above. Between the third 27 80473 and the second stage and the third and fourth stages, respectively, there are intermediate compositions which are semi-stable. Such compositions have spherulite blocks of surfactant that do not completely fill the 5 spaces, as indicated by the high aqueous layer obtained by G-centrifugation for 90 minutes, or the spherulites are capable of irreversible degradation. Although such compositions may be stable when standing at room temperature, they are often unstable under a variety of stress conditions, such as exposure to high shear stress, elevated or reduced temperature, or pH changes. Their ability to suspend particulate solids is often limited.

A large number of previously proposed compositions are in this semi-stable range.

It has now been found that the general compositions in these semi-stable "boundary regions" can be modified in accordance with the teachings of the present invention by adjusting the electrolyte concentration so that the composition 20 comes closer to the Stage III stable region.

When centrifuging the stage III compositions according to the invention, an aqueous layer containing an electrolyte and 90 to 50% by weight of the total active ingredients, typically 80 to 50% by weight, more usually 75 to 55% by weight, e.g. 70 to 55% by weight, is usually separated from them. % of the total amount of active ingredients, and at least one other layer, which preferably contains 15 to 50% by weight of the total amount of active ingredients and a substantial part of the enhancer. The viscosities of the compositions of the invention at a shear rate of 136 seconds are typically 0.1 to 2, preferably 0.2 to 1.5, e.g. 0.25 to 0.6 Pa.sec, and the viscosity reduction is typically 0.4 to 2, e.g. 0.45 - 1.5 Pa.sec.

Phase III compositions are non-shear sensitive and usually shear stable. Instead, the half-line compositions tend to become unstable due to high shear forces. Viscosity often increases substantially even with moderate shear stress and can often sediment rapidly. This can cause practical difficulties during manufacture and bottling. The Phase III compositions of the invention are generally stable at high pH and storage temperatures of about 40 ° C or below 5 ° C, in contrast to several semi-stable compositions.

Phase III compositions typically do not show a lamellar phase by neutron diffraction analysis, although some compositions may show signs of low levels of C phase near the Phase IV cut-off.

Proposed Structure 15 It is believed that the behavior described above can be easily explained by assuming that the surfactant gradually transitions from the micellar phase to the spherulite phase as the electrolyte concentration increases. It is believed that the spherulites are initially in the form of multiple vesicles in which several bilayers are arranged substantially concentrically, however, with gaps that are larger and more irregular than in the conventional "G" phase.

It is possible that there are two aqueous phases, the L 2 and the lye phase, the latter of which may also be the L 2 phase, which contains fewer micelles and more electrolyte than the former. One of these phases, possibly the lye phase, may be the phase inside the vesicles. It has been found that by increasing the electrolytic content and decreasing the relative proportion of active substance, compositions are obtained which are less viscous while maintaining the same stability and solid payload. This is believed to be due to a decrease in the proportion of micellar surfactant without a decrease in the number of spherulites. The reduced amount of micelles reduced the viscosity while maintaining a spherulite phase sufficient to maintain stability.

It is believed that in the preferred, stable composition of the invention, the spherulites are so closely packaged as to form an aggregated junction that is substantially space-filling, i. extends through the entire volume of liquid. The spherulites are likely to interact to form a weak three-dimensional matrix strong enough to support the suspended particles, but therefore weak in that it disintegrates and becomes easy to flow under the action of shear forces, and re-forms when the effect of the shear forces ceases. There appears to be a correlation between spherulite size and stability; compositions with spherulites of 15, 5 or more are less stable than compositions in which the majority of the surfactant is in the form of spherulites with a size of 0.5 to 5.

As the electrolyte concentration increases, the spherulites become smaller and possibly denser, approaching the denser, more regular structure of the spherical "G" phase. As a result, the "G" phase feulites are no longer space-filling and the composition tends to sediment.

Active Ingredients The compositions of the invention preferably contain at least 5% by weight, but less than 30% by weight, generally less than 25% by weight of surfactants. More preferably, the surfactants are present in an amount of 5 to 20% by weight of the composition, e.g. 8 to 15% by weight, typically 10 to 14.5% by weight, particularly preferably less than 14, often less than 13% by weight.

The concentration of active ingredients may be a critical factor in the preparation of the compositions of the invention. When there are less than a certain amount of mini-35 active ingredients, which varies depending on the active system used, the composition cannot be stabilized by adding more electrolyte, however, the maximum is also important to avoid too viscous compositions.

Semi-stable spherical compositions representative of the prior art often contain relatively large amounts of active ingredients. This has resulted in a relatively high viscosity of the aqueous suspending medium, which in turn has severely limited the amount of enhancer that can be suspended within acceptable viscosity limits. Thus, the ratio of the total amount of enhancer to the amount of active ingredient has been low compared to the corresponding ratio of washing powders, and as a result, the washing performance is poor.

It is quite clear that the amount of active ingredients in these compositions cannot be reduced without completely losing the stability of the system. It has now surprisingly been found that if the electrolyte concentration is sufficiently increased, the concentration of the active ingredients can be substantially reduced and thus an aqueous medium with equal or even better stability and lower viscosity can be obtained. Such media can suspend larger amounts of enhancer without losing proper mobility, and at the same time, the resulting large increase in enhancer and active ingredient produces a substantial increase in potency corresponding to the cost.

In general, it is substantially easier to prepare spherical flocs from mixtures of surfactants than from individual surfactants. Thus, mixtures of one or more non-ethoxylated anionic surfactants, such as alkyl benzene sulfonate and / or alkyl sulfate, with one or more additional stable foam-forming surfactants, such as alkyl ether sulfonates and / or ethoxylated non-ionic surfactants. substances 35 or alkanolamides or amine oxides are more suitable than any of these surfactants alone. Minor amounts of ethoxylated nonionic or amphoteric surfactants or cationic fabric softeners may be used.

The surfactant mixture may contain, for example, one or more salts of at least to some extent water-soluble sulfonic acid or monoesterifying sulfuric acid, e.g. , or a salt of an N-sulfo fatty acid or an ester thereof each having at least one alkyl or alkenyl group having 8 to 22, more usually 10 to 20 aliphatic carbon atoms.

Said alkyl or alkenyl groups are preferably straight-chain primary groups, but may optionally be secondary or branched-chain groups. The term "ether" hereinafter refers to polyoxy-20 ethylene, polyoxypropylene and glyceryl groups and polyoxyethylene-oxypropylene or glyceryl-oxyethylene or glyceryl-oxypropylene mixed groups, typically containing 1-20 oxyalkylene groups. For example, the sulfanated or sulfated surfactant 25 may be sodium dodecylbenzenesulfonate, potassium hexadecylbenzene isulfonate, sodium dodecyldimethylbenzenesulfonate, sodium lauryl sulfate, sodium tallow sulfate, ethanesulfate sodium monosulfate, or potassium molecular sulfate;

Other anionic surfactants suitable for use in the invention include paraffin sulfonates, olefin sulfonates, fatty alkyl sulfosuccinates, fatty alkyl ether sulfosuccinates, fatty alkyl sulfosuccinic acid β-namates, fatty alkyl ether acylates, acyl sulfosuccinates, fatty alkyl ether sulfosuccinamates, palmitates, resinates, oleates, linoleates and alkyl ether carboxylates. Anionic phosphate esters can also be used. In all cases, the anionic surfactant typically contains at least one aliphatic hydrocarbon chain of 8 to 22, preferably 10 to 20 carbon atoms, and in the case of ethers, one or more glyceryl and / or 1 to 20 ethyleneoxy or propyleneoxy groups.

Preferred anionic surfactants are sodium salts. Other salts of commercial interest include potassium, lithium, calcium, magnesium, ammonium, monoethanolamine, diethanolamine, triethanolamine salts and alkylamine salts having up to 7 aliphatic carbon atoms.

The mixture of surfactants may optionally contain non-ionic surfactants, or less preferably consist of them. The nonionic surfactant may be, for example, coconut monoethanolamide of a mono- or di-lower alkanololamine C10-22 "" a ^ ^ ano ^ ^ am ^ ^ ^ '

Possible other nonionic surfactants present include ethoxylated alcohols, ethoxylated carboxylic acids, ethoxylated amines, ethoxylated alkyl; lolamides, ethoxylated alkylphenols, ethoxylated glyceryl esters, ethoxylated sorbitan esters, ethoxylated phosphate esters, and propoxylated or ethoxylated and propoxylated groups of all of the above ethoxylated nonionic surfactants. ethyleneoxy and / or propylene-30 oxy groups, or any other nonionic surfactant hitherto used in the powdered or liquid detergent composition, e.g. amine oxides. The latter typically have at least one C 1 -C 22 ~ 'preferably C 1 -C 20 alkyl group or alkenyl group and 35 1 or 2 lower alkyl groups (e.g. or * 33 80473

Preferred active ingredients or mixtures thereof for use in the invention are those having an HLB greater than 7, preferably greater than 8, more preferably greater than 10, most preferably greater than 12, and more preferably less than 18, more preferably less than 16, and most preferably less than 15 .

Some of the detergents according to the invention may contain a small proportion of the total active substance in the amount of cationic surfactants, in particular cationic textile softeners and / or bactericides.

