Dye composition and method for producing dyed goods using said dye composition

Abstract

To provide a dye composition containing a naturally derived dye, and a production method of a dyed article using the dye composition.SOLUTION: The dye composition contains a naturally derived dye, a printing binder including an acid, chitosan, a urethane resin, and a mineral spirit, and a mordant. The production method comprises: dissolving the chitosan in the acid, adding the urethane resin, the mineral spirit, and water to the acquired chitosan solution to execute stirring, and preparing the printing binder (step I); adding a naturally derived dye liquid to the printing binder to execute stirring, and then adding the mordant and water to execute stirring and preparing the dye composition (step II); and applying the acquired dye composition to a fiber to execute printing, and acquiring a dyed article through a drying step and a steaming step (step III).SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a dye composition, particularly a dyeing composition containing plant dyes (including some insect dyes), and also to a method for producing dyed articles using the dye composition. [Background technology]

[0002] With the growing trend towards natural products, plant dyes have been attracting attention, and plant-dyed printing has become popular. However, dyeability varies depending on the type of plant dye and the fiber being dyed. To solve this problem, for example, Patent Document 1 listed below discloses the use of chemical dyes in combination to improve fastness and obtain stable colors. Furthermore, in the case of plant dyes, the direct dyeing ability of the dye is low depending on the material to be dyed, such as cellulose fibers. Therefore, in order to improve dyeing ability, a pretreatment process is carried out using a cationizing agent such as a cationic polymer or a quaternary ammonium salt, thereby increasing the adsorption efficiency of the dye and mordant during the printing process and achieving deep dyeing. For example, Patent Document 2 listed below proposes pretreatment with a plant dye adsorption aid, which is a cationic compound such as a quaternary ammonium salt.

[0003] However, when producing printed (dyed) products, such conventional methods can cause staining by the dye that has fallen off along with the sizing agent during post-treatment soaping, being re-adhered by the plant dye adsorption aid, resulting in the problem of white spot staining during the washing process.

[0004] Furthermore, in the case of conventional dyeing methods that have been used up until now, the dyeability of natural dyes varies depending on the material being dyed, and any dye that does not absorb is discharged into the drainage system together with the mordant and printing paste by soaping, which places a heavy burden on the drainage system throughout the entire process. For this reason, in order to reduce the drainage load, there is a demand for printing methods that do not use printing paste, and there is also a demand for methods that can dye deeply and efficiently. Furthermore, there is a need for dyeing methods that can efficiently achieve deep dyeing with plant dyes for various fibers other than cellulose fibers, and there is also a general misconception that all plant dyes have medicinal effects, so this is also something that needs to be taken into consideration. [Prior art documents] [Patent documents]

[0005] [Patent Document 1] Patent No. 5791955 [Patent Document 2] Patent No. 3779287 Summary of the Invention [Problem to be solved by the invention]

[0006] The present invention aims to provide a dyeing composition that does not require a pretreatment step for improving dyeability, and that can absorb plant dyes and mordants without leaving any residue and dye fibers. Another object of the present invention is to provide a method for producing dyed products by printing natural or synthetic fibers with such a dyeing composition. [Means for solving the problem]

[0007] As a result of extensive investigations, the present inventors have found that, instead of the conventionally used printing pastes for plant dyeing (anionic or nonionic water-soluble printing pastes), chitosan, a naturally occurring polymer obtained from crab shells and the like, is dissolved in an acid (preferably an organic acid), and then, in order to overcome the drawbacks of chitosan's hard coating and low solubility, a polyurethane resin is added as a binder resin to prepare a printing binder, and if necessary, a thickener is added to adjust the viscosity to prepare a dyeing composition, and that by using the dyeing composition thus obtained, it is possible to omit the pretreatment step for improving the dyeability of fibers such as cellulose fibers, and to enable the plant dye and mordant to be absorbed without any waste and to dye the fibers, thereby completing the present invention.

[0008] The dye composition of the present invention, which can be used to print natural fibers or synthetic fibers using a complex dye composition obtained using only naturally occurring dyes and a mordant, comprises the following components A to C: Ingredient A: Natural dyes and Component B: a printing binder containing acid, chitosan, urethane resin, and mineral spirits; Component C: a mordant; The compound is characterized by containing

[0009] The present invention also provides a dye composition having the above-mentioned characteristics, characterized in that the naturally derived dye is a liquid dye product of a plant dye and / or a pigment component extracted from an insect.

