JPH08277368A - Composition for dyeing and its production - Google Patents

Abstract

PURPOSE: To obtain a composition capable of freely providing arbitrary color, size and unevenness of spot of density and thereby sensitively corresponding to mode and readily forming new appearance by preparing dye-containing particles by extremely simple method in after-treatment process of fabrics. CONSTITUTION: This composition for dyeing comprises a substantially water- insoluble solidified material of a polyanionic polymer with a polyamine or a polyamine salt and contains a dye in particles whose particle form is substantially granular, spindle-like or linear. This method for producing a composition for dyeing comprises forming granular water-insoluble material containing dye by stirring and mixing an aqueous solution containing a dye and a polyanionic polymer with an aqueous solution of a polyamine or a polyamine salt.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a dyeing composition. More specifically, it relates to a dyeing composition capable of dyeing fine spots having an arbitrary color tone on a cloth and a method for producing the same.

[0002]

2. Description of the Related Art Conventionally, a color mix to which fine color spots are scattered on a synthetic fiber cloth for the purpose of natural color unevenness seen in wool or linen, or for the purpose of a new visual effect. It is common practice to apply the coloring. In this case, it was necessary to take the following method in order to impart a shade of light and shade to the synthetic fiber cloth which originally had a uniform dyed foot, or to form a spot having a distinct different color or a shade of color difference.

That is, (1) a method of forming a fabric by using a spun yarn prepared by mixing fibers that have been dyed separately at the cotton stage in advance and a yarn that has been dyed separately at the yarn stage, and knitting and weaving. (2) A method in which fibers having different dyeability are mixed, knitted and woven into a cloth, and then dyed (3) A method in which spot patterns are printed by the number of colors by roll printing or screen printing (4) Particles containing a dye Examples of the method include a method of producing, applying to fabric, and developing color.

However, in the method (1), preparation must be carried out from the cotton wool dyeing stage in order to obtain a fabric having a desired color tone, and a very long process must be passed. Therefore, it is difficult to cope with the short delivery time in accordance with the recent trend of short cycles and the production of small lots of various kinds, and there is a problem that the cost becomes high.

Also in the method (2), although the dyeing can be performed in the post-processing stage, it is necessary to prepare a specific cloth, and the density and size of the uneven spots of color are determined at this stage. Further, regarding the color tone, the combination of dyeing methods and materials that can be dyed in different colors is limited, so there is a problem that there are at most a few colors and the usable color combinations are also limited. The method of printing in (3) is often used, but in this case, the engraving pattern of the roll that determines the density and size of the spots and the production of the screen mold are time-consuming and costly, so there is no freedom. Low,
Furthermore, if the number of colors of spots is large, printing must be repeated for that number of sheets. Also, the size of the obtained spots is too small to engrave because the screen mesh and roll engraving are limited.

All of the above-mentioned methods have a common problem that they have a low degree of freedom in the color pattern of spots and are difficult to perform in a small lot. Therefore, a method such as (4) is known. That is, in the method (4), after the dye is made into coarse particles, the dispersion is applied by means of screen printing, coating, dipping, or the like, which can be easily applied by post-processing, and can be performed by a single treatment. Since particles of different colors can be applied, there is an advantage that multicolor spot dyeing can be easily performed.

However, among these known examples, Japanese Patent Publication No. 55-42194 and Japanese Patent Publication No. 40-2203.
No. 2 and Japanese Patent Publication No. 48-22876, a technique in which a coagulated product of a water-soluble polymer or an activator and a dye is once separated by filtration, dried, pulverized and sieved before use. In the case of, the size of the particles is arbitrary and uniform, and the stability is high, but the process is quite complicated and the energy loss for drying the wet mud is large, so a small amount of many kinds There is a basic problem that it is difficult to take immediate action. The dye-containing particles can be prepared in advance, but in that case, the color and the size of the particles are fixed, which causes a problem that the versatility of the color pattern is lost.

[0008] On the other hand, if the dye-encapsulated coagulated product which has been granulated in water can be used as it is, it is simple and has a high degree of freedom at the dyeing site, but another problem remains.

That is, in JP-B-53-42833, a liquid consisting of a water-soluble polymer having a salting-out property and a dye is added to a liquid having a function of coagulating the polymer and coagulated with stirring. A technique is disclosed in which dye-encapsulated capsule particles are obtained and dispersed in water to be used as a composition for multicolor spot dyeing.

