Sodium percarbonate particles possessing shell layer including thiosulphate

FIELD: chemistry.

SUBSTANCE: invention refers to sodium percarbonate particles. According to the invention the coated sodium percarbonate particles possessing the inner shell layer including as basic component at least one inorganic hydrate-forming salt and outer shell layer including alkali metal thiosulphate, alkali-earth metal thiosulphate and/or ammonium thiosulphate are described. The method of such sodium percarbonate particles preparation and application of these particles as bleaching agent in detergents and cleansers are also the subjects of an invention.

EFFECT: increasing of stability of sodium percarbonate particles in detergents and cleansers during storage.

23 cl, 4 dwg, 4 tbl

 

The invention relates to particles of percarbonate sodium, which include at least one inorganic, hydrocortisol salt in the inner shell layer and a thiosulfate of an alkali metal, thiosulfate alkaline-earth metal and/or ammonium thiosulfate in the outer shell layer. Moreover, the object of the invention is a method for preparing such particles percarbonate sodium, as well as detergents and cleaning agents comprising such particles percarbonate sodium.

Percarbonate sodium finds increasing application in detergents and cleaning products as an effective chemical bleaching component. For this purpose, percarbonate sodium must have adequate storage stability in the compositions of detergents and cleansers, because otherwise, during storage of detergents and cleaning agents is undesirable loss of active oxygen and, therefore, the bleaching action. Percarbonate sodium sensitive to moisture and under the influence of moisture in the compositions of detergents and cleansers decomposes with loss of active oxygen. Therefore, for the preparation of detergents or cleansers percarbonate sodium is usually used in the form of a coating, and the shell layer prevents the action of moisture on percarbonate sodium coated. Acceptable Obolo the major layers of the inorganic gidrotoraksa salts, such as, for example, sodium carbonate, sodium sulfate, magnesium sulfate and mixtures of such salts, are known for example from DE 2417572, EP-A 0863842 and US 4325933.

In addition to stability during storage in the detergent or cleansing agent percarbonate sodium used for preparation of detergents and cleaning agents, should also possess a high stability when stored in bulk, because before cooking washing or cleansing it, usually stored in bins large volume. If percarbonate sodium does not have adequate stability in the mass, during storage in such bins may occur accelerating decomposition of stored material emitting a large amount of heat. Therefore, the shell material used for coating the particles of percarbonate sodium should not be subjected to exothermic heat-generating chemical reactions with percarbonate sodium.

Some ingredients used in detergents and cleaning products, such as, for example, enzymes, fragrances or dyes that are sensitive to oxidation during storage of the detergent or cleaning agent can be exposed to hydrogen peroxide, which is produced in percarbonate sodium, loss of its activity. Oxidative degradation of these components can be avoided by adding to m the abuser or cleanser reductant. As can be seen from EP-A 0717102, p.9, pages 37 to 44, the specialist in the art it is known that percarbonate sodium exclusively incompatible with such reducing agents, in particular with sodium thiosulfate. Therefore, the person skilled in the technical field generally avoids combination of percarbonate sodium with a reducing agent and a detergent or cleansing product contains components that are incompatible, separately from each other.

Accordingly, to apply percarbonate sodium in detergents and cleaners, there is a need in the particles percarbonate sodium, which simultaneously possess high stability in mass, good storage stability in detergent compositions or cleaning agent under the action of moisture and weak oxidizing effect on oxidation-sensitive components of detergents or cleansers.

It was found that the particles percarbonate sodium, prepared in accordance with the invention from the core of percarbonate sodium, the inner shell layer that includes inorganic hydrocortisol salt as a main component, and an outer shell layer, which includes thiosulfate, incompatibility percarbonate sodium thiosulfate, providing a dampening effect no longer occurs, and such particles percarbonate the three who have a high storage stability in mass. Moreover, particles percarbonate sodium in accordance with the invention also show an unexpectedly high storage stability in the compositions of detergents and cleaning agents and attenuated oxidative effect on oxidation-sensitive components of such compositions.

Accordingly, an object of the present invention are particles of percarbonate sodium coated, including:

a) the core percarbonate sodium

b) an inner shell layer comprising as a main component at least one inorganic hydrocortisol salt,

C) the outer shell layer comprising a thiosulfate of an alkali metal, thiosulfate alkaline-earth metal and/or ammonium thiosulfate.

The object of the invention is also a method of preparation of such particles percarbonate sodium coated, which includes the following stages:

a) applying inner shell layer on the core material from percarbonate sodium spraying an aqueous solution in which is dissolved at least one hydrocortisol inorganic salt,

b) applying the coated material from stage a) of the outer shell layer by spraying an aqueous solution in which is dissolved at least one thiosulfate of an alkali metal, thiosulfate alkaline-earth metal and/or ammonium thiosulfate.

the more, the object of the invention are detergents and cleansers that include particles of percarbonate sodium coated in accordance with the invention.

Preferred options detergents and cleaning agents in accordance with the invention are detergents and cleaners, which include extruded molded body, and particles percarbonate sodium are an integral part of these pressed molded bodies, and detergents for dishwashing machines in the form of pills, which include particles of percarbonate sodium coated in accordance with the invention and a means of corrosion protection for silver.

Particles percarbonate sodium in accordance with the invention include a core, which is essentially includes bergerat sodium carbonate composition 2Na2CO3·3H2O2. Moreover, they may also include small amounts of known stabilizers for peroxy compounds, such as, for example, magnesium salts, silicates, phosphates and/or chelate complexing agents. In a preferred embodiment, the content percarbonate sodium in the core particles percarbonate sodium in accordance with the invention is more than 95 wt.%, and particularly preferably more than 98 wt.%. In a preferred embodiment, the content of organic carbon compounds in Serdtsev the e is less than 1 wt.%, especially preferably less than 0.1 wt.%.

In a preferred embodiment, the core includes a small amount of additives, which have a stabilizing effect on the content of active oxygen, preferably the content of stabilizing additives in the core is less than 2 wt.%. Stability additives, which are used in the preferred embodiment, are magnesium salts, liquid glass, stannate, pyrophosphates, polyphosphates and chelate complexing agents from the series, including hydroxycarbonate acid, aminocarbonyl acid, aminophosphonate acid, phosphonobutane acid and hydroxyphosphonic acid, and their alkali metal salts, ammonium or magnesium. In a particularly preferred embodiment, as a stabilizing additive core includes a silicate of an alkali metal, preferably liquid glass with module SiO2/Na2O in the interval from 1 to 3, in the amount of from 0.1 to 1 wt.%. In the most preferred embodiment, the core also includes in addition to the quantity of alkali metal silicate magnesium compound in an amount of from 50 to 2000 ppm million Mg2+.

The core particles percarbonate sodium in accordance with the invention can be produced by any of known methods of obtaining percarbonate is the atrium. An acceptable method of obtaining percarbonate sodium is crystallized percarbonate sodium from aqueous solutions of hydrogen peroxide and sodium carbonate, and this crystallization can be carried out both in the presence and in the absence of vasilevousa additives, for example, in which reference should refer to EP-A 0703190. Particles percarbonate sodium obtained by the method of crystallization in the presence of vasilevousa additives may also include small amounts used vasilevousa additives, such as, for example, sodium chloride. An acceptable method of obtaining is also the granulation with the cultivation of the granules in the fluidized bed by spraying an aqueous solution of hydrogen peroxide and an aqueous solution of soda on the seed crystals percarbonate sodium in the fluidized bed with simultaneous evaporation of water, and as an example you can refer to WO 95/06615. In addition, an acceptable method of obtaining is also the reaction of solid sodium carbonate with an aqueous solution of hydrogen peroxide, followed by drying. In a preferred embodiment, the core particles percarbonate sodium in accordance with the invention are produced by granulating with the cultivation of the granules in the fluidized bed. Particles percarbonate sodium coated in accordance with the invention, the core to the x manufactured by granulation with the cultivation of the granules in the fluidized bed, demonstrate improved stability during storage in the compositions of detergents and cleansers in comparison with particles, the core of which is obtained by another method.

Particles percarbonate sodium coated in accordance with the invention also include, in addition to the core percarbonate sodium inner shell layer, which includes at least one inorganic hydrocortisol salt as a main component, and an outer shell layer, which includes a thiosulfate of an alkali metal, thiosulfate alkaline-earth metal and/or ammonium thiosulfate. The inner shell layer includes at least one inorganic hydrocortisol salt as a main component, if it does not include an additional component in the mass content, which exceeds the total content of all inorganic gidrotoraksa salts. The inner shell layer in the preferred embodiment, includes one or more inorganic gidrotoraksa salts to the extent of at least 50 wt.%. Inorganic hydratherapie salt in the context of describing the invention are salts, which can bind water in the crystal lattice, do not contain organic radicals and oxidized by percarbonate sodium.

In addition to these internal and external shell SL is nm particles percarbonate sodium in accordance with the invention may also include one or more additional shell layers, moreover, they can be placed between the core and the inner shell layer and between the inner and outer shell layers, as well as outside of the outer shell layer.

