JP3755162B2 - Dyeing composition, method for producing the same, and dyeing method - Google Patents

Description

このポリアミン水溶液に上記の染料と水不溶性液体を含むポリアニオン水溶液を滴下しながら、市販のミキサーで攪拌し、水中に大きさ２００μｍ前後の染料含有粒子が分散した状態の液を得た。
【００５９】
この粒子液５０部に対し、糊剤としてタンテルガムＦ１８重量％液（大日本製薬株式会社製）５０部を混合し、染料粒子が分散した状態の糊を得た。
【００６０】
この糊を顕微鏡で観察したところ、糊中に平均２００μｍ程度の大きさの染料含有粒子が分散した状態であった。
【００６１】
ポリエステルブロード布帛に、上記の糊を３５メッシュのスクリーンを用いて、ピックアップ１００％で全面コーティングし、通常の発色、洗浄工程を経て、斑点着色布帛を得た。
【００６２】
布帛は、２００μｍから３００μｍ程度の非常に淡い茶系色の斑点が、白い生地の上に均一かつランダムに分散しており、一見生成り調のナチュラル感のある素材に仕上がった。
【００６３】
結果を表１に示す。
【００６４】
【表１】

［実施例２］
以下の水溶性高分子と水不溶性液体のエマルジョン液に対して、ＡからＣの染料をそれぞれ添加して、各染料を含むエマルジョン液４種類を５０部ずつ用意した。また、染料を添加しないものをＤとして５０部用意した。
【００６５】
スノーアルギン Ｍ １．０重量％
（富士化学株式会社製、アルギン酸ソーダ）
ミネラルスピリットＡ ５０．０重量％
（日本石油株式会社製、第４類第２石油類）
ノニポール９５ １．０重量％
（三洋化成工業株式会社製、界面活性剤）
Ａ ダイアニックス レッド Ｂ−Ｐ（Dyanix Red B-P） ４．０重量％
Ｂ ダイアニックス ブルー ＫＲＮ（Dyanix Blue KRN ） ３．０重量％
Ｃ ダイアニックス ブルー ＢＧ−Ｐ（Dyanix BlueBG-P）１．０重量％
ダイアニックス レッド Ｂ−Ｐ（Dyanix Red B-P） ０．１重量％
Ｄ 染料なし
（以上、三菱化成株式会社製、分散染料）
各液とも水を加えて１００％とした。
【００６６】
また、以下の構造のポリアミン塩酸塩６％を含む水溶液を１００部ずつ用意し、実施例１と同様に攪拌しながら上記のＡからＣの染料を含むエマルジョン液とＤ無色のエマルジョン液をそれぞれ混合し、ＡからＤの粒子液を調製した。
【００６７】
【化２】

次に、ＡからＤの粒子液を等量ずつ混合したもの４００部を、下記の色糊４００部と混ぜパディング液を得た。
【００６８】
タンテルＦ ３重量％
ダイアニックス ブラック ＦＧ−Ｐ（Dyanix Black FG-P ）０．５重量％
水 ９６．５重量％
このパディング液を、顕微鏡で観察したところ、長径が平均３００μｍ程度の粒子が分散した状態であった。
【００６９】
ポリエステルファイユ布帛を上記パディング液でパディングして、２キロのマングルで絞り、通常の発色、洗浄工程を経て、斑点着色布帛を得た。
【００７０】
この布帛は、一見パープル系でありながら、４つの異なる色調の斑点および着色されていない白の斑点が淡いグレーの地にランダムに付与されており、目新しい感覚の布帛となった。
【００７１】
結果を併せて表１に示す。
【００７２】
［比較例］
以下の染料、ポリアニオン高分子を含む水溶液を、１００部用意した。これは、実施例１から水不溶性液体を抜いた系である。
【００７３】
ダイアニックス イエロー ＡＮ−Ｐ（Dianix Yellow AN-P）０．５重量％
ダイアニックス ブルー Ｂ−Ｐ（Dianix Red B-P）０．３重量％
ダイアニックス ブルー ＫＲＮ−Ｐ（Dianix Blue KRN-P ）０．１重量％
（以上、三菱化成株式会社製、分散染料）
スノーアルギン Ｍ １．５重量％
（富士化学株式会社製、アルギン酸ソーダ）
ノニポール９５ １．０重量％
（三洋化成工業株式会社製、界面活性剤）
水 ９６．６重量％
実施例１と同様のポリアミン塩酸塩水溶液を攪拌しながら、上記の染料を含むポリアニオン水溶液と混合し、染料含有粒子液を得た。
【００７４】
この粒子液５０部に対し、糊剤としてタンテルガムＦ（大日本製薬株式会社製）１８重量％液５０部を混合し、染料粒子が分散した状態の糊を得た。
【００７５】
この糊を顕微鏡で観察したところ、糊中に平均７０μｍ程度の長さの糸状染料含有粒子が分散した状態であった。
【００７６】
ポリエステルブロード布帛に、上記の糊を３５メッシュのスクリーンを用いて、ピックアップ１００％で全面コーティングし、通常の発色、洗浄工程を経て、斑点着色布帛を得た。
【００７７】
布帛は、５０μｍから８０μｍ程度の非常に微細な茶系色の斑点が、白い生地の上に均一かつランダムに分散しているが、実施例１に比べて、その数は非常に少なく、また斑点の面積は小さいものであった。また、斑点自身の色は、実施例１に比べて、非常に濃く、淡色の斑点は出来ていない状態であった。
【００７８】
つまり全体に小さな濃い点がまばらに散らばっており、実施例１のようなマイルドな生成り調の品位とはほど遠い状態であった。
【００７９】
結果を併せて表１に示す。
【００８０】
【発明の効果】
本発明によれば、布帛の後処理工程において、非常に簡便な方法で調製した粒子を用いて、自由に任意の色濃度や大きさ、密度の斑点むらを付与できるため、流行に敏感に対応し、かつ、新規な外観を容易に形成することが可能となり、特にファッション分野において有用性がある。[0001]
[Industrial application fields]
The present invention relates to a dyeing composition. More specifically, the present invention relates to a dyeing composition having a high color developability that can dye fine spots of an arbitrary color tone on a fabric, a method for producing the same, and a dyeing method.
[0002]
[Prior art]
