Sodium percarbonate particles with increased stability during storage

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

 

The present invention relates to particles of percarbonate sodium with increased storage stability in the presence of modifying agents, especially in the presence of silicate modifiers.

Percarbonate sodium is used as a bleaching tools, as well as having the bleaching effect of the component of detergents and cleaning agents. The lack of percarbonate sodium is in its tendency to decomposition in the presence able to absorb moisture and again to give its modifiers and result in the loss of active oxygen, and thus in the loss of bleaching steps. Therefore, in modifying additives containing bleaching, washing or cleaning tools percarbonate sodium to increase its stability during storage is preferably used in the form of particles coated with a layer of stabilizing their shell.

From DE 870092 it is known that powder percarbonate sodium can be stabilized by dry blending to him pyrogenic oxides, preferably pyrogenic silicic acid, in an amount of about 1%. However, we provide this by stabilizing the particles percarbonate sodium insufficient to prevent its decomposition in mixtures with silica modifying additives.

In the patent US 4215990 described the e containing modifying additives, bleaching agents, which along with 5-50 wt.% percarbonate sodium is 0.1 to 2 wt.% highly dispersed silicic acid with a particle size from 1 to 150 microns. Such bleaching agents in order to avoid them sticking together optionally contain from 0.05 to 1 wt.% corn starch and/or diethylphthalate. In the mentioned patent does not contain any information about the application gidrofobizirovannogo silicic acid or stability described therein bleaching products in the presence of modifiers.

In the publication WO 92/07057 describes liquid detergent compositions containing a solid, water-soluble permissione compound, a surfactant and a hydrophobic silicic acid. Such detergent compositions contain from 0.5 to 5 wt.% hydrophobic silicic acid, as well as permissione compound in an amount to provide selection from 0.5 to 3 wt.% active oxygen. The addition of hydrophobic silicic acid causes the thickening of the liquid detergent composition, which implies that hydrophobic silicic acid is present in dispergirovannom form in the liquid phase of the detergent composition.

In patents US 5374368 and US 5496542 described releasing free hydrogen peroxide compositions in liquid or gel state, which along with 55-90 wt.% polyalkyleneglycol and 5-20 wt.% percarbonate sodium also contain from 0.5 to 3 wt.%, accordingly, the t of 0.5 to 6 wt.% colloidal silicic acid. As suitable for use in such compositions colloidal silicic acid is also known as gidrofobizirovannym silicic acid Aerosil®R972. In this case, silicic acid serves as a thickener of polyalkyleneglycol and therefore dispersed in the liquid phase of the composition.

In the publication WO 95/02724 described granular detergents containing percarbonate alkali metal with an average particle size of from 250 to 900 μm and a hydrophobic material selected from the group comprising silicic acid, talc, zeolite, DAY and hydrotalcite, in a mass ratio of from 4:1 to 40:1. As the hydrophobic material, it is preferable to use gidrofobizirovannogo silicic acid, for example, Aerosil®R972. In one embodiment, to obtain a detergent composition of the hydrophobic material is sprayed on the surface percarbonate particles with carrying out this stage in a rotating drum mixer or a fluidized bed. Percarbonate, part described in this publication granular detergents, has improved resistance to decomposition even in the presence of modifiers.

In the specified publication WO 95/02724 on C.2 in the fourth paragraph States that it describes the mass ratio between percarbonate alkali metal and a hydrophobic material, which mo is et to vary from 4:1 to 40:1, an important feature that helps improve the stability of percarbonate described in this publication detergent composition during storage. However, compared to commercially available matriarchate products that do not contain gidrofobizirovannogo silicic acid, the particles percarbonate sodium, which in a specified quantitative ratio was napisana gidrofobizirovannym silicic acid, inherent disadvantages associated with working with them, as well as their application in bleaching, washing and cleaning agents. When working with particles percarbonate sodium intense dust obstructing the pneumatic transport of particles and their subsequent processing in the production process of bleaching, washing or cleaning agents. In addition to that described in WO 95/02724 particles percarbonate sodium containing deposited on their surface gidrofobizirovannogo silicic acid, difficult to disperse in water and are prone to clumping and emphasis added gidrofobizirovannogo silicic acid and its accumulation on the surface of the water. Therefore, the use of such particles percarbonate sodium in the composition of bleaching, washing and cleaning agents leads to a deterioration of their consumer properties.

Based on the foregoing, the present invention was based on the objectives is to offer the particles percarbonate sodium, who would possess high storage stability in the presence of the modifying additives and which had permitted the opportunity to work with them and store them without dust and sticking together. In addition, such particles percarbonate sodium should also be able to easily and without residue to dispergirujutsja in the water, to their use in the bleaching composition, detergents did not lead to a deterioration of their consumer properties.

With the invention it has been unexpectedly found that the above problem can be solved using particle percarbonate sodium, having on its surface gidrofobizirovannym highly dispersed oxide in an amount constituting only from 0.01 to 1 wt.%, preferably from 0.1 to 0.5 wt.%.