Between shell layers and between the inner shell layer and the core may be a sharp edge near which the composition suddenly changed. However, in each case between the individual shell layers and between the inner shell layer and a core, as a rule, forms the transition zone, which includes both components between adjacent layers. Such transition zones are formed, for example, when applying the shell layer in the form of an aqueous solution, where in the beginning of the formation of a layer of some part of the layer lying underneath, exposed surface dissolution, resulting formed a transition zone, which includes components of both layers. Thus, between the core and the inner shell layer may be formed by a transition layer, which includes percarbonate sodium, sodium carbonate, sodium bicarbonate and inorganic hydrocortisol salt of the inner shell layer. In a similar manner between the inner shell layer and outer shell layer may be formed by a transition layer that includes inorganic hydrocortisol salt of the inner shell layer and thiosulfate the Yu Sol outer shell layer.

In the preferred embodiment, are formed in the inner shell layer and the outer shell layer, so that they close underneath the material in the degree above 95%, preferably to the extent in excess of 98%, in particular completely.

The inner shell layer particles percarbonate sodium coated in accordance with the invention as a main component includes at least one inorganic hydrocortisol salt, preferably one or more gidrotoraksa salts of alkali metal and/or alkaline-earth metal. The number of the material of the inner shell layer particles percarbonate sodium coated in accordance with the invention in the preferred embodiment is in the range from 0.1 to 10 wt.%, particularly preferably in the range from 2 to 7 wt.%. The content of inorganic, gidrotoraksa salt in the material of the inner shell layer in the preferred embodiment, is at least 50 wt.%, especially preferably at least 90 wt.%. These mass amounts in each case calculated on inorganic hydrocortisol salt in anhydrous form. Inorganic hydrocortisol salt of the inner shell layer in the preferred embodiment, is chosen from the range, including sodium sulfate, sodium carbonate, sodium bicarbonate and magnesium sulfate. The reception is neither well as mixtures and mixed salts of these compounds. As inorganic gidrotoraksa salt of the inner shell layer in a particularly preferred embodiment includes sodium sulfate. In a particularly preferred embodiment, the inner shell layer consists essentially of sodium sulfate.

The outer shell layer particles percarbonate sodium coated in accordance with the invention as a main component includes a thiosulfate of an alkali metal, thiosulfate alkaline-earth metal and/or ammonium thiosulfate. The amount of material of the outer shell layer particles percarbonate sodium coated in accordance with the invention in the preferred embodiment is in the range from 0.1 to 10 wt.%, particularly preferably from 0.5 to 5 wt.%, in particular from 1 to 3 wt.%. The content of the thiosulfate of an alkali metal, thiosulfate alkaline-earth metal and ammonium thiosulfate in the material of the outer shell layer in the preferred embodiment, is at least 5 wt.%, particularly preferably at least 50 wt.%, in particular more than 90 wt.%. These mass amounts in each case calculated on a thiosulfate of an alkali metal, thiosulfate alkaline-earth metal and/or ammonium thiosulfate in anhydrous form. The outer shell layer in the preferred embodiment, includes sodium thiosulfate. In a particularly preferred embodiment, the EXT is th shell layer consists essentially of sodium thiosulfate.

Particles percarbonate sodium coated in accordance with the invention show unexpectedly high stability during storage, although they include (in the same particle), the oxidizing agent and the reducing agent that can interact with the release of a large amount of heat. The heat generation particles percarbonate sodium coated in accordance with the invention, installed by definition MTA monitor thermal activity of the company Thermometric AB, Jarfalla (Sweden), in the preferred embodiment, after storage at 40°C for 48 h is less than 10 μw/g, and particularly preferably less than 7 µw/year High storage stability and low heat generation causes the possible retention of particles percarbonate sodium coated in accordance with the invention in large bunkers without danger of self-accelerating decomposition stored in this bin material.

Particles percarbonate sodium coated in accordance with the invention unexpectedly also demonstrate higher stability during storage in the compositions of detergents and cleansers than coated particles percarbonate sodium without thiosulfinates shell layer, which includes a comparable amount of shell material. Improved stability when stored in the compositions of detergents and cleansing creditprovider to lower losses in the content of active oxygen during storage of such compositions in a wet environment.

In yet another embodiment, the particles percarbonate sodium coated have additional shell layer as a main component includes an alkali metal silicate having a SiO module2/alkali metal oxide 2.5. This additional shell layer in the preferred embodiment, is located on top of the inner shell layer and may be located between the inner and outer shell layers, and on top of the outer shell layer. Additional shell layer as a main component includes a silicate of an alkali metal, if it does not include an additional component in the mass content that exceeds the content of the alkali metal silicate. Module silicate of alkaline metal in the preferred embodiment is in the range from 3 to 5, and particularly preferably in the range from 3.2 to 4.2. The quantity of this additional shell layer particles percarbonate sodium coated in accordance with the invention in the preferred embodiment is in the range from 0.2 to 3 wt.%. The content of the alkali metal silicate in the material of the additional shell layer in the preferred embodiment, is more than 50 wt.%, and especially preferably more than 80 wt.%. The alkali metal silicate used in more the positive shell layer, in the preferred embodiment, is a silicate of sodium, and particularly preferably sodium silicate.

Particles percarbonate sodium, covered in accordance with the invention with an additional shell layer as a main component includes an alkali metal silicate having a SiO module2/alkali metal oxide 2.5, additionally demonstrated a longer time to dissolve in water and improved stability when stored in an aqueous liquid or gel-like environments with a water content up to 15 wt.%. Therefore, in a suitable embodiment, they can be used in the preparation of liquid or gel detergent compositions or cleaning agent.

In yet another embodiment, the particles percarbonate sodium coated possess, in addition, on its surface from 0.01 to 1 wt.%, preferably from 0.1 to 0.5 wt.% finely dispersed oxide element is Si, Al or Ti, or a mixed oxide of these elements. Acceptable finely dispersed oxides are, for example, paragenetically oxides, which are in the flame hydrolysis of volatile compounds of such elements as silicon, aluminum and titanium, or mixtures of these compounds. Paragenetically oxides or mixed oxides that can be obtained this way, preferably the variant have an average primary particle size of less than 50 nm and is able to stick together into larger particles, the average size of which in the preferred embodiment, is less than 20 μm. Acceptable also precipitated oxides, which are deposited from aqueous solutions of compounds of elements such as silicon, aluminum and titanium, or mixtures of these compounds. Precipitated oxides or mixed oxides can also, in addition to silicon, aluminum and/or titanium to include small amounts of ions of an alkali metal or alkaline-earth metal. The average particle size of precipitated oxides in the preferred embodiment, is less than 50 μm, and especially preferably less than 20 microns. Specific surface area of finely dispersed oxides, determined by BET method, in the preferred embodiment is in the range from 100 to 300 m2/year

In a preferred embodiment, particles of percarbonate sodium coated possess on their surface gidrofobizirovannym finely dispersed oxide, and particularly preferably gidrofobizirovannym paragenetically or deposited silicon dioxide. Hydrophobizated oxides in the context of describing the invention are the oxides, which contain on their surface organic radicals linked through chemical bonds, and are not wetted by water. Hydrophobizated oxides can be obtained, for example, by reaction paragenetically or deposited oxides with organosilanes is, silazane or polysiloxane. Acceptable to obtain hydrophobized oxide silicon compounds known from EP-A 0722992 from p.3, 9 on p.6, p.6. Especially preferred hydrophobizated oxides, which are produced by reaction of finely dispersed oxide with a silicon compound of the compounds of classes (a) through (d) and (l) through (n), listed in EP-A 0722992. Hydrophobizated finely dispersed oxides in the preferred embodiment, have a methanol wettability of at least 40.

Particles percarbonate sodium, covered in accordance with the invention, which, in addition, have on their surface a finely dispersed oxide, optionally show a weaker tendency to caking during storage, mainly during storage under pressure of the cargo, resulting in they can be kept without caking in bunkers. Such particles besides demonstrate stability during storage, which additionally increases the compositions of detergents and cleaning agents.

Particles percarbonate sodium in accordance with the invention in a preferred embodiment, have an average size in the range from 0.2 to 5 mm, and particularly preferably in the range from 0.5 to 2 mm, the Preferred particle percarbonate sodium, having a low content of fine particles, preferably having a content of IU is the more 10 wt.% particles less than 0.2 mm, and especially preferably less than 10 wt.% of particles having a size less than 0.3 mm

Particles percarbonate sodium in accordance with the invention in a preferred embodiment, have an essentially spherical shape with a smooth surface. The particles have a smooth surface have a surface roughness less than 10% of the particle diameter, and preferably less than 5% of the diameter of the particles.

The storage stability of the particles percarbonate sodium in accordance with the invention in the compositions of detergents and cleansers can be improved additionally by appropriate choice of particle size and particle shape.

A method of obtaining particles percarbonate sodium coated in accordance with the invention includes the following stages:

a) applying inner shell layer on the core material from percarbonate sodium spraying an aqueous solution in which is dissolved at least one hydrocortisol inorganic salt,

b) applying the coated material from stage a) of the outer shell layer by spraying an aqueous solution in which is dissolved at least one thiosulfate of an alkali metal, thiosulfate alkaline-earth metal and/or ammonium thiosulfate.

