RU2575241C2 - Liquid washing composition with abrasive particles - Google Patents

Abstract

FIELD: chemistry.

SUBSTANCE: described is a liquid composition containing 1.0-50 wt % of a surfactant, one or more suspendable agents selected from the group consisting of crystalline wax structure-forming agents, diamide gelling agents having the molecular weight of 150 g/mol to 1500 g/mol, wherein the said diamide gelling agents contain at least two nitrogen atoms, wherein the said at least two nitrogen atoms form amide functional substitution groups, microfibre cellulose and mixtures thereof, and polymer particles obtained from a polymer foamed material. Also described is the method of producing the composition and using the polymer particles obtained from a foamed material in a manual dishwashing composition.

EFFECT: providing good cleaning efficiency, good surface safety profile and soft skin peel.

28 cl, 6 tbl, 8 dwg

Description

FIELD OF THE INVENTION

The present invention relates to a dishwashing composition containing abrasive particles and a suspending agent, selected from the group consisting of crystalline wax builders, microfiber cellulose, amide gel builders, dibenzylidene polyol acetals and mixtures thereof.

State of the art

Cleaning compositions such as solid formulations or liquid formulations (including gel, paste type) containing abrasive components are well known in the art. Such compositions are used for cleaning and / or deep cleaning various surfaces, especially those surfaces that are usually contaminated by stains and dirt that are difficult to remove.

Among the currently known cleaning compositions, the most popular of them are based on abrasive particles with various shapes from spherical to irregular. The most common abrasive particles are either inorganic, such as carbonate salt, clay, silica, silicate, shale ash, perlite and silica sand, or organic polymer beads such as polypropylene, PVC, melamine, urea, polyacrylate and derivatives, and are obtained in as a liquid composition having a creamy consistency, with abrasive particles suspended in it.

The surface safety profile of such currently known cleaning compositions is insufficient, alternatively, poor cleaning performance and / or poor peeling to provide the desired beneficial skin care effect are shown for compositions with an adequate surface safety profile. In fact, due to the presence of very hard abrasive particles, these compositions can damage, that is, scratch, the surfaces on which they were applied and irritate and / or damage the user's skin, while for less hard material the level of cleaning performance and skin peeling is inadequate. In fact, the drafter of the dishwashing detergent manually must choose between good cleaning performance, but exhibiting severe surface and skin damage, or damage to cleaning performance, while at the same time exhibiting an acceptable surface safety and skin safety profile. Additionally, the compiler of the dishwashing composition manually must ensure that such a cleaning is achieved, while ensuring adequate rheology of the product, optimal dissolution of the product and the foaming profile, and the beneficial effects of mild skin peeling.

There remains, therefore, the need to create a liquid composition for washing dishes by hand, acceptable for cleaning various surfaces of dishes, where the composition provides good performance for cleaning stubborn, difficult to remove dirt, and soft peeling of the skin, while ensuring a good surface safety profile. Additional desired formulation characteristics include optimal product rheology, dissolution and foaming profile.

An advantage in accordance with the present invention is that in the compositions in this application, the particles can be mixed at low levels, while still providing the above beneficial effects. In fact, in general for other abrasive materials, high particle levels are necessary to achieve good performance, which leads to a high product cost, processing complexity, incompatibility with many packaging configurations, for example, soft atomizers or aerosol sprays, poor rinsing, insufficient dissolution of the product and foaming profiles, as well as unattractive aesthetic properties of products and unpleasant sensations to the hands.

SUMMARY OF THE INVENTION

In one aspect, the present invention relates to a liquid dishwashing liquid manually, comprising: one or more suspending agents selected from the group consisting of crystalline wax builders, amide gel builders, microfiber cellulose, dibenzylidene polyol acetals and mixtures thereof; and polymer particles derived from polymeric foam. The polymer material is selected from the group consisting of polyurethane, derivatives of polyhydroxyalkanoate (PHA), aliphatic polyesters, derivatives of polylactic acid (PLA), polystyrene, melamine-formaldehyde, polyacrylate, polyolefins, polyvinyl and mixtures thereof.

In another aspect, the present invention relates to a method comprising the steps of: fragmenting a polymer foam material to form polymer particles, preferably by cutting, grinding, grinding and / or crushing said foam; and adding said particles to a composition containing one or more suspending agents selected from the group consisting of crystalline wax builders, amide gel builders, microfiber cellulose, dibenzylidene polyol acetal derivatives and mixtures thereof. The polymer material is selected from the group consisting of polyurethane, derivatives of polyhydroxyalkanoate (PHA), aliphatic polyesters, derivatives of polylactic acid (PLA), polystyrene, melamine-formaldehyde, polyacrylate, polyolefins, polyvinyl and mixtures thereof.

In yet another aspect, the present invention relates to the use of particles selected from the group consisting of polymer particles derived from polymeric foam, natural abrasive particles and mixtures thereof, in a dishwashing composition manually to provide a beneficial skin care effect, preferably soft peeling of the skin, while these natural particles are contained at a level of more than 2% by weight of the composition.

Brief Description of the Drawings

FIG. 1 is an illustration of a radius of a curve.

FIG. 2 is an illustration of how to calculate particle roughness.

FIG. 3 is an illustration of a convex hull area and particle area.

FIG. 4a is an electron microscope image showing a polyurethane particle A.

FIG. 4b is an electron microscope image showing a polyurethane particle B.

FIG. 5a is an electron microscope image showing closed cell polyurethane foam with a membrane wall.

FIG. 5b is an electron microscope image showing open cell polyurethane foam without a membrane wall.

FIG. 6a is an electron microscope image showing polyurethane foam having a density of 33 kg / m ³ .

FIG. 6b is an electron microscope image showing polyurethane foam having a density of 120 kg / m ³ .

FIG. 6c is an electron microscope image showing polyurethane foam having a density of 320 kg / m ³ .

FIG. 7a is an electron microscope image showing the polyurethane particles obtained from the polyurethane foam shown in FIG. 6a.

FIG. 7b is an electron microscope image showing the polyurethane particles obtained from the polyurethane foam shown in FIG. 6b.

FIG. 7c is an electron microscope image showing the polyurethane particles obtained from the polyurethane foam shown in FIG. 6c.

FIG. 8 is a graph illustrating a skin peeling performance of a composition containing polyurethane foam particles or natural particles.

DETAILED DESCRIPTION OF THE INVENTION

As used in this application, “fat” means materials containing at least partially (ie, at least 0.5 wt.% By weight of fat) saturated and unsaturated fats and oils, preferably oils and fats, derived from animal sources, such as beef and / or chicken, and / or vegetable sources.

As used in this application, “shelf stable” means a clean liquid dishwashing detergent for washing dishes by hand, which under ambient conditions is not susceptible to phase separation for at least two weeks, preferably for at least six months , and more preferably never.

As used in this application, “utensils” refers to a hard surface, such as plates, glasses, pots, pans, baking dishes and cutlery made of ceramic, porcelain, metal, glass, plastic (polyethylene, polypropylene, polystyrene, etc. .d.), wood, enamel, Inox®, Teflon® or any other material commonly used in the manufacture of products used for eating and / or cooking.

As used in this application, “liquid detergent composition for washing dishes by hand” refers to those compositions that are used for manual (ie hands) washing dishes. Such compositions, as a rule, have high foaming or foaming in nature and are stable during storage.

As used herein, “beneficial effect of hand skin care” means any beneficial effect related to the appearance of the skin of the hands (eg, smoothness, firmness, lack of redness and lack of lines and wrinkles), skin sensation (eg, softness and elasticity) and skin moisture level.

As used in this application, “peeling or soft peeling of the skin” means the removal of dead skin cells from the outer layer of the skin, while minimizing the risk of excessive skin peeling, which otherwise could lead to damage and redness of the hands.

As used in this application, “foaming profile” means the amount of foaming (high or low) and the preservation of foaming (sustainable or prevention) during the entire washing process as a result of using the liquid detergent composition in accordance with the present invention. Liquid dishwashing detergents require high foaming and stable foam. This is especially important for liquid dishwashing detergents, as the consumer uses high foaming as an indicator of the performance of the detergent composition and as an indicator that the washing solution still contains active detergent ingredients. The consumer typically updates the wash solution when foaming subsides. Thus, low foaming for liquid dishwashing detergents will tend to be replaced by the consumer more often than necessary due to the low level of foaming.

As used in this application, “surface safety” means that the surface to be cleaned is not damaged by the composition in accordance with the present invention, which is evident due to the absence of visual scratches on the surface of the dishes after cleaning.

As used in this application, “stubborn stains” means highly sticky stains that are generally very difficult to remove. Such contaminants include, but are not limited to, burnt and / or baked food debris.

As used herein, “polyurethane foam particles” means particles formed by cutting, grinding, grinding and / or crushing polyurethane foam.

As used in this application, “polymer foam” means a polymer structure having a lightweight cellular form as a result of the introduction of gas bubbles (or any other suitable method) during the manufacturing process.

As used in this application, "polyurethane foam" means a polyurethane structure having a light honeycomb shape as a result of the introduction of gas bubbles (or by any other suitable method) in the manufacturing process.

As used herein, “natural particles or natural abrasive particles” means particles obtained from materials available in nature. Such particles are selected from the group consisting of walnut shell particles, particles obtained from other plant sources, and mixtures thereof.

Liquid composition

The composition in accordance with the present invention is obtained in the form of a liquid dishwashing detergent composition containing abrasive particles and a suspending agent, selected from the group consisting of crystalline wax builders, microfiber cellulose, amide gellants, dibenzylidene polyol acetals and mixtures thereof.

Liquid dishwashing compositions in this application may additionally contain from 30% to 90% by weight of an aqueous liquid carrier in which other essential and optional components of the composition are dissolved, dispersed or suspended. Preferably, the aqueous liquid carrier will contain from 45% to 80%, more preferably from 45% to 70% by weight of the compositions described herein. One preferred component of an aqueous liquid carrier is water. An aqueous liquid carrier, however, may contain other materials that are liquid or that dissolve in the liquid carrier at room temperature (20 ° C-25 ° C), and which may also perform some other functions, in addition to the function of an inert filler. Such materials may include, for example, hydrotropes and solvents.

The liquid dishwashing composition may have any acceptable pH. Preferably, the pH of the composition is adjusted from 4 to 14. Typically, the composition has a pH of from 6 to 13, preferably from 7 to 10, more preferably from 7 to 9, and most preferably from 8 to 9. The pH of the composition can be adjusted using pH modifying ingredients known in the art.

