JPH01113498A - Granular coloring composition - Google Patents

Abstract

PURPOSE:To obtain the title composition giving a bleaching agent composition which has a beautiful appearance, is free from color contamination and misuse, maintains excellent coloration even in long-term storage, and therefore has an excellent commodity value, by using a specified water-soluble dye, an antioxidant, and a water-soluble binder as its principal constituents, and mixing a base material therewith as required. CONSTITUTION:The title composition having a grain size of about 8-60 mesh is obtained by mixing its principal constituents comprising 0.0005-5wt.% water- soluble dye (A), such as C.I. Acid Blue 9, which will fade through decomposition in an aqueous solution of an oxygen-base bleaching agent, 0.01-5wt.% antioxidant (B) such as sodium L-ascorbate, and 0.1-20wt.% water-soluble binder (C) which comprises CMC, hydroxyethylcellulose, PVA, a naphthalenesulfonate, or an anionic or nonionic surface active agent with, as required, 30-98wt.% base material (D) comprising various water-soluble salts, an extender pigment, a white pigment, etc., and additives (E), such as an enzyme, a chelating agent, a mildewproofing agent, and a perfume, so as to provide a total of 100wt.%, and granulating this mixture.

Description

DETAILED DESCRIPTION OF THE INVENTION (Field of Industrial Application) The present invention relates to a novel granular coloring composition, and particularly to a granular coloring composition useful as an additive for oxygen bleaches.

(Prior art and its problems) Conventionally, chlorine bleach and oxygen bleach have been known as bleaching agents, but oxygen bleach has been widely used in recent years because the former has a chlorine odor. It's starting to look like this.

These oxygen bleaches are white granules whose main ingredients are bleaching agents such as sodium percarbonate and sodium perborate, and are used to improve the product image of these oxygen bleaches and to impart a bluing effect to white clothing. There is one product on the market in which a small amount of a blue granular coloring composition is added to white bleach granules.

If this blue-colored granular additive is not added to the white bleach granule, the bleach granule is simply a white odorless powder, which contains sugar commonly used in households.
In some cases, it is difficult to distinguish between salt, potato starch, wheat flour, detergent, etc.

Furthermore, in households with infants and children, it is easy to mistake white bleach for food, and there is a risk of accidentally putting it in the mouth. In such a case, if a small amount of colored granules are added, it will be possible to distinguish between the two, and accidents can be prevented.

The present inventors previously disclosed in Japanese Patent Publication No. 56-35718 a granular additive for bleaching agents 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. proposed a composition. However, when washing and bleaching fabrics using a bleach composition containing such a small amount of colored granules, the blue pigment stains the fabrics depending on the method of use, resulting in a blue color on the fabrics after drying. There was a considerable risk of spotting. In addition, in general, most of the woven fabrics to be bleached are plain white, and they also have the disadvantage that if even a small amount of blue pigment is dyed onto the fabric, staining becomes more noticeable. In particular, if you soak clothing in a small amount of water in a wash basin, sprinkle bleach containing colored granules on top, and leave it as is without stirring, no matter what kind of pigment you use, it will affect the texture of the fabric. Pigment particles penetrated deeply into Part H, and even after thorough washing with water, spot-like staining was observed.

(Means for Solving the Problems) As a result of intensive research in order to solve the above-mentioned drawbacks, the present inventor has developed a granular coloring composition using a specific dye and oxygen bleach granules in a solid state. When mixed and stored, the granular coloring composition retains its bright color for a long period of time; however, when bleaching clothing etc., the granular coloring composition dissolves in the aqueous bleach solution and further The present invention was completed by discovering that the dye in the granular coloring composition immediately decomposes and fades due to the oxidizing action of the bleaching agent, thereby eliminating color staining on woven fabrics.

That is, the present invention is a granular coloring composition comprising as main components a water-soluble dye that decomposes and fades in an aqueous oxygen bleach solution, an antioxidant, and a water-soluble binder.

(Function) The most important finding that led to the completion of the present invention is that, among conventionally known dyes, granular coloring containing triphenylmethane dyes, xanthine dyes, or dyes with other specific structures The composition dissolves uniformly in an aqueous oxygen bleach solution and easily decomposes and decolors these dyes before they adhere to clothing fibers, preventing staining of woven fabrics. This is a technical finding that when the granular coloring composition of the invention is uniformly mixed in a solid state, no decomposition reaction occurs because no water is present, and a stable colored state is maintained for a long period of time.