However, if the polymer coagulated product produced by salting out is to be used as it is, it is necessary to disperse the necessary coagulated product of the dye and the polyanion polymer in water in the form of particles of an appropriate size. , It's very difficult to control. That is, the purpose of the present invention is not to cure the polyanion polymer aqueous solution in the form of predetermined droplets using a device such as a special sprayer in advance in the coagulating liquid, but to simply form the particles in the liquid by the shearing force of stirring. In such a case, the properties of the solidified product are very important, and if the solidified product is highly tacky, the solidified products will stick to each other during stirring, resulting in a large amorphous mass. Further, if the coagulated product is too tough, it will not be granulated by the shearing force due to stirring and will become a long lint-like bundle, which cannot be used as it is as the dye-containing particles. Alternatively, the coagulated product may become an extremely fine powder, and in this case, when applied to the cloth, the color unevenness becomes a plain state invisible to the naked eye. Also, depending on the compatibility of the polymer coagulate and the dye, the dye that escapes from the coagulate colors the liquid even if the coagulate is made into particles, so when applied to the fabric, the background color other than the spots may be colored. become. In that case, the color of the spots is not clear, and in the case of color mixing, the background color portion is completely mixed, so that there is a problem that outstanding spot dyeing cannot be performed.

[0011]

DISCLOSURE OF THE INVENTION In order to eliminate these drawbacks, the present inventors have diligently studied the problems, and as a result, when an aqueous solution of polyamine or polyamine salt was used for an aqueous solution of a polyanion polymer containing a dye. , A dyeing composition in which the properties of the solidified product produced by the complex of both are suitable for particle formation by stirring and a stable dyeing composition is obtained, and furthermore, since the dye-containing particles are not covered with a hard coating, the dyeing It has been found to have the advantage of high property.

The object of the present invention is to prepare dye-containing particles of any color and size, which have high dyeability and are ready for immediate use. It is an object of the present invention to provide a dyeing composition capable of producing a cloth provided with a multicolored speckled colored pattern.

[0013]

The dyeing composition of the present invention has the following constitution in order to achieve the above object.

That is, the dye is contained in particles which are substantially water-insoluble, consist of a coagulation product of a polyanionic polymer and a polyamine or a polyamine salt, and have a substantially granular, spindle-shaped or linear particle shape. It is a composition for dyeing which is contained.

The method for producing the dyeing composition of the present invention has the following constitution.

That is, a dyeing composition characterized in that a granular water-insoluble material containing a dye is formed by stirring and mixing an aqueous solution containing a dye and a polyanionic polymer with an aqueous solution of a polyamine or a polyamine salt. Is a manufacturing method.

[0017]

The present invention will be described in more detail below.

The dyeing composition of the present invention is a dye-containing particle comprising a dye and a coagulated product obtained by a complex of a polyanionic polymer and a polyamine or a polyamine salt.

The dye is preferably a disperse dye, a disperse cationic dye or an oil dye from the viewpoint of preventing the dye from flowing out of the dye-containing particles.

In the present invention, a dye is mixed in a desired color to prepare dye-containing particles. When a disperse dye is used, particle formation is inhibited depending on the nature and concentration of the dispersant contained in the dye. Therefore, in order to prevent this inhibition, it is preferable to use a dispersant of 20 to 150% based on the pure dye.

Generally, those commercially available as nonionic or anionic disperse dye liquids fall under this category. From the viewpoint of dyeability, the dye concentration is usually preferably 15% by weight or less based on the polyanion polymer aqueous solution.

The polyanionic polymer as used in the present invention means-
COOM or, - (O) refers to a water-soluble polymer having an anionic group of -SO ₃ M, for example, sodium alginate,
Vegetable acidic polysaccharides such as pectin, gum arabic, agar, carrageenin, fucoidin, and laminarin, anionic cellulose derivatives such as carboxymethyl cellulose, acrylic acid-based polymers such as sodium polyacrylate, water-soluble polyester having -SO ₃ M group , Polyamide, etc. can be used. Among them, from the viewpoint of the affinity between the dye and a polymer complex formed from these and a polyamine or a polyamine salt, in particular, the above-mentioned vegetable acidic polysaccharides are preferable, and particularly sodium alginate of seaweed extract is more preferably used. .

The concentration of the polyanionic polymer is preferably 0.1% by weight to 10% by weight as an aqueous solution, from the viewpoints of forming the dye-containing particles and dyeing property of the dye, and 0.3
More preferably, it is about 6% by weight.

