JPH0721158B2 - Granular coloring composition - Google Patents

Description

TECHNICAL FIELD The present invention relates to a granular coloring composition which is useful as an additive for a novel oxygen-based bleaching detergent containing the bleaching agent.

(Prior art and its problems) Conventionally, chlorine-based bleaching agents and oxygen-based bleaching agents are known as bleaching agents, but the oxygen-based bleaching agents are widely used in recent years because the former have chlorine odor. Is starting to appear.

These oxygen-based bleaching agents are white granules containing bleaching agents such as sodium percarbonate and sodium perborate as the main components, and are intended to improve the product image of these oxygen-based bleaching agents and to impart a bluing effect to white clothing. Thus, a white bleach granule containing a small amount of a blue-based granular coloring composition added thereto is marketed.

If this blue colored granular additive is not added to the white bleach granules, the bleach granules are simply white odorless powders, sugars commonly used in the home,
There are also situations where it is difficult to distinguish from salt, potato starch, wheat flour, detergent, etc.

In addition, in a household with infants and children, it is easy to mistake the white bleaching agent for food and there is a risk of accidentally putting it in the mouth. In such a case, if a small amount of the colored granules is added, the colored granules can be easily identified and the accident can be prevented.

The present inventors have previously disclosed in JP-B-56-35718 that a granular additive for a bleaching agent comprising a blue pigment and a surfactant having an aromatic sulfonic acid group or an alkali metal base thereof and a bleaching agent containing the same. A composition was proposed. However, when a bleaching composition containing such a small amount of colored granules is used and the cloth is washed and bleached, the blue pigment is dyed on the cloth depending on the method of use, and the cloth after drying has a blue color. There was a considerable risk of spotting. In general, bleached woven fabrics are often white and plain, and there is a drawback that even if a small amount of a blue pigment is dyed on the fabric, contamination is more noticeable. In particular, if you put a small amount of water in a washbasin, soak your clothes, sprinkle a bleach containing colored granules from the top, and leave it as it is without stirring, no matter what pigment you use, Pigment particles deeply penetrated and adhered into the stitch, and spot-like contamination was observed even after sufficient washing with water.

(Means for Solving Problems) As a result of earnest research to solve the above-mentioned drawbacks, the present inventors have found that a granular coloring composition containing a specific dye and an oxygen-based bleaching granule in a solid state. When mixed and stored, the granular coloring composition retains a bright color for a long period of time, but when bleaching clothes and the like, the granular coloring composition dissolves in the bleaching solution, and The dye in the granular coloring composition immediately decomposes and fades due to the oxidizing action of the bleaching agent,
The present invention has been completed by finding that colored stains on a woven fabric can be eliminated.

That is, the present invention is an oxygen-based bleaching agent and a granular coloring composition for addition of an oxygen-based bleaching agent-containing detergent, which comprises a water-soluble dye and a water-soluble binder as main components which decompose and discolor in an aqueous oxygen-based bleaching agent solution.

(Function) The most important finding that the present invention has been completed is that a granular coloring composition containing a triphenylmethane dye, a xanthene dye, or another dye having a specific structure among known dyes. The present invention dissolves uniformly in an aqueous solution of oxygen-based bleaching agent and easily decomposes and decolorizes these dyes before adhering to the fibers of clothing, and prevents the fabric from being contaminated. It is a technical finding that, in the state where the granular colored composition of (1) is mixed uniformly in a solid state, no decomposition reaction occurs because water does not exist, and a stable colored state is maintained for a long period of time.

On the other hand, when a conventional pigment is used, when it is added to water, the concentration of the pigment locally increases in the bleaching washing liquid, and the pigment is insoluble and has oxidation resistance as compared with the dye. Therefore, the pigment remains as it is, and the pigment particles may penetrate between the fibers and be physically dyed. On the other hand, in the case of using a specific water-soluble dye in the present invention, the dye is dissolved and diffused in the bleaching agent aqueous solution and further has an oxidative decolorizing property, so that the dye is easily decolorized by the bleaching agent, and the conventional technique is used. The risk of contamination of the bleached woven fabric can be eliminated.

(Preferred Embodiment) Next, the present invention will be described in more detail with reference to preferred embodiments.

As the dye used in the present invention, any dye can be used as long as it is a dye that decomposes and fades in an aqueous solution of an oxygen-based bleaching agent.

