JPH0565558B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a liquid cleaning composition, and more specifically, a liquid cleaning agent having an appropriate viscosity that can efficiently and safely remove black to pink mold stains attached to bathroom tile joints, room walls, etc. The present invention relates to a drug composition. Mold grows wherever the humidity and temperature conditions are right, and the mold or its excrement adheres to produce black to pink so-called mold stains. Mold stains are often found in humid areas such as tile joints in bathrooms and washrooms, poorly ventilated drawers, and behind refrigerators, etc. Mold stains penetrate deep into the surface and are difficult to remove. Cleaning agents containing oxidizing bleach are effective for cleaning such mold stains, but conventional cleaning agents containing oxidizing bleach have a low viscosity, so when applied to vertical surfaces, they wash off quickly and are not effective enough. In addition to not being effective, there were problems in use, such as scattering and adhesion to clean and unnecessary areas. If it does not contain an oxidizing bleach, it is relatively easy to prepare a product that has good retention properties for highly viscous stains, but this does not have sufficient cleaning power. Therefore, as a result of intensive research to overcome such drawbacks, the present inventors used a specific partially crosslinked polyacrylic acid as a thickener, and used an inorganic alkaline agent and an alkali or alkaline earth agent of hypochlorous acid. The present invention has been completed based on the discovery that when a metal salt is blended, a liquid detergent composition can be obtained that has good retention on vertical surfaces, has little scattering, and can easily remove mold stains. Therefore, the present invention provides (a) a partially crosslinked polyacrylic acid having a viscosity of 1000 to 16000 cp in a 2.5% by weight, 0.2N NaOH aqueous solution (20°C) and a Bruckfield yield value of 100 to 1600 g/seccm; (b) 0.1-15% by weight of an inorganic alkaline agent; (c) 0.1-15% by weight of an alkali or alkaline earth metal salt of hypochlorous acid. It is something. The partially crosslinked polyacrylic acid used as a thickener in the present invention has a viscosity of 2.5% by weight, 0.2N-NaOH aqueous solution of 1000 to 16000 cp, and a Burckfield yield value of 100 to 1600 g/sec cm. be. Here, the Bruckfield yield value is a value obtained by measuring the viscosity of the above aqueous solution at 20°C and using the following formula, and when the molecular weight is the same, a larger value means a higher degree of crosslinking. . Burtskfield yield value = B8H type viscometer rotor No.
3. Apparent viscosity at 0.5 rpm/100* *-B8H type viscometer rotor No. 3, Apparent viscosity at 1 rpm/ In addition, as a crosslinking agent for the partially crosslinked polyacrylic acid of the present invention, for example, polyvalent acrylic acid or methacrylic acid One or more selected from metal salts, glyoxal alkenyl compounds, allylated glycerin, allylated pentaerythritol, allyl (meth)acrylate oligomers, triallyl isocyanurate, triallyl phosphate, tetraallylsilane, polyalkenyl sulfones, and butadiene oligomers. Examples include: The content of these crosslinking agents is preferably 0.3 to 15% by weight based on the acrylic acid; if the amount of the crosslinking agent is too small, sufficient viscosity cannot be obtained, and if it is too large, the solubility will deteriorate, which is not preferable. The partially crosslinked polyacrylic acid of the present invention exhibits a sufficient thickening effect both in aqueous solutions containing oxidizing bleaches and in aqueous solutions with high ionic strength, and shows almost no change in viscosity over time. It is stable. On the other hand, ordinary polyacrylic acid, polybonyl alcohol, locust bean gum, etc. do not have sufficient viscosity in an aqueous solution containing an oxidizing bleach. In addition, even if xantham gum, carboxymethyl cellulose, or crosslinked polyacrylic acid is used as a crosslinking agent, such as allylated sucrose or diethylene glycol bismethallyl ether, it has sufficient viscosity when preparing a solution, but in an aqueous solution containing an oxidizing bleach, Particularly in the summer when the temperature is high, the viscosity decreases significantly over time, the retention of dirt is poor, and the oxidative bleach decomposes, resulting in insufficient cleaning effects. In the present invention, the partially crosslinked polyacrylic acid is blended in the composition in an amount of 0.5 to 5% by weight, preferably 0.5 to 3.5% by weight. If the amount of partially crosslinked polyacrylic acid is less than this, the viscosity will be less than 100 cp, and if it is used on a vertical surface, it will quickly run off, and if it is more than this, the composition will become gel-like, causing problems in use. Examples of inorganic alkaline agents include alkali metal hydroxides, silicates, carbonates, phosphates, borates, etc. Specific examples include sodium hydroxide, potassium hydroxide, sodium silicate, and sodium carbonate. etc. These alkaline agents have the effect of preventing the decomposition of oxidative bleaching agents and removing oil stains adhering to mold stains. When the cation of the alkali agent is a polyvalent metal such as Ca, Mg, Al, etc., the solubility of the partially crosslinked polyacrylic acid deteriorates, which is not preferable. These alkaline agents are present in the composition in an amount of 0.1 to 15% by weight, preferably 0.5 to 10% by weight.
It is blended. The alkali or alkaline earth metal salts of hypochlorous acid used as oxidizing bleaches include those that generate hypochlorous acid species in aqueous solution, such as Na, K, Li, and
Examples include Ca and Mg salts. These exhibit bleaching and sterilizing effects on mold stains due to the strong oxidizing effect of hypochlorous acid species. These oxidizing bleaches are present in the composition in an amount of 0.1 to 15% by weight, preferably 0.5 to 10% by weight.
It is blended. The liquid cleaning composition of the present invention has the above essential components (a) to
It is sufficient to contain (c), but a surfactant or (and) a water-insoluble abrasive can also be added thereto. As the surfactant, cleaning active ingredients used in general household detergents can _be used; _C8-22 ) sulfonate, alkyl ( _C8-22 ) sulfate ester salt, monoalkyl, dialkyl or sesqui( _C8-22 alkyl) phosphate, polyoxyethylene (1-6 mol) monoalkyl, dialkyl or sesqui(alkyl _C8-22 ) phosphates,
N,N-dimerthyl-N-carboxymethyl long chain ( _C8-22 ) alkyl ammonium salt, _C8 - _C22 fatty acid salt, _C8 - _C22 α-sulfonated fatty acid salt, _C8
-C22 alkyldimethylamine oxides and the like are preferred. These surfactants are included in the composition.
It is blended in an amount of 0.1 to 20% by weight, preferably 0.5 to 10% by weight. Examples of water-insoluble abrasives include silicon dioxide, aluminum oxide, magnesium oxide, titanium oxide, aluminosilicase, silicon carbide, calcium carbonate, calcium phosphate, chromium oxide or corundum, emery, silica, quartz sand, dolomite, sand, and shells. Naturally crushed products such as Of these, crushed silica or quartz sand is most commonly used. The particle size of the abrasive may be coarse, but a particle size of 2 to 150 microns is preferred in order not to damage the surface to be polished. These abrasives are preferably blended in the composition in an amount of 5 to 70% by weight, particularly 10 to 60% by weight. This abrasive enhances the cleaning effect through its abrasive effect, and also has the effect of thickening the viscosity and making it opaque, thereby making it possible to confirm the location and degree of adhesion of the cleaning composition. In addition to the above-mentioned components, the liquid detergent composition of the present invention includes optional components that are generally incorporated in such cases,
For example, small amounts of fragrances, pigments, dyes, bactericides, solubilizers, etc. may be added. Next, an example will be given and explained. In addition, % in examples
is expressed as a weight ratio. Example 1 A cleaning agent having the composition shown in Table 1 was prepared, and its viscosity and storage stability were examined. (1) Viscosity The detergent was placed in a viscosity beaker, heated to 20°C, and measured using a B-type viscometer (rotation speed: 30 rpm). (2) Retention property on vertical surfaces A cleaning agent stored at 35°C for 40 days was attached to a vertically erected polypropylene plate, and its retention property was investigated. ○ does not flow down. △ gradually flows down.
× flows down quickly.