As a substance for coagulating such a water-soluble polymer, polyvalent metal salts, polyamines, polymers of aliphatic quaternary ammonium salts and quaternary ammonium salts are generally known, but they are low. For molecular compounds, the coagulated product is easily pulverized, and the coagulated product using only the quaternary ammonium salt type drug is sticky, and the dye separates from the coagulated product to color the liquid. It has the property that it is not suitable for forming various particles. On the other hand, the polyamine used in the present invention means a polymer containing a large number of amino groups in which hydrogen atoms of ammonia are substituted with 1 to 3 hydrocarbon groups,
By using these primary, secondary, and tertiary amine type polymers, uniform dye-containing particles can be formed, and a dyeing composition can be easily obtained. Examples of such polyamines include polyalkylene polyamines, condensates of polyalkylene polyamines and guanidine derivatives, polyethyleneimines, polyamide polyamines, polyaminoalkyl acrylates, polyaminoalkyl methacrylates, polyaminoalkyloxyalkyl acrylates, polyaminoalkyloxy. Alkylmethacrylates, polyaminoalkylacrylamides, polyaminoalkylmethacrylamides, polyaminoalkyloxyalkylacrylamides, polyaminoalkyloxyalkylmethacrylamides, polyamines such as poly-4-vinylpyridine hydrochloride, dimethylamine-epichlorohydrin condensation polymer, A polyepichlorohydrin-trimethylamine reaction product or the like can be used.

The polyamine salt used in the present invention is
A salt formed from the polyamine and an acid such as hydrochloric acid or acetic acid.

From the viewpoint of particle forming property, a primary amine salt in which an amino group is bonded as a side chain of polyalkylene, either directly or through a hydrocarbon group, is preferable.

Further, a polyamine or a polyamine salt may be used as a main component, and quaternary ammonium salt polymers may be combined and used as a mixed solution in order to change the shape and size of particles by utilizing the properties of both.

From the viewpoint of forming the dye-containing particles and preventing redissolution of the particles, the concentration of the polyamine or polyamine salt as an aqueous solution is preferably 0.5 to 20% by weight, and preferably 1 to 10% by weight. More preferable.

Next, a method for producing the dyeing composition of the present invention will be described.

The dyeing composition of the present invention is a liquid in which a fine coagulated product is dispersed by gradually dropping the aqueous solution of the above-mentioned dye and polyanionic polymer into an aqueous solution of polyamine or polyamine salt which is being stirred by a mixer or the like. Can be obtained. The size and shape of the obtained dye-containing particles can be changed also by the stirring speed.

From the viewpoint of quality when applied to a cloth, the diameter of the dye-containing particles is preferably 20 μm to 2000 μm, more preferably 20 μm to 500 μm, and 20 μm.
To 200 μm is more preferable.

The diameter of the dye-containing particles is represented by the diameter in the case of a true sphere, and the spindle-shaped or linearly extended shape is represented by the major axis.

The mixing ratio of the polyanion aqueous solution containing the dye and the polyamine aqueous solution or the polyamine salt aqueous solution can be arbitrarily set depending on the concentration of each liquid and the particle concentration in the desired liquid, and is adjusted by the polyamine aqueous solution or the polyamine salt aqueous solution used. can do.

From the viewpoint of making the dye-containing particles insoluble particles, the ratio of the weight of the polyanion polymer aqueous solution containing the dye to the polyamine aqueous solution or the polyamine salt aqueous solution is (dye + polyanion polymer aqueous solution): polyamine aqueous solution or polyamine salt aqueous solution = 1. It is preferably: 10 to 3: 1.

The dyeing composition thus obtained may be used as it is or diluted for dyeing, or may be used by concentrating the amount of the dye-containing particles in water as it is by a means such as centrifugation. Good.

It is also possible to mix particles of two or more colors to obtain a composition for multicolor color mixing. Furthermore, in the production method of the present invention, the dye flows out into water which is a dispersion medium of the particles. It is easy to perform independent multi-color mix coloring because each color is sharp.

It is also possible to blend spots and background color at the same time by blending with an ordinary dye. The means for dyeing the cloth is not particularly limited, but a dipping method, a pad method, a coating method by adding it to a nonionic sizing agent, a printing method, or the like can be performed. More preferably, a screen coating method, a knife coating method or the like which is not affected by the surface condition of the cloth and the size of the dye-containing particles is desirable.