In accordance with the invention as the core material from percarbonate sodium in this way, in principle, the mod is et to be used any product received by one of the known methods of obtaining percarbonate sodium. In the preferred embodiment, using the core material, which is obtained by a known method from an aqueous solution of hydrogen peroxide and an aqueous solution of soda by way of granulation with the cultivation of the granules in the fluidized bed, and particularly preferably according to the method described in EP-A 0716640. In this context, in the preferred embodiment, use hydrogen peroxide and a solution of soda when the value of the molar ratio of N2About2to Na2CO3from 1.4 to 1.7, particularly preferably from 1.5 to 1.65. Hydrogen peroxide is used in the form of an aqueous solution at a preferred concentration of from 30 to 75 wt.% H2About2, particularly preferably from 40 to 70 wt.% H2About2. The hydrogen peroxide solution may also include stabilizing additives, such as, for example, complexing agents and compounds of magnesium. The soda solution in the preferred embodiment, are used in concentrations ranging from 10 wt.% sodium carbonate to a concentration of saturated sodium carbonate, particularly preferably in the range from 20 wt.% sodium carbonate to a concentration of saturated sodium carbonate. The soda solution may also include stabilizing additives, such as, for example, liquid glass. In the method of granulation with the cultivation is of renul in the fluidized bed water input source substances, is evaporated and removed by the flow in fluidized bed drying gas. As the drying gas in the preferred embodiment, use air or a gaseous product of combustion, which is produced by burning fuel, such as natural gas, with air. In a preferred embodiment, the drying gas is sent to a fluidized bed temperature in the range from 120 to 400°C., particularly preferably in the range from 200 to 400°C. In a preferred embodiment, the temperature in the fluidized bed maintained within the range of from 40 to 95°C., in particular in the range from 40 to 80°C, and predominantly in the range of 50 to 70°C.

In a preferred embodiment, in a fluidized bed direct seeding material in an amount which leads to the formation of granules having an average size in the range from 0.2 to 2 mm In the preferred embodiment, the core material away from the fluidized bed by way of grain-size sorting, and particularly preferably according to the method described in EP-A 0938922, resulting in a preferred embodiment, greater than 90 wt.% particle core material withdrawn from the fluidized bed, have a diameter of 0.2 mm

In the method in accordance with the invention, the application of the inner shell layer is conducted by spraying an aqueous solution, to the torus dissolve at least one hydrocortisol inorganic salt. In addition to dissolved gidrotoraksa inorganic salt aqueous solution in the preferred embodiment, does not contain more dissolved components in mass quantities that exceed the mass of dissolved gidrotoraksa inorganic salts, calculated on the anhydrous form. In a particularly preferred embodiment, the inner shell layer is applied by spraying an aqueous solution of sodium sulfate. During deposition of this aqueous solution the main part of the contained water, in particular more than 90% of the water contained in the aqueous solution, in the preferred embodiment already evaporated by the heat supply, resulting during application of the inner shell layer re-surface dissolution is subjected to only a small portion of the core material, and during spraying is durable shell layer, which includes hydrocortisol inorganic salt. In a preferred embodiment, the inner shell layer is applied by spraying an aqueous solution containing hydrocortisol inorganic salt, in the fluidized bed, and particularly preferably according to the method described in EP-A 0970917, whereby a dense shell layer can be achieved using small amounts of shell material layer. In a preferred embodiment, struck the of the inner shell layer in the fluidized bed is carried out at a double feed in a fluidized bed drying gas so so in the fluidized bed to set the temperature in the range from 30 to 90°C. the Amount of the sprayed solution in the preferred embodiment, is chosen so that the number of the material of the inner shell layer particles percarbonate sodium coated, prepared as a final product of the process was in the range of from 0.1 to 10 wt.%, particularly preferably in the range from 2 to 7 wt.%.

In the method in accordance with the invention, the application of the exterior shell layer is conducted by spraying an aqueous solution in which is dissolved at least one thiosulfate of an alkali metal, one thiosulfate alkaline earth metal and/or one ammonium thiosulfate. In addition to thiosulfate of an alkali metal, thiosulfate alkaline-earth metal and/or ammonium thiosulfate aqueous solution in the preferred embodiment, contains not more than 95 wt.%, especially preferably not more than 50 wt.%, in particular not more than 10 wt.% additional dissolved components. The outer shell layer in the preferred embodiment, is applied by spraying an aqueous solution, which contains sodium thiosulfate. While spraying an aqueous solution the main part of the contained water, in particular more than 90% of the water contained in the aqueous solution, in the preferred embodiment already evaporated by the heat supply, wsle the result of which during application of the outer shell layer is only a small part of the underneath material is subjected to the second surface dissolution, and during the coating already formed strong thiosulfinates shell layer. The outer shell layer in the preferred embodiment, is applied by spraying in a fluidized bed water thiosulfinates solution, and particularly preferably according to the method described in EP-A 0970917, whereby a dense shell layer can already be achieved using small amounts of shell material layer. In a preferred embodiment, the application of the exterior shell layer in the fluidized bed is carried out at a double feed in a fluidized bed drying gas, whereupon the temperature in the fluidized bed is set in the range from 30 to 90°C. the Amount of the sprayed solution in the preferred embodiment, is chosen so that the amount of material of the outer shell layer particles percarbonate sodium coated, prepared as a final product of the process was in the range of from 0.1 to 10 wt.%, particularly preferably from 0.5 to 5 wt.%, in particular from 1 to 3 wt.%.

In yet another variant, additional shell layer is applied by spraying an aqueous solution containing alkali metal silicate, and the module SiO2the oxide of the alkali metal silicate of the alkali metal is greater than 2.5, and preferably is in the range from 3 to 5, especially PR is doctitle in the range from 3.2 to 4.2. In the preferred embodiment, using an aqueous solution having a concentration of alkali metal silicate in the range of from 2 to 20 wt.%, particularly preferably from 3 to 15 wt.%, in particular 5 to 10 wt.%. In a preferred embodiment for applying shell layer sprayed so-called liquid glass, essentially of sodium silicate. In addition to the alkali metal silicate aqueous solution in the preferred embodiment, does not contain more dissolved components in mass quantities that exceed the weight of a silicate of an alkali metal. The inner shell layer in a particularly preferred embodiment, is applied by spraying an aqueous solution of sodium water glass. The application of this additional shell layer can occur before applying the inner shell layer between the application of internal and external application shell layers or after application of the outer shell layer. Additional shell layer in the preferred embodiment, is applied after application of the inner shell layer. While spraying an aqueous solution containing alkali metal silicate, the main part of the contained water, in particular more than 90% of the water contained in the aqueous solution, in the preferred embodiment already evaporated by the heat supply, resulting in time on the Eseniya additional shell layer only a small part of the underneath material is subjected to the second surface dissolution, and during the coating already formed a solid shell layer comprising alkali metal silicate. This additional shell layer in the preferred embodiment, is applied by spraying in a fluidized bed with an aqueous solution containing a silicate of an alkali metal, and particularly preferably according to the method described in EP-A 0970917, whereby a dense shell layer can already be achieved using small amounts of shell material layer. In a preferred embodiment, application of an additional shell layer in the fluidized bed is carried out at a double feed in a fluidized bed drying gas, whereupon the temperature in the fluidized bed is set in the range from 30 to 90°C. the Amount of the sprayed solution in the preferred embodiment, is chosen so that the amount of material additional shell layer particles percarbonate sodium coated, prepared as a final product of the process was in the range of from 0.2 to 3 wt.%.

In a preferred variant of the method after the application of shell layers by spraying aqueous solutions on the surface of the particles percarbonate sodium coating is applied from 0.01 to 1 wt.%, preferably from 0.1 to 0.5 wt.% finely dispersed oxide element is Si, Al or Ti, or a mixed oxide of these elements is impressive. In a preferred embodiment, the finely dispersed oxide applied to the surface of coated particles percarbonate sodium mixing particles percarbonate sodium coated with finely dispersed oxide in the dry state. In the preferred embodiment for mixing with finely dispersed oxide particles percarbonate sodium is dispersed in the gas phase. In this preferred embodiment, applying the process of mixing can be performed, for example, in the fluidized bed in a vertical tube or conveyor carried away by the stream.

As finely dispersed oxides can be used paragenetically oxides, which are in the flame hydrolysis of volatile compounds of such elements as silicon, aluminum and titanium, or mixtures of these compounds, and in the preferred embodiment, they have an average primary particle size of less than 50 nm and an average particle size of aggregates of primary particles less than 20 microns. Acceptable also precipitated oxides, which are deposited from aqueous solutions of compounds of elements such as silicon, aluminum and titanium, or mixtures of these compounds, and in the preferred embodiment, they have an average particle size of less than 50 μm, particularly preferably less than 20 microns. In a preferred embodiment, use hydrophobizated finely dispersed oxides, and particularly preferably gidrofobizirovannym biogenetics is s or precipitated silicon dioxide. In the context of describing the invention hydrophobizated oxides are the oxides, which contain on their surface organic radicals linked through chemical bonds and is not wettable by water.

In a suitable embodiment, the particles percarbonate sodium coated in accordance with the invention can be used as an effective chemical bleaching component in detergents and cleaners. Detergents in the context of describing the invention are all songs that are acceptable for cleaning textile materials in an aqueous washing solution. Cleansing means in the context of describing the invention are all songs that are acceptable in interaction with water for cleaning surfaces that do not absorb or absorb only a little water. Detergents for dishwashers that are acceptable for mechanical cleaning of utensils and knife products are a form of cleansing products that are preferred in the context of the description.

The object of the invention are detergents and cleansers that include particles of percarbonate sodium, covered in accordance with the invention. In a preferred embodiment, the detergents and cleaners according to the invention include particles of percarbonate NAT the Oia coated in accordance with the invention in an amount of from 1 to 40 wt.% in terms of the total number of the washing or cleaning agent.

