JPH06507160A - Thickening composition - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

[Detailed description of the invention] Thickening composition TECHNICAL FIELD This invention relates to thickened compositions, particularly peroxygen compositions with increased viscosity.

Recently, in Western Europe and chemical America, industry and general society have There is growing interest in the environmental impact of many of the substances in our environment. This is it One class of substances that has been widely used in be caught. These types of compounds have been reported to produce carcinogenic compounds under certain circumstances. As a result, industry has taken steps to alleviate the social unrest that still exists. Looking for alternatives or replacements for such compounds.

Another type of compound is peroxygen compounds, and one of particular interest is - CD-00) is a peracid containing a portion of 1. Peracids, like hydrogen peroxide, are an environmental problem. Unlike chlorine and active chlorine species, which researchers are currently suspecting, It has the great advantage of generating oxygen in its active form during use. moreover , a wide range of purposes such as disinfection, oxidation, and bleaching (many of which are encountered in the home) Because of this, peracids are generally more effective than hydrogen peroxide.

Many peracids are made by themselves or in liquid form, or advantageously as an aqueous solution. Ru. Is such a composition particularly suitable for treating or adding to a liquid medium? Solid surfaces (especially non-horizontal surfaces) are surface) is not well suited for processing. As a result, to widen the application range of peracids , it would be desirable to develop peracid-containing compositions that are less free-flowing.

In principle, a substance that increases the viscosity of a liquid, that is, a substance that gives structure to the liquid. By adding a liquid composition, it is possible to make it less free-flowing. Wear. However, substances that have previously been effective thickeners for other liquids, or It is reasonable to predict that the viscosity of peracids or peracid solutions would be suitable for increasing the viscosity of peracids or peracid solutions. unconventional. This difficulty is due to the very nature of peracid, which makes it an effective oxidizing agent and bleaching agent. arises from its nature. Interaction with thickener during storage or interaction between peracid and thickener This may lead to decomposition, which not only eliminates the effectiveness of the thickener, but also The ability of the peracid to do the desired work also decreases over time. This problem is especially true for itself or liquids. It has been observed that this occurs in the case of peracids present in the dissolved state. cormorant. Additionally, another important difficulty arises when attempting to increase the viscosity of peracid solutions. do. The presence or increase of peracid and the corresponding carboxylic acid (from which the peracid is derived) It tends to significantly suppress viscosity. This difficulty is due to the fact that surfactants and similar substances are soluble in water. Resulting from the interaction of peracids and/or carboxylic acids with aqueous structuring mechanisms that thicken liquids. It is thought that it does. However, the present invention does not depend on the accuracy of the foregoing discussion or description. It is understood that the Probably.

Virtually insoluble, suspended in particulate form in an aqueous medium, compared to soluble peracids This problem is somewhat alleviated in the case of solid peracids. Because peracid and liquid? different physical phases (which in turn minimizes the degree of chemical interaction between them) formation) and with reduced risk of interference from dissolved peracid species. This is because thickening of the aqueous phase occurs.

Some other thickeners produce very thick sets initially or after short-term storage. rather unsettling in that the resulting viscosity drops rapidly from its peak. It will be appreciated that a fixed composition can be obtained. anionic polyacrylamide Tests that use this fall into this category.

The purpose of the present invention is to search for thickening substances capable of increasing the viscosity of peroxygen compositions. The purpose is to identify and identify it. A second object of preferred embodiments is to provide a soluble peracid composition. Identified substances that can increase the viscosity of The goal is to obtain a composition that is A third object of another aspect of the invention is to Identifying substances that can increase the viscosity of compositions for disinfection and/or cleaning The objective is to create a viscous composition that can be applied to non-horizontal surfaces for cleaning purposes.

According to the invention, the thickening agent is sufficient to increase the viscosity to at least 100 cPs. together with the thickener, characterized in that it contains an amount of an alkali metal silicate salt. Also provided are aqueous compositions containing partially dissolved peroxygen compounds.

With the thickening system of the present invention, peroxygen compounds are at most acceptable during storage. It is possible to obtain a thickened solution that decomposes only once. In other words, the book The composition has both physical and chemical stability.