The object of the present invention are in accordance with these particles percarbonate sodium, characterized in that they contain on their surface gidrofobizirovannym highly dispersed silicon dioxide, aluminum or titanium or a mixed oxide of these elements in amounts of from 0.01 to 1 wt.%, preferably from 0.1 to 0.5 wt.%, this gidrofobizirovannym highly dispersed oxide preferably is gidrofobizirovannogo pyrogenic or precipitated silicic acid.

In the invention it is also proposed a method of obtaining such particles pescarmona the sodium, characterized in that the particles of percarbonate sodium, which does not necessarily have a one - or multi-layer membrane, mixed, preferably in a dry state, from 0.01 to 1 wt.%, preferably 0.1 to 0.5 wt.%, gidrofobizirovannogo highly dispersed oxide of silicon, aluminum or titanium or a mixed oxide of these elements.

The invention relates further to the use of the proposed therein particles of percarbonate sodium as a bleaching component in the composition of the bleaching, washing or cleaning products.

Proposed in the invention particles percarbonate sodium contain on their surface from 0.01 to 1 wt.%, preferably from 0.1 to 0.5 wt.%, gidrofobizirovannogo highly dispersed oxide of silicon, aluminum or titanium or a mixed oxide of these elements. As gidrofobizirovannogo finely dispersed oxide particles percarbonate sodium in a preferred embodiment, contain gidrofobizirovannogo pyrogenic or precipitated silicic acid.

As an example, suitable for use in accordance with the present invention highly dispersed oxides can be called pyrogenic oxides produced by flame hydrolysis of volatile compounds of silicon, aluminum or titanium or mixtures of such compounds. The primary particles obtained in this way pyrogenic oxides or mixed oaks is Dov preferably have an average size less than 50 nm and can be aggregated into larger particles, the average size of which is preferably less than 20 microns.

Similarly, the use of precipitated oxides, precipitated from aqueous solutions of compounds of silicon, aluminum or titanium or mixtures of these compounds. Precipitated oxides, respectively mixed oxide along with silicon, aluminum and titanium may also contain small amounts of ions of alkali or alkaline-earth metals. The average particle size of precipitated oxides is preferably less than 50 μm, particularly preferably less than 20 microns.

Under gidrofobizirovannym oxides according to the invention are oxides having on their surface a related chemical compounds of organic residues and is not wetted by water. Hydrophobizated oxides can be obtained, for example, the interaction of pyrogenic or precipitated oxides with organic silicon compounds (organosilane), silazane or polysiloxane. Suitable for hydrophobized oxide silicon compound as described in the application EP-A 0722992 (p.3, line 9, to p.6, line 6). Especially preferred hydrophobizated oxides obtained by the interaction of highly dispersed oxide with a silicon compound, related to given in EP-A 0722992 classes of compounds (a)-(e) and (k)-(m). Wettability hydrophobized fine on the seeds methanol is preferably at least 40.

The average size of the proposed invention particles percarbonate sodium is preferably from 0.2 to 5 mm, particularly preferably from 0.5 to 2 mm, the Preferred particle percarbonate sodium with low content of fine fraction, preferably containing less than 10 wt.% particle size of less than 0.2 mm, particularly preferably less than 10 wt.% a particle size of less than 0.3 mm. Proposed in the invention particles percarbonate preferably sodium are mostly spherical in shape with smooth surface. The particles with a smooth surface, its roughness is less than 10%, preferably less than 5%, of the diameter of the particles.

Proposed in the invention particles percarbonate sodium can be obtained from particles percarbonate sodium, received one of the known methods of obtaining percarbonate sodium. One of the methods suitable for obtaining percarbonate sodium, is the crystallization of sodium carbonate from aqueous solutions of hydrogen peroxide and sodium carbonate, which can be performed in the presence and in the absence of vicalvaro means, for example in accordance with EP-A 0703190. Equally the original particles percarbonate sodium can be obtained by using spray granulation in the fluidized bed, in which the Foundation or nabryzgivanii aqueous lane is xida hydrogen and aqueous soda solution into the fluidized bed in the germ percarbonate sodium with simultaneous evaporation of water, for example in accordance with WO 95/06615. Another suitable method of obtaining the original particles percarbonate sodium is the interaction of solid sodium carbonate with an aqueous solution of hydrogen peroxide, followed by drying the obtained product. Obtained by this method particles percarbonate sodium consist primarily of perpetrate sodium carbonate composition 2Na2CO3·3H2O2. Obtained by this method, the particles may also contain small amounts of known stabilizers permissionid compounds, for example magnesium salts, silicates, phosphates and/or chelating agents. Obtained by the method of crystallization in the presence of vicalvaro funds particles percarbonate sodium may in addition also contain small amounts of used wasalways agent, for example sodium chloride. Proposed in the invention particles percarbonate sodium preferably be obtained from particles percarbonate sodium obtained by the method of spray granulation in the fluidized bed.

