The method of obtaining the bleaching compositions containing sources of chlorine and bromine, and its product

 

(57) Abstract:

The invention relates to methods for alkaline bleaching compounds - products designed for cleaning hard surfaces, bleaching, and disinfecting. This method consists of at least three stages, including in sequence: (1) the stage of pre-synthesized, (2) the stage of adding prosteradlo connection, and (3) the stage of stabilization of the product. The product obtained above, includes specific sources bleaching chlorine and bromine and specific amidofunctional compounds such as sulfamate with low content of impurities. The technical result - the receipt of the products, with high efficiency of bleaching and disinfection, and reduced aggressiveness in the application. 2 S. and 19 C.p. f-crystals, 1 Il.

The invention relates to methods for alkaline bleaching compositions of the products are useful to consumers, especially for cleaning hard surfaces, bleaching or disinfection. The products contain sources as chlorine and bromodomain bleaching compounds. The method includes the sequence of mixing and the selection of the initial ingredients, solid surfaces, bleaching and disinfection are well-described known consumer products. They are used for processing all types of contaminated surfaces, kitchens, bathrooms, sinks, tubs, toilets, showers and counters (counter tops).

It is known that these consumer products include hypochlorite bleach. Hypochlorite is desirable due to the high efficiency of its bleaching and disinfecting action. However, it has several disadvantages, including the fact that he can sometimes show increased aggression tends to leave in the hands of an unpleasant smell and is not always stable when stored in the composition of consumer funds.

Brominated compounds used for bleaching and disinfection in special cases. However, they usually are more expensive and often more demanding in terms of storage conditions than chlorinated analogues.

Sulfamic acid is also used as a cleaning agent, especially in the acidic cleaning compositions with a high concentration of acid.

Chemistry sulfamethazine systems with Halogens is extremely complex, and research in this area continue meets the need for cleaning hard surfaces bleaching and disinfection, suitable for use by consumers and improved in relation to one or more of their properties, including the achievement of greater efficiency as bleaches and disinfectants, less aggressiveness, ability to leave in the hands of a very weak or even a pleasant smell and have a high storage stability.

Accordingly, this invention provides an improved method of making such compositions and thus protects these alkaline bleaching compositions.

The described method has several advantages, including the fact that it is easy to manage and is safe and effective to achieve the desired goals. Surprisingly, it receive the products that are truly superior to the compositions obtained by the use of numerous other sequences of mixing.

Prior art

Patents US 3583922 and CA 860279 And describe solid composition for the rapid removal of stains tanimowo acid having a pH value not lower than the 10.5 consisting of 0-95% abrasive, up to 10% surfactant, 0 to 60% alkaline amendment, sustainable connections, preferably, chlorinefree preferred ratio of chlorine to sulfamic acid from 500 to 1:1, preferably from 3:1 to 6: 1, optionally with additives. Such additives may include bromides, flavors or borax (sodium tetraborate). The compositions can be used for cleaning sinks or mechanical washing.

Patent JP 63108099 describes a bleaching agent for controlled odor of chlorine containing hypochlorite and sulfamic acid in a specific ratio and/or sulpham and agents that support pH. This ratio represents 2-8 wt.% hypochlorite, based on the number of active chlorine" (see below), and is the ratio of 0.25 moles of sulfamic acid and/or sulpham to 1.5 moles of hypochlorite.

Patent JP 63161088 And describes the whitening composition to tissue, comprising mainly hydrogen peroxide and sulfamic acid and/or water-soluble sulpham and gipogalaktiyu acid and/or water-soluble gipogalaktiyu salt, such as NaClO, Ca(OCl)2, bleaching powder or NaBrO; sulpham is present in the amount of 0.5-5 moles per mole of hypokalaemia.

Patent US 4992209 describes bactericidal, fungicidal system having nitidulinae corrosion inhibitor, for example, chilled system, prepared by the reaction of NaBr with NaOCl or Cl2"ptx2">

Patent US 5431839 describes cleaning/sirusa compositions comprising heteropolysaccharide thickeners. Patent US 5047164 describes compositions containing megalogenis compounds and acids, specially adapted for cleaning and disinfection of equipment dairy and food industry. Patent US 4279764 describes encapsulated bleaches, including stable during storage chlorinated isocyanates. Patents US 4233173 and US 4201687 describe the composition of surface-active substances containing chloromethanesulfonyl whitening agent. Patent US 5470499 describes thickened abrasive water cleanser with improved ability to washout. Widely known patent US 4051056 describes abrasive cleanser compositions with perlite and hypochlorite bleach. Widely known patent US 3715314 describes cleansing disinfectant compositions. Patent US 5384061 describes stable, thickened aqueous bleaching compositions comprising chlorine bleach and Pytalovo (phytic) acid. Industrial use of sulfamic acid are described in the literature, for example, Inorganic Sulfur Chemistry", G. Nickless, Ed. , Elsevier, 1968, Chapter 18 "Amido - and Imido - sulphonic acids", 607-667, and cited references; see also Kirk Othmer "Encyclopedia of Chemical Technology", 3rd Ed., Wiley - Encyclopedia of Chemical Technology", 4th Ed. vol 5, page 911-932; see also the relevant Chapter in the 3rd edition of the same encyclopedia. Chlorine gas was pre-mixed with solutions containing sulfamic acid: see Korshak et al., Zh. Obsch. Khim., vol 18 (1948), pages 753-756, but the mixture was decomposed.