[0010] The present invention also provides a dye composition having the above characteristics, characterized in that the mordant is a mordant solution containing a salt of a metal selected from the group consisting of aluminum, titanium, and iron.

[0011] The present invention also provides a dye composition having the above characteristics, wherein the acid is selected from the group consisting of hydrochloric acid, nitric acid, formic acid, acetic acid and propionic acid.

[0012] Furthermore, the present invention is also characterized in that, in the dye composition having the above characteristics, the content of the acid is 2.4 to 6.4 parts by weight, the content of chitosan is 2.4 to 6.4 parts by weight, the content of urethane resin is 3.2 to 8.0 parts by weight (solid content equivalent), and the content of mineral spirits is 4 to 20 parts by weight, per 100 parts by weight of the dye composition.

[0013] The dye composition of the present invention is Ingredient A: Indian indigo and Component B: a printing binder containing acid, chitosan, urethane resin, and mineral spirits; The proportions of each component contained in component B are the same as those described above.

[0014] The present invention also provides a method for producing a dyed product using the dye composition, the method comprising the following steps I to III: Step I: a step of dissolving 3 to 8 parts by weight of chitosan in 3 to 8 parts by weight of acid, adding 4 to 10 parts by weight (in terms of solid content) of urethane resin, 5 to 25 parts by weight of mineral spirits, and water in an amount that makes the total solution 100 parts by weight, and stirring the mixture to prepare a binder for textile printing; Step II: adding 0.6 to 15 parts by weight of a naturally-derived dye solution to 70 to 85 parts by weight of the printing binder obtained in Step I, stirring, then adding 1 to 3 parts by weight (solid content equivalent) of a mordant, and adding water in an amount that makes the total solution 100 parts by weight, and stirring, to prepare a dye composition; Step III: A step of applying the dye composition obtained in Step II to a fiber to be dyed to perform printing, followed by a drying step and a steaming step to develop the color and obtain a dyed product. The present invention is characterized by comprising:

[0015] The present invention is also characterized in that the acid used in step I in the method for producing a dyed product having the above characteristics is selected from the group consisting of hydrochloric acid, nitric acid, formic acid, acetic acid and propionic acid.

[0016] The present invention is also characterized in that the fibers printed in step III in the method for producing a dyed product having the above characteristics are selected from the group consisting of cellulose fibers, protein fibers, and synthetic fibers.

[0017] The present invention also provides a method for producing a dyed product using Indian indigo, the method comprising the following steps I to III: Step I: a step of dissolving 3 to 8 parts by weight of chitosan in 3 to 8 parts by weight of acid, adding 4 to 10 parts by weight (in terms of solid content) of urethane resin, 5 to 25 parts by weight of mineral spirits, and water in an amount that makes the total solution 100 parts by weight, and stirring the mixture to prepare a binder for textile printing; Step II: adding 0.6 to 15 parts by weight of an Indian indigo-containing dye solution to 70 to 85 parts by weight of the printing binder obtained in Step I, stirring, and then adding water in an amount that makes the total solution 100 parts by weight, and stirring the mixture to prepare a dye composition; Step III: A step of applying the dye composition obtained in Step II to a fiber to be dyed to perform printing, followed by a drying step and a steaming step to develop the color and obtain a dyed product. The present invention is characterized by comprising: [Effects of the Invention]

[0018] By using the dye composition of the present invention, the series of printing steps from pretreatment to soaping can be simplified without particularly deteriorating the color fastness in current plant dyeing, and by eliminating soaping, the wastewater load can be reduced. In addition, when dyed with plant dyes, chitosan can be used to impart antibacterial and antiviral properties to various fibers. DETAILED DESCRIPTION OF THE INVENTION

[0019] Components A to C contained in the dye composition of the present invention will be explained below. As the naturally derived dye, component A, a wide variety of plant dyes known to contain mordant pigments and liquid dyes made from pigment components extracted from insects can be used, including, for example, products commercially available from Tanaka Direct Dye Store Co., Ltd. Specific examples include, but are not limited to, sophora japonica (tragonathus) liquid, scutellaria baicalensis liquid, walnut liquid, catechu liquid, lac dye liquid, logwood liquid, and indigo liquid. The solids concentration in the dye solution of commercially available plant dyes varies depending on the type of plant dye. Note that a mordant is not required for printing using indigo alone. The content of the above-mentioned Component A (naturally-derived dye) in 100 parts by weight of the dye composition of the present invention is preferably 0.1 to 7 parts by weight, particularly preferably 0.3 to 5 parts by weight. When the naturally-derived dye is only Indian indigo, the content of Indian indigo is preferably 0.6 to 9.6 parts by weight (as a paste product).