In contrast, when conventional pigments are used, when added to water, the pigment concentration locally increases in the bleach cleaning solution, and pigments are insoluble and have less oxidation resistance than dyes. Because of this, the pigment remains as it is, and the pigment particles sometimes penetrate between the fibers and cause physical dyeing. On the other hand, when a specific water-soluble dye is used in the present invention, the dye dissolves and diffuses into the bleach aqueous solution and has oxidative decolorization properties, so the dye is easily decolorized by the bleach, and the conventional technique The risk of contamination of bleached fabrics such as woven fabrics can be eliminated.

However, when storing the solid mixture of the above-mentioned granular coloring composition and oxygen bleach in a closed container, there is no noticeable change in the short term, but when stored for a long time, the dye decomposes, albeit slightly. This caused a problem in that the color of the granular coloring composition gradually progressed. Therefore, in order to impart long-term fading stability to the dye,
By adding an antioxidant to the granular coloring composition, it is possible to completely block the influence of the nascent oxygen that occurs in a closed container, allowing the granular coloring composition to maintain its sharpness for a long time and prevent bleaching. The product image of the agent composition is not deteriorated.

(Preferred Embodiments) Next, the present invention will be described in more detail by citing preferred embodiments.

As the dye used in the present invention, any dye can be used as long as it decomposes and fades in an aqueous solution of an oxygen bleach.

The dye that can be suitably used in the present invention is prepared by preparing a 1% by weight aqueous solution of sodium percarbonate, dissolving the dye therein to a concentration of 0.1% by weight, and observing the state of fading while stirring at 25°C. This means that the hue of the dye becomes almost unperceivable after about 12 hours. On the other hand, dyes whose hue can be clearly perceived even after about 12 hours stain various woven fabrics to be bleached during the bleaching process.

For example, preferred dyes include C,1, acid violet 15.43.49, C,
1, Acid Blue 1.7.9.15.22.83.9
0.93.100.103.104, C,1, Acid Green 3.9.16, C,1, Basic Violet 1.3.14, C,1, Basic Blue 1.5.7
．． 19.26, C,1, Basic Green 1.4, C,1, Mordant Violet 1, C,1, Mordant Blue 1.29.47, (:, 1.
Triphenylmethane water-soluble dye such as Direct Blue 41: C,! , Acid Red 51.52.87.92.94
, C-■・Basic Red 1, C,1, Basic Violet 1O1C,1, Mordant Red 2) Xanthine dyes such as: c,r, Acid Bluff 4, C,t, Acid Violet 43, C,1 , Mordant Blue 13, etc. These dyes can be used alone or in combination of two or more.

The amount of these dyes used is as follows:
In terms of the amount of 0ffi, it is preferably in the range of 0.0005% to 5% by weight, preferably 0.001% to 0.5% by weight. If the amount of dye is too large, the coloring properties of the dye will be poor and clear colors will not be obtained.

As the antioxidant used in the present invention, any conventionally known antioxidant can be used. For example, preferred ones are ascorbic acid and its sodium salt, erythorbic acid and its sodium salt, isopropyl citrate, and dibutyl. Hydroxytoluene, OL-α-tocophenol, nordihydroguaretic acid, butylhydroxyanisole, propyl gallate, 2,2'-methylene-bis-(4-methyl-6-ter
(t-butylphenol), dilaurylthiodipropionate, triphenylphosphite, and the like. These antioxidants can be used alone or in combination of two or more.

The amount of these antioxidants used is preferably in the range of 0.01% to 5% by weight, more preferably 0.05% to 2% by weight in 100 parts by weight of the granular coloring composition of the present invention.
This is the range that accounts for % by weight.

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 bleach, but also acts as a binder and fluidizer when making a granular coloring composition. It also functions as an agent, dispersant, etc.