Suitable cationic fabric softeners for use in the invention include, for example, quaternary amines having two long chain (e.g., C 1-6 alkyl) or alkenyl groups and either two short chain (e.g., C 1-4) alkyl groups or one also suitable are imidazolines and quaternized imidazolines having two long-chain alkyl or alkenyl groups, and amidoamines and quaternized amidoamines having all two long-chain alkyl or alkenyl groups. provide a certain water solubility, such as formates, acetates, lactates, tartrates, chlorides, methosulfates, ethosulfates, sulfates, and nitrates The compositions of the invention that have textile softening properties may also contain smectite clays.

The compositions of the invention may also contain amphoteric surfactants, which may typically be included in surfactants with a cationic fabric softener, but may also be included in any of the other types of detergents discussed above, usually as a minor component of the active ingredients.

Among the amphoteric surfactants, betaines, sulfobetaines and phosphobetaines formed by reacting a suitable tertiary nitrogen compound having a long-chain alkyl or alkenyl group with a suitable reagent such as chloroacetic acid or propane can be mentioned. Examples of suitable tertiary nitrogen-containing compounds are: tertiary amines having one or two long chain alkyl or alkenyl groups, optionally a benzyl group and another substituent such as a lower alkyl group; imidazoline having one or two long chain alkyl or alkenyl groups, and amidoamines having one or two long chain alkyl or alkenyl groups.

It will be apparent to one skilled in the art of detergents that the specific surfactants described above are only 15 examples of the most common surfactants suitable for use in the invention. Any surfactants that work well in the wash liquor can be included in the composition. A more complete description of the main types of commercially available surfactants is provided in the last edition of "MaCutcheon's Emulsifiers & Detergents", published by the MaCutcheon division of Manufacturing Confectioners Puhlishing Company.

The electrolyte is an essential component for the surfactant to form a spherulitic system. However, the concentration of the electrolyte is preferably not such as to obtain a substantial number of overlapping planar bilayers which form a non-spherical lamellar phase. Such a lamellar phase may affect the formation of an unstable or shear-unstable composition, unless the payload is so high that the lamellar phase forms a stable structure according to EP 8614A. However, these latter compositions with a relatively strong matrix generally have an unfavorably high viscosity. According to the applicant's findings, a suitable surfactant system with a suitable concentration of 35 can be obtained according to the invention by incorporating a suitable amount of electrolyte into the composition.

When an insufficient amount of electrolyte is obtained, an unstable or shear or temperature sensitive system and / or a system with an unfavorably high viscosity is obtained. The relative amount of electrolyte must therefore be chosen taking into account the nature of the surfactant and the amount of hydrotrope present in order to obtain the composition according to the invention.

The relative proportion of electrolyte can generally be determined by adding increasing amounts of electrolyte to an aqueous micelle solution of active ingredients (typically 15 to 20% by weight of active ingredient) and observing one or more of the following properties of the system: turbidity, electrical conductivity, yield strength, yield limit, appearance high in G-spinning.

When the composition is found to have the above-described Stage III properties described above, e.g., the composition is cloudy, at or near the first electrical conductivity names, has spherulite blocks without clear isotropic regions, the composition does not form a clear layer in high G-centrifugation, and the spherulite region is identified.

The relative proportion of electrolyte can be optimized for this range by determining the amount required for high G-centrifugation to not produce a clear layer in 90 minutes. If the composition is intended for use where low viscosity is more important than, for example, low temperature storage stability, the optimized composition may be gradually diluted until a suitable viscosity is reached or signs of instability are observed. If the latter occurs, then the electrolyte can be added until a sufficiently stable composition is obtained.

36 80 473

The amount of electrolyte is preferably greater than the amount in the first conductivity minimum of the electrical conductivity / electrolyte concentration curve, and the amount corresponds to the amount by which the yield strength of the composition is greater than 0.15 N m -1.

Preferably, functional electrolytes such as carbonates, silicates, pyrophosphates, nitriloacetates and citrates are used, all of which are builders, however, the effective concentration of some electrolytes, e.g. carbonates, may be limited by their solubility. In such cases, it may be necessary to add a more soluble non-functional electrolyte. Sodium chloride and sodium nitrate in particular have been found to be suitable.

Often the relative proportion of electrolyte in one or more predominantly aqueous phases is such that the concentration of alkali metal, alkaline earth metal and / or ammonium cations is at least 0.3, preferably at least 1.2, e.g. 2.0 to 4.5 grammaionia / liter.

In preferred compositions of the invention, the enhancer is normally assumed to be at least partially suspended as solid solid crystals in the composition. The size of the crystals is typically at most 60 μm, e.g. 1-50 μm.

Applicant has found that formulations containing at least a large amount of sodium tripolyphosphate in admixture with other excipients have stability and mobility over a wider dry weight range than similar formulations containing other excipients. Such formulations are thus preferred. However, the invention also relates to compositions containing other adjuvants, such as, for example, potassium tripolyphosphate, carbonates, zeolites, 37 80473 nitrilotriacetates, citrates, metaphosphates, pyrophosphates, phosphonates from EDTA and / or poly-carboxylates, optionally is preferred. Orthophosphates may be present as minor components, as may alkali metal lysates and carbonates.

Silicates and carbonates are particularly preferred because they have several valuable functions. They cause free alkalinity, which is desirable for soaping fats in dirt, they act as builders and, in the case of silicates, prevent corrosion of the aluminum surfaces of the washing machine. In addition, they are active electrolytes necessary for the formation of a spherulitic system.

When silicates are used in the compositions of the invention, their Na 2 O: SiO 2 ratio is typically 1: 1 to 1: 2 or 1: 1.5 to 1: 1.8. However, it should be noted that other ratios of Na 2 O (or other base) to SiO 2, or even silicic acid, are also suitable for use in obtaining silicate 20 in the composition, with the additional alkalinity required being obtained by adding another base such as sodium carbonate or hydroxide. In formulations which; not intended for use in washing machines, silicates need not be used, provided that the alkalinity is obtained from 25 alternative sources.

Applicant does not exclude from the scope of the invention compositions in which the enhancer is substantially solely in solution, such as when the excipient is sodium nitrilotriacetate, sodium citrate, sodium silicate or mixtures thereof.

The proportion of enhancer is normally at least 15% by weight, preferably at least 20% by weight of the composition. Preferably the ratio of enhancer to surfactant is greater than 1: 1, preferably 1.2: 1 to 35: 4.

38 80473

For economic reasons, most of the cations in the composition should be sodium ions. Thus, the preferred enhancer is, for example, sodium tripolyphosphate, preferred anionic surfactants are the sodium salts of sulfated and sulfonated anionic surfactants, and possible anti-redeposition agents, e.g. carboxymethylcellulose or alkali, e.g. silicate or carbonate, are also preferably used. 10 format. Sodium chloride, sodium nitrate or other inorganic sodium salts may be added to increase the electrolyte concentration. Calcium is normally used only when the active ingredients include surfactants such as olefin sulfonates or nonionic surfactants which are not disturbed by calcium. Magnesium salts may be present and are more compatible with surfactants than calcium.

Alternatively, but less preferably, it is possible to select potassium, ammonium, lower amine, alkanolamine cations or mixtures thereof. However, compositions containing large amounts of such cations are not likely to be cost effective compared to conventional washing powders.

The compositions of the invention are preferably temporal and are preferably buffered with an alkaline buffer to obtain the pH of the composition as measured: with a glass calomel electrode greater than 8.5, preferably greater than 9, most preferably greater than 9.2, e.g. 9.5 to 12, especially 10 to 11. It is particularly preferred that the compositions are such that, when used, the pH of the 0.5% (dry weight) washing liquid becomes more than 9.7, e.g. more than 10, in particular 10.5 to 11.5. Their free alkalinity is preferably such that a dilute composition solution (100 ml) containing 0.5% (dry weight) requires at least 0.4 ml, preferably at least 0.8 ml. most preferably 1 to 12 ml, e.g., 3 to 10 ml, typically 4 to 9 ml of 0.1 M HCl solution to lower the pH to 9, although more strongly alkaline compositions may also be commercially acceptable. In general, lower alkalinity is less commercially acceptable, although this is not excluded from the scope of the invention.

The alkaline buffer is preferably sodium tripolyphosphate and the alkalinity is preferably obtained at least in part with sodium carbonate. Other preferred time buffers include, for example, sodium silicates.

Hitherto known liquid detergent compositions have usually contained a considerable concentration of hydrotropes and / or organic water-miscible solvents, such as methanol, ethanol, isopropanol, glycol, glycerol, polyethylene glycol or polypropylene glycol. However, they are expensive and are not functional ingredients. They may, under certain conditions, promote pourability or facilitate the formation of a spherulite phase of surfactant. They are thus not completely excluded from all compositions according to the invention, but their amount is limited to the minimum necessary to ensure a spherulitic composition and suitable pourability. If they are not needed for these reasons, it is more advantageous not to use them.

25 Solvents sometimes need to be added as components of perfumes or other common minor ingredients.

The dry weight of the composition affects its stability and pourability. The optimal dry weight may vary considerably depending on the type of formulation, and the dry weight is selected taking into account the required viscosity. In general, it has not been observed to possibly * obtain stable compositions with a dry weight of less than about 35% by weight, although some types of formulations can be obtained as stable containing less than 30% by weight and sometimes even less than 25% by weight. Thus, the possibility of preparing 80473 stable compositions with a dry weight of up to only 20% is not excluded from the invention.