[0020] The printing binder (aqueous binder solution) of Component B contained in the dye composition of the present invention contains an acid, chitosan, a urethane resin, and mineral spirits, and the chitosan is contained as cationic chitosan produced by dissolving it in the presence of an acid (preferably an organic acid). In the present invention, the acid for dissolving chitosan is preferably a volatile acid such as hydrochloric acid, nitric acid, formic acid, acetic acid, or propionic acid in order to prevent re-dissolution, and among these, acetic acid is particularly preferred from the viewpoints of safety and volatility. The content of the acid in 100 parts by weight of the dye composition of the present invention is 2.4 to 6.4 parts by weight, preferably 3.2 to 5.0 parts by weight, and the content of chitosan is 2.4 to 6.4 parts by weight, preferably 2.4 to 4.8 parts by weight.

[0021] In addition, in the present invention, by incorporating a urethane resin into the printing binder, the viscosity of the dye composition can be increased, and the coating formed on the surface of the fiber to be dyed can be made flexible, improving the texture and reducing tackiness of the coating. In the present invention, such a urethane resin is preferably incorporated in the form of a water-soluble emulsion. As the urethane resin suitable for the present invention, a polyurethane resin based on polyester polyol is particularly preferred from the viewpoints of hydrolysis resistance, stability, and weather resistance. In the present invention, a nonionic blocked isocyanate crosslinking agent may be used in combination to improve the fastness of the urethane resin. The content of the urethane resin in 100 parts by weight of the dye composition of the present invention is 3.2 to 8.0 parts by weight, preferably 4.0 to 5.6 parts by weight, calculated as solid content, and the content of the crosslinking agent when used in combination is 0.8 to 4.0 parts by weight, preferably 1.6 to 2.4 parts by weight.

[0022] In addition to the above components, the dye composition of the present invention contains mineral spirits, a non-polar solvent, to achieve a viscosity suitable for textile printing, since chitosan dissolved in an acid (preferably acetic acid) has a high viscosity and is not suitable for textile printing. The content of mineral spirits in 100 parts by weight of the dye composition of the present invention is 4 to 20 parts by weight, preferably 5 to 17 parts by weight. Furthermore, in the present invention, it is preferable to emulsify a highly viscous liquid obtained by dissolving chitosan in acid by blending mineral spirits with the liquid and then adding a viscosity modifier. After adjusting the viscosity by adding the viscosity modifier, the urethane resin can be added to obtain a viscosity suitable for use as a binder for textile printing.

[0023] Preferred viscosity modifiers in the present invention include nonionic ether-type cellulose derivatives, nonionic ether-ester-type starches, nonionic locust bean gum, tamarind guar gum, cationic guar gum, cationic starches, and cationic cellulose derivatives. In the present invention, naturally processed thickeners and chemically resistant nonionic surfactants with high HLB values ​​can be used as viscosity modifiers, and nonionic surfactants with high HLB values ​​are preferred from the viewpoint of film flexibility and thickening properties. The content of the viscosity modifier in 100 parts by weight of the dye composition of the present invention is 0.8 to 2.4 parts by weight, preferably 1.2 to 2.0 parts by weight.

[0024] In addition, in the present invention, the addition of a sequestering agent is preferable because mixing chitosan in the printing binder with metal ions (natural dyes and mordants) forms an insoluble complex, destabilizing the resulting mixture. The sequestering ability of the agent temporarily chelates the metal ions of the mordant, stabilizing the chitosan binder. The dry heat in the drying step and the steaming step volatilize the sequestering agent together with the acid, completing the formation of a chitosan-containing coating and the complexation of the natural dye. The content of the sequestering agent per 100 parts by weight of the dye composition of the present invention is 2.4 to 4.8 parts by weight, preferably 3.0 to 4.0 parts by weight. Acetylacetone is preferred as the sequestering agent. Furthermore, in the present invention, it is preferable to incorporate a moisture absorbent into the printing binder in order to improve color development, and the moisture absorption and delayed action of the moisture absorbent allows for uniform film formation and steaming effects. The content of the moisture absorbent in 100 parts by weight of the dye composition of the present invention is 4.8 to 9.6 parts by weight, preferably 6.4 to 8.0 parts by weight, and preferred examples of the moisture absorbent include ethylene glycol, propylene glycol, and polyethylene glycol.