The water-soluble binder used in the present invention may be any polymer or other relatively high molecular weight material that is water-soluble and has adhesive properties when it contains water, such as methylcellulose. , carboxymethylcellulose, and droxymethylcellulose, hydroxyethylcellulose, sodium alginate, guar gum, gum arabic, gelatin, casein, collagen, chitin,
Water-soluble polymers such as chitosan, polyvinyl alcohol, sodium polyacrylate, polyethylene oxide, polyoxyethylene oxypropylene copolymers, polyvinylpyrrolidone, etc., propylated naphthalene sulfonates,
Naphthalene sulfonate surfactants such as butylated naphthalene sulfonates, formaldehyde condensates of naphthalene sulfonates, linear alkylbenzene sulfonates having 8 to 22 carbon atoms, α-olefin sulfonates having 8 to 22 carbon atoms, polyoxylic acids having 8 to 22 carbon atoms Ethylene alkyl ether sulfate, carbon number 8 to 22
anionic surfactants such as alkyl phosphate ester salts, polyoxyethylene alkyl ethers having 8 to 22 carbon atoms, polyoxyethylene alkyl phenyl ethers having 8 to 22 carbon atoms, sorbitan fatty acid esters having 8 to 22 carbon atoms, glycerin Examples include nonionic surfactants such as fatty acid esters. These water-soluble polymers or surfactants may be used alone or in combination, and one or two of them may be used alone or in combination.
One or more types can be used in combination.

The amount of these water-soluble binders used is 10% of the granular coloring composition.
The content is preferably 0.1% to 20% by weight, more preferably 0.5% to 10% by weight based on 0 parts by weight.

In the present invention, it is preferable to use various water-soluble salts as bases, extender pigments, white pigments, etc. in addition to the above-mentioned ingredients. The main purposes of these bases are to moderately reduce the dye concentration in the granular coloring composition of the present invention to improve the coloring properties of the dye, and to make the water-soluble binder exhibit better performance. , and other bleaching agents. For example, preferred examples include sodium tripolyphosphate, sodium carbonate, sodium sulfate,
Examples include zeolite, talc, titanium oxide, and the like. These bases can be used preferably in an amount of about 30 to 95 ffl in 100 parts by weight of the pre-granular one-color composition of the present invention.

The main components of the granular coloring composition of the present invention are as described above, but chromatic pigments and other dyes may be used in combination to the extent that staining of clothing is not observed. Furthermore, various conventionally known additives can be added to the extent that they do not impede the objectives and effects of the present invention. These additives include enzymes, chelating agents, fungicides, fragrances, and the like.

Next, to explain the method for manufacturing the above granular coloring composition, each of the above components is mixed uniformly, an amount of liquid, preferably water, is added to the extent that the mixture has plasticity, and then normal granulation is carried out. The powder mixture is granulated to an appropriate degree by a method such as crushing granulation, crushing granulation, extrusion granulation, rotary granulation, or spray granulation, or by a fluidized bed granulation method in which a water-soluble binder solution is sprayed onto the powder mixture. It is grained. The preferred particle size is the additive i
Although it varies depending on the shape and particle size of the Ff whitening agent, the most common range is usually about 8 to 60 meshes, preferably about 12 to 28 meshes.

The granular coloring composition of the present invention obtained as described above is added to various bleaching agents, but sodium percarbonate and sodium perborate are preferable as these bleaching agents, and the addition ratio is determined depending on the granular coloring composition. It varies depending on the dye concentration, coloring power, etc. of the product, but basically the granular coloring composition in the bleach composition is at least to the extent that it can be easily detected with the naked eye, for example,
As a granular coloring composition, O is added in an amount of 15 to 5%.

(Effects) A bleach composition prepared by adding the granular coloring composition of the present invention to a granular or powdered oxygen-type bleach is visually impaired because the granular coloring composition is mixed therein. It is beautiful, does not lose its coloring properties even after long-term storage, and has excellent commercial value. Furthermore, there is no possibility of misuse with other products having similar appearance, such as sugar, salt, detergent, etc.

Furthermore, during the actual bleaching process, dyes that are dissolved in water are easily bleached by bleaching agents, so that no spot staining occurs on clothing.

In addition to bleaching agents, the granular coloring composition of the present invention can also be used by mixing with detergents, mold removers, water pipe cleaners, toilet cleaners, bathtub cleaners, etc., and can be used as a colorant for different purposes. By changing , it becomes possible to easily identify them, and misuse can be prevented.

Hereinafter, the present invention will be further explained with reference to Examples and Comparative Examples. In the text, parts and percentages are based on weight unless otherwise specified.

Example I C, 91.0 parts of acid blue, 40 parts of a formaldehyde condensate of sodium naphthalene sulfonate, 10 parts of sodium ascorbate, 929 parts of Glauber's salt, and 20 parts of titanium oxide were uniformly blended in a high-speed mixer. did. After stirring and raising the temperature to 60℃ using a kneader, 60 parts of water was added and 3
After kneading for 0 minutes, the mixture was continuously taken out, crushed in a crusher, and dried in a fluidized bed. The mixture was then sieved to obtain 450 parts of the blue granular colored composition of the present invention having 12 to 32 meshes.