The formulations according to the invention are characterized in that their dry weight range is such that the composition is both stable and pourable. Sedimentation usually occurs below this range and above this the formulation is too viscous. The acceptable range can be determined for a particular formulation in a conventional manner by preparing a suspension, using a minimum amount of water to still obtain a miscible composition, diluting several samples progressively to higher dilutions, and observing possible sedimentation over a suitable period of time. In some formulations the acceptable dry matter range may range from 30% or 35% to 60 or even 70% by weight, in other formulations this range may be much narrower, e.g. 40-45% by weight.

If the above methods fail to determine a stable pourable range, the formulation should be modified as described above, e.g., by adding more sodium carbonate, sodium silicate, or other electrolyte solution if the composition has Phase I or II properties, or by reducing the electrolyte content or by adding a hydrotrope if the composition has Phase IV or V properties. Alternatively, if there are difficulties in obtaining a stable spherical system by simply changing the electrolyte concentration, then the active ingredients may be modified by the addition of a foam stabilizing surfactant such as alkyl ether sulfate, alkanolamide or amine oxide if the composition is V, or by adding alkyl benzene sulfonate or alkyl sulfate if steps I or 35 II are predominant.

4i 80473

In many cases, the compositions of the invention can be readily prepared by normally mixing the ingredients together. However, the preferred compositions according to the invention are characterized in that they do not become unstable or thicker when exposed to high shear forces.

The order in which the ingredients are mixed is sometimes important in preparing the structurally stable compositions of the invention.

The compositions of the invention can typically be prepared from any suitable active ingredient by first preparing a clear aqueous solution of the active ingredients in a suitable concentration (e.g. 15-30% by weight of active ingredients) of L 2, if necessary by heating and dissolving the electrolyte in L 2 solution. or by adding a concentrated electrolyte solution (preferably a functional electrolyte) until the mixture becomes cloudy. A sample of the mixture is then centrifuged at 20,000 G for 5 min. If a clear aqueous phase is formed, more electrolyte is added to the mixture until high G centrifugation no longer separates the substantially clear aqueous phase. The weight ratio r of active ingredient to dissolved electrolyte is recorded.

A composition containing all the desired ingredients, the weight ratio of the active ingredient to the electrolyte has already been determined, can then be prepared with the desired dry matter content (typically 40-50%). The formation of a clear aqueous lye by high G-centrifugation indicates the presence of a lamellar phase, whereby the amount of electrolyte is reduced until high G-centrifugation no longer gives a clear phase. The formulation thus obtained can be sampled at different dry matter contents to determine optimal mobility / stability properties.

35 If it is difficult to find a suitable active ingredient / electrolyte ratio in the first step of the above procedure 42 8G473, the procedure can be repeated using a more soluble electrolyte, e.g. a non-functional electrolyte such as sodium chloride or sodium nitrate. Alternatively, the active system 5 may be modified by the addition of surfactants which promote the formation of stable dispersions according to the invention, e.g. ether sulphates, amine oxides or alkanolamides if the properties of stage IV or V are observed, or a non-ethoxylated anionic surfactant if phase I or II characteristics.

Stirring is typically performed at room temperature, with certain ingredients, e.g., nonionic surfactants, such as coconut monoethanolamide, being gently heated, e.g., to 40 ° C, to obtain acceptable dispersion. This heating is usually obtained from the heat of hydration of sodium tripolyphosphate. To ensure adequate heating, the tripolyphosphate is preferably added in anhydrous form containing a sufficiently high proportion of the high temperature modification, commonly referred to as "Phase I". The above process is just one of many methods that can be satisfactorily used in the preparation of all or most of the compositions of the invention. Some formulations are more sensitive to mixing order and temperature than others.

When considering in detail the different types of formulations according to the invention, a distinction must be made in particular between formulations of the high-foaming sulphate or sulphonate type and low-foaming formulations.

High foaming formulations may be based on one or more non-ethoxylated anionic surfactants, preferably a sulphate or sulphonate surfactant with the addition of 43 80473 one or more other stable foam-forming surfactants, such as an ethoxylated anionic surfactant. active substance, amine oxide or fatty alkanolamide. The first component of the active ingredients, i.e. a non-ethoxylated anionic surfactant, may be, for example, a C 1-6 alkyl sulfate and / or a C 1-4 alkylbenzenesulfonate. The second component or additional surfactant may be sodium C 1 -C 20 straight or branched chain alkyl (C 1 -C 4 mol) ether sulfate 10 or alternatively alkyl phenol ether sulfate, amine ether sulfate, alkanolamide ether sulfate or fatty acid ether sulfate, or be an amine oxide or a fatty alkylolamide. The weight ratio of the total amount of non-ethoxylated anionic surfactant to the additional surfactant is typically 5: 1 to 1: 3, preferably 4: 1 to 1: 2, e.g. 3: 1 to 1: 1. The composition may contain minor amounts (e.g.

1% by weight of the total composition) soap to facilitate rinsing of the fabric. The composition may contain minor amounts of nonionic ethoxylates, typically up to 20% by weight of the total active ingredients, preferably less than 15%, usually less than 10%.

In the above formulations, the sodium alkyl sulfate or sulfonate may be replaced in whole or in part by other sulfonated, non-ethoxylated surfactants, examples of which are fatty alkyl xylene or toluenesulfonates, or paraffin sulfonates, laxyl sulfate and olefin sulfone esters and amides, including sulfosuccinates and sulfosuccinamates.

The alkyl ether sulfate may be partially or completely replaced with other ether sulfates, such as alkylphenyl ether sulfates, fatty acyl monoethanolamide ether sulfates, or mixtures thereof.

Thus, in a particular embodiment of the invention, a stable, pourable, spherulitic composition is prepared, 44 8G473 containing water, 12 to 40% by dry weight of active ingredient based on dry weight of the composition and 20 to 80% by dry weight of excipient based on dry weight of the composition, which is at least partially suspended as a solid. as a substance in the composition and in part as at least a part of said dissolved electrolyte, and the active ingredient consists of (A) 30 to 80% by weight of a non-alkoxylated anionic sulfated or sulfonated surfactant and (B) 20 to 70% by weight of at least one a foam stabilizing additive surfactant such as an alkoxylated anionic surfactant, an alkanolamide or an amine oxide.

The above composition may optionally further contain up to 6% by dry weight of the composition 15 soaps. The non-alkoxylated sulfated or sulfonated anionic surfactant preferably consists essentially of an alkyl sulfate or alkyl benzene sulfonate, preferably sodium alkyl benzene sulfonate, e.g., C 1-10 alkyl benzene sulfonate.

Alternatively, the anionic surfactant may consist of a mixture of alkyl benzene sulphonate and / or alkyl sulphate with alkyl ether sulphate and / or alkyl phenol ether sulphate in a weight ratio of e.g.

1: 3 to 5: 1, typically 1: 2 to 4: 1, preferably 1: 1 to 3: 1, e.g. 2: 1.

The low foaming compositions of the invention may be prepared using suitable antifoaming agents. Care must be taken in the selection of antifoams, as certain commercially available antifoams may lose their potency in the compositions of the invention during storage of the composition, and others are effective only at concentrations that affect the viscosity or stability of the composition. Mixtures of organopolysiloxane and colloidal silicic acid have been found to be particularly effective.

45 80473

Another specific embodiment of the invention is a stable, pourable, liquid, aqueous detergent composition containing 12-40% by dry weight of active ingredients consisting of 30-90% by dry weight of 5 non-alkoxylated sulfated and / or sulfonated surfactants. the remainder being alkyl ether sulfate and / or alkanolamide or amine oxide; an aqueous phase containing an amount of electrolyte dissolved to be sufficient to form a space-filling spherulitic joy consisting of said active ingredients sprinkled with said aqueous phase; suspended active ingredient particles; an effective amount of at least one antifoam agent and possibly minor minor ingredients.

In addition, one embodiment of the invention provides a pourable, stable detergent composition having a payload of 30 to 50% and consisting essentially of 12 to 40% by dry weight of the composition of active ingredients, at least 30% of the dry weight of the composition 20 of the builder, and wherein the builder and the weight ratio of the active ingredient is greater than 1.1: 1, and wherein said active ingredient comprises substantially an alkyl benzene sulfonate having 8 to 18 aliphatic carbon atoms and an alkylethanolamide selected from C 1-4 alkyl monoethanolamides and diethanolamides, wherein the weight ratio of alkylbenzenesulfonate to ethanolamide is 1.5: 1 to 4: 1, and wherein said enhancer is selected from sodium tripolyphosphate, sodium carbonate, zeolite, sodium nitrile triacetate, sodium silicate and mixtures thereof, such that the enhancer is in an amount of Provides a yield point over 0,15 N m "2.

A particularly preferred embodiment of the invention comprises a pourable, stable liquid detergent composition comprising substantially: 468 0 4 7 3 A. (i) sodium alkylbenzenesulfonate having 10 to 18 aliphatic carbon atoms, preferably 10 to 14 aliphatic carbon atoms, and ( ii) a mixture of sodium alkyl ether containing on average 8 to 18, preferably 10 to 14 carbon atoms and 1 to 20, preferably 2 to 10, e.g. 3-5 ethyleneoxy and / or propyleneoxy groups in a ratio of (i) :( ii) 10: 1 to 1 : 10, especially 10: 1.5 to 10: 5, e.g. 10: 2 to 10: 4; B. an enhancer selected from sodium tripolyphosphate, zeolite, sodium nitrilotriacetate 10 and mixtures thereof in a weight ratio of B: A of 1.1: 1 to 4: 1, preferably 1.2: 1 to 3.5: 1, e.g. 2: 1 - 3: 1; C. an electrolyte selected from sodium carbonate, sodium silicate, sodium nitrate, sodium chloride and mixtures thereof in a concentration of 2 to 20% by weight, preferably 3 to 18% by weight, especially 7 to 15% by weight, based on the weight of the composition. the load is from 30 to 50% by weight, preferably from 35 to 50% by weight, e.g. from 38 to 45% by weight, and which composition preferably contains small but effective amounts of anti-redeposition agents, preferably sodium carboxymethylcellulose, perfume, color and optical brightener.