[0025] Furthermore, the mordant, component C, in the dye composition of the present invention is a component necessary for forming a complex with the plant dye, and it is necessary for various hues (colors) to be expressed depending on the combination. However, taking into consideration sewage treatment and the like, it is preferable to blend a mordant solution containing a salt of a metal selected from the group consisting of aluminum, titanium, and iron. In the present invention, a wide range of known mordants for plant dyes can be used, and by appropriately selecting the type of mordant, the fiber to be dyed can be dyed to the desired color. The content of the mordant in 100 parts by weight of the dye composition of the present invention is preferably 0.1 to 3 parts by weight (solid content equivalent). However, when indigo alone is used as the plant dye, the mordant (component C) is not necessary.

[0026] The dye composition of the present invention, which is an aqueous emulsion containing a urethane resin, contains each component in a proportion within the ranges described above, but the remainder is mainly water or water alone.

[0027] Next, each step in the method of the present invention for producing dyed goods using the dye composition will be described. In step I of the production method of the present invention, 3 to 8 parts by weight of chitosan is dissolved in 3 to 8 parts by weight of acid, and to the resulting chitosan solution, 4 to 10 parts by weight (solids content), 5 to 25 parts by weight of mineral spirits, and water in an amount that makes the total solution 100 parts by weight are added, followed by stirring to prepare a printing binder. In this case, a commercially available chitosan (powder) can be used, the acid is preferably selected from the group consisting of hydrochloric acid, nitric acid, formic acid, acetic acid, and propionic acid, and the urethane resin can be a commercially available aqueous urethane resin (a material in which polyurethane resin is dispersed in water).

[0028] In step II of the production method of the present invention, 0.6 to 15 parts by weight of a dye solution containing a naturally-derived dye (naturally-derived dye solution) is added to 70 to 85 parts by weight of the printing binder obtained in step I, and after stirring, 1 to 15 parts by weight of a mordant is added, and then water is added in an amount that makes the total solution 100 parts by weight, and the mixture is stirred to prepare a dye composition. In this case, the naturally-derived dye solution and mordant used are those described above. In the present invention, the naturally occurring dye solution may be in a paste form in addition to a liquid form.

[0029] In step III of the production method of the present invention, the dye composition prepared in step II is applied to a fiber to be dyed to perform printing, followed by drying and steaming steps to develop the color and obtain a dyed product. When the dye composition of the present invention is used, the printing binder is fixed on the fiber after printing, and the water-soluble emulsion is converted into a water-insoluble solid by the steaming step. Therefore, in the production method of the present invention, no post-treatment or soaping is particularly required, and even if a post-process is performed, only a water washing step to remove impurities is required. The conditions for the drying step in the above step III are preferably 120 to 150°C for about 1 to 3 minutes, and the conditions for the steaming step are preferably 95 to 110°C for about 10 to 30 minutes.

[0030] In the production method of the present invention, the fibers of the dyed object to which the dyeing composition is applied in step III are not limited to cellulose fibers such as cotton and hemp, or protein fibers such as wool and silk, which are generally used for plant dyeing, but also include synthetic fibers such as polyester fibers and polyamide fibers (nylon fibers), which are generally not dyed with plant dyes, and any fiber that can be bonded with the above-mentioned printing binder can be printed using a plant dye. In the present invention, the method for applying the dye composition to the material to be dyed is not particularly limited, but it is preferable to use a screen printing machine such as a flat screen or rotary screen, or a roller printing machine.