The invention

The present invention includes a method of obtaining alkaline bleaching composition, preferably aqueous liquid bleaching composition, the method contains at least three stages. These three stages occur in sequence: (I) the stage of pre-synthesized, (II) the stage of adding prosteradlo connections, and (III) the stage of stabilization of the product, and each of these stages has at least one mixing operation.

In the specified manner, specified stage of pre-synthesized (I) includes the operation (a) mixing in any order components, including sources of hypochlorite and amidofunctional compounds containing stable N - halide group; thus is formed a mixture of stage (I); if this process is carried out so that by the end of this stage a preliminary synthesized the mixture of stage (I) had a pH value not exceeding about pH and includes the operation (b) mixing in any order prosteradlo connection with the specified mixture of stage (I): thus is formed a mixture of stage (II); the phase stabilization of the product (III) includes at least one operation (C) mixing in any order with a mixture of stage (II) alkali in a quantity sufficient to achieve a final pH value of the product of the above method, at least about 13.

The product obtained in this way has unique properties, manifested in a great otbelivayushe action and, at the same time, providing a minimum "the smell of bleach on the skin. The preferred product is a clear yellow aqueous liquid, which may be optionally thickened and/or flavored.

All percentages, ratios, and proportions herein are given on a mass basis, except where specifically noted.

A brief description of the drawings.

Fig. 1 is a schematic view of the proposed method, showing the transformation of raw materials (ingredients) in the product as a result of a series of stages, comprising, in sequence, Stage (I) Stage (II) and Stage (III). Each stage, as shown, includes one or more operations. Stage (I) includes a significant operation, namely the Operation (a). Stage (II) vkluchu (C). The proposed method in the most simplified form, which can be recreated in the drawing, consists of a sequence of three operations, in which after (a), (b) and after (b) implies (c). Each of the major stages and operations, as well as suitable ingredients and product features, described in detail below.

Detailed description of the invention

In accordance with the present invention it was found that in order to obtain an alkaline bleaching composition having excellent technical characteristics and needs of consumers, it is necessary to ensure the presence of two specific types of halogen-containing ingredients, including at least one with at the beginning of the form prosteradlo connection, and at least one having at the beginning of the form gipoholesterinova connection. It was also found especially significant to select and enable certain amidofunctional connection and to create a certain way, especially in parts of the sequence of mixing, to obtain a useful product.

Alkaline bleaching compositions

Thus the present invention relates to methods for alkaline bleaching compositions and products on their on cnie bleaching compositions according to this invention have a pH value of at least about 13, and made from ingredients contains the source hypokalaemia and promotergene connection along with at least one specially selected amidofunctional connection. Alkaline bleaching compositions according to the present invention are useful for consumers as a means for cleaning hard surfaces, bleaching or disinfection. They may, generally, be any suitable physical form, such as granules, tablets, paste, gel or liquid form, and may be aqueous or nonaqueous. However, the method according to this invention is particularly well adapted for the production of aqueous alkaline liquid or gel bleaching compositions: technical problems in the production of such compositions are the greatest. Except as expressly provided herein, the embodiments of the present invention, which illustrate the method and product according to the invention it is, therefore, to the aqueous liquid forms.

Stage of the way

The method according to this invention typically includes at least three stages:

(I) the Stage of pre-synthesized;

(II) the Stage of adding prosteradlo connection and

(III) Stage of stabilization of the product.

Stage is carried out in the order (I), then nfiguration the method includes at stage (I) operation (a); at stage (II) operation (b) and stage (III) operation (c). Additional operations, such as adding and/or mixing of other ingredients, such as perfume, surfactant and the like, can be introduced before or after any of the essential operations in such a way that they will not affect the designated sequence of essential operations and, in addition, that they will be compatible in relation to the requirements for pH, disclosed in this specification.

More stage (I) stage pre-synthesized is the stage for putting a source of hypochlorite and special amidofunctional connection; stage (II), stage add prosteradlo connection is the stage for the introduction of prosteradlo connection; and stage (III), the stage of stabilization of the product is the stage to stabilize the product by increasing the pH value.

Thus, the present invention includes a method of obtaining alkaline bleaching composition, and the method comprises at least three stages, comprising the sequence: (I) the stage of pre-synthesized, (II) the stage of adding prosteradlo connections, and (III) the stage of the om specified stage of pre-synthesized includes the operation (a) mixing in any order components, including sources of hypochlorite and amidofunctional compounds containing stable N-halide group; thereby forming a mixture of stage (I); and the process is carried out so that by the end of this stage a preliminary synthesized, the mixture of stage (I) had a pH value not exceeding about 11, the specified stage add the brominated compounds (II) begins at the specified pH and includes the operation (b) mixing in any order prosteradlo connection with the specified mixture of stage (I); thus is formed a mixture of stage (II); and the specified stage of stabilization of the product (III) includes at least one operation (C) mixing in any order with a mixture of stage (II) alkali in a quantity sufficient to achieve a final pH value of the product of the above method, at least about 13.

Particularly preferred methods according to this invention are limited relative to that moment can be added promotergene connection. In preferred ways no other stage than the stage (II), and no operations other than the operation (b), which add promotergene connection. Surprisingly it was found that adding prosteradlo connections, navigate to operations of way

The present method may include various optional operations. Optional operations that may be useful in this invention, illustrate operations such as the operation of the dilution included in the method after the completion of stage (III). This operation, as dilution, can be effectively carried out or by the manufacturer or user of the product stages (I), (II) and (III). In General, the operation of dilution may be included in stage (I) stage (II) or stage (III) of the present method, although it is preferable to avoid dilution at these stages. Usually, for better stability during storage, the operation of dilution is not the plant, but rather a consumer that uses the composition. Dilution may be seen in the deviation of the pH value, usually in the lower pH.