Abrasive particles

The compositions in this application contain abrasive particles. Particles in this application are obtained by cutting, crushing, grinding and / or grinding a rigid polymer foam obtained from polyurethane; derivatives of polyhydroxyalkanoate (PHA), such as, but not limited to, polyhydroxybutyrate, polyhydroxyhexanoate, polyhydroxyvalerate, polyhydroxybutyrate-valerate, polyhydroxybutyrate-hexanoate and mixtures thereof; aliphatic polyesters such as polybutylene succinate (PBS), polybutylene adipate (PBA), polybutylene succinate-co-adipate (PBSA), and mixtures thereof; polylactic acid derivatives (PLA); polystyrene; melamine formaldehyde; polyacrylate; polyolefins, such as polyethylene, polypropylene; polyvinyl chloride and / or polyvinyl acetate.

In a preferred embodiment, the particles in this application are substantially biodegradable and the polymer foam is selected from the group consisting of degradable polyurethane; derivatives of polyhydroxyalkanoate (PHA), such as, but not limited to, polyhydroxybutyrate, polyhydroxyhexanoate, polyhydroxyvalerate, polyhydroxybutyrate-valerate, polyhydroxybutyrate-hexanoate and mixtures thereof; aliphatic polyesters such as polybutylene succinate (PBS), polybutylene adipate (PBA), polybutylene succinate-co-adipate (PBSA), and mixtures thereof; polylactic acid derivatives (PLA) and mixtures thereof. By "degradable polyurethane" in this application is meant polyurethane obtained by the reaction of isocyanate monomers and a degradable polyol with and / or without natural or degradable fillers, as will be discussed in more detail below.

Such polymer foams are synthesized to impart specific gravity, pore size, brittleness and hardness.

Most preferably, the abrasive particles are made of rigid polyurethane foam formed by the interaction between diisocyanate monomers and polyols.

Such foam particles are selected to show effective forms, for example: defined by roughness, strength and roundness, and sufficient hardness.

It was unexpectedly found that the abrasive particles in accordance with the present invention show good cleaning performance and soft peeling of the skin, even at relatively low levels, for example from 0.1% to 20%, preferably from 0.1% to 10%, more preferably from 0.5% to 5% by weight of the total composition of these abrasive particles. If the abrasive particles are formed by cutting, crushing, grinding and / or grinding polyurethane foam, the levels can be from 0.2% to 3%, more preferably from 0.5% to 2% by weight of the total composition of these abrasive particles.

In a preferred embodiment, the abrasive particles are non-rolling, for example: they are characterized by roundness, which facilitates the effective sliding of the abrasive particles in comparison with typical abrasive particles, where a more efficient rolling motion is more desirable. As a rule, roundness should satisfy the criteria in order to facilitate effective sliding instead of rolling particles, and is in the range from 0.1 to 0.4.

In another preferred embodiment, the abrasive cleaning particles are sharp. Applicant has found that non-rolling and / or sharp abrasive cleaning particles provide better cleaning performance. Applicant has found that very specific particle shapes help to achieve good contaminant removal while limiting and / or substantially eliminating the risk of scratching dishes and damaging the user's skin, while at the same time providing a highly desirable soft peeling of the skin.

The shape of the abrasive particle can be defined in different ways. The present invention defines a particle shape of an abrasive particle that displays the geometric proportions of the particle and a more pragmatic particle population. The most recent analytical methods allow accurate simultaneous measurement of particle shapes of a large number of particles, typically more than 10,000 particles (preferably more than 100,000). This makes it possible to fine tune and / or select the shape of the average population of particles with a discriminatory characteristic. This measurement analysis of particle shape is performed using the Occhio Nano 500 Particle Characterization Instrument with accompanying software Callistro version 25 (Occhio s.a. Liege, Belgium). This tool is used for preparation, dispersion, image acquisition and analysis of particle samples, according to the manufacturer’s instructions, as well as the following instrument settings: White prescribed = 180, vacuum time = 5000 ms, deposition time = 5000 ms, automatic threshold, number of particles counted / analyzes = from 8000 to 500000, the minimum number of duplicates / sample = 3, the lens setting is 1x / 1.5x.

Abrasive particles in accordance with the present invention are determined by quantitative description of the form. In a quantitative description, a shape descriptor is understood as quantities that can be calculated from particle images or physical properties of particles using mathematical or numerical operations. While the particle shape can be determined in 3 dimensions by the selected analytical method, the applicant found that the particle shape characteristics in 2 dimensions are most relevant and correlate with the abrasive characteristic of the abrasive particles. During the protocols of particle shape analysis, the particles are oriented towards the surface - using gravitational deposition - similar to the expected orientation of the particles during the cleaning process. Thus, an object of the present invention relates to the characteristics of a 2-D particle shape / population of particles, as determined by the projection of their shape onto the surface on which the particle / population of particles is deposited.

The abrasive particles in this application preferably have sharp edges, and each particle has at least one edge or surface having a concave curvature. More preferably, the particles in this application have many sharp edges and each particle has at least one edge or surface having a concave curvature. The sharp edges of the particles are defined as edges having a radius of curvature of less than 20 microns, preferably less than 8 microns, most preferably less than 5 microns. The radius of curvature is determined by the diameter of the imaginary circle of the corresponding curvature of the end edge. Figure 1 is an illustration of a radius of a curve.

Roughness of abrasive particles

Roughness is a quantitative 2-dimensional description of shape image analysis, and is measured in accordance with ISO 9276-6: 2008 (E) section 8.2, implemented using the Occhio Nano 500 Particle Characterization Instrument with accompanying Callistro software version 25 (Occhio sa Liege, Belgium )

Roughness is useful in abrasive particles, since the particle in this application preferably has a significant mass of material available at the periphery of its core as useful abrasives. This peripheral mass is useful for optimal cleaning and peeling characteristics, as well as to prevent particles from rolling.

The roughness is determined in 2D measurements of the equivalent effective surface area outside the surface area of the particle core in the range 0-1, while surface roughness 0 describes a particle with a non-useful mass available at the periphery of the particle core mass.

The roughness is calculated as follows:

Rgγ = (A-A (Oγ) / A,

where A represents the area of the particle and A (Oγ) represents the surface area, which is considered the "core of the particle." A-A (Oγ) represents the “usable area at the periphery of the particle” and roughness represents a fraction of such usable area compared to the total particle area. Oγ is called a tunable tolerance factor and is typically set to 0.8, so the definition of roughness is Rgγ = (AA (0.8) / A. In order to calculate A (0.8), the maximum number of disks is entered into the particle contour at each point of the edge of the particle.The size, for example, the area of the inscribed disks, is determined by the diameter of the disks, while the diameter value varies from 0.8 × Dmax to Dmax (where Dmax is the diameter of the largest disk inscribed in the particle). 0.8) is determined by the area of the corresponding project s all inscribed discs.

Figure 2 is a drawing showing how to calculate the particle roughness.

In a preferred embodiment, the abrasive particles have an average roughness of from 0.1 to 0.3, preferably from 0.15 to 0.28, and more preferably from 0.18 to 0.25. Not wishing to be bound by theory, it is believed that such average roughnesses contribute significantly to providing improved cleaning performance and surface safety, and highly desirable soft peeling of the skin, increasing the average surface area in contact with the surface to be treated. Average data is obtained from measurements based on volume compared to measurements based on quantities.

Roundness of abrasive particles

Roundness is a quantitative, 2-dimensional description of form image analysis and is measured in accordance with ISO 9276-6: 2008 (E) section 8.2, implemented using the Occhio Nano 500 Particle Characterization Instrument with accompanying Callistro software version 25 (Occhio sa Liege, Belgium ) Roundness is the preferred descriptor of mesoforms and is widely available in a form analysis tool such as in the Occhio Nano 500 or in Malvern Morphologi G3. Roundness is sometimes described in the literature as the difference between the shape of the particle and the ideal sphere. The roundness values range from 0 to 1, where roundness 1 describes perfectly spherical particles or disk particles measured in a two-dimensional image.

$$C=\sqrt{\frac{\mathrm{four}\pi A}{P^2}}$$

where A is the projection area, which is a 2D descriptor and P is the length of the perimeter of the particle.

In a preferred embodiment, the abrasive particles have an average roundness of from 0.1 to 0.4, preferably from 0.15 to 0.35, and more preferably from 0.2 to 0.35. Not wishing to be bound by theory, it is believed that this roundness provides improved cleaning performance and surface safety, and a soft peeling of the skin is highly desirable, allowing sufficient rolling resistance to provide the necessary fat shift and / or effective removal of dead cells from the outer layer of the skin. Average data is obtained from measurements based on volume compared to measurements based on quantities. Abrasive Strength

Strength is a quantitative, 2-dimensional description of shape image analysis, and is measured in accordance with ISO 9276-6: 2008 (Ε) section 8.2, implemented using the Occhio Nano 500 Particle Characterization Instrument with accompanying Callistro software version 25 (Occhio sa Liege, Belgium). The particle in this application preferably has at least one edge or surface having a concave curvature. Strength is a mesoform parameter that describes the overall concavity of a particle / particle population. Strength values range from 0 to 1, where a strength value of 1 describes a non-concave particle, measured in the literature as:

Strength = A / Ac

where A represents the area of the particle and Ac represents the area of the convex hull bounding the particle. The area of the convex hull is better understood using FIG. 3. In FIG. 3, the convex hull is clearly indicated by a dashed line that connects all the outer edges of the particle, and the area of the convex hull is the area bounded therein.

In a preferred embodiment, the abrasive particles have an average strength of from 0.4 to 0.75, preferably a strength of from 0.5 to 0.7, and more preferably from 0.55 to 0.65. Average data is obtained from measurements based on volume compared to measurements based on quantities.

Strength is also sometimes referred to as bulge in the literature or in some hardware software using the strength formula at its definition described in ISO 9276-6 (bulge = Pc / P, where P is the length of the perimeter of the particle and Pc is the length of the perimeter of the convex hull - shell bounding the particle). Although the strength and bulge are similar to the descriptors of the mesoform in concept, the applicant refers in this application to the strength measure expressed above the Occhio Nano 500, as described above.

Under the terms "average roundness", "average strength" or "average roughness", the applicant considers the average value of the roundness or strength or roughness of each particle taken from a population of at least 10,000 particles, preferably more than 50,000 particles, more preferably more 100,000 particles, after exclusion from measurements and calculations, data on the roundness or strength or roughness of particles with an area equivalent diameter (ECD) of less than 10 microns. Average data is obtained from measurements based on volume compared to measurements based on quantities.