Detergents and cleaning agents in accordance with the invention can be in solid form, and then in addition to the particles percarbonate sodium coated in accordance with the invention may also include additional components in the form of a powder or in granular form. In addition, they may also include extruded molded body, and particles percarbonate sodium coated in accordance with the invention can be an integral part of these extruded molded phone Such extruded molded body in the form of extrudates, pellets, briquettes or tablets can be prepared by methods agglomeration pressing, in particular by extrusion, pressing bars, punching, pressing with a rolling of powders or pelletizing. To conduct sintering by hot pressing, in detergents or cleaning agents according to the invention can optionally enter a binding substance, which gives a molded bodies of a higher strength during the agglomeration process. However, in the preferred embodiment, in the case of detergents and cleaning agents in accordance with the invention, which include extruded molded body, any additional binder is not used, and the function of the binder performs one of the active detergent components, such as seionage the second surface-active substance.

Detergents and cleaning agents in accordance with the invention can also be in liquid form or gel form and include particles percarbonate sodium coated in accordance with the invention dispersed in the liquid phase or gel phase. In addition to the particles percarbonate sodium coated in accordance with the invention in the liquid phase or gel phase can be dispersed more particles. The rheological properties of the liquid phase or gel phase in the preferred embodiment, adjust so that the dispersed therein particles remained suspended and during storage was not settled.

Consequently, the composition of the liquid phase in the preferred embodiment, is chosen so that it had the properties of a thixotropic or pseudoplastic-type currents. For controlling the properties of this course you can add suspension excipients, such as swelling clays, in particular montmorillonite, besieged and paragenetically silica, vegetable gums, in particular xantana, and polymer gelatinizing agents, such as vinyl polymers containing carboxyl groups.

In a preferred embodiment, the detergents and cleaners according to the invention in liquid form or gel form include particles percarbonate the sodium coated in accordance with the invention, with additional shell layer which comprises as the main component an alkali metal silicate having a SiO module2/alkali metal oxide 2.5. In this embodiment, detergents and cleaners may contain up to 15 wt.% water produced by the surface of the dissolving particles percarbonate sodium coated and release of hydrogen peroxide in the liquid phase or gel phase, which occurs during storage.

In addition to the particles percarbonate sodium coated in accordance with the invention as additional components of detergents and cleaning agents in accordance with the invention may also include, for example, surface-active substances, supplements, alkaline components, activators chemical brighteners, enzymes, chelating agents, inhibitors Pomerania, defoamers, optical brighteners, perfumes and dyes.

Acceptable surfactants for detergents and cleaning agents in accordance with the invention are mainly anionic, nonionic and cationogenic surfactants.

Acceptable anionic surfactants are, for example, surfactants, containing sulphonate groups, predpochtitel is but alkylbenzenesulfonate, alkanesulfonyl, alpha reincorporate, fatty esters of alpha-sulphonic acids or sulfosuccinate. In cases of alkylbenzenesulfonates preferred those who have pravarasena or branched alkyl group containing from 8 to 20 carbon atoms, particularly containing from 10 to 16 carbon atoms. Preferred alkanesulfonyl are those who have remotemachine alkyl groups containing from 12 to 18 carbon atoms. In the cases of alpha-reincorporates in a preferred embodiment, use of the reaction products of sulfonation of alpha-olefins containing from 12 to 18 carbon atoms. In cases of fatty esters of alpha-sulfonic acids are preferred products of sulfonation of fatty acid esters containing from 12 to 18 carbon atoms and short chain alcohols containing from 1 to 3 carbon atoms. Acceptable anionic surfactants are surface-active substances containing in the molecule sulfate group, preferably an alkyl sulphates and sulfates ethers. The preferred alkyl sulphates are those who have remotemachine alkyl radicals containing from 12 to 18 carbon atoms. In addition, acceptable beta-branched alkyl sulphates and alkyl sulphates, mono - and polyamidine the alkyl in the middle of the length of the Noah alkyl chain. Preferred sulfates ethers are sulfates of aliphatic esters, which are oksietilirovannye linear alcohols containing from 12 to 18 carbon atoms and comprising from 2 to 6 ethylenoxide links, and subsequent sulfonation. Finally, as anionic surfactants can also be used Soaps, such as, for example, alkali metal salts of lauric acid, myristic acid, palmitic acid, stearic acid and/or naturally occurring mixtures of fatty acids, such as, for example, fatty acids of coconut, palm kernel or tallow oils.

Acceptable nonionic surfactants are, for example, oxyalkylene compounds, in particular ethoxylated and propoxycarbonyl connection. Especially acceptable products of the reactions of condensation of ALKYLPHENOLS and fatty alcohols containing from 1 to 50 moles, preferably from 1 to 10 moles, ethylenoxide and/or propylenoxide links. Acceptable amides of fatty polyhydroxylated, whose organic radical containing one or more hydroxyl groups, which can also be oxyalkylene, linked to the amide nitrogen atom. As nonionic surfactants acceptable to Alkylglucoside, including remotemachine or branched alkyl group, containing from 8 to 22 carbon atoms, particularly containing from 12 to 18 carbon atoms, and mono - or diglycoside radical, which in the preferred embodiment, derivatisation from glucose.

Acceptable cationogenic surfactants are, for example, mono - and dioxyalkylene Quaternary amines, including alkyl radical with C6C18associated with the nitrogen atom, and one or two hydroxyalkyl groups.

Detergents and cleaning agents in accordance with the invention include, in addition, supplements that during the application capable of binding to dissolved calcium and magnesium ions. Acceptable supplements are phosphates of alkali metals and alkali metal polyphosphates, in particular pentanedithiol; water-soluble and water-insoluble silicates of sodium, in particular, the layered silicates of the formula Na5Si2O5; zeolites structures A, X and/or R and trinatriytsitrat. In addition to active additives can be used, in addition, organic jointly used active additives, such as, for example, copolymers of polyacrylic acid, poliasparaginovaya acid and/or acrylic acid with methacrylic acid, acrolein or vinyl monomers containing sulfonylurea group, and their salts SEL is cnyh metals.

In addition, the detergents and cleaners according to the invention typically include alkaline components that, when used as intended in the washing solution or aqueous solution cleanser, provide a pH value in the range from 8 to 12. Acceptable alkaline components are mainly sodium carbonate, sesquicarbonate sodium, metasilicate sodium and other soluble alkali metal silicates.

Acceptable activators chemical brighteners for detergents and cleaning agents in accordance with the invention are mainly compounds comprising one or more acyl groups linked to the nitrogen atom or oxygen, which is capable of peligroso and interaction in the washing solution or aqueous solution cleansing with hydrogen peroxide released from the particles percarbonate sodium, education peroxocarbonate acids. Examples of such compounds are polyallylamine alkylenediamine, such as, in particular, tetraacetylethylenediamine (TAED); acylated triazine derivatives, in particular 1,5-diacetyl-2,4-dioxohexane-1,3,5-triazine (DADHT); acylated glycoluril, in particular tetraaceticacid (TAGU), N-acylamide, in particular N-nonavailability (WEAR); acylated phenolsulfonate, Castolin-nonanol and isanonymousallowed (n - and ISO-NOBS); the anhydrides of carboxylic acids, such as phthalic anhydride; acylated polyhydric alcohols, such as etilenglikolevye, 2,5-diacetoxy-2,5-dihydrofuran, acetylated sorbitol and mannitol and acylated sugar, such as pentaacetate; enol esters and N-the acylated lactams, in particular N-alloplasty and N-acellularity. As activators of chemical bleaches also acceptable functionalized amines NITRILES and their salts (nitrile Katy), which are known, for example, from the log Tenside Surf. Det. 1997, 34(6), SS-409. As activators of chemical bleaches can be used, in addition, complexes of transition metals, which are able to activate hydrogen peroxide to remove stains by chemical bleaching. Acceptable transition metal complexes are known, for example, from EP-A 0544490 with C.2, p.4 on p.3, p.57; WO 00/52124 from p.5, p.9 on p.8, p.7 and p.8, page 19 on page 11, p.14; WO 04/039932 with C.2, p.25 on p.10, p.21; WO 00/12808 with p.6, on p.29 p.33, p.29; WO 00/60043 with p.6, 9 on p.17, p.22; WO 00/27975 with C.2, pages 1 through 18 and p.3, p.7, on p.4, p.6; WO 01/05925 with C.1, page 28 on p.3, p.14; WO 99/64156 with C.2, p.25 on p.9, p.18 and GB-A 2309976 from p.3 1 on p.8, p.32.

In addition, the detergents and cleaners according to the invention can include enzymes that enhance the cleansing action, in particular lipases, cutinase, amyl is SHL, neutral and alkaline protease, esterase, cellulase, pectinase, lactase, and/or peroxidase. In the context of this description, the enzymes can be adsorbed on substances carriers or enclosed in substance coatings in order to protect them from decay.

In addition, the detergents and cleaners according to the invention may include chelate complexing agents for transition metals, using them in the washing solution or aqueous solution cleanser can be ingibirovalo catalytic decomposition of compounds with active oxygen. Acceptable agents are, for example, phosphonates, such as hydroxyethane-1,1-diphosphonate, nitrilotriethanol, diethylenetriaminepenta(methylenephosphonate), ethylenediaminetetra(methylenephosphonate), hexamethylenediaminetetra(methylenephosphonic) and their alkali metal salts. Acceptable nitryltriacetic acid and polyaminocarboxylic acid, such as, in particular, ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, Ethylenediamine-N,N'-diantara acid, methylpyridoxine acid and polyaspartate, as well as their salts of alkali metals and ammonium. Finally, as a chelate complexing agents also acceptable polybasic carboxylic acids, in particular hydroxycarbonate acid, such as, n is the sample, tartaric acid and citric acid.

