JP2588345B2 - Colored liquid cleaning bleach composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

FIELD OF THE INVENTION The present invention relates to a colored liquid washing and bleaching composition having excellent storage stability.

[0002]

2. Description of the Related Art Many detergent compositions based on alkali metal hypochlorite as a main base have been known. Currently, such cleaning compositions are used for disinfecting tableware used in public facilities, employee cafeterias, general cafeterias, etc .; bleaching kitchen utensils and clothing supplies in general households; cleaning, bleaching, and clogging toilets and drains. It is widely used for the purpose of disinfection, deodorization, bleaching of mold stains generated in bathrooms and the like.

[0003] Many attempts have heretofore been made to improve the storage stability of alkali metal hypochlorite in these compositions. For example, Japanese Patent Publication No. 32-1714 discloses a method for producing a storage-stable sodium hypochlorite solution using gelatin or casein as a stabilizer, and Japanese Patent Publication No. 39-6652 discloses a method for producing CMC or polyacrylic acid. Japanese Patent Publication No. 42-531 discloses a method for stabilizing sodium hypochlorite with a synthetic polymer electrolyte, which discloses a method for removing heavy metals by adding crystalline sodium silicate and solution sodium silicate. JP-A-51-39966 discloses a stable liquid detergent bleach comprising polyoxyethylene alkylphenol ether sulfate, hypochlorite, caustic alkali and aromatic sulfonate. In Japanese Patent Publication No. 57-40081, a stable aqueous solution of hypochlorite containing periodate ion is disclosed in JP-A-63-273700. No. Acrylic acid, polyhydroxy acrylic acid or mixtures thereof and chlorine resistant phosphonate or stable sodium hypochlorite containing detergent compositions by applying the organic phosphonates are disclosed respectively. The composition according to these techniques contributes to the improvement of the stability of hypochlorite, and an effective composition having excellent performance has been proposed.

[0004] Alkali metal hypochlorite is a strong oxidizing agent, and its handling requires great care. For this reason, in consideration of the safety of the user, the cleaning agent is colored to clarify the application site of the cleaning agent. However, in the case of oxidized bleaching agents such as chlorine-based ones, the selection of the colorant is particularly important because the colorant is liable to fade over time. For example, a method has been reported in which a specific copper phthalocyanine-based pigment is blended with a system composed of hypochlorite and caustic alkali for coloring (JP-A-53-8604), which is stable to hypochlorite. A blue-based coloring method is disclosed.

[0005] However, in this method, long-term storage stability, particularly under severe conditions, is not always required when implementing a blended system in which the concentration of caustic alkali is lowered in order to improve safety. It turns out that it is not guaranteed. This is not improved even by applying the above-mentioned means for improving the stability of hypochlorite. On the other hand, if the number of substituted halogens in the phthalocyanine-based pigment exceeds a specific range, discoloration proceeds due to high-temperature storage or long-term storage, so that this method cannot be applied. Therefore, further improvement is demanded for the storage stability of the colored washing / bleaching composition under severe conditions and the prevention of fading with time.

[0006]

DISCLOSURE OF THE INVENTION The present inventors have conducted intensive studies on an oxidized bleaching agent system to obtain a stable coloring composition even under severe conditions for a long period of time. As a result, a water-soluble polymer having a sulfonic acid group was obtained. It has been found that such a problem can be solved by adding to the aqueous solution of the alkali metal hypochlorite. Furthermore, surprisingly, it has been found that by applying the stabilizing method according to the present invention, a stable colored liquid washing / bleaching composition of blue to green can be obtained without limiting the substituted halogen number of the phthalocyanine pigment. Was completed.

That is, the present invention provides a coloring characterized by comprising (a) an alkali metal hypochlorite, (b) an alkali agent, (c) a water-soluble polymer having a sulfonic acid group, and (d) a phthalocyanine pigment. A liquid wash bleach composition is provided.

The amount of the alkali metal hypochlorite (a) used in the present invention in the composition is preferably 0.1 to 10% by weight, more preferably 1 to 6% by weight. (a) If the compounding amount of the component is less than 0.1% by weight, the bleaching performance, particularly the bleaching speed, becomes insufficient. If the amount exceeds 10% by weight, the compounding stability such as separation cannot be obtained, and the hypo-smell becomes strong. Is not preferred in terms of product form. As the alkali metal hypochlorite, a potassium salt or a sodium salt is preferable,
Those mixed with each other at an arbitrary ratio are also preferably used.
Generally, sodium chloride is contained in the alkali metal hypochlorite, but reducing this content to 5% by weight or less is also effective for improving stability. Further, other alkali metal hypohalites have problems of cost and safety, and are not suitable for the present invention.