The dye that can be preferably used in the present invention is prepared by preparing a 1% by weight aqueous solution of sodium percarbonate and adding 0.1% by weight of the dye therein.
It means that the color of the dye becomes almost imperceptible after about 12 hours by observing the fading state while stirring at 25 ° C with stirring. On the other hand, the dye whose hue can be clearly perceived even after about 12 hours contaminates various woven fabrics which are bleached substances during the bleaching treatment. For example,
Preferred dyes are CI acid violet 15,43,49, CI acid blue 1,7,9,15,22,83,90,93,
100, 103, 104, CI Acid Green 3, 9, 16, CI Basic Violet 1, 3, 14, CI Basic Blue 1, 5, 7, 19, 26, CI Basic Green 1, 4, CI Moldant Violet 1, Triphenylmethane-based water-soluble dyes such as CI Mordant Blue 1, 29, 47, CI Direct Blue 41; CI Acid Red 51, 52, 87, 92, 94, CI Basic Red 1, CI Basic Violet 10, CI Mol Xanthene dyes such as Dant Red 27; CI Acid Blue 74, CI Acid Violet 43, CI Moldant Blue 13 and the like. These dyes can be used alone or in combination of two or more.

The amount of these dyes used is the granular coloring composition 100 of the present invention.
Generally, 0.0005% to 5% by weight is preferable, and 0.001% to 0.5% by weight is preferable.
The range that occupies is good. If the amount of the dye is too large, the color development of the dye is poor and a clear color cannot be obtained.

The water-soluble binder used in the present invention not only acts as a protective layer for the dye in an oxidizing atmosphere when added to an oxygen-based bleaching agent, but also a binder and a fluidizing agent when producing a granular coloring composition. And also functions as a dispersant.

As the water-soluble binder used in the present invention, any material may be used as long as it is water-soluble and is a polymer having tackiness when containing water or other relatively high molecular weight material, for example, methyl cellulose. , Carboxymethyl cellulose, hydroxymethyl cellulose, hydroxyethyl cellulose, sodium alginate, guar gum, gum arabic, gelatin, casein, collagen, chitin,
Water-soluble polymers such as chitosan, polyvinyl alcohol, sodium polyacrylate, polyethylene oxide, polyoxyethyleneoxypropylene copolymer, polyvinylpyrrolidone, etc., propylated naphthalene sulfonate,
Butylated naphthalene sulfonates, naphthalene sulfonate-based surfactants such as formaldehyde condensation products of naphthalene sulfonates, linear alkylbenzene sulfonates having 8 to 22 carbon atoms, α-olefin sulfonates having 8 to 22 carbon atoms, and polyoxy having 8 to 22 carbon atoms. Anionic surfactants such as ethylene alkyl ether sulfate, alkyl phosphate salt having 8 to 22 carbon atoms, polyoxyethylene alkyl ether having 8 to 22 carbon atoms, polyoxyethylene alkylphenyl ether having 8 to 22 carbon atoms, Examples thereof include nonionic surfactants such as sorbitan fatty acid esters having 8 to 22 carbon atoms and glycerin fatty acid esters. These water-soluble polymers or surfactants are used alone or in combination, and one kind or a combination of two or more kinds can be used.

The amount of these water-soluble binders is 100
The range of 0.1 to 20% by weight is preferable, and the range of 0.5 to 10% by weight is more preferable.

In the present invention, in addition to the above two components, it is preferable to use various water-soluble salts as base materials, extender pigments, white pigments and the like. These bases have the main purpose of appropriately lowering the dye concentration in the granular coloring composition of the present invention to improve the color developability of the dye and the purpose of better exhibiting the performance of the water-soluble binder. , And other correlates with bleach. For example, preferred examples include sodium tripolyphosphate, sodium carbonate, sodium sulfate, zeolite, talc, titanium oxide and the like. These bases can be used in an amount of preferably about 30 to 98% by weight in 100 parts by weight of the granular coloring composition of the present invention.

The main components of the granular coloring composition of the present invention are as described above, but chromatic color pigments and other dyes may be used in combination to the extent that contamination of clothing is not recognized. Further, various conventionally known additives can be added to the extent that the objects and effects of the present invention are not impaired. Examples of these additives include enzymes, chelating agents, antifungal agents, and fragrances.