In the above composition, the sodium cation may optionally, but not preferably, be partially replaced by potassium, lithium or ammonium ions. The enhancer-25 is preferably 40 to 95% of the total weight of the substance, e.g.

45-80% sodium tripolyphosphate. The composition for automatic washing machines preferably contains at least one anti-foaming agent.

The above compositions may optionally contain minor amounts of an alkanolamide, such as coconut monoethanolamide or diethanolamide, or an ethoxylated nonionic surfactant.

The compositions of the invention may contain the usual minor ingredients. These are mainly 35 anti-redeposition agents, dispersants, optical brighteners and proteins.

47 80473

The most commonly used anti-redeposition agent in the manufacture of detergents is sodium carboxymethylcellulose (SCMC), which may be included in the compositions of the invention, e.g., in an effective amount that does not prevent the desired viscosity and stability from being achieved. In general, SCMC is effective at concentrations of about 1%, and this concentration is preferably not exceeded, as higher amounts of SCMC greatly increase the viscosity of the liquid composition and may also affect stability.

Alternative anti-redeposition and / or soil release agents include potassium, ammonium and other soluble salts of CMC, phosphonates, methylcellulose, polyvinylpyrrolidone, carboxymethyl starch and similar polyelectrolytes, all of which can be used in place of SCMC.

Optical brighteners (OBA) are optional but preferred ingredients of the compositions of the invention. In contrast to some known formulations, the compositions of the invention 20 are not stability dependent on OBA, so any suitable and cost effective OBA can be selected as OBA, or OBA can be omitted altogether. It has been found that any of the fluorescent media hitherto preferred for use as brighteners in liquid detergents, as well as many of the dyes normally suitable for washing powders, are suitable for use. OBA may be present in the composition in a conventional amount. Typical OBA concentrations of 0.05 to 0.5% are sufficient, e.g. 0.075 to 0.3%, typically 0.1 to 0.2%. Lower concentrations can be used, but are hardly effective, whereas higher concentrations, which are not ruled out, are unlikely to prove cost-effective and may in some cases cause compatibility problems.

Examples of typical optical brighteners that can be used in the present invention include: 48 80473 ethoxylated-1,2- (benzimidazolyl) ethylene; 2-styryylinaft / ϊ, 2-d / oxazole; 1,2-bis (5-methyl-2-benzoxazolyl) ethylene; disodium 4,4'-bis (6-methylethanolamine-3-anilino-1,3,5-triazin-2 "-yl) -2,2'-5 stilbenesulfonate; N- (2-hydroxyethyl-4, 41-bis- (benzimidazolyl) stilbene; tetrasodium 4,4'-bis- [4 "-bis (2" -hydroxyethyl) amino-6 "- (3" -sulfophenyl) -amino-1 ", 3", 5 "-triazin-2" -ylamino] -2,2'-stilbene disulfonate; disodium 4- (6 "-sulfonaphtho [2 ', 21-diazriazol-10 2-yl) -2-stilbene enulfonate; disodium 4,4 '-bis / 4- (2-hydroxyethoxy) -6 "-amino-1", 3 ", 5" -triazin-2 "-ylamino] -2,2'-stilbene disulfonate; 4-methyl-7-dimethylaminocoumarin and alkoxylated 4,4'-bis (benzimidazolyl) stilbene.

Bleaching agents which do not affect the chemical stability and are compatible with the ingredients of the composition may optionally be added to the liquid detergent compositions of the invention. Encapsulated bleaches may be part of a suspended solid. The effect of the peroxygen bleaches in the compositions of the invention can be enhanced by the use of effective amounts of bleach activators such as tetraacetylethylenediamine. Light-activated bleaches such as zinc-25 or aluminum sulfonated phthalocyanine can also be used.

Fragrances and dyes are common in detergent compositions up to 1 or 2% and can also be used in the compositions of the invention. Sometimes care must be taken in the selection of suitable fragrances, as the solvents in them may alter the behavior of the active ingredients.

The compositions may contain conventional amounts of proteolytic and amylolytic enzymes together with any enzyme stabilizers and carriers. The enzymes generated by Capse-35 can be suspended in the composition.

49 80473

Other minor ingredients include antifoams, alkalis, buffers, microbicides such as formaldehyde, opacifiers such as vinyl latex emulsion, inert abrasives such as silicic acid and corrosion inhibitors such as benzotriazole.

The compositions of the invention are generally suitable for laundry and can be used to wash clothes by mixing them in a washing liquid containing one of the compositions of the invention described herein. The low foaming compositions described herein are particularly suitable for use in automatic washing machines. The compositions can also be used to wash dishes or to clean hard surfaces, making low foaming products particularly suitable for use in dishwashers. These uses form a further aspect of the invention.

The compositions of the invention can generally be used for washing clothes in boiling water or for washing in warm or cool water, e.g.

At 50 to 80 ° C, in particular at 55 to 68 ° C, or at 20 to 50 ° C, in particular at 30 to 40 ° C. Typically, the compositions are added to the wash water in an amount of 0.05 to 3% by dry weight of the wash water, preferably 0.1 to 2%, more usually 0.3 to 1%, e.g. 0.4 to 0.8%.

The invention is illustrated by the following examples. The compositions of the examples were stable and pourable. They withstood storage: at 40 ° C and were non-shear sensitive. They were temperature and seasonally stable with the exception of the composition of Example 83.

so 80473

<D

ε ΙΛ ΙΛ 00 ο I ^ '"Ι. ^

• Ρ 2 cnT '“Ι ^ CVJO ^ .1 I

W

LD

ro η νο r · * ro ro ^ J _ * «· v« * i · *. '«Σ> es *» o * csjiio

• H ^ I

C/O

w • m S O w m r-. i i r tn 1 ~ o. . , w n H O tn m co eri ι t '"" i.

M ^ ^ Olli

M

es i o tn in ui. 2. · 2. “l O.

In ^ ^ o ι o es w. . 1-1 ui. O ui in un I 2 ι "" 1.

g ^ es - <Oli ι

•B

M

w en

O

l (1) • HO) l m -h

-H 44 -P -P

rW O -P -P

>, (Ö -P -P (0> 1 en 0) ro lö X O -. (Ö 4-1 r-t o ή ι — ι en

iej ι-1 O ί> ι O

ι 3 E en m C iH 44 -h a>

eu .H ro o H C

C Q> - -P> i -H

• h -h tn ι ei)> i nj

P -P -H -H - Ai O

(Tj -p ι — I ι-H ι — I rH -p (0> ι> ι ΟΠ3 en

<D -P Ό (d> 1> 1 β I O

3 -P -P -P 4-1 -P 44 ooC

-HfOg-pen ei) ή oo γη O

-h dj ees -P oe <t »a> - 'ι ό I 3 -P rd 4-1 -rl I -P -P to Λ • s * O rH nj> 1 en <ä en« hh to rH 4 -i O 3 rH x HeeJOU «3 I -P 3 OOOI 44 .3 I>

0 3 (β Λ (¾ <Λ es P O -H

RHen + JP-H P <—l -P 44 Ό 3 u -p (1) 1 «P -H (Ö U -P 44 P eu

1 3 -P 44 -P -P 44 l-P (ÖHJ C

E 0) Ί) 6 e -PE E -P 3 I -Π -H

3 <D en 3 3 -H 3 3 (00) 03 3

• H eO O -H * H -H -H * H fö 3 Ή I O

P .p 44 P P P P P P 44 -H ΙΟ -P

-PCO-P-P O-P -P P -P CN 3 I

(tstUO eeJ rd 0) ed reJ 3 CU PO -p

Z Λ «Z Z CS3Z Z en O U S W

ς1 80473 (N 51

"B

• S

0) Ä LO * -H

M O to LO 00 O *> K t t I

* -H f-H O O

"B

rH

J *} - 5 m cm cnj lo oo - <ir> o • H · * * »“ VV · * V * v · *

CflOt ^ UlcOOO 1 o O I «H

w ^ o

I-i

‘LO CM CO r- <LO 2 LO CM

"* *» ** V * N * »*»

H Oi * 5j- CO oo I O O CM I

CO «—1 w« Ti

«T

. ro CM CM O O «HIO

pv * »» »· *» * »·» o * to σ> σι ιοο ι ι tn u 00 ^

CM «O« O LO «H LO LO

»·» S · »H S * 6 O» m ι ι o O cm t

• H CM

to w

r *. LO

• O LO ίο ΙΟ I ^ '"' t. | | I

K * H CM «H O

tn w to o 0) tn I Ή

• H P

rH P

> 1 (0 G

>, to (0

X OP

rH O to

to rH O

ι 3 m G rH -P 0)