The material of the cloth is not particularly limited as long as the dye used is dyed, and knitted woven fabrics such as acetate, polyester and nylon, non-woven fabrics and the like can be used according to the purpose.

Since the shape of the particles is formed by shearing, most of the particles are not a true sphere but a substantially spindle-shaped or linearly-stretched shape. Therefore, when imparted to a fiber structure and colored, Although the shape is blurred to some extent by bleeding, it has an advantage that it has a natural feeling similar to that of a fiber.

[0040]

EXAMPLES Hereinafter, the dyeing composition of the present invention will be described in more detail with reference to Examples and Comparative Examples.

Example 1 100 g of the following dye was mixed and dispersed in an aqueous solution of sodium alginate, which is a polyanionic polymer, was prepared.

Dyanics Yellow AN-P (D
ianix Yellow AN-P, Mitsubishi Kasei Co., Ltd.
Disperse dye) 2% by weight Dyanix Yellow BP (Dianix R)
ed BP, Mitsubishi Kasei Co., Ltd. disperse dye) 1.2% by weight Dyanix Yellow KRN-P (Dianix)
Blue KRN-P, Mitsubishi Kasei Co., Ltd. disperse dye)
0.3% by weight Snow Algin M (sodium alginate manufactured by Fuji Chemical Co., Ltd.) 1.5% by weight In addition, polyamine hydrochloride 4 having a structure represented by the following formula (I)
An aqueous solution containing 150% by weight was prepared.

[0043]

Embedded image In the formula (I), n is about 100 and the number average molecular weight is about 5
It was 000.

While the dye-polyanion aqueous solution was added dropwise to this polyamine salt aqueous solution, the mixture was stirred with a mixer (TK homomixer manufactured by Tokushu Kika Kogyo Co., Ltd.) to disperse the dye-containing particles having a size of about 70 microns in water. A liquid in a state was obtained.

To 50 g of this particle liquid, as a sizing agent, 5% by weight of tantalum gum F liquid (manufactured by Dainippon Pharmaceutical Co., Ltd.) 5
0 g was mixed to obtain a paste in which dye particles are dispersed.

Polyester broad cloth was coated with the above-mentioned glue using a 70-mesh screen with 100% by weight of pickup (weight ratio of the amount adhering to the weight of cloth) of the entire surface, followed by ordinary coloring and washing steps to give spots. A colored fabric was obtained.

The cloth has very fine brown-colored spots of about 100 to 150 microns dispersed uniformly and randomly on a white cloth, and the spots are not perfect circles but have lengths. Because it has a certain spindle shape, it became a material that seemed to be dyed and had a natural feel to it.

Example 2 50 g of each of the following dyes was prepared by dispersing it in an aqueous solution of 0.6% by weight of sodium alginate which is a polyanion.

A DIANIX RED BP (D
yanix Red BP, Mitsubishi Kasei Co., Ltd. disperse dye) 4% by weight B Dianex Blue KRN (Dyanix)
Blue KRN, Mitsubishi Kasei Co., Ltd. disperse dye) 3% by weight C Dianix Blue BG-P (Dyanix)
Blue BG-P, Mitsubishi Kasei Co., Ltd. disperse dye) 2
Weight% Dianex Red BP (Dyanix Re
d BP, Mitsubishi Kasei Co., Ltd. disperse dye) 0.5% by weight D Dianix Black FG-P (Dyani)
x Black FG-P, a disperse dye manufactured by Mitsubishi Kasei Co., Ltd.) 1% by weight Further, an aqueous solution containing 6% by weight of a polyamine hydrochloride having a structure of the following formula (II) was prepared. The above dyes A to D-sodium alginate solutions were added in the same manner as in Example 1 to obtain 100 g each.
To prepare a dye-containing particle liquid.

[0050]

Embedded image In the formula (II), n is about 40 and the number average molecular weight is about 20.
It was 00.

Equal amounts of the dye-containing particle liquids A to D were mixed and mixed with Tantel F 3% by weight liquid at a ratio of 1: 1 to obtain a padding liquid.

Polyester faille fabric dyed with pale green in advance was padded with the above padding solution and squeezed with a ² kg / cm ² mangle to give a normal color development.
A spot colored fabric was obtained through the washing step.

Although this cloth is purple at first glance, very fine spots of four different color tones are randomly provided on a pale green background, and the cloth has a novel feeling.