Other optional operations useful in this invention include the operation of adding a surfactant or the operation of adding or mixing of any suitable optional component, such as the components shown below, in the section "optional ingredients".

The equipment for implementing the method

Any suitable equipment may be used for the asset is increased to the halogen bleach and strongly alkaline conditions, preferably the use of devices that are connected by lines from plastics and/or borosilicate glass, as for long-term use, and to reduce contamination of the product metal. The reactors should not be designed to work at high pressure, but should be provided with suitable ventilation. Mixing of the ingredients can be carried out using any suitable mixer, such as a blade driven by the motor. Alternatively, to provide recirculation flow solution of the product of the mixing process, can be used centrifugal pump. Another useful equipment for the method according to this invention includes equipment for removing vapor from the working space. Such equipment includes standard scrubbers, etc.

Conditions of implementation of the method

Temperature

Generally, the present method can be carried out in a wide temperature range. Preferably, each of these operations (b) and (c) is conducted at a temperature in the range from about 5oC to about 80oC, preferably from about 10oC to about 45oC, more preferably about room temperature, for example, about 20o

The pH values

This method requires special restrictions on the change of pH values. There is a General requirement that in late stage pre-synthesized and in the early stages of synthesized, the pH value of the mixture of stage (I) did not exceed the value of about 11. In the preferred embodiment of this pH value not greater than about 8, more preferred it is within the range from about 1 to about 6.9.

In preferred embodiments of the invention from the end of stage I, the entire method is carried out at increasing pH values. This increase pH, preferably, corresponds to the value of dpH/dt, at least about +0,1 pH units/min, preferably about 0.5 pH units/min or higher.

It should be understood that in such embodiments of the method, the method, in General, has a minimum pH value. The position of this minimum in the entire sequence of the proposed method is at the end of stage (I).

Pressure

The proposed method can be carried out at any convenient pressure. For example, chlorine gas and alkali can react under pressure in stage (I is to be carried out at atmospheric pressure or even under reduced pressure, if you use scrubbers or refrigerators for collecting residual halogen. The preferred methods is performed at atmospheric pressure.

Time

The proposed method can be implemented as a periodic or continuous. Until and unless specifically noted, the illustrations of the way in this description to refer to the periodic method. The time required to complete periodic way can, in General, very different. Typically, the time from about 5 minutes to about 1.5 hours is typical for each of the stages (I), (II) and (III). In preferred embodiments, step (II) is at least as much time as is required for essentially complete dissolution prosteradlo connection before processing stage (III). Also preferably, stage (II) continued, until you see the yellow color of the mixture of stage (II). In General, the longer the time, the method associated with methods with large scale production. This description is preferred to minimize the total reaction time, and, in particular, when the separation stage (II) sufficient time to continue the process without delay from this stage to the end stage (III). Moreover, h is at the end of the operation (b) and the beginning of the operation (c).

Concentration and concentration ratio

The proposed method can be implemented in a wide range of concentrations of ingredients in the water. In a preferred embodiment the method is characterized by the dilution factor, the total for all stages following the stage (I) of not more than about 2. In General, the concentration of the ingredients set such that the product of stage (III) contain from about 0.01% to about 10% active chlorine. Furthermore, in units relative proportions of ingredients, the proposed method, preferably, based on megalogenis the ratio [Br]: [OCl-] from about 10:1 to about 1:10, preferably from 1: 2 to 1:5, where [Br] represents the total number of moles of Br added to the specified process from the specified prosteradlo connection, and [OCl-] represents the total number of moles of hypochlorite added to the specified process from the specified source of hypochlorite. Moreover, in preferred methods according to this invention using the ratio of amine-halogen [A] : [X] from about 10:1 to about 1:10, where [A] represents the total number of moles of amino groups specified amidofunctional compounds used to form the composition, and where [X] predstavlenie chlorine.

Most preferably, if the specified ratio of amine-halogen is from about 1.0:1.0 to about 1.5:1.0 in.

To illustrate that, as the above quantities, sulfamic acid, which contains one amino group per mole of the compound can be easily identified in the above equation: [A] is simply the number of moles of sulpham; but in the other illustrations when using melamine, [And] represents the number of moles used melamine, multiplied by the number of moles of amino groups (in which the melamine 3) contained in each mole of melamine.

Ingredients

Sources of hypochlorite

In General, the proposed method can be applied to any suitable source of hypochlorite. The preferred sources of hypochlorite sources are selected from chlorine, hypochlorous acid, hypochlorites of alkali metals, alkaline earth metal hypochlorites, food mixing hypochlorite-releasing compounds with aqueous alkali and mixtures thereof. Suitable hypochlorite-releasing compounds, in light of the above, as an illustration, can be dichloroisocyanurate acid and its sodium salts and hydrates, which are fast enough gidrolizuemye choose hypochlorites of alkali metals and products mixing these hypochlorite-releasing compounds and aqueous alkali.

Amidofunctional connection

From the thousands available amidofunctional compounds in the present invention selected a limited number of compounds which have been found are valid. In the methods according to this invention is suitable amidofunctional compounds are those that form stable N-halide derivatives. The term "forming stable N-halide derivatives" in this description to determine how "capable of forming N-halogen derivative, which is sustainable, rather than as needed "stable N-halide group" at the beginning of the implementation of the method according to the present invention.