Conventionally, synthetic fiber fabrics are colored in a color mix with fine color spots scattered, aiming at the natural color unevenness seen in wool and linen, or for the purpose of new visual effects. Is well done. However, in order to give shades of color unevenness to synthetic fiber fabrics that are originally dyed uniformly or to create spots with distinct color differences or shades of color difference, it is necessary to take the following method. That is,
(1) A method in which a spun yarn obtained by blending fibers separately dyed at the cotton stage in advance and a yarn dyed separately at the yarn stage are mixed and knitted to form a fabric. (2) Dyeability A method of knitting and knitting fabrics mixed with different fibers, and then dyeing (3) A method of printing spot patterns by the number of colors by roll printing or screen printing (4) Creating dye-containing particles on the fabric For example, a method of coloring by applying.
[0003]
However, in the method (1), in order to obtain a fabric having the desired color tone, preparations must be made from the stage of cotton dyeing, and a very long process must be passed. Therefore, there is a problem that it is difficult to cope with the short delivery time according to the recent trend of a short cycle and the production of a small amount of various varieties, resulting in high costs.
[0004]
In the method (2), although dyeing can be performed at the post-processing stage, it is necessary to prepare a specific fabric, and the density and size of the color spot unevenness are determined at this stage. Furthermore, the color tone is limited to combinations of dyeing methods and materials that can be dyed in different colors, so that there are a few color combinations at most, and there is a problem that the combinations of colors that can be used are also limited.
[0005]
In many cases, the printing method of (3) is used, but in this case, it takes time and effort to produce a sculpture pattern of a roll that determines the density and size of the spots and a screen mold, so the degree of freedom is high. If it is low and the number of speckled colors is large, the number of prints must be repeated. Also, the size of the obtained spots cannot be very fine because the screen mesh and roll engraving are limited.
[0006]
Each of the above methods has a common problem that the degree of freedom in the color pattern of the spots is low and it is difficult to carry out with a small lot.
[0007]
Regarding the method (4), there are some known examples regarding the production method of the dye-containing particles. After the dye is coarsely grained, the dispersion is applied by means of screen printing, coating, dipping, or the like. This method can be easily applied by post-processing, and can give particles of any color in a single process. Since it is possible, there is an advantage that multicolor spot dyeing can be easily performed.