In one of the preferred embodiments of the invention the particles percarbonate sodium additionally have at their core percarbonate sodium membrane, which contains as a main component one or more forming hydrate inorganic Sol is th.

Forming a hydrate of an inorganic salt, respectively, forming a hydrate of an inorganic salt is preferably selected from the group including sodium sulfate, sodium carbonate, sodium bicarbonate and magnesium sulfate, as well as mixtures of these compounds and/or their mixed salts. Especially preferred forming a hydrate of an inorganic salt is sodium sulfate. In one of the preferred options the shell consists mainly of sodium sulfate. The share of the lining of the particles percarbonate sodium should preferably have from 1 to 20 wt.%, most preferably from 2 to 10 wt.%, in terms of UN-hydrated form forming a hydrate of the salt, respectively forming the hydrate salts.

The shell is applied to the particles percarbonate sodium known methods. Fundamentally all of these methods are the most uniform single or multiple administrations covered by the shell of the particles in contact with containing one or more components of the shell solution with simultaneous or subsequent drying of the particles. This introduction made in the shell of the particles in contact with this solution can be, for example, the granulation bowl or mixer, such as eccentric mixer (mixer type "drunken barrel"). Particles percarbonate sodium is preferable to cover bolocco the method of coating in the fluidized bed, lying in the Foundation or nabryzgivanii aqueous solution forming a hydrate of an inorganic salt, respectively, forming a hydrate of the inorganic salts in the fluidized bed primary particles percarbonate sodium, respectively, already covered with one layer or multi - layer shell particles percarbonate sodium with simultaneous drying fluidizing gas.

Fluidizing gas may be any gas, especially air, is heated by direct contact with the gaseous products of the combustion air with CO2for example, from 0.1 to about 15%, net CO2, nitrogen and inert gases. Apply shell particles percarbonate sodium most preferably as described in EP-A 0970917.

Applied to particles percarbonate sodium shell forming a hydrate of an inorganic salt preferably should completely cover the core percarbonate sodium. When applying the membrane from the aqueous solution, occurring when applying the membrane dissolving the surface layer of the particles percarbonate sodium at the interface between the core material and the sheath material may form the boundary area, which, along with percarbonate sodium and the sheath material may contain other compounds. Thus, in particular, this boundary zone is when drawing the shell primarily of sodium sulfate can along with percarbonate sodium and sodium sulfate also contain sodium bicarbonate, as well as double salts of sodium bicarbonate and sodium sulfate, such as sesquicarbonate or salt of Versager.

Shell of forming a hydrate inorganic salts can be applied directly to the core percarbonate sodium or already deposited one layer or multi - layer membrane. In addition, and on top of the shell optionally apply one layer or multi - layer shell.

In another preferred embodiment, the particles percarbonate sodium have on top of the form containing the inorganic hydrate salt shell second shell, which as a main component contains an alkali metal silicate with a modulus SiO2to M2O (M denotes an alkali metal)in excess of 2.5. In the most preferred embodiment, the second shell consists mainly of silicate of an alkali metal. Under the alkali metal silicate thus refers to all those alkali metal silicates, in which the module corresponds to an average of the above value. This module is meant the molar ratio of SiO2to M2Oh, where M denotes an alkali metal, preferably lithium, sodium or potassium or a mixture of these alkali metals. Particularly preferred sodium silicate. Module alkali metal silicate is preferably from 3 to 5, most preferably from 3.2 to 4.2. On the Liu second shell particles possess percarbonate sodium should preferably be from 0.2 to 3 wt.%.

The second shell is preferably applied with a Foundation or nabrasyvaniem aqueous solution containing alkali metal silicate at a concentration of component preferably from 2 to 20 wt.%, more preferably from 3 to 15 wt.%, first of all, from 5 to 10 wt.%. For the application of membranes, consisting mainly of sodium silicate, preferably aprecciate the solution of the so-called liquid glass.

Proposed in the invention particles percarbonate sodium are compared with comparable particles percarbonate sodium, not having on its surface gidrofobizirovannogo highly dispersed oxide, improved storage stability in the presence of modifying agents, especially in the presence of silicate modifying additives, such as zeolites. When stabilization proposed in the invention particles percarbonate sodium applying them to the shell of forming the inorganic hydrate salt is the same as the comparable particles, but not containing on its surface gidrofobizirovannym highly dispersed oxide, stability during storage could be achieved with much lower consumption of sheath material. For example, when a shell from the sodium sulfate proposed in the invention the particles percarbonate sodium already in the content of the shell equal to 2 wt.%, Odets is to give the same stability indicators, which in the case of particles percarbonate sodium without gidrofobizirovannogo highly dispersed oxide on their surface could be achieved only when the content of the shell is equal to 6 wt.%. Thus according to the invention may receive proposed therein particles of percarbonate sodium shell of forming a hydrate of an inorganic salt, which at the same stability during storage have high content of active oxygen.

