LT4955B - Colloid composition comprising peroxosulfate, process for preparing thereof and uses therof - Google Patents

Abstract

The colloidal composition belongs to the manufacturing of household cleaners and textile finishing preparation. In mass percentage, the colloidal composition consists of: ammonium peroxysulphate 2-20, natrium or potassium chloride 0-8, polydimethyl diallyl ammonium chloride (MM<70,000) 3-30, in the mass ratio of polyquarter ammonium salt and peroxysulphate of 1:(0.6-0.7). The colloidal composition is obtained when monovalent metal chloride is dissolved in polyquarter ammonium salt hydro solution then hydro solution of ammonium peroxide is poured slowly in and then slowly mixed until it becomes whitish in colour. The colloidal composition containing peroxysulphate can be used for washing, bleaching, stain removal or disinfection.

Description

BACKGROUND OF THE INVENTION Field of the Invention The present invention relates to a process for the production of household chemistry and textile finishing compositions which can be used for cleaning-bleaching-stain-cleaning-disinfection purposes.

In bleaching practice, thickened bleach formulations are increasingly used because they are convenient for dosing, as well as for large objects that cannot be soaked in the solution, and for cleaning non-horizontal surfaces.

Suspensions of insoluble organic peroxyacids, which are easily thickened using starch derivatives, are known [cf. U.S. Pat. 4017412, Int cl. D 06L 3/02, C11D 3/395, 1977], xanthene and agar polysaccharides [cf. U.S. Patent No. 4879057, Int. cl. Cl ID 7/18, Cl ID 7/38, Cl ID 7/56, 1989], mixtures of anionic and cationic detergents [cf. U.S. Patent No. 4,642,198, Int. cl. C11D 3/395, 1987], synthetic polymers having hydrophilic and hydrophobic groups [cf. U.S. Patent No. 4,992,194, Int. cl. C11D 3/37, C11D 3/39, 1991; U.S. Patent No. 5073285, Int. cl. C11D 7/35, C11D 7/56, 1991], Sodium perborate tetrahydrate powder is proposed [see, e.g. U.S. Pat.

It is also known that water-soluble bleach solutions can be thickened: a solution of hydrogen peroxide using detergents [cf. U.S. Patent No. 4,130,501, Int.cl. C01B 15/02, 1978], solutions of peroxycarboxylic acids (C = 2 6), polysaccharide thickeners, further cross-linked with boric acid, borates, urea [cf. U.S. Patent No. 5597791, Int.cl. C11D 3/22, C11D 3/3/39, C11D 3/395, C11D 7/38, 1997], Liquid viscous peracetic acid containing compositions are also obtained [cf. U.S. Patent No. 5296239, Int.cl. A01N 39/00, A62D 3/00, 1994] by adding at least 1 thickener and stabilizing agents and free radical scavengers (phenolic derivatives) to retard its degradation.

The disadvantages of these formulations are that the said thickeners, in particular polysaccharide derivatives, cannot be used to thicken solutions of strong oxidants, since they undergo destruction, liquefaction, and the bleach itself decomposes and loses some of its activity. By the way, ?

the additives used (cross-linking agents, stabilizers or free radical scavengers) are environmentally harmful.

The closest inventions are solutions of inorganic peroxosulfates which are potent oxidants. Their aqueous solution is proposed for use in tissue bleaching [see WO Patent No. 9923197, Int.cl. C11D 3/39, D06L 3/02, 1999], Such a solution is diluted with water to the required concentration and soaked in tissue. It cleans stains well, does not damage fibers or discolour dyed fabric. An aqueous solution of inorganic peroxosulfate according to the above patent is a prototype of the present invention.

However, aqueous solutions of peroxosulfates are unstable [cf. kn .: KpaTKaa χΗΜΗηεοκΜ OHUHKJionenna, τ. 1, 1961, p. 208], degrades rapidly and gradually loses its whitening activity. In addition, liquid bleach solution is difficult to dispense when cleaning stains, washing large objects, or cleaning horizontal surfaces.

No method has been found in the literature for the preparation of thick aqueous compositions of inorganic peroxosulfates. These very strong oxidants react with many organic thickeners, destroy them, and themselves gradually lose their activity.