FIG. 4a is an electron microscope image showing a polyurethane particle A (formed from polyurethane foam having a density of 60 kg / m ³ ) of abrasive cleaning particles in accordance with the present invention and FIG. 4B is an electron microscope image showing a polyurethane particle B (formed from polyurethane foam having a density of 33 kg / m ³ ) of abrasive particles in accordance with the present invention.

The size of the abrasive particles can be crucial to achieve an effective cleaning performance, while an overly abrasive population with small particle sizes, for example typically less than 10 micrometers, has a polishing effect compared to cleaning, despite the characteristic of a large number of particles on the filling of particles in a cleaner for the inherent small particle size. On the other hand, an abrasive population with an excessively high particle size, for example, more than 1000 micrometers, does not provide optimal cleaning efficiency, since the number of particles per filling of particles in the cleaning agent is significantly reduced, which is inherent in a large particle size. Additionally, an excessively small particle size is not desirable in a cleaning agent / cleaning task, since in practice, small and numerous particles are often difficult to remove from surfaces of various topologies, which requires excessive user effort to remove them if only to leave a surface with visible residues particles. Additionally, very small particles do not provide the experience of the desired skin peeling, since they are often not tactilely detected by the user and may increase the risk of excessive skin peeling, since the user does not feel their effect. However, too large a particle is too easy to detect visually or it provides a poor tactile experience when processing or using a cleaning agent. Therefore, applicants in this application determine the optimal range of particle sizes, which provides both optimal cleaning performance, and peeling, and experience in use.

The abrasive particles have a size determined by their diameter equivalent to the area (ISO 9276-6: 2008 (E) clause 7), also called the equivalent circular diameter ECD (ASTM F1877-05 clause 11.3.2). The average ECD of a particle population is calculated as the average value of the corresponding ECD of each particle of a particle population of at least 10,000 particles, preferably more than 50,000 particles, more preferably more than 100,000 particles after excluding from measurement and calculation of these particles having a diameter equivalent to area (ECD ) less than 10 micrometers. Average data is obtained from measurements based on volume compared to measurements based on quantities.

In a preferred embodiment, the abrasive cleaning particles have an average ECD of 10 μm to 1000 μm, preferably 50 μm to 500 μm, more preferably 100 μm to 400 μm, and most preferably 150 to 355 μm.

In a preferred embodiment, the abrasive particles are made of polyurethane foam, which is formed as a result of the interaction between diisocyanate monomers and polyols, where the diisocyanate monomer can be aliphatic and / or aromatic, in the presence of a catalyst, materials for controlling the cellular structure and surfactants. Polyurethane foam can be made at different densities and hardness by changing the type of diisocyanate monomer (s) and polyols and by adding other substances to change their characteristics. Other additives can be used to improve the stability of the polyurethane foam and other properties of the polyurethane foam. The particles used in the present invention must be hard enough to provide good cleaning and peeling properties without damaging the surface on which the composition was applied, and without excessive peeling. Polyurethane is highly preferred in the compositions in accordance with the present invention because of its effective processability into a foam structure with different densities, in the range of hardness that can be achieved, and the potential for biodegradable foam compared to other materials, and in particular compared to other polymers.

Although the properties of polyurethane foam are mainly determined by the choice of polyol, diisocyanate has some effect. The choice of diisocyanate affects the stability of the polyurethane when exposed to light. Polyurethane foams are made of aromatic diisocyanates, yellow when exposed to light, while those made of aliphatic diisocyanates have color stability. Due to the bleaching of polyurethane foam containing aromatic diisocyanates, aliphatic diisocyanates are preferred in the manufacture of polyurethane foam. However, the Applicant has found that by mixing aliphatic and aromatic diisocyanate monomers, and maintaining the aromatic diisocyanate monomer levels of less than 60% by weight of diisocyanates, preferably less than 50% and more preferably less than 40% by weight of diisocyanates, color stable foam and polyurethane foam particles can be provided for use as cleaning abrasives in accordance with the present invention.

Suitable diisocyanate monomers, as used herein, are aliphatic diisocyanate monomers, preferably selected from the group consisting of hexamethylene diisocyanate (HDI), dicyclohexylmethanediisocyanate (H12MDI), isophorone diisocyanate (IPI), lysine diisocyanate, lysine diisocyanate, lysine, above and mixtures thereof.

The choice of polyols does not have a large effect on the color stability of the foam, but it affects the foam hardness and biodegradation more.

An example of acceptable polyols as used herein is preferably selected from the group consisting of castor and / or soybean oil (including ethoxylated or propoxylated oils, including sulfated oils); sugars and polysaccharides such as glucose, sucrose, dextrose, lactose, fructose, starch, cellulose; sugar alcohols such as glycol, glycerin, erythritol, tereitol, arabit, xylitol, ribite, mannitol, sorbitol, dulcite, idol, isomalt, maltitol, lactitol, polyglycite and trimethylolpropane.

Common useful polyols are also obtained by reacting the above polyols (including dianiline toluene derivatives) with diethanolamine and propylene oxide (a non-exhaustive example is “sucrose” propoxylate).

Other suitable polyols for use in this application are ethylene glycol and polymer derivatives such as polyethylene glycol diol, propylene glycol and polymer derivatives such as polypropylene glycol diol, tetramethylene glycol and polymer derivatives such as polytetramethylene glycol.

Polyester polyols are also acceptable polyols and polyester polyols obtained by reacting acids (adipic, succinic, decanedicarboxylic, azelaic, phthalic anhydride, isophthalic, terephthalic) and alcohols (ethylene glycol, 1,2 propylene glycol, 1,4-butanediol 1,3-propanediol, neopentyl glycol, diethylene glycol, 1,6-hexanediol, trimethylolpropane, glycerol). Non-exhaustive examples are polyethylene diol adipate, polypropylene diol adipate, polybutanediol adipate.

Other suitable polyols are polyethylene terephthalate and copolymer derivatives such as polyethylene terephthalate glycols, acrylic polyols, polycarbonate polyols, polyols derived from dimethyl carbonate in reaction with polyols such as hexanediol, Mannich polyols and polyamino and polycaprolactone polyols. Mixtures of the above alcohols are sometimes desirable to achieve the desired chemical and mechanical properties of polyurethane foam.

Preferred polyols as used in this application are selected from the group consisting of polypropylene glycol, polytetramethylene glycol having a molecular weight of from 400 to 4000, soybean oil and castor oil, and mixtures thereof.

The most preferred polyols are selected from the group consisting of ethylene glycol, glycerol, polyethylene glycol, polypropylene glycol, polytetramethylene glycol, polycaprolactone diol, poly (ethylene adipate) diol, poly (hexamethylene adipate) diol, castor oil, soybean oil, sugars and polysaccharides.

The choice of polyol has an effect on biodegradability and hardness of polyurethane foam. For example, to achieve biodegradable foams, the preferred polyols are hydrophilic polyols, such as ethylene glycol or caprolactone-based polyols and / or polyols containing cleavable ester or carboxylic anhydride, such as adipate-based polyols, optionally mixed with natural polyols such as sugars and derivatives of sugar alcohols, castor oil and mixtures thereof.

Alternatively, the addition of bioactive or biodegradable material during foaming is also a means to achieve sufficient biodegradation of the resulting polyurethane composite. In particular, the addition of lignin, molasses, polyhydroxyalkanoates, polylactide, polycaprolactone or amino acids is particularly preferred.

Additionally, the abrasive particles can be made of polyurethane foam, which is formed from a mixture of aliphatic diisocyanate and aromatic diisocyanate monomers and polyols. In a diisocyanate mixture containing aliphatic and aromatic diisocyanates, aromatic diisocyanate monomers contain less than 60% by weight of diisocyanates, preferably less than 50% and more preferably less than 40% by weight of diisocyanates. Suitable aromatic diisocyanate monomers as used herein are selected from the group consisting of toluene diisocyanate (TDI), methylene diphenyl diisocyanate (MDI), polymer methylene diphenyl diisocyanate (PMDI), polymer toluene diisocyanate (PTDI), and mixtures thereof.

There are two main options for polyurethane foam: one in which most foam cells remain closed and gas (s) remains trapped, the other is a system that has mostly open cells (i.e. interconnected porosity). In the present invention, an open cell structure is the preferred foam with a minimal suspended remainder of the membrane wall. The desired cellular structure is directly related to the optimum desired particle size for application, for example: a large cell size is more suitable for achieving large particle sizes and vice versa.

FIG. 5a is an electron microscope image showing closed cell polyurethane foam with a membrane wall, and FIG. 5b is an electron microscope image showing open cell polyurethane foam without a wall membrane in accordance with the present invention.

The applicant has found that a good cleaning effect will be achieved with abrasive particles that are made of polyurethane foam having a density of up to 500 kg / m ³ . However, the applicant unexpectedly discovered that a significantly better cleaning and peeling effect can be achieved when the density of the polyurethane foam is below 100 kg / m ³ , more preferably from 50 kg / m ³ to 100 kg / m ³ and most preferably from 5 kg / m ³ 50 kg / m ³ . Not wishing to be bound by theory, it is believed that the final shape of the particles is due to the density of the polyurethane foam, if the density of the foam is too high, then the resulting particles after cutting, crushing, grinding and / or grinding the foam will have a more round shape and less sharp edges, and will also provide lower productivity of cleaning and peeling due to non-optimal particle shape, as determined by the shape parameters described in this application.

FIG. 6a, 6b and 6c are electron microscopy images of polyurethane foams having a density of 33 kg / m ³ , 120 kg / m ³ and 320 kg / m ^3, respectively. FIG. 7a, 7b and 7c are electron microscopy images of polyurethane particles obtained from the polyurethane foams shown in FIG. 6a, 6b and 6c, respectively.

Preferred abrasive particles suitable for use in this application are hard enough to provide good cleaning / deep cleaning performance, while providing a good surface safety profile and very desirable mild skin peeling.

Preferred abrasive cleaning and exfoliating particles in the present invention have a hardness of from 3 to 50 kg / mm ² , preferably from 4 to 25 kg / mm ² and most preferably from 5 to 15 kg / mm ² of Vickers hardness HV.