Detergents according to the invention may additionally include inhibitors Pomerania that suspension keep pollution separated from the fibers and prevent re-deposition of contamination on the fiber. Acceptable inhibitors Pomerania represent, for example, ethers of cellulose, such as carboxymethylcellulose and their alkali metal salts, methylcellulose, hydroxyethylcellulose and hydroxypropylcellulose. Acceptable also polyvinylpyrrolidone.

In addition, the detergents and cleaners according to the invention may also include defoamers, which reduce foaming in the washing solution. Acceptable defoamers are, for example, polyorganosiloxanes, such as polydimethylsiloxane, paraffins and/or waxes, and mixtures thereof with finely dispersed silica.

Detergents according to the invention optionally can include optical brighteners, which are absorbed by the fibers absorb radiation in the UV-region and exhibit a blue fluorescence, thereby compensating yellowing of the fibers. Acceptable optical brighteners are, for example, derivatives diaminodiphenylsulfone acid, such as alkali metal salts of 4,4'-bis(2-aniline-4-morpholino-1,3,5-Tr is azinyl-6-amino)stilbene-2,2'-disulfonic acid, or substituted definitiely, such as alkali metal salts of 4,4'-bis(2-colfosceril)of diphenyl.

Finally, detergents and cleaning agents in accordance with the invention can also optionally include perfumes and dyes.

Detergents and cleaning agents in accordance with the invention in liquid form or gel form can also optionally include up to 30 wt.% organic solvents, such as, for example, methanol, ethanol, n-propanol, isopropanol, n-butanol, ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,4-butyleneglycol, glycerin, diethylene glycol, etilenglikolevye ether, ethanolamine, diethanolamine and/or triethanolamine.

Detergents and cleaning agents in accordance with the invention exhibit higher stability during storage with lower losses in the content of active oxygen during storage in humid conditions, when compared with detergents and cleansing agents, which include particles of percarbonate sodium, which were not provided with a coating in accordance with the invention. At the same time it weakened oxidative effect on oxidation-sensitive components of the detergent or cleaning agent, such as, for example, enzymes, optical brighteners, perfumes and dyes. This oxidative effect on sensitive ocil which the components are much weaker than in cases of detergents and cleansers that include particles of percarbonate sodium with a coating that does not correspond to the invention, and apart from them by a comparable number of thiosulfate.

Detergents for dishwashing machines in the form of tablets are the preferred choice of cleaning agents in accordance with the invention, and these tablets include in addition to the particles percarbonate sodium coated in accordance with the invention a means of corrosion protection for silver. Means of corrosion protection for silver in the context of describing the invention are additives that prevent or reduce the fading of non-ferrous metals, in particular silver, during the mechanical cleaning and detergent. Remedies silver from corrosion, which is used in the preferred embodiment, comprise one or more compounds from the series, including triazoles, benzotriazoles, bisbenzimidazole, aminotriazole and alkylaminocarbonyl. In the context of the description of the compounds of the substances mentioned classes may also include substituents, such as, for example, linear or branched alkyl group containing from 1 to 20 C atoms, and vinyl, hydroxyl, thiol or halide radicals. As bisbenzimidazole, it is preferable from the organisations, have both benzotriazole groups in each case are connected in the 6th position by means of the group X, where X can be a associated remotemachine alkylenes group containing in the preferred embodiment, from 1 to 6 carbon atoms and optionally substituted by one or more alkyl groups With1With4, cycloalkenyl radical containing at least 5 carbon atoms, carbonyl group, sulfonyloxy group or an oxygen atom, or sulfur. Especially preferred means of corrosion protection for silver is tolyltriazole.

Dishwasher means in accordance with the invention in the form of tablets, including the means of corrosion protection for silver, show much weaker yellowing tablets during storage dishwasher funds compared to detergents for dishwashers that include particles of percarbonate sodium without thiosulfinates shell layer.

Description of the DRAWINGS

Figure 1 shows a graph of the release of energy from particles percarbonate sodium in accordance with the invention of example 1 in µw/g during storage at 40°C, specified by monitor thermal activity MTA®company Thermometric AB, Jarfalla (Sweden), built depending on storage time in hours.

Figure 2 depict the of Allen schedule release energy, determined under the same conditions, particles of percarbonate sodium example 2, which does not correspond to the invention.

Figure 3 shows a graph of the energy release determined in the same conditions, particles of percarbonate sodium example 3, which does not correspond to the invention.

Figure 4 shows a graph of the energy release determined in the same conditions, particles of percarbonate sodium example 4, which does not correspond to the invention.

Examples

Obtaining particles of percarbonate sodium coated

When preparing particles percarbonate sodium coated used particles percarbonate sodium, which was prepared from an aqueous solution of hydrogen peroxide and an aqueous solution of soda granulation with the cultivation of the granules in the fluidized bed according to the method described in EP-0716640, had a mean diameter of X500.65 mm and a content of fine particles smaller than 0.2 mm below 2 wt.%. Shell layers were applied to these particles by the method described in paragraph [0021] EP-0863842, spraying aqueous solutions of shell substance in a fluidized bed at a temperature fluidized bed of from 50 to 70°C and simultaneous evaporation of water. The sodium sulfate deposited in the form of an aqueous solution concentration of 20 wt.% and sodium thiosulfate in aqueous solution concentration of 20 wt.%. The liquid level is lo deposited in the form of an aqueous solution concentration of 10 wt.% sodium liquid glass, possessing module SiO2/Na2O 3.3V. The number of shell substance specified in mass percentages in the examples are amounts deposited shell substance, calculated without water of crystallization in terms of the total number of particles percarbonate sodium and sprayed shell substances.

Determination of stability when stored in bulk

The storage stability of the particles percarbonate sodium with coverage in the mass has set the microcalorimeter energy definition, vysvobozhdavshej during storage at 40°C using thermal monitor activity MTA®company Thermometric AB, Jarfalla (Sweden), and the value of MTA after 48 h was determined as the measured value. Percarbonate sodium is sufficiently stable during storage, if the value of the MTA for the energy released after 48 hours, is not more than 10 μw/g, and further during subsequent storage is not increased.

As mentioned above, particles percarbonate sodium inflicted the first shell layer of sodium sulfate and a second shell layer of reducing agent. Used reducing agents and the quantity of these shell layers are presented in table 1 with values MTA after 48 hours the Process of heat dissipation time is reproduced in Fig. 1-4.

Table 1
If-
measures
Shell layer 1 [wt.%]Shell layer 2 [wt.%]MTA [µw/g]
13% Na2SO43% Na2S2O35,0
2*3% Na2SO43% Na2SO3105
3*3% Na2SO43% Na2S2O513,7
4*5% Na2SO41% Na2HPO312,1
* not in accordance with the invention
Na2S2O3mean sodium thiosulfate; Na2SO3mean sodium sulfite;
Na2S2O5means pyrosulfite sodium; Na2HPO3means postit sodium

Examples 1 through 4 show that particles percarbonate sodium adequate stability in storage the AI was prepared only with the outer shell layer of sodium thiosulfate. Particles percarbonate sodium possessing an outer shell layer of sodium sulfite, sodium pyrosulfite or phosphite sodium was found to be unstable during storage due to incompatibility between percarbonate sodium and reducing agent.

Define the time of dissolution

2.5 g of particles percarbonate sodium was dissolved in 1 l of water at 20°C in a thermostatically controlled measurement chamber made of glass (diameter 130 mm, height 150 mm) whilst stirring with a magnetic stirrer. The mixing speed was chosen so that the formed crater with a depth of 4 see During the process of dissolution was measured by the change in electrical conductivity of the solution. By the time of the dissolution was the period during which reached 90%of final conductivity.

The stability during storage of washing powder

To determine the stability during storage of washing powder 405 g of zeolite-containing detergent for heavily soiled fabrics in the drum mixer was mixed with 15 g of TAED and 80 g percarbonate sodium. The mixture was filled packing washing powder E2 (sizes 19×14×4.5 cm), which is pre-impregnated water-repellent, and it was closed with the use of hot melt glue. Then packing washing powder was kept in the chamber for climatic tests at 35°C and the atmosphere is fere 80%relative humidity. The content of active oxygen after storage was determined by conventional permanentresidence way. The content of active oxygen before storage and the content of active oxygen after storage for 8 weeks was determined by maintaining the content of active oxygen (save AK) in percent.

As described above, particles percarbonate sodium inflicted one, two or three shell layer. Used shell substance and quantity of materials shell layers are listed in table 2 with the values of the MTA, the time of dissolution and preservation of the content of active oxygen in the mixture with washing powder after 8 weeks.