Suitable amidofunctional connection that meets the requirements of the present invention, are selected from (I) primary amidofunctional compounds selected from sulfamic acid, sulfamate alkali metals, sulfamates alkaline earth metals, sulfamates of tetraalkylammonium and mixtures thereof; (ii) secondary amidofunctional compounds selected from derivatives of secondary amines having the formula RR'NH or (R)2NH, where R,R' and R" are organic groups in which the carbon atoms indicated organised, iminodiacetate, benzosulfimide, alkylsulfonamides and mixtures thereof; (iv) melamine, cyanamide; and (v) mixtures thereof.

Suitable secondary amidofunctional of compound (ii) include such compounds, which are not specifically defined in groups (i), (iii), (iv) and (v) in which R,R' and R" independently represents a C1-C12linear saturated and C3-C12branched saturated group which may be alkyl, aryl or heterocyclic, optionally substituted residues of carboxylic acids or carboxylates: an example of the latter carboxyamide derivatives are alpha aminobutyrate. Preferred secondary amidofunctional connection, as is known, is used as a disinfectant, especially those that are water soluble and contain N - halide group, are relatively insensitive to shock.

In other words, we must assume that the method according to the present invention can be successfully applied in the case, if amidofunctional connection is the hydrolysis constant, K, defined by the equations:

K=[HOCl][RNH2]/[RNHCl],

or K=[HOCl][RR'NH]/[RR'NCI],

or K=[HOCl][(R)2NH/[(R)2NCl]

in the range is cyanurate the essential amidofunctional connections.

Hydrolysis constants, such as the above, well known in this field and are defined in the usual way. See, for example, "Encyclopedia of chemical technology", Kirk Othmer, 3rd Ed., vol. 5, in an article entitled "Chloramines and bromamines, especially page 567, "Encyclopedia of chemical technology", Kirk Othmer, 3rd Ed., vol. 3, page 940 - 941, these articles are included in this description as a reference.

In accordance with the requirements set forth above, the preferred secondary amidofunctional compounds may be selected from compounds described in "Encyclopedia of chemical technology", Kirk Othmer, 4th Ed., 1993, pp. 918-925, and include the compounds described under the headings "Organic chloramines and bromamines", "Aliphatic compound", "Aromatic compounds" and "Heterocyclic compounds".

Sulfamic acid or sulpham sodium are the most preferred amidofunctional compounds in this invention.

Alkali

Suitable for the proposed method, the alkali is selected from oxides, hydroxides, carbonates, bicarbonates, silicates, phosphates, borates, alkali metal, alkaline earth metal, tetraalkylammonium, and mixtures thereof.

Brominated compounds

Suitable for this pic is hypobromide, hypobromite acid and mixtures thereof.

The most preferred combination of ingredients

In the most preferred implementation of the method according to this invention, the said source of hypochlorite selected from the hypochlorites of alkali metals and product mixing hypochlorite-releasing compounds and aqueous alkali; specified amidofunctional compound selected from sulfamic acid, sulfamate alkali metals, sulfamates alkaline earth metals, sulfamates of tetraalkylammonium and mixtures thereof: and specified promotergene compound selected from the group consisting of water-soluble bromides. Most preferred is a method, wherein said source of hypochlorite is a sodium hypochlorite specified amidofunctional connection - sulfamic acid, and the specified promotergene compound selected from sodium bromide, potassium bromide and mixtures thereof.

Ingredients or impurities that it is desirable to eliminate

In the method and product according to this invention, it is preferable to limit the presence of certain compounds, which was found to adversely effect on the stability and efficiency of the product. Especially neiasyt stable N-halide derivatives. Such compounds include simple ammonium (NH4+) salts such as ammonium sulfate, urea, amino acids such as aspartic acid and mixtures thereof, each of which may, for example, to produce unpleasant odors or objectionable chloramines. Preferably, in this case, are the ways in which everywhere, and, at least in significant amidofunctional connection, no compounds containing more than about 1% amidofunctional impurity compounds with unstable N-halide derivatives. Translating these requirements into practice, commercially available sulfamic acid of different varieties, some of them may contain as impurities urea.

It was found that crystalline grade sulfamic acid, in which the minimum impurity content of urea is preferred in the method according to the present invention. In other embodiments of the method, the method according to the present invention carried out using the original materials, all of which are water soluble, i.e., this excludes insoluble materials, such as abrasives, excluding thus any tendency for the decomposition of bleach, rolled the eyes or the base can be used in the method according to this invention, as agents, establishing pH to increase, and any suitable acid can be used in the present invention as a pH setting agent to lower the pH; it should always be ensured that such alkali or acid did not react with gipohloridom. Preferred alkali to bring the pH include water-soluble alkali, such as sodium hydroxide, potassium hydroxide or mixtures thereof, and the preferred acids include conventional mineral acids such as sulfuric, hydrochloric or nitric, although sulfuric acid is preferred in this group. Alternatively, you can use a relatively weak acid; these include acetic acid.

Examples of bases that will be completely excluded from use in the method according to the present invention experienced staff is ammonium hydroxide, because of its chemical reaction with the other essential ingredients of the method used for purposes other than the change in pH, forming, for example, undesirable type of bleach, when it reacts with hypochlorite.