In addition, the proposed invention the particles percarbonate sodium have compared to particles percarbonate sodium, containing on its surface gidrofobizirovannym highly dispersed oxide, less tendency to stick together and especially when stored in conditions where they are exposed to compressive loads. Therefore, the proposed invention the particles percarbonate sodium admit the possibility of their storage bins over a longer period of time and even after long storage in the bunker have good mobility (flowability) and do not show a noticeable tendency to clumping or caking. The advantage of a reduced tendency to stick together most pronounced among those proposed in the invention particles percarbonate sodium, which on top of the shell containing the hydrate forming inorganic salt, have a second Obolo is, which as a main component contains a silicate of an alkali metal.

When working with the proposed invention the particles percarbonate sodium compared to known from WO 95/02724 particles that have a mass ratio between percarbonate alkali metal and a hydrophobic material lies in the range from 4:1 to 40:1, there is much less dust because gidrofobizirovannym highly dispersed oxide have proposed in the invention particles percarbonate sodium unexpectedly strongly coupled to their surface and not practically used up and is not conducive to dust generation. Therefore, the proposed invention the particles percarbonate sodium can unlike known from WO 95/02724 particles percarbonate move through pneumatic transport without fear of dust and increased abrasion or stratification of percarbonate sodium and gidrofobizirovannogo highly dispersed oxide. Unlike known from WO 95/02724 particles percarbonate alkali metal proposed in the invention particles percarbonate sodium practically do not show the disadvantages from the point of view of their dispersive ability of the pigment in water in comparison with particles of percarbonate sodium, containing on its surface gidrofobizirovannym highly dispersed oxide. Proposed in the invention particles percarbonate sodium with the same ol dissolve quickly in water, as particles percarbonate sodium, not containing gidrofobizirovannym highly dispersed oxide, and when dissolved in water in amounts in which they are commonly used in the bleaching composition, detergents, do not lead to adverse selection gidrofobizirovannogo highly dispersed oxide.

The object of the invention is further a method of obtaining a offer in the invention particles percarbonate sodium, which consists in the fact that the particles of percarbonate sodium, optional with one - or multi-layer membrane, mixed with 0.01 to 1 wt.%, preferably 0.1 to 0.5 wt.%, gidrofobizirovannogo highly dispersed oxide of silicon, aluminum or titanium or a mixed oxide of these elements. As gidrofobizirovannogo highly dispersed oxide is preferable to use gidrofobizirovannogo pyrogenic or precipitated silicic acid.

The average size used in the implementation of this method particles percarbonate sodium should preferably be from 0.2 to 5 mm, particularly preferably from 0.5 to 2 mm, the Average particle size gidrofobizirovannogo highly dispersed oxide should preferably be less than 20 microns. The ratio between the average size of the particles percarbonate sodium and used particles gidrofobizirovannogo highly dispersed oxide is preferably exceed 20:1, and most preferably should not exceed 50:1.

Used in the implementation of the method described above particles percarbonate sodium preferably be mixed in the dry state with gidrofobizirovannym highly dispersed oxide. The process of mixing can have all suitable for mixing solids devices. In a preferred embodiment, particles of percarbonate sodium for their mixing with gidrofobizirovannym highly dispersed oxide is dispersed in the gas phase. The process of mixing in this preferred embodiment, the method can be performed, for example, in the fluidized bed, gravity pipe or in the pneumatic conveyor with a fluidized bed of particles.

With the invention it has been unexpectedly found that even when the dry mixing of the particles percarbonate sodium from 0.01 to 1 wt.% gidrofobizirovannogo highly dispersed oxide it is almost entirely associated with the surface of the used particles percarbonate sodium and therefore almost no leads to the formation of fines and dust in the final product.

The mixture of the used particles percarbonate sodium gidrofobizirovannym highly dispersed oxide in the gravity pipe or in the pneumatic conveyor with a fluidized bed of particles provides a simple way the possibility of continuous floor of the texts proposed in the invention particles percarbonate sodium and does not require any mixing with additional moving parts. Continuous mixing of particles in a gravity pipe or in the pneumatic conveyor with a fluidized bed of particles provides obtaining a particularly homogeneous product, which is basically all particles percarbonate sodium have on their surface gidrofobizirovannym highly dispersed oxide with a relative mass content corresponding to the proposed invention the values.

Figure 1 and 2 shows obtained using scanning electron microscope images proposed in the invention particles percarbonate sodium, having a shell made of sodium sulfate in the amount of 6 wt.% and containing on its surface gidrofobizirovannogo silicic acid Aerosil®R812 in the amount of 0.5 wt.%. Such particles were obtained by using spray granulation in the fluidized bed, application of particle shell by sprayed on them of a solution of sodium sulfate in the fluidized bed with simultaneous evaporation of water and the final dry mixing the coated particles with gidrofobizirovannogo silicic acid in eccentric mixer. In the images proposed in the invention particles percarbonate sodium clearly shows that gidrofobizirovannym silicic acid is almost completely linked to their surface.