Next, explaining the method for producing the above granular coloring composition, the above components are uniformly mixed, and a liquid, preferably water, is added in an amount such that the mixture has plasticity, and then the usual granulation is performed. A method such as crushing granulation, crushing granulation, extrusion granulation, rotary granulation, or spray granulation, or a fluidized bed granulation method of spraying a water-soluble binder solution on a powder mixture to an appropriate degree. Be grained. The preferred particle size varies depending on the shape and particle size of the bleaching agent as an additive, but usually 8 to
The most common range is about 60 mesh, preferably about 12-28 mesh.

The granular coloring composition of the present invention obtained as described above is added to various bleaching agents. As these bleaching agents, sodium percarbonate and sodium perborate are preferable, and the addition ratio is the granular coloring composition. It varies depending on the dye concentration of the product, the coloring power, etc., but basically, the granular coloring composition in the bleaching composition is at a level that is easily perceptible to the naked eye, for example,
The granular coloring composition is added in a proportion of 0.5 to 5% by weight.

(Effect) A bleaching agent composition in which the granular coloring composition of the present invention is added to a granular or powdery oxygen-type bleaching agent has a granular coloring composition mixed therein, so that the bleaching composition is visually recognizable. It is beautiful and has excellent commercial value, and does not cause misuse with other similar articles such as sugar, salt and detergent.

Furthermore, in the actual bleaching process, the dye is easily decolorized by the bleaching agent when dissolved in water, so that no spot-like contamination of clothes occurs.

In addition to the bleaching agent, the granular coloring composition of the present invention is mixed with an oxygen-based bleaching agent-containing cleaning agent, for example, a detergent, a fungicide, a water pipe cleaning agent, a toilet cleaning agent, a bath kettle cleaning agent, etc. They can be used for different purposes, and by changing the color according to the purpose, they can be easily identified and misuse can be prevented.

Hereinafter, the present invention will be described more specifically with reference to Examples and Comparative Examples. In the text, parts and% are based on weight unless otherwise specified.

Example 1 1.0 part of CI Acid Blue 9, 40 parts of formaldehyde condensate of sodium naphthalene sulfonate and sodium sulfate
959 parts were blended uniformly with a high speed mixer. This was stirred and heated to 60 ° C. in a kneader, 60 parts of water was added, and the mixture was kneaded for 30 minutes, continuously taken out, crushed by a crusher and fluidized bed dried. Then, it was sieved to obtain 450 parts of the blue granular coloring composition of the present invention having 12 to 32 mesh.

Examples 2 to 22 and Comparative Examples 1 to 6 Various granular coloring compositions of the present invention and comparative examples were prepared in the same manner as in Example 1 except that the formulations shown in Table 1 below were used.

In the above table, each symbol has the following meaning.

AB; Acid blue NSFA; Formaldehyde condensate of sodium naphthalene sulfonate AV; Acid violet AG; Acid green BV; Basic violet BB; Basic blue BG; Basic green MV; Moldant violet TPPA; Sodium tripolyphosphate AR; Acid red BR; Basic Red MR; Mordant Red PEG; Polyethylene Glycol PAANa; Sodium Polyacrylate 20% Aqueous Solution PVP; Polyvinylpyrrolidone DBSNa; Dodecylbenzene Sulfonate MB; Mordant Blue DB; Direct Blue Comparative Test Examples Examples 1 to 22 and Comparison 0.5 parts each of the granular coloring compositions obtained according to Examples 1 to 6 and 5 parts of sodium percarbonate were lightly blended in a closed container.

Dissolve this in 1,000 parts of water and add cotton cloth (7 × 10c
m) was dipped, left standing overnight, taken out the next day, and visually inspected for dyeability of the dye or pigment after washing with water for 5 minutes and drying. I was not able to admit. On the other hand, in all Comparative Examples, spot-like contamination was observed on the entire cotton cloth. still,
Similar results were obtained using vinylon, rayon and acetate cloths instead of cotton cloths.

Further, even when the above blended product was stored in a glass bottle for a long period of time, no fading of the granular coloring composition was observed.

Claims (1)

[Claims] 1. A granular coloring composition for adding an oxygen-based bleaching agent and a cleaning agent containing an oxygen-based bleaching agent, which comprises a water-soluble dye and a water-soluble binder which are decomposed and discolored in an aqueous solution of an oxygen-based bleaching agent as main components.