In General, adding any simple mineral acids or bases in the method according to the present invention should thus chromowanie sulfamic acid as amidofunctional connections adding mineral acid is carried out at sufficiently diluted, to avoid decomposition of sulfamic acid. It is known, for example, concentrated nitric acid decomposes sulfamic acid at a concentration of HNO373%, especially at elevated temperatures, with the formation of nitric oxide, and this combination of concentrated mineral acid and high temperature is not allowed in this way.

Water

The water used for the preparation of liquid compositions according to the present invention, is a suitable city water. In General, hard, soft, softened or deionized water can be used. Distilled or received reverse osmosis water is particularly desirable. When using water of uncertain quality, for example, iron containing water or water with high content of manganese from drilled wells, it is desirable to reduce the content of dissolved metal using a suitable method of water treatment, for example, oxygenlive, filtration, and sedimentation. Moreover, for processing water for this method can be used complexing or binding agents. Wisely to keep or to periodically check, and if necessary, to reduce the content is known, affect the stability of the bleaching products. Appropriate methods of analysis are atomic absorption spectroscopy or inductive plasma spectroscopy (ICP).

Measurement of pH

the pH in this invention is measured using a glass electrode or a combined electrode, such as Coming General Purpose Combination electrode Cat. N. 476530, and commercial pH meter, such as f-40 pH meter company Beckman.

Changing pH

Preferably, and as is now well known, and, of course, characterizes the proposed method, that should be a constant decrease of the pH value ("constant change" means in this description relative to the linear increase or decrease in pH over time), followed by a constant increase of the pH value, so that there is a distinct minimum in the pH values, as indicated in the description of the method. In the later stages of the method, as mentioned above, the constant increase in the pH value, measured as dpH/dt, is characterized by a specific range of values and is probably related to the stability and efficiency of the product.

Measurement of the whitening ingredient: Active chlorine

The term "active chlorine", sometimes abbreviated to "AvCl2"use the th Wiley-interscience.

These reactions produce the oxidant of chlorine:

< / BR>
< / BR>
< / BR>
< / BR>
The total concentration or the quantity of any given oxidant chlorine-based often expressed on an equivalent basis as if all the oxidants were chlorine. Active chlorine is thus equivalent to the concentration or amount of chlorine required for the formation of an oxidant, for example, in accordance with the above reactions, and can be measured by conventional methods, such as iodometric methods discussed in Kirk - Othmer (link above).

Active chlorine can be calculated using the following relationship:

Active chlorine(%) =

70,9 x moles of oxidizing agent x (the number of active Cl atoms in the molecule) x 100

In the ratio above, the term "active Cl atoms" needs explanation: because the molecule Cl2only accepts two electrons, as well as HOCl and monochloramine, it contains only one "active" atoms Cl in accordance with this definition.

When determining the content of active chlorine, expected in the product during the implementation of the method, the above ratio should be replaced by "moles of oxidant" to "the total number of moles of halogen bleaching for bleach, in fact, the hypochlorite solution is not formed, for example, in bromoderma the bleach and other bleaches, chlorine, replacing the number of accepted electrons divided by two, the number of active chlorine atoms, in the ratio above. In addition, it can be defined also in the iodometric titration.

Note also that the "active chlorine" is measured in dimensionless percentages and not in the interest of the masses. It should be clear from the definition that, in fact, it is possible to obtain the value of "active chlorine" that is greater than 100%; this can occur if chlorine bleach is more effective by weight than Cl2given that only one chlorine atom in the molecule Cl2refers to chlorine bleaching; however, these concentrations do not occur in the method according to the present invention.

The number and relations ingredients

In General, quantities and concentrations of ingredients in the water in this invention can greatly vary; however, there is a special preference to the ratio of halogen, as already noted in this description, and which is commercially attractive to use ingredients such as sodium hypochlorite at the most is ALOS, the present invention has significant advantages, such as improved bleaching. Under the "whitening" is to be understood that the composition obtained by the method in accordance with the present invention, shows the best efficiency of bleaching under the action otbelivajushaja impurities, such as stains from tea, compared with the effectiveness of bleach that has the same composition prepared by another method, for example, by a method that includes many different orders of mixing or adding ingredients. It is important that along with improved bleaching properties of the product obtained in this way, leaving a low residual odor on the skin and is softer than other products, obtained different way by a different choice of ingredients and/or the order they were added. In short, the combination of overall efficiency and desirable soft safe exposure to skin /aesthetics, in accordance with the present method, allows us to assert that there is a real superiority of it in comparison with other, known from the prior art methods

Product features

The product in accordance with the present invention in General not livadnyi liquids or aqueous gels. Another possible form of the product, is preferred for this invention, is to form rapidly soluble solid concentrate or form rapidly soluble tablets. Such product forms do not contain abrasives. The product in accordance with the present invention preferably transparent and, as described elsewhere in the present description, can be painted and have a pleasant smell.

The introduction of optional ingredients

The method in accordance with the present invention and its product allow for the presence of at least one additional transaction mix, in addition to a significant minimum (a), (b), (c); during which adds an ingredient selected from the group consisting of surface-active substances (surfactants), buffers, binders, chelates, perfume fragrances, agents, giving color, colorants, stabilizers, brighteners, pigments, defoamers, antilocapridae and/or anticorrosion agents, agents, suspensorysex pollution, antibacterial agents, sources of alkali, hydrotropes, antioxidants, agents that removes /prevents the deposition of clay-like dirt, thickeners, solvents, and mixtures thereof.

In other obliged patent relates to solid compositions, which differ from liquids according to the present invention.