The object of the present invention is to obtain stable colloidal peroxosulphate-containing systems by incorporating peroxosulphates into poorly soluble or insoluble polyelectrolyte complexes, thereby "preserving", stabilizing and increasing their efficiency in the washing-cleaning process of dyed articles.

The object is achieved by the use of aqueous compositions containing from 2 to 20% by weight of ammonium peroxosulfate (NHLt) ₂ S ₂ O ₈ , 3-K 3O by weight of polydimethyldiallylammonium chloride (PDMDAAC1) having a molecular weight (AYA7) of <70000, 0 ~ 8 % by weight of a monovalent metal chloride by weight ratio of peroxosulphate to polyketric ammonium salt (0,6 - ^ - 0,7): 1. They are prepared by dissolving the low molecular weight salt in an aqueous cationic polymer solution, then slowly adding a pre-formulated aqueous peroxosulfate solution and stirring slowly until a white color appears. The compositions may then be left at rest.

The claims of the invention are supported by the data in Tables 1-3: Table 1 shows the consistency of the compositions depending on their composition, Table 2 shows that the proposed compositions protect white fabrics or their white background from soaking with colored laundry, and Table 3 results of stains of different origin are presented.

From Table 1, it can be seen that by varying the reactant concentrations, the molecular weight of the polymer, brittle gels, pastes of varying densities, layered dispersions or clear solutions can be obtained. It is an object of the present invention to provide gels and stable pastes which do not release liquid. Stable colloidal compositions can be prepared only at a weight ratio of peroxosulfate to cationic polymer (0.6 + 0.7): 1. When excess bleach is present (e.g., Table 1, # 8), layered dispersions are obtained and a Cl ₂ odor is produced. If peroxosulfate is not sufficient (# 14, 15), the liquid does not become cloudy and does not turn white - colloids do not form.

Gels are formed if the polymer concentration in the system exceeds 12-13%. Compositions more concentrated than those shown in Table 1 (20% APS maximum and 30% PDMDAAC1) are difficult to homogenize due to high viscosity under stirring. When PDMDAAC1 is less than 12%, white pastes are obtained. Their stabilization requires small molecule chloride salts (NaCl, KC1). The more salts are added, the lower the APS and PDMDAAC1 concentrations. When the latter reached the 2.5 + 4 weight percent threshold, depending on the polymer MM _t , either a very liquid aqueous dispersion was formed or the liquid remained clear.

Colloidal systems are most easily prepared using lower molecular weight cationic polyketal ammonium salts When the MM of the polymer is> 70000, the compositions are difficult to homogenize (Table 1) because the resulting curd mass tends to bump into balls.

The order of the reactants is important in the preparation of colloidal compositions. The salt should be added to the polymer solution and dissolved in the solution, followed by slow addition of the separately prepared aqueous peroxosulphate solution. The last addition of salt often often fails to homogenize the system well.

The proposed colloidal bleach containing compositions may be used for conventional cleaning - bleaching - disinfection purposes. They can be used alone or in combination with detergents. It should be noted that, unlike the prototype aqueous peroxosulfate solution, the proposed compositions protect the background of the printed products from staining or white products by soaking them together with non-stained colored laundry. This is illustrated by the data in Table 2.

table

Yesterday No. APS% PDMDAACI APS / PDMDAACI NaCI% Consistency MM % 1 20th 29th 0.7 0 A fragile gel 2 12.9 19.7 0.7 0 A fragile gel 3 9.1 13th 0.7 0 Paste, over a long period of time, may contain up to -7% of its volume of liquid 4 8.4 2000 12th 0.7 0 Quickly flaking paste 5 8.5 12.2 0.7 2.4 Stable paste 6th 2.5 3.5 0.7 5.6 Liquid stable paste 7th 2.9 4.1 0.7 4.8 * Liquid stable paste 8th 1.3 1.8 0.7 7.6 A whitish aqueous dispersion 9th 17.5 25th 0.7 0 A fragile gel 10th 12.2 17.5 0.7 0 Paste + ~ 5% liquid 11th 10.0 12th 0.8 2.4 Stripping paste. Cb odor 12th 8.5 12.2 0.7 2.4 Stable paste 13th 6.9 5000 12th 0.6 2.5 Stable paste 14th 6.5 12.5 0.5 2.5 Clear liquid 15th 5.0 12.6 0.4 2.5 Clear liquid 16th 3.6 5.1 0.7 2.6 Liquid stable paste 17th 1.9 2.7 0.7 3.3 Clear liquid 18th 6.9 9.8 0.7 2.0 A fragile gel 19th 6.9 70,000 9.8 0.7 5.5 Very thick paste, difficult to homogenize 20th 4.0 5.7 0.7 8.2 Very thick paste, difficult to homogenize 21st 22nd 10th 4.5 270000 14.5 10th 0.69 0.45 0 4.0 Curd mass, water different Curd-like mass, Cb smell

