JP2983761B2 - 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 oxidized bleaching agents to obtain a stable coloring composition even under severe conditions for a long period of time. It has been found that such a problem can be solved by adding an alkali metal hypochlorite aqueous solution within the range. 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 relates to (a) 0.5 to 10% by weight of alkali metal hypochlorite, (b) 0.1 to 5% by weight of caustic alkali and / or silicate, and (c) aminophosphonic acid-N
0.001 to 0.3% by weight of the oxide sequestering agent and
(d) A colored liquid washing / bleaching composition characterized by containing 0.0002 to 0.01% by weight of a phthalocyanine pigment.

The amount of (a) the alkali metal hypochlorite used in the present invention in the composition is preferably 0.5 to 10% by weight, more preferably 1 to 6% by weight. (a) If the amount of the component is less than 0.5% 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 or the hyposmite 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 caustic alkali and / or silicate (b) used in the present invention may be used alone or mixed with each other at an arbitrary ratio. 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 caustic and / or silicate in the composition ranges from 0.1 to 5% by weight in total, preferably from 0.5 to 3% by weight. Their content is 0.1
If the amount is less than 5% by weight, the stability of the system is poor. If the amount is more than 5% by weight, the effect on the skin and eye mucosa is considered, and the effect of the combination cannot be exhibited.

In the present invention, an aminophosphonic acid-N-oxide type sequestering agent is used because a chelating agent having high chlorine resistance is particularly useful and does not decrease the effective chlorine content in the composition during storage. You. Aminophosphonic acid-N
As the oxide sequestering agent, aminotrimethylenephosphonic acid-N-oxide is particularly preferred.

In addition, other known sequestering agents other than the aminophosphonic acid-N-oxide type sequestering agent, for example, aminocarboxylic acid type such as ethylenediamine tetraacetate and nitrilotriacetate; citrate, malate , Oxycarboxylic acid types such as tartrate; succinic acid, glutaric acid,
2-phosphonobutane-1,2,4- which is known as a sequestering agent or a chlorine-resistant chelating agent of a dicarboxylate type such as adipic acid; a phosphate type such as pyrophosphate, tripolyphosphate or hexametaphosphate; Tricarboxylate, 1
Any application of an agent such as -hydroxyethane-1,1-diphosphonate is not suitable because the decomposition of the agent itself in a hypochlorous aqueous solution is large.

The content of the aminophosphonic acid-N-oxide type sequestering agent in the composition is 0.001 to 0.3% by weight, preferably 0.01 to 0.2% by weight. (c) If the content of the component is out of this range, no additional effect is exhibited,
This is only detrimental to the stability of the alkali metal hypochlorite and does not enjoy the usefulness of the improvement effect of the present invention.

The phthalocyanine pigment (d) used in the present invention includes 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, M = metal Atoms) are particularly preferably used. Specifically, X is preferably one or more combinations of Br, I, and Cl, and M is preferably a phthalocyanine pigment obtained from one or more combinations of Fe, Co, and Cu. 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. It can also be suitably used as a mixed pigment as adjusted.

The content of the phthalocyanine pigment in the composition is in the range of 0.0002 to 0.01% by weight. If the content in the composition is less than 0.0002% 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 colored liquid washing and bleaching composition of the present invention includes:
Further, builders exhibiting chlorine resistance as commonly used can be blended. Further, alkane sulfonate, fatty acid salt, alkyl sulfate salt as a surfactant,
Alkyl benzene sulfonate, alkyl naphthalene sulfonate, alkyl sulfosuccinate / alkyl diphenyl ether disulfonate, alkyl phosphate, polyoxyethylene alkyl sulfate, polyoxyethylene alkyl allyl sulfate, polyoxyethylene alkyl phenyl ether Anionic surfactants such as sulfonates (excluding nitrogen-containing anions such as amino acid derivatives); polyoxyethylene alkyl ethers,
Polyoxyethylene alkyl allyl ether, oxyethylene / oxypropylene block copolymer, lower /
Nonionic surfactants such as ethylene oxide / propylene oxide adducts of higher alcohols (excluding esters, sugar skeletons, amines and amides); cationic surfactants such as sulfobetaine, carbobetaine and alkyldimethylamine oxide An appropriate amount of one or a combination of two or more agents or amphoteric active agents can be blended.

PTS (paratoluenesulfonic acid)
Aromatic sulfonic acids such as MXS (meta-xylene sulfonic acid) and cumene sulfonic acid; fluorescent dyes; radical scavengers such as BHT; clay minerals such as montmorillonite and snactite; inorganic salts such as NaCl, sodium sulfate and calcium carbonate; It is also possible to incorporate components such as acrylic acid, allylic acid / maleic acid copolymer, cross-linked polycarboxylic acid; 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 colored liquid washing / bleaching composition having the composition shown in Table 1 was prepared, and the detergency, storage stability and 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 cleaning power was evaluated by selecting a general household flush toilet bowl to which dirt that could not be removed only by flowing water was attached as the surface to be cleaned, and then applying the liquid detergent composition for evaluation to the flush toilet bowl. After sprinkling with 30 g and standing for 3 minutes, rinsing by flushing, the state of the inner surface of the toilet bowl was visually judged. Evaluation criteria ：: Stain is reduced by 80% or more △: Stain is reduced by 40 to 80% ×: Stain is hardly removed (2) Storage stability was evaluated by using a colored liquid washing and bleaching composition for evaluation as a polyethylene cylinder. A bottle (higher bottle: filled volume: 725 ml, bottom wall thickness: 0.6 mm) was filled with 600 ml and sealed, and stored at 40 ° C. for 3 months. 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.) (3) 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]

────────────────────────────────────────────────── (5) Continuation of the front page (51) Int.Cl. ⁶ identification code FI C11D 7:36 7:54) (56) References JP-A-3-88898 (JP, A) JP-A-61-264098 (JP) (A) U.S. Pat. No. 3,629,124 (US, A) (58) Fields investigated (Int. Cl. ⁶ , DB name) C11D 7/60 C09B 47/14 C11D 7:06 C11D 7:14 C11D 7:36 C11D 7: 54 CA (STN) CAOLD (STN) REGISTRY (STN)

Claims (2)

(57) [Claims] (1) An alkali metal hypochlorite salt of 0.5 to 10
(B) 0.1 to 5% by weight of a caustic alkali and / or silicate; and (c) an aminophosphonic acid-N-oxide type sequestering agent.
A colored liquid washing and bleaching composition comprising 0.001 to 0.3% by weight and (d) 0.0002 to 0.01% by weight of a phthalocyanine pigment. 2. The colored liquid washing / bleaching composition according to claim 1, wherein the phthalocyanine pigment comprises a compound represented by the following general formula. _{C 32 H (16-n)} X n N 8 M ( where, n = 0~16, X = a halogen atom, M = metal atom)