Other types

In accordance with the present process can be entered perfume and agents, to give the color, the most preferred famous resistant to bleaching of the dyes, such as various yellow; and perfume with citrus or pine scent. It is desirable to substitute for the process of the present invention were hydrophobic, having a relatively high distribution coefficients in the system octanol/water, such as 6 or higher. In the process, it was found desirable to introduce odorants during the operation, which follows (III)(a). Without being limited to theory, we can assume that this reduces the likelihood of a response derived sulpham with giving the smell of aldehydes, in that moment, when they are introduced into the process at the later stages. Also can be successfully combined stable to the bleaching thickeners, such as mentioned in the description of the prior art and/or Laponite , special clay, suitable from Laporte, and/or fatty aminoxide, when using the present process to obtain a product having a wide range of useful properties.

Details about the global ingredients. Such ingredients, as noted, include surfactants, stabilizers, bleach, dyes, foaming agents, defoamers, Antiprotozoal and/or anticorrosion agents, agents, suspendiruemye pollution, antibacterial agents, sources of alkali, hydrotropes, antioxidants, agents that removes/prevents the deposition of clay-like dirt, polymeric dispersing agents and the like and mixtures thereof.

In the process, in accordance with the described invention can be used taken in an amount from about 0.1% to about 95% of the composition of the product surfactant or mixtures thereof, selected from the group comprising anionic, nonionic, amphoteric and zwitterionic surface-active agents. In liquid systems, the surfactant is preferably present in the range from about 0.1% to 20%, with a higher concentration, for example, 30%, namely, viscous gels, aqueous pastes or semi-solid products.

Anionic surfactants in accordance with the present invention may include water-soluble salts, especially alkali metal salts, C8-C22the products of the sulfonation Orot. Useful to use the sodium or potassium alkyl sulphates, especially those obtained by sulfonation C8-C18alcohols, as well as linear or branched alkylbenzenesulfonate, especially C9- C15alkyl substituted forms of the sodium or potassium salts; also used esters of the sodium sulfonates acylglycerides, especially those ethers of higher alcohols derived from tallow or coconut oil; sodium sulfates and sulfonates of monoglyceride coconut oil fatty acids; sodium or potassium salts of esters of sulfuric acid, the reaction product of one mole of higher fatty alcohol (e.g. tallow or coconut alcohol and from about 1 to about 10 moles of ethylene oxide; sodium or potassium salts of sulfate esters of alkylphenolethoxylate with from about 1 to about 10 units of ethylene oxide per molecule, and in which the alkyl groups contain from 8 to 12 carbon atoms; the reaction products of fatty acids derived from coconut oil and sodium or potassium salts of fatty acid amides of methyltaurine, in which the fatty acids, for example, are derived from coconut oil; and sodium or potassium beta-acetoxy-or beta-acetamidomalonate, where the alkane has from 8 to 22 carbon atoms.

In addition, the selected secondary (2,3) surface-active alkyl sulphates used in accordance with the present invention include structures of formulas I and II

CH3(CH2)x(CHOSO3-M+)CH3I

CH3(CH2)y-1(CHOSO3-M+) CH2CH3II,

for 2-sulfate and 3-Sul the formulas I and II, x and (y) respectively are integers of at least about 6 and can be in the range of from about 7 to about 20, preferably from about 10 to about 16. M represents a cation, such alkali metal, ammonium, alkanolammonium, triethanolamine, potassium, ammonium and the like can be used.

The above-mentioned secondary alkyl sulphates such compounds that can be obtained by adding H2SO4to olefins. Conventional synthesis using alpha-olefin and sulfuric acid disclosed in US 3.234.258, Morris, published. 08.02.1966 or US 5.075.041, Lutz, published. 24.12.1991. Carried out in solvents synthesis allows for the cooling translate secondary (2,3) alkyl sulphates in the products after purification, when remove unreacted substances, sulfonated random substances, not sulfonated by-products, such as C10and higher alcohols, secondary the olefin sulfonates, and the like, are usually a mixture with a purity of 90% 2 - and 3-sulfonated products (may contain some sodium sulfate), having a white color, not sticky, apparently, crystalline solid. Some 2,3-disulfate may also be present, but they are usually contained in an amount of not more than 5% of a mixture of secondary (2,3) alkylphosphocholine for use in accordance with the present invention, surfactants are those which have the highest possible whitening stability, including C8-C22fatty aminoxide, such as hexadecyldimethylamine N-oxide or saturated fatty alkylalkoxysilane. Particularly relevant to this invention are those surfactants, which have a high degree of unsaturation, and any surfactant containing nitrogen residues that can react with gipohloridom. Somewhat less problematic, but still difficult, is the use of any of the alcohols. Thus, especially preferred when used alkylalkoxysilane, for example, so-called capped (kupirovanie) form, in which the terminal-Oh group substituted by a group-OCH3or similar directionspanel group.

The most resistant to bleaching and hydrolytically stable surface-active substances can be introduced at various operations of the method according to the present invention, but for convenience, their introduction as a rule, should be carried out so as to reduce the formation of foam, which may not be desirable to slow down the process. To limit the formation of foam is desirable silicone antispyware; such antispyware, commercially available from Dow Corning Corp.

at it can be entered into the product in accordance with the present invention at any time, in which the pH of the mixture of ingredients in excess of about 7, preferably, when the specified pH greater than about 8.

Although the preferred methods and compositions in accordance with the present invention is free from insoluble products and are not abrasive products in accordance with the method of the present invention can be obtained in a solid or viscous semi-solid form, further containing abrasive material such as expanded perlite in combination with surface-active substance, filter material or other optional wash ingredients listed in this description. If necessary, abrasive materials can be selected from those listed in the patent US 4.051.056.