• No. 7 replaced NaCI with KCI

Colored fabric prepared for washing tests, dyed in the standard "cold" intensive with 10% w / w Cl Reactive Red 2, 60 g / l NaCl and 10 g / l Na ₂ CO ₃ , and washed only after cold running water. Pieces of dyed tissue, together with non-colored white specimens of the same size, were placed in solutions of the substances listed in Table 2 and maintained for a period of time, occasionally shaking with a glass rod. Using a leukometer (Kari Zeiss, Jena), the light reflectance coefficients R of unpainted but smeared specimens were measured and the color intensity K / S calculated (Kubelka and

Munk function):

_{K / s} Jk &

2R

The higher the K / S values, the more soiled the specimens.

The analysis of the data in Table 2 shows that the addition of colloidal peroxosulphate-containing composition (PS gel) to the soaking solutions results in significantly less white staining of the adjacent red tissue. The results are also good when anionic or nonionic detergent is added to the gel. Meanwhile, in a solution of normal ammonium peroxosulfate, the tissue was stained two to three times more in a shorter time than soaking in pure water or detergent solutions.

The resulting stains on paint, as well as wine, tea, and coffee can be cleaned by applying the proposed colloidal compositions (pastes) to the stained spot and maintaining them for longer periods of time at room temperature or higher. Stain removal is illustrated by the data in Table 3.

table

Composition of the soaking solution Soaking time h K / S Pure water 4 0.154 0.5 g / L Prevocel WOF-100 4 0.122 0.5 g / L Volganat 4 0.150 3 g / l APS and 0.5 g / l Volganat 2 0.393 4 g / 1 PS gel 4 0.094 4 g / 1 PS gel and 0.5 g / 1 Volganat 4 0.089 4 g / l PS gel and 0.5 g / l Prevocel WOF-100 4 0.093

Notes: The composition of the PS gel corresponds to Ref. 18 of Table 1. Prevocel WOF-100 is non-ionic and Volganat is an anionic detergent.

table

Method of treatment K7S Tea Kava Wine Some * Untreated 0.243 0.076 0.099 0.197 Maintained for 18-20 h at 20 ° C 0.046 0.061 0.04 - 45 min at 60 ° C - - 0.064 0.115 30 min at 80 ° C 0.136 - - 0.109 Heat for 15 minutes on a napkin at max. iron heaters - - 0.083 0.048

* C.I. Reactive Red 2 paint stain

Colloidal peroxosulfate compositions have bactericidal properties and can therefore be used for disinfecting surfaces. Agarized medium, when cultured for 24 h at 37 ° C, destroyed up to 60% of coliforms at 0.4 cm and prevented the formation of entire overlapping colonies of saprophytes at 0.7 cm.

Specific examples of the preparation and application of colloidal peroxosulfate-containing compositions are given below.

example

To 160 g of 50% PDMDAAC1 (TU 6-09-5236-85, MM = 2000) was added 57 g of ammonium peroxosulphate (GOST 20478-75) dissolved in 0.060 dm ^{3 of} water. After a couple of minutes the solution fades and the stirring is stopped. A stable, brittle gel is obtained. No degradation of peroxosulfate was observed after 30 days of gel storage. Example ²

190 g of a 36% solution of PDMDAAC1 (TU 6-05-2009-86, MM = 70000) is diluted with 0.23 dm of water and dissolved in 10 g of NaCl. After stirring, a gram of ammonium peroxosulfate dissolved in 0.040 dm ^{3 of} water was added. After a couple of minutes the solution fades and the stirring is stopped. A stable, brittle gel is obtained. No degradation of peroxosulfate was observed after 30 days of gel storage.