【table】

[Table] Example 2 A cleaning agent having the composition shown in Table 2 was prepared and used in Example 1.
The viscosity and storage stability were examined in the same manner as above. The results are shown in Table-2.

[Table] Example 3 The cleaning power of the cleaning agents shown in Table 3 was investigated. (1) Cleaning power We used mold stains that occur on the tile joints of bathroom walls in ordinary homes and cannot be removed by rubbing with a sponge dampened with water. Various cleaning agents were applied to the tile joints on the bathroom interior walls where the mold stains had adhered, and then rubbed lightly with a sponge.The cleaning power was determined by measuring the number of times of rubbing until the stains were completely removed. Therefore, the smaller the number of times of rubbing, the better the cleaning power. (2) Results

【table】

Claims (1)

[Claims] 1 (a) 2.5% by weight, 0.2N NaOH aqueous solution (20°C)
0.5 to 5% by weight of partially crosslinked polyacrylic acid having a viscosity of 1000 to 16000 cp and a Burckfield yield value of 100 to 1600 g/seccm, (b) 0.1 to 15% by weight of an inorganic alkali agent, (c) Hypochlorous acid A liquid cleaning composition containing as an essential component 0.1 to 15% by weight of an alkali or alkaline earth metal salt. 2. The crosslinking agent of the partially crosslinked polyacrylic acid is a polyvalent metal salt of acrylic acid or methacrylic acid, a glyoxal alkenyl compound, allylated glycerin, allylated pentaerythritol, allyl (meth)acrylate oligomer, triallyl isocyanurate, triallyl phosphate, The liquid detergent composition according to claim 1, which is one or more selected from tetraallylsilane, polyalkenyl sulfone, and butadiene oligomer, and contains 0.3 to 15% by weight of acrylic acid. 3. The liquid cleaning composition according to claim 1, wherein the inorganic alkaline agent is an alkali metal hydroxide, silicate, carbonate, phosphate, or borate. 4. The liquid cleaning composition according to claim 1, containing 5 to 70% by weight of a water-insoluble abrasive. 5 The water-insoluble abrasive is silicon dioxide, aluminum oxide, magnesium oxide, titanium oxide, aluminosilicate, silicon carbide, calcium carbonate,
calcium phosphate, chromium oxide or corundum,
5. The liquid cleaning composition according to claim 4, which is a natural crushed product of emery, silica, quartz sand, dolomite, sand, shell, etc. 6. The liquid detergent composition according to claim 1 or 4, which contains 0.1 to 20% by weight of a surfactant selected from anionic, nonionic, cationic and amphoteric surfactants.