[0008]
However, among these known examples, water-soluble polymers and activators, such as the production methods described in Japanese Patent Publication No. 55-42194, Japanese Patent Publication No. 40-22032 and Japanese Patent Publication No. 48-22876. In the case of the technology in which the solidified product of the dye is once filtered, dried, pulverized and used after sieving, it is possible to obtain a uniform particle size of any size, high stability, but considerably complicated process In addition, there is a basic problem that it is difficult to take an immediate response because it has a large energy loss for drying wet mud and is not suitable for a small variety of products. Although dye-containing particles can be prepared in advance, 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.
[0009]
On the other hand, if the dye-containing coagulated liquid formed into particles 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.
[0010]
That is, in Japanese Patent Publication No. 53-42833, a dye-encapsulated capsule is prepared by adding a solution comprising a water-soluble polymer having a salting-out property and a dye to a solution having a function of coagulating the polymer and coagulating the mixture while stirring. There is disclosed a technique in which particles obtained and dispersed in water are used as a composition for multicolor spot dyeing.
[0011]
However, in such a case, in order to have the stability that the particles are formed in the liquid and the dye does not flow out of the capsule, a strong coagulation film with a water-soluble polymer must be formed. A high concentration of the water-soluble polymer is not preferable because there is a problem that the dyeing property of the dye on the fabric is hindered. The present inventors have previously submitted a technique that can easily produce dye-containing particles without the outflow of dye (Japanese Patent Application No. 7-80428). In this case, since the water-soluble polymer is formed into particles even at a low concentration and the dye does not flow out of the particles, clear spot dyeing in which the ground color and the spot color are different can be obtained by a simple method.
[0012]
However, there is no problem when aiming for dark-colored fine-particle spots, but if you want to create particles to give ultra-light-colored spots, you can reduce the concentration of the dye solution before creating the particles. However, since the dye concentration of the final dye-containing particles becomes very high, there is a problem that the desired light color cannot be obtained. Even when dark particles are intended, there is a problem that it is difficult to make large particles because the particles are considerably thin and small.
[0013]
[Problems to be solved by the invention]
The object of the present invention is to prepare highly dyeable particles of any color tone, color density and size, with immediate response and simple preparation. It is providing the dyeing | staining composition which can produce the fabric which provided the speckled coloring pattern, its manufacturing method, and the dyeing | staining method.
[0014]
[Means for Solving the Problems]
In order to achieve the above object, the dyeing composition of the present invention has the following constitution.
[0015]
That is, a water-based dyeing composition in which a particulate gel material composed of a complex of a polyanionic polymer and a cationic material is dispersed , wherein the inside of the particulate gel material and / or the particulate gel material is dispersed. A dye composition comprising an aqueous sea component and a water-insoluble liquid inside a particulate gel substance .
[0016]
Moreover, the manufacturing method of the composition for dyeing | staining of this invention has the following structure.
[0017]
That is, by mixing and stirring a dye, a solution containing a polyanionic polymer dissolved in water and an emulsified water-insoluble liquid, and an aqueous solution of a cationic substance, a particulate gel is formed , or in water A liquid containing a dye is added after forming a particulate gel by mixing and stirring a solution containing a dissolved polyanionic polymer and an emulsified water-insoluble liquid and an aqueous solution of a cationic substance. It is a manufacturing method of the composition for water-system dyeing | dye | dye | dye formed by disperse | distributing the particulate gel-like material made into .
[0018]
Furthermore, the dyeing | staining method of this invention has the following structures.
[0019]
That is, a water-based dyeing composition in which a particulate gel-like material composed of a complex of a polyanionic polymer containing one or more kinds of colored particles and a cationic material is dispersed, and the inside of the particulate gel-like material or / And a dyeing composition characterized by containing a dye in water in which the particulate gel-like substance is dispersed and a water- insoluble liquid inside the particulate gel-like substance. This is a staining method.
[0020]
[Action]
Hereinafter, the present invention will be described in detail.
[0021]
When the present inventors stir a solution containing a polyanionic polymer dissolved in water and an emulsified water-insoluble liquid into an aqueous solution of a cationic substance, the generated particulate gel is stable and easy. It has been found that large particles and light-colored particles can be produced, and the present invention has been achieved.
[0022]
The particulate gel of the dyeing composition of the present invention can stably produce particles of any size even when the concentration of the water-soluble polymer is low compared to the case where no emulsified water-insoluble liquid is added. In addition to being able to produce, when dyes are added, most of the substances that form particles are water and water-insoluble liquids. Have.