Another object of the invention is the use of the facilities is utilized therein particles of percarbonate sodium as having bleaching action of the component in the detergent composition, bleaching or cleaning agents. Under bleach, detergents or cleaners are meant, in particular, those containing at least one of the modifying additive, preferably silicate modifying additive. Under the modifying additives are referring to all those soluble or insoluble compounds, which when using detergent, bleach or cleaners are able to link contained in the used water ions of calcium and/or magnesium or to form complexes with them. As an example, silicate modifying additives can be called soluble silicates, insoluble layered silicates and zeolites, especially zeolite a and zeolite X.

As part of washing, bleaching or cleaning agents proposed in the invention particles percarbonate sodium is preferably used in an amount of 5 to 50 wt.%, more preferably from 10 to 40 wt.%, first of all, from 15 to 20 wt.%. Washing, bleaching and cleaning products along with the proposed invention the particles percarbonate sodium may also contain other components and especially the following:

- one or more surfactants, preferably selected from the group comprising cationic, anionic, nonionic and amphoteric surfactants,

one or the number of inorganic and/or organic modifiers, preferably selected from the group comprising zeolites, layered silicates, soluble silicates, polyphosphates, aminopolyamide acid, aminophosphonate acid, and policyabout acid,

- one or more having an alkaline action of the components, preferably selected from the group comprising carbonates of alkali metals, alkali metal silicates and alkanolamine,

- one or more bleach activators, preferably selected from the group of N-acyl and O-acyl compounds, such as tetraacetylethylenediamine (TAED) or nonanoyloxybenzenesulfonate (NOBS),

- one or more enzymes, preferably selected from the group comprising lipase, cutinase, amylase, protease, esterase, cellulase, pectinase, lactase and peroxidase, and

- one or more auxiliary substances, preferably selected from the group comprising stabilizers peroxides, antiresonance (means of preventing the resorption of pollution), optical brighteners, defoamers, disinfectants, corrosion inhibitors, perfumes and fragrances and dyes.

The application of the proposed invention particles percarbonate sodium as a bleaching component in the composition of washing, bleaching or cleaning agents can improve their stability during storage the situation and decrease occurring during storage loss of active oxygen.

Examples

Percarbonate sodium used in the examples below, to receive his offer in the invention of the particles was obtained by narushitelei granulation in the fluidized bed method described in WO 95/06615. The average size used in the examples of particles percarbonate sodium was 0.65 mm and practically full absence among them of particles with a diameter less than 0.3 mm Of the basic particles percarbonate sodium particles with a shell of 2 wt.% sodium sulfate was obtained on the laboratory equipment that is either sprayed or nabryzgivaniya to particles of an aqueous solution of sodium sulfate with simultaneous evaporation of water. Particles percarbonate sodium with a shell of 6 wt.% sodium sulfate was obtained by sprayed or nabryzgivaniya to particles of an aqueous solution of sodium sulfate in the manner described in the application EP-A 0670917.

To obtain the proposed invention particles percarbonate sodium source percarbonate sodium for 30 min was mixed in eccentric mixer with highly dispersed silicic acid, the number and types which are presented in tables 1-3 and table 5. Used highly dispersed silicic acid had the following properties:

- Aerosil®R812: gidrofobizirovannym hexamethyldisilazane pyrogenic silicic acid with a specific BET method is useful surface 260 m 2/g, an average size of primary particles of 7 nm and a methanol wettability 50,

- Aerosil®R972: gidrofobizirovannym a clear pyrogenic silicic acid with a specific BET-method specific surface area of 110 m2/g, an average size of primary particles of 16 nm and a methanol wettability 35,

- Aerosil®200: not modified pyrogenic silicic acid with a specific BET-method specific surface area of 200 m2/g and an average size of primary particles of 12 nm,

- Sipernat®D17: gidrofobizirovannym precipitated silicic acid with a specific BET-method specific surface area of 100 m2/g, an average size of primary particles of 7.0 μm and a methanol wettability 55,

- Sipernat®22S: not modified precipitated silicic acid with a specific BET-method specific surface area 190 m2/g and an average size of primary particles of 7.0 microns.

To determine the stability of the particles percarbonate sodium during storage in the presence of zeolite modifying additives 15 g of the obtained product was mixed with 15 g of zeolite A (Zeocros CG 180) and kept in an open state in a period of 68 hours in a climatic chamber at 38°C and 75%relative humidity. Before and after storage of the samples by permanentresidence titration was determined by their content of active oxygen and OS is implement these data to calculate the concentration of active oxygen during storage (relates. the residual content of OA). The results of the experiments are presented in tables 1-3 and show that proposed in the invention particles percarbonate sodium have better storage stability in the presence of zeolite modifying additives than particles percarbonate sodium, containing on their surface a finely dispersed oxide or highly dispersed hydrophilic silicic acid, such as Aerosil®200 or Sipernat®22S.