The thickening system of the invention is particularly suitable for thickening soluble peracids. However, this thickening system the viscosity of other peroxygen compositions, including compositions that thicken more easily than soluble peracid compositions; It will be understood that it can also be used to increase In the aspect of Oxygen compounds are organic compounds. Thus, for example, this system i.e. alkyl, cycloalkyl or aryl peroxides, acyl peroxides, -C-0-0-, including hydrocarbonates and organic hydroperoxides. Organic compounds containing H or c-o-o-c moieties, and poorly soluble or is a more poorly soluble peroxyacid (e.g. containing at least 8 carbons) applied to compositions containing.

However, this system is particularly sensitive to low molecular weight aliphatic peroxy acids (e.g. up to 6 of soluble peracids, including those containing carbon atoms of Particularly preferred examples of aliphatic peroxy acids include peracetic acid and perpropionic acid. It will be done. Other examples include the harsh acids, persuccinic acid and perglutaric acid. Main group The composition also contains soluble aromatic peroxy acids such as monoperphthalic acid and sulfonate. May contain benzoic acid. Mixtures of peracids can also be utilized if desired.

Peroxygen compounds such as peracids are present in a wide range of concentrations, e.g. up to about 40%. can do. With respect to any ingredient, unless otherwise indicated, the % herein is by weight based on the total weight of the composition. The lower limit depends on the user's thoughts. Generally about 0. Not lower than 1%. The present invention particularly provides low concentrations of activity. Compositions containing peroxygen compounds, e.g. on hard surfaces, especially non-horizontal surfaces Ready-to-use compositions intended for application for cleaning and/or disinfection purposes applied to make it. Such dilute compositions generally contain from 0.25% to about 5% by weight. of an organic peroxygen compound, preferably a peracid, such as peracetic acid, in many embodiments. The content of peroxygen compounds would then be approximately 0.5-2%. Such compositions include e.g. 10% to 12% of the composition, in many embodiments 3 to 10%. It is understood that the scales contain hydrogen peroxide.

Peracid compositions, especially those containing aliphatic peracids, often contain a corresponding aliphatic carboxylic acid. is advantageously derived by oxidizing phosphoric acid with an aqueous solution of hydrogen peroxide, often with residual will contain both carbonic acid and hydrogen peroxide. Thus, this composition contains 40% of the corresponding carboxylic acid and up to 40% hydrogen peroxide, usually with a minimum content of 20% % of water. However, in dilute peracid solutions, carboxylic acids The concentration of hydrogen peroxide and the concentration of hydrogen peroxide tend to be selected in the range of about 1 to 12%, respectively. . The total concentration of carboxylic acids and percarboxylic acids is often 3-20%, and in many cases It is 3-15%. The concentration of hydrogen peroxide should be limited to no higher than 7%. is often advantageous. Many preferred compositions include carboxylic acids, percarboxylic acids, There is an equilibrium amount of acid and hydrogen peroxide.

The thickening system of the present invention contains an alkali metal salt of silicic acid. The amount of silicate used is , depends on how viscous the composition is desired. Adjust the concentration of silicate By adjusting it accordingly, it is possible to obtain various compositions. one pole At the edges, the composition remains free-flowing, while its silicate-free counterpart It is clearly more viscous than the other compositions. At the other extreme, this composition gels to form a virtually solid product. The concentration of silicate is such that the viscosity is approximately 30 selected in the range of at least 2% by weight to obtain compositions with 0 cPs or more. I have a tendency to get swollen. In many embodiments, the concentration is no higher than 6% by weight.

Silicates are usually used as silicates because they are widely available at economical cost. Sodium icate, but also all other silicates like potassium or lithium Alternatively, it can be used in place of some sodium silicate.

Alkali metal salts of silicic acid are generally represented by the following formula (MJ), (Si20)- , where M represents an alkali metal and m represents an alkali metal oxide (e.g. soda) Represents the molar ratio of silica. Silicates are obtained with m=approximately 1-4. particularly effective A good result was obtained in the region of m=2. The viscosity of the composition is to some extent alkali metal oxide It will be understood that it depends on the molar ratio of silica to silica. Same concentration of alkali gold silicate When introducing a metal salt, the viscosity tends to decrease as the molar ratio m increases. .