[0023]
In the dyeing composition of the present invention, in order to obtain various color expressions, a dye is contained inside the particulate gel, inside and outside the particulate gel, or outside the particulate gel. It is.
[0024]
In the present invention, dye-containing particles having an arbitrary blending color can be prepared by adding a dye in advance to a liquid containing a polyanionic polymer dissolved in water and an emulsified water-insoluble liquid.
[0025]
In this case, the dye is preferably a dye that does not substantially dissolve in water, such as a disperse dye, a dispersive cationic dye, or an oil dye, from the viewpoint of preventing the dye from flowing out of the particles.
[0026]
In the present invention, dyes can be blended in a desired color to prepare arbitrary dye-containing particles from light colors to dark colors.
[0027]
When using a disperse dye, from the viewpoint of stabilizing the state of particle formation, it is usually preferable to use a dispersant of 20 to 150% by weight with respect to the pure dye. As a commercial item, this is generally a nonionic or anionic disperse dye liquid. From the viewpoint of dyeing property, the dye concentration is usually preferably within 15% by weight with respect to a liquid containing a polyanionic polymer dissolved in water and a water-insoluble liquid.
[0028]
In the present invention, even when the dye concentration is very low, the particle formation is stable, and large and light-colored spots can be imparted to the fabric. Furthermore, since it can be formed into particles even if the dye does not enter the interior at all, for the purpose of imparting stain-resistant spots to the ground dye, colorless particles are prepared, and the outside of the dye, that is, water that is a sea component, Ordinary dyes can be included in the paste.
[0029]
Furthermore, a more complex color expression is possible by adding a normal dye to the sea component in which particles containing the dye are dispersed.
[0030]
The water-insoluble liquid referred to in the present invention means a liquid that is not compatible with water and does not substantially dissolve the water-soluble polymer. Specifically, n-decane, n-dodecane, n-heptane, n-octane, kerosene, mineral terpene, liquid paraffin, petroleum benzine, benzene, aliphatic or aromatic hydrocarbons such as toluene, trichlorethylene , Halogenated hydrocarbons such as tetrachloroethylene, methylene chloride, chloroform, carbon tetrachloride, dichloroethane, dichloropropane, dichlorobutane and chlorobenzene, plastics such as tributyl phosphate, dioctyl phosphate, dioctyl phthalate and dibutyl phthalate An agent or the like can be used.
[0031]
Among them, a water-insoluble liquid having a boiling point of 250 ° C. or lower is preferably used because it has little remaining on the fabric after drying and has little odor. Specifically, aliphatic hydrocarbon-based mineral terpenes, kerosene, and the like can be used. These may be used alone or in combination of two or more.
[0032]
It is also preferable to add a surfactant in order to easily emulsify the above water-insoluble liquid.
[0033]
Here, the surfactant is not particularly limited as long as it forms an oil-in-water emulsion in which a water-insoluble liquid is an island component, but it is high etch LB (HLB). Hydrophilic and nonionic ones are preferred, and polyoxyethylene fatty acid esters, polyoxyethylene alkyl ethers, polyoxyethylene alkyl allyl ethers, polyhydric alcohol fatty acid esters, polyoxyethylene sorbitan fatty acid esters, and the like can be used.
[0034]
As a usage-amount, it is preferable to contain 0.5-10% in a process liquid, and it is more preferable to contain 1-4%.
[0035]
In view of the effect of maintaining the volume of the coagulated particles as an emulsion and the ease of emulsification, the addition amount of the water-insoluble liquid to the aqueous anionic polymer solution is preferably 10% by weight to 70% by weight, more preferably 30% by weight. 60% by weight is more preferred.
[0036]
The polyanionic polymer referred to in the present invention refers to a water-soluble polymer having an anion group of —COOM or — (O) —SO ₃ M. Specifically, vegetable acidic polysaccharides such as sodium alginate, pectin, gum arabic, agar, carrageenin, fucoidin, laminarin, anionic cellulose derivatives such as carboxymethylcellulose, acrylic acid polymers such as sodium polyacrylate, -SO Water-soluble polyesters having ₃ M groups, polyamides and the like can be used. From the viewpoint of the affinity between the polymer complex and the dye, the above-mentioned vegetable acidic polysaccharides are particularly preferably used, and the seaweed extract sodium alginate is more preferably used.
[0037]
Therefore, from the viewpoint of preventing particle formation and dyeing dyeing inhibition, usually, the aqueous solution is preferably 0.1 to 10% by weight, more preferably 0.3 to 6% by weight.