Vickers hardness test method:

Vickers hardness HV is measured at 23 ° C in accordance with standard methods ISO 14577-1, ISO 14577-2, ISO 14577-3. Vickers hardness is measured in a solid block of raw materials of at least 2 mm in thickness. Vickers hardness microcoughing is measured using a micro hardness tester (MNT) manufactured by CSM Instruments SA, Peseux, Switzerland.

According to the instructions of ISO 14577, the test surface must be flat and smooth, with a roughness value (Ra) of less than 5% of the maximum penetration depth of the indenter. For a maximum depth of 200 μm, this corresponds to a Ra value of less than 10 μm. In accordance with ISO 14577, such a surface can be obtained by any suitable method, which may include cutting a block of test material with a new sharp microtome or a scalpel blade, grinding, polishing or casting the molten material on an even, smooth casting mold, which allows thorough curing before testing.

Acceptable general installation parameters for a micro hardness tester (MNT) are as follows:

Control mode: moving, continuous

Maximum displacement: 200 microns

Approach Speed: 20 nm / s

Zero point detection: on contact

Retention period for measuring temperature drift on contact: 60 s

Force application time: 30 s

Data recording rate: at least every second

Retention time at maximum force: 30 s

Forced removal time: 30 s

Shape / Material of Indenter Tip: Vickers Pyramid Shape / Diamond Tip

Alternatively, the hardness of the abrasive cleaning particles in the present invention can also be expressed on the corresponding Mohs hardness scale. Preferably, the Mohs hardness of the particles is from 0.5 to 4 and most preferably 1 to 3. The Mohs hardness scale is an internationally recognized scale for measuring the hardness of a compound compared to a compound with known hardness, see Encyclopedia of Chemical Technology, Kirk-Othmer , 4 th Edition Vol 1, page 18 or Lide, DR (ed) CRC Handbook of Chemistry and Physics, 73 rd edition, Boca Raton, Fla .: The Rubber Company, 1992-1993. Many Mohs test kits are commercially available containing materials of known Mohs hardness. In order to measure and select an abrasive material with a selected Mohs hardness, it is recommended to perform Mohs hardness measurements with unformed particles, for example, particles with a spherical or granular shape of the abrasive material, since the measurement of angular particles by Mohs will give erroneous results.

In order to facilitate the conversion of the foam into particles, the foam preferably has sufficient brittleness, for example, under tension, the foam has a slight tendency to deform and is subject to destruction.

In one preferred example, the abrasive polyurethane particles used in the present invention remain visible when the liquid composition is stored in the bottle, while during the efficient cleaning process, the abrasive particles disperse or break into smaller particles and become invisible to the eye.

One suitable method for converting foam into abrasive cleaning particles in this application is to grind or grind the foam. Other suitable methods include the use of erosion tools, such as a high-speed erosion wheel with a dust collector, where a pattern is engraved on the surface of the wheel or coated with abrasive sanding paper or the like, to help foam form abrasive particles in this application.

Alternatively, and in a highly preferred embodiment in this application, the foam can be converted into particles in several stages. First, the volume of the foam can be broken into pieces a few centimeters by grinding or cutting by hand, or using mechanical means such as a lump breaker, such as model 2036 from S Howes, Inc. of Silver Creek, NY. In the second stage, the lumps are mixed using a propeller or a dispersing tool with a sawtooth toothed disk, which causes the release of trapped water from the foam and forms a liquid suspension of polymer particles dispersed in the aqueous phase. In a third step, a high shear mixer (e.g., an Ultra Turrax rotor-stator mixer from IKA Works, Inc., Wilmington, NC) can be used to reduce the particle size of the primary slurry that is required for abrasive particles.

Preferably, the abrasive particles obtained by the grinding or grinding operation are single particles that do not have a cellular structure.

The abrasive particles used in the present invention may be a mixture of polymer, preferably polyurethane, foam particles and other suitable abrasive particles, such as natural particles. However, as a rule, all abrasive particles will have a hardness on the Vickers scale HV less than 50 kg / mm ² .

In one embodiment, the compositions described herein may contain natural abrasive particles, alone and / or in combination with polymer particles derived from foam. Natural particles in this application are usually obtained by cutting, crushing, grinding and / or grinding the shell of a nut, or other vegetable sources, such as, but not limited to, wood, stems, roots, leaves, seeds, roots, fruits and mixtures thereof.

Preferably, the nutshell is selected from the group consisting of walnuts, almonds, hazelnuts, macadamia shells, pine nutshells and mixtures thereof. The most preferred walnut shell is a walnut shell.

When other plant sources are used to produce abrasive particles of the composition of the present invention, they are preferably derived from rice, ears of corn, palm biomass, bamboo, kenaf, loofah, apple seeds, apricot kernels, olive seeds, cherry seeds, ivory seeds (Phyleteas genus), doom palm seeds (Hyphaene genus), sago palm seeds (Metroxylon genus), wood and mixtures thereof. Particles made from wood, olive seeds, cherry seeds, and the endosperm of ivory palm seeds, known as plant ivory, are preferred.

The natural abrasive particles used in this application can be coated, dyed and / or bleached by any suitable method available in the art to produce particles with an appearance that can provide more attractive aesthetic properties of the product.

The whitening process is also known to help inhibit the growth of bacteria, mold or fungi, which are essentially present in products of natural origin.

The abrasive particles in accordance with the present invention provide a double benefit to the user: firstly, excellent removal of harsh food contaminants from the dishes without substantially damaging delicate surfaces such as stainless steel, Inox®, Teflon®, painted and or decorated ceramics, crystal and plastics; and secondly, the beneficial effects of hand skin care, mainly softness / smoothness of the skin and improving the appearance of the skin through mild skin peeling.

If natural particles are used, they are contained at a level of more than 2%, preferably more than 2.5%, more preferably greater than or equal to 3%, even more preferably 3% to 10%, most preferably 3% to 6 % by weight of the composition.

If natural particles are used in combination with polymer particles, these natural particles may be present at a level of from 2% to 5%, preferably from 2% to 4%, more preferably from 2% to 3%, even more preferably from 2.5% to 3% by weight of the composition.

Suspending Agents (or Forming Agents)

The present invention includes one or more suspending agents selected from the group consisting of crystalline wax builders, amide gel builders, microfiber cellulose (MFC), dibenzylidene polyol acetal derivatives and mixtures thereof. These suspending agents can form a filamentous structuring system throughout the composition matrix, which prevents abrasive particles from sedimentation or emulsification in the product, thereby ensuring excellent stability of the liquid dishwashing composition by hand. This stability allows the formulation of particles with a density different from the density of the liquid composition and a preferred particle size (i.e., diameter equivalent to area) of from 50 to 400 microns, more preferably from 150 to 355 microns, to deliver effective cleaning without damaging delicate surfaces, and is highly desirable with soft skin peeling.

If present, said crystalline wax builder is typically comprised between 0.02% and 5%, preferably between 0.025% and 3%, more preferably between 0.05% and 2%, most preferably between 0.1% and 1.5% by weight of the total composition. Preferred crystalline wax builders are hydroxyl-containing crystalline builders, such as hydroxyl-containing fatty acid, fatty ester or fatty soap-like wax materials. The specified crystalline hydroxyl-containing structure-forming agent is not soluble in water under ambient conditions and in conditions close to environmental conditions.

A preferred crystalline hydroxyl-containing builder is selected from the group consisting of builders with the formula (I), (II), or mixtures thereof.

Formula (I)

,where R ¹ represents a chemical fragment described below, R ¹ represents

,

R ² represents R ¹ or H

R ³ represents R ¹ or H

R ⁴ is independently C ₁₀ -C ₂₂ alkyl or alkenyl containing at least one hydroxyl group;

,Formula (II)

,

where R ⁷ represents R4 as defined above in (I), M represents Na ⁺ , K ⁺ , Mg ⁺⁺ or Al ³⁺ or H.

Some preferred hydroxyl-containing stabilizers include 12-hydroxystearic acid, 9,10-dihydroxystearic acid, tri-9,10-dihydroxystearin and tri-12-hydroxystearin. Tri-12-hydroxystearin is most preferred for use in liquid dishwashing compositions by hand in this application.

.

.

Castor wax or hydrogenated castor oil is obtained by hydrogenation (saturation of triglycerides of fatty acids) of pure castor oil and mainly consists of tri-12-hydroxystearin. Commercially available castor oil-based crystalline, hydroxyl-containing suspending agents include THIXCIN® from Rheox, Inc (now Elementis).

Another preferred rheology modifier for use in the present invention is microfiber cellulose (MFC), such as described in US patent 2008/0108714 (CP Kelco) or US 2010/0210501 (P&G): microfiber cellulose bacterially obtained or otherwise can be used to provide a suspension of solid particles in a surface-active-thickened system, as well as in compositions with high concentrations of surface-active substances. Such MFCs are usually present in concentrations from about 0.01% to about 1%, and the concentration will depend on the desired product. For example, while 0.02 to 0.05% is preferred for suspending small mica plates in liquid detergent compositions, higher levels may be necessary to suspend large particles. Preferably, MFCs are used with co-agents and / or co-processing agents such as CMC, xanthan and / or microfibre guar gum. US 2008/0108714 describes MFC in combination with xanthan gum, and CMC in a ratio of 6: 3: 1, and MFC; guar gum, and CMC in a ratio of 3: 1: 1. These mixtures make it possible to obtain MFC in the form of a dry product that can be “activated” with high shear or high tensile stirring in water or other water-based solutions. “Activation” occurs when MFC mixtures are added to water and co-agents / co-agents are hydrated. After hydration of the co-agents / co-processing agents, a high shear is usually necessary for the effective dispersion of the MFC in order to obtain a three-dimensional functional network that shows the true yield strength. One example of a commercially available MFC is Cellulon® from CPKelko.

In another preferred embodiment, the external structuring system may comprise a diamide gelling agent having a molecular weight of from 150 g / mol to 1500 g / mol, preferably from 500 g / mol and 900 g / mol. Such diamide gelling agents may contain at least two nitrogen atoms, while at least two of these nitrogen atoms form amido functional substitution groups. In one embodiment, the amido groups are different. In a preferred embodiment, the amidofunctional groups are the same. The diamide gelling agent has the following formula:

Where

R ₁ and R ₂ represent an amino functional end group, preferably an amido functional end group, more preferably R ₁ and R ₂ may contain a pH-tunable group, where the pH-tunable amide gellant may have a pKa from 1 to 30, more preferably from 2 up to 10. In a preferred embodiment, the pH tunable group may contain pyridine. In one embodiment, R ₁ and R ₂ may be different. In a preferred embodiment, may be the same.