Alkali metal silicates are relatively pure, especially with excessive residues of transition metals. It is advisable to choose a sample that is less contaminated. By doing so, The stability of peroxygen compounds can be maintained. For example, increasing the viscosity of peracid compositions silicates supplied with an iron content of about 20 ppm or less, or It has been found preferable to use silicates purified as such. However, this Of course, there are some contaminant metal ions present that may promote the decomposition of peroxygen compounds. If expected, one or more chelating stabilizers as described below may be added. It is desirable to add more than that.

The silicate is used to promote homogeneous dispersion and mixing of the silicate and peroxygen compound solution. silicic acid in the form of an aqueous solution, preferably concentrated (e.g. about 30-50% by weight). It is conveniently introduced into the composition as a solution (containing alkali metal salt). solid silicon Direct introduction of acid salts is not recommended.

The physical state of the composition is also influenced by the presence of one or more viscosity modifiers. Can be changed. By doing so, the ability of the composition to flow is at least It is possible to fine-tune the degree.

The pH of the composition depends on the viscosity reached by the thickened composition during storage and in the present invention. Thickening is another factor that influences the rate at which thickening occurs. In particular, thickening occurs. It is preferable to use a pH of approximately at least 1 to encourage The pH is usually no higher than about 4.5. As a general expression of the trend, the pH of the solution Thickening becomes progressively faster and easier to achieve as the temperature increases. Composition preferred The pH range is about 3-4.5. Conveniently, like dilute peracetic acid compositions, Many compositions achieve this range without further adjustment.

The thickening composition of the present invention does not reach its maximum viscosity immediately, but rather over a period of time. It will be appreciated that this tends to increase the viscosity over time. Advantageously, This means that for a considerable period after the introduction of the thickening system, conventional bottling or The use of transport equipment also means that the composition can be easily handled. There is.

The composition may contain peracid and/or peracid so as to increase the chemical stability of the thickened product. One or more stabilizers for hydrogen hydride may be included. peroxy compound Known stabilizers for compounds include aminopolycarboxylic acids such as EDTA and DTPA. , or N-heteroaromatic carboxylic acids such as quinolinic acid, picric acid and Contains dipicolinic acid. Particularly effective stabilizers are organic polyphosphonic acids, Contains troquinoethylidene-sophosphonic acid and aminopolymethylenephosphonic acid . The latter has the general formula XzN-(-CHR-CHR-NX-)n-NX2 where X represents -CH, -PO, H2 and R represents H or two R positions The substituents together complete a cyclohexane ring, and n is an integer from 1 to 3. . Examples of this formula are ethylenenoaminethitra(methylenephosphonic acid), diethyl Thylenetriaminepenta(methylenephosphonic acid) and cyclohexanediamine Contains tetra(methylenephosphonic acid).

In addition to the above ingredients, the composition may contain one or more surfactants, such as amine oxy and/or one or more fragrances and/or dyes, preferably at least oxidation resistance, selected in part based on oxidation resistance.

The compositions of the invention are aqueous precursor compositions containing essentially water and peroxygen compounds (e.g. (e.g., an aqueous peracid solution that may contain residual amounts of the corresponding carboxylic acid and hydrogen peroxide). , introducing a predetermined amount of an alkali metal silicate, preferably as a concentrated aqueous solution; The resulting mixture is agitated to substantially homogeneously distribute the thickener in the mixture. You can make more. The silicate solution introduced is saturated at more than 30% (W/W) It is preferable that the concentration is up to a solution.

Preferably, the pH of the solution is measured, and if the solution is insufficiently acidic, an inorganic acid is added. If the acidity of the solution is too strong, by introducing an alkali with an appropriate selection. , adjust the pH of the solution if necessary. What is the appropriate temperature for this method? For example, it is carried out at ambient temperature, which is generally in the range of 10-35°C.

In addition, in order to quickly distribute the thickener, the mixture may be heated to a temperature of up to 50°C. The mixture may be heated quickly, after which the mixture is cooled to ambient temperature.