As the cationic substance that forms a complex with such a water-soluble polymer, polyvalent metal salts, polyamines, aliphatic quaternary ammonium salts, polymers of quaternary ammonium salts, and the like are generally known. According to the present inventor, low molecular weight compounds and quaternary ammonium salt type drugs do not coagulate polyanionic polymer liquid containing emulsion, the coagulated product is sticky, or the dye is separated from the coagulated product. In many cases, it exhibits properties that are incompatible with simple particle formation by stirring. On the other hand, a salt of a polyamine polymer containing a large number of amino groups in which hydrogen atoms of ammonia are substituted with 1 to 3 hydrocarbon groups is more preferably used because uniform particles can be formed. Such polyamines include polyalkylene polyamines, condensates of polyalkylene polyamines and guanidine derivatives, polyethyleneimines, polyamide polyamines, polyaminoalkyl acrylates, polyaminoalkyl methacrylates, polyaminoalkyloxyalkyl acrylates, polyaminoalkyloxy. Polyamines such as alkyl methacrylates, polyaminoalkyl acrylamides, polyaminoalkyl methacrylamides, polyaminoalkyloxyalkyl acrylamides, polyaminoalkyloxyalkyl methacrylamides, poly-4-vinylpyridine hydrochloride, dimethylamine-epichlorohydrin polycondensate, A polyepichlorohydrin-trimethylamine reactant or the like can be used.
[0038]
In the present invention, the polyamine is preferably used as an amine salt such as hydrochloride from the viewpoint of particle formation.
[0039]
Among these, a primary amine salt to which an amino group is bonded is particularly preferable as a side chain of polyalkylene, directly or via a hydrocarbon group. Further, in order to change the shape and size of the particles, a quaternary ammonium salt polymer mainly containing polyamine may be used as a mixed solution.
[0040]
The concentration of the polyamine is usually preferably 0.5 to 20% by weight, more preferably 1 to 10% by weight as an aqueous solution, from the viewpoint of preventing particle formation and re-dissolution of the aggregate.
[0041]
Next, the manufacturing method of the dyeing | staining composition of this invention is demonstrated.
[0042]
The dyeing composition of the present invention is a method in which a liquid containing a polyanionic polymer dissolved in water and a water-insoluble liquid such as an emulsified terpene is gradually dropped into an aqueous solution of a cationic substance that is stirred with a mixer or the like. It can be obtained by forming a fine gel.
[0043]
When obtaining a dye-containing material inside the particle, the dye may be added in advance to a liquid containing a polyanionic polymer and an emulsified water-insoluble liquid.
[0044]
Depending on the stirring speed, the size and shape of the resulting particles can be changed. The particle size is preferably 20 to 2000 μm, more preferably 20 to 500 μm, and still more preferably 20 to 200 μm from the quality when applied to the fabric.
[0045]
Further, the shape of the particles can be variously changed depending on the stirring speed as described above, and is not particularly limited. However, according to the knowledge of the present inventors, it is less true than the case where it is obtained as a true sphere. Actually, it is often obtained as a sphere. In particular, it is obtained as a substantially spindle-like shape or a linear shape.
[0046]
Among these, the substantially spindle-shaped one has the advantage that when it is imparted to the fiber structure and colored, the shape is somewhat bleed but approximates the shape of the fiber and the natural feeling is particularly remarkable. Therefore, it is preferable to adjust the stirring speed or the like so that the spindle shape can be obtained.
[0047]
The ratio of the polyanionic polymer dissolved in water and the emulsified insoluble liquid to the aqueous solution of the cationic substance can be arbitrarily determined depending on the concentration of each liquid and the desired particle concentration in the liquid. Is preferably about 1:10 to 3: 1.
[0048]
In order to improve the dispersibility of the particles, a paste having no coagulability can be added to the liquid containing the particles obtained in this way, or it can be used as it is or after being diluted. The amount of particles in water can be concentrated and used as it is by means of centrifugation or the like.
[0049]
In addition, it is possible to mix two or more dye-containing particles to form a multicolor color mix composition. In the present invention, the dye does not flow out into the water, which is a dispersion medium. It is easy to perform super multicolor mix coloring.
[0050]
In addition, it is possible to add spots and ground colors at once by adding a normal dye that is not granulated to the sea component outside the particles.