Table 1

Stability percarbonate sodium without shell during storage in the presence of zeolite And
ExampleHighly dispersed oxideThe amount of finely dispersed oxide wt.%Relates. the residual content of OA in %
1*no77
2*Aerosil R8120,187
3Aerosil R8120,289
4Aerosil R8120,390
5*Aerosil 2000,381
*Note: example is not relevant to the invention.

Table 2

Stability percarbonate sodium with sheath from 2 wt.% Na2SO4when stored in the presence of zeolite And
ExampleHighly dispersed oxideThe amount of finely dispersed oxide wt.%Relates. the residual content of OA in %
6*no80
7Aerosil R8120,0582
8Aerosil R8120,189
9Aerosil R8120,290
10Aerosil R8120,389
11Aerosil R9720,390
12*Aerosil R2000,380
13Sipernat D170,391
14*Sipernat 22S0,382
*Note: example is not relevant to the invention.
Table 3

Stability percarbonate sodium with a shell of 6 wt.% Na2/sub> SO4when stored in the presence of zeolite And
ExampleHighly dispersed oxideThe amount of finely dispersed oxide wt.%Relates. the residual content of OA in %
15*no85
16Aerosil R8120,190
17Aerosil R8120,395
18Aerosil R9720,189
19*Aerosil R9722,591
* Note: example is not relevant to the invention.

In table 4 some of the samples obtained particles percarbonate sodium shows the content of active oxygen and practical properties, which include the duration of dissolution and abrasion. The content of active oxygen was determined by permanentresidence titration. The duration of dissolution was determined by conductometric as the time after which after dissolving 2.5 g of product per liter of water at 20°and stirring the conductivity of the solution reaches 90% of final value. Abrasion ODA is delali in accordance with ISO 5937. The products of examples 6, 10, 16, and 18 did not show when determining the duration of the dissolution tendency to clumping and formed clear solutions. The product from example 19 Komsomolka when determining the duration of dissolution, and even after complete dissolution of percarbonate sodium on the surface of the solution were notable highlight hydrophobic silicic acid.

Table 4

The content of active oxygen in the particles percarbonate sodium and their practical properties
ExampleThe content of active oxygen, wt.%The duration of dissolution in minAbrasion wt.%
6*14,171,53,4
1014,141,53,2
1613,591,4
1813,351,051,2
19*made 13.366,14,2
*Note: example is not relevant to the invention.

From table 4 presents the data clearly follows that proposed in the invention particles percarbonate sodium (example 10) duration of dissolution and pileup the application as a result of abrasion not differ from comparable particles percarbonate sodium (example 6) without finely dispersed oxide on their surface. For obtained as described in WO 95/02724 way of product (example 19) is characterized by a much higher dust generation as a result of abrasion, as well as a longer time of dissolution, in which there is a clumping of particles percarbonate sodium, even after complete dissolution are observed adverse selection contained in the product of silicic acid.

Table 5 shows a specific sieve analysis particle size distribution of samples from examples 6 and 10, with the sample of example 10 differs from the sample from example 6 only in the presence deposited on the surface of the particles in the amount of 0.3 wt.% silica Aerosil®R812. The lack of a small fraction with particle size less than 0.3 mm indicates that deposited on particles of percarbonate sodium silicic acid Aerosil®strongly linked to their surface.

Table 5

The results of sieve analysis particle percarbonate sodium
Granulometric fraction in mmThe content of the granulometric fractions in wt.%
Example 6*Example 10
less than 0.100
0,1-0,20,10
of 0.2-0.3 0,10
0,3-0,42,31,8
0,4-0,524,416,1
0,5-0,622,821,0
0,6-0,722,925,7
0,7-0,8the 11.614.4V
0,8-1,010,614,0
1,0-1,254,56,0
1,25-1,40,60,7
1,4-1,60,20,2
more than 1.600,1
*Note: example is not relevant to the invention.

For the samples of examples 15, 18 and 19 were determined, in addition, their suitability for storage in the hopper, measuring the degree of compaction of the particles as a function of time Jenike method described in EP-863842 on p.5, lines 20-38. A measure of the mobility of the bulk material after storage under the influence of compressive loads, characteristic for the storage of bulk materials in the hopper, is a measure of the mobility of the ffc. Bulk materials with higher mobility ffc exhibit reduced degree of compaction over time and be less prone to caking and even after longer storage in the bunker still retain the ability is obodno to precipates. Presented in table 6, the results indicate that the proposed invention the particles percarbonate sodium (example 18) as compared with particles of percarbonate sodium (example 15) without finely dispersed oxide on their surfaces are less prone to compaction over time and thus have better mobility and suitability for storage in the bunker, then obtained as described in WO 95/02724 way the product (example 19) have shown an increased tendency to compaction over time and thus has the worst mobility and worst suitability for storage in the bunker.

Table 6

The degree of compaction of the particles percarbonate sodium as a function of time
ExampleThe mobility rates ffc method Jenike
Without storageAfter storage for 1 dayAfter storage for 7 days
15*771515
18612323
19*199,37,7
*Note: example is not relevant to the invention.