Some of the compositions of the invention, particularly those having a viscosity in the range of about 200 to 600 cPs, , for domestic use on surfaces where disinfection and cleaning are desired (e.g. non-horizontal surfaces). The purpose is to improve the bactericidal properties of peroxygen compounds (especially peracids) and the cleaning detergents. Characteristics are used. Solid peroxygen compositions can be used for cleaning or disinfection in granular or granular form. Added to the composition or dispersed in blocks or bars. Blogs like this A pack or bar is a mixture of a composition of peroxygen compounds and a liquid, such as water in a flush toilet. For example waxes, natural or synthetic polymers, very poorly soluble aliphatic carboxylic acids or poorly soluble derivatives. It may also include substances such as bodies and/or mixtures thereof.

Accordingly, a second aspect of the invention provides for applying the composition of the invention to hard surfaces, To disinfect and clean by maintaining contact until some disinfection occurs. of the composition of the invention as described above.

The composition of the invention can be applied using conventional means and the physical state of the composition Among other things, consideration will be given to whether it is a viscous flowing liquid or a gel. write Most simply, pour the composition onto a dispensing device such as a cloth or sponge, or The composition is applied to the receiving surface by smearing and passing a dispensing device across the surface. Applies to faces. Also, compositions having a viscosity low enough to flow may be used, for example Direct application from a dispensing nozzle onto a receiving surface by squeezing a shapeable elastic storage container be done. The composition in gel form can be applied with a spatula or similar instrument or as indicated above. by formulating it into a host composition or block.

Surfaces to which the present compositions can be applied are often domestic (particularly kitchens) and where microorganisms are present. It's somewhere else. Suitable receiving surfaces generally include wood, glass, and ceramic-filled plastics. Constructed from solid laminate and metal, it can be used on work surfaces, sinks, pipework, walls, floors, etc. Especially if the toilet bowl is included. However, similar potentially infectious surfaces are kitchen, food processing equipment or containers, brewery or distillery containers, hospitals , animal or poultry facilities, greenhouses or other areas critical to maintaining sanitary conditions. It is understood that it exists in places other than the home. The present invention is suitable for such households. This includes the use of the compositions of the invention in external locations.

The composition is then applied, optionally using a cloth, sponge or similar article. It is removed from the surface by washing with water.

Another use of the gelling composition is to form it into blocks and leave it as is. or in a permeable container for disinfection or for the desired liquid medium (e.g. process water, industrial circulation). It is made to float in water (at home, in the toilet supply water).

Having thus generally described the present invention, a more detailed discussion of specific aspects thereof will now be presented. This will be explained as an example.

For use in the examples, sodium silicate with a molar ratio of 5i02.NatO or 21 Powder (trademarked as Crystal C Powder by Joseph Crossfield) available from SephCrossf 1eld) to a concentration of 40%, A batch of silicate solution was prepared. This solution was analyzed to contain less than 10 ppm Fe. It contained.

Example 1 In this example, the silicate solution (5 g) and the trade name DEQUEST (available after grade 2010) Hydroxyethylidene diphosphonic acid (looppm) was mixed with peracetic acid (1%) and vinegar. Interocross analyzed to contain acid (9%), hydrogen peroxide (6%), and balance water. ・Peracetic acid available from Interox Chemicals A thickened peracid composition was prepared by adding to a long solution with stirring. Obtained The composition had a pH of about 3.5, which decreased to about pH 3.3 during storage. 16 weeks After a while, the viscosity of this composition is Brookfield Synchro Electric Viscosity. I measured it with a meter and it was 400cPS. The available oxygen (Avox) of this composition is Ordinary cerium(IV) sulfate/sodium thiosulfate at 22°C at the time of manufacture and after 16 weeks of storage. Measured using the lium method.

By comparing these two analytical values, this composition shows that 69% of its Avox was found to hold.

Example 2 In this example, Example 1 was repeated but using 7g of sodium silicate solution. Ta. The resulting composition has a pH of 35, rising to pH 4 after 20 days of storage; The viscosity after 12 days was approximately +500 cPs. This composition lasts for 20 weeks at 22°C. It solidifies during storage and retains 86% of its AvoX until then. Was.