Table 2
If-
measures
Shell layer 1 [wt.%]Shell layer 2 [wt.%]Shell layer 3 [wt.%]MTA [µw/g]The solution
of [min]
Save AK
5*6% Na2SO41,81,048%
1 3% Na2SO43% Na2S2O35,01,186%
6*3% Na2S2O33% Na2SO48344%
73% Na2SO43% Na2S2O30,9% LGLthe 5.72,185%
83% Na2SO40,9% LGL3% Na2S2O33,6the 4.782%
* not in accordance with the invention
Na2S2About3mean sodium thiosulfate; LGL means sodium silicate, module: 3,3

Particles percarbonate sodium coated in accordance with the invention, examples 1, 7 and 8 had significantly more than the high stability during storage of washing powder, than the product of example 5, which covered only sodium sulfate. Particles percarbonate sodium example 6, which did not correspond to the invention and included sodium thiosulfate in the inner shell layer in direct contact with the core material was found to be unstable in the mass, with a value of MTA 83 μw/g, and exhibited superior stability during storage of washing powder. Particles percarbonate sodium coated in accordance with the invention examples 7 and 8 showed that the additional shell layer of sodium water glass with module 3.3, which increased the time of dissolution of the particles.

The storage stability in liquid detergent

To determine the stability during storage in liquid detergent particles percarbonate sodium was mixed with the liquid base formulation of 9.7 wt.% of monoethanolamine, 4.0 wt.% water, 3.7 wt.% ethanol, 16.1 wt.% of Phenoxyethanol, of 23.6 wt.% ether fatty13-C15alcohol and polyglycol, and 25.8 wt.% dodecylbenzensulfonate and 17.2 wt.% fatty acids of coconut oil, whereupon the resulting mixture consisted of 10 wt.% percarbonate sodium. This liquid mixture was kept at 23°C in 50-ml polyethylene cylinders within 2 days, and in order to keep the particles percarbonate sodium in the suspended state, these cylinders mechanical and turned over the head with a speed of 15 rpm The content of active oxygen after storage was determined by conventional iodometric way. The content of active oxygen before storage and the content of active oxygen after storage for 2 days was determined by maintaining the content of active oxygen (save AK) in percent.

As described above, particles percarbonate sodium inflicted one, two or three shell layer. Used shell substance and quantity of materials shell layers are shown in table 3 with preservation of the content of active oxygen in the liquid detergent after 2 days.

td align="center"> 0,9% LGL
Table 3
If-
measures
Shell layer 1 [wt.%]Shell layer 2 [wt.%]Shell layer 3 [wt.%]Save AK
5*6% Na2SO483%
9*6% Na2SO40,9% LGL88%
83% Na2SO43% Na2S2O394%
* in accordance with the invention
Na2S2O3mean sodium thiosulfate; LGL means sodium silicate, module: 3,3

Particles percarbonate sodium coated in accordance with the invention, of example 8 was also significantly higher storage stability in liquid detergent than particles percarbonate sodium, which did not correspond to the invention from examples 5 and 9, and which had no thiosulfinates shell layer.

Manufacturing of tablets dishwasher tools

Particles percarbonate sodium was mixed with powder and detergent, which included 1.2 wt.% TIED and 0.2 wt.% benzotriazole, so that the mixture consisted of 12.2 wt.% percarbonate sodium. This mixture was kept at room temperature for 4 days and then determined the value of the MTA mixture. After that, in each case, 15 g of the mixture was pressed in a tablet press under a pressure of 50 kN with a duration of pressing 15 in parallelepipeds tablets with dimensions 4×3×1 see These tablets were Packed in individual plastic envelopes with sealing clip and kept in CDF is BKE from a dense paper (dimensions 14×14×6 cm), which was closed with the use of hot melt glue at 50°C for 14 days. After storage by iodometric determined the content of active oxygen and determined the preservation of the content of active oxygen (save AK) in percent. In addition, the stored tablets by measuring the ability of tablets to reflect light determined their yellowing.

As described above, particles percarbonate sodium inflicted one or two shell layers. Used shell substance and quantity of materials shell layers are shown in table 4. These particles percarbonate sodium coated as they are presented above, made of dishwasher tablets tools and used a mixture of powdered dishwasher tools and particles percarbonate sodium and made of her tablets were analyzed.

Table 4
If-
measures
Shell layer 1 [wt.%]Shell layer 2 [wt.%]MTA mixture [µw/g]Save AKReflection AK
10*6% Na2SO440 93%68%
113% Na2SO43% Na2S2O3of 5.499%77%
* not in accordance with the invention, Na2S2O3mean sodium thiosulfate

Particles percarbonate sodium coating of example 11 in accordance with the invention showed higher stability during storage in the form of non-compacted mixtures and in the form of compressed tablets, than particles percarbonate sodium example 10 in accordance with the invention, which had thiosulfinates shell layer. Moreover, particles percarbonate sodium coated in accordance with the invention also showed a smaller effect of yellowing tablets. Because the yellowing is a result of oxidation of benzotriazole contained in the dishwasher means of this result can be concluded weaker oxidizing effect on the components of the dishwasher tools.

1. Particles percarbonate sodium coated, including
a) the core percarbonate sodium
b) an inner shell layer comprising as the main component is less than the least one inorganic hydrocortisol salt, and
C) the outer shell layer comprising a thiosulfate of an alkali metal, thiosulfate alkaline-earth metal and/or ammonium thiosulfate.

2. Particles percarbonate sodium according to claim 1,
characterized in that
the core is manufactured by granulation with the cultivation of the granules in the fluidized bed or by crystallization.

3. Particles percarbonate sodium according to claim 1,
characterized in that
the number of the material of the inner shell layer particles percarbonate sodium coated is in the range from 0.1 to 10 wt.%.

4. Particles percarbonate sodium according to claim 1,
characterized in that
the amount of inorganic gidrotoraksa salt in the inner shell layer is at least 50 wt.%.

5. Particles percarbonate sodium according to claim 1,
characterized in that
inorganic hydrocortisol salt of the inner shell layer is selected from sodium sulfate, sodium carbonate, sodium bicarbonate and magnesium sulfate, and mixtures or mixed salts of these compounds.

6. Particles percarbonate sodium according to claim 5, characterized in that the inorganic gidrotoraksa salt of the inner shell layer includes sodium sulfate.

7. Particles percarbonate sodium according to claim 6, characterized in that the inner shell layer consists of sodium sulfate.

8. Particles percarbonate sodium according to claim 1,
different those who, what
the amount of material of the outer shell layer particles percarbonate sodium coated is in the range from 0.1 to 10 wt.%.

9. Particles percarbonate sodium according to claim 1,
characterized in that
the content of the thiosulfate of an alkali metal, thiosulfate alkaline-earth metal and/or ammonium thiosulfate in the outer shell layer is at least 50 wt.%.

10. Particles percarbonate sodium according to claim 1,
characterized in that
the outer shell layer comprises sodium thiosulfate.

11. Particles percarbonate sodium of claim 10,
characterized in that
the outer shell layer consists of sodium thiosulfate.

12. Particles percarbonate sodium according to claim 1,
characterized in that
they have additional shell layer as a main component includes an alkali metal silicate having a SiO module2the oxide of the alkali metal 2.5.

13. Particles percarbonate sodium according to claim 1,
characterized in that
they contain on their surface from 0.01 to 1 wt.%, preferably from 0.1 to 0.5 wt.%, gidrofobizirovannogo finely dispersed oxide element is Si, Al or Ti, or a mixed oxide of these elements.

14. Particles percarbonate sodium indicated in paragraph 13
characterized in that
fine oxide is gidrofobizirovannym paragenetically or precipitated dioxide cream the Oia.

15. A method of obtaining particles percarbonate sodium with a coating, comprising the following stages:
a) applying inner shell layer on the core material from percarbonate sodium spraying an aqueous solution in which is dissolved at least one hydrocortisol inorganic salt, and
b) applying the coated material from stage a) of the outer shell layer by spraying an aqueous solution in which is dissolved at least one thiosulfate of an alkali metal, thiosulfate alkaline-earth metal and/or ammonium thiosulfate.

16. The method according to item 15,
characterized in that
the core material is prepared by granulation with the cultivation of the granules in the fluidized bed by spraying particles percarbonate sodium aqueous solution of hydrogen peroxide and an aqueous solution of soda in the fluidized bed and at the same time evaporation of the water.

17. The method according to item 15 or 16,
characterized in that
at stages (a) and (b) the application of the shell layer is carried out by spraying in a fluidized bed and during application shell layer is evaporated more than 90% of the water contained in aqueous solutions.

18. The use of particles percarbonate sodium according to one of claims 1 to 14 as an effective chemical bleaching component in detergents and cleaners.

19. Washing and cleaning agent comprising particles perk is rbonate sodium according to one of claims 1 to 14.

20. Washing and cleaning agent according to claim 19,
characterized in that
they include from 1 to 40 wt.% particles percarbonate sodium.

21. Washing and cleaning agent according to claim 19 or 20,
characterized in that
they include extruded molded body, and the component of these pressed molded bodies are particles percarbonate sodium.

22. Dishwasher means in the form of tablets, including the remedy of silver from corrosion,
characterized in that
tablets include particles percarbonate sodium according to one of claims 1 to 14.

23. Dishwasher tool on p.22,
characterized in that
as a means of protecting silver from corrosion it includes one or more compounds from the series, including triazoles, benzotriazoles, bisbenzimidazole, aminotriazole, alkylaminocarbonyl and/or one or more transition metal complexes of these compounds.



 

Same patents:

FIELD: chemistry.