In table 7 the results of the of spitoni in a climatic chamber, the purpose of which was to determine the stability of percarbonate sodium storage in the composition of commercially available universal detergent. For the tests in the climate chamber percarbonate sodium mixed with besfosfatnye zeolite-containing detergent and TIED as activator in an amount such that the content of TAED in the mixture was 5 wt.%, and the content of active oxygen was about to 2.35 wt.%. Washing powder contains the following components (in wt.%):

anionic surfactants12
non-ionic surfactants8
zeolite And36
soda10
sodium silicate3
the rest (including moisture)31

800 g of the mixture is kept in a climatic chamber at 35°C and 80%relative humidity in a commercially available impregnated with water-repellent agent and a sealed packet E1 for packing washing powder. After 4 and 8 weeks of climatic chambers extract the package in the usual way and method permanentresidence titration to determine the concentration of active oxygen. On the basis of the scientific research Institute of a certain way of OA content and data about the original content of OA compute the relative residual content of OA after 4, respectively 8 weeks.

In example 20 was used particles percarbonate sodium is larger than 0.4 mm, coated with 6 wt.% sodium sulfate. In example 21 was used proposed in the invention particles percarbonate sodium, the surface of which is in addition to the same shell that had the above particles percarbonate sodium from example 20 was applied gidrofobizirovannym silicic acid Aerosil®R812 in the amount of 0.5 wt.%.

Table 7

Stability percarbonate sodium when stored in a generic detergent
ExampleHighly dispersed oxideRelates. the residual content of OA after 4 weeks as %Relates. the residual content of OA after 8 weeks %
20*no9586
210.5 wt.% Aerosil R8129888
* Note: example is not relevant to the invention.

In table 7 the results indicate that the use proposed in the invention particles percarbonate sodium as a bleaching component in the detergent reduces p is compared with particles of percarbonate sodium without fine gidrofobizirovannogo oxide on their surface loss of active oxygen during storage of the detergent.

1. Particles percarbonate sodium with bleaching effect, characterized in that they contain on their surface gidrofobizirovannym highly dispersed silicon oxide, in amounts of from 0.01 to 1 wt.%.

2. Particles percarbonate sodium according to claim 1, characterized in that gidrofobizirovannym highly dispersed oxide is gidrofobizirovannogo pyrogenic or precipitated silicic acid.

3. Particles percarbonate sodium according to claim 1 or 2, characterized in that the average particle size gidrofobizirovannogo highly dispersed oxide is less than 20 microns.

4. Particles percarbonate sodium according to claim 1 or 2, characterized in that they have an average size of from 0.2 to 5 mm, preferably from 0.5 to 2 mm.

5. Particles percarbonate sodium according to claim 1 or 2, characterized in that they are mostly spherical in shape with smooth surface.

6. Particles percarbonate sodium according to claim 1 or 2, characterized in that they are obtained by using spray granulation in the fluidized bed.

7. Particles percarbonate sodium according to claim 1 or 2, characterized in that they have at their core percarbonate sodium membrane, which, as a main component contains one or more hydrate forming inorganic salts.

8. Particles percarbonate sodium according to claim 7, wherein forming the hydrate of norgani the mini-Sol, respectively forming a hydrate of an inorganic salt selected, respectively, selected from the group including sodium sulfate, sodium carbonate, sodium bicarbonate and magnesium sulfate, and mixtures and mixed salts of these compounds, preferably represents sodium sulfate.

9. Particles percarbonate sodium according to claim 7, characterized in that the proportion of the shell particles percarbonate sodium varies from 1 to 20 wt.%, preferably from 2 to 10 wt.%.

10. Particles percarbonate sodium according to claim 7, characterized in that they have, on top of the form containing the inorganic hydrate salt shell second shell, which as a main component contains an alkali metal silicate with a modulus SiO2to M2(M denotes an alkali metal)in excess of 2.5.

11. Particles percarbonate sodium of claim 10, wherein the second shell is marked with Foundation or nabrasyvaniem aqueous solution containing alkali metal silicate in a concentration of from 2 to 20 wt.%.

12. A method of obtaining particles percarbonate sodium according to one of claims 1 to 11, characterized in that the particles of percarbonate sodium, optional with one - or multi-layer membrane, mixed with 0.01 to 1 wt.% gidrofobizirovannogo highly dispersed silica.

13. The method according to item 12, characterized in that the particles percarbonate soda which I dry mixed with gidrofobizirovannym highly dispersed oxide.

14. The method according to item 12 or 13, characterized in that the average size of the particles percarbonate sodium ranges from 0.2 to 5 mm, preferably from 0.5 to 2 mm, and the average particle size gidrofobizirovannogo highly dispersed oxide is less than 20 microns.

15. The method according to item 12 or 13, characterized in that the particles of percarbonate sodium for their mixing with gidrofobizirovannym highly dispersed oxide is dispersed in the gas phase.

16. The method according to item 15, wherein gidrofobizirovannym highly dispersed oxide admixed to the particles percarbonate sodium gravity pipe or conveyor with a fluidized bed of particles.