[0031] When the method for producing dyed products of the present invention is used, naturally derived dyes can be developed and fixed on the fibers to be dyed without particularly reducing the color fastness of current plant dye dyes, and the dyes can be fixed together with the printing binder, thereby simplifying the entire printing process from pretreatment to soaping. Furthermore, when a dyed product is printed with a plant dye using the manufacturing method of the present invention, the plant dye is fixed onto the fiber together with the printing binder, and therefore not only does the color development unique to the plant dye become visible, but the product also has the antibacterial and antiviral properties derived from chitosan. [Example]

[0032] Example 1 Acetic acid was prepared as an organic acid, and 4 parts by weight of commercially available chitosan (powder) was dispersed in a small amount of warm water. The dispersion was added to 6 parts by weight of acetic acid and stirred to prepare a chitosan solution. To this chitosan solution, 20 parts by weight of a water-soluble emulsion containing a polyurethane resin based on polyester polyol (manufactured by Murayama Chemical Laboratory Co., Ltd., product name: Simplex PUE-C200B, solids concentration: 30%) and 20 parts by weight of mineral spirits were added, and further 4 parts by weight of acetylacetone was added as a sequestering agent. The mixture was stirred, and water was added to make the total amount 100 parts by weight, thereby preparing a printing binder. Then, a commercially available plant dye, a sophora japonica extract (solid content concentration: 25%), was prepared as a naturally derived dye solution. Five parts by weight of this sophora japonica extract was added to 80 parts by weight of the above-prepared textile printing binder, and the mixture was thoroughly stirred. Then, 5 parts by weight of an aluminum mordant (10% aluminum acetate solution) and 2 parts by weight of a blocked isocyanate crosslinking agent (manufactured by Murayama Chemical Laboratory Co., Ltd., trade name: Fixer #220) diluted with water were added to make the total solution 100 parts by weight, and the mixture was thoroughly stirred to prepare the dyeing composition of the present invention. A 60 / 2 cotton lawn was prepared as the substrate to be dyed, and the dyeing composition obtained above was applied to this 60 / 2 cotton lawn to perform printing (textile printing process), followed by drying at 140°C for 2 minutes, a steaming process at 103°C for 20 minutes in a continuous steamer, and then a water-washing process to obtain a dyed product. The dyed products obtained using the above method did not show any bleeding of the color, even though Sophora japonica, which has a weak waterfastness to begin with, and it was confirmed that the binder, the dyed product, and the plant dye were sufficiently fixed.

[0033] Example 2 Dyed products were produced in the same manner as in Example 1, except that 9 parts by weight of ethylene glycol was further added when preparing the printing binder. The dyed product thus obtained had better color development than the composition obtained in Example 1, and the chitosan-containing coating was uniform.

[0034] Example 3 As a naturally derived dye solution, a commercially available botanical dye, Scutellaria extract (solid content: 50%), was prepared, and a dyeing composition of the present invention was prepared using 5 parts by weight of this Scutellaria extract in the same manner as in Example 2 above. The dyeing composition was applied to the same 60 / 2 cotton lawn as in Example 1 above, and printing was carried out in the same manner as in Example 1 above. Thereafter, a drying step (140°C x 2 minutes) and a steaming step (103°C x 20 minutes) were carried out, and then a water-washing step was carried out to obtain a dyed product. The dyed products obtained using the above method were confirmed to have no bleeding of color and the plant dyes were fixed with sufficient fixing power.

[0035] Example 4 As a naturally derived dye solution, a commercially available plant dye, walnut extract (solid content: 50%), was prepared, and a dyeing composition was prepared using 5 parts by weight of this walnut extract in the same manner as in Example 2 above.This dyeing composition was then applied to a 60 / 2 cotton lawn, and the same steps as in Example 1 were carried out to obtain a dyed product. The dyed products obtained by the above method showed no bleeding of the color even when subjected to a washing step.

[0036] Example 5 As a naturally derived dye solution, a commercially available plant dye, catechu extract (solids concentration: 25%), was prepared, and a dyeing composition was prepared using 5 parts by weight of this catechu extract in the same manner as in Example 2 above.This dyeing composition was then applied to a 60 / 2 cotton lawn, and the same process as in Example 1 was carried out to obtain a dyed product. The dyed products obtained by the above method did not lose their color even after washing.

[0037] Example 6 A commercially available lac dye extract (solid content: 10%), which is a naturally occurring dye solution, was prepared. Five parts by weight of this lac dye extract was used to prepare a dyeing composition in the same manner as in Example 2. This dyeing composition was applied to a 60 / 2 cotton lawn, and then the same steps as in Example 1 were carried out to obtain a dyed product. The dyed products obtained by the above method were found to have only slight loss of color even when washed with water, and were therefore of no practical use.