The alkaline agents (b) used in the present invention may be used alone or mixed with each other at an arbitrary ratio. The alkali agent is not particularly limited,
Examples include caustic alkalis and silicates. Sodium hydroxide or the like is used as the caustic alkali, and sodium metasilicate or the like is used as the silicate. The content of the alkali agent in the composition is in the range of 0.1 to 5% by weight, preferably 0.5 to 3% by weight. If the content is less than 0.1% by weight, the stability of the system is poor, and if it exceeds 5% by weight, the effects on the skin and eye mucous membrane are considered, and the effect of the combination cannot be exhibited.

In the composition of the present invention, a water-soluble polymer (c) having a sulfonic acid group is used, which acts as a dispersant. As the water-soluble polymer having a sulfonic acid group, a water-soluble polymer composed of a formaldehyde condensate of an aromatic compound containing a sulfonic acid group or a sulfonic acid group or a salt thereof, or styrene sulfonic acid,
2-acrylamido-2-methylpropanesulfonic acid,
Polymers or copolymers of one or more monomers selected from the group consisting of allyl sulfonic acid, vinyl sulfonic acid, methallyl sulfonic acid and sulfopropyl methacrylate or salts thereof are mentioned. Further, the aromatic compound containing a sulfonic acid group or a sulfonic acid group,
Desirable are petroleum sulfonic acids or salts thereof, naphthalene sulfonic acids or salts thereof, lignin sulfonic acids or salts thereof, creosote oil sulfonic acids or salts thereof, and cresol alkylene sulfonic acids or salts thereof. Specific examples of the water-soluble polymer having a sulfonic acid group include a metacresol methylene sulfonic acid-shepheric acid formalin condensate (for example, Demol SSL, a trade name of Kao Corporation), a metacresol methylene sulfonic acid formalin condensate ( For example, Demol SC30, trade name of Kao Corporation),
Creosote oil sulfonic acid formalin condensate (eg, Demol C, trade name of Kao Corporation), naphthalene sulfonate formalin condensate (eg, Demol NL, Kao
(Trade name of Co., Ltd.), ligninsulfonic acid formalin condensate, melaminesulfonic acid formalin condensate, and sodium styrenesulfonate polymer salt.

In the composition of the present invention, as a component (c), a salt of a formalin condensate of naphthalenesulfonate and a meta-cresol methylenesulfonic acid, which keeps the stability of the phthalocyanine pigment in the blended composition favorable during storage. Formalin condensate salt of shepferic acid, formalin condensate salt of meta-cresol methylenesulfonic acid, and formalin condensate salt of creosote oil are preferably used.

[0012] The content of the water-soluble polymer (c) having a sulfonic acid group in the composition of the present invention is 0.001 to 1% by weight,
Preferably it is 0.01 to 0.5% by weight.

The (d) phthalocyanine pigment used in the present invention has the following general formula: C ₃₂ H _(16-n) X _n N ₈ M (where n = 0 to 16, X = halogen atom, M = A metal atom). Specifically, X is
One or a combination of two or more of Br, I, and Cl is preferable, and a phthalocyanine-based pigment obtained from one or a combination of two or more of Fe, Co, and Cu is suitably used. On the contrary, it was confirmed that the sulfonate or carboxylate of the compound represented by the above general formula could not exhibit the stability improving effect of the present invention.

In the present invention, the phthalocyanine pigment represented by the above general formula is effective, and any one having a halogen substitution number of 0 to 16 can be suitably used, and it can be used alone. It can also be suitably used as a mixed pigment whose color has been adjusted. The content of the phthalocyanine pigment in the composition is in the range of 0.00001 to 0.01% by weight. If the content in the composition is less than 0.00001% by weight, the effect of coloring is small, while if it exceeds 0.01% by weight, the dispersion stability decreases. The pigment represented by the above general formula is an aqueous dispersion at room temperature and has a particle size of 0.01 to 0.3 μm.

The above components (c) and (d) are (c) /
(d) It is desirable to mix in the composition such that the weight ratio is in the range of 10 to 1000.

The colored liquid washing / bleaching composition of the present invention includes:
Further, a surfactant which is usually used can be blended. Further, alkane sulfonates, fatty acid salts, alkyl sulfate salts, alkyl benzene sulfonates, alkyl naphthalene sulfonates,
Anionic surfactants such as alkyl sulfosuccinates / alkyl diphenyl ether disulfonates, alkyl phosphates, polyoxyethylene alkyl sulfates, polyoxyethylene alkyl allyl sulfates, and polyoxyethylene alkyl phenyl ether sulfonates ( Excluding nitrogen-containing anions such as amino acid derivatives); polyoxyethylene alkyl ether, polyoxyethylene alkyl allyl ether, oxyethylene /
Nonionic surfactants such as oxypropylene block copolymers, ethylene oxide / propylene oxide adducts of lower / higher alcohols (excluding ester type, sugar skeleton type, amine type and amide type); sulfobetaine, carbobetaine, alkyldimethyl An appropriate amount of one or a combination of two or more amphoteric surfactants such as amine oxides or cationic surfactants can be blended.