L is a binder moiety with a molecular weight of from 14 to 500 g / mol. In one implementation, L may contain a carbon chain containing from 2 to 20 carbon atoms. In another implementation, L may contain a pH-tunable group. In a preferred embodiment, the pH tunable group is a secondary amine.

In one embodiment, at least one of R1, R2, or L may contain a pH tunable group.

Non-limiting examples of diamide gelling agents are:

N, N ′ - (2S, 2′S) -1,1 ′ - (dodecane-1,12-diylbis (azanediyl)) bis (3-methyl-1-oxobutane-2,1-diyl) diisonicotinamide

dibenzyl (2S, 2′S) -1,1 ′ - (propane-1,3-diylbis (azanediyl)) bis (3-methyl-1-oxobutane-2,1-diyl) dicarbamate

dibenzyl (2S, 2′S) -1,1 ′ - (dodecane-1,12-diylbis (azanediyl)) bis (1-oxo-3-phenylpropan-2,1-diyl) dicarbamate

Another preferred embodiment includes dibenzylidene polyol acetal derivatives (DBPA). The liquid detergent composition may contain from 0.01% to 1% by weight of a dibenzylidene polyol acetal derivative (DBPA), preferably from 0.05% to 0.8%, more preferably from 0.1% to 0.6%, most preferably from 0 , 3% to 0.5%. In one embodiment, the DBPA derivative may comprise a dibenzylidene sorbitetal derivative (DBS), such as described in US Pat. No. 6,102,999, Cobb et al., Col. 2, line 43 - count. 3, line 65. In another embodiment, the DBPA derivative comprises a sorbitol derivative, a ribite derivative, xylitol derivative, tartrate, or a mixture thereof.

Hydrophobic Emollient

The composition in accordance with the present invention may contain one or more hydrophobic emollients. Hydrophobic emollients are agents that soften or soothe the skin, slowing the evaporation of water. Hydrophobic emollients form an oily layer on the surface of the skin, which slows down the loss of water, increasing the moisture content of the skin and the skin's ability to retain water. Not wishing to be bound by theory, it is believed that a hydrophobic emollient complements the beneficial effect of skin care, providing exfoliation of particles in accordance with the present invention, by soothing exfoliated skin. If a hydrophobic emollient is present, said dishwashing liquid according to the present invention contains high levels of a hydrophobic emollient, typically up to 10% by weight. The hydrophobic emollient is preferably present from 0.25% to 10%), more preferably from 0.3% to 8%, most preferably from 0.5% to 6% by weight of the total composition.

Hydrophobic emollients suitable for use in the compositions of this application are hydrocarbon oils and waxes; silicones; fatty acid derivatives; glyceride esters, di- and triglycerides, acetoglyceride esters; alkyl and alkenyl esters; cholesterol and cholesterol derivatives; vegetable oils, vegetable oil derivatives, liquid non-digestible oils, or mixtures of liquid digestible or non-digestible oils with solid polyester polyols; natural waxes such as lanolin and its derivatives, beeswax and its derivatives, spermaceti, candelilla and carnauba waxes; phospholipids, such as lecithin and its derivatives; sphingolipids such as ceramide, and mixtures thereof.

Preferred hydrophobic emollients are hydrocarbons such as petroleum jelly, mineral oil and / or mixtures of petroleum jelly and mineral oil; triglycerides, such as those derived from vegetable oils, including castor oil, soybean oil, safflower oil, cottonseed oil, corn oil, walnut oil, peanut oil, olive oil, almond oil, avocado oil, coconut oil, jojoba oil, cocoa butter and the like; Sugar oil derivatives, such as sucrose fatty acid esters; beeswax; lanolin and its derivatives, including, but not limited to, lanolin oil, lanolin wax, lanolin alcohols, lanolin fatty acids, isopropyl lanolate, cetylated lanolin, acetylated lanolin alcohols, lanolin alcohol ethanol linoleate, lanolin ethanolate ranololeate.

Enzymes

The composition in accordance with the present invention may contain an enzyme, such as amylase, protease, cellulase, mannanase, pectinase, xyloglucanase and / or lipase; preferably protease. Not wishing to be bound by theory, it is believed that the protease will interact with the surface of the skin to provide additional beneficial peeling effects.

Enzymes can be included in the compositions in accordance with the present invention at a level of from 0.00001% to 1% of the enzyme protein by weight of the whole composition, preferably at a level of from 0.0001% to 0.5% of the enzyme protein by weight of the whole composition, more preferably at a level of from 0.0001% to 0.1% of the protein of the enzyme by weight of the entire composition.

These enzymes may be provided as a stabilized liquid or as a protected liquid or encapsulated enzyme. Liquid enzyme preparations may, for example, be stabilized by the addition of a polyol, such as propylene glycol, sugar or sugar alcohol, lactic acid or boric acid, or a protease stabilizer, such as 4-formyl phenylboronic acid in accordance with established methods. Surfactants

A preferred additional ingredient in the composition of the invention is a surfactant selected from nonionic, anionic, cationic surfactants, amphoteric, zwitterionic, semi-polar nonionic surfactants, and mixtures thereof. Surfactants may be present at a level of from about 1.0% to about 50% by weight, preferably from about 5% to about 40% by weight, more preferably from about 10% to about 30% by weight, and even more preferably from from about 5% to about 20% by weight of a liquid detergent composition. Non-limiting examples of acceptable surfactants are described below.

In a preferred embodiment, effective but hand-gentle surfactant systems will typically contain from about 4% to about 40%, preferably from about 6% to about 32%, more preferably from about 11% to about 25%, and most preferably from about 11% to about 18% by weight of the total composition of the anionic surfactant and therefore preferably not more than about 15%, preferably not more than about 10%, more than respectfully not more than about 5% by weight of the total composition, sulfonate surfactant.

Suitable anionic surfactants to be used in the compositions and methods of the present invention are sulfates, sulfosuccinates, sulfonate and / or sulfoacetate; preferably alkyl sulfate and / or alkyl ethoxysulfates; more preferably a combination of alkyl sulfates and / or alkyl ethoxysulfates with a combined degree of ethoxylation of less than about 5, preferably less than about 3, more preferably less than about 2.

In an alternative embodiment, the surfactant system may be based on high levels of non-ionic surfactant (e.g., from about 10% to about 45%, preferably from about 15 to about 40%, more preferably from about 20 to about 35%, by weight) weight of the entire composition), preferably in combination with an amphoteric surfactant, and more preferably with a low level of anionic surfactant (for example, less than 20%, preferably itelno less than 10%, more preferably less than about 5% by weight of the total composition).

Sulphate Surfactants

Suitable sulfate surfactants for use in the compositions herein include water soluble salts or acids of C ₁₀ -C ₁₄ alkyl or hydroxyalkyl, sulfate and / or sulfate ester. Suitable counterions include hydrogen, an alkali metal or ammonium cation, or substituted ammonium, but preferably sodium.

Where the hydrocarbyl chain branches, it preferably includes C _1-4 alkyl branching units. The average branching percentage of the sulfate surfactant is preferably more than 30%, more preferably from 35% to 80% and most preferably from 40% to 60% of all hydrocarbyl chains.

Sulfate surfactants can be selected from C ₈ -C ₂₀ primary, branched chains and random alkyl sulfates (AS); C ₁₀ -C ₁₈ secondary (2, 3) alkyl sulfates; C ₁₀ -C ₁₈ alkyl alkoxysulfates (AE _x S), where x is preferably 1-30; C ₁₀ -C ₁₈ alkylalkoxycarboxylates, preferably including 1-5 ethoxy units; mid-chain branched alkyl sulfates as described in US Pat. No. 6,020,303 and US Pat. No. 6,060,443; mid-chain branched alkyl alkoxysulfates as described in US Pat. No. 6,008,181 and US Pat. No. 6,020,303.

Alkylsulfosuccinates-Sulfoacetate

Other suitable anionic surfactants are alkyl, preferably dialkyl, sulfosuccinates and / or sulfoacetate. Dialkyl sulfosuccinates can be C _6-15 linear or branched dialkyl sulfosuccinates. Alkyl moieties may be symmetric (i.e., the same alkyl moieties) or asymmetric (i.e., different alkyl moieties). Preferably, the alkyl moiety is symmetrical.

Sulfonate Surfactants

Compositions in accordance with the present invention will preferably contain not more than 10% by weight, preferably not more than 8%, even more preferably not more than 5% by weight of the total composition, sulfonate surfactant. These include water-soluble salts or acids of C ₁₀ -C ₁₄ alkyl or hydroxyalkyl, sulfonates; C ₁₁ -C ₁₈ alkylbenzenesulfonates (LAS), modified alkylbenzenesulfonates (MLAS) as described in WO 99/05243, WO 99/05242, WO 99/05244, WO 99/05082, WO 99/05084, WO 99/05241, WO 99/07656, WO 00/23549 and WO 00/23548; methyl ester sulfonate (MES) and alpha olefin sulfonate (AOS). They also include paraffin sulfonates, can be monosulfonates and / or disulfonates obtained by sulfonation of paraffins containing from 10 to 20 carbon atoms. Sulfonate surfactants also include alkyl glyceryl sulfonate surfactants.

Amphoteric and zwitterionic surfactants

The amphoteric and zwitterionic surfactant may be present at a level of from 0.01% to 20%, preferably from 0.2% to 15%, more preferably from 0.5% to 12% by weight of a liquid detergent composition. Suitable amphoteric and zwitterionic surfactants are amine oxides and betaines.

Most preferred are amine oxides, especially cocodimethyl amine oxide or cocoamidopropyl dimethyl amine oxide. The amine oxide may have a linear or mid-chain branched alkyl moiety. Typical linear amine oxides include water-soluble amine oxides of the formula R ¹ —N (R ² ) (R ³ ) → 0, where R ¹ is a C _8-18 alkyl moiety; R ² and R ^{3 are} independently selected from the group consisting of C _1-3 alkyl groups and C _1-3 hydroxyalkyl groups and preferably include methyl, ethyl, propyl, isopropyl, 2-hydroxyethyl, 2-hydroxypropyl and 3-hydroxypropyl. Linear amine oxide surfactants, in particular, may include linear C ₁₀ -C ₁₈ alkyl dimethyl amine oxides and linear C ₈ -C ₁₂ alkoxyethyl dihydroxyethyl amine oxides. Preferred amine oxides include linear C ₁₀ , linear C ₁₀ -C ₁₂ and linear C ₁₂ -C ₁₄ alkyl dimethyl amine oxides. As used in this application, “branched in the middle of the chain” means that the amine oxide has one alkyl fragment having n ₁ carbon atoms, with one alkyl branching on the alkyl fragment having n ₂ carbon atoms. Alkyl branching is located on the α carbon atom from nitrogen on the alkyl moiety. This type of branching for amine oxide is also known in the art as internal amine oxide. The total amount of n ₁ and n ₂ is from 10 to 24 carbon atoms, preferably from 12 to 20, and more preferably from 10 to 16. For the one alkyl moiety (n ₁₎ number of carbon atoms should be approximately the same number of carbon atoms for one alkyl branch (n ₂ ) such that one alkyl fragment and one alkyl branch are symmetrical. As used in this application, "symmetric" means that | n ₁ -n ₂ | less than or equal to 5, preferably 4, most preferably from 0 to 4 carbon atoms in at least 50 wt. %, more preferably at least 75 wt. % to 100 wt. % mid-chain branched amine oxides for use in this application.