O) rH rH G

G 0)> 1 'P

• h -h tn> 1 rö O

p -h -p -h λ; cd c G rö -P rH I — I -P Ή

tO -H -H G> i G tn tO

0) P g G> 1 I 0) O

G P 3 -H Ή P 00 GP

-Hto-HPtn d) »H Otn rHtOrHpO g 0) I Ό 0)

I G O tO MH »HP« o .G G

m <O G (ö> i tntn rH (OO

rH P (0 G rH Aitoo (0 Ό ι rH p o o o x ι>, c O 3 0) .Q O. <, Ω P -P 3

rH CO O P -P ρ · ρ Ό G <tJ

O -P G (0 P -P (ΰ X 0)>

IGO ^ PP X ta G H

g 0) g g g P g G -n -H G

30) 0) 33 -rl 3 0) GO

• H tn O -H -rl -rl -rl G I O Ai

P P X P P «H P -P o -P -H

PCOPPO PPG I rH

(00) 0 (0 (00 (ΟΛΟ -H-H

2ΛΧΖΖΝ ZOS WU) 52 80473 σ \ ιΗ e ° ν ° ν ° s ^ ^ η ^ 2 ί '' - ο "ο '

W

00 I — ί

ε 'Ί. ° »_" * · ^ S

rl _Τ ν 00 ». «. - tn 00 00 ® * - · 1 ι ιοι ι

ι I

• _ Λ LΛ ε *. ν Ί -η ο ^ mcoorHi ιοι ι

UJ "Ί — 4 rH

Η to γΗ Ε ο ο ^ m2 ^ mcoo-Tcs? I o 'I ι W ^ m

pH

‘^ ^ TO ^ - ^« Tl LT) 2

• H 1 2 3 n - «» rT I I r-T o "cT I I

to ^ w rH IT)

O O O H OI

c5 w> m m ι r — ι cnj _iq i ^ h S'-4 cnj

•B

C/O

M

'' ID

- * ι — I O. — ι: ':. 2 m m in 1 ^, ι o 'I.

. t - * H

tn "w il

I -H

• rl tn ή

Ή .¾ -P

> ι Ο 3 -P

> ι + j tn m 2 Q) o (0 ι rH - O h tn

(¾ ιΗ ι — I ί> ι O

10 3 tn tp cg ή λ: · η ω

0) ι — I O rH C

Cn Q) -P> i -h • rH "r -rl tn O> 1 CU CÖ

p -H -P -H .—. Ai CO., LTD

(Oi — I -P l — II — I rH -rl-P

(0 -H> 1 (0> ί O 3 S0?

(0 -P> 1 <tJ> i E I 0 <U

C -P Ai Ή 4H -P CO -PC

rinJiH-Ptn tooo rH tno

H 3 (0 -P O E ~ itntJtUO

ι e ι io 4-i -r-ι -h to o ό e si · o co ro tn r-ι i — itutnOtö rH Ή rH C rH Ai OU tfi (0 Ό «0 IH 10 O 0, CI -H Ai Ä> 3 γη Λ Λ <! Λ O -HPP 3 rHtn HP · η pa; ό <0 · η 3 e L) -HU -Η 3 Ρ --H 3 Ή -Ρ rV> α> iCi-ΡΛί HJ + j ^ to (dtn -ne

gtU E-PE E -P E I -ntOC C -H

3 (0 3 (03 3 -H 3 oo -H <0 O C

• rl tn -rl 3 -rl -rl -H -H rH I -P C X O

p 4J p 4h P p rH P l O-P-P -H -H

4-1 C OHO -P O -p PH C 3 -P rH I

ro CU (033 3 tsp) 3 H 03CO-H -H

Λ 2 tn Z Z IS1 Z CJ S 44 O CO W

53 80473

""B

CM

^ t ® o o o m £ Ή _ ♦ "·» »». ... ^ __ M® '' »» a-cr.onj oo W rH · - · o

CN

e Ί ®. ° "o» “01« m ® σ '· o θ'

W

tn

I -H O

h -P ω: G -n ω

Φ td -H

φ td M

tn μη Φ

+ J -H -P

c 3 M

Φ m Φ

n -H -H

-h tn -h -p rH X -P 4->> 1 O -P td> i -p td a

Md) n3 MH

r-l <- »rH tn td Ή> i o 10 tn 4-i G g X <* Φ O ή G ro 4-1> 1 • H w -H Φ> 1

p -H 4-> - X

(0 r-l 4- · i — I i — I

td> λ nj O <d φ> i td ei G X -H 144 oo • H r-l 4-> tn OO r-l r-l (d 4J O ^ I Φ | I Φ MH -rl to 4-1

Tjt ^ td 5 * 1 * —i i — i tn rH r-H G Ή O O <d

I I O O Λ IX

O · Η ίΝ Λ & i <0 -HP

H 4J Ή p -H, * Ό -H

CJ4-> U <dP -rl rH X

i id i λ; 4J 4J td td

e td g g 6 4-i i -Γ-, G

3 G 3 3 3 -rl oo Φ

-H O 'P * H * rl * P rH I G

P MH P PP rH I O -H

4-> rH4-> 4-> 4- »o m C 4-1 td 3 td td td φ> -H oOi

Z tn S S Z isi u SO

54 80473 'a * es m o • -h «s - m Π k ·» * ΙΛ h «rr ^ co,, tn w ro ® σ» «Λ f- r *.

e * ^ ^ ^ ui1 2 '-t _r _t

•B

tn w es:: tN es es io o, oo co. cc «· to Π I ^ g ^

•B

tn w

. Γ -H

tn -h a; -p o -p 4-> (0 <D ro

.-. I-i

H> i I -ho tn e -pe -ha <<υ -m + jo C (0 00 4-) + j • H t0 '- "-H (0 0) MC -H +) (0 - (0 O Ή -P 4-> Ή

tO 4-1> i (0 (1) O -H

CD Ή>, (0 tn E Ό

C C M -H m (0 -H

• h tn .H gj tn -h oo E

* -t -H (04-) OM ^ rO

1C I (0> 4-1 4- »-H-H

S'tD 00 (0> i O Ή r — I

rH (D i — I C (—li — I O O

.: l tfl I O O H Λ e

0 4-) rs X! Cu M O tO

r-ic Ή M -H 4-> -P

U CU U-Hto M -H H CD

1 Λ I -P M -P C cd -H

E -H g -P g g g I Ό 3 ή dedd e 3 oo tn M £> ι · γΗ (0 · Μ · Η »H γΗ Ο Μ>, ΜΜ-Ι Μ Μ Μ ιλ;

4->, * · Ρ -Η 4-> 4-> 4-> CSO

(0 Η (03 (0 (0 (0 ι — ΙΟ 2 cd 2 ϋ) 2 2 2 U «55 80 4 73 vo ^ co rr en cr> i oo ^ ^» V. * - • οο ^ ιΐΛΐ ^ - t cvj o toi E cm

•B

tn

W

in (N ΙΛ r — i c I LT) σι cf) I «t o 'ΙΛ. — l -5

«I

w • H Ή c 4-> αι -μ 01 <0 W (0 4-1 4-1

G

01 3 Λ m - • H -H Ή: r-ι tn>, ro Λί vo

>, tn O

, ¾ O -H Ή rH O 01

(0 i — I -— · O

I 3 rH (M

C H O <0 0) Ή E 2 G 0) -H -ι-l tn o cn 01

P -rH 4-1 -H 2 O G

ro Ό 4-> rH -H -H -H

(0 -H fÖ> i pH C / 5 (0

01 g (0> 1> i '—O

G (0 -pH V (_ | 4-1> 1 4-1 -H -H 4-> «0) A! -H tn P — I .H 4J o ε pH01 4-101

I O <0 4H -H (0 4-> 4-1 G

g <0> i tn oo tn too rH r0 G H X rH r0 ¢ 0¾

I4-IOO o ia; a: -G

O -H 0), Ο Οι <Λ CN> H -H r0 rl +1 O 4 H> H pH H tH (0 0 4-> G r0> H -H r0 U X -H>

1 t0 O Ai 4-> 4-> Ai I tn -H

E to ε ε ε 4-> ε eg eg 3 G tn 3 3 -H 3 3 oi 30

• H O O · Η · Η ** H Ή Ή G -H fX

U x M O Ή> H μ -H M -H

4J pH O 4-1 44 O 4-1 4-14-1 4-> Ή

rO 3 O rö r0 0) (0 rö Oi r0-H

2 tn 2 2 2 n 2 20 2W

56 8 O 4 7 3

C/O

IN

W ® 2 ro

e ® H 10 S O * O? I

H ™ co w. . t "rs) '2 · UO,

H CM

•B

C/O

W

•B

Ό

•B

(0

X

o p β

I · Η * P

β -P -P

<u -p e c ro δ -H (0 -H · Η0) P β -H -P Ή β nj O Ό -P> i -h fl -H (0> 1 (ti

Q) rH g (0 -P O

β β Cd -H M-l d) -P

• P CO -P -P CO g CO

i — I * P i — I + J O O * P d) I β O Cd «n -P Ό β

- <* d> β Cd> 1 CO -H O

Γ — I QJ cd β iH Cd H Ό i co + j o o x> 1 x; O + JCUXJ (¾ P> 1 cd nH β o P -P -H X cd

UdificdPx-H>

1 X5 o X -P Cd -H

ε -h ε ε e β ι β 3 h ci) d 3 d) ^ o

• P> i O -P -P β Ή X

P> j λ; p p -h ι -p -D ^ O-P-P -P 04 Ή id rp o cd cd Dj * —ι · ρ

2 cd * Z 2 O O CO

„57 80473 ro E IT) Wf> • Η · *. · **

W ^ CVJ * —I f I CSJ I »O

w cnj »-h ro c un un 5 ^ · *** · *.