SUBSTANCE: detergent contains the components as follows, wt %: anionic surface active agent (SAG) - alkylbenzol sodium sulphonate 10-16; nonionic SAG - oxyethylated fatty alcohols or oxyethylated alkylphenol 2-5; sodium tripolyphosphate 15-25; organophosphonate compound - sodium salt 1-hydroxyethylidene of phosphonic acid or sodium diethylentriaminopentaxys-(methylene phosphonate) 0.2-0.6; polycarboxylate 0.5-1.5; carboxymethyl cellulose 0.3-0.6; modified polyalkylene glycol 0.2-0.6; optical bleaching agent 0.05-0.3; soda ash 3-6; liquid glass 3.5-6.0; enzyme 0.4-0.7; defoaming agent 0.05-1.5; aromatiser 0.15-0.3; sodium sulphate and water to 100.

EFFECT: higher efficiency of bleaching detergent, all type decontamination with additional softening of fabric and without irritation of hand skin during manual washing, lower temperature modes of washing, reduced damage effect on metal parts of washing machines.

10 cl, 2 tbl, 5 ex

FIELD: chemistry.

SUBSTANCE: invention is meant for soaking, washing and bleaching all types of textile articles, except articles from natural silk and wool, in any kind of machine, and also hand wash. Substance contains in % mass: an anionic surfactant 7-15, nonionic surfactant oxyethylated fatty alcohol 2-5, sodium tripolyphosphate 15-25, sodium ethylene-diaminotetraacetate (versene) 0.3-1, polycarboxylate, containing monomers of acrylic acid 0.2-0.6, carboxymethyl cellulose (CMC) (in terms of 100% of the share of the main substance) 0.4-0.6, sodium silicate (in terms of SiO2) - 2-5, sodium perborate or sodium percarbonate (in terms of activated oxygen) 1.5-4, tetraacetylethylenediamine (TAED) 0.5-3, enzymes 0.4-1, caustic ash 5-15, mixture of sodium carbonate and amorphous sodium silicate 2-5, optical brightener 0.05-0.4, perfume 0.1-0.3, sodium sulphate and water till 100.

EFFECT: increase in the effectiveness of the detergent with a whitening effect, removal of all kinds of dirt while adding extra softness without an irritating effect on the skin during hand washing, reducing the temperature regimes of washing, reduction in the harmful effect to the metallic part of the washing machine.

9 cl, 2 tbl

FIELD: chemistry.

SUBSTANCE: invention concerns chemical bleaches applied in cleansers and detergents. Invention claims sodium percarbonate granules with coating of high storage endurance, including a) core obtained by dispersion granulation in pseudoliquefied layer with sodium percarbonate as main component, b) internal coating layer with non-organic hydrate-forming salt as main component, selected out of group including sodium sulfate, sodium carbonate, sodium bicarbonate, magnesium sulfate and mixes or mixed salts of these compounds, and c) outer coating layer with surfactant containing sulfate or sulfonate groups in the form of alkaline metal, alkaline-earth of ammonium salt, as main component.

EFFECT: enhanced storage endurance, high stability and active oxygen content in percarbonate granules.

22 cl, 1 ex

FIELD: chemistry.

SUBSTANCE: sodium percarbonate particles have bleaching effect, their surface contain hydrophobized superfine silica in proportion 0.01-1 wt %. Method for proposed particles production consists in mixing of sodium percarbonate particles, preferably being dried, and 0.01-1 wt % of hydrophobized superfine silica. Particles of the invention have high stability during storage, permit handling and storage without dust formation and agglutination; they are dispersed in water readily and completely.

EFFECT: simplification of particles obtaining technology, and reducing equipment needed.

17 cl, 21 ex, 7 tbl, 2 dwg

FIELD: chemistry.

SUBSTANCE: particles contain inner coating layer that consist of at least one hydrate-forming mineral salt, and outer coating layer, including 0.2-3 wt % alkali metal silicate with module more than 2.5, particularly 3 to 5. Outer layer is obtained using alkali metal silicate solution with alkali metal silicate concentration 2 to 20 wt %. Dissolution time can be extended by alkali metal silicate concentration lowering in solution used, coating material amount being the same. Dissolution time can be extended significantly according to coating layers sequence and solution concentration with low quantity of alkali metal silicate.

EFFECT: extension of dissolution time.

18 cl, 7 tbl, 18 ex

FIELD: chemistry.

SUBSTANCE: invention concerns liquid detergent compositions with high stability during long-term storage. The liquid detergent composition includes fluid medium with water content up to 15 mass % and coated bleaching powder suspended in it. Dissolution time of the bleach is not less than 5 minutes; the bleach coating has at least two layers: inner layer includes one or more hydrate-forming non-organic salts as the main component, and outer layer comprises 0.2 to 5% of bleach and includes an alkali metal silicate with module of SiO2 to M2O (M is an alkali metal atom) over 2.5 as the main component. Preferable compositions include sodium percarbonate with an inner layer consisting mainly of sodium sulfate and an outer layer consisting mainly of 0.5 to 1.5 mass % of sodium silicate (with module of 3.2 to 4.2) as a bleach.

EFFECT: improved detergent efficiency and stability of the claimed composition.

14 cl, 3 tbl, 12 ex

FIELD: chemistry.

SUBSTANCE: invention pertains to compositions of granulated synthetic detergents, meant for manual and machine washing (in any type of machine) and soaking all types of textiles, including coloured and other household needs. The detergent contains the following components in the given % mass: anionic surface active agent sodium alkylbenzenesulfonate 9-12; non-ionic surfactant 2-5; sodium tripolyphosphate 15-30; dispergator 0.3-1.2; carboxymethyl cellulose 0.3-0.7; sodium silicate 3-6; modified polyalkylene glycol 0.2-0.6; enzyme 0.3-0.8; sodium carbonate 6-12; photo-bleaching agent 0.003-0.020; optical brightener 0.05-0.20; fragrance component 0.1-0.3; sodium sulphate and water up to 100. The non-ionic surfactant preferably contains oxyethylated monoalkylphenols based on propylene trimers or oxyethylated fatty alcohols. The dispergator used is sodium polyacrylate or sodium salt of a copolymer of maleic or acrylic acid or a sodium salt of a copolymer of acrylic, methacrylic and maleic acid. Alternatives of the synthetic detergent are also described.

EFFECT: increased effectiveness of the detergent, bleaching effect after washing, wider assortment of high quality granulated synthetic detergents.

7 cl, 1 tbl

FIELD: household chemistry, in particular compositions for bleaching of white and random dyeing textile made of natural, artificial, synthetic and mixed fibers.

SUBSTANCE: claimed composition contains (mass %): hydrogen peroxide 7-11; oxanole 0.5-1.0; oxyethylidenediphosphonic acid 0.1-0.3; optical bleaching agent, namely mixture of benzoxyzaryl derivative 0.1-0.2 and stilbenesulfo acid 0.1-0.2; and balance: water.

EFFECT: non-layered composition during storage; decreased chemical failure of materials.

2 tbl, 12 ex

FIELD: organic chemistry, chemical technology.

SUBSTANCE: invention relates to a whitening composition comprising: (a) monomeric ligand or catalyst with transient metal of ligand of the formula (I): wherein R represents hydrogen atom; R1 and R2 are chosen independently from (C1-C4)-alkyl, pyridine-2-yl-methyl and (C2-C4)-alkylmethyl; X represents -C=O; R3 and R4 are similar and represent -(CH2)nC(O)O-(C1-C4)-alkyl; n = 0-4, and (b) equilibrating carriers and additional components. This composition is useful for catalytic whitening substrates with atmosphere oxygen. Also, invention describes a method for whitening the substrate involving applying step of the whitening composition on substrate in aqueous medium.

EFFECT: valuable properties of substances, improved whitening method.

11 cl, 2 tbl

FIELD: chemical industry; production of sodium percarbonate and other chemical products.

SUBSTANCE: the invention is pertaining to the field of chemical industry and may be used in production of sodium percarbonate (SPC) and other chemical products, where the synthesis process is combined with the synthesized product granulation. The granulated sodium percarbonate is produced by the steady growing-up of the products of interaction of the stabilized water solutions of the soda and hydrogen dioxide on the inoculation particles-granules. To chokes give torrents of The streams of the stabilized water solutions of soda and hydrogen dioxide are fed into the reactors at keeping the time of their interaction from 5 up to 21 sec and concentration of the sodium carbonate and the hydrogen dioxide in the ratio of 1 : 1.45-1.57. The produced reaction mass in the form of a solution is fed into the mixers-granulators, where it is distributed along the surface of the inoculation particles of sodium percarbonate, moisten and saturate them within 12-25 seconds up to achieving the average humidity of 6-12 mass %. Then the wet granules are brought out into the drying room on the gas-distributing grate, on which there is a slotted clearance with the gas-feeding channel, formed as a semi-circled groove on the gas-distribution grate and the upper end of the inclined chute. The feeding of the heated flue-gases is exercised under the gas-distribution grate through the gas duct, in which there is an erected septum being the prolongation of the upper wall of the channel and separating up to 6 % of total volume of the fed flue-gases, which are coming in through the channel with adjustment of the speed of their passage through the slotted clearance into the drying room, where they form a gas curtain in the form of the semi-tabernacle, in which the dried granules are classified according to their flying speeds in such a manner, that granules with the diameter less than the preset dimension, for example 500 microns, are carried out by the two equivolumetric streams formed by splitter made in the form of a triangular prism, to the windows and are def into the mixers-granulators as the recycle for a following cycle of granularity, and the granules with the diameter exceeding the preset lower limit, for example - 500 microns and above, fall through the gaseous curtain and on the inclined chute through the outlet window get into the classifier for the final classification according to the high limit of the preset fractionized composition of the final product, for example 800 microns. From the intermediate part of the classifier the granules the preset fraction are delivered for storage. The production output of the granules of the preset fraction, for example, 500-800 microns, is up to 99 %, the bulk weight is 1093-1138 kg/m3, the contents of the active oxygen is - 13.94-14.1 %, stability is 55.91-56.83 %. The invention allows production of sodium percarbonate with the preset range of the composition of the granules without reduction of productivity of the installation.