Other optional ingredients in accordance with the present invention may include buffers for pH control of the surface being cleaned and to optimize the efficiency of the cleansing composition of solid surfaces in relation to certain types of dirt and stains. Buffers may also be included to stabilize the additional ing the ranks aesthetic ingredients. Cleaner hard surface in accordance with the present invention optionally contains buffers that help to regulate and maintain the pH from about 13 or in the range of above about 13. Examples of such suitable, but not limiting of buffers are buffers as potassium carbonate, sodium carbonate, trinacria phosphate, and the manufacturer is not limited to the above examples or combinations thereof.

Cleaning composition obtained in accordance with the process of the present invention, it is also desirable to prepare with the inclusion of the systems that control the content of heavy metal ions, in particular, it includes one or more agents to control the decomposition of the bleach caused by soluble, insoluble or colloidal iron and/or manganese and/or copper. Simple but effective agent is sodium tripolyphosphate, not necessarily supported, at least partially polymeric aqueous sodium silicate. Examples of other chelating controlling heavy metals agents are fialova acid and ethane-1-hydroxy-1,1-diphosphonic acid (EHDP), and thus can be used other substances, such as the number of commercial connections factorie not contain alcohol groups, nitrogen groups, reacting with Halogens, and hydrolytically sensitive groups. In the preferred process conditions the introduction of at least a chelating agent or agent, controlling the content of heavy metal ions occurs at the beginning or shortly after the beginning of the process, for example directly prior to or simultaneously with step 1(a). However, when introducing the silicate with the aim of at least partial assistance in monitoring heavy metal ions, it is introduced at a point process, which is removed from the minimum point pH, and the maximum point of the pH process.

Perfume, in case of their use, are usually in concentration from 0 to 5%. Cm. patent US 4.246.129.

The compositions obtained in accordance with the present invention, usually have yellow color. However, it is possible to obtain the preferred solution, which is any other color, for example, by adding resistant to bleach the dye; more preferred solutions can be quickly diluted, and in this case, the yellow color is hard to determine. In terms of the way the dyes are preferably added to the end of the process, and in this case, the resulting product may be more saltiest with the present invention, can be made with varying degrees of viscosity. In one of the embodiments of the present invented obtained in accordance with the present invention, the compositions have a viscosity from about 1 to about 150 centipoise. These structures are suitable for use with bottles of spray. Also, these compositions obtained in accordance with the present invention, can optionally be thickened, for example, by adding more resistant to bleach thickener, such as commercially available DOWAX. Suitable composition in the form of a gel has a viscosity of from about 100 centipoise to about 2000 centipoise, preferably from 300 up to 1000 SDRs SDRs, measured, for example, using techniques and methods described in Physico-chemical methods Reily, J. Rae, W. N.; vol1 (5thed), pages 667-692; D. Van Nostran pub. Thickeners, when they are used in the present process, it is desirable to introduce to the end of the process, for example, immediately after or simultaneously with the stage (III).

EXAMPLE I

(1). Stage pre-synthesized

All operations is carried out at room temperature, about 20oC. 30 grams of distilled water are placed in a chemically inert reaction vessel with a plastic pipe. The vessel is prepared for held the small amount of chlorine gas which should be removed. The vessel will be equipped with an inert plastic-covered paddle stirrer. Under stirring at a speed of 300 rpm type of 13.05 grams of aqueous sodium hypochlorite containing of 10.73% active chlorine. Immediately after that add sulfamic acid (2,2 grams, Aldrich, 99,3 %, crystalline) with continued stirring while adding the solid has dissolved. At this point the pH of the mixture of stage (1) is about 1.0.

Stage add prosteradlo connection

To stir the mixture of stage (1) was added sodium bromide (0.5 g, EM SCIENCE). The mixture is stirred until dissolved introduce solid (about 5 minutes) and will not appear yellow. At this point the mixture can be identified as a mixture of stage (II).

(Ill) the stage of stabilization of the product

To stir the mixture of stage (II) is added sodium hydroxide (about to 3.0 grams, 50 % in water) until the pH of the mixture will not be about 13,2.

Water is added until the total weight of the mixture of stage (III) reaches about 100 grams.

EXAMPLE II

The process of example I is repeated with the following differences: the Scale of operations increases 1000 times. At the preliminary operations gaseous TA sodium miss in the above-described reactor, placed in a bath, where it is treated with sulfamic acid, with formation of a mixture of stage (1). Operations following stage (1) is carried out analogously to example I.

EXAMPLE III

The process of example II is repeated with the following differences: sulfamic acid is replaced by sulpham sodium.

In the examples below, the highlighted line separates the associated separate stages (I), (II) and (III) of the process.

EXAMPLE IV

The process of example III is repeated with the following differences: until the completion of stage 1 was added aqueous hydrochloric acid to lower the pH to around 7.0.

Examples V - IX is given at the end of the description.

1. The method of obtaining alkaline bleaching composition, characterized in that it consists of at least three stages including them in sequence (I) stage pre-synthesized, (II) the stage of adding prosteradlo connections, and (III) the stage of stabilization of the product, with each of these stages includes at least one mixing operation, and the stage of pre-synthesized (I) includes the operation (a) mixing in any order components, including sources of hypochlorite and amidofunctional connection is carried out so that in late stage pre-synthesized mixture of stage (I) has a pH value not exceeding about 11, and stage add prosteradlo of compound (II) begins at the specified pH and includes the operation (b) mixing in any order a mixture of stage (I) and prosteradlo connection with the formation thus a mixture of stage (II), and phase stabilization of the product (III) contains at least one operation (C) mixing in any order a mixture of stage (II) and alkali in a quantity sufficient to achieve a final pH value of the resulting product of the above method at least about 13.