[0038] Example 7 A commercially available logwood extract (solid content: 67%), which is a naturally derived dye solution, was prepared. Five parts by weight of this logwood extract was used, and five parts by weight of an iron mordant (a 4.5% solution of iron pyroacetate) was used as a mordant. A dyeing composition was prepared in the same manner as in Example 2 above. This dyeing composition was applied to a 60 / 2 cotton lawn, and then the same steps as in Example 1 were carried out to obtain a dyed product. When the dyed product obtained by the above method was subjected to a washing step, no coloration of the wastewater was observed.

[0039] Example 8 As a naturally derived dye solution, a paste of Indian indigo (commonly known as indigo), a commercially available plant dye (manufactured by Tanaka Direct Dye Store Co., Ltd., product name: purified Indian indigo paste) and the sophora japonica extract used in Example 1 were prepared, and 0.5 parts by weight of the Indian indigo paste and 4.5 parts by weight of the sophora japonica extract were mixed to prepare a dyeing composition in the same manner as in Example 2 above.This dyeing composition was applied to 60 / 2 cotton lawn, and then the same steps as in Example 1 were carried out to obtain a dyed product. In the case of dyed products obtained using the above method, even green colors, which are said to be difficult to achieve with plant dyes, only slight color transfer occurred and there was almost no color loss, even with post-treatment involving only a water washing process.It was also confirmed that the dyed products met the washing fastness test of the A-1 method of JIS-L-0844.

[0040] Example 9 A dyeing composition was prepared by preparing a paste (5 parts by weight) of Indian indigo (commonly known as indigo) described in Example 8 above as a naturally derived dye solution, and stirring it with only the printing binder described in Example 2 above without using a mordant (component C) in combination. This dyeing composition was then applied to a 60 / 2 cotton lawn, and the same steps as in Example 1 were carried out to obtain a dyed product. When the dyed product obtained by the above method was subjected to a washing step, no coloration of the wastewater was observed.

[0041] In the following Comparative Examples 1 to 7, 60 / 2 cotton lawn was cationized using a commonly used quaternary ammonium salt cationizing agent and a caustic alkali agent, then printed with a commonly used printing paste using the plant dyes and mordants described in Examples 1 to 9 above, then dried under the same conditions as in Examples 1 to 9 above, steamed in a continuous steamer at 103°C for 20 minutes, and then washed to obtain dyed products. The dyed products thus obtained were compared with those obtained in the above Examples.

[0042] Comparative Example 1 A printing paste composition was prepared by preparing an extract of Sophora japonica, a commercially available plant dye, as the naturally derived dye solution, and aluminum acetate as the mordant. 55 parts by weight of a commercially available printing paste (Yoshikawa Chemical Industry Co., Ltd., product name: ND-20) was added to the same amount as in Example 1, and water was added to make 100 parts by weight, followed by stirring. This printing paste composition was then used to print 60 / 2 cotton lawn in the same manner as in Example 1, followed by a steaming process (103°C x 20 minutes) and a desizing treatment by desizing soaping (60-70°C x 10 minutes), yielding a dyed product. The dyed products obtained using the above method had soaping stains on the white areas, and the color strength was clearly 20-30% lighter than when a printing binder was used.

[0043] Comparative Example 2 A walnut extract solution, a commercially available plant dye, was prepared as a naturally derived dye solution, and aluminum acetate was prepared as a mordant. The same amounts as in Example 4 of commercially available printing paste (the same as in Comparative Example 1) and water were added to make 100 parts by weight, and the mixture was stirred to prepare a printing paste composition. This printing paste composition was then used to print 60 / 2 cotton lawn in the same manner as in Comparative Example 1, followed by a steaming process and a desizing treatment using desizing soaping to obtain a dyed product. In the case of the above method, when the wastewater was observed after the desizing soaping, it was found that the wastewater was only slightly contaminated, but the color depth of the dyed product obtained was lighter than when a printing binder was used.

[0044] Comparative Example 3 A commercially available botanical dye, Scutellaria extract, was prepared as a naturally derived dye solution, and aluminum acetate was prepared as a mordant. The same amounts as in Example 3 of commercially available printing paste (the same as in Comparative Example 1) and water were added to make 100 parts by weight, and the mixture was stirred to prepare a printing paste composition. This printing paste composition was then used to print 60 / 2 cotton lawn in the same manner as in Comparative Example 1, followed by a steaming process and a desizing treatment with desizing soaping to obtain a dyed product. In the case of the above method, when the wastewater was observed after the desizing soaping, it was found that the wastewater was only slightly contaminated, but the color strength of the dyed products obtained was lighter than when a printing binder was used. The dyed products obtained by the above method had a color strength about 30% lighter than those dyed using a printing binder, and the dye came off along with the sizing agent, causing coloration in the wastewater.