The cotton fabric is dyed the standard cold-cold intensive with 10% w / w CI Reactive Red 2, 60 g / l NaCl and 10 g / l Na 2 CO 2 and rinsed with cold running water after dyeing. A 2 g piece of dyed cloth, together with a non-colored white piece of cloth of the same size, is immersed in 0.60 dm ³ solution containing 0.5 g / l Volganat anionic detergent and 4 g / l gel and left for 4 hours at room temperature, occasionally stirring with a glass rod. The gel breaks into small pieces and turns red. After completion, the samples are rinsed with running water and dried separately. The white specimen stain, expressed as Kubelka and Munk's function, is only 0.089. Meanwhile, it is 0.154 in pure water and 0.339 in Volganat 3 g / l prototype and 0.5 g / l.

example

125 g of a 40% (MM = 5000) solution of PDMDAAC1 (Allied Colloids Ltd) is diluted with 0.35 dm of water to dissolve 23 g of NaCl in stirring. Aqueous ammonium peroxosulphate solution obtained by dissolving 35 g of ammonium peroxosulphate in 0.05 dm ^{3 of} water is added dropwise to this solution with slow stirring. After the addition of the reagent, stir slowly for another 15 minutes. A whitish paste with a viscosity of ~ 7 Pa-s is obtained. The paste remains stable for almost a month, after which it gradually begins to separate from the liquid. One month later, it contains about 90% of the active ingredient, peroxosulfate.

sample g 50% dilution of PDMDAAC1 (TU 6-09-5236-85, MM =. 2000) with 0.4 dm ^{3 of} water. It is dissolved in 70 g of NaCi. A solution of ammonium peroxosulphate obtained by dissolving 17.5 g of peroxosulphate in 0.4 dm ^{3 of} water is added dropwise. Stir for another 30 minutes until the solution begins to cloud. After 2 hours of rest, a very liquid paste of -0.01 Pa viscosity is obtained. A month later, it found peroxosulfate in 65% of its initial content.

The following examples confirm that stable colloidal compositions, gels or pastes containing 2-20% by weight of bleach peroxosulfate, can be obtained by the addition of 0-8% by weight of monovalent metal chloride as well as polydimethyldiallylammonium chloride

70000) at a weight ratio of 1: (0.6-0.7) to peroxosulfate. Such colloidal compositions may be used for conventional washing-bleaching-stain-cleaning-disinfection purposes. At the same time, they also have a new positive feature (Table 2), unlike the prototype aqueous peroxosulfate solution, which protects white laundry or white printed fabrics from staining with textile dyes, making them very suitable for washing colored products. The proposed dense formulations are convenient for dosage and application on a stain remover. Because of their viscosity, they do not absorb or wet other parts of the product, which is important when cleaning large items, and does not leak when working on horizontal surfaces.

DEFINITION OF INVENTION

Claims (5)

DEFINITION OF INVENTION 1. Colloidal composition containing peroxosulphate, characterized in that it comprises by weight: ammonium peroxosulfate - 2-20 monovalent metal chloride - 0-8 polyketric ammonium salt - 3-30 at a weight ratio of polyketric ammonium salt to peroxosulfate of 1: 0.60.7. 2. The colloidal composition of claim 1, wherein the polyketric ammonium salt is polydimethyldiallylammonium chloride and the monovalent metal chloride is sodium chloride or potassium chloride. 3. The colloidal composition of claims 1 and 2, wherein the polydimethyldiallylammonium chloride has a molecular weight of <70,000. 4. A process for the preparation of a colloidal composition comprising dissolving a monovalent metal chloride in an aqueous solution of a polyketal ammonium salt, then slowly adding the prepared aqueous ammonium peroxosulfate solution and stirring until a whitish color develops. Use of colloidal peroxosulfate-containing compositions according to claims 1, 2 and 3 for washing and / or bleaching and / or stain cleaning and / or disinfection.