Example 3 In this example, Example 1 was repeated but using 13g of sodium silicate solution. there was. The resulting composition has a pH of 3.9 and after storage for 20 days I) H4° 0, and the viscosity after 16 weeks was over 80,000 cPs. This composition retained 47% of its Avox after 16 weeks of storage at 22°C.

Example 4 In this example, Example 4 was repeated, but with an additional 1.2 ml of concentrated sulfuric acid.

The obtained composition is 1. 2 p) (with a viscosity of approximately 1400 cP after 16 weeks) It was s. This composition has an AVOX of 74 after storage at 22°C for 16 weeks. % was retained.

Example 5 In this example, Example 3 was repeated or Stepan It is available under the trade name STEPANQUAT F. Alkylammonium trisulfate (2 g) was added. The resulting composition was heated to 1 at 22°C. It has a viscosity of 22.0 OOc'Ps after 6 weeks of storage and 99% of its AVOX was held.

Example Example 3 was repeated but with additional amine oxide (2 g). Ta. After storage for 16 weeks at 22°C, this composition has a viscosity of 3000 cPs in N and retained 72% of its Avox.

Copy and translation of written amendment) Submission (Article 184-8 of the Patent Law) November 4, 1993

Claims (21)

[Claims] 1. silicic acid in an amount sufficient to cause the thickener to increase the viscosity to at least 100 cPs at least partially soluble with said thickener, characterized in that it comprises an alkali metal salt. An aqueous composition containing a peroxygen compound having a chemical composition. 2. The thickening composition according to claim 1, characterized in that the oxygen-forming compound is a peracid. 3. Thickening composition according to claim 2, characterized in that the peracid is soluble. 4. Thickening composition according to claim 3, characterized in that the peracid is peracetic acid. 5.Claims 1 to 5, characterized in that they contain from 0.25 to 5% w/w peracid. 4. The thickening composition according to any one of 4. 6. Carboxylic acid and water peroxide in amounts selected in the range of 1 to 12 wt/wt% each The thickening composition according to any one of claims 1 to 5, characterized in that it contains a base. 7. characterized in that the total ratio of peracid and carboxylic acid is in the range of 3 to 15%, The thickening composition according to claim 6. 8. An alkali metal silicate has the formula (M2O), (SiO2), where m is The thickening composition according to any one of claims 1 to 7, characterized in that the thickening composition is 9. The amount of alkali metal silicate used is selected in the range of 2 to 6% w/w of the composition. Thickening composition according to any one of claims 1 to 8, characterized in that it is 10. Claim characterized in that the alkali metal silicate is sodium silicate Item 10. The thickening composition according to any one of Items 1 to 9. 11. The silicate used must have an iron impurity content of 20 ppm or less calculated as Fe. The thickening composition according to any one of claims 1 to 10, characterized in that it has. 12. The composition after thickening has a pH in the range of pH 3 to 4.5. The thickening composition according to any one of claims 1 to 11. 13. Sufficient alkali silicate to obtain a viscosity of about 250-600 cPs after storage The thickening composition according to any one of claims 1 to 12, characterized in that a metal salt is used. thing. 14. using sufficient alkali metal silicate salt to coagulate the composition; Thickening composition according to any one of claims 1 to 12, characterized in that: 15. A claim characterized in that it further contains alkylammonium methosulfate. Item 15. The thickening composition according to any one of Items 1 to 14. 16. The method according to claims 1 to 15, characterized in that it contains a stabilizer for oxygen permeable compounds. The thickening composition according to any one of the above. 17. Introducing an effective amount of an alkali metal silicate into an aqueous composition containing a peroxygen compound and stirring the mixture. 18. Alkali metal silicate salts from a concentrated aqueous solution, preferably 30% w/w 18. Process according to claim 17, characterized in that it is introduced in the form of a solution up to saturation. 19. A claim characterized in that it uses one or more of the features of claims 2 to 16. The method according to claim 17 or 18. 20. According to any of claims 1 to 16, or claims 17, 18 or 19 Use of a thickened peroxygen composition prepared by the method as a disinfectant. 21. No novel features or combinations of novel features are substantially described herein. A thickened peroxygen composition, or a method for preparing a thickened peroxygen composition, or a thickened composition. Use of the product as a disinfectant.