Further, it is possible to further improve the stability in a system thickened by the combination of the above-mentioned surfactants and the addition of an electrolyte such as an inorganic water-soluble salt such as NaCl, sodium sulfate, calcium salt and magnesium salt by known techniques. It is. Further stabilization can also be achieved by trapping heavy metals contained in the system in trace amounts with a chelating agent. For example, aminophosphonic acid-N-oxide, especially [nitrilotris (methylene)] trisphosphonic acid-N-oxide, 2-phosphonobutane-1,2,4-tricarboxylate,
Application of 1-hydroxyethane-1,1-diphosphonate, cross-linked polycarboxylate and the like can be cited as application examples of known techniques. Here, for example, ethylenediamine 4
Aminocarboxylic acid forms such as acetate and nitrilotriacetate; oxycarboxylic acid forms such as citrate, malate and tartrate; dicarboxylate forms such as succinic acid, glutaric acid and adipic acid; pyrophosphate and tripolyphosphate Acid salts,
Any application of a phosphate type sequestering agent such as hexametaphosphate is not suitable because the decomposition itself in an aqueous solution of hypochlorous acid is large.

Other builders that improve the cleaning performance include aromatic sulfonates such as toluenesulfonate, xylenesulfonate, cumenesulfonate, and naphthalenesulfonate; fluorescent dyes; radical scavengers such as BHT. Abrasives such as calcium carbonate, silica, montmorillonite, and smectite; scumming agents; and components such as fragrances typified by terpene alcohols. The colored liquid washing / bleaching composition of the present invention is usually prepared by adding a balanced amount of water to the above essential components and optional components.

[0019]

The present invention will be described below with reference to examples, but the present invention is not limited to these examples.

Example 1 Each of the colored liquid washing and bleaching compositions having the compositions shown in Table 1 were prepared, and the storage stability of each composition and the color stability after storage were evaluated. In the table, the numerical value of each component is% by weight, and the balance is an amount for making the whole 100% by weight. Table 1 shows the results. (1) The storage stability was evaluated by filling 600 ml of the colored liquid washing and bleaching composition for each evaluation into a polyethylene cylinder bottle (higher bottle: 725 ml full volume, 0.6 mm bottom thickness) and sealing at 40 ° C. After storing for 3 months, the bottle was taken out and the swelling of the cylinder bottle was visually observed. Evaluation criteria ○: No change △: The bottom of the bottle swelled slightly and the bottle became uncomfortable ×: The bottom of the bottle swelled and the bottle fell (0.6k
(This state is reached at an internal pressure of g / cm ² or more.) (2) For the evaluation of color stability, a part of the sample having the same storage stability as that after storage was taken, and observed visually. When the color did not change, it was rated as ○, when the color was slightly faded, as △, and when the color was bleached, as ×.

[0021]

[Table 1]

Note) * Demol NL manufactured by Kao Corporation ** Demol SC 30 manufactured by Kao Corporation * * Polinas (PS-1) manufactured by Tosoh Corporation

Claims (4)

(57) [Claims] 1. A (a) a water-soluble polymer and (d) a phthalocyanine pigment C ₃₂ consisting of compounds represented by the following general formula having an alkali metal hypochlorite (b) an alkali agent (c) a sulfonic acid group _{H (16-n) X n} n 8 M ( where, n = 0~16, X = a halogen atom, M = metal atom) colored liquid cleaning bleach composition characterized by containing a. 2. A water-soluble polymer having a sulfonic acid group.
(c) is a water-soluble polymer comprising a formaldehyde condensate of an aromatic compound containing a sulfonic acid group or a sulfonic acid group or a salt thereof, or styrene sulfonic acid, 2-acrylamido-2-methylpropane sulfonic acid, allyl sulfonic acid 3. The colored liquid washing and bleaching agent according to claim 2, which is a water-soluble polymer or copolymer comprising one or more monomers selected from the group consisting of vinyl sulfonic acid, methallyl sulfonic acid and sulfopropyl methacrylate or salts thereof. Composition. 3. An aromatic compound containing a sulfonic acid group or a sulfonic acid group, wherein petroleum sulfonic acid or a salt thereof, naphthalene sulfonic acid or a salt thereof, lignin sulfonic acid or a salt thereof, creosote oil sulfonic acid or a salt thereof, and cresol 3. The colored liquid washing and bleaching composition according to claim 2, which is selected from alkylene sulfonic acids or salts thereof. (4) (a) 0.1 to 10 alkali metal hypochlorites
% By weight, (b) 0.1 to 5% by weight of an alkali agent, and (c) 0.001 to 1% by weight of a water-soluble polymer having an aromatic sulfonic acid group.
And (d) 0.00001 to 0.01% by weight of a phthalocyanine-based pigment comprising a compound represented by the following general formula: C ₃₂ H _(16-n) X _n N ₈ M (where n = 0 to 16, X = halogen atom, A colored liquid washing / bleaching composition comprising: M = metal atom; and (c) / (d) weight ratio in the range of 10 to 1,000.