The amine oxide further comprises two fragments independently selected from a C _1-3 alkyl, C _1-3 hydroxyalkyl group or a polyethylene oxide group containing on average from about 1 to about 3 ethylene oxide groups. Preferably, two fragments are selected from C _1-3 alkyl, more preferably both are selected as C ₁ alkyl.

Other suitable surfactants include betaines such as alkyl betaines, alkyl amidobetaine, amidazolinium betaine, sulfobetaine (INCI sultaines) and phosphobetaine.

Examples of suitable betaines and sulfobetaine are as follows [designated according to INCI]: amidopropyl betaines almonds, amidopropyl betaines apricot, amidopropyl betaines avocado, amidopropyl betaines babassu begenamidopropilbetainy betaines behenyl, betaines, amidopropyl betaines canola oil, caprylic / kaproamidopropilbetainy, carnitine, cetyl betaine, kokamidoetilbetainy, cocamidopropyl betaine, kokamidopropilgidroksisultain , cocobetaines, cocohydroxy sultaine, coco / oleamidopropyl betaines, cocosultain, decyl betaines, dihydroxyethyl oleyl itsinat, digidroksietilglitsinat soy digidroksietilstearilglitsinat, digidroksietilzhirny glycinate, dimetikonpropiliz PG-betaine, erukamidopropil gidroksisultain, hydrogenated tallow betaine, izostearamidopropilbetainy, lauramidopropyl, lauryl, laurilgidroksisultain, laurilsultain, amidopropyl betaines milk minkamidopropilbetainy, miristamidopropilbetainy, miristilbetainy, oleamidopropilbetainy, oleamidopropilgidroksisultain, oleyl betaine, amidopropyl betaines olives, palm trees dopropyl betaine, palmitamido propilbetainy, palmitoylcarnitine, palm kernel amidopropyl betaines, politetraftoretilenatsetoksipropil betaines, amidopropyl betaines castor, sesamidopropilbetainy, soya amidopropyl betaines, stearamidopropilbetainy, stearilbetainy fatty amidopropyl betaines, fatty amidopropilgidroksisultain fatty betaines, fatty digidroksietilbetainy, undetsilenamidopropilbetainy amidopropyl betaines and wheat germ.

Preferred betaine is, for example, cocoamidopropyl betaine (cocoamidopropyl betaine).

A preferred surfactant system is a mixture of an anionic surfactant and amphoteric or zwitterionic surfactants in a ratio in the range from 1: 1 to 5: 1, preferably from 1: 1 to 3.5: 1.

It has been found that such a surfactant system will provide the excellent cleaning and foaming profile required of a liquid dishwashing liquid by hand, while being gentle on the hands.

Nonionic Surfactants

The non-ionic surfactant, when present as an auxiliary surfactant, is present in a typical amount of from 0.1% to 20%, preferably from 0.5% to 15%, more preferably from 0.5% to 10% by weight of liquid detergent composition. When present as the main surfactant, it is present in a typical amount of from 0.1 to 45%, preferably from 15 to 40%, more preferably from 20 to 35% by weight of the total composition. Suitable nonionic surfactants include condensation products of aliphatic alcohols with from 1 to 25 moles of ethylene oxide. The alkyl chain of an aliphatic alcohol can be either straight or branched, primary or secondary, and usually contains from 8 to 22 carbon atoms. Especially preferred are condensation products of alcohols having an alkyl group containing from 10 to 18 carbon atoms, preferably from 10 to 15 carbon atoms, from 2 to 18 moles, preferably from 2 to 15, more preferably 5-12 moles of ethylene oxide per mole of alcohol .

Also suitable are alkyl polyglycosides having the formula R ² O (C _n H _2n O) _t (glycosyl) _x (formula (V)), where R ^{2 of} formula (V) are selected from the group consisting of alkyl, alkyl phenyl, hydroxyalkyl, hydroxyalkylphenyl and mixtures thereof, where the alkyl groups contain from 10 to 18, preferably from 12 to 14 carbon atoms; n of formula (V) is 2 or 3, preferably 2; t of formula (V) is from 0 to 10, preferably 0; and x of formula (V) is from 1.3 to 10, preferably from 1.3 to 3, most preferably from 1.3 to 2.7. Glycosyl is preferably derived from glucose. Alkyl glycerol esters and sorbitol esters are also suitable.

Also suitable are fatty acid amide surfactants having an alkyl group containing from 7 to 21, preferably from 9 to 17 carbon atoms, and an amide group selected from C ₈ -C ₂₀ ammonia amides, monoethanolamides, diethanolamides, and isopropanolamides.

Cationic Surfactants

Cationic surfactants, if present in the composition, are present in an effective amount, more preferably from 0.1% to 20% by weight of a liquid detergent composition. Suitable cationic surfactants are quaternary ammonium surfactants. Suitable quaternary ammonium surfactants are selected from the group consisting of mono C ₆ -C ₁₆ , preferably C ₆ -C ₁₀ N-alkyl or alkenyl ammonium surfactants, where the remaining N positions are substituted with methyl, hydroxyethyl or hydroxypropyl groups . Another preferred cationic surfactant is an C ₆ -C ₁₈ alkyl or alkenyl ester of a quaternary ammonium alcohol, such as quaternary chlorine esters complex.

Cationic polymer

The liquid dishwashing compositions in this application may contain at least one cationic polymer for delivering beneficial skin conditioning effects that can enhance the softness of the skin provided by the mild skin peeling provided by the abrasive particles of the present invention.

If present in the composition, the cationic polymer will typically be present at a level of from 0.001% to 10%, preferably from 0.01% to 5%, more preferably from 0.05% to 1% by weight of the total composition.

Suitable cationic polymers for use in the present invention contain cationic nitrogen-containing moieties, such as quaternary ammonium or cationic-protected amino fragments. Non-limiting examples include cationic polysaccharides, such as cationic cellulose derivatives, cationic starch, and cationic guar gum derivatives. Also included are synthetically prepared copolymers, such as homopolymers of diallyl quaternary ammonium salts, copolymers of diallyl quaternary ammonium salt / acrylamide copolymer, quaternized derivatives of polyvinylpyrrolidone, polyglycol polyamine condensates, copolymers of vinylimidazolium trichloride / vinylpyrrolidone copolymers, dimethyldiallylammonium chloride copolymers, vinylpyrrolidone / quaternized dimethylaminoethyl methacrylate copolymers, polyvinylpyrrolidone / alkylamino acrylate polyvinylpyrrolidone / alkylamino copolymers acrylate / vinylcaprolactam, vinylpyrrolidone / methacrylamidopropyl trimethylammonium chloride copolymers, alkyl acrylamide / acrylate / alkylaminoalkylacrylamide / polyethylene glycol methacrylate copolymers, adipic acid / dimethylaminohydroxypropyl ethylene copolymers.

Preferred cationic polymers are cationic polysaccharides, more preferably cationic cellulose derivatives, such as hydroxyethyl cellulose salts, reacting with trimethylammonium substituted epoxide, commercially known as CTFA Polyquaternium-10, commercially available examples of which are the UCARE series of former polymers. Dow Amerchol; and / or cationic guar gum derivatives, such as hydroxypropyltrimonium guar chloride, commercially available examples of which are former Jaguar® series. Rhodia, the N-Hance® and AquaCat® polymer series available from Aqualon.

Humidifier

In a preferred embodiment, the composition of the present invention may further comprise one or more humectants. It was found that such a composition, including a moisturizer, will provide additional beneficial effects for hand skin care.

If present, a humectant will typically be present in the composition of the present invention at a level of from 0.1% to 50%, preferably from 1% to 20%, more preferably from 1% to 10%, even more preferably from 1% to 6 %, and most preferably from 2% to 5% by weight of the total composition.

Humidifiers that can be used in accordance with the present invention include those that have an affinity for water and help to increase the absorption of water by a substrate, preferably skin. Specific non-limiting examples of particularly suitable humectants include glycerin; diglycerin; polyethylene glycol (PEG-4) and its derivatives; propylene glycol; hexylene glycol; butylene glycol; (di) propylene glycol; glyceryl triacetate; lactic acid; urea polyols such as sorbitol, xylitol and maltitol; polymeric polyols such as polydextrose and mixtures thereof. Additional suitable humectants are polymeric humectants of the family of water-soluble and / or water-swellable polysaccharides, such as hyaluronic acid, chitosan and / or fructose-rich polysaccharide, which, for example, is available as Fucogel® 1000 (CAS-Nr 178463-23-5 ) from SOLABIA S. If present, then the moisturizer will further enhance the beneficial effect of moisturizing the skin, provided by soft peeling of the skin, provided by abrasive particles. Removing dead cells from the outer layer of the skin through peeling eliminates dry scales and leads to noticeably more moisturized skin. Moisturizers will further enhance the moisturized state of the skin by retaining water.

Pearlescent agent and opacifying agents

The composition in accordance with the present invention may contain an organic and / or inorganic pearlescent agent and / or an agent that makes the composition opaque in order to provide a composition that is substantially hazy (substantially opaque). The composition is “substantially cloudy,” as assumed in this application, if it transmits no more than 50% of the light at any one wavelength in the visible range, i.e. from 400 to 800 nm, preferably from 550 to 700 nm, measured in a 1 cm cuvette in the absence of dyes and abrasive particles. Preferably, the transmittance is not more than 30%, more preferably not more than 20%. Pearlescent agents and / or agents that make the composition opaque make the aesthetic properties of the product containing particles more attractive to consumers.