2. The method according to p. 1, characterized in that none of the stages, except for (II) and none of the operations, but (b) does not include adding prosteradlo connection.

3. The method according to p. 2, characterized in that each of these operations (b) and (C) is carried out at a temperature in the range of from about 5 to about 80o.

4. The method according to p. 3, characterized in that the pH value at the end of stage (I) and early stage (II) is in the range from about 1 to about 6.9.

5. The method according to p. 3, characterized in that starting from the end of stage (I) the entire process is conducted with the increase of pH.

6. The method according to p. 5, characterized in that Czechowice fact, what is the dilution factor for the amount of mixtures stages following the stage (I), does not exceed two.

8. The method according to p. 7, characterized in that the source of hypochlorite selected from the group consisting of chlorine, hypochlorite acid, hypochlorites, alkali metal hypochlorite alkali-earth metals, product mixing hypochlorites connection alkali and water and mixtures thereof.

9. The method according to p. 8, characterized in that amidofunctional compound selected from (I) primary amidofunctional compounds selected from sulfamic acid, sulfamate alkali metals, sulfamates alkaline-earth metals, sulfamates of tetraalkylammonium, and mixtures thereof; (ii) secondary amidofunctional compounds selected from derivatives of secondary amines having the formula RR'NH or ((R)2NH, where R, R' and R" represent organic residues and where the carbon atoms of these residues covalently linked to the nitrogen of the group; (iii) sulfonamide selected from a sulphonamide, n-toluensulfonate, iminodiacetate, benzosulfimide, alkylsulfonamides and mixtures thereof; (iv) melamine, cyanamide and (v) mixtures thereof.

10. The method according to p. 9, characterized in that promotergene connection choose s and mixtures thereof.

11. The method according to p. 10, characterized in that the source of hypochlorite selected from hypochlorite shelochnogo metal and product mixing hypochlorites compounds and aqueous alkali; amidofunctional compound selected from sulfamic acid, sulfamate alkali metal, sulfamates alkaline-earth metal, sulfamates of tetraalkylammonium and mixtures thereof; promotergene compound selected from the group consisting of water-soluble bromides.

12. The method according to p. 11, characterized in that the source of hypochlorite is a sodium hypochlorite, amidofunctional connection is a sulfamic acid and promotergene compound selected from sodium bromide, potassium bromide and mixtures thereof.

13. The method according to p. 12, characterized in that amidofunctional compounds contain no more than about 1% impurities amidofunctional compounds with unstable N-halide derivatives.

14. The method according to p. 13, characterized in that the alkali selected from the group consisting of oxides, hydroxides, carbonates, bicarbonates, silicates, phosphates, borates, alkaline and alkaline-earth metal, tetraalkylammonium, and mixtures thereof.

15. The method according to p. 14, characterized t the th of surface-active substances, buffers, binders, chelates, abrasives, perfumes and fragrances, agents, giving color, dyes, bleach stabilizers, pigments, defoamers, antilocapridae and/or anticorrosion agents, agents, suspensorysex pollution, antibacterial agents, sources of alkali, hydrotropes, antioxidants, agents that removes/prevents the deposition of clay-like dirt, thickeners, solvents, and mixtures thereof.

16. The method according to p. 1, characterized in that it is carried out in the absence of insoluble solid materials.

17. Alkaline bleaching composition obtained by the method according to p. 1.

18. Alkaline bleaching composition under item 17, characterized in that it contains from about 0.01 to about 10% active chlorine.

19. Alkaline bleaching composition according to p. 18, characterized in that it has migalinaa the ratio [Br] : [OCl-] from about 10 : 1 to about 1 : 10, where [Br] denotes the total number of moles of Br input in the process from the specified prosteradlo connection and [OCl-] denotes the total number of moles of hypochlorite is introduced into the process from the specified source of hypochlorite.

20. Alkaline bleaching composition according to p. 19, characterized in that the TATKO Amin specified amidofunctional connection used to retrieve a specified composition, and where [X] denotes the total number of moles of halogen bleaching, defined as active chlorine present in the specified structure.

21. Alkaline bleaching composition according to p. 19, characterized in that the ratio of amine-halogen is from about 1.0 : 1.0 to about 1.5 : 1.0 in.

 

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Cleaning agent // 2277123

FIELD: cleaning solid surfaces from dirt.

SUBSTANCE: removal of fatty dirt from surface includes the following stages: (a) treatment of surface with composition containing detergent-surfactant and anti-oxidant; (b) setting of dirt; (c) cleaning the surface for removal of dirt. Anti-oxidant is used for preparation of liquid product and removal of fatty dirt settled on surface; anti-oxidant is selected from tannic acid, tannates and tannic acid salts; liquid has pH7 of below. It is good practice to use natural anti-oxidants. Liquid composition contains 0.05-45% of detergent-surfactant and 0.1-10% of natural anti-oxidant having 1,2- or 1,4-dihydroxybenzene substructure. Liquid composition has pH below 12 and viscosity lesser than 100 Mpa.s at shift rate of 21 s-1.

EFFECT: enhanced efficiency of cleaning.

38 cl, 2 tbl, 5 ex

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