Example 2 C, [, 491.0 parts of acid violet, 40 parts of formaldehyde condensate of sodium naphthalene sulfonate,
5 parts of sodium erythorbate, 934 parts of Glauber's salt, and 20 parts of titanium oxide were blended according to Example 1 to obtain 500 parts of a purple granular colored composition of the present invention having 12 to 32 meshes.

Example 3 (:, 1. Acid blue 931.0 parts, isopropyl citrate 5 parts, polyethylene glycol '11,000
40 parts of sodium carbonate and 954 parts of sodium carbonate were blended according to Example 1 to obtain 480 parts of a blue granular colored composition of the present invention having 12 to 32 meshes.

Example 4 c, r, basic violet l 1.0 part, DL-
10 parts of α-tocopherol, 100 parts of 20% sodium polyacrylate aqueous solution, 950 parts of Glauber's salt, and 1 part of titanium oxide
9 parts were compounded according to Example 1 to obtain 520 parts of a purple granular coloring composition of the present invention having 12 to 32 meshes.

Example 5 10.5 parts of C,1 acid blue, 5.0 parts of dibutylhydroxytoluene, 50 parts of formaldehyde condensate of sodium naphthalene sulfonate, and 945 parts of sodium carbonate
A portion was treated according to the recipe of Example 1 to obtain 480 parts of a blue granular colored composition of the present invention having 12 to 32 meshes.

Example 6 c, r, 521.0 parts of acid red, 50 parts of formaldehyde condensate of sodium naphthalene sulfonate, 9 parts of Glauber's salt
50 parts of titanium oxide and 10 parts of titanium oxide were mixed according to the recipe of Example 1 to obtain 12 to 32 meshes of the red granular coloring composition SOO part of the present invention.

Comparative Example 1 Using the same formulation as in Example 1 except for 10 parts of sodium monoascorbate, 12 to 3
450 parts of 2 meshes of H color powder colored composition were obtained.

Comparative Example 2 400 parts of a 12 to 32 mesh blue granular coloring composition was obtained using the same formulation as in Example 2 except for 5 parts of sodium erythorbate.

Comparative Example 3 Using the same formulation as in Example 3 except for 5 parts of isopropyl citrate, 500 parts of a 12 to 32 mesh blue granular coloring composition was obtained.

Comparative Example 4 Using the same formulation as in Example 4 except for 10 parts of DL-α-tocopherol, 450 parts of a h-color powder colored composition having 12 to 32 meshes was obtained.

Comparative Test Example 5 parts of each of the granular coloring compositions obtained in Examples 1 to 6 and Comparative Examples 1 to 3 and 95 parts of sodium percarbonate were lightly blended in a closed container, allowed to stand, and then left to stand for a certain period of time. The fading property of the granular colored composition was visually determined.

The results are listed in Table 1 below, and since the examples contain antioxidants, almost no fading was observed in the presence of sodium percarbonate, and long-term fading stability was observed. It was done.

In addition, cotton was soaked in 1,000 parts of a 1% aqueous solution of sodium percarbonate, and Examples 1 to 6 and Comparative Examples 1 to 3 were soaked in it.
Sprinkle 0.5 part of the granular colored composition obtained by
- After being left to stand overnight, the dye was taken out the next day, washed with water and dried, and then tested for dyeability. No dyeability was observed in any of the dyestuffs on cotton.

γ-J 1 3 combination 1 piece ' 2 pieces ' 3 pieces 'Example 1
◎ ◎ ◎Example 2
◎ ◎ ◎Example 3 ◎
◎ O Example 4 ◎ ◎
O Example 5 ◎ ◎
O Example 6 ◎ ◎ O Reference example 1 0 △ △ Reference example 2 0
△ △Reference example 3 0
Δ △Reference example 4 0 △
Δ◎: No fading is observed visually.

O: Slight fading is visually observed.

△: Slight fading is observed visually.

Patent Applicant Dainichiseika Kagyo Co., Ltd. Agent Patent Attorney Yoshi 1) Katsuhiro, ゛- Procedural Notice (Spontaneous) November 30, 1988

Claims (2)

[Claims] (1) A granular coloring composition containing as main components a water-soluble dye that decomposes and fades in an aqueous oxygen bleach solution, an antioxidant, and a water-soluble binder. (2) The granular coloring composition according to claim (1), further comprising a base.