Organic pearlescent agents are usually contained at an active level of from 0.05% to 2.0 wt. %, preferably from 0.1% to 1.0 wt. % of the total composition. Suitable organic pearlescent agents include monoester and / or alkylene glycol diester. Typical examples are fatty monoesters and / or diesters of ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, triethylene glycol or tetraethylene glycol. Non-limiting examples of commercially available fatty acid esters are ex. PEG6000MS®. Stepan, Empilan EGDS / A® ex. Albright & Wilson, and Euperlan® PK711 manufactured by Cognis Corp.

Inorganic pearlescent agents are usually contained at an active level of from 0.005% to 1.0 wt. %, preferably from 0.01% to 0.2% by weight of the composition of 100% active inorganic pearlescent agents. Inorganic pearlescent agents include aluminosilicates and / or borosilicates, preferably silica, metal oxides, aluminosilicate and / or borosilicates coated with oxychloride. More preferably, the inorganic pearlescent agent is mica, even more preferably mica treated with titanium dioxide, such as BASF Mearlin Superfine. Other commercially available acceptable inorganic pearlescent agents are available from Merck under the trademarks Iriodin, Biron, Xirona, Timiron Colorona, Dichrona, Candurin and Ronastar; from BASF (Engelhard, Mearl) under the trademarks Biju, Bi-Lite, Chroma-Lite, Pearl-Glo, Mearlite and from Eckart under the trademarks Prestige Soft Silver and Prestige Silk Silver Star.

Agents that make the composition opaque, if present, are contained at an active level of from 0.005% to 1%, preferably from 0.01% to 0.5%, more preferably from 0.02% to 0.3% by weight of the composition. Acceptable materials may be selected from the Acusol ™ 0P30X range (formerly Rohm and Haas), the PuriColour White range (formerly Ciba), and the LameSoft ™ range (formerly Cognis).

Cleaning polymer

The liquid dishwashing liquid in this application may optionally additionally contain one or more alkoxylated polyethyleneimine polymers. The composition may contain from 0.01% to 10%, preferably from 0.01% to 2%, more preferably from 0.1% to 1.5%, even more preferably from 0.2% to 1.5% by weight of the entire composition, alkoxylated polyethyleneimine polymer, as described on page 2, line 33 to page 5, line 5 and illustrated in examples 1-4 on pages 5 to 7 of WO 2007/135645 The Procter & Gamble Company.

The composition may further comprise amphiphilic grafted polymers based on water-soluble polyalkylene oxides (A) as the grafted backbone and side chains formed by polymerizing the vinyl ester component (B), said polymers having an average of ≤1 grafting site per 50 alkylene oxide units and an average the molar mass Mw from 3000 to 100000 described in the patent application BASF WO 2007/138053 on page 2 line 14 to page 10, line 34 and illustrated on pages 15-18.

Other optional components:

Liquid detergent compositions in this application may additionally contain a number of other optional ingredients suitable for use in liquid detergent compositions, such as magnesium ions, solvents, hydrotropes, polymer foam stabilizers, polymer rheology modifiers, linear or cyclic carboxylic acids, diamines, perfume, dyes , chelating agents, pH buffers. Further discussion of acceptable optional ingredients suitable for use in a lightweight liquid detergent composition can be found in US Pat. No. 5,798,505. The density of the composition

Liquid dishwashing compositions in this application preferably have a viscosity of from 100 to 10,000 mPa * s (100-10000 centipoise), more preferably from 200 to 8000 mPa * s (200-8000 centipoise), even more preferably 400-6500 mPa * with (400-6500 centipoise), and most preferably from 800 to 5000 mPa * s (800-5000 cP) at 3.06 sec ^-1 and 20 ° C. Viscosity can be determined by conventional methods. The viscosity in accordance with the present invention is measured using a Brookfield LVDV II viscometer with a cylindrical steel spindle (spindle No. 31) in accordance with the manufacturer's instructions.

The preferred rheology described in this application can be achieved by using existing internal structuring with detergent ingredients or by using an external rheology modifier and / or builder that provides the composition with a pseudo-plasticity or rheology profile with a decrease in shear viscosity and a time-dependent recovery of viscosity after shear (thixotropy).

The method of cleaning / processing dishes

In a preferred embodiment, the method of cleaning dishes with a liquid dishwashing composition containing the abrasive particles described in this application includes the step of applying the composition to the surface of the dishes, usually diluted and / or pure, and rinsing or allowing the composition to dry on the specified surface without rinsing the specified surface.

By “in its pure form” means in this application that said liquid composition is applied directly to the surface to be treated and / or to a cleaning device or apparatus, such as a dishcloth, sponge or dishwasher brush, without any dilution by the user (immediately) before application. By “diluted” means in this application that the liquid composition is diluted by the user with an appropriate solvent, usually water. By “rinsing” is meant in this application the contacting of dishes, cleaned by the method in accordance with the present invention, with substantial amounts of an appropriate solvent, usually water, after the stage of applying the liquid composition in this application to said dishes. By "substantial quantities" is meant, as a rule, from 5 to 20 liters.

Way

A method for producing compositions containing abrasive particles in this application includes the steps of: (i) fragmenting the polymer foam into polymer particles, preferably by cutting, grinding, grinding and / or crushing said foam; (ii) adding and / or mixing said particles to and / or with a composition, preferably a dishwashing composition, by hand, and (iii) adding and / or mixing one or more suspending agents selected from the group consisting of crystalline wax builders , amide gelling agents, microfiber cellulose, dibenzylidene polyol acetal derivatives and mixtures thereof. The polymer material is selected from the group consisting of polyurethane, derivatives of polyhydroxyalkanoate (PHA), aliphatic polyesters, derivatives of polylactic acid (PLA), polystyrene, melamine-formaldehyde, polyacrylate, polyolefins, polyvinyl and mixtures thereof.

In an implementation, steps (ii) and (iii) occur essentially simultaneously. In an alternative embodiment, step (iii) may occur before step (ii).

In a preferred embodiment, step (i) comprises a step in which the polymer foam is fragmented, preferably polyurethane foam, having a density of less than 100 kg / m ³ and / or having an open cell structure.

In one embodiment, the method comprises the step of fragmenting a material selected from the group consisting of walnut shells, other vegetable sources, and also mixtures thereof, preferably by cutting, grinding, grinding and / or crushing said material to form natural abrasive particles. This stage can occur essentially simultaneously either before or after stage (i). This step may be followed by the addition and / or mixing of such natural particles with the composition described in this application.

Test method for cleaning performance

For the first time, the cleaning performance of a “pure” product can be estimated using the following test method: A tile, usually glossy, white, enamel 24 cm × 4 cm, is obtained by applying to it either 0.6 g of a pure mixture of vegetable oils (peanut, sunflower and corn oil in equal proportions) or 0.5 g Knorr mixture of white sauces (obtained in accordance with the manufacturer's instructions). Contaminants are spread using a paint roller to get an even layer on top of the tile. The tile is fired in an oven at 145 ° C for 2 hours and 10 minutes (a mixture of vegetable oils) or at 180 ° C for 45 minutes (white sauce) and stored in a cabinet with constant temperature and humidity (25 ° C, 70% relative) humidity) before use. To test the cleaning performance, the tiles are placed on a wet abrasion tester with four treatment paths equipped with four sponge holders (e.g., from Shttn Instruments Ltd. Kingston, England). Four new kitchen cellulose sponges (e.g. Spontex®) of 4 cm × 8.5 cm (and 4.5 cm thick) dimensions were wetted with 25 g of water at 15 gpg of water hardness and placed in sponge holders. Four g of either test or benchmark formulations were applied to the sponge. The sponge holders are turned down so that the sponges are located directly on top of the dirty tile. The abrasion tester can be configured to provide pressure (for example 200 g, 400 g, 600 g or 700 g), and move the sponge along the test surface with a set of step lengths (for example: 30 cm), at a set speed (for example: 37 steps per minute) . The ability of the composition to remove impurities was measured by the number of steps required for excellent surface cleaning, according to a visual assessment. In this context, one step means one movement of a device equipped with four sponges containing a cleaning product on the tile to be cleaned. The smaller the number of steps, the higher the cleansing ability of the composition.

Contamination was considered completely removed if the operator could no longer observe the pollution with the naked eye. Eight contaminated tiles were used for one test and the position of the product was randomly distributed so that each product was tested in four different cleaning paths of the wet abrasion scraper tester at least once.

Surface Damage Method:

To measure surface damage caused by test particles, 4 g of aqueous solutions containing particles of the present invention (3 wt.% - 5 wt.% Of particles in deionized water) were applied to new kitchen cellulose sponges (e.g. Spontex®) of size 4 cm × 8.5 cm (and 4.5 cm thick), 25 g of deionized water were wetted, mounted on a wet scraper test instrument, as described in the test method of cleaning performance with the particle coated side facing the test surface. Two benchmarks were used: Benchmark 1 is the same cellulose kitchen sponge moistened with 25 g of deionized water and filled with 4 g of particle-free water, Benchmark 2 is a medium-performance scraper sponge, such as the 3M sold under the Scotch-Brite brand, placed on the scraper sponge holder wet abrasion tester with a green scraper side facing the test surface, moistened and filled as a reference 1 sponge. The test surface to be used must be a new sheet of colorless, transparent, untreated poly (methyl methacrylate) (also known as PMMA, Plexiglass, Perspex, Lucite) having a Vickers hardness value of HV 25 kg / mm ² (+/- 2 ) (when measured using the standard test method ISO 14577). The abrasion tester should be configured to provide 600 g of pressure and move the sponge along the test surface with a step length of 30 cm, at a speed of 37 steps per minute. A wet abrasion scraper tester should be allowed to perform 200 steps (i.e. 200 offsets in one direction), then the sponge will be refilled with an additional 4 g of abrasive particles in water. The sponge must be refilled this way every 200 steps, for five consecutive fillings (i.e. 1000 steps in total on the test surface). Damage to the test surface is evaluated after 1000 steps are completed.

To assess surface damage on a poly (methyl methacrylate) test surface, a visual assessment was performed using the following 5 level scale for assessing surface damage: 0 = I do not see any scratches; 1 = I think I see scratches; 2 = I definitely see slight scratches; 3 = I see a lot of scratches; 4 = I see a lot of damage. A visual assessment of damage is an average rating provided by 2 independent evaluators.