EFFECT: the invention ensures production of sodium percarbonate with the preset range of the composition of the granules without reduction of productivity of the installation.

9 cl, 2 tbl, 4 dwg

FIELD: biotechnologies; textile; paper.

SUBSTANCE: means for fermentative cleaning of textile fabrics contains microorganisms of species Penicillium pinophilum or of species Trametes versicolor, able to produce enzymes, useful in said cleaning method. Said means is made in form of sachet, permeable for said enzymes, but impermeable for said organisms. In addition claimed is fermentative method of textile fabric cleaning, according to which soiled fabrics are soaked in water in presence of claimed means.

EFFECT: increase of efficiency of fabric cleaning and more convenient for user cleaning method.

9 cl, 6 dwg, 1 tbl, 3 ex

FIELD: chemistry.

SUBSTANCE: invention concerns chemical bleaches applied in cleansers and detergents. Invention claims sodium percarbonate granules with coating of high storage endurance, including a) core obtained by dispersion granulation in pseudoliquefied layer with sodium percarbonate as main component, b) internal coating layer with non-organic hydrate-forming salt as main component, selected out of group including sodium sulfate, sodium carbonate, sodium bicarbonate, magnesium sulfate and mixes or mixed salts of these compounds, and c) outer coating layer with surfactant containing sulfate or sulfonate groups in the form of alkaline metal, alkaline-earth of ammonium salt, as main component.

EFFECT: enhanced storage endurance, high stability and active oxygen content in percarbonate granules.

22 cl, 1 ex

FIELD: chemistry.

SUBSTANCE: claimed invention relates to multi-phase bars for personal washing, which appear to be skillfully hand-made. Soap bar contains 25-90% of surface-active substance base, suitable for skin cleaning, water-soluble and dispersible in water solid matrix, which contains, at least, 1 wt % of surface-active substance. Dispersion phase has the largest size within 3-70 mm. Hardness of solid phase measured at temperature 33-50°C, constitutes 1.9-2.5 bars, and ratio λ, determined as solid phase hardness at temperature 25°C, divided by hardness at temperature 33°C, is more that 2.0. Dispersion phase constitutes 1-35 wt % of bar. In second variant, bar contains 25-90% of surface-active substance base, composed of fatty acids soaps, synthetic detergents and their mixtures, 0.1-15% of plastifying agent, 1 wt % of surface-active substance, 5-95 wt % of water-soluble or dispersible in water solid matrix, 0.25-15 wt % of hardening agent. Dispersion phase has largest size within 3-45 mm. Hardness of solid phase, measured at temperature 33-50°C, constitutes 1.9-2.5 bars, and ratio λ, determined as solid phase hardness at temperature 25°C, divided by hardness at temperature 33°C, is more than 2.0. Dispersion phase constitutes 1-35 wt % of bar. Method includes formation of mixture, by adding two solid phases, mixture extrusion, cutting and moulding extruded mass in form of bar. Method of skin cleaning and moisturising, as well as method of deep cleaning, includes skin washing with soap bar and washing with water.

EFFECT: obtaining multi-phase soap bar, which appears to be skillfully hand-made and which can be manufactured by high-rate extrusion method.

31 cl, 8 tbl, 4 ex

FIELD: chemistry.

SUBSTANCE: sodium percarbonate particles have bleaching effect, their surface contain hydrophobized superfine silica in proportion 0.01-1 wt %. Method for proposed particles production consists in mixing of sodium percarbonate particles, preferably being dried, and 0.01-1 wt % of hydrophobized superfine silica. Particles of the invention have high stability during storage, permit handling and storage without dust formation and agglutination; they are dispersed in water readily and completely.

EFFECT: simplification of particles obtaining technology, and reducing equipment needed.

17 cl, 21 ex, 7 tbl, 2 dwg

FIELD: chemistry.

SUBSTANCE: particles contain inner coating layer that consist of at least one hydrate-forming mineral salt, and outer coating layer, including 0.2-3 wt % alkali metal silicate with module more than 2.5, particularly 3 to 5. Outer layer is obtained using alkali metal silicate solution with alkali metal silicate concentration 2 to 20 wt %. Dissolution time can be extended by alkali metal silicate concentration lowering in solution used, coating material amount being the same. Dissolution time can be extended significantly according to coating layers sequence and solution concentration with low quantity of alkali metal silicate.

EFFECT: extension of dissolution time.

18 cl, 7 tbl, 18 ex

FIELD: chemistry.

SUBSTANCE: invention concerns liquid detergent compositions with high stability during long-term storage. The liquid detergent composition includes fluid medium with water content up to 15 mass % and coated bleaching powder suspended in it. Dissolution time of the bleach is not less than 5 minutes; the bleach coating has at least two layers: inner layer includes one or more hydrate-forming non-organic salts as the main component, and outer layer comprises 0.2 to 5% of bleach and includes an alkali metal silicate with module of SiO2 to M2O (M is an alkali metal atom) over 2.5 as the main component. Preferable compositions include sodium percarbonate with an inner layer consisting mainly of sodium sulfate and an outer layer consisting mainly of 0.5 to 1.5 mass % of sodium silicate (with module of 3.2 to 4.2) as a bleach.

EFFECT: improved detergent efficiency and stability of the claimed composition.

14 cl, 3 tbl, 12 ex

FIELD: soap boiling industry.

SUBSTANCE: invention proposes soap that comprises a whitening substance, "Antal P-2", ethylenediaminetetraacetic acid di- or tetrasodium salts, cosmetic cream with wheat embryos oil, perfume principles and soap chips. As perfuming principles the following perfume principles are used: "Moloko i med" ("Milk and honey") or "Tsvetok lotosa i vitamin E" ("Lotus flower and vitamin E"), or "Apelsin i myata" ("Orange and mint") wherein components are taken in the definite ratio. Invention provides enhancing stability of odor during storage, reducing dissolving rate and swelling of soap in its using.

EFFECT: improved properties of toilet soap.

5 cl, 2 tbl

FIELD: cosmetic industry.

SUBSTANCE: composition of soft toilet soap contains 20-60 mass % of one or more synthetic surfactants, 10-50 % of moistening agent and peeling particles, wherein at least 20 % of particles have major axis length from 100 to 600 mum.

EFFECT: soap with improved peeling and moistening properties.

17 cl, 9 tbl

Liquid soap // 2309981

FIELD: fat-and-oil products, in particular liquid soaps.

SUBSTANCE: claimed soap contains potassium carbonate, water, gel-wax soap-waste precipitate, pigment and perfume flavor, Said gel-wax soap-waste precipitate is obtained by sequential treatment of hydrated vegetable oil at 15-35°C with 6-8 % citric acid aqueous solution in amount of 0.5-1.5 % based on oil mass, sodium silicate aqueous solution with density of 1.05-1.15 g/cm3 in amount of 0.5-2.0 % based on oil mass, and sodium silicate aqueous solution with density of 1.20-1.35 g/cm3 in amount of 0.5-4.0 % based on oil mass, exposing of obtained mixture to produce gel-wax soap-waste precipitate followed by isolation thereof from treated oil. All component are used in specific component ratio.

EFFECT: soap of high storage stability, high washing ability and high efficiency.

1 tbl, 3 ex

Liquid soap // 2309980

FIELD: fat-and-oil products, in particular liquid soaps.

SUBSTANCE: claimed soap contains potassium carbonate, water, phospholipid-gel-wax precipitate, pigment and perfume flavor, Said phospholipid-gel-wax precipitate is obtained by sequential treatment of non-refined vegetable oil at 15-35°C with 3-5 % sodium chloride aqueous solution in amount of 1.0-2.0 % based on oil mass, 6-8 % citric acid aqueous solution in amount of 0.5-1.5 % based on oil mass, and sodium silicate aqueous solution with density of 1.05-1.35 g/cm3 in amount of 0.5-2.0 % based on oil mass, exposing of obtained mixture to produce phospholipid-gel-wax precipitate followed by isolation thereof from treated oil.

EFFECT: soap of high storage stability, high washing ability and high efficiency.

3 ex

FIELD: chemistry.

SUBSTANCE: invention concerns chemical bleaches applied in cleansers and detergents. Invention claims sodium percarbonate granules with coating of high storage endurance, including a) core obtained by dispersion granulation in pseudoliquefied layer with sodium percarbonate as main component, b) internal coating layer with non-organic hydrate-forming salt as main component, selected out of group including sodium sulfate, sodium carbonate, sodium bicarbonate, magnesium sulfate and mixes or mixed salts of these compounds, and c) outer coating layer with surfactant containing sulfate or sulfonate groups in the form of alkaline metal, alkaline-earth of ammonium salt, as main component.

EFFECT: enhanced storage endurance, high stability and active oxygen content in percarbonate granules.

22 cl, 1 ex

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