, ri ON CM «—4 I I CVJ o I I

w CVJ f— (w m m • tr »ε ·» • H O e in i i O i cvj i tn

W

ΓΜ n ε • HO i i m i r-. i ιλ i en · - * <- <^

W

m. and un

C

5 O i i and i * j- r *. »I w w o ro g σι i i csj p ^. and ι i • H w · —i en w ΟΊ

(OF

* O ir> ι ι i cvj o ι · ε «—ι cvj t — ι

-B

tn w o 4-> <L>

r-I

IHO I

e -μ ε ^ QJ + j o -p

C td n -P -P

• h td - tl) <d M d -H -H - -H (0 td O rH Ό Ή -P 4-> (d Ή> 1 -H -HO -P φ 0) <H> 1 BOB min dd M td -h -h td td

• H tn> H -H e CO 4-1 <44 -H

nH-Htd · η «j - -ptnn idi o -h -h td o -p

t * QJ CO d rH rH td <44 O

ι — ίο ι — ι td o o diH1 ^

I tn I 4-> d £ O Ή -H

04J CN -H <U Ido <Λ O H

rH d t — I 4-1 0-ΡΛ! H Λ 4->

U <U U -P C Φ H -H <d -H -H

I -Q I td .0 -H td -H 4-1 JX M C

ε -h ε φ ε όι-ρ-ρ ε + j ε d ή 3 4-1 tn tnco4 - »- H d d d H * H rH O O ι — I td · Η · Η · Η Ή

H> 1 H d M> ilfd <H U> 4 H

4 ->, * 4-> ΐη O O CM rH O 44 -P -P

td h td -h O o ή> «<d td co td

ZtdZtn «« utntsi 2 2 2 58 80473 oo ro e ^ «m H 00 '« Γ. cc

tn CH

W

r- co

. ^ CM CSJ CC CO

^ -H -H -sr I

m · “· w

SD

C/O

g O 1 "^ 2 '

•B

tn

W

* * H

tn - X Ή

: O

-P SD

Q)

I-i

rH O

IHO <N

Ö -P g (0 <1) -P 2 C (0 ro ··

H (O-H (N

PC -H -H -P O

H} O Ή Ό -P -H

<0 4H> ι -H (0 CO

<U -H> 1 g «J ~

C 3 Λί (0 MO

• H tn rH -H tn -H

rH * P (0 rH O * P

I C I O tH + J

H- O OO C> 1 (0 r-l O) Ή fO rH <0 i tn i + j o m

O -P (N <u <a -H

i-H C i— | O * H iH

U 0) U -H c -h P -H

I Λ I -P O -P -P tn g-p g -P g -P g g

CrHCrtJtn-HC 3 • H> ί -rH fO O -H · Η Ή p> i P U-l ^ rH p p

P -P rH O O -P -P

(drH (030 0) (0 (0 Z (0Ztn «tS32 2 i? 59 80473 3 ° v °° ^ ~ ^ - h *« * · »00, o O o, * r • φ ά ~ ° - - S 2 s

W 1/1 ^ ^ £ '1 o' o 'o' I

m rr § »o o o E £ o * 2 ^ s ° ° *

CM

-H ^ ® °° - °°. - ~ O

Mvofncooj'o ~ o. _T

rH

ε O m «3- CM σ> o 2 o

to ^ ^ r? 1 cm cm o i ^ T

ω 00 o "= 3 · g“ I ° CO «> - o t * * - * 8 '° ° ° - w σι ro. oooooo £ E m

«^« • toLoeo ^ H o o o I

to w

• P I — I

> 1> 1 3 p to 0)

O O I

O T3 --- t to rH · Ρ P 0

I H 3 g -P * P

g p I — t fO rO · Ρ (U -Μ> -H I 3 Ή C 3 <U -P MH> i

Η (0 -H to f-t rH> i O

PC -P Ή id 3 M (S

nJO P Ή -P to <H -P

(«4-Ι-Η 3> i ^ -H 3 3

0) ι-Η Ό 3> i I rH I O

C 3 · <Η -Η Ή -P P>, 00 -P

-P tO g P 10 <1) I> i rH £ rH -H 3 -P O g-H4-> 0) 1 0)

1C -H 3 MH · Ρ r — I 3 4JVO C

• tf- <D rH 3> 1 tO> 1 g t0 rH O

rHtUOCrH X> 1 -P 3U 'O

I to C O O 0-PC, * I A

ο -P 3 Λ 3ι (<Λ 0> -rt P; P Λ 2 rl Ö 4) p PP g -P pn3t0 3 UQ) Q) 3 P · Η 3 I rH X q> I Λ Ή X -P - PA rHO ^ Ό 2 '2

§ · Η Ό g g P g l to C -n m C

rH to 3 3 -P 3 -P -P 3 -P 0

• p> 1 Ο -P -P -P -P rH 3 C I -P A

p>,, * P P rH p 3¾ -POP -P

ΡΛίΟ -P P Ο P p-p P C 3 rH

3 H 0 3 3 0) 3 lg Οι03 -P

2 3 2 2 2 N 2 cm-P O S Mh W

60 80 473 00

-K

• o o / —s * and £ - ^ o o LT> • H O ^ f -fcT ** ^ N. *> v

CO ~ 2 Ä cr> o O

W

Γ "^ ° o o q * u> • o '^ ° ~ ^« .¾ 2 ^ CO o o co w

Cl> <r 00 LO> cr pv ». ct \ or> rr O »*« · ».« .. · —1 ^ r g "^ 2 -. o 'o-

•B

C/O

: w

C/O

o

(U

C/O

P

P

P

(0 (0

P

C/O

O

I-P MH

CP Ή <U -M - p C Π3 Ή> 1 p ίο · ρ ·· ίρ p c · ρ P co p;

cö O T3 P - H

0 lu rl <ϋ rH d

(1) rH g cd * I

C d (δ -H MH * 00 • P CO-P P CO-P Ή

rH-PHPO p ^ Q) I

ICOOJP P, —I P CO

"Sftucnl>, to ·· to rH

rHOJfOC rH ti rH (ti O

i to p o o p: * ps i

ΟΡ <υΛ & <· Ρ P -P

PCOP -H rPO-PO

Ud) C 03 P -P -P 04 PS

1 PO PS PP CO (0 03 g -PS ggpg ZC -n 3-Pto d dP d ·· <u • p> 1 O -P -P -P -P (N di P> i ^ PP Ή PO · Ρ o ppso PPO PP P c

ιί H O Π3 (Ö Φ njc / 3 CXQ

Z rd «Z Z n Z'- O S

no 80473

<n

m

i <= ° o o H

W ^ m ° '' O I

r-i in g ° v o o o o 2 0

«2 'S 1 -« oK

W 1 0 m s ° ° ° ° 2 H 2 ^ 1 2 3 4 5 2 w. 'o' o ',, ° - w σ \

* 10 «Μ Μ ΙΟ S

• H <«» I CO θ ',, o' v ®

01 -H 1 o o I I esT

W

B

-H 4-1 Ή 4-1

> i (0 (0 I

>, 01 (Ö 01

Ai O 0-4 -H

• H O 01 X

(0 rH O Π3 2

I 3 4-1 H

G r-1 -H -H 4-1 Q) H rH 4-1 dl G 0)>, 44 44

• H -H 01> 1 (0 -H -H

> 4 -H 4-> -H Ai «3 G 4J

«5 T3 44 M MC -H 44 (0 -H -H (0> i -H« 3 -H -H <0 0) 4-1 S (0> i -Ö IX g - «3 G 44 n3 - H 44 44 -H 00 Ai «3 -H 44 • Ηΐϋ · Η4-> 01 dig MC -H 44 01

• H (0 M 4- »O £ 10 0) I 01 Ό 44 O

3 ICO (0 44 -H -H 44 ID O -H «3 4-1

O C <0> 1 01 M 01 M 4-4 G (0 O

rH 44 «J G Ή K O« CJ M (DC 44 I M 44 0 0 O G A! I 3 0) 0 84

Ο30), 00, <Λ «384 -h 01 rH 44 O

-H01OM-H 8 44 · Η Ό g> .01 £ U-HG (084-H «30) Ai 3 440 3 4

I G O Ai 44 44 A! -H (0 -H 0) 4-4 -H

£ 0) £££ 44 £ OC -m 84 £ 0 M

30) 0133-H 3010) 44 3 C 44 • H 01 O -H -H -H -H O c I <0 -HO) «3 844M 88H 8ϋ · Η O C 1-4 44 3

4-1C04-14J044044 G -H 44Q) -H

«30) 0 (0 (00) 1000, O 3-4 (0 £ 84 5 H 2—„ e2 80473

ID

i% ^ ^ ~ s

w 3 ^ 1-0-0 I o o I

w -1 ^ r- in s £ "" "° ~ ° - ^"