Comparative Example 1 4% by weight of barium chloride was used instead of the polyamine salt aqueous solution, and the mixture was mixed with the dye-polyanion aqueous solution of Example 1 while stirring as in Example 1.

Since no polyamine salt aqueous solution is used,
The solidified substances stuck to each other during stirring, and formed into a large lint-like mass. This coagulated product was so large that it could not be used as it was as dye-containing particles. A coating paste was applied as it was to the polyester cloth in the same manner as in Example 1 except for a large lump of solidified matter, and a print was applied to a polyester cloth, but a uniform spotted pattern could not be formed due to scattered dark spots in some places. .

[Comparative Examples 2 and 3] 6% by weight of a quaternary ammonium salt type polymer having the structure of the following formula (III) as Comparative Example 2 instead of the polyamine hydrochloride of Example 2 and as the Comparative Example 3 2% by weight of the cyclic quaternary ammonium salt type polymer of IV) was used and mixed with the dye-polyanion liquid of each color in the same manner as in Example 2.

[0057]

Embedded image In the formula (III), n is about 300 and the number average molecular weight is about 3
It was good.

[0058]

[Chemical 4] In the formula (IV), n is about 200 and the number average molecular weight is about 2
It was good.

Since neither polyamine salt is contained, and the coagulated product in the liquid is amorphous and not water-insoluble, the size and shape are uneven, and the dye flows out into the water and the color of the dye is deep in the liquid. It was in a colored state. A padding solution was prepared by mixing the colors in the same manner as in Example 2.

Padding was applied to the same light green fabric as in Example 2, but since each color was completely mixed in the sea component of the liquid, the ground green was dyed in a color close to gray, and spots were not clear. Met.

[Comparative Example 4] As a dye, the following acidic dye was blended and used, and a dye-sodium alginate aqueous solution and a polyamine salt aqueous solution were mixed in the same manner as in Example 1.

Kayanor Milling Ultra Sky SE (Kayanol Milling Ultra)
Sky SE Nippon Kayaku Co., Ltd. acid dye) 2% by weight Kayanol Milling Red 3BW (Kayano)
1 MillingRed 3BW Acid dye manufactured by Nippon Kayaku Co., Ltd. 1% by weight Snow Algin M (sodium alginate manufactured by Fuji Chemical Co., Ltd.) 1.5% by weight When the liquid was observed, the coagulated product formed in the liquid was Although fine particles were formed as in Example 1, the dye did not have cohesiveness and flowed out of the particles into water, so that the liquid portion was strongly colored.

As a coating paste, a nylon cloth was print-coated, but the whole was colored in a plain state, and spots were hardly seen.

[0064]

EFFECTS OF THE INVENTION According to the present invention, dye-containing particles can be prepared by a very simple method in the post-treatment step of the fabric, and spots of any color, size and density can be imparted freely. Due to uneven dyeing of material style, multicolor mix, etc.,
This makes it possible to respond to trends and easily form a new appearance.

Claims (9)

[Claims] 1. A dye which is substantially water-insoluble, comprises a coagulated product of a polyanionic polymer and a polyamine or a polyamine salt, and has a substantially granular, spindle-shaped or linear particle shape. A dyeing composition containing the same. 2. The dyeing composition according to claim 1, which has a particle diameter of 20 μm to 2000 μm. 3. The dye according to claim 1, which is a disperse dye, a disperse-type cationic dye or an oil dye.
The dyeing composition as described. 4. The dyeing composition according to claim 1, 2 or 3, wherein the polyanionic polymer is a vegetable acidic polysaccharide. 5. The dyeing composition according to claim 1, wherein the polyamine or the polyamine salt contains a primary amine salt as a main component. 6. A dyeing composition characterized in that a granular water-insoluble substance containing a dye is formed by stirring and mixing an aqueous solution containing a dye and a polyanionic polymer with an aqueous solution of a polyamine or a polyamine salt. Manufacturing method. 7. The method for producing a dyeing composition according to claim 6, wherein the dye is a disperse dye, a dispersion type cationic dye or an oily dye. 8. The method for producing a dyeing composition according to claim 6 or 7, wherein the polyanionic polymer is a vegetable acidic polysaccharide. 9. The method for producing a dyeing composition according to claim 6, 7 or 8, wherein the polyamine or the polyamine salt contains a primary amine salt as a main component.