TABLE 3: Visual assessment of surface damage of illustrative cleaning and abrasive particles dispersed in deionized water at indicated levels. Try Visual assessment of surface damage 3% particles of polyurethane foam (1) 0 5% particles of bleached walnut shell (2) 0 Benchmark 1 - soft sponge + water 0 Benchmark 2 - scraper sponge + water 3 (1) Of a foam having a foam density of 33 kg / m ³ / Vickers hardness of 7 kg / mm ² / Milled in a blade mill and a sieve fraction of 50-355 microns (2) Chats size ~ 200 microns. Evonik industries

Peeling method

The "in vivo" peeling method is based on the removal of dihydroxyacetone-induced artificial skin coloration. Dihydroxyacetone has the ability to stain only fully keratinized epidermal cells. Removal of dihydroxyacetone-induced contamination is associated with the removal of completely keratinized cells and, therefore, can provide an assessment of skin peeling.

The areas of the inner forearm of the left and right hands of two volunteers were artificially stained using a commercially available artificial tan containing dihydroxyacetone. Artificial tanning was applied once a day for a week in accordance with the manufacturer's instructions until a uniform artificial tan was obtained.

Three treatment areas on the arm were noted using a waterproof marker. Three treatment areas of each arm should be centered on the inner area of the forearm between the wrist and the inside of the elbow. Care should be taken not to use the area closest to the inside of the elbow and wrist. One of the 3 treatment areas on each forearm is not a particle control, which is included to demonstrate the beneficial peeling effects provided by the particles. The location of both the control section without particles and the two treatment sections by particles was randomly distributed for each arm and each subject to minimize positioning effects.

Product treatment: 0.5 ml of each prototype was applied twice a day, at least four hours elapsed between product application only 4 times in their designated treatment areas of each forearm. The product was dispensed onto the skin with a 2 ml syringe and wiped with a gloved finger for 10 seconds in a circular motion, after all the products were applied to one forearm, the skin was washed with warm tap water and patted with a dry soft paper cloth, taking care not to wipe the treatment areas. Skin color measurements were taken as L *, a *, b * values according to the CIELab color scale using the BYK Gloss Spectroscopy Guide 6801 before each application of the product, and one hour after the last (4th) application of the product, in accordance with the equipment instructions . The CIELab color scale is based on the theory of complementary colors, which assumes that the human eye perceives color as the following pairs of opposites: light-dark, red-green, yellow-blue. The L * value for each scale indicates the level of light or dark, a * the value of red or green, and b * the value of yellowness or blueness.

The beneficial effects of peeling provided by illustrative hand-washing products containing abrasive particles (formulations G, H, I) are shown in TABLE 5 and FIG. 8 to reduce the b * value (color removal) after each treatment (T1-T4) with the product containing the particles and the difference b * value (Δb *) between the color of the artificially tanned skin before starting treatment with the product (b * BT) and after the last (4th) treatment (b * T4), so Δb * = b * BT-b * T4. Large Δb * indicate greater color removal and greater skin peeling. Particle exposure can be seen by increasing Δb * after treatment with particle-containing prototypes. Similarly, skin treated with particle prototypes shows a b * value closer to non-tanned (untreated) skin, which was measured in the inner part of the forearm and which has an average value of b * 15.77, demonstrating that prototypes with particles are more effective at removing the dead layer cells stained with artificial tan, as well as when the skin returns to its original color.

The average value of b * is not artificial tanned skin, i.e. the skin of the inner part of the forearm, not treated with artificial tan containing dihydroxyacetone, is 15.77.

EXAMPLES: Liquid detergents for washing dishes by hand

(1) Of a foam having a foam density of 33 kg / m ³ / Vickers hardness of 7 kg / mm ² / Milled in a blade mill and a sieve fraction of 50-355 microns

(2) Milled in a paddle mill and sieve fraction 250-355 microns

(3) Milled in a paddle mill and sieve fraction 150-250 microns

(4) Evonik Industries

(5) J. Rettenmaier & Sönne Gmbh + Co.KG

(6) Guar hydroxypropyl trimonium chloride

(7) Millithix 925S Milliken

(8) N, N ′ - (2S, 2′S) -1,1 ′ - (dodecane-1,12-diylbis (azanediyl)) bis (3-methyl-1-oxobutane-2,1-diyl) diisonicotinamide

The dimensions and values described in this application should not be understood as strictly limited in accuracy to the given numerical values. Instead, unless otherwise indicated, each such dimension shall indicate both the quoted value and the functionally equivalent range surrounding the given value. For example, a dimension disclosed as “40 mm” should mean “approximately 40 mm”.

Claims (28)

1. A liquid composition for washing dishes by hand, containing:
a. from 1.0% to 50%, by weight of composition, surfactant;
b. one or more suspending agents selected from the group consisting of crystalline wax builders, diamide gel builders having a molecular weight of from 150 g / mol to 1500 g / mol, said diamide gel builders containing at least two nitrogen atoms, at least at least two of these nitrogen atoms form amide functional groups of substitution, microfiber cellulose and mixtures thereof; and
c. polymer particles obtained from polymer foam material,
wherein said polymeric material is selected from the group consisting of polyurethane, polyhydroxyalkanoate derivatives (PHA), aliphatic polyesters, polylactic acid derivatives (PLA), polystyrene, melamine-formaldehyde, polyacrylate, polyolefins, polyvinyl and mixtures thereof, said polymeric foam material characterized by a density of less than 100 kg / m ³ , and these polymer particles are characterized by an average particle size, expressed by a diameter equivalent to an area of 10 μm to 1000 μm in accordance with ISO 92 76-6, and moreover, these polymer particles are contained at a level of from 0.1% to 10% by weight of the composition, and moreover, these polymer particles are characterized by average strength from 0.4 to 0.75. 2. The composition according to p. 1, characterized in that the specified polymer foam material has a structure with open cells. 3. The composition according to p. 1, characterized in that the said polymer particles are polyurethane particles. 4. The composition according to p. 1, characterized in that the polymer particles are contained at a level of from 0.3% to 10% by weight of the composition. 5. The composition according to p. 4, characterized in that the polymer particles are contained at a level of from 0.5% to 5% by weight of the composition. 6. The composition according to p. 5, characterized in that the polymer particles are contained at a level of from 0.5% to 3% by weight of the composition. 7. The composition according to p. 1, characterized in that the said polymer particles are characterized by Vickers hardness HV from 3 to 50 kg / mm ² . 8. The composition according to p. 7, characterized in that the said polymer particles are characterized by Vickers hardness HV from 4 to 25 kg / mm ² . 9. The composition according to p. 8, characterized in that said polymer particles are characterized by Vickers hardness HV from 5 to 15 kg / mm ² . 10. The composition according to p. 1, characterized in that the polymer particles are characterized by an average particle size, expressed by a diameter equivalent to an area of from 50 μm to 500 μm in accordance with ISO 9276-6. 11. The composition according to p. 10, characterized in that the polymer particles are characterized by an average particle size, expressed by a diameter equivalent to the area, from 100 μm to 400 μm in accordance with ISO 9276-6. 12. The composition according to p. 11, characterized in that the polymer particles are characterized by an average particle size, expressed by a diameter equivalent to the area, from 150 microns to 355 microns in accordance with ISO 9276-6. 13. The composition according to p. 1, characterized in that the polymer particles are characterized by an average roughness of from 0.1 to 0.3, measured in accordance with the method disclosed in the description of the application. 14. The composition according to p. 13, characterized in that the polymer particles are characterized by an average roughness of from 0.15 to 0.28, measured in accordance with the method disclosed in the description of the application. 15. The composition according to p. 14, characterized in that the polymer particles are characterized by an average roughness of from 0.18 to 0.25, measured in accordance with the method disclosed in the description of the application. 16. The composition according to p. 1, characterized in that the polymer particles are characterized by an average roundness from 0.1 to 0.4, measured in accordance with the method disclosed in the description of the application. 17. The composition according to p. 16, characterized in that the polymer particles are characterized by an average roundness from 0.15 to 0.35, measured in accordance with the method disclosed in the description of the application. 18. The composition according to p. 17, characterized in that the polymer particles are characterized by an average roundness from 0.2 to 0.35, measured in accordance with the method disclosed in the description of the application. 19. The composition according to p. 1, characterized in that the polymer particles are characterized by an average strength of from 0.5 to 0.7, measured in accordance with the method disclosed in the description of the application. 20. The composition according to p. 19, characterized in that the polymer particles are characterized by an average strength of from 0.55 to 0.65, measured in accordance with the method disclosed in the description of the application. 21. The composition according to p. 1, characterized in that the specified agent that promotes suspension is contained at a level of from 0.01% to 5% by weight of the composition. 22. The composition according to p. 21, characterized in that the specified agent that promotes suspension is contained at a level of from 0.03% to 2% by weight of the composition. 23. The composition according to p. 22, characterized in that the specified agent that promotes suspension is contained at a level of from 0.08% to 1.5% by weight of the composition. 24. The composition according to p. 1, characterized in that it contains at least one hydrophobic emollient. 25. The composition according to any one of paragraphs. 1-24, characterized in that it contains a cationic polymer, preferably a cationic polysaccharide, more preferably a cationic polysaccharide selected from the group consisting of cationic cellulose derivatives, cationic guar gum derivatives and mixtures thereof. 26. A method of obtaining a liquid composition for washing dishes manually according to claim 1, including the stages in which
(i) fragmenting the polymer foam to form polymer particles;
(ii) provide one or more suspending agents selected from the group consisting of crystalline wax builders, diamide gel builders having a molecular weight of from 150 g / mol to 1500 g / mol, said diamide gel builders containing at least two nitrogen atoms wherein at least two of said nitrogen atoms form amide functional groups of substitution, microfiber cellulose and mixtures thereof; and
(iii) form a liquid composition by combining fragmented polymer particles, a suspending agent, and other components of the liquid composition;
wherein said polymeric material is selected from the group consisting of polyurethane, derivatives of polyhydroxyalkanoate (PHA), aliphatic polyesters, derivatives of polylactic acid (PLA), polystyrene, melamine-formaldehyde, polyacrylate, polyolefins, polyvinyl and mixtures thereof. 27. The method according to p. 26, characterized in that at stage (i) the polymer foam is fragmented to form polymer particles by cutting, grinding, grinding and / or crushing of the specified foam. 28. The use of particles selected from the group consisting of polymer particles obtained from polymeric foam material in the composition for washing dishes by hand according to claim 1, to provide a positive effect of skin care, preferably soft peeling of the skin, and these particles are kept at a level from 0.5% to 5% by weight of the total composition.

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