HO ^^ · '22 ^ ~ O I

w

VO

ID

H ^ “1. · »O o r- * 2 S 2 ~" 2 <* v - o o ',

ID

ID

ε * λ -a- p ^ 0 r »2 co o ^> to fn σΓ I o 'o' i w - o Ό

ID

• CT'OO CvJoq

5 2 - - · f o '-Γ o' o '~ T

CO o o w

1/1 ^ ^ ^ ^ O ^ 0__ r- o O

. O 0O »VO Π σι o o o 't-« ~ E ~

•B

C/O

W

-—- Ή

rH CO

, * VO (0 0

'CO -P

<- (O 0) 0 - Ο rH Ή -H CN 3 0 I 4-> id ή g

C -P Z H

a) id ·· o) ro C Id CN -H CO ^ 0)

rl β -H O 4-> -Η -Η C

44 Ο Ό -H 4-) rH rH · Η id 4-4 -H cn id> i> i id (CJ-Hg - Id> 1> 1 0

0) 3 «J -H 4-1 4J Λί -P

C CO -H 4-) -H CO ¢) rH CO

• H -H> Η 44 -H O £ Id 0) 0)

-HCOld 4-) 4-1 -H1 -PC

iN-QJCid rd> i cooo eno Ή a> id C td rH ^ 4 rH Id Ό ico-po λ: o oi x, & 04-1 0) Λ -H ft <C Λ CN pld »HCO 44 Ή -H 44 '- I - H (d aa) e id -HP-HidU-H>;>

IX) O M CO -P -P, * I 4-> -H

E -H EE E 6 -P £ £ -P CC

3 Ή CO e C 3 -H 3 3 id 0) 0

H £> -H -H -H -H -H -H id C

44> ι Λί M M 44 rH 4 4 Ή -H -H

4) ϋ 0 + j -P + j 0 -Ρ-ΡΉ 4-1 rH

id ή o id id id a) id <d 3 ft -h Z (d «Z Z Z N Z Z co o w 63 8G473

LO

ε • 'ί- cm m co oo cm · <-h rft * ~ · *. · *. · * - · * σι oo in oo · O o

W CM

"5T

vo ‘« r ε cm m co σι —i • H · «. · *. · «. · ».

Μ σ> co in oo ι o o W cm m io e * r .5 σι cm io oo t

, n ~ ·> · · »* s« V

to co m in ι ι O

W CM

CM

ID

Em • p * J- r- »σι m hi ^ · * ω σι cm tn σι ι ι o

w CM

ι I

ID

. «T’ in * 3- σι r ~ - ι E -

• Η σι cm in σι ι · O

in cm w o

‘.ID" C

cn in co o o ^

. * »^ - * K · K

t- σι n m co · —ι · o

•B

ω

; W

σι «cr in n m co o · * -» · K s * v c c σ% ro in σ> ι ι o • p ^ in w «3 in 0 0

* H »“ I

G -P 3

Q) + J H

G Id Ή • P id · Ρ Φ PC -P in

Π3 0 -P -H

(d 4-1 -P id H

Φ I — I Ό id> 1 C 3 -P 'P 4M>, -h in g + j in -p P -P (d -PO 0) Φ ι G -H (d Μ-l E -p Φ ι —Ι id -p in ha) oc ι — ι in id

ι in c 0 0 X X

o-p id Λ ft <O P

ι-1 G -P P · Ρ Λ -H

ΟΦΦ (dP-PPAi 1 Λ -P X -P -P id ε -p T3 ε Ε -p a: c 3 p in 3 3 · ρ ε d>

• P> 1 Ο -p -p -P 3 G

P> 1, ¾ P P ip -P -P

pa: o -p -pop -p (dip o id <0 φ-p ft 2 id x 2 2 nmo 2 64 80473 0 Γ "s ^ ω Λ N jo ^ CO σ 'OO 1 n N ^ oT H l < -T ^ ^ m -ho _i i ro CTi vo 1 "l ® ^ oo ;. vo U> £ ω ° ΟθΟ 1 m« MO rt, ~ - ·> W, - * 1 0 -hi cvj 00 vo _ g “L ° l“ l «Ί <MO -r« Ϊ £ a »oo _-, j: -, s.

w Γ "VO LT) O 'CO OO CO VO. — i —® * I I I κΛ“ “* ·> ·% <" V - ^ o e ~ 10 ΰ Π ° ~ o O -Γ.

C/O

W

VO —I * 3- 5; r ^ LO

VO, | | _ * “· * ···» *. · *, "“ 1 * 3-01. * ”10 S s ° 'CO cT cT,

E

I Ή

C/O

w: en o <u • I to

I -H -H

• H CO -P -H

Ή X -P -P

> 1 <C0 <Ö P

> i co -P G G

X O 0) M-c <Ö rH O - CO Ή G Ή H O> 1

I 3 0 P CO

: -H G H ε -H CU Λ!

-PO) H -H G O

-P G QJ ro> ι · Η P

• G -H -H to 'r> i G CL) G G -P -H -G X O ~.

G G p, —I Ή rH P rH

: O G -H -G G> i> i G CO O

MHCU-POG> i> i I 0) E

HG-P-H-HUh -P X 00 G

H3-HG0-PW Φ i — I rH O CO

Ό CO -H G G P O EG Φ I Ό

• Η · Η I G -H G P -Hl -P vo Λ -H

MG '' f O rH G> 1 to 00 CO rH G rH

^ (UrHtHOCrH, ¾ rH G OGO

oaii-Hcjoo oi x i> .c

GrHOGG-Q & CPCNG -H O

Ό> i rH CO -p G -H G rH -H Ό C> i o> iMU-ho) GG -h g u -g λ: o h

a ^ ΐ I RH ^ L) P Ai I P G G G

aSEEOJOEE + J0E-PC -n -hi G333OC033-H33GCD Goo

.G Ή -H -G CO O · Η -H -H -G -H G G 1 0 rH

>, GGGPa! GP rHGGMH-H O -H I

-n-P-P-P GO-P G O P P P p Cl (N

HGGGOOGG Q) G G 3 O-i 0-GrH

NZZcoO 2 W U

65 80473 n γ- ~ c ^

c - 'VO CM

Η ** · ν _ ^ CO

tn o cm fvT 'v «*« a ~

CM

oc rv. J £? ιλ • *. _ ° 0 CO CM ^ 5 “> => ~ - £> en cm

W

66 80473 Γ "*. ° o κο ^ - m 5 <Τ> ΙΛ _> h oj '- · ο σ ·:': W 1

II

-Η • Η 05 Η ^> 1 O Φ> ι 4-> 05 XV ο Ή ~ Ο Γ (0 Ή «Η I Ο 3 c ε η φ η C m φ -Η '· Η 01 VI -Η 4- > · Η φ ι-4 4-5 Ή Φ --4> ι φ> ι Φ 4-1> ι Φ> 1 · Η C 4-1 X 44 · Η 4-> 05 • Η Φ -Η 0) 4- »Φ Φ Ή Φ Φ O 4-> g Φ> ICI 4-1 Φ · Η 4-> ^ Ο 00> i Φ 05 05 - H m Ή» —f G φ · Η: I Ή I Ο Ο Ο Λί> 4 Η φ (Ν ft Λ Λ> 4: φ> -4 05 ι-4 -Η> 4 Μ -Η>

U -H U · Η U φ Φ X

1C I 4-) 44 XX

βω β 4-ι β β β c ω Φ Φ Φ Φ Φ Φ Φ 5 4-5 Η 05 · Η φ · Η · Η · Η C 05> 4 4-> 54 44> 4> 4 54 -rl φ 4 -5 φ 4-5 Η 4-5 4-1 4-5 4-> 'Π ΦΦ ΦΦ Φ Φ Φ ft Φ Ζ XI <2 05 3 2 2 Ο Κ 67 8 0 4 7 3 s S- Z'. ...... · ° ° -

§ CM

a 3 · * ·· S ^ ~. . ,, • ^ rocoo- ^ · Ln i— o • 5 - 03 w cs 00 ^

Ill'll 1, 0 'Obrien § rO 1 1 1 ~ 1 · νΐι ^ ι ^^ ν m o o o o

C \ J

a ®. ««,, «,,, * ®, o, ^ ®

g <7> 0 C \ j “^ CM O O O

cn ω § ~ - ,,,. . ^ ° ι. ° ,, - a j; 11 1 «5 ro 0 • 5 ^ ^ s CTi go J". ° ° ~ I ^, .§ <* CM O ^ rr σ> en σ a 00 Γ ^> _ m POr-jr ^. LT) OOO - t | vo cn 1 cm 1 r- m co cm or ** e ° - ° - III, I o ° oo I «m 'co' ^ 'o' -Γ w --1 V £> ^ S 'S' ..... ° - ° ~,, - r □ ^ m ιλ oa in ®,,, vo <r> r. <O 2 3 $ ™ ~, cT rC ^ 'oo "3 H ~ ii α) -h I o I -Η -P - HP +} • 'j 5 (0 | rH + JrH Tj 03 + * r · *

<0QJ>, + J Ο Ή -H 0) 03 (0> i TO

(DO)> i fl 8 Ό 0 -H 10 <0> i O

C 03 44 td h td η ω <D Ή p -P m

• HP H m 00 ε -H> 1 W 0 W

rHC rd Η ~ H> t I -H P P Η Ο ε Q) 0)

Id) I 3 -H -H O P vo-Prd-P ·· Ή -H P g

^ τ, α to μη r — I c <u .η p td td> x> · η> ι ω tnO

I — ι-H Η H -H 0 0 td ε U (ί fi Λ ‘Ό Η 44 (β-Ο I H p I M Xl -rl Ö P · Η I (0 0Λ! Η · γΙ 0 0 44 -g

O> 1 4-) CN44OPtd0) H-H-HM-1, Q-H p C3, <C £ | HfO

rH>, (d Η 0Λ -P + J 0 tO P Ό 03 MOO Ή H (d -H fo u 44 föU-pr-tnJd) ci-P-P 0 (0 · ηοηρ-η (00344>

I Η β I OJ «} (0 -H O I rdrd> P, X03rd44PP44O -H

ε rd ο ε - I ή t3 ε ε to · η · η ε ε z ε ε ρ ε ocg β I Ρ β H 00> 1 03 03 PC rH PP ·· PP -HP hoo • H ti M -HO M03 O Ο · Η OI>, -H -H <NH -H -H -HP g ^ 4

P 0) P p ε ΛΙ P Ή o> 1 P P O P

4J ti 03 -P (NO O O -PM C 44 P4-I-P-P P OPM + JrP

re-H- «i (0 n i — lp O O <Ö P OH tO (0 to rd to OtOOOiH

2 P ti Z ^ -002 ¢ 4 Z 03 S <0 2 ^^ 2 Z & Q203O (O

68 80473

The drawings illustrate changes in electrical conductivity, yield point and viscosity depending on the electrolyte concentration and the active ingredient.