17. The use of particles percarbonate sodium according to one of claims 1 to 11 as a bleaching component in otbelivayushe, detergent or detergent.



 

Same patents:

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

The invention relates to catalytic bleaching of substrates, for example, subjected to washing fabrics, atmospheric oxygen or air

The invention relates to a method of stabilizing insoluble colorant containing hypochlorite compositions intended for bleaching fabrics and hard surfaces

The invention relates to an improved method for producing a detergent in the form of a gel and can be used for cleaning sanitary products, boiler equipment, household and industrial premises

The invention relates to detergent-disinfectants and can be used for sanitization underground maintenance, cleaning and disinfection of milking machines with a long pipeline
Cleaner // 2194071
The invention relates to household chemicals and can be used for cleaning cookers, sinks, tubs, toilets, tile, plastic

The invention relates to pre-treatment of contaminated tissues, to compositions suitable for use in pre-processing and pre-processing

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: household chemical goods.

SUBSTANCE: invention relates to solid molded detergent compositions for cleaning hard surfaces, washing of textiles, or for personal hygiene. Cleaning agent contains 5 to 95% active detergent, 0 to 90% inorganic substance particles or other common ingredients, and at least 5% water. Outside surface of cleaning agent is covered by at least one polymer film formed by radiation hardening of polymer composition capable of being hardened under irradiation.

EFFECT: improved strength characteristics and imparted preservation of shape and integrity of cleaner lumps on prolonged contact with water.

22 cl, 6 tbl, 6 ex

FIELD: household chemical goods.

SUBSTANCE: cleaning agent contains 5 to 95% active detergent, 0 to 90% inorganic substance particles or other conventional components, while outside surfaces of agent are closed by protection coating in the form of film having thickness between 5 and 1000 μm and at least one side of cleaner is uncoated. Film is prepared from one or more materials with melting points above 30°C. Coating materials are essentially water-insoluble and water-resistant, are adhered to outside surface of cleaner, and are capable or being removed in time of use. These materials are selected from: (a) naturally occurring or modified natural polymers with water vapor permeability factors below 5000x10-13 [cm3][cm]/[cm2]sec[Pa] and (b) synthetic polymers with water vapor permeability factors below 1000 x10-13 [cm3][cm]/[cm2]sec[Pa], where cm3 relates to volume at 273.15K and pressure 1.013x105 Pa. Advantageously, coating material is a polymer material capable of being polymerized or hardened under the action of heating, ultraviolet, and electron beam irradiation.

EFFECT: improved strength characteristics and imparted preservation of shape and integrity of cleaner in use time.

12 cl, 1 dwg, 5 tbl, 5 ex

FIELD: fat-and-oil industry, in particular production of cosmetic soaps.

SUBSTANCE: claimed cake of soap includes fat acid-based soap, anionic surfactant other than soap, latent acidifier, and water in specific component ratio. Acidifier is selected from organic or inorganic compounds or mixtures thereof, or complexes which releases no gas under pH alteration. Moreover acidifier is used in amount effective to produce delta-pH in aqueous suspension more 0.5.

EFFECT: soft for skin cosmetic soap useful in human body cleaning.

29 cl, 7 tbl, 3 ex

FIELD: soap industry, in particular detergents.

SUBSTANCE: claimed bar of soap contains 10-50 mass % of anionic surfactant; 5-30 mass % of fat acid-based soap; 2-20 % of hydroxyacid salt, and 1-15 mass % of water. As hydroxyacid salt substances of general formula (Ra)(Rb)C(OH)COOM are used, wherein Ra and Rb represent H, F, Cl, Br, alkyl, aralkyl, or aryl groups of saturated or unsaturated, isomeric or non-isomeric, linear or branched, chain or cyclic form containing from 1 to 25 carbon atoms, or OH, CHO, COOH and C1-C9-alkoxy group; M represents organic base or inorganic alkali. Bar of soap is extruded at the rate of at least 150 g/min in laboratory scale extruder. Bar of soap also contains calcite filler wherein ratio of calcite filler and hydroxyacid salt is 0.75:1-2:1 or more.

EFFECT: bars of soap having plasticity necessary for extrusion, having no excessive softness, adhesiveness, hardness, and fragility.

5 cl, 1 tbl, 4 ex

FIELD: mineral fertilizers.

SUBSTANCE: invention relates to ammonium nitrate-based fertilizer manufacture and consists in treatment of ammonium nitrate granules with solution containing chemical reagent and inert component, the former being potassium sulfate aqueous solution, with which prilled ammonium nitrate granules are treated at 40-50°C followed by treating granules with phosphogypsum (inert component) having moisture content 2-3% and grinding fineness no larger than 30 μm until its percentage in the granules attains 1-20%.

EFFECT: preserved high strength of ammonium nitrate granules at greater number of thermal cycles at temperatures 20 to 50C and increased temperature resistance.

3 cl, 1 tbl, 6 ex

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