[0051]
The means for dyeing the fabric is not particularly limited, and a dyeing method, a pad method, a coating method or a printing method can be performed by adding a particle solution to a nonionic paste. More preferably, screen coating, knife coating, or the like that does not depend on the surface state of the fabric or the size of the dye-containing particles can be used.
[0052]
The coloring means after application to the fabric is not particularly limited, and HT steamer, high pressure steamer, cottage steamer, etc. can be selected according to the dye used and the material of the fabric.
[0053]
The fabric after coloring can be washed with water, hot water, RC, and the like to remove unfixed dye and paste.
[0054]
The material of the fabric is not particularly limited as long as the used dye acts, and various materials can be used, and the structure can be used according to the use such as knitted fabric and nonwoven fabric.
[0055]
Hereinafter, the present invention will be described in more detail with reference to examples.
[0056]
【Example】
[Example 1]
The following dye, polyanionic polymer, water-insoluble liquid and surfactant were mixed to prepare 100 parts as an oil-in-water emulsion liquid.
[0057]
Dianix Yellow AN-P 0.5% by weight
Dianix Red BP (Dianix Red BP) 0.3 wt%
Dianix Blue KRN-P 0.1% by weight
(The above, manufactured by Mitsubishi Chemical Corporation, disperse dye)
Snow Algin M 1.5% by weight
(Fuji Chemical Co., Ltd., sodium alginate)
Mineral Spirit A 40.0% by weight
(Nippon Oil Co., Ltd., Class 4 2nd Petroleum)
Nonipol 95 1.0% by weight
(Sanyo Chemical Industries, Ltd., surfactant)
56.6% by weight of water
In addition, 150 parts of a polyamine hydrochloride having the following structure was prepared as a 4% by weight aqueous solution.
[0058]
[Chemical 1]

While dropping the polyanion aqueous solution containing the dye and the water-insoluble liquid into the polyamine aqueous solution, the mixture was stirred with a commercially available mixer to obtain a liquid in which dye-containing particles having a size of about 200 μm were dispersed in water.
[0059]
To 50 parts of this particle liquid, 50 parts of Tanter Gum F18 wt% liquid (manufactured by Dainippon Pharmaceutical Co., Ltd.) was mixed as a paste to obtain a paste in which dye particles were dispersed.
[0060]
When this glue was observed with a microscope, dye-containing particles having an average size of about 200 μm were dispersed in the glue.
[0061]
A polyester broad cloth was coated with 100% of the above-mentioned paste with a 35-mesh screen using a 35-mesh screen, and a spot-colored cloth was obtained through normal coloring and washing steps.
[0062]
The fabric had very light brown-colored spots of about 200 μm to 300 μm dispersed uniformly and randomly on a white fabric, and finished with a material that seemed to be natural in appearance.
[0063]
The results are shown in Table 1.
[0064]
[Table 1]

[Example 2]
The dyes A to C were added to the following water-soluble polymer and water-insoluble liquid emulsion solutions, respectively, to prepare 50 parts of 4 types of emulsion liquids containing each dye. In addition, 50 parts were prepared as D without adding the dye.
[0065]
Snow Algin M 1.0wt%
(Fuji Chemical Co., Ltd., sodium alginate)
Mineral Spirit A 50.0% by weight
(Nippon Oil Co., Ltd., Class 4 2nd Petroleum)
Nonipol 95 1.0% by weight
(Sanyo Chemical Industries, Ltd., surfactant)
A Dianics Red BP (Dyanix Red BP) 4.0 wt%
B Dyanix Blue KRN (Dyanix Blue KRN) 3.0 wt%
C Dyanix Blue BG-P (Dyanix BlueBG-P) 1.0 wt%
Dyanix Red BP (Dyanix Red BP) 0.1% by weight
D No dye (Made by Mitsubishi Kasei Co., Ltd., disperse dye)
Water was added to each solution to make 100%.
[0066]
In addition, 100 parts each of an aqueous solution containing 6% of polyamine hydrochloride having the following structure was prepared, and the above emulsion liquid containing dyes A to C and D colorless emulsion liquid were mixed with stirring as in Example 1. A to D particle liquids were prepared.
[0067]
[Chemical 2]

Next, 400 parts of a mixture of equal amounts of the A to D particle liquids were mixed with 400 parts of the following color paste to obtain a padding liquid.