Figure 1 shows the electrical conductivity of an aqueous solution containing 20.6% of active ingredients 5 (active ingredients consisting of 2 parts by weight of sodium dodecyl sulfonate and 1 part by weight of sodium C12-allyl (3 mol) of ethoxysulfate) at different sodium silicate concentrations. 2 mol ratio 1: 1.6) as a function. The figures on the horizontal axis 10 indicate the amount of silicate in the composition as a percentage by weight of the solids in the composition.

The addition of 0 to 7% silicate provides a substantially clear, optically isotropic composition, typically as described in Step I above. Between the points marked A: 11a and B 15, a stage II composition is obtained which is cloudy, unstable and contains spherulite blocks which do not fill the space. Between B and C, a phase III composition according to the invention is obtained. It is a cloudy, stable composition containing substantially ti-20 la spherulite flocs, as the yield point and high G-centrifugation give a single liquid phase. After point C, a step IV composition is obtained which contains non-space-filling flocs of spherical G-phase and which is unstable. It can be seen that stable Phase III compositions are obtained in the region near the first electrical conductivity minimum.

Figure 2 shows the effect of sodium nitrate addition on the same aqueous active system. After step IV, point C, there is a second electrical conductivity maximum, followed by a second electrical conductivity name corresponding to the formation of the step V lamellar composition at approximately point D. The horizontal axis figures indicate the amount of sodium nitrate added as a weight percent of the composition solids.

Il 69 8G473

Figure 3 shows the changes in viscosity, electrical conductivity and yield point in the same active system when sodium carbonate is added.

The left vertical axis has a viscosity of 5 (Pa.s) at 136 s ~ and electrical conductivity in parentheses (mS.cm *); the right vertical axis has a yield point _2 (Nm); the horizontal axis is the dry weight of sodium carbonate based on the total weight of the composition.

10 When sodium carbonate is added, no minimum is observed in the electrical conductivity curve (dashed line). This is due to the fact that the solubility limit of sodium carbonate has been reached and when further sodium carbonate is added it is suspended and does not increase the concentration of dissolved electrolyte.

15 Phase IV therefore does not occur. The steep rise in yield strength (right-hand peak) coincides with point B of stage III. This is typical of the compositions of the invention.

Figure 4 shows the effect of changes in the relative proportions of sodium dodecylbenzene sulfonate and coconut monoethanolamide in a composition containing sodium dodecylbenzene sulfonate, sodium tripolyphosphate, sodium carbonate and water in a ratio of 0.2: 0.5, -0.1: 1.0. The horizontal axis has a weight ratio of coconut monoethanolamide to sodium dodecylbenzenesulfonate.

The vertical axis has electrical conductivity (m.S.cm ~ *) (circles) and viscosity (Pa.s x 10) (triangles).

Figure 5 is a similar view, however, in which coconut monoethanolamide has been replaced by sodium C 1-4 alkyl (3 mol) ethoxysulfate. The horizontal axis has a weight ratio of ether sulfate to alkyl benzene sulfonate.

Figures 4 and 5 show how it is possible to prepare the compositions according to the invention by modifying the active ingredients.

70 80473

Figure 6 shows the changes in electrical conductivity (mS.cm-1) when sodium nitrate is added to a detergent composition containing different amounts of suspended builder (horizontal axis figures indicate the amount by weight of sodium nitrate-5 in weight of the solids of the composition having the following formulation): -%

Sodium dodecylbenzenesulphonate 9

Sodium C12-13 alyl, cyclo (3 mol) ethoxysulphate 4 10 Silicone antifoam 1

Scent 0.6

Cl2-18 ~ mono_ ~ ^^ a ^ yy ^^ os ^ aa ^ iseos 0/5

Optical brightness 0.15

Sodium tripolyphosphate 19 15 Zeolite A 12

Since the composition already contains dissolved tripolyphosphate, step I is not shown in the curve. The electrical conductivity decreases from a maximum of A to the beginning of phase III B.

Figure 7 shows the changes in the yield strength _2 (Nm) of the same system and Figure 8 the changes in viscosity (Pa.sx 10) at 136 cm-1 (lower curve) and 21 cm ~ (upper curve) and the viscosity decrease (Pa.sx 10) ( mean curve). In both Figure 7 and Figure 8, the figures on the horizontal axis indicate the amount of sodium nitrate addition as a weight percent of the solids in the composition.

Figure 9 shows the changes in electrical conductivity at different concentrations of sodium silicate in an aqueous solution containing 20.6% by weight of sodium dodecylbenzene sulfonate and coconut monoethanolamide in a weight ratio of 10: 4. In this figure, the numbers on the horizontal axis indicate the amount of sodium silicate addition as a percentage by weight of the solids in the composition.

Phase I is not observed in this case either, because the active ingredients of tl 71 80473 are not completely soluble in water at room temperature. The composition is thus cloudy and unstable without the addition of electrolyte.

Figures 10 and 11 show X-ray micrographs of Pt / C replicas with freezing fractures at a linear magnification of 45,000 x and 110,000 x, respectively.

Micrographs prepared with a Lancaster University transmission electron microscope are from a sample of: 10% by weight

Sodium dodecylbenzenesulphonate 11.8

Sodium C12-acetyl (3 mol) ethoxysulphate 5.2 Sodium silicate (Na2O: SiO2 1.6: 1) 17.4

Water difference 15

Spherulites with a diameter of 0.2 to 1 μm are seen in the micrographs, which appear to be multiple concentric vesicles with repetitive intervals of 8.0 nm (including one thickness of surfactant shell and one adjacent aqueous layer).

Claims (10)

72. G 4 7 3 A stable, pourable, liquid detergent composition comprising water, a surfactant, a dissolved electrolyte salt seeking to desolubilize the surfactant, and suspended particles of a solid enhancer salt, wherein the total weight ratio of the enhancer salt, optionally a surfactant salt, the surfactant is greater than 10 1.5: 1, and wherein the weight ratio of surfactant to water is such that when said salt is continuously dissolved in an aqueous micelle solution of said surfactant having said weight ratio , the electrical conductivity curve of said solution as a function of the concentration of said salt passes through a waveguide region containing an electrical conductivity name in which the mixture is stable and thick, characterized in that said salt, including any dissolved effect salt, is dissolved in said composition in a total amount, corresponds to said aa a base range selected from minimum and maximum amounts in which the composition is stable for at least three months at both ambient temperature and below 5 ° C, for example at 0 ° C and preferably also at 40 ° C. Composition according to claim 1, characterized in that the amount of said salt is greater than the maximum amount at which the composition is shear-sensitive. Composition according to Claim 1 or 2, characterized in that the amount of said salt is chosen between maximum and minimum amounts in which the decrease in viscosity of the composition is greater than 0.4 Pa.s, preferably 0.4 to 2 Pa.s. for example 0.475 to 1.5 Pa. p. Composition according to one of Claims 1 to 3, characterized in that the viscosity is 0.1 to 2 Pa.s at a shear rate of 136 s-1 and preferably 0.3 to 0.6 Pa.s . Composition according to any one of Claims 1 to 4, characterized in that the amount of said salt is chosen between minimum and maximum amounts which do not separate the clear aqueous layer when centrifuged at 20,000 G for 5 minutes or preferably 90 minutes. Composition according to any one of claims 1 to 5, characterized in that the amount of said salt is sufficient to stabilize the composition after the composition has been subjected to strong shear. Composition with an aqueous composition according to one of Claims 1 to 6, characterized in that a comminuted solid, such as a comminuted excipient or an inert abrasive, is suspended therein. Composition according to any one of claims 1 to 6, characterized in that said salt contains a water-soluble excipient in a total amount greater than its solubility in said composition at ambient temperature, and in that said composition also contains said excipient suspended as a comminuted solid. Composition according to one of Claims 1 to 8, characterized in that its yield strength is greater than -2 -2 greater than 0.15 N m (1.5 dyn. Cm) and preferably less than -2 -2 4.0 N m (40 dyn.cm) and that its viscosity at a cut-off speed of 136 s-1 is less than 0.28 Pa.s. Composition according to one of Claims 1 to 9, characterized in that the weight ratio of enhancer salt to surfactant is preferably 1.5: 1 to 3.5: 1. 74 8 □ 4 7 3