[0045] Comparative Example 4 A commercially available plant dye, catechu extract, was prepared as a naturally derived dye solution, and aluminum acetate was prepared as a mordant. The same amount as in Example 5 was added to commercially available printing paste (the same as in Comparative Example 1) and water to make 100 parts by weight, and the mixture was stirred to prepare a printing paste composition. This printing paste composition was then used to print 60 / 2 cotton lawn in the same manner as in Comparative Example 1, followed by a steaming process and a desizing treatment using desizing soaping to obtain a dyed product. In the case of the above method, the color of the wastewater after desizing soaping was not deep, but the color strength (dyeing concentration) of the obtained dyed product was felt to be about 30% lighter than the color strength when printing was performed using a printing binder.

[0046] Comparative Example 5 A lac dye extract, a commercially available plant dye, was prepared as a naturally derived dye solution, and aluminum acetate was prepared as a mordant. The same amounts as in Example 6 of commercially available printing paste (the same as in Comparative Example 1) and water were added to make 100 parts by weight, and the mixture was stirred to prepare a printing paste composition. This printing paste composition was then used to print 60 / 2 cotton lawn in the same manner as in Comparative Example 1, followed by a steaming process and a desizing treatment with desizing soaping to obtain a dyed product. In the case of dyed products obtained using the above method, when desizing soaping was performed after the steaming process, the white areas of the cotton fabric were more stained than when a printing binder was used, and the color strength was about 30% lighter.

[0047] Comparative Example 6 A logwood extract, a commercially available plant dye, was prepared as a naturally derived dye solution, and ferric pyroacetate was prepared as a mordant. The same amount as in Example 7 was added to a commercially available printing paste (the same as in Comparative Example 1) and water to make 100 parts by weight, and the mixture was stirred to prepare a printing paste composition. This printing paste composition was then used to print 60 / 2 cotton lawn in the same manner as in Comparative Example 1, followed by a steaming process and a desizing treatment using desizing soaping to obtain a dyed product. The color strength of the dyed products obtained using the above method was about 30% lighter than that obtained using a printing binder, and considerable staining was observed.

[0048] Comparative Example 7 As natural dye solutions, commercially available plant dyes, Indian indigo paste and Sophora japonica extract (same as in Example 8), were prepared, and an aluminum acetate mordant was prepared. A blend of this Indian indigo paste, Sophora japonica extract, and mordant was added to a commercially available printing paste (same as in Comparative Example 1) and stirred to prepare a printing paste composition. This printing paste composition was then used to carry out the same process as in Comparative Example 1, to obtain a dyed product. In Comparative Example 7, Indian indigo has substantivity, and the fabric was specifically subjected to a cationization treatment for the Sophora japonica extract, and 60 / 2 cotton lawn was used as the substrate to be dyed. In the case of the dyed products obtained using the above method, considerable staining was observed on the white areas, much of the dye was removed, and spots were also observed in the dyed color.

[0049] In all of the above Comparative Examples 1 to 7, after rinsing with water, the dyed products were subjected to the commonly performed soaping (60 to 70°C x 10 minutes). When the dyed products were observed after drying, it was found that the white areas were stained with the color of the residual soaping liquid, and the color intensity of the plant dye was clearly 30 to 40% lower than in Examples 1 to 9.

[0050] Furthermore, when #50 polyester satin was prepared as the substrate and the dyeing compositions described in each example were used to carry out the same processing tests as for the cotton lawn, a slight decrease in density was observed, but this was thought to be due to the difference in the amount of binder applied depending on the substrate, and it was confirmed that the same results in terms of dye density as for cotton lawn were obtained.The experiment using #50 polyester satin proved that the dyeing compositions of the present invention can also be used to print synthetic fibers using plant dyes and mordants.