[0068]
Tantel F 3% by weight
Dyanix Black FG-P (Dyanix Black FG-P) 0.5 wt%
96.5% by weight of water
When this padding solution was observed with a microscope, particles having an average major axis of about 300 μm were dispersed.
[0069]
A polyester fiber fabric was padded with the above padding solution, squeezed with 2 kg of mangle, and a spot-colored fabric was obtained through normal coloring and washing steps.
[0070]
Although this fabric was a purple system at first glance, four different color spots and uncolored white spots were randomly given to a light gray background, and the fabric had a novel feel.
[0071]
The results are also shown in Table 1.
[0072]
[Comparative example]
100 parts of an aqueous solution containing the following dye and polyanionic polymer were prepared. This is a system obtained by removing the water-insoluble liquid from Example 1.
[0073]
Dianix Yellow AN-P 0.5% by weight
Dianix Blue BP (Dianix Red BP) 0.3 wt%
Dianix Blue KRN-P (Dianix Blue KRN-P) 0.1% by weight
(The above, manufactured by Mitsubishi Chemical Corporation, disperse dye)
Snow Algin M 1.5% by weight
(Fuji Chemical Co., Ltd., sodium alginate)
Nonipol 95 1.0% by weight
(Sanyo Chemical Industries, Ltd., surfactant)
96.6% by weight of water
While stirring the same polyamine hydrochloride aqueous solution as in Example 1, it was mixed with the polyanion aqueous solution containing the above dye to obtain a dye-containing particle solution.
[0074]
50 parts of this particle liquid was mixed with 50 parts of 18% by weight tanter gum F (Dainippon Pharmaceutical Co., Ltd.) as a paste to obtain a paste in which the dye particles were dispersed.
[0075]
When this paste was observed with a microscope, it was in a state where filamentous dye-containing particles having an average length of about 70 μm were dispersed in the paste.
[0076]
A polyester broad cloth was coated on the entire surface with 100% of the above-mentioned glue using a 35-mesh screen, and a spot-colored cloth was obtained through normal coloring and washing steps.
[0077]
In the fabric, spots of very fine brown color of about 50 μm to 80 μm are uniformly and randomly dispersed on the white fabric, but the number is very small compared to Example 1, and the spots are The area of was small. Further, the color of the spot itself was much darker than that of Example 1, and no light spot was formed.
[0078]
That is, small dark spots are scattered sparsely as a whole, which is far from the quality of the mild production tone as in the first embodiment.
[0079]
The results are also shown in Table 1.
[0080]
【The invention's effect】
According to the present invention, in the post-treatment process of the fabric, it is possible to freely impart uneven spots of any color density, size, and density using particles prepared by a very simple method, so it is sensitive to fashion. In addition, it is possible to easily form a new appearance, which is particularly useful in the fashion field.

Claims (9)

A water-based dyeing composition in which a particulate gel-like material composed of a complex of a polyanionic polymer and a cationic material is dispersed , wherein the inside of the particulate gel-like material and / or the water-based sea in which the particulate gel-like material is dispersed A dyeing composition comprising a dye as a component and a water-insoluble liquid inside a particulate gel substance . Dyeing composition according to claim 1, wherein the boiling point of the water-soluble liquid is characterized in that at 250 ° C. or less. The dyeing composition according to claim 1 or 2, wherein the water-insoluble liquid is contained as an oil-in-water emulsion. The dyeing composition according to claim 1, 2 or 3, wherein the particle shape is substantially granular, spindle-shaped or linear. The dyeing composition according to claim 1, 2, 3 or 4, wherein the particle size is 20 µm to 2000 µm. 6. The dyeing composition according to claim 1, 2, 3, 4 or 5 , wherein the dye is a disperse dye, a dispersive cationic dye or an oily dye. The dyeing composition according to any one of claims 1 to 6 , wherein the polyanion polymer is a vegetable acidic polysaccharide. By mixing and stirring a solution containing a dye, a polyanionic polymer dissolved in water and an emulsified water-insoluble liquid and an aqueous solution of a cationic substance, a particulate gel is formed or dissolved in water. A liquid containing a dye is added after forming a particulate gel by mixing and stirring a liquid containing a polyanionic polymer and an emulsified water-insoluble liquid and an aqueous solution of a cationic substance. A method for producing a composition for dyeing water-based dyeing, in which a particulate gel is dispersed . A dyeing method comprising applying a dyeing composition according to any one of claims 1 to 7 containing one or more kinds of particles to a fabric to cause color development.