[0051] As described above, when the dyeing composition of the present invention containing a printing binder containing chitosan is used, a pretreatment step for improving dyeability is not required, and the plant dye and the mordant can be absorbed without any waste and dyed into the fiber, so the method for producing a dyed product of the present invention using the dyeing composition is excellent as a printing method. Furthermore, a chitosan-containing binder can be used for all plant dyes, and the chitosan-containing binder is fixed on the surface of the fiber after printing. Therefore, by using the method for producing a dyed product of the present invention, it is possible to impart an antibacterial effect to fibers printed with naturally derived dyes of various colors. In addition, the representative color printed portions of the dyed products obtained in Examples 1 to 9 above were subjected to an antibacterial test using Staphylococcus aureus according to the JIS-L-1902 bacterial liquid absorption method, and the results showed that all of the dyed products had antibacterial properties. [Industrial Applicability]

[0052] The dye composition of the present invention comprises 1) It can contribute to labor-saving in the printing process using plant dyes. 2) Printing with chitosan-containing binders reduces waste of plant dyes and mordants. 3) No soaping is required, reducing drainage load. 4) It can give antibacterial effect to the printed part. These advantages make it possible to print both natural and synthetic fibers, and it can be said that the method is highly applicable industrially.

Claims

1. Component A: a dye of natural origin, Component B: a printing binder containing an acid, chitosan, a urethane resin, and mineral spirits; Component C: a mordant, A dye composition comprising:

2. 2. The dye composition according to claim 1, wherein the naturally occurring dye is a liquid dye product of a plant dye and / or a pigment component extracted from an insect.

3. 3. The dye composition according to claim 1, wherein the mordant is a mordant solution containing a salt of a metal selected from the group consisting of aluminum, titanium and iron.

4. 4. The dye composition according to claim 1, wherein the acid is selected from the group consisting of hydrochloric acid, nitric acid, formic acid, acetic acid and propionic acid.

5. 5. The dye composition according to claim 1, wherein, based on 100 parts by weight of the dye composition, the acid content is 2.4 to 6.4 parts by weight, the chitosan content is 2.4 to 6.4 parts by weight, the urethane resin content is 3.2 to 8.0 parts by weight (solid content equivalent), and the mineral spirit content is 4 to 20 parts by weight.

6. Component A: Indian indigo, Component B: a printing binder containing an acid, chitosan, a urethane resin, and mineral spirits; A dye composition comprising:

7. The following steps I to III: Step I: a step of dissolving 3 to 8 parts by weight of chitosan in 3 to 8 parts by weight of acid, adding 4 to 10 parts by weight (in terms of solid content) of urethane resin, 5 to 25 parts by weight of mineral spirits, and water in an amount that makes the total solution 100 parts by weight, and stirring the mixture to prepare a binder for textile printing; Step II: adding 0.6 to 15 parts by weight of a naturally-derived dye solution to 70 to 85 parts by weight of the printing binder obtained in Step I, stirring, then adding 0.1 to 3 parts by weight (solid content equivalent) of a mordant, and adding water in an amount that makes the total solution 100 parts by weight, followed by stirring to prepare a dye composition; Step III: A step of applying the dye composition obtained in Step II to a fiber to be dyed to perform printing, followed by a steaming step to develop color and obtain a dyed product. A method for producing a dyed product, comprising:

8. 8. The method for producing a dyed product according to claim 7, wherein the acid is selected from the group consisting of hydrochloric acid, nitric acid, formic acid, acetic acid and propionic acid.

9. 9. The method for producing a dyed product according to claim 7 or 8, wherein the fibers to be printed in step III are selected from the group consisting of cellulose fibers, protein fibers and synthetic fibers.

10. The following steps I to III: Step I: a step of dissolving 3 to 8 parts by weight of chitosan in warm water and 3 to 8 parts by weight of acid, adding 4 to 10 parts by weight (in terms of solid content) of urethane resin, 5 to 25 parts by weight of mineral spirits, and water in an amount that makes the total solution 100 parts by weight, and stirring the mixture to prepare a binder for textile printing; Step II: adding 0.6 to 15 parts by weight of an Indian indigo-containing dye solution to 70 to 85 parts by weight of the printing binder obtained in Step I, stirring, and then adding water in an amount that makes the total solution 100 parts by weight, and stirring the mixture to prepare a dye composition; Step III: A step of applying the dye composition obtained in Step II to a fiber to be dyed to perform printing, followed by a drying step and a steaming step to develop color and obtain a dyed product. A